FUKUDA TERUYUKI (JP)
MINAMI SHINICHI (JP)
MAEDA MASAHIKO (JP)
MASUTANI TETSUYA (JP)
HUPFIELD PETER CHESHIRE (GB)
DOW CORNING (US)
MORITA MASAMICHI (JP)
FUKUDA TERUYUKI (JP)
MINAMI SHINICHI (JP)
MAEDA MASAHIKO (JP)
MASUTANI TETSUYA (JP)
HUPFIELD PETER CHESHIRE (GB)
| WO2006121171A1 | 2006-11-16 |
| US6641805B1 | 2003-11-04 | |||
| US5945108A | 1999-08-31 | |||
| EP1000602A1 | 2000-05-17 |
CLAIMS
1. A fluorine-containing polymer for cosmetic comprising a fluorine- containing polymer comprising repeating units derived from: (A) a monomer which comprises;
(a) a fluorine-containing monomer of the formula:
CH 2 =C(X)COOYRf wherein X is a hydrogen atom, a monovalent organic group, or a halogen atom,
Y is a direct bond or a divalent organic group, and Rf is a fluoroalkyl group having 1 to 6 carbon atoms, and
(B) a mercapto functional organopolysiloxane.
2. The fluorine-containing polymer according to claim 1 , wherein the monomer (A) comprises: (b) optionally present, a monomer which does not contain a fluorine atom, and (c) optionally present, a crosslinkable monomer, in addition to the fluorine-containing monomer (a).
3. The fluorine-containing polymer according to claim 1 or 2, wherein the fluorine-containing monomer (a) is a compound of the formula:
CH 2 =C(X)C(=O)O-Y-Rf (I) wherein X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a halogen atom, a CFX 1 X 2 group (wherein X 1 and X 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a iodine atom.), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group,
Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic or cycloaliphatic group having 6 to 10 carbon atoms, a -CHhCHbN(R 1 )Sθ2- group (wherein R 1 is an alkyl group having 1 to 4 carbon atoms.) or
-CH 2 CH(OY 1 )CH 2 - group (wherein Y 1 is a hydrogen atom or an acetyl group.), and
Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms.
4. The fluorine-containing polymer according to anyone of claims 1 to 3, wherein the fluorine-free monomer (b) is acrylates of the general formula:
CH 2 =CA 1 COOA 2 wherein A 1 is a hydrogen atom, a methyl group, or a halogen atom (for example, a chlorine atom, a bromine atom and a iodine atom) other than a fluorine atom, and A 2 is an alkyl group represented by C n H 2n+I (n = 1 to 30).
5. The fluorine-containing polymer according to anyone of claims 1 to 3, wherein the crosslinkable monomer (c) is a fluorine-free monomer having at least two reactive groups and/or carbon-carbon double bonds.
6. The fluorine-containing polymer according to anyone of claims 1 to 5, wherein the monomer (A) comprises: (b) a Cio- 3 o-alkyl (meth)acrylate, and (c) glycerol (meth)acrylate and/or glycidyl (meth)acrylate, in addition to the fluorine-containing monomer (a).
7. The fluorine-containing polymer according to anyone of claims 1 to 5, wherein the monomer (A) comprises:
(b) at least one alkyl (meth)acrylate methacrylate selected from the group consisting of one lauryl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate and/or stearyl (meth)acrylate, and
(c) glycerol (meth)acrylate and/or glycidyl (meth)acrylate, in addition to the fluorine-containing monomer (a).
8. The fluorine-containing polymer according to anyone of claims 1 to 7, wherein the mercapto functional organopolysiloxane (designated B') comprises siloxy units having the average formula: (R 2 SiO)a(RR F SiO) b (RR s SiO)c where; a is 0-4000, b is 1-1000, c is 1- 1000,
R is independently a monovalent organic group, R F is a monovalent functional organic group,
R s is a monovalent mercapto functional organic group.
9. The fluorine-containing polymer according to claims 8, wherein R F is an amino functional organic group (R N ).
10. The fluorine-containing polymer according to anyone of claims 1 to 9, wherein the mercapto group-containing silicone (B) is of the formula:
R 1 R 2 R 3
R 1 — O-fSiOfH-SiO-HfSiO-) — R .
A a B b R 3 c I I
SH C
wherein R 1 is a methyl group, a methoxy group, a phenyl group, or a hydroxyl group,
R 2 is a methyl group, a methoxy group, a phenyl group, or a hydroxyl group,
R 3 is a methyl group, a methoxy group, a phenyl group, or a hydroxyl group, R 1 is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, or MesSi,
A is a divalent saturated hydrocarbon group having 1-10 carbon atoms which may be interrupted with one or two ether linkages,
B is a divalent saturated hydrocarbon group having 1-10 carbon atoms which may be interrupted with one or two ether linkages, C is hydroxyls, amines, amides, sulfonamides, quaternaries, ethers, epoxy, phenols, esters, carboxyls, ketones, halogen-substituted alkyls or aryls, a, b, and c are integers showing the number of repeat units, a is from 0 to 4000, b is from 1 to 1000, , and c is from 0 to 1000.
11. The fluorine-containing polymer according to anyone of claims 1 to 10, wherein (A) the monomer which comprises; (a) the fluorine-containing monomer of the formula:
CH 2 =C(X)COOYRf wherein X is a hydrogen atom, a monovalent organic group, or a halogen atom,
Y is a direct bond or a divalent organic group, and Rf is a fluoroalkyl group having 1 to 6 carbon atoms, and
(b) a Cio- 3 o-alkyl (meth)acrylate, and
(c) glycerol (meth)acrylate and/or glycidyl (meth)acrylate, and (B) the mercapto functional organopolysiloxane, are emulsion-polymerized in water in the presence of an alkyl ether sulfate salt and a nonionic surfactant to give the fluorine-containing polymer.
12. A cosmetic comprising the fluorine-containing polymer for cosmetic according to anyone of claims 1 to 11.
13. A powder for cosmetic having surface covered with the fluorine- containing polymer for cosmetic according to anyone of claims 1 to 11.
14. A cosmetic comprising the powder for cosmetic according to claim 13. |
DESCRIPTION
COSMETIC COMPRISING SILICONE-CONTAINING
FLUOROACRYLATE POLYMER
CROSS REFERENCE TO RELATED APPLICATIONS
This application has priority from US Application No. 61/016,853, disclosures of which are incorporated herein by reference.
Field of the Invention
The present invention relates to a fluorine-containing polymer for cosmetic, having a skeleton derived from mercapto silicone and having a short- chain (at most 6 carbon atoms) fluoroalkyl (Rf) group, to powder for the cosmetics having surfaces covered with said fluorine-containing polymer for cosmetic, and to the cosmetics comprising these.
Since perfluorooctanoic acid (PFOA) is not contained, this fluorine- containing polymer for cosmetic has excellent safety, and is excellent in the water resistance, the water-repellent, oil repellency, the use feeling, and affinity with other materials.
Related Art
It is known that, when a fluorine-containing polymer comprising the repeat units derived from a fluoroacrylate having at least 8 carbon atoms in a Rf group is incorporated as a film forming agent into a cosmetic, a property of preventing the makeup coming off against sweat and sebum can be provided (WO98/55078, WO99/48464).
