(en)A washing or cleaning composition shaped body comprising a cavity which has at least two orifices on the surface of the shaped body, characterized in that the orifices of the cavity are sealed by two separate sealing elements, are suitable for the combined formulation of solid and liquid or free-flowing washing or cleaning compositions in one dosage unit.

1.ApplicationNumber: US-73609907-A
1.PublishNumber: US-2007244025-A1
2.Date Publish: 20071018
3.Inventor: TIMMANN ULF A.
FILECCIA SALVATORE
BARTHEL WOLFGANG
DUFFELS ARNO

4.Inventor Harmonized: TIMMANN ULF A(DE)
FILECCIA SALVATORE(DE)
BARTHEL WOLFGANG(DE)
DUFFELS ARNO(DE)

5.Country: US
6.Claims:
(en)A washing or cleaning composition shaped body comprising a cavity which has at least two orifices on the surface of the shaped body, characterized in that the orifices of the cavity are sealed by two separate sealing elements, are suitable for the combined formulation of solid and liquid or free-flowing washing or cleaning compositions in one dosage unit.

7.Description:
(en)CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation under 35 U.S.C. § 365 and 35 U.S.C. § 120 of International Application PCT/EP2005/011066, filed Oct. 14, 2005. This application also claims priority under 35 U.S.C. § 119 of DE 10 2004 051 553.0, filed Oct. 22, 2004. Each application is incorporated herein by reference in its entirety.


STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not Applicable
INCORPORATION-BY-REFERENCE OF MATERIAL SUBMITTED ON A COMPACT DISC
Not Applicable
BACKGROUND OF THE INVENTION
(1) Field of the Invention
The present invention lies in the field of washing or cleaning compositions. In particular, the present invention relates to a process for producing washing or cleaning compositions, especially dosage units of washing or cleaning compositions.
Washing or cleaning compositions are nowadays available to the consumer in various supply forms. In addition to washing powders and granules, this range also includes, for example, detergent concentrates in the form of extruded or tableted compositions. These solid, concentrated and compacted supply forms feature reduced volume per dosage unit and hence reduce the costs for packaging and transport. The washing or cleaning composition tablets, in particular, additionally satisfy the wish of the consumer for simple dosage. The corresponding compositions have been described comprehensively in the prior art. In addition to the advantages cited, compacted washing or cleaning compositions, however, also have a series of disadvantages. Tableted supply forms, in particular, owing to their high compaction, frequently feature retarded decomposition and hence retarded release of their ingredients. To solve this “conflict” between sufficient tablet hardness and short decomposition times, the patent literature discloses numerous technical solutions, and reference shall be made at this point by way of example to the use of so-called tablet disintegrants. These disintegration accelerants are added to the tablets in addition to the washing- or cleaning-active substances, but generally do not have any washing- or cleaning-active properties of their own, and in this way increase the complexity and the costs of these compositions. A further disadvantage of the tableting of active substance mixtures, especially washing- or cleaning-active substance-containing mixtures, is the inactivation of the active substances present as a result of the compacting pressure which occurs in the tableting. An inactivation of the active substances can also be effected by chemical reaction owing to the increased contact surfaces of the ingredients resulting from the tableting.
As an alternative to the above-described particulate or compacted washing or cleaning compositions, solid or liquid washing or cleaning compositions which have water-soluble or water-dispersible packaging have increasingly been described in the last few years. Like the tablets, these compositions feature simplified dosage, since they can be dosed together with the outer packaging into the washing machine or the machine dishwasher, and, on the other hand, they simultaneously also enable the formulation of liquid or pulverulent washing or cleaning compositions which feature better dissolution and more rapid activity compared to the compactates.
(2) Description of Related Art, Including Information Disclosed Under 37 C.F.R. §§1.97 and 1.98.
For example, European Patent No. EP 1 314 654 A2 (Unilever) discloses a dome-shaped pouch with a receiving chamber which comprises a liquid.
Published International Application WO 01/83657 A2 (Procter & Gamble), in contrast, provides pouches which comprise two particulate solids, each of which is present in fixed regions and does not mix with the other, in a receiving chamber.
In addition to the packages which have only one receiving chamber, the prior art also discloses supply forms which comprise more than one receiving chamber or more than one formulation type.
European Patent Application No. EP 1 256 623 A1 (Procter & Gamble) provides a kit composed of at least two pouches with different composition and different appearance. The pouches are present separately from one another and not as a compact individual product.
A process for producing multichamber pouches by adhesive-bonding of two individual chambers is described in International Patent Application WO 02/85736 A1 (Reckitt Benckiser).
BRIEF SUMMARY OF THE INVENTION
It is an object of the present application to provide a process for producing washing or cleaning compositions which enables the combined formulation of solid and liquid or free-flowing washing or cleaning compositions in mutually separate regions of a compact dosage unit. The process end product should be notable for an attractive appearance.
This object is achieved by washing or cleaning composition shaped bodies comprising a cavity which has at least two orifices on the surface of the shaped body, characterized in that the orifices of the cavity are sealed by two separate sealing elements.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)
Not Applicable


DETAILED DESCRIPTION OF THE INVENTION
Surprisingly, these inventive compositions not only achieve the aforementioned object of the invention but also feature improved washing and cleaning performance compared to conventional washing or cleaning compositions.
The shaped bodies used in the inventive compositions are preferably compacted, preferably tableted, or extruded or cast shaped bodies. However, particular preference is given in the context of the present application to tableted shaped bodies.
Washing or cleaning composition tablets are produced in the manner known to those skilled in the art by compressing particulate starting substances. To produce the tablets, the premixture is compacted in a die between two punches to form a solid compact. This operation, which is informally referred to below as “tableting,” divides into four sections: dosage, compaction (elastic deformation), plastic deformation and expulsion. The tableting is preferably effected on rotary tableting presses.
In the case of tableting with rotary tableting presses, it has been found to be advantageous to perform the tableting with minimum weight deviations of the tablet. In this way, it is also possible to reduce the hardness variations of the tablet. Low weight variations can be achieved in the following ways:
use of plastic inlays having low thickness tolerances; low rotational speed of the rotor; large filling shoe; adjustment of the rotational speed of the filling shoe vane to the rotational speed of the rotor; filling shoe with constant powder height; and decoupling of filling shoe and powder reservoir.

To reduce caking on the punches, it is possible to use all anti-adhesion coatings known from the prior art. Plastic coatings, plastic inlays or plastic punches are particularly advantageous. Rotary punches have also been found to be advantageous, in which case upper and lower punches should be designed so as to be capable of rotating, if possible. In the case of rotating punches, it is generally possible to dispense with a plastic inlay. Here, the punch surfaces should be electropolished.
Processes preferred in the context of the present invention are characterized in that the compression is effected at pressures of from 0.01 to 50 kNcm −2 preferably from 0.1 to 40 kNcm −2 and, in particular, from 1 to 25 kNcm −2 .
The individual phases of biphasic or multiphasic tablets are preferably arranged in layers. The weight ratio of the phase with the lowest proportion by weight of the tablet is preferably at least 50% by weight, preferentially at least 10% by weight and, in particular, at least 20% by weight. The proportion by weight of the phase with the highest proportion by weight in the tablet in biphasic tablets is preferably not more than 90% by weight, preferentially not more than 80% by weight and, in particular, between 55 and 70% by weight. In triphasic tablets, the proportion by weight of the phase with the highest proportion by weight in the tablet is preferably not more than 80% by weight, preferentially not more than 70% by weight and, in particular, between 40 and 60% by weight.
In a further preferred embodiment of the inventive washing or cleaning composition shaped bodies, the tablet has a structure like onion skin. In such a tablet, at least one inner layer is surrounded completely by at least one outer layer.
In the context of the present invention, the term “cavity” indicates either depressions or apertures or holes which pass through the shaped body and join two sides of the shaped body, preferably opposite sides of the shaped body, for example, the bottom and top surface of the shaped body, to one another.
The shape of the cavity, which is preferably a depression, can be selected freely, preference being given to tablets in which at least one depression has a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonally, heptagonally and octagonally prismatic, and rhombohedral shape. It is also possible to realize entirely irregular depression shapes, such as arrow or animal shapes, trees, clouds, etc. As in the case of the base shaped bodies too, preference is given to depressions with rounded corners and edges or with rounded corners and chamfered edges. The bottom surface of the depression may be planar or tilted.
In a particularly preferred embodiment, the cavity is an aperture which connects two opposite sides of the shaped body to one another. A corresponding shaped body can be referred to as an annulus. The opening surfaces of the aperture in the surface of this annulus may have the same size, but may also differ with regard to their size. When the shaped body used is a tablet, the shaped body with such an aperture corresponds to a so-called ring tablet. Particular preference is given to using such shaped bodies with an aperture, in which the opening surfaces of the aperture on the opposite sides of the shaped body, based on the larger of the two opening surfaces, differ by less than 80%, preferably by less than 60%, preferentially by less than 40%, more preferably by less than 20% and, in particular, by less than 10%. Particular preference is given to using ring tablets in which the opening surfaces of the aperture have the same size. The cross section of the aperture may be angular or round Cross sections having one, two, three, four, five, six or more corners are realizable, but particular preference is given in the context of the present application to those shaped bodies which have an aperture without corners, preferably an aperture having a round or oval cross section. “Cross section” refers to a surface which is at right angles to a straight connecting line between the centers of the two opposite opening surfaces of the shaped body.
Of course, the shaped body may also have more than one cavity. Particular preference is given in the context of the present application to shaped bodies having two, three, four, five, six, seven, eight, nine, ten, eleven, twelve or more cavities When the shaped body has more than one cavity, these cavities may either be the above-described depressions or the above-described apertures. Particular preference is given in the context of the present application to shaped bodies which have more than one cavity, at least one of the cavities being a depression, and at least one other of the cavities being an aperture.
The volume of the cavity is preferably between 0.1 and 20 ml, preferably between 0.2 and 15 ml, more preferably between 1 and 10 ml and, in particular, between 2 and 7 ml.
Preference is given in accordance with the invention to washing or cleaning composition shaped bodies, characterized in that the cavity has two orifices which are present on opposite sides of the shaped body.
The inventive washing or cleaning composition shaped bodies are characterized by the two separate sealing elements on the orifices of the cavity of the shaped body. The sealing elements usable in accordance with the invention are a multitude of different media, preference being given in accordance with the invention to washing or cleaning composition shaped bodies, characterized in that the sealing element is a film, a filled water-soluble vessel or a second shaped body.
In a preferred process variant, the sealing element used is a film material, preferably a film material comprising one or more water-soluble polymer(s), preferably a material from the group of (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives and mixtures thereof.
“Polyvinyl alcohols” (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure


which also comprise structural units of the


type in small fractions (approximately 2%).

Commercial polyvinyl alcohols, which are supplied as white-yellowish powders or granules with degrees of polymerization in the range from approximately 100 to 2,500 (molar masses from approximately 4,000 to 100,000 g/mol), have degrees of hydrolysis of 98-99 or 87-89 molar %, and thus also comprise a residual content of acetyl groups. The polyvinyl alcohols are characterized by the manufacturer by specifying the degree of polymerization of the starting polymer, the degree of hydrolysis, the hydrolysis number or the solution viscosity. Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); they are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexing with nickel or copper salts or by treatment with dichromates, boric acid or borax. The coatings made of polyvinyl alcohol are largely impenetrable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow steam to pass through.
In the context of the present invention, it is preferred that the film material used in the process according to the invention comprises at least in part a polyvinyl alcohol whose degree of hydrolysis is from 70 to 100 molar %, preferably from 80 to 90 molar %, more preferably from 81 to 89 molar % and, in particular, from 82 to 88 molar %. In a preferred embodiment, the first film material used in the process according to the invention consists to an extent of at least 20% by weight, more preferably to an extent of at least 40% by weight, even more preferably to an extent of at least 60% by weight and, in particular, to an extent of at least 80% by weight of a polyvinyl alcohol whose degree of hydrolysis is from 70 to 100 molar %, preferably from 80 to 90 molar %, more preferably from 81 to 89 molar % and, in particular, from 82 to 88 molar %.
The film materials used are preferably polyvinyl alcohols of a certain molecular weight range, preference being given in accordance with the invention to the film material comprising a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol −1 , preferably from 11,000 to 90,000 gmol −1 , more preferably from 12,000 to 80,000 gmol −1 and, in particular, from 13,000 to 70,000 gmol −1 .
The degree of polymerization of such preferred polyvinyl alcohols is between about 200 and about 2,100, preferably between about 220 and about 1,890, more preferably between about 240 and about 1,680 and, in particular, between about 260 and about 1,500.
The polyvinyl alcohols described above are widely available commercially, for example, under the trade name Mowiol® (Clariant). Polyvinyl alcohols which are particularly suitable in the context of the present invention are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88 and Mowiol® 8-88.
Further polyvinyl alcohols which are particularly suitable as a film material can be taken from the table below:
Degree of Molar mass Melting point Name hydrolysis [%] [kDa] [° C.] Airvol ® 205 88 15-27 230 Vinex ® 2019 88 15-27 170 Vinex ® 2144 88 44-65 205 Vinex ® 1025 99 15-27 170 Vinex ® 2025 88 25-45 192 Gohsefimer ® 5407 30-28 23 600 100 Gohsefimer ® LL02 41-51 17 700 100

Further polyvinyl alcohols suitable as a film material are ELVANOL® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX® 72.5, 78, B72, F80/40, F88/4, F88/26, F88/40, F88/47 (trademark of Harlow Chemical Co.), Gohsenol® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (trademark of Nippon Gohsei K.K.).

The water solubility of PVAL can be altered by aftertreatment with aldehydes (acetalization) or ketones (ketalization). In this context, particularly preferred polyvinyl alcohols which are particularly advantageous due to their exceptionally good solubility in cold water have been found to be those which are acetalized or ketalized with the aldehyde and keto groups, respectively, of saccharides or polysaccharides or mixtures thereof. The reaction products of PVAL and starch can be used exceptionally advantageously.
In addition, the solubility in water can be altered by complexation with nickel or copper salts or by treatment with dichromates, boric acid, borax, and thus be adjusted in a controlled manner to desired values. Films of PVAL are largely impenetratable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow steam to pass through.
Examples of suitable water-soluble PVAL films are the PVAL films obtainable under the name “SOLUBLON®” from Syntana Handelsgesellschaft E. Harke GmbH & Co. Their solubility in water can be adjusted to a precise degree, and films of this product series are obtainable which are soluble in the aqueous phase in all temperature ranges relevant for the application.
Polyvinylpyrrolidones, referred to for short as PVP, can be described by the following general formula:


PVPs are prepared by free-radical polymerization of 1-vinylpyrrolidone. Commercially available PVPs have molar masses in the range from approximately 2,500 to 750,000 g/mol and are supplied as white, hygroscopic powders or as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula

H—[O—CH 2 —CH 2 ] n —OH

which are prepared industrially by base-catalyzed polyaddition of ethylene oxide (oxirane) in systems containing usually small amounts of water, with ethylene glycol as the starter molecule. They have molar masses in the range from about 200 to 5,000,000 g/mol, corresponding to degrees of polymerization n of from about 5 to >100,000. Polyethylene oxides have an exceptionally low concentration of reactive hydroxyl end groups and exhibit only weak glycol properties.

