KR20120103318A - Copolymer based on monomer containing phosphorylcholine-like group, booster for blocking ultraviolet light, personal care product for blocking ultraviolet light - Google Patents

Abstract

PURPOSE: A phosphorylcholine-like group-containing monomer-based copolymer is provide to provide SPF(sun protection factor) and PA(protect A) boosting effect to a personal care product for UV shielding and to provide improved moisturizing performance and biocompatibility at the same time. CONSTITUTION: A phosphorylcholine-like group-containing monomer-based copolymer comprises one or more of first monomers selected from a group consisting of alkyl ester of acrylic acid, alkyl ester of methacrylic acid, and alkenyl ester of alkanoic acid, a second monomer different with the first monomer, which is one or more selected from a group consisting of acrylic alkyl ester, alkyl ester of methacryl acid, alkenyl ester of alkanoic acid, and at least one or more phosphorylcholine-line group-containing monomers expressed in chemical formula 1.

Description

Copolymer based on monomer containing phosphorylcholine-like group, booster for blocking ultraviolet light, personal care product for blocking ultraviolet light}

The present invention relates to a phosphorylcholine like group-containing monomer-based copolymer, a sunscreen booster, and a sunscreen personal care product, and more particularly, sun protection factor (PAF) and PA ( Protect A) A phosphorylcholine like group-containing monomer, a sunscreen booster composed of an emulsion comprising the copolymer, and the copolymer or the ultraviolet light to impart a boosting effect and at the same time to provide enhanced moisturization and biocompatibility. The present invention relates to a sunscreen personal care article comprising a cutoff booster.

UV rays included in sunlight can be divided into UVA (400-320nm), UVB (320-280nm) and UVC (280-200nm). UVC, the strongest ultraviolet rays passing through the atmosphere, is absorbed in the ozone layer and UVA and UVB Is reached to the surface. When irradiated with ultraviolet UVB waves on the skin, the energy of the ultraviolet wavelength penetrates the epidermis and causes inflammation around the capillaries, so short-term irradiation can cause skin erythema or edema. In this case, it may be accompanied by fever or pain. If there is no proper measure, pigmentation may occur over time and skin peeling may occur. On the other hand, in the case of irradiating the skin with UVA, which is a long-wavelength ultraviolet rays, since the irradiation energy reaches the dermal layer and damages the collagen elastic fibers, recent research results indicate that skin wrinkles and elasticity are reduced.

The effects of ultraviolet radiation are not limited to skin. When the human body is exposed to ultraviolet radiation for a long time, it is reported that the risk of skin cancer caused by decreased immune function or DNA damage is increased. Therefore, to reduce the risk of ultraviolet irradiation to the human body technology for sunscreen is constantly being studied.

Sunscreens are basically divided into UV absorbers and UV scatterers. Early ultraviolet absorbers were mainly those in which only organic ultraviolet absorbers were dissolved in liquid oil, or simply emulsified them. As an organic ultraviolet absorber, organic compounds, such as a salicylic acid derivative, a cinnamic acid derivative, or a benzophenone derivative, are mentioned. They absorb ultraviolet light and become an excited state, and the energy is converted into heat or light energy that is less irritating to the skin and released, thereby returning to the ground state.

However, these early organic UV absorbers are poor in use, such as stickiness persists when applying the skin, there was a limit to the technology for compounding a large amount effective in the nature of the emulsification. In order to overcome this problem, research has been conducted in the direction of formulating an inorganic ultraviolet scattering agent. The metal oxide of zinc oxide or titanium oxide has a band structure in the energy state in which electrons exist due to the periodic potential field, and the energy difference between the upper end of the valence band and the lower end of the conduction band is called band gap energy. do. Zinc oxide has a bandgap energy of 3.2 eV, and when more energy is irradiated, electrons are excited, and the electrons are indirectly transitioned and photoexcitation occurs below 320 nm, which is used as UVB and UVA wave blockers. Titanium oxide has the same effect and is used as a UVB wave blocker.

However, the fine particle powder of titanium oxide used as an inorganic UV scattering agent has a high blocking effect of UVB waves, but when combined with a sunscreen agent, a metallic blue film is formed on the skin, making it difficult to be used in cosmetic personal care products. Catalytic activity is strong enough to decompose organic matter into hydrogen and oxygen, and tends to deteriorate the performance of other components of the sunscreen. This tendency also applies to zinc oxide, which can be used as a UVB and UVA wave blocker. To solve this problem, a technique for blocking catalytic activity by coating the surface of the fast particulate powder with an emulsion or silicon has been established. Moreover, the effect of controlling cohesion was also obtained by performing such fine particle powder coating.

However, recent studies have shown that the sunscreen index SPF (UVB) and PA (UVA) are largely dependent on the uniform dispersion of the sunscreen, and the development of the blocker itself and the method of maintaining the dispersion of the blocker particles. It is being studied.

Methods of dispersing the sunscreen agent include a method using a dispersant and a method using SPF / PA booster (Booster). In the case of using a dispersant, silicone oil is generally used to form the W / O emulsion of the sunscreen particles, and these have low viscosity and light skin spreadability and feel. In this method, control of the phase separation of the sunscreen fine particles in the oil-based component is very important for maintaining the function and storage stability of the sunscreen. However, there is a disadvantage in that the usability is excellent while the lasting effect of the sunscreen effect is rapidly lowered over time.

As an alternative to this problem, a method using SPF / PA boosters has been developed. Korean Patent Publication No. 10-1000275 discloses a sunscreen booster consisting of an emulsion comprising an aqueous medium and an acrylic copolymer. However, the acrylic copolymer is one selected from the group consisting of at least one first monomer selected from the group consisting of alkyl esters of acrylic acid and alkyl esters of methacrylic acid, alkyl esters of acrylic acid and alkyl esters of methacrylic acid A second monomer composed of a material different from the first monomer as described above; And a crosslinking agent including at least two or more unsaturated bonds, so that the sunscreen can be more densely distributed, while not giving biocompatible or moisturizing properties to the sunscreen personal care article including the sunscreen. There is no limit.

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 to uniformly and stably disperse the sunscreen to impart a SPF (Sun Protection Factor) and PA (Protect A) boosting effect to the sunscreen personal care products And at the same time to provide a monomer based copolymer of phosphorylcholine like group that confers improved moisturization and biocompatibility.

