KR101249687B1 - Crosslinked copolymer based on monomer containing phosphorylcholine-like group, inverse emulsion, and cosmetic composition - Google Patents

Abstract

The present invention relates to a novel crosslinking copolymer comprising an anionic monomer, a neutral monomer, a phosphorylcholine like group containing monomer and a crosslinking agent, a reverse phase emulsion thereof and a cosmetic composition comprising the crosslinking copolymer or a reverse phase emulsion.
The crosslinked copolymer according to the present invention is phosphorylcholine in addition to anionic monomers such as 2-acrylamido-2-methylpropane-sulphonic acid (AMPS) and neutral monomers such as acrylamide and the like. In addition to the thickening and / or emulsification stability properties of conventional acrylamide / alkalimetal acrylate copolymers or acrylamide / sodium 2-acrylamido-2-methylpropanesulfonate copolymers, they contain similar group-containing monomers. 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.

Description

Crosslinked copolymer based on monomer containing phosphorylcholine-like group, inverse emulsion, and cosmetic composition

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 and corn starch have disadvantages in industrial use due to price fluctuations, supply problems, and difficulty in maintaining a certain quality. Generally, synthetic polymers are used in powder form containing acidic functional groups. Since it is present as a solid, it must be dispersed in a solvent in order to obtain a thickening effect, and since it is pH dependent, there is a disadvantage in that neutralization of acidic functional groups is required in use. 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. The polymer contained in the reverse phase emulsion is generally an acrylamide / alkalimetal acrylate copolymer or an acrylamide / 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, an object of the present invention is that the conventional acrylamide / alkali metal acrylate copolymer or acrylamide / sodium 2-acrylamido-2-methylpropanesulfonate copolymer In addition to the thickening or emulsifying stability properties, further to provide a novel cross-linked copolymer based on the phosphoryl choline like group containing monomer having excellent biocompatibility, improved moisturizing power, proper nutrition.

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 is at least one having an anionic monomer, a neutral monomer, at least one phosphorylcholine like group-containing monomer represented by the following formula (1), and at least two unsaturated ethylene bond groups A crosslinking polymer comprising one crosslinking agent, wherein the anionic monomer is 2-acrylamido-2-methylpropane-sulphonic acid (AMPS) and the neutral monomer is acrylic Amide, N, N-dimethylacrylamide, methacrylamide, diacetone acrylamide, and N-isopropylacrylamide, and are composed of at least one selected from the group consisting of the anionic monomer, the neutral monomer, and phosphoryl The choline analog group-containing monomer is based on a phosphorylcholine analog group-containing monomer, which is cross-linked by the crosslinking agent. It provides a cross-linked co-polymer.

[Chemical 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). R ¹ represents a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ represent the same or different groups and represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a hydroxy hydrocarbon group. m is 0 or 1, and n is an integer of 2-4.

In the crosslinked copolymer according to the present invention, the anacryl monomer 2-acrylamido-2-methylpropane-sulfonic acid is at least partly or entirely at the point of reliable thickening effect, emulsion stability, moisture retention and biocompatibility at various pHs. It is preferable to exist in the form of a valent salt, and the neutral monomer is preferably acrylamide or methacrylamide, and the phosphorylcholine like group-containing monomer is 2- (methacryloyloxy) ethyl-2 '-(trimethylammonium). 5) ethyl phosphate [2- (methacryloyloxy) ethyl-2'- (trimethylammonio) ethyl phosphate], the crosslinking agent is N, N- methylene-bis-acrylamide (N, N-methylene-bis-acrylamide), Trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, diallyl pentaerythritol ether, triallyl pentaerythritol ether, tetraallyl pentaerythritol ether, diallyl sucrose ether, triallyl sucrose ether, and It is preferably composed of one or more materials selected from the group consisting of tetraallyl sucrose ether.

In order to solve the other 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 water-in-oil droplet in which the aqueous phase, which is a dispersed phase in the continuous phase, is dispersed in the form of fine particles. As an emulsion in 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 copolymer according to the present invention is phosphorylcholine in addition to anionic monomers such as 2-acrylamido-2-methylpropane-sulphonic acid (AMPS) and neutral monomers such as acrylamide and the like. In addition to the thickening and / or emulsification stability properties of conventional acrylamide / alkalimetal acrylate copolymers or acrylamide / sodium 2-acrylamido-2-methylpropanesulfonate copolymers, they contain similar group-containing monomers. 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.

