English
Tiếng Việt
(en)Disclosed are cosmetic formulation comprising (a) particulates having an absorption in the range of 400 to 800 nm; and (b) UV filters selected from (b 1 ) particulate organic UV-filters; and (b 2 ) soluble organic UV filters.
1.ApplicationNumber: US-201715586818-A
1.PublishNumber: US-2017231889-A1
2.Date Publish: 20170817
3.Inventor: EHLIS THOMAS
SOHN MYRIAM
4.Inventor Harmonized: EHLIS THOMAS(DE)
SOHN MYRIAM(FR)
5.Country: US
6.Claims:
(en)Disclosed are cosmetic formulation comprising (a) particulates having an absorption in the range of 400 to 800 nm; and (b) UV filters selected from (b 1 ) particulate organic UV-filters; and (b 2 ) soluble organic UV filters.
7.Description:
(en)The present invention relates to cosmetic compositions comprising micronized and/or soluble UV absorbers and one or more color pigments.
It has long been known that prolonged exposure to that UV radiation which reaches the surface of the earth can lead to the formation of erythemas or light dermatoses, as well as to an increased incidence of skin cancers or accelerated skin aging.
Various sunscreen formulations have been proposed which include actives which are intended to counteract UV radiation, thereby inhibiting the said undesired effects on the skin.
A great number of compounds has been proposed for the use as UV protectants in sunscreen formulations, especially soluble organic UV absorbers and also insoluble micronized organic and inorganic compounds, wich become more and more common in sunscreen formulations.
Micronised, insoluble organic UV absorbers, when used in sunscreen formulations, provide excellent UV protection and have a high SPF rating. Moreover, micronised, insoluble organic UV absorbers show no tendency, under the influence of light, to generate radicals which could damage or sensitise human skin.
Unfortunately, due to light scattering sun screen compostitions comprising organic and/or inorganic particulate filters show an articulate whitening aspect when applied on the skin.
The whitening aspect increases with higher concentration of the corresponding UV filters and will therefore limit their required quantity.
Furthermore, soluble and particulate UV filters which have absorption maximum in the UV-A region are mostly not colourless since these substances will absorb also light in the visible range of the spectrum. Due to the particular colour of these UV-A filters the resulting cosmetic sun screen formulations will be coloured. The hue of such formulations (in most cases yellowish) is considered as unnatural since it derivates significantly from the natural skin hue.
Furthermore, it is known that some UV filters show significant fluorescence. Artificial illuminations with a high UV ratio therefore generate very unnatural skin tones.
Surprisingly it has been found that the combination of particulate or soluble organic UV filters with one or more colour pigments provides cosmetic sunscreen formulations which have a hue that corresponds to the natural skin tone and is therefore not considered as unnatural.
Therefore the present invention relates to a cosmetic formulation comprising
(a) particulates having an absorption in the range of 400 to 800 nm; and
(b) UV filters selected from
(b 1 ) particulate organic UV-filters; and (b 2 ) soluble organic UV filters.
Preferably component (a) is selected from
(a 1 ) inorganic colour pigments; and
(a 2 ) organic colour pigments.
Most preferably the inorganic pigments (a 1 ) are selected from iron (III) oxide, magnetite and mixtures of these pigments; manganese doped TiO 2 or ZnO; ultramarine pigments; chromium oxide green; chromium hydrate green; metal-particles; mica, bismuth oxychloride; glass flakes (borosilicates); interference-pigments based on mica (synthetic or of natural origin); or borosilicates (glass flakes), typically coated with thin layers of titanium dioxide (rutile or anastas), iron oxides or mixtures thereof and talcum.
The organic pigments (a 2 ) are preferably selected from D&C Red 30 (Vat Red 1); D&C Red 36 (Pigment Red 4); Carmine; D&C Red 6 Ba Lake; D&C Red 7 Ca Lake; D&C Red 30 Al Lake; D&C Red 30 Talc Lake; D&C Red 27 Al Lake; D&C Red 28 Al Lake; D&C Red 33 Al Lake; D&C Red 21 Al Lake.
Of specific interest are the pigments/colours listed in Table 1 below:
TABLE 1a
Examples of pigments/colours (component (b))
Color index
CAS registry
number
Official and common name
number
10006
Pigment Green 8
16143-80-9
10020
Acid Green 1
19381-50-1
10316 (2)
Ext. D & C Yellow No. 7; Acid Yellow 1; Naphthol Yellow S
846-70-8
11680
Pigment Yellow 1
2512-29-0
11710
Pigment Yellow 3
6486-23-3
11725
Pigment Orange 1
6371-96-6
11920
Solvent Orange 1
2051-85-6
12010
Solvent Red 3
6535-42-8
12085 (2)
D & C Red No. 36; Pigment Red 4; Flaming Red
2814-77-9
12120
Pigment Red 3
2425-85-6
12150
Solvent Red 1
1229-55-6
12370
Pigment Red 112
6535-46-2
12420
Pigment Red 7
6471-51-8
12480
Pigment Brown
6410-40-8
12490
Pigment Red 5
6410-41-9
12700
Disperse Yellow 16
4314-14-1
13015
E 105; Acid Yellow 9
2706-28-7
14270
E 103; Acid Orange 6
547-57-9
14700
FD & C Red No. 4; Food Red 1; Ponceau SX
4548-53-2
14720
E 122; Acid Red 14; Food Red 3; Azorubine; Carmoisine
3567-69-9
14815
E 125; Food Red 2
3257-28-1
15510 (2)
D&C Orange No. 4; Acid Orange 7; Orange II
633-96-5
15525
Pigment Red 68
5850-80-6
15580
Pigment Red 51
227-459-1
15620
Acid Red 88
1658-56-6
15630
Pigment Red 49
1248-18-6
15800:1
D&C Red No. 31; Pigment Red 64:1; Brilliant Lake Red R
6371-76-2
15850
D&C Red No. 6; Pigment Red 57; Lithol Rubin B
5858-81-1
15850:1 (2)
D&C Red No. 7; Pigment Red 57:1; Lithol Rubin B Ca
5281-04-9
15865 (2)
Pigment Red 48
3564-21-4
15880:1
D&C Red No. 34; Pigment Red 63:1; Deep Maroon; Fanchon
6417-83-0
Maroon; Lake Bordeaux B
15980
E 111; Food Orange 2
2347-72-0
15985 (2)
FD&C Yellow No. 6; E 110; Food Yellow 3; Sunset Yellow;
2783-94-0
Sunset Yellow FCF; Orange Yellow S
16035
FD&C Red No. 40; Food Red 17; Allura Red; Allura Red AC
25956-17-6
16230
Acid Orange 10
1936-15-8
16255 (2)
E 124; Acid Red 18; Food Red 7; Ponceau 4R; Cochineal Red A
2611-82-7
16290
E 126; Acid Red 41
5850-44-2
17200 (2)
D&C Red No. 33; Acid Red 33; Acid Fuchsine
3567-66-6
18050
Acid Red 1
3734-67-6
18130
Acid Red 155
10236-37-0
18690
Acid Yellow 121
5601-29-6
18736
Acid Red 180
6408-26-0
18820
Acid Yellow 11
6359-82-6
18965
Acid Yellow 17
6359-98-4
19140 (2)
FD&C Yellow No. 5; E 102; Acid Yellow 23; Tartrazine
1934-21-0
20040
Pigment Yellow 16
5979-28-2
20170
D&C Brown No. 1; Acid Orange 24; Resorcin Brown
1320-07-6
20470
Noir W 699
1064-48-8
21100
Pigment Yellow 13
5102-83-0
21108
Pigment Yellow 83
5567-15-7
21230
Solvent Yellow 29
6706-82-7
24790
Acid Red 163
13421-53-9
26100
D&C Red No. 17; Solvent Red 23; Sudan III; Toney Red
85-86-9
27290 (2)
Acid Red 73
5413-75-2
27755
E152; Food Black 2
2118-39-0
28440
E 151; Brilliant Black 1; Food Black 1; Brilliant Black BN; Black P
2519-30-4
40215
Direct Orange 34
1325-54-8
40800
Beta Carotene (synthetic); Food Orange 5
7235-40-7
40820
E 160e; Food Orange 6; β-Apo-8′ Carotenal (C 30)
1107-26-2
40825
E 160f; Food Orange 7; Ethyl Ester of β-Apo-8′ Carotenic Acid
1109-11-1
(C 30)
40850
Canthaxanthin; E 161g; Food Orange 8
514-78-3
42045
Acid Blue 1
129-17-9
42051 (2)
E 131; Acid Blue 3; Patent Blue V
3536-49-0
42053
FD&C Green No. 3; Food Green 3; Fast Green FCF
2353-45-9
42080
Acid Blue 7
3486-30-4
42090
FD&C Blue No. 1; Acid Blue 9 (Sodium salt); Food Blue 2;
3844-45-9
Brilliant Blue FCF; Patent Blue AC
FD&C Blue No. 4; Acid Blue 9 (Ammonium salt); Alphazurine
6371-85-3
FG; Erioglaucine
42100
Acid Green 9
4857-81-2
42170
Acid Green 22
5863-51-4
42510
Basic Violet 14
632-99-5
42520
Basic Violet 2
3248-91-7
42735
Acid Blue 104
6505-30-2
44045
Basic Blue 26
2580-56-5
44090
E142; Acid Green 50; Green S
3087-16-9
45100
Acid Red 52
3520-42-1
45190
Acid Violet 9
6252-76-2
45220
Acid Red 50
5873-16-5
45350
D&C Yellow No. 8; Acid Yellow 73; Uranine
518-47-8
45350:1
D&C Yellow No. 7; Solvent Yellow 94; Fluorescein
2321-07-5
45370 (2)
Acid Orange 11
45370:1
D&C Orange No. 5; Solvent Red 72; Dibromofluorescein
596-03-2
45380 (2)
D&C Red No. 22; Acid Red 87; Eosin Y
17372-87-1
45380:2
D&C Red No. 21; Solvent Red 43; Tetrabromofluorescein
15086-94-8
45396
Solvent Orange 16
24545-86-6
45405
Acid Red 98
6441-77-6
45410 (2)
D&C Red No. 28; Acid Red 92; Phloxine B
18472-87-2
45410:1
D&C Red No. 27; Solvent Red 48; Tetrabromotetrachloro-;
13473-26-2
Fluorescein
45425
D&C Red No. 11; Acid Red 95; Erythrosine Yellowish Na
33239-19-9
45425:1
D&C Orange No. 10; Solvent Red 73; Diiodofluorescein
38577-97-8
45430 (2)
E 127; FD&C Red No. 3; Acid Red 51; Erythrosine; Food Red
16423-68-0
14
47000
D&C Yellow No. 11; Solvent Yellow 33; Quinoline Yellow SS
8003-22-3
47005
D&C Yellow No. 10; E104; Acid Yellow; Food Yellow 13;
8004-92-0
Quinoline Yellow; Canary Yellow
50325
Acid Violet 50
229-951-1
50420
Acid Black 2
8005-03-6
51319
Pigment Violet 23
6358-30-1
58000
Pigment Red 83; Alizarin
72-48-0
59040
D&C Green No. 8; Solvent Green 7; Pyranine Concentrated
6358-69-6
60724
Disperse Violet 27
19286-75-0
60725
D&C Violet No. 2; Solvent Violet 13; Alizurol Purple SS
81-48-1
60730
Ext D&C Violet No. 2; Acid Violet 43
4430-18-6
61565
D&C Green No. 6; Solvent Green 3; Quinizarin Green SS
128-80-3
61570
D&C Green No. 5; Acid Green 25
4403-90-1
61585
Acid Blue 80
4474-24-2
62045
Acid Blue 65
4368-56-3
69800
E 130; Vat Blue 4
81-77-6
69825
D&C Blue No. 9; Vat Blue 6; Indanthrene Blue; Carbanthrene
130-20-1
Blue
71105
Vat Orange 7; Pigment Orange 43
4424-06-0
73000
Vat Blue 1; Indigo
482-89-3
73015
FD&C Blue No. 2; E 132; Food Blue 1; Indigotine; Indigo
860-22-0
Carmine
73360
D&C Red No. 30; Vat Red 1; Helindone Pink CN
2379-79-0
73385
Vat Violet 2
5462-29-3
73900
Pigment Violet 19
1047-16-1
73915
Pigment Red 122
16043-40-6
74100
Pigment Blue 16
547-93-6
74160
Pigment Blue 15
147-14-8
74180
Direct Blue 86
1330-38-7
74260
Pigment Green 7
1328-53-6
75100
Natural Yellow 6
27876-94-4
75120
Annatto extract; E 160b; Natural Orange 4
1393-63-1
75125
E 160d; Lycopene
502-65-8
75130
Beta Carotene (Natural); E 160a; Natural Browns 5; Natural
7235-40-7
Yellow 26
75135
E 161d; Natural Yellow 27; Rubixanthin
3763-55-1
75170
Guanine; Natural White 1
73-40-5
75300
E 100; Natural Yellow 3; Turmeric Yellow; Curcumin; Indian
458-37-7
Saffron
75470
Cochineal extract; E120; Natural Red 4; Cochineal; Carmine;
1343-78-8
Carminic Acid ...
1390-65-4
1260-17-9
75480
Henna
83-72-7
75810
E 140 & E 141; Chlorophyll; Copper complexes of chlorophyll
11006-34-1
and chlorophyllins; Potassium sodium copper; Chlorophyllin;
Natural Green 3
77000
Aluminum Powder; E 173; Pigment Metal 1; Aluminum
4729-90-5
77002
Alumina; Pigment White 24
1332-73-6
77004
Pigment White 19; Bentonite
1302-78-9
77007
Ultramarine Blue; Pigment Blue 29
1317-97-1
Ultramarine Red
1345-00-2
Ultramarine Violet; Pigment Violet 15
12769-96-9
77013
Ultramarine Green; Pigment Green 24
77015
Pigment Red 101; Pigment Red 102
77019
Mica; Pigment White 20
12001-26-2
Talc; Pigment white 26
14807-96-9
77120
Pigment White 21; Pigment White 22
7727-43-7
77163
Bismuth oxychloride; Pigment White 14
7787-59-9
77220
Calcium carbonate; E 170; Pigment White 18
471-34-1
77231
Pigment White 25; Calcium Sulfate
7778-18-9
77288
Chromium Oxide Greens; Pigment Green 17
1308-38-4
77289
Chromium hydroxide Green; Pigment Green 18; Guignet Green;
12001-99-9
Veridian
77346
Cobalt Blue; Pigment Blue 28
1345-16-0
77400
Bronze powder; Copper powder; Pigment Metal 2
7440-50-8
77400
77480
E 175; Gold; Pigment Metal 3
7740-57-5
77489
E 172; Ferrous oxide
1345-25-1
77491
Ferric oxide; E 172; Pigments Red 101 & 102; Pigments Brown
1309-37-1
6 & 7
77492
Hydrated Ferric oxide; E 172; Pigments Yellow 42 & 43;
20344-49-4
Pigments Brown 6 & 7
77499
Ferrous Ferric oxide; E 172; Pigment Black 11; Pigments Brown
1317-61-9
6 & 7
77510
Ferric ferrocyanide; Pigment Blue 27; Prussian Blue
14038-43-8
77520
77713
Magnesium Carbonate; Pigment White 18
546-93-0
77742
Manganese Violet; Pigment Violet 16
10101-66-3
77745
Manganous Phosphate
10124-54-6
77820
Silver; E 174
7440-22-4
77891
Titanium Dioxide; E 171; Pigment White 6
13463-67-7
77947
Zinc Oxide; Pigment White 4
1317-13-2
Acid red 195
12220-24-5
Aluminum distearate
300-92-5
Anthocyanins; E 163
11029-12-2
Beetroot red; E 162
89957-89-1
7659-95-2
Bismuth citrate
Bromocresol green
76-60-8
Bromothymol blue
76-59-5
Calcium stearate
1592-23-0
Capsanthin, Capsorubin; E 160c; Paprika extract
465-42-9
E 150; Natural Brown 10; Caramel
8028-89-5
Ferric ammonium ferrocyanide
25869-00-5
E 101; Lactoflavin; Riboflavin
83-88-5
Lead acetate
301-04-2
Magnesium Stearate
557-04-0
Zinc Stearate
557-05-1
indicates data missing or illegible when filed
TABLE 1b
Structure of the Lakes:
Lakes (FDA name)
CI No
name
structure of corresponding dye
D & C Red #6 Ba Lake
15850
Pigment Red 57 Sodium Salt
D & C Red #7
15850:1
Pigment Red 57.1 Calcium Salt
D & C Red #21 Al Lake
45380:2
Solvent Red 43
D & C Red #22 Al Lake
45380
Acid Red 87
D & C Red #27 Al Lake
45410:1
Solvent Red 48
D & C Red #28 Al Lake
45410
Acid Red 92
D & C Red #30 Al & Talk Lake
73360
Vat Red 1 = Pigment Red 181
D & C Red #33 Al & Zr Lake
17200
Acid Red 33
D & C Red #10 Al Lake
47005
Food Yellow 13
and
FD & C Yellow #5 Al Lake
19140
Acid Yellow 23 Na Salt
FD & C Yellow #6 Al Lake
15985
Food Yellow 3 Na Salt
FD & C Blue #1 Al Lake
42090
Acid blue 9
TABLE 1c
Calisha colour pigments (Ciba):
Name
INCI Name
Treated Pearls
Calisha Romance Silver Pearl OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Romance Glamour Violet OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Romance Glamour Blue Pearl OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Romance Glamour Green OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Romance Gold Pearl OD
Mica and Titanium Dioxide and Red Iron Oxide
and Cetyl Dimethicone
Calisha Romance Bronze Pearl OD
Mica and Red Iron Oxide and Cetyl
Dimethicone
Calisha Romance Orange Pearl OD
Mica and Red Iron Oxide and Cetyl
Dimethicone
Calisha Romance Red Pearl OD
Mica and Red Iron Oxide and Cetyl
Dimethicone
Calisha Contemporary Starlight Pearl OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Contemporary Glamour Blue Pearl
Mica and Titanium Dioxide and Cetyl
OD
Dimethicone
Calisha Contemporary Glamour Gold Pearl
Mica and Titanium Dioxide and Cetyl
OD
Dimethicone
Calisha Contemporary Glamour Violet OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Contemporary Claret Pearl OD
Mica and Red Iron Oxide and Titanium Dioxide
and Cetyl Dimethicone
Calisha Contemporary Sienna Pearl OD
Mica and Red Iron Oxide and Titanium Dioxide
and Cetyl Dimethicone
Calisha Contemporary Black Pearl OD
Mica and Titanium Dioxide and Black Iron
Oxide and Cetyl Dimethicone
Calisha Contemporary Sable Pearl OD
Mica and Titanium Dioxide and and Red Iron
Oxide Carmine and Cetyl Dimethicone
Calisha Contemporary Green Pearl OD
Mica and Titanium Dioxide and Red Iron Oxide
and Ferric Ferrocyanide and Cetyl Dimethicone
Calisha Contemporary Silver Pearl OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Contemporary Glamour Green OD
Mica and Titanium Dioxide and Tin Dioxide and
Cetyl Dimethicone
Calisha Contemporary Gold Pearl OD
Mica and Titanium Dioxide and Red Iron Oxide
and Cetyl Dimethicone
Calisha Contemporary Bronze Pearl OD
Mica and Red Iron Oxide and Cetyl
Dimethicone
Calisha Contemporary Rose Red Pearl OD
Mica and Red Iron Oxide and Cetyl
Dimethicone
Calisha Art Deco Silver Pearl OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Art Deco Glamour Violet OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Art Deco Glamour Blue Pearl OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Art Deco Glamour Green OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Art Deco Gold Pearl OD
Mica and Red Iron Oxide and Titanium Dioxide
and Cetyl Dimethicone
Calisha Art Deco Bronze Pearl OD
Mica and Red Iron Oxide and Cetyl
Dimethicone
Calisha Art Deco Orange Pearl OD
Mica and Red Iron Oxide and Cetyl
Dimethicone
Calisha Art Deco Red Pearl OD
Mica and Red Iron Oxide and Cetyl
Dimethicone
Untreated Pearls
Calisha Romance Silver Pearl CL
Mica and Titanium Dioxide
Calisha Romance Glamour Violet CL
Mica and Titanium Dioxide
Calisha Romance Glamour Blue Pearl CL
Mica and Titanium Dioxide
Calisha Romance Glamour Green CL
Mica and Titanium Dioxide
Calisha Romance Gold Pearl CL
Mica and Titanium Dioxide and Red Iron Oxide
Calisha Romance Bronze Pearl CL
Mica and Red Iron Oxide
Calisha Romance Orange Pearl CL
Mica and Red Iron Oxide
Calisha Romance Red Pearl CL
Mica and Red Iron Oxide
Calisha Contemporary Starlight Pearl CL
Mica and Titanium Dioxide
Calisha Contemporary Glamour Blue Pearl
Mica and Titanium Dioxide
CL
Calisha Contemporary Glamour Gold Pearl
Mica and Titanium Dioxide
CL
Calisha Contemporary Glamour Violet CL
Mica and Titanium Dioxide
Calisha Contemporary Claret Pearl CL
Mica and Red Iron Oxide and Titanium Dioxide
Calisha Contemporary Sienna Pearl CL
Mica and Red Iron Oxide and Titanium Dioxide
Calisha Contemporary Black Pearl CL
Mica and Titanium Dioxide and Black Iron
Oxide
Calisha Contemporary Sable Pearl CL
Mica and Titanium Dioxide and Red Iron Oxide
and Carmine
Calisha Contemporary Green Pearl CL
Mica and Titanium Dioxide Red Iron Oxide
Ferric Ferrocyanide
Calisha Contemporary Silver Pearl CL
Mica and Titanium Dioxide
Calisha Contemporary Glamour Green CL
Mica and Titanium Dioxide and Tin Dioxide
Calisha Contemporary Gold Pearl CL
Mica and Titanium Dioxide and Red Iron Oxide
Calisha Contemporary Bronze Pearl CL
Mica and Red Iron Oxide
Calisha Contemporary Rose Red Pearl CL
Mica and Red Iron Oxide
Calisha Art Deco Silver Pearl CL
Mica and Titanium Dioxide
Calisha Art Deco Glamour Violet CL
Mica and Titanium Dioxide
Calisha Art Deco Glamour Blue Pearl CL
Mica and Titanium Dioxide
Calisha Art Deco Glamour Green Pearl CL
Mica and Titanium Dioxide
Calisha Art Deco Gold Pearl CL
Mica and Red Iron Oxide and Titanium Dioxide
Calisha Art Deco Bronze Pearl CL
Mica and Red Iron Oxide
Calisha Art Deco Orange Pearl CL
Mica and Red Iron Oxide
Calisha Art Deco Red Pearl CL
Mica and Red Iron Oxide
Inorganic Pigments
Calisha Contemporary Salmon Red Oxide
Red Iron Oxide
Calisha Contemporary Medium Red Oxide
Red Iron Oxide
Calisha Contemporary Deep Red Oxide
Red Iron Oxide
Calisha Contemporary Black Oxide
Black Iron Oxide
Calisha Contemporary Jet Black Oxide
Black Iron Oxide
Calisha Contemporary Sun Yellow Oxide
Yellow Iron Oxide
Calisha Contemporary Yellow Oxide
Yellow Iron Oxide
Calisha Contemporary Ultramarine Blue
Ultramarine Blue
Calisha Contemporary Ultramarine Violet
Ultramarine Violet
Calisha Art Deco Hydroxide Chrome Green
Chromium Hydroxide Green
Calisha Art Deco Chrome Oxide Green
Chromium Oxide Greens
Lakes
Calisha Art Deco Blue 1 Lake
FD&C Blue No. 1 Al Lake
Calisha Art Deco Red 21 Lake
D&C Red No. 21 Al Lake
Calisha Art Deco Red 27 Lake
D&C Red No. 27 Al Lake
Calisha Art Deco Red 30 AL. Lake
D&C Red No. 30 Al Lake
Calisha Art Deco Red 30 Talc Lake
D&C Red No. 30 Talc Lake
Calisha Art Deco Red 33 Lake
D&C red No. 33 Al Lake
Calisha Art Deco Red 40 AL. Lake
FD&C Red No. 40 Al lake
Calisha Art Deco Red 6 Lake HD
D&C Red No. 6 Ba Lake
Calisha Art Deco Red 7 Lake HD
D&C Red No. 7 Ca lake
Calisha Art Deco Yellow 5 Lake HD
FD&C Yellow No. 5 Al Lake
Calisha Art Deco Yellow 6 AL. Lake
FD&C Yellow No. 6 Al lake
The interference pigments as used in the present invention are platelet particulates. The platelet particulates preferably have a thickness of no more than about 5 micrometers, more preferably no more than about 2 micrometers, still more preferably no more than about 1 micrometer. The platelet particulates preferably have a thickness of at least about 0.02 micrometers, more preferably at least about 0.05 micrometers, even more preferably at least about 0.1 micrometers, and still more preferably at least about 0.2 micrometers.