In addition, another object of the present invention to provide a sunscreen booster comprising a copolymer based on the phosphoryl choline like group-containing monomer.

In addition, another object of the present invention is to provide a UV-protecting personal care article comprising the copolymer based on the phosphoryl choline-like monomer or the sunscreen booster.

In order to solve the object of the present invention, the present invention is one or more first monomers selected from the group consisting of alkyl esters of acrylic acid, alkyl esters of methacrylic acid, and alkenyl esters of alkanoic acid; A second monomer composed of at least one member selected from the group consisting of alkyl esters of acrylic acid, alkyl esters of methacrylic acid, and alkenyl esters of alkanoic acid; And at least one phosphorylcholine like group-containing monomer represented by Formula (1) below, wherein the alkyl group of the alkyl ester of acrylic acid and the alkyl ester of methacrylic acid has 1 to 20 carbon atoms The alkannoic acid has 2 to 20 carbon atoms, and the alkenyl group of the alkenyl ester of the alkanoic acid has 2 to 10 carbon atoms. To provide a 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.

In addition, in order to solve one object of the present invention, the present invention is preferably one or more selected from the group consisting of alkyl esters of acrylic acid, alkyl esters of methacrylic acid, and alkenyl esters of alkanoic acid. A first monomer; A second monomer composed of at least one member selected from the group consisting of alkyl esters of acrylic acid, alkyl esters of methacrylic acid, and alkenyl esters of alkanoic acid; 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; wherein the alkyl group of the alkyl ester of acrylic acid and the alkyl ester of methacrylic acid has 1 to 20 carbon atoms, and the alkanoic acid acid) has 2 to 20 carbon atoms, the alkenyl group of the alkenyl ester of the alkanoic acid has 2 to 10 carbon atoms, and the first monomer, the second monomer, and the phosphorylcholine like group-containing monomer are Provided is a phosphorylcholine like group-containing monomer based copolymer which is crosslinked by a crosslinking agent.

[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 addition, in order to solve the other object of the present invention, the present invention provides a sunscreen booster consisting of an emulsion comprising the copolymer described above, wherein the emulsion is preferably a fine particles of the copolymer dispersed in the aqueous phase medium Characterized in that it is in the form of underwater remains dispersed in the form.

In addition, in order to solve another object of the present invention, the present invention is a sunscreen personal care article comprising a sunscreen and the copolymer described above or a sunscreen personal care article comprising a sunscreen and the above-mentioned sunscreen booster To provide.

The copolymer according to the present invention or the sunscreen booster including the same distributes the sunscreen densely and uniformly to improve the UVB blocking effect and UVA blocking effect of the sunscreen personal care article. In addition, the copolymer according to the present invention includes a phosphorylcholine-like group-containing monomer, thereby significantly improving the biocompatibility (for example, adhesion and spreadability) and moisturizing properties of the sunscreen personal care product, thereby maximizing user convenience. Let's do it.

Hereinafter, the present invention will be described in detail.

Copolymer for sun protection booster

One aspect of the present invention is a phosphorylcholine like group-containing monomer-based monomer that imparts a SPF (Sun Protection Factor) and a PA (Protect A) boosting effect to a sunscreen personal care article, and at the same time gives improved moisturizing properties and biocompatibility. It relates to a copolymer for sun protection booster.

The copolymer for the sun protection booster according to the present invention comprises a first monomer, a second monomer and a phosphorylcholine like group-containing monomer, and preferably further comprises a crosslinking agent.

(a) a first monomer and a second monomer

In the copolymer for sun protection booster according to the present invention, the first monomer and the second monomer are different materials, and an alkyl ester of acrylic acid, an alkyl ester of methacrylic acid, and an alkenyl ester of alkanoic acid. It consists of 1 or more types chosen from.

At this time, the alkyl ester of acrylic acid and the alkyl ester of methacrylic acid are not particularly limited in the range of satisfying that the alkyl group has 1 to 20 carbon atoms, ease of copolymerization, efficiency of polymerization, and commercial availability. It is preferable that the alkyl group of the alkyl ester of acrylic acid and the alkyl ester of methacrylic acid has 1-8 carbon atoms from a viewpoint of the ease of the etc. The alkyl ester of acrylic acid is, for example, methyl acrylate (methyl acrylate), ethyl acrylate (ethyl acrylate), butyl acrylate (butyl acrylate), 2-ethylhexyl acrylate (2-ethylhexyl acrylate), lauryl acrylate (lauryl acrylate), stearyl acrylate (stearyl acrylate) and the like. In addition, the alkyl ester of methacrylic acid is, for example, methyl methacrylate (methyl methacrylate), ethyl methacrylate (ethyl methacrylate), butyl methacrylate (butyl methacrylate), 2-ethylhexyl methacrylate (2- ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, and the like.

In addition, the alkenyl ester of the alkannoic acid (alkanoic acid) is not particularly limited in the range that satisfies that the carbon number of the alkanoic acid is 2 to 20, the carbon number of the alkenyl group is 2 to 10, Alkanoic acid has 2 to 10 carbon atoms, and alkenyl groups of alkenyl esters of alkanoic acid have 2 carbon atoms in view of ease of copolymer preparation, efficiency of polymerization reaction and ease of commercial availability. It is preferable that it is -5. The alkanoic acid is, for example, acetic acid (Acetic acid), propionic acid (Propanoic acid), butyric acid (Butyric acid), valeric acid (Valeric acid), caproic acid (Caproic acid), enanthic acid (Enanthic acid), caprylic acid (Caprylic acid) acid), Pelargonic acid, Capric acid, Lauric acid, Palmitic acid, Stearic acid, and the like. . In addition, the alkenyl group may be preferably selected from a vinyl group or an allyl group. In the copolymer for sun protection booster according to the present invention, the alkenyl ester of alkanoic acid used as the first monomer or the second monomer is preferably vinyl acetate, allyl acetate, Vinyl propionate, allyl propionate, vinyl butyrate, allyl butyrate, and the like.

Further, in the copolymer for sun protection booster according to the present invention, as a preferred combination of the first monomer and the second monomer, the first monomer is selected from alkyl esters of acrylic acid, and the second monomer is alkyl ester or alkanoic acid of methacrylic acid ( It may be selected from the alkenyl ester of alkanoic acid). For example, the first monomer is selected from ethyl acrylate or butyl acrylate and the second monomer is selected from methyl methacrylate or vinyl acetate.