Gelatin is a polypeptide (molar mass: from approximately 15,000 to >250,000 g/mol) which is obtained primarily by hydrolysis of the collagen present in skin and bones of animals under acidic or alkaline conditions. The amino acid composition of the gelatin corresponds substantially to that of the collagen from which it has been obtained and varies depending on its provenance.
In the context of the present invention, preference is also given to film materials which comprise a polymer from the group of starch and starch derivatives, cellulose and cellulose derivatives, in particular, methylcellulose and mixtures thereof.
Starch is a homoglycan, the glucose units being linked α-glycosidically. Starch is made up of two components of different molecular weight: of from approximately 20 to 30% of straight-chain amylose (MW from approximately 50,000 to 150,000) and from 70 to 80% of branched-chain amylopectin (MW from approximately 300,000 to 2,000,000). In addition, small amounts of lipids, phosphoric acid and cations are also present. While the amylose forms long, helical, intertwined chains having from approximately 300 to 1,200 glucose molecules owing to the binding in the 1,4-arrangement, the chain branches in the case of amylopectin after, on average, 25 glucose units by a 1,6-bond to give a branch-like structure having from about 1,500 to 12,000 molecules of glucose. In addition to pure starch, suitable substances for the preparation of water-soluble coatings of the laundry detergent, dishwasher detergent and cleaning composition portions in the context of the present invention are also starch derivatives which are obtainable from starch by polymer-like reactions. Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. However, starches in which the hydroxyl groups have been replaced by functional groups which are not bonded by means of an oxygen atom can also be used as starch derivatives. The group of starch derivatives includes, for example, alkali metal starches, carboxymethyl starch (CMS), starch esters and starch ethers, and also amino starches.
Pure cellulose has the formal gross composition (C 6 H 10 O 5 ), and, considered in a formal sense, constitutes a β-1,4-polyacetal of cellobiose which is itself formed from two molecules of glucose. Suitable celluloses consist of from approximately 500 to 5,000 glucose units and accordingly have average molar masses of from 50,000 to 500,000. Cellulose-based disintegrants usable in the context of the present invention also include cellulose derivatives which are obtainable from cellulose by polymer-like reactions. Such chemically modified celluloses comprise, for example, products of esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bonded by means of an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxy-methylcellulose (CMC), cellulose esters and cellulose ethers, and also aminocelluloses.
Further preferred film materials are characterized in that they comprise hydroxypropylmethyl cellulose (HPMC) which has a degree of substitution (average number of methoxy groups per anhydroglucose unit of cellulose) of from 1.0 to 2.0, preferably of from 1.4 to 1.9, and a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose) of from 0.1 to 0.3, preferably of from 0.15 to 0.25.
The film material used is preferably transparent. In the context of this invention, transparency means that the transmittance within the visible spectrum of light (410 to 800 nm) is greater than 20%, preferably greater than 30%, exceptionally preferably greater than 40% and, in particular, greater than 50%. Thus, as soon as one wavelength of the visible spectrum of light has a transmittance greater than 20%, it should be considered as transparent in the context of the invention.
Compositions produced in accordance with the invention, which have been produced using transparent film material, may comprise a stabilizer. In the context of the invention, stabilizers are materials which protect the ingredients at least partly enclosed by the film material from decomposition or deactivation by incident light. It has been found that antioxidants, UV absorbers and fluorescent dyes are particularly suitable here.
In the context of the invention, particularly suitable stabilizers are the antioxidants. In order to prevent undesired changes to the formulations caused by incident light and thus free-radical decomposition, the formulations may comprise antioxidants. The antioxidants used may be, for example, phenols, bisphenols and thiobisphenols substituted by sterically hindered groups. Further examples are propyl gallate, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long-chain (C 8 -C 22 ) esters of gallic acid, such as dodecyl gallate. Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus, such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives such as isopropyl citrate, compounds containing enediol groups, known as reductones, such as ascorbic acid and derivatives thereof such as ascorbyl palmitate, organosulfur compounds such as the esters of 3,3′-thio-dipropionic acid with C 1-18 -alkanols, especially C 10-18 -alkanols, metal ion deactivators which are capable of complexing the autoxidation-catalyzing metal ions, for example, copper, such as nitrilotriacetic acid, and derivatives and mixtures thereof. Antioxidants may be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, more preferably from 0.01 to 20% by weight and, in particular, from 0.03 to 20% by weight. A further class of stabilizers which can be used with preference is that of the UV absorbers. UV absorbers can improve the photostability of the formulation constituents. They include organic substances (light protection filters) which are capable of absorbing ultraviolet rays and emitting the energy absorbed again in the form of longer-wavelength radiation, for example heat. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone having substituents in the 2- and/or 4-position which are effective by virtue of radiationless deactivation. Also suitable are substituted benzotriazoles, for example, the water-soluble monosodium 3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(methylpropyl)benzenesulfonate (Cibafast® H), 3-phenyl-substituted acrylates (cinnamic acid derivatives), optionally having cyano groups in the 2-position, salicylates, organic nickel complexes and natural substances such as umbelliferone and endogenous urocanic acid. Of particular significance are biphenyl and, in particular, stilbene derivatives which are available commercially as Tinosorb® FD or Tinosorb® FR ex Ciba UV-B absorbers include 3-benzylidenecamphor or 3-benzylidenenorcamphor and derivatives thereof, for example, 3-(4-methylbenzylidene)camphor; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4-(dimethylamino)benzoate, 2-octyl 4-(dimethylamino)benzoate and amyl 4-(dimethylamino)benzoate; esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene); esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomethyl salicylate; derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone; esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzomalonate; triazine derivatives, for example, 2,4,6-trianilino(p-carbo-2′-ethyl-1′-hexyloxy)-1,3,5-triazine and octyltriazone or dioctylbutamidotriazone (Uvasorb® HEB); propane-1,3-diones, for example, 1-(4-tert-butylphenyl)-3-(4′-methoxyphenyl)propane-1,3-dione; ketotricyclo-(5.2.1.0)decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and the alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts thereof; sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; sulfonic acid derivatives of 3-benzylidenecamphor, for example, 4-(2-oxo-3-bornylidenemethyl)benzenesulfonic acid and 2-methyl-5-(2-oxo-3-bornylidene)sulfonic acid and salts thereof.
Useful typical UV-A filters are, in particular, derivatives of benzoylmethane, for example 1-(4′-tert-butylphenyl)-3-(4′-methoxyphenyl)propane-1,3-dione, 4-tert-butyl-4′-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3-(4′-isopropylphenyl)propane-1,3-dione, and enamine compounds. The UV-A and UV-B filters can of course also be used in mixtures. In addition to the soluble substances mentioned, insoluble light protection pigments are also suitable for this purpose, specifically finely dispersed, preferably nanoized, metal oxides or salts. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and additionally oxides of iron, zirconium, silicon, manganese, aluminum and cerium, and mixtures thereof. The salts used may be silicates (talc), barium sulfate or zinc stearate. The oxides and salts are already used in the form of pigments for skincare and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and, in particular, between 15 and 30 nm. They may have a spherical shape, although it is also possible to use particles which have an ellipsoidal shape or a shape which deviates in some other way from the spherical form. The pigments may also be surface-treated, i.e., hydrophilicized or hydrophobicized. Typical examples are coated titanium dioxides, for example, titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Suitable hydrophobic coating compositions are, in particular, silicones and especially trialkoxyoctylsilanes or simethicones Preference is given to using micronized zinc oxide.
A further class of stabilizers to be used with preference is that of the fluorescent dyes They include the 4,4′-diamino-2,2′-stilbenedisulfonic acids (flavonic acids), 4,4′-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diaryl-pyrazolines, naphthalimides, benzoxazole, benzisoxazole and benzimidazole systems, and pyrene derivatives substituted by heterocycles. Of particular significance in this connection are the sulfonic salts of diaminostilbene derivatives, and polymeric fluorescent substances.
Preferred compositions have, as a sealing element, a film material having a thickness between 5 and 2,000 μm, preferably between 10 and 1,000 μm, more preferably between 15 and 500 μm, even more preferably between 20 and 200 μm and, in particular, between 25 and 100 μm.
The films used may be single-layer or multilayer films (laminate films). Irrespective of their chemical or physical structure, the water content of the film materials is preferably below 10% by weight, more preferably below 7% by weight, even more preferably below 5% by weight and, in particular, below 4% by weight.
To spatially fix shaped body and sealing element, the shaped body and the sealing element are adhesively bonded to one another. Preference is given to effecting the adhesive bond close to the opening of the cavity. The adhesive bonds are more preferably along a circumferential seal seam. This seal seam is realizable by a number of different procedures. However, preference is given to those processes in which the adhesive bond is effected by the action of adhesives and/or solvents and/or pressing or squeezing forces. In the case of heat-sealing too, particular preference is given to a circumferential seal seam, i.e a continuous seal seam. A number of different tools and processes are available to the person skilled in the art for the heat-sealing of shaped body and film material.
In a first preferred embodiment, the heat-sealing is effected by the action of heated sealing tools.
In a second preferred embodiment, the heat-sealing is effected by the action of a laser beam.
In a third preferred embodiment, the heat-sealing is effected by the action of hot air.
With particular preference, the shaped body and the seal seam(s) in the inventive washing or cleaning composition shaped bodies are sealed to one another by a heat-sealed seam.
The cavity of the inventive washing or cleaning composition shaped bodies, i.e., the space surrounded by the shaped body and the separate sealing elements, is preferably filled with one of more further washing- or cleaning-active substances or substance mixtures. For the filling, solid and also liquid substances or substance mixtures are suitable.
With preference, the cavity is filled with free-flowing washing- and cleaning-active formulations, preferably liquid(s), especially melts, and/or gel(s) and/or powders and/or granule(s) and/or extrudate(s) and/or compactate(s).
In the present application, the term “liquid” denotes substances or substance mixtures, and equally solutions or suspensions which are present in the liquid state of matter.
Powder is a general term for a form of commination of solid substances and/or substance mixtures which is obtained by commination, i.e., trituration or grinding in a mortar (pulverizing), grinding in mills, or as a consequence of atomization or freeze-drying. A particularly fine division is often known as atomization or micronization; the corresponding powders are referred to as micropowders.
According to particle size, a rough division of the powders into coarse, fine and ultrafine powders is customary; pulverulent bulk materials are classified more precisely by means of their apparent density and by sieve analysis. However, powders preferred in the context of the present application have lower particle sizes below 5,000 μm, preferably less than 3,000 μm, more preferably less than 1,000 μm, even more preferably between 50 and 1,000 μm and, in particular, between 100 and 800 μm.
Powders can be compacted and agglomerated by extrusion, pressing, rolling, briqueting, pelletizing and related processes. Any method known in the prior art for agglomerating particulate mixtures is suitable in principle for preparing the solids present in the inventive compositions. Agglomerates used as solid(s) with preference in the context of the present invention are, in addition to the granules, the compactates and extrudates.
Granules refer to accumulations of small granule particles. A granule particle is an asymmetric aggregate of powder particles. Granulation processes are described widely in the prior art. Granules can be produced by wet granulation, by dry granulation or compaction, and by melt solidification granulation.
The most commonly used granulation technique is wet granulation, since this technique is subject to the fewest restrictions and leads the most reliably to granules with favorable properties. Wet granulation is effected by moistening the powder mixtures with solvents and/or solvent mixtures and/or solutions of binders and/or solutions of adhesives, and is preferably performed in mixers, fluidized beds or spray towers, in which case said mixers may be equipped, for example, with stirring and kneading tools. However, it is also possible to use combinations of fluidized bed(s) and mixer(s) for the granulation, or combinations of various mixers. Depending on the starting material and the product properties desired, the granulation is effected under the action of low to high shear forces.
When the granulation is effected in a spray tower, the starting materials used may, for example, be melts (melt solidification) or preferably aqueous slurries (spray-drying) of solid substances, which are sprayed in at the top of a tower in defined particle size, solidify or dry in free fall and are obtained as granule at the bottom of the tower. Melt solidification is suitable generally particularly for the shaping of low-melting substances which are stable in the region of the melting point (for example urea, ammonium nitrate and various formulations such as enzyme concentrates, medicaments, etc.); the corresponding granules are also referred to as prills. Spray drying is used particularly for the production of washing compositions or washing composition constituents.
Further agglomeration techniques described in the prior art are extruder or perforated roll granulations, in which powder mixtures optionally admixed with granulation fluid are deformed plastically in the course of pressing through perforated disks (extrusion) or on perforated rolls. The products of the extruder granulation are also referred to as extrudates.
Particular preference is given to washing or cleaning composition shaped bodies, characterized in that the cavity is filled with a free-flowing substance, preferably a particulate substance or a liquid.
In a preferred embodiment, the cavity is filled with a bi- or multiphasic composition.
In a particularly preferred embodiment, the cavity has two orifices on opposite sides of the shaped body (ring tablet), the orifices of the cavity being sealed by two separate sealing elements, and the cavity, i.e., the space surrounded by the shaped body and the separate sealing elements, is filled with a bi- or multiphasic composition.
The bi- or multiphasic composition may comprise one or more liquid(s), one or more solid(s) or a mixture of one or more liquid(s) and one or more solids. Preferred compositions are bi-, tri- tetra- or pentaphasic. Particularly preferred bi- or multiphasic compositions comprise at least one liquid and at least one solid.
The individual phases are separated from one another in the simplest case along a common phase boundary. Examples of such compositions are powders pressed onto one another, liquids with solids dispersed therein, or tablets or castings surrounded by a powder.
In a preferred embodiment, the individual phases are separated from one another by a separate separating layer. Such separating layers may, for example, be sprayed on or poured on. Preference is given, in particular, to separating layers composed of film materials, especially water-soluble polymeric film materials. Suitable water-soluble film materials are, in particular, the water-soluble polymers disclosed above as materials for the sealing elements.
Particular preference is therefore given to shaped bodies with a cavity which has two orifices on opposite sides of the shaped body (ring tablet), the orifices of the cavity being sealed by two separate sealing elements and the cavity, i.e., the space surrounded by the shaped body and the separate sealing elements, being filled with a bi- or multiphasic composition and at least two phases of the bi- or multiphasic composition being separated from one another by a water-soluble film.
This specific embodiment is suitable, in particular, for the formulation of liquid and solid washing or cleaning compositions in a single dosage unit.
Particular preference is therefore given to shaped bodies with a cavity which has two orifices on opposite sides of the shaped body (ring tablet), the orifices of the cavity being sealed by two separate sealing elements and the cavity, i.e., the space surrounded by the shaped body and the separate sealing elements, being filled by a bi- or multiphasic composition which comprises at least one liquid and at least one solid, and at least one liquid of the bi- or multiphasic composition being separated from at least one solid of the bi- or multiphasic composition by a water-soluble film. The sealing elements used with preference in this particularly preferred embodiment are water-soluble films.
The table below gives an overview of a series of preferred inventive washing or cleaning composition shaped bodies with biphasic filling. The quantitative data are each based on the total weight of the shaped body or of phase 1 or phase 2.
Shaped body Separating layer Phase 1 Phase 2 monophasic water-soluble liquid powder, granule or film extrudate biphasic water-soluble liquid powder, granule or film extrudate monophasic with 5-80% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 1 to builder surfactant and 100% by wt. of bleach preferably from 10 to 50% by wt. of organic solvent monophasic with 5-80% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 1 to builder surfactant and 95% by wt. of bleach preferably from 10 to and from 0.1 to 10% by 50% by wt. of organic wt. of bleach activator solvent monophasic with 5-80% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 0.1 builder surfactant and to 100% by wt. of preferably from 10 to enzyme 50% by wt. of organic solvent monophasic with 5-80% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 0.1 builder surfactant and to 100% by wt. of glass preferably from 10 to corrosion inhibitor 50% by wt. of organic solvent monophasic with 5-80% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 0.1 builder surfactant and to 100% by wt. of silver preferably from 10 to corrosion inhibitor 50% by wt. of organic solvent monophasic with water-soluble liquid with from 10 to powder, granule or water-soluble film film 90% by wt. of nonionic extrudate with from 0.1 5-80% by wt. of surfactant and to 100% by wt. of builder preferably from 10 to cationic or amphoteric 50% by wt. of organic polymers solvent biphasic with 5-80% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 1 to builder surfactant and 100% by wt. of bleach preferably from 10 to 50% by wt. of organic solvent biphasic with 5-80% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 1 to builder surfactant and 95% by wt. of bleach preferably from 10 to and from 0.1 to 10% by 50% by wt. of organic wt. of bleach activator solvent biphasic with 5-80% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 1 to builder surfactant and 100% by wt. of enzyme preferably from 10 to 50% by wt. of organic solvent biphasic with 5-80% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 0.1 builder surfactant and to 100% by wt. of glass preferably from 10 to corrosion inhibitor 50% by wt. of organic solvent biphasic with 5-80% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 0.1 builder surfactant and to 100% by wt. of silver preferably from 10 to corrosion inhibitor 50% by wt. of organic solvent biphasic with 5-80% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 0.1 builder surfactant and to 100% by wt. of preferably from 10 to cationic or amphoteric 50% by wt. of organic polymer solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-8% by wt. of film 90% by wt. of nonionic extrudate with from 1 to surfactant surfactant and 100% by wt. of bleach preferably from 10 to 50% by wt. of organic solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-8% by wt. of film 90% by wt. of nonionic extrudate with from 1 to surfactant surfactant and 95% by wt. of bleach preferably from 10 to and from 0.1 to 10% by 50% by wt. of organic wt. of bleach activator solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-8% by wt. of film 90% by wt. of nonionic extrudate with from 1 to surfactant surfactant and 100% by wt. of enzyme preferably from 10 to 50% by wt. of organic solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-8% by wt. of film 90% by wt. of nonionic extrudate with from 0.1 surfactant surfactant and to 100% by wt. of glass preferably from 10 to corrosion inhibitor 50% by wt. of organic solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-8% by wt. of film 90% by wt. of nonionic extrudate with from 0.1 surfactant surfactant and to 100% by wt. of silver preferably from 10 to corrosion inhibitor 50% by wt. of organic solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-8% by wt. of film 90% by wt. of nonionic extrudate with from 0.1 surfactant surfactant and to 100% by wt. of preferably from 10 to cationic or amphoteric 50% by wt. of organic polymer solvent biphasic with 0.1-8% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 1 to surfactant surfactant and 100% by wt. of bleach preferably from 10 to 50% by wt. of organic solvent biphasic with 0.1-8% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 1 to surfactant surfactant and 95% by wt. of bleach preferably from 10 to and from 0.1 to 10% by 50% by wt. of organic wt. of bleach activator solvent biphasic with 0.1-8% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 1 to surfactant surfactant and 100% by wt. of enzyme preferably from 10 to 50% by wt. of organic solvent biphasic with 0.1-8% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 0.1 surfactant surfactant and to 100% by wt. of glass preferably from 10 to corrosion inhibitor 50% by wt. of organic solvent biphasic with 0.1-8% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 0.1 surfactant surfactant and to 100% by wt. of silver preferably from 10 to corrosion inhibitor 50% by wt. of organic solvent biphasic with 0.1-8% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 0.1 surfactant surfactant and to 100% by wt. of preferably from 10 to cationic or amphoteric 50% by wt. of organic polymer solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-8% by wt. of film 90% by wt. of nonionic extrudate with from 1 to enzyme surfactant and 100% by wt. of bleach preferably from 10 to 50% by wt. of organic solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-8% by wt. of film 90% by wt. of nonionic extrudate with from 1 to enzyme surfactant and 95% by wt. of bleach preferably from 10 to and from 0.1 to 10% by 50% by wt. of organic wt. of bleach activator solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-8% by wt. of film 90% by wt. of nonionic extrudate with from 1 to enzyme surfactant and 100% by wt. of enzyme preferably from 10 to 50% by wt. of organic solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-8% by wt. of film 90% by wt. of nonionic extrudate with from 0.1 enzyme surfactant and to 100% by wt. of glass preferably from 10 to corrosion inhibitor 50% by wt. of organic solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-8% by wt. of film 90% by wt. of nonionic extrudate with from 0.1 enzyme surfactant and to 100% by wt. of silver preferably from 10 to corrosion inhibitor 50% by wt. of organic solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-8% by wt. of film 90% by wt. of nonionic extrudate with from 0.1 enzyme surfactant and to 100% by wt. of preferably from 10 to cationic or amphoteric 50% by wt. of organic polymer solvent biphasic with 0.1-8% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 1 to enzyme surfactant and 100% by wt. of bleach preferably from 10 to 50% by wt. of organic solvent biphasic with 0.1-8% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 1 to enzyme surfactant and 95% by wt. of bleach preferably from 10 to and from 0.1 to 10% by 50% by wt. of organic wt. of bleach activator solvent biphasic with 0.1-8% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 1 to enzyme surfactant and 100% by wt. of enzyme preferably from 10 to 50% by wt. of organic solvent biphasic with 0.1-8% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 0.1 enzyme surfactant and to 100% by wt. of glass preferably from 10 to corrosion inhibitor 50% by wt. of organic solvent biphasic with 0.1-8% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 0.1 enzyme surfactant and to 100% by wt. of silver preferably from 10 to corrosion inhibitor 50% by wt. of organic solvent biphasic with 0.1-8% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 0.1 enzyme surfactant and to 100% by wt. of preferably from 10 to cationic or amphoteric 50% by wt. of organic polymer solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-15% by wt. of film 90% by wt. of nonionic extrudate with from 1 to disintegration surfactant and 100% by wt. of bleach assistant preferably from 10 to 50% by wt. of organic solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-15% by wt. of film 90% by wt. of nonionic extrudate with from 1 to disintegration surfactant and 95% by wt. of bleach assistant preferably from 10 to and from 0.1 to 10% by 50% by wt. of organic wt. of bleach activator solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-15% by wt. of film 90% by wt. of nonionic extrudate with from 1 to disintegration surfactant and 100% by wt. of enzyme assistant preferably from 10 to 50% by wt. of organic solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-15% by wt. of film 90% by wt. of nonionic extrudate with from 0.1 disintegration surfactant and to 100% by wt. of glass assistant preferably from 10 to corrosion inhibitor 50% by wt. of organic solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-15% by wt. of film 90% by wt. of nonionic extrudate with from 0.1 disintegration surfactant and to 100% by wt. of silver assistant preferably from 10 to corrosion inhibitor 50% by wt. of organic solvent monophasic with water-soluble liquid with from 10 to powder, granule or 0.1-15% by wt. of film 90% by wt. of nonionic extrudate with from 0.1 disintegration surfactant and to 100% by wt. of assistant preferably from 10 to cationic or amphoteric 50% by wt. of organic polymer solvent biphasic with 0.1-15% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 1 to disintegration surfactant and 100% by wt. of bleach assistant preferably from 10 to 50% by wt. of organic solvent biphasic with 0.1-15% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 1 to disintegration surfactant and 95% by wt. of bleach assistant preferably from 10 to and from 0.1 to 10% by 50% by wt. of organic wt. of bleach activator solvent biphasic with 0.1-15% water-soluble liquid with from 10 to powder, granule or by wt. of 90% by wt. of nonionic extrudate with from 1 to disintegration film surfactant and 100% by wt. of enzyme assistant preferably from 10 to 50% by wt. of organic solvent biphasic with 0.1-15% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 0.1 disintegration surfactant and to 100% by wt. of glass assistant preferably from 10 to corrosion inhibitor 50% by wt. of organic solvent biphasic with 0.1-15% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 0.1 disintegration surfactant and to 100% by wt. of silver assistant preferably from 10 to corrosion inhibitor 50% by wt. of organic solvent biphasic with 0.1-15% water-soluble liquid with from 10 to powder, granule or by wt. of film 90% by wt. of nonionic extrudate with from 0.1 disintegration surfactant and to 100% by wt. of assistant preferably from 10 to cationic or amphoteric 50% by wt. of organic polymer solvent