Crosslinked copolymer

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 crosslinked by a crosslinking agent. It is characterized by.

(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 it present in the form of a salt from the viewpoint of thickening effect and emulsion stability, and 2-acrylamido-2-methylpropane- Examples of the salt of sulfonic acid include alkali metal salts (for example, lithium salts, sodium salts, potassium salts, etc.), ammonium salts, amino alcohol salts, and the like.

In the crosslinked copolymer according to the present invention, the neutral monomer is at least one selected from the group consisting of acrylamide, N, N-dimethylacrylamide, methacrylamide, diacetone acrylamide, and N-isopropylacrylamide It is preferably composed of acrylamide or methacrylamide from the viewpoint of thickening effect, emulsion stability, commercial availability, economy and the like.

The weight ratio of the anionic monomer to the neutral monomer in the crosslinked copolymer according to the present invention is not particularly limited, and is preferably 80:20 to 20:80 from the viewpoint of thickening effect and emulsion stability, and is 70:30 to 30. It is more preferable that it is: 70.

(b) phosphorylcholine like group-containing monomers

The crosslinked copolymer according to the 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).

[Chemical 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). R ¹ represents a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ represent the same or different groups and represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, 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 according to the present invention is not particularly limited, but 2- (methacryloyloxy) ethyl-2 '-(trimethyl) in terms of availability and biocompatibility. Ammonio) 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 And / or have an emulsion 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 included 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, butyl Butylene Glycol Diacrylate, Butylene Glycol Dimethacrylate, Hexylene Glycol Dimethacrylate, Hexylene Glycol Dimethacrylate, Hexylene Glycol Dimethacrylate, Diethylene glycol diacrylate 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 malonate (diallyl malonate), diallyl citrate, diallyl fumarate, diallyl oxyacetate, diallyl urea, divinyl benzene, trivinyl benzene, trivinyl bezene Vinyl crotonate, N, N-methylene-bis-acrylamide, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, diallyl pentaerythritol ether, triallyl pentaerythritol ether, triallyl pentaerythritol ether, tetraallyl pentaerythritol ether, diallyl sucrose ether ), Triallyl sucrose ether, and tetraallyl sucrose ether N, N-methylene-bis-acrylamide (N, N-methylene-bis-acrylamide) in view of the double thickening effect, emulsion stability, reactivity in the manufacturing process of the crosslinked polymer, Trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, diallyl pentaerythritol ether, triallyl pentaerythritol ether, One selected from the group consisting of tetraallyl pentaerythritol ether, diallyl sucrose ether, trially sucrose ether, and tetraallyl sucrose ether It is preferable to consist of the above materials.

Although the content of the crosslinking agent in the crosslinking copolymer according to the present invention is not particularly limited, the total weight 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, and it is more preferable that it is 0.1-5 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 a desired level of thickening effect in a wide pH range, and the content of the crosslinking agent If it exceeds 10 parts by weight per 100 parts by weight of the total weight of the combined anionic monomers and neutral monomers, some or all of the crosslinking 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. Double emulsion polymerization, particularly reverse phase emulsion polymerization, in which the oil phase is a continuous phase and the monomers are included in the aqueous phase, which is a dispersed phase, is preferable in view of usability and dispersibility in the cosmetic composition.

Inverse phase emulsion

Another aspect of the present invention relates to a reversed 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. The emulsion comprises 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 a continuous phase, is dispersed in fine particle form, and the aqueous phase is described above. It is characterized by including a crosslinking copolymer of. 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 which is difficult to be mixed with water, and its kind is not particularly limited, and there are, for example, mineral oil, hydrocarbons such as paraffin or mixtures thereof, and isoparaffin having C ₁₂ to C ₁₆ . The content of the oily medium in the reverse phase emulsion is 10-40% by weight, preferably 15-30% 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 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 30 to 60% by weight, preferably 40 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). If the water-in-oil emulsifier is generally included in the water phase, and if the HLB satisfies 10 or more, the kind of known commercial emulsifier, etc. are not particularly limited, 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.