In addition, the weight ratio of the first monomer to the second monomer in the copolymer for the sunscreen booster according to the present invention is not particularly limited, and 80:20 to 20:80 from the viewpoint of densification and uniformity of the sunscreen by different monomers. Is preferably. In particular, when the first monomer is selected from alkyl esters of acrylic acid and the second monomer is selected from alkyl esters of methacrylic acid or alkenyl esters of alkanoic acid, the weight ratio of the first monomer to the second monomer is 60: It is more preferable that it is 40-20: 80.

(b)

The copolymer for sun protection booster 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).

[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 the phosphorylcholine like group-containing monomer used in the copolymer for sunscreen booster according to the present invention is not particularly limited, but 2- (methacryloyloxy) ethyl-2 'from the viewpoint of commercial 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 copolymer for the sunscreen booster according to the present invention is not particularly limited. It is preferable that it is 0.1-20 weight part per 100 weight part of the total weight of the dimer combined, It is more preferable that it is 0.2-10 weight part, It is most preferable that it is 0.5-5 weight part. If 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 first monomer and the second monomer, there is a possibility that the moisturizing property and biocompatibility of the 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 first monomer and the second monomer, there is a fear that the booster effect for UV protection of the copolymer may not reach the desired level.

(c) crosslinking agent

The copolymer for sun protection booster according to the present invention may preferably further comprise at least one crosslinking agent having two or more unsaturated ethylene bond groups as monomers. In the present invention, the crosslinking agent cross-links the first monomer and the second monomer, the first monomer and the phosphorylcholine analog group-containing monomer, or the second monomer and the phosphorylcholine analog group-containing monomer to form a network structure to prevent ultraviolet rays blocking. Booster effect for improve.

In the copolymer for sun protection booster according to the present invention, the cross-linking agent may be bound by the addition polymerization reaction with the unsaturated ethylene bond group contained in the first monomer, the second monomer, and the phosphorylcholine-like group-containing monomer. Not particularly limited, specifically, 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 dimethacrylate glycol dimethacrylate), diethylene glycol diacrylate e glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate ( tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate, methallyl acrylate acrylate, allyl ethacrylate, ethallyl acrylate, methallyl methacrylate, diallyl phthalate, diallyl maleate, diallyl Diallyl succinate, triallyl phosphate, di Diallyl oxalate, diallyl malonate, diallyl citrate, diallyl citrate, diallyl fumarate, diallyl oxyacetate, diallyl urea, divinyl benzene ), Trivinyl bezene, vinyl crotonate, N, N-methylene-bis-acrylamide, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, diallyl pentaerythritol ether, triallyl pentaerythritol ether, tetraallyl pentaerythritol ether, tetraallyl pentaerythritol ether pentaerythritol ether, diallyl sucrose ether, triallyl sucrose ether, and tetraallyl sucrose ether crose ether) may be composed of one or more materials selected from the group consisting of.

The content of the crosslinking agent in the copolymer for the sunscreen booster according to the present invention is not particularly limited, but in view of the densification and uniformity of the copolymer with the sunscreen, the emulsion stability of the produced copolymer itself, and economics, etc. It is preferable that it is 0.01-5 weight part per 100 weight part of the total weight of the monomer and the 2nd monomer combined, and it is more preferable that it is 0.02-2 weight part. When 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 first monomer and the second monomer, there is a concern that the effect of densification and homogenization of the copolymer on the sunscreen is insignificant, and the content of the crosslinking agent is insufficient. If it exceeds 5 parts by weight per 100 parts by weight of the total weight of the first monomer and the second monomer, there is a concern that the emulsion stability and economical efficiency of the produced copolymer itself are deteriorated.

The copolymer for phosphorylcholine like group-containing monomers for UV protection booster according to the present invention can be prepared using a general free radical polymerization reaction, specifically, precipitation polymerization, emulsion polymerization, bulk polymerization, solution polymerization, gel polymerization, etc. Production is possible, and double emulsion polymerization is preferred.

emulsion  Form of sun protection booster

Another aspect of the present invention is directed to a sunscreen booster that imparts a SPF (Sun Protection Factor) and a PA (Protect A) boosting effect to a sunscreen personal care article and at the same time provides improved moisturizing and biocompatibility.

The sunscreen booster according to the invention preferably consists of an emulsion comprising the copolymer of the invention described above. In this case, the emulsion preferably has an oil-in-water form in which a copolymer in a dispersed phase is dispersed in a fine particle form in an aqueous medium. In addition, the UV protection booster in the emulsion form according to the present invention may further include an oil-in-water emulsifier (O / W type emulsifier) or stabilizer.

 In the sunscreen booster in the form of emulsions according to the invention, the aqueous medium generally consists of water or a mixed solution of water and other hydrophilic solvents. The content of the aqueous medium in the sunscreen booster in the emulsion form according to the invention is about 50 to 85% by weight, preferably 55 to 80% by weight, based on the total weight of the emulsion.

In addition, the content of the copolymer in the emulsion type sunscreen booster according to the present invention is not significantly limited, and considering the ease of manufacture of the copolymer, the applicability to the sunscreen personal care article, etc., based on the total weight of the emulsion It is preferable that it is 15-50 weight%, and it is more preferable that it is 20-35 weight%.

In addition, the sunscreen booster in the emulsion form according to the present invention may preferably further comprise an oil-in-water emulsifier (O / W type emulsifier). The oil-in-water emulsifier generally forms an aqueous phase with an aqueous medium, and if the hydrophilic lipophilic balance (HLB) satisfies 8 or more, the type of known commercial emulsifier is not greatly limited. Is preferably 10 or more, and 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. Among these, oil-in-water emulsifiers in the form of polyethyleneglycol ethers of 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 emulsion-type sunscreen booster according to the invention is 1 to 10% by weight, preferably 1.5 to 6% by weight, based on the total weight of the emulsion. In the present invention, the oil-in-water emulsifying agent may be added at the time of preparing the water phase, or at the time of emulsification of the water phase and the oil phase.