The particle size determines the opacity and luster. The particle size is determined by measuring the diameter thickness of the particulate material. The term “diameter” as used herein, means the largest distance across the major axis of the particulate material. Diameter can be determined by any suitable method known in the art, such as particle size analyzer Mastersizer 2000 manufactured by Malvern Instruments. The interference pigments preferably have an average diameter not greater than about 200 micrometers, more preferably not greater than 150 micrometers. The interference pigments preferably have a diameter of at least about 0.1 micrometer, more preferably at least about 1.0 micrometer, even more preferably at least about 2.0 micrometer, and still more preferably at least about 5.0 micrometer.
The interference pigments comprise a multilayer structure. The center of the particulates is a flat substrate with a refractive index (RI) normally below 1.8. A wide variety of particle substrates are useful herein. Nonlimiting examples are natural mica, synthetic mica, graphite, talc, kaolin, alumina flake, bismuth oxychloride, silica flake, glass flake, ceramics, titanium dioxide, CaSO 4 , CaCO 3 , BaSO 4 , borosilicate and mixtures thereof, preferably mica, silica and alumina flakes.
A layer of thin film or a multiple layer of thin films are coated on the surface of a substrate described above. The thin films are made of highly refractive materials. The refractive index of these materials is normally above 1.8.
A wide variety of thin films are useful herein. Nonlimiting examples are TiO 2 , Fe 2 O 3 , SnO 2 , Cr 2 O 3 , ZnO, ZnS, SnO, ZrO 2 , CaF 2 , Al 2 O 3 , BiOCl, and mixtures thereof or in the form of separate layers, preferably TiO 2 , Fe 2 O 3 , Cr 2 O 3 , and SnO 2 .
For the multiple layer structures, the thin films can be consisted of all high refractive index materials or alternation of thin films with high and low RI materials with the high RI film as the top layer.
The interference pigment color is a function of the thickness of thin film, the thickness for a specific color may be different for different materials. For TiO 2 , a layer of 40 nm to 60 nm or a whole number multiple thereof gives silver color, 60 nm to 80 nm yellow color, 80 nm to 100 nm red color, 100 nm to 130 nm blue color, 130 nm to 160 nm green color.
In addition to the interference color, other transparent absorption pigments can be precipitated on top of or simultaneously with the TiO 2 layer. Common materials are red or black iron oxide, ferric ferrocyanide, chromium oxide or carmine. It is found that the color of the interference pigment in addition to its brightness has a significant influence on human perception of skin tone. In general, preferred colors are silver, gold, red, green and mixtures thereof.
Nonlimiting examples of the interference pigments useful herein include those supplied by Persperse, Inc. under the trade name PRESTIGE®, FLONAC®; supplied by EMD Chemicals, Inc. under the trade name TIMIRON®, COLORONA®, DICHRONA® and XIRONA®; supplied by Engelhard Co. under the trade name FLAMENCO®, TIMICA®, DUOCHROME®; and supplied by Ciba under the trade name CALISHA®.
Although there are no critical limitations to the sizes of the pigment particles, preferably pigment particles having a size from about 0.01 to about 500 micrometers, more preferably having a size of about 1 to about 200 micrometers, most preferably having a size from about 5 to about 150 micrometers are modified with the silicone compounds according to formula
R1 is C1 to C22 branched or straight chain alkyl or aryl of six to ten carbon atoms;
R2 is C1 to C22 branched or straight chain alkyl or aryl of six to ten carbon atoms;
R3 is C1 to C22 branched or straight chain alkyl or aryl of six to ten carbon atoms;
R4 is C11 to C22 branched or straight chain alkyl or aryl of six to ten carbon atoms;
q is from 1 to about 2000;
t is from 1 to about 2000; the sum of q+t is from 2 to about 2000;
R5 is C1 to C22 branched or straight chain alkyl or aryl of six to ten carbon atoms;
R6 is C1 to C22 branched or straight chain alkyl or aryl of six to ten carbon atoms;
R7 is C1 to C22 branched or straight chain alkyl or aryl of six to ten carbon atoms;
R8 is C1 to C22 branched or straight chain alkyl or aryl of six to ten carbon atoms;
a is from 1 to about 100;
b is from 1 to about 100; the sum of a+b is from 2 to about 100; and
x is an integer from 1 to about 2000.
It will often be desirable to coat the pigment particles with, for example, one or more hydrous inorganic oxides, for example, hydrated silica or alumina, TiO 2 , Fe-oxides, tin oxide, mica, zinc oxide, colorants like carmine or Prussian blue.
Examples of pigments include inorganic pigments, metal oxides and hydroxides, mica, organic pigments, pearlescent pigments, mineral silicates, porous materials, carbons, interference pigments, and the like.
Preferred pigment particles are selected from the group consisting of inorganic pigments, metal oxides and hydroxides, mica, organic pigments, pearlescent pigments, mineral silicates, porous materials, carbons, and interference pigments.
Examples of the inorganic pigments capable of being modified are ultramarine blue, Prussian blue, manganese violet, titanium-coated mica, bismuth oxychloride, iron oxides, iron hydroxide, titanium dioxide, titanium lower oxides, and chromium hydroxide.
Examples of the metal oxides and hydroxides capable of being modified are magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxides, aluminum oxide, aluminum hydroxide, silica, iron oxides (α-Fe 2 O 3 , γ-Fe 2 O 3 , Fe 3 O 4 , FeO), iron hydroxides, titanium dioxide, titanium lower oxides, zirconium oxide, chromium oxides, chromium hydroxides, man-ganese oxides, cobalt oxides, nickel oxides, and zinc oxides. These oxides and hydroxides may be used alone or in any mixture thereof. Furthermore, composite oxides and composite hydroxides such as iron titanate, cobalt titanate, and cobalt aluminate can also be used in the present invention.
Composite materials comprising metal oxides or hydroxides coated on the core materials (e.g., titanium oxides coated mica, iron oxides coated nylon) can also be used in the present Invention.
Examples of the organic pigments capable of being modified with the silicone compounds of formula (SC1), SC(2), or (SC3) are C.I. 15850, C.I. 15850:1, C.I. 15585:1, C.I. 15630, C.I. 15880:1, C.I. 73360, C.I. 12085, C.I. 15865:2, C.I. 12075, C.I. 21110, C.I. 21095, and C.I. 11680, C.I. 74160 and zirconium, barium, or aluminum lakes of C.I. 45430, C.I. 45410, C.I. 45100, C.I. 17200, C.I. 45380, C.I. 45190, C.I. 14700, C.I. 15510, C.I. 19140, C.I. 15985, C.I. 45350, C.I. 47005, C.I. 42053, C.I. 42090.
C.I. means Colour Index as compiled by the by The Society of Dyers and Colourists and The American Association of Textile Chemists and Colourists.
The range of interesting organic pigments may additionally comprise monoazo, disazo, naphthol, dioxazone, azomethin, azocondensation, metal complex, nitro, perinone, quinoline, anthraquinone, benzimidozolone, isoindoline, isoindolinone, triarylmethane, quinacridone, hydroxyanthraquinone, aminoanthraquinone, anthrapyrimidine, indanthrone, flavanthrone, pyranthrone, anthantrone, isoviolanthrone, diketopyrrolopyrrole, carbazole, indigo or thiolndigo pigments.
Mixtures of the organic pigments may be used.
Examples of these pigments and also further pigments can be found in the monograph: W. Herbst, K. Hunger “Industrielle Organische Pigmente,” 2.sup.nd edition, 1995, VCH Verlagsgesellschaft.
Preferred pigments are mono- or disazo pigments, preferably mono- or diarylides, or metal complexes, preferably a copper phthalocyanine pigment, or naphthol pigments, preferably β-naphthol or α,β-oxynaphthoic acid (BONA) pigments, or quinacridones or indanthrones.
More preferably, the following organic pigments are used inventively:
Mono- or diarylide yellow pigments selected from C.I. Pigment Yellow 1, 2, 10, 12, 13, 14, 17, 61, 62, 63, 64, 65, 73, 74, 75, 83, 127, 168, 174, 176, 188 and 191; Monoarylide yellow pigments selected from C.I. Pigment Yellow 1, C.I. Pigment Yellow 2, C.I. Pigment Yellow 65, C.I. Pigment Yellow 73, C.I. Pigment Yellow 74 and C.I. Yellow 75; Diarylide yellow pigments selected from C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 17 and C.I. Pigment Yellow 83; Disazo orange pigments selected from C.I. Pigment Orange 16 and C.I. Pigment Orange 34; Naphthol red pigments selected from C.I. Pigment Red 48:1, C.I. Pigment Red 48:2, C.I. Pigment Red 48:3, C.I. Pigment Red 48:4, C.I. Pigment Red 48:5, C.I. Pigment Red 49:1, C.I. Pigment Red 52:1, C.I. Pigment Red 52:2, C.I. Pigment Red 52:3, C.1 Pigment Red 53:1, C.I. Pigment Red 53:2, C.I. Pigment Red 53:3, C.I. Pigment Red 57:1, C.I. Pigment Red 57:2, C.I. Pigment Red 58:2, C.I. Pigment Red 58:4, C.I. Pigment Red 63:1 and C.I. Pigment Red 64:1; Quinacridone red pigments such as C.I. Pigment Red 202; Blue or green copper phthalocyanine pigments selected from C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Green 7 and C.I. Pigment Green 36; Blue indanthrone pigments such as C.I. Pigment Blue 60.
The surfaces of these organic pigments may be treated additionally with, for example, rosins.
Examples of pearlescent pigments (or nacreous pigments) are mica-titanium composite materials containing, as a titanium component, titanium dioxide, titanium lower oxides, titanium oxynitride, mica-iron oxide composite materials, bismuth oxychloride, and guanine. The mica-titanium composite materials may be mixed with colored pigments such as iron oxides, Prussian blue, chromium oxide, carbon black, and carmine. These pearlescent pigments may be used alone or in any mixture thereof.
The interference pigments are platelet particulates. The platelet particulates preferably have a thickness of no more than about 5 micrometers, more preferably no more than about 2 micrometers, still more preferably no more than about 1 micrometer. The platelet particulates preferably have a thickness of at least about 0.02 micrometers, more preferably at least about 0.05 micrometers, even more preferably at least about 0.1 micrometers, and still more preferably at least about 0.2 micrometers.
The particle size determines the opacity and luster. The particle size is determined by measuring the diameter thickness of the particulate material. The term “diameter” as used herein, means the largest distance across the major axis of the particulate material. Diameter can be determined by any suitable method known in the art, such as particle size analyzer Mastersizer 2000 manufactured by Malvern Instruments. The interference pigments preferably have an average diameter not greater than about 200 micrometers, more preferably not greater than 150 micrometers. The interference pigments preferably have a diameter of at least about 0.1 micrometer, more preferably at least about 1.0 micrometer, even more preferably at least about 2.0 micrometer, and still more preferably at least about 5.0 micrometer.
The interference pigments comprise a multilayer structure. The center of the particulates is a flat substrate with a refractive index (RI) normally below 1.8. A wide variety of particle substrates are useful herein. Nonlimiting examples are natural mica, synthetic mica, graphite, talc, kaolin, alumina flake, bismuth oxychloride, silica flake, glass flake, ceramics, titanium dioxide, CaSO 4 , CaCO 3 , BaSO 4 , borosilicate and mixtures thereof, preferably mica, silica and alumina flakes.
A layer of thin film or a multiple layer of thin films are coated on the surface of a substrate described above. The thin films are made of highly refractive materials. The refractive index of these materials is normally above 1.8.
A wide variety of thin films are useful herein. Nonlimiting examples are TiO 2 , Fe 2 O 3 , SnO 2 , Cr 2 O 3 , ZnO, ZnS, SnO, ZrO 2 , CaF 2 , Al 2 O 3 , BiOCl, and mixtures thereof or in the form of separate layers, preferably TiO 2 , Fe 2 O 3 , Cr 2 O 3 and SnO 2 .
For the multiple layer structures, the thin films can be consisted of all high refractive index materials or alternation of thin films with high and low RI materials with the high RI film as the top layer.
The interference pigment color is a function of the thickness of thin film, the thickness for a specific color may be different for different materials. For TiO 2 , a layer of 40 nm to 60 nm or a whole number multiple thereof gives silver color, 60 nm to 80 nm yellow color, 80 nm to 100 nm red color, 100 nm to 130 nm blue color, 130 nm to 160 nm green color. In addition to the interference color, other transparent absorption pigments can be precipitated on top of or simultaneously with the TiO 2 layer. Common materials are red or black iron oxide, ferric ferrocyanide, chromium oxide or carmine. It is found that the color of the interference pigment in addition to its brightness has a significant influence on human perception of skin tone. In general, preferred colors are silver, gold, red, green and mixtures thereof.
Nonlimiting examples of the interference pigments useful herein include those supplied by Persperse, Inc. under the trade name PRESTIGE®, FLONAC®; supplied by EMD Chemicals, Inc. under the trade name TIMIRON®, COLORONA®, DICHRONA® and XIRONA®; supplied by Engelhard Co. under the trade name FLAMENCO®, TIMICA®, DUOCHROME®; and supplied by Ciba under the trade name CALISHA®.
The particulate organic UV-filter (b 1 ) is preferably selected from benztriazoles of formula
wherein
R 1 and R 2 independently from each other are C 1 -C 18 alkyl which may be substituted by one or more radicals selected from C 1 -C 4 alkyl, C 5 -C 12 cycloalkyl and C 6 -C 10 aryl.
More preferably the particulate organic UV-filters (b 1 ) is Methylene Bis-Benzotriazolyl Tetramethylbutylphenol and corresponds to formula
Preferably the organic UV-filter (b 1 ) is also selected from the triazine derivatives of formula
wherein
R 3 and R 4 independently from each other are hydrogen; C 1 -C 18 alkyl; or C 6 -C 12 aryl; R 5 , R 6 and R 7 independently from each other are hydrogen; hydroxy; halogen; C 1 -C 18 alkyl; C 1 -C 8 alkoxy; C 6 -C 12 aryl; biphenylyl; C 6 -C 12 aryloxy; C 1 -C 18 alkylthio; carboxy; —COOM; C 1 -C 18 -alkylcarboxyl; aminocarbonyl; mono- or di-C 1 -C 18 alkylamino; C 1 -C 10 acylamino; or —COOH; and M is an alkali metal ion.
More preferably, in formula (3) R 3 and R 4 is hydrogen; and
R 5 and R 6 are hydrogen; and R 7 is hydrogen; phenyl; or biphenylyl.
Most preferably the organic UV-filter (b 1 ) corresponds to the formula
In a preferred embodiment of the present inveniton, component (b 1 ) represents a mixture of the compounds of formula (2) and (4).
In another preferred embodiment of the present inveniton the particulate organic UV-filter (b 1 ) is selected from the benzophenone derivatives of formula
wherein
R 8 and R 9 independently from each other are C 1 -C 20 alkyl; C 2 -C 20 alkenyl; C 3 -C 10 cycloalkyl; C 3 -C 10 cycloalkenyl; or R 8 and R 9 together with the linking nitrogen atom form a 5- or 6-membered heterocyclic ring; R 10 is an alkylene-, cycloalkylene, alkenylene or phenylene radical which is optionally substituted by a carbonyl- or carboxy group; a radical of formula *—CH 2 —C≡C—CH 2 *; or R 10 together with A forms a bivalent radical of the formula (1a)
wherein
n 2 is a number from 1 to 3.
Most preferably the particulate organic UV-filter (b 1 ) corresponds to formula
The particulate organic UV filters (b 1 ) according to the present invention, preferably the UV filters of formulas (2), (4) and (6) can be mixed together directly with the particulates (a) and provided as trade products.
In a preferred embodiment the particulate organic UV filters (b 1 ) according to the present invention, preferably the UV filters of formulas (2), (4) and (6) can be co-micronized directly with the particulates (a).
Preferably the soluble organic UV-filter (b 2 ) is selected from triazine derivatives of formula
wherein
R 12 and R 13 , independently of one another, are C 1 -C 18 alkyl; or C 2 -C 18 alkenyl; A l is a radical of the formula
R 14 is hydrogen; C 1 -C 10 alkyl, —(CH 2 CHR 5 —O) n 1 —R 15 ; or a radical of the formula —CH 2 —CH(—OH)—CH 2 —O-T 1 ;
R 15 is hydrogen; M; C 1 -C 5 alkyl; or a radical of the formula —(CH 2 ) m 2 —O-T 1 ;
T 1 is hydrogen; or C 1 -C 8 alkyl;
Q1 C 1 -C18alkyl;
M is a metal cation;
m 2 is 1 to 4; and
n 1 is 1-16.
Most preferably the soluble organic UV-filter (b 2 ) corresponds to formula
In another preferred embodiment of the present invention (b 2 ) is a dibenzoylmethane derivative, more preferably butyl methoxydibenzoylmethane (Avobenzone).
In another preferred embodiment of the present invention (b 2 ) is a 2-hydroxy benzophenone derivative of formula
wherein
R 16 and R 17 independently from each other are hydrogen, C 1 -C 20 alkyl; C 2 -C 10 alkenyl; C 3 -C 10 cyclalkyl; or C 3 -C 10 cycloalkenyl; R 18 and R 19 independently from each other are C 1 -C 20 alkyl; C 2 -C 10 alkenyl; C 3 -C 10 cycloalkenyl; C 1 -C 12 alkoxy; C 1 -C 20 alkoxycarbonyl; C 1 -C 12 alkylamino; di(C 1 -C 12 )alkylamino; aryl or heteroaryl radical which are optionally substituted; or a water-solubilizing substitutent selected from a carboxylate group, a sulphonate group or an ammonium residue; X is hydrogen; COR 19 ; or COOR 19 ; or CONR 19 R 20 ; R 19 , and R 20 independently from each other are hydrogen; C 1 -C 20 alkyl; C 2 -C 10 alkenyl; C 3 -C 10 cycloalkenyl; a —(Y—O)—Z-group; or aryl; Y is *—(CH 2 ) 2 —*; *—(CH 2 ) 3 —*; *—(CH 2 ) 4 —*; or *—(CH)—(CH 3 )—CH 2 —*; Z is *—CH 2 —CH 3 ; *—CH 2 —CH 2 —CH 3 ; *—CH 2 —CH 2 —CH 2 —CH 3 ; or *—CH(CH 3 )—CH 3 ; m is a number from 0 to 3; n is a number from 0 to 3; and o is 1; or 2.
Most preferably the soluble organic UV-filter (b 2 ) is Diethylamino Hydroxybenzoyl Hexyl Benzoate [CAS Regno. 302776-68-7].
In another preferred embodiment of the present invention the soluble organic UV-filter (b 2 ) is a merocyanine derivative of formula
wherein
R 21 and R 22 are each independently of the other hydrogen; C 1 -C 22 alkyl; cyclo-C 3 -C 8 alkyl; or unsubstituted or C 1 -C 6 alkyl- or C 1 -C 6 alkoxy-substituted C 6 -C 20 aryl; or R 21 and R 22 together with the nitrogen atom linking them form a —(CH 2 ) m — ring which is uninterrupted or interrupted by —O— or by —NH—; R 23 is a cyano group; —COOR 25 ; —CONHR 25 ; —COR 25 ; or —SO 2 R 25 ; or —CONR 25 R 26 ; R 24 is a cyano group; —COOR 27 ; —CONHR 27 ; —COR 27 ; or —SO 2 R 27 ; or —CONR 26 R 28 ; R 25 , R 26 , R 27 and R 28 are each independently of the other C 1 -C 22 alkyl; cyclo-C 3 -C 8 alkyl; or unsubstituted or C 1 -C 6 alkyl-substituted C 6 -C 20 aryl; or R 21 and R 22 , R 23 and R 24 , R 25 and R 26 or R 27 and R 28 together form a 5- to 7-membered, monocyclic, carbocyclic or heterocyclic ring; Z 1 and Z 2 are each independently of the other a —(CH 2 ) l — group which is uninterrupted or interrupted by —O—, —S—, or by —NR 29 —, and/or is unsubstituted or substituted by C 1 -C 6 alkyl; R 29 is C 1 -C 5 alkyl; l is a number from 1 to 4; m is a number from 1 to 7; n is from 1 to 4; when n=2, R 21 , R 23 or R 24 is a bivalent alkyl group; or R 23 and R 24 together with the 2 nitrogen atoms linking them form a —(CH 2 ) m — ring; when n=3, R 21 , R 23 or R 24 is a trivalent alkyl group; when n=4, R 21 , R 23 or R 24 is a tetravalent alkyl group.
