CN1325293A - 身体护理品和家庭用品的稳定 - Google Patents
身体护理品和家庭用品的稳定 Download PDFInfo
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- CN1325293A CN1325293A CN99812992.5A CN99812992A CN1325293A CN 1325293 A CN1325293 A CN 1325293A CN 99812992 A CN99812992 A CN 99812992A CN 1325293 A CN1325293 A CN 1325293A
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- -1 dosing frost Substances 0.000 claims description 63
- 238000002360 preparation method Methods 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 25
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- 239000001257 hydrogen Substances 0.000 claims description 21
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- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- IBYFOBGPNPINBU-UHFFFAOYSA-N tetradecenoic acid Natural products CCCCCCCCCCCC=CC(O)=O IBYFOBGPNPINBU-UHFFFAOYSA-N 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 235000010487 tragacanth Nutrition 0.000 description 1
- 229940116362 tragacanth Drugs 0.000 description 1
- IBYFOBGPNPINBU-OUKQBFOZSA-N trans-2-tetradecenoic acid Chemical compound CCCCCCCCCCC\C=C\C(O)=O IBYFOBGPNPINBU-OUKQBFOZSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LKOVPWSSZFDYPG-WUKNDPDISA-N trans-octadec-2-enoic acid Chemical compound CCCCCCCCCCCCCCC\C=C\C(O)=O LKOVPWSSZFDYPG-WUKNDPDISA-N 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- OHOTVSOGTVKXEL-UHFFFAOYSA-K trisodium;2-[bis(carboxylatomethyl)amino]propanoate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C(C)N(CC([O-])=O)CC([O-])=O OHOTVSOGTVKXEL-UHFFFAOYSA-K 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
- A61K8/496—Triazoles or their condensed derivatives, e.g. benzotriazoles
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
- A61K8/4966—Triazines or their condensed derivatives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
- A61Q1/06—Lipsticks
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/08—Preparations containing skin colorants, e.g. pigments for cheeks, e.g. rouge
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q13/00—Formulations or additives for perfume preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q15/00—Anti-perspirants or body deodorants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q3/00—Manicure or pedicure preparations
- A61Q3/02—Nail coatings