In addition, the sunscreen booster in the form of an emulsion according to the invention may preferably further comprise a stabilizer. In emulsion polymerization in which a polymer is prepared by using a dispersion medium such as water in a continuous phase, a susceptible component such as an emulsifier and an ionic initiator is added to the polymer so that it may serve as a steric stabilization to compensate for it. Water-soluble polymers such as vinyl alcohol can be used as protective colloids. The polymers prepared under the conditions comprising the stabilizer can maintain the colloidal state more stably, thereby improving the phase stability of the emulsion. The content of stabilizer in the emulsion type sun protection booster according to the invention is 1 to 10% by weight, preferably 2 to 6% by weight, based on the total weight of the emulsion. Stabilizers in the present invention can be added during the production of the water phase, or during the emulsification of the water phase and the oil phase.

In addition to the above materials, the emulsion type sunscreen booster according to the present invention may further include a polymerization initiator introduced during the emulsion polymerization process. The polymerization initiator content is about 0.01 to 0.5% by weight based on the total weight of the emulsion.

The copolymer or sunscreen booster according to the present invention is preferably prepared by emulsion polymerization, which is as follows. First, an aqueous oil-in-water emulsifier or stabilizer is added to water, which is an aqueous medium, and stirred to prepare an aqueous phase. In addition, the oil phase is prepared by mixing and stirring the first monomer, the second monomer, and the phosphorylcholine like group-containing monomer separately from the aqueous phase. The oil phase may further include a crosslinking agent. After the aqueous phase is added to the polymerization reactor and purged with an inert gas, a part of the oil phase and a part of the polymerization initiator are added thereto to react at about 50 to 90 ° C. for about 0.1 to 30 minutes to form a seed. After the seed formation, the remaining oil phase and the remaining polymerization initiator are slowly introduced into the emulsion polymerization reactor at the same time to grow the seed at about 50 ~ 90 ℃ and polymerization reaction. After completion of the polymerization reaction, the reaction product is aged at about 50-90 ° C. for 0.5-5 hours to obtain an emulsion-type sunscreen booster. The preparation of the polymers and emulsions comprising them in the present invention is preferably carried out in 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, and specifically, azo initiators such as azobisisobutylonitrile (AIBN), azobisdimethylvaleronitrile, and benzoyl peroxide ( Peroxide initiators such as Benzoyl peroxide, Lauroyl peroxide, Potassium persulfate, Ammonium persulfate, and the like.

UV protection personal Care  goods

Another aspect of the invention relates to a sunscreen personal care article.

The sunscreen personal care article according to the present invention includes, for example, a sunscreen and a copolymer for a sunscreen booster based on the above-described phosphorylcholine like group-containing monomer. The sunscreen personal care article according to the present invention also includes, as another example, a sunscreen and a sunscreen booster in the form of the emulsion described above. The sunscreen personal care article according to the present invention includes a copolymer or an emulsion thereof that provides improved sunscreen booster effect, excellent biocompatibility and moisturizing properties, thereby providing a user with excellent sunscreen ability, feeling, and the like.

When the sunscreen personal care article according to the present invention includes a sunscreen and a copolymer, the copolymer content in the sunscreen personal care article is not limited to a large amount, but the sunscreen may be used in terms of a UV booster effect, a feeling of use, and a moisturizing feeling. It is preferably 0.1 to 5% by weight and more preferably 0.5 to 2% by weight based on the total weight of the personal care article. In addition, when the sunscreen personal care article according to the present invention includes a sunscreen and an emulsion sunscreen booster, the content of the sunscreen booster in the sunscreen personal care article is not significantly limited, but the UV booster effect, feeling of use, moisturizing feeling It is preferable that it is 0.5-10 weight% with respect to the total weight of a sunscreen personal care article from a viewpoint of etc., and it is more preferable that it is 1-5 weight%.

In the sunscreen personal care article according to the present invention, the sunscreen is a well-known active ingredient having a sunscreen function or a UV absorbing function, and its kind is not particularly limited. For example, PABA (p-Aminobenzoic acid), Ensulizole, OMC (Octyl methoxycinnamate), Avobenzone, Ecamsule, Titanium dioxide, and zinc oxide.

The sunscreen personal care article according to the present invention may further include higher fatty acids, higher alcohols, hydrocarbons, and the like, in addition to a sunscreen, a copolymer for a sunscreen booster, and an emulsion sunscreen booster. Silicone, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, water soluble polymer, coating agent, metal ion sequestrant, lower alcohol, polyhydric alcohol, sugar, amino acid, organic amine, polymer emulsion, pH adjuster, skin nutrient , Vitamins, antioxidants, antioxidants, fragrances, and the like may be appropriately blended, and may be prepared in various formulations for the purpose of lotion, essence, rinse, lotion, wax, etc. by known methods.

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  Similar group containing monomer-based copolymer for sun protection booster and its emulsion  Produce

Example 1.

600 g of water, 0.42 g of polysorbate 40 and 37.68 g of polyglyceryl-3 were added to a polymerization reactor, and stirred at about 60 ° C. to prepare an aqueous phase. In addition, separately from the preparation of the aqueous phase, 177.8 g of allyl acetate, 76.2 g of lauryl acrylate, and 2.54 g of MPC were added to the oil phase mixing tank and stirred to prepare an oil phase. In addition, 1.524 g of benzoyl peroxide was added and dissolved in 105.6 g of water to prepare a polymerization initiator solution.

After purging the polymerization reactor with nitrogen and raising the temperature of the polymerization reactor to about 90 ° C., 25.65 g of an oil phase and 48.2 g of a polymerization initiator solution were added in this order and reacted for about 30 minutes to form a seed. The oil phase and the polymerization initiator solution remaining after seed formation were slowly introduced into the polymerization reactor for about 5 hours to grow the seeds and polymerize. After completion of the polymerization reaction, the reaction product was aged at about 70 ℃ for about 5 hours to obtain an emulsion containing a copolymer.

Example 2.

An emulsion comprising a copolymer was obtained in the same manner as in Example 1, except that 0.05 g of divinyl benzene and 0.05 g of diallyl phthalate were further added as a crosslinking agent in the oil phase preparation. .

Example 3.

