WO2009084705A1 - Produit cosmétique comprenant un polymère de fluoroacrylate contenant de la silicone - Google Patents

Produit cosmétique comprenant un polymère de fluoroacrylate contenant de la silicone Download PDF

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Publication number
WO2009084705A1
WO2009084705A1 PCT/JP2008/073907 JP2008073907W WO2009084705A1 WO 2009084705 A1 WO2009084705 A1 WO 2009084705A1 JP 2008073907 W JP2008073907 W JP 2008073907W WO 2009084705 A1 WO2009084705 A1 WO 2009084705A1
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WIPO (PCT)
Prior art keywords
group
fluorine
monomer
acrylate
containing polymer
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PCT/JP2008/073907
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English (en)
Inventor
Masamichi Morita
Teruyuki Fukuda
Shinichi Minami
Masahiko Maeda
Tetsuya Masutani
Peter Cheshire Hupfield
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Daikin Industries, Ltd.
Dow Corning Corporation
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Application filed by Daikin Industries, Ltd., Dow Corning Corporation filed Critical Daikin Industries, Ltd.
Publication of WO2009084705A1 publication Critical patent/WO2009084705A1/fr

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Classifications

    • 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/897—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing halogen, e.g. fluorosilicones
    • 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • 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
    • 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
    • A61Q1/12—Face or body powders for grooming, adorning or absorbing

Definitions

  • 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.
  • 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.
  • 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:
  • 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.
  • 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.
  • 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.
  • PFOA perfluorooctanoic acid
  • This invention provides a cosmetic comprising a fluorine-containing polymer comprising repeating units derived from: (A) a monomer which comprises;
  • 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
  • Rf is a fluoroalkyl group having 1 to 6 carbon atoms
  • B a mercapto functional organopolysiloxane
  • the monomer (A) which forms a fluorine-containing polymer in this invention comprises:
  • 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).
  • 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:
  • Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms.
  • 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.
  • 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 is a linear or branched fluoroalkyl group having, for example, 1 to 6 carbon atoms.
  • the above-mentioned fluorine-containing monomer (a) is a C 4 - or C 6 -(per)fluoroalkyl-ethyl alpha-CI acrylate or a C ⁇ (per)fluorohexyl-ethyl methacrylate.
  • 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.
  • fluorine-free monomer (b) examples 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.
  • the fluorine-free monomer (b) may be acrylates of the general formula:
  • 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
  • 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.
  • 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.
  • crosslinkable monomer (c) examples 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.
  • 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.
  • Tg glass transition temperature
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • organofunctional groups include, hydroxyls, amines, amides, sulfonamides, quaternaries, ethers, epoxy, phenols, esters, carboxyls, ketones, halogen- substituted alkyls and aryls group, to name a few.
  • 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.
  • 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(CH 2 CH 3 )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 -.
  • the alkyl groups R 2 are as illustrated above for R. When R 2 is an alkyl group, it is typically methyl.
  • Suitable amino-functional hydrocarbon groups are;
  • 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, -
  • the mercapto functional group is -CH 2 CH 2 CH 2 SH.
  • 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).
  • 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.
  • the organopolysiloxane can be terminated with a trimethylsilyl group.
  • the mercapto group-containing silicone (B) is of, for example, the formula:
  • 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.
  • mercapto group-containing silicone (B) is as follows.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a suitable 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,
  • 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.
  • 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.
  • 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.
  • the ionicity of a hydrophilic group any of nonionic one, anionic one, cationic one and amphoteric one may be used.
  • 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
  • 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.
  • a compatibilizing agent capable of sufficiently compatibilizing them e.g., a water-soluble organic solvent and a low-molecular weight monomer
  • the compatibilizing agent By the addition of the compatibilizing agent, the emulsifiability and polymerizability can be improved.
  • water-soluble organic solvent examples 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.
  • 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.
  • the anionic emulsifying agent is polyoxyethylene alkyl (preferably Ci to C 30 alkyl) ether sulfate salt
  • 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.
  • 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.
  • a strong shearing energy e.g., a high-pressure homogenizer and an ultrasonic homogenizer
  • 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
  • the fluorosilicone may be prepared according to the process of the present invention comprising; I) reacting,
  • 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
  • Rf is a fluoroalkyl group having 1 to 21 carbon atoms, in the presence of
  • 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.
  • 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.
  • the polymer may be dissolved (or dispersed) in solvents (or water) after the isolation of only the polymers.
  • 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.
  • hydrocarbon-based solvents examples include 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.
  • hydrocarbon-based solvents examples 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.
  • the alcohol-based solvents examples include ethanol and isopropyl alcohol.
  • ester-based solvents examples include butyl acetate, ethyl acetate, amyl acetate and acyl acetate.
  • ketone-based solvents examples include methyl ethyl ketone, methyl isobutyl ketone and acetone.
  • silicone-based solvents examples 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(polyoxypropylene)- siloxane copolymer.
  • hexamethylcyclotrisiloxane that is, a cyclic silicone trimer
  • octamethylcyclo- tetrasiloxane that is, a cyclic silicone tetramer
  • fluorine-containing solvents examples 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
  • 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,
  • FC examples 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.
  • 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
  • isoparaffin which is a hydrocarbon
  • 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.
  • 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.
  • the powder may be a fluorine compound-treated powder.
  • 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.
  • 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 s
  • 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.
  • 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.
  • 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.
  • 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.
  • a stirring device is used, for example, a Henschel mixer, a vibratory ball mill, a rotary ball mill, a supermixer and a planetary mixer.
  • 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.
  • the polymer is adhered to the powder surface by, after stirring, adding an alcohol or a polyvalent salt and coagulating the emulsion.
  • the alcohol include methanol, ethanol and isopropyl alcohol
  • the polyvalent salt include those having the ionicity which is counter to the ionicity (sign of zeta potential) of the emulsion.
  • 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.
  • the treated powder 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.
  • a juicer for home use or a speed cutter may be used.
  • 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.
  • proper chemicals to improve the feeling in use may, if needed, be used together at the surface-treatment.
  • the chemicals to improve the feeling in use include lecithin, N-mono-long-chain-acyl basic amino acids, silicone, chitosan, collagen and wax.
  • 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).
  • silanol terminated polydimethylsiloxane 323g Mn about 900 and 38Og Mn about 300
  • mercaptopropylmethyldimethoxysilane 23Og
  • aminopropylmethyl- diethoxysilane 27g
  • trimethylethoxysilane 42g
  • barium hydroxide (0.62g
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • the evaluation was done by five panelists specialized in functional evaluation. The average of their evaluations was taken as the result.
  • 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.
  • 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.
  • PFOA perfluorooctanoic acid