Recent study results (EPA Report "PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO
PERFLUOROOCTANOIC ACID AND ITS SALTS"
(http://www.epa.gov/opptintr/pfoa/pfoara.pdf)) and the like clarify that a PFOA (perfluorooctanoic acid) doubtfully has a potential risk of environmental load. EPA (Environmental Protection Agency of USA) announced on April 14, 2003 that the EPA intensifies the scientific investigation.
On the other hand, Federal Register (FR Vol. 68, No. 73/April 16, 2003 [FRL-2303-8]) (http://www.epa.gov/opptintr/pfoa/pfoafr.pdf), EPA Environmental News for release Monday April, 2003 "EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID" (http://www.epa.gov/opptintr/pfoa/pfoaprs. pdf), and
EPA OPPT FACT SHEET April 14, 2003
(http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf) announced that a fluorinated "telomer" may metabolize or decompose to PFOA. It is also announced that the telomer is used in a large number of commercial products including fire fighting foams, care products and cleaning products as well as soil, stain and grease resistant coating on carpets, textiles, paper, and leather.
The fluorine-containing polymer comprising the repeat units derived from the fluoroacrylate having at least 8 carbon atoms in the Rf group has the problems that:
1. When the Rf group in the fluorine-containing polymer has at least 8 carbon atoms, the PFOA and PFOA analogue substance having the living body accumulation are generated; and 2. the fluorine-containing polymer has poor affinity with human skin and
other materials (such as powder, oil and solvent) incorporated into the cosmetic formulation.
Accordingly, the prompt convert to a fluorine-containing polymer comprising a fluoroacrylate having at most 6 carbon atoms in short-chain Rf group, and the development of a fluorine-containing polymer having the improved affinity with other materials and skin are required.
Means for Solving the Problem The present inventors intensively studied to solve above-mentioned problems, and discovered that a polymer comprising a specified fluoroacrylate having a mercapto silicone skeleton can have excellent properties for the polymer for cosmetic.
Since the fluorine-containing polymer for cosmetic of this invention does not contain perfluorooctanoic acid (PFOA), the fluorine-containing polymer for cosmetic has excellent safety, and is excellent in the water resistance, the water-repellent, oil repellency, the use feeling, and affinity with other materials.
This invention provides a cosmetic comprising a fluorine-containing polymer comprising repeating units derived from: (A) a monomer which comprises;
(a) a fluorine-containing monomer of the formula:
CH 2 =C(X)COOYRf wherein X is a hydrogen atom, a monovalent organic group, or a halogen atom,
Y is a direct bond or a divalent organic group, and Rf is a fluoroalkyl group having 1 to 6 carbon atoms, and (B) a mercapto functional organopolysiloxane.
Detailed Description of the Solving Means
The monomer (A) which forms a fluorine-containing polymer in this invention comprises:
(a) a fluorine-containing monomer,
(b) optionally present, a monomer which is free from a fluorine atom, and (c) optionally present, a crosslinkable monomer.
The fluorine-containing polymer is a homopolymer which consists of one monomer, or it may be a copolymer which consists of two or more monomers.
The homopolymer has the repeat unit derived from a fluorine-containing monomer (a).
The polymer may have the repeat units derived from at least two fluorine- containing monomers (a), or may have the repeat units derived from at least one fluorine-containing monomer (a), the repeat units derived from at least one fluorine-free monomer (b) and optionally at least one crosslinkable monomer (c).
The fluorine-containing polymer can be obtained by polymerizing the monomer (A) in the presence of mercapto group-containing silicone (B).
(A) Monomer
(a) Fluorine-containing Monomer
The component (a) of the present invention is a fluorine-containing monomer of the formula: CH 2 =C(X)COO-Y-Rf where Rf is a fluoroalkyl group having 1 to 6 carbon atoms, X is a hydrogen atom, a monovalent organic group, or a halogen atom, and Y is a direct bond or a divalent organic group. Y may be for example a linear or branched alkylene group having 1 to 20 carbon atoms, for example a group of the formula -(CH 2 ) X - where x is 1 to 10, a group of the formula -SO 2 N (R 1 )R 2 - or of the formula -CON(R 1 )R 2 -, where R 1 is an alkyl group having 1 to 10 carbon atoms and R 2 is a linear or branched alkylene group having 1 to 10 carbon atoms, or a group of the formula -CH 2 CH(OR 3 )CH 2 - where R 3 represents a hydrogen atom or an acyl group having 1 to 10 carbon atoms such as formyl or acetyl, or a group of the formula -Ar-CH 2 - where Ar is an arylene group optionally having a substituent. X may be for example H, Me (methyl group), Cl, Br, I, F, CN and CF 3 .
The fluorine-containing monomer (a) is preferably a compound of the formula:
CH 2 =C(X)C(=O)O-Y-Rf (I) wherein X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, a iodine atom), a CFX 1 X 2 group (wherein X 1 and X 2 is a
hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a iodine atom.), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic or cycloaliphatic group having 6 to 10 carbon atoms, a -CHhCHbN(R 1 )SC>2- group (wherein R 1 is an alkyl group having 1 to 4 carbon atoms.) or
-CHaCH(OY 1 )CH 2 - group (wherein Y 1 is a hydrogen atom or an acetyl group.), and
Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms.
The alpha-position of the fluorine-containing monomer may be substituted with, for example, a halogen atom. Accordingly, in the formula (I), X may be a linear or branched alkyl group having 2 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, a iodine atom, a CFX 1 X 2 group (wherein X 1 and X 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a iodine atom.), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group.
In the formula (I), the Rf group is preferably a perfluoroalkyl group. The carbon number of the Rf group is from 1 to 6, particularly from 4 to 6.
Y is preferably an aliphatic group having 1 to 10 carbon atoms, an
aromatic group or cycloaliphatic group having 6 to 10 carbon atoms, a - CH2CH 2 N(R 1 )SO 2 - group (R 1 is an alkyl group having 1 to 4 carbon atoms.) or a -CH 2 CH(OY 1 )CH 2 - group (Y 1 is a hydrogen atom or an acetyl group.). The aliphatic group is preferably an alkylene group (particularly the carbon number is from 1 to 4, for example, 1 or 2.). The aromatic group and cycloaliphatic group may be substituted or unsubstituted.
The examples of the fluorine-containing monomer (a) are as follows:
Rf-CH 2 CH 2 — 0- ICf-?C=CH 2
Rf-CH 2
CH 2
— 0- ?Cι- ?C N
-CH 2
wherein Rf is a linear or branched fluoroalkyl group having, for example, 1 to 6 carbon atoms.