As can be discerned from this table, particular preference is given to inventive washing or cleaning composition shaped bodies with a liquid surfactant-containing filling. These compositions, especially compositions having a content of disintegration assistant in the preferably tableted shaped body, compared to shaped bodies with a correspondingly increased surfactant content in the shaped body, are notable for very high cleaning performance, improved storage stability and improved processability, especially tabletability of the shaped bodies.
In the context of the present application, particular preference is accordingly given to washing or cleaning composition shaped bodies, characterized in that the cavity is divided by a water-soluble film into two separate chambers, particular preference being given to those washing or cleaning composition shaped bodies in which one of the two chambers is filled with a liquid washing or cleaning composition, the other of the two chambers with a solid washing or cleaning composition.
The separation of the individual phases by means of a water-soluble film can be configured in different ways. In a first preferred embodiment, the water-soluble films are adhesive-bonded to the shaped body. In a second preferred embodiment, the water-soluble films, preferably together with one of the sealing elements, form a receiving vessel, for example, in the form of a pouch.
The water-soluble film used for the separation of the different washing and cleaning compositions in the cavity preferably has a common seal seam, preferably a common heat sealing seam, with one of the sealing elements which seals the cavity.
To improve the appearance of the shaped body and to increase the adhesion strength of the bond between washing and cleaning composition shaped body and sealing element, these shaped bodies preferably have a coating. Particular preference is given to inventive washing or cleaning composition shaped bodies, characterized in that the shaped body has a coating. The shaped body surface is preferably coated with a surface coverage between 0.2 and 50 mg/cm 2 .
Shaped bodies preferred in accordance with the invention feature a surface coverage of the shaped body between 0.4 and 40 mg/cm 2 , preferably between 0.8 and 30 mg/cm 2 and, in particular, between 1 and 20 mg/cm 2 . The proportion by weight of the coating in the total weight of the coated shaped body is preferably less than 2% by weight, preferentially less than 1% by weight, more preferably less than 0.7% by weight and, in particular, less than 0.4% by weight.
The shaped bodies preferably have a spray coating or a dip coating. Suitable apparatus for spraying the shaped bodies is all apparatus known to those skilled in the art for this purpose. The spraying is effected preferably by means of one-substance or high-pressure spray nozzles, two-substance spray nozzles or three-substance spray nozzles. For spraying with one-substance spray nozzles, the use of a high bulk pressure (5-15 MPa) is required, while spraying in two-substance spray nozzles is effected with the aid of a compressed air stream (at 0.15-0.3 MPa). Spraying with two-substance spray nozzles is more favorable particularly with regard to possible blockages of the nozzle, but costlier as a result of the high compressed air consumption. In addition, it is also possible to use three-substance spray nozzles which, as well as the compressed air stream for atomization, a further airflow system which is intended to prevent blockages and droplet formation at the nozzle. In the process according to the invention, particular preference is given to the use of two-substance spray nozzles, preferably two-substance spray nozzles with a liquid bore between 1 and 6 mm, in particular, between 3 and 5 mm.
The coating materials used are preferably water-soluble organic polymers. In a preferred process variant, the coating material comprises one or more water-soluble polymer(s), preferably a material from the group of (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof. Further details of these substances can be found above in the description.
In the process according to the invention, preference is given to coating materials which comprise a polymer from the group of starch and starch derivatives, cellulose and cellulose derivatives, especially methylcellulose and mixtures thereof.
Preferred shaped bodies have a multiple coating. A “multiple” or “repeat” coating of the shaped body can be effected by at least surface-drying the shaped body between the individual coating steps. The coating steps are consequently interrupted by a drying step, but at least by a waiting time which preferably exceeds at least one minute, preferentially at least two minutes and, in particular, at least three minutes. Drying steps which are performed under more drastic conditions, i.e., at elevated temperature and/or stronger vacuum, can be reduced preferably to at least 10 seconds, more preferably at least 30 seconds, preferably at least 40 seconds and, in particular, to at least 50 seconds.
The surface coverage of the shaped bodies with a multiple coating is preferably between 0.2 and 100 mg/cm 2 , preferably between 1 and 80 mg/cm 2 , more preferably between 10 and 70 mg/cm 2 and, in particular, between 20 and 60 mg/cm 2 .
Preference is given, in particular, to those inventive compositions in which the shaped body is coated twice, three times or four times. When the coating is repeated more than once, it is also possible for different coating compositions to be used in the individual coating operations according to the field of use of the washing or cleaning composition shaped bodies. Particular preference is given in accordance with the invention to such compositions in which different coating materials are used.
Further coating materials which are suitable in combination with the particularly preferred water-soluble polymers, for example, in the form of a molten, dissolved or dispersed mixture, or as a second or third coating material in a repeated coating of the shaped bodies, are
a) the LCST substances;
b) the waxes; and
c) the paraffins.
LCST substances are substances which have a better solubility at lower temperatures than at higher temperatures. They are also referred to as substances with a lower critical separation temperature. These substances are generally polymers. Depending on the use conditions, the lower critical separation temperature should be between room temperature and the temperature of heat treatment, for example, between 20° C., preferably 30° C., and 100° C., in particular, between 30° C. and 50° C. The LCST substances are preferably selected from alkylated and/or hydroxyalkylated polysaccharides, cellulose ethers, polyisopropylacrylamide, copolymers of polyisopropylacrylamide and blends of these substances.
Examples of alkylated and/or hydroxyalkylated polysaccharides are methylhydroxypropylmethylcellulose (MHPC), ethyl(hydroxyethyl)cellulose (EHEC), hydroxypropylcellulose (HPC), methylcellulose (MC), ethylcellulose (EC), carboxymethylcellulose (CMC), carboxymethylmethylcellulose (CMMC), hydroxybutylcellulose (HBC), hydroxybutylmethylcellulose (HBMC), hydroxyethylcellulose (HEC), hydroxyethylcarboxymethylcellulose (HECMC), hydroxyethylethylcellulose (HEEC), hydroxypropylcellulose (HPC), hydroxypropylcarboxymethylcellulose (HPCMC), hydroxyethylmethylcellulose (HEMC), methylhydroxyethylcellulose (MHEC), methylhydroxyethylpropylcellulose (MHEPC), methylcellulose (MC) and propylcellulose (PC), and mixtures thereof, preference being given to carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose and methylhydroxypropylcellulose, and also the alkali metal salts of CMC and the readily ethoxylated MC, or mixtures of the above.
Further examples of LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethylcellulose (CMC). Further polymers which exhibit a lower critical separation temperature in water and are likewise suitable are polymers of mono- or di-N-alkylated acrylamides, copolymers of mono- or di-N-substituted acrylamides with acrylates and/or acrylic acids, or mixtures of intertwined networks of the above-mentioned (co)polymers. Also suitable are polyethylene oxide or copolymers thereof, such as ethylene oxide/propylene oxide copolymers and graft copolymers of alkylated acrylamides with polyethylene oxide, polymethacrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methyl ether, particular proteins such as poly(VATGVV), a repeat unit in the natural protein elastin, and particular alignates. Mixtures of these polymers with salts or surfactants may likewise be used as LCST substances. The LCST (lower critical separation temperature) can be modified appropriately by such additives or by means of the degree of crosslinking of the polymers.
“Waxes” are understood to mean a series of natural or synthetic substances which melt without decomposition generally above 35° C. and have comparatively low viscosity and do not string even a little above the melting point. They have highly temperature-dependent consistency and solubility. According to their origin, the waxes are divided into three groups: the natural waxes, chemically modified waxes and the synthetic waxes.
The natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax or montan wax, animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax) or uropygial grease, mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or microwaxes.
The chemically modified waxes include, for example, hard waxes such as montan ester waxes, sassol waxes or hydrogenated jojoba waxes.
Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Usable coating materials also include compounds from other substance classes which fulfill the requirements mentioned with regard to the softening point. Suitable synthetic compounds have been found to be, for example, higher esters of phthalic acid, especially dicyclohexyl phthalate, which is commercially available under the name Unimoll® 66 (Bayer AG). Also suitable are synthetic waxes formed from lower carboxylic acids and fatty alcohols, for example dimyristyl tartrate, which is obtainable under the name Cosmacol® ETLP (Condea). Conversely, it is also possible to use synthetic or partly synthetic esters formed from lower alcohols with fatty acids from native sources. This substance class includes, for example, Tegin® 90 (Goldschmidt), a glyceryl monostearate palmitate Shellac, for example Schellack-KPS-Dreiring-SP (Kalkhoff GmbH) is also usable as a further substance.
Likewise included in the waxes in the context of the present invention are, for example, the so-called wax alcohols. Wax alcohols are relatively high molecular weight, water-insoluble fatty alcohols having generally from 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of high molecular weight fatty acids (wax acids) as a main constituent of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating may optionally also comprise wool wax alcohols, which is understood to mean triterpenoid and steroid alcohols, for example lanolin, which is obtainable, for example, under the name Argowax® (Pamentier & Co.). In the context of the present invention, it is likewise possible to use as a constituent of the coating, at least in part, fatty acid glyceryl esters or fatty acid alkanolamides, but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.
Paraffin is the name for a solid or liquid mixture of purified, saturated aliphatic hydrocarbons (paraffins). It is readily soluble in ether and chloroform but insoluble in water. In the context of the present invention, it is possible to use either liquid paraffins or paraffin melts.
Owing to their dissolution properties, the liquid and solid paraffins are preferably used as a solution or dispersion in an organic solvent or solvent mixture. However, the use of the paraffins without addition of solvent in the form of melts or liquids is also possible.
Paraffin waxes have the advantage over the other natural waxes mentioned in the context of the present invention that, in the case of use of preferred washing or cleaning composition shaped bodies coated with paraffin waxes, no hydrolysis of the waxes takes place in an alkaline cleaning composition environment (as is to be expected, for example, in the case of the wax esters) since paraffin wax does not contain any hydrolysable groups.
Paraffin waxes consist mainly of alkanes and low proportions of iso- and cycloalkanes. The paraffin to be used in accordance with the invention preferably has essentially no constituents having a melting point of more than 70° C., more preferably of more than 60° C.
Preferred coating materials comprise at least one paraffin wax having a melting range of from 40° C. to 60° C.
The content in the paraffin wax used of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature (generally from about 10 to about 30° C.) is preferably at a maximum. The more solid wax constituents are present in a wax at room temperature, the more usable it is in the context of the present invention.
Paraffin waxes which are applied in the form of their melts solidify preferably within 10 minutes, preferentially within 5 minutes and, in particular, within 2 minutes.
The use of hydrophobic substances as coating material is preferred in the present invention, since these substances improve the storage performance of the inventive washing or cleaning composition shaped bodies at high air humidities. The increased moisture resistance of the coated bodies enables sealing with a water-soluble or water-dispersible film to be dispensed with after application of a hydrophobic substance. However, this is just one preferred embodiment of the process according to the invention. On the other hand, it may be preferred to apply a film to the hydrophobically coated shaped body. The film may be fused at least partly to the coating, adjoin it loosely, i.e., enclose the body, or else contain an air cushion, so that the shaped body is additionally protected from mechanical influences.
In a preferred embodiment, the shaped bodies are coated twice, three time or four times, in which case the same or different coating materials may be used in each case in the coating operation. In principle, in the context of the present invention, a distinction is drawn between coating materials from the group of the water-soluble polymers (for example PVA, PVP, gelatin or LCST polymers) and the water-insoluble waxes and the paraffins. The table which follows gives an overview of a series of particularly preferred sequences of these coating materials. The coating applied as the first layer corresponds to the layer applied first to the shaped body.
Within the table which follows, the slash (/) assumes the meaning of a “and/or” linkage.
1st layer 2nd layer 3rd layer 4th layer PVA PVA/LCST wax/paraffin wax/paraffin PVA PVA — — PVA PVA PVA — PVA PVA PVA PVA PVA LCST — — PVA LCST wax/paraffin — PVA PVA LCST — PVA PVA LCST wax/paraffin PVA LCST PVA PVA PVA PVA LCST PVA PVA PVA PVA LCST PVA wax/paraffin LCST PVA PVA PVA wax/paraffin LCST wax/paraffin PVA PVA PVA wax/paraffin PVA LCST PVA

Active substances can be added to the coating materials. Preference is given to adding dyes, fragrances or bitter substances to the coating materials.
Coated shaped bodies surprisingly feature exceptional adhesion strength of the bond between washing and cleaning composition shaped body and the sealing element, i.e., the water-soluble film used as the separating element in the cavity.
The present application therefore preferably further provides a coated shaped body with a cavity which has two orifices on opposite sides of the shaped body (ring tablet), the orifices of the cavity being sealed by two separate sealing elements and the cavity, i.e., the space surrounded by the shaped body and the separate sealing elements, being filled with a bi- or multiphasic composition and at least two phases of the bi- or multiphasic composition being separated from one another by a water-soluble film.
Owing to the improved adhesion between the shaped body and the sealing element, or the shaped body and the separating film in the cavity, this specific embodiment is suitable with particular preference for the formulation of liquid and solid washing or cleaning compositions in an individual dosage unit.
Particular preference is therefore given to coated shaped bodies with a cavity which has two orifices on opposite sides of the shaped body (ring tablet), the orifices of the cavity being sealed by two separate sealing elements and the cavity, i.e., the space surrounded by the shaped body and the separate sealing elements, being filled with a bi- or multiphasic composition which comprises at least one liquid and at least one solid, and at least one liquid of the bi- or multiphasic composition being separated from at least one solid of the bi- or multiphasic composition by a water-soluble film. The sealing elements used with preference in this particularly preferred embodiment are water-soluble films.
The weight of inventive washing or cleaning composition shaped bodies is preferably between 5 and 40 g, preferentially between 7 and 30 g and, in particular, between 10 and 25 g. The inventive washing or cleaning composition shaped bodies are preferably formulated in such a way that they can be dosed by means of the detergent compartments of textile washing machines or machine dishwashers. The volume of preferred washing or cleaning composition shaped bodies is therefore preferably between 4 and 50 ml, preferably between 6 and 30 ml and, in particular, between 8 and 25 ml.
The present application further provides a process for producing a portioned washing or cleaning composition, comprising the steps of
a) providing a washing or cleaning composition shaped body with a cavity which has two orifices on opposite sides of the shaped body; b) sealing one of the orifices with a first sealing element to form a receiving chamber formed by the sealing element and the shaped body; c) filling the receiving chamber; and d) sealing the second orifice to a second sealing element.

In a preferred embodiment of the process according to the invention, the sealing element used in step b) and/or d) is a water-soluble or water-dispersible film.
In a further preferred embodiment of the process according to the invention, the receiving chamber is filled with two different washing- or cleaning-active substances or compositions, these different substances or compositions preferably being separated from one another by a water-soluble film material.
The present application therefore further preferably provides a process for producing a portioned washing or cleaning composition, comprising the steps of
a) providing a washing or cleaning composition shaped body with a cavity which has two orifices on opposite sides of the shaped body; b) sealing one of the orifices with a first sealing element to form a receiving chamber formed by the sealing element and the shaped body; c) partly filling the receiving chamber; d) applying a water-soluble film material to the second orifice of the shaped body and shaping the film material into the cavity to form a further receiving chamber; e) filling the further receiving chamber; and f) sealing the second orifice to a second sealing element.

The film material is shaped into the partly filled cavity preferably by the action of pressure and/or vacuum. The film material can be pretreated before or during the shaping-in by the action of heat and/or solvent and/or conditioning by means of relative air humidities and/or temperatures altered compared to ambient conditions. The pressure can act through a mold which behaves as a “positive” to the cavity which behaves as a “negative.” However, a suitable compressive force is also the action of compressed air and/or the intrinsic weight of the film and/or the intrinsic weight of active substance placed on the upper side of the film.
The shaping of the film material into the cavity in step d) of the process according to the invention forms a receiving chamber from the film material in the cavity. This receiving depression is then filled with a washing- or cleaning-active substance in the next step e). The shape and the volume of the receiving depression will of course be guided by the shape and the volume of the cavity of the shaped body on which the process is based. Preference is given, in particular, to those processes in which the volume of the receiving depression formed by the film material is at least 5% by volume, preferably at least 10% by volume, most preferably at least 20% by volume, of the volume of the washing or cleaning composition shaped body.
The reduced pressure can be generated in the cavity by different procedures. In the simplest case, the sealing element applied in step b) has an orifice through which a vacuum can be generated in the cavity.
In a further preferred process variant, the reduced pressure in the cavity is generated by applying a reduced pressure to a hole or a notch which connects the cavity to the part of the surface of the shaped body (outside the cavity) which is not covered by the first sealing element from step b). Such a hole may, for example, be a bore which connects the cavity to a side surface or the underside of the shaped body. Such a bore preferably has a diameter below 5 mm, preferably below 3 mm and, in particular, below 2 mm. It will be appreciated that the cavity may also be connected to one or more outer sides by more than one hole. Alternatively or additionally, the shaped body may also have notches. These notches or grooves open out in the orifice of the cavity orifice and lead from there preferably up to a side surface of the shaped body. The width of these notches is preferably less than 10 mm, preferentially less than 7 mm, more preferably less than 4 mm, and, in particular, less than 2 mm. The depth of the notches is preferably in the range between 1 and 15 mm, preferably between 1 and 10 mm and, in particular, between 1 and 5 mm.
In a further variant of the process according to the invention, the first film material is shaped into the cavity by applying a reduced pressure to a hole or a notch which connects the cavity to the part of the surface of the shaped body (outside the cavity) which is not covered by the first film material from step b).
When the shaped body has sufficient porosity, the reduced pressure in the cavity can be generated by applying a reduced pressure to the shaped body surface (outside the cavity). Surprisingly, it has been found that the above-mentioned washing or cleaning composition tablets are suitable for such a process. Compaction, preferably tableting, of particulate starting mixtures accordingly allows the production of shaped bodies which have sufficient porosity to generate a sufficient reduced pressure within the cavity by applying a reduced pressure on the surface of the shaped body which is not covered by the film material, in order to thermoform the film material covering the orifice of the cavity into this cavity.
In a further process variant preferred in accordance with the invention, the first film material is thermoformed into the cavity by applying a reduced pressure to the part of the surface of the shaped body (outside the cavity) which is not covered by the film material from step b).
In the process variants described so far, the reduced pressure is generated in the cavity by virtue of the air present in the cavity below the film material applied in step d) having been removed from this cavity “through the tablet,” i.e., by applying a reduced pressure to bores, notches or holes provided specifically for this purpose, or with utilization of the tablet porosity. In a further particularly preferred process variant, the reduced pressure is generated in the cavity by removing the air present in the cavity below the film applied in step d) through holes in this film material.
Preference is given in the context of the present application to processes for producing a dosage unit for washing or cleaning compositions, comprising the steps of
a) providing a shaped body with at least one cavity which has two orifices on opposite sides of the shaped body; b) sealing one of the orifices with a first sealing element to form a receiving chamber formed by the sealing element and the shaped body; c) partly filling the receiving chamber; d) applying a water-soluble film material to the second orifice of the shaped body and shaping the film material into the cavity to form a further receiving chamber by generating a reduced pressure in the cavity by virtue of the air present in the cavity below the film escaping at least partly through orifices in the film material applied in step b); e) filling the further receiving chamber; and f) sealing the second orifice to a second sealing element.

