WO2012099384A2 - Monomer-based cross-linked copolymer containing a phosphorylcholine-like group, inverse emulsion, and cosmetic composition - Google Patents

Abstract

The present invention relates to a novel cross-linked copolymer, comprising an anionic monomer, a neutral monomer, a monomer containing a phosphorylcholine-like group, and a cross-linking agent, to an inverse emulsion of the copolymer, and to a cosmetic composition comprising the cross-linked copolymer or the inverse emulsion. The cross-linked copolymer according to the present invention comprises an anionic monomer such as 2-acrylamido-2-methylpropane-sulphonic acid (AMPS), a neutral monomer, and a monomer containing a phosphorylcholine-like group, thus improving thickening properties and/or emulsion stability, and further achieving improved moisturizing properties and excellent biocompatibility. Therefore, the cross-linked copolymer of the present invention may function as a thickening agent, an emulsion stabilization agent and a moisturizing agent in a cosmetic composition, particularly in a skin care composition or hair care composition.

Description

Crosslinked copolymers, reverse phase emulsions and cosmetic compositions based on phosphorylcholine like groups

FIELD OF THE INVENTION The present invention relates to crosslinking copolymers, reverse phase emulsions and cosmetic compositions based on phosphorylcholine like groups, more particularly phosphorylcholine like which can be used as a moisturizer as well as a thickener and / or emulsion stabilizer. Novel crosslinking copolymers based on group-containing monomers, reverse phase emulsions thereof, and cosmetic compositions comprising said crosslinking copolymers or reverse phase emulsions.

Personal care products or cosmetics applied to skin protection or hair protection are generally prepared in formulations such as lotions, creams, gels, etc., all of which are used thickeners and / or emulsifying stabilizers to modify fluidity and improve stability. .

Thickeners used for this purpose can be broadly divided into natural products and synthetic polymers. Natural products such as guar gum or corn starch have disadvantages in industrial use due to price fluctuations, supply problems, and difficulty in maintaining a certain quality. Synthetic polymers generally used are present in the form of a solid such as powder containing acidic functional groups, so that they must first be dispersed in a solvent to obtain a thickening effect, and have a disadvantage of requiring neutralization of the acidic functional groups when used. In addition, prolonged stirring is required to produce a stable emulsion, and care must be taken to prevent aggregation and coagulation. Their viscosity is expressed at a pH of 6.5 or more, there is a disadvantage that the dissolution becomes difficult depending on the state of use.

In order to overcome the disadvantages of the solid powder synthetic polymer as described above, a thickener prepared in a reverse phase emulsion type in which the continuous phase is an oil has been developed. The thickener prepared in the reversed phase emulsion type is rapidly mixed with cosmetics and is present at a neutral pH, unlike synthetic polymers, so that the process of neutralizing acidic functional groups is unnecessary. Polymers contained in the reversed phase emulsions are generally acrylamide / alkalimetal acrylate copolymers, acrylamide / sodium 2-acrylamido-2-methylpropanesulfonate copolymers, hydroxyalkyl acrylate / alkalimetal acrylate copolymers Or hydroxyalkyl acrylate / sodium 2-acrylamido-2-methylpropanesulfonate copolymer. They are already neutralized and, for example, when dissolved in water at a concentration of 1%, the pH is generally observed to be 6 or more.

On the other hand, the phosphorylcholine-like group-containing polymer is due to the phospholipid-like structure derived from the biological membrane, and is known to have excellent properties in biocompatibility, antifouling properties, moisturizing properties such as inactivation of blood components and nonadsorption of biomaterials. In addition, research and development on the synthesis of the phosphorylcholine-like group-containing polymer and its use for the purpose of developing bio-related materials utilizing these functions are being actively conducted. Such phosphorylcholine like group-containing polymers include phosphorylcholine like group containing monomers, of which 2- (methacryloyloxy) ethyl-2 '-(trimethylammonio) ethylphosphate [2- (methacryloyloxy) ethyl -2 '-(trimethylammonio) ethylphosphate, also referred to as 2-methacryloyloxyethylphosphocholine, hereinafter abbreviated as MPC], has a phosphorylcholine-like group structurally similar to the phosphatidylcholine, a cell wall component It is known to give excellent biocompatibility and excellent moisture retention.

The present invention is derived from the above background, one object of the present invention is a conventional acrylamide / alkali metal acrylate copolymer, acrylamide / sodium 2-acrylamido-2-methylpropanesulfonate copolymer, hydride In addition to the thickening or emulsification stability properties of the oxyalkyl acrylate / alkalimetal acrylate copolymer, or hydroxyalkyl acrylate / sodium 2-acrylamido-2-methylpropanesulfonate copolymer, in addition to excellent biocompatibility, improved moisturizing properties, It is to provide a novel crosslinked copolymer based on a phosphorylcholine like group-containing monomer having proper nutritional supply and the like.

It is a further object of the present invention to provide a reversed phase emulsion which can be used not only as a thickener and / or emulsion stabilizer but also as a moisturizer.

Further, another object of the present invention is to provide a cosmetic composition that can be used for such purposes as skin care or hair care.

In order to solve one object of the present invention, the present invention has an anionic monomer, a neutral monomer, at least one phosphorylcholine like group-containing monomer represented by the following formula (1), and two or more unsaturated ethylene bond groups A crosslinked polymer comprising at least one crosslinker, wherein the anionic monomer is 2-acrylamido-2-methylpropane-sulphonic acid (AMPS) and the neutral monomer Is composed of at least one selected from the group consisting of acrylamide, N, N-dimethylacrylamide, methacrylamide, diacetone acrylamide, N-isopropylacrylamide and ethylenically unsaturated monomers, the anionic monomers , Neutral monomers, and phosphorylcholine like group-containing monomers are crosslinked by the crosslinking agent. It provides a similar choline group-containing monomer based on the cross-linked co-polymer.

[Formula (1)]

In the formula (1), X represents a divalent organic residue, Y represents an alkyleneoxy group having 1 to 6 carbon atoms, Z represents a hydrogen atom or R ⁵ -O-CO-, wherein R ⁵ represents 1 to 10 carbon atoms. An alkyl group or a hydroxyalkyl group having 1 to 10 carbon atoms). In addition, R <^1> represents a hydrogen atom or a methyl group, and R <^2> , R <^3> and R <^4> represent the same or another group and represent a hydrogen atom, a C1-C6 hydrocarbon group, or a hydroxy hydrocarbon group. m is 0 or 1, and n is an integer of 2-4.

In order to solve another object of the present invention, the present invention includes an oil phase, an aqueous phase, and a water-in-oil emulsifier (W / O type emulsifier), and the oil phase in which the aqueous phase, which is a dispersed phase in the continuous phase, is dispersed in fine particle form. As an emulsion in aqueous form, the aqueous phase provides a reversed phase emulsion characterized in that it comprises the aforementioned crosslinking copolymer. The reversed phase emulsion according to the present invention may preferably further comprise an oil-in-water emulsifier (O / W type emulsifier).