Non-limiting specific examples of the fluorine-containing monomer (a) include the followings: CF 3 (CF 2 )5(CH2)2θCOCH=CH2 CF 3 (CF 2 )5(CH 2 ) 2 θCOC(CH3)=CH 2 CF 3 (CF 2 )S(CH 2 )IOOCOCH=CH 2
CF 3 (CF 2 )5(CH 2 )IOOCOC(CH 3 )=CH2 CF 3 (CF 2 )4CH 2 OCOCH=CH 2 CF 3 (CF 2 ) 3 CH 2 OCOCH=CH 2 (CF 3 ) 2 CF(CF 2 ) 3 (CH 2 ) 2 OCOCH=CH 2
(CF 3 )2CF(CF 2 )2(CH2)2OCOCH=CH2
(CF 3 )2CFCF 2 (CH2)2OCOCH=CH2
(CF 3 )2CF(CF2)3(CH2)2θCOC(CH 3 )=CH2
(CF 3 )2CF(CF 2 )2(CH 2 )2θCOC(CH 3 )=CH2 (CF 3 ) 2 CFCF2(CH2)2OCOC(CH 3 )=CH2
CF 3 (CF 2 )2(CH 2 )2OCOCH=CH2
CF 3 (CF 2 )2(CH 2 )2OCOC(CH 3 )=CH2
CF 3 (CH 2 ) 2 OCOCH=CH 2
CF 3 (CH 2 ) 2 OCOC(CH 3 )=CH 2 CF 3 (CF 2 )SSO 2 N(CH 3 )(CHZ) 2 OCOCH=CH 2
CF 3 (CF 2 )sSO 2 N(C 2 H 5 χCH2) 2 OCOCH=CH2
(CF 3 ) 2 CF(CF 2 ) 3 CH 2 CH(OCOCH 3 )CH 2 OCOC(CH 3 )=CH2
(CFS) 2 CF(CF 2 )SCH 2 CH(OH)CH 2 OCOCH=CH 2
C 6 Fi 3 -O-Ph-CH 2 OCOCH=CH 2 (where Ph represents 1 ,4-phenylene) C 5 FiI-O-Ph-CH 2 OCOC(CHs)=CH 2
C 4 F 9 -O-Ph-COOCH 2 CH(OH)CH 2 OCOC(CHs)=CH 2
(CFs) 2 CFOCOC(CHs)=CH 2
(CFs) 2 CF(CH 2 ) 2 OCOC(CH 3 )=CH 2
CF 3 (CF 2 ) S SO 2 N(CH 3 )(CH 2 )2OCOC(F)=CH 2 CF 3 (CF 2 )5SO 2 N(CH 3 )(CH 2 ) 2 OCOC(CI)=CH2
CF 3 (CF 2 ) 5 SO 2 N(CH 3 )(CH 2 )2OCOC(Br)=CH2
CF 3 (CF 2 ) 5 SO 2 N(CH 3 )(CH 2 ) 2 OCOC(I)=CH 2
CF 3 (CF 2 )sSO 2 N(CH 3 )(CH 2 )2OCOC(CF 3 )=CH2
CF 3 (CF 2 ) 5 SO 2 N(CH 3 )(CH 2 )2OCOC(CN)=CH2 CF 3 (CF 2 )sSO 2 N(CH 3 )(CH2)2OCOC(C6H5)=CH2
CF 3 (CF 2 )5(CH2)2θCOC(F)=CH2 CF 3 (CF 2 ) 5 (CH 2 ) 2 OCOC(CI)=CH 2 CF 3 (CF 2 )5(CH 2 )2θCOC(Br)=CH2 CF 3 (CF 2 )5(CH2)2θCOC(l)=CH2 CF 3 (CF2)5(CH 2 )2θCOC(CF3)=CH2 CF 3 (CF 2 )5(CH2)2OCOC(CN)=CH2 CF 3 (CF 2 )5(CH 2 ) 2 OCOC(C 6 H 5 )=CH 2
Especially, the above-mentioned fluorine-containing monomer (a) is a C 4 - or C 6 -(per)fluoroalkyl-ethyl alpha-CI acrylate or a Cβ (per)fluorohexyl-ethyl methacrylate.
(b) Fluorine-free monomer
The fluorine-containing polymer may have the repeating units derived from the fluorine-free monomer (b). The fluorine-free monomer (b) is other than the crosslinkable monomer (c). The monomer (b) is preferably a fluorine-free monomer having a carbon-carbon double bond. The monomer (b) is preferably a vinyl monomer which is free from fluorine. The fluorine-free monomer (b) is generally a compound having one carbon-carbon double bond. Preferable examples of the fluorine-free monomer (b) include, for example, ethylene, vinyl acetate, vinyl halide such as vinyl chloride, vinylidene halide such as vinylidene chloride, acrylonitrile, styrene, polyethyleneglycol (meth)acrylate, polypropyleneglycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, methoxypolypropyleneglycol (meth)acrylate, vinyl alkyl ether and isoprene. The fluorine-free monomer (b) is not limited to these examples. The fluorine-free
monomer (b) may contain vinyl halide and/or vinylidene halide.
The fluorine-free monomer (b) may be a (meth)acrylate ester having an alkyl group. The number of carbon atoms of the alkyl group may be from 1 to 30, for example, from 6 to 30, e.g., from 10 to 30. For example, the fluorine-free monomer (b) may be acrylates of the general formula:
CH 2 =CA 1 COOA 2 wherein A 1 is a hydrogen atom, a methyl group, or a halogen atom (for example, a chlorine atom, a bromine atom and a iodine atom) other than a fluorine atom, and
A 2 is an alkyl group represented by C n H2n+i (n = 1 to 30).
The fluorine-free monomer (b) is preferably a Cio- 3 o-alkyl (meth)acrylate, more preferably lauryl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate and/or stearyl (meth)acrylate, particularly preferably stearyl acrylate.
(c) Crosslinkable monomer
The fluorine-containing polymer may contain the repeating units derived from the crosslinkable monomer (c). The crosslinkable monomer (c) may be a fluorine-free monomer having at least two reactive groups and/or carbon-carbon double bonds. The crosslinkable monomer (c) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group,
a blocked isocyanate group, an amino group and a carboxyl group.
Examples of the crosslinkable monomer (c) include diacetoneacrylamide, (meth)acrylamide, N-methylolacrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, N 1 N- dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, butadiene, chloroprene, glycerol (meth)acrylate and glycidyl (meth)acrylate, to which the crosslinkable monomer is not limited.
The crosslinkable monomer (c) is preferably glycerol (meth)acrylate and/or glycidyl (meth)acrylate.
The copolymerization of the monomer (b) and/or the monomer (c) with the monomer (a) can optionally improve various properties such as the prevention of makeup coming off, the adherence to skin and the feeling in use.
In the fluorine-containing polymer, the amount of the fluorine-free monomer (b) may be from 0.1 to 100 parts by weight, for example, from 0.1 to 50 parts by weight, and the amount of the crosslinkable monomer (c) may be at most 50 parts by weight, for example, at most 20 parts by weight, particularly, from 0.1 to 15 parts by weight, based on 100 parts by weight of the fluorine-containing monomer (a).