Particular preference is given to processes according to the invention in which the reduced pressure is generated both within the cavity, i.e., below the film material applied in step d), and outside the cavity, above the film material applied in step d). Such a particularly advantageous process can be realized, for example, by placing the shaped body covered with the film material into a reduced-pressure chamber. Owing to the orifices present in the film material, application of a vacuum to the reduced-pressure chamber generates both in the cavity of the shaped body, i.e., below the film material applied in step b), and outside the shaped body, above the film material applied in step b), since the air present below the film material applied in step b) passes through these orifices into the space above the film material applied in step b), whence it is removed from the reduced-pressure chamber by the vacuum applied In a subsequent process step, the film web applied in step d) is sealed to the filled vessel such that the vessel is sealed on all sides and, in particular, no further air can pass through the orifices of the film web applied in step d) into the vessel. When the sealed vessel is then removed from the reduced-pressure chamber, the atmospheric pressure acting on the vessel from outside has the effect that the outer walls of the vessel, especially the film web applied in step d), fit closely to the shaped body into the cavity.
Preference is given in the context of the present application to processes for producing a dosage unit for washing or cleaning compositions, comprising the steps of
a) providing a shaped body with at least one cavity which has two orifices on opposite sides of the shaped body; b) sealing one of the orifices with a first sealing element to form a receiving chamber formed by the sealing element and the shaped body; c) partly filling the receiving chamber; d) applying a water-soluble film web to the second orifice of the shaped body and shaping the film material into the cavity to form a further receiving chamber by placing the shaped body covered with the film web into a reduced-pressure chamber and generating a reduced pressure in this chamber, which generates a reduced pressure into the cavity by virtue of the air present in the cavity below the film escaping at least partly through orifices in the film material applied in step b); e) filling the further receiving chamber; f) sealing the second orifice to a second sealing element.

Finally, a particularly preferred process comprises the step of
a) providing a shaped body with at least one cavity which has two orifices on opposite sides of the shaped body; b) sealing one of the orifices with a first water-soluble film to form a receiving chamber formed by the film and the shaped body; c) partly filling the receiving chamber with a washing- or cleaning-active composition, preferably a solid washing- or cleaning-active composition, which more preferably comprises at least one substance from the group of the builders, enzymes, bleaches, bleach activators, bleach catalysts, silver protectants and glass corrosion inhibitors; d) applying a second water-soluble film to the second orifice of the shaped body and shaping the film into the cavity to form a further receiving chamber by placing the shaped body covered with the film into a reduced-pressure chamber and generating a reduced pressure in this chamber, which generates a reduced pressure into the cavity by virtue of the air present in the cavity below the film escaping at least partly through orifices in the film material applied in step b); e) filling the further receiving chamber with a washing- or cleaning-active composition, preferably a liquid washing- or cleaning-active composition, which more preferably comprises at least one nonionic surfactant; f) sealing the second orifice to a second sealing element.

The above-described inventive compositions or the compositions produced by the above-described process according to the invention comprise washing- and cleaning-active substances, preferably washing- and cleaning-active substances from the group of the builders, surfactants, polymers, bleaches, bleach activators, enzyme, glass corrosion inhibitors, corrosion inhibitors, disintegration assistants, fragrances and perfume carriers. These preferred ingredients will be described in detail below.
Builders.
The builders include especially the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological objections to their use, also the phosphates.
The finely crystalline, synthetic, bound water-containing zeolite used is preferably zeolite A and/or P. The zeolite P is more preferably Zeolite MAP® (commercial product from Crosfield). Also suitable, however, are zeolite X, and mixtures of A, X and/or P. Also commercially available and usable with preference in accordance with the present invention is, for example, a cocrystal of zeolite X and zeolite A (approximately 80% by weight of zeolite X), which is sold by CONDEA Augusta S.p.A. under the trade name VEGOBOND AX® and can be described by the formula

nNa 2 O.(1- n )K 2 O.Al 2 O 3 .(2-2.5)SiO 2 (3.5-5.5)H 2 O.

The zeolite may be used either as a builder in a granular compound or in a kind of “powdering” of a granular mixture, preferably of a mixture to be compacted, and both ways of incorporating the zeolite into the premixture are typically utilized. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain from 18 to 22% by weight, in particular, from 20 to 22% by weight, of bound water.
Suitable crystalline, sheet-type sodium silicates have the general formula NaMSi x O 2x+1 H 2 O where M is sodium or hydrogen, x is a number from 1.9 to 4, y is a number from 0 to 20, and preferred values for x are 2, 3 or 4. Preferred crystalline sheet silicates of the formula specified are those in which M is sodium and x assumes the values of 2 or 3. In particular, preference is given to both β- and also δ-sodium disilicates Na 2 Si 2 O 5 .yH 2 O.
With particular preference, especially as a constituent of machine dishwasher detergents, crystalline sheet-type silicates of the general formula NaMSi x O 2x+1 .yH 2 O are used, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, and y is a number from 0 to 33. The crystalline sheet-type silicates of the formula NaMSi x O 2x+1 .yH 2 O are sold, for example, by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, makatite).
Particularly suitable for the purposes of the present invention are crystalline sheet silicates of the formula NaMSi x O 2x+1 .yH 2 O in which x is 2. Among these, suitable, in particular, are Na-SKS-5 (α-Na 2 Si 2 O 5 ), Na-SKS-7 (β-Na 2 Si 2 O 5 , natrosilite), Na-SKS-9 (NaHSi 2 O 5 .H 2 O), Na-SKS-10 (NaHSi 2 O 5 .3H 2 O, kanemite), Na-SKS-11 (t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but, in particular, Na-SKS-6 (δ-Na 2 Si 2 O 5 ).
When the silicates are used as a constituent of machine dishwasher detergents, these compositions preferably comprise a proportion by weight of the crystalline sheet-type silicate of the formula NaMSi x O 2x+1 .yH 2 O of from 0.1 to 20% by weight, of from 0.2 to 15% by weight and, in particular, from 0.4 to 10% by weight, based in each case on the total weight of these compositions. It is particularly preferred especially when such machine dishwasher detergents have a total silicate content below 7% by weight, preferably below 6% by weight, preferentially below 5% by weight, more preferably below 4% by weight, even more preferably below 3% by weight and, in particular, below 2.5% by weight, this silicate, based on the total weight of the silicate present, being silicate of the general formula NaMSi x O 2x+1 .yH 2 O preferably to an extent of at least 70% by weight, preferentially to an extent of at least 80% by weight and, in particular, to an extent of at least 90% by weight.
It is also possible to use amorphous sodium silicates having an Na 2 O:SiO 2 modulus of from 1:2 to 1:3.3, preferably from 1:2 to 1:2.8 and, in particular, from 1:2 to 1:2.6, which have retarded dissolution and secondary washing properties. The retardation of dissolution relative to conventional amorphous sodium silicates may have been brought about in a variety of ways, for example, by surface treatment, compounding, compacting or by overdrying. In the context of this invention, the term “amorphous” also includes “X-ray-amorphous.” This means that, in X-ray diffraction experiments, the silicates do not afford any sharp X-ray reflections typical of crystalline substances, but rather yield at best one or more maxima of the scattered X-radiation, which have a width of several degree units of the diffraction angle. However, it may quite possibly lead to even particularly good builder properties if the silicate particles in electron diffraction experiments yield vague or even sharp diffraction maxima. This is to be interpreted such that the products have microcrystalline regions with a size of from 10 to several hundred nm, preference being given to values up to a maximum of 50 nm and, in particular, up to a maximum of 20 nm. Such X-ray-amorphous silicates likewise have retarded dissolution compared with conventional waterglasses. Special preference is given to compacted amorphous silicates, compounded amorphous silicates and overdried X-ray-amorphous silicates.
In the context of the present invention, it is preferred that this/these silicate(s), preferably alkali metal silicates, more preferably crystalline or amorphous alkali metal disilicates, are present in washing or cleaning compositions in amounts of from 10 to 60% by weight, preferably from 15 to 50% by weight and, in particular, from 20 to 40% by weight, based in each case on the weight of the washing or cleaning composition.
It is, of course, also possible to use the commonly known phosphates as builder substances, as long as such a use is not to be avoided for ecological reasons. This is especially true for the use of inventive compositions or compositions produced by processes according to the invention as machine dishwasher detergents, which is particularly preferred in the context of the present application. Among the multitude of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium triphosphate or pentapotassium triphosphate (sodium tripolyphosphate or potassium tripoly-phosphate), have the greatest significance in the washing and cleaning products industry.
Alkali metal phosphates is the collective term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, for which a distinction may be drawn between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 , in addition to higher molecular weight representatives. The phosphates combine a number of advantages: they act as alkali carriers, prevent limescale deposits on machine components and lime encrustations in fabrics, and additionally contribute to the cleaning performance.
Suitable phosphates are, for example, sodium dihydrogenphosphate, NaH 2 PO 4 , in the form of the dihydrate (density 1.91 gcm −3 melting point 60°) or in the form of the monohydrate (density 2.04 gcm −3 ), disodium hydrogenphosphate (secondary sodium phosphate), Na 2 HPO 4 , which is in anhydrous form or can be used with 2 mol of water (density 2.066 gcm −3 loss of water at 95°), 7 mol of water (density 1.68 gcm −3 melting point 48° with loss of 5H 2 O) and 12 mol of water (density 1.52 gcm −3 melting point 35° with loss of 5H 2 O), but, in particular, trisodium phosphate (tertiary sodium phosphate) Na 3 PO 4 , which can be used as the dodecahydrate, as the decahydrate (corresponding to 19-20% P 2 O 5 ) and in anhydrous form (corresponding to 39-40% P 2 O 5 ).
A further preferred phosphate is tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 . Preference is further given to tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , which exists in anhydrous form (density 2.534 gcm −3 melting point 988°, 880° also reported) and as the decahydrate (density 1.815-1.836 gcm −3 melting point 94° with loss of water), and also the corresponding potassium salt, potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 .
The industrially important pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate), is a nonhygroscopic, colorless, water-soluble salt which is anhydrous or crystallizes with 6H 2 O and has the general formula NaO—[P(O)(ONa)—O] n -Na where n=3. The corresponding potassium salt, pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripoly-phosphate), is available commercially, for example, in the form of a 50% by weight solution (>23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates find wide use in the washing and cleaning products industry There also exist sodium potassium tripolyphosphates which can likewise be used in the context of the present invention. They are formed, for example, when sodium trimetaphosphate is hydrolyzed with KOH:

(NaPO 3 ) 3 +2KOH→Na 3 K 2 P 3 O 10 +H 2 O

They can be used in accordance with the invention in precisely the same way as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of the two; mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate, or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate, or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used in accordance with the invention.
When phosphates are used as washing- or cleaning-active substances in washing or cleaning compositions in the context of the present application, preferred compositions comprise these phosphate(s), preferably alkali metal phosphate(s), more preferably pentasodium triphosphate or pentapotassium triphosphate (sodium tripolyphosphate or potassium tripolyphosphate), in amounts of from 5 to 80% by weight, preferably from 15 to 75% by weight and, in particular, from 20 to 70% by weight, based in each case on the weight of the washing or cleaning composition.
It is especially preferred to use potassium tripolyphosphate and sodium tripolyphosphate in a weight ratio of more than 1:1, preferably more than 2:1, preferentially more than 5:1, more preferably more than 10:1 and especially more than 20:1. It is particularly preferred to use exclusively potassium tripolyphosphate without additions of other phosphates.
Further builders are the alkali carriers Alkali carriers include, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the aforementioned alkali metal silicates, alkali metal metasilicates and mixtures of the aforementioned substances, preference being given in the context of this invention to using the alkali metal carbonates, especially sodium carbonate, sodium hydrogencarbonate or sodium sesquicarbonate. Particular preference is given to a builder system comprising a mixture of tripolyphosphate and sodium carbonate. Particular preference is likewise given to a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate. Owing to their low chemical compatibility with the remaining ingredients of washing or cleaning compositions in comparison with other builder substances, the alkali metal hydroxides are preferably used only in small amounts, preferably in amounts below 10% by weight, preferentially below 6% by weight, more preferably below 4% by weight and, in particular, below 2% by weight, based in each case on the total weight of the washing or cleaning composition. Particular preference is given to compositions which, based on their total weight, contain less than 0.5% by weight of and, in particular, no alkali metal hydroxides.
Particular preference is given to the use of carbonate(s) and/or hydrogencarbonate(s), preferably alkali metal carbonate(s), more preferably sodium carbonate, in amounts of from 2 to 50% by weight, preferably from 5 to 40% by weight and, in particular, from 7.5 to 30% by weight, based in each case on the weight of the washing or cleaning composition. Particular preference is given to compositions which, based on the weight of the washing or cleaning composition, contain less than 20% by weight, preferably less than 17% by weight, preferentially less than 13% by weight and, in particular, less than 9% by weight of carbonate(s) and/or hydrogencarbonate(s), preferably alkali metal carbonate(s), more preferably sodium carbonate.
Organic cobuilders include, in particular, polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates. These substance classes are described below.
Organic builder substances which can be used are, for example, the polycarboxylic acids usable in the form of their sodium salts, polycarboxylic acids referring to those carboxylic acids which bear more than one acid function. Examples of these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such a use is not objectionable on ecological grounds, and mixtures thereof. Preferred salts are the salts of the polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
The acids themselves may also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of washing or cleaning compositions. In this connection, particular mention should be made of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof.
Also suitable as builders are polymeric polycarboxylates; these are, for example, the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example, those having a relative molecular mass of from 500 to 70,000 g/mol.
In the context of this document, the molar masses specified for polymeric polycarboxylates are weight-average molar masses M W of the particular acid form, which have always been determined by means of gel-permeation chromatography (GPC) using a UV detector. The measurement was against an external polyacrylic acid standard which, owing to its structural similarity to the polymers under investigation, provides realistic molecular weight values. These figures deviate considerably from the molecular weight data when polystyrenesulfonic acids are used as the standard. The molar masses measured against polystyrenesulfonic acids are generally distinctly higher than the molar masses specified in this document.
Suitable polymers are, in particular, polyacrylates which preferably have a molecular mass of from 2,000 to 20,000 g/mol. Owing to their superior solubility, preference within this group may be given in turn to the short-chain polyacrylates which have molar masses of from 2,000 to 10,000 g/mol and more preferably from 3,000 to 5,000 g/mol.
Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers which have been found to be particularly suitable are those of acrylic acid with maleic acid which contain from 50 to 90% by weight of acrylic acid and from 50 to 10% by weight of maleic acid. Their relative molecular mass, based on free acids, is generally from 2,000 to 70,000 g/mol, preferably from 20,000 to 50,000 g/mol and, in particular, from 30,000 to 40,000 g/mol.
The (co)polymeric polycarboxylates can either be used in the form of powders or in the form of aqueous solutions. The (co)polymeric polycarboxylate content of the washing or cleaning compositions is preferably from 0.5 to 20% by weight, in particular, from 3 to 10% by weight.
To improve the water solubility, the polymers may also contain allylsulfonic acids, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
Also especially preferred are biodegradable polymers composed of more than two different monomer units, for example those which contain, as monomers, salts of acrylic acid and of maleic acid, and vinyl alcohol or vinyl alcohol derivatives, or those which contain, as monomers, salts of acrylic acid and of 2-alkylallylsulfonic acid, and sugar derivatives.
Further preferred copolymers are those which preferably have, as monomers, acrolein and acrylic acid/acrylic acid salts or acrolein and vinyl acetate.
Further preferred builder substances which should likewise be mentioned are polymeric aminodicarboxylic acids, salts thereof or precursor substances thereof. Particular preference is given to polyaspartic acids or salts thereof.
Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have from 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde, and mixtures thereof, and from polyolcarboxylic acids such as gluconic acid and/or glucoheptonic acid.
Further suitable organic builder substances are dextrins, for example, oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid-catalyzed or enzyme-catalyzed, processes. The hydrolysis products preferably have average molar masses in the range from 400 to 500,000 g/mol. Preference is given to a polysaccharide having a dextrose equivalent (DE) in the range from 0.5 to 40, in particular, from 2 to 30, where DE is a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100. It is also possible to use maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37, and also yellow dextrins and white dextrins having relatively high molar masses in the range from 2,000 to 30,000 g/mol.
The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediaminedisuccinate, are also further suitable cobuilders. In this case, ethylenediamine-N,N′-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Furthermore, in this connection, preference is also given to glyceryl disuccinates and glyceryl trisuccinates. Suitable use amounts in zeolite-containing and/or silicate-containing formulations are from 3 to 15% by weight.
Further organic cobuilders which can be used are, for example, acetylated hydroxycarboxylic acids or salts thereof, which may also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
In addition, it is possible to use all compounds which are capable of forming complexes with alkaline earth metal ions as builders.
Surfactants.
The group of the surfactants includes not only the nonionic surfactants but also the anionic, cationic and amphoteric surfactants.
The nonionic surfactants used may be all nonionic surfactants known to those skilled in the art. The preferred surfactants used are low-foaming nonionic surfactants. With particular preference, washing or cleaning compositions, especially cleaning compositions for machine dishwashing, comprise nonionic surfactants, especially nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular, primary alcohols having preferably from 8 to 18 carbon atoms and on average from 1 to 12 mol of ethylene oxide (EO) per mole of alcohol in which the alcohol radical may be linear or preferably 2-methyl-branched, or may contain a mixture of linear and methyl-branched radicals, as are typically present in oxo alcohol radicals. However, especially preferred alcohol ethoxylates have linear radicals of alcohols of natural origin having from 12 to 18 carbon atoms, for example of coconut, palm, tallow fat or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C 12-14 -alcohols having 3 EO or 4 EO, C 9-11 -alcohol having 7 EO, C 13-15 -alcohols having 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 -alcohols having 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 -alcohol having 3 EO and C 12-18 -alcohol having 5 EO. The degrees of ethoxylation specified are statistical average values which may be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, it is also possible to use fatty alcohols having more than 12 EO. Examples thereof are tallow fatty alcohol having 14 EO, 25 EO, 30 EO or 40 EO.
In addition, further nonionic surfactants which may be used are also alkyl glycosides of the general formula RO(G) x in which R is a primary straight-chain or methyl-branched, in particular, 2-methyl-branched, aliphatic radical having from 8 to 22, preferably from 12 to 18, carbon atoms and G is the symbol which is a glycose unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which specifies the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably from 1.2 to 1.4.
A further class of nonionic surfactants used with preference, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and of the fatty acid alkanolamide type may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular, not more than half thereof.
Further suitable surfactants are polyhydroxy fatty acid amides of the formula


in which R is an aliphatic acyl radical having from 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having from 3 to 10 carbon atoms and from 3 to 10 hydroxyl groups The polyhydroxy fatty acid amides are known substances which can typically be obtained by reductively aminating a reducing sugar with ammonia, an alkylamine or an alkanolamine, and subsequently acylating with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula


in which R is a linear or branched alkyl or alkenyl radical having from 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having from 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms, preference being given to C 1-4 -alkyl or phenyl radicals, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this radical.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example, glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted to the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
With particular preference, moreover, surfactants which contain one or more tallow fat alcohols with 20 to 30 EO in combination with a silicone defoamer are used.
Nonionic surfactants from the group of the alkoxylated alcohols, more preferably from the group of the mixed alkoxylated alcohols and, in particular, from the group of the EO-AO-EO nonionic surfactants, are likewise used with particular preference.
Special preference is given to nonionic surfactants which have a melting point above room temperature, particular preference being given to nonionic surfactants having a melting point above 20° C., preferably above 25° C., more preferably between 25 and 60° C. and, in particular, between 26.6 and 43.3° C.
Suitable nonionic surfactants which have melting or softening points in the temperature range specified are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. When nonionic surfactants which have a high viscosity at room temperature are used, they preferably have a viscosity above 20 Pas, preferably above 35 Pas and, in particular, above 40 Pas. Nonionic surfactants which have a waxlike consistency at room temperature are also preferred.
Surfactants which are solid at room temperature and are to be used with preference are derived from the groups of alkoxylated nonionic surfactants, in particular, the ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants, such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants). Such (PO/EO/PO) nonionic surfactants are additionally notable for good foam control.
In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which has resulted from the reaction of a monohydroxyalkanol or alkylphenol having from 6 to 20 carbon atoms with preferably at least 12 mol, more preferably at least 15 mol, in particular, at least 20 mol, of ethylene oxide per mole of alcohol or alkylphenol.
A particularly preferred nonionic surfactant which is solid at room temperature is obtained from a straight-chain fatty alcohol having from 16 to 20 carbon atoms (C 16-20 -alcohol), preferably a C 1-8 -alcohol, and at least 12 mol, preferably at least 15 mol and, in particular, at least 20 mol, of ethylene oxide. Of these, the “narrow range ethoxylates” (see above) are particularly preferred.
With particular preference, ethoxylated nonionic surfactants which have been obtained from C 6-20 -monohydroxyalkanols or C 6-20 -alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and, in particular, more than 20 mol of ethylene oxide per mole of alcohol are therefore used.
The room temperature solid nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably such PO units comprise up to 25% by weight, more preferably up to 20% by weight and, in particular, up to 15% by weight, of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol moiety of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and, in particular, more than 70% by weight, of the total molar mass of such nonionic surfactants. Preferred compositions are characterized in that they comprise ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule comprise up to 25% by weight, preferably up to 20% by weight and, in particular, up to 15% by weight, of the total molar mass of the nonionic surfactant.
Further nonionic surfactants which have melting points above room temperature and are to be used with particular preference contain from 40 to 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend which contains 75% by weight of an inverse block copolymer of polyoxyethylene and polyoxypropylene having 17 mol of ethylene oxide and 44 mol of propylene oxide, and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 mol of ethylene oxide and 99 mol of propylene oxide per mole of trimethylolpropane.
Nonionic surfactants which can be used with particular preference are obtainable, for example, under the name Poly Tergent® SLF-18 from Olin Chemicals.
Surfactants of the formula

R 1 O[CH 2 CH(CH 3 )O] x [CH 2 CH 2 O] y CH 2 CH(OH)R 2

in which R 1 is a linear or branched aliphatic hydrocarbon radical having from 4 to 18 carbon atoms or mixtures thereof, R 2 is a linear or branched hydrocarbon radical having from 2 to 26 carbon atoms or mixtures thereof, and x is from 0.5 to 1.5, and y is a value of at least 15 are further particularly preferred nonionic surfactants.