Most preferably the soluble organic UV-filter (b 2 ) is a merocyanine derivative of formula
In a preferred embodiment of the present invention (b) represents a mixture selected from (mix 1 ) the compounds of formulae (2), (4) (8) and butyl methoxydibenzoylmethane;
(mix 2 ) the compounds of formulae (2), (4), (6) and butyl methoxydibenzoylmethane; (mix 3 ) the compounds of formulae (8), (12) and butyl methoxydibenzoylmethane; (mix 4 ) the compounds of formulae (2), (4), (6), (8), (11), (12) and butyl methoxydibenzoylmethane; (mix 4 ) the compounds of formulae (2), (4) and (6); (mix 5 ) the compounds of formulae (2), (4), (6) and (8).
More preferably, (b) represents a mixture of at least one particulate organic UV filter (b 1 ) and at least one soluble organic UV filter (b 2 ).
In a most preferred embodiment of the present invention the cosmetic formulation comprises
(a) particulates selected from interference-pigments based on mica and coated with iron oxide; and (b) a mixture of particulate organic UV filters selected from triazine and benzotriazole derivatives.
Most preferably the particulate UV filters (b) is a mixture of the compound of formula (2) and (4).
The cosmetic formulation according to the present invention preferably comprises
0.01 to 10% b.w of particulates (a); and
0.1 to 40% b.w of UV filters (b).
Preferred is a formulation which is free of soluble organic UV filters (b 2 ) and other soluble UV filters.
The particulate organic UV-filters (b 1 ) according to the present invention are present in the micronized state. They may be prepared by any known process suitable for the preparation of microparticles, for example:wet-milling, wet-kneading, spray-drying from a suitable solvent, by expansion according to the RESS process (Rapid Expansion of Supercritical Solutions) of supercritical fluids (e.g. CO 2 , by reprecipitation from suitable solvents, including supercritical fluids (GASR process=Gas Anti-Solvent Recrystallisation/PCA process=Precipitation with Compressed Anti-solvents).
As milling apparatus for the preparation of the sparingly soluble micronised organic compounds there may be used, for example, a jet mill, ball mill, vibratory mill or hammer mill, preferably a high-speed mixing mill. Even more preferable mills are modern ball mills; manufacturers of these types of mill are, for example, Netzsch (LMZ mill), Drais (DCP-Viscoflow or Cosmo), Bühler AG (centrifugal mills) or Bachhofer.
Examples of kneading apparatus for the preparation of the micronised organic UV absorbers are typical sigma-blade batch kneaders but also serial batch kneaders (IKA-Werke) or continuous kneaders (Continua from Werner and Pfleiderer).
The grinding of organic compounds used in the present invention is preferably carried out with a grinding aid.
Preferably, a dispersing agent is used as a low molecular weight grinding aid for all the above micronisation processes.
Preferred useful grinding aids for an aqueous dispersion are anionic surfactants with a HLB (Hydrophile-Lipophile Balance) value higher than 8, more preferably higher than 10.
Any conventionally usable anionic, non-ionic or amphoteric surfactants can be used as dispersing agents (component (b)). Such surfactant systems may comprise for example: carboxylic acids and their salts: alkaline soap of sodium, potassium and ammonium, metallic soap of calcium or magnesium, organic basis soap such as Lauric, myristic, palmitic, stearic and oleic acid etc., alkyl phosphates or phosphoric acid esters, acid phosphate, diethanolamine phosphate, potassium cetyl phosphate, ethoxylated carboxylic acids or polyethylene-glycol esters, PEG-n acrylates, fatty alcohol polyglycolether such as laureth-n, myreth-n, ceteareth-n, steareth-n, oleth-n, fatty acid polyglycolether such as PEG-n stearate, PEG-n oleate, PEG-n cocoate, monoglycerides and polyol esters, C12-C22 fatty acid mono- and di-esters of addition products of from 1 to 100 mol of ethylene oxide with polyols,fatty acid and polyglycerol ester such as monostearate glycerol, diisostearoyl polyglyceryl-3-diisostearates, polyglyceryl-3-diisostearates, triglyceryl diisostearates, polyglyceryl-2-sesquiisostearates or polyglyceryl dimerates. mixtures of compounds from a plurality of those substance classes are also suitable, fatty acid polyglycolesters such as monostearate diethylene glycol, fatty acid and polyethylene glycol esters, fatty acid and saccharose esters such as sucro esters, glycerol and saccharose esters such as sucro glycerides. Sorbitol and sorbitan, sorbitan mono- and di-esters of saturated and unsaturated fatty acids having from 6 to 22 carbon atoms and ethylene oxide addition products, polysorbate-n series, sorbitan esters such as sesquiisostearate, sorbitan, PEG-(6)-isostearate sorbitan, PEG-(10)-sorbitan laurate, PEG-17-dioleate sorbitan, glucose derivatives, C8-C22 alkyl-mono and oligo-glycosides and ethoxylated analogues with glucose being preferred as the sugar component, O/W emulsifiers such as methyl gluceth-20 sesquistearate, sorbitan stearate/sucrose cocoate, methyl glucose sesquistearate, cetearyl alcohol/cetearyl glucoside, W/O emulsifiers such as methyl glucose dioleate/methyl glucose isostearate. Sulfates and sulfonated derivatives, dialkylsulfosuccinates, dioctyl succinate, alkyl lauryl sulfonate, linear sulfonated parafins, sulfonated tetraproplyne sulfonate, sodium lauryl sulfates, amonium and ethanolamine lauryl sulfates, lauryl ether sulfates, sodium laureth sulfates [Texapon N70] or sodium myreth sulfates [Texapon K14S], sulfosuccinates, aceyl isothionates, alkanolamide sulfates, taurines, methyl taurines, imidazole sulfates, zwitterionic or amphoteric surfactants that carry at least one quaternary ammonium group and at least one carboxylate and/or sulfonate group in the molecule, zwitterionic surfactants that are especially suitable are betaines, such as N-alkyl-N,N-dimethylammonium glycinates, cocoalkyldimethylammonium glycinate, N-acylamino-propyl-N,N-dimethylammonium glycinates, cocoacylaminopropyldimethylammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethylcarboxymethylglycinate, N-alkylbetaine, N-alkylaminobetaines.
Examples of suitable mild surfactants as dispersing agents, that is to say surfactants especially well tolerated by the skin, include fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and/or di-alkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, a-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines and/or protein fatty acid condensation products, the latter preferably being based on wheat proteins.
Non ionic surfactants such as PEG-6 beeswax (and) PEG-6 stearate (and) polyglyceryl—2-isostearate [Apifac], glyceryl stearate (and) PEG-100 stearate. [Arlacel 165], PEG-5 glyceryl stearate [arlatone 983 S], sorbitan oleate (and) polyglyceryl-3 ricinoleate.[Arlacel 1689], sorbitan stearate and sucrose cocoate [arlatone 2121], glyceryl stearate and laureth-23 [Cerasynth 945], cetearyl alcohol and ceteth-20 [Cetomacrogol Wax], cetearyl alcohol and colysorbate 60 and PEG-150 and stearate-20[Polawax GP 200, Polawax NF], cetearyl alcohol and cetearyl polyglucoside [Emulgade PL 1618], cetearyl alcohol and ceteareth-20 [Emulgade 1000NI, Cosmowax], cetearyl alcohol and PEG-40 castor oil [Emulgade F Special], cetearyl alcohol and PEG-40 castor oil and sodium cetearyl sulfate [Emulgade F], stearyl alcohol and steareth-7 and steareth-10 [Emulgator E 2155], cetearyl alcohol and szeareth-7 and steareth-10 [Emulsifying wax U.S.N.F], glyceryl stearate and PEG-75 stearate [Gelot 64], propylene glycol ceteth-3 acetate .[Hetester PCS], propylene glycol isoceth-3 acetate [Hetester PHA], cetearyl alcohol and ceteth-12 and oleth-12 [Lanbritol Wax N 21], PEG-6 stearate and PEG-32 stearate [Tefose 1500], PEG-6 stearate and ceteth-20 and steareth-20 [Tefose 2000], PEG-6 stearate and ceteth-20 and glyceryl stearate and steareth-20 [Tefose 2561], glyceryl stearate and ceteareth-20 [Teginacid H, C, X].
Anionic emulsifiers such as PEG-2 stearate SE, glyceryl stearate SE [Monelgine, Cutina KD], propylene glycol stearate [Tegin P], cetearyl Alcohol and Sodium cetearyl sulfate [Lanette N, Cutina LE, Crodacol GP], cetearyl alcohol and sodium lauryl sulfate [Lanette W], trilaneth-4 phopshate and glycol stearate and PEG-2 stearate [Sedefos 75], glyceryl stearate and sodium lauryl Sulfate [Teginacid Special]. Cationic acid bases such as cetearyl alcohol and cetrimonium bromide.
Most preferred dispersing agents are sodium alkyl sulfates or sodium alkyl ether sulfates, such as sodium laureth sulfate [Texapon N70 from Cognis] or sodium myreth sulfate [Texapon K14 S from Cognis].
Useful solvents are water, brine, (poly-)ethylene glycol, glycerol or cosmetically acceptable oils. Other useful solvents are disclosed below in the sections entitled “Esters of fatty acids”, “Natural and synthetic triglycerides, including glyceryl esters and derivatives”, “Pearlescent waxes”, “Hydrocarbon oils” and “Silicones or siloxanes”.
The micronised particulate organic compounds so obtained usually have an average particle size from 0.02 to 2 micrometres, preferably from 0.03 to 1.5 micrometres and more especially from 0.05 to 1.0 micrometres.
The aqueous dispersion comprising a micronized UV absorber used in the present invention generally comprises
30-60, preferably 35 to 55 parts of the sparingly soluble organic micronized substance;
2-20, preferably 3 to 10 parts of the dispersing agent;
0.1-1 part, preferably 0.1 to 0.5 parts of a thickening agent (for example xanthan gum); and
20-67.9 parts of water;
The cosmetic formulations or pharmaceutical compositions according to the present invention can also comprise one or more than one further UV filter which are different from the particulate organic UV-filters (b 1 ); and the soluble organic UV filters (b 2 ) as listed in Table 1:
TABLE 2
Suitable UV filter substances and adjuvants which can be additionally used with the
UV absorbers according to the present invention
No.
Chemical Name
CAS No.
1
(+/−)-1,7,7-trimethyl-3-[(4-methylphenyl)methylene]bicyclo-
36861-47-9
[2.2.1]heptan-2-one; p-methyl benzylidene camphor
2
1,7,7-trimethyl-3-(phenylmethylene)bicyclo[2.2.1]heptan-2-one;
15087-24-8
benzylidene camphor
3
(2-Hydroxy-4-methoxyphenyl)(4-methylphenyl)methanone
1641-17-4
4
2,4-dihydroxybenzophenone
131-56-6
5
2,2′,4,4′-tetrahydroxybenzophenone
131-55-5
6
2-Hydroxy-4-methoxy benzophenone;
131-57-7
7
2-Hydroxy-4-methoxy benzophenone-5-sulfonic acid
4065-45-6
8
2,2′-dihydroxy-4,4′-dimethoxybenzophenone
131-54-4
9
2,2′-Dihydroxy-4-methoxybenzophenone
131-53-3
10
Alpha-(2-oxoborn-3-ylidene)toluene-4-sulphonic acid and its salts
56039-58-8
(Mexoryl SL)
12
Methyl N,N,N-trimethyl-4-[(4,7,7-trimethyl-3-oxobicyclo[2,2,1]hept-2-
52793-97-2
ylidene)methyl]anilinium sulphate (Mexoryl SO)
22
3,3,5-Trimethyl cyclohexyl-2-hydroxy benzoate; homosalate
118-56-9
23
Isopentyl p-methoxycinnamate; isoamyl methoxy cinnamate
71617-10-2
27
Menthyl-o-aminobenzoate
134-09-8
28
Menthyl salicylate
89-46-3
29
2-Ethylhexyl 2-cyano,3,3-diphenylacrylate; Octocrylene
6197-30-4
30
2-ethylhexyl 4-(dimethylamino)benzoate
21245-02-3
31
2-ethylhexyl 4-methoxycinnamate; Octyl Methoxy Cinnamate
5466-77-3
32
2-ethylhexyl salicylate
118-60-5
34
4-aminobenzoic acid
150-13-0
35
Benzoic acid, 4-amino-, ethyl ester, polymer with oxirane
113010-52-9
38
2-phenyl-1H-benzimidazole-5-sulphonic acid;
27503-81-7
phenylbenzimidazolsulfonic acid
39
2-Propenamide, N-[[4-[(4,7,7-trimethyl-3-oxobicyclo[2.2.1]hept-2-
147897-12-9
ylidene)methyl]phenyl]methyl]-, homopolymer
40
Triethanolamine salicylate
2174-16-5
41
3,3′-(1,4-phenylenedimethylene)bis[7,7-dimethyl-2-oxo-
90457-82-2
bicyclo[2.2.1]heptane-1 methanesulfonic acid] (Cibafast H)
42
Titanium dioxide (primary particle size 10-50 nm); for example
13463-67-7
T805 or Eusolex T-AVO, Eusolex T-2000, Titaniumdioxid VT 817
44
Zinc oxide (primary particle size 20-100 nm); for example Zinc oxide
1314-13-2
NDM, Zinc oxide Z-Cote HP1, Nanox Zinc oxide
47
1H-Benzimidazole-4,6-disulfonic acid, 2,2′-(1,4-phenylene)bis-, di-
180898-37-7
sodium salt
48
Benzoic acid, 4,4′-[[6-[[4-[[(1,1-dimethylethyl)amino]carbonyl]-
154702-15-5
phenyl]amino]1,3,5-triazine-2,4-diyl]diimino]bis-, bis(2-ethylhexyl)-
ester; diethylhexyl butamido triazone (Uvasorb HEB)
49
Phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-
155633-54-8
tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]-; drometrizole
trisiloxane (Mexoryl XL)
50
Dimethicodiethylbenzalmalonate; Polysilicone 15 (Parsol SLX)
207574-74-1
51
Benzenesulfonic acid, 3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-
92484-48-5
methylpropyl)-, monosodium salt (Tinogard HS)
53
1-Dodecanaminium, N-[3-[[4-(dimethylamino)benzoyl]amino]propyl]-
156679-41-3
N,N-dimethyl-, salt with 4-methylbenzenesulfonic acid (1:1) (Escalol
HP610)
54
1-Propanaminium, N,N,N-trimethyl-3-[(1-oxo-3-phenyl-2-propenyl)-
177190-98-6
amino]-, chloride
55
1H-Benzimidazole-4,6-disulfonic acid, 2,2′-(1,4-phenylene)bis-
170864-82-1
56
1,3,5-Triazine, 2,4,6-tris(4-methoxyphenyl)-
7753-12-0
57
1,3,5-Triazine, 2,4,6-tris[4-[(2-ethylhexyl)oxy]phenyl]-
208114-14-1
58
1-Propanaminium, 3-[[3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethyl-
340964-15-0
ethyl)-4-hydroxyphenyl]-1-oxopropyl]amino]-N,N-diethyl-N-methyl-,
methyl sulfate (salt)
59
2-Propenoic acid, 3-(1H-imidazol-4-yl)-
104-98-3
60
Benzoic acid, 2-hydroxy-, [4-(1-methylethyl)phenyl]methyl ester
94134-93-7
61
1,2,3-Propanetriol, 1-(4-aminobenzoate) (Glyceryl PABA)
136-44-7
62
Benzeneacetic acid, 3,4-dimethoxy-a-oxo-
4732-70-1
63
2-Propenoic acid, 2-cyano-3,3-diphenyl-, ethyl ester
5232-99-5
64
Anthralinic acid, p-menth-3-yl ester
134-09-8
65
2,2′-bis(1,4-phenylene)-1H-benzimidazole-4,6-disulphonic acid mono
349580-12-7
sodium salt or Disodium phenyl dibenzimidazole tetrasulfonate
(Neo Heliopan AP)
69
sterols (cholesterol, lanosterol, phytosterols), as described in
WO0341675
70
mycosporines and/or mycosporine-like amino acids as described in
WO2002039974, e.g. Helioguard 365 from Milbelle AG, isolated
mycosporine like amino acids from the red alga porphyra umbilicalis
(INCI: Porphyra Umbilicalis ) that are encapsulated into liposomes,)
71
alpha-lipoic-acid as described in DE 10229995
72
synthetic organic polymers as described in EP 1 371 358,
[0033]-[0041]
73
phyllosilicates as described in EP 1371357 [0034]-[0037]
74
silica compounds as described in EP1371356, [0033]-[0041]
75
inorganic particles as described in DE10138496 [0043]-[0055]
76
latex particles as described in DE10138496 [0027]-[0040]
77
1H-Benzimidazole-4,6-disulfonic acid, 2,2′-(1,4-phenylene)bis-,
180898-37-7
disodium salt; Bisimidazylate (Neo Heliopan APC)
82
Di-2-ethylhexyl-3,5-dimethoxy-4-hydroxy-benzalmalonate (Oxynex
ST, EMD Chemicals, as described in US 20040247536)
83
T-LiteTM MAX: Titanium Dioxide (and) Dimethoxydiphenylsilane
(and) Triethoxycaprylylsilane Crosspolymer (and) Hydrated Silica
(and) Aluminum Hydroxyde
84
T-Lite SF: Titanium Dioxide (and) Aluminum Hydroxide (and)
Dimethicone/Methicone Copolymer
85
T-Lite SF-S: Titanium Dioxide (and) Hydrated Silica (and)
Dimethicone/Methicone Copolymer (and) Aluminum Hydroxide
86
Z-COTE ® MAX: Zinc Oxide (and) Diphenyl Capryl Methicone
87
Z-COTE HP1: Zinc Oxide (and) Triethoxycaprylylsilane
88
1,3,5-Triazine-2,4,6-triamine, N2,N4-bis[4-[5-(1,1-dimethylpropyl)-2-
288254-16-0
benzoxazolyl]phenyl]-N6-(2-ethylhexyl)-(Uvasorb K2A)
The cosmetic or pharmaceutical preparations can be prepared by physically mixing the UV absorber(s) with the adjuvant using customary methods, for example by simply stirring together the individual components, especially by making use of the dissolution properties of already known cosmetic UV absorbers, like octyl methoxy cinnamate, salicylic acid isooctyl ester, etc.
The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments. In addition to the above mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.
As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/W emulsions or microemulsions) the preparations contain, for example, from 0.1 to 30% by weight, preferably from 0.1 to 15% by weight and especially from 0.5 to 10% by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60% by weight, especially from 5 to 50% by weight and preferably from 10 to 35% by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30% by weight, especially from 1 to 30% by weight and preferably from 4 to 20% by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90% by weight, especially from 30 to 90% by weight, based on the total weight of the composition, of water, and from 0 to 88.9% by weight, especially from 1 to 50% by weight, of further cosmetically acceptable adjuvants.
The cosmetic or pharmaceutical compositions/preparations according to the invention may also contain one or one more additional compounds as like fatty alcohols, esters of fatty acids, natural or synthetic triglycerides including glyceryl esters and derivatives, pearlescent waxes, hydrocarbon oils, silicones or siloxanes (organosubstituted polysiloxanes), fluorinated or perfluorinated oils, emulsifiers, djuvants and additives, super-fatting agents, surfactants, consistency regulators/thickeners and rheology modifiers, polymers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, antioxidants, hydrotropic agents, preservatives, bacteria-inhibiting agents, perfume oils, colourants, polymeric beads or hollow spheres as SPF enhancers.
Cosmetic or Pharmaceutical Preparations
Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic preparations. There come into consideration, for example, especially the following preparations: skin-care preparations, bath preparations, cosmetic personal care preparations, foot-care preparations, light-protective preparations, skin-tanning preparations, depigmenting preparations, insect-repellents, deodorants, antiperspirants, preparations for cleansing and caring for blemished skin, hair-removal preparations in chemical form (depilation), shaving preparations, fragrance preparations, cosmetic hair-treatment preparations,
Presentation Forms
The final formulations listed may exist in a wide variety of presentation forms, for example:
in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W or PIT emulsion and all kinds of microemulsions, in the form of a gel, in the form of an oil, a cream, milk or lotion, in the form of a powder, a lacquer, a tablet or make-up, in the form of a stick, in the form of a spray (spray with propellent gas or pump-action spray) or an aerosol, in the form of a foam, or in the form of a paste.
Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams. Of particular interest are sun protection creams, sun protection lotions, sun protection milk and sun protection preparations in the form of a spray.
Of special importance as cosmetic preparations for the hair are the above-mentioned preparations for hair treatment, especially hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-straightening preparations, liquid hair-setting preparations, hair foams and hairsprays. Of special interest are hair-washing preparations in the form of shampoos.
Other typical ingredients in such formulations are preservatives, bactericides and bacteriostatic agents, perfumes, dyes, pigments, thickening agents, moisturizing agents, humectants, fats, oils, waxes or other typical ingredients of cosmetic and personal care formulations such as alcohols, poly-alcohols, polymers, electrolytes, organic solvents, silicon derivatives, emollients, emulsifiers or emulsifying surfactants, surfactants, dispersing agents, antioxidants, anti-irritants and anti-inflammatory agents etc.
Preferably the particulates (a) are used which can easily be removed from textiles in customary laundering processes.
Other embodiments of the present invention are the use of the cosmetic formulation according to the present invention
for minimizing and/or masking the whitening effect and/or the particular color of a sunscreen composition; for the visualization of a consistent application of a sunscreen formulation; for the protection against electromagnetic radiation in the range >380 nm; for adjusting a natural skin-like color tone of the sunscreen formulation; for promoting an even skin tone; and for minimising fine lines and wrinkles.
The composition is used for preventing the damaging effect of UVA and blue light and provides an optimal protection against UVA-induced photoaging of human skin also in conjunction with excessive exposure to longer wave-length light and IR The cosmetic compositions according to the present invention may also be used for preventing and treating undesired skin pigmentation; preventing and treating photoaging of human skin; inhibiting the degradation or condensations of endogenous vitamins, antioxidants and cellular modulators such as carotenoids, flavonoids or unsaturated lipids present in the skin; treating skin disorders caused by sunlight such as pigment spots, actinic keratosis and actinic dermatitis and solar urticaria; protecting against UVA1-induced expression of matrix-degrading enzymes such as metallo-proteinases or elastases, e.g. metallo-proteinase-1 or neutrophil elastase or of cytokines such as interleukin-1 or interleukin-6; preventing the generation of reactive oxygen species such as by photosensitizing molecules, via UV-induced inflammatory reactions or via impaiment of mitochondria function; protecting UV-A-sensitive pharmaceuticals and cosmetics.
The compositions according to the present invention may constitute a skin care product, in particular for the face, neck, contours of the eye or the body, or a skin makeup product such as a tinting product, an eye shadow, a blusher, an eyeliner, a concealer, a body makeup product, a daily care product, a sun protection product or a skin cleansing product.
The cosmetic preparation according to the invention is distinguished by excellent protection of human skin against the damaging effect of sunlight.