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Abstract

L'invention concerne un produit cosmétique présentant d'excellentes propriétés, qui peut être obtenu à partir d'un polymère contenant du fluor pour produits cosmétiques contenant un polymère contenant du fluor, qui comprend des unités de répétition dérivées de : (A) un monomère qui comprend : (a) un monomère contenant du fluor de formule : CH2=C(X)COOYRf, dans laquelle X représente un atome d'hydrogène, un groupe organique monovalent ou un atome d'halogène, Y représente une liaison directe ou un groupe organique bivalent, et Rf représente un groupe fluoroalkyle contenant 1 à 6 atomes de carbone, et (B) un organopolysiloxane à fonction mercapto.
PCT/JP2008/073907 2007-12-27 2008-12-22 Produit cosmétique comprenant un polymère de fluoroacrylate contenant de la silicone WO2009084705A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010030041A1 (fr) * 2008-09-15 2010-03-18 Daikin Industries, Ltd. Fluorosilicones et agent de traitement de surface
WO2010044479A1 (fr) * 2008-10-13 2010-04-22 Daikin Industries, Ltd. Agent de traitement contenant du fluor et du silicium pour des bétons
WO2011062292A1 (fr) * 2009-11-20 2011-05-26 Daikin Industries, Ltd. Fluoropolymères et agent de traitement
US20130078880A1 (en) * 2009-11-20 2013-03-28 Norimasa Uesugi Fluoropolymers And Surface Treatment Agent
CN117343565A (zh) * 2023-12-05 2024-01-05 北京特思迪半导体设备有限公司 一种双疏涂层的制备方法、所制备的双疏涂层及应用

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Publication number Priority date Publication date Assignee Title
US5945108A (en) * 1995-06-26 1999-08-31 Daikin Industries Ltd. Water-and oil-repellent powder for cosmetic and cosmetic containing said powder
EP1000602A1 (fr) * 1997-06-04 2000-05-17 Daikin Industries, Limited Copolymeres pour cosmetiques
US6641805B1 (en) * 1998-03-23 2003-11-04 Daikin Industries Ltd. Copolymer for cosmetic preparation
WO2006121171A1 (fr) * 2005-05-09 2006-11-16 Daikin Industries, Ltd. Fluorosilicones et agent de traitement de surface contenant du silicium et du fluor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5945108A (en) * 1995-06-26 1999-08-31 Daikin Industries Ltd. Water-and oil-repellent powder for cosmetic and cosmetic containing said powder
EP1000602A1 (fr) * 1997-06-04 2000-05-17 Daikin Industries, Limited Copolymeres pour cosmetiques
US6641805B1 (en) * 1998-03-23 2003-11-04 Daikin Industries Ltd. Copolymer for cosmetic preparation
WO2006121171A1 (fr) * 2005-05-09 2006-11-16 Daikin Industries, Ltd. Fluorosilicones et agent de traitement de surface contenant du silicium et du fluor

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010030041A1 (fr) * 2008-09-15 2010-03-18 Daikin Industries, Ltd. Fluorosilicones et agent de traitement de surface
WO2010044479A1 (fr) * 2008-10-13 2010-04-22 Daikin Industries, Ltd. Agent de traitement contenant du fluor et du silicium pour des bétons
WO2011062292A1 (fr) * 2009-11-20 2011-05-26 Daikin Industries, Ltd. Fluoropolymères et agent de traitement
US20130078880A1 (en) * 2009-11-20 2013-03-28 Norimasa Uesugi Fluoropolymers And Surface Treatment Agent
US9365714B2 (en) 2009-11-20 2016-06-14 Daikin Industries, Ltd. Fluoropolymers and surface treatment agent
US9677220B2 (en) 2009-11-20 2017-06-13 Daikin Industries, Ltd. Fluoropolymers and treatment agent
CN117343565A (zh) * 2023-12-05 2024-01-05 北京特思迪半导体设备有限公司 一种双疏涂层的制备方法、所制备的双疏涂层及应用
CN117343565B (zh) * 2023-12-05 2024-02-13 北京特思迪半导体设备有限公司 一种双疏涂层的制备方法、所制备的双疏涂层及应用

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