Further nonionic surfactants which can be used with preference are the terminally capped poly(oxyalkylated) nonionic surfactants of the formula

R 1 O[CH 2 CH(R 3 )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2

in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is from 1 to 30, k and j are from 1 to 12, preferably from 1 to 5. When the value x=2, each R 3 in the above formula R 1 O[CH 2 CH(R 3 )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2 may be different. R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 6 to 22 carbon atoms, particular preference being given to radicals having from 8 to 18 carbon atoms. For the R 3 radical, particular preference is given to H, —CH 3 or —CH 2 CH 3 . Particularly preferred values for x are in the range from 1 to 20, in particular, from 6 to 15.

As described above, each R 3 in the above formula may be different if x=2. This allows the alkylene oxide unit in the square brackets to be varied. When x is, for example, 3, the R 3 radical may be selected so as to form ethylene oxide (R 3 ═H) or propylene oxide (R 3 ═CH 3 ) units which can be joined together in any sequence, for example (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for x has been selected here by way of example, and it is entirely possible for it to be larger, the scope of variation increasing with increasing x values and embracing, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa.
Particularly preferred terminally capped poly(oxyalkylated) alcohols of the above formula have values of k=1 and j=1, so that the above formula is simplified to

R 1 O[CH 2 CH(R 3 )O] x CH 2 CH(OH)CH 2 OR 2 .

In the latter formula, R 1 , R 2 and R 3 are each as defined above and x is a number from 1 to 30, preferably from 1 to 20 and, in particular, from 6 to 18. Particular preference is given to surfactants in which the R 1 and R 2 radicals have from 9 to 14 carbon atoms, R 3 is H and x assumes values of from 6 to 15.

If the latter statements are summarized, preference is given to the terminally capped poly(oxyalkylated) nonionic surfactants of the formula

R 1 O[CH 2 CH(R 3 )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2

in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is from 1 to 30, k and j are from 1 to 12, preferably from 1 to 5, particular preference being given to surfactants of the

R 1 O[CH 2 CH(R 3 )O] x CH 2 CH(OH)CH 2 OR 2

type in which x is a number from 1 to 30, preferably from 1 to 20 and, in particular, from 6 to 18.

Particularly preferred nonionic surfactants in the context of the present invention have been found to be low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, preference is given in turn to surfactants having EO-AO-EO-AO blocks, and in each case from one to ten EO and/or AO groups are bonded to one another before a block of the other groups in each case follows. Preference is given here to nonionic surfactants of the general formula


in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 -alkyl or -alkenyl radical; each R 2 or R 3 group is independently selected from —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 —CH 3 , CH(CH 3 ) 2 and the indices w, x, y, z are each independently integers from 1 to 6.

The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 —OH and ethylene oxide or alkylene oxide. The R 1 radical in the above formula may vary depending on the origin of the alcohol. When native sources are utilized, the R 1 radical has an even number of carbon atoms and is generally unbranched, and preference is given to the linear radicals of alcohols of native origin having from 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol. Alcohols obtainable from synthetic sources are, for example, the Guerbet alcohols or 2-methyl-branched or linear and methyl-branched radicals in a mixture, as are typically present in oxo alcohol radicals. Irrespective of the type of the alcohol used to prepare the nonionic surfactants present in the compositions, preference is given to nonionic surfactants in which R 1 in the above formula is an alkyl radical having from 6 to 24, preferably from 8 to 20, more preferably from 9 to 15 and, in particular, from 9 to 11 carbon atoms.
The alkylene oxide unit which is present in the preferred nonionic surfactants in alternation to the ethylene oxide unit is, as well as propylene oxide, especially butylene oxide. However, further alkylene oxides in which R 2 and R 3 are each independently selected from —CH 2 CH 2 —CH 3 and CH(CH 3 ) 2 are also suitable. Preference is given to using nonionic surfactants of the above formula in which R 2 and R 3 are each a —CH 3 radical, w and x are each independently 3 or 4, and y and z are each independently 1 or 2.
In summary, preference is given, in particular, to nonionic surfactants which have a C 9-15 -alkyl radical having from 1 to 4 ethylene oxide units, followed by from 1 to 4 propylene oxide units, followed by from 1 to 4 ethylene oxide units, followed by from 1 to 4 propylene oxide units. In aqueous solution, these surfactants have the required low viscosity and can be used with particular preference in accordance with the invention.
Further nonionic surfactants usable with preference are the terminally capped poly(oxyalkylated)nonionic surfactants of the formula

R 1 O[CH 2 CH(R 3 )O] x R 2

in which R 1 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms, R 2 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals which have from 1 to 30 carbon atoms and preferably have between 1 and 5 hydroxyl groups and are preferably further functionalized with an ether group, R 3 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is from 1 to 40.

In a particularly preferred embodiment of the present application, R 3 in the aforementioned general formula is H From the group of the resulting terminally capped poly(oxyalkylated) nonionic surfactants of the formula

R 1 O[CH 2 CH 2 O] x R 2 ,

preference is given, in particular, to those nonionic surfactants in which R 1 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms, preferably having from 4 to 20 carbon atoms, R 2 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals which have from 1 to 30 carbon atoms and preferably have between 1 and 5 hydroxyl groups, and x is from 1 to 40.

Preference is given, in particular, to those terminally capped poly(oxyalkylated) nonionic surfactants which, according to the formula

R 1 O[CH 2 CH 2 O] x CH 2 CH(OH)R 2 ,

have not only an R 1 radical which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms, preferably having from 4 to 20 carbon atoms, but also a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having from 1 to 30 carbon atoms which is adjacent to a monohydroxylated intermediate group —CH 2 CH(OH)—In this formula, x is from 1 to 90.

Particular preference is given to nonionic surfactants of the general formula

R 1 O[CH 2 CH 2 O] x CH 2 CH(OH)R 2

which have not only an R 1 radical which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, but also a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having from 1 to 30 carbon atoms, preferably from 2 to 22 carbon atoms, which is adjacent to a monohydroxylated intermediate group —CH 2 CH(OH)— and in which x is from 40 to 80, preferably from 40 to 60.

The corresponding terminally capped poly(oxyalkylated) nonionic surfactants of the above formula can be obtained, for example, by reacting a terminal epoxide of the formula R 2 CH(O)CH 2 with an ethoxylated alcohol of the formula R 1 O[CH 2 CH 2 O] x-1 CH 2 CH 2 OH.
Particular preference is further given to those terminally capped poly(oxyalkylated) nonionic surfactants of the formula

R 1 O[CH 2 CH 2 O] x [CH 2 CH(CH 3 )O] y CH 2 CH(OH)R 2

in which R 1 and R 2 are each independently a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having from 2 to 26 carbon atoms, R 3 is independently selected from —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 —CH 3 , CH(CH 3 ) 2 , but preferably —CH 3 , and x and y are each independently from 1 to 32, particular preference being given to nonionic surfactants with values for x of from 15 to 32 and y of 0.5 and 1.5.

Surfactants of the general formula


in which R 1 and R 2 are each independently a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having from 2 to 26 carbon atoms, R 3 is independently selected from —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 —CH 3 , CH(CH 3 ) 2 , but preferably —CH 3 , and x and y are each independently from 1 to 32, are preferred in accordance with the invention, very particular preference being given to nonionic surfactants with values for x of from 15 to 32 and y of 0.5 and 1.5.

The specified carbon chain lengths and degrees of ethoxylation or degrees of alkoxylation of the aforementioned nonionic surfactants constitute statistical averages which may be a whole number or a fraction for a specific product. As a consequence of the preparation process, commercial products of the formulas specified do not usually consist of one individual representative, but rather of mixtures, as a result of which average values and consequently fractions can arise both for the carbon chain lengths and for the degrees of ethoxylation or degrees of alkoxylation.
It will be appreciated that the aforementioned nonionic surfactants may be used not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants. Surfactant mixtures refer not only to mixtures of nonionic surfactants which, in their entirety, fall under one of the above-mentioned general formulas, but also those mixtures which comprise two, three, four or more nonionic surfactants which can be described by different general formulas among those above.
The anionic surfactants used are, for example, those of the sulfonate and sulfate type. Useful surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, i.e., mixtures of alkene- and hydroxyalkanesulfonates, and disulfonates, as are obtained, for example, from C 12-18 -monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are obtained from C 12-18 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfo fatty acids (ester sulfonates), for example, the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also likewise suitable
Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters refer to the mono-, di- and triesters, and mixtures thereof, as are obtained in the preparation by esterification of a monoglycerol with from 1 to 3 mol of fatty acid or in the transesterification of triglycerides with from 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfation products of saturated fatty acids having from 6 to 22 carbon atoms, for example, of caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
Preferred alk(en)yl sulfates are the alkali metal and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example, of coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or of C 10 -C 20 oxo alcohols and those monoesters of secondary alcohols of these chain lengths. Also preferred are alk(en)yl sulfates of the chain length mentioned which contain a synthetic straight-chain alkyl radical prepared on a petrochemical basis and which have analogous degradation behavior to the equivalent compounds based on fatty chemical raw materials. From the washing point of view, preference is given to the C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates, and C 14 -C 15 -alkyl sulfates 2,3-Alkyl sulfates, which can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
Also suitable are the sulfuric monoesters of the straight-chain or branched C 7-21 -alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9-11 -alcohols with on average 3.5 mol of ethylene oxide (EO) or C 12-18 fatty alcohols with from 1 to 4 EO. Owing to their high tendency to foam, they are used in cleaning compositions only in relatively small amounts, for example amounts of from 1 to 5% by weight.
Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and are the monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and, in particular, ethoxylated fatty alcohols. Preferred sulfosuccinates contain C 8-18 fatty alcohol radicals or mixtures thereof. Especially preferred sulfosuccinates contain a fatty alcohol radical which is derived from ethoxylated fatty alcohols which, considered alone, constitute nonionic surfactants. In this context, particular preference is again given to sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols with a narrowed homolog distribution. It is also equally possible to use alk(en)ylsuccinic acid having preferably from 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof.
Useful further anionic surfactants are, in particular, soaps. Suitable soaps are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and soap mixtures derived, in particular, from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
The anionic surfactants, including the soaps, may be present in the form of their sodium, potassium or ammonium salts, and also in the form of soluble salts of organic bases, such as mono-, di- or triethanolamine The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular, in the form of the sodium salts.
When the anionic surfactants are a constituent of machine dishwasher detergents, their content, based on the total weight of the compositions, is preferably less than 4% by weight, preferentially less than 2% by weight and most preferably less than 1% by weight. Special preference is given to machine dishwasher detergents which do not contain any anionic surfactants.
Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and/or amphoteric surfactants.
The cationic active substances used may, for example, be cationic compounds of the following formulas:


in which each R 1 group is independently selected from C 1-6 -alkyl, -alkenyl or -hydroxyalkyl groups; each R 2 group is independently selected from C 8-28 -alkyl or -alkenyl groups; R 3 =R 1 or (CH 2 ) n -T-R 2 ; R 4 =R 1 or R 2 or (CH 2 ) n -T-R 2 ; T=—CH 2 —, —O—CO— or —CO—O— and n is an integer from 0 to 5.

In machine dishwasher detergents, the content of cationic and/or amphoteric surfactants is preferably less than 6% by weight, preferentially less than 4% by weight, even more preferably less than 2% by weight and, in particular, less than 1% by weight. Particular preference is given to machine dishwasher detergents which do not contain any cationic or amphoteric surfactants.
Polymers.
The group of polymers includes, in particular, the washing- or cleaning-active polymers, for example, the rinse aid polymers and/or polymers active as softeners. Generally, not only nonionic polymers but also cationic, anionic and amphoteric polymers can be used in washing or cleaning compositions.
“Cationic polymers” in the context of the present invention are polymers which bear a positive charge in the polymer molecule. This can be realized, for example, by (alkyl)ammonium moieties present in the polymer chain or other positively charged groups. Particularly preferred cationic polymers stem from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymer dimethyldiallylammonium salts and copolymers thereof with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and -methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols, or the polymers specified under the INCI designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
“Amphoteric polymers” in the context of the present invention have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may, for example, be carboxylic acids, sulfonic acids or phosphonic acids.
Preferred washing or cleaning compositions, especially preferred machine dishwasher detergents, are characterized in that they comprise a polymer a) which contains monomer units of the formula R 1 R 2 C=CR 3 R 4 in which each R 1 , R 2 , R 3 , R 4 radical is independently selected from hydrogen, derivatized hydroxyl group, C 1-30 linear or branched alkyl groups, aryl, aryl-substituted C 1-30 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroaromatic organic groups having at least one positive charge without charged nitrogen, at least one quaternized nitrogen atom or at least one amino group having a positive charge in the partial region of the pH range from 2 to 11, or salts thereof, with the proviso that at least one R 1 , R 2 , R 3 , R 4 radical is a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized nitrogen atom or at least one amino group having a positive charge.
Cationic or amphoteric polymers particularly preferred in the context of the present application contain, as a monomer unit, a compound of the general formula


in which R 1 and R 4 are each independently H or a linear or branched hydrocarbon radical having from 1 to 6 carbon atoms; R 2 and R 3 are each independently an alkyl hydroxyalkyl or aminoalkyl group in which the alkyl radical is linear or branched and has between 1 and 6 carbon atoms, which is preferably a methyl group; x and y are each independently integers between 1 and 3. X − represents a counterion, preferably a counterion from the group of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumenesulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred R 1 and R 4 radicals in the above formula are selected from —CH 3 , —CH 2 —CH 3 , —CH 2 —CH 2 —CH 3 , —CH(CH 3 )—CH 3 , —CH 2 —OH, —CH 2 —CH 2 —OH, —CH(OH)—CH 3 , —CH 2 —CH 2 —CH 2 —OH, —CH 2 CH(OH)—CH 3 , —CH(OH)—CH 2 —CH 3 , and —(CH 2 CH 2 —O) n H.
Very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R 1 and R 4 are each H, R 2 and R 3 are each methyl and x and y are each 1. The corresponding monomer units of the formula

H 2 C=CH—(CH 2 )—N + (CH 3 ) 2 —(CH 2 )—CH=CH 2

X −

are, in the case that X − =chloride, also referred to as DADMAC (diallyldimethylammonium chloride).

Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

R 1 HC=CR 2 —C(O)—NH—(CH 2 ) x —N + R 3 R 4 R 5

in which R 1 , R 2 , R 3 , R 4 and R 5 are each independently a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having from 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from —CH 3 , —CH 2 —CH 3 , —CH 2 —CH 2 —CH 3 , —CH(CH 3 )—CH 3 , —CH 2 —OH, —CH 2 —CH 2 —OH, —CH(OH)—CH 3 , —CH 2 —CH 2 —CH 2 —OH, —CH 2 CH(OH)—CH 3 , —CH(OH)—CH 2 —CH 3 , and —(CH 2 CH 2 —O) n H, and x is an integer between 1 and 6.

Very particular preference is given in the context of the present application to polymers which have a cationic monomer unit of the above general formula in which R 1 is H and R 2 , R 3 , R 4 and R 5 are each methyl and x is 3. The corresponding monomer units of the formula

H 2 C=C(CH 3 )—C(O)NH—(CH 2 ) x —N + (CH 3 ) 3

X −

are, in the case that X − =chloride, also referred to as MAPTAC (methacrylamidopropyltrimethylammonium chloride).

Preference is given in accordance with the invention to using polymers which contain, as monomer units, diallyldimethylammonium salts and/or acrylamidopropyltrimethylammonium salts.
The aforementioned amphoteric polymers have not only cationic groups, but also anionic groups or monomer units. Such anionic monomer units are derived, for example, from the group of the linear or branched, saturated or unsaturated carboxylates, the linear or branched, saturated or unsaturated phosphonates, the linear or branched, saturated or unsaturated sulfates or the linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, (meth)acrylic acid, (dimethyl)acrylic acid, (ethyl)acrylic acid, cyanoacrylic acid, vinylacetic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and derivatives thereof, the allylsulfonic acids, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, or the allylphosphonic acids.
Preferred usable amphoteric polymers are derived from the group of the alkylacrylamide/acrylic acid copolymers, the alkylacrylamide/methacrylic acid copolymers, the alkylacrylamide/methylmethacrylic acid copolymers, the alkylacrylamide/acrylic acid/alkylaminoalkyl (meth)acrylic acid copolymers, the alkylacrylamide/methacrylic acid/alkylaminoalkyl (meth)acrylic acid copolymers, the alkylacrylamide/methylmethacrylic acid/alkylaminoalkyl (meth)acrylic acid copolymers, the alkylacrylamide/alkyl methacrylate/alkylaminoethyl methacrylate/alkyl methacrylate copolymers, and the copolymers formed from unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.
Zwitterionic polymers usable with preference are derived from the group of the acrylamidoalkyltrialkylammonium chloride/acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride/methacrylic acid copolymers and their alkali metal and ammonium salts, and the methacryloylethylbetaine/methacrylate copolymers.
Preference is further given to amphoteric polymers which, in addition to one or more anionic monomers, comprise, as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl(diallyl)-ammonium chloride.
Particularly preferred amphoteric polymers stem from the group of the methacrylamidoalkyltrialkylammonium chloride/dimethyl(diallyl)ammonium chloride/acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride/dimethyl(diallyl)ammonium chloride/methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride/dimethyl(diallyl)ammonium chloride/alkyl(meth)acrylic acid copolymers and their alkali metal and ammonium salts.
Especially preferred are amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammonium chloride/acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammonium chloride/acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammonium chloride/alkyl(meth)acrylic acid copolymers and their alkali metal and ammonium salts.
In a particularly preferred embodiment of the present invention, the polymers are present in prefinished form. Suitable means of finishing the polymers include
the encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers; the encapsulation of the polymers by means of water-insoluble, meltable coating compositions, preferably by means of water-insoluble coating compositions from the groups of the waxes or paraffins having a melting point above 30° C.; the cogranulation of the polymers with inert support materials, preferably with support materials from the group of the washing- or cleaning-active substances, more preferably from the group of the builders or cobuilders.

