TW201708278A - Copolymer - Google Patents

Abstract

The present invention addresses the problem of providing a novel copolymer having an elastic feeling. A copolymer having a weight-average molecular weight of 20,000-110,000, having one or more types of constituent units (a) derived from a hydrophobic monomer having a specific structure, and one or more types of constituent units (b) derived from a hydrophilic monomer represented by general formula (2) as essential constituent units.

Description

Copolymer

This invention relates to a novel copolymer which is a copolymer of a hydrophobic monomer and a hydrophilic monomer.

Further, the present invention relates to an emulsified composition which is emulsified using a water-soluble copolymer.

Further, the present invention relates to a skin cleansing agent comprising a water-soluble copolymer.

Further, the present invention relates to a sunscreen cosmetic comprising a water-soluble copolymer.

Further, the present invention relates to a film having a sea-island structure of island particles in which an amphiphilic copolymer is dispersed in a sea of an aqueous gel, and a composition thereof.

In general, the oily agent has a good feeling of elasticity or moist feeling, and has been used as a material for cosmetics since ancient times. However, the oil agent exerts the above-described excellent feeling of use, and when it is blended, it may cause a sticky feeling and deteriorate the feeling of use.

Under such circumstances, attempts have been made to reduce the stickiness caused by the oil agent by designing the composition or structure of the cosmetic or the like. For example, Patent Document 1 proposes a technique for suppressing a sticky feeling by reducing an emulsified particle size in a cosmetic composition of an emulsified composition.

However, the technique of reducing the feeling of stickiness by designing a composition or a structure of a cosmetic as described in Patent Document 1 has a problem of being limited to an applicable dosage form.

On the other hand, a novel material which has both a moist feeling and a non-sticky feeling is proposed. For example, Patent Document 2 discloses a cosmetic base containing an alkylene oxide derivative which has excellent touch and moisture retention.

Further, an emulsified composition in which an oil phase component and an aqueous phase component are mixed by an emulsifier is widely used as a formulation of a cosmetic. However, general low molecular emulsifiers have problems such as irritation or stickiness to the skin.

In order to solve such a problem, various emulsification techniques using a polymer emulsifier have been proposed in recent years.

Patent Document 3 discloses an emulsified composition using hydroxyethyl cellulose as an emulsifier.

Further, Patent Document 4 discloses an emulsified composition using an alkyl-modified polyvinyl carbomer as an emulsifier.

In addition, in the skin cleansing agent such as facial cleanser, a potassium salt of a higher fatty acid is often used from the viewpoints of excellent foaming property, good cleansing power, and refreshing feeling after rinsing. However, a skin cleansing agent containing a potassium salt of a higher fatty acid as a main component has such an excellent property, and it is also difficult to obtain a dense foam quality, which is easy to excessively degrease due to washing, and is caused by scum. ) The problem that remains on the skin and makes the skin easy to tighten after use.

As a method for improving such a problem, a combination of a higher fatty acid and a surfactant such as a mercapto tauryl salt type, a mercapto isethionate type, a phosphate type, or a mercapto amino acid type is proposed (for example, patent document) 5) Blending of an additive other than the surfactant (for example, an anthrone compound, a specific glycolipid, raffinose, a plant seed slime, or a polymer compound of various kinds) (for example, Patent Documents 6 to 12).

In addition, it is attempted to improve the above problem by combining a thioglycine type surfactant and a specific polymer compound without using a potassium salt of a higher fatty acid as a main component (see Patent Document 13).

Moreover, the oil-based emulsified sunscreen cosmetic has a refreshing feeling of use and is easy to use continuously. In order to enhance the ultraviolet protection effect, an ultraviolet light scattering agent of a metal oxide powder such as an ultraviolet absorber, zinc oxide or titanium oxide is used in the oil-in-water emulsion cosmetic. However, when a large amount of the ultraviolet absorber is blended, there is a problem that the feeling of use such as discoloration, poor elongation, and stickiness is deteriorated. Further, when the metal oxide powder is blended in a large amount, not only the aggregation or precipitation of the powder occurs over time, but also the problem that the viscosity stability, emulsification separation, precipitation, and the like are lowered in stability with time. When these are used together, there is a tendency that the above problem becomes more likely to occur.

In order to improve these problems, it is proposed to use a combination of an ultraviolet absorber such as a benzoylmethane derivative and a titanium oxide treated with decane and/or an anthrone (see Patent Document 14).

Further, an oil-in-water emulsion cosmetic using a water-soluble polymer such as polyacrylamide, santral, or sodium acrylate/acrylonitrile dimethyltaurine copolymer has been proposed (see Patent Documents 15 and 16).

In addition, the sea-island structure refers to a structure in which two kinds of polymers which are incompatible with each other are phase-separated, and a continuous phase (sea phase) containing one polymer is dispersed with a dispersed phase (island phase) containing the other polymer. . As described above, since the sea-island structure has a phase-separated uneven structure, it has a property different from that of a composition having a uniform structure. In order to take advantage of this property, research and development in the technical fields of plastics or rubber, toners, and adhesives are actively carried out for the island structure.

For example, Patent Document 17 discloses a tire which is coated with a coating mixture having a sea-island structure including a thermoplastic resin and an island structure including a polyurethane-based thermoplastic elastomer.

However, in the field of cosmetics, attempts to utilize island structures have not been carried out to this end.

Then, in Patent Document 18, a two-parent copolymer containing a constituent unit derived from a specific hydrophobic acrylate monomer and a constituent unit derived from a specific hydrophilic acrylic monomer is disclosed. External preparation for skin.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2012-116783

Patent Document 2 Japanese Re-issue 2006/038724

Patent Document 3 Japanese Patent Laid-Open Publication No. 2011-231049

Patent Document 4 Japanese Patent Publication No. 09-019631

Patent Document 5 Japanese Patent Laid-Open No. Hei 6-248298

Patent Document 6 Japanese Patent Laid-Open No. Hei 10-77206

Patent Document 7 Japanese Patent Laid-Open Publication No. 2001-72574

Patent Document 8 Japanese Patent Laid-Open Publication No. 2000-178172

Patent Document 9 Japanese Patent Laid-Open No. Hei 11-209799

Patent Document 10 Japanese Patent Laid-Open Publication No. 2003-73257

Patent Document 11 Japanese Patent Laid-Open Publication No. 2007-277140

Patent Document 12 Japanese Patent Laid-Open No. Hei 10-183193

Patent Document 13 Japanese Patent Publication No. 9-78082

Patent Document 14 Japanese Patent Publication No. 9-2929

Patent Document 15 Japanese Patent Laid-Open Publication No. 2003-104859

Patent Document 16 Japanese Patent Laid-Open Publication No. 2010-215602

Patent Document 17 Japanese Patent Laid-Open Publication No. 2013-180652

Patent Document 18 Japanese Patent Publication No. 2014-9189

As described above, the oil agent has a feeling of better use of the elastic feeling, and has a problem such as a sticky feeling. Under such circumstances, a novel material having an elastic feeling such as an oil agent is required.

An object of the present invention is to provide a novel copolymer having a strong elastic feeling. Further, in a preferred embodiment of the present invention, a copolymer which is less likely to cause a sticky feeling and has a moist feeling is provided as the first problem.

Further, the above-mentioned polymer emulsifier has little effect on the skin, and although it has an advantage of being low in concentration, it has a small stickiness, and the emulsifying power is inferior to the conventional low molecular emulsifier. Therefore, in order to ensure the stability of the emulsified state, it is necessary to highly blend the polymer emulsifier of the emulsified composition to have a high viscosity, and as a result, there is a problem of stickiness.

In view of the above, the present invention provides a emulsified composition which is less irritating to the skin, has less stickiness, and has excellent emulsion stability, and is a second problem.

Due to the high consumer demand in recent years, especially with regard to the quality of the foam or the feel after washing, such methods are not fully met and further improvements are needed.

In view of the above, the third object to be solved by the present invention is to provide a novel technique for reducing the feeling of tightness of the skin after use of the skin cleansing agent.

Moreover, it is possible to provide a skin cleansing agent which does not impair the cleansing power, the foaming property, the good foam quality, the non-sticky feeling after use, and the ease of stretching of the skin, and A technique that can reduce the feeling of tightness of the skin after use is the fourth problem.

Further, in the field of technology of oil-based sunscreen cosmetics in water, both the ultraviolet defense function and the feeling of use or emulsion stability are the subject. In the past, various techniques have been proposed to solve this problem, but they are not sufficient.

In view of the above circumstances, the fifth object to be solved by the present invention is to provide an oil-in-water type sunscreen cosmetic which has good ultraviolet protection function, has no sticky feeling or moisturizing feeling, and has emulsion stability. .

Further, an object of the present invention is to provide a film having a sea-island structure having a water-soluble component as a main component and a technique for forming the film. In addition, a technique of imparting a feeling of touch such as milk containing an oil agent to a film containing a water-soluble component as a main component is provided. question. It is preferable to provide a film having both moisture retention and flexibility and a technique for forming the film as the sixth object of the present invention.

In view of the state of the first subject, the inventors of the present invention have carefully studied the results of the pursuit of the elastic copolymer, and found that the acrylate having a hydrophobic, polymerizable carboxyl group and two sulfhydryl groups having a specific branched structure is used. The copolymer polymerized with a hydrophilic acrylic monomer having a specific structure has good solubility, particularly solubility in water, and has a tactile sensation such as an elastic property of an oil agent, thereby completing the present invention. That is, the present invention is as follows.

A copolymer which is one or two or more kinds of constituent units (a) derived from a hydrophobic monomer represented by the following formula (1) and a hydrophilic sheet represented by the following formula (2) One or two or more kinds of constituent units (b) derived from the body are contained as essential constituent units, and the weight average molecular weight is from 20,000 to 110,000.

(In the formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² and R ³ may be the same or different, and represent a carbon number 6 to 22 having a branch structure which does not have a ring structure. Sulfhydryl. X represents a group from which an OH group is desorbed from a triol.

(In the formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵ represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R ⁶ represents a hydrogen atom and a carbon number of 6~ An aromatic hydrocarbon group of 10, an aliphatic hydrocarbon group having 1 to 14 carbon atoms or a fluorenyl group having 1 to 12 carbon atoms. n represents an integer of 6 to 40).

The copolymer thus has a feeling of elasticity when applied to the skin, and has a non-sticky feeling or a moist feeling.

In a preferred embodiment of the present invention, the mass ratio of the structural unit (a) to the structural unit (b) is 25:75 to 35:65.

The copolymer having a mass ratio of the constituent unit (a) to the constituent unit (b) in the above range is excellent in the feeling of elasticity and the feeling of not having a sticky feeling.

In a preferred embodiment of the present invention, the molar ratio of the structural unit (a) to the structural unit (b) is 35:65 to 46:54.

The copolymer having a mass ratio of the constituent unit (a) to the constituent unit (b) in the above range is excellent in the feeling of elasticity and the feeling of not having a sticky feeling.

In a preferred embodiment of the present invention, the hydrophobic monomer is a hydrophobic monomer represented by the following formula (3).

General formula (3)

(In the formula (3), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁸ and R ⁹ may be the same or different and each represents a branched carbon number 10 to 22 which does not have a ring structure. A fluorenyl group or a fluorenyl group having 6 to 9 carbon atoms having two or more branches without a ring structure. Y represents a group from which an OH group is desorbed from a triol.

As the hydrophobic monomer, a copolymer having a more excellent touch can be obtained by using the above monomer.

Further, in a preferred embodiment of the present invention, the hydrophilic monomer is a hydrophilic monomer represented by the following formula (4).

(In the formula (4), R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹¹ represents a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 14 carbon atoms or carbon. The number of thiol groups from 1 to 12, m represents an integer from 6 to 40).

As the hydrophilic monomer, a copolymer having a more excellent touch can be obtained by using the above monomer.

In a preferred embodiment of the invention, the triol is glycerol, trimethylolpropane or trimethylolethane.

By becoming such a form, the feeling of elasticity can be enhanced.

The hydrophobic monomer is a compound represented by the following formula (5).

(In the formula (5), R ¹² and R ¹³ may be the same or different and each represents a fluorenyl group having a branched carbon number of 18 which does not have a ring structure.

By using such a hydrophobic monomer, the elastic feeling can be improved.

In a preferred embodiment of the present invention, the hydrophilic monomer is a hydrophilic monomer represented by the following formula (6).

(In the formula (6), l represents an integer of 6 to 40).

By using such a hydrophilic monomer, the elastic feeling can be enhanced.

Further, the present invention relates to a skin external preparation containing the above-described copolymer of the present invention. The external preparation for skin has a feeling of elasticity after application to the skin. Also, there is no sticky feeling or good moist feeling.

The present invention which solves the second problem is an emulsified composition comprising one or more kinds derived from the hydrophobic monomer represented by the above formula (1), the following (7) or (8). The constituent unit (c) and one or more constituent units (d) derived from the hydrophilic monomer are water-soluble copolymers as essential constituent units, and substantially do not contain an emulsifier other than the water-soluble copolymer. .

(In the formula (7), R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁵ represents a branched hydrocarbon group having a ring structure of 13 to 30 or a ring structure having no ring structure; The above branch has a carbon number of 6 to 12).

General formula (8)

(In the formula (8), R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different, and represent a carbon number 6 having no branch structure.醯 group of ~22. Y represents a group from which a OH group is desorbed from a tetrahydric alcohol).

The emulsified composition of the present invention contains a water-soluble copolymer as described above and has less stickiness during use.

In a preferred embodiment of the present invention, the hydrophilic monomer is selected from the group consisting of a polymerizable carboxylic acid, a hydrophilic monomer represented by the above formula (2), and a hydrophilicity represented by the following formula (9). One or two or more kinds of hydrophilic monomers of a monomer, a hydrophilic monomer represented by the following formula (10), and a hydrophilic monomer represented by the following formula (11).

(In the formula (9), R ²⁰ represents a hydrogen atom or a methyl group).

General formula (10)

(In the formula (10), R ²¹ represents a hydrogen atom or a methyl group, and GO- represents a group in which hydrogen is removed from the hydroxyl group at the 1-position of the reducing sugar. m represents an integer of 2 or 3, and l represents an integer of 1 to 5).

(In the formula (11), R ²² represents a hydrogen atom or a methyl group, and R ²³ represents an amino acid residue, a polyamine residue or an amine alcohol residue. Q represents an oxygen atom or a group represented by NH).

By containing the water-soluble copolymer containing the structural unit (d) derived from such a hydrophilic monomer, the sticky feeling at the time of use of the emulsified composition of the present invention can be further reduced.

In a preferred embodiment of the present invention, the hydrophobic monomer is a hydrophobic monomer represented by the above formula (1), and the water-soluble monomer is a hydrophilic monomer represented by the above formula (2).

A water-soluble copolymer comprising a constituent unit derived from such a hydrophobic monomer and a hydrophilic monomer has a good emulsifying power and is excellent in the effect of reducing the stickiness at the time of use of the emulsified composition of the present invention.

In a preferred embodiment of the present invention, the content of the water-soluble copolymer is from 0.5 to 30% by mass.

By setting the content of the water-soluble copolymer to the above range, the stability of the emulsified composition can be improved.

In a preferred embodiment of the invention, the content of the oil phase component is from 0.1 to 70% by mass.

The emulsified composition of the present invention having the oil phase component content within the above range is excellent in stability.

Since the emulsified composition of the present invention has less stickiness, it is preferable as a cosmetic.

Further, the present invention relates to a constituent unit (c) comprising a hydrophobic monomer derived from the above formula (1), (7) or (8) and a self-hydrophilic single One or two or more kinds of constituent units (d) derived from the body are used as an emulsifier of the water-soluble copolymer which the essential constituent unit has.

The emulsifier has low irritation and at the same time has excellent emulsifying power.

Further, the present invention relates to a production method which is a method for producing an emulsified composition comprising the step of emulsifying using the emulsifier, and is characterized in that an emulsifier other than the emulsifier is substantially not used.

According to this method, a conventional emulsifier which produces a sticky feeling is not used, and an emulsified composition can be easily produced even if the emulsifier is not highly blended.

The present invention for solving the third and fourth problems includes one or two or more constituent units (e) derived from the hydrophobic monomer represented by the above formula (1), (7) or (8). One or two or more kinds of constituent units (f) derived from a hydrophilic monomer are used as a skin cleansing agent of a water-soluble copolymer which is an essential constituent unit.

The skin cleansing agent of the present invention has a good foaming property and a dense foam quality by including the above-mentioned water-soluble copolymer, and at the same time, the feeling of tightness after use can be reduced.

In a preferred embodiment of the present invention, the hydrophilic monomer is selected from the group consisting of a polymerizable carboxylic acid, a hydrophilic monomer represented by the above formula (2), and a hydrophilic single sheet represented by the above formula (9). One or two or more kinds of hydrophilic monomers of the group of the hydrophilic monomer represented by the above formula (10) and the hydrophilic monomer represented by the above formula (11).

By including the water-soluble copolymer containing the constituent unit (e) derived from such a hydrophilic monomer, the feeling of tightness after use of the skin cleansing agent of the present invention can be further reduced.

In a preferred embodiment of the present invention, the hydrophobic monomer is a hydrophobic monomer represented by the above formula (1), and the water-soluble monomer is a hydrophilic monomer represented by the above formula (2).

By including a water-soluble copolymer having a constituent unit derived from such a hydrophobic monomer and a hydrophilic monomer, the feeling of tightness after use of the skin cleansing agent of the present invention can be further reduced.

In the embodiment of the present invention, the content of the water-soluble copolymer is from 0.1 to 20% by mass.

By setting the content of the water-soluble copolymer to the above range, the stickiness of the skin cleansing agent of the present invention can be reduced.

The present invention is preferably applied to a foaming detergent.

According to the present invention, the foaming property or the foam quality of the foaming detergent is not hindered, and the feeling of tightness of the skin after use can be reduced.

The present invention is preferably applied to a gel-like skin cleansing agent.

According to the present invention, it is possible to enhance the stretchability of the gel-like skin cleansing agent on the skin, and at the same time, to reduce the tightness of the skin after use.

Since the skin cleansing agent containing the surfactant has a strong cleaning power, the feeling of tightness after use is also strong. Therefore, the present invention is preferably applied to a skin cleansing agent comprising a form of a surfactant. According to the present invention, the excellent cleaning power of the surfactant can be not impaired, or the skin feeling of the skin cleansing agent can be reduced while improving the cleaning power.

A skin cleanser containing fatty acid soap, which has good foaming properties, has a dense foam quality, and has good cleansing power, but feels a strong tightness after use. Therefore, the present invention is preferably applied to a skin cleansing agent comprising a form of a fatty acid soap. According to the present invention, the skin cleansing agent containing the fatty acid soap is not detracted from the advantageous effects, and the feeling of tightness of the skin after use can be reduced.

In a preferred embodiment of the present invention, the ratio of the water-soluble copolymer to the mass of the fatty acid soap is 1:500 to 1:2, preferably 1:200 to 1:3, more preferably 1:100. 1:5.

By setting the content of the water-soluble copolymer to the above range, the feeling of tightness after use of the skin cleansing agent containing the fatty acid soap can be more effectively reduced.

It is also preferred that the present invention be applied to a skin cleansing agent comprising a nonionic surfactant.

According to the present invention, the cleansing power of the skin cleansing agent containing the nonionic surfactant is enhanced, and at the same time, the tightness of the skin after use is reduced.

In a preferred embodiment of the present invention, the ratio of the content of the water-soluble copolymer to the nonionic surfactant is from 1:20 to 1:0.5, preferably from 1:15 to 1:0.7, more preferably 1:10~1:1.

By setting the ratio of the content of the water-soluble copolymer to the nonionic surfactant to be in the above range, the feeling of tightness after use can be more effectively reduced.

The present invention for solving the fifth problem is an oil-in-water type sunscreen cosmetic containing the components (A) to (D).

(A) one or two or more kinds of constituent units (g) derived from the hydrophobic monomer represented by the above formula (1), (7) or (8) and one kind derived from a hydrophilic monomer Or two or more constituent units (h) as a necessary constituent unit having a water-soluble copolymer

(B) a polyglycerol fatty acid ester obtained by condensing 1 molecule of polyglycerol having a degree of polymerization of 10 with a 2 to 5 molecule of a fatty acid having 16 or more carbon atoms

(C) ionic surfactant

(D) UV scattering agent and / or UV absorber

The sunscreen cosmetic of the present invention has an ultraviolet defense function, and has less stickiness and good moisture retention. Further, the sunscreen cosmetic of the present invention has emulsion stability.

In a preferred embodiment of the present invention, the hydrophilic monomer is selected from the group consisting of a polymerizable carboxylic acid, a hydrophilic monomer represented by the above formula (2), and a hydrophilic single sheet represented by the above formula (9). Body, as shown in the above formula (10) One or two or more kinds of hydrophilic monomers of the group of the hydrophilic monomer and the hydrophilic monomer represented by the above formula (11).

By using a water-soluble copolymer containing the constituent unit (h) derived from such a hydrophilic monomer, it is possible to improve the feeling of use such as less stickiness or moisturizing feeling.

In a preferred embodiment of the present invention, the hydrophobic monomer is a hydrophobic monomer represented by the above formula (1), and the water-soluble monomer is a hydrophilic monomer represented by the above formula (2).

A sunscreen cosmetic comprising a water-soluble copolymer having a constituent unit derived from such a hydrophobic monomer and a hydrophilic monomer has a more excellent feeling of use.

In a preferred embodiment of the invention, the component (C) is an anionic surfactant.

As an ionic surfactant, emulsification stability can be further improved by using an anionic surfactant. Further, the sunscreen cosmetic of the present invention using an anionic surfactant has a good feeling of use.

In a preferred embodiment of the invention, the anionic surfactant is sodium decyl lactate.

As an anionic surfactant, emulsification stability can be further improved by using sodium decyl lactate. Further, the sunscreen cosmetic of the present invention using sodium decyl lactate has a good feeling of use.

In a preferred embodiment of the present invention, the component (B) is polyglyceryl pentoxide.

The sunscreen cosmetic of the present invention comprising bispolystearate-10 is excellent in both emulsion stability and feeling of use.

In a preferred embodiment of the present invention, the component (D) is a water-dispersible ultraviolet scattering agent.

Since the water-dispersible ultraviolet scattering agent is uniformly dispersed in the aqueous phase, the sunscreen cosmetic of the present invention in such a form has excellent ultraviolet defense function.

In a preferred embodiment of the present invention, the water-dispersible ultraviolet scattering agent is an ultraviolet scattering agent which is surface-treated with sodium polyacrylate.

In the sunscreen cosmetic of the above form, the ultraviolet ray scattering agent is more uniformly dispersed, and the ultraviolet ray defense function is good.

The present invention which solves the sixth problem includes one or two or more constituent units (j) derived from one or two or more kinds of constituent units (i) derived from a hydrophobic monomer and from a hydrophilic monomer. The amphiphilic copolymer, the water-soluble polymer, and/or its salt, and water, which are contained in the essential constituent unit, are hydrolyzed by the water, in the aqueous gel formed of the water-soluble polymer and/or its salt, A composition of a film having a sea-island structure in which island particles dispersed by the above-described amphiphilic copolymer is formed is formed.

The film has a sea-island structure in which a water-soluble component is a main component, and has a tactile sensation such as milk containing an oil agent. According to the composition of the present invention, a film having such a sea-island structure can be formed on the skin.

In a preferred embodiment of the present invention, the island particles have an average major axis minor axis ratio of 0.8 or more, and the number of the island particles having an average particle diameter of 1 to 5 μm is 80% or more.

The film having such a structural feature is excellent in moisture retention and flexibility.

Then, the composition of the present invention can be easily formed into a film having such excellent properties by being applied to the skin.

In a preferred embodiment of the present invention, the water-soluble polymer is one or more water-soluble polymers selected from the group consisting of an acrylic water-soluble polymer, a water-soluble polypeptide, and a water-soluble polysaccharide. And / or its salt.

By adopting the form of the water-soluble polymer as described above, the water solubility of the components of the composition can be improved, and the stability of the composition can be improved by suppressing the occurrence of precipitation.

In a preferred embodiment of the present invention, the water-soluble polymer is selected from the group consisting of sodium polyacrylate, (acrylate/alkyl acrylate (C10-30)) cross-linked polymer, sodium polyglutamate, and triterpene And one or more water-soluble polymers of the group of Tremella polysaccharides.

By forming the form containing the water-soluble polymer as described above, the stability of the composition can be further improved.

In a preferred embodiment of the present invention, the composition includes a polyol that promotes phase separation between the aqueous gel and the amphiphilic copolymer, and/or inhibits the aqueous gel and the amphiphilic copolymer. Phase separated polyol.

By including such a polyol, the uniformity of the aforementioned film can be improved.

In a preferred embodiment of the present invention, the phase-promoting polyol is mixed with an aqueous solution of a nonionic surfactant having a polyether chain in a hydrophilic portion to increase the cloud point of the aqueous solution. The polyol; the polyol which inhibits phase separation is a polyol which is mixed with an aqueous solution of a nonionic surfactant having a polyether chain in a hydrophilic portion to lower the cloud point of the aqueous solution.

By including such a polyol, the uniformity of the aforementioned film can be improved.

In a preferred embodiment of the present invention, the polyol which promotes phase separation is one or more selected from the group consisting of 1,3-butanediol and polyethylene glycol.

By using such a polyol, phase separation of the aqueous gel from the amphiphilic copolymer can be effectively promoted, and the uniformity of the film can be improved.

In a preferred embodiment of the present invention, the polyol which inhibits phase separation is one or more selected from the group consisting of glycerin, diglycerin, sorbitol, and maltitol.

By using such a polyol, phase separation of the aqueous gel from the amphiphilic copolymer can be effectively promoted, and the uniformity of the film can be improved.

In a preferred embodiment of the present invention, the mass ratio of the total amount of the phase-separating polyol and the phase-inhibiting polyol to the total amount of the amphiphilic copolymer and the water-soluble polymer is 5: 1~20:1.

By adopting such a form, the uniformity of the aforementioned film can be improved.

In a preferred embodiment of the present invention, the mass ratio of the phase-separating polyol and the phase-inhibiting polyol is 3.5:1 to 1:2.5.

By adopting such a form, the uniformity of the aforementioned film can be improved.

In a preferred embodiment of the present invention, the content of the amphiphilic copolymer is from 0.1 to 5% by mass.

By setting the content of the amphiphilic copolymer to the above range, it is possible to further form a composition of the above-mentioned film which is excellent in soft touch.

In a preferred embodiment of the present invention, the content of the oil agent is 1% by mass or less.

By adopting such a form, it is possible to form a composition of the above-mentioned film which is less sticky.

In a preferred embodiment of the present invention, the amphiphilic copolymer contains one or more copolymers selected from the group consisting of the following E groups.