In addition to the above materials, the reverse phase emulsion according to the present invention may be prepared from a group consisting of a polymerization initiator, a complexing agent, a transfer agent, and a chain-limiting agent, which are introduced during the reverse phase emulsion polymerization process. It may further comprise one or more additives selected. As the polymerization initiator, 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 the reaction transfer agent. Known chain reaction limiters and the like can be used. The complexing agent, the reaction transfer agent 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 6-10 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 initiator and a reaction transfer agent 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 ° C. . After completion of the polymerization reaction, the reaction product is heated to about 60 ~ 65 ℃ and aged for about 2 ~ 10 hours. The matured reaction product is cooled to about 45-55 [deg.] C. and an oil-in-water emulsifier is added thereto and stirred to obtain a reversed phase emulsion. The preparation of the crosslinked polymers according to the invention and reverse phase emulsions comprising them is preferably carried out under an inert gas atmosphere such as nitrogen, carbon dioxide, 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 for the reaction transfer with the polymerization initiator, which is composed of a reducing agent such as sodium bisulfite and iron (II) sulfate.

Cosmetics  Composition

Another aspect of the present invention relates to a cosmetic composition comprising the aforementioned crosslinked copolymer or a reverse phase emulsion thereof as an active ingredient. 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.

One. Phosphoryl  Cross-linked copolymers based on similar group-containing monomers and their Inverse phase  Preparation of Emulsion

Production 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 ° C. or lower. 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 introduced into the reactor and emulsified at a speed of 5000 rpm for 30 minutes using a homomixer while maintaining the temperature of the reactor at 20 ° C. or lower. 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 transfer agent for 1 hour. The polymerization reaction was carried out while maintaining the reactor temperature at about 40 ~ 45 ℃ while adding the reaction transfer agent. After the temperature of the reactor was raised to about 60 ~ 65 ℃ After the reaction product was aged for about 6 hours. After aging, the temperature of the reactor was cooled to 50 ° C., 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 ° C. under the spindle No. 6 of the Brookfield RVT Viscometer) About 80,000 centipoise (cP).

Production 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 ° C. under the spindle No. 6 of the Brookfield RVT Viscometer) 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 ° C. under the spindle No. 6 of the Brookfield RVT Viscometer) 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 ° C. under the spindle No. 6 of the Brookfield RVT Viscometer) About 70,000 centipoise (cP).

2. Skin For care  Preparation of the composition and its phase stability, Brittle , Moisturizing evaluation

(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.

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 Balance

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.

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

The skin care compositions prepared in Examples 1 to 3 and Comparative Example 1 were alternately stored at -5 ° C. for 1 day and at 45 ° C. for 1 day. Phase stability was evaluated, and the results are shown in Table 2.

Example 1 Example 2 Example 3 Comparative Example 1 Phase stability evaluation result ○ ○ ○ △

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

By performing a panel test on the feeling of application (appliability) when the skin care compositions prepared in Examples 1 to 3 and Comparative Example 1 were applied to the skin, and the degree of moisture retention of the skin after application (moisturization) The applicability and moisture retention of the composition for skin care were evaluated. The results are shown in Tables 3 and 4.

Coating feeling (applicability) panel Example 1 Example 2 Example 3 Comparative Example 1 PJH 10 10 10 8 MJL 8 10 8 5 LSY 10 10 10 5 LMI 10 10 10 8 SSM 8 10 10 8 PYS 10 10 10 10 HYA 10 10 10 8 KJH 10 8 10 5 YSS 10 10 8 5 KJK 10 10 10 8

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

The degree to which the moist feeling of the skin is maintained after application (moisturizing) panel Example 1 Example 2 Example 3 Comparative Example 1 PJH 10 10 10 8 MJL 10 10 10 5 LSY 8 10 10 5 LMI 10 10 10 5 SSM 10 10 8 3 PYS 10 10 10 8 HYA 10 10 10 5 KJH 10 10 10 3 YSS 10 10 10 3 KJK 10 10 10 8

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

3. hair For care  Preparation of the composition and evaluation of its hair conditioning effect

(1) Preparation of the composition for hair care

Example 4.