EXAMPLES
Preparation of Sunscreen Formulation
Examples 1, 2 and 4 show advantage over Examples 3 and 5 which do not contain color pigments.
INCI
Ex. 1
Ex. 2
Ex. 3
Part A
Glyceryl Stearate (and) PEG 100 Stearate
2.00
2.00
2.00
Butylene Glycol Cocoate
5.00
5.00
5.00
Isopropyl Palmitate
4.00
4.00
4.00
Trioctanion
4.00
4.00
4.00
TiO 2 (and) Stearic Acid (and) Aluminium Hydroxide
3.20
3.20
3.20
Part B
Water
Tinoderm SGP (Ciba)
3.00
3.00
3.00
Disodium EDTA
0.20
0.20
0.20
Xanthan Gum
0.20
0.20
0.20
Potassium cetyl Phosphate
1.50
1.50
1.50
Part B2
Calisha Contemporary jet black (Iron oxide)
0.01
0.005
—
Calisha Contemporary medium red (iron oxide)
0.1
0.025
—
Calisha Contemporary yellow (iron oxide)
0.55
0.27
—
Part C
Phenyl Trimethicone
2.00
2.00
2.00
Cyclomethicone
4.00
4.00
4.00
Dimethicone (and) Dimethicone/Vinyl Dimethicone
3.00
3.00
3.00
Crosspolymer
Part D
Mica (and) Titanium Dioxide (and) Red iron oxide (and) Cetyl
0.30
Dimethicone
Micronized Methylene Bis-Benzotriazolyl Tetra-
4.00
5.00
3.00
methylbutylphenol
Micronized 1,3,5-Triazine, 2,4,6-tris([1,1′-biphenyl]-4-yl)-(CAS
5.00
5.00
5.00
Regn. 31274-51-8)
Phenoxyethanol (and) Methylparaben (and) Ethylparaben (and)
1.00
Butylparaben (and) Propylparaben Isobutylparaben
Tinoderm E
0.50
Water
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INCI
Ex. 4
Ex. 5
Phase A
Glyceryl Stearate (and) PEG 100 Stearate
5.00
5.00
Phenethyl Benzoate
6.00
6.00
Isopropyl Palmitate
5.00
5.00
Triheptanoin
3.00
3.00
Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine
2.00
2.00
Ethylhexyl Triazone
1.50
1.50
Phase B
Water
Butylene Glycol
2.00
2.00
Sodium EDTA
0.20
0.20
Phase B2
Calisha Contemporary jet black (Iron oxide)
0.01
Calisha Contemporary medium red (iron oxide)
0.08
Calisha Contemporary yellow (iron oxide)
0.55
Phase C
Sodium Acrylates Copolymer (and) Mineral Oil (and) PPG-1
1.20
1.20
Trideceth-6
Phase D
Cyclomethicone
3.00
3.00
Cyclomethicone
4.00
4.00
Phase E
Methylene Bis-Benzotriazolyl Tetramethylbutylphenol
14.00
14.00
Methylparaben (and) Ethylparaben (and) Butylparaben
1.00
1.00
(and) Propylparaben
Water
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Manufacturing Process:
Heat up part A and B to 75° C.
Add Amphisol K into B and stirr for 5 more minutes, then Add part B2.
Add part A into part B, then homogenize with an Ultra Turrax for 1 min pos 21200 g
Add part C by 60° C., and turrax again
Add part D below 50° C.
B. Application Examples
Example B1: O/W Emulsion (1)
Part
INCI
A
B
C
A
Glyceryl Stearate (and) PEG 100 Stearate
2.00
2.00
2.00
Butylene Glycol Cocoate
5.00
5.00
5.00
Isopropyl Palmitate
4.00
4.00
4.00
Triethylhexanoin
4.00
4.00
4.00
TIO2 (and) Stearic Acid (and) Aluminum Hydroxide
3.20
3.20
3.20
B
Pentylene Glycol (and) Sclerotium Gum
3.00
3.00
3.00
Disodium EDTA
0.20
0.20
0.20
Xanthan Gum
0.20
0.24
0.24
Potassium cetyl Phosphate
1.50
1.50
1.50
B 2
Iron Oxides (CALISHA Contemprorary Jet Black Oxide)
0.01
0.005
0.005
Iron Oxides (CALISHA Contemporary Medium Red
0.10
0.025
0.025
Oxide)
Iron Oxides (CALISHA Contemporary Yellow Oxide)
0.55
0.27
0.27
C
Phenyl Trimethicone
2.00
2.00
2.00
Cyclomethicone
4.00
4.00
4.00
Dimethicone (and) Dimethicone/Vinyl Dimethicone
3.00
3.00
3.00
Crosspolymer
D
Micronized Methylene Bis-Benzotriazolyl Tetramethyl-
4.00
4.00
4.00
butylphenol
Micronized 1,3,5-Triazine, 2,4,6-tris([1,1′-biphenyl]-4-yl)-
5.00
5.00
5.00
(CAS Regn. 31274-51-8)
Micronized Methanone, 1,1′-(1,4-piperazinediyl)bis[1-[2-[4-
1.00
2.00
4.00
(diethylamino)-2-hydroxybenzoyl]phenyl]-
(CAS Regn. 919803-06-8)
Mica (and) Titanium Dioxide (and)Tin oxide
0.30
0.30
Phenoxyethanol (and) Methylparaben (and) Ethylparaben
1.00
1.00
1.00
(and) Butylparaben (and) Propylparaben (and)
Isobutylparaben
Aqua (and) Tocopheryl Acetate (and) Caprylic/Capric
0.50
Triglyceride (and) Polysorbate 80 (and) Lecithin
Water
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100
100
100
Example B2: O/W Emulsion (2)
INCI
A
B
C
D
E
F
Glyceryl Stearate (and) PEG 100 Stearate
5.00
5.00
5.00
5.00
5.00
5.00
Phenethyl Benzoate
6.00
6.00
6.00
6.00
6.00
6.00
Isopropyl Palmitate
5.00
5.00
5.00
5.00
5.00
5.00
Triethylhexanoin
3.00
3.00
3.00
3.00
3.00
3.00
Bis-Ethylhexyloxyphenol Methoxyphenyl
2.00
2.00
2.00
2.00
2.00
2.00
Triazine
Ethylhexyl Triazone
1.50
1.50
1.50
1.50
1.50
1.50
Butylene Glycol
2.00
2.00
2.00
2.00
2.00
2.00
Disodium EDTA
0.20
0.20
0.20
0.20
0.20
0.20
Iron Oxides (CALISHA Contemprorary Jet
0.01
0.02
0.01
0.01
0.01
0.01
Black Oxide)
Iron Oxides (CALISHA Contemporary
0.08
0.5
0.08
0.08
0.08
0.08
Medium Red Oxide)
Iron Oxides (CALISHA Contemporary Yellow
0.55
0.5
0.55
0.55
0.55
0.55
Oxide
Sodium Acrylates Copolymer (and) Mineral
1.20
1.20
1.20
1.20
1.20
1.20
Oil (and) PPG-1 Trideceth-6
Cyclomethicone
4.00
4.00
4.00
4.00
4.00
4.00
Micronized Methylene Bis-Benzotriazolyl
4.00
4.00
4.00
1.00
2.00
2.00
Tetramethylbutylphenol
Butyl Methoxydibenzoymethane
0.5
4.00
4.00
0.5
Ethylhexyl Methoxycinnamate
0.5
3.00
3.00
0.5
Octocrylene
0.5
4.00
4.00
0.5
Propanedinitrile, 2-[3-[bis(2-ethylhexyl)-
2.00
0.5
amino]-2-cyclohexen-1-ylidene]-(CAS Regn.
923271-36-7) or merocyanine derivative of
formula (14) or 1,3,5-Triazine-2,4,6-triamine,
N2,N4-bis[4-[5-(1,1-dimethylpropyl)-2-benzoxazolyl]phenyl]-
N6-(2-ethylhexyl)-(Uvasorb
K2A) (CAS Regn 288254-16-0)
Acetic acid, 2-cyano-2-[5,5-dimethyl-3-[(1-
2.00
1.00
0.5
methylpropyl)amino]-2-cyclohexen-1-ylidene]-,
2-ethylhexyl ester (CAS Regn. 923271-35-6)
Uvinul A plus (CAS Regn. 302776-68-7)
0.5
0.5
2.00
2.00
Micronized 1,3,5-Triazine, 2,4,6-tris([1,1′-
2.00
2.00
2.00
2.00
2.00
2.00
biphenyl]-4-yl)-(CAS Regn. 31274-51-8)
2,4-Pentadienoic acid, 5-(diethylamino)-2-
2.00
0.5
0.5
0.5
0.5
(phenylsulfonyl)-, octyl ester (CAS Regn.
98835-90-6)
Micronized Methanone, 1,1′-(1,4-piperazine-
2.00
2.00
2.00
2.00
2.00
diyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-
(CAS Regn. 919803-06-8)
Mica (and) Titanium Dioxide (and)Tin oxide
1.00
1.00
1.00
1.00
1.00
1.00
Phenoxyethanol (and) Methylparaben (and)
1.00
1.00
1.00
1.00
1.00
1.00
Ethylparaben (and) Butylparaben (and)
Propylparaben (and) Isobutylparaben
Water
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100
100
100
100
100
100
Example B3: O/W Emulsion (3)
INCI
A
B
C
D
E
F
Tribehenin PEG-20 esters
5.00
5.00
5.00
5.00
5.00
5.00
Stearyl Alcohol
0.50
0.50
0.50
0.50
0.50
0.50
Dibutyl Adipate
5.00
5.00
5.00
5.00
5.00
5.00
PPG-2 Myristyl Ether Propionate
5.00
5.00
5.00
5.00
5.00
5.00
Triheptanoin
3.00
3.00
3.00
3.00
3.00
3.00
Ethylhexyl Salicylate
5.00
5.00
5.00
5.00
5.00
5.00
Butyl Methoxydibenzoymethane
3.00
3.00
3.00
3.00
3.00
3.00
Bis-Ethylhexyloxyphenol Methoxyphenyl
3.00
3.00
3.00
3.00
3.00
3.00
Triazine
Ethylhexyl Triazone
3.00
3.00
3.00
3.00
3.00
3.00
Micronized Methylene Bis-Benzotriazolyl
2.00
2.00
2.00
2.00
2.00
2.00
Tetramethylbutylphenol
Butyl Methoxydibenzoymethane
4.00
0.5
0.5
0.5
Bis-Ethylhexyloxyphenol Methoxyphenyl
1.00
1.00
1.00
1.00
1.00
1.00
Triazine
Ethylhexyl Triazone
0.5
0.5
0.5
0.5
0.5
0.5
Ethylhexyl Methoxycinnamate
4.00
Octocrylene
4.00
0.5
0.5
0.5
Propanedinitrile, 2-[3-[bis(2-ethylhe-
2.00
0.5
1.0
xyl)amino]-2-cyclohexen-1-ylidene]-
(CAS Regn. 923271-36-7) or merocya-
nine derivative of formula (14) or 1,3,5-
Triazine-2,4,6-triamine, N2,N4-bis[4-[5-
(1,1-dimethylpropyl)-2-benzoxazolyl]-
phenyl]-N6-(2-ethylhexyl)- (Uvasorb
K2A) (CAS Regn 288254-16-0)
Acetic acid, 2-cyano-2-[5,5-dimethyl-3-
2.00
[(1-methylpropyl)amino]-2-cyclohexen-1-
ylidene]-, 2-ethylhexyl ester (CAS Regn.
923271-35-6)
Uvinul A plus (CAS Regn. 302776-68-7)
2.00
Micronized 1,3,5-Triazine, 2,4,6-tris-
2.00
5.00
2.00
2.00
2.00
4.00
([1,1′-biphenyl]-4-yl)- (CAS Regn.
31274-51-8)
2,4-Pentadienoic acid, 5-(diethylamino)-
2.00
2-(phenylsulfonyl)-, octyl ester (CAS
Regn. 98835-90-6)
Micronized Methanone, 1,1′-(1,4-pipe-
2.00
2.00
5.00
4.00
2.00
2.00
razinediyl)bis[1-[2-[4-(diethylamino)-2-
hydroxybenzoyl]phenyl]-
(CAS Regn. 919803-06-8)
Sodium Polyacrylate
0.60
0.60
0.60
0.60
0.60
Disodium EDTA
0.20
0.20
0.20
0.20
0.20
0.20
Xanthan Gum
0.50
0.50
0.50
0.50
0.50
Iron Oxides (CALISHA Contemprorary
0.020
0.020
0.020
0.020
0.020
0.020
Black Oxide)
Iron Oxides (CALISHA Contemporary
0.08
0.08
0.08
0.08
0.08
Salmon Red)
Iron Oxides (CALISHA Contemporary
0.55
0.55
0.55
0.55
0.55
Sun Yellow)
Cyclomethicone
5.00
5.00
5.00
5.00
5.00
5.00
Mica (and) Titanium Dioxide (and) Iron
0.50
0.50
0.50
0.50
0.50
0.50
Oxides (and) Cetyl Dimethicone
Mica (and) Titanium Dioxide (and) Cetyl
0.50
0.50
0.50
0.50
0.50
0.50
Dimethicone (and) Iron Oxides (and)
Carmine
Phenoxyethanol (and) Methylparaben
1.00
1.00
1.00
1.00
1.00
1.00
(and) Ethylparaben (and) Butylparaben
(and) Propylparaben (and) Isobutyl-
paraben
Water
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100
100
100
100
100
100
Example B4: W/O Emulsion (1)
INCI
A
B
C
D
E
Polyglyceryl-4 Isostearate (and) Cetyl PEG/PPG-
4.50
4.50
4.50
4.50
4.50
10/1 Dimethicone (and) Hexyl Laurate
Cetyl PEG/PPG-10/1 Dimethicone
2.20
2.20
2.20
2.20
2.20
Sorbitan Sesquioleate
1.00
1.00
1.00
1.00
1.00
Cera Alba
1.80
1.80
1.80
1.80
1.80
Hydrogenated Vegetable Oil
2.00
2.00
2.00
2.00
2.00
Phenethyl Benzoate
2.00
2.00
2.00
2.00
2.00
Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine
1.00
1.00
3.00
1.00
1.00
Ethylhexyl Methoxycinnamate
5.00
5.00
5.00
10.00
5.00
Titanium Dioxide (and) Silica (and) Dimethicone
5.00
5.00
5.00
5.00
5.00
Iron Oxides (and) Cetyl Dimethicone
0.13
0.13
0.13
0.13
0.13
Iron Oxides (and) Cetyl Dimethicone
0.60
0.60
0.60
0.60
0.60
Iron Oxides (and) Cetyl Dimethicone
0.20
0.20
0.20
0.20
0.20
Cyclomethicone (and) Disteardimonium Hectorite
5.00
5.00
5.00
5.00
5.00
(and) Propylene Carbonate
Cyclopentasiloxane
6.00
6.00
6.00
6.00
6.00
Ethyl Trisiloxane
8.00
8.00
8.00
8.00
8.00
Dimethicone
6.00
6.00
6.00
6.00
6.00
Cyclopentasiloxane (and) C30-45 Alkyl Cetearyl
1.00
1.00
1.00
1.00
1.00
Dimethicone Crosspolymer (and) PEG/PPG-20/23
Dimethicone
Water
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100
100
100
100
100
Sodium Chloride
1.00
1.00
1.00
1.00
1.00
Pentylene Glycol (and) Scerotium Gum
3.00
3.00
3.00
3.00
3.00
Aqua (and) Retinyl Palmitate (and) Capryic/Capric
3.00
3.00
3.00
3.00
3.00
Triglyceride (and) Polysorbate 80 (and) Lecithin
(and) Benzalkonium Chloride
Butylen Glycol
3.00
3.00
3.00
3.00
3.00
Phenoxyethanol (and) Methylparaben (and)
1.00
1.00
1.00
1.00
1.00
Ethylparaben (and) Butylparaben (and)
Propylparaben (and) Isobutylparaben
Aluminum Starch Octenylsuccinate
2.00
2.00
2.00
2.00
2.00
Talc
2.00
2.00
2.00
2.00
2.00
Silica
5.00
5.00
5.00
5.00
5.00
Mica (and) Iron Oxides (and) Cetyl Dimethicone
2.00
2.00
2.00
2.00
2.00
Mica (and) Titanium Dioxide (and) Iron Oxides (and)
1
0.5
Cetyl Dimethicone
Micronized Methylene Bis-Benzotriazolyl Tetra-
0.5
6.00
4.00
2.00
1.00
methylbutylphenol
Butyl Methoxydibenzoymethane
5.00
5.00
5.00
5.00
5.00
Ethylhexyl Triazone
0.60
0.60
0.60
0.60
0.60
Octocrylene
4.00
0.5
0.5
0.5
0.5
Propanedinitrile, 2-[3-[bis(2-ethylhexyl)amino]-2-
2.00
1.00
5.00
2.00
1.00
cyclohexen-1-ylidene]-(CAS Regn. 923271-36-7) or
merocyanine derivative of formula (14) or 1,3,5-
Triazine-2,4,6-triamine, N2,N4-bis[4-[5-(1,1-di-
methylpropyl)-2-benzoxazolyl]phenyl]-N6-(2-ethylhexyl)-
(Uvasorb K2A) (CAS Regn 288254-16-0)
Acetic acid, 2-cyano-2-[5,5-dimethyl-3-[(1-methyl-
6.00
6.00
6.00
6.00
6.00
propyl)amino]-2-cyclohexen-1-ylidene]-, 2-ethyl-
hexyl ester (CAS Regn. 923271-35-6)
Uvinul A plus (CAS Regn. 302776-68-7)
8.00
8.00
8.00
8.00
8.00
Micronized 1,3,5-Triazine, 2,4,6-tris([1,1′-biphenyl]-
6.00
6.00
6.00
6.00
6.00
4-yl)-(CAS Regn. 31274-51-8)
2,4-Pentadienoic acid, 5-(diethylamino)-2-(phenylsulfonyl)-,
1.00
1.00
1.00
1.00
1.00
octyl ester (CAS Regn. 98835-90-6)
Micronized Methanone, 1,1′-(1,4-piperazine-
1.00
3.00
2.00
4.00
0.5
diyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]-
phenyl]-(CAS Regn. 919803-06-8)
Example B5: W/O Emulsion (2)
INCI
A
B
C
D
E
PEG-30 Dipolyhydroxystearate
3.00
3.00
3.00
3.00
3.00
Butylen Glycol Cocoate
2.00
2.00
2.00
2.00
2.00
Isodecyl neopentanoate
4.00
4.00
4.00
4.00
4.00
Isopropyl Isosterate
3.00
3.00
3.00
3.00
3.00
Beeswax
1.00
1.00
1.00
1.00
1.00
Hydrogenated Castor Oil
0.80
0.80
0.80
0.80
0.80
Ethylhexyl Methoxycinnamate
5.00
5.00
5.00
5.00
5.00
Iron Oxides (and) Cetyl Dimethicone (Calisha
0.10
0.10
0.10
0.10
0.10
Contemporary Black Oxide OD)
Iron Oxides (and) Cetyl Dimethicone (Calisha
0.57
0.57
0.57
0.57
0.57
Contemporary Yellow Oxide OD)
Iron Oxides (and) Cetyl Dimethicone (Calisha
0.13
0.13
0.13
0.13
0.13
Contemporary Medium Red Oxide OD)
Caprylyl Methicone
2.50
2.50
2.50
2.50
2.50
Water
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100
100
100
100
100
Sodium Chloride
1.00
1.00
1.00
1.00
1.00
Pentylene Glycol (and) Scerotium Gum
3.00
3.00
3.00
3.00
3.00
Aqua (and) Retinyl Palmitate (and)
3.00
3.00
3.00
3.00
3.00
Caprylic/Capric Triglyceride (and) Polysorbate
80 (and) Lecithin (and) Benzalkonium Chloride
Butylen Glycol
5.00
5.00
5.00
5.00
5.00
Polysorbate 80
0.25
0.25
0.25
0.25
0.25
Caprylyl Methicone
5.50
5.50
5.50
5.50
5.50
Dimethicone
7.00
7.00
7.00
7.00
7.00
Micronized Methylene Bis-Benzotriazolyl Tetra-
3.00
6.00
3.00
6.00
2.00
methylbutylphenol
Phenoxyethanol (and) Methylparaben (and)
1.00
1.00
1.00
1.00
1.00
Ethylparaben (and) Butylparaben (and)
Propylparaben (and) Isobutylparaben
Silica
3.00
3.00
3.00
3.00
3.00
Nylon-12
6.00
6.00
6.00
6.00
6.00
Bis-Ethylhexyloxyphenol Methoxyphenyl
1.00
1.00
1.00
1.00
1.00
Triazine
Butyl Methoxydibenzoymethane
5.00
5.00
5.00
5.00
5.00
Bis-Ethylhexyloxyphenol Methoxyphenyl
0.13
0.13
0.13
0.13
0.13
Triazine
Ethylhexyl Triazone
0.60
0.60
0.60
0.60
0.60
Octocrylene
4.00
0.5
0.5
0.5
0.5
Propanedinitrile, 2-[3-[bis(2-ethylhexyl)amino]-2-
2.00
1.00
5.00
2.00
1.00
cyclohexen-1-ylidene]-(CAS Regn. 923271-36-
7) or merocyanine derivative of formula (14) or
1,3,5-Triazine-2,4,6-triamine, N2,N4-bis[4-[5-
(1,1-dimethylpropyl)-2-benzoxazolyl]phenyl]-N6-
(2-ethylhexyl)-(Uvasorb K2A) (CAS Regn
288254-16-0
Acetic acid, 2-cyano-2-[5,5-dimethyl-3-[(1-
6.00
6.00
6.00
6.00
6.00
methylpropyl)amino]-2-cyclohexen-1-ylidene]-,
2-ethylhexyl ester (CAS Regn. 923271-35-6)
Uvinul A plus (CAS Regn. 302776-68-7)
8.00
8.00
8.00
8.00
8.00
Micronized 1,3,5-Triazine, 2,4,6-tris([1,1′-
6.00
6.00
6.00
6.00
6.00
biphenyl]-4-yl)-(CAS Regn. 31274-51-8)
2,4-Pentadienoic acid, 5-(diethylamino)-2-
1.00
1.00
1.00
1.00
1.00
(phenylsulfonyl)-, octyl ester (CAS Regn. 98835-
90-6)
Micronized Methanone, 1,1′-(1,4-piperazine-
1.00
3.00
2.00
4.00
0.5
diyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-
(CAS Regn. 919803-06-8)
(Manganese modified) Titanium Dioxide
4.00
1.00
Diethylhexyl Syringylidene Malonate
2.00
1.00
3.00
4.00
0.5
Propanedioic acid, 2-[(4-hydroxy-3,5-dimethoxy-
1.00
1.00
5.00
phenyl)methyl]-, 1,3-bis(2-ethylhexyl) ester;
(CAS Regn. 872182-46-2)
1.PublishNumber: US-2017231889-A1
2.Date Publish: 20170817
3.Inventor: EHLIS THOMAS
SOHN MYRIAM
4.Inventor Harmonized: EHLIS THOMAS(DE)
SOHN MYRIAM(FR)
5.Country: US
6.Claims:
(en)Disclosed are cosmetic formulation comprising (a) particulates having an absorption in the range of 400 to 800 nm; and (b) UV filters selected from (b 1 ) particulate organic UV-filters; and (b 2 ) soluble organic UV filters.