Group E: polyquaternium-51, polyquaternium-61, (glyceryl methacrylate-ethyl methacrylate / stearyl methacrylate) copolymer, and comprising self-selected from the formula (1), 7), (8) Hydrophobic monomer derived constituent unit (i) acrylic amphiphilic copolymer

The composition of the present invention comprising such an amphiphilic copolymer has a stronger touch, such as milk, and can form the above-mentioned film which is more flexible.

In a preferred embodiment of the present invention, the acrylic amphiphilic copolymer contains a constituent unit (j) derived from one or two or more hydrophilic monomers selected from the group F below.

Group F: a polymerizable carboxylic acid, a copolymer represented by the above formula (2), a copolymer represented by the above formula (9), a copolymer represented by the above formula (10), and the above formula (11) Copolymer shown

The composition of the present invention comprising an amphiphilic copolymer having a constituent unit (j) derived from such a hydrophilic monomer, such as milk, has a stronger touch and can form the above-mentioned film which is more flexible.

In a preferred embodiment of the present invention, the acrylic amphiphilic copolymer comprises a structural unit (i) derived from the hydrophobic monomer represented by the above formula (1) and the above formula (2). The constituent unit (j) derived from the hydrophilic monomer is shown.

According to the composition of the present invention containing the acrylic amphiphilic copolymer, the film having excellent moisture retention and flexibility can be further formed.

Further, the present invention relates to a film comprising a film having a sea-island structure in which island particles dispersed in an amphiphilic copolymer are contained in an aqueous gel formed of a water-soluble polymer, and the amphiphilic copolymer is One or two or more kinds of constituent units (i) derived from a hydrophobic monomer and one or two or more constituent units (j) derived from a hydrophilic monomer are contained as essential constituent units.

The film of the present invention has a sea-island structure mainly composed of a water-soluble component. Then, regardless of whether or not the water-soluble component is used as a main component, it has a tactile sensation such as milk containing an oil.

In a preferred embodiment of the present invention, the island particles have an average major axis minor axis ratio of 0.8 or more, and the number of the island particles having an average particle diameter of 1 to 5 μm is 80% or more.

The aforementioned film having such a structural feature, such as milk containing an oil agent, has a good touch.

Further, the present invention relates to a method of forming the above-described film of the present invention, comprising one or more constituent units (i) derived from a hydrophobic monomer and a self-hydrophilic monomer-derived 1 The two or more constituent units (j) are applied to the skin as an amphiphilic copolymer, a water-soluble polymer, and/or a salt thereof and a composition of water, which are required constituent units.

According to the method of the present invention, the aforementioned film can be easily formed.

Further, in a preferred aspect of the present invention, the composition includes a polyol which promotes phase separation between the amphiphilic copolymer and the aqueous gel, and/or inhibits copolymerization of the aqueous gel and the amphiphilic copolymer. A phase separated polyol.

By using an aqueous solution containing such a polyol, the above-mentioned film having good uniformity can be formed.

According to the present invention, a copolymer having a feeling of elasticity and an external preparation for skin can be provided.

Moreover, according to the present invention, it is possible to provide an emulsified composition which is less irritating to the skin, has less stickiness, and has excellent emulsification stability.

Further, according to the present invention, it is possible to provide a skin cleansing agent which has a reduced feeling of tightness after use.

Further, when the present invention is applied to a skin cleansing agent containing a fatty acid soap, it does not inhibit the good foaming property or the foam quality, and the feeling of tightness after use can be reduced.

Further, when the present invention is applied to a gel-like skin cleansing agent, the effect of reducing the feeling of tightness after use can be obtained.

Further, according to the present invention, it is possible to provide an oil-in-water type sunscreen cosmetic which has a good ultraviolet protection function, has no feeling of stickiness or moisturizing feeling, and has an emulsion stability.

Moreover, according to the present invention, it is possible to provide a film having a sea-island structure in which a water-soluble component is a main component and a technique of forming the film. The film described above has a tactile sensation such as milk containing an oil agent regardless of whether or not the water-soluble component is used as a main component.

Further, in a preferred embodiment of the present invention, it is possible to provide the film having no stickiness and a technique for forming the film.

1‧‧‧Example 103

2‧‧‧Example 104

3‧‧‧Example 105

4‧‧‧Example 106

5‧‧‧Example 107

6‧‧‧Example 108

7‧‧‧Example 109

8‧‧‧Example 110

9‧‧‧Example 111

10‧‧‧Example 112

11‧‧‧Example 113

12‧‧‧Example 114

13‧‧‧Example 115

14‧‧‧Example 116

15‧‧‧Example 117

16‧‧‧Example 118

17‧‧‧Example 119

18‧‧‧Example 120

19‧‧‧Example 121

20‧‧‧Example 122

21‧‧‧Example 123

Fig. 1 is a bar graph showing the results of evaluation of a gel-like cosmetic comprising the copolymer of Example 1 and Comparative Example 1.

Figure 2 is a graph showing the blending ratio of glyceryl diisostearate methacrylate/methoxypropionate PEG-23 copolymer of Examples 9 to 31 with squalane and water. Composition phase diagram.

Figure 3 shows the copolymer of (glyceryl diisostearate methacrylate/methoxypropionate PEG-23) and tris(caprylic/capric acid) glyceride and water of Examples 32-62. The three-component phase diagram of the blend ratio plot.

Figure 4 is a graph showing the blend ratio of the copolymer of (glyceryl diisostearate methacrylate/methoxypropionate PEG-23) of Examples 63 to 89 with dimethicone and water. The three components of the cartography are phase diagrams.

Figure 5 shows 1,3-butanediol, glycerol, triterpene and (methyl methacrylate PEG-23/diisostearate methacrylate) contained in Examples 104-124. The 3-component phase diagram of the total amount of the ester) copolymer.

Fig. 6 shows a photomicrograph of the compositions of Examples 105, 106, 108, 111, 113, 114, 115, 119, 120, 122, 123.

Fig. 7 is a pie chart showing the results of the tactile sensation evaluation of the composition of Example 104 of Test Example 7.

[Formation of the Invention]

The copolymer of the present invention which solves the first problem is one or two or more kinds of constituent units (a) derived from the hydrophobic monomer represented by the above formula (1) and from the following formula (2) One or two or more kinds of constituent units (b) derived from the hydrophilic monomer are shown as essential constituent units.

In the present invention, the "composition unit derived from a monomer" means a constituent unit formed by cleavage of a carbon-carbon unsaturated bond of a corresponding monomer by a polymerization reaction.

Hereinafter, the hydrophobic monomer represented by the formula (1) and the hydrophilic monomer represented by the formula (2) will be described.

<1> Hydrophobic monomer

The copolymer of the present invention contains one or two or more kinds of constituent units derived from the hydrophobic monomer represented by the above formula (1) (hereinafter sometimes simply referred to as "constituting unit (1)") as essential constituent units.

Here, examples of the alkyl group represented by R ^{1 include} a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group. In the present invention, R ¹ is preferably hydrogen or a methyl group.

Further, as the fluorenyl group having a branched carbon number of 6 to 22 which does not contain a ring structure represented by R ² or R ³ , 2-methylpentanyl group, 3-methylpentanyl group and 4-methyl group are exemplified. Pentamidine, 2-ethylbutylidene, 2-ethylbutylidene, 2,2-dimethylbutanyl, 3,3-dimethylbutyryl, 2-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,2-dimethylpentanyl, 4,4-dimethylpentenyl, 2-methylheptyl, 2-ethylhexyl, 2-propylpentanyl Base, 2,2-dimethylhexyl, 2,2,3-trimethylpentanyl, 2-methyloctyl, 3,3,5-trimethylhexyl, 2-methylindole Indenyl, 4-methylindenyl, 8-methylindenyl, 4-ethyloctyl, 2-ethyloctyl, 2-butylhexyl, 2-tert-butylhexyl, 2 ,2-diethylhexyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methylindenyl, 2-methyl-2-ethyl Octyl, 2-methylundecyl, 10-methylundecyl, 2,2-dimethylindenyl, 2-ethylindenyl, 2-butyloctyl, diethyloctyl, 2-tert-butyl-2,2,4-trimethylpentanyl, 10-methyldodepinyl, 3- Methyldodecyl, 4-methyldodedecyl, 11-methyldodecanyl, 10-ethylundecyl, 12-methyltridecyl, 2-butylfluorenyl , 2-hexyloctyl, 2-butyl-2-ethyloctyl, 12-methyltetradecyl, 14-methylpentadecyl, 2-butyldodedecyl, 2-hexyldecyl ,16-methylheptadecanyl, 2,2-dimethylhexyl, 2-butylhexadecanyl, 2-hexyldodedecyl, 2,4,10,14-tetramethylpentyl Anthracenyl, 18-methylundecyl, 3,7,11,15-tetra-methylhexadecanyl, 19-methylindolyl, and the like.

In a further preferred embodiment of the present invention, the hydrophobic monomer represented by the above formula (1) is a hydrophobic monomer represented by the above formula (3).

The fluorenyl group having a branched carbon number of 10 to 22 which does not contain a ring structure represented by R ⁸ and R ⁹ in such a preferred embodiment is exemplified by 2-methylindenyl group and 4-methylindenyl group. , 8-methylindenyl, 4-ethyloctyl, 2-ethyloctyl, 2-butylhexyl, 2-tert-butylhexyl, 2,2-diethylhexyl , 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl), 7-methylindenyl, 2-methyl-2-ethyloctyl, 2-methyl eleven Indenyl, 10-methylundecyl, 2,2-dimethylindenyl, 2-ethylindenyl, 2-butyloctyl, diethyloctyl, 2-tert-butyl-2 , 2,4-trimethylpentanyl, 10-methyldodepinyl, 3-methyldodepinyl, 4-methyldodecanyl, 11-methyldodedecyl, 10- Ethyl undecyl, 12-methyltridecyl, 2-butylindenyl, 2-hexyloctyl, 2-butyl-2-ethyloctyl, 12-methyltetradecyl, 14 -methyl decyl fluorenyl, 2-butyl fluorenyl, 2-hexyl fluorenyl, 16-methyl heptadecyl, 2,2-dimethylhexyl, 2-butyl Sulfhydryl, 2-hexyldodedecyl, 2,4,10,14-tetra Pent-acyl, 18-acyl methyl nineteen, 3,7,11,15-tetramethyl - methyl acyl sixteen, twenty 19-methyl acyl and the like.

Further, as a fluorenyl group having 6 to 9 carbon atoms having two or more branches and having no ring structure, which are represented by R ⁸ and R ⁹ in a preferred embodiment, 2,2-dimethylbutanyl group and 3 may be exemplified. ,3-dimethylbutyryl, 2,2-dimethylpentanyl, 4,4-dimethylpentenyl, 2,2-dimethylhexyl, 2,2,3-trimethyl Pentamidine, 3,5,5-trimethylhexyl, and the like.

The carbon number of the fluorenyl group of R ⁸ and R ^{9 in} the formula (3) is preferably 12 to 22, more preferably 14 to 20, particularly preferably 16 to 20.

Further, the carbon number of the main chain of the fluorenyl group of R ⁸ and R ^{9 in} the formula (3) is preferably 9 to 21, more preferably 12 to 20, particularly preferably 16 to 18.

Further, the number of branches of the fluorenyl group of R ⁸ and R ^{9 in} the formula (3) is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.

Further, in the fluorenyl group of R ⁸ and R ⁹ of the formula (3), the position number of the carbon of the main chain of the branched chain bond is preferably as large as possible. Specifically, the branched chain is preferably bonded to the first to third carbons at the end of the autonomous chain, more preferably the first or second carbon, and particularly preferably the first carbon.

Specific examples of R ⁸ and R ⁹ include 10-methylundecyl group, 10-methyldodedecyl group, 11-methyldodedecyl group, and 10-ethylundecyl group. 12-methyltridecyl, 12-methyltetradecyl, 14-methylpentadecanyl, 16-methylheptadecanyl, 2,4,10,14-tetramethylpentanyl , 18-methyl 19-mercapto, 3,7,11,15-tetra-methylhexadecanyl, 19-methylindolyl, and the like.

In the above formulae (1) and (3), the group derived from a triol represented by X or Y is not particularly limited as long as it is a group from which an OH group is desorbed from a triol, and may be appropriately selected from a group selected from The triol of the group containing glycerol, trimethylolpropane, and trimethylolethane desorbs the group of the OH group.

In a preferred embodiment of the present invention, the monomer represented by the above formula (5) is preferably used as the hydrophobic monomer.

The hydrophobic monomer represented by the formula (5) is exemplified by the compounds represented by the following formulas (12) to (14). It is preferred to use a compound represented by the following formula (12) in which a branching chain is added to the terminal of the fluorenyl group.

Formula (13)

The hydrophobic monomer represented by the formula (1) constituting the copolymer of the present invention can be synthesized, for example, by the following method.

a) ketalization of the triol. As a specific synthesis method, for example, the method described in Production Example 1 of JP-A-2009-136749 can be exemplified.

b) transesterification of the ketalized triol synthesized by a with the alkyl (meth) acrylate, synthesizing the (meth) acrylate of the ketal, and performing the obtained ketal (meth) acrylate The ketone reaction synthesizes a mono(meth) acrylate of a triol. As a specific synthesis method, for example, the method described in Example 1 of JP-A-2004-18389 can be exemplified.

c) The mono(meth) acrylate of the triol obtained in b is reacted with a carboxylic acid having a predetermined branched structure or an anhydride thereof or a chloride thereof to obtain a hydrophobic monomer represented by the formula (1).

Further, since a commercially available product is also present in the ketalized triol, the commercially available product can be used, and the ester of the triol of the present invention can be obtained by the above steps b) and c). As such a commercial item, (S)-(+)-2,2-dimethyl-1,3-dioxolane-4-methanol, (R)-(+)-2,2 can be illustrated. -Dimethyl-1,3-dioxolane-4-methanol (both Tokyo) Chemical industry (shares) system). Further, since a commercially available product is also present in the mono(meth)acrylate of the triol, the commercially available product can be used, and the ester of the triol of the present invention can be obtained by the above step c). As such a commercial item, "Blenmer GLM" (produced by glycerin monomethacrylate Japan Oil Co., Ltd.) can be exemplified.

The proportion of the constituent unit (a) of the copolymer of the present invention in the total constituent unit is preferably from 1 to 40% by mass, more preferably from 5 to 35% by mass.

By making the ratio of the constituent unit (a) to the above range, the elasticity of the copolymer of the present invention can be improved.

<2> Hydrophilic monomer

The copolymer of the present invention contains one or more of the constituent units derived from the hydrophilic monomer represented by the above formula (2) as an essential constituent unit.

The alkyl group represented by R ⁴ in the above formula (2) may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group or a cyclopropyl group. In the present invention, R ⁴ is preferably a hydrogen atom or a methyl group.

Further, examples of the alkylene group represented by R ^{5 include} an exoethyl group, a propyl group, an exo-propyl group, a 2-hydroxyl-propyl group, a 1-hydroxy-2-methyl-extended ethyl group, and a 2-hydroxy group. 1-methylethyl or the like, but among these, an ethyl group or a propyl group is preferred, and an ethyl group is more preferred.

Further, in the group represented by R ⁶ , examples of the aromatic group having 6 to 10 carbon atoms include a phenyl group, a benzyl group, a tolyl group, and an ethylphenyl group; and the aliphatic hydrocarbon group having 1 to 14 carbon atoms may be used. Methyl, ethyl, butyl, tert-butyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, lauryl, etc. are suitably exemplified; as the fluorenyl group having 1 to 12 carbon atoms, a fluorenyl group can be suitably exemplified. , ethyl sulfhydryl, propyl sulfonyl, butyl sulfhydryl, isobutyl sulfhydryl, pentamidine, laurel. Among these, the group represented by R ^{5 is} preferably an aliphatic hydrocarbon group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms.

Further, n of the general formula (2) is a numerical range of 6 to 40.

Among the monomers represented by the above formula (2), examples of the monomer in which R ⁵ is a propyl group include polypropylene glycol (9) monoacrylate, polypropylene glycol (13) monoacrylate, and polycondensation. Propylene glycol (9) monomethacrylate, polypropylene glycol (13) monomethacrylate, and the like. Furthermore, the number in parentheses represents N. Most of these polymers are commercially available. Specific examples of such commercially available products include "Blenmer" AP-400, AP-550, AP-800, PP-500, and PP-800 (all manufactured by Nippon Oil & Fats Co., Ltd.).

Among the monomers represented by the above formula (2), examples of the monomer in which R ⁵ is an ethyl group extend include polyethylene glycol (10) monoacrylate and polyethylene glycol (8). Methacrylate, polyethylene glycol (23) monoacrylate, polyethylene glycol (23) monomethacrylate, methoxy polyethylene glycol (9) acrylate, methoxy polyethylene glycol ( 9) methacrylate, methoxy polyethylene glycol (23) methacrylate, oleyl polyethylene glycol (18) methacrylate, lauryloxy polyethylene glycol (18) acrylate, Laurel oxime polyethylene glycol (10) methacrylate, stearyloxy polyethylene glycol (30) monomethacrylate, and the like.

In a preferred embodiment of the present invention, the monomer represented by the above formula (6) is used as the hydrophilic monomer.

1 in the above formula (6) is preferably 6 to 30, more preferably 8 to 30.

The above hydrophilic monomer can be obtained in a high yield by esterification reaction of a corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with a chloride or anhydride of acrylic acid or methacrylic acid. Moreover, since many commercial products already exist, this commercial item can also be utilized. Specific examples of such commercially available products include Blenmer, AE-400, PE-350, AME-400, PME-400, PME-1000, ALE-800, and PSE-1300 (all of which are Japanese fats and oils). ))).

The constituent unit derived from the hydrophilic monomer contained in the copolymer of the present invention may be only one type. However, as long as the above conditions are satisfied, two or more types of constituent units may be combined and contained.

The proportion of the constituent unit (b) derived from the hydrophilic monomer of the copolymer of the present invention in the total constituent unit is from 30 to 95% by mass, preferably from 40 to 90% by mass.

By making the ratio of the constituent unit (b) to the above range, the elastic feeling of the copolymer of the present invention can be improved.

<3> Any other constituent unit

In addition to the above-mentioned structural unit 1 and the structural unit 2, the copolymer of the present invention may contain a unit derived from a monomer used in a general copolymer as an arbitrary constituent unit within a range not impairing the effects of the invention. Examples of the optional constituent unit include (meth)acrylic acid decylamine and methyl (meth)acrylate such as decylamine amide, decyl methacrylate, monoalkyl decylamine methacrylate or monoalkyl decylamine methacrylate. , ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-octyl (meth)acrylate, (methyl) 2-ethylhexyl acrylate, n-dodecyl methacrylate, (meth)acrylic acid a (alkyl) alkyl (meth)acrylate such as stearyl ester or isostearyl (meth)acrylate, a cycloalkyl ester of (meth)acrylic acid such as cyclohexyl (meth)acrylate, or (meth)acrylic acid 2 - hydroxyethyl (meth) acrylate, hydroxyalkyl (meth) acrylate, etc., such as 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. Alkenyl acrylate, methyl methacrylate, methoxyethyl (meth) acrylate, etc., vinyl acetate, vinyl pyrrolidone, styrene, α- A constituent unit derived from a monomer such as methyl styrene or acrylonitrile. These monomers are almost commercially available.

<4> Copolymer of the present invention

The copolymer of the present invention is a copolymer containing a constituent unit (a) and a constituent unit (b) in its skeleton. Further, the copolymer of the present invention is usually a random copolymer in which the constituent units are randomly bonded, and may be a block copolymer or a graft copolymer.

The copolymer of the present invention is characterized by a weight average molecular weight of from 20,000 to 110,000. When the weight average molecular weight is in the above range, the copolymer of the present invention is elastic.

The weight average molecular weight of the copolymer of the present invention is preferably from 20,000 to 80,000, further preferably from 30,000 to 80,000, more preferably from 40,000 to 70,000, further preferably from 50,000 to 70,000, and particularly preferably from 57,000 to 66,000.

Here, the weight average molecular weight means a weight average molecular weight in terms of polystyrene measured by GPC.

The method for producing the copolymer of the present invention is not particularly limited. For example, a monomer which derivatizes each constituent unit can be used in a solvent. The mixture is mixed and obtained by a method in which a polymerization reaction is carried out by a method generally used for polymerization of an acrylic monomer.

Here, the weight average molecular weight of the copolymer can be adjusted by changing the reaction time or the reaction temperature of the polymerization reaction. Specifically, the weight average molecular weight can be reduced by shortening the reaction time.

Further, in the copolymer of the present invention, water solubility is preferred from the viewpoint of ease of handling when it is used. The copolymer herein is defined as a copolymer having a transmittance of a 20% by mass aqueous solution of a copolymer of 90% or more at 25 °C. In order to obtain such a polymer, in the above polymerization method, a polymerization method in which the above monomer mixture is subjected to radical polymerization in a mixed solvent of an aqueous solution and an aqueous solvent mixed with water at any ratio at 25 ° C is particularly preferable. Further, from the viewpoint of a small amount of residual monomers after the polymerization reaction, a polymerization method using a buffer solution instead of water is particularly preferable. The aqueous solution having a buffering action to be used in the method is not particularly limited as long as it is a buffer solution which is generally used. Specifically, potassium chloride-hydrochloric acid solution, potassium hydrogen phthalate-hydrochloric acid solution, and dihydrogen phosphate can be exemplified. Potassium-dihydrogen phosphate disodium solution, potassium hydrogen citrate-citric acid solution, sodium carbonate-sodium hydrogencarbonate, and the like. Further, an aqueous solution of a salt, an acid or a base such as an ion-forming buffer solution with an initiator may be used, and a buffer solution may be prepared at the time of adding the initiator. Further, as the aqueous solvent to be mixed with water at any ratio of 25 ° C and used in the method, specifically, an alcohol having 1 to 3 carbon atoms such as methanol, ethanol, n-propanol or isopropanol, and acetone may be exemplified. a ketone such as methyl ethyl ketone, a glycol such as ethylene glycol, polyethylene glycol, propylene glycol or 1,3-butanediol, ethylene glycol monomethyl ether or ethylene glycol monoether such as ethylene glycol monoethyl ether Ether, tetrahydrofuran, and the like. Among these aqueous solvents, an alcohol having 1 to 3 carbon atoms such as methanol, ethanol, n-propanol or isopropanol is particularly preferable from the viewpoint of facilitating the polymerization reaction.

In the present invention, the mass ratio of the constituent unit (a) constituting the copolymer to the constituent unit (b) is preferably 5:95 to 50:50, further preferably 10:90 to 45:55, more preferably 20:80~40:60, especially good for 25:75~35:65.

Further, the molar ratio of the constituent unit (a) constituting the copolymer and the constituent unit (b) is preferably 8:92 to 62:38, more preferably 15:85 to 57:43, still more preferably 29: 71~52:48, especially good is 35:65~46:54.

By setting the mass ratio of the constituent unit (a) and the constituent unit (b) of the copolymer to the above range, the elastic feeling can be further enhanced.

<5> A skin external preparation comprising the copolymer of the present invention

The external preparation for skin containing the copolymer of the present invention has a feeling of elasticity and is less likely to cause a sticky feeling.

The content of the copolymer of the present invention in the external preparation for skin is preferably from 0.5 to 30% by mass, more preferably from 1 to 25% by mass.

The external preparation for skin of the present invention may, for example, be an externally used pharmaceutical such as an ointment or a cosmetic. In addition, as a cosmetic, skin care products such as skin care products such as creams, lotions, lotions, beauty liquids, and sunscreen cosmetics, foundation makeup, foundation, eyeliner, mascara, and the like, skin cleansers, hair conditioners, and the like can be exemplified. A hair cosmetic such as a hair lotion or a styling spray.

The skin external preparation of the present invention usually contains a component used as an external preparation for skin as an optional component insofar as the effects of the invention are not impaired. As the optional component, specifically, In particular, macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower seed oil, cottonseed oil, jojoba oil, coconut oil, palm oil, liquid can be exemplified. Flavors of lanolin, hardened coconut oil, hardened oil, wood wax, hardened castor oil, beeswax, candelilla wax, carnauba wax, insect wax, lanolin, reduced lanolin, hard lanolin, jojoba wax, etc. , waxes, mobile paraffin, squalane, isooctadecane, ceresin, paraffin, mineral wax, petrolatum, microcrystalline wax, etc., oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid Higher fatty acids such as stearic acid, behenic acid, undecylenic acid, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, octyldodecanol, myristyl alcohol, and cetyl wax a higher alcohol such as stearyl alcohol, cetyl isooctanoate, isopropyl myristate, hexadecyl isostearate, diisopropyl adipate, di-2-ethylhexyl sebacate, Cetyl lactate, diisostearyl malate, ethylene di-2-ethylhexanoate, neopentyl glycol dicaprate, and di-2-heptyldecanoate Synthetic esters of alcohol, tris-2-ethylhexanoic acid glycerol ester, tri-2-ethylhexanoic acid, trimethylolpropane triisostearate, tetrakisethyl ethyl-2-pentanoate Chain polyoxyalkylene, octamethylcyclotetraoxane, decamethylcyclopentane, etc. of oil, dimethyl polyoxyalkylene, methylphenyl polyoxyalkylene, diphenyl polyoxyalkylene a cyclic polyoxyalkylene such as a decyl alkane or a dodecylcyclohexane oxime, an amine modified polyoxyalkylene oxide, a polyether modified polyoxyalkylene oxide, an alkyl modified polyoxyalkylene, An oil agent such as a fluorenone oil such as a modified polysiloxane or a fatty acid soap (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, or triethanolamine alkyl sulfate Anionic surfactants, stearyltrimethylammonium chloride, benzyldimethylammonium chloride, laurylamine oxide and other cationic surfactants, imidazoline-based amphoteric interfacial activity Agent (2-cocoyl-2-hydrazinium imidazolium-1-carboxyethoxy 2 sodium salt, etc.), betaine surfactant (alkylbetaine, amidinobetaine, thiobetaine, etc.) , amphoteric surfactants such as mercaptomethyl taurine, sorbitan fatty acid esters (sorbitan monostearate, sorbitan sesquioleate, etc.), glycerol Fatty acids (such as glycerol monostearate), propylene glycol fatty acid esters (such as propylene glycol monostearate), hardened castor oil derivatives, and POE sorbitan fatty acid esters (POE sorbitan monooleate) , polystearic acid sorbitan monostearate, etc., POE sorbitol fatty acid esters (POE-sorbitol monolaurate, etc.), POE glycerol fatty acid esters (POE-glycerol mono-isolated) Stearate, etc., POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE2-octyldodecane, etc.), POE alkyl phenyl ether Classes (POE-p-phenylene ether, etc.), Pluronic type, POE‧POP alkyl ethers (POE‧POP2-decyltetradecyl ether, etc.), Tetronics, POE castor oil, hardening Castor oil derivative (POE castor oil) Non-ionic surfactants such as POE hardened castor oil, sucrose fatty acid esters, alkyl glucosides, polyethylene glycol, glycerol, 1,3-butanediol, erythritol, sorbitol , xylitol, maltitol, propylene glycol, dipropylene glycol, diglycerol, isoprene glycol, 1,2-pentanediol, 2,4-hexanediol, 1,2-hexanediol, 1,2 - Polyhydric alcohols such as octanediol, sodium pyrrolidone carboxylate, lactic acid, sodium lactate, etc., moisturizing into a classification, Guanhua bean gum, alfalfa seeds, carrageenan, galactan, gum arabic, pectin, nectar Glycan, starch, sanxian gum, cadmium gum, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, methyl hydroxypropyl cellulose, chondroitin sulfate, dermatan sulfate, glycogen, Heparin sulfate, hyaluronic acid, sodium hyaluronate, tragacanth, keratin , chondroitin, sulfated polysaccharide, hydroxyethyl Guanhua bean gum, carboxymethyl Guanhua bean gum, dextran, keratan sulfate, locust bean gum, amber gluten, saponin, chitin, shell Gum, carboxymethyl chitin, agar, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl, sodium polyacrylate, polyethylene glycol, bentonite and other tackifiers, ethanol, isopropanol, etc. Alcohol, diethylaminohydroxybenzoylbenzoic acid hexyl ester, and tert-butylmethoxybenzylidene methane, p-aminobenzoic acid ultraviolet absorber, o-amine benzoic acid ultraviolet absorber, water An ultraviolet absorber such as a salicylic acid ultraviolet absorber or a cinnamic acid ultraviolet absorber, vitamin A or a derivative thereof, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 or Derivatives, vitamin B12, vitamin B15 or its derivatives, vitamin B, alpha-tocopherol, beta-tocopherol, gamma-tocopherol, vitamin E acetate, vitamin E, vitamin D, vitamin H , the dimensions of pantothenic acid, pantethine, pyrroloquinoline, etc. Life and the like.