In order to solve another object of the present invention, the present invention provides a cosmetic composition comprising the aforementioned crosslinked copolymer or the aforementioned reverse phase emulsion. In the cosmetic composition according to the present invention, the crosslinked copolymer or the reverse phase emulsion imparts biocompatibility and moisture retention in the thickening effect and emulsion stability to the cosmetic composition, so that the cosmetic composition according to the present invention can be used for skin care or hair care. Can be.

The crosslinked copolymers according to the invention are anionic monomers such as 2-acrylamido-2-methylpropane-sulphonic acid (AMPS) and acrylamide or 2-hydroxyethyl acrylic In addition to the neutral monomers, such as the rate, it contains a phosphorylcholine like group-containing monomer, so that conventional acrylamide / sodium 2-acrylamido-2-methylpropanesulfonate, or hydroxyalkyl acrylate / sodium 2-acrylamido In addition to the thickening and / or emulsification stability properties of the 2-methylpropanesulfonate copolymer, it exhibits further improved moisturizing power and good biocompatibility.

Accordingly, the crosslinked copolymer according to the present invention simultaneously functions as a thickener, emulsion stabilizer and moisturizer in cosmetic compositions, in particular compositions for skin care or compositions for hair care.

Hereinafter, the present invention will be described in detail.

One aspect of the present invention relates to a novel crosslinked copolymer based on a phosphorylcholine-like group that imparts a thickening effect, emulsion stability, moisturizing power and biocompatibility to the cosmetic composition, containing a phosphorylcholine-like group according to the present invention. Monomer based crosslinked copolymers include anionic monomers, neutral monomers, phosphorylcholine like group containing monomers and crosslinking agents, wherein the anionic monomers, neutral monomers, and phosphorylcholine like group containing monomers are formed by crosslinking agents. It is characterized by crosslinking.

Crosslinked copolymer

(a) anionic monomers and neutral monomers

The anionic monomer in the crosslinked copolymer according to the present invention is 2-acrylamido-2-methylpropane-sulphonic acid (AMPS). 2-acrylamido-2-methylpropane-sulfonic acid, which is the anionic monomer, preferably has some or all of its salts in the form of salts in view of reliable thickening effect, emulsion stability, moisturizing property and biocompatibility at various pH, Forms of salts of 2-acrylamido-2-methylpropane-sulfonic acid include alkali metal salts (eg lithium salts, sodium salts, potassium salts, etc.), ammonium salts, or amino alcohol salts.

In the crosslinked copolymer according to the invention, the neutral monomers are acrylamide, methacrylamide, N, N-dimethylacrylamide, diacetone acrylamide, and N-isopropylacrylamide, methyl acrylate, ethyl Ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, lauryl acrylate, stearyl acrylate, benzyl acrylate , Polypropylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, methyl methacrylate, ethyl meta Ethyl methacrylate, propyl methacrylate, 2-ethyl hexyl methacrylate, Lauryl methacrylate, stearyl methacrylate, benzyl methacrylate, polypropylene glycol methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate (2- hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, styrene, methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl Vinyl propionate, vinyl butyrate, vinyl caprolate, phenoxyethyl acrylate, cyclohexyl acrylate, phenoxyethyl methacrylate, cyclohexyl methacrylate, 4-hydrate Oxybutyl methacrylate, chloromethylstyrene, butadiene, isoprene, vinyl chloride, vinylidene chloride at least one selected from the group consisting of idene chloride, methylvinyl ether, butylvinyl ether, p-chloro styrene, isopropyl styrene, and vinyl toluene The above can be mixed and used.

In the crosslinking copolymer according to the present invention, the weight ratio of the anionic monomer to the neutral monomer is not particularly limited, and is preferably 99: 1 to 20:80 in terms of thickening effect and emulsion stability, and is 95: 5 to It is more preferable that it is 30:70.

(b) phosphorylcholine like group-containing monomers

The crosslinked copolymer according to the present invention comprises at least one phosphorylcholine like group containing monomer. The phosphorylcholine like group-containing monomer is a compound represented by the following formula (1).

[Formula (1)]

In the formula (1), X represents a divalent organic residue, Y represents an alkyleneoxy group having 1 to 6 carbon atoms, Z represents a hydrogen atom or R ⁵ -O-CO-, wherein R ⁵ represents 1 to 10 carbon atoms. An alkyl group or a hydroxyalkyl group having 1 to 10 carbon atoms). In addition, R <^1> represents a hydrogen atom or a methyl group, and R <^2> , R <^3> and R <^4> represent the same or another group and represent a hydrogen atom, a C1-C6 hydrocarbon group, or a hydroxy hydrocarbon group. m is 0 or 1, and n is an integer of 2-4.

As a phosphorylcholine like group containing compound represented by General formula (1), for example, 2-((meth) acryloyloxy) ethyl-2 '-(trimethylammonio) ethylphosphate, 3-((meth) ) Acryloyloxy) propyl-2 '-(trimethylammonio) ethyl phosphate, 4-((meth) acryloyloxy) butyl-2'-(trimethylammonio) ethyl phosphate, 5-((meth) acrylic Royloxy) pentyl-2 '-(trimethylammonio) ethylphosphate, 6-((meth) acryloyloxy) hexyl-2'-(trimethylammonio) ethylphosphate, 2-((meth) acryloyl jade Ethyl-2 '-(triethylammonio) ethylphosphate, 2-((meth) acryloyloxy) ethyl-2'-(tripropylammonio) ethylphosphate, 2-((meth) acryloyl jade Ethyl-2 '-(tributylammonio) ethyl phosphate, 2-((meth) acryloyloxy) propyl-2'-(trimethylammonio) ethyl phosphate, 2-((meth) acryloyl jade Butyl-2 '-(trimethylammonium) 5) ethylphosphate, 2-((meth) acryloyloxy) pentyl-2 '-(trimethylammonio) ethylphosphate, 2-((meth) acryloyloxy) hexyl-2'-(trimethylammonio) Ethylphosphate, 2- (vinyloxy) ethyl-2 '-(trimethylammonio) ethylphosphate, 2- (allyloxy) ethyl-2'-(trimethylammonio) ethylphosphate, 2- (p-vinylbenzyloxy) Ethyl-2 '-(trimethylammonio) ethylphosphate, 2- (p-vinylbenzoyloxy) ethyl-2'-(trimethylammonio) ethylphosphate, 2- (styryloxy) ethyl-2 '-(trimethylammonium 5) ethylphosphate, 2- (p-vinylbenzyl) ethyl-2 '-(trimethylammonio) ethylphosphate, 2- (vinyloxycarbonyl) ethyl-2'-(trimethylammonio) ethylphosphate, 2- ( Allyloxycarbonyl) ethyl-2 '-(trimethylammonio) ethylphosphate, 2- (acryloylamino) ethyl-2'-(trimethylammonio) ethylphosphate, 2- (vinylcarbonylamino) ethyl-2 '-(Trimethyl Ammonio) ethylphosphate, 2- (allyloxycarbonylamino) ethyl-2 '-(trimethylammonio) ethylphosphate, 2- (buteroyloxy) ethyl-2'-(trimethylammonio) ethylphosphate, 2 -(Crotonoyloxy) ethyl-2 '-(trimethylammonio) ethylphosphate, ethyl- (2'-trimethylammonio ethylphosphorylethyl) fmaleate, butyl- (2'-trimethylammonio ethylphosphorylethyl ) Fmaleate, hydroxyethyl- (2'-trimethylammonio ethylphosphorylethyl) phmaleate, ethyl- (2'-trimethylammonio ethylphosphorylethyl) fmaleate, butyl- (2'-trimethylammonio ethyl Phosphorylethyl) fmaleate, hydroxyethyl- (2'-trimethylammonio ethylphosphorylethyl) fmaleate, and the like, which can be used alone or in a mixture. "((Meth) acryloyloxy) ethyl" etc. in the said phosphorylcholine like group containing compound means both acryloyloxyethyl, methacryloyloxyethyl, etc.