The monomer (A) can be polymerized in the presence of the mercapto
organopolysiloxane (B). Examples of an olefinically unsaturated co-monomer included in the monomer (A) include alkyl acrylate or methacrylate esters having 1 to 30 carbon atoms in the alkyl group such as butyl acrylate, ethyl acrylate, methyl acrylate, methyl methacrylate or butyl methacrylate. The alkyl acrylate or methacrylate can be used to adjust the glass transition temperature (Tg) of the resulting polymeric product resulting from the reaction of the fluorine- containing monomer (A) and the amino-mercapto organopolysiloxane (B); for example an acrylate having a long chain alkyl group of 4-20, particularly 8-20 carbon atoms such as stearyl acrylate or methacrylate, octyl acrylate, 2- ethylhexyl acrylate or dodecyl acrylate or methacrylate can be used to form a softer polymer of lower Tg. Copolymers with an alkyl acrylate or methacrylate monomer may improve various properties such as the prevention of makeup coming off, the adherence to skin and the feeling in use. Other acrylate or methacrylate comonomers which can be used include polyethylene glycol acrylate or methacrylate, polypropylene glycol acrylate or methacrylate, methoxypolyethylene glycol acrylate or methacrylate and methoxypolypropylene glycol acrylate or methacrylate. Other olefinically unsaturated comonomers which can be used include vinyl chloride, vinylidene chloride, styrene, acrylonitrile, methacrylonitrile, ethylene, a vinyl alkyl ether, isoprene or a vinyl ester such as vinyl acetate or vinyl propionate. The olefinically unsaturated comonomer can be used which contains a functional group that, although not reactive with amine groups, may be reactive with other functional groups to give properties such as increased substantivity on textiles and other substrates. Examples of such functional groups are hydroxyl, amino and amide, and examples of olefinically unsaturated comonomers containing them are
acrylamicle, methacryiamide, N-methylolacry!amide, hydroxyethyl methacrylate, hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate or methacrylate, N, N- dimethylaminoethyl acrylate or methacrylate and diethylaminoethyl acrylate or methacrylate.
(B) The Mercapto Functional Orαanopolvsiloxane
Component (B) of the present invention is a mercapto functional organopolysiloxane, that is, an organopolysiloxane having a mercapto functional organic group present in the molecule. As used herein, a "mercapto functional organic group" is any organic group containing a sulfur atom.
Mercapto group-containing silicone (B) (that is, the mercapto functional organopolysiloxane (B)) is a siloxane compound which has at least one (for example, 1 to 500, particularly 2 to 50) mercapto group and a silicone moiety having two or more siloxane linkages. The mercapto group-containing silicone (B) functions as a chain transfer agent. In a polymerization reaction, a H radical is generated from a -SH group, and a S atom bonding to the silicone moiety bond to the fluorine-containing polymer.
Organopolysiloxanes are well known in the art and are often designated by the general formula R n Si0(4- n y2, where the organopolysiloxanes may comprise any number of "M" (mono functional) siloxy units (RaSiOo.s ), "D" (difunctional) siloxy units (R 2 SiO), "T" (trifunctional) siloxy units (RSiOi.s), or "Q" siloxy units (SiO 2 ) where R is independently a monovalent organic group. These siloxy units can be combined in various manners to form cyclic, linear, or
branched structures. The chemical and physical properties of the resulting polymeric structures can vary. For example organopolysiloxanes can be volatile or low viscosity fluids, high viscosity fluids/gums, elastomers or rubbers, and resins. R is independently a monovalent organic group, alternatively R is a hydrocarbon group containing 1 to 30 carbons, alternatively R is an alkyl group containing 1 to 30 carbon atoms, or alternatively R is methyl.
The organopolysiloxanes useful as component (B) in the present invention are characterized by having at least one of the R groups in the formula R n Si0(4-n) / 2 be a mercapto group, or alternatively at least one of the R groups be a mercapto group and one of the R groups be an organofunctional group, or alternatively one of the R groups be an organofunctional group also containing a mercapto group. The organofunctional group and mercapto functional group may be present on any siloxy unit having an R substituent, that is, they may be present on any M, D, or T unit. Typically, the organofunctional groups and mercapto groups are present as a R substituent on a D siloxy unit.
As used herein, "organofunctional group" means an organic group containing any number of carbon atoms, but the group contains at least one atom other than carbon and hydrogen. Representative examples of such organofunctional groups include, hydroxyls, amines, amides, sulfonamides, quaternaries, ethers, epoxy, phenols, esters, carboxyls, ketones, halogen- substituted alkyls and aryls group, to name a few. Alternatively, the organofunctional group is an amino-functional organic group.
When the organofunctional group is an amino-functional organic group, the amino-functional organic group is designated in the formulas herein as R N and is illustrated by groups having the formula: -R 1 NHR 2 , -R 1 NR 2 2 , or - R 1 NHR 1 NHR 2 , wherein each R 1 is independently a divalent hydrocarbon group having at least 2 carbon atoms, and R 2 is hydrogen or an alkyl group. Each R 1 is typically an alkylene group having from 2 to 20 carbon atoms. R 1 is illustrated by groups such as; -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CHCH 3 -, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 -, -CH 2 CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH(CH 2 CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -, and -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -. The alkyl groups R 2 are as illustrated above for R. When R 2 is an alkyl group, it is typically methyl.
Some examples of suitable amino-functional hydrocarbon groups are;
-CH 2 CH 2 NH 2 , -CH 2 CH 2 CH 2 NH 2 , -CH 2 CHCH 3 NH, -CH 2 CH 2 CH 2 CH 2 NH 2 , -CH 2 CH 2 CH 2 CH 2 CH 2 NH 2 , -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 NH 2 ,
-CH 2 CH 2 NHCH 3 , -CH 2 CH 2 CH 2 NHCH 3 , -CH 2 (CH 3 )CHCH 2 NHCH 3 ,
-CH 2 CH 2 CH 2 CH 2 NHCH 31 -CH 2 CH 2 NHCH 2 CH 2 NH 2 ,
-CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 NH 21 -CH 2 CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 CH 2 NH 21
-CH 2 CH 2 NHCH 2 CH 2 NHCH 31 -CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 NHCH 3 , -CH 2 CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 CH 2 NHCH 3 , and
-CH 2 CH 2 NHCH 2 CH 2 NHCH 2 CH 2 CH 2 CH 3 . Typically, the amino functional group is -CH 2 CH 2 CH 2 NH 2 .
The mercapto-functional organic group is designated in the formulas herein as R s and is illustrated by groups having the formula: -R 1 SR 2 , wherein
each R 1 and R 2 is as defined above. The mercapto-functional group is illustrated by the following formulae; CH 2 CH 2 CH 2 SH, -CH 2 CHCH 3 SH, -
CH 2 CH 2 CH 2 CH 2 SH,
-CH 2 CH 2 CH 2 CH 2 CH 2 SH, -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 SH 1 -CH 2 CH 2 SCH 3 . Typically, the mercapto functional group is -CH 2 CH 2 CH 2 SH.