The external preparation for skin of the present invention can be prepared by treating the above-mentioned essential components and optional components by a usual method.

Moreover, the emulsified composition of the present invention which solves the second problem is characterized by comprising a water-soluble copolymer having a structural unit (c) derived from a hydrophobic monomer and a structural unit (d) derived from a hydrophilic monomer. Hereinafter, in the item of <1>, a hydrophobic monomer, a hydrophilic monomer, and a water-soluble copolymer of the copolymers will be described.

<1> Water-soluble copolymer [1] Hydrophobic monomer

In the present invention, a constituent unit derived from the hydrophobic monomer represented by the above formula (1), (7) or (8) (hereinafter sometimes simply referred to as "structural unit (7)") is used. One or two or more kinds of water-soluble copolymers contained as essential constituent units.

Further, in the present invention, the "constituting unit derived from a monomer" means a constituent unit formed by cleavage of a carbon-carbon unsaturated bond of a corresponding monomer by a polymerization reaction.

The hydrophobic monomer represented by the formula (1), (7) or (8) will be described below.

(1-1) a hydrophobic monomer represented by the formula (7)

In the above formula (7), R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁵ represents a branched hydrocarbon group having a ring structure of 13 to 30 or a ring structure having no ring structure; More than one branch of a hydrocarbon group having 6 to 12 carbon atoms.

Here, examples of the alkyl group represented by R ^{14 include} a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group. In the present invention, R ¹⁴ is preferably a hydrogen atom or a methyl group.

Further, examples of the branched hydrocarbon group having a ring structure of 13 to 30 carbon atoms represented by R ¹⁵ include 1-methyldodecyl group, 11-methyldodecyl group, 3-ethylundecyl group, and 3 -ethyl-4,5,6-trimethyloctyl, 1-methyltridecyl, 1-hexyloctyl, 2-butyldecyl, 2-hexyloctyl, 4-ethyl-1- Isobutyloctyl, 1-methylpentadecyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 16-methylheptyl, 9-methylheptyl, 7-Methyl-2-(3-methylhexyl)indenyl, 3,7,11,15-tetra-methylhexadecyl, 2-octyldodecyl, 2-decyltetradecyl, 2 - Twelve bases and sixteen bases.

Further, as the hydrocarbon group having 6 to 12 carbon atoms having two or more branches and having no ring structure represented by R ¹⁵ , 2,2-dimethylbutyl group and 2,3-dimethylbutyl group can be exemplified. 3,3-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1-dimethylpentyl, 1-isopropylbutyl, 1-isopropyl-2-methylpropyl, 1,1-diethylpropyl, 1-ethyl-1-isopropylpropyl, 2-ethyl-4-methylpentyl, 1- Propyl-2,2-dimethylpropyl, 1,1,2-trimethyl-pentyl, 1-isopropyl-3-methylbutyl, 1,2-dimethyl-1-B Butyl, 1,3-dimethyl-1-ethylbutyl, 1-ethyl-1-isopropyl-propyl, 1,1-dimethylhexyl, 1-methyl-1-B Pentyl, 1-methyl-1-propylbutyl, 1,4-dimethylhexyl, 1-ethyl-3-methylpentyl, 1,5-dimethylhexyl, 1-ethyl -6-methylheptyl, 1,1,3,3-tetramethylbutyl, 1,2-dimethyl-1-isopropylpropyl, 3-methyl-1-(2,2- Dimethylethyl)butyl, 1-isopropylhexyl, 3,5,5-trimethylhexyl, 2-isopropyl-5-methylhexyl, 1,5-dimethyl-1-B Hexyl, 3,7-dimethyloctyl, 2,4,5-trimethylheptyl, 2,4,6-trimethylheptyl, 3,5-dimethyl 1-(2,2-dimethylethyl)hexyl and the like.

(1-2) a hydrophobic monomer represented by the formula (1) or (8)

In the above formulae (1) and (8), R ¹ and R ^{16 each} represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² , R ³ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different. And represents a fluorenyl group having 6 to 22 carbon atoms having a branch having no ring structure. X represents a group from which an OH group is desorbed from a triol.

Here, examples of the alkyl group represented by R ¹ and R ^{16 include} a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group. In the present invention, R ¹ is preferably hydrogen or a methyl group.

Further, as the fluorenyl group having a branched carbon number of 6 to 22 which does not contain a ring structure represented by R ² , R ³ , R ¹⁷ , R ¹⁸ or R ¹⁹ , 2-methylpentanyl group and 3-methyl group are exemplified. Pentylmethyl, 4-methylpentyl, 2-ethylbutyryl, 2-ethylbutyryl, 2,2-dimethylbutenyl, 3,3-dimethylbutenyl, 2-methylhexyl , 4-methylhexyl, 5-methylhexyl, 2,2-dimethylpentenyl, 4,4-dimethylpentenyl, 2-methylheptyl, 2-B Hexyl, 2-propylpentyl, 2,2-dimethylhexyl, 2,2,3-trimethylpentanyl, 2-methyloctyl, 3,3,5-trimethyl Hexyl, 2-methylindenyl, 4-methylindenyl, 8-methylindenyl, 4-ethyloctyl, 2-ethyloctyl, 2-butylhexyl, 2- Tertiary butylhexyl, 2,2-diethylhexyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methylindenyl, 2-methyl-2-ethyloctyl, 2-methylundecyl, 10-methylundecyl, 2,2-dimethylindenyl, 2-ethylindenyl, 2- Butyl octyl, diethyl octyl, 2-tert-butyl-2,2,4-trimethylpentanyl, 10 -methyldodecyl, 3-methyldodedecyl, 4-methyldodedecyl, 11-methyldodedecyl, 10-ethylundecyl, 12-methyltride Indenyl, 2-butylindenyl, 2-hexyloctyl, 2-butyl-2-ethyloctyl, 12-methyltetradecyl, 14-methylpentadecyl, 2-butyl Dimercapto, 2-hexyldecyl, 16-methylheptadecanyl, 2,2-dimethylhexyl, 2-butylhexadecanyl, 2-hexyldodedecyl, 2, 4,10,14-tetramethylpentanyl, 18-methylundecyl, 3,7,11,15-tetra-methylhexadecanyl, 19-methylindolyl, and the like.

Further, in a preferred embodiment of the present invention, in the general formulae (1) and (8), R ² , R ³ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different and have no ring structure. The fluorenyl group having a branched carbon number of 10 to 22 or a fluorenyl group having 6 to 9 carbon atoms having two or more branches without a ring structure.

As a thiol group having a branched carbon number of 10 to 22 which does not contain a ring structure represented by R ² , R ³ , R ¹⁷ , R ¹⁸ or R ¹⁹ in such a preferred embodiment, 2-methyl fluorene is exemplified. , 4-methylindenyl, 8-methylindenyl, 4-ethyloctyl, 2-ethyloctyl, 2-butylhexyl, 2-tert-butylhexyl, 2, 2-Diethylhexyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methylindenyl, 2-methyl-2-ethyloctyl , 2-methylundecyl, 10-methylundecyl, 2,2-dimethylindenyl, 2-ethylindenyl, 2-butyloctyl, diethyloctyl, 2 - tert-butyl-2,2,4-trimethylpentanyl, 10-methyldodepinyl, 3-methyldodepinyl, 4-methyldodedecyl, 11-methyl Twelve indenyl, 10-ethylundecyl, 12-methyltridecyl, 2-butylindenyl, 2-hexyloctyl, 2-butyl-2-ethyloctyl, 12-A Tetradedyl, 14-methylpentadecanyl, 2-butyldodecanyl, 2-hexyldecyl, 16-methylheptadecanyl, 2,2-dimethylhexanyl 2-butylhexadecanyl, 2-hexyldodefluorene , 2,4,10,14-tetramethylpentanyl, 18-methylundecyl, 3,7,11,15-tetra-methylhexadecanyl, 19-methylindolyl Wait.

Further, as a preferred embodiment, R ² , R ³ , R ¹⁷ , R ¹⁸ and R ¹⁹ having a ring structure and having two or more branches having 6 to 9 carbon atoms can be exemplified as 2 , 2-dimethylbutyryl, 3,3-dimethylbutyryl, 2,2-dimethylpentanyl, 4,4-dimethylpentenyl, 2,2-dimethylhexyl, 2,2,3-trimethylpentanyl, 3,5,5-trimethylhexyl, and the like.

In the formula (1), the group derived from the triol represented by X is not particularly limited as long as it is a group from which an OH group is desorbed from the triol. A group derived from a ternary alcohol selected from the group consisting of glycerin, trimethylolpropane, and trimethylolethane, which desorbs an OH group, is suitably exemplified.

Further, in the general formula (8), the group derived from the tetrahydric alcohol represented by Y is not particularly limited as long as it is a group from which an OH group is desorbed from the tetrahydric alcohol, and may be suitably selected from the group consisting of dipropylene-containing The tetrahydric alcohol of the group of alcohol, pentaerythritol, erythritol, D-threitol, and L-threitol desorbs the group of the OH group.

In the present invention, it is particularly preferable to use a water-soluble copolymer comprising the constituent unit (1).

Further, in a further preferred embodiment of the present invention, the hydrophobic monomer represented by the formula (1) is a hydrophobic monomer represented by the following formula (15).

(In the formula (15), R ²⁴ and R ²⁵ may be the same or different and each represents a fluorenyl group having a branched carbon number of 16 to 22 which does not have a ring structure. Z represents a desorption of an OH group from a triol. base).

The fluorenyl group of R ²⁴ and R ^{25 in} the formula (15) has a carbon number of 12 to 22, more preferably 14 to 20, particularly preferably 16 to 20.

Further, the carbon number of the main chain of the fluorenyl group of R ²⁴ and R ^{25 in} the formula (15) is preferably 9 to 21, more preferably 12 to 20, particularly preferably 16 to 18.

Further, the number of branches of the fluorenyl group of R ²⁴ and R ^{25 in} the formula (15) is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.

Further, in the fluorenyl group of R ²⁴ and R ²⁵ of the formula (15), the position number of the carbon of the main chain of the branched chain bond is preferably as large as possible. Specifically, the branched chain is preferably bonded to the first to third carbons at the end of the autonomous chain, more preferably the first or second carbon, and particularly preferably the first carbon.

Specific examples of R ²⁴ and R ²⁵ include 10-methylundecyl group, 10-methyldodedecyl group, 11-methyldodedecyl group, and 10-ethylundecyl group. 12-methyltridecyl, 12-methyltetradecyl, 14-methylpentadecanyl, 16-methylheptadecanyl, 2,4,10,14-tetramethylpentanyl , 18-methyl 19-mercapto, 3,7,11,15-tetra-methylhexadecanyl, 19-methylindolyl, and the like.

In the general formula (15), the triol-derived group represented by Z is not particularly limited as long as it is a group from which an OH group is desorbed from a triol, and may be appropriately selected from the group consisting of glycerol and tris. The triol of the group of methylolpropane and trimethylolethane desorbs the group of the OH group.

[2] Hydrophilic monomer

As the hydrophilic monomer of the present invention, a polymerizable carboxylic acid, and a compound represented by the above formula (2) and the above formulas (9), (10) and (11) can be used.

(2-1) Polymeric carboxylic acid,

In the present invention, specific examples of the polymerizable carboxylic acid or a salt thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, and sodium, potassium, ammonium, and amine salts thereof. . Among these, acrylic acid, methacrylic acid, and a salt thereof are particularly preferable from the viewpoint of high polymerizability. in When the water-soluble copolymer of the present invention is introduced into a constituent unit derived from a polymerizable carboxylate, the polymerizable carboxylic acid may be previously prepared as a salt to carry out a polymerization reaction, or may be derived from a self-polymerizable carboxylic acid by a polymerization reaction. After the constituent unit is derivatized as a water-soluble copolymer, it is neutralized with a base to prepare a salt.

(2-2) a hydrophilic monomer represented by the formula (2)

In the above formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵ represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R ⁶ represents a hydrogen atom and a carbon number of 6~. An aromatic hydrocarbon group of 10, an aliphatic hydrocarbon group having 1 to 14 carbon atoms or a fluorenyl group having 1 to 12 carbon atoms. n represents an integer from 6 to 40.

The alkyl group represented by R ⁴ in the above formula (2) may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group or a cyclopropyl group. In the present invention, R ⁴ is preferably a hydrogen atom or a methyl group.

Further, examples of the alkylene group represented by R ^{5 include} an exoethyl group, a propyl group, an exo-propyl group, a 2-hydroxyl-propyl group, a 2-hydroxy-2-methyl-extended ethyl group, and a 2-hydroxy group. 1-methylethyl or the like, but among these, an ethyl group or a propyl group is preferred, and an ethyl group is more preferred.

Further, in the group represented by R ⁶ , examples of the aromatic group having 6 to 10 carbon atoms include a phenyl group, a benzyl group, a tolyl group, and an ethylphenyl group; and the aliphatic hydrocarbon group having 1 to 14 carbon atoms may be used. Methyl, ethyl, butyl, tert-butyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, lauryl, etc. are suitably exemplified; as the fluorenyl group having 1 to 12 carbon atoms, a fluorenyl group can be suitably exemplified. , ethyl sulfhydryl, propyl sulfonyl, butyl sulfhydryl, isobutyl sulfhydryl, pentamidine, laurel. Among these, the group represented by R ^{5 is} preferably an aliphatic hydrocarbon group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms.

Further, n of the general formula (2) is a numerical range of 6 to 40.

Among the monomers represented by the above formula (2), examples of the monomer in which R ⁵ is a propyl group include polypropylene glycol (9) monoacrylate, polypropylene glycol (13) monoacrylate, and polycondensation. Propylene glycol (9) monomethacrylate, polypropylene glycol (13) monomethacrylate, and the like. Furthermore, the number in parentheses represents N. Most of these polymers are commercially available. Specific examples of such commercially available products include "Blenmer" AP-400, AP-550, AP-800, PP-500, and PP-800 (all manufactured by Nippon Oil & Fats Co., Ltd.).

Among the monomers represented by the above formula (2), examples of the monomer in which R ⁵ is an ethyl group extend include polyethylene glycol (10) monoacrylate and polyethylene glycol (8). Methacrylate, polyethylene glycol (23) monoacrylate, polyethylene glycol (23) monomethacrylate, methoxy polyethylene glycol (9) acrylate, methoxy polyethylene glycol ( 9) methacrylate, methoxy polyethylene glycol (23) methacrylate, oleyl polyethylene glycol (18) methacrylate, lauryloxy polyethylene glycol (18) acrylate, Laurel oxime polyethylene glycol (10) methacrylate, stearyloxy polyethylene glycol (30) monomethacrylate, and the like.

The above hydrophilic monomer can be obtained in a high yield by esterification reaction of a corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with a chloride or anhydride of acrylic acid or methacrylic acid. Moreover, since many commercial products already exist, this commercial item can also be utilized. Specific examples of such commercially available products include Blenmer, AE-400, PE-350, AME-400, PME-400, PME-1000, ALE-800, and PSE-1300 (all of which are Japanese fats and oils). ))).

(2-3) a hydrophilic monomer represented by the formula (9)

As the hydrophilic monomer of the present invention, a hydrophilic monomer represented by the above formula (9) can also be used.

Specific examples of the hydrophilic monomer represented by the above formula (9) include 2-acryloxyethylphosphocholine (APC) and 2-methylpropenyloxyethylphosphocholine ( MPC). These monomers can be synthesized, for example, by the following methods described in Polymer Journal, Vol. 22, No. 5.

<Synthesis method>

The 2-bromoethylphosphonium dichloride is reacted with 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate to obtain 2-methylpropenyloxyethyl-2'-bromoethylphosphoric acid or 2- After propylene oxiranylethyl-2'-bromoethylphosphoric acid, the compounds are reacted with triethylamine in methanol.

(2-4) a hydrophilic monomer represented by the formula (10)

As the hydrophilic monomer of the present invention, a hydrophilic monomer represented by the above formula (10) can also be used.

In the hydrophilic monomer represented by the formula (10), the reducing sugar which is a group in which hydrogen is removed from the hydroxyl group at the 1-position of the self-reducing sugar represented by GO- is specifically selected from the group consisting of glucose and mannose. a monosaccharide such as sugar, galactose, arabinose, xylose or ribose, a disaccharide such as maltose, lactose or cellobiose, a trisaccharide such as maltotriose or a group of oligosaccharides such as malto-oligosaccharide One or two or more kinds of them are preferably selected from one or more selected from the group consisting of glucose, galactose, arabinose, xylose, ribose, maltose, lactose, and cellobiose, and glucose is particularly preferred. Further, as a monomer represented by the formula (10), glucosyl methacrylate Ethyl ester (hereinafter abbreviated as GEMA) or glucosyloxyethyl acrylate (hereinafter abbreviated as GEA) is preferred.

(2-5) a hydrophilic monomer represented by the formula (11)

As the hydrophilic monomer of the present invention, a hydrophilic monomer represented by the above formula (11) can also be used.

In the monomer of the formula (11), the amino acid which is an amino acid residue represented by R ²³ is not particularly limited as long as it is a generally known amino acid, and specifically, glycine can be exemplified. Acid, alanine, glutamic acid, lysine, arginine, and the like. Among these, since the skin barrier of the obtained water-soluble copolymer has a good recovery effect, it is particularly preferable to be an amino acid residue.

Further, the polyamine of the polyamine residue represented by R ²³ means an amine having two or more amine groups which may be substituted by an alkyl group in the same molecule, and specific examples thereof include a diamine, a triamine, a tetraamine or An amine in which the hydrogen atom of the amine group is substituted with an alkyl group. Among these, diamine is preferred from the viewpoint of the excellent use feeling of the skin external preparation containing the obtained water-soluble copolymer, and a particularly preferable specific example can be obtained from the viewpoint of easiness of raw materials at the time of synthesis. Ethylenediamine, 1,4-diamino-n-butane, 1,6-diamino-n-hexane, etc. are mentioned.

Further, the amine alcohol as the amine alcohol residue represented by R ²³ means a compound having an amino group which may be substituted with an alkyl group and an alcoholic hydroxyl group in the same molecule. The amine alcohol is not particularly limited as long as it is generally known, and specific examples thereof include ethanolamine and triethylaminoethanol.

The salt of the monomer represented by the formula (11) is not particularly limited, and specific examples thereof include a sodium salt, a potassium salt, an ammonium salt, an amine salt, etc., in which an acid moiety is neutralized with a base, or an amine group. Partially acid-neutralized hydrochloric acid Salt, sulfate, nitrate, phosphate, citrate, oxalate, carbonate, and the like. When the water-soluble copolymer of the present invention is introduced into a constituent unit derived from the monomer salt represented by the formula (11), the monomer represented by the formula (11) can be previously prepared into a salt to carry out a polymerization reaction. The constituent unit derived from the monomer represented by the formula (11) is derivatized into a water-soluble copolymer by a polymerization reaction, and then neutralized to prepare a salt.

Specific examples of the monomer represented by the formula (11) and the salt thereof include compounds 1 to 11 and salts thereof having the following structures.

Compound 3

Compound 6

Compound 9

The hydrophilic monomer represented by the formula (11), for example, can be esterified by using (meth)acrylic acid or (meth)acrylofluorene chloride as shown in the following reaction formulas (1) and (2). Synthesis by hydrazylation reaction.

(In the reaction formula, R ²² represents a hydrogen atom or a methyl group, and R ²³ represents an amino acid residue, a polyamine residue or an amine alcohol residue. Q represents an oxygen atom or a group represented by NH).

As described above, in the present invention, as the hydrophilic polymer, the above formula (2), the above formula (9), the above formula (10), and the above formula (11) can be used.

In a preferred embodiment of the present invention, the water-soluble copolymer comprises the structural unit (2) derived from the above formula (2).

[3] Water-soluble copolymer

In the present invention, a water-soluble copolymer having a constituent unit (1) and a constituent unit (2) can be suitably used. Further, a water-soluble copolymer having a constituent unit (15) and a constituent unit (2) can be preferably used.

Among such water-soluble copolymers, a copolymer of (methoxy methacrylate PEG-23/diisostearate methacrylate) can be preferably used.

By containing such a water-soluble copolymer, it is possible to obtain an emulsified composition which is low in irritation, has less stickiness, and has excellent emulsion stability.

(Methoxy methacrylate PEG-23/diisostearate methacrylate) copolymer, as the constituent unit (c), mainly contained in the hydrophobic monomer represented by the above formula (15), R ²⁴ and R ²⁵ are a structural unit (c) derived from a hydrophobic monomer of 16-methylheptadecanyl group.

Further, the constituent unit (d) mainly contains a hydrophilic monomer represented by the above formula (2), wherein R ⁴ is a methyl group, R ⁵ is an exoethyl group, R ⁶ is a methyl group, and n is 23 A hydrophilic monomer-derived constituent unit (d).

In general, a highly hydrophobic surfactant is suitable for the formation of an emulsified composition of an oily type in oil, whereas a surfactant having a high hydrophilicity is suitable for the formation of an oily type emulsified composition. Similarly, in the water-soluble copolymer of the present invention, when the proportion of the hydrophobic structural unit (c) is high, it is suitable for forming an emulsified composition of an oil-in-oil type, and the hydrophilic constituent unit (d) is occupied. When the ratio is high, it is suitable for forming an oily type emulsified composition.

As described above, the emulsified form of the formed emulsified composition can be adjusted by appropriately adjusting the ratio and ratio of the constituent unit (c) and the constituent unit (d).

In the present invention, the proportion of the constituent unit (c) of the water-soluble copolymer in the total constituent unit is preferably from 1 to 50% by mass, more preferably from 20 to 50% by mass, and from 30 to 40% by mass.

By setting the ratio of the constituent unit (c) of the water-soluble copolymer to the above range, it is possible to provide an oil-based emulsified composition in which the viscosity is further reduced.

In the present invention, the proportion of the constituent unit (d) of the water-soluble copolymer in the total constituent unit is preferably from 50 to 99% by mass, more preferably from 50 to 80% by mass, and from 60 to 70% by mass.

By setting the ratio of the constituent unit (d) of the water-soluble copolymer to the above range, it is possible to provide an oil-borne emulsified composition in which the viscosity is further reduced.

In the present invention, the mass ratio of the constituent unit (c) constituting the water-soluble copolymer to the constituent unit (d) is preferably from 10:90 to 50:50, more preferably from 20:80 to 50:50. It is 30:70~40:60.

Further, the molar ratio of the constituent unit (c) constituting the water-soluble copolymer to the constituent unit (d) is preferably 15:85 to 62:38, more preferably 29:71 to 62:38, and particularly preferably 41. :59~52:48.

When the mass ratio of the structural unit (c) and the structural unit (d) of the water-soluble copolymer and the molar ratio are in the above range, the water-soluble copolymer which is suitable for forming an emulsified composition of an oil-in-water type can be obtained. Things.

In the present invention, the average molecular weight of the water-soluble copolymer is preferably from 20,000 to 110,000, further preferably from 20,000 to 80,000, more preferably from 30,000 to 80,000, further preferably from 40,000 to 70,000, and particularly preferably from 50,000 to 70,000. Further excellent is 57000~66000.

Here, the average molecular weight means a weight average molecular weight in terms of polystyrene measured by GPC.

<2> Emulsified composition

The emulsified composition of the present invention is characterized in that it does not substantially contain an emulsifier other than the above water-soluble copolymer.

Here, the term "the emulsifier other than the water-soluble copolymer is not substantially contained" means that the content of the emulsifier other than the water-soluble copolymer is 0.3% by mass or less, preferably 0.1% by mass or less, and particularly preferably 0.01%. The mass% or less is particularly preferably 0.001% by mass or less. Further, an emulsifier other than the above water-soluble copolymer is particularly preferred.

The content of the above water-soluble copolymer of the emulsified composition is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass.

By setting the content of the water-soluble copolymer to the above range, the emulsion stability of the emulsified composition can be further improved.

The content of the aqueous phase and the oil phase of the emulsified composition of the present invention can be appropriately adjusted by changing the ratio of the constituent unit (c) and the constituent unit (d) of the water-soluble copolymer.

Hereinafter, the content of the oil phase and the water phase in the case where the water-soluble copolymer constituting the unit (c) and the constituent unit (d) is contained in a ratio suitable for forming the above-described oil-oil type emulsified composition will be described.

In the present specification, the oil phase and the oil phase component, and the water phase and the water phase component are not included in the water-soluble copolymer of the present invention.

The content of the oil phase component of the emulsified composition of the present invention is preferably from 0.01 to 80% by mass, more preferably from 0.1 to 70% by mass.

By setting the content of the oil phase component to the above range, the emulsion stability of the emulsified composition can be improved.

Further, the oil phase component is an oil agent and a lipophilic component, and refers to a component contained in the oil phase in the emulsified composition.

In the emulsified composition of the present invention, the mass ratio of the water-soluble copolymer to the oil phase component is preferably from 1:100 to 1:0.2, more preferably from 1:70 to 1:0.3.

By setting the mass ratio of the water-soluble copolymer to the oil phase component to the above range, the emulsion stability of the emulsified composition can be improved.

In the emulsified composition of the present invention, the mass ratio of the oil phase to the water phase is preferably from 0.1:99.9 to 80:20, more preferably from 1:99 to 65:35.