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
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- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
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Abstract
本发明涉及式(1)和/或(2)的光稳定剂在保护身体护理品和家庭用品防止光解降解中的用途。
Description
本发明涉及选择的光稳定剂在保护身体护理品和家庭用品防止光降解中的用途。
近年来在化妆品制剂和家庭用品中越来越多地使用透明(玻璃)容器。尽管玻璃和普通塑料本身具有一定的固有B范围紫外光的吸收,但是对A范围紫外光的吸收是非常低的。
结果是产品随时间通过光解变化。
这导致例如粘度的下降和颜色或气味的改变。
本发明的目的是提供身体护理品和家庭用品防止光降解的添加剂。
令人惊异的是已经发现某些基于苯并三唑和三嗪的光稳定剂满足了这些要求。
R8为氢;C1-C5烷基;C1-C5烷氧基;卤素,优选氯;或羟基;
R4和R5相互独立地为氢;或C1-C5烷基;
m为1或2;
n为0或1;
如果m为1,则
R2为氢;未取代或苯基取代的C1-C12烷基;C6-C10芳基;
如果m为2,则
R2为一直接键;-(CH2)p-;和
p为1到3;
L1为C1-C22烷基、C2-C22链烯基或C5-C7环烷基;
L2和L6相互独立地为H、OH、卤素、C1-C22烷基、卤甲基;
L3、L5和L7相互独立地为H、OH、OL1、卤素、C1-C22烷基、卤甲基;
L4为H、OH、OL1、卤素、C1-C22烷基、苯基、卤甲基;
j为0、1、2或3。
C1-C22烷基为直链或分支烷基,诸如甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、戊基、异戊基或叔戊基、庚基、辛基、异辛基、壬基、癸基、十一基、十二基、十四基、十五基、十六基、十七基、十八基或二十基。
C1-C22烷硫基为直链或分支烷硫基,诸如甲硫基、乙硫基、正丙硫基、异丙硫基、正丁硫基、仲丁硫基、叔丁硫基、戊硫基、庚硫基、辛硫基、异辛硫基、壬硫基、癸硫基、十一烷硫基、十二烷硫基、十四烷硫基、十五烷硫基、十六烷硫基、十七烷硫基、十八烷硫基或二十烷硫基。
C2-C18链烯基为例如烯丙基、甲基烯丙基、异丙烯基、2-丁烯基、3-丁烯基、异丁烯基、正戊-2,4-二烯基、3-甲基-丁-2-烯基、正辛-2-烯基;正十二-2-烯基、异十二烯基、正十二-2-烯基或正十八-4-烯基。
C5-C7环烷基为环戊基、环庚基或优选的环己基。
C7-C9苯基烷基为苯丙基、苯乙基和优选的苄基。
如果L-取代基被定义为烷基或链烯基或如果它们为芳族或脂族环系统,则它们在所述意义的范围内通常包含1到50个碳原子并且可一次或多次被O、S、NR’、SO2、CO、亚苯基、亚环己基、COO、OCO、-(SiRpRqO)-间断和/或一次或多次被OH、OR’、NR’R”、卤素、-CN、链烯基、苯基、-SiRpRqRr或COOH取代,其中R’和R”相互独立地为H、烷基、链烯基或酰基,Rp、Rq和Rr相互独立地为H、烷基、链烯基、苯基、烷氧基、酰基或酰氧基。
上面的基团也还可带有取代基。也可以是二聚物或聚合物。
其中:
n为1或2,和
L1(其中n为1)为C1-C22烷基或被一个或几个O间断的和/或被一个或多个OH、缩水甘油氧基、C2-C22链烯氧基、COOH、COORe、O-CO-Rf取代的C1-C22烷基;或C2-C22链烯基、C5-C7环烷基;未取代或被OH、Cl或CH3取代的苯烷基;CORg;SO2-Rh;CH2CH(OH)-Rj;其中
Re为C1-C22烷基;C2-C22链烯基;C1-C22羟烷基;被一个或几个O间断的C1-C22烷基或C1-C22羟烷基;C5-C7环烷基;苄基;C1-C5烷基苯基;苯基;苯基-C1-C5烷基;糠基;或CH2CH(OH)-Rj;
Rf、Rg相互独立地为C1-C22烷基、C2-C22链烯基或苯基;
Rh为C1-C22烷基、芳基或烷基芳基;
Rj为芳烷基或CH2ORk;
Rk为C5-C7环己基、苯基、甲苯基或苄基;和
L1(其中n为2)为亚烷基;亚链烯基;亚二甲苯基;被一个或几个O间断的亚烷基或羟基亚烷基;羟基亚烷基;
L2和L’2相互独立地为H、C1-C22烷基或OH;
L4和L’4相互独立地为H、烷基、OH、烷氧基、卤素和当n为1时为OL1;
L3和L’3相互独立地为H、C1-C22烷基或卤素。
L1、L2、L’2、L3、L’3、L4、L’4可在所述的意义范围内带有另外的取代基,例如烯不饱和可聚合基团。也可以是二聚物或聚合物。特别优选的三嗪化合物为下式的化合物:
其中
L1为C2-C30烷基;C2-C30链烯基;未取代或被一个或几个C1-C5烷基取代的C5-C12环烷基、C1-C5烷氧基-C1-C12烷基;氨基-C1-C12烷基;C1-C5单烷基-氨基-C1-C12烷基;C1-C5二烷基氨基-C1-C12烷基。
尤其可提出的这类化合物的例子有:
2,4,6-三(2-羟基-4-辛氧基苯基)-1,3,5-三嗪;
2-(2,4-二羟苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪;