40.05 g of water was added to a mixing bath, and then 0.8 g of a reversed phase emulsion prepared in Preparation Example 1 was added thereto, followed by heating to 75 ° C. in 1 g of propylene glycol.

18 g of sodium lauryl sulfate, 17 g of sodium laureth sulfate, 2.5 g of cocofatty acid diethanolamide, 8 g 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 uniform at 75 ° C, and then cooled to 45 ° C.

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 ° C, thereby preparing 100g of hair care composition.

Example 5.

100 g of the composition for hair care was prepared in the same manner as in Example 4, 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 6.

100 g of the composition for hair care was prepared in the same manner as in Example 4, 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 2

100 g of the composition for hair care was prepared in the same manner as in Example 4, 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.

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

Panels about the feeling of washing the hair after applying the respective hair care compositions prepared in Examples 4 to 6 and Comparative Example 2 to the hair, combing wet, combing after drying, hair volume, hair gloss, etc. Tests were performed to evaluate the hair conditioning effect of the hair care composition. The results are shown in Tables 5 to 9 below.

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

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

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

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

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

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

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

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

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

(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. Accordingly, the protection scope of the present invention should not be construed as being limited to the particular embodiments disclosed as the best mode contemplated for carrying out the invention but to cover all embodiments falling within the scope of the appended claims.

Claims (20)

As a copolymer in which an anionic monomer, a neutral monomer, and a phosphorylcholine like group-containing monomer represented by the following formula (1) are crosslinked by a crosslinking agent,
The anionic monomer is 2-acrylamido-2-methylpropane-sulphonic acid (AMPS),
The neutral monomer is composed of one or more selected from the group consisting of acrylamide, N, N-dimethylacrylamide, methacrylamide, diacetone acrylamide, and N-isopropylacrylamide,
The phosphorylcholine like group-containing monomer is 2- (methacryloyloxy) ethyl-2 '-(trimethylammonio) ethylphosphate [2- (methacryloyloxy) ethyl-2'-trimethylammonio) ethylphosphate]
The crosslinker is diallyl pentaerythritol ether,
The weight ratio of the anionic monomer to the neutral monomer is 80:20 to 20:80 phosphorylcholine like group-containing monomer-based crosslinking copolymer.
[Chemical 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). R ¹ represents a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ represent the same or different groups and represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a hydroxy hydrocarbon group. m is 0 or 1, and n is an integer of 2-4.
delete The cross-linked copolymer based on the phosphorylcholine like group containing monomer according to claim 1, wherein the anacryl monomer 2-acrylamido-2-methylpropane-sulfonic acid is present in at least part or all in the form of a salt. .
4. The crosslinking based on phosphorylcholine like group according to claim 3, 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.
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.
delete According to claim 1, wherein the content of the cross-linking agent in the cross-linking copolymer is based on the phosphoryl choline analog 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.
delete 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 emulsion, characterized in that the water phase comprises the cross-linked copolymer of any one of claims 1, 3, 4, 5 and 7.
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.
10. The reverse phase emulsion of claim 9 wherein the oil phase comprises C ₁₂ -C ₁₆ isoparaffins.
The method of claim 9, wherein the water-in-oil 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. Reversed phase emulsion, characterized in that composed of one or more selected from the group consisting of.
10. The reverse phase emulsion of claim 9 further comprising an oil-in-water emulsifier (O / W type emulsifier).
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 consisting of one or more selected from the group consisting of -20 methyl glucose sesquistearate, and polyethylene glycol-100 stearate.
A cosmetic composition comprising the crosslinking copolymer of any one of claims 1, 3, 4, 5 and 7.
The cosmetic composition according to claim 15, wherein the cosmetic composition is a composition for skin care or a composition for hair care.
The cosmetic composition according to claim 15, wherein the crosslinking copolymer content in the composition is 0.02 to 5% by weight based on the total weight of the composition.
A cosmetic composition comprising the reversed phase emulsion of claim 9.
The cosmetic composition according to claim 18, wherein the cosmetic composition is a composition for skin care or a composition for hair care.
19. The cosmetic composition according to claim 18, wherein the reverse phase emulsion content in the composition is 0.1 to 10% by weight based on the total weight of the composition.