By setting the mass ratio of the oil phase to the water phase to the above range, a stable oil-type emulsified composition in water can be formed.

The components contained in the oil phase and the aqueous phase are not particularly limited.

Examples of the oil agent constituting the oil phase include liquid fats and oils, solid fats and oils, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, and fluorenone oils.

Examples of the liquid fats and oils include avocado oil, camellia oil, sea turtle oil, Australian walnut oil, corn oil, oyster sauce, olive oil, rapeseed oil, egg butter, sesame oil, apricot kernel oil, wheat germ oil, and camellia. Oil, castor oil, linseed oil, safflower seed oil, cottonseed oil, perilla oil, white mango seed oil, soybean oil, peanut oil, bitter tea oil, Japanese eucalyptus seed oil, rice bran oil, octopus tung oil, Japanese tung oil, lotus Jojoba oil, germ oil, triglycerol, tricaprylic glycerol, triisopalmitic acid glycerol, and the like.

Examples of the solid fats and oils include cocoa butter, coconut oil, horse fat, hardened coconut oil, palm oil, tallow, sheep fat, hardened tallow, palm kernel oil, lard, beef bone fat, wood wax oil, and hardened oil. Beef foot oil, wood wax, hardened castor oil, etc.

Examples of the wax include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, insect wax, cetyl wax, montan wax, wax, lanolin, kapok wax, lanolin acetate, and liquid. Lanolin, sugar cane wax, lanolin fatty acid isopropyl ester, hexyl laurate, reduced lanolin, jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol, POE sheep A fatty alcohol acetate, a POE cholesterol ether, a lanolin fatty acid polyethylene glycol, a POE hydrogenated lanolin ether, and the like.

Examples of the hydrocarbon oil include flowing paraffin, ceresin, isooctadecane, paraffin, mineral wax, squalene, petrolatum, and microcrystalline wax.

The higher fatty acid may, for example, be lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid (sulinic acid), 12-hydroxystearic acid, undecylenic acid or tall oil acid ( Tall oil acid) and so on.

Examples of the higher alcohol include cetyl alcohol, stearyl alcohol, behenyl alcohol, saraphanol, myristyl alcohol, cetearyl alcohol and the like.

Examples of the synthetic ester oil include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, and myristate. Ester, decyl oleate, hexyl decyl dimethyl octoate, cetyl lactic acid, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, sucrose hard Fatty acid ester, sucrose oleate, cholesterol ester of 12-hydroxystearic acid, ethylene glycol di-2-ethylhexanoate, fatty acid ester of dipentaerythritol, N-alkylene glycol monoisostearate, diterpene Acid neopentyl glycol, diisostearyl malate, glyceryl di-2-heptyldecanoate, trimethylolpropane tris-2-ethylhexanoate, trimethylolpropane triiso Stearate, pentaerythritol tetra-2-ethylhexanoate, glycerol tris-2-ethylhexanoate, trimethylolpropane triisostearate, cetyl 2-ethyl caproate , 2-ethylhexyl palmitate, glycerol trimyristate, tris-2-heptyldecanoic acid glyceride, castor oil fatty acid methyl ester, oleic acid oil ester, cetearyl alcohol, glycerol acetate Ester, palmitic acid 2-heptyl eleven , Cetyl palmitate, diisobutyl adipate, N- lauroyl -L- glutamic acid acyl-2-octyl dodecyl acrylate, adipate, di-2-heptylundecanoate Ester, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyl decyl myristate, 2-hexyl decyl palmitate, 2-hexyl decyl adipate, diisophthalic acid diiso Propyl ester, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate, and the like.

Examples of the fluorenone oil include a chain polyoxyalkylene such as dimethyl polyoxyalkylene, methylphenyl polyoxyalkylene or methyl hydrogen polyoxyalkylene, or decamethyl polyoxyalkylene. a cyclic polysiloxane such as dodecamethyl polysiloxane or tetramethyltetrahydropolysiloxane.

The oil agent may be used alone or in combination of two or more.

The emulsified composition of the present invention may be blended with any of the additives which are usually blended with a cosmetic, insofar as the effects of the present invention are not impaired. Examples of such an additive include humectants such as polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, and maltitol; and ethanol and the like. Lower alcohol; antioxidants such as butylhydroxytoluene, tocopherol, phytic acid; antibacterial agents such as benzoic acid, salicylic acid, sorbic acid, alkyl p-hydroxybenzoate, hexachlorophene; p-aminobenzoic acid (below) Abbreviated as "PABA"), PABA monoglyceride, N,N-dipropoxy PABA ethyl ester, N,N-diethoxy PABA ethyl ester, N,N-dimethyl PABA methyl ester, N,N - benzoic acid-based ultraviolet absorbers such as dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, N,N-dimethyl PABA2-ethylhexyl ester; high menthyl-N-ethyl fluorenyl group An ortho-benzoic acid-based ultraviolet absorber such as o-amine benzoate; amyl salicylate, menthyl salicylate, permentyl salicylate, octyl salicylate, phenyl salicylate, salicylic acid Salicylic acid ultraviolet absorber such as benzyl ester or p-isopropanol phenyl salicylate; octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diiso cinnamate Propyl ester, ethyl 2,4-diisopropyl cinnamate, meat Methyl 2,4-diisopropyl laurate, propyl-p-methoxy cinnamate, isopropyl-p-methoxy cinnamate, isoamyl-p-methoxy cinnamate, cinnamon Acid octyl-p-methoxy ester (2-ethylhexyl-p-methoxy cinnamate), 2-ethoxyethyl-p-methoxy cinnamate, cyclohexyl-p-methoxy cinnamate, Ethyl cinnamate ethyl-α-cyano-β-phenyl ester, 2-ethylhexyl-α-cyano-β-phenyl cinnamate, glyceryl glyceryl mono-2-ethylhexyl-di-pair Cinnamate-based ultraviolet absorber such as oxyester; cinnamic acid [3-bis(trimethylmethoxy)methylmercapto-1-methylpropyl]-3,4,5-trimethoxy ester, cinnamic acid [3-Bis(trimethyldecyloxy)methylmercapto-3-methylpropyl]-3,4,5-trimethoxy ester, cinnamic acid [3-bis(trimethyldecyloxy) A Mercaptopropyl]-3,4,5-trimethoxy ester, cinnamic acid [3-bis(trimethylmethoxy)methylmercaptobutyl]-3,4,5-trimethoxy ester, cinnamon Acid [3-para(trimethyldecyloxy)decylbutyl]-3,4,5-trimethoxy ester, cinnamic acid [3-para(trimethyldecyloxy)decylbutyl]-3 ,4,5-trimethoxy ester, cinnamic acid [3-gin(trimethyldecyloxy)decyl-1-methylpropyl]-3,4-di An oxime ketone-based cinnamic acid ultraviolet absorber; 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy- 4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4 -Methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl- a benzophenone system such as 4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octyloxybenzophenone, 4-hydroxy-3-carboxybenzophenone or the like UV absorber; 3-(4'-methylbenzylidene)-d,l-camphor, 3-benzylidene-d,l-camphor, 4-imidazolium acrylate, 2-phenyl-5 -methylbenzone Oxazole, 2,2'-hydroxy-5-tolylbenzotriazole, 2-(2'-hydroxy-5'-tert-butyloctylphenyl) benzotriazole, 2-(2'-hydroxy- 5'-tolyl)benzotriazole, dibenzylhydrazine, di-p-methoxybenzoylmethane, 4-methoxy-4'-t-butyldiphenylmethylmethane, 5-(3, UV absorbers such as 3'dimethyl-2-norbornyl)-3-pentan-2-one; thioglycine (for example, sodium lauryl sarcosinate), glutathione, lemon Organic acids such as acid, malic acid, tartaric acid, lactic acid; vitamin A and its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and its derivatives, vitamin B12, Vitamin B such as vitamin B15 and its derivatives, vitamin B, α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, vitamin E, vitamin D, vitamin H, pantothenic acid, and panthion B Vitamins such as amines, niacinamide, benzyl nicotinic acid, etc.; γ-avirics, allantoin, glycyrrhizic acid (salt), glycyrrhetinic acid and its derivatives, tranexamic acid and its derivatives [As a tranexamic acid derivative, a dimer of tranexamic acid (for example, hydrochloric acid Formula-4-(trans-amine methylcyclohexanecarbonyl)amine methylcyclohexanecarboxylic acid, etc.), ester of tranexamic acid and hydroquinone (for example, trans-4-aminomethylcyclohexanecarboxylate) Acid 4'-hydroxyphenyl ester, etc.), ester of tranexamic acid and gentisic acid (for example, 2-(trans-4-aminomethylcyclohexylcarbonyloxy)-5-hydroxybenzoic acid and its salts, etc.) , a guanamine of tranexamic acid (for example, trans-4-aminomethylcyclohexanecarboxylic acid methyl decylamine and its salt, trans-4-(P-methoxybenzhydryl)amine methyl Cyclohexanecarboxylic acid and its salt, trans-4-indole methylcyclohexanecarboxylic acid and its salt)], eucalyptus, bisabolol, macro-furfural, thymol, inositol, saikosapon soap Various ingredients such as saponin, ginseng saponin, loofah saponin, saponin such as saponin, pantothenic acid ethyl ether, ethinyl estradiol, tranexamic acid, arbutin, ginseng, placenta, etc.; , Japanese Pampas grass, orange, sage, alfalfa, mallow, medicine, thyme, east angelica, spruce, birch, wattle, loofah, horse chestnut, saxifrage, rabbit chrysanthemum, lily, que Extracts of plants of Artemisia, Peony, Aloe, Gardenia, Japanese cypress, etc.; pigment; porous and/or absorbent An aqueous powder (for example, a starch obtained from corn or potato, phthalic anhydride, talc, kaolin, magnesium aluminum silicate, calcium alginate, etc.); a neutralizing agent; a preservative; a fragrance; a pigment, and the like.

The emulsified composition of the present invention can be produced by separately preparing an aqueous phase component and an oil phase component containing the above water-soluble copolymer, and mixing and mixing them by a usual method.

The emulsified composition of the present invention is low in irritation, and is preferably used as a cosmetic, a skin external preparation, a medicinal product or a pharmaceutical product such as an emulsion, a cream, a cosmetic liquid, a sunscreen, a liquid foundation, or the like from the viewpoint of less stickiness.

<3>Emulsifier

The invention also relates to an emulsifier comprising the above water-soluble copolymer. The matters relating to the above water-soluble copolymer and the emulsified composition can be applied to the emulsifier of the present invention.

<4> Method for producing emulsified composition

The invention also relates to a method of making an emulsified composition using the emulsifier of the invention described above. The method of the present invention is characterized in that an emulsifier other than the emulsifier of the present invention is not used. The matters relating to the above water-soluble copolymer and the emulsified composition can be applied to the production method of the present invention.

The skin cleansing agent of the present invention which solves the third and fourth problems is characterized by comprising a water-soluble copolymer having a constituent unit (e) derived from a hydrophobic monomer and a constituent unit (f) derived from a hydrophilic monomer. Hereinafter, in the item of <1>, a hydrophobic monomer, a hydrophilic monomer, and a water-soluble copolymer of the copolymers will be described.

<1> Water-soluble copolymer [1] Hydrophobic monomer

In the present invention, a constituent unit derived from the hydrophobic monomer represented by the above formula (1), (7) or (8) (hereinafter sometimes simply referred to as "structural unit (7)") is used. One or two or more kinds of water-soluble copolymers contained as essential constituent units.

In the present invention, the "composition unit derived from a monomer" means a constituent unit formed by cleavage of a carbon-carbon unsaturated bond of a corresponding monomer by a polymerization reaction.

The hydrophobic monomer represented by the formula (1), (7) or (8) will be described below.

(1-1) a hydrophobic monomer represented by the formula (7)

In the above formula (7), R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁵ represents a branched hydrocarbon group having a ring structure of 13 to 30 or a ring structure having no ring structure; More than one branch of a hydrocarbon group having 6 to 12 carbon atoms.

Here, examples of the alkyl group represented by R ^{14 include} a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group. In the present invention, R ¹⁴ is preferably a hydrogen atom or a methyl group.

Further, examples of the branched hydrocarbon group having a ring structure of 13 to 30 carbon atoms represented by R ¹⁵ include 1-methyldodecyl group, 11-methyldodecyl group, 3-ethylundecyl group, and 3 -ethyl-4,5,6-trimethyloctyl, 1-methyltridecyl, 1-hexyloctyl, 2-butyldecyl, 2-hexyloctyl, 4-ethyl-1- Isobutyloctyl, 1-methylpentadecyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 16-methylheptyl, 9-methylheptyl, 7-Methyl-2-(3-methylhexyl)indenyl, 3,7,11,15-tetra-methylhexadecyl, 2-octyldodecyl, 2-decyltetradecyl, 2 - Twelve bases and sixteen bases.

Further, as the hydrocarbon group having 6 to 12 carbon atoms having two or more branches and having no ring structure represented by R ¹⁵ , 2,2-dimethylbutyl group and 2,3-dimethylbutyl group can be exemplified. 3,3-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1-dimethylpentyl, 1-isopropylbutyl, 1-isopropyl-2-methylpropyl, 1,1-diethylpropyl, 1-ethyl-1-isopropylpropyl, 2-ethyl-4-methylpentyl, 1- Propyl-2,2-dimethylpropyl, 1,1,2-trimethyl-pentyl, 1-isopropyl-3-methylbutyl, 1,2-dimethyl-1-B Butyl, 1,3-dimethyl-1-ethylbutyl, 1-ethyl-1-isopropyl-propyl, 1,1-dimethylhexyl, 1-methyl-1-B Pentyl, 1-methyl-1-propylbutyl, 1,4-dimethylhexyl, 1-ethyl-3-methylpentyl, 1,5-dimethylhexyl, 1-ethyl -6-methylheptyl, 1,1,3,3-tetramethylbutyl, 1,2-dimethyl-1-isopropylpropyl, 3-methyl-1-(2,2- Dimethylethyl)butyl, 1-isopropylhexyl, 3,5,5-trimethylhexyl, 2-isopropyl-5-methylhexyl, 1,5-dimethyl-1-B Hexyl, 3,7-dimethyloctyl, 2,4,5-trimethylheptyl, 2,4,6-trimethylheptyl, 3,5-dimethyl 1-(2,2-dimethylethyl)hexyl and the like.

(1-2) a hydrophobic monomer represented by the formula (1) or (8)

In the above formulae (1) and (8), R ¹ and R ^{16 each} represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² , R ³ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different. And represents a fluorenyl group having 6 to 22 carbon atoms having a branch having no ring structure. X represents a group from which an OH group is desorbed from a triol.

Here, examples of the alkyl group represented by R ¹ and R ^{16 include} a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group. In the present invention, R ¹ is preferably hydrogen or a methyl group.

Further, as the fluorenyl group having a branched carbon number of 6 to 22 which does not contain a ring structure represented by R ² , R ³ , R ¹⁷ , R ¹⁸ or R ¹⁹ , 2-methylpentanyl group and 3-methyl group are exemplified. Pentylmethyl, 4-methylpentyl, 2-ethylbutyryl, 2-ethylbutyryl, 2,2-dimethylbutenyl, 3,3-dimethylbutenyl, 2-methylhexyl , 4-methylhexyl, 5-methylhexyl, 2,2-dimethylpentenyl, 4,4-dimethylpentenyl, 2-methylheptyl, 2-B Hexyl, 2-propylpentyl, 2,2-dimethylhexyl, 2,2,3-trimethylpentanyl, 2-methyloctyl, 3,3,5-trimethyl Hexyl, 2-methylindenyl, 4-methylindenyl, 8-methylindenyl, 4-ethyloctyl, 2-ethyloctyl, 2-butylhexyl, 2- Tertiary butylhexyl, 2,2-diethylhexyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methylindenyl, 2-methyl-2-ethyloctyl, 2-methylundecyl, 10-methylundecyl, 2,2-dimethylindenyl, 2-ethylindenyl, 2- Butyl octyl, diethyl octyl, 2-tert-butyl-2,2,4-trimethylpentanyl, 10 -methyldodecyl, 3-methyldodedecyl, 4-methyldodedecyl, 11-methyldodedecyl, 10-ethylundecyl, 12-methyltride Indenyl, 2-butylindenyl, 2-hexyloctyl, 2-butyl-2-ethyloctyl, 12-methyltetradecyl, 14-methylpentadecyl, 2-butyl Dimercapto, 2-hexyldecyl, 16-methylheptadecanyl, 2,2-dimethylhexyl, 2-butylhexadecanyl, 2-hexyldodedecyl, 2, 4,10,14-tetramethylpentanyl, 18-methylundecyl, 3,7,11,15-tetra-methylhexadecanyl, 19-methylindolyl, and the like.

Further, in a preferred embodiment of the present invention, in the general formulae (1) and (8), R ² , R ³ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different and have no ring structure. The fluorenyl group having a branched carbon number of 10 to 22 or a fluorenyl group having 6 to 9 carbon atoms having two or more branches without a ring structure.

As a thiol group having a branched carbon number of 10 to 22 which does not contain a ring structure represented by R ² , R ³ , R ¹⁷ , R ¹⁸ or R ¹⁹ in such a preferred embodiment, 2-methyl fluorene is exemplified. , 4-methylindenyl, 8-methylindenyl, 4-ethyloctyl, 2-ethyloctyl, 2-butylhexyl, 2-tert-butylhexyl, 2, 2-Diethylhexyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methylindenyl, 2-methyl-2-ethyloctyl , 2-methylundecyl, 10-methylundecyl, 2,2-dimethylindenyl, 2-ethylindenyl, 2-butyloctyl, diethyloctyl, 2 - tert-butyl-2,2,4-trimethylpentanyl, 10-methyldodepinyl, 3-methyldodepinyl, 4-methyldodedecyl, 11-methyl Twelve indenyl, 10-ethylundecyl, 12-methyltridecyl, 2-butylindenyl, 2-hexyloctyl, 2-butyl-2-ethyloctyl, 12-A Tetradedyl, 14-methylpentadecanyl, 2-butyldodecanyl, 2-hexyldecyl, 16-methylheptadecanyl, 2,2-dimethylhexanyl 2-butylhexadecanyl, 2-hexyldodefluorene , 2,4,10,14-tetramethylpentanyl, 18-methylundecyl, 3,7,11,15-tetra-methylhexadecanyl, 19-methylindolyl Wait.

Further, as a preferred embodiment, R ² , R ³ , R ¹⁷ , R ¹⁸ and R ¹⁹ having a ring structure and having two or more branches having 6 to 9 carbon atoms can be exemplified as 2 , 2-dimethylbutyryl, 3,3-dimethylbutyryl, 2,2-dimethylpentanyl, 4,4-dimethylpentenyl, 2,2-dimethylhexyl, 2,2,3-trimethylpentanyl, 3,5,5-trimethylhexyl, and the like.

In the formula (1), the group derived from the triol represented by X is not particularly limited as long as it is a group from which an OH group is desorbed from the triol. A group derived from a ternary alcohol selected from the group consisting of glycerin, trimethylolpropane, and trimethylolethane, which desorbs an OH group, is suitably exemplified.

Further, in the general formula (8), the group derived from the tetrahydric alcohol represented by Y is not particularly limited as long as it is a group from which an OH group is desorbed from the tetrahydric alcohol, and may be suitably selected from the group consisting of dipropylene-containing The tetrahydric alcohol of the group of alcohol, pentaerythritol, erythritol, D-threitol, and L-threitol desorbs the group of the OH group.

In the present invention, it is particularly preferable to use a water-soluble copolymer comprising the constituent unit (1).

Furthermore, in a further preferred embodiment of the present invention, the hydrophobic monomer represented by the formula (1) is a hydrophobic monomer represented by the above formula (15).

The fluorenyl group of R ²⁴ and R ^{25 in} the formula (15) has a carbon number of 12 to 22, more preferably 14 to 20, particularly preferably 16 to 20.

Further, the carbon number of the main chain of the fluorenyl group of R ²⁴ and R ^{25 in} the formula (15) is preferably 9 to 21, more preferably 12 to 20, particularly preferably 16 to 18.

Further, the number of branches of the fluorenyl group of R ²⁴ and R ^{25 in} the formula (15) is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.

Further, in the fluorenyl group of R ²⁴ and R ²⁵ of the formula (15), the position number of the carbon of the main chain of the branched chain bond is preferably as large as possible. Specifically, the branched chain is preferably bonded to the first to third carbons at the end of the autonomous chain, more preferably the first or second carbon, and particularly preferably the first carbon.

Specific examples of R ²⁴ and R ²⁵ include 10-methylundecyl group, 10-methyldodedecyl group, 11-methyldodedecyl group, and 10-ethylundecyl group. 12-methyltridecyl, 12-methyltetradecyl, 14-methylpentadecanyl, 16-methylheptadecanyl, 2,4,10,14-tetramethylpentanyl , 18-methyl 19-mercapto, 3,7,11,15-tetra-methylhexadecanyl, 19-methylindolyl, and the like.

In the general formula (15), the triol-derived group represented by Z is not particularly limited as long as it is a group from which an OH group is desorbed from a triol, and may be appropriately selected from the group consisting of glycerol and tris. The triol of the group of methylolpropane and trimethylolethane desorbs the group of the OH group.

[2] Hydrophilic monomer

As the hydrophilic monomer of the present invention, a polymerizable carboxylic acid and a compound represented by the above formulas (2), (9), (10) and (11) can be used.

(2-1) Polymeric carboxylic acid

In the present invention, specific examples of the polymerizable carboxylic acid or a salt thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, and sodium, potassium, ammonium, and amine salts thereof. . Among these, acrylic acid, methacrylic acid, and a salt thereof are particularly preferable from the viewpoint of high polymerizability. When the water-soluble copolymer of the present invention is introduced into a constituent unit derived from a polymerizable carboxylate, the polymerizable carboxylic acid may be previously prepared as a salt to carry out a polymerization reaction, or may be derived from a self-polymerizable carboxylic acid by a polymerization reaction. The constituent unit is derived from a water-soluble copolymer and then neutralized with a base to form a salt.

(2-2) a hydrophilic monomer represented by the formula (2)

In the above formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵ represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R ⁶ represents a hydrogen atom and a carbon number of 6~. An aromatic hydrocarbon group of 10, an aliphatic hydrocarbon group having 1 to 14 carbon atoms or a fluorenyl group having 1 to 12 carbon atoms. n represents an integer from 6 to 40.

The alkyl group represented by R ⁴ in the above formula (2) may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group or a cyclopropyl group. In the present invention, R ⁴ is preferably a hydrogen atom or a methyl group.

Further, examples of the alkylene group represented by R ^{5 include} an exoethyl group, a propyl group, an exo-propyl group, a 2-hydroxyl-propyl group, a 2-hydroxy-2-methyl-extended ethyl group, and a 2-hydroxy group. 1-methylethyl or the like, but among these, an ethyl group or a propyl group is preferred, and an ethyl group is more preferred.

Further, in the group represented by R ⁶ , examples of the aromatic group having 6 to 10 carbon atoms include a phenyl group, a benzyl group, a tolyl group, and an ethylphenyl group; and the aliphatic hydrocarbon group having 1 to 14 carbon atoms may be used. Methyl, ethyl, butyl, tert-butyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, lauryl, etc. are suitably exemplified; as the fluorenyl group having 1 to 12 carbon atoms, a fluorenyl group can be suitably exemplified. , ethyl sulfhydryl, propyl sulfonyl, butyl sulfhydryl, isobutyl sulfhydryl, pentamidine, laurel. Among these, the group represented by R ^{5 is} preferably an aliphatic hydrocarbon group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms.

Further, n of the general formula (2) is a numerical range of 6 to 40.

Among the monomers represented by the above formula (2), examples of the monomer in which R ⁵ is a propyl group include polypropylene glycol (9) monoacrylate, polypropylene glycol (13) monoacrylate, and polycondensation. Propylene glycol (9) monomethacrylate, polypropylene glycol (13) monomethacrylate, and the like. Furthermore, the number in parentheses represents N. Most of these polymers are commercially available. Specific examples of such commercially available products include "Blenmer" AP-400, AP-550, AP-800, PP-500, and PP-800 (all manufactured by Nippon Oil & Fats Co., Ltd.).

Among the monomers represented by the above formula (2), examples of the monomer in which R ⁵ is an ethyl group extend include polyethylene glycol (10) monoacrylate and polyethylene glycol (8). Methacrylate, polyethylene glycol (23) monoacrylate, polyethylene glycol (23) monomethacrylate, methoxy polyethylene glycol (9) acrylate, methoxy polyethylene glycol ( 9) methacrylate, methoxy polyethylene glycol (23) methacrylate, oleyl polyethylene glycol (18) methacrylate, lauryloxy polyethylene glycol (18) acrylate, Laurel oxime polyethylene glycol (10) methacrylate, stearyloxy polyethylene glycol (30) monomethacrylate, and the like.

The above hydrophilic monomer can be obtained in a high yield by esterification reaction of a corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with a chloride or anhydride of acrylic acid or methacrylic acid. Moreover, since many commercial products already exist, this commercial item can also be utilized. Specific examples of such commercially available products include Blenmer, AE-400, PE-350, AME-400, PME-400, PME-1000, ALE-800, and PSE-1300 (all of which are Japanese fats and oils). ))).

(2-3) a hydrophilic monomer represented by the formula (9)

As the hydrophilic monomer of the present invention, a hydrophilic monomer represented by the above formula (9) can also be used.

Specific examples of the hydrophilic monomer represented by the above formula (9) include 2-acryloxyethylphosphocholine (APC) and 2-methylpropenyloxyethylphosphocholine ( MPC). These monomers can be synthesized, for example, by the following methods described in Polymer Journal, Vol. 22, No. 5.

<Synthesis method>

The 2-bromoethylphosphonium dichloride is reacted with 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate to obtain 2-methylpropenyloxyethyl-2'-bromoethylphosphoric acid or 2- After propylene oxiranylethyl-2'-bromoethylphosphoric acid, the compounds are reacted with triethylamine in methanol.

(2-4) a hydrophilic monomer represented by the formula (10)

As the hydrophilic monomer of the present invention, a hydrophilic monomer represented by the above formula (10) can also be used.

In the hydrophilic monomer represented by the formula (10), the reducing sugar which is a group in which hydrogen is removed from the hydroxyl group at the 1-position of the self-reducing sugar represented by GO- is specifically selected from the group consisting of glucose and mannose. a monosaccharide such as sugar, galactose, arabinose, xylose or ribose, a disaccharide such as maltose, lactose or cellobiose, a trisaccharide such as maltotriose or a group of oligosaccharides such as malto-oligosaccharide One or two or more kinds of them are preferably selected from one or more selected from the group consisting of glucose, galactose, arabinose, xylose, ribose, maltose, lactose, and cellobiose, and glucose is particularly preferred. Further, as the monomer represented by the formula (10), glucosyloxyethyl methacrylate (hereinafter abbreviated as GEMA) or glucosyloxyethyl acrylate (hereinafter abbreviated as GEA) is preferred.