In a preferable embodiment, the mercapto functional organopolysiloxane (designated B ' ) comprises siloxy units having the average formula: (R 2 SiO)a(RR N SiO) b (RR s SiO)c where; a is 0-4000, alternatively 1 to 1000, alternatively 2 to 400, b is 1-1000, alternatively 2 to 100, alternatively 3 to 50, c is 1- 1000, alternatively 2 to 100, alternatively 3 to 50; R each is independently a monovalent organic group, alternatively R each is a hydrocarbon containing 1- 30 carbon atoms, alternatively R each is a monovalent alkyl group containing 1 - 12 carbons, or alternatively R each is a methyl group;
R N each is a monovalent amino functional organic group as defined above, R s each is a monovalent mercapto functional organic group as defined above.
The R N group may be R F wherein R F may be a monovalent organofunctional organic group as defined above, such as hydroxyls, amines, amides, sulfonamides, quaternaries, ethers, epoxy, phenols, esters, carboxyls, ketones, halogen-substituted alkyls and aryls group. The mercapto functional organopolysiloxane may comprise siloxy units having the average formula (R 2 SiO) a (RR F SiO)b(RR s SiO)c
wherein the groups and subscripts (that is, a, b and c) are the same define above.
Organopolysiloxane (B ' ) may be terminated with a hydrogen atom (resulting in a silanol group on the terminal siloxy unit of the terpolymer), or with an alkyl group containing 1 - 30 carbon atoms (resulting in an alkoxy group on the terminal siloxy unit of the terpolymer). When an alkyl group is used, the alkyl group can be a linear or branched alkyl, containing 1 - 30 carbons, alternatively the alkyl group can be a long chain alkyl group of 4-20, alternatively 8-20 carbon atoms such as stearyl. Alternatively the organopolysiloxane can be terminated with a trimethylsilyl group.
The mercapto group-containing silicone (B) is of, for example, the formula:
R 1 R 2 R 3
R'—O-fSiO-)— -(-SiO-M-SiO-) — R 1
A a B b R 3 C I I S H C wherein R 1 is a methyl group, a methoxy group, a phenyl group, or a hydroxyl group,
R 2 is a methyl group, a methoxy group, a phenyl group, or a hydroxyl group,
R 3 is a methyl group, a methoxy group, a phenyl group, or a hydroxyl group, R' is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, or MesSi,
A is a divalent saturated hydrocarbon group having 1-10 carbon atoms which may be interrupted with one or two ether linkages,
B is a divalent saturated hydrocarbon group having 1-10 carbon atoms which may be interrupted with one or two ether linkages,
C is hydroxyls, amines, amides, sulfonamides, quaternaries, ethers, epoxy, phenols, esters, carboxyls, ketones, halogen-substituted alkyls or aryls group, a, b, and c are integers showing the number of repeat units, a is from 1 to 4000, for example, 2 to 2000, b is from 1 to 1000, preferably from 2 to 800 ,and c is from 0 to 1000, preferably from 1 to 800.
The example of mercapto group-containing silicone (B) is as follows.
R 1 R 2 R 3
R 3 3 Si— 0-(-SiO-)- fSiO-)— fSiO-) — SiR 3 3
A a B b R 3 c I I SH C
wherein the groups such as the R 1 group and the subscripts are defined as the same as above-mentioned.
The functional group C is particularly preferably an amino group (that is, the mercapto group-containing silicone (B) is an amino mercapto silicone). The amino group has the effect of remarkably improving the affinity with other materials constituting the cosmetic and with a human body skin.
The organopolysiloxane (B') of the above-mentioned preferable embodiment can be represented by the following average formula for example;
(CH 2 ) 3 SH
R 1 O(SiMe 2 O) 3 (SiMeO) 15 (SiMeO) 0 R 1
(CH 2 J 3 NH 2
where; a is 0-4000, alternatively 1 to 1000, alternatively 2 to 400, b is 1-1000, alternatively 2 to 100, alternatively 3 to 50, c is 1- 1000, alternatively 2 to 100, alternatively 3 to 50; and R ' is H, an alkyl group having 1 to 40 carbon atoms, or Me 3 Si.
The amino-mercapto functional organopolysiloxane terpolymers of this preferable embodiment (B ' ) can be prepared by any technique known in the art for preparation of organopolysiloxane terpolymers containing amino and/or mercapto functional groups. Typically, the organopolysiloxanes (B ' ) are prepared via a condensation polymerization reaction of an amino functional alkoxy silane, a mercapto functional silane monomer, and organopolysiloxane having alkoxy or silanol termination as illustrated by the following general reaction scheme.
HO(SiMe 2 O) n H (CH 2 ) 3 SH
+
ROH
(MeO) 2 SiMe(CH 2 ) 3 NH 2 RO(SiMe 2 O) a (SiMeO) b (SiMeO) c R + Catalyst
(EtO) 2 Si(CH 2 ) 3 SH (CH 2 ) 3 NH 2
Condensation of organopolysiloxanes is well known in the art and is
typically catalyzed by the addition of a strong base, such as an alkaline metal hydroxide or a tin compound. Alternatively co-polymerization of the functionalized cyclosiloxanes could be used.
The fluorine-containing polymer may have a weight-average molecular weight of 2,000 to 5,000,000, particularly 3,000 to 5,000,000, especially 10,000 to 1 ,000,000. The weight-average molecular weight (in terms of polystyrene) of the fluorine-containing polymer can be determined by GPC (Gel Permeation Chromatography).
The fluorine-containing polymer of the present invention can be produced by bulk polymerization, solution polymerization and emulsion polymerization.
In the bulk polymerization, a method is adopted in which a mixture of the monomers and the mercapto silicone is purged by nitrogen, a polymerization initiator is then added, and the mixture is stirred in the range of from 30 to 80°C for several (2 to 15) hours to be polymerized. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate. The polymerization initiator may be used in the amount within the range from 0.01 to 20 parts by weight, for example, from 0.01 to 10 parts by weight, based on 100 parts by weight of the monomers.
In the case of the solution polymerization, the mixture of the monomers and the mercapto silicone is dissolved in a suitable organic solvent in which
these can dissolve and to which these are inert, and then polymerized in the same manner as described earlier. Examples of the organic solvent include a hydrocarbon-based solvent, an ester-based solvent, a ketone-based solvent, an alcohol-based solvent, a silicone-based solvent, and a fluorine-containing solvent. The organic solvent is inert to the monomer and dissolves the monomer, and examples thereof include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1 ,1 ,2,2- tetrachloroethane, 1 ,1 ,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane and trichlorotrifluoroethane. The organic solvent may be used in the amount within the range from 50 to 2,000 parts by weight, for example, from 50 to 1 ,000 parts by weight, based on 100 parts by weight of total of the monomers.
In the solution polymerization, there can be used a method of dissolving the monomer(s) into an organic solvent in the presence of a polymerization initiator, replacing the atmosphere by nitrogen, and stirring the mixture with heating, for example, at the temperature within the range from 30 degrees C to 120 degrees C for 1 hour to 10 hours.