The type of phosphorylcholine-like group-containing monomer used in the crosslinked copolymer (1) according to the present invention is not particularly limited, but 2- (methacryloyloxy) ethyl-2 'in terms of availability and biocompatibility. -(Trimethylammonio) ethylphosphate [also called 2- (methacryloyloxy) ethyl-2 '-(trimethylammonio) ethylphosphate, 2-methacryloyloxyethylphosphorylcholine, hereinafter abbreviated as MPC] Is preferred.

The content of the phosphorylcholine like group-containing monomer in the crosslinked copolymer according to the present invention is not particularly limited, but in terms of thickening effect, emulsion stability, moisture retention and biocompatibility, the total weight of the anionic monomer and the neutral monomer is 100 It is preferable that it is 0.1-20 weight part per weight part, and it is more preferable that it is 0.5-10 weight part. When the content of the phosphorylcholine like group-containing monomer is less than 0.1 part by weight per 100 parts by weight of the total weight of the anionic monomer and the neutral monomer, there is a fear that the moisturizing properties and biocompatibility of the crosslinked copolymer are insufficient. When the content of the group-containing monomer exceeds 20 parts by weight per 100 parts by weight of the total weight of the anionic monomer and the neutral monomer, there is a fear that the thickening effect of the crosslinked copolymer may not reach the desired level.

(c) crosslinking agent

The crosslinked copolymer according to the present invention comprises at least one crosslinking agent having two or more unsaturated ethylene bond groups. In the present invention, the crosslinking agent crosslinks the anionic monomer, the neutral monomer, and the phosphorylcholine like group-containing monomer to form a network structure, and the crosslinking copolymer according to the present invention has a stable thickening effect in a wide pH range and in the presence of a salt. And / or emulsification stabilizing effect.

The crosslinking agent in the crosslinking copolymer according to the present invention is not particularly limited as long as the crosslinking agent is capable of binding by an unsaturated polymerization reaction with an unsaturated ethylene bond group contained in the anionic monomer, the neutral monomer, and the phosphorylcholine like group-containing monomer. Specifically, ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, propylene glycol dimethacrylate, Butylene Glycol Diacrylate, Butylene Glycol Dimethacrylate, Hexylene Glycol Dimethacrylate, Hexylene Glycol Dimethacrylate, Hexylene Glycol Dimethacrylate , Diethylene glycol diacrylate ycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate glycol diacrylate, tetraethylene glycol dimethacrylate, allyl acrylate, allyl methacrylate, allyl acrylate, allyl ethacrylate ), Ethallyl acrylate, methallyl methacrylate, diallyl phthalate, diallyl maleate, diallyl succinate, diallyl succinate, triaryl phosphate (triallyl phosphate), diallyl oxalate, diallyl malone Diallyl malonate, diallyl citrate, diallyl fumarate, diallyl oxyacetate, diallyl urea, divinyl benzene, trivinyl benzene, vinyl Crotonate, N, N-methylene-bis-acrylamide, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether triallyl ether, diallyl pentaerythritol ether, triallyl pentaerythritol ether, triallyl pentaerythritol ether, tetraallyl pentaerythritol ether, diallyl sucrose ether ether), triallyl sucrose ether, and tetraallyl sucrose ether. N, N-methylene-bis-acrylamide (N, N-methylene-bis-acrylamide) may be composed of one or more substances, and in view of double thickening effect, emulsion stability, and reactivity in the preparation of the crosslinked polymer. , Trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, diallyl pentaerythritol ether, triallyl pentaerythritol ether , Tetraallyl pentaerythritol ether, diallyl sucrose ether, trially sucrose ether, trially sucrose ether, and tetraallyl sucrose ether. It is preferably composed of one or more materials.

Although the content of the crosslinking agent in the crosslinking copolymer according to the present invention is not particularly limited, the total of the anionic monomer and the neutral monomer combined in terms of reliably exposing the thickening effect and / or the emulsion stability effect under various pH and salt conditions. It is preferable that it is 0.01-10 weight part per 100 weight part of weight, and it is more preferable that it is 0.02-5 weight part. If the content of the crosslinking agent is less than 0.01 part by weight per 100 parts by weight of the total weight of the anionic monomer and the neutral monomer, there is a concern that the crosslinking copolymer may not exhibit the desired level of thickening effect in a wide pH range. If the content exceeds 10 parts by weight per 100 parts by weight of the total weight of the anionic monomer and the neutral monomer combined, some or all of the crosslinked copolymer may not be dissolved in water, which may cause difficulties in use as a thickener.

The crosslinked copolymer based on the phosphorylcholine like group-containing monomer according to the present invention can be prepared using a general free radical polymerization reaction, specifically, prepared by precipitation polymerization, emulsion polymerization, bulk polymerization, solution polymerization, gel polymerization, and the like. From the viewpoint of usability and dispersibility in the double emulsion polymerization, in particular in the cosmetic composition, the oil phase is a continuous phase, and the water-in-oil emulsification polymerization including monomers in the aqueous phase, which is a dispersed phase, is easily added to the aqueous phase by adding a reverse phase emulsifier. Reverse phase emulsion polymerization is preferred.

Another aspect of the present invention relates to a reverse phase emulsion comprising a novel crosslinked copolymer based on a phosphorylcholine like group containing monomer that imparts a thickening effect, emulsification stability, moisturizing power and biocompatibility to the cosmetic composition.

Reversed phase emulsion

The reverse phase emulsion according to the present invention includes an oil phase, an aqueous phase, and a water-in-oil emulsifier (W / O-type emulsifier), and have an oil-in-water form in which the aqueous phase, which is a dispersed phase in the continuous phase, is dispersed in fine particle form. It is characterized in that it comprises a cross-linked co-polymer of the present invention described above. In addition, the reverse phase emulsion according to the present invention may preferably further comprise an oil-in-water emulsifier (O / W type emulsifier).

In the reversed phase emulsion according to the invention the oil phase is present in the continuous phase and consists of an oil phase medium which is in principle incompatible with the water of the water phase. The oily medium is a hydrophobic organic solvent that is difficult to be mixed with water, and the kind thereof is not particularly limited, and for example, mineral oil, hydrocarbons such as paraffin, hydrogenated polydecene, squalane, polyisobutene (polyisobutene) or and mixtures thereof, preferably a C ₁₂ ~ C ₁₆ isoparaffin or of dihydro jeneyi suited polydecene (hydrogenated polydecene). The content of the oily medium in the reverse phase emulsion is 10 to 40% by weight, preferably 15 to 30% by weight, based on the total weight of the reverse phase emulsion.