In the monomer of the formula (11), the amino acid which is an amino acid residue represented by R ²³ is not particularly limited as long as it is a generally known amino acid, and specifically, glycine can be exemplified. Acid, alanine, glutamic acid, lysine, arginine, and the like. Among these, since the skin barrier of the obtained water-soluble copolymer has a good recovery effect, it is particularly preferable to be an amino acid residue.

Further, the polyamine of the polyamine residue represented by R ²³ means an amine having two or more amine groups which may be substituted by an alkyl group in the same molecule, and specific examples thereof include a diamine, a triamine, a tetraamine or An amine in which the hydrogen atom of the amine group is substituted with an alkyl group. Among these, diamine is preferred from the viewpoint of the excellent use feeling of the skin external preparation containing the obtained water-soluble copolymer, and a particularly preferable specific example can be obtained from the viewpoint of easiness of raw materials at the time of synthesis. Ethylenediamine, 1,4-diamino-n-butane, 1,6-diamino-n-hexane, etc. are mentioned.

Further, the amine alcohol as the amine alcohol residue represented by R ²³ means a compound having an amino group which may be substituted with an alkyl group and an alcoholic hydroxyl group in the same molecule. The amine alcohol is not particularly limited as long as it is generally known, and specific examples thereof include ethanolamine and triethylaminoethanol.

The salt of the monomer represented by the formula (11) is not particularly limited, and specific examples thereof include a sodium salt, a potassium salt, an ammonium salt, an amine salt, etc., in which an acid moiety is neutralized with a base, or an amine group. Partially acid-neutralized hydrochloride, sulfate, nitrate, phosphate, citrate, oxalate, carbonate, and the like. When the water-soluble copolymer of the present invention is introduced into a constituent unit derived from the monomer salt represented by the formula (11), the monomer represented by the formula (11) can be previously prepared into a salt to carry out a polymerization reaction. The constituent unit derived from the monomer represented by the formula (11) is derivatized into a water-soluble copolymer by a polymerization reaction, and then neutralized to prepare a salt.

Specific examples of the monomer represented by the formula (11) and the salt thereof include the above-mentioned compounds 1 to 11 and salts thereof.

The hydrophilic monomer represented by the formula (11), for example, as shown in the above reaction formulas (1) and (2), can be esterified by using (meth)acrylic acid or (meth)acrylofluorene chloride. Synthesis by hydrazylation reaction.

As described above, in the present invention, as the hydrophilic polymer, the above formula (2), the above formula (9), the above formula (10), and the above formula (11) can be used.

In a preferred embodiment of the present invention, the water-soluble copolymer comprises the structural unit (2) derived from the above formula (2).

[3] Water-soluble copolymer

In the present invention, a water-soluble copolymer having a constituent unit (1) and a constituent unit (2) can be suitably used. Further, a water-soluble copolymer having a constituent unit (15) and a constituent unit (2) can be preferably used.

Among such water-soluble copolymers, a copolymer of (methoxy methacrylate PEG-23/diisostearate methacrylate) can be preferably used.

By containing such a water-soluble copolymer, it is possible to provide a skin cleansing agent which is less tight after use.

(Methoxy methacrylate PEG-23/diisostearate methacrylate) copolymer, as the constituent unit (e), mainly contained in the hydrophobic monomer represented by the above formula (15), R ²⁴ and R ²⁵ are a structural unit (e) derived from a hydrophobic monomer of a 16-methylheptadecanyl group.

Further, the constituent unit (f) mainly contains a hydrophilic monomer represented by the above formula (2), wherein R ⁴ is a methyl group, R ⁵ is an exoethyl group, R ⁶ is a methyl group, and n is 23 A hydrophilic monomer-derived constituent unit (f).

In the present invention, the proportion of the constituent unit (e) of the water-soluble copolymer in the total constituent unit is preferably from 1 to 60% by mass, more preferably from 10 to 50% by mass, and from 20 to 40% by mass.

By setting the ratio of the constituent unit (e) of the water-soluble copolymer to the above range, it is possible to provide a skin cleansing agent which is further reduced in tightness after use.

In the present invention, the proportion of the constituent unit (f) of the water-soluble copolymer in the total constituent unit is preferably 40 to 99% by mass, more preferably 50 to 90% by mass, and 60 to 80% by mass.

By setting the ratio of the constituent unit (f) of the water-soluble copolymer to the above range, it is possible to provide a skin cleansing agent which is further reduced in tightness after use.

In the present invention, the mass ratio of the constituent unit (e) constituting the water-soluble copolymer to the constituent unit (f) is preferably from 1:99 to 60:40, more preferably from 10:90 to 50:50. It is 20:80~40:60.

Further, the molar ratio of the constituent unit (e) constituting the water-soluble copolymer to the constituent unit (f) is preferably 1:99 to 71:29, more preferably 15:85 to 62:38, more preferably 29:71~52:48, especially good is 35:65~45:55.

By setting the mass ratio of the constituent unit (e) and the constituent unit (f) of the water-soluble copolymer to the above range, it is possible to obtain a water-soluble copolymer having a better effect of reducing the feeling of tightness.

In the present invention, the average molecular weight of the water-soluble copolymer is preferably from 20,000 to 110,000, further preferably from 20,000 to 80,000, more preferably from 30,000 to 80,000, further preferably from 40,000 to 70,000, and particularly preferably from 50,000 to 70,000. Further excellent is 57000~66000.

Here, the average molecular weight means a weight average molecular weight in terms of polystyrene measured by GPC.

<2>Skin cleanser [1] dosage form

The skin cleanser refers to a composition containing a cleansing component, and is used for the purpose of washing off dirt of skin such as sebum. As described above, the skin cleansing agent has the effect of washing off the sebum present on the skin, and therefore has a problem of causing a feeling of tightness to the skin after use.

The skin cleansing agent of the present invention is characterized by comprising the above water-soluble copolymer. According to the present invention, the cleansing power originally possessed by the skin cleansing agent is not hindered, or the feeling of tightness of the skin after use can be reduced while improving the cleaning power.

The dosage form of the skin cleansing agent of the present invention is not particularly limited as long as it is a dosage form generally used for a skin cleansing agent. A typical skin cleansing agent is a solid, powdered, creamy, liquid, gel-like skin cleanser or the like, and any of the dosage forms can be applied to the present invention.

The content of the above-mentioned water-soluble copolymer of the skin cleansing agent of the liquid in the form of a cream, a liquid, a gel or the like is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, particularly preferably 1 ~3 mass%.

By setting the content of the water-soluble copolymer to the above range, the cleansing power originally possessed by the skin cleansing agent is not inhibited, and the feeling of tightness of the skin after use can be further reduced.

Skin cleansers can be divided into foaming and use type and non-foaming. The present invention can be applied to any type of skin cleansing agent without impeding the original cleaning power of the skin cleansing agent, and can reduce the tightness of the skin after use.

In the foaming and use-type skin cleansing agent, the content of the water-soluble copolymer is 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 0.8%, from the viewpoint of improving the foaming property. % or more, particularly preferably 1% by mass or more.

Moreover, the content of the water-soluble copolymer is preferably 20% by mass or less from the viewpoint of reducing the stickiness of the skin after use, and further preferably 10% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less.

As a skin cleansing agent which is used for foaming, a creamy skin cleanser is especially mentioned.

In the non-foaming and use-type skin cleansing agent, the content of the water-soluble copolymer is preferably from 0.1 to 10% by mass, and more preferably from 0.5 to 5%, from the viewpoint of improving the ease of stretching to the skin. %, more preferably 0.6 to 3 mass%, and particularly preferably 0.7 to 2 mass%.

A skin cleansing agent which is used as a non-foaming type, particularly a gel-like skin cleanser.

(2) Skin cleanser containing surfactant

A skin cleanser containing a surfactant as a cleansing component, which has a strong cleansing power, and has a problem of strong tightness of the skin after use. Therefore, it is preferred to apply the present invention to a skin cleanser comprising a surfactant.

The surfactant to be used in the skin cleansing agent of the present invention is not particularly limited as long as it is generally used for a skin cleansing agent, and any of an ionic surfactant and a nonionic surfactant can be used.

As the ionic surfactant, any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant can be used.

As the anionic surfactant, for example, a fatty acid soap such as sodium fatty acid, potassium fatty acid or fatty acid triethanolamine, sodium lauryl sulfate which can have a polyoxyethylene group, potassium lauryl sulfate, and the like can be exemplified. An alkyl sulphate salt which may have a polyoxyethylene group such as triethanolamine sulfate, a sodium lauryl phosphate which may have a polyoxyethylene group, a potassium lauryl phosphate, a triethanolamine lauryl phosphate or the like may have a polyoxyethylene group. An alkyl phosphate salt, an alkyl sulfosuccinate salt or the like.

As the anionic surfactant, for example, an alkyltrimethylammonium salt, an alkylpyridinium salt, a distearyldimethylammonium dialkyldimethylammonium salt, or a chlorinated poly(N, N'-dimethyl-3,5-methylene piperidine), alkyl quaternary ammonium salt, alkyl dimethyl benzyl ammonium salt, alkyl isoquinoline salt, dialkyl morpholine salt, POE-alkylamine, alkylamine salt, polyamine fatty acid derivative, pentanol fatty acid derivative, benzyldimethylammonium chloride, benzethonium chloride, and the like.

As the amphoteric surfactant, examples of the amphoteric surfactant include an imidazoline-based amphoteric surfactant and a betaine-based surfactant.

Examples of the nonionic surfactant include glycerin fatty acid ester, polyglycerol fatty acid ester, polyoxyethylene glycerin fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene sorbitan. Fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl phenyl ethers, polyoxyethylene lanolins, lanolin alcohols, beeswax derivatives, polyoxyethylene castor oil, hardened castor oil, polyoxyethylene solids Alcohol ‧ hydrogen sterol, polyoxyethylene alkyl ether, polyoxyethylene polyoxy propylene ether ether, polyoxyethylene fatty acid ester, polyoxyethylene alkyl ether fatty acid ester, polyoxyethylene hardened castor oil fatty acid ester, polyoxyethylene Trimethylolpropane fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene polyoxypropylene block copolymer, organic modified anthrone, and the like.

The content of the surfactant is not particularly limited and may be appropriately set depending on the type of the surfactant.

Hereinafter, the skin cleansing agent containing a form of a fatty acid soap, a form containing a nonionic surfactant, and a gel form will be more specifically described.

(2-1) Skin cleanser containing fatty acid soap

The present invention can reduce the tightness of the skin after use by applying to a skin cleansing agent containing a fatty acid soap without impairing the good foaming property and the foaming quality of the skin cleansing agent.

The form of the skin cleansing agent containing a fatty acid soap may be in the form of a solid, a liquid or a cream, but it is preferably in the form of a liquid or a cream. In particular, a creamy skin cleansing agent which is used for foaming is preferred.

The fatty acid constituting the fatty acid soap is not particularly limited as long as it can be applied to a skin cleansing agent, and may be any of saturated or unsaturated, and preferably has a carbon number of 8 to 24, particularly 10 to 22. Specific examples of preferred examples include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, hydroxystearic acid, hydroxydecenoic acid, coconut fatty acid, and reduced coconut oil. Fatty acids, tallow fatty acids, reduced tallow fatty acids, palm kernel fatty acids, etc. Among these fatty acids, one or two or more selected from the group consisting of myristic acid, palmitic acid, and stearic acid are preferred from the viewpoints of foaming property, safety, and stability, and in particular, myristic acid is used. Three kinds of palmitic acid and stearic acid are preferred. Examples of the alkaline agent for forming the higher fatty acid and the salt include an alkali metal salt such as sodium or potassium, an ammonium salt, a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt, and a 2-amino group. An alkanolamine salt such as 2-methylpropanol or 2-amino-2-methylpropanediol; a basic amino acid salt such as lysine or arginine; and the like.

The content of the fatty acid contained in the skin cleanser is not particularly limited. In the case of a creamy skin cleansing agent, the content of the fatty acid is preferably from 10 to 70% by mass, more preferably from 20 to 60% by mass, and particularly preferably from 30 to 50% by mass.

The ratio of the mass ratio of the water-soluble copolymer to the fatty acid is preferably from 1:500 to 1:2, more preferably from 1:200 to 1:3, from the viewpoint of reducing the feeling of tightness after use of the skin cleansing agent. , especially good for 1:100~1:5.

Further, from the viewpoint of improving the benignness of the foaming property, the ratio of the content of the water-soluble copolymer to the fatty acid is preferably from 1:200 to 1:2, more preferably from 1:100 to 1:5. The ratio of the water-soluble copolymer to the fatty acid is preferably 1:500 to 1:10, from the viewpoint of reducing the stickiness of the skin after use. More preferably 1:200~1:20, especially good is 1:100~1:50.

(2-2) Skin cleanser containing nonionic surfactant

When the present invention is applied to a skin cleansing agent containing a nonionic surfactant, it can also more effectively reduce the feeling of tightness of the skin after use. As the nonionic surfactant, the above may be used without limitation.

In the form of the nonionic surfactant, the content of the water-soluble copolymer is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more, from the viewpoint of reducing the feeling of tightness after use. It is 1% by mass or more.

Moreover, the content of the water-soluble copolymer is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and particularly preferably 3% by mass or more, from the viewpoint of improving the cleaning power. .

The ratio of the mass of the water-soluble copolymer to the nonionic surfactant is preferably from 1:20 to 1:0.5, more preferably from the viewpoint of reducing the feeling of tightness after use of the skin cleansing agent. 10~1:0.7, especially good to be 1:5~1:1.

Further, from the viewpoint of improving the cleaning power, the ratio of the mass of the water-soluble copolymer to the nonionic surfactant is preferably from 1:10 to 1:0.5, more preferably from 1:5 to 1:0.5. More preferably, it is 1:3~1:0.6, and the best is 1:1.5~1:0.7.

Further, in the case of forming a gel-like skin cleansing agent containing a nonionic surfactant, the water-soluble copolymer and the nonionic surfactant are used from the viewpoint of improving the ease of stretching to the skin at the time of use. The ratio of mass to mass is preferably from 1:15 to 1:0.7, more preferably from 1:10 to 1:1, and particularly preferably from 1:7 to 1:3.

[3] Other

In the skin cleansing agent of the present invention, in addition to the above components, any component which is usually used for the external preparation for skin may be contained. As such an optional component, for example, Australian walnut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower seed oil, cottonseed oil, jojoba oil, coconut oil, palm oil , liquid lanolin, hardened coconut oil, hardened oil, wood wax, hardened castor oil, beeswax, candelilla wax, carnauba wax, insect wax, lanolin, reduced lanolin, hard lanolin, jojoba wax, etc. Oil, wax; mobile paraffin, squalane, different Hydrocarbons such as octadecane, ceresin, paraffin, mineral wax, petrolatum, microcrystalline wax, etc.; oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, ten Higher fatty acids such as monoenoic acid; higher alcohols such as cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, octyldodecanol, myristyl alcohol, cetearyl alcohol; isooctanoic acid Cetyl ester, isopropyl myristate, hexadecyl isostearate, cetyl lactate, diisostearyl malate, ethylene di-2-ethylhexanoate, neopentyl diacetate Alcohol, bis-2-heptyldecanoic acid glycerol ester, tris-2-ethylhexanoic acid glycerol ester, trimethylolpropane tris-2-ethylhexanoate, trimethylolpropane tri Chains of synthetic ester oils such as isostearate, pentaerythritol tetra-2-ethylhexanoate, dimethyl polyoxane, methylphenyl polyoxyalkylene, diphenyl polyoxyalkylene, etc. Polycyclic oxane, octamethylcyclotetraoxane, decamethylcyclopentaoxane, dodecamethylcyclohexane decane, etc.; amine-modified polyoxyl Alkane, polyether modified polyoxyalkylene, alkyl modified polyoxyalkylene, fluorine reform An oil agent such as a fluorenone oil such as a polysiloxane or a modified polyoxane; polyethylene glycol, glycerin, 1,3-butanediol, erythritol, sorbitol, wood Sugar alcohol, maltitol, propylene glycol, dipropylene glycol, diglycerol, isoprene, 1,2-pentanediol, 2,4-hexanediol, 1,2-hexanediol, 1,2-octane Polyols such as diols; moisturizing classification of sodium pyrrolidonecarboxylate, lactic acid, sodium lactate, etc.; mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, phthalic anhydride (2) which can be treated on the surface矽), aluminum oxide, barium sulfate and other powders, iron-dan, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine blue, indigo, titanium oxide, zinc oxide inorganic pigments that can be treated on the surface; Surface treatment of mica titanium, surimi foil, bismuth oxychloride and the like; pearlescent red color 202, red 228 No., red 226, yellow 4, blue 404, yellow 5, red 505, red 230, red 223, orange 201, red 213, yellow 204, yellow 203, blue 1 Organic pigments such as No., Green No. 201, Purple No. 201, Red No. 204; organic powders such as polymethyl methacrylate, nylon powder, and organic polyoxyalkylene elastomer; and p-aminobenzoic acid Ultraviolet absorber; o-amine benzoic acid ultraviolet absorber; salicylic acid ultraviolet absorber, cinnamic acid ultraviolet absorber, benzophenone ultraviolet absorber; sugar ultraviolet absorber, 2-(2'-hydroxyl Ultraviolet absorbers such as -5'-t-butyloctylphenyl)benzotriazole, 4-methoxy-4'-t-butyldibenzopyranylmethane; ethanol, isopropanol, etc. Lower alcohols; vitamin A or its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 or its derivatives, vitamin B12, vitamin B15 or its derivatives Class B; Vitamins such as α-tocopherol, β-tocopherol, γ-tocopherol, and vitamin E acetate Vitamins such as E, vitamin D, vitamin H, pantothenic acid, pantethine, pyrroloquinoline, etc.; antibacterial agents such as phenoxyethanol.

The skin cleansing agent of the present invention can be produced by treating each of the above components in accordance with a conventional method.

The invention is preferably applied to facial cleansers. According to the present invention, it is possible to provide a facial cleanser which does not easily feel the tightness of the skin after washing.

The sunscreen cosmetic of the present invention which solves the fifth problem is characterized in that the four components of the above [1] to [4] are contained as essential components. The details of the components [1] to [4] are detailed below.

<1>Component (A)...Water-soluble copolymer [1] Hydrophobic monomer

The component (A) is a structural unit derived from the hydrophobic monomer represented by the above formula (1), (7) or (8) (hereinafter sometimes simply referred to as "constituting unit (7)"). One or two or more water-soluble copolymers contained as essential constituent units.

In the present invention, the "composition unit derived from a monomer" means a constituent unit formed by cleavage of a carbon-carbon unsaturated bond of a corresponding monomer by a polymerization reaction.

The hydrophobic monomer represented by the formula (1), (7) or (8) will be described below.

(1-1) a hydrophobic monomer represented by the formula (7)

In the above formula (7), R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁵ represents a branched hydrocarbon group having a ring structure of 13 to 30 or a ring structure having no ring structure; More than one branch of a hydrocarbon group having 6 to 12 carbon atoms.

Here, examples of the alkyl group represented by R ^{14 include} a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group. In the present invention, R ¹⁴ is preferably a hydrogen atom or a methyl group.

Further, examples of the branched hydrocarbon group having a ring structure of 13 to 30 carbon atoms represented by R ¹⁵ include 1-methyldodecyl group, 11-methyldodecyl group, 3-ethylundecyl group, and 3 -ethyl-4,5,6-trimethyloctyl, 1-methyltridecyl, 1-hexyloctyl, 2-butyldecyl, 2-hexyloctyl, 4-ethyl-1- Isobutyloctyl, 1-methylpentadecyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 16-methylheptyl, 9-methylheptyl, 7-Methyl-2-(3-methylhexyl)indenyl, 3,7,11,15-tetra-methylhexadecyl, 2-octyldodecyl, 2-decyltetradecyl, 2 - Twelve bases and sixteen bases.

Further, as the hydrocarbon group having 6 to 12 carbon atoms having two or more branches and having no ring structure represented by R ¹⁵ , 2,2-dimethylbutyl group and 2,3-dimethylbutyl group can be exemplified. 3,3-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1-dimethylpentyl, 1-isopropylbutyl, 1-isopropyl-2-methylpropyl, 1,1-diethylpropyl, 1-ethyl-1-isopropylpropyl, 2-ethyl-4-methylpentyl, 1- Propyl-2,2-dimethylpropyl, 1,1,2-trimethyl-pentyl, 1-isopropyl-3-methylbutyl, 1,2-dimethyl-1-B Butyl, 1,3-dimethyl-1-ethylbutyl, 1-ethyl-1-isopropyl-propyl, 1,1-dimethylhexyl, 1-methyl-1-B Pentyl, 1-methyl-1-propylbutyl, 1,4-dimethylhexyl, 1-ethyl-3-methylpentyl, 1,5-dimethylhexyl, 1-ethyl -6-methylheptyl, 1,1,3,3-tetramethylbutyl, 1,2-dimethyl-1-isopropylpropyl, 3-methyl-1-(2,2- Dimethylethyl)butyl, 1-isopropylhexyl, 3,5,5-trimethylhexyl, 2-isopropyl-5-methylhexyl, 1,5-dimethyl-1-B Hexyl, 3,7-dimethyloctyl, 2,4,5-trimethylheptyl, 2,4,6-trimethylheptyl, 3,5-dimethyl 1-(2,2-dimethylethyl)hexyl and the like.

(1-2) a hydrophobic monomer represented by the formula (1) or (8)

In the above formulae (1) and (8), R ¹ and R ^{16 each} represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² , R ³ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different. And represents a fluorenyl group having 6 to 22 carbon atoms having a branch having no ring structure. X represents a group from which an OH group is desorbed from a triol.

Here, examples of the alkyl group represented by R ¹ and R ^{16 include} a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group. In the present invention, R ¹ is preferably hydrogen or a methyl group.

Further, as the fluorenyl group having a branched carbon number of 6 to 22 which does not contain a ring structure represented by R ² , R ³ , R ¹⁷ , R ¹⁸ or R ¹⁹ , 2-methylpentanyl group and 3-methyl group are exemplified. Pentylmethyl, 4-methylpentyl, 2-ethylbutyryl, 2-ethylbutyryl, 2,2-dimethylbutenyl, 3,3-dimethylbutenyl, 2-methylhexyl , 4-methylhexyl, 5-methylhexyl, 2,2-dimethylpentenyl, 4,4-dimethylpentenyl, 2-methylheptyl, 2-B Hexyl, 2-propylpentyl, 2,2-dimethylhexyl, 2,2,3-trimethylpentanyl, 2-methyloctyl, 3,3,5-trimethyl Hexyl, 2-methylindenyl, 4-methylindenyl, 8-methylindenyl, 4-ethyloctyl, 2-ethyloctyl, 2-butylhexyl, 2- Tertiary butylhexyl, 2,2-diethylhexyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methylindenyl, 2-methyl-2-ethyloctyl, 2-methylundecyl, 10-methylundecyl, 2,2-dimethylindenyl, 2-ethylindenyl, 2- Butyl octyl, diethyl octyl, 2-tert-butyl-2,2,4-trimethylpentanyl, 10 -methyldodecyl, 3-methyldodedecyl, 4-methyldodedecyl, 11-methyldodedecyl, 10-ethylundecyl, 12-methyltride Indenyl, 2-butylindenyl, 2-hexyloctyl, 2-butyl-2-ethyloctyl, 12-methyltetradecyl, 14-methylpentadecyl, 2-butyl Dimercapto, 2-hexyldecyl, 16-methylheptadecanyl, 2,2-dimethylhexyl, 2-butylhexadecanyl, 2-hexyldodedecyl, 2, 4,10,14-tetramethylpentanyl, 18-methylundecyl, 3,7,11,15-tetra-methylhexadecanyl, 19-methylindolyl, and the like.

Further, in a preferred embodiment of the present invention, in the general formulae (1) and (8), R ² , R ³ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different and have no ring structure. The fluorenyl group having a branched carbon number of 10 to 22 or a fluorenyl group having 6 to 9 carbon atoms having two or more branches without a ring structure.

As a thiol group having a branched carbon number of 10 to 22 which does not contain a ring structure represented by R ² , R ³ , R ¹⁷ , R ¹⁸ or R ¹⁹ in such a preferred embodiment, 2-methyl fluorene is exemplified. , 4-methylindenyl, 8-methylindenyl, 4-ethyloctyl, 2-ethyloctyl, 2-butylhexyl, 2-tert-butylhexyl, 2, 2-Diethylhexyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methylindenyl, 2-methyl-2-ethyloctyl , 2-methylundecyl, 10-methylundecyl, 2,2-dimethylindenyl, 2-ethylindenyl, 2-butyloctyl, diethyloctyl, 2 - tert-butyl-2,2,4-trimethylpentanyl, 10-methyldodepinyl, 3-methyldodepinyl, 4-methyldodedecyl, 11-methyl Twelve indenyl, 10-ethylundecyl, 12-methyltridecyl, 2-butylindenyl, 2-hexyloctyl, 2-butyl-2-ethyloctyl, 12-A Tetradedyl, 14-methylpentadecanyl, 2-butyldodecanyl, 2-hexyldecyl, 16-methylheptadecanyl, 2,2-dimethylhexanyl 2-butylhexadecanyl, 2-hexyldodefluorene , 2,4,10,14-tetramethylpentanyl, 18-methylundecyl, 3,7,11,15-tetra-methylhexadecanyl, 19-methylindolyl Wait.

Further, as a preferred embodiment, R ² , R ³ , R ¹⁷ , R ¹⁸ and R ¹⁹ having a ring structure and having two or more branches having 6 to 9 carbon atoms can be exemplified as 2 , 2-dimethylbutyryl, 3,3-dimethylbutyryl, 2,2-dimethylpentanyl, 4,4-dimethylpentenyl, 2,2-dimethylhexyl, 2,2,3-trimethylpentanyl, 3,5,5-trimethylhexyl, and the like.

In the formula (1), the group derived from the triol represented by X is not particularly limited as long as it is a group from which an OH group is desorbed from the triol. A group derived from a ternary alcohol selected from the group consisting of glycerin, trimethylolpropane, and trimethylolethane, which desorbs an OH group, is suitably exemplified.

Further, in the general formula (8), the group derived from the tetrahydric alcohol represented by Y is not particularly limited as long as it is a group from which an OH group is desorbed from the tetrahydric alcohol, and may be suitably selected from the group consisting of dipropylene-containing The tetrahydric alcohol of the group of alcohol, pentaerythritol, erythritol, D-threitol, and L-threitol desorbs the group of the OH group.

In the present invention, it is particularly preferable to use a water-soluble copolymer comprising the constituent unit (1).

Further, in a further preferred embodiment of the present invention, the hydrophobic monomer represented by the formula (1) is a hydrophobic monomer represented by the above formula (15).