7.Description:
(en)The present invention relates to cosmetic compositions comprising micronized and/or soluble UV absorbers and one or more color pigments.
It has long been known that prolonged exposure to that UV radiation which reaches the surface of the earth can lead to the formation of erythemas or light dermatoses, as well as to an increased incidence of skin cancers or accelerated skin aging.
Various sunscreen formulations have been proposed which include actives which are intended to counteract UV radiation, thereby inhibiting the said undesired effects on the skin.
A great number of compounds has been proposed for the use as UV protectants in sunscreen formulations, especially soluble organic UV absorbers and also insoluble micronized organic and inorganic compounds, wich become more and more common in sunscreen formulations.
Micronised, insoluble organic UV absorbers, when used in sunscreen formulations, provide excellent UV protection and have a high SPF rating. Moreover, micronised, insoluble organic UV absorbers show no tendency, under the influence of light, to generate radicals which could damage or sensitise human skin.
Unfortunately, due to light scattering sun screen compostitions comprising organic and/or inorganic particulate filters show an articulate whitening aspect when applied on the skin.
The whitening aspect increases with higher concentration of the corresponding UV filters and will therefore limit their required quantity.
Furthermore, soluble and particulate UV filters which have absorption maximum in the UV-A region are mostly not colourless since these substances will absorb also light in the visible range of the spectrum. Due to the particular colour of these UV-A filters the resulting cosmetic sun screen formulations will be coloured. The hue of such formulations (in most cases yellowish) is considered as unnatural since it derivates significantly from the natural skin hue.
Furthermore, it is known that some UV filters show significant fluorescence. Artificial illuminations with a high UV ratio therefore generate very unnatural skin tones.
Surprisingly it has been found that the combination of particulate or soluble organic UV filters with one or more colour pigments provides cosmetic sunscreen formulations which have a hue that corresponds to the natural skin tone and is therefore not considered as unnatural.
Therefore the present invention relates to a cosmetic formulation comprising
(a) particulates having an absorption in the range of 400 to 800 nm; and
(b) UV filters selected from
(b 1 ) particulate organic UV-filters; and (b 2 ) soluble organic UV filters.
Preferably component (a) is selected from
(a 1 ) inorganic colour pigments; and
(a 2 ) organic colour pigments.
Most preferably the inorganic pigments (a 1 ) are selected from iron (III) oxide, magnetite and mixtures of these pigments; manganese doped TiO 2 or ZnO; ultramarine pigments; chromium oxide green; chromium hydrate green; metal-particles; mica, bismuth oxychloride; glass flakes (borosilicates); interference-pigments based on mica (synthetic or of natural origin); or borosilicates (glass flakes), typically coated with thin layers of titanium dioxide (rutile or anastas), iron oxides or mixtures thereof and talcum.
The organic pigments (a 2 ) are preferably selected from D&C Red 30 (Vat Red 1); D&C Red 36 (Pigment Red 4); Carmine; D&C Red 6 Ba Lake; D&C Red 7 Ca Lake; D&C Red 30 Al Lake; D&C Red 30 Talc Lake; D&C Red 27 Al Lake; D&C Red 28 Al Lake; D&C Red 33 Al Lake; D&C Red 21 Al Lake.
Of specific interest are the pigments/colours listed in Table 1 below:
TABLE 1a
Examples of pigments/colours (component (b))
Color index
CAS registry
number
Official and common name
number
10006
Pigment Green 8
16143-80-9
10020
Acid Green 1
19381-50-1
10316 (2)
Ext. D & C Yellow No. 7; Acid Yellow 1; Naphthol Yellow S
846-70-8
11680
Pigment Yellow 1
2512-29-0
11710
Pigment Yellow 3
6486-23-3
11725
Pigment Orange 1
6371-96-6
11920
Solvent Orange 1
2051-85-6
12010
Solvent Red 3
6535-42-8
12085 (2)
D & C Red No. 36; Pigment Red 4; Flaming Red
2814-77-9
12120
Pigment Red 3
2425-85-6
12150
Solvent Red 1
1229-55-6
12370
Pigment Red 112
6535-46-2
12420
Pigment Red 7
6471-51-8
12480
Pigment Brown
6410-40-8
12490
Pigment Red 5
6410-41-9
12700
Disperse Yellow 16
4314-14-1
13015
E 105; Acid Yellow 9
2706-28-7
14270
E 103; Acid Orange 6
547-57-9
14700
FD & C Red No. 4; Food Red 1; Ponceau SX
4548-53-2
14720
E 122; Acid Red 14; Food Red 3; Azorubine; Carmoisine
3567-69-9
14815
E 125; Food Red 2
3257-28-1
15510 (2)
D&C Orange No. 4; Acid Orange 7; Orange II
633-96-5
15525
Pigment Red 68
5850-80-6
15580
Pigment Red 51
227-459-1
15620
Acid Red 88
1658-56-6
15630
Pigment Red 49
1248-18-6
15800:1
D&C Red No. 31; Pigment Red 64:1; Brilliant Lake Red R
6371-76-2
15850
D&C Red No. 6; Pigment Red 57; Lithol Rubin B
5858-81-1
15850:1 (2)
D&C Red No. 7; Pigment Red 57:1; Lithol Rubin B Ca
5281-04-9
15865 (2)
Pigment Red 48
3564-21-4
15880:1
D&C Red No. 34; Pigment Red 63:1; Deep Maroon; Fanchon
6417-83-0
Maroon; Lake Bordeaux B
15980
E 111; Food Orange 2
2347-72-0
15985 (2)
FD&C Yellow No. 6; E 110; Food Yellow 3; Sunset Yellow;
2783-94-0
Sunset Yellow FCF; Orange Yellow S
16035
FD&C Red No. 40; Food Red 17; Allura Red; Allura Red AC
25956-17-6
16230
Acid Orange 10
1936-15-8
16255 (2)
E 124; Acid Red 18; Food Red 7; Ponceau 4R; Cochineal Red A
2611-82-7
16290
E 126; Acid Red 41
5850-44-2
17200 (2)
D&C Red No. 33; Acid Red 33; Acid Fuchsine
3567-66-6
18050
Acid Red 1
3734-67-6
18130
Acid Red 155
10236-37-0
18690
Acid Yellow 121
5601-29-6
18736
Acid Red 180
6408-26-0
18820
Acid Yellow 11
6359-82-6
18965
Acid Yellow 17
6359-98-4
19140 (2)
FD&C Yellow No. 5; E 102; Acid Yellow 23; Tartrazine
1934-21-0
20040
Pigment Yellow 16
5979-28-2
20170
D&C Brown No. 1; Acid Orange 24; Resorcin Brown
1320-07-6
20470
Noir W 699
1064-48-8
21100
Pigment Yellow 13
5102-83-0
21108
Pigment Yellow 83
5567-15-7
21230
Solvent Yellow 29
6706-82-7
24790
Acid Red 163
13421-53-9
26100
D&C Red No. 17; Solvent Red 23; Sudan III; Toney Red
85-86-9
27290 (2)
Acid Red 73
5413-75-2
27755
E152; Food Black 2
2118-39-0
28440
E 151; Brilliant Black 1; Food Black 1; Brilliant Black BN; Black P
2519-30-4
40215
Direct Orange 34
1325-54-8
40800
Beta Carotene (synthetic); Food Orange 5
7235-40-7
40820
E 160e; Food Orange 6; β-Apo-8′ Carotenal (C 30)
1107-26-2
40825
E 160f; Food Orange 7; Ethyl Ester of β-Apo-8′ Carotenic Acid
1109-11-1
(C 30)
40850
Canthaxanthin; E 161g; Food Orange 8
514-78-3
42045
Acid Blue 1
129-17-9
42051 (2)
E 131; Acid Blue 3; Patent Blue V
3536-49-0
42053
FD&C Green No. 3; Food Green 3; Fast Green FCF
2353-45-9
42080
Acid Blue 7
3486-30-4
42090
FD&C Blue No. 1; Acid Blue 9 (Sodium salt); Food Blue 2;
3844-45-9
Brilliant Blue FCF; Patent Blue AC
FD&C Blue No. 4; Acid Blue 9 (Ammonium salt); Alphazurine
6371-85-3
FG; Erioglaucine
42100
Acid Green 9
4857-81-2
42170
Acid Green 22
5863-51-4
42510
Basic Violet 14
632-99-5
42520
Basic Violet 2
3248-91-7
42735
Acid Blue 104
6505-30-2
44045
Basic Blue 26
2580-56-5
44090
E142; Acid Green 50; Green S
3087-16-9
45100
Acid Red 52
3520-42-1
45190
Acid Violet 9
6252-76-2
45220
Acid Red 50
5873-16-5
45350
D&C Yellow No. 8; Acid Yellow 73; Uranine
518-47-8
45350:1
D&C Yellow No. 7; Solvent Yellow 94; Fluorescein
2321-07-5
45370 (2)
Acid Orange 11
45370:1
D&C Orange No. 5; Solvent Red 72; Dibromofluorescein
596-03-2
45380 (2)
D&C Red No. 22; Acid Red 87; Eosin Y
17372-87-1
45380:2
D&C Red No. 21; Solvent Red 43; Tetrabromofluorescein
15086-94-8
45396
Solvent Orange 16
24545-86-6
45405
Acid Red 98
6441-77-6
45410 (2)
D&C Red No. 28; Acid Red 92; Phloxine B
18472-87-2
45410:1
D&C Red No. 27; Solvent Red 48; Tetrabromotetrachloro-;
13473-26-2
Fluorescein
45425
D&C Red No. 11; Acid Red 95; Erythrosine Yellowish Na
33239-19-9
45425:1
D&C Orange No. 10; Solvent Red 73; Diiodofluorescein
38577-97-8
45430 (2)
E 127; FD&C Red No. 3; Acid Red 51; Erythrosine; Food Red
16423-68-0
14
47000
D&C Yellow No. 11; Solvent Yellow 33; Quinoline Yellow SS
8003-22-3
47005
D&C Yellow No. 10; E104; Acid Yellow; Food Yellow 13;
8004-92-0
Quinoline Yellow; Canary Yellow
50325
Acid Violet 50
229-951-1
50420
Acid Black 2
8005-03-6
51319
Pigment Violet 23
6358-30-1
58000
Pigment Red 83; Alizarin
72-48-0
59040
D&C Green No. 8; Solvent Green 7; Pyranine Concentrated
6358-69-6
60724
Disperse Violet 27
19286-75-0
60725
D&C Violet No. 2; Solvent Violet 13; Alizurol Purple SS
81-48-1
60730
Ext D&C Violet No. 2; Acid Violet 43
4430-18-6
61565
D&C Green No. 6; Solvent Green 3; Quinizarin Green SS
128-80-3
61570
D&C Green No. 5; Acid Green 25
4403-90-1
61585
Acid Blue 80
4474-24-2
62045
Acid Blue 65
4368-56-3
69800
E 130; Vat Blue 4
81-77-6
69825
D&C Blue No. 9; Vat Blue 6; Indanthrene Blue; Carbanthrene
130-20-1
Blue
71105
Vat Orange 7; Pigment Orange 43
4424-06-0
73000
Vat Blue 1; Indigo
482-89-3
73015
FD&C Blue No. 2; E 132; Food Blue 1; Indigotine; Indigo
860-22-0
Carmine
73360
D&C Red No. 30; Vat Red 1; Helindone Pink CN
2379-79-0
73385
Vat Violet 2
5462-29-3
73900
Pigment Violet 19
1047-16-1
73915
Pigment Red 122
16043-40-6
74100
Pigment Blue 16
547-93-6
74160
Pigment Blue 15
147-14-8
74180
Direct Blue 86
1330-38-7
74260
Pigment Green 7
1328-53-6
75100
Natural Yellow 6
27876-94-4
75120
Annatto extract; E 160b; Natural Orange 4
1393-63-1
75125
E 160d; Lycopene
502-65-8
75130
Beta Carotene (Natural); E 160a; Natural Browns 5; Natural
7235-40-7
Yellow 26
75135
E 161d; Natural Yellow 27; Rubixanthin
3763-55-1
75170
Guanine; Natural White 1
73-40-5
75300
E 100; Natural Yellow 3; Turmeric Yellow; Curcumin; Indian
458-37-7
Saffron
75470
Cochineal extract; E120; Natural Red 4; Cochineal; Carmine;
1343-78-8
Carminic Acid ...
1390-65-4
1260-17-9
75480
Henna
83-72-7
75810
E 140 & E 141; Chlorophyll; Copper complexes of chlorophyll
11006-34-1
and chlorophyllins; Potassium sodium copper; Chlorophyllin;
Natural Green 3
77000
Aluminum Powder; E 173; Pigment Metal 1; Aluminum
4729-90-5
77002
Alumina; Pigment White 24
1332-73-6
77004
Pigment White 19; Bentonite
1302-78-9
77007
Ultramarine Blue; Pigment Blue 29
1317-97-1
Ultramarine Red
1345-00-2
Ultramarine Violet; Pigment Violet 15
12769-96-9
77013
Ultramarine Green; Pigment Green 24
77015
Pigment Red 101; Pigment Red 102
77019
Mica; Pigment White 20
12001-26-2
Talc; Pigment white 26
14807-96-9
77120
Pigment White 21; Pigment White 22
7727-43-7
77163
Bismuth oxychloride; Pigment White 14
7787-59-9
77220
Calcium carbonate; E 170; Pigment White 18
471-34-1
77231
Pigment White 25; Calcium Sulfate
7778-18-9
77288
Chromium Oxide Greens; Pigment Green 17
1308-38-4
77289
Chromium hydroxide Green; Pigment Green 18; Guignet Green;
12001-99-9
Veridian
77346
Cobalt Blue; Pigment Blue 28
1345-16-0
77400
Bronze powder; Copper powder; Pigment Metal 2
7440-50-8
77400
77480
E 175; Gold; Pigment Metal 3
7740-57-5
77489
E 172; Ferrous oxide
1345-25-1
77491
Ferric oxide; E 172; Pigments Red 101 & 102; Pigments Brown
1309-37-1
6 & 7
77492
Hydrated Ferric oxide; E 172; Pigments Yellow 42 & 43;
20344-49-4
Pigments Brown 6 & 7
77499
Ferrous Ferric oxide; E 172; Pigment Black 11; Pigments Brown
1317-61-9
6 & 7
77510
Ferric ferrocyanide; Pigment Blue 27; Prussian Blue
14038-43-8
77520
77713
Magnesium Carbonate; Pigment White 18
546-93-0
77742
Manganese Violet; Pigment Violet 16
10101-66-3
77745
Manganous Phosphate
10124-54-6
77820
Silver; E 174
7440-22-4
77891
Titanium Dioxide; E 171; Pigment White 6
13463-67-7
77947
Zinc Oxide; Pigment White 4
1317-13-2
Acid red 195
12220-24-5
Aluminum distearate
300-92-5
Anthocyanins; E 163
11029-12-2
Beetroot red; E 162
89957-89-1
7659-95-2
Bismuth citrate
Bromocresol green
76-60-8
Bromothymol blue
76-59-5
Calcium stearate
1592-23-0
Capsanthin, Capsorubin; E 160c; Paprika extract
465-42-9
E 150; Natural Brown 10; Caramel
8028-89-5
Ferric ammonium ferrocyanide
25869-00-5
E 101; Lactoflavin; Riboflavin
83-88-5
Lead acetate
301-04-2
Magnesium Stearate
557-04-0
Zinc Stearate
557-05-1
indicates data missing or illegible when filed
TABLE 1b
Structure of the Lakes:
Lakes (FDA name)
CI No
name
structure of corresponding dye
D & C Red #6 Ba Lake
15850
Pigment Red 57 Sodium Salt
D & C Red #7
15850:1
Pigment Red 57.1 Calcium Salt
D & C Red #21 Al Lake
45380:2
Solvent Red 43
D & C Red #22 Al Lake
45380
Acid Red 87
D & C Red #27 Al Lake
45410:1
Solvent Red 48
D & C Red #28 Al Lake
45410
Acid Red 92
D & C Red #30 Al & Talk Lake
73360
Vat Red 1 = Pigment Red 181
D & C Red #33 Al & Zr Lake
17200
Acid Red 33
D & C Red #10 Al Lake
47005
Food Yellow 13
and
FD & C Yellow #5 Al Lake
19140
Acid Yellow 23 Na Salt
FD & C Yellow #6 Al Lake
15985
Food Yellow 3 Na Salt
FD & C Blue #1 Al Lake
42090
Acid blue 9
TABLE 1c
Calisha colour pigments (Ciba):
Name
INCI Name
Treated Pearls
Calisha Romance Silver Pearl OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Romance Glamour Violet OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Romance Glamour Blue Pearl OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Romance Glamour Green OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Romance Gold Pearl OD
Mica and Titanium Dioxide and Red Iron Oxide
and Cetyl Dimethicone
Calisha Romance Bronze Pearl OD
Mica and Red Iron Oxide and Cetyl
Dimethicone
Calisha Romance Orange Pearl OD
Mica and Red Iron Oxide and Cetyl
Dimethicone
Calisha Romance Red Pearl OD
Mica and Red Iron Oxide and Cetyl
Dimethicone
Calisha Contemporary Starlight Pearl OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Contemporary Glamour Blue Pearl
Mica and Titanium Dioxide and Cetyl
OD
Dimethicone
Calisha Contemporary Glamour Gold Pearl
Mica and Titanium Dioxide and Cetyl
OD
Dimethicone
Calisha Contemporary Glamour Violet OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Contemporary Claret Pearl OD
Mica and Red Iron Oxide and Titanium Dioxide
and Cetyl Dimethicone
Calisha Contemporary Sienna Pearl OD
Mica and Red Iron Oxide and Titanium Dioxide
and Cetyl Dimethicone
Calisha Contemporary Black Pearl OD
Mica and Titanium Dioxide and Black Iron
Oxide and Cetyl Dimethicone
Calisha Contemporary Sable Pearl OD
Mica and Titanium Dioxide and and Red Iron
Oxide Carmine and Cetyl Dimethicone
Calisha Contemporary Green Pearl OD
Mica and Titanium Dioxide and Red Iron Oxide
and Ferric Ferrocyanide and Cetyl Dimethicone
Calisha Contemporary Silver Pearl OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Contemporary Glamour Green OD
Mica and Titanium Dioxide and Tin Dioxide and
Cetyl Dimethicone
Calisha Contemporary Gold Pearl OD
Mica and Titanium Dioxide and Red Iron Oxide
and Cetyl Dimethicone
Calisha Contemporary Bronze Pearl OD
Mica and Red Iron Oxide and Cetyl
Dimethicone
Calisha Contemporary Rose Red Pearl OD
Mica and Red Iron Oxide and Cetyl
Dimethicone
Calisha Art Deco Silver Pearl OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Art Deco Glamour Violet OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Art Deco Glamour Blue Pearl OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Art Deco Glamour Green OD
Mica and Titanium Dioxide and Cetyl
Dimethicone
Calisha Art Deco Gold Pearl OD
Mica and Red Iron Oxide and Titanium Dioxide
and Cetyl Dimethicone
Calisha Art Deco Bronze Pearl OD
Mica and Red Iron Oxide and Cetyl
Dimethicone
Calisha Art Deco Orange Pearl OD
Mica and Red Iron Oxide and Cetyl
Dimethicone
Calisha Art Deco Red Pearl OD
Mica and Red Iron Oxide and Cetyl
Dimethicone
Untreated Pearls
Calisha Romance Silver Pearl CL
Mica and Titanium Dioxide
Calisha Romance Glamour Violet CL
Mica and Titanium Dioxide
Calisha Romance Glamour Blue Pearl CL
Mica and Titanium Dioxide
Calisha Romance Glamour Green CL
Mica and Titanium Dioxide
Calisha Romance Gold Pearl CL
Mica and Titanium Dioxide and Red Iron Oxide
Calisha Romance Bronze Pearl CL
Mica and Red Iron Oxide
Calisha Romance Orange Pearl CL
Mica and Red Iron Oxide
Calisha Romance Red Pearl CL
Mica and Red Iron Oxide
Calisha Contemporary Starlight Pearl CL
Mica and Titanium Dioxide
Calisha Contemporary Glamour Blue Pearl
Mica and Titanium Dioxide
CL
Calisha Contemporary Glamour Gold Pearl
Mica and Titanium Dioxide
CL
Calisha Contemporary Glamour Violet CL
Mica and Titanium Dioxide
Calisha Contemporary Claret Pearl CL
Mica and Red Iron Oxide and Titanium Dioxide
Calisha Contemporary Sienna Pearl CL
Mica and Red Iron Oxide and Titanium Dioxide
Calisha Contemporary Black Pearl CL
Mica and Titanium Dioxide and Black Iron
Oxide
Calisha Contemporary Sable Pearl CL
Mica and Titanium Dioxide and Red Iron Oxide
and Carmine
Calisha Contemporary Green Pearl CL
Mica and Titanium Dioxide Red Iron Oxide
Ferric Ferrocyanide
Calisha Contemporary Silver Pearl CL
Mica and Titanium Dioxide
Calisha Contemporary Glamour Green CL
Mica and Titanium Dioxide and Tin Dioxide
Calisha Contemporary Gold Pearl CL
Mica and Titanium Dioxide and Red Iron Oxide
Calisha Contemporary Bronze Pearl CL
Mica and Red Iron Oxide
Calisha Contemporary Rose Red Pearl CL
Mica and Red Iron Oxide
Calisha Art Deco Silver Pearl CL
Mica and Titanium Dioxide
Calisha Art Deco Glamour Violet CL
Mica and Titanium Dioxide
Calisha Art Deco Glamour Blue Pearl CL
Mica and Titanium Dioxide
Calisha Art Deco Glamour Green Pearl CL
Mica and Titanium Dioxide
Calisha Art Deco Gold Pearl CL
Mica and Red Iron Oxide and Titanium Dioxide
Calisha Art Deco Bronze Pearl CL
Mica and Red Iron Oxide
Calisha Art Deco Orange Pearl CL
Mica and Red Iron Oxide
Calisha Art Deco Red Pearl CL
Mica and Red Iron Oxide
Inorganic Pigments
Calisha Contemporary Salmon Red Oxide
Red Iron Oxide
Calisha Contemporary Medium Red Oxide
Red Iron Oxide
Calisha Contemporary Deep Red Oxide
Red Iron Oxide
Calisha Contemporary Black Oxide
Black Iron Oxide
Calisha Contemporary Jet Black Oxide
Black Iron Oxide
Calisha Contemporary Sun Yellow Oxide
Yellow Iron Oxide
Calisha Contemporary Yellow Oxide
Yellow Iron Oxide
Calisha Contemporary Ultramarine Blue
Ultramarine Blue
Calisha Contemporary Ultramarine Violet
Ultramarine Violet
Calisha Art Deco Hydroxide Chrome Green
Chromium Hydroxide Green
Calisha Art Deco Chrome Oxide Green
Chromium Oxide Greens
Lakes
Calisha Art Deco Blue 1 Lake
FD&C Blue No. 1 Al Lake
Calisha Art Deco Red 21 Lake
D&C Red No. 21 Al Lake
Calisha Art Deco Red 27 Lake
D&C Red No. 27 Al Lake
Calisha Art Deco Red 30 AL. Lake
D&C Red No. 30 Al Lake
Calisha Art Deco Red 30 Talc Lake
D&C Red No. 30 Talc Lake
Calisha Art Deco Red 33 Lake
D&C red No. 33 Al Lake
Calisha Art Deco Red 40 AL. Lake
FD&C Red No. 40 Al lake
Calisha Art Deco Red 6 Lake HD
D&C Red No. 6 Ba Lake
Calisha Art Deco Red 7 Lake HD
D&C Red No. 7 Ca lake
Calisha Art Deco Yellow 5 Lake HD
FD&C Yellow No. 5 Al Lake
Calisha Art Deco Yellow 6 AL. Lake
FD&C Yellow No. 6 Al lake
The interference pigments as used in the present invention are platelet particulates. The platelet particulates preferably have a thickness of no more than about 5 micrometers, more preferably no more than about 2 micrometers, still more preferably no more than about 1 micrometer. The platelet particulates preferably have a thickness of at least about 0.02 micrometers, more preferably at least about 0.05 micrometers, even more preferably at least about 0.1 micrometers, and still more preferably at least about 0.2 micrometers.