The reversed phase emulsions according to the present invention include water-in-oil emulsifiers (W / O type emulsifiers), which are typically included in the oil phase. Water-in-oil emulsifiers contribute to the stabilization of the oil and water phases in the emulsion and serve to reduce phase separation. In addition, stabilization of the reverse phase emulsion to improve the compatibility with other materials when preparing a cosmetic composition including the reverse phase emulsion. Water-in-oil emulsifiers (W / O type emulsifiers) are those that satisfy a hydrophilic lipophilic balance (HLB) of 9 or less, the type of known commercial emulsifiers, such as known commercial emulsifiers are not greatly limited, HLB is 4-6 Is preferably. Water-in-oil emulsifiers are for example sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan Sorbitan monooleate, Sorbitan sesquioleate, Glyceryl laurate, Glyceryl stearate, Glycol stearate, Glycol stearate, Lecithin, Selected from the group consisting of polyethylene glycol-30 dipolyhydroxystearate, polyethylene glycol-4 dilaurate, and polyethylene glycol-8 dioleate It may be composed of one or more. Other oil-in-water emulsifiers include Steareth-2, Oleth-2, Ceteth-2, Sorbitan Stearate and Sucrose Cocate, and Methyl Glucose Sesquistearate. Can be used. The content of the water-in-oil emulsifier in the reverse phase emulsion is 1.0 to 10% by weight, preferably 2 to 6% by weight, based on the total weight of the reverse phase emulsion.

The reversed phase emulsions according to the invention comprise an aqueous phase, which largely comprises the aqueous phase medium and the crosslinking copolymers of the invention described above. The aqueous phase medium generally consists of water or a mixed solution of water and other hydrophilic solvents. The content of the crosslinked copolymer in the reverse phase emulsion is 20 to 60% by weight, preferably 30 to 50% by weight, based on the total weight of the reverse phase emulsion.

In addition, the reverse phase emulsion according to the present invention may further include an oil-in-water emulsifier (O / W type emulsifier). The oil-in-water emulsifier is generally included in the water phase, and if the HLB satisfies 10 or more, the kind of known commercial emulsifier, etc. is not particularly limited, and the HLB is preferably 11 or more, more preferably 12 or more. Oil-in-water emulsifiers are for example Polysorbate 20, Polysorbate 40, Polysorbate 60, Polysorbate 80, Polyethylenes of fatty or fatty alcohols. Glycol ether, polyethylene glycol-7 oleate, polyethylene glycol-8 laurate, polyethylene glycol-60 almond glyceride, polyethylene glycol-20 methylglucose It may be composed of one or more selected from the group consisting of sesquistearate (PEG-20 methyl glucose sesquistearate), and polyethylene glycol-100 stearate. Underwater oil emulsifiers in the form of polyethyleneglycol ethers of double fatty acids or fatty alcohols include Laureth-7, Laureth-23, Steareth-20, Steareth-21, Steareth-100, Ceteareth-20, Ceteth-10, Ceteth-20, Isoceteth -20, Oleth-10, Oleth-20. In addition, oil-in-water emulsifiers include polyethylene glycol-7 glyceryl cocoate, stearamide MEA, cetearyl glucoside, polyglyceryl-3 methylglucose distearate ( Polyglyceryl-7 methylglucose distearate) and the like can be used. The content of oil-in-water emulsifier in the reverse phase emulsion is 1 to 10% by weight, preferably 2 to 6% by weight, based on the total weight of the reverse phase emulsion. In the present invention, the oil-in-water emulsifying agent may be added to the aqueous phase medium before the polymerization reaction in the process of preparing a reverse phase emulsion by polymerization, or may be added to the emulsion after the polymerization reaction.

The reverse phase emulsion according to the present invention, in addition to the above materials, at least one additive selected from the group consisting of a polymerization catalyst, a complexing agent, a reaction initiator and a chain-limiting agent introduced during the reverse phase emulsion polymerization process. It may further include. As the polymerization catalyst, for example, AIBN and the like can be used, the content of which is 0.01 to 0.05% by weight based on the total weight of the reverse phase emulsion. As the complexing agent, for example, ethylene-diamine tetraacetic acid (EDTA), nitrilotriacetic acid (NTA), 1,2-cyclo-hexadiamine tetraacetic acid (CyDTA), etc. may be used, and sodium bisulfite may be used as a reaction initiator. Known chain reaction limiters and the like can be used. The complexing agent, the reaction initiator and the chain reaction limiting agent are generally used in the polymer polymerization reaction, and the total content thereof is about 0.05 to 0.2% by weight based on the total weight of the reverse phase emulsion.

Reversed phase emulsion according to the present invention is prepared by reversed phase emulsion polymerization, look at this as follows. An aqueous phase is prepared by first adding an anionic monomer, a neutral monomer, a phosphorylcholine like group-containing monomer, and a crosslinking agent to water, which is an aqueous medium, and adjusting the pH to 5-10 with an aqueous sodium hydroxide solution. In addition, a water phase emulsifier in water and the like is added to isoparaffin, which is an oil phase medium separately from the aqueous phase, and stirred to prepare an oil phase. The oil phase and the water phase are added to the polymerization reactor and emulsified with a homomixer, and then purged with an inert gas, a polymerization catalyst and a reaction initiator are added, and the polymerization reaction is performed for about 0.5 to 2 hours while maintaining the reaction temperature at about 40 to 45 degrees. After completion of the polymerization reaction, the reaction product is heated to about 60 ~ 65 degrees and aged for about 2 to 10 hours. The matured reaction product is cooled to about 45-55 ° C. to which an oil-in-water emulsifier is added and stirred to obtain a reversed phase emulsion. The preparation of the crosslinked polymer according to the invention and the reversed phase emulsion comprising the same is preferably carried out under an inert gas atmosphere such as nitrogen, argon, helium or the like. In addition, the type of polymerization initiator is not particularly limited as long as it is a conventional radical initiator. peroxide), lauroyl peroxide, potassium persulfate, and the like. Commercial products of the polymerization initiator include Vazo 52, Vazo 64, Vazo 67, Vazo 88, etc. of Dupont. In addition, a redox system is used to transfer the reaction together with the polymerization initiator, and the redox system is composed of a reducing agent such as sodium bisulfite and ferrous sulfate.

Cosmetic composition

In the present invention, the cosmetic composition is an article used in the human body to clean and beautify the human body to add charm and brighten the appearance, or to maintain or promote the health of the skin and hair, and includes a personal hygiene care article such as a cleaner or a bath solvent. It is a broad concept to include.