R ²⁴ and R ^{25 in the} formula (15) are preferably a fluorenyl group having 10 to 22 carbon atoms which have no branch structure and have a branched structure.

The fluorenyl group of R ²⁴ and R ^{25 in} the formula (15) has a carbon number of 12 to 22, more preferably 14 to 20, particularly preferably 16 to 20.

Further, the carbon number of the main chain of the fluorenyl group of R ²⁴ and R ^{25 in} the formula (15) is preferably 9 to 21, more preferably 12 to 20, particularly preferably 16 to 18.

Further, the number of branches of the fluorenyl group of R ²⁴ and R ^{25 in} the formula (15) is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.

Further, in the fluorenyl group of R ²⁴ and R ²⁵ of the formula (15), the position number of the carbon of the main chain of the branched chain bond is preferably as large as possible. Specifically, the branched chain is preferably bonded to the first to third carbons at the end of the autonomous chain, more preferably the first or second carbon, and particularly preferably the first carbon.

Specific examples of R ²⁴ and R ²⁵ include 10-methylundecyl group, 10-methyldodedecyl group, 11-methyldodedecyl group, and 10-ethylundecyl group. 12-methyltridecyl, 12-methyltetradecyl, 14-methylpentadecanyl, 16-methylheptadecanyl, 2,4,10,14-tetramethylpentanyl , 18-methyl 19-mercapto, 3,7,11,15-tetra-methylhexadecanyl, 19-methylindolyl, and the like.

In the general formula (15), the triol-derived group represented by Z is not particularly limited as long as it is a group from which an OH group is desorbed from a triol, and may be appropriately selected from the group consisting of glycerol and tris. The triol of the group of methylolpropane and trimethylolethane desorbs the group of the OH group.

[2] Hydrophilic monomer

As the hydrophilic monomer of the water-soluble copolymer constituting the component (A), a polymerizable carboxylic acid, and a compound represented by the above formula (2) and the above formula (9), (10) and (11) can be used. .

(2-1) Polymeric carboxylic acid,

In the present invention, specific examples of the polymerizable carboxylic acid or a salt thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, and sodium, potassium, ammonium, and amine salts thereof. . Among these, acrylic acid, methacrylic acid, and a salt thereof are particularly preferable from the viewpoint of high polymerizability. When the water-soluble copolymer of the present invention is introduced into a constituent unit derived from a polymerizable carboxylate, the polymerizable carboxylic acid may be previously prepared as a salt to carry out a polymerization reaction, or may be derived from a self-polymerizable carboxylic acid by a polymerization reaction. The constituent unit is derived from a water-soluble copolymer and then neutralized with a base to form a salt.

(2-2) a hydrophilic monomer represented by the formula (2)

In the above formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵ represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R ⁶ represents a hydrogen atom and a carbon number of 6~. An aromatic hydrocarbon group of 10, an aliphatic hydrocarbon group having 1 to 14 carbon atoms or a fluorenyl group having 1 to 12 carbon atoms. n represents an integer from 6 to 40.

The alkyl group represented by R ⁴ in the above formula (2) may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group or a cyclopropyl group. In the present invention, R ⁴ is preferably a hydrogen atom or a methyl group.

Further, examples of the alkylene group represented by R ^{5 include} an exoethyl group, a propyl group, an exo-propyl group, a 2-hydroxyl-propyl group, a 2-hydroxy-2-methyl-extended ethyl group, and a 2-hydroxy group. 1-methyl-ethyl or the like, among these, preferably an ethyl group or a propyl group, more preferably an ethyl group.

Further, in the group represented by R ⁶ , examples of the aromatic group having 6 to 10 carbon atoms include a phenyl group, a benzyl group, a tolyl group, and an ethylphenyl group; and the aliphatic hydrocarbon group having 1 to 14 carbon atoms may be used. Methyl, ethyl, butyl, tert-butyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, lauryl, etc. are suitably exemplified; as the fluorenyl group having 1 to 12 carbon atoms, a fluorenyl group can be suitably exemplified. , ethyl sulfhydryl, propyl sulfonyl, butyl sulfhydryl, isobutyl sulfhydryl, pentamidine, laurel. Among these, the group represented by R ^{5 is} preferably an aliphatic hydrocarbon group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms.

Further, n of the general formula (2) is a numerical range of 6 to 40.

Among the monomers represented by the above formula (2), examples of the monomer in which R ⁵ is a propyl group include polypropylene glycol (9) monoacrylate, polypropylene glycol (13) monoacrylate, and polycondensation. Propylene glycol (9) monomethacrylate, polypropylene glycol (13) monomethacrylate, and the like. Furthermore, the number in parentheses represents N. Most of these polymers are commercially available. Specific examples of such commercially available products include "Blenmer" AP-400, AP-550, AP-800, PP-500, and PP-800 (all manufactured by Nippon Oil & Fats Co., Ltd.).

Among the monomers represented by the above formula (2), examples of the monomer in which R ⁵ is an ethyl group extend include polyethylene glycol (10) monoacrylate and polyethylene glycol (8). Methacrylate, polyethylene glycol (23) monoacrylate, polyethylene glycol (23) monomethacrylate, methoxy polyethylene glycol (9) acrylate, methoxy polyethylene glycol ( 9) methacrylate, methoxy polyethylene glycol (23) methacrylate, oleyl polyethylene glycol (18) methacrylate, lauryloxy polyethylene glycol (18) acrylate, Laurel oxime polyethylene glycol (10) methacrylate, stearyloxy polyethylene glycol (30) monomethacrylate, and the like.

The above hydrophilic monomer can be obtained in a high yield by esterification reaction of a corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with a chloride or anhydride of acrylic acid or methacrylic acid. Moreover, since many commercial products already exist, this commercial item can also be utilized. Specific examples of such commercially available products include Blenmer, AE-400, PE-350, AME-400, PME-400, PME-1000, ALE-800, and PSE-1300 (all of which are Japanese fats and oils). ))).

(2-3) a hydrophilic monomer represented by the formula (9)

As the hydrophilic monomer of the present invention, a hydrophilic monomer represented by the above formula (9) can also be used.

Specific examples of the hydrophilic monomer represented by the above formula (9) include 2-acryloxyethylphosphocholine (APC) and 2-methylpropenyloxyethylphosphocholine ( MPC). These monomers can be synthesized, for example, by the following methods described in Polymer Journal, Vol. 22, No. 5.

<Synthesis method>

The 2-bromoethylphosphonium dichloride is reacted with 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate to obtain 2-methylpropenyloxyethyl-2'-bromoethylphosphoric acid or 2- After propylene oxiranylethyl-2'-bromoethylphosphoric acid, the compounds are reacted with triethylamine in methanol.

(2-4) a hydrophilic monomer represented by the formula (10)

As the hydrophilic monomer of the present invention, a hydrophilic monomer represented by the above formula (10) can also be used.

In the hydrophilic monomer represented by the formula (10), the reducing sugar which is a group in which hydrogen is removed from the hydroxyl group at the 1-position of the self-reducing sugar represented by GO- is specifically selected from the group consisting of glucose and mannose. a monosaccharide such as sugar, galactose, arabinose, xylose or ribose, a disaccharide such as maltose, lactose or cellobiose, a trisaccharide such as maltotriose or a group of oligosaccharides such as malto-oligosaccharide One or two or more kinds of them are preferably selected from one or more selected from the group consisting of glucose, galactose, arabinose, xylose, ribose, maltose, lactose, and cellobiose, and glucose is particularly preferred. Further, as the monomer represented by the formula (10), glucosyloxyethyl methacrylate (hereinafter abbreviated as GEMA) or glucosyloxyethyl acrylate (hereinafter abbreviated as GEA) is preferred.

(2-5) a hydrophilic monomer represented by the formula (11)

As the hydrophilic monomer of the present invention, a hydrophilic monomer represented by the above formula (11) can also be used.

In the monomer of the formula (11), the amino acid which is an amino acid residue represented by R ²³ is not particularly limited as long as it is a generally known amino acid, and specifically, glycine can be exemplified. Acid, alanine, glutamic acid, lysine, arginine, and the like. Among these, since the skin barrier of the obtained water-soluble copolymer has a good recovery effect, it is particularly preferable to be an amino acid residue.

Further, the polyamine of the polyamine residue represented by R ²³ means an amine having two or more amine groups which may be substituted by an alkyl group in the same molecule, and specific examples thereof include a diamine, a triamine, a tetraamine or An amine in which the hydrogen atom of the amine group is substituted with an alkyl group. Among these, diamine is preferred from the viewpoint of the excellent use feeling of the skin external preparation containing the obtained water-soluble copolymer, and a particularly preferable specific example can be obtained from the viewpoint of easiness of raw materials at the time of synthesis. Ethylenediamine, 1,4-diamino-n-butane, 1,6-diamino-n-hexane, etc. are mentioned.

Further, the amine alcohol as the amine alcohol residue represented by R ²³ means a compound having an amino group which may be substituted with an alkyl group and an alcoholic hydroxyl group in the same molecule. The amine alcohol is not particularly limited as long as it is generally known, and specific examples thereof include ethanolamine and triethylaminoethanol.

The salt of the monomer represented by the formula (11) is not particularly limited, and specific examples thereof include a sodium salt, a potassium salt, an ammonium salt, an amine salt, etc., in which an acid moiety is neutralized with a base, or an amine group. Partially acid-neutralized hydrochloride, sulfate, nitrate, phosphate, citrate, oxalate, carbonate, and the like. When the water-soluble copolymer of the present invention is introduced into a constituent unit derived from the monomer salt represented by the formula (11), the monomer represented by the formula (11) can be previously prepared into a salt to carry out a polymerization reaction. The constituent unit derived from the monomer represented by the formula (11) is derivatized into a water-soluble copolymer by a polymerization reaction, and then neutralized to prepare a salt.

The monomer represented by the formula (11), and specific examples of the salt thereof, the compounds 1 to 11 and salts thereof can be appropriately exemplified.

The hydrophilic monomer represented by the formula (11), for example, as shown in the above reaction formulas (1) and (2), can be esterified by using (meth)acrylic acid or (meth)acrylofluorene chloride. Synthesis by hydrazylation reaction.

As described above, in the present invention, the above-described general formulae (2), (9), (10), and (11) can be used as the hydrophilic polymer.

In a preferred embodiment of the present invention, the water-soluble copolymer comprises the structural unit (2) derived from the above formula (2).

[3] Water-soluble copolymer

In the present invention, a water-soluble copolymer having a constituent unit (1) and a constituent unit (2) can be suitably used. Further, a water-soluble copolymer having a constituent unit (15) and a constituent unit (2) can be preferably used.

Among such water-soluble copolymers, a copolymer of (methoxy methacrylate PEG-23/diisostearate methacrylate) can be preferably used.

By containing such a water-soluble copolymer, it is possible to obtain an emulsified composition which is low in irritation, has less stickiness, and has excellent emulsion stability.

(Methoxy methacrylate PEG-23/diisostearate methacrylate) copolymer, as a constituent unit (g), mainly contained in the hydrophobic monomer represented by the above formula (15), R ²⁴ and R ²⁵ are a structural unit (g) derived from a hydrophobic monomer of 16-methylheptadecanyl group.

Further, the constituent unit (h) mainly contains a hydrophilic monomer represented by the above formula (2), wherein R ⁴ is a methyl group, R ⁵ is an exoethyl group, R ⁶ is a methyl group, and n is 23 A hydrophilic monomer-derived constituent unit (h).

In the present invention, the proportion of the constituent unit (g) of the water-soluble copolymer in the total constituent unit is preferably from 1 to 50% by mass, more preferably from 5 to 40% by mass, and from 10 to 30% by mass.

By setting the ratio of the constituent unit (g) of the water-soluble copolymer to the above range, it is possible to provide a sunscreen cosmetic which is excellent in moisturizing feeling and further reduced in stickiness.

In the present invention, the proportion of the constituent unit (h) of the water-soluble copolymer in the total constituent unit is preferably from 50 to 99% by mass, more preferably from 60 to 95% by mass, and from 70 to 90% by mass.

By setting the ratio of the constituent unit (h) of the water-soluble copolymer to the above range, it is possible to provide a sunscreen cosmetic which is excellent in moisturizing feeling and further reduced in stickiness.

In the present invention, the mass ratio of the constituent unit (g) constituting the water-soluble copolymer to the constituent unit (h) is preferably 5:95 to 50:50, further preferably 10:90 to 45:55, more preferably Good for 20:80~40:60, especially good for 25:75~35:65.

Further, the molar ratio of the constituent unit (g) constituting the water-soluble copolymer to the constituent unit (h) is preferably from 8:92 to 62:38, more preferably from 15:85 to 57:43, more preferably 29:71~52:48, especially good for 35:65~46:54.

By setting the mass ratio of the constituent unit (g) and the constituent unit (h) of the water-soluble copolymer to the above range, the feeling of use of the sunscreen cosmetic can be further enhanced.

In the present invention, the average molecular weight of the water-soluble copolymer is preferably from 20,000 to 110,000, further preferably from 20,000 to 80,000, more preferably from 30,000 to 80,000, further preferably from 40,000 to 70,000, and particularly preferably from 50,000 to 70,000. Further excellent is 57000~66000.

The content of the water-soluble copolymer is not particularly limited, but is usually 0.001 to 15% by mass, preferably 0.01 to 10% by mass.

<2>Ingredient (B)...polyglycerol fatty acid ester

The sunscreen cosmetic of the present invention is characterized in that a polyglycerol fatty acid ester obtained by condensing one molecule of polyglycerol having a degree of polymerization of 10 and a molecule of 2 to 5 carbon atoms having a carbon number of 16 or more is used as the component (B).

The polyglycerol fatty acid ester constituting the component (B) has a carbon number of 16 or more and may have a branched chain, and may be saturated or unsaturated.

In particular, oleic acid and isostearic acid are exemplified.

Further, the number of molecules of the fatty acid bonded to the polyglycol 1 molecule may be 2 to 5, preferably 5 molecules.

In the present invention, polyglyceryl pentastearate-10 is particularly used as the component (B).

The content of the polyglycerol fatty acid ester of the component (B) can be usually 0.1 to 10% by mass.

In addition, the content of the component (B) is 0.3% by mass or more, more preferably 0.5% by mass, and particularly preferably 0.7% by mass or more from the viewpoint of the improvement of the emulsification stability.

In addition, the content of the component (B) is preferably 7% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less from the viewpoint of suppression of the feeling of stickiness.

<3>Ingredient (C)...ionic surfactant

The sunscreen cosmetic of the present invention contains an ionic surfactant as the component (C). As an ionic surfactant, as long as The cosmetic device is not particularly limited, and any of an anionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used.

The anionic surfactant may, for example, be a fatty acid soap such as fatty acid sodium, fatty acid potassium or fatty acid triethanolamine, sodium lauryl sulfate which may have a polyoxyethylene group, potassium lauryl sulfate or triethanolamine lauryl sulfate. An alkyl oxysulfate salt of a polyoxyethylene group, a decyl lactate, a sodium lauryl phosphate which may have a polyoxyethylene group, a potassium lauryl phosphate, a triethanolamine laurylamine or the like which may have a polyoxyethylene group. Phosphate salt, alkyl sulfosuccinate salt, and the like.

As the cationic surfactant, for example, an alkyltrimethylammonium salt, an alkylpyridinium salt, a distearyldimethylammonium dialkyldimethylammonium chloride, or a chlorinated poly(N, N'-dimethyl-3,5-methylene piperidine), alkyl quaternary ammonium salt, alkyl dimethyl benzyl ammonium salt, alkyl isoquinoline salt, dialkyl morpholine salt, POE-alkylamine, alkylamine salt, polyamine fatty acid derivative, pentanol fatty acid derivative, benzyldimethylammonium chloride, benzethonium chloride, and the like.

As the amphoteric surfactant, examples of the amphoteric surfactant include an imidazoline-based amphoteric surfactant and a betaine-based surfactant.

Among the above surfactants, an anionic surfactant is preferably used as the component (C), and a thiol lactate is preferably used.

As the thiol lactate, a sodium salt is preferable, and specifically, sodium lauryl lactate, sodium isostearyl succinate, sodium stearyl succinate, and the like are exemplified.

The content of the ionic surfactant is not particularly limited, but is usually 0.01 to 2.0% by mass, and more preferably 0.1 to 1% by mass.

In addition, the content of the ionic surfactant is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, and particularly preferably 0.1% by mass or more from the viewpoint of the improvement of the emulsification stability.

In addition, the content of the ionic surfactant is preferably 1.5% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less from the viewpoint of suppression of stickiness.

<4>Ingredient (D)...UV scattering agent and/or UV absorber

The sunscreen cosmetic of the present invention contains a UV scattering agent and/or an ultraviolet absorber as the component (D).

The ultraviolet ray scattering agent refers to a particulate metal oxide having an action of scattering ultraviolet rays, and the type thereof is not particularly limited as long as it is blendable with an emulsified cosmetic. Examples of the metal oxide include titanium oxide, zinc oxide, zirconium oxide, and cerium oxide.

The content of the ultraviolet ray scattering agent is not particularly limited, but is usually 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and particularly preferably 1 to 10% by mass.

The ultraviolet ray scattering agent is a particle diameter having a particle diameter in the technical field. For example, the primary particle diameter is observed by an electron microscope, and is usually 5 nm or more, preferably 10 nm or more, and usually 100 nm or less, preferably 80 nm. The following.

The ultraviolet light scattering agent used in the present invention preferably contains at least one selected from the group consisting of fine particle titanium oxide and fine particle zinc oxide from the viewpoint of excellent ultraviolet light scattering effect.

The ultraviolet light scattering agent used in the present invention can be produced by a usual method such as thermal decomposition of the metal salt in the gas phase. However, since many commercially available products are also available, commercially available products can be used as they are. Specific examples of such a commercially available product include "MTY-110M3S" (manufactured by Tayca Co., Ltd.), "MTY-02" (manufactured by Tayca Co., Ltd.), and "MT-100TV" (Tayca). (share) system, "MT-500HSA" (Tayca (share) system), "MT-100T" (Tayca (share) system), "MT-01" (Tayca (share) system), "MT-10EX" (Tayca), MT-05 (Tayca), MT-100Z (Tayca), MT-150EX (Tayca), MT- 100AQ" (Tayca), "MT-100WP" (Tayca), "MT-100SA" (Tayca), "MT-500B" (Tayca) MT-500SA" (Tayca), "MT-600B" (Tayca), "MT-500SAS" (Tayca), "TIPAQUE CR-50" (Ishihara Industry Co., Ltd.) System, "TIPAQUE TTO-M-1" (Ishihara Industry Co., Ltd.), "TIPAQUE TTO-V4" (Ishihara Industry Co., Ltd.), "ST-455" (Titan Kogyo Co., Ltd.), " STT-65C-S" (made by Titan Kogyo Co., Ltd.), "STT-30EHS" (made by Titan Kogyo Co., Ltd.), "Bayer Titan R-KB-1" (made by Bayer).

In addition, "MZ-300" (manufactured by Tayca Co., Ltd.), "MZY-303S" (manufactured by Tayca Co., Ltd.), "MZ-306X" (manufactured by Tayca Co., Ltd.), " MZ-500" (Tayca), "MZY-505S" (Tayca), "MZ-506X" (Tayca), and "MZ-510HPSX" (Tayca) "WSX-MZ-700" (Tayca), "SAMT-UFZO-450" (Sanko Kasei Co., Ltd.), "SAMT-UFZO-500" (Sanko Kasei Co., Ltd.), "FZO" -50" (stone "Original industry (stock) system), "Maxlight ZS-032" (Showa Denko (share) system), "Maxlight ZS-032" (Showa Denko (share) system).

In the present invention, the ultraviolet ray scattering agent is preferably coated with an inorganic compound such as cerium oxide or aluminum oxide or an organic compound such as sodium polyacrylate, fatty acid metal soap or fluorenone.

The ultraviolet scattering agent is preferably water-dispersible. Since the water-dispersible ultraviolet scattering agent is uniformly dispersed in the aqueous phase, the sunscreen cosmetic of the present invention in such a form has excellent ultraviolet defense function.

As the water-dispersible ultraviolet ray scattering agent, an ultraviolet ray scattering agent whose surface is coated with a hydrophilic compound can be exemplified.

As such a water-dispersible ultraviolet scattering agent, an ultraviolet scattering agent which is surface-treated with sodium polyacrylate is preferred. The sunscreen cosmetic of the present invention comprising the ultraviolet scattering agent surface-treated with sodium polyacrylate as the component (D) is excellent in dispersibility and excellent in ultraviolet defense function.

The ultraviolet absorber is not particularly limited as long as it is a UV absorber which can be blended in a general emulsion type cosmetic, but contains UV-A which absorbs ultraviolet rays having a wavelength of 320 to 400 nm (A region) in order to absorb ultraviolet rays having a wide wavelength. An absorbent and a UV-B absorber which absorbs ultraviolet rays having a wavelength of 290 to 320 nm (B region) are preferred.

The content of the ultraviolet absorber is not particularly limited, but is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, and usually 20% by mass or less, preferably 15% by mass or less. More preferably, it is 10% by mass or less.

As the UV-A absorber, 2-hydroxy-4-methoxybenzophenone, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, dimethoxybenzylidene can be exemplified. Bilateral oxyimidazopyridine propionic acid 2-ethylhexyl ester, bis(resoric acid) three A compound such as methylenebisbenzotriazolyl tetramethylbutanol, diethylaminohydroxybenzhydrylbenzoic acid hexyl ester or tert-butylmethoxydibenzoylmethane methane. Among them, from the viewpoint of good ultraviolet absorption energy, ethyl hexyl hydroxybenzimidyl benzoate and tributyl butyl benzomethanyl methane are particularly preferable. Since there are commercially available products among these compounds, commercially available products can be used as they are. As a specific commercial item, "Uvinul A Plus Granular" (manufactured by BASF Corporation, diethyl hydroxybenzhydrylbenzoate) and "Parsol 1789" (third butyl methoxybenzhydrylmethane DSM) can be exemplified. Company system).

The content of the UV-A absorbent is usually 0.01% by mass or more, preferably 0.1% by mass or more, and usually 5% by mass or less, preferably 3% by mass or less.

Specific examples of the UV-B absorber include 2-ethylhexyl p-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and polydimethylene. Oxane diethyl benzylidene malonate, 2,4,6-triphenylamino-p-(carbon-2'-ethylhexyl-1'-oxy)-1,3,5- three a compound of 2-hydroxy-4-methoxybenzophenone, salicylic acid menthyl ester, octyl salicylate or the like. Since there are commercially available products among these compounds, commercially available products can be used as they are. As a specific commercial item, "Uvinul MC80" (manufactured by 2-ethylhexyl methoxycinnamate BASF) and "Uvinul T150" (2,4,6-triphenylamino-p-(carbon) can be exemplified. -2'-ethylhexyl-1'-oxy)-1,3,5-three "BASF"), "Uvinul M40" (2-hydroxy-4-methoxybenzophenone BASF), "Parsol SLX" (dimethyl siloxane) "Parsol 340" (manufactured by DSM, 2-cyano-3,3-diphenylacrylate) and "Parsol HMS" (manufactured by Salicylic Acid Menthate DSM) "Parsol HMS" (manufactured by octyl salicylate DSM).

The content of the UV-B absorbent is usually 0.1% by mass or more, preferably 0.5% by mass or more, and usually 10% by mass or less, preferably 7% by mass or less.

<5>Other components

The components contained in the oil phase and the aqueous phase are not particularly limited.

Examples of the oil agent constituting the oil phase include liquid fats and oils, solid fats and oils, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, and fluorenone oils.

Examples of the liquid fats and oils include avocado oil, camellia oil, sea turtle oil, Australian walnut oil, corn oil, oyster sauce, olive oil, rapeseed oil, egg butter, sesame oil, apricot kernel oil, wheat germ oil, and camellia. Oil, castor oil, linseed oil, safflower seed oil, cottonseed oil, perilla oil, white mango seed oil, soybean oil, peanut oil, bitter tea oil, Japanese eucalyptus seed oil, rice bran oil, octopus tung oil, Japanese tung oil, lotus Jojoba oil, germ oil, triglycerol, tricaprylic glycerol, triisopalmitic acid glycerol, and the like.

Examples of the solid fats and oils include cocoa butter, coconut oil, horse fat, hardened coconut oil, palm oil, tallow, sheep fat, hardened tallow, palm kernel oil, lard, beef bone fat, wood wax oil, and hardened oil. Beef foot oil, wood wax, hardened castor oil, etc.

Examples of the wax include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, insect wax, cetyl wax, montan wax, wax, lanolin, kapok wax, lanolin acetate, and liquid. Lanolin, sugar cane wax, Lanolin fatty acid isopropyl ester, hexyl laurate, reduced lanolin, jojoba wax, hard lanolin, shellac wax, POE lanolin ether, POE lanolin acetate, POE cholesterol ether, lanolin fatty acid Polyethylene glycol, POE hydrogenated lanolin ether, and the like.

Examples of the hydrocarbon oil include flowing paraffin, ceresin, isooctadecane, paraffin, mineral wax, squalene, petrolatum, and microcrystalline wax.

Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid (sulinic acid), 12-hydroxystearic acid, undecylenic acid, tall oil acid, and the like. .

Examples of the higher alcohol include cetyl alcohol, stearyl alcohol, behenyl alcohol, saraphanol, myristyl alcohol, cetearyl alcohol and the like.

Examples of the synthetic ester oil include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, and myristate. Ester, decyl oleate, hexyl decyl dimethyl octoate, cetyl lactic acid, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, sucrose hard Fatty acid ester, sucrose oleate, cholesterol ester of 12-hydroxystearic acid, ethylene glycol di-2-ethylhexanoate, fatty acid ester of dipentaerythritol, N-alkylene glycol monoisostearate, diterpene Acid neopentyl glycol, diisostearyl malate, glyceryl di-2-heptyldecanoate, trimethylolpropane tris-2-ethylhexanoate, trimethylolpropane triiso Stearate, pentaerythritol tetra-2-ethylhexanoate, glycerol tris-2-ethylhexanoate, trimethylolpropane triisostearate, cetyl 2-ethyl caproate , 2-ethylhexyl palmitate, glycerol trimyristate, tris-2-heptyldecanoic acid glyceride, castor oil fatty acid methyl ester, oleic acid oil ester, cetearyl alcohol, glycerol acetate Ester, palmitic acid 2- Heptyl undecyl ester, cetyl palmitate, diisobutyl adipate, N-lauryl-L-glutamic acid-2-octyldodecanate, di-2-heptyl adipate Monoester, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyl decyl myristate, 2-hexyl decyl palmitate, 2-hexyl decyl adipate, azelaic acid Isopropyl ester, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate, and the like.

Examples of the fluorenone oil include a chain polyoxyalkylene such as dimethyl polyoxyalkylene, methylphenyl polyoxyalkylene or methyl hydrogen polyoxyalkylene, or decamethyl polyoxyalkylene. a cyclic polysiloxane such as dodecamethyl polysiloxane or tetramethyltetrahydropolysiloxane.