600 g of water, 0.42 g of Cetheth-10, and 37.68 g of polysorbate 80 (trade name Tween 80) were added to a polymerization reactor, and the aqueous phase was prepared by stirring at about 60 ° C. In addition to the preparation of the aqueous phase, 145.2 g of ethyl acrylate, 108.8 g of methyl methacrylate, and 5.08 g of MPC were added to an oil phase mixing tank and stirred to prepare an oil phase. In addition, 1.524 g of azobisisobutylonitrile (AIBN) was added and dissolved in 105.6 g of water to prepare a polymerization initiator solution.

After purging the polymerization reactor with nitrogen and raising the temperature of the polymerization reactor to about 70 ° C., 25.65 g of an oil phase and 48.2 g of a polymerization initiator solution were added in this order and reacted for about 15 minutes to form a seed. The oil phase and the polymerization initiator solution remaining after seed formation were slowly introduced into the polymerization reactor for about 5 hours to grow the seeds and polymerize. After completion of the polymerization reaction, the reaction product was aged at about 90 ℃ for about 5 hours to obtain an emulsion containing a copolymer.

Example 4.

An emulsion comprising a copolymer was obtained in the same manner as in Example 3, except that 0.08 g of divinyl benzene and 0.08 g of diallyl phthalate were further added as a crosslinking agent in the oil phase preparation. .

Comparative Example 1

600 g of water, 0.42 g of polysorbate 40 and 37.68 g of polyglyceryl-3 were added to a polymerization reactor, and stirred at about 60 ° C. to prepare an aqueous phase. In addition to the production of the aqueous phase, 177.8 g of allyl acetate, 76.2 g of lauryl acrylate, 0.05 g of divinyl benzene and 0.05 g of diallyl phthalate were added to the oil phase mixing tank and stirred, followed by stirring. Was prepared. In addition, 1.524 g of benzoyl peroxide was added and dissolved in 105.6 g of water to prepare a polymerization initiator solution.

After purging the polymerization reactor with nitrogen and raising the temperature of the polymerization reactor to about 90 ° C., 25.65 g of an oil phase and 48.2 g of a polymerization initiator solution were added in this order and reacted for about 30 minutes to form a seed. The oil phase and the polymerization initiator solution remaining after seed formation were slowly introduced into the polymerization reactor for about 5 hours to grow the seeds and polymerize. After completion of the polymerization reaction, the reaction product was aged at about 70 ℃ for about 5 hours to obtain an emulsion containing a copolymer.

Comparative Example 2

600 g of water, 0.42 g of Cetheth-10, and 37.68 g of polysorbate 80 (trade name Tween 80) were added to a polymerization reactor, and the aqueous phase was prepared by stirring at about 60 ° C. Apart from the preparation of the aqueous phase, 145.2 g of ethyl acrylate, 108.8 g of methyl methacrylate, 0.08 g of divinyl benzene and 0.08 g of diallyl phthalate were added to the oil phase mixing tank, and stirred. An oil phase was prepared. In addition, 1.524 g of azobisisobutylonitrile (AIBN) was added and dissolved in 105.6 g of water to prepare a polymerization initiator solution.

After purging the polymerization reactor with nitrogen and raising the temperature of the polymerization reactor to about 70 ° C., 25.65 g of an oil phase and 48.2 g of a polymerization initiator solution were added in this order and reacted for about 15 minutes to form a seed. The oil phase and the polymerization initiator solution remaining after seed formation were slowly introduced into the polymerization reactor for about 5 hours to grow the seeds and polymerize. After completion of the polymerization reaction, the reaction product was aged at about 70 ℃ for about 5 hours to obtain an emulsion containing a copolymer.

2. Copolymer Emulsion  UV protection personal Care  Manufacture of supplies

Using the copolymer emulsion prepared in Examples 1 to 4 and Comparative Examples 1 to 2, a sunscreen for sun protection was prepared as shown in Table 1 below.

Main Phase Ingredient Control group Production Example 1 Production Example 2 Production Example 3 Production Example 4 Comparative Preparation Example 1 Comparative Production Example 2 A Distilled water 70 65 65 65 65 65 65 Dissolvine Na2-S 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Propylene glycol 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Copolymer emulsion - 5.0 5.0 5.0 5.0 5.0 5.0 B Finsolv TN 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Protachem SMO 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Escalol 557 Octinoxate 7.5 7.5 7.5 7.5 7.5 7.5 7.5 Escalol 567 Oxybenzone 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Escalol 587 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Crodafos ces 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Ceterayl Alcohol 50/50 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Crodafos C320 Acid 1.33 1.33 1.33 1.33 1.33 1.33 1.33 C Liquid Germall Plus 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Frangrance 0.15 0.15 0.15 0.15 0.15 0.15 0.15 TEA 99% 0.1 0.1 0.1 0.1 0.1 0.1 0.1 D TiO ₂ 4.0 4.0 4.0 4.0 4.0 4.0 4.0 ZnO 2.0 2.0 2.0 2.0 2.0 2.0 2.0 DC 345 8.0 8.0 8.0 8.0 8.0 8.0 8.0

In Table 1, the units of the components are all "g", Preparation Examples 1 to 4 used the copolymer emulsions prepared in Examples 1 to 4, respectively, as the copolymer emulsion, Comparative Preparation Example 1 and Comparative In Preparation Example 2, a copolymer emulsion prepared in Comparative Example 1 and Comparative Example 2 was used as a copolymer emulsion, respectively.

3. Copolymer Emulsion  UV protection In sunscreen  About SPF Boosting  effect

(1) Test method

Among healthy healthy men and women between the ages of 18 and 60 years with no skin disease, 10 or more persons with skin types of Fitzpatrick optical skin type I to III with a minimum erythema of 20mJ / cm 2 to 50mJ / cm 2 were selected. It was carried out according to the method and criteria for measuring the sunscreen effect according to Article 9 of the Cosmetic Act.

After sectioning the product-free area at the back of the subject, the subject is allowed to take a comfortable position and irradiates with UVB to determine the subject's erythema state at a predetermined time within the range of 16 to 24 hours. Erythema is judged by two or more skilled people under sufficiently bright light sources. The minimum amount of UVB light irradiated to the erythema appeared on the front surface is the minimum amount of erythema (MED). Based on the minimum amount of erythema of each subject, the range of light is determined based on the expected blocking index of the standard sample and the test product, and then the standard sample application site and the test product application site are divided on the subject's back. Put a rubber thimble on your finger and apply the appropriate amount of standard sample and test product. After drying at room temperature for 15 minutes, measure the same amount as the minimum erythema of the product-free area. The erythema determination is made by the same person at the same time as the minimum erythema measurement time of the product-free area.