The crosslinked copolymers of the present invention or their reversed phase emulsions are added as one component of the cosmetic composition and serve as thickeners, emulsion stabilizers, and moisturizers and impart excellent biocompatibility to the cosmetic composition. Cosmetic compositions comprising the cross-linked copolymer of the present invention or a reversed-phase emulsion thereof as an active ingredient may be specifically used for skin care or hair care, and when used for skin care, improved skin absorption and application properties (coating Sex), moisturizing properties, etc., when used for hair care, shows improved solubility and protection of damaged hair. The content of the crosslinked copolymer in the cosmetic composition may have various ranges according to the use and formulation of the cosmetic composition, and is 0.02 to 5% by weight based on the total weight of the composition in terms of usability (for example, applicability), moisture retention, and the like. It is preferable, and it is more preferable that it is 0.1-2 weight%. In addition, the reverse phase emulsion content in the cosmetic composition may also have a variety of ranges depending on the use and formulation of the cosmetic composition, from 0.1 to 10% by weight based on the total weight of the composition in terms of usability (for example, applyability), moisturizing feeling, etc. It is preferable that it is 0.5-5 weight%.

The cosmetic composition for skin care according to the present invention may further include higher fatty acids, higher alcohols, hydrocarbons, and the like as an oily medium in addition to the aqueous medium and the crosslinked copolymer (or reverse phase emulsion). , Anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, water soluble polymers, coatings, UV absorbers, metal ion sequestrants, lower alcohols, polyhydric alcohols, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, Skin nutrients, vitamins, antioxidants, antioxidants, fragrances and the like are suitably blended, and can be prepared in various formulations for the purpose of lotion, essence, rinse, lotion, wax and the like by known methods.

In addition, the cosmetic composition for hair care according to the present invention, in addition to the above-mentioned crosslinked copolymer (or reverse phase emulsion), suitable carriers, surfactants, fragrances, opacifiers, bonding aids, proteins, aerosol accelerators ( It may contain one or more conventional additives such as aerosol propellents, a gelling agent, and the like, and may be prepared in various formulations including shampoo, rinse, hair fixative wax, hair care conditioner, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples merely illustrate the present invention more clearly and do not limit the protection scope of the present invention.

1. Preparation of Crosslinked Copolymers Based on Phosphoryl-Like Group-containing Monomers and Their Reversed-Phase Emulsions

Preparation Example 1.

219 g of water was added to the aqueous mixing tank, followed by 125 g of acrylamide, 257.6 g of 2-acrylamido-2-methylpropane-sulphonic acid (AMPS), and 1.92 g of MPC. After that, the contents were dissolved by stirring while maintaining the temperature of the aqueous phase mixing tank at 20 degrees or less. Thereafter, 5 g of diallyl pentaerythritol ether was added to the aqueous phase mixing tank as a crosslinking agent, followed by stirring. Then, about 100 g of 50% aqueous sodium hydroxide solution was added thereto to adjust the pH of the contents to about 6.0. Prepared. In addition, 193.8 g of isoparaffin M and 26.7 g of Span 80 (Sorbitan monooleate, manufactured by KOA) were added to the oil phase mixing tank separately from the preparation of the aqueous phase, followed by stirring to prepare an oil phase.

The prepared oil and water phases were put in a reactor and emulsified at a speed of 5000 rpm for 30 minutes using a homomixer while maintaining the temperature of the reactor at 20 degrees or less. After emulsification, the reactor was purged with nitrogen, and a solution obtained by dissolving 0.29 g of azobisisobutylonitrile (AIBN) as a polymerization catalyst in 4 g of isopropanol was introduced into the reactor for 1 minute. In addition, to build a redox system, a solution of 0.25 g of sodium bisulfite dissolved in 4 g of water was added as a reaction initiator for 1 hour. The polymerization was carried out while maintaining the reactor temperature at about 40 to 45 degrees while the reaction initiator was added. Thereafter, the temperature of the reactor was raised to about 60 to 65 degrees, and the reaction product was aged for about 6 hours. After aging, the temperature of the reactor was cooled to 50 degrees, and 22.5 g of Laureth-7 was added thereto, followed by stirring to obtain a reverse phase emulsion including a crosslinked copolymer. The obtained reverse phase emulsion was white, and the viscosity of the aqueous solution in which the reverse phase emulsion was diluted to a concentration of 2% (measured at 5 rpm and 25 degrees with spindle No. 6 of the Brookfield RVT Viscometer) was about 80,000 centipoise (cP).

Preparation Example 2.

A reverse phase emulsion containing a crosslinked copolymer was obtained in the same manner as in Preparation Example 1, except that 3.83 g of MPC was added to prepare an aqueous phase. The obtained reverse phase emulsion was white, and the viscosity of the aqueous solution in which the reverse phase emulsion was diluted to a concentration of 2% (measured at 5 rpm and 25 degrees with spindle No. 6 of the Brookfield RVT Viscometer) was about 78,000 centipoise (cP).

Preparation Example 3.

A reverse phase emulsion containing a crosslinked copolymer was obtained in the same manner as in Preparation Example 1, except that 7.64 g of MPC was added to prepare the aqueous phase. The obtained reverse phase emulsion was white, and the viscosity of the aqueous solution in which the reverse phase emulsion was diluted to a concentration of 2% (measured at 5 rpm and 25 degrees with spindle No. 6 of the Brookfield RVT Viscometer) was about 86,000 centipoise (cP).

Comparative Production Example 1.

A reverse phase emulsion containing a crosslinked copolymer was obtained in the same manner as in Preparation Example 1, except that MPC was not added during the preparation of the aqueous phase. The obtained reverse phase emulsion was white, and the viscosity of the aqueous solution in which the reverse phase emulsion was diluted to a concentration of 2% (measured at 5 rpm and 25 degrees with spindle No. 6 of the Brookfield RVT Viscometer) was about 70,000 centipoise (cP).

Preparation Example 4.

1003 g of water was added to the aqueous mixing tank, where 102 g of 2-hydroxyethyl acrylate, 1642 g of 2-acrylamido-2-methylpropane-sulphonic acid (AMPS), and MPC were added. After adding 9.5 g, the contents were dissolved by stirring while maintaining the temperature of the aqueous phase mixing tank at 20 degrees or less. Then, 0.62 g of N, N-methylene-bis-acrylamide (N, N-methylene-bis-acrylamide) was added to the aqueous phase mixing tank as a crosslinking agent, followed by stirring, and about 357.5 g of an aqueous 50% sodium hydroxide solution was added thereto. The aqueous phase was prepared by adjusting the pH of the contents to about 5.0. In addition, 1100 g of hydrogenated polydecene (trade name: Nexbase 2006) and 162 g of Span 80 (Sorbitan monooleate, manufactured by KAO) were added and stirred in an oil phase mixing tank to prepare an oil phase.

The prepared oil and water phases were put in a reactor and emulsified at a speed of 5000 rpm for 30 minutes using a homomixer while maintaining the temperature of the reactor at 20 degrees or less. After emulsification, the reactor was purged with nitrogen, and a solution obtained by dissolving 1.44 g of azobisisobutyronitrile (AIBN) as a polymerization catalyst in 10 g of isopropanol was added to the reactor for 1 minute. In addition, in order to build a redox system, a solution in which 1.25 g of sodium bisulfate was dissolved in 10 g of water as a reaction initiator was added thereto for 1 hour. The polymerization reaction by the addition of the reaction initiator is an exothermic reaction, and after completion of the polymerization reaction, the temperature of the reactor was about 60 degrees, and the reaction product was aged at this temperature for about 2 hours. After aging, the temperature of the reactor was cooled to 50 degrees, and 125 g of Polysorbate 80 (trade name: Tween 80) was added thereto and stirred to obtain a reverse phase emulsion including a crosslinked copolymer. The resulting reverse phase emulsion was pale yellow, and the viscosity of the aqueous solution in which the reverse phase emulsion was diluted to a concentration of 3% (measured at 5 rpm and 25 degrees with spindle No. 6 of the Brookfield RVT Viscometer) was about 132,000 centipoise (cP).