2,4-双(2-羟基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪;
2-(2-羟基-4-辛氧基苯基)-4,6-双(4-甲基苯基)-1,3,5-三嗪;
2-(2-羟基-4-十二烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪;
2-[2-羟基-4-(2-羟基-3-丁氧基丙氧基)苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪;
2-[2-羟基-4-(2-羟基-3-辛氧基丙氧基)苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪;
上面各式中所用的缩写词:
i=异构混合物;n=直链基团;t=叔基;邻-、间-、对表示相对于三嗪环的基团的位置。
式(1)和(2)的光稳定剂也可与生育酚或生育酚乙酸酯一起使用。
式(1)和(2)的光稳定剂也可与空间位阻胺一起使用。
这些光稳定剂优选包括含至少一个下式基团的2,2,6,6-四烷基哌啶衍生物或(59)
式中G、G1和G2相互独立地为氢或甲基,优选为氢。
可按照本发明使用的四烷基哌啶的例子可参见EP-A-356677的3-17页,a)到f)段。该EP-A的所引用段落被作为本说明书的一部分。特别有用的是下面的四烷基哌啶衍生物:
双(2,2,6,6-四甲基哌啶-4-基)癸二酸酯、双(2,2,6,6-四甲基哌啶-4-基)丁二酸酯、双(1,2,2,6,6-五甲基哌啶-4-基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基哌啶-4-基)癸二酸酯、正丁基-3,5-二叔丁基-4-羟基苄基丙二酸-双(1,2,2,6,6-五甲基哌啶)酯、1-羟乙基-2,2,6,6-四甲基-4-羟基哌啶和丁二酸的缩合物、N,N’-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-叔辛基氨基-2,6-二氯-1,3,5-s-三嗪的缩合物、三(2,2,6,6-四甲基-4-哌啶基)次氮基三乙酸酯、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四酸酯、1,1’-(1,2-乙烷二基)-双(3,3,5,5-四甲基哌嗪酮)、4-苯甲酰基-2,2,6,6-四甲基哌啶、4-硬脂氧基-2,2,6,6-四甲基哌啶、双(1,2,2,6,6-五甲基哌啶)-2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮、双(1-辛氧基-2,2,6,6-四甲基哌啶)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基哌啶)丁二酸酯、N,N-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-吗啉基-2,6-二氯-1,3,5-三嗪的缩合物、2-氯-4,6-二(4-正丁基氨基-2,2,6,6-四甲基哌啶)-1,3,5-三嗪和1,2-双(3-氨基丙氨基)乙烷的缩合物、2-氯-4,6-二(4-正丁基氨基-1,2,2,6,6-五甲基哌啶)-1,3,5-三嗪和1,2-双(3-氨基丙氨基)乙烷的缩合物、8-乙酰基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮、3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯烷-2,5-二酮、3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)-吡咯烷-2,5-二酮、4-十六烷氧基-和4-十八烷氧基-2,2,6,6-四甲基哌啶的混合物、N,N’-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-环己基氨基-2,6-二氯-1,3,5-三嗪的缩合物、1,2-双(3-氨基丙氨基)乙烷和2,4,6-三氯-1,3,5-三嗪的缩合物和4-丁基氨基-2,2,6,6-四甲基哌啶(CAS登记号[136504-96-6]);(2,2,6,6-四甲基-4-哌啶基)-正十二烷基-琥珀酰亚胺、(1,2,2,6,6-五甲基-4-哌啶基)-正十二烷基琥珀酰亚胺、2-十一基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代-螺[4.5]癸烷、7,7,9,9-四甲基-2-环十一基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷和表氯醇的反应产物、四(2,2,6,6-四甲基哌啶-4-基)-丁烷-1,2,3,4-四羧酸酯、四(1,2,2,6,6-五甲基哌啶-4-基)-丁烷-1,2,3,4-四羧酸酯、2,2,4,4-四甲基-7-氧杂-3,20-二氮杂-21-氧代-二螺[5.1.11.2]-二十一烷、8-乙酰基-3-十二烷基-1,3,8-三氮杂-7,7,9,9-四甲基螺[4.5]-癸烷-2,4-二酮或下面各式的化合物:式中m具有5-50的值,
R=H或CH3或
R=H或CH3
此外,式(1)和(2)的光稳定剂也可与络合物形成体、特别是含氮络合物形成体一起使用,这种络合物形成体的例子有乙二胺四乙酸(EDTA)、次氮基三乙酸(NTA)、β-氨基丙酸二乙酸(EDETA)或乙二胺二丁二酸(EDDS)。