In the case of the emulsion polymerization, the polymerization is carried out in the same manner as described above after emulsifying a mixture of the monomers and the mercapto silicone in water using a proper emulsifier. In some combinations of the monomers (a) to (c) and the mercapto silicone, a
poor compatibility of the monomers and the mercapto silicone in water results in a poor copolymerizability. In such a case, a method in which a proper auxiliary solvent such as glycols and alcohols and/or a low molecular weight monomer is added to improve the compatibility of the mixture is adopted. A hydrophobic group in the emulsifier to be used in the emulsion polymerization may be any of hydrocarbon type, silicon-containing type and fluorine-containing type. As for the ionicity of a hydrophilic group, any of nonionic one, anionic one, cationic one and amphoteric one may be used. As the polymerization initiator for emulsion polymerization, for example, water-soluble initiators (e.g., benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1 -hydroxycyclohexyl hydroperoxide, 3- carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate) and oil-soluble initiators (e.g., azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate) are used. The polymerization initiator may be used in the amount within the range from 0.01 to 10 parts by weight based on 100 parts by weight of the monomers.
In the emulsion polymerization, there can be used a method of emulsifying monomers in water in the presence of a polymerization initiator and an emulsifying agent, replacing the atmosphere by nitrogen, and polymerizing with stirring, for example, at the temperature within the range from 30 degrees C to 120 degrees C, for example, from 50 degrees C to 80 degrees C, for 1 hour to 10 hours.
When the monomers are not completely compatibilized, a compatibilizing agent capable of sufficiently compatibilizing them (e.g., a water-soluble organic solvent and a low-molecular weight monomer) is preferably added to these monomers. By the addition of the compatibilizing agent, the emulsifiability and polymerizability can be improved.
Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol and ethanol. The water-soluble organic solvent may be used in the amount within the range from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight, based on 100 parts by weight of water. Examples of the low-molecular weight monomer are methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate. The low- molecular weight monomer may be used in the amount within the range from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight, based on 100 parts by weight of total of monomers.
As the emulsifying agent, various emulsifying agents such as an anionic emulsifying agent, a cationic emulsifying agent and a nonionic emulsifying agent can be used in the amount within the range from 0.5 to 20 parts by weight based on 100 parts by weight of the monomers. The emulsifying agent used in the emulsion polymerization may have a hydrophobic group which may be a hydrocarbon, a silicone or a fluorine-containing compound, and hydrophilic group which may be nonionic, anionic, cationic or amphoteric. A combination of the anionic emulsifying agent and the nonionic emulsifying agent is preferable in
order to obtain both the stability of the emulsion and safety to skin. The amount of the anionic emulsifying agent is from 5 to 80 % by weight, preferably from 10 to 60 % by weight, based on the total of the anionic emulsifying agent and the nonionic emulsifying agent. Preferably, the anionic emulsifying agent is polyoxyethylene alkyl (preferably Ci to C 30 alkyl) ether sulfate salt, and the nonionic emulsifying agent is fatty acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester, polyoxyethylene hardened castor oil and/or polyoxyethylene fatty acid sorbit ester.
In order to obtain a polymer dispersion in water, which has a high polymer solid content and which has very fine and stable particles, it is desirable that the mixture of the monomers and the mercapto silicone is dispersed in water by using an emulsifying device capable of applying a strong shearing energy (e.g., a high-pressure homogenizer and an ultrasonic homogenizer) to prepare the fine particles of the mixture, and then the polymerization is conducted.
In the polymerization, a chain transfer agent other than the mercapto silicone or a pH modifier may be added, if necessary. The weight average molecular weight (measured by GPC) of the fluorine-containing polymer obtained after the polymerization is from 10,000 to 1 ,000,000, preferably from
20,000 to 300,000.
The fluorosilicone reaction product of the fluorine-containing monomer
(A) and the mercapto organopolysiloxane (B) may be prepared by any reaction process known in the art to effect polymerisation of such monomers. Preferably,
the fluorosilicone may be prepared according to the process of the present invention comprising; I) reacting,
(A) a monomer comprising a fluorine-containing monomer of the formula: CH 2 =C(X)COOYRf
X is a hydrogen atom, a monovalent organic group, or a halogen atom,
Y is a direct bond or a divalent organic group having 1 to 20 carbon atoms, and Rf is a fluoroalkyl group having 1 to 21 carbon atoms, in the presence of
(B) a mercapto functional organopolysiloxane, via a polymerization reaction, preferably a free radical polymerisation reaction.
Components (A) and (B) in the process are the same as described above.
The process may also be conducted in the presence of a polar organic solvent. The polar organic solvent can be one or more alcohol, ketone or ester solvents selected from butanol, t-butanol, isopropanol, butoxyethanol, methyl isobutyl ketone, methyl ethyl ketone, butyl acetate or ethyl acetate and/or an aromatic hydrocarbon such as xylene, toluene or trimethylbenzene a blend of one or more of these.
The initiator for the free radical polymerisation reaction can be any compound known in the art for initiating free radical reactions, such as organic
peroxides or azo compounds. Representative, non-limiting examples are; azo compounds such as azobisisobutyronitrile or azobisisovaleronitrile (AIVN) 1 peroxides such as benzoyl peroxide. The polymerisation temperature typically ranges 50-120°C.
Alternatively the polymeric reaction product can be obtained using the technique of emulsion polymerisation, where all the components are polymerised in the presence of water, surfactants and polymerisation initiator.
The fluorosilicone reaction product can contain various ratios of the fluorine-containing monomer (A) and the mercapto organopolysiloxane (B), as controlled by the amount of each components (A) and (B). The fluorosilicone may contain 5 to 99.9% by weight, preferably 10 to 95 by weight of the monomer (A), and 0.1 to 95%by weight, preferably 5 to 90 by weight of the mercapto organopolysiloxane (B) with the proviso that sum of the wt % of (A) and (B) equals 100%. A fluorosilicone product having a high proportion of mercapto organopolysiloxane may provide greater substantivity to fibrous substrates or softness of handle of the treated material. A polymeric product having a high proportion of fluorine-containing monomer may provide maximum hydrophobicity and oleophobicity.
A fluorine-containing polymer prepared by solution polymerization or emulsion polymerization may be blended directly in the form of a reaction liquid into cosmetic preparations for forming a film. Alternatively, the polymer may be dissolved (or dispersed) in solvents (or water) after the isolation of only the
polymers.
Although the fluorine-containing polymer may be an isolated polymer, it is preferable that the polymer is supplied as a raw material of cosmetics in the form dissolved or dispersed in water or at least one of hydrocarbon-based solvents, alcohol-based solvents, ester-based solvents, ketone-based solvents, silicone-based solvents and fluorine-containing solvents. The fluorine- containing polymer may be contained in an amount of from 1 to 60% by weight, preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight relative to the total amount [the fluorine-containing polymer plus (water or a solvent)]. When it is from 1 to 60% by weight, the amount of the fluorine- containing polymer blended in a cosmetic preparation is sufficient for imparting insufficient waterproofing property or water- and oil-repellency, and the stability as a raw material is sufficient.
Examples of hydrocarbon-based solvents, alcohol-based solvents, ester- based solvents, ketone-based solvents, silicone-based solvents and fluorine- containing solvents, which can dissolve or disperse the fluorine-containing polymer, are mentioned below.
Examples of the hydrocarbon-based solvents include n-hexane, n- heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, isohexane, isoheptane, isooctane, isononane, isodecane, isoundecane, isododecane, cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, liquid paraffin, isoparaffin, toluene, benzene and xylene.