Washing or cleaning compositions comprise the aforementioned cationic and/or amphoteric polymers preferably in amounts of between 0.01 and 10% by weight, based in each case on the total weight of the washing or cleaning composition. However, preference is given in the context of the present application to those washing or cleaning compositions in which the proportion by weight of the cationic and/or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferentially between 0.01 and 4% by weight, more preferably between 0.01 and 2% by weight and, in particular, between 0.01 and 1% by weight, based in each case on the total weight of the machine dishwasher detergent.
Polymers effective as softeners are, for example, the polymers containing sulfonic acid groups, which are used with particular preference.
Polymers which contain sulfonic acid groups and can be used with particular preference are copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionic monomers.
In the context of the present invention, preference is given, as a monomer, to unsaturated carboxylic acids of the formula

R 1 (R 2 )C=C(R 3 )COOH

in which R 1 to R 3 are each independently —H, —CH 3 , a straight-chain or branched saturated alkyl radical having from 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having from 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by —NH 2 , —OH or —COOH, or are —COOH or —COOR 4 where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having from 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the formula above, preference is given, in particular, to acrylic acid (R 1 =R 2 ═R 3 =H), methacrylic acid (R 1 =R 2 =H; R 3 =CH 3 ) and/or maleic acid (R 1 =COOH; R 2 ═R 3 =H).
The monomers containing sulfonic acid groups are preferably those of the formula

R 5 (R 6 )C=C(R 7 )—X—SO 3 H

in which R 5 to R 7 are each independently —H, —CH 3 , a straight-chain or branched saturated alkyl radical having from 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having from 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by —NH 2 , —OH or —COOH, or are —COOH or —COOR 4 where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having from 1 to 12 carbon atoms, and X is an optionally present spacer group which is selected from —(CH 2 ) n — where n=from 0 to 4, —COO—(CH 2 ) k — where k=from 1 to 6, —C(O)—NH—C(CH 3 ) 2 — and —C(O)—NH—CH(CH 2 CH 3 )—.

Among these monomers, preference is given to those of the formulas

H 2 C=CH—X—SO 3 H

H 2 C=C(CH 3 )—X—SO 3 H

HO 3 S—X—(R 6 )C=C(R 7 )—X—SO 3 H

in which R 6 and R 7 are each independently selected from —H, —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH(CH 3 ) 2 and X is an optionally present spacer group which is selected from —(CH 2 ) n — where n=from 0 to 4, —COO—(CH 2 ) k — where k=from 1 to 6, —C(O)—NH—C(CH 3 ) 2 — and —C(O)—NH—CH(CH 2 CH 3 )—.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of the acids mentioned.
Useful further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. The content of these further ionic or nonionic monomers in the polymers used is preferably less than 20% by weight, based on the polymer. Polymers to be used with particular preference consist only of monomers of the formula R 1 (R 2 )C=C(R 3 )COOH and of monomers of the formula R 5 (R 6 )C=C(R 7 )—X—SO 3 H.
In summary, particular preference is given to copolymers of
i) unsaturated carboxylic acids of the formula R 1 (R 2 )C=C(R 3 )COOH in which R 1 to R 3 are each independently —H, —CH 3 , a straight-chain or branched saturated alkyl radical having from 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having from 2 to 12 carbon atoms, alkyl or alkenyl radicals as defined above and substituted by —NH 2 , —OH or —COOH, or are —COOH or —COOR 4 where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having from 1 to 12 carbon atoms, ii) sulfonic acid-containing monomers of the formula R 5 (R 6 )C=C(R 7 )—X—SO 3 H in which R 5 to R 7 are each independently —H, —CH 3 , a straight-chain or branched saturated alkyl radical having from 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having from 2 to 12 carbon atoms, alkyl or alkenyl radicals as defined above and substituted by —NH 2 , —OH or —COOH, or are —COOH or —COOR 4 where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having from 1 to 12 carbon atoms, and X is an optionally present spacer group which is selected from —(CH 2 ) n — where n=from 0 to 4, —COO—(CH 2 ) k — where k=from 1 to 6, —C(O)—NH—C(CH 3 ) 2 — and —C(O)—NH—CH(CH 2 CH 3 )—, iii) optionally further ionic or nonionic monomers.

Further particularly preferred copolymers consist of
i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and/or maleic acid, ii) one or more monomers containing sulfonic acid groups of the formulas:

H 2 C=CH—X—SO 3 H

H 2 C=C(CH 3 )—X—SO 3 H

HO 3 S—X—(R 6 )C=C(R 7 )—SO 3 H

in which R 6 and R 7 are each independently selected from —H, —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH(CH 3 ) 2 and X is an optionally present spacer group which is selected from —(CH 2 ) n — where n=from 0 to 4, —COO—(CH 2 ) k — where k=from 1 to 6, —C(O)—NH—C(CH 3 ) 2 — and —C(O)—NH—CH(CH 2 CH 3 )—
i) optionally further ionic or nonionic monomers.

The copolymers may contain the monomers from groups i) and ii) and optionally iii) in varying amounts, and it is possible to combine any of the representatives from group i) with any of the representatives from group ii) and any of the representatives from group iii). Particularly preferred polymers have certain structural units which are described below.
Thus, preference is given, for example, to copolymers which contain structural units of the formula

—[CH 2 —CHCOOH] m —[CH 2 —CHC(O)—Y—SO 3 H] p —

in which m and p are each a whole natural number between 1 and 2,000, and Y is a spacer group which is selected from substituted or unsubstituted, aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, preference being given to spacer groups in which Y is —O—(CH 2 ) n — where n=from 0 to 4, is —O—(C 6 H 4 )—, is —NH—C(CH 3 ) 2 — or —NH—CH(CH 2 CH 3 )—.

These polymers are prepared by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. Copolymerizing the acrylic acid derivative containing sulfonic acid groups with methacrylic acid leads to another polymer, the use of which is likewise preferred. The corresponding copolymers contain structural units of the formula

—[CH 2 —C(CH 3 )COOH] m —[CH 2 —CHC(O)—Y—SO 3 H] p —

in which m and p are each a whole natural number between 1 and 2,000, and Y is a spacer group which is selected from substituted or unsubstituted, aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, preference being given to spacer groups in which Y is —O—(CH 2 ) n — where n=from 0 to 4, is —O—(C 6 H 4 )—, is —NH—C(CH 3 ) 2 — or —NH—CH(CH 2 CH 3 )—.

Acrylic acid and/or methacrylic acid can also be copolymerized entirely analogously with methacrylic acid derivatives containing sulfonic acid groups, thereby changing the structural units within the molecule. Thus, copolymers which contain structural units of the formula

[CH 2 —CHCOOH] m —[CH 2 —C(CH 3 )C(O)—Y—SO 3 H] p —

in which m and p are each a whole natural number between 1 and 2,000, and Y is a spacer group which is selected from substituted or unsubstituted, aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, where spacer groups in which Y is —O—(CH 2 ) n — where n=from 0 to 4, is —O—(C 6 H 4 )—, is —NH—C(CH 3 ) 2 — or —NH—CH(CH 2 CH 3 )— are just as preferred as copolymers which contain structural units of the formula

—[CH 2 —C(CH 3 )COOH] m —[CH 2 —C(CH 3 )C(O)—Y—SO 3 H] p —

in which m and p are each a whole natural number between 1 and 2,000, and Y is a spacer group which is selected from substituted or unsubstituted, aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, preference being given to spacer groups in which Y is —O—(CH 2 ) n — where n=from 0 to 4, is —O—(C 6 H 4 )—, is —NH—C(CH 3 ) 2 — or —NH—CH(CH 2 CH 3 )—.

Instead of acrylic acid and/or methacrylic acid, or in addition thereto, it is also possible to use maleic acid as a particularly preferred monomer from group i) This leads to copolymers which are preferred in accordance with the invention and contain structural units of the formula

—[HOOCCH—CHCOOH] m —[CH 2 —CHC(O)—Y—SO 3 H] p —

in which m and p are each a whole natural number between 1 and 2,000, and Y is a spacer group which is selected from substituted or unsubstituted, aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, preference being given to spacer groups in which Y is —O—(CH 2 ) n — where n=from 0 to 4, is —O—(C 6 H 4 )—, is —NH—C(CH 3 ) 2 — or —NH—CH(CH 2 CH 3 )—. Preference is further given in accordance with the invention to copolymers which contain structural units of the formula

—[HOOCCH—CHCOOH] m —[CH 2 —C(CH 3 )C(O)O—Y—SO 3 H] p —

in which m and p are each a whole natural number between 1 and 2,000, and Y is a spacer group which is selected from substituted or unsubstituted, aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, preference being given to spacer groups in which Y is —O—(CH 2 ) n — where n=from 0 to 4, is —O—(C 6 H 4 )—, is —NH—C(CH 3 ) 2 — or —NH—CH(CH 2 CH 3 )—.

In summary, preference is given according to the invention to those copolymers which contain structural units of the formulas

—[CH 2 —CHCOOH] m —[CH 2 —CHC(O)—Y—SO 3 H] p —

—[CH 2 —C(CH 3 )COOH] m —[CH 2 —CHC(O)—Y—SO 3 H] p —

—[CH 2 —CHCOOH] m —[CH 2 —C(CH 3 )C(O)—Y—SO 3 H] p —

—[CH 2 —C(CH 3 )COOH] m —[CH 2 —C(CH 3 )C(O)—Y—SO 3 H] p —

—[HOOCCH—CHCOOH] m —[CH 2 —CHC(O)—Y—SO 3 H] p —

—[HOOCCH—CHCOOH] m —[CH 2 —C(CH 3 )C(O)O—Y—SO 3 H] p —

in which m and p are each a whole natural number between 1 and 2,000, and Y is a spacer group which is selected from substituted or unsubstituted, aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, preference being given to spacer groups in which Y is —O—(CH 2 ) n — where n=from 0 to 4, is —O—(C 6 H 4 )—, is —NH—C(CH 3 ) 2 — or —NH—CH(CH 2 CH 3 )—.

In the polymers, all or some of the sulfonic acid groups may be in neutralized form, i.e., the acidic hydrogen atom of the sulfonic acid group may be replaced in some or all of the sulfonic acid groups by metal ions, preferably alkali metal ions and, in particular, by sodium ions. The use of copolymers containing partially or completely neutralized sulfonic acid groups is preferred in accordance with the invention.
The monomer distribution of the copolymers used with preference in accordance with the invention is, in the case of copolymers which contain only monomers from groups i) and ii), preferably in each case from 5 to 95% by weight of i) or ii), more preferably from 50 to 90% by weight of monomer from group i) and from 10 to 50% by weight of monomer from group ii), based in each case on the polymer.
In the case of terpolymers, particular preference is given to those which contain from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii), and from 5 to 30% by weight of monomer from group iii).
The molar mass of the sulfo copolymers used with preference in accordance with the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred washing or cleaning compositions are characterized in that the copolymers have molar masses of from 2,000 to 200,000 gmol −1 , preferably from 4,000 to 25,000 gmol −1 and, in particular, from 5,000 to 15,000 gmol −1 .
Bleaches.
The bleaches are a washing- or cleaning-active substance used with particular preference. Among the compounds which serve as bleaches and supply H 2 O 2 in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular significance. Further bleaches which can be used are, for example, peroxypyrophosphates, citrate perhydrates, and H 2 O 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
It is also possible to use bleaches from the group of the organic bleaches. Typical organic bleaches are the diacyl peroxides, for example, dibenzoyl peroxide. Further typical organic bleaches are the peroxy acids, particular examples being the alkyl peroxy acids and the aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and ring-substituted derivatives thereof, such as alkylperoxybenzoic acids, but it is also possible to use peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxy-hexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid and N,N-terephthaloyldi(6-aminopercaproic acid).
The bleaches used may also be substances which release chlorine or bromine. Among suitable chlorine- or bromine-releasing materials, useful examples include heterocyclic N-bromoamides and N-chloroamides, for example, trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and/or dichloroisocyanuric acid (DICA) and/or salts thereof with cations such as potassium and sodium. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin, are likewise suitable.
According to the invention, preference is given to washing or cleaning compositions, especially machine dishwasher detergents, which contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, more preferably from 3.5 to 20% by weight and, in particular, from 5 to 15% by weight of bleach, preferably sodium percarbonate.
The active oxygen context of the washing or cleaning compositions, especially machine dishwasher detergents, is based in each case on the total weight of the composition, preferably between 0.4 and 10% by weight, more preferably between 0.5 and 8% by weight and, in particular, between 0.6 and 5% by weight. Particularly preferred compositions have an active oxygen content above 0.3% by weight, preferably above 0.7% by weight, more preferably above 0.8% by weight and, in particular, above 1.0% by weight.
Bleach Activators.
Bleach activators are used, for example, in washing or cleaning compositions, in order to achieve improved bleaching action when cleaning at temperatures of 60° C. and below. Bleach activators which may be used are compounds which, under perhydrolysis conditions, give rise to aliphatic peroxocarboxylic acids having preferably from 1 to 10 carbon atoms, in particular, from 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. Suitable substances bear O-acyl and/or N-acyl groups of the number of carbon atoms specified, and/or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular, tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular, 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular, tetraacetylglycoluril (TAGU), N-acylimides, in particular, N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular, n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular, phthalic anhydride, acylated polyhydric alcohols, in particular, triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
Further bleach activators used with preference in the context of the present application are compounds from the group of the cationic nitrites, especially cationic nitriles of the formula


in which R 1 is —H, —CH 3 , a C 2-24 -alkyl or -alkenyl radical, a substituted C 2-24 -alkyl or -alkenyl radical having at least one substituent from the group of —Cl, —Br, —OH, —NH 2 , —CN, an alkyl- or alkenylaryl radical having a C 1-24 -alkyl group, or is a substituted alkyl- or alkenylaryl radical having a C 1-24 -alkyl group and at least one further substituent on the aromatic ring, R 2 and R 3 are each independently selected from —CH 2 —CN, —CH 3 , —CH 2 —CH 3 , —CH 2 —CH 2 —CH 3 , —CH(CH 3 )—CH 3 , —CH 2 —OH, —CH 2 —CH 2 —OH, —CH(OH)—CH 3 , —CH 2 —CH 2 —CH 2 —OH, —CH 2 —CH(OH)—CH 3 , —CH(OH)—CH 2 —CH 3 , —(CH 2 —CH 2 —O) n H where n=1, 2, 3, 4, 5 or 6, and X is an anion.

Particular preference is given to a cationic nitrile of the formula


in which R 4 , R 5 and R 6 are each independently selected from —CH 3 , —CH 2 —CH 3 , —CH 2 —CH 2 —CH 3 , —CH(CH 3 )—CH 3 , where R 4 may additionally also be —H, and X is an anion, it being preferred that R 5 =R 6 =—CH 3 and, in particular, R 4 =R 5 =R 6 =—CH 3 , and particular preference being given to compounds of the formulas (CH 3 ) 3 N (+) CH 2 —CN X − , (CH 3 CH 2 ) 3 N (+) CH 2 —CN X − , (CH 3 CH 2 CH 2 ) 3 N (+) CH 2 —CN X − , (CH 3 CH(CH 3 )) 3 N (+) CH 2 —CN X − or (HO—CH 2 —CH 2 ) 3 N (+) CH 2 —CN X − , particular preference being given in turn, from this group of substances, to the cationic nitrile of the formula (CH 3 ) 3 N (+) CH 2 —CN X − in which X − is an anion which is selected from the group of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate.