The light source has a continuous emission spectrum similar to sunlight and uses a solar simulator or similar light source equipped with a Xenon arc lamp that does not exhibit a specific peak. At this time, the wavelength of less than 290nm should be removed using a suitable filter, and maintain a constant amount of light for the test time.

As the standard sample, a high UV blocking index (SPF20 or higher) standard sample was used, and the UV blocking index was 15.5 ± 3.0. The product application amount is 2.0 mg / cm 2 or 2.0 μL / cm 2, and the product application area is 24 cm 2 (6 cm × 4 cm = 24 cm 2) or more and five or more irradiation sites having an area of 0.5 cm 2 or more are divided. The amount of light at each irradiation site is adjusted so that the area where minimal erythema is expected is medium (eg 3 or 4 positions) and accordingly equal to 25% or less when the estimated UVF is less than 20 and less than 20 or less than 30 If less than 15%, if more than 30 less than 10%) increase the amount of light at intervals.

The UV protection index (SPF) is obtained by calculating the minimum amount of erythema (MEDu) of the product-free area and the minimum amount of erythema (MEDp) of the product application area, and calculating the UV-protection index (SPFi) of each subject according to the following equation. It is done. The 95% confidence interval of the sunscreen index should be within ± 20% of the sunscreen index. However, if this condition is not met, test again by increasing the number of samples or by resetting the test conditions.

The sunscreen index (SPF) is expressed as an integer after the decimal point of the sunscreen index (SPF) value obtained according to the sunscreen index calculation method is discarded.

The standard samples used in the test were prepared and used as shown in Table 2 below according to the method for measuring the UV blocking effect according to 2008-60 No. 2008-60, and the high SPF standard sample preparation method presented in the standards.

Main Phase ingredient amount(%) A Cetostearyl alcohol (and) PEG-40 caster oil (and) Sodium cetearyl sulphate 3.15 Decyl oleate 15.0 Octyl methoxycinnamate 3.0 Butyl methoxydibenzoylmethane 0.5 Propyl hydroxybenzoate 0.1 B Purified water 53.57 Phenylbenzimidazole sulphonic acid 2.78 Sodium hydroxide (45% solution) 0.9 Methyl hydroxybenzoate 0.3 Disodium edetate 0.1 C Purified water 20.0 Carbomer 0.3 Sodium hydroxide (45% solution) 0.3

(2) test result

The SPF boosting test results for 10 subjects are shown in Table 3 below.

Subject age Control group Production Example 1 Production Example 2 Production Example 3 Production Example 4 Comparative Preparation Example 1 Comparative Production Example 2 KWK 39 30.3 43.1 50.3 42.1 50.1 48.5 38.3 PYS 25 35.3 44.3 46.8 42.6 46.7 41.2 42.6 KJH 20 27.2 47.1 49.3 45.1 44.2 39.8 45.1 LSJ 21 33.5 41.5 45.3 44.3 47.1 41.6 38.9 KBS 25 38.1 49.7 49.6 39.8 46.2 45.2 43.4 CKS 25 26.0 43.6 52.4 42.3 43.2 43.1 42.2 LTU 23 29.9 39.3 48.6 43.5 48.1 42.5 41.9 LJS 22 30.2 43.5 54.5 48.6 54.2 41.8 46.1 JYK 22 32.5 46.1 46.3 41.7 52.4 44.4 40.2 CES 25 25.1 51.8 47.1 40.5 47.8 42.1 41.4 Average 24.7 30 44 49 43 48 43 42

4. Copolymer Emulsion  UV protection In sunscreen  About PA Boosting  effect

(1) Test method

Ten healthy males and females aged 18-60 years without skin disease were selected as subjects and were performed according to the method and criteria for measuring the effect of sunscreen according to Article 9 of the Cosmetic Act. After sectioning the uncoated test site on the subject's back, the subject is placed in a comfortable position and irradiated with UVA. Do not move the subject while irradiating ultraviolet light. The blackening state of the subject is determined at a fixed time within 2 to 4 hours after the investigation is completed. Two or more skilled people will judge under a sufficiently bright light source. The minimum amount of UVA light irradiated to the site where blackening appears on the entire surface is the minimum sustained instant blackening amount (MPPD).

After determining the range of irradiated light based on the minimum sustained instantaneous blackening amount of each subject, the standard sample application site and the product application site are divided on the subject's back. Put a rubber thimble on your finger and apply the standard sample and product as appropriate. After drying for 15 minutes at room temperature, measure the same as the minimum continuous instantaneous blackening (MPPD) measurement of the product uncoated area. The judgment is made by the same person at the same time as the minimum continuous instantaneous blackening measurement time of the product-free area.

The light source uses an artificial light source that satisfies the following and maintain and check that the following conditions are always satisfied. The light source should have a continuous spectrum similar to sunlight in the UVA range. In addition, the ratio of UVA I (340-400 nm) and UVA II (320-340 nm) should be similar to the ratio of sunlight (ultraviolet A II / total UV A = 8-20%). To avoid excessive sun burn, ultraviolet rays below wavelength 320 nm are removed using an appropriate filter. The standard sample used the standard sample of Table 4, and the ultraviolet-ray A blocking index was 3.75 +/- 1.

Main Phase ingredient amount (%) A Purified water 57.13 Dipropylene glycol 5.00 Potassium Hydroxide 0.12 Trisodium EDTA 0.05 Phenoxyethanol 0.30 B Stearic acid 3.00 Glyceryl Monostearate, selfemulsifying 3.00 Cetearyl Alcohol 5.00 Petrolatum 3.00 Triethylhexanoin 15.0 Ethylhexylmethoxycinnamate 3.00 (Ethylhexyl Methoxycinnamate) 5.00 Butylmethoxydibenzoylmethane 0.20 Ethylparaben Methylparaben 0.20

The product application amount is 2 mg / cm 2 or 2 μL / cm 2, and the product application area is 24 cm 2 or more, and five or more irradiation sites having an area of 0.5 cm 2 or more are partitioned. The partitioning method is the same as the UV blocking index measurement method. The amount of light at each irradiation site is adjusted so that the minimum sustained instantaneous blackening is expected to be in the middle (eg, 3 or 4 positions) and accordingly increases the amount of light at equal intervals. The rate of increase is up to 25%.