Carb1、Carb2和Carb3相互独立地为基团C1-C8单-或二羧酸;和
m1为1到5。
特别优选的化合物为式(66)的化合物,式中
Q1为单羧酸;或式-(CH2)m1-OH的基团;
Q2为氢或单羧酸;和
Q3是式(1b);或一种单羧酸。
特别有意义的络合物形成体是式(66)的化合物,式中Carb2和Carb3相互独立地为式(66c)的基团:
(66c)-[(CH2)]n1-COOH(其中n1为0到5)。
次氮基三乙酸(NTA)也适用。
满足式(71)的天冬酰胺二乙酸或
满足式(72)的甲基甘氨酸二乙酸(MGDA)
其它适合的络合物形成体是例如含磷酸根、膦酸根或甲基膦酸根的聚阴离子源的天然多糖,诸如甲壳质衍生物如磺基甲壳质、羧甲基甲壳质、磷酸甲壳质、脱乙酰壳多糖衍生物如磺基脱乙酰壳多糖、羧甲基脱乙酰壳多糖或特别优选的磷酸脱乙酰壳多糖,其满足式(73):其中
R11为氢或式(73a)的基团
R12为式(73a)的基团;
X1和X2相互独立地为氢、C1-C5烷基或碱金属离子或铵离子;和
n为10到4000。
R1为氢;C1-C22烷基;C1-C22烷硫基;C5-C7环烷基;苯基;或C7-C9苯基烷基;或SO3M;
R2为C1-C22烷基;C5-C7环烷基;苯基;或C7-C9苯基烷基;
V为-O-;或-NH-;
a为0;1;或2;
b、c和d相互独立地为0或1;
e为1到4的整数;
f为1到3的整数;和
m、n和p相互独立地为1到3的整数;
如果e为1,那么
R3为氢;M;C1-C22烷基;C5-C7环烷基;C1-C22烷硫基;C2-C18链烯基;C1-C18-苯基烷基;式(74d)的基团: 或(74f)
M为碱金属;铵;如果e为2,那么R3为一直接键;-CH2-;-O-;或-S-;
如果e为3,那么
R4和R5相互独立地为氢;或C1-C22烷基。
式(1)和(2)的光稳定剂以及这些化合物与空间位阻胺、酚类抗氧化剂或络合物形成体的混合物特别适合于保护身体护理产品和家庭用品免受光降解。所述化合物或这些不同类型化合物的混合物具体可用于护肤品、沐浴和淋浴添加剂、含香料和香味物质的制剂、护发品、洁齿剂、脱臭剂和防汗剂、美饰剂、光防护制剂和含活性成分的制剂。
适合的护肤品具体为洁身油、爽身水、洁身胶、加药霜、护肤膏、剃须制剂如剃须泡沫或剃须胶、爽身粉如婴儿爽身粉、保湿胶、保湿喷雾剂、revitalizing body sprays、蜂窝织炎药膏和磨肤剂。
适合的沐浴和淋浴添加剂为淋浴胶、浴盐、泡沫浴剂和肥皂。
含香料和香味物质的制剂具体有香水、香精、盥洗用香水和剃须液(剃须后用制剂)。
适合的护发品为例如人用和动物(特别是狗)用香波、头发调理剂、美发和滋润头发的产品、长效卷发剂、发胶和发蜡、发用凝胶、发型固定剂和头发染色或漂发剂。
适合的洁齿剂具体有牙膏(tooth creams)、牙膏、漱口剂、口腔清洗剂、防牙菌斑剂和假牙清洁剂。
适合的美饰剂具体有唇膏、指甲油、眼影膏、睫毛油、干和湿化妆品、胭脂、底粉、脱毛剂和晒黑剂。
适合的含活性成分的化妆品制剂具体有激素制剂、维生素制剂、植物提取物制剂和抗菌剂。
所述的身体护理品可以是乳油、软膏、膏剂、泡沫体、凝胶、洗剂、粉、化妆品、喷雾剂、棒剂或气溶胶剂的形式。它们在水相中优选包含式(1)和/或(2)的光稳定剂和任选的空间位阻胺、络合剂和酚抗氧化剂。
因此本发明也涉及含至少一种式(1)和/或(2)的光稳定剂的身体护理品。
所述光稳定剂通常以50-1000ppm的浓度存在于所述新的身体护理品中。
乳油是含50%以上水的水包油乳液。此中所用的含油基质通常主要为脂肪醇如月桂醇、鲸蜡醇或硬脂醇,脂肪酸如棕榈酸或硬脂酸,液态或固态蜡如肉豆蔻酸异丙酯或蜂蜡和/或烃化合物如石蜡油。适合的乳化剂为主要为亲水性的表面活性剂,诸如相应的非离子乳化剂,象多元醇脂肪酸酯的环氧乙烷加合物,如聚甘油脂肪酸酯或聚氧乙烯脱水山梨醇脂肪酸醚(商标为吐温);聚氧乙烯脂肪醇醚或其酯或相应的离子乳化剂,诸如脂肪醇磺酸的碱金属盐、鲸蜡基硫酸钠或硬脂基硫酸钠,其通常与脂肪醇如鲸蜡醇或硬脂醇一起使用。此外,乳油包含降低蒸发时的失水量的试剂如多元醇象甘油、山梨醇、丙二醇和/或聚乙二醇。
软膏为含高至70%、优选不超过20-50%的水或水相的油包水乳液。所述含油相主要包含烃类诸如优选含羟基化合物的石蜡油和/或固态石蜡,例如脂肪醇或其酯诸如鲸蜡醇或羊毛蜡,用以改善吸水性。乳化剂为相应的亲脂物质诸如脱水山梨醇脂肪酸酯。此外,所述软膏包含润湿剂诸如多元醇象甘油、丙二醇、山梨醇和/或聚乙二醇以及防腐剂。
浓乳油为无水制剂并且在烃化合物的基础上制备,所述烃化合物的例子有石蜡、天然或部分合成的脂肪,例如椰油脂肪酸三甘油酯或优选的硬化油和甘油偏脂肪酸酯。
膏剂为含有用于吸收分泌物的粉末成分如金属氧化物象二氧化钛或氧化锌以及用于结合水分或吸收的分泌物的牛脂和/或硅酸铝的乳油和软膏。
泡沫体为气溶胶形式的液体水包油乳液。对于含油相来说,尤其使用了烃化合物,例如石蜡油、脂肪醇如鲸蜡醇、脂肪酸酯如肉豆蔻酸异丙酯和/或蜡。特别适合的乳化剂有主要为亲水性的乳化剂如聚氧乙烯脱水山梨醇脂肪酸酯与主要为亲脂性的乳化剂如脱水山梨醇脂肪酸酯的混合物。通常另外还使用商业上可得的添加剂如保存剂。
凝胶具体为胶凝剂分散或溶胀于其中的活性物质的水溶液或悬浮液,胶凝剂的例子具体有纤维素醚诸如甲基纤维素、羟乙基纤维素、羧甲基纤维素或植物水胶体如藻酸钠、黄蓍胶或阿拉伯胶。所述凝胶优选另外还包含作为加湿剂的多元醇如丙二醇或甘油和润湿剂如聚氧乙烯脱水山梨醇脂肪酸酯。所述凝胶还包含商业可得的保存剂如苯甲醇、苯乙醇、苯氧基乙醇等。