Preparation Example 5.

A reverse phase emulsion including a crosslinked copolymer was obtained in the same manner as in Preparation Example 4, except that 19.1 g of MPC was added to prepare an aqueous phase. The resulting reverse phase emulsion was pale yellow, and the viscosity of the aqueous solution in which the reverse phase emulsion was diluted to a concentration of 3% (measured at 5 rpm and 25 degrees with spindle No. 6 of the Brookfield RVT Viscometer) was about 130,000 centipoise (cP).

Preparation Example 6.

A reverse phase emulsion containing a crosslinked copolymer was obtained in the same manner as in Preparation Example 4, except that 38.2 g of MPC was added to prepare the aqueous phase. The resulting reverse phase emulsion was pale yellow, and the viscosity of the aqueous solution in which the reverse phase emulsion was diluted to a concentration of 3% (measured at 5 rpm and 25 degrees with spindle No. 6 of the Brookfield RVT Viscometer) was about 141,000 centipoise (cP).

Comparative Preparation Example 2.

A reverse phase emulsion containing a crosslinked copolymer was obtained in the same manner as in Preparation Example 4, except that MPC was not added during the preparation of the aqueous phase. The resulting reverse phase emulsion was pale yellow, and the viscosity of the aqueous solution in which the reverse phase emulsion was diluted to a concentration of 3% (measured at 5 rpm and 25 degrees with spindle No. 6 of the Brookfield RVT Viscometer) was about 122,000 centipoise (cP).

2. Preparation of skin care composition and evaluation of its phase stability, spreadability, and moisture retention

(1) Preparation of the composition for skin care

Example 1.

The skin care composition of the cream formulation containing the reverse phase emulsion prepared in the preparation example 1 was prepared in the composition ratio shown in Table 1.

Table 1

ingredient	Component Content (wt%)
Cyclomethicone	10.0
Reverse phase emulsion of Preparation Example 1	0.8
Montanov 68	2.0
Cetearyl alcohol	1.0
Preservative	0.65
Lysine	0.025
Disodium EDTA	0.05
Xanthan Gum	0.2
Glycerol	3.0
water	Remaining amount

Example 2.

A skin care composition of the cream formulation was prepared in the same manner as in Example 1 except for using the reverse phase emulsion prepared in Preparation Example 2 instead of the reverse phase emulsion prepared in Preparation Example 1.

Example 3.

A skin care composition of the cream formulation was prepared in the same manner as in Example 1, except that the reverse phase emulsion prepared in Preparation Example 3 was used instead of the reverse phase emulsion prepared in Preparation Example 1.

Comparative Example 1.

A composition for skin care of a cream formulation was prepared in the same manner as in Example 1 except for using the reverse phase emulsion prepared in Comparative Preparation Example 1 instead of the reverse phase emulsion prepared in Preparation Example 1.

Example 4.

A skin care composition of the cream formulation was prepared in the same manner as in Example 1 except for using the reverse phase emulsion prepared in Preparation Example 4 instead of the reverse phase emulsion prepared in Preparation Example 1.

Example 5.

The skin care composition of the cream formulation was prepared in the same manner as in Example 1 except that the reverse phase emulsion prepared in Preparation Example 5 was used instead of the reverse phase emulsion prepared in Preparation Example 1.

Example 6.

A skin care composition of the cream formulation was prepared in the same manner as in Example 1, except that the reverse phase emulsion prepared in Preparation Example 6 was used instead of the reverse phase emulsion prepared in Preparation Example 1.

Comparative Example 2.

A composition for skin care of a cream formulation was prepared in the same manner as in Example 1 except for using the reverse phase emulsion prepared in Comparative Preparation Example 2 instead of the reverse phase emulsion prepared in Preparation Example 1.

(2) Phase stability evaluation of the composition for skin care

The skin care compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 2 were alternately stored at -5 to 1 day at 45 degrees for 1 day, and then stored for 5 cycles for a total of 5 cycles. Observation was conducted to evaluate phase stability, and the results are shown in Table 2.

TABLE 2

	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Comparative Example 1	Comparative Example 2
Phase stability assessment	○	○	○	○	○	○	△	△

In Table 2, the evaluation criteria are as follows.

○: no separation of oil phase and water phase was observed.

△: separation of oil phase and water phase is slightly observed

×: separation of oil phase and water phase is clearly observed

(3) Evaluation of applicability and moisture retention of skin care composition

The panel test was carried out for the feeling of application (appliability) when the skin care composition prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were applied to the skin, and the degree of moist feeling of the skin after application (moisturization). By applying, the applicability and moisturizing properties of the skin care composition were evaluated. The results are shown in Tables 3 and 4.

TABLE 3 Coating feeling (applicability)

panel	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Comparative Example 1	Comparative Example 2
PJH	10	10	10	10	10	10	8	5
MJL	8	10	8	10	10	10	5	8
LSY	10	10	10	10	10	10	5	5
LMI	10	10	10	10	10	8	8	8
SSM	8	10	10	8	8	10	8	8
PYS	10	10	10	10	10	10	10	8
HYA	10	10	10	10	10	10	8	10
KJH	10	8	10	8	10	10	5	5
YSS	10	10	8	10	10	8	5	8
KJK	10	10	10	10	10	10	8	5

(10: Very good / 8: Good / 5: Fair / 3: Bad / 1: Very bad)

Table 4 The degree to which the moist feeling of skin is maintained after application (moisturizing)

panel	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Comparative Example 1	Comparative Example 2
PJH	10	10	10	10	10	10	8	8
MJL	10	10	10	10	10	10	5	5
LSY	8	10	10	10	10	10	5	3
LMI	10	10	10	10	10	10	5	5
SSM	10	10	8	10	10	10	3	5
PYS	10	10	10	10	10	8	8	8
HYA	10	10	10	8	10	10	5	5
KJH	10	10	10	10	10	10	3	8
YSS	10	10	10	10	10	10	3	3
KJK	10	10	10	10	10	10	8	3

(10: Very good / 8: Good / 5: Fair / 3: Bad / 1: Very bad)

3. Preparation of Hair Care Composition and Evaluation of Hair Conditioning Effect thereof

(1) Preparation of hair care composition

Example 7.

40.05 g of water was added to a mixing bath and 0.8 g of a reversed phase emulsion prepared in Preparation Example 1 was added while warming up. Then, 1 g of propylene glycol was added and warmed to 75 degrees.