The UVA blocking index (PFA) is obtained by determining the minimum sustained instantaneous blackening amount (MPPDu) of the product-free coating site and the minimum sustained instantaneous blackening amount (MPPDp) of the product coating site, and according to the following equation, Calculate (PFAi) and use the arithmetic mean value. In this case, the standard error of the UVA blocking index (PFA) should be within ± 10% of the obtained UVA blocking index (PFA) value. However, if this condition is not met, test again by increasing the number of samples or by resetting the test conditions.

(2) test result

The PA test results for ten subjects are shown in Table 5 below.

Subject age Control group Production Example 1 Production Example 2 Production Example 3 Production Example 4 Comparative Preparation Example 1 Comparative Production Example 2 KWK 39 5.01 7.31 7.93 7.22 7.91 7.22 7.23 PYS 25 5.65 7.61 8.45 7.54 7.88 7.41 7.35 KJH 20 5.87 6.98 8.11 7.11 7.36 7.74 6.98 LSJ 21 5.16 6.87 8.03 7.91 8.22 6.99 6.88 KBS 25 5.54 7.73 7.96 6.92 8.49 7.24 7.41 CKS 25 5.98 7.84 7.85 6.79 7.66 7.05 6.99 LTU 23 6.23 8.16 8.25 7.31 7.71 6.83 7.11 LJS 22 6.39 7.28 8.34 6.97 7.91 6.58 6.53 JYK 22 4.91 7.91 8.69 7.65 7.23 7.39 7.63 CES 25 6.55 7.51 8.17 7.35 8.11 7.94 7.09 Average 24.7 5.73 7.52 8.18 7.28 7.85 7.24 7.12

5. UV protection Sunscreen  Adhesiveness, Brittle , Moisturizing evaluation

(1) Test method

The subjects who participated in the UV blocking index measurement method were evaluated for skin adhesion, application, and moisturizing based on the following score criteria.

* Score criteria for cohesive sensory evaluation (same application of moisture and moisture) *

Very good: 3 points, Excellent: 2 points, Normal: 1 point, Bad: -1 point,

Very bad: -2 points

(2) test result

Adhesion, applicability, and moisturizing test results for 10 subjects are shown in the table below.

Adhesiveness Subject age Control group Production Example 1 Production Example 2 Production Example 3 Production Example 4 Comparative Preparation Example 1 Comparative Production Example 2 KWK 39 -One 3 3 3 3 One One PYS 25 One 2 3 3 3 2 3 KJH 20 -One 3 2 3 3 2 2 LSJ 21 -2 3 3 3 3 2 2 KBS 25 One 3 3 3 3 3 2 CKS 25 2 3 3 2 3 One One LTU 23 One 2 3 3 3 3 One LJS 22 -One 3 3 3 3 2 3 JYK 22 -2 3 3 One 2 3 2 CES 25 -2 3 3 3 3 3 3 Average 24.7 -0.4 2.8 2.9 2.7 2.9 2.2 2.0

Brittle Subject age Control group Production Example 1 Production Example 2 Production Example 3 Production Example 4 Comparative Preparation Example 1 Comparative Production Example 2 KWK 39 One 3 3 3 3 2 One PYS 25 2 One 3 3 3 3 3 KJH 20 One 3 3 3 3 3 2 LSJ 21 One 3 3 3 3 2 2 KBS 25 3 3 2 3 3 3 3 CKS 25 2 3 3 3 3 2 3 LTU 23 One 3 3 3 3 One 2 LJS 22 -One 3 3 3 3 3 3 JYK 22 -One 3 3 3 3 2 One CES 25 One 3 3 2 3 3 2 Average 24.7 1.0 2.8 2.9 2.9 3.0 2.4 2.2

Moisturizing Subject age Control group Production Example 1 Production Example 2 Production Example 3 Production Example 4 Comparative Preparation Example 1 Comparative Production Example 2 KWK 39 -One 2 3 3 3 2 One PYS 25 One 3 3 3 2 -One -One KJH 20 2 3 3 3 3 2 2 LSJ 21 -2 3 3 3 3 One 2 KBS 25 One 3 3 3 3 One One CKS 25 One 3 3 3 3 2 One LTU 23 One 2 3 3 3 One 2 LJS 22 2 3 3 3 3 2 One JYK 22 One 3 3 One 3 -One 2 CES 25 -One 3 3 3 3 2 -One Average 24.7 0.5 2.8 3.0 2.8 2.9 1.1 1.0

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.

Claims (27)