The particle size determines the opacity and luster. The particle size is determined by measuring the diameter thickness of the particulate material. The term “diameter” as used herein, means the largest distance across the major axis of the particulate material. Diameter can be determined by any suitable method known in the art, such as particle size analyzer Mastersizer 2000 manufactured by Malvern Instruments. The interference pigments preferably have an average diameter not greater than about 200 micrometers, more preferably not greater than 150 micrometers. The interference pigments preferably have a diameter of at least about 0.1 micrometer, more preferably at least about 1.0 micrometer, even more preferably at least about 2.0 micrometer, and still more preferably at least about 5.0 micrometer.
The interference pigments comprise a multilayer structure. The center of the particulates is a flat substrate with a refractive index (RI) normally below 1.8. A wide variety of particle substrates are useful herein. Nonlimiting examples are natural mica, synthetic mica, graphite, talc, kaolin, alumina flake, bismuth oxychloride, silica flake, glass flake, ceramics, titanium dioxide, CaSO 4 , CaCO 3 , BaSO 4 , borosilicate and mixtures thereof, preferably mica, silica and alumina flakes.
A layer of thin film or a multiple layer of thin films are coated on the surface of a substrate described above. The thin films are made of highly refractive materials. The refractive index of these materials is normally above 1.8.
A wide variety of thin films are useful herein. Nonlimiting examples are TiO 2 , Fe 2 O 3 , SnO 2 , Cr 2 O 3 , ZnO, ZnS, SnO, ZrO 2 , CaF 2 , Al 2 O 3 , BiOCl, and mixtures thereof or in the form of separate layers, preferably TiO 2 , Fe 2 O 3 , Cr 2 O 3 , and SnO 2 .
For the multiple layer structures, the thin films can be consisted of all high refractive index materials or alternation of thin films with high and low RI materials with the high RI film as the top layer.
The interference pigment color is a function of the thickness of thin film, the thickness for a specific color may be different for different materials. For TiO 2 , a layer of 40 nm to 60 nm or a whole number multiple thereof gives silver color, 60 nm to 80 nm yellow color, 80 nm to 100 nm red color, 100 nm to 130 nm blue color, 130 nm to 160 nm green color.
In addition to the interference color, other transparent absorption pigments can be precipitated on top of or simultaneously with the TiO 2 layer. Common materials are red or black iron oxide, ferric ferrocyanide, chromium oxide or carmine. It is found that the color of the interference pigment in addition to its brightness has a significant influence on human perception of skin tone. In general, preferred colors are silver, gold, red, green and mixtures thereof.
Nonlimiting examples of the interference pigments useful herein include those supplied by Persperse, Inc. under the trade name PRESTIGE®, FLONAC®; supplied by EMD Chemicals, Inc. under the trade name TIMIRON®, COLORONA®, DICHRONA® and XIRONA®; supplied by Engelhard Co. under the trade name FLAMENCO®, TIMICA®, DUOCHROME®; and supplied by Ciba under the trade name CALISHA®.
Although there are no critical limitations to the sizes of the pigment particles, preferably pigment particles having a size from about 0.01 to about 500 micrometers, more preferably having a size of about 1 to about 200 micrometers, most preferably having a size from about 5 to about 150 micrometers are modified with the silicone compounds according to formula
R1 is C1 to C22 branched or straight chain alkyl or aryl of six to ten carbon atoms;
R2 is C1 to C22 branched or straight chain alkyl or aryl of six to ten carbon atoms;
R3 is C1 to C22 branched or straight chain alkyl or aryl of six to ten carbon atoms;
R4 is C11 to C22 branched or straight chain alkyl or aryl of six to ten carbon atoms;
q is from 1 to about 2000;
t is from 1 to about 2000; the sum of q+t is from 2 to about 2000;
R5 is C1 to C22 branched or straight chain alkyl or aryl of six to ten carbon atoms;
R6 is C1 to C22 branched or straight chain alkyl or aryl of six to ten carbon atoms;
R7 is C1 to C22 branched or straight chain alkyl or aryl of six to ten carbon atoms;
R8 is C1 to C22 branched or straight chain alkyl or aryl of six to ten carbon atoms;
a is from 1 to about 100;
b is from 1 to about 100; the sum of a+b is from 2 to about 100; and
x is an integer from 1 to about 2000.
It will often be desirable to coat the pigment particles with, for example, one or more hydrous inorganic oxides, for example, hydrated silica or alumina, TiO 2 , Fe-oxides, tin oxide, mica, zinc oxide, colorants like carmine or Prussian blue.
Examples of pigments include inorganic pigments, metal oxides and hydroxides, mica, organic pigments, pearlescent pigments, mineral silicates, porous materials, carbons, interference pigments, and the like.
Preferred pigment particles are selected from the group consisting of inorganic pigments, metal oxides and hydroxides, mica, organic pigments, pearlescent pigments, mineral silicates, porous materials, carbons, and interference pigments.
Examples of the inorganic pigments capable of being modified are ultramarine blue, Prussian blue, manganese violet, titanium-coated mica, bismuth oxychloride, iron oxides, iron hydroxide, titanium dioxide, titanium lower oxides, and chromium hydroxide.
Examples of the metal oxides and hydroxides capable of being modified are magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxides, aluminum oxide, aluminum hydroxide, silica, iron oxides (α-Fe 2 O 3 , γ-Fe 2 O 3 , Fe 3 O 4 , FeO), iron hydroxides, titanium dioxide, titanium lower oxides, zirconium oxide, chromium oxides, chromium hydroxides, man-ganese oxides, cobalt oxides, nickel oxides, and zinc oxides. These oxides and hydroxides may be used alone or in any mixture thereof. Furthermore, composite oxides and composite hydroxides such as iron titanate, cobalt titanate, and cobalt aluminate can also be used in the present invention.
Composite materials comprising metal oxides or hydroxides coated on the core materials (e.g., titanium oxides coated mica, iron oxides coated nylon) can also be used in the present Invention.
Examples of the organic pigments capable of being modified with the silicone compounds of formula (SC1), SC(2), or (SC3) are C.I. 15850, C.I. 15850:1, C.I. 15585:1, C.I. 15630, C.I. 15880:1, C.I. 73360, C.I. 12085, C.I. 15865:2, C.I. 12075, C.I. 21110, C.I. 21095, and C.I. 11680, C.I. 74160 and zirconium, barium, or aluminum lakes of C.I. 45430, C.I. 45410, C.I. 45100, C.I. 17200, C.I. 45380, C.I. 45190, C.I. 14700, C.I. 15510, C.I. 19140, C.I. 15985, C.I. 45350, C.I. 47005, C.I. 42053, C.I. 42090.
C.I. means Colour Index as compiled by the by The Society of Dyers and Colourists and The American Association of Textile Chemists and Colourists.
The range of interesting organic pigments may additionally comprise monoazo, disazo, naphthol, dioxazone, azomethin, azocondensation, metal complex, nitro, perinone, quinoline, anthraquinone, benzimidozolone, isoindoline, isoindolinone, triarylmethane, quinacridone, hydroxyanthraquinone, aminoanthraquinone, anthrapyrimidine, indanthrone, flavanthrone, pyranthrone, anthantrone, isoviolanthrone, diketopyrrolopyrrole, carbazole, indigo or thiolndigo pigments.
Mixtures of the organic pigments may be used.
Examples of these pigments and also further pigments can be found in the monograph: W. Herbst, K. Hunger “Industrielle Organische Pigmente,” 2.sup.nd edition, 1995, VCH Verlagsgesellschaft.
Preferred pigments are mono- or disazo pigments, preferably mono- or diarylides, or metal complexes, preferably a copper phthalocyanine pigment, or naphthol pigments, preferably β-naphthol or α,β-oxynaphthoic acid (BONA) pigments, or quinacridones or indanthrones.
More preferably, the following organic pigments are used inventively:
Mono- or diarylide yellow pigments selected from C.I. Pigment Yellow 1, 2, 10, 12, 13, 14, 17, 61, 62, 63, 64, 65, 73, 74, 75, 83, 127, 168, 174, 176, 188 and 191; Monoarylide yellow pigments selected from C.I. Pigment Yellow 1, C.I. Pigment Yellow 2, C.I. Pigment Yellow 65, C.I. Pigment Yellow 73, C.I. Pigment Yellow 74 and C.I. Yellow 75; Diarylide yellow pigments selected from C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 17 and C.I. Pigment Yellow 83; Disazo orange pigments selected from C.I. Pigment Orange 16 and C.I. Pigment Orange 34; Naphthol red pigments selected from C.I. Pigment Red 48:1, C.I. Pigment Red 48:2, C.I. Pigment Red 48:3, C.I. Pigment Red 48:4, C.I. Pigment Red 48:5, C.I. Pigment Red 49:1, C.I. Pigment Red 52:1, C.I. Pigment Red 52:2, C.I. Pigment Red 52:3, C.1 Pigment Red 53:1, C.I. Pigment Red 53:2, C.I. Pigment Red 53:3, C.I. Pigment Red 57:1, C.I. Pigment Red 57:2, C.I. Pigment Red 58:2, C.I. Pigment Red 58:4, C.I. Pigment Red 63:1 and C.I. Pigment Red 64:1; Quinacridone red pigments such as C.I. Pigment Red 202; Blue or green copper phthalocyanine pigments selected from C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Green 7 and C.I. Pigment Green 36; Blue indanthrone pigments such as C.I. Pigment Blue 60.
The surfaces of these organic pigments may be treated additionally with, for example, rosins.
Examples of pearlescent pigments (or nacreous pigments) are mica-titanium composite materials containing, as a titanium component, titanium dioxide, titanium lower oxides, titanium oxynitride, mica-iron oxide composite materials, bismuth oxychloride, and guanine. The mica-titanium composite materials may be mixed with colored pigments such as iron oxides, Prussian blue, chromium oxide, carbon black, and carmine. These pearlescent pigments may be used alone or in any mixture thereof.
The interference pigments are platelet particulates. The platelet particulates preferably have a thickness of no more than about 5 micrometers, more preferably no more than about 2 micrometers, still more preferably no more than about 1 micrometer. The platelet particulates preferably have a thickness of at least about 0.02 micrometers, more preferably at least about 0.05 micrometers, even more preferably at least about 0.1 micrometers, and still more preferably at least about 0.2 micrometers.
The particle size determines the opacity and luster. The particle size is determined by measuring the diameter thickness of the particulate material. The term “diameter” as used herein, means the largest distance across the major axis of the particulate material. Diameter can be determined by any suitable method known in the art, such as particle size analyzer Mastersizer 2000 manufactured by Malvern Instruments. The interference pigments preferably have an average diameter not greater than about 200 micrometers, more preferably not greater than 150 micrometers. The interference pigments preferably have a diameter of at least about 0.1 micrometer, more preferably at least about 1.0 micrometer, even more preferably at least about 2.0 micrometer, and still more preferably at least about 5.0 micrometer.
The interference pigments comprise a multilayer structure. The center of the particulates is a flat substrate with a refractive index (RI) normally below 1.8. A wide variety of particle substrates are useful herein. Nonlimiting examples are natural mica, synthetic mica, graphite, talc, kaolin, alumina flake, bismuth oxychloride, silica flake, glass flake, ceramics, titanium dioxide, CaSO 4 , CaCO 3 , BaSO 4 , borosilicate and mixtures thereof, preferably mica, silica and alumina flakes.
A layer of thin film or a multiple layer of thin films are coated on the surface of a substrate described above. The thin films are made of highly refractive materials. The refractive index of these materials is normally above 1.8.
A wide variety of thin films are useful herein. Nonlimiting examples are TiO 2 , Fe 2 O 3 , SnO 2 , Cr 2 O 3 , ZnO, ZnS, SnO, ZrO 2 , CaF 2 , Al 2 O 3 , BiOCl, and mixtures thereof or in the form of separate layers, preferably TiO 2 , Fe 2 O 3 , Cr 2 O 3 and SnO 2 .
For the multiple layer structures, the thin films can be consisted of all high refractive index materials or alternation of thin films with high and low RI materials with the high RI film as the top layer.
The interference pigment color is a function of the thickness of thin film, the thickness for a specific color may be different for different materials. For TiO 2 , a layer of 40 nm to 60 nm or a whole number multiple thereof gives silver color, 60 nm to 80 nm yellow color, 80 nm to 100 nm red color, 100 nm to 130 nm blue color, 130 nm to 160 nm green color. In addition to the interference color, other transparent absorption pigments can be precipitated on top of or simultaneously with the TiO 2 layer. Common materials are red or black iron oxide, ferric ferrocyanide, chromium oxide or carmine. It is found that the color of the interference pigment in addition to its brightness has a significant influence on human perception of skin tone. In general, preferred colors are silver, gold, red, green and mixtures thereof.
Nonlimiting examples of the interference pigments useful herein include those supplied by Persperse, Inc. under the trade name PRESTIGE®, FLONAC®; supplied by EMD Chemicals, Inc. under the trade name TIMIRON®, COLORONA®, DICHRONA® and XIRONA®; supplied by Engelhard Co. under the trade name FLAMENCO®, TIMICA®, DUOCHROME®; and supplied by Ciba under the trade name CALISHA®.
The particulate organic UV-filter (b 1 ) is preferably selected from benztriazoles of formula
wherein
R 1 and R 2 independently from each other are C 1 -C 18 alkyl which may be substituted by one or more radicals selected from C 1 -C 4 alkyl, C 5 -C 12 cycloalkyl and C 6 -C 10 aryl.
More preferably the particulate organic UV-filters (b 1 ) is Methylene Bis-Benzotriazolyl Tetramethylbutylphenol and corresponds to formula
Preferably the organic UV-filter (b 1 ) is also selected from the triazine derivatives of formula
wherein
R 3 and R 4 independently from each other are hydrogen; C 1 -C 18 alkyl; or C 6 -C 12 aryl; R 5 , R 6 and R 7 independently from each other are hydrogen; hydroxy; halogen; C 1 -C 18 alkyl; C 1 -C 8 alkoxy; C 6 -C 12 aryl; biphenylyl; C 6 -C 12 aryloxy; C 1 -C 18 alkylthio; carboxy; —COOM; C 1 -C 18 -alkylcarboxyl; aminocarbonyl; mono- or di-C 1 -C 18 alkylamino; C 1 -C 10 acylamino; or —COOH; and M is an alkali metal ion.
More preferably, in formula (3) R 3 and R 4 is hydrogen; and
R 5 and R 6 are hydrogen; and R 7 is hydrogen; phenyl; or biphenylyl.
Most preferably the organic UV-filter (b 1 ) corresponds to the formula
In a preferred embodiment of the present inveniton, component (b 1 ) represents a mixture of the compounds of formula (2) and (4).
In another preferred embodiment of the present inveniton the particulate organic UV-filter (b 1 ) is selected from the benzophenone derivatives of formula
wherein
R 8 and R 9 independently from each other are C 1 -C 20 alkyl; C 2 -C 20 alkenyl; C 3 -C 10 cycloalkyl; C 3 -C 10 cycloalkenyl; or R 8 and R 9 together with the linking nitrogen atom form a 5- or 6-membered heterocyclic ring; R 10 is an alkylene-, cycloalkylene, alkenylene or phenylene radical which is optionally substituted by a carbonyl- or carboxy group; a radical of formula *—CH 2 —C≡C—CH 2 *; or R 10 together with A forms a bivalent radical of the formula (1a)
wherein
n 2 is a number from 1 to 3.
Most preferably the particulate organic UV-filter (b 1 ) corresponds to formula
The particulate organic UV filters (b 1 ) according to the present invention, preferably the UV filters of formulas (2), (4) and (6) can be mixed together directly with the particulates (a) and provided as trade products.
In a preferred embodiment the particulate organic UV filters (b 1 ) according to the present invention, preferably the UV filters of formulas (2), (4) and (6) can be co-micronized directly with the particulates (a).
Preferably the soluble organic UV-filter (b 2 ) is selected from triazine derivatives of formula
wherein
R 12 and R 13 , independently of one another, are C 1 -C 18 alkyl; or C 2 -C 18 alkenyl; A l is a radical of the formula
R 14 is hydrogen; C 1 -C 10 alkyl, —(CH 2 CHR 5 —O) n 1 —R 15 ; or a radical of the formula —CH 2 —CH(—OH)—CH 2 —O-T 1 ;
R 15 is hydrogen; M; C 1 -C 5 alkyl; or a radical of the formula —(CH 2 ) m 2 —O-T 1 ;
T 1 is hydrogen; or C 1 -C 8 alkyl;
Q1 C 1 -C18alkyl;
M is a metal cation;
m 2 is 1 to 4; and
n 1 is 1-16.
Most preferably the soluble organic UV-filter (b 2 ) corresponds to formula
In another preferred embodiment of the present invention (b 2 ) is a dibenzoylmethane derivative, more preferably butyl methoxydibenzoylmethane (Avobenzone).
In another preferred embodiment of the present invention (b 2 ) is a 2-hydroxy benzophenone derivative of formula
wherein
R 16 and R 17 independently from each other are hydrogen, C 1 -C 20 alkyl; C 2 -C 10 alkenyl; C 3 -C 10 cyclalkyl; or C 3 -C 10 cycloalkenyl; R 18 and R 19 independently from each other are C 1 -C 20 alkyl; C 2 -C 10 alkenyl; C 3 -C 10 cycloalkenyl; C 1 -C 12 alkoxy; C 1 -C 20 alkoxycarbonyl; C 1 -C 12 alkylamino; di(C 1 -C 12 )alkylamino; aryl or heteroaryl radical which are optionally substituted; or a water-solubilizing substitutent selected from a carboxylate group, a sulphonate group or an ammonium residue; X is hydrogen; COR 19 ; or COOR 19 ; or CONR 19 R 20 ; R 19 , and R 20 independently from each other are hydrogen; C 1 -C 20 alkyl; C 2 -C 10 alkenyl; C 3 -C 10 cycloalkenyl; a —(Y—O)—Z-group; or aryl; Y is *—(CH 2 ) 2 —*; *—(CH 2 ) 3 —*; *—(CH 2 ) 4 —*; or *—(CH)—(CH 3 )—CH 2 —*; Z is *—CH 2 —CH 3 ; *—CH 2 —CH 2 —CH 3 ; *—CH 2 —CH 2 —CH 2 —CH 3 ; or *—CH(CH 3 )—CH 3 ; m is a number from 0 to 3; n is a number from 0 to 3; and o is 1; or 2.
Most preferably the soluble organic UV-filter (b 2 ) is Diethylamino Hydroxybenzoyl Hexyl Benzoate [CAS Regno. 302776-68-7].
In another preferred embodiment of the present invention the soluble organic UV-filter (b 2 ) is a merocyanine derivative of formula
wherein
R 21 and R 22 are each independently of the other hydrogen; C 1 -C 22 alkyl; cyclo-C 3 -C 8 alkyl; or unsubstituted or C 1 -C 6 alkyl- or C 1 -C 6 alkoxy-substituted C 6 -C 20 aryl; or R 21 and R 22 together with the nitrogen atom linking them form a —(CH 2 ) m — ring which is uninterrupted or interrupted by —O— or by —NH—; R 23 is a cyano group; —COOR 25 ; —CONHR 25 ; —COR 25 ; or —SO 2 R 25 ; or —CONR 25 R 26 ; R 24 is a cyano group; —COOR 27 ; —CONHR 27 ; —COR 27 ; or —SO 2 R 27 ; or —CONR 26 R 28 ; R 25 , R 26 , R 27 and R 28 are each independently of the other C 1 -C 22 alkyl; cyclo-C 3 -C 8 alkyl; or unsubstituted or C 1 -C 6 alkyl-substituted C 6 -C 20 aryl; or R 21 and R 22 , R 23 and R 24 , R 25 and R 26 or R 27 and R 28 together form a 5- to 7-membered, monocyclic, carbocyclic or heterocyclic ring; Z 1 and Z 2 are each independently of the other a —(CH 2 ) l — group which is uninterrupted or interrupted by —O—, —S—, or by —NR 29 —, and/or is unsubstituted or substituted by C 1 -C 6 alkyl; R 29 is C 1 -C 5 alkyl; l is a number from 1 to 4; m is a number from 1 to 7; n is from 1 to 4; when n=2, R 21 , R 23 or R 24 is a bivalent alkyl group; or R 23 and R 24 together with the 2 nitrogen atoms linking them form a —(CH 2 ) m — ring; when n=3, R 21 , R 23 or R 24 is a trivalent alkyl group; when n=4, R 21 , R 23 or R 24 is a tetravalent alkyl group.