指甲油包含:
-成膜剂,通常为硝基纤维素;
- 溶剂,如乙酸乙酯、醇、甲苯、二甲苯、己烷、庚烷、乙酸的乙基-异丙基酯、(异)丁酯或(异)戊酯、石油醚或乙醚;
- 树脂,如对甲苯磺酰胺和甲醛的缩合产物;聚醚树脂;基于多元醇二元酯的树脂;马来酸醇酸树脂;丙烯酸酯;乙烯基树脂或聚酰胺树脂;
- 增塑剂,例如邻苯二甲酸二丁酯、樟脑、蓖麻油、柠檬酸乙酰基三乙酯、己二酸二异丁酯、丁基辛基己二酸酯、蔗糖乙酸酯-异丁酸酯和/或乙基甲苯磺酰胺;
- 有机和/或无机颜料和/或彩色漆,通常为水溶性染料;
- 光稳定剂、抗氧化剂和多价螯合剂。用于唇膏、化妆品或发蜡的含蜡基质包括:
- 液体成分,如蓖麻油、油醇、羊毛脂、PEG、PPG和其酯,象肉豆蔻酸异丙酯和/或硅氧烷如二甲基硅氧烷,偶尔还包括水;
- 蜡,如蜂蜡、地蜡、纯地蜡、巴西棕榈蜡、小烛树蜡或石蜡;
- 有机和/或无机颜料和/或彩色漆,也是水溶性染料,例如曙红型染料,但也可以是所有其它水溶性染料以及油溶性染料;
- 用于发/唇的化妆品或闪光效果颜料(例如氯氧化铋或光学效果颜料);
- 香料;
- 抗氧化剂、光稳定剂和多价螯合剂。
下表列出了本发明的身体护理品的典型实例和其组分:
身体护理品 | 组分 |
加湿乳油 | 植物油,乳化剂,稠化剂,香料,水,式(1)或(2)的光稳定剂 |
香波 | 表面活性剂,乳化剂,保存剂,香料,式(1)或(2)的光稳定剂 |
牙膏 | 洁齿剂,稠化剂,甜味剂,调味剂,着色剂,式(1)或(2)的光稳定剂,水 |
唇膏 | 植物油,蜡,TiO2,式(1)或(2)的光稳定剂 |
所述新的身体护理品对颜色变化和其中存在的成分的光解降解具有高的稳定性。这归结于所用光稳定剂的效力、颜色稳定性、易混性和水解稳定性。
所述式(1)和(2)的光稳定剂也用于家庭清洁剂和处理剂中,例如用于液体擦洗剂、玻璃洗涤剂、中性清洁剂(万能清洁剂)、酸性家用洗净剂(浴室)、洁厕剂,优选用于洗涤、漂洗和餐具洗涤剂,透明漂洗剂、洗餐具机用洗涤剂、鞋油、擦光蜡、地板洗涤剂和地板蜡、金属、玻璃和陶瓷清洁剂、织物护理剂、除锈剂、着色剂和染色剂(去污剂盐)、家具和多用途抛光剂和皮革整理剂(皮革喷雾剂)。
家用洗净剂是水溶液或醇(乙醇或异丙醇)溶液,含一种或多种下面的组分:
- 阴离子、非离子、两性和/或阳离子表面活性剂;
- 肥皂,经动物和植物油脂的皂化制备;
- 无机酸,如盐酸、磷酸或硫酸;
- 用于碱性产品的无机碱(NaOH或KOH)或有机碱;
- 改善表面清洁的研磨剂;
- 蜡和/或硅氧烷,用于表面的维护和保护;
- 多磷酸盐;
- 消除次氯酸盐或卤素的物质;
- 过氧化物(包含漂白活性剂如TAED),如过硼酸钠或过氧化氢;
- 酶;
- 在洗涤用洗涤剂中的脱色抑制剂、去污化合物、灰度抑制剂、抑泡剂、荧光增白剂;
- 基于蜡的洗净剂可包含选自挥发油、松节油和/或石蜡的溶剂和基于蜡的乳化剂;
- 用于粉末洗净剂的填充剂如硅酸盐、多磷酸盐、Zeolithes;
- 颜料、色淀或可溶性染料;
- 香料;和
- 光稳定剂、抗氧化剂和螯合剂。
彩色洗净剂和美饰化妆品可包含下面的染料:
- 无机颜料,如氧化铁(氧化铁红、氧化铁黄、氧化铁黑等)、群青、氧化铬绿或炭黑;
- 天然或合成有机颜料;
- 可溶解于溶剂中的分散染料如HC型直接染发剂,如HC RedNo.3、HC Blue No.2和所有列在International CosmeticIngredient Dictionary and Handbook,第七版1997中的其它染发剂或列在Color Index International or Society of Dyers andColourists中的分散染料;
- 彩色漆(可溶性染料的不溶性盐,如许多阴离子染料的钙盐、钡盐或铝盐);
- 可溶性阴离子或阳离子染料,如酸性染料(阴离子)、碱性染料(阳离子)、直接染料、活性染料或溶剂染料。
一般对于家庭用品和身体护理品着色来说,所有在可见光区的电磁辐射(波长为约4000-700nm)具有吸收的物质均是适合的。所述吸收通常由下面的生色团产生:
偶氮(一、二、三或多)均二苯代乙烯-、类胡萝卜素-、二芳基甲烷-、三芳基甲烷-、呫吨-、吖啶-、喹啉、次甲基-(以及聚甲炔-)、噻唑-、吲达胺-、靛酚-、吖嗪-、噁嗪、噻嗪-、蒽醌-、靛青-、酞菁-和其它合成、天然和/或无机生色团。
新家用洗净剂和处理剂的典型例子为:
家用洗净剂/家用处理剂 | 组分 |
洗涤剂浓缩液 | 表面活性剂混合物,乙醇,式(1)和(2)的光稳定剂,水 |
鞋油 | 蜡,蜡乳化剂,式(1)和(2)的光稳定剂,水,防腐剂 |
含蜡地板清洁剂 | 乳化剂,蜡,氯化钠,式(1)和(2)的光稳定剂,水,防腐剂 |
所述光稳定剂通常通过溶解于液体配制组分(油、水、醇)中混入。
适合的所用的表面活性剂的例子为阴离子、非离子、阳离子、两性离子和两性的合成去污物质。
适合的阳离子去污物质有:
- 硫酸盐,诸如象其烷基链具有8到18个碳原子的脂肪醇硫酸盐,诸如象硫酸化月桂醇;
- 脂肪醇醚硫酸盐,诸如象2到30摩尔环氧乙烷与1摩尔C8-C22脂肪醇的聚加合物的酸酯或盐;
- 所谓肥皂的C8-C20脂肪酸诸如象椰油脂肪酸的碱金属盐、铵盐或胺盐;
- 烷基酰胺基硫酸盐;
- 烷基氨基硫酸盐,诸如象单乙醇胺月桂基硫酸盐;