The bleach activators used may also be compounds which, under perhydrolysis conditions, give rise to aliphatic peroxocarboxylic acids having preferably from 1 to 10 carbon atoms, in particular, from 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. Suitable substances bear O-acyl and/or N-acyl groups of the number of carbon atoms specified, and/or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular, tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular, 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular, tetraacetylglycoluril (TAGU), N-acylimides, in particular, N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular, n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular, phthalic anhydride, acylated polyhydric alcohols, in particular, triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methylmorpholiniumacetonitrile methylsulfate (MMA), and also acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular, pentaacetylglucose (PAG), pentaacetylfructose, tetraacetyl-xylose and octaacetyllactose, and acetylated, optionally N-alkylated, glucamine and gluconolactone, and/or N-acylated lactams, for example. N-benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are likewise used with preference Combinations of conventional bleach activators can also be used.
When further bleach activators are to be used in addition to the nitrile quats, preference is given to using bleach activators from the group of the polyacylated alkylene-diamines, in particular, tetraacetylethylenediamine (TAED), N-acylimides, in particular, N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular, n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methylmorpholiniumacetonitrile methylsulfate (MMA), preferably in amounts up to 10% by weight, in particular, from 0.1% by weight to 8% by weight, particularly from 2 to 8% by weight and more preferably from 2 to 6% by weight, based in each case on the total weight of the composition containing bleach activator.
In addition to the conventional bleach activators, or instead of them, it is also possible to use so-called bleach catalysts. These substances are bleach-boosting transition metal salts or transition metal complexes, for example, salen or carbonyl complexes of Mn, Fe, Co, Ru or Mo. It is also possible to use complexes of Mn, Fe, Co, Ru, Mo, Ti, V and Cu with N-containing tripod ligands, and also Co-, Fe-, Cu- and Ru-ammine complexes as bleach catalysts.
Bleach-boosting transition metal complexes, in particular, with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and/or Ru, preferably selected from the group of manganese and/or cobalt salts and/or complexes, more preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, and manganese sulfate, are used in customary amounts, preferably in an amount up to 5% by weight, in particular, from 0.0025% by weight to 1% by weight and more preferably from 0.01% by weight to 0.25% by weight, based in each case on the total weight of the composition containing bleach activator. In specific cases, though, it is also possible to use a greater amount of bleach activator.
Enzymes.
To increase the washing or cleaning performance of washing or cleaning compositions, it is possible to use enzymes. These include, in particular, proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; starting from the natural molecules, improved variants are available for use in washing and cleaning compositions and are preferably used accordingly. Washing or cleaning compositions preferably contain enzymes in total amounts of from 1×10 −6 to 5% by weight based on active protein. The protein concentration may be determined with the aid of known methods, for example, the BCA method or the biuret method.
Among the proteases, preference is given to those of the subtilisin type. Examples thereof include the subtilisins BPN′ and Carlsberg, protease PB92, the subtilisins 147 and 309, Bacillus lentus alkaline protease, subtilisin DY and the enzymes thermitase and proteinase K which can be classified to the subtilases but no longer to the subtilisins in the narrower sense, and the proteases TW3 and TW7. The subtilisin Carlsberg is available in a developed form under the trade name Alcalase® from Novozymes A/S, Bagsværd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase® and Savinase® respectively by Novozymes. The variants listed under the name BLAP® are derived from the protease of Bacillus lentus DSM 5483.
Further examples of useful proteases are the enzymes available under the trade names Durazym®, Relase®, Everlase®, Nafizym, Natalase®, Kannase® and Ovozymes® from Novozymes, those under the trade names Purafect®, Purafect®OxP and Properase® from Genencor, that under the trade name Protosol® from Advanced Biochemicals Ltd., Thane, India, that under the trade name Wuxi® from Wuxi Snyder Bioproducts Ltd., China, those under the trade names Proleather® and Protease P® from Amano Pharmaceuticals Ltd., Nagoya, Japan and that under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
Examples of amylases which can be used in accordance with the invention are the α-amylases from Bacillus licheniformis , from B. amyloliquefaciens or from B. stearothermophilus and developments thereof which have been improved for use in washing and cleaning compositions. The B. licheniformis enzyme is available from Novozymes under the name Termamyl® and from Genencor under the name Purastar®ST. Development products of this α-amylase are obtainable from Novozymes under the trade names Duramyl® and Termamyl®ultra, from Genencor under the name Purastar®OxAm and from Daiwa Seiko Inc., Tokyo, Japan as Keistase®. The B. amyloliquefaciens α-amylase is sold by Novozymes under the name BAN®, and variants derived from the B. stearothermophilus α-amylase under the names BSG® and Novamyl®, likewise from Novozymes.
Additional enzymes which should be emphasized for this purpose are the α-amylase from Bacillus sp. A 7-7 (DSM 12368), and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
Also suitable are the developments of α-amylase from Aspergillus niger and A. oryzae , which are available under the trade names Fungamyl® from Novozymes. Another commercial product is Amylase-LT®, for example.
Furthermore, lipases or cutinases may be used according to the invention, especially owing to their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. Examples thereof include the lipases which were originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or have been developed, in particular, those with the D96L amino acid substitution. They are sold, for example, under the trade names Lipolase®, Lipolase®Ultra, LipoPrime®, Lipozyme® and Lipex® by Novozymes. It is additionally possible, for example, to use the cutinases which have originally been isolated from Fusarium solani pisi and Humicola insolens . Lipases which are also useful can be obtained under the designations Lipase CE®, Lipase P®, Lipase B®, Lipase CES®, Lipase AKG®, Bacillis sp. Lipase®, Lipase AP®, Lipase M-AP® and Lipase AML® from Amano. Examples of lipases and cutinases from Genencor which can be used are those whose starting enzymes have originally been isolated from Pseudomonas mendocina and Fusarium solanii . Other important commercial products include the M1 Lipase® and Lipomax® preparations originally sold by Gist-Brocades and the enzymes sold under the names Lipase MY-30®, Lipase OF® and Lipase PL® by Meito Sangyo KK, Japan, and also the product Lumafast® from Genencor.
It is also possible to use enzymes which are combined under the term hemicellulases. These include, for example, mannanases, xanthane lyases, pectin lyases (=pectinases), pectin esterases, pectate lyases, xyloglucanases (=xylanases), pullulanases and β-glucanases. Suitable mannanases are available, for example, under the names Gamanase® and Pektinex AR® from Novozymes, under the name Rohapec® B1L from AB Enzymes and under the name Pyrolase® from Diversa Corp., San Diego, Calif. The β-glucanase obtained from B. subtilis is available under the name Cereflo® from Novozymes.
To enhance the bleaching action, it is possible in accordance with the invention to use oxidoreductases, for example, oxidases, oxygenases, catalases, peroxidases, such as haloperoxidases, chloroperoxidases, bromoperoxidases, lignin peroxidases, glucose peroxidases or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases). Suitable commercial products include Denilite® 1 and 2 from Novozymes. Advantageously, preferably organic, more preferably aromatic, compounds which interact with the enzymes are additionally added in order to enhance the activity of the oxidoreductases concerned (enhancers), or to ensure the electron flux in the event of large differences in the redox potentials of the oxidizing enzymes and the soilings (mediators).
The enzymes are derived, for example, either originally from microorganisms, for example, of the genera Bacillus, Streptomyces, Humicola , or Pseudomonas , and/or are produced in biotechnology processes known per se by suitable microorganisms, for instance, by transgenic expression hosts of the genera Bacillus or filamentous fungi.
The enzymes in question are preferably purified by means of processes which are established per se, for example, by means of precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, the action of chemicals, deodorization or suitable combinations of these steps.
The enzymes may be used in any form established in the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization, or, especially in the case of liquid or gel-form compositions, solutions of the enzymes, advantageously highly concentrated, low in water and/or admixed with stabilizers.
Alternatively, the enzymes may be encapsulated either for the solid or for the liquid administration form, for example, by spray-drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, for example, those in which the enzymes are enclosed as in a solidified gel, or in those of the core-shell type, in which an enzyme-containing core is coated with a water-, air- and/or chemical-impermeable protective layer. It is possible in layers applied thereto to additionally apply further active ingredients, for example, stabilizers, emulsifiers, pigments, bleaches or dyes. Such capsules are applied by methods known per se, for example, by agitated or roll granulation or in fluidized bed processes. Advantageously, such granules, for example, as a result of application of polymeric film formers, are low-dusting and storage-stable owing to the coating.
It is also possible to formulate two or more enzymes together, so that a single granule has a plurality of enzyme activities.
Particularly during storage, a protein and/or enzyme may be protected from damage, for example, inactivation, denaturation or decay, caused by physical influences, oxidation or proteolytic cleavage. When the proteins and/or enzymes are obtained microbially, particular preference is given to inhibiting proteolysis, especially when the compositions also comprise proteases. For this purpose, washing or cleaning compositions may comprise stabilizers; the provision of such compositions constitutes a preferred embodiment of the present invention.
One group of stabilizers is that of reversible protease inhibitors Frequently, benzamidine hydrochloride, borax, boric acids, boronic acids or salts or esters thereof are used, and of these, in particular, derivatives having aromatic groups, for example, ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or the salts or esters thereof. Peptidic protease inhibitors which should be mentioned include ovomucoid and leupeptin; an additional option is the formation of fusion proteins of proteases and peptide inhibitors.
Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. Terminally capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders are additionally capable of stabilizing an enzyme present.
Lower aliphatic alcohols, but, in particular, polyols, for example, glycerol, ethylene glycol, propylene glycol or sorbitol, are other frequently used enzyme stabilizers. Calcium salts are likewise used, for example, calcium acetate or calcium formate, as are magnesium salts.
Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and/or polyamides stabilize the enzyme preparation against influences including physical influences or pH fluctuations. Polyamine N-oxide-containing polymers act as enzyme stabilizers. Other polymeric stabilizers are the linear C 8 -C 18 polyoxyalkylenes. Alkylpolyglycosides can stabilize the enzymatic components and even increase their performance. Crosslinked N-containing compounds likewise act as enzyme stabilizers.
Reducing agents and antioxidants increase the stability of the enzymes against oxidative decay. An example of a sulfur-containing reducing agent is sodium sulfite.
Preference is given to using combinations of stabilizers, for example, of polyols, boric acid and/or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The action of peptide-aldehyde stabilizers is increased by the combination with boric acid and/or boric acid derivatives and polyols, and further enhanced by the additional use of divalent cations, for example, calcium ions.
Preference is given to using one or more enzymes and/or enzyme preparations, preferably solid protease preparations and/or amylase preparations, in amounts of from 0.1 to 5% by weight, preferably of from 0.2 to 4.5% by weight and, in particular, from 0.4 to 4% by weight, based in each case on the overall composition containing enzyme. Glass Corrosion Inhibitors.
Glass corrosion inhibitors prevent the occurrence of cloudiness, smears and scratches, but also the iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors stem from the group of the magnesium and/or zinc salts and/or magnesium and/or zinc complexes.
A preferred class of compounds which can be used to prevent glass corrosion is that of insoluble zinc salts.
In the context of this preferred embodiment, insoluble zinc salts are zinc salts which have a maximum solubility of 10 grams of zinc salt per liter of water at 20° C. Examples of insoluble zinc salts which are particularly preferred in accordance with the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn 2 (OH) 2 CO 3 ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn 3 (PO 4 ) 2 ) and zinc pyrophosphate (Zn 2 (P 2 O 7 )).
The zinc compounds mentioned are preferably used in amounts which bring about a content of zinc ions in the compositions of between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and, in particular, between 0.2 and 1.0% by weight, based in each case on the overall composition containing glass corrosion inhibitor. The exact content in the compositions of the zinc salt or the zinc salts is by its nature dependent on the type of the zinc salts—the less soluble the zinc salt used, the higher its concentration in the compositions.
Since the insoluble zinc salts remain for the most part unchanged during the dishwashing operation, the particle size of the salts is a criterion to be considered, so that the salts do not adhere to glassware or parts of the machine. Preference is given here to compositions in which the insoluble zinc salts have a particle size below 1.7 millimeters.
When the maximum particle size of the insoluble zinc salts is less than 1.7 mm, there is no risk of insoluble residues in the dishwasher. The insoluble zinc salt preferably has an average particle size which is distinctly below this value in order to further minimize the risk of insoluble residues, for example, an average particle size of less than 250 μm. The lower the solubility of the zinc salt, the more important this is. In addition, the glass corrosion-inhibiting effectiveness increases with decreasing particle size. In the case of very sparingly soluble zinc salts, the average particle size is preferably below 100 μm. For even more sparingly soluble salts, it may be lower still; for example, average particle sizes below 60 μm are preferred for the very sparingly soluble zinc oxide.
A further preferred class of compounds is that of magnesium and/or zinc salt(s) of at least one monomeric and/or polymeric organic acid. These have the effect that, even upon repeated use, the surfaces of glassware are not altered as a result of corrosion, and, in particular, no cloudiness, smears or scratches, and also no iridescence of the glass surfaces, are caused.
Even though all magnesium and/or zinc salt(s) of monomeric and/or polymeric organic acids may be used, preference is given to the magnesium and/or zinc salts of monomeric and/or polymeric organic acids from the groups of the unbranched, saturated or unsaturated monocarboxylic acids, the branched, saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and/or the polymeric carboxylic acids.
The spectrum of the zinc salts, preferred in accordance with the invention, of organic acids, preferably of organic carboxylic acids, ranges from salts which are sparingly soluble or insoluble in water, i.e., have a solubility below 100 mg/l, preferably below 10 mg/l, in particular, below 0.01 mg/l, to those salts which have a solubility in water above 100 mg/l, preferably above 500 mg/l, more preferably above 1 g/l and, in particular, above 5 g/l (all solubilities at water temperature 20° C.). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate; the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.
With particular preference, the glass corrosion inhibitor used is at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt from the group of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and/or zinc citrate. Preference is also given to zinc ricinoleate, zinc abietate and zinc oxalate.
In the context of the present invention, the content of zinc salt in cleaning compositions is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and, in particular, between 0.4 and 3% by weight, or the content of zinc in oxidized form (calculated as Zn 2+ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and, in particular, between 0.04 and 0.2% by weight, based in each case on the total weight of the composition containing glass corrosion inhibitor.
Corrosion Inhibitors.
Corrosion inhibitors serve to protect the ware or the machine, particularly silver protectants having particular significance in the field of machine dishwashing. It is possible to use the known substances from the prior art. In general, it is possible, in particular, to use silver protectants selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes. Particular preference is given to using benzotriazole and/or alkylaminotriazole. Examples of the 3-amino-5-alkyl-1,2,4-triazoles to be used with preference in accordance with the invention include: propyl-, -butyl-, -pentyl-, -heptyl-, -octyl-, -nonyl-, -decyl-, -undecyl-, -dodecyl-, -isononyl-, -Versatic-10 acid alkyl-, -phenyl-, -p-tolyl-, -(4-tert-butylphenyl)-, -(4-methoxyphenyl)-, -(2-, -3-, -4-pyridyl)-, -(2-thienyl)-, -(5-methyl-2-furyl)-, -(5-oxo-2-pyrrolidinyl)-3-amino-1,2,4-triazole. In machine dishwasher detergents, the alkylamino-1,2,4-triazoles or their physiologically compatible salts are used in a concentration of from 0.001 to 10% by weight, preferably from 0.0025 to 2% by weight, more preferably from 0.01 to 0.04% by weight. Preferred acids for the salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulfurous acid, organic carboxylic acids such as acetic acid, glycolic acid, citric acid, succinic acid. Very particularly effective are 5-pentyl-, 5-heptyl-, 5-nonyl-, 5-undecyl-, 5-isononyl-, 5-Versatic-10 acid alkyl-3-amino-1,2,4-triazoles, and also mixtures of these substances.
Frequently also found in cleaning formulations are active chlorine-containing agents which can significantly reduce the corrosion of the silver surface. In chlorine-free cleaners, particularly oxygen- and nitrogen-containing organic redox-active compounds are used, such as di- and trihydric phenols, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol and derivatives of these classes of compound Salti- and complex-type inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, also frequently find use. Preference is given in this context to the transition metal salts which are selected from the group of manganese and/or cobalt salts and/or complexes, more preferably cobalt (ammine) complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, and manganese sulfate. Zinc compounds may likewise be used to prevent corrosion on the ware.
Instead of, or in addition to, the above-described silver protectants, for example, the benzotriazoles, it is possible to use redox-active substances. These substances are preferably inorganic redox-active substances from the group of the manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and/or complexes, the metals preferably being in one of the oxidation states II, III, IV, V or VI.
The metal salts or metal complexes used should be at least partially soluble in water. The counterions suitable for the salt formation include all customary singly, doubly or triply negatively charged inorganic anions, for example oxide, sulfate, nitrate, fluoride, but also organic anions, for example, stearate.
Metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands, and optionally additionally one or more of the above-mentioned anions. The central atom is one of the above-mentioned metals in one of the above-mentioned oxidation states. The ligands are neutral molecules or anions which are mono- or polydentate; the term “ligands” in the context of the invention is explained in more detail, for example, in “Römpp Chemie Lexikon, Georg Thieme Verlag, Stuttgart/New York, 9th edition, 1990, page 2507.” When the charge of the central atom and the charge of the ligand(s) within a metal complex do not add up to zero, depending on whether there is a cationic or an anionic charge excess, either one or more of the above-mentioned anions or one or more cations, for example sodium, potassium, ammonium ions, ensure that the charge balances. Suitable complexing agents are, for example, citrate, acetyl acetonate or 1-hydroxyethane-1,1-diphosphonate.
The definition of “oxidation state” customary in chemistry is reproduced, for example, in “Römpp Chemie Lexikon, Georg Thieme Verlag, Stuttgart/New York, 9th edition, 1991, page 3168.”
Particularly preferred metal salts and/or metal complexes are selected from the group of MnSO 4 , Mn(II) citrate, Mn(II) stearate, Mn(II) acetylacetonate, Mn(II) [1-hydroxyethane-1,1-diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , K 2 TiF 6 , K 2 ZrF 6 , CoSO 4 , Co(NO 3 ) 2 , Ce(NO 3 ) 3 , and mixtures thereof, so that the metal salts and/or metal complexes selected from the group of MnSO 4 , Mn(II) citrate, Mn(II) stearate, Mn(II) acetylacetonate, Mn(II) [1-hydroxyethane-1,1-diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , K 2 TiF 6 , K 2 ZrF 6 , CoSO 4 , Co(NO 3 ) 2 , Ce(NO 3 ) 3 are used with particular preference.
These metal salts or metal complexes are generally commercial substances which can be used in the washing or cleaning compositions for the purposes of silver corrosion protection without prior cleaning. For example, the mixture of penta- and tetravalent vanadium (V 2 O 5 , VO 2 , V 2 O 4 ) known from the preparation of SO 3 (contact process) is, therefore, suitable, as is the titanyl sulfate, TiOSO 4 , which is obtained by diluting a Ti(SO 4 ) 2 solution.
The inorganic redox-active substances, especially metal salts or metal complexes, are preferably coated, i.e., covered completely with a material which is water-tight, but slightly soluble at the cleaning temperatures, in order to prevent their premature disintegration or oxidation in the course of storage. Preferred coating materials which are applied by known methods, for instance by the melt coating method according to Sandwik from the foods industry, are paraffins, micro waxes, waxes of natural origin, such as carnauba wax, candelilla wax, beeswax, relatively high-melting alcohols, for example hexadecanol, soaps or fatty acids. The coating material, which is solid at room temperature, is applied to the material to be coated in the molten state, for example, by centrifuging finely divided material to be coated in a continuous stream through a likewise continuously generated spray-mist zone of the molten coating material. The melting point has to be selected such that the coating material readily dissolves or rapidly melts during the silver treatment. Ideally, the melting point should be in the range between 45° C. and 65° C. and preferably in the 50° C. to 60° C. range.
The metal salts and/or metal complexes mentioned are present in cleaning compositions preferably in an amount of from 0.05 to 6% by weight, preferably from 0.2 to 2.5% by weight, based in each case on the overall composition containing corrosion inhibitor.
Disintegration Assistants.
In order to ease the decomposition of prefabricated tablets, it is possible to incorporate disintegration assistants, known as tablet disintegrants, into these compositions, in order to shorten disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt “Lehrbuch der pharmazeutischen Technologie” [Textbook of pharmaceutical technology] (6th edition, 1987, p. 182-184), tablet disintegrants or disintegration accelerants refer to assistants which ensure the rapid decomposition of tablets in water or gastric juice and the release of pharmaceuticals in absorbable form.
These substances, which are also referred to as “breakup” agents owing to their action, increase their volume on ingress of water, and it is either the increase in the intrinsic volume (swelling) or the release of gases that can generate a pressure that causes the tablets to disintegrate into smaller particles. Disintegration assistants which have been known for some time are, for example, carbonate/citric acid systems, although other organic acids may also be used. Swelling disintegration assistants are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and derivatives thereof, alginates or casein derivatives.
Preference is given to using disintegration assistants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and, in particular, from 4 to 6% by weight, based in each case on the total weight of the composition comprising disintegration assistant.