Most preferably the soluble organic UV-filter (b 2 ) is a merocyanine derivative of formula
In a preferred embodiment of the present invention (b) represents a mixture selected from (mix 1 ) the compounds of formulae (2), (4) (8) and butyl methoxydibenzoylmethane;
(mix 2 ) the compounds of formulae (2), (4), (6) and butyl methoxydibenzoylmethane; (mix 3 ) the compounds of formulae (8), (12) and butyl methoxydibenzoylmethane; (mix 4 ) the compounds of formulae (2), (4), (6), (8), (11), (12) and butyl methoxydibenzoylmethane; (mix 4 ) the compounds of formulae (2), (4) and (6); (mix 5 ) the compounds of formulae (2), (4), (6) and (8).
More preferably, (b) represents a mixture of at least one particulate organic UV filter (b 1 ) and at least one soluble organic UV filter (b 2 ).
In a most preferred embodiment of the present invention the cosmetic formulation comprises
(a) particulates selected from interference-pigments based on mica and coated with iron oxide; and (b) a mixture of particulate organic UV filters selected from triazine and benzotriazole derivatives.
Most preferably the particulate UV filters (b) is a mixture of the compound of formula (2) and (4).
The cosmetic formulation according to the present invention preferably comprises
0.01 to 10% b.w of particulates (a); and
0.1 to 40% b.w of UV filters (b).
Preferred is a formulation which is free of soluble organic UV filters (b 2 ) and other soluble UV filters.
The particulate organic UV-filters (b 1 ) according to the present invention are present in the micronized state. They may be prepared by any known process suitable for the preparation of microparticles, for example:wet-milling, wet-kneading, spray-drying from a suitable solvent, by expansion according to the RESS process (Rapid Expansion of Supercritical Solutions) of supercritical fluids (e.g. CO 2 , by reprecipitation from suitable solvents, including supercritical fluids (GASR process=Gas Anti-Solvent Recrystallisation/PCA process=Precipitation with Compressed Anti-solvents).
As milling apparatus for the preparation of the sparingly soluble micronised organic compounds there may be used, for example, a jet mill, ball mill, vibratory mill or hammer mill, preferably a high-speed mixing mill. Even more preferable mills are modern ball mills; manufacturers of these types of mill are, for example, Netzsch (LMZ mill), Drais (DCP-Viscoflow or Cosmo), Bühler AG (centrifugal mills) or Bachhofer.
Examples of kneading apparatus for the preparation of the micronised organic UV absorbers are typical sigma-blade batch kneaders but also serial batch kneaders (IKA-Werke) or continuous kneaders (Continua from Werner and Pfleiderer).
The grinding of organic compounds used in the present invention is preferably carried out with a grinding aid.
Preferably, a dispersing agent is used as a low molecular weight grinding aid for all the above micronisation processes.
Preferred useful grinding aids for an aqueous dispersion are anionic surfactants with a HLB (Hydrophile-Lipophile Balance) value higher than 8, more preferably higher than 10.
Any conventionally usable anionic, non-ionic or amphoteric surfactants can be used as dispersing agents (component (b)). Such surfactant systems may comprise for example: carboxylic acids and their salts: alkaline soap of sodium, potassium and ammonium, metallic soap of calcium or magnesium, organic basis soap such as Lauric, myristic, palmitic, stearic and oleic acid etc., alkyl phosphates or phosphoric acid esters, acid phosphate, diethanolamine phosphate, potassium cetyl phosphate, ethoxylated carboxylic acids or polyethylene-glycol esters, PEG-n acrylates, fatty alcohol polyglycolether such as laureth-n, myreth-n, ceteareth-n, steareth-n, oleth-n, fatty acid polyglycolether such as PEG-n stearate, PEG-n oleate, PEG-n cocoate, monoglycerides and polyol esters, C12-C22 fatty acid mono- and di-esters of addition products of from 1 to 100 mol of ethylene oxide with polyols,fatty acid and polyglycerol ester such as monostearate glycerol, diisostearoyl polyglyceryl-3-diisostearates, polyglyceryl-3-diisostearates, triglyceryl diisostearates, polyglyceryl-2-sesquiisostearates or polyglyceryl dimerates. mixtures of compounds from a plurality of those substance classes are also suitable, fatty acid polyglycolesters such as monostearate diethylene glycol, fatty acid and polyethylene glycol esters, fatty acid and saccharose esters such as sucro esters, glycerol and saccharose esters such as sucro glycerides. Sorbitol and sorbitan, sorbitan mono- and di-esters of saturated and unsaturated fatty acids having from 6 to 22 carbon atoms and ethylene oxide addition products, polysorbate-n series, sorbitan esters such as sesquiisostearate, sorbitan, PEG-(6)-isostearate sorbitan, PEG-(10)-sorbitan laurate, PEG-17-dioleate sorbitan, glucose derivatives, C8-C22 alkyl-mono and oligo-glycosides and ethoxylated analogues with glucose being preferred as the sugar component, O/W emulsifiers such as methyl gluceth-20 sesquistearate, sorbitan stearate/sucrose cocoate, methyl glucose sesquistearate, cetearyl alcohol/cetearyl glucoside, W/O emulsifiers such as methyl glucose dioleate/methyl glucose isostearate. Sulfates and sulfonated derivatives, dialkylsulfosuccinates, dioctyl succinate, alkyl lauryl sulfonate, linear sulfonated parafins, sulfonated tetraproplyne sulfonate, sodium lauryl sulfates, amonium and ethanolamine lauryl sulfates, lauryl ether sulfates, sodium laureth sulfates [Texapon N70] or sodium myreth sulfates [Texapon K14S], sulfosuccinates, aceyl isothionates, alkanolamide sulfates, taurines, methyl taurines, imidazole sulfates, zwitterionic or amphoteric surfactants that carry at least one quaternary ammonium group and at least one carboxylate and/or sulfonate group in the molecule, zwitterionic surfactants that are especially suitable are betaines, such as N-alkyl-N,N-dimethylammonium glycinates, cocoalkyldimethylammonium glycinate, N-acylamino-propyl-N,N-dimethylammonium glycinates, cocoacylaminopropyldimethylammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethylcarboxymethylglycinate, N-alkylbetaine, N-alkylaminobetaines.
Examples of suitable mild surfactants as dispersing agents, that is to say surfactants especially well tolerated by the skin, include fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and/or di-alkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, a-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines and/or protein fatty acid condensation products, the latter preferably being based on wheat proteins.
Non ionic surfactants such as PEG-6 beeswax (and) PEG-6 stearate (and) polyglyceryl—2-isostearate [Apifac], glyceryl stearate (and) PEG-100 stearate. [Arlacel 165], PEG-5 glyceryl stearate [arlatone 983 S], sorbitan oleate (and) polyglyceryl-3 ricinoleate.[Arlacel 1689], sorbitan stearate and sucrose cocoate [arlatone 2121], glyceryl stearate and laureth-23 [Cerasynth 945], cetearyl alcohol and ceteth-20 [Cetomacrogol Wax], cetearyl alcohol and colysorbate 60 and PEG-150 and stearate-20[Polawax GP 200, Polawax NF], cetearyl alcohol and cetearyl polyglucoside [Emulgade PL 1618], cetearyl alcohol and ceteareth-20 [Emulgade 1000NI, Cosmowax], cetearyl alcohol and PEG-40 castor oil [Emulgade F Special], cetearyl alcohol and PEG-40 castor oil and sodium cetearyl sulfate [Emulgade F], stearyl alcohol and steareth-7 and steareth-10 [Emulgator E 2155], cetearyl alcohol and szeareth-7 and steareth-10 [Emulsifying wax U.S.N.F], glyceryl stearate and PEG-75 stearate [Gelot 64], propylene glycol ceteth-3 acetate .[Hetester PCS], propylene glycol isoceth-3 acetate [Hetester PHA], cetearyl alcohol and ceteth-12 and oleth-12 [Lanbritol Wax N 21], PEG-6 stearate and PEG-32 stearate [Tefose 1500], PEG-6 stearate and ceteth-20 and steareth-20 [Tefose 2000], PEG-6 stearate and ceteth-20 and glyceryl stearate and steareth-20 [Tefose 2561], glyceryl stearate and ceteareth-20 [Teginacid H, C, X].
Anionic emulsifiers such as PEG-2 stearate SE, glyceryl stearate SE [Monelgine, Cutina KD], propylene glycol stearate [Tegin P], cetearyl Alcohol and Sodium cetearyl sulfate [Lanette N, Cutina LE, Crodacol GP], cetearyl alcohol and sodium lauryl sulfate [Lanette W], trilaneth-4 phopshate and glycol stearate and PEG-2 stearate [Sedefos 75], glyceryl stearate and sodium lauryl Sulfate [Teginacid Special]. Cationic acid bases such as cetearyl alcohol and cetrimonium bromide.
Most preferred dispersing agents are sodium alkyl sulfates or sodium alkyl ether sulfates, such as sodium laureth sulfate [Texapon N70 from Cognis] or sodium myreth sulfate [Texapon K14 S from Cognis].
Useful solvents are water, brine, (poly-)ethylene glycol, glycerol or cosmetically acceptable oils. Other useful solvents are disclosed below in the sections entitled “Esters of fatty acids”, “Natural and synthetic triglycerides, including glyceryl esters and derivatives”, “Pearlescent waxes”, “Hydrocarbon oils” and “Silicones or siloxanes”.
The micronised particulate organic compounds so obtained usually have an average particle size from 0.02 to 2 micrometres, preferably from 0.03 to 1.5 micrometres and more especially from 0.05 to 1.0 micrometres.
The aqueous dispersion comprising a micronized UV absorber used in the present invention generally comprises
30-60, preferably 35 to 55 parts of the sparingly soluble organic micronized substance;
2-20, preferably 3 to 10 parts of the dispersing agent;
0.1-1 part, preferably 0.1 to 0.5 parts of a thickening agent (for example xanthan gum); and
20-67.9 parts of water;
The cosmetic formulations or pharmaceutical compositions according to the present invention can also comprise one or more than one further UV filter which are different from the particulate organic UV-filters (b 1 ); and the soluble organic UV filters (b 2 ) as listed in Table 1:
TABLE 2
Suitable UV filter substances and adjuvants which can be additionally used with the
UV absorbers according to the present invention
No.
Chemical Name
CAS No.
1
(+/−)-1,7,7-trimethyl-3-[(4-methylphenyl)methylene]bicyclo-
36861-47-9
[2.2.1]heptan-2-one; p-methyl benzylidene camphor
2
1,7,7-trimethyl-3-(phenylmethylene)bicyclo[2.2.1]heptan-2-one;
15087-24-8
benzylidene camphor
3
(2-Hydroxy-4-methoxyphenyl)(4-methylphenyl)methanone
1641-17-4
4
2,4-dihydroxybenzophenone
131-56-6
5
2,2′,4,4′-tetrahydroxybenzophenone
131-55-5
6
2-Hydroxy-4-methoxy benzophenone;
131-57-7
7
2-Hydroxy-4-methoxy benzophenone-5-sulfonic acid
4065-45-6
8
2,2′-dihydroxy-4,4′-dimethoxybenzophenone
131-54-4
9
2,2′-Dihydroxy-4-methoxybenzophenone
131-53-3
10
Alpha-(2-oxoborn-3-ylidene)toluene-4-sulphonic acid and its salts
56039-58-8
(Mexoryl SL)
12
Methyl N,N,N-trimethyl-4-[(4,7,7-trimethyl-3-oxobicyclo[2,2,1]hept-2-
52793-97-2
ylidene)methyl]anilinium sulphate (Mexoryl SO)
22
3,3,5-Trimethyl cyclohexyl-2-hydroxy benzoate; homosalate
118-56-9
23
Isopentyl p-methoxycinnamate; isoamyl methoxy cinnamate
71617-10-2
27
Menthyl-o-aminobenzoate
134-09-8
28
Menthyl salicylate
89-46-3
29
2-Ethylhexyl 2-cyano,3,3-diphenylacrylate; Octocrylene
6197-30-4
30
2-ethylhexyl 4-(dimethylamino)benzoate
21245-02-3
31
2-ethylhexyl 4-methoxycinnamate; Octyl Methoxy Cinnamate
5466-77-3
32
2-ethylhexyl salicylate
118-60-5
34
4-aminobenzoic acid
150-13-0
35
Benzoic acid, 4-amino-, ethyl ester, polymer with oxirane
113010-52-9
38
2-phenyl-1H-benzimidazole-5-sulphonic acid;
27503-81-7
phenylbenzimidazolsulfonic acid
39
2-Propenamide, N-[[4-[(4,7,7-trimethyl-3-oxobicyclo[2.2.1]hept-2-
147897-12-9
ylidene)methyl]phenyl]methyl]-, homopolymer
40
Triethanolamine salicylate
2174-16-5
41
3,3′-(1,4-phenylenedimethylene)bis[7,7-dimethyl-2-oxo-
90457-82-2
bicyclo[2.2.1]heptane-1 methanesulfonic acid] (Cibafast H)
42
Titanium dioxide (primary particle size 10-50 nm); for example
13463-67-7
T805 or Eusolex T-AVO, Eusolex T-2000, Titaniumdioxid VT 817
44
Zinc oxide (primary particle size 20-100 nm); for example Zinc oxide
1314-13-2
NDM, Zinc oxide Z-Cote HP1, Nanox Zinc oxide
47
1H-Benzimidazole-4,6-disulfonic acid, 2,2′-(1,4-phenylene)bis-, di-
180898-37-7
sodium salt
48
Benzoic acid, 4,4′-[[6-[[4-[[(1,1-dimethylethyl)amino]carbonyl]-
154702-15-5
phenyl]amino]1,3,5-triazine-2,4-diyl]diimino]bis-, bis(2-ethylhexyl)-
ester; diethylhexyl butamido triazone (Uvasorb HEB)
49
Phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-
155633-54-8
tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]-; drometrizole
trisiloxane (Mexoryl XL)
50
Dimethicodiethylbenzalmalonate; Polysilicone 15 (Parsol SLX)
207574-74-1
51
Benzenesulfonic acid, 3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-
92484-48-5
methylpropyl)-, monosodium salt (Tinogard HS)
53
1-Dodecanaminium, N-[3-[[4-(dimethylamino)benzoyl]amino]propyl]-
156679-41-3
N,N-dimethyl-, salt with 4-methylbenzenesulfonic acid (1:1) (Escalol
HP610)
54
1-Propanaminium, N,N,N-trimethyl-3-[(1-oxo-3-phenyl-2-propenyl)-
177190-98-6
amino]-, chloride
55
1H-Benzimidazole-4,6-disulfonic acid, 2,2′-(1,4-phenylene)bis-
170864-82-1
56
1,3,5-Triazine, 2,4,6-tris(4-methoxyphenyl)-
7753-12-0
57
1,3,5-Triazine, 2,4,6-tris[4-[(2-ethylhexyl)oxy]phenyl]-
208114-14-1
58
1-Propanaminium, 3-[[3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethyl-
340964-15-0
ethyl)-4-hydroxyphenyl]-1-oxopropyl]amino]-N,N-diethyl-N-methyl-,
methyl sulfate (salt)
59
2-Propenoic acid, 3-(1H-imidazol-4-yl)-
104-98-3
60
Benzoic acid, 2-hydroxy-, [4-(1-methylethyl)phenyl]methyl ester
94134-93-7
61
1,2,3-Propanetriol, 1-(4-aminobenzoate) (Glyceryl PABA)
136-44-7
62
Benzeneacetic acid, 3,4-dimethoxy-a-oxo-
4732-70-1
63
2-Propenoic acid, 2-cyano-3,3-diphenyl-, ethyl ester
5232-99-5
64
Anthralinic acid, p-menth-3-yl ester
134-09-8
65
2,2′-bis(1,4-phenylene)-1H-benzimidazole-4,6-disulphonic acid mono
349580-12-7
sodium salt or Disodium phenyl dibenzimidazole tetrasulfonate
(Neo Heliopan AP)
69
sterols (cholesterol, lanosterol, phytosterols), as described in
WO0341675
70
mycosporines and/or mycosporine-like amino acids as described in
WO2002039974, e.g. Helioguard 365 from Milbelle AG, isolated
mycosporine like amino acids from the red alga porphyra umbilicalis
(INCI: Porphyra Umbilicalis ) that are encapsulated into liposomes,)
71
alpha-lipoic-acid as described in DE 10229995
72
synthetic organic polymers as described in EP 1 371 358,
[0033]-[0041]
73
phyllosilicates as described in EP 1371357 [0034]-[0037]
74
silica compounds as described in EP1371356, [0033]-[0041]
75
inorganic particles as described in DE10138496 [0043]-[0055]
76
latex particles as described in DE10138496 [0027]-[0040]
77
1H-Benzimidazole-4,6-disulfonic acid, 2,2′-(1,4-phenylene)bis-,
180898-37-7
disodium salt; Bisimidazylate (Neo Heliopan APC)
82
Di-2-ethylhexyl-3,5-dimethoxy-4-hydroxy-benzalmalonate (Oxynex
ST, EMD Chemicals, as described in US 20040247536)
83
T-LiteTM MAX: Titanium Dioxide (and) Dimethoxydiphenylsilane
(and) Triethoxycaprylylsilane Crosspolymer (and) Hydrated Silica
(and) Aluminum Hydroxyde
84
T-Lite SF: Titanium Dioxide (and) Aluminum Hydroxide (and)
Dimethicone/Methicone Copolymer
85
T-Lite SF-S: Titanium Dioxide (and) Hydrated Silica (and)
Dimethicone/Methicone Copolymer (and) Aluminum Hydroxide
86
Z-COTE ® MAX: Zinc Oxide (and) Diphenyl Capryl Methicone
87
Z-COTE HP1: Zinc Oxide (and) Triethoxycaprylylsilane
88
1,3,5-Triazine-2,4,6-triamine, N2,N4-bis[4-[5-(1,1-dimethylpropyl)-2-
288254-16-0
benzoxazolyl]phenyl]-N6-(2-ethylhexyl)-(Uvasorb K2A)
The cosmetic or pharmaceutical preparations can be prepared by physically mixing the UV absorber(s) with the adjuvant using customary methods, for example by simply stirring together the individual components, especially by making use of the dissolution properties of already known cosmetic UV absorbers, like octyl methoxy cinnamate, salicylic acid isooctyl ester, etc.
The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments. In addition to the above mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.
As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/W emulsions or microemulsions) the preparations contain, for example, from 0.1 to 30% by weight, preferably from 0.1 to 15% by weight and especially from 0.5 to 10% by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60% by weight, especially from 5 to 50% by weight and preferably from 10 to 35% by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30% by weight, especially from 1 to 30% by weight and preferably from 4 to 20% by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90% by weight, especially from 30 to 90% by weight, based on the total weight of the composition, of water, and from 0 to 88.9% by weight, especially from 1 to 50% by weight, of further cosmetically acceptable adjuvants.
The cosmetic or pharmaceutical compositions/preparations according to the invention may also contain one or one more additional compounds as like fatty alcohols, esters of fatty acids, natural or synthetic triglycerides including glyceryl esters and derivatives, pearlescent waxes, hydrocarbon oils, silicones or siloxanes (organosubstituted polysiloxanes), fluorinated or perfluorinated oils, emulsifiers, djuvants and additives, super-fatting agents, surfactants, consistency regulators/thickeners and rheology modifiers, polymers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, antioxidants, hydrotropic agents, preservatives, bacteria-inhibiting agents, perfume oils, colourants, polymeric beads or hollow spheres as SPF enhancers.
Cosmetic or Pharmaceutical Preparations
Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic preparations. There come into consideration, for example, especially the following preparations: skin-care preparations, bath preparations, cosmetic personal care preparations, foot-care preparations, light-protective preparations, skin-tanning preparations, depigmenting preparations, insect-repellents, deodorants, antiperspirants, preparations for cleansing and caring for blemished skin, hair-removal preparations in chemical form (depilation), shaving preparations, fragrance preparations, cosmetic hair-treatment preparations,
Presentation Forms
The final formulations listed may exist in a wide variety of presentation forms, for example:
in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W or PIT emulsion and all kinds of microemulsions, in the form of a gel, in the form of an oil, a cream, milk or lotion, in the form of a powder, a lacquer, a tablet or make-up, in the form of a stick, in the form of a spray (spray with propellent gas or pump-action spray) or an aerosol, in the form of a foam, or in the form of a paste.
Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams. Of particular interest are sun protection creams, sun protection lotions, sun protection milk and sun protection preparations in the form of a spray.
Of special importance as cosmetic preparations for the hair are the above-mentioned preparations for hair treatment, especially hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-straightening preparations, liquid hair-setting preparations, hair foams and hairsprays. Of special interest are hair-washing preparations in the form of shampoos.
Other typical ingredients in such formulations are preservatives, bactericides and bacteriostatic agents, perfumes, dyes, pigments, thickening agents, moisturizing agents, humectants, fats, oils, waxes or other typical ingredients of cosmetic and personal care formulations such as alcohols, poly-alcohols, polymers, electrolytes, organic solvents, silicon derivatives, emollients, emulsifiers or emulsifying surfactants, surfactants, dispersing agents, antioxidants, anti-irritants and anti-inflammatory agents etc.
Preferably the particulates (a) are used which can easily be removed from textiles in customary laundering processes.
Other embodiments of the present invention are the use of the cosmetic formulation according to the present invention
for minimizing and/or masking the whitening effect and/or the particular color of a sunscreen composition; for the visualization of a consistent application of a sunscreen formulation; for the protection against electromagnetic radiation in the range >380 nm; for adjusting a natural skin-like color tone of the sunscreen formulation; for promoting an even skin tone; and for minimising fine lines and wrinkles.
The composition is used for preventing the damaging effect of UVA and blue light and provides an optimal protection against UVA-induced photoaging of human skin also in conjunction with excessive exposure to longer wave-length light and IR The cosmetic compositions according to the present invention may also be used for preventing and treating undesired skin pigmentation; preventing and treating photoaging of human skin; inhibiting the degradation or condensations of endogenous vitamins, antioxidants and cellular modulators such as carotenoids, flavonoids or unsaturated lipids present in the skin; treating skin disorders caused by sunlight such as pigment spots, actinic keratosis and actinic dermatitis and solar urticaria; protecting against UVA1-induced expression of matrix-degrading enzymes such as metallo-proteinases or elastases, e.g. metallo-proteinase-1 or neutrophil elastase or of cytokines such as interleukin-1 or interleukin-6; preventing the generation of reactive oxygen species such as by photosensitizing molecules, via UV-induced inflammatory reactions or via impaiment of mitochondria function; protecting UV-A-sensitive pharmaceuticals and cosmetics.
The compositions according to the present invention may constitute a skin care product, in particular for the face, neck, contours of the eye or the body, or a skin makeup product such as a tinting product, an eye shadow, a blusher, an eyeliner, a concealer, a body makeup product, a daily care product, a sun protection product or a skin cleansing product.
The cosmetic preparation according to the invention is distinguished by excellent protection of human skin against the damaging effect of sunlight.