- 烷基酰胺醚硫酸盐;
- 烷芳基聚醚硫酸盐;
- 甘油一硫酸酯盐;
- 其烷基链含8到20个碳原子的链烷磺酸盐,诸如十二烷基磺酸盐;- 烷基酰胺基磺酸盐;- 烷芳基磺酸盐;- α-烯烃磺酸盐;- 磺基丁二酸衍生物,诸如象烷基磺基丁二酸盐、烷基醚磺基丁二酸盐或烷基磺基丁二酰胺衍生物;- 下式的N-(烷基酰胺基烷基)氨基酸式中:X为氢、C1-C4烷基或-COOM+;Y为氢或C1-C4烷基;Z为-(CH2)m1-1;n1为6到18的整数和M为碱金属阳离子或铵阳离子;- 式(105)CH3-X-Y-A的烷基和烷芳基醚羧酸盐式中:X为基团-(CH2)5-19-O-;;或
R为氢或C1-C4烷基;Y为-(CHCHO)1-50-;A为-(CH2)m2-1COO-M+;或
m2为1到6和
M为碱金属阳离子或铵阳离子。
其它使用的阴离子表面活性剂为脂肪酸甲基氨基乙磺酸盐、烷基羟乙磺酸盐、脂肪酸多肽缩合物和脂肪醇磷酸酯。这些化合物中的烷基优选具有8到24个碳原子。
阴离子表面活性剂通常是其水溶性盐的形式,诸如碱金属盐、铵盐或胺盐。这类盐的例子有锂、钠、钾、铵、三乙胺、乙醇胺、二乙醇胺或三乙醇胺的盐。特别是使用钠盐、钾盐或铵(NR1R2R3)盐,其中R1、R2和R3相互独立地为氢、C1-C4烷基或C1-C4羟烷基。
特别优选的阴离子表面活性剂是单乙醇胺月桂基硫酸盐或脂肪醇硫酸的碱金属盐,特别是月桂基硫酸钠和2到4摩尔环氧乙烷与月桂基醚硫酸钠之间的反应产物。
适合的两性离子和两性表面活性剂为C8-C18甜菜碱、C8-C18磺基甜菜碱、C8-C24烷基酰胺基-C1-C4亚烷基甜菜碱、咪唑啉羧酸盐、烷基两性羧基羧酸、烷基两性羧酸(例如月桂基两性氨基乙酸盐)和N-烷基-β-氨基丙酸盐或-亚氨基二丙酸盐、C10-C20烷基酰胺基-C1-C4亚烷基甜菜碱并特别优选椰油脂肪酸酰胺基丙基甜菜碱。
非离子表面活性剂的例子是分子量为1000-15000的环氧丙烷/环氧乙烷加合物的衍生物、脂肪醇乙氧基化物(1-50EO)、烷基苯酚聚乙二醇醚(1-50 EO)、乙氧基化碳水化合物、脂肪酸二醇偏酯,诸如象二甘醇单硬脂酸酯、脂肪酸链烷醇酰胺和二链烷醇酰胺、脂肪酸链烷醇酰胺乙氧基化物和脂肪胺氧化物。
此外,所述表面活性剂可以是饱和和不饱和C8-C22脂肪酸本身或其混合物或其与上面提及的其它去污物质的混合物。这些脂肪酸的例子有癸酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、花生酸、山萮酸、癸烯酸、十二碳烯酸、十四碳烯酸、十八碳烯酸、油酸、二十碳烯酸和芥酸,和这些酸的技术级混合物诸如象椰油脂肪酸。这些酸为盐的形式,适合的阳离子为碱金属阳离子诸如钠离子和钾离子、金属原子如锌和铝原子,或足够碱性的含氮有机化合物如胺或乙氧基化胺。这些盐也可就地制备。
可用于香波和头发调理剂的阳离子表面活性剂和调理剂的例子有:
- 鲸蜡基三甲基溴化铵(CTAB)
- 聚二甲基硅氧烷共聚醇
- 酰胺基甲基硅氧烷
- 丙烯酰胺基丙基氯化三monium/丙烯酰胺共聚物
- 瓜耳羟丙基氯化三monium
- 羟基十六烷基羟乙基氯化二monium
- 在International Cosmetic Ingredient Dictionary and Handbook,第七版1997中列出的quaternium化合物如Quatemium-80
- 如在International Cosmetic Ingredient Dictionary and Handbook,第七版1997中列出的季化羟乙基纤维素(polyquaternium)如季化羟乙基纤维素-5、季化羟乙基纤维素-6、季化羟乙基纤维素
- 7、季化羟乙基纤维素-10、季化羟乙基纤维素-11、季化羟乙基纤维素-17、季化羟乙基纤维素-18、季化羟乙基纤维素-24或季化羟乙基纤维素-27、季化羟乙基纤维素-28、季化羟乙基纤维素-32、季化羟乙基纤维素-37。
所述表面活性剂优选为肥皂,即支化或非支化长链烷基-或链烯基-羧酸盐,诸如象钠、钾、铵或取代铵的盐。
下面的实施例说明本发明的情况。
身体护理品制剂的制备
实施例1:喷雾美发胶的制备
相 组分 (w/w)%
A 丙烯酸聚合物(1%分散体) 0.30
软化水 30.00
B 甘油 2.00
对羟基苯甲酸甲酯 0.20
C 软化水 到100
PVP/VA共聚物 8.00
三乙醇胺(88%) 0.12
EDTA二钠盐 0.01
式(53)的光稳定剂 0.01
制备:在室温下将组分(A)分散。加热下混合(B)直到对羟基苯甲酸甲酯完全溶解并然后在轻轻搅拌下将(B)加入到(A)中。将(C)共混直到其完全溶解并在搅拌下缓慢加入到(A)和(B)的混合物中。通过加入少量三乙醇胺(pH=5.6-5.75)增加凝胶的透明性。
实施例2:婴儿香波的制备组分 (w/w)%椰油酰胺基丙基甜菜碱 35.00软化水 到100柠檬酸 适量(pH)季化羟乙基纤维素-15 0.15芳香油 0.30叶绿素 0.20式(54)的光稳定剂 0.15式(102)的抗氧化剂 0.05着色剂(D&C Yellow No.5) 0.02氯化钠 0.30
制备:将表面活性剂和水共混直到获得均匀溶液。用柠檬酸将pH调节到6.0-6.5并按所表明的顺序加入其它组分。搅拌所述混合物直到完全溶解。
实施例3:盥洗香水的制备组分 (w/w)%乙醇,96% 60d-柠檬烯 5柏木烯 1.5香茅醇 0.5桧油 0.5式(53)的光稳定剂 0.25式(99)的抗氧化剂 0.10S,S-EDDS 0.01着色剂(D&C Yellow No.5) 0.1水 到100