Examples of the alcohol-based solvents include ethanol and isopropyl alcohol.
Examples of the ester-based solvents include butyl acetate, ethyl acetate, amyl acetate and acyl acetate.
Examples of the ketone-based solvents include methyl ethyl ketone, methyl isobutyl ketone and acetone.
Examples of the silicone-based solvents include hexamethylcyclotrisiloxane (that is, a cyclic silicone trimer), octamethylcyclo- tetrasiloxane (that is, a cyclic silicone tetramer), decamethylcyclopentasiloxane (that is, a cyclic silicone pentamer), dodecamethylcyclohexasiloxane (that is, a cyclic silicone hexamer), dimethylpolysiloxane, methylphenylpolysiloxane and a dimethylpolysiloxane/methyl(polyoxyethylene)siloxane/ethyl(p olyoxypropylene)- siloxane copolymer.
Examples of the fluorine-containing solvents include hydrofluorocarbon (HFC), hydrofluoroether (HFE), fluoroether, fluorocarbon (FC) and nitrogen- containing fluorocarbon.
The HFC may be 1 ,1 ,1 ,2,2,3,4,5,5,5-decafluoropentane (HFC-4310), benzotrifluoride, m-xylene hexafluoride and the like.
The HFE may be represented by the general formula: C n HmF|OCχHyF z wherein n is a number of from 1 to 12, m is a number of from 0 to 25, I is a number of from 0 to 11 , m+l=2n+1 , x is a number of from 1 to 12, y is a number of from 0 to 25, z is a number of from 0 to 11 and y+z=2x+1 , provided that m and y are not simultaneously zero and I and z are not simultaneously zero. The HFE may be, for example, C 4 F 9 OCH 3 and C 4 F9OC 2 H5.
The fluoroether may be represented by the general formula: (C n
F 2n+
O 2
O wherein n is a number of from 3 to 5. The fluoroether may be, for example,
Examples of the FC include perfluorohexane, perfluorooctane, perfluorononane, perfluorobenzene, perfluorotoluene, perfluoroxylene, perfluorodecalin and perfluoromethyldecalin.
The nitrogen-containing fluorocarbon may be represented by the general formula: (C n F 2n+ O 3 N wherein n is a number of from 1 to 5.
The nitrogen-containing fluorocarbon may be, for example, perfluorotripropylamine and perfluorotributylamine.
These solvents may be used either alone or in admixtures. Solvents having a property to evaporate easily at the skin temperature (about 30 0 C) are preferred since they can provide a cool feeling during their volatilization and can form films on the skin easily. Particularly, octamethylcyclotetrasiloxane (that is, a cyclic silicone tetramer), decamethylcyclopentasiloxane (that is, a cyclic silicone pentamer), dimethylpolysiloxanes having viscosities of not greater than 10 cSt, which are silicone-based solvents, and isoparaffin, which is a hydrocarbon, are preferably used. In the case of using the fluorine-containing solvent, use of C 4 F 9 OCH 3 , C 4 F 9 OC 2 H 5 , C 4 F 9 OC 3 H 7 or C 4 F 9 OC 4 H 9 , particularly C 4 F 9 OCH 3 or C 4 F 9 OC 2 Hs, which are HFEs, is most desirable. This type of solvents are volatile and soluble in many solvents and oils widely used for cosmetics. They also have high solubilities of fluorine-containing polymers.
Raw materials to be used for the cosmetics in which the fluorine- containing polymer of the present invention is blended are not particularly restricted as long as they are generally used for cosmetics.
For example, powders may be exemplified by inorganic powders such as talc, kaolin, mica, mica titanium, titanium oxide, iron oxide, magnesium oxide, zinc monooxide, zinc dioxide, heavy or light calcium carbonate, calcium secondary phosphate, aluminum hydroxide, barium sulfate, silica, alumina, silica gel, carbon black, antimony oxide, magnesium silicate aluminate, magnesium metasilicate aluminate and synthesized mica; and organic powders such as protein powder, fish scale foil, metal soap, polyvinyl chloride, nylon-12, microcrystalline fiber powder, tar pigment and lake. These may be ones either
untreated or treated with a silicone or a fluorine compound. For example, the powder may be a fluorine compound-treated powder.
Furthermore, examples other than powders include solid or semi-solid fats such as vaseline, lanoline, ceresin, microcrystalline wax, camauba wax, candelilla wax, higher fatty acids and higher alcohols; liquid fats such as squalane, liquid paraffin, ester oil, diglyceride, triglyceride and silicone oil; fluorine-containing oils such as perfluoropolyether, perfluorodecalin and perfluorooctane; water-soluble or oil-soluble polymers, surfactants, colorants such as organic dyes, ethanol, antiseptics, antioxidants, colorant, thickeners, pH modifiers, perfumes, ultraviolet absorbers, humectants, blood circulation promoters, cold feeling agents, antiperspirants, germicides and skin activators.
The cosmetic of the present invention can be produced in accordance with conventional methods and can be used as a finishing cosmetic such as foundation, face powder, cheek color, eye color, mascara, eyeliner and nail color; basic cosmetics such as a milky lotion and cream; hair cosmetics.
A fluorine-containing polymer for cosmetic of this invention can be used for coating the surface of powder for the cosmetics. Examples of the powder to be coated include inorganic powders such as talc, kaolin, mica, mica titanium, titanium oxide, iron oxide, magnesium oxide, zinc monooxide, zinc dioxide, heavy or light calcium carbonate, calcium secondary phosphate, aluminum hydroxide, barium sulfate, silica, alumina, silica gel, carbon black, antimony oxide, magnesium silicate aluminate, magnesium metasilicate aluminate and
synthesized mica; and organic powders such as protein powder, fish scale foil, metal soap, polyvinyl chloride, nylon-12, microcrystalline fiber powder, tar pigment and lake. When the surface of the powder is treated with the polymer, at least two may be mixed. Also when the treated powder is blended with cosmetics, at least two may be mixed.
The polymer for cosmetics is made to be adhered to the surface of a powder by a wet method or a dry method, and the wet method is preferred for uniform surface treatment. For example, a liquid prepared by diluting an aqueous dispersion of polymer with water or diluting a solution of polymer with an organic solvent is mixed with the powder, and the stirring is conducted until the powder is homogeneously wet with water or an organic solvent at a room temperature or an elevated temperature. For the stirring in the above procedure, a stirring device is used, for example, a Henschel mixer, a vibratory ball mill, a rotary ball mill, a supermixer and a planetary mixer. In stirring in a laboratory scale, a juicer for home use may be employed. The concentration of the polymer in a solution in an organic solvent is not particularly limited, but is adjusted so that the viscosity does not become too high during the stirring in the mixing of powder.