EXAMPLES
Preparation of Sunscreen Formulation
Examples 1, 2 and 4 show advantage over Examples 3 and 5 which do not contain color pigments.
INCI
Ex. 1
Ex. 2
Ex. 3
Part A
Glyceryl Stearate (and) PEG 100 Stearate
2.00
2.00
2.00
Butylene Glycol Cocoate
5.00
5.00
5.00
Isopropyl Palmitate
4.00
4.00
4.00
Trioctanion
4.00
4.00
4.00
TiO 2 (and) Stearic Acid (and) Aluminium Hydroxide
3.20
3.20
3.20
Part B
Water
Tinoderm SGP (Ciba)
3.00
3.00
3.00
Disodium EDTA
0.20
0.20
0.20
Xanthan Gum
0.20
0.20
0.20
Potassium cetyl Phosphate
1.50
1.50
1.50
Part B2
Calisha Contemporary jet black (Iron oxide)
0.01
0.005
—
Calisha Contemporary medium red (iron oxide)
0.1
0.025
—
Calisha Contemporary yellow (iron oxide)
0.55
0.27
—
Part C
Phenyl Trimethicone
2.00
2.00
2.00
Cyclomethicone
4.00
4.00
4.00
Dimethicone (and) Dimethicone/Vinyl Dimethicone
3.00
3.00
3.00
Crosspolymer
Part D
Mica (and) Titanium Dioxide (and) Red iron oxide (and) Cetyl
0.30
Dimethicone
Micronized Methylene Bis-Benzotriazolyl Tetra-
4.00
5.00
3.00
methylbutylphenol
Micronized 1,3,5-Triazine, 2,4,6-tris([1,1′-biphenyl]-4-yl)-(CAS
5.00
5.00
5.00
Regn. 31274-51-8)
Phenoxyethanol (and) Methylparaben (and) Ethylparaben (and)
1.00
Butylparaben (and) Propylparaben Isobutylparaben
Tinoderm E
0.50
Water
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INCI
Ex. 4
Ex. 5
Phase A
Glyceryl Stearate (and) PEG 100 Stearate
5.00
5.00
Phenethyl Benzoate
6.00
6.00
Isopropyl Palmitate
5.00
5.00
Triheptanoin
3.00
3.00
Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine
2.00
2.00
Ethylhexyl Triazone
1.50
1.50
Phase B
Water
Butylene Glycol
2.00
2.00
Sodium EDTA
0.20
0.20
Phase B2
Calisha Contemporary jet black (Iron oxide)
0.01
Calisha Contemporary medium red (iron oxide)
0.08
Calisha Contemporary yellow (iron oxide)
0.55
Phase C
Sodium Acrylates Copolymer (and) Mineral Oil (and) PPG-1
1.20
1.20
Trideceth-6
Phase D
Cyclomethicone
3.00
3.00
Cyclomethicone
4.00
4.00
Phase E
Methylene Bis-Benzotriazolyl Tetramethylbutylphenol
14.00
14.00
Methylparaben (and) Ethylparaben (and) Butylparaben
1.00
1.00
(and) Propylparaben
Water
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Manufacturing Process:
Heat up part A and B to 75° C.
Add Amphisol K into B and stirr for 5 more minutes, then Add part B2.
Add part A into part B, then homogenize with an Ultra Turrax for 1 min pos 21200 g
Add part C by 60° C., and turrax again
Add part D below 50° C.
B. Application Examples
Example B1: O/W Emulsion (1)
Part
INCI
A
B
C
A
Glyceryl Stearate (and) PEG 100 Stearate
2.00
2.00
2.00
Butylene Glycol Cocoate
5.00
5.00
5.00
Isopropyl Palmitate
4.00
4.00
4.00
Triethylhexanoin
4.00
4.00
4.00
TIO2 (and) Stearic Acid (and) Aluminum Hydroxide
3.20
3.20
3.20
B
Pentylene Glycol (and) Sclerotium Gum
3.00
3.00
3.00
Disodium EDTA
0.20
0.20
0.20
Xanthan Gum
0.20
0.24
0.24
Potassium cetyl Phosphate
1.50
1.50
1.50
B 2
Iron Oxides (CALISHA Contemprorary Jet Black Oxide)
0.01
0.005
0.005
Iron Oxides (CALISHA Contemporary Medium Red
0.10
0.025
0.025
Oxide)
Iron Oxides (CALISHA Contemporary Yellow Oxide)
0.55
0.27
0.27
C
Phenyl Trimethicone
2.00
2.00
2.00
Cyclomethicone
4.00
4.00
4.00
Dimethicone (and) Dimethicone/Vinyl Dimethicone
3.00
3.00
3.00
Crosspolymer
D
Micronized Methylene Bis-Benzotriazolyl Tetramethyl-
4.00
4.00
4.00
butylphenol
Micronized 1,3,5-Triazine, 2,4,6-tris([1,1′-biphenyl]-4-yl)-
5.00
5.00
5.00
(CAS Regn. 31274-51-8)
Micronized Methanone, 1,1′-(1,4-piperazinediyl)bis[1-[2-[4-
1.00
2.00
4.00
(diethylamino)-2-hydroxybenzoyl]phenyl]-
(CAS Regn. 919803-06-8)
Mica (and) Titanium Dioxide (and)Tin oxide
0.30
0.30
Phenoxyethanol (and) Methylparaben (and) Ethylparaben
1.00
1.00
1.00
(and) Butylparaben (and) Propylparaben (and)
Isobutylparaben
Aqua (and) Tocopheryl Acetate (and) Caprylic/Capric
0.50
Triglyceride (and) Polysorbate 80 (and) Lecithin
Water
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Example B2: O/W Emulsion (2)
INCI
A
B
C
D
E
F
Glyceryl Stearate (and) PEG 100 Stearate
5.00
5.00
5.00
5.00
5.00
5.00
Phenethyl Benzoate
6.00
6.00
6.00
6.00
6.00
6.00
Isopropyl Palmitate
5.00
5.00
5.00
5.00
5.00
5.00
Triethylhexanoin
3.00
3.00
3.00
3.00
3.00
3.00
Bis-Ethylhexyloxyphenol Methoxyphenyl
2.00
2.00
2.00
2.00
2.00
2.00
Triazine
Ethylhexyl Triazone
1.50
1.50
1.50
1.50
1.50
1.50
Butylene Glycol
2.00
2.00
2.00
2.00
2.00
2.00
Disodium EDTA
0.20
0.20
0.20
0.20
0.20
0.20
Iron Oxides (CALISHA Contemprorary Jet
0.01
0.02
0.01
0.01
0.01
0.01
Black Oxide)
Iron Oxides (CALISHA Contemporary
0.08
0.5
0.08
0.08
0.08
0.08
Medium Red Oxide)
Iron Oxides (CALISHA Contemporary Yellow
0.55
0.5
0.55
0.55
0.55
0.55
Oxide
Sodium Acrylates Copolymer (and) Mineral
1.20
1.20
1.20
1.20
1.20
1.20
Oil (and) PPG-1 Trideceth-6
Cyclomethicone
4.00
4.00
4.00
4.00
4.00
4.00
Micronized Methylene Bis-Benzotriazolyl
4.00
4.00
4.00
1.00
2.00
2.00
Tetramethylbutylphenol
Butyl Methoxydibenzoymethane
0.5
4.00
4.00
0.5
Ethylhexyl Methoxycinnamate
0.5
3.00
3.00
0.5
Octocrylene
0.5
4.00
4.00
0.5
Propanedinitrile, 2-[3-[bis(2-ethylhexyl)-
2.00
0.5
amino]-2-cyclohexen-1-ylidene]-(CAS Regn.
923271-36-7) or merocyanine derivative of
formula (14) or 1,3,5-Triazine-2,4,6-triamine,
N2,N4-bis[4-[5-(1,1-dimethylpropyl)-2-benzoxazolyl]phenyl]-
N6-(2-ethylhexyl)-(Uvasorb
K2A) (CAS Regn 288254-16-0)
Acetic acid, 2-cyano-2-[5,5-dimethyl-3-[(1-
2.00
1.00
0.5
methylpropyl)amino]-2-cyclohexen-1-ylidene]-,
2-ethylhexyl ester (CAS Regn. 923271-35-6)
Uvinul A plus (CAS Regn. 302776-68-7)
0.5
0.5
2.00
2.00
Micronized 1,3,5-Triazine, 2,4,6-tris([1,1′-
2.00
2.00
2.00
2.00
2.00
2.00
biphenyl]-4-yl)-(CAS Regn. 31274-51-8)
2,4-Pentadienoic acid, 5-(diethylamino)-2-
2.00
0.5
0.5
0.5
0.5
(phenylsulfonyl)-, octyl ester (CAS Regn.
98835-90-6)
Micronized Methanone, 1,1′-(1,4-piperazine-
2.00
2.00
2.00
2.00
2.00
diyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-
(CAS Regn. 919803-06-8)
Mica (and) Titanium Dioxide (and)Tin oxide
1.00
1.00
1.00
1.00
1.00
1.00
Phenoxyethanol (and) Methylparaben (and)
1.00
1.00
1.00
1.00
1.00
1.00
Ethylparaben (and) Butylparaben (and)
Propylparaben (and) Isobutylparaben
Water
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100
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Example B3: O/W Emulsion (3)
INCI
A
B
C
D
E
F
Tribehenin PEG-20 esters
5.00
5.00
5.00
5.00
5.00
5.00
Stearyl Alcohol
0.50
0.50
0.50
0.50
0.50
0.50
Dibutyl Adipate
5.00
5.00
5.00
5.00
5.00
5.00
PPG-2 Myristyl Ether Propionate
5.00
5.00
5.00
5.00
5.00
5.00
Triheptanoin
3.00
3.00
3.00
3.00
3.00
3.00
Ethylhexyl Salicylate
5.00
5.00
5.00
5.00
5.00
5.00
Butyl Methoxydibenzoymethane
3.00
3.00
3.00
3.00
3.00
3.00
Bis-Ethylhexyloxyphenol Methoxyphenyl
3.00
3.00
3.00
3.00
3.00
3.00
Triazine
Ethylhexyl Triazone
3.00
3.00
3.00
3.00
3.00
3.00
Micronized Methylene Bis-Benzotriazolyl
2.00
2.00
2.00
2.00
2.00
2.00
Tetramethylbutylphenol
Butyl Methoxydibenzoymethane
4.00
0.5
0.5
0.5
Bis-Ethylhexyloxyphenol Methoxyphenyl
1.00
1.00
1.00
1.00
1.00
1.00
Triazine
Ethylhexyl Triazone
0.5
0.5
0.5
0.5
0.5
0.5
Ethylhexyl Methoxycinnamate
4.00
Octocrylene
4.00
0.5
0.5
0.5
Propanedinitrile, 2-[3-[bis(2-ethylhe-
2.00
0.5
1.0
xyl)amino]-2-cyclohexen-1-ylidene]-
(CAS Regn. 923271-36-7) or merocya-
nine derivative of formula (14) or 1,3,5-
Triazine-2,4,6-triamine, N2,N4-bis[4-[5-
(1,1-dimethylpropyl)-2-benzoxazolyl]-
phenyl]-N6-(2-ethylhexyl)- (Uvasorb
K2A) (CAS Regn 288254-16-0)
Acetic acid, 2-cyano-2-[5,5-dimethyl-3-
2.00
[(1-methylpropyl)amino]-2-cyclohexen-1-
ylidene]-, 2-ethylhexyl ester (CAS Regn.
923271-35-6)
Uvinul A plus (CAS Regn. 302776-68-7)
2.00
Micronized 1,3,5-Triazine, 2,4,6-tris-
2.00
5.00
2.00
2.00
2.00
4.00
([1,1′-biphenyl]-4-yl)- (CAS Regn.
31274-51-8)
2,4-Pentadienoic acid, 5-(diethylamino)-
2.00
2-(phenylsulfonyl)-, octyl ester (CAS
Regn. 98835-90-6)
Micronized Methanone, 1,1′-(1,4-pipe-
2.00
2.00
5.00
4.00
2.00
2.00
razinediyl)bis[1-[2-[4-(diethylamino)-2-
hydroxybenzoyl]phenyl]-
(CAS Regn. 919803-06-8)
Sodium Polyacrylate
0.60
0.60
0.60
0.60
0.60
Disodium EDTA
0.20
0.20
0.20
0.20
0.20
0.20
Xanthan Gum
0.50
0.50
0.50
0.50
0.50
Iron Oxides (CALISHA Contemprorary
0.020
0.020
0.020
0.020
0.020
0.020
Black Oxide)
Iron Oxides (CALISHA Contemporary
0.08
0.08
0.08
0.08
0.08
Salmon Red)
Iron Oxides (CALISHA Contemporary
0.55
0.55
0.55
0.55
0.55
Sun Yellow)
Cyclomethicone
5.00
5.00
5.00
5.00
5.00
5.00
Mica (and) Titanium Dioxide (and) Iron
0.50
0.50
0.50
0.50
0.50
0.50
Oxides (and) Cetyl Dimethicone
Mica (and) Titanium Dioxide (and) Cetyl
0.50
0.50
0.50
0.50
0.50
0.50
Dimethicone (and) Iron Oxides (and)
Carmine
Phenoxyethanol (and) Methylparaben
1.00
1.00
1.00
1.00
1.00
1.00
(and) Ethylparaben (and) Butylparaben
(and) Propylparaben (and) Isobutyl-
paraben
Water
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Example B4: W/O Emulsion (1)
INCI
A
B
C
D
E
Polyglyceryl-4 Isostearate (and) Cetyl PEG/PPG-
4.50
4.50
4.50
4.50
4.50
10/1 Dimethicone (and) Hexyl Laurate
Cetyl PEG/PPG-10/1 Dimethicone
2.20
2.20
2.20
2.20
2.20
Sorbitan Sesquioleate
1.00
1.00
1.00
1.00
1.00
Cera Alba
1.80
1.80
1.80
1.80
1.80
Hydrogenated Vegetable Oil
2.00
2.00
2.00
2.00
2.00
Phenethyl Benzoate
2.00
2.00
2.00
2.00
2.00
Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine
1.00
1.00
3.00
1.00
1.00
Ethylhexyl Methoxycinnamate
5.00
5.00
5.00
10.00
5.00
Titanium Dioxide (and) Silica (and) Dimethicone
5.00
5.00
5.00
5.00
5.00
Iron Oxides (and) Cetyl Dimethicone
0.13
0.13
0.13
0.13
0.13
Iron Oxides (and) Cetyl Dimethicone
0.60
0.60
0.60
0.60
0.60
Iron Oxides (and) Cetyl Dimethicone
0.20
0.20
0.20
0.20
0.20
Cyclomethicone (and) Disteardimonium Hectorite
5.00
5.00
5.00
5.00
5.00
(and) Propylene Carbonate
Cyclopentasiloxane
6.00
6.00
6.00
6.00
6.00
Ethyl Trisiloxane
8.00
8.00
8.00
8.00
8.00
Dimethicone
6.00
6.00
6.00
6.00
6.00
Cyclopentasiloxane (and) C30-45 Alkyl Cetearyl
1.00
1.00
1.00
1.00
1.00
Dimethicone Crosspolymer (and) PEG/PPG-20/23
Dimethicone
Water
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100
100
100
100
Sodium Chloride
1.00
1.00
1.00
1.00
1.00
Pentylene Glycol (and) Scerotium Gum
3.00
3.00
3.00
3.00
3.00
Aqua (and) Retinyl Palmitate (and) Capryic/Capric
3.00
3.00
3.00
3.00
3.00
Triglyceride (and) Polysorbate 80 (and) Lecithin
(and) Benzalkonium Chloride
Butylen Glycol
3.00
3.00
3.00
3.00
3.00
Phenoxyethanol (and) Methylparaben (and)
1.00
1.00
1.00
1.00
1.00
Ethylparaben (and) Butylparaben (and)
Propylparaben (and) Isobutylparaben
Aluminum Starch Octenylsuccinate
2.00
2.00
2.00
2.00
2.00
Talc
2.00
2.00
2.00
2.00
2.00
Silica
5.00
5.00
5.00
5.00
5.00
Mica (and) Iron Oxides (and) Cetyl Dimethicone
2.00
2.00
2.00
2.00
2.00
Mica (and) Titanium Dioxide (and) Iron Oxides (and)
1
0.5
Cetyl Dimethicone
Micronized Methylene Bis-Benzotriazolyl Tetra-
0.5
6.00
4.00
2.00
1.00
methylbutylphenol
Butyl Methoxydibenzoymethane
5.00
5.00
5.00
5.00
5.00
Ethylhexyl Triazone
0.60
0.60
0.60
0.60
0.60
Octocrylene
4.00
0.5
0.5
0.5
0.5
Propanedinitrile, 2-[3-[bis(2-ethylhexyl)amino]-2-
2.00
1.00
5.00
2.00
1.00
cyclohexen-1-ylidene]-(CAS Regn. 923271-36-7) or
merocyanine derivative of formula (14) or 1,3,5-
Triazine-2,4,6-triamine, N2,N4-bis[4-[5-(1,1-di-
methylpropyl)-2-benzoxazolyl]phenyl]-N6-(2-ethylhexyl)-
(Uvasorb K2A) (CAS Regn 288254-16-0)
Acetic acid, 2-cyano-2-[5,5-dimethyl-3-[(1-methyl-
6.00
6.00
6.00
6.00
6.00
propyl)amino]-2-cyclohexen-1-ylidene]-, 2-ethyl-
hexyl ester (CAS Regn. 923271-35-6)
Uvinul A plus (CAS Regn. 302776-68-7)
8.00
8.00
8.00
8.00
8.00
Micronized 1,3,5-Triazine, 2,4,6-tris([1,1′-biphenyl]-
6.00
6.00
6.00
6.00
6.00
4-yl)-(CAS Regn. 31274-51-8)
2,4-Pentadienoic acid, 5-(diethylamino)-2-(phenylsulfonyl)-,
1.00
1.00
1.00
1.00
1.00
octyl ester (CAS Regn. 98835-90-6)
Micronized Methanone, 1,1′-(1,4-piperazine-
1.00
3.00
2.00
4.00
0.5
diyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]-
phenyl]-(CAS Regn. 919803-06-8)
Example B5: W/O Emulsion (2)
INCI
A
B
C
D
E
PEG-30 Dipolyhydroxystearate
3.00
3.00
3.00
3.00
3.00
Butylen Glycol Cocoate
2.00
2.00
2.00
2.00
2.00
Isodecyl neopentanoate
4.00
4.00
4.00
4.00
4.00
Isopropyl Isosterate
3.00
3.00
3.00
3.00
3.00
Beeswax
1.00
1.00
1.00
1.00
1.00
Hydrogenated Castor Oil
0.80
0.80
0.80
0.80
0.80
Ethylhexyl Methoxycinnamate
5.00
5.00
5.00
5.00
5.00
Iron Oxides (and) Cetyl Dimethicone (Calisha
0.10
0.10
0.10
0.10
0.10
Contemporary Black Oxide OD)
Iron Oxides (and) Cetyl Dimethicone (Calisha
0.57
0.57
0.57
0.57
0.57
Contemporary Yellow Oxide OD)
Iron Oxides (and) Cetyl Dimethicone (Calisha
0.13
0.13
0.13
0.13
0.13
Contemporary Medium Red Oxide OD)
Caprylyl Methicone
2.50
2.50
2.50
2.50
2.50
Water
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100
100
100
100
Sodium Chloride
1.00
1.00
1.00
1.00
1.00
Pentylene Glycol (and) Scerotium Gum
3.00
3.00
3.00
3.00
3.00
Aqua (and) Retinyl Palmitate (and)
3.00
3.00
3.00
3.00
3.00
Caprylic/Capric Triglyceride (and) Polysorbate
80 (and) Lecithin (and) Benzalkonium Chloride
Butylen Glycol
5.00
5.00
5.00
5.00
5.00
Polysorbate 80
0.25
0.25
0.25
0.25
0.25
Caprylyl Methicone
5.50
5.50
5.50
5.50
5.50
Dimethicone
7.00
7.00
7.00
7.00
7.00
Micronized Methylene Bis-Benzotriazolyl Tetra-
3.00
6.00
3.00
6.00
2.00
methylbutylphenol
Phenoxyethanol (and) Methylparaben (and)
1.00
1.00
1.00
1.00
1.00
Ethylparaben (and) Butylparaben (and)
Propylparaben (and) Isobutylparaben
Silica
3.00
3.00
3.00
3.00
3.00
Nylon-12
6.00
6.00
6.00
6.00
6.00
Bis-Ethylhexyloxyphenol Methoxyphenyl
1.00
1.00
1.00
1.00
1.00
Triazine
Butyl Methoxydibenzoymethane
5.00
5.00
5.00
5.00
5.00
Bis-Ethylhexyloxyphenol Methoxyphenyl
0.13
0.13
0.13
0.13
0.13
Triazine
Ethylhexyl Triazone
0.60
0.60
0.60
0.60
0.60
Octocrylene
4.00
0.5
0.5
0.5
0.5
Propanedinitrile, 2-[3-[bis(2-ethylhexyl)amino]-2-
2.00
1.00
5.00
2.00
1.00
cyclohexen-1-ylidene]-(CAS Regn. 923271-36-
7) or merocyanine derivative of formula (14) or
1,3,5-Triazine-2,4,6-triamine, N2,N4-bis[4-[5-
(1,1-dimethylpropyl)-2-benzoxazolyl]phenyl]-N6-
(2-ethylhexyl)-(Uvasorb K2A) (CAS Regn
288254-16-0
Acetic acid, 2-cyano-2-[5,5-dimethyl-3-[(1-
6.00
6.00
6.00
6.00
6.00
methylpropyl)amino]-2-cyclohexen-1-ylidene]-,
2-ethylhexyl ester (CAS Regn. 923271-35-6)
Uvinul A plus (CAS Regn. 302776-68-7)
8.00
8.00
8.00
8.00
8.00
Micronized 1,3,5-Triazine, 2,4,6-tris([1,1′-
6.00
6.00
6.00
6.00
6.00
biphenyl]-4-yl)-(CAS Regn. 31274-51-8)
2,4-Pentadienoic acid, 5-(diethylamino)-2-
1.00
1.00
1.00
1.00
1.00
(phenylsulfonyl)-, octyl ester (CAS Regn. 98835-
90-6)
Micronized Methanone, 1,1′-(1,4-piperazine-
1.00
3.00
2.00
4.00
0.5
diyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-
(CAS Regn. 919803-06-8)
(Manganese modified) Titanium Dioxide
4.00
1.00
Diethylhexyl Syringylidene Malonate
2.00
1.00
3.00
4.00
0.5
Propanedioic acid, 2-[(4-hydroxy-3,5-dimethoxy-
1.00
1.00
5.00
phenyl)methyl]-, 1,3-bis(2-ethylhexyl) ester;
(CAS Regn. 872182-46-2)
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