At least one first monomer selected from the group consisting of alkyl esters of acrylic acid, alkyl esters of methacrylic acid, and alkenyl esters of alkanoic acid; A second monomer composed of at least one member selected from the group consisting of alkyl esters of acrylic acid, alkyl esters of methacrylic acid, and alkenyl esters of alkanoic acid; And at least one phosphorylcholine like group-containing monomer represented by the following formula (1);
The alkyl group of the alkyl ester of acrylic acid and alkyl ester of methacrylic acid has 1 to 20 carbon atoms,
The alkanoic acid has 2 to 20 carbon atoms,
The alkenyl group of the alkenyl ester of the alkanoic acid is a phosphoryl choline-like monomer-based copolymer, characterized in that 2 to 10 carbon atoms.
[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.
The phosphorylcholine according to claim 1, wherein the first monomer is selected from alkyl esters of acrylic acid and the second monomer is selected from alkyl esters of methacrylic acid or alkenyl esters of alkanoic acid. Similar group-containing monomer based copolymer.
The method of claim 1, wherein the alkyl ester of acrylic acid is methyl acrylate (methyl acrylate), ethyl acrylate (ethyl acrylate), butyl acrylate (butyl acrylate), 2-ethylhexyl acrylate (2-ethylhexyl acrylate), Uryl acrylate (lauryl acrylate), and stearyl acrylate (stearyl acrylate), and the alkyl ester of methacrylic acid is methyl methacrylate (methyl methacrylate), ethyl methacrylate (ethyl methacrylate), One selected from the group consisting of butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate A phosphorylcholine like group-containing monomer based copolymer.
According to claim 1, wherein the alkanoic acid (alkanoic acid) is selected from the group consisting of acetic acid (Proetic acid), propionic acid (Propanoic acid), butyric acid (Butyric acid), and valeric acid (Valeric acid) Copolymer based on polycholine-like group monomers.
5. The copolymer of claim 4, wherein the alkenyl group of the alkenyl ester of alkanoic acid is a vinyl group or an allyl group. 6.
The copolymer of claim 1, wherein the weight ratio of the first monomer to the second monomer is 80:20 to 20:80.
The content of the phosphorylcholine like group-containing monomer in the copolymer is 0.1 to 20 parts by weight per 100 parts by weight of the total weight of the sum of the first monomer and the second monomer. Group-based monomer based copolymers.
8. The method of claim 7, wherein the phosphoryl choline analog group-containing monomer is 2- (methacryloyloxy) ethyl-2 '-(trimethylammonio) ethylphosphate [2- (methacryloyloxy) ethyl-2'-(trimethylammonio) ethylphosphate], a copolymer based on phosphorylcholine like group-containing monomers.
At least one first monomer selected from the group consisting of alkyl esters of acrylic acid, alkyl esters of methacrylic acid, and alkenyl esters of alkanoic acid; A second monomer composed of at least one member selected from the group consisting of alkyl esters of acrylic acid, alkyl esters of methacrylic acid, and alkenyl esters of alkanoic acid; 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 alkyl group of the alkyl ester of acrylic acid and alkyl ester of methacrylic acid has 1 to 20 carbon atoms,
The alkanoic acid has 2 to 20 carbon atoms,
Alkenyl group of the alkenyl ester of the alkanoic acid has 2 to 10 carbon atoms,
The first monomer, the second monomer, and the phosphorylcholine like group-containing monomer are cross-linked by the crosslinking agent.
[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.
10. The phosphorylcholine according to claim 9, wherein the first monomer is selected from alkyl esters of acrylic acid and the second monomer is selected from alkyl esters of methacrylic acid or alkenyl esters of alkanoic acid. Similar group-containing monomer based copolymer.
10. The method of claim 9, wherein the alkyl ester of acrylic acid is methyl acrylate (methyl acrylate), ethyl acrylate (ethyl acrylate), butyl acrylate (butyl acrylate), 2-ethylhexyl acrylate (2-ethylhexyl acrylate), Uryl acrylate (lauryl acrylate), and stearyl acrylate (stearyl acrylate), and the alkyl ester of methacrylic acid is methyl methacrylate (methyl methacrylate), ethyl methacrylate (ethyl methacrylate), One selected from the group consisting of butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate A phosphorylcholine like group-containing monomer based copolymer.
10. The method of claim 9, wherein the alkanoic acid (alkanoic acid) is selected from the group consisting of acetic acid (Proetic acid), propionic acid (Propanoic acid), butyric acid (Butyric acid), and valeric acid (Valeric acid) Copolymer based on polycholine-like group monomers.
13. The monomer based copolymer of phosphorylcholine like group according to claim 12, wherein the alkenyl group of the alkenyl ester of alkanoic acid is a vinyl group or an allyl group.
10. The copolymer of claim 9 wherein the weight ratio of the first monomer to the second monomer is 80:20 to 20:80.
10. The method according to claim 9, wherein the content of the phosphoryl choline like group-containing monomer in the copolymer is 0.1 to 20 parts by weight per 100 parts by weight of the total weight of the sum of the first monomer and the second monomer. Group-based monomer based copolymers.
16. The method of claim 15, wherein the phosphoryl choline like group-containing monomer is 2- (methacryloyloxy) ethyl-2 '-(trimethylammonio) ethylphosphate [2- (methacryloyloxy) ethyl-2'-(trimethylammonio) ethylphosphate], a copolymer based on phosphorylcholine like group-containing monomers.
10. The method according to claim 9, wherein the content of the crosslinking agent in the copolymer is based on phosphorylcholine like group-containing monomer, characterized in that 0.01 to 5 parts by weight per 100 parts by weight of the total weight of the first monomer and the second monomer. Copolymer.
18. The method of claim 17, 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, vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate, meta Allyl acrylate, allyl ethacrylate, ethallyl acrylate, methallyl methacrylate, diallyl phthalate, diallyl malate maleate, diallyl succinate, triallyl phosphate, diallyl oxalate, diallyl malonate, diallyl citrate, diallyl citrate, diallyl citrate Diallyl fumarate, diallyl oxyacetate, diallyl urea, divinyl benzene, trivinyl bezene), vinyl crotonate, N, N-methylene-bis-acrylamide, trimethylolpropane diallyl ether, trimethylolpropane tri Allyl ether (trimethylolpropane triallyl ether), diallyl pentaerythritol ether, triallyl pentaerythritol ether, triallyl pentaerythritol ether, tetraallyl pentaerythritol ether, diallyl sucrose Phosphorylcholine like group-containing monomers, characterized in that it is composed of one or more materials selected from the group consisting of ether, trially sucrose ether, and tetraallyl sucrose ether. Based copolymers.
19. A sunscreen booster comprising an emulsion comprising the copolymer of any one of claims 1-18.
20. The sunscreen booster according to claim 19, wherein the emulsion is in the form of oil droplets in which a copolymer dispersed in a water phase medium is dispersed in a fine particle form.
20. The sunscreen booster according to claim 19, wherein the copolymer content in the emulsion is 15 to 50% by weight based on the total weight of the emulsion.
20. The sunscreen booster of claim 19, wherein the emulsion further comprises an oil-in-water emulsifier or stabilizer.
20. The sunscreen booster according to claim 19, wherein the content of the oil-in-water emulsifier in the emulsion is 1 to 10% by weight based on the total weight of the emulsion, and the content of the stabilizer in the emulsion is 1 to 10% by weight. .
A personal care article for sun protection comprising a sunscreen and a copolymer of any one of claims 1 to 18.
25. The sunscreen personal care article of claim 24, wherein the copolymer content in the sunscreen personal care article is 0.1-5% by weight based on the total weight of the sunscreen personal care article.
A sunscreen personal care product comprising a sunscreen and a sunscreen booster according to claim 9.
27. The sunscreen personal care product according to claim 26, wherein the sunscreen booster content in the sunscreen personal care article is 0.5 to 10% by weight based on the total weight of the sunscreen personal care article.