In the case that the aqueous dispersion of polymer is diluted with water, the polymer is adhered to the powder surface by, after stirring, adding an alcohol or a polyvalent salt and coagulating the emulsion. Examples of the alcohol include methanol, ethanol and isopropyl alcohol, and examples of the polyvalent salt include those having the ionicity which is counter to the ionicity
(sign of zeta potential) of the emulsion. For example, when the zeta potential of the emulsion is anionic, for example, -50 mV, the coagulation of the emulsion is carried out by using calcium chloride, aluminum chloride or the like. After adhering the polymer to the powder, the treated powder is washed, filtered and dried, and the treated powder is homogeneously dispersed by the above- mentioned stirring device. In stirring in a laboratory scale, a juicer for home use or a speed cutter may be used.
In the case that the polymer solution is diluted with the organic solvent, the organic solvent, after stirring, is distilled off at vacuum or at an elevated temperature and the treated powder is homogeneously dispersed by the above- mentioned device.
In the present invention, proper chemicals to improve the feeling in use may, if needed, be used together at the surface-treatment. Examples of the chemicals to improve the feeling in use include lecithin, N-mono-long-chain-acyl basic amino acids, silicone, chitosan, collagen and wax.
Preferred Embodiments of the Invention Examples of the present invention will be described, but Examples do not limit the present invention.
Synthetic Example 1 Preparation of amino mercapto silicone: Into a three necked round bottomed flask fitted with a condenser,
overhead stirrer and thermocouple were charged a silanol terminated polydimethylsiloxane (323g Mn about 900 and 38Og Mn about 300), mercaptopropylmethyldimethoxysilane (23Og), aminopropylmethyl- diethoxysilane (27g), trimethylethoxysilane (42g), barium hydroxide (0.62g) and sodium orthophosphate (0.25g). The reaction mixture was heated to 75 0 C and held at this temperature for three hours after which volatile removal was carried out at 75 0 C and a reduced pressure of 200mbar for four hours to give an amino mercapto silicone polymer. The resulting polymer had an Mn of 4396, viscosity of 74Cts, % N of about 0.26 w/w and % SH of about 4.1w/w, and 9% of the end groups were SiMe3 and the remainder was a mixture of SiOH and SiOMe/SiOEt.
Preparative Example 1
Preparation of C6 Hybrid polymer emulsion:
A mixture of CF 3 CF2-(CF2CF2)2-CH2CH2OCOC(CH3)=CH 2 (hereinafter referred to as "Rf(C6) methacrylate") (9.2 g), stearyl acrylate (StA) (1.15 g), glycerol methacrylate (GLM) (0.22 g), glycidyl methacrylate (GMA) (0.07 g), amino mercapto silicone prepared in Synthetic Example 1 (1.42 g), pure water (23.3 g), dipropylene glycol (4.25 g), sodium polyoxyethylene(2)lauryl ether sulfate (0.76 g), sorbitan monopalmitate (0.13 g) and polyoxyethylene (100) hardened caster-oil derivatives (0.635 g) was heated at 60 degrees C and previously emulsified by a homomixer. Then the mixture was emulsified by the ultrasonic homogenizer to give the particle diameter of about 200 nm (measured by a dynamic-light-scattering method).
The monomer emulsion was transferred to an autoclave. After
replacement of nitrogen gas, vinyl chloride (3.36 g) was injected. 2,2'-azobis(2- amidinopropane) dihydrochloride (0.18 g) was added, and the reaction was conducted at 60 degrees C for 5 hours to give an aqueous emulsion of polymer. The emulsion was diluted to a solid content of 20 % by weight which is measured from an evaporation residue after heating the emulsion at 130 degrees C for 2 hours.
Comparative Preparative Examples 1 (C6 non-Hybrid), 2 (C6 no-amino), and 3 (C6 Si-methacrylate) The procedure of Preparative Example 1 was repeated except that, in place of the amino mercapto silicone, n-dodecyl mercaptan ( 0.23 g) was used in Comparative Preparative Example 1 (C6 non-Hybrid) , a mercapto silicone free from amino group (2-8032 manufactured by Dow Corning) (1.42 g) was used in Comparative Preparative Example 2 (C6 no- amino), and polydimethylsiloxane methacrylate (SILAPLANE FM0721 manufactured by Chisso Corp.) (1.42g) was used in Comparative Preparative Example 3 (C6 Si- methacrylate).
Example 1 and Comparative Examples 1 -3
The polymer emulsions produced in Preparative Examples 1 and Comparative Preparative Examples 1 , 2 and 3 were cast on a flat 6,6-nylon film and kept stand for one day to be dried, and heat-treated at 130 degrees C for 10 minutes to form a polymer film. The water- and oil-repellency was evaluated
by the contact angles of water or n-hexadecane (HD) on these coating polymer films. Water resistance was evaluated by immersing the film into water for one hour, heat-treating the film at 130 degrees C for 10 minutes and then measuring the contact angle of water. All the test were conducted at 25 degrees C. Results are shown in Table 1.
Table 1
Water repellency, oil repellency and water resistance of fluorine-containing ol mer
In the following Examples and Comparative Examples, a powder prepared by treating a mixture powder shown Table 2 with the fluorine- containing polymer having a solid content of 5% was mixed with a silicone- treated power having the ingredients shown in Table 3 to prepare a cosmetic. The treatment method of the mixture powder is as follows. The C6 Hybrid polymer emulsion prepared in Preparative Example 1 (10 g), water (200 g) and the mixture power shown in Table 2 (40 g) were charged into a juice mixer and stirred for 30 seconds. A 1% aqueous solution of aluminum chloride was gradually added to coagulate the emulsion so that the polymer was uniformly adhered to the powder surface. The treated powder was washed with water,
filtered and dried for one day in a steam dryer (60 degrees C). The dried power was stirred in a juice mixer for one minute to fragmentate the agglomerated powder.
Table 2
Ingredients of mixture powder to be fluorine-treated
The silicone-treated powder having the ingredients shown in Table 3 was mixed with this fluorine-treated powder to prepare a mixture powder to be mixed with a cosmetic. The silicone-treated powders (2) to (4) shown in Table 3 were those treated with 2% of methyl hydrogen polysiloxane.
Table 3 Ingredients of mixture powder
Make-up lastingness (derived from the water- and oil-repellency of a film) and feelings in use (the "sleek feeling" and the "dry feeling") were evaluated according to the following criteria:
OO: Very good
O: Good
δ: Average X: Poor XX: Very poor
The evaluation was done by five panelists specialized in functional evaluation. The average of their evaluations was taken as the result.
Example 2 and Comparative Examples 4 to 6
A powdery foundation was manufactured by using the ingredients shown in Table 4. The ingredients (1 ) to (5) were mixed and pulverized by an atomizer, the pulverized ingredients were transferred to a Henschel mixer, the ingredient (6) and (7) were added and mixed uniformly. The mixture was charged into a mold and press molded to give the powdery foundation. Make-up lastingness and feelings in use were evaluated for the powdery foundation. The results are shown in Table 4.
Table 4 Powdery foundation
Numerical values in the table are in weight %.
EFFECT OF THE INVENTION
Since the fluorine-containing polymer for cosmetic of this invention does not contain perfluorooctanoic acid (PFOA), the fluorine-containing polymer gives the cosmetic which has excellent safety, and is excellent in the water resistance, the water-repellent, oil repellency, the use feeling, and affinity with other materials.
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