The preferred disintegration assistants used are disintegration assistants based on cellulose, so that preferred washing and cleaning compositions contain such a cellulose-based disintegration assistant in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and, in particular, from 4 to 6% by weight. Pure cellulose has the formal empirical composition (C 6 H 10 O 5 ), and, viewed in a formal sense, is a β-1,4-polyacetal of cellobiose which is in turn formed from two molecules of glucose. Suitable celluloses consist of from approximately 500 to 5,000 glucose units and accordingly have average molar masses of from 50,000 to 500,000. Useful cellulose-based disintegration assistants in the context of the present invention are also cellulose derivatives which are obtainable by polymer-like reactions from cellulose. Such chemically modified celluloses comprise, for example, products of esterifications and etherifications in which hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bonded by means of an oxygen atom can also be used as cellulose derivatives. The group of the cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and amino celluloses. The cellulose derivatives mentioned are preferably not used alone as disintegration assistants based on cellulose, but rather in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, more preferably below 20% by weight, based on the disintegration assistant based on cellulose. The disintegration assistant based on cellulose which is used is more preferably pure cellulose, which is free of cellulose derivatives.
The cellulose used as a disintegration assistant is preferably not used in finely divided form, but rather converted to a coarser form before admixing with the premixtures to be compressed, for example, granulated or compacted. The particle sizes of such disintegration assistants are usually above 200 μm, preferably to an extent of at least 90% by weight between 300 and 1,600 μm and, in particular, to an extent of at least 90% by weight between 400 and 1,200 μm. The aforementioned coarser cellulose-based disintegration assistants which are described in detail in the documents cited are to be used with preference as disintegration assistants in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from Rettenmaier.
As a further cellulose-based disintegration assistant or as a constituent of this component, it is possible to use microcrystalline cellulose. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and fully dissolve only the amorphous regions (approximately 30% of the total cellulose mass) of the celluloses, but leave the crystalline regions (approximately 70%) undamaged. A subsequent deaggregation of the microfine celluloses formed by the hydrolysis affords the microcrystalline celluloses which have primary particle sizes of approximately 5 μm and can be compacted, for example, to granules having an average particle size of 200 μm.
Preferred disintegration assistants, preferably a cellulose-based disintegration assistant, preferably in granulated, cogranulated or compacted form, are present in the compositions containing disintegration assistant in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and, in particular, from 4 to 6% by weight, based in each case on the total weight of the composition containing disintegration assistant.
According to the invention, gas-evolving effervescent systems may preferably additionally be used as tablet disintegration assistants. The gas-evolving effervescent system may consist of a single substance which releases a gas on contact with water. Among these compounds, mention should be made of magnesium peroxide, in particular, which releases oxygen on contact with water. Typically, however, the gas-releasing effervescent system itself consists of at least two constituents which react with one another to form gas. While a multitude of systems which release, for example, nitrogen, oxygen or hydrogen are conceivable and practicable here, the effervescent system used in the washing and cleaning compositions will be selectable on the basis of both economic and environmental considerations. Preferred effervescent systems consist of alkali metal carbonate and/or alkali metal hydrogencarbonate and of an acidifier which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.
In the case of the alkali metal carbonates and/or alkali metal hydrogencarbonates, the sodium and potassium salts are distinctly preferred over the other salts for reasons of cost. It is, of course, not mandatory to use the pure alkali metal carbonates or alkali metal hydrogencarbonates in question; rather, mixtures of different carbonates and hydrogencarbonates may be preferred.
The effervescent system used is preferably from 2 to 20% by weight, preferably from 3 to 15% by weight and, in particular, from 5 to 10% by weight of an alkali metal carbonate or alkali metal hydrogencarbonate, and from 1 to 15% by weight, preferably from 2 to 12% by weight and, in particular, from 3 to 10% by weight of an acidifier, based in each case on the overall weight of the composition.
Acidifiers which release carbon dioxide from the alkali metal salts in aqueous solution and can be used are, for example, boric acid and also alkali metal hydrogensulfates, alkali metal dihydrogenphosphates and other inorganic salts. Preference is given, however, to the use of organic acidifiers, citric acid being a particularly preferred acidifier. However, it is also possible, in particular, to use the other solid mono-, oligo- and polycarboxylic acids. From this group, preference is given in turn to tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid, and polyacrylic acid. It is likewise possible to use organic sulfonic acids such as amidosulfonic acid. A commercially available acidifier which can likewise be used with preference in the context of the present invention is Sokalan® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).
Preference is given to acidifiers in the effervescent system from the group of the organic di-, tri- and oligocarboxylic acids, or mixtures of these.
Fragrances.
In the context of the present invention, the perfume oils and/or fragrances used may be individual odorant compounds, for example, the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Odorant compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenylglycinate, allyl cyclohexylpropionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals having 8-18 carbon atoms, citral, citronellal, citronellyloxy-acetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; the ketones include, for example, the ionones, α-isomethylionone and methyl cedryl ketone; the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons include primarily the terpenes such as limonene and pinene. However, preference is given to using mixtures of different odorants which together produce a pleasing fragrance note. Such perfume oils may also comprise natural odorant mixtures, as are obtainable from vegetable sources, for example pine oil, citrus oil, jasmine oil, patchouli oil, rose oil or ylang-ylang oil. Likewise suitable are muscatel, sage oil, camomile oil, clove oil, balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, and also orange blossom oil, neroli oil, orange peel oil and sandalwood oil.
The general description of the perfumes which can be used (see above) is a general representation of the different classes of odorant substances. In order to be perceptible, an odorant must be volatile, for which an important role is played not only by the nature of the functional groups and by the structure of the chemical compound but also by the molar mass. Thus, the majority of odorants have molar masses of up to about 200 daltons, while molar masses of 300 daltons or more tend to be an exception. On the basis of the different volatility of odorants there is a change in the odor of a perfume or fragrance composed of two or more odorants during its evaporation, and the perceived odors are divided into top note, middle note or body, and end note or dryout. Since the perception of odor is to a large extent also based on the odor intensity, the top note of a perfume or fragrance does not consist only of volatile compounds, whereas the end note consists for the most part of less volatile odorants, i.e., odorants which adhere firmly. In the composition of perfumes it is possible for more volatile odorants, for example, to be bound to certain fixatives, which prevent them from evaporating too rapidly. The subsequent classification of the odorants into “more volatile” and “firmly adhering” odorants, therefore, states nothing about the perceived odor and about whether the odorant in question is perceived as a top note or as a middle note.
Examples of firmly adhering odorants which can be used in the context of the present invention are the essential oils such as angelica root oil, anise oil, arnica blossom oil, basil oil, bay oil, bergamot oil, champaca blossom oil, noble fir oil, noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, guaiacwood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, camomile oil, camphor oil, canaga oil, cardamom oil, cassia oil, pine needle oil, copaiva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemon grass oil, lime oil, mandarin oil, balm oil, musk seed oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, orange oil, origanum oil, palmarosa oil, patchouli oil, peru balsam oil, petitgrain oil, pepper oil, peppermint oil, pimento oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery oil, spike oil, star anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniperberry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, citronella, lemon oil and cypress oil. However, the higher-boiling or solid odorants of natural or synthetic origin may also be used in the context of the present invention as firmly adhering odorants or odorant mixtures, i.e., fragrances. These compounds include the following compounds and mixtures thereof: ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anisyl alcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol, bornyl acetate, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, methyl heptynecarboxylate, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrol, jasmone, camphor, carvacrol, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl methylanthranilate, p-methylacetophenone, methylchavicol, p-methylquinoline, methyl β-naphthyl ketone, methyl-n-nonylacetaldehyde, methyl n-nonyl ketone, muscone, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, nitrobenzene, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxyacetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyl acetal, phenylacetic acid, pulegone, safrol, isoamyl salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, santalol, skatole, terpineol, thymene, thymol, γ-undecalactone, vanillin, veratrum aldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, ethyl cinnamate, benzyl cinnamate. The more volatile odorants include, in particular, the lower-boiling odorants of natural or synthetic origin, which may be used alone or in mixtures. Examples of more volatile odorants are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linalyl acetate and linalyl propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
The fragrances can be processed directly, but it may also be advantageous to apply the fragrances to carriers which ensure long-lasting fragrance by slower fragrance release. Useful carrier materials have been found to be, for example, cyclodextrins, and the cyclodextrin-perfume complexes may additionally also be coated with further assistants.
Dyes.
Preferred dyes, whose selection presents no difficulty at all to the person skilled in the art, have high storage stability and insensitivity toward the other ingredients of the compositions and to light, and also have no pronounced substantivity toward the substrates to be treated with the dye-containing compositions, such as textiles, glass, ceramic or plastic dishware, so as not to stain them.
In the selection of the colorant, it has to be ensured that the colorants, in the case of textile washing compositions, do not have too strong an affinity toward the textile surfaces and here, in particular, toward synthetic fibers, while, in the case of cleaning compositions, too strong an affinity toward glass, ceramic or plastic dishware has to be avoided. At the same time, it should be taken into account when selecting suitable colorants that colorants have different stabilities toward oxidation. It is generally the case that water-insoluble colorants are more stable toward oxidation than water-soluble colorants. The concentration of the colorant in the washing or cleaning compositions varies depending on the solubility and hence also upon the oxidation sensitivity. In the case of highly water-soluble colorants, for example, the above-mentioned Basacid® Green or the likewise above-mentioned Sandolan® Blue, typical colorant concentrations in the region of a few 10 −2 to 10 −3 % by weight are selected. In the case of the pigmentary dyes, which are especially preferred owing to their brilliance but are less readily water-soluble, for example the above-mentioned Pigmosol® dyes, the suitable concentration of the colorant in washing or cleaning compositions, in contrast, is typically a few 10 −3 to 10 −4 % by weight.
Preference is given to colorants which can be destroyed oxidatively in the washing process, and to mixtures thereof with suitable blue dyes, known as bluing agents. It has been found to be advantageous to use colorants which are soluble in water or, at room temperature, in liquid organic substances. Examples of suitable colorants are anionic colorants, for example, anionic nitroso dyes. One example of a possible colorant is naphthol green (Color Index (Cl) Part 1: Acid Green 1; Part 2: 10020), which is available as a commercial product, for example as Basacid® Green 970 from BASF, Ludwigshafen, Germany, and mixtures thereof with suitable blue dyes. Further suitable colorants are Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (CI 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamin EB400 (CI 45100), Basacid® Yellow 094 (CI 47005), Sicovit® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acid Blue 183), Pigment Blue 15 (CI 74160), Supranol® Blue GLW (CAS 12219-32-8, CI Acid Blue 221)), Nylosan® Yellow N-7GL SGR(CAS 61814-57-1, CI Acid Yellow 218) and/or Sandolan® Blue (CI Acid Blue 182, CAS 12219-26-0).
In addition to the components described in detail so far, the washing and cleaning compositions may comprise further ingredients which further improve the performance and/or esthetic properties of these compositions. Preferred compositions comprise one or more substances from the group of electrolytes, pH modifiers, fluorescers, hydrotropes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, graying inhibitors, shrink preventatives, anticrease agents, dye transfer inhibitors, active antimicrobial ingredients, germicides, fungicides, antioxidants, antistats, ironing aids, repellency and impregnation agents, antiswell and antislip agents and UV absorbers.
The electrolytes used from the group of the inorganic salts may be a wide range of highly varying salts. Preferred cations are the alkali metals and alkaline earth metals; preferred anions are the halides and sulfates. From a production point of view, preference is given to the use of NaCl or MgCl 2 in the washing or cleaning compositions.
In order to bring the pH of the washing or cleaning compositions into the desired range, it may be appropriate to use pH modifiers. It is possible here to use all known acids or alkalis, as long as their use is not forbidden on performance or ecological grounds or on grounds of consumer protection. Typically, the amount of these modifiers does not exceed 1% by weight of the overall formulation.
Useful foam inhibitors include soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials. Suitable support materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the aforementioned materials. Compositions which are preferred in the context of the present application comprise paraffins, preferably unbranched paraffins (n-paraffins) and/or silicones, preferably linear polymeric silicones which have the composition according to the scheme (R 2 SiO) x and are also referred to as silicone oils. These silicone oils are commonly clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight between 1,000 and 150,000, and viscosities between 10 and 1,000,000 mPa·s.
Suitable antiredeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers, such as methylcellulose and methylhydroxypropyl-cellulose having a proportion of methoxy groups of from 15 to 30% by weight and of hydroxypropyl groups of from 1 to 15% by weight, based in each case on the nonionic cellulose ethers, and the prior art polymers of phthalic acid and/or terephthalic acid or derivatives thereof, in particular, polymers of ethylene terephthalates and/or polyethylene glycol terephthalates or anionically and/or nonionically modified derivatives thereof. Among these, particular preference is given to the sulfonated derivatives of phthalic acid polymers and terephthalic acid polymers.
Optical brighteners (known as “whiteners”) may be added to the washing or cleaning compositions in order to eliminate graying and yellowing of the treated textiles. These substances attach to the fibers and bring about brightening and simulated bleaching action by converting invisible ultraviolet radiation to visible longer-wavelength light, in the course of which the ultraviolet light absorbed from sunlight is radiated as pale bluish fluorescence and, together with the yellow shade of the grayed or yellowed laundry, results in pure white. Suitable compounds are derived, for example, from the substance classes of 4,4′-diamino-2,2′-stilbenedisulfonic acids (flavonic acids), 4,4′-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and benzimidazole systems, and the pyrene derivatives substituted by heterocycles.
Graying inhibitors have the task of keeping the soil detached from the fiber suspended in the liquor, thus preventing the soil from reattaching. Suitable for this purpose are water-soluble colloids, usually of organic nature, for example the water-soluble salts of polymeric carboxylic acids, size, gelatin, salts of ether sulfonic acids of starch or of cellulose, or salts of acidic sulfuric esters of cellulose or of starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. In addition, it is possible to use soluble starch preparations, and starch products other than those mentioned above, for example degraded starch, aldehyde starches, etc. It is also possible to use polyvinylpyrrolidone. Also usable as graying inhibitors are cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.
Since textile fabrics, in particular, those made of rayon, viscose, cotton and mixtures thereof, can tend to crease because the individual fibers are sensitive toward bending, folding, compressing and crushing transverse to the fiber direction, synthetic anti-crease agents may be used. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty acid alkylol esters, fatty acid alkylolamides or fatty alcohols, which have usually been reacted with ethylene oxide, or products based on lecithin or modified phosphoric esters.
Repellency and impregnation processes serve to finish textiles with substances which prevent the deposition of soil or make it easier to wash out. Preferred repellency and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum and zirconium salts, organic silicates, silicones, polyacrylic esters having a perfluorinated alcohol component or polymerizable compounds having a coupled, perfluorinated acyl or sulfonyl radical. Antistats may also be present. The soil-repellent finish with repellency and impregnating agents is often classified as an easycare finish. The penetration of the impregnating agents in the form of solutions or emulsions of the active ingredients in question may be eased by adding wetting agents which lower the surface tension. A further field of use of repellency and impregnating agents is the water-repellent finishing of textiles, tents, tarpaulins, leather, etc., in which, in contrast to waterproofing, the fabric pores are not sealed and the substance thus remains breathable (hydrophobizing). The hydrophobizing agents used for the hydrophobization coat textiles, leather, paper, wood, etc., with a very thin layer of hydrophobic groups such as relatively long alkyl chains or siloxane groups. Suitable hydrophobizing agents are, for example, paraffins, waxes, metal soaps, etc., with additives of aluminum or zirconium salts, quaternary ammonium compounds having long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones, organotin compounds and glutaraldehyde, and also perfluorinated compounds. The hydrophobized materials do not have a greasy feel, but water drops, similarly to the way they do on greased substances, run off them without wetting them. For example, silicone-impregnated textiles have a soft hand and are water- and soil-repellent; stains of ink, wine, fruit juices and the like can be removed more easily.
Active antimicrobial ingredients can be used to control microorganisms. A distinction is drawn here, depending on the antimicrobial spectrum and mechanism of action, between bacteriostats and bactericides, fungistats and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenylmercuric acetate, although it is also possible to dispense entirely with these compounds.
In order to prevent undesired changes, caused by the action of oxygen and other oxidative processes, to the washing and cleaning compositions and/or the textiles treated, the compositions may comprise antioxidants. This class of compound includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines, and also organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
Increased wear comfort can result from the additional use of antistats. Antistats increase the surface conductivity and thus permit improved discharge of charges formed. External antistats are generally substances having at least one hydrophilic molecular ligand and impart to the surfaces a more or less hygroscopic film. These usually interface-active antistats can be subdivided into nitrogen antistats (amines, amides, quaternary ammonium compounds), phosphorus antistats (phosphoric esters) and sulfur antistats (alkylsulfonates, alkyl sulfates). Lauryl- (or stearyl)dimethylbenzylammonium chlorides are likewise suitable as antistats for textiles or as additives for washing compositions, in which case a softening effect is additionally achieved.
For the care of the textiles and for an improvement in the textile properties such as a softer “hand” (softening) and reduced electrostatic charge (increased wear comfort), fabric softeners may be used. The active ingredients in fabric softener formulations are ester quats, quaternary ammonium compounds having two hydrophobic radicals, for example. distearyldimethylammonium chloride which, however, owing to its inadequate biodegradability, is increasingly being replaced by quaternary ammonium compounds which contain ester groups in their hydrophobic radicals as intended cleavage sites for biodegradation.
Such ester quats having improved biodegradability are obtainable, for example, by esterifying mixtures of methyldiethanolamine and/or triethanolamine with fatty acids and subsequently quaternizing the reaction products with alkylating agents in a manner known per se. Another suitable finish is dimethylolethyleneurea.
To improve the water-absorption capacity and the rewettability of the treated textiles, and to ease the ironing of these textiles, it is possible to use silicone derivatives. They additionally improve the rinse-out performance of the washing or cleaning compositions by virtue of their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl- or alkylarylsiloxanes in which the alkyl groups have from one to five carbon atoms and are fully or partly fluorinated. Preferred silicones are polydimethylsiloxanes which may optionally be derivatized and are, in that case, amino-functional or quaternized or have Si—OH, Si—H and/or Si—Cl bonds. Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, i.e., polysiloxanes which have polyethylene glycols, for example, and the polyalkylene oxide-modified dimethyl polysiloxanes.
Finally, it is also possible in accordance with the invention to use UV absorbers, which attach to the treated textiles and improve the photoresistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone having substituents in the 2- and/or 4-position, which are active by virtue of radiationless deactivation. Also suitable are substituted benzotriazoles, 3-phenyl-substituted acrylates (cinnamic acid derivatives), optionally having cyano groups in the 2-position, salicylates, organic nickel complexes and natural substances such as umbelliferone and endogenous urocanic acid.
Owing to their fibercare action, protein hydrolyzates are further preferred active substances from the field of washing and cleaning compositions in the context of the present invention. Protein hydrolyzates are product mixtures which are obtained by acid-, base- or enzyme-catalyzed degradation of proteins. According to the invention, protein hydrolyzates either of vegetable or animal origin may be used. Animal protein hydrolyzates are, for example, elastin, collagen, keratin, silk and milk protein hydrolyzates which may also be present in the form of salts. Preference is given in accordance with the invention to the use of protein hydrolyzates of vegetable origin, for example, soybean, almond, rice, pea, potato and wheat protein hydrolyzates. Although preference is given to the use of the protein hydrolyzates as such, it is in some cases also possible to use in their stead amino acid mixtures or individual amino acids obtained in other ways, for example arginine, lysine, histidine or pyroglutamic acid. It is likewise possible to use derivatives of protein hydrolyzates, for example, in the form of their fatty acid condensates.
The nonaqueous solvents which can be used in accordance with the invention include, in particular, the organic solvents, of which only the most important can be listed here: alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, diethylene glycol), ethers and glycol ethers (diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ethers), ketones (acetone, butanone, cyclohexanone), esters (ethyl acetate, glycol esters), amides and other nitrogen compounds (dimethylformamide, pyridine, N-methylpyrrolidone, acetonitrile), sulfur compounds (carbon disulfide, dimethyl sulfoxide, sulfolane), nitro compounds (nitrobenzene), halohydrocarbons (dichloromethane, chloroform, tetrachloromethane, tri-, tetrachloroethene, 1,2-dichloroethane, chlorofluorocarbons), hydrocarbons (benzines, petroleum ether, cyclohexane, methylcyclohexane, decalin, terpene solvents, benzene, toluene, xylenes). Alternatively, it is also possible instead of the pure solvents to use mixtures thereof which, for example, advantageously combine the dissolution properties of different solvents. Such a solvent mixture which is particularly preferred in the context of the present application is, for example, petroleum benzine, a mixture of different hydrocarbons which is suitable for chemical purification, preferably having a content of C 12 to C 14 hydrocarbons above 60% by weight, more preferably above 80% by weight and, in particular, above 90% by weight, based in each case on the total weight of the mixture, preferably having a boiling range of from 81 to 110° C.