18 grams of sodium lauryl sulfate, 17 grams of sodium laureth sulfate, 2.5 grams of cocofatty acid diethanolamide, 8 grams of Cocamido propyl betain, Soy 3 g of amidopropylamine oxide, 0.5 g of cetearyl alcohol, 2 g of disodium cocoamphodiacetate, 0.6 g of ethylene glycol distearate, polyglyceryl- 2 g of polyglyceryl-2 caprate, 0.5 g of cyclopentasiloxane (and) dimethiconol, 1 g of dimethicone and 0.05 g of tetrasodium EDTA were added to the mixing bath. The mixture was mixed for about 30 minutes until it became uniform at 75 degrees, and then cooled to 45 degrees.

Followed by 0.05 g of Alantion, 0.05 g of methyl chloroisothiazolinone & Methyl isothiazolinone, 0.1 g of DL-Panthenol, 0.5 g of citric acid and fragrance ) 0.3g was added to the mixing tank and mixed until uniform at 45 degrees, thereby preparing 100g of hair care composition.

Example 8.

100 g of the composition for hair care was prepared in the same manner as in Example 7, except that the reverse phase emulsion prepared in Preparation Example 2 was used instead of the reverse phase emulsion prepared in Preparation Example 1.

Example 9.

100 g of the composition for hair care was prepared in the same manner as in Example 7, except that the reverse phase emulsion prepared in Preparation Example 3 was used instead of the reverse phase emulsion prepared in Preparation Example 1.

Comparative Example 3.

100 g of the composition for hair care was prepared in the same manner as in Example 7, except that the reverse phase emulsion prepared in Comparative Preparation Example 1 was used instead of the reverse phase emulsion prepared in Preparation Example 1.

Example 10.

100 g of the composition for hair care was prepared in the same manner as in Example 7, except that the reverse phase emulsion prepared in Preparation Example 4 was used instead of the reverse phase emulsion prepared in Preparation Example 1.

Example 11.

100 g of the composition for hair care was prepared in the same manner as in Example 7, except that the reverse phase emulsion prepared in Preparation Example 5 was used instead of the reverse phase emulsion prepared in Preparation Example 1.

Example 12.

100 g of the composition for hair care was prepared in the same manner as in Example 7, except that the reverse phase emulsion prepared in Preparation Example 6 was used instead of the reverse phase emulsion prepared in Preparation Example 1.

Comparative Example 4.

100 g of the composition for hair care was prepared in the same manner as in Example 7, except that the reverse phase emulsion prepared in Comparative Preparation Example 2 was used instead of the reverse phase emulsion prepared in Preparation Example 1.

(2) Evaluation of Hair Conditioning Effect of Hair Care Composition

Feeling when the hair is wound after applying each of the hair care compositions prepared in Examples 7 to 12 and Comparative Examples 3 to 4, combing wet, combing after drying, hair volume, hair gloss, etc. The hair conditioning effect of the hair care composition was evaluated by performing a panel test in relation to it. The results are shown in Tables 5 to 9 below.

Table 5 Winding feeling

panel	Example 7	Example 8	Example 9	Example 10	Example 11	Example 12	Comparative Example 3	Comparative Example 4
PJH	10	10	10	10	10	10	8	5
MJL	8	10	10	8	10	8	5	5
LSY	10	10	10	10	10	10	5	5
LMI	10	10	10	10	10	10	5	8
SSM	10	10	8	10	10	10	8	8
PYS	8	10	10	10	10	10	8	8
HYA	10	10	10	10	10	10	5	5
KJH	10	10	10	8	10	10	5	8
YSS	10	10	10	10	10	10	8	5
KJK	10	10	10	10	10	10	5	5

(10: Very good / 8: Good / 5: Fair / 3: Bad / 1: Very bad)

Table 6 Wet combing

panel	Example 7	Example 8	Example 9	Example 10	Example 11	Example 12	Comparative Example 3	Comparative Example 4
PJH	10	10	10	10	10	10	5	5
MJL	10	10	10	10	10	10	3	3
LSY	8	10	10	8	10	10	5	5
LMI	10	10	10	8	10	10	8	8
SSM	10	10	10	10	10	10	5	5
PYS	10	10	10	10	10	10	5	3
HYA	8	10	10	10	10	10	8	5
KJH	10	10	8	10	10	10	3	5
YSS	10	10	10	10	10	10	5	5
KJK	8	10	10	8	10	8	5	8

(10: Very good / 8: Good / 5: Fair / 3: Bad / 1: Very bad)

TABLE 7 Combing after drying

panel	Example 7	Example 8	Example 9	Example 10	Example 11	Example 12	Comparative Example 3	Comparative Example 4
PJH	10	10	10	10	10	8	3	5
MJL	10	10	8	10	10	10	5	8
LSY	8	10	10	10	10	10	5	5
LMI	8	10	10	10	10	10	5	3
SSM	10	10	8	10	10	8	5	5
PYS	10	10	10	10	10	10	3	3
HYA	10	10	10	8	10	10	3	3
KJH	10	10	10	10	10	10	8	5
YSS	10	10	10	10	10	10	5	5
KJK	10	10	10	8	10	10	5	5

(10: Very good / 8: Good / 5: Fair / 3: Bad / 1: Very bad)

Table 8 Hair volume

panel	Example 7	Example 8	Example 9	Example 10	Example 11	Example 12	Comparative Example 3	Comparative Example 4
PJH	10	10	10	10	10	10	5	3
MJL	10	10	10	10	10	10	5	5
LSY	10	10	10	10	10	8	5	5
LMI	10	10	10	10	10	10	3	3
SSM	8	10	10	10	10	10	3	3
PYS	10	10	10	10	10	10	5	5
HYA	8	10	10	8	10	10	8	5
KJH	10	10	10	8	10	10	5	5
YSS	10	10	10	10	10	10	5	8
KJK	10	10	8	10	10	10	8	8

(10: Very good / 8: Good / 5: Fair / 3: Bad / 1: Very bad)

Table 9 Hair shine

panel	Example 7	Example 8	Example 9	Example 10	Example 11	Example 12	Comparative Example 3	Comparative Example 4
PJH	10	10	10	10	10	10	8	5
MJL	10	10	10	8	10	10	5	5
LSY	10	10	10	10	10	10	5	5
LMI	10	10	10	10	10	10	5	8
SSM	10	10	10	10	10	10	8	8
PYS	10	10	10	10	10	10	3	3
HYA	8	10	10	8	10	10	3	3
KJH	10	10	10	10	10	10	5	3
YSS	10	10	10	10	10	10	5	5
KJK	8	10	10	10	10	10	3	5

(10: Very good / 8: Good / 5: Fair / 3: Bad / 1: Very bad)

Although the present invention has been described through the above embodiments as described above, the present invention is not necessarily limited thereto, and various modifications can be made without departing from the scope and spirit of the present invention. In addition, many modifications may be made to adapt a particular situation and material to the teachings of the invention without departing from the essential scope thereof. Therefore, the protection scope of the present invention should not be construed as limited to the specific embodiments disclosed as the best mode contemplated for carrying out the invention, but including all embodiments falling within the scope of the claims appended hereto.

According to the present invention, the phosphorylcholine like group-containing monomer-based crosslinked copolymer can be used not only as a thickener and / or an emulsifying stabilizer but also as a moisturizing agent, and its effect is also improved compared to the copolymers used in the past. In particular, the composition may be usefully used in a skin care composition or a hair care composition.