制备:将各组分在以所示顺序在50℃下充分混合,获得透明均相溶液。
家庭用品制剂的制备
实施例4:绿色玻璃洗涤剂的制备组分 (w/w)%阴离子/两性表面活性剂(Lumorol RK) 0.7丁基乙二醇 5.0异丙醇 20.0d-柠檬烯 4.00着色剂(D&C Green No.2) 0.05式(54)的光稳定剂 0.10软化水 到100
制备:以所述顺序将各组分溶解直到获得透明均匀混合物。
实施例5:地板蜡的制备组分 (w/w)%蜡混合物 12石油溶剂 到100d-柠檬烯 4.00式(55)的光稳定剂 0.10
制备:以所示顺序搅拌各组分直到获得均匀混合物。
实施例6:非油性唇膏的制备组分 (w/w)%巴西棕榈蜡 2.5白色蜂蜡 20.0Ozekerite 10.0羊毛脂,无水 5.0鲸蜡醇 2.0液体石蜡 3.0肉豆蔻酸异丙酯 3.0丙二醇recinoleate 4.0CI颜料红4 9.0CI颜料蓝15 1.0式(55)的光稳定剂 0.1蓖麻油 到100
实施例7:耐转移唇膏的制备组分 (w/w)%环甲基硅酮 41.50异癸烷 10.00D&C Red No.7 8.00合成蜡 6.00异硬脂基三甲基丙烷甲硅烷氧基硅酸酯 5.00硬脂酸鲸蜡酯/乙酰基化羊毛脂,90∶10 5.00纯地蜡 4.00石蜡 3.00二氧化钛 2.00对羟基苯甲酸甲酯 0.30对羟基苯甲酸丙酯 0.10式(104)的抗氧化剂 0.10式(54)的光稳定剂 0.10
实施例8:胭脂(粉)的制备组分 (w/w)%滑 56硬脂酸锌 15大米淀粉 15氧化铁红 12香料 适量式(53)的光稳定剂 0.1
实施例9:粉底霜的制备组分 (w/w)%二氧化 12.79油醇 4.57硬脂酸甘油酯 3.65丙二醇 3.65硬脂酸 1.83硅酸铝镁 0.91三乙醇胺99% 0.91氧化铁黄 0.64氧化铁红 0.32CI颜料棕6 0.37羧甲基纤维素 0.10式(53)的光稳定剂 0.10水 到100
实施例10:眼线膏的制备组分 (w/w)%多糖树脂(Kama KM 13,Kama) 8.00氧化铁黑 6.50巴西棕榈蜡 1.00三乙醇胺,99% 1.00氢化聚异丁烷 1.00氢化聚癸烯 1.00脱水山梨醇倍半油酸酯 1.00Xanthum gum 0.50羧甲基纤维素 0.40硅酸铝镁 0.40对羟基苯甲酸甲酯 0.35硬脂酸 2.50卵磷脂 0.20咪唑烷基脲 0.10式(53)的光稳定剂 0.10式(100)的抗氧化剂 0.05水 到100
实施例11:睫毛化妆品的制备组分 (w/w)%石蜡 10.00淀粉 5.00聚乙烯 5.00氧化铁黑 7.00Carbomer(Carbopol,EFGoodrich) 0.50羟乙基纤维素 0.50泛醇 2.00式(53)的光稳定剂 0.10水 到100
实施例12:指甲油的制备组分 (w/w)%聚(1-三甲基甲硅烷基丙烯) 0.30硝基纤维素 12.00醇酸树脂 10.00邻苯二甲酸二丁酯 4.00樟脑 2.00乙酸丁酯 49.50甲苯 20.00颜料红57.1 1.00季化膨润土 1.00式(54)的光稳定剂 0.10式(103)的抗氧化剂 0.10
Claims (15)
在保护身体护理品和家庭用品防止光解降解中的用途,其中:
R1为C1-C12烷基;C1-C5烷氧基;C1-C5烷氧基羰基;C5-C7环烷基;C6-C10芳基;芳烷基;-SO3M;式(1a)的基团:R8为氢;C1-C5烷基;C1-C5烷氧基;卤素,优选氯;或羟基;R4和R5相互独立地为氢;或C1-C5烷基;m为1或2;n为0或1;如果m为1,则R2为氢;未取代或苯基取代的C1-C12烷基;C6-C10芳基;如果m为2,则R2为一直接键;-(CH2)p-;和p为1到3;L1为C1-C22烷基、C2-C22链烯基或C5-C7环烷基;
L2和L6相互独立地为H、OH、卤素、C1-C22烷基、卤甲基;
L3、L5和L7相互独立地为H、OH、OL1、卤素、C1-C22烷基、卤甲基;
L4为H、OH、OL1、卤素、C1-C22烷基、苯基、卤甲基;
j为0、1、2或3。
3.按照权利要求1的用途,其包括使用式(52)的苯并三唑其中
T2为氢;或C1-C12烷基。
5.按照权利要求1到4中任一项的光稳定剂在用于皮肤和其附件的身体护理品中的用途。
6.按照权利要求5的用途,其中所述身体护理品选自护肤品、沐浴和淋浴添加剂、含香料和香味物质的制剂、护发品、洁齿剂、脱臭剂和防汗剂、美饰剂、光防护制剂和含活性成分的制剂。
7.按照权利要求6的用途,其中所述皮肤护理品选自洁身油、爽身水、洁身胶、加药霜、护肤膏、剃须制剂和爽身粉。
8.按照权利要求6的用途,其中所述含香料和香味物质的制剂选自香水、香精、盥洗用香水和剃须液(剃须后用制剂)。
9.按照权利要求6的用途,其中所述护发品选自香波、头发调理剂、美发和滋润头发的产品、长效卷发剂、发胶和发蜡、发用凝胶、发型定型剂和头发染色剂或漂发剂。
10.按照权利要求6的用途,其中所述美饰剂选自唇膏、指甲油、眼影膏、睫毛油、干和湿化妆品、胭脂、底粉、脱毛剂和晒黑剂。
11.按照权利要求6的用途,其中所述含活性成分的化妆品制剂选自激素制剂、维生素制剂、植物提取物制剂和抗菌剂。
12.按照权利要求1的光稳定剂在家庭清洁剂和处理剂中的用途。