The oil agent may be used alone or in combination of two or more.

In the sunscreen cosmetic of the present invention, any additive component which is usually blended with a usual cosmetic may be blended in a range which does not impair the effects of the present invention. Examples of such an additive include humectants such as polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, and maltitol; and ethanol and the like. Lower alcohol; antioxidants such as butylhydroxytoluene, tocopherol, phytic acid; antibacterial agents such as benzoic acid, salicylic acid, sorbic acid, alkyl p-hydroxybenzoate, hexachlorophenol; , sodium lauric acid, sodium glutamate, glutathione, citric acid, malic acid, tartaric acid, lactic acid, etc.; vitamin A and its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamins B6 dicaprylate, vitamin B2 and its derivatives, vitamin B12, vitamin B15 and its derivatives such as vitamin B, alpha-tocopherol, beta-tocopherol, gamma-tocopherol, vitamin E acetate, etc. Vitamin E, Vitamin D, Vitamin H, Pantothenic Acid, Panthenamide, Nicotinic Acid, Nicotinic Benzoate Vitamins such as esters; γ-avirics, allantoin, glycyrrhizic acid (salt), glycyrrhetinic acid and its derivatives, and tranexamic acid and its derivatives [as derivatives of tranexamic acid, a polymer (for example, trans-4-(trans-aminomethylcyclohexanecarbonyl)amine methylcyclohexanecarboxylic acid, etc.), an ester of tranexamic acid and hydroquinone (for example, trans-4- Amide methylcyclohexanecarboxylic acid 4'-hydroxyphenyl ester, etc.), ester of tranexamic acid and gentisic acid (for example, 2-(trans-4-aminomethylcyclohexylcarbonyloxy)-5-hydroxyl Benzoic acid and its salts, and guanamines of tranexamic acid (for example, trans-4-aminomethylcyclohexanecarboxylic acid methyl decylamine and its salts, trans-4-(P-methoxybenzene) Mercapto)amine methylcyclohexanecarboxylic acid and its salt, trans-4-indole methylcyclohexanecarboxylic acid and its salts, etc.), eucalyptus, bisabolol, macro-furfural, thyme Phenol, inositol, saikosaponin, ginseng saponin, loofah saponin, saponin such as saponin, pantothenic acid ethyl ether, ethinyl estradiol, tranexamic acid, arbutin, ginseng, placenta, etc. Various medicinal agents; sheep's hoof, sophora flavescens, Japanese poncho, orange, sage, alfalfa, mallow, medicine, musk , East Angelica, spruce, birch, wattle, loofah, horse chestnut, saxifrage, rabbit chrysanthemum, lily, wormwood, peony, aloe, medlar, Japanese cypress, and other plant extracts; pigment; porous a powder of a quality and/or water absorption (for example, a starch obtained from corn or potato, phthalic anhydride, talc, kaolin, magnesium aluminum silicate, calcium alginate, etc.); a neutralizing agent; a preservative; a fragrance; Pigments, etc.

The sunscreen cosmetic of the present invention can be produced, for example, by the following method.

The oil agent and the component (B) are mixed, and then the other oil phase components are mixed and heated and dissolved to prepare a mixture of the oil phase components. When an ultraviolet scattering agent (component (D)) is contained, an ultraviolet scattering agent is added to the mixture, and dispersion is carried out using a disperser.

Next, the aqueous phase component and the component (C) were mixed, and the mixture of the oil phase components was added during heating, and emulsified by a homogenizer. After the emulsification, the water-dispersible ultraviolet ray scattering agent (component (D)) is added as needed, and the mixture is cooled while stirring and mixing, whereby the sunscreen cosmetic of the present invention can be produced.

<1> Film having an island structure

The sea-island structure refers to a structure in which two kinds of polymers which are incompatible with each other cause phase separation, and a continuous phase containing one polymer is dispersed with a dispersed phase containing the other polymer. Then, the continuous phase of the island structure is called the ocean phase, the dispersed phase is called the island phase, and the particles of the dispersed phase are called island particles.

The film of the present invention has a sea-island structure in which island particles containing an amphiphilic copolymer are dispersed in a sea phase containing an aqueous gel formed of a water-soluble polymer.

Then, the amphiphilic copolymer contained in the island particles has a constituent unit (i) and a constituent unit (j) as essential constituent units.

The constituent unit (i) is one or two or more constituent units derived from a hydrophobic monomer, and the constituent unit (j) is one or two or more constituent units derived from a hydrophilic monomer.

The film of the present invention having such a structural feature has a tactile sensation such as milk containing an oil agent regardless of whether or not the aqueous component is used as a main component.

The film of the present invention will be further described in detail below.

<1-1> Island particles

In the present invention, the amphiphilic copolymer contained in the island particles of the sea-island structure has a constituent sheet derived from the aforementioned hydrophobic monomer. The element (i) and the constituent unit (j) derived from the aforementioned hydrophilic monomer are regarded as essential constituent units.

As the amphiphilic copolymer of the present invention, a water-soluble copolymer comprising a constituent unit derived from the hydrophobic monomer described in the following [1] and [2] and a hydrophilic monomer is preferably used.

[1] Hydrophobic monomer

In the present invention, a constituent unit derived from the hydrophobic monomer represented by the above formula (1), (7) or (8) (hereinafter sometimes simply referred to as "structural unit (7)") is used. One or two or more kinds of amphiphilic copolymers (also referred to as acrylic amphiphilic copolymers) contained as essential constituent units are preferred.

In the present invention, the "composition unit derived from a monomer" means a constituent unit formed by cleavage of a carbon-carbon unsaturated bond of a corresponding monomer by a polymerization reaction.

The hydrophobic monomer represented by the formula (1), (7) or (8) will be described below.

(1-1) a hydrophobic monomer represented by the formula (7)

In the above formula (7), R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁵ represents a branched hydrocarbon group having a ring structure of 13 to 30 or a ring structure having no ring structure; More than one branch of a hydrocarbon group having 6 to 12 carbon atoms.

Here, examples of the alkyl group represented by R ^{14 include} a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group. In the present invention, R ¹⁴ is preferably a hydrogen atom or a methyl group.

Further, examples of the branched hydrocarbon group having a ring structure of 13 to 30 carbon atoms represented by R ¹⁵ include 1-methyldodecyl group, 11-methyldodecyl group, 3-ethylundecyl group, and 3 -ethyl-4,5,6-trimethyloctyl, 1-methyltridecyl, 1-hexyloctyl, 2-butyldecyl, 2-hexyloctyl, 4-ethyl-1- Isobutyloctyl, 1-methylpentadecyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 16-methylheptyl, 9-methylheptyl, 7-Methyl-2-(3-methylhexyl)indenyl, 3,7,11,15-tetra-methylhexadecyl, 2-octyldodecyl, 2-decyltetradecyl, 2 - Twelve bases and sixteen bases.

Further, as the hydrocarbon group having 6 to 12 carbon atoms having two or more branches and having no ring structure represented by R ¹⁵ , 2,2-dimethylbutyl group and 2,3-dimethylbutyl group can be exemplified. 3,3-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1-dimethylpentyl, 1-isopropylbutyl, 1-isopropyl-2-methylpropyl, 1,1-diethylpropyl, 1-ethyl-1-isopropylpropyl, 2-ethyl-4-methylpentyl, 1- Propyl-2,2-dimethylpropyl, 1,1,2-trimethyl-pentyl, 1-isopropyl-3-methylbutyl, 1,2-dimethyl-1-B Butyl, 1,3-dimethyl-1-ethylbutyl, 1-ethyl-1-isopropyl-propyl, 1,1-dimethylhexyl, 1-methyl-1-B Pentyl, 1-methyl-1-propylbutyl, 1,4-dimethylhexyl, 1-ethyl-3-methylpentyl, 1,5-dimethylhexyl, 1-ethyl -6-methylheptyl, 1,1,3,3-tetramethylbutyl, 1,2-dimethyl-1-isopropylpropyl, 3-methyl-1-(2,2- Dimethylethyl)butyl, 1-isopropylhexyl, 3,5,5-trimethylhexyl, 2-isopropyl-5-methylhexyl, 1,5-dimethyl-1-B Hexyl, 3,7-dimethyloctyl, 2,4,5-trimethylheptyl, 2,4,6-trimethylheptyl, 3,5-dimethyl 1-(2,2-dimethylethyl)hexyl and the like.

(1-2) a hydrophobic monomer represented by the formula (1) or (8)

In the above formulae (1) and (8), R ¹ and R ^{16 each} represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² , R ³ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different. And represents a fluorenyl group having 6 to 22 carbon atoms having a branch having no ring structure. X represents a group from which an OH group is desorbed from a triol.

Here, examples of the alkyl group represented by R ¹ and R ^{16 include} a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group. In the present invention, R ³ is preferably a hydrogen atom or a methyl group.

Further, as the fluorenyl group having a branched carbon number of 6 to 22 which does not contain a ring structure represented by R ² , R ³ , R ¹⁷ , R ¹⁸ or R ¹⁹ , 2-methylpentanyl group and 3-methyl group are exemplified. Pentylmethyl, 4-methylpentyl, 2-ethylbutyryl, 2-ethylbutyryl, 2,2-dimethylbutenyl, 3,3-dimethylbutenyl, 2-methylhexyl , 4-methylhexyl, 5-methylhexyl, 2,2-dimethylpentenyl, 4,4-dimethylpentenyl, 2-methylheptyl, 2-B Hexyl, 2-propylpentyl, 2,2-dimethylhexyl, 2,2,3-trimethylpentanyl, 2-methyloctyl, 3,3,5-trimethyl Hexyl, 2-methylindenyl, 4-methylindenyl, 8-methylindenyl, 4-ethyloctyl, 2-ethyloctyl, 2-butylhexyl, 2- Tertiary butylhexyl, 2,2-diethylhexyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methylindenyl, 2-methyl-2-ethyloctyl, 2-methylundecyl, 10-methylundecyl, 2,2-dimethylindenyl, 2-ethylindenyl, 2- Butyl octyl, diethyl octyl, 2-tert-butyl-2,2,4-trimethylpentanyl, 10 -methyldodecyl, 3-methyldodedecyl, 4-methyldodedecyl, 11-methyldodedecyl, 10-ethylundecyl, 12-methyltride Indenyl, 2-butylindenyl, 2-hexyloctyl, 2-butyl-2-ethyloctyl, 12-methyltetradecyl, 14-methylpentadecyl, 2-butyl Dimercapto, 2-hexyldecyl, 16-methylheptadecanyl, 2,2-dimethylhexyl, 2-butylhexadecanyl, 2-hexyldodedecyl, 2, 4,10,14-tetramethylpentanyl, 18-methylundecyl, 3,7,11,15-tetra-methylhexadecanyl, 19-methylindolyl, and the like.

Further, in a preferred embodiment of the present invention, in the general formulae (1) and (8), R ² , R ³ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different and have no ring structure. The fluorenyl group having a branched carbon number of 10 to 22 or a fluorenyl group having 6 to 9 carbon atoms having two or more branches without a ring structure.

As a thiol group having a branched carbon number of 10 to 22 which does not contain a ring structure represented by R ² , R ³ , R ¹⁷ , R ¹⁸ or R ¹⁹ in such a preferred embodiment, 2-methyl fluorene is exemplified. , 4-methylindenyl, 8-methylindenyl, 4-ethyloctyl, 2-ethyloctyl, 2-butylhexyl, 2-tert-butylhexyl, 2, 2-Diethylhexyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methylindenyl, 2-methyl-2-ethyloctyl , 2-methylundecyl, 10-methylundecyl, 2,2-dimethylindenyl, 2-ethylindenyl, 2-butyloctyl, diethyloctyl, 2 - tert-butyl-2,2,4-trimethylpentanyl, 10-methyldodepinyl, 3-methyldodepinyl, 4-methyldodedecyl, 11-methyl Twelve indenyl, 10-ethylundecyl, 12-methyltridecyl, 2-butylindenyl, 2-hexyloctyl, 2-butyl-2-ethyloctyl, 12-A Tetradedyl, 14-methylpentadecanyl, 2-butyldodecanyl, 2-hexyldecyl, 16-methylheptadecanyl, 2,2-dimethylhexanyl 2-butylhexadecanyl, 2-hexyldodefluorene , 2,4,10,14-tetramethylpentanyl, 18-methylundecyl, 3,7,11,15-tetra-methylhexadecanyl, 19-methylindolyl Wait.

Further, as a preferred embodiment, R ² , R ³ , R ¹⁷ , R ¹⁸ and R ¹⁹ having a ring structure and having two or more branches having 6 to 9 carbon atoms can be exemplified as 2 , 2-dimethylbutyryl, 3,3-dimethylbutyryl, 2,2-dimethylpentanyl, 4,4-dimethylpentenyl, 2,2-dimethylhexyl, 2,2,3-trimethylpentanyl, 3,5,5-trimethylhexyl, and the like.

In the formula (1), the group derived from the trihydric alcohol represented by X is not particularly limited as long as it is a group from which an OH group is desorbed from the triol, and may be suitably selected from the group consisting of glycerol and tris. The triol of the group of methylolpropane and trimethylolethane desorbs the group of the OH group.

Further, in the general formula (8), the group derived from the tetrahydric alcohol represented by Y is not particularly limited as long as it is a group from which an OH group is desorbed from the tetrahydric alcohol, and may be suitably selected from the group consisting of dipropylene-containing The tetrahydric alcohol of the group of alcohol, pentaerythritol, erythritol, D-threitol, and L-threitol desorbs the group of the OH group.

In the present invention, it is particularly preferable to use an amphiphilic copolymer comprising the constituent unit (1).

Further, in a further preferred embodiment of the present invention, the hydrophobic monomer represented by the formula (1) is a hydrophobic monomer represented by the above formula (15).

The fluorenyl group of R ²⁴ and R ^{25 in} the formula (15) has a carbon number of 12 to 22, more preferably 14 to 20, particularly preferably 16 to 20.

Further, the carbon number of the main chain of the fluorenyl group of R ²⁴ and R ^{25 in} the formula (15) is preferably 9 to 21, more preferably 12 to 20, particularly preferably 16 to 18.

Further, the number of branches of the fluorenyl group of R ²⁴ and R ^{25 in} the formula (15) is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.

Further, in R ^{24 of the} formula (15), in the fluorenyl group of R ²⁵ , the position number of the carbon of the main chain of the branched chain bond is preferably as large as possible. Specifically, the branched chain is preferably bonded to the first to third carbons at the end of the autonomous chain, more preferably the first or second carbon, and particularly preferably the first carbon.

Specific examples of R ²⁴ and R ²⁵ include 10-methylundecyl group, 10-methyldodedecyl group, 11-methyldodedecyl group, and 10-ethylundecyl group. 12-methyltridecyl, 12-methyltetradecyl, 14-methylpentadecanyl, 16-methylheptadecanyl, 2,4,10,14-tetramethylpentanyl , 18-methyl 19-mercapto, 3,7,11,15-tetra-methylhexadecanyl, 19-methylindolyl, and the like.

In the general formula (15), the triol-derived group represented by Z is not particularly limited as long as it is a group from which an OH group is desorbed from a triol, and may be appropriately selected from the group consisting of glycerol and tris. The triol of the group of methylolpropane and trimethylolethane desorbs the group of the OH group.

[2] Hydrophilic monomer

As the hydrophilic monomer of the present invention, a polymerizable carboxylic acid and a compound represented by the above formulas (2), (9), (10) and (11) can be used.

(2-1) Polymeric carboxylic acid,

In the present invention, specific examples of the polymerizable carboxylic acid or a salt thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, and sodium, potassium, ammonium, and amine salts thereof. . Among these, acrylic acid, methacrylic acid, and a salt thereof are particularly preferable from the viewpoint of high polymerizability. When the amphiphilic copolymer of the present invention is introduced into a constituent unit derived from a polymerizable carboxylate, the polymerizable carboxylic acid may be previously prepared as a salt to carry out a polymerization reaction, or a polymerization reaction may be employed to form a self-polymerizable carboxylic acid. The acid-derived constituent unit is derived from an amphiphilic copolymer and then neutralized with a base to form a salt.

(2-2) a hydrophilic monomer represented by the formula (2)

In the above formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵ represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R ⁶ represents a hydrogen atom and a carbon number of 6~. An aromatic hydrocarbon group of 10, an aliphatic hydrocarbon group having 1 to 14 carbon atoms or a fluorenyl group having 1 to 12 carbon atoms. n represents an integer from 6 to 40.

The alkyl group represented by R ⁴ in the above formula (2) may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group or a cyclopropyl group. In the present invention, R ⁶ is preferably a hydrogen atom or a methyl group.

Further, examples of the alkylene group represented by R ^{5 include} an exoethyl group, a propyl group, an exo-propyl group, a 2-hydroxyl-propyl group, a 2-hydroxy-2-methyl-extended ethyl group, and a 2-hydroxy group. 1-methylethyl or the like, but among these, an ethyl group or a propyl group is preferred, and an ethyl group is more preferred.

Further, in the group represented by R ⁶ , examples of the aromatic group having 6 to 10 carbon atoms include a phenyl group, a benzyl group, a tolyl group, and an ethylphenyl group; and the aliphatic hydrocarbon group having 1 to 14 carbon atoms may be used. Methyl, ethyl, butyl, tert-butyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, lauryl, etc. are suitably exemplified; as the fluorenyl group having 1 to 12 carbon atoms, a fluorenyl group can be suitably exemplified. , ethyl sulfhydryl, propyl sulfonyl, butyl sulfhydryl, isobutyl sulfhydryl, pentamidine, laurel. Among these, the group represented by R ^{5 is} preferably an aliphatic hydrocarbon group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms.

Further, n of the general formula (2) is a numerical range of 6 to 40.

Among the monomers represented by the above formula (2), examples of the monomer in which R ⁵ is a propyl group include polypropylene glycol (9) monoacrylate, polypropylene glycol (13) monoacrylate, and polycondensation. Propylene glycol (9) monomethacrylate, polypropylene glycol (13) monomethacrylate, and the like. Furthermore, the number in parentheses represents N. Most of these polymers are commercially available. Specific examples of such commercially available products include "Blenmer" AP-400, AP-550, AP-800, PP-500, and PP-800 (all manufactured by Nippon Oil & Fats Co., Ltd.).

Among the monomers represented by the above formula (2), examples of the monomer in which R ⁵ is an ethyl group extend include polyethylene glycol (10) monoacrylate and polyethylene glycol (8). Methacrylate, polyethylene glycol (23) monoacrylate, polyethylene glycol (23) monomethacrylate, methoxy polyethylene glycol (9) acrylate, methoxy polyethylene glycol ( 9) methacrylate, methoxy polyethylene glycol (23) methacrylate, oleyl polyethylene glycol (18) methacrylate, lauryloxy polyethylene glycol (18) acrylate, Laurel oxime polyethylene glycol (10) methacrylate, stearyloxy polyethylene glycol (30) monomethacrylate, and the like.

The above hydrophilic monomer can be obtained in a high yield by esterification reaction of a corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with a chloride or anhydride of acrylic acid or methacrylic acid. Moreover, since many commercial products already exist, this commercial item can also be utilized. Specific examples of such commercially available products include Blenmer, AE-400, PE-350, AME-400, PME-400, PME-1000, ALE-800, and PSE-1300 (all of which are Japanese fats and oils). ))).

(2-3) a hydrophilic monomer represented by the formula (9)

As the hydrophilic monomer of the present invention, a hydrophilic monomer represented by the above formula (9) can also be used.

Specific examples of the hydrophilic monomer represented by the above formula (9) include 2-acryloxyethylphosphocholine (APC) and 2-methyl group. Acryloxyethylphosphocholine (MPC). These monomers can be synthesized, for example, by the following methods described in Polymer Journal, Vol. 22, No. 5.

<Synthesis method>

The 2-bromoethylphosphonium dichloride is reacted with 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate to obtain 2-methylpropenyloxyethyl-2'-bromoethylphosphoric acid or 2- After propylene oxiranylethyl-2'-bromoethylphosphoric acid, the compounds are reacted with triethylamine in methanol.

(2-4) a hydrophilic monomer represented by the formula (9)

As the hydrophilic monomer of the present invention, a hydrophilic monomer represented by the above formula (10) can also be used.

In the hydrophilic monomer represented by the formula (10), the reducing sugar which is a group in which hydrogen is removed from the hydroxyl group at the 1-position of the self-reducing sugar represented by GO- is specifically selected from the group consisting of glucose and mannose. a monosaccharide such as sugar, galactose, arabinose, xylose or ribose, a disaccharide such as maltose, lactose or cellobiose, a trisaccharide such as maltotriose or a group of oligosaccharides such as malto-oligosaccharide One or two or more kinds of them are preferably selected from one or more selected from the group consisting of glucose, galactose, arabinose, xylose, ribose, maltose, lactose, and cellobiose, and glucose is particularly preferred. Further, as the monomer represented by the formula (10), glucosyloxyethyl methacrylate (hereinafter abbreviated as GEMA) or glucosyloxyethyl acrylate (hereinafter abbreviated as GEA) is preferred.

(2-5) a hydrophilic monomer represented by the formula (11)

As the hydrophilic monomer of the present invention, a hydrophilic monomer represented by the above formula (11) can also be used.

In the monomer of the formula (11), the amino acid which is an amino acid residue represented by R ²³ is not particularly limited as long as it is a generally known amino acid, and specifically, glycine can be exemplified. Acid, alanine, glutamic acid, lysine, arginine, and the like. Among these, since the obtained amphiphilic copolymer has a good skin barrier recovery effect, it is particularly preferable to be an amino acid residue.

Further, the polyamine of the polyamine residue represented by R ²³ means an amine having two or more amine groups which may be substituted by an alkyl group in the same molecule, and specific examples thereof include a diamine, a triamine, a tetraamine or An amine in which the hydrogen atom of the amine group is substituted with an alkyl group. Among these, diamine is preferred from the viewpoint of the excellent use feeling of the skin external preparation containing the obtained amphiphilic copolymer, and the viewpoint of easiness of obtaining raw materials at the time of synthesis is particularly preferable as a specific example. Examples thereof include ethylenediamine, 1,4-diamino-n-butane, 1,6-diamino-n-hexane, and the like.

Further, the amine alcohol as the amine alcohol residue represented by R ²³ means a compound having an amino group which may be substituted with an alkyl group and an alcoholic hydroxyl group in the same molecule. The amine alcohol is not particularly limited as long as it is generally known, and specific examples thereof include ethanolamine and triethylaminoethanol.

The salt of the monomer represented by the formula (11) is not particularly limited, and specific examples thereof include a sodium salt, a potassium salt, an ammonium salt, an amine salt, etc., in which an acid moiety is neutralized with a base, or an amine group. Partially acid-neutralized hydrochloride, sulfate, nitrate, phosphate, citrate, oxalate, carbonate, and the like. When the amphiphilic copolymer of the present invention is introduced into a constituent unit derived from the monomer salt represented by the formula (11), the monomer represented by the formula (11) can be previously prepared into a salt to carry out a polymerization reaction. Can also use polymerization, will The constituent unit derived from the monomer represented by the formula (11) is derivatized into an amphiphilic copolymer, and then neutralized to prepare a salt.

The monomer represented by the formula (11), and specific examples of the salt thereof, the compounds 1 to 11 and salts thereof can be appropriately exemplified.

The hydrophilic monomer represented by the formula (11), for example, as shown in the above reaction formulas (1) and (2), can be esterified by using (meth)acrylic acid or (meth)acrylofluorene chloride. Synthesis by hydrazylation reaction.

As described above, in the present invention, the above-described general formulae (2), (9), (10), and (11) can be used as the hydrophilic polymer.

In a preferred embodiment of the present invention, the amphiphilic copolymer comprises a constituent unit (2) derived from the above formula (2).

[3] Amphiphilic copolymer

In the present invention, an amphiphilic copolymer having a constituent unit (1) and a constituent unit (2) can be suitably used. Further, an amphiphilic copolymer having a constituent unit (15) and a constituent unit (2) can be preferably used.

Among the acrylic amphiphilic copolymers, a (methoxy methacrylate PEG-23/diisostearate methacrylate) copolymer can be preferably used.

By containing such an acrylic amphiphilic copolymer, the moisture retention and flexibility of the film can be improved.

(Methoxy methacrylate PEG-23/diisostearate methacrylate) copolymer, as the constituent unit (i), mainly contained in the hydrophobic monomer represented by the above formula (15), R ²⁴ and R ²⁵ are a constituent unit (i) derived from a hydrophobic monomer of 16-methylheptadecanyl group.

Further, the constituent unit (j) mainly contains, from the hydrophilic monomer represented by the above formula (2), R ⁴ is a methyl group, R ⁵ is an exoethyl group, R ⁶ is a methyl group, and n is 23 A hydrophilic monomer-derived constituent unit (j).

As the amphiphilic copolymer of the present invention, in addition to the above copolymer, a conventional copolymer can also be used. Specifically, as the amphiphilic copolymer, the conventional copolymer described below can be used.

That is, polyquaternium-51 (a copolymer comprising 2-methylpropenyl oxyethylphosphocholine and butyl methacrylate in a molar ratio of about 8:2), polyquaternium can be used. -61 (copolymer containing 2-methacryloyloxyethylphosphocholine and stearyl methacrylate at a molar ratio of about 3:7), (glyceryl methacrylate) Stearyl acrylate copolymer (weight average of glyceryl-N-(2-methylpropoxy oxyethyl) carbamide and stearyl methacrylate at a molar ratio of about 6:4 Copolymer with a molecular weight of about 40,000), PEG/PPG/polybutanediol-8/5/3 glycerol, (hydrolyzed silk protein/PG propyl methyl decanediol) cross-linked polymer (N-[2 -hydroxy-3-[3-(hydroxymethyldecyl)propoxy]propyl]hydrogenated silk protein decylated copolymer), (eicosanedioic acid/tetradecanedioic acid) polyglycerol-10 (containing an oligomeric ester of eicosanedioic acid, tetradecanoic acid dibasic acid and an average degree of polymerization of 10 polyglycerol), (glycerol/butylene oxide) copolymer stearyl ether (in Stearyl alcohol reacts both glycidol and tetrahydrofuran, and the HLB of the addition polymerization is 18.0. Compound), polyquaternium-7 (copolymer of dimethyldiallyl ammonium chloride and acrylamide), polyquaternium-39 (acrylic acid, dimethyldiallylammonium chloride and A conventional copolymer of acrylamide terpolymer), a copolymer of (Na/acrylonitrile dimethyltaurine) (a copolymer of sodium acrylate and sodium acryloyldimethyltaurate).

Among these, a polyquaternium-51, a polyquaternium-61, a (glyceryl methacrylate-ethyl methacrylate/stearyl methacrylate) copolymer can be suitably exemplified.

In the present invention, the proportion of the constituent unit (i) of the amphiphilic copolymer in the total constituent unit is preferably from 1 to 50% by mass, more preferably from 5 to 40% by mass, and from 10 to 30% by mass.