Claims (18)

1. As a crosslinking polymer comprising an anionic monomer, a neutral monomer, at least one phosphorylcholine like group-containing monomer represented by the following formula (1), and at least one crosslinking agent having two or more unsaturated ethylene bond groups. ,

   The anionic monomer is 2-acrylamido-2-methylpropane-sulphonic acid (AMPS),

   The neutral monomer may be acrylamide, N, N-dimethylacrylamide, methacrylamide, diacetone acrylamide, and N-isopropylacrylamide, methyl acrylate, ethyl acrylate, propyl acryl Propyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, lauryl acrylate, stearyl acrylate, benzyl acrylate, polypropylene glycol acrylate, 2- Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, methyl methacrylate, ethyl methacrylate, propyl meta Acrylate, 2-ethyl hexyl methacrylate, lauryl methacrylate, stearyl methacrylate Methacrylate, benzyl methacrylate, polypropylene glycol methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy Butyl methacrylate, 2-hydroxybutyl methacrylate, styrene, methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, It consists of at least one or a mixture of two or more selected from the group consisting of vinyl propionate, vinyl butyrate and vinyl caprolate, the anionic monomer, neutral monomer , And the phosphorylcholine like group-containing monomers are crosslinked by a crosslinking agent. Of the body-based cross-linked co-polymer.

   [Formula (1)]

   

   In the formula (1), X represents a divalent organic residue, Y represents an alkyleneoxy group having 1 to 6 carbon atoms, Z represents a hydrogen atom or R ⁵ -O-CO-, wherein R ⁵ represents 1 to 10 carbon atoms. An alkyl group or a hydroxyalkyl group having 1 to 10 carbon atoms). In addition, R <^1> represents a hydrogen atom or a methyl group, and R <^2> , R <^3> and R <^4> represent the same or another group and represent a hydrogen atom, a C1-C6 hydrocarbon group, or a hydroxy hydrocarbon group. m is 0 or 1, and n is an integer of 2-4.
2. The crosslinked copolymer of claim 1, wherein the weight ratio of the anionic monomer to the neutral monomer is 99: 1 to 20:80.
3. 2. The cross-linked air based on the phosphorylcholine-like monomer according to claim 1, wherein the anionic monomer 2-acrylamido-2-methylpropane-sulfonic acid is present in at least part or all in the form of a salt. coalescence.
4. The phosphorylcholine like group-containing monomer-based crosslinking according to claim 1, wherein the salt of 2-acrylamido-2-methylpropane-sulfonic acid is any one of an alkali metal salt, an ammonium salt, or an amino alcohol salt. Binding copolymer.
5. The content of the phosphorylcholine like group-containing monomer in the crosslinking copolymer is 0.1 to 20 parts by weight per 100 parts by weight of the total weight of the anion monomer and the neutral monomer. Cross-linked copolymers based on group containing monomers.
6. 6. The method of claim 5, wherein the phosphoryl choline analog group-containing monomer is 2- (methacryloyloxy) ethyl-2 '-(trimethylammonio) ethylphosphate [2- (methacryloyloxy) ethyl-2'-(trimethylammonio) ethylphosphate], a crosslinking copolymer based on a phosphorylcholine like group-containing monomer.
7. According to claim 1, wherein the content of the cross-linking agent in the cross-linking copolymer is based on phosphoryl choline similar group-containing monomer, characterized in that 0.01 to 10 parts by weight per 100 parts by weight of the total weight of the anionic monomer and the neutral monomer combined Crosslinked copolymers.
8. The method of claim 7, wherein the crosslinking agent is ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate (propylene glycol dimethacrylate), butylene glycol diacrylate, butylene glycol dimethacrylate, hexylene glycol diacrylate, hexylene glycol dimethacryl Hexylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacryl Triethylene glycol dimethacrylate, tetraethylene Tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, allyl acrylate, allyl methacrylate, allyl acrylate, allyl Allyl ethacrylate, ethallyl acrylate, methallyl methacrylate, diallyl phthalate, diallyl maleate, diallyl urea, divinyl Divinyl benzene, trivinyl bezene, vinyl crotonate, N, N-methylene-bis-acrylamide, trimethylolpropane diallyl Trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, diallyl pentaerythritol ether, Triallyl pentaerythritol ether, tetraallyl pentaerythritol ether, diallyl sucrose ether, triallyl sucrose ether, and tetraallyl sucrose ether A phosphorylcholine like group-containing monomer-based crosslinking copolymer, characterized in that it is composed of one or more materials selected from the group consisting of ether (tetraallyl sucrose ether).
9. As an oil-in-water emulsion containing an oil phase, an aqueous phase, and a water-in-oil emulsifier (W / O-type emulsifier), in which the water phase, which is a dispersed phase, is dispersed in fine particle form,

   Reverse phase emulsions characterized in that the water phase comprises the crosslinking copolymer of claim 1.
10. The reverse phase emulsion according to claim 9, wherein the content of the crosslinked copolymer in the reverse phase emulsion is 30 to 60 wt% based on the total weight of the reverse phase emulsion.
11. The method of claim 9, wherein the oil phase is C ₁₂ ~ C ₁₆ isoparaffin, mineral oil, hydrogenated polydecene (hydrogenated polydecene), Squalane (squalane), characterized in that it comprises polyisobutene (polyisobutene) Reversed phase emulsion.
12. 10. The method of claim 9, wherein the oil-in-water emulsifier is Sorbitan monolaurate, Sorbitan monopalmitate, Sorbitan monostearate, Sorbitan tristearate ), Sorbitan monooleate, Sorbitan sesquioleate, Glyceryl laurate, Glyceryl stearate, Glycol stearate, Lecithin (Lecithin), polyethylene glycol-30 dipolyhydroxystearate, polyethylene glycol-4 dilaurate, and polyethylene glycol-8 dioleate. Reverse phase emulsion, characterized in that composed of one or more selected from the group consisting of.
13. 10. The reverse phase emulsion of claim 9 further comprising an oil-in-water emulsifier (O / W type emulsifier).
14. The method of claim 13, wherein the oil-in-water emulsifier is Polysorbate 20, Polysorbate 40, Polysorbate 60, Polysorbate 80, fatty acid or Polyethylene glycol ethers of fatty alcohols, polyethylene glycol-7 oleate, polyethylene glycol-8 laurate, polyethylene glycol-60 almond glycerides, polyethylene glycol Reverse phase emulsion, characterized in that it is composed of one or more selected from the group consisting of -20 methyl glucose sesquistearate, and polyethylene glycol-100 stearate.
15. A cosmetic composition comprising the crosslinking copolymer of claim 1.
16. The cosmetic composition according to claim 15, wherein the cosmetic composition is a composition for skin care or a composition for hair care.
17. The cosmetic composition according to claim 16, wherein the content of the crosslinked copolymer in the composition is 0.02 to 5% by weight based on the total weight of the composition.
18. The cosmetic composition according to claim 16, wherein the reverse phase emulsion content in the composition is 0.1 to 10% by weight based on the total weight of the composition.