13.按照权利要求12的用途,其中所述家庭清洁剂和处理剂选自洗涤、漂洗和餐具洗涤剂、鞋油、擦光蜡、地板洗涤剂和地板蜡、金属、玻璃和陶瓷清洁剂、织物护理剂、除锈剂、着色剂和染色剂(去污剂盐)、家具和多用途抛光剂。
14.包含至少一种按照权利要求1的光稳定剂的身体护理品。
15.包含至少一种按照权利要求1的光稳定剂的家庭清洁剂和处理剂。
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JP3322587B2 (ja) * | 1996-04-26 | 2002-09-09 | ライオン株式会社 | 非イオン界面活性剤の製造方法及び該非イオン界面活性剤を含有する液体洗浄剤組成物 |
EP0824909B1 (de) * | 1996-08-23 | 2003-09-10 | Ciba Specialty Chemicals Holding Inc. | Verwendung von ausgewählten Benzotriazol- und Triazinderivaten zum Schützen von menschlichem Haar vor der schädigenden Einwirkung von UV-Strahlung |
JP3944274B2 (ja) * | 1997-03-13 | 2007-07-11 | 住友化学株式会社 | 有機エレクトロルミネッセンス素子 |
-
1999
- 1999-10-21 JP JP2000579175A patent/JP2002528475A/ja active Pending
- 1999-10-21 ES ES99953902T patent/ES2348372T3/es not_active Expired - Lifetime
- 1999-10-21 AU AU10417/00A patent/AU1041700A/en not_active Abandoned
- 1999-10-21 ID IDW00200101086A patent/ID29252A/id unknown
- 1999-10-21 AT AT99953902T patent/ATE472992T1/de not_active IP Right Cessation
- 1999-10-21 WO PCT/EP1999/007980 patent/WO2000025730A1/en active Application Filing
- 1999-10-21 BR BR9914982-6A patent/BR9914982A/pt not_active Application Discontinuation
- 1999-10-21 CN CNB998129925A patent/CN1146384C/zh not_active Expired - Lifetime
- 1999-10-21 DE DE69942567T patent/DE69942567D1/de not_active Expired - Lifetime
- 1999-10-21 EP EP99953902A patent/EP1135093B1/en not_active Expired - Lifetime
-
2001
- 2001-04-30 MX MXPA01004305 patent/MX237925B/es not_active IP Right Cessation
-
2012
- 2012-11-05 JP JP2012243734A patent/JP2013047265A/ja active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101166511B (zh) * | 2005-04-28 | 2011-09-14 | 西巴特殊化学制品控股公司 | 苯并三唑衍生物用于光稳定的用途 |
TWI488649B (zh) * | 2007-08-24 | 2015-06-21 | Ciba Holding Inc | 包含苯并三唑與部花青素之混合物 |
Also Published As
Publication number | Publication date |
---|---|
JP2002528475A (ja) | 2002-09-03 |
ES2348372T3 (es) | 2010-12-03 |
JP2013047265A (ja) | 2013-03-07 |
EP1135093A1 (en) | 2001-09-26 |
BR9914982A (pt) | 2001-08-14 |
ID29252A (id) | 2001-08-16 |
ATE472992T1 (de) | 2010-07-15 |
AU1041700A (en) | 2000-05-22 |
MX237925B (en) | 2006-06-21 |
WO2000025730A1 (en) | 2000-05-11 |
CN1146384C (zh) | 2004-04-21 |
EP1135093B1 (en) | 2010-07-07 |
DE69942567D1 (de) | 2010-08-19 |
MXPA01004305A (en) | 2001-07-01 |
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