By setting the ratio of the constituent unit (i) of the amphiphilic copolymer to the above range, the moisture retaining property and flexibility of the film of the present invention can be improved.

In the present invention, the proportion of the constituent unit (j) of the amphiphilic copolymer in the total constituent unit is preferably from 50 to 99% by mass, more preferably from 60 to 95% by mass, and from 70 to 90% by mass.

By setting the ratio of the constituent unit (j) of the amphiphilic copolymer to the above range, the moisture retaining property and flexibility of the film of the present invention can be improved.

In the present invention, the mass ratio of the constituent unit (i) constituting the amphiphilic copolymer to the constituent unit (j) is preferably 5:95 to 50:50, further preferably 10:90 to 45:55. More preferably, it is 20:80~40:60, and the best is 25:75~35:65.

By setting the mass ratio of the constituent unit (i) and the constituent unit (j) of the amphiphilic copolymer to the above range, the moisture retaining property and flexibility of the film of the present invention can be improved.

In the present invention, the molar ratio of the constituent unit (i) constituting the amphiphilic copolymer and the constituent unit (j) is preferably 8:92 to 62:38, further preferably 15:85 to 57: 43, better preferably 29:71~52:48, especially good 35:65~46:54.

By setting the molar ratio of the constituent unit (i) and the constituent unit (j) of the amphiphilic copolymer to the above range, the moisture retaining property and flexibility of the film of the present invention can be improved.

In the present invention, the average molecular weight of the amphiphilic copolymer is preferably from 20,000 to 110,000, further preferably from 20,000 to 80,000, more preferably from 30,000 to 80,000, further preferably from 40,000 to 70,000, and particularly preferably from 50,000 to 50,000. 70000, further preferably 57000~66000.

By setting the molecular weight of the amphiphilic copolymer to the above range, the elasticity of the film of the present invention can be improved, and the feeling of stickiness can be suppressed.

Here, the average molecular weight means a weight average molecular weight in terms of polystyrene measured by GPC.

<1-2> Marine

The above island particles are dispersed in the marine phase of the aqueous gel. In the present invention, the aqueous gel is formed using water-soluble polymer and/or a salt thereof and water hydrated to the water-soluble polymer.

The water-soluble polymer and/or its salt which forms the aqueous gel is not particularly limited as long as the phase containing the amphiphilic polymer is dispersed as an island particle, and it is preferably selected from the group consisting of acrylic-based water-soluble polymerization. One or two or more kinds of water-soluble polymers and/or salts thereof, which are a group of a substance, a water-soluble polypeptide, and a water-soluble polysaccharide.

As the acrylic water-soluble polymer, a non-crosslinking type acrylic polymer or a crosslinkable acrylic copolymer can be exemplified. Further, as the non-crosslinking type acrylic polymer, sodium polyacrylate is exemplified, and as the crosslinkable acrylic copolymer, sodium polyacrylate or (acrylate/alkyl acrylate (C10-30)) is exemplified. Crosslinked polymer.

As the water-soluble multi-peptide, a poly-sodium glutamate is particularly exemplified.

As the water-soluble polysaccharide, Sanxian gum or Tremella polysaccharide is particularly exemplified. It is especially suitable for Sanxian gum as a water-soluble polysaccharide.

By using such a water-soluble polymer and/or a salt thereof, the moisture retaining property and flexibility of the film of the present invention can be improved.

<1-3> Island structure

The film of the present invention has a sea-island structure in which an island phase containing an amphiphilic copolymer is dispersed in a sea phase containing an aqueous gel.

In the film having the sea-island structure of the present invention, the ratio of the area of the sea phase to the island phase is preferably 2:8 to 10:1, more preferably 3:7 to 9:1, and particularly preferably 6:4 to 7. :3.

The film of the present invention having an area ratio of the sea phase to the island phase in the above range has good elasticity, less stickiness, and good moisture retention and softness.

In a preferred embodiment of the present invention, the average major axis minor axis ratio of the island particles is preferably 0.6 or more, more preferably 0.7 or more, particularly preferably 0.8 or more, and most preferably 0.9 or more.

By making the average major axis minor axis ratio of the island particles into the above range, the moisture retaining property and flexibility of the film of the present invention can be improved.

Further, the average major axis short axis ratio can be measured by observing the composition by a microscope. Specifically, the composition can be observed by a microscope, and the major axis minor axis ratio of 100 island particles can be measured and averaged.

Further, in a preferred embodiment of the present invention, the all-island particle contained in the film has a major axis minor axis ratio of less than 0.6, more preferably less than 0.7, and particularly preferably less than 0.8, and the ratio of the island particles is 10% or less.

Furthermore, in a more preferred embodiment of the present invention, the ratio of the island particles contained in the composition to the minor axis minor axis ratio of less than 0.8 is 5% or less, more preferably 1% or less.

The film of such an embodiment has better moisture retention and flexibility.

In a preferred embodiment of the present invention, the island particles having an average particle diameter of 0.5 to 10 μm, more preferably the number of island particles having an average particle diameter of 1 to 5 μm, is 80% or more.

Further, in a more preferred embodiment of the present invention, the number of island particles having an average particle diameter of 1 to 5 μm is 85% or more, and more preferably 90% or more.

By setting the particle diameter distribution of the island particles having such a small particle diameter to the above range, the moisture retention and flexibility of the film of the present invention can be further improved.

Further, the average particle diameter of the island particles can be measured by observing the composition by a microscope. Specifically, the composition can be observed by a microscope, and the major axis and the minor axis of the island particles can be measured and averaged.

The film of the present invention may contain any component which is usually used for a skin external preparation. Examples of such a component include oils, waxes, hydrocarbons, higher fatty acids, higher alcohols, synthetic ester oils, anthrone-based oils, surfactants, polyols, moisturizing classification, and viscosity-increasing. Agents, powders, inorganic pigments, organic pigments, organic powders, ultraviolet absorbers, lower alcohols, vitamins, polymers with a biomimetic structure, and the like.

Examples of the oils and waxes include Australian walnut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, coconut oil, and palm. Oil, liquid lanolin, hardened coconut oil, hardened oil, wood wax, hardened castor oil, bee Wax, candelilla wax, carnauba wax, insect wax, lanolin, reduced lanolin, hard lanolin, jojoba wax, etc.; as the hydrocarbon, for example, mobile paraffin, squalane, isooctadecane , ceresin, paraffin, mineral wax, petrolatum, microcrystalline wax, etc.; as higher fatty acids, for example, oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, stearic acid, twenty Diacid, undecylenic acid, etc.; as higher alcohols, for example, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, octyldodecanol, myristyl alcohol, and cetyl hard can be mentioned. Examples of the synthetic ester oils include, for example, cetyl isooctanoate, isopropyl myristate, hexadecyl isostearate, diisopropyl adipate, and sebacic acid di-2. -ethylhexyl ester, cetyl lactate, diisostearyl malate, ethylene glycol di-2-ethylhexanoate, neopentyl glycol dicaprate, propionate di-2-heptyldecanoate Alcohol ester, tris-2-ethylhexanoic acid glycerol ester, trimethylolpropane tris-2-ethylhexanoate, trimethylolpropane triisostearate, tetra-2-ethylhexyl Acid pentaerythritol ester, etc.; Examples of the ketone-based oil agent include a chain polyoxyalkylene such as dimethyl polyoxyalkylene, methylphenyl polyoxyalkylene or diphenyl polyoxyalkylene, and octamethylcyclotetrazepine. a cyclic polyoxyalkylene such as oxane, decamethylcyclopentaoxane or dodecamethylcyclohexane decane, an amine-modified polyoxyalkylene, a polyether modified polyoxyalkylene or an alkane An oxime oil such as a modified polyoxyalkylene or a modified polyoxyalkylene such as a fluorine-modified polysiloxane or the like.

The surfactant may be either an anionic surfactant or a nonionic surfactant.

Examples of the anionic surfactants include fatty acid soaps (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, and triethanolamine alkyl sulfate. Examples of the nonionic surfactants include, for example, nonionic surfactants. , sorbitan fatty acid esters (sorbitan monostearate, sorbitan sesquioleate, etc.), glycerol fatty acids (monostearate glycerol, etc.), propylene glycol fatty acid esters Classes (propylene glycol monostearate, etc.), hardened castor oil derivatives, glycerol alkyl ethers, POE sorbitan fatty acid esters (POE sorbitan monooleate, monostearate polyoxyethylene sorbose) Alcohol anhydride, etc., POE sorbitol fatty acid esters (POE-sorbitol monolaurate), POE glycerol fatty acid esters (POE-glycerol monoisostearate, etc.), POE fatty acid esters Classes (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE2-octyldodecan ether, etc.), POE alkyl phenyl ethers (POE nonylphenyl ether, etc.), Pluronic type, POE‧POP alkyl ether (POE‧POP2-decyltetradecyl ether, etc.), special window, POE castor oil, hardened castor oil derivative (POE castor oil, PO E hardened castor oil, etc.), sucrose fatty acid ester, alkyl glucoside, and the like.

Examples of the polyhydric alcohols include polyethylene glycol, erythritol, xylitol, propylene glycol, dipropylene glycol, isoprene glycol, 1,2-pentanediol, and 2,4-hexanediol. 1,2-hexanediol, 1,2-octanediol, etc., and examples of the moisturizing classification include sodium pyrrolidonecarboxylate, lactic acid, and sodium lactate; and examples of the tackifier include, for example, Chinese bean gum, alfalfa seeds, carrageenan, galactan, gum arabic, pectin, mannan, starch, carbene gum, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, Methyl hydroxypropyl cellulose, chondroitin sulfate, dermatan sulfate, glycogen, heparin sulfate, hyaluronic acid, sodium hyaluronate, tragacanth, keratan sulfate, chondroitin, mucopolysaccharide, hydroxyethylguana Gum, carboxymethyl Guanhua bean gum, dextran, keratan sulfate, locust bean gum, amber gluten, saponin, chitin, chitosan, carboxymethyl chitin, agar, polyvinyl alcohol , polyvinylpyrrolidone, carbopol, polyethylene glycol, bentonite, and the like.

Examples of the powder include mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, phthalic anhydride (cerium oxide), alumina, barium sulfate, and the like which can be treated on the surface; and as inorganic pigments, for example, Examples thereof include iron oxide, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine blue, indigo, titanium oxide, and zinc oxide which can be treated on the surface. Examples of the organic coloring matter include mica which can treat the surface. A pearlescent agent such as titanium, surimi foil, bismuth oxychloride, etc., reddish color red 202, red 228, red 226, yellow 4, blue 404, yellow 5, red 505, Red 230, red 223, orange 201, red 213, yellow 204, yellow 203, blue 1, green 201, purple 201, red 204, etc.; as an organic powder, For example, polyethylene powder, polymethyl methacrylate, nylon powder, organopolysiloxane elastomer, and the like.

Examples of the ultraviolet absorbers include an aminobenzoic acid-based ultraviolet absorber, an ortho-anisic acid-based ultraviolet absorber, a salicylic acid-based ultraviolet absorber, a cinnamic acid-based ultraviolet absorber, and a benzophenone-based system. UV absorber, sugar UV absorber, 2-(2'- Hydroxy-5'-t-butyloctylphenyl)benzotriazole, 4-methoxy-4'-t-butyldibenzopyridylmethane, etc.; as the lower alcohol, for example, ethanol , isopropanol, phenoxyethanol, etc.; as a vitamin, for example, vitamin A or its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 or Vitamin E, vitamin D, vitamins, vitamin B, vitamin B, vitamin B, vitamin B, vitamin B, vitamin B, vitamin B, vitamin B, vitamin B, vitamin B, vitamin B, vitamin B, vitamin B, vitamin B, vitamin B, vitamin B, vitamin B H, pantothenic acid, pantethine, pyrroloquinoline quinone and the like.

As the polymer having a biomimetic structure, for example, polymethacryl lysine lysine, polyglycoside ethyl methacrylate, or the like can be exemplified.

In the present invention, the content of the oil agent such as oil, wax, hydrocarbon, higher fatty acid, higher alcohol, synthetic ester oil or ketone oil is preferably 10% by mass or less, and further preferably. It is 5% by mass or less, more preferably 2.5% by mass or less, further more preferably 2% by mass or less, particularly preferably 1% by mass or less, and further preferably 0.5% by mass or less.

Further, in a preferred embodiment of the present invention, no oil agent is contained.

The film having the sea-island structure of the present invention can exert a feeling of use such as milk containing an oil agent regardless of whether or not the aqueous component is used as a main component.

Therefore, the film having the sea-island structure of the present invention can be in an oil-free form.

Further, in the present invention, the content of the surfactant is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 2.5% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1% by mass or less, and more preferably 0.5% by mass or less.

Further, in a preferred embodiment of the present invention, no surfactant is contained.

The film of the present invention can form a stable island structure regardless of whether or not a surfactant is contained.

Therefore, the film having the sea-island structure of the present invention can be in the form of no surfactant.

<2> Forming a film composition

The present invention also relates to a composition in which a film having the above-described sea-island structure of the present invention can be formed on the skin by coating on the skin.

The composition of the present invention contains the above-mentioned amphiphilic copolymer, a water-soluble polymer and/or a salt thereof, and water.

By applying to the skin and evaporating water in the composition, the amphiphilic copolymer can be separated from the water-soluble polymer. As a result of this phase separation, the film of the present invention is formed on the skin. Further, after the phase separation, the water and the polyol in the composition enter the aqueous gel formed of the water-soluble polymer.

The composition of the present invention is further detailed below. Further, the composition of the present invention can be applied to the film of the present invention described in the item of the above <1>.

In the composition of the present invention, the content of the amphiphilic copolymer is preferably from 0.01 to 10% by mass, further preferably from 0.5 to 7% by mass, more preferably from 0.1 to 5% by mass, particularly preferably from 0.5 to 5% by mass. 3 mass%.

According to the composition of the present invention in which the content of the amphiphilic copolymer is in the above range, a film having a good elasticity and a small stickiness can be formed on the skin.

In the present invention, the proportion of the water-soluble polymer in the entire composition is preferably 0.001 to 10% by mass, more preferably 0.005 to 5% by mass, still more preferably 0.01 to 1% by mass, particularly preferably 0.05 to 0.5% by mass.

According to the composition of the present invention in which the content of the water-soluble polymer is within the above range, a film having excellent moisture retention and flexibility can be formed on the skin.

In a preferred embodiment of the present invention, the mass ratio of the content of the water-soluble polymer to the amphiphilic copolymer is preferably from 1:100 to 1:2, more preferably from 1:50 to 1:5. More preferably 1:30~1:10, especially good 1:25~1:15.

According to the composition of the present invention in which the mass ratio of the water-soluble polymer to the amphiphilic copolymer is in the above range, a film having high uniformity can be formed.

In the present invention, it is preferred to include a polyol which promotes the separation of the sea phase from the island phase.

That is, in a preferred embodiment of the present invention, a polyol (hereinafter also referred to as a promoting polyol) which promotes phase separation of the aqueous gel and the amphiphilic copolymer is contained, and/or the aqueous gel is inhibited. A phase-separated polyol of an amphiphilic copolymer (hereinafter also referred to as an inhibitory polyol). Further, it is particularly preferable to include both a promoting polyol and an inhibitory polyol.

According to the composition of the present invention containing such a polyol, a film having a sea-island structure having high uniformity can be formed on the skin.

As the promoter polyol, a polyol which is obtained by mixing an aqueous solution of a nonionic surfactant having a polyether chain in a hydrophilic portion to enhance the cloud point of the aqueous solution can be exemplified. As such a promoting polyol, 1,3-butanediol and polyethylene glycol are especially exemplified.

By using such a polyol, a film having higher uniformity can be formed.

In the present invention, the content of the promoting polyol of the entire composition of the present invention is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, still more preferably 3 to 20% by mass, particularly preferably 5~15% by mass.

By setting the content of the promoting polyol of the entire composition of the present invention to the above range, the uniformity of the formed film can be further improved.

As the inhibitory polyol, a polyol which is mixed with an aqueous solution of a nonionic surfactant having a polyether chain in a hydrophilic portion to lower the cloud point of the aqueous solution can be exemplified. As such an inhibitory polyol, glycerol, diglycerin, sorbitol, and maltitol are especially exemplified.

By using such a polyol, a film having higher uniformity can be formed.

The content of the inhibitory polyol in the entire composition of the present invention is preferably 0.5 to 30% by mass, more preferably 1 to 25% by mass, still more preferably 5 to 20% by mass, particularly preferably 8 to 15% by mass. .

By setting the content of the promoting polyol to the above range, the uniformity of the formed film can be further improved.

Further, in the present invention, the cloud point means that in a transparent or translucent liquid, phase separation occurs depending on a temperature change, and the result becomes The opaque temperature refers specifically to the temperature at which the solute and water begin to separate when the aqueous solution of the nonionic surfactant is warmed.

The cloud point of the aqueous solution of the nonionic surfactant having a polyether chain in the hydrophilic portion is increased or decreased, and specifically, it can be confirmed by the following method.

An aqueous solution of a nonionic surfactant having a polyether chain in a hydrophilic portion was heated, and the temperature at which the aqueous solution began to turbid, that is, the cloud point was recorded. Next, the polyol was added to the aqueous solution, and the mixture was heated, and the cloud point was recorded in the same manner.

When the cloud point of the aqueous solution after the addition was higher than the aqueous solution before the addition of the polyol, the added polyol was evaluated as "increasing the cloud point of the aqueous solution".

On the other hand, when the cloud point of the aqueous solution after the addition was lower than that of the aqueous solution before the addition of the polyol, the added polyol was evaluated as "decreasing the cloud point of the aqueous solution".

As the nonionic surfactant having a polyether chain in the hydrophilic portion, which is used for measurement of the above cloud point, a nonionic surfactant having polyethylene glycol in a hydrophilic portion can be exemplified.

Specific examples of such a nonionic surfactant include polyoxyethylene oleyl ether (POE(n)OE, n=3, 10, 15, 20, 23) (manufactured by NIHON EMULSION Co., Ltd.), POE ( 20) sorbitan monostearate (manufactured by Toho Chemical Co., Ltd.), POE (20) glycerol monostearate (manufactured by Riken VITAMIN Co., Ltd.), POE (10) monostearate (Daily Chemical Co., Ltd.), polyglycerol (6) monolaurate (manufactured by Sakamoto Pharmaceutical Co., Ltd.).

In the present invention, the mass ratio of the promoting polyol and the inhibitory polyol is preferably from 10:1 to 1:10, further preferably from 6:1 to 1:5, more preferably from 4:1 to 1: 3, further better is 3.5:1~1:2.5, especially good is 1.6:1~1:1.

By setting the mass ratio of the promoting polyol and the inhibitory polyol to the above range, it is possible to provide a composition of a film which can form a sea-island structure having high stability.

In the present invention, the ratio of the total mass of the promoting polyol and the inhibitory polyol to the mass ratio of the amphiphilic copolymer is from 5:1 to 20:1, more preferably from 7:1 to 15:1. Good for 8:1~12:1.

By setting the ratio of the total mass of the promoting polyol and the inhibitory polyol to the mass of the amphiphilic copolymer to the above range, it is possible to provide a composition having a sea-island structure having high stability.

Further, in the present invention, the ratio of the total mass of the promoting polyol and the inhibitory polyol to the total mass of the amphiphilic copolymer and the water-soluble polymer is from 5:1 to 20:1, more preferably 7: 1~15:1, especially good 8:1~12:1.

By setting the ratio of the total mass of the promoting polyol and the inhibitory polyol to the mass of the amphiphilic copolymer to the above range, it is possible to provide a composition having a sea-island structure having high stability.

In a preferred embodiment of the present invention, the content of the promoting polyol of the total amount of the three components of the auxiliary polyol, the inhibitory polyol, and the amphiphilic copolymer is preferably from 10 to 80% by mass. It is preferably 20 to 70% by mass, more preferably 30 to 70% by mass, still more preferably 40 to 60% by mass, and particularly preferably 40 to 55% by mass.

By setting the content of the promoting polyol to the above range, precipitation can be prevented from occurring in the composition, and the stability of the composition can be improved. Further, as the composition of the above aspect, a film having excellent moisture retention and flexibility can be formed.

Further, in a preferred embodiment of the present invention, the content of the inhibitory polyol in the total amount of the three components of the auxiliary polyol, the inhibitory polyol, and the amphiphilic copolymer is preferably from 10 to 80% by mass. Further, it is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, and particularly preferably 35 to 50% by mass.

By setting the content of the inhibitory polyol to the above range, precipitation can be prevented from occurring in the composition, and the stability of the composition can be improved. Further, as the composition of the above aspect, a film having excellent moisture retention and flexibility can be formed.

Further, in a preferred embodiment of the present invention, the content of the amphiphilic copolymer of the total amount of the three components of the auxiliary polyol, the inhibitory polyol, and the amphiphilic copolymer is preferably from 1 to 50. The mass % is further preferably from 3 to 20% by mass, more preferably from 5 to 15% by mass, particularly preferably from 8 to 12% by mass.

By setting the content of the amphiphilic copolymer to the above range, it is possible to provide a composition having a viscosity which is easy to apply to the skin. Further, as the composition of the above aspect, a film having excellent moisture retention and flexibility can be formed.

In a preferred embodiment of the present invention, the content of the promoting polyol is 20 to 70% by mass in the total amount of the three components of the promoting polyol, the inhibitory polyol, and the amphiphilic copolymer, and the inhibitory plural The content of the alcohol is 20 to 70% by mass, and the content of the amphiphilic copolymer is 5 to 20% by mass.

By becoming such an embodiment, the stability of the composition can be improved.

Further, the content of the promoting polyol, the content of the inhibitory polyol, and the content of the amphiphilic copolymer are the total amount of the three components of the promoting polyol, the inhibitory polyol, and the amphiphilic copolymer. By adjusting to the above range, the major axis minor axis ratio and the average particle diameter of the island particles of the film formed by the composition of the present invention can be adjusted to a preferred range as described in the item of <1-3>.

The composition of the present invention can be produced by stirring and mixing a raw material at normal temperature.

The content of water in the composition of the present invention is preferably 60 to 99% by mass, more preferably 70 to 95% by mass, particularly preferably 80 to 90% by mass.

The coating of the present invention can be easily formed on the skin by applying the composition of the present invention having a water content within the above range to the skin.

<3> Method of forming a film on the skin

The present invention also relates to a method of forming the above-described film of the present invention on the skin.

The method of the present invention is characterized in that the composition of the present invention is applied to the skin. By using the water in the coating evaporation composition, the aqueous gel formed by the water-soluble polymer can be separated from the amphiphilic copolymer. As a result of this phase separation, a film having the sea-island structure of the present invention can be formed on the skin.

In the present invention, it is preferred to use an aqueous solution containing a polyol which promotes phase separation of the amphiphilic copolymer from the aqueous gel and/or a polyol which inhibits phase separation of the aqueous gel from the amphiphilic copolymer. .

By using such an aqueous solution, a film having good uniformity can be formed on the skin.

Further, in the composition of the present invention, the content of the oil agent such as oil, wax, hydrocarbon, higher fatty acid, higher alcohol, synthetic ester oil or ketone oil is preferably 2% by mass. In the following, it is more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

Further, in a preferred embodiment of the present invention, no oil agent is contained.

Moreover, in the composition of the present invention, the content of the surfactant is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

Further, in a preferred embodiment of the present invention, no surfactant is contained.

The preferred embodiment of the composition and film of the method of the present invention is as described in the above items <1> and <2>.

[Examples] <1> Synthesis of hydrophobic monomer

The production example of the hydrophobic monomer represented by the above formula (1) is shown below.

(Production Example 1) Synthesis of glycerol monoacrylate

In a 3-L 4-neck flask, R)-(+)-2,2-dimethyl-1,3-dioxolane-4-methanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 79.5 g of acrylic acid. The methyl ester was 258.0 g and the tetramethoxy titanium was 3.7 g. Then, the reaction liquid was stirred, and a gas exchange reaction was carried out at 105 to 110 ° C for 2.5 hours while introducing nitrogen gas into the liquid. After completion of the reaction, ketal acrylate 1 (intermediate 1) was obtained by fractional distillation under reduced pressure.

90.2 g of water, 28.4 ml of a cation exchange resin RCP160M (manufactured by Mitsubishi Chemical Corporation), and 94.2 g of an intermediate 1 were placed in a 3-liter three-necked flask. Then, the reaction liquid was stirred, and a deketalization reaction of a ketal was carried out at 24 ° C for 27 hours while introducing nitrogen gas into the liquid. After completion of the reaction, the cation exchange resin was filtered from the reaction solution, and the filtered reaction solution was washed 6 times with 100 ml of hexane to remove unreacted raw materials. Then, 200 ml of ethyl acetate was added to the aqueous layer to extract the product. Then, this ethyl acetate extract liquid was distilled off under reduced pressure (800 Pa) and 40 ° C or less to obtain glyceryl monoacrylate.

(Production Example 2) Synthesis of Trimethylolpropane Monoacrylate

Step (1): In an eggplant type flask equipped with a calcium tube, a cooling tube and a Dean-Stark separator, 145.7 g of trimethylolpropane, 300 ml of acetone, 3 g of p-toluenesulfonic acid monohydrate and 300 ml of petroleum ether are added. It was heated to reflux in an oil bath set to 50 °C. After 12 hours, after confirming that there was no newly formed water, the reaction mixture was cooled to room temperature. Next, 3 g of sodium fatty acid was added, and after stirring for 30 minutes, petroleum ether and acetone were distilled off by an evaporator. The obtained crude product was distilled under reduced pressure to obtain ketalized trimethylolpropane (Intermediate 2).

Step (2): In a 3-L 4-neck flask, 104.8 g of the intermediate 2 obtained in the step (1), 258.0 g of methyl acrylate, and 3.7 g of tetramethoxytitanium were added. Then, the reaction liquid was stirred, and a gas exchange reaction was carried out at 105 to 110 ° C for 2.5 hours while introducing nitrogen gas into the liquid. After completion of the reaction, the ketalized trimethylolpropane acrylate (intermediate 3) was obtained by fractional distillation under reduced pressure distillation.

Step (3): In a 3-L 4-neck flask, 90.2 g of water, 28.4 ml of a cation exchange resin RCP160M (manufactured by Mitsubishi Chemical Corporation), and 115.3 g of an intermediate 3 obtained in the step (2) were added. Then, the reaction liquid was stirred, and a deketalization reaction of a ketal was carried out at 24 ° C for 27 hours while introducing nitrogen gas into the liquid. After completion of the reaction, the cation exchange resin was filtered from the reaction solution, and the filtered reaction solution was washed 6 times with 100 ml of hexane to remove unreacted raw materials. Then, 200 ml of ethyl acetate was added to the aqueous layer to extract the product. Then, this ethyl acetate extract liquid was distilled off under reduced pressure (800 Pa) and 40 ° C or less to obtain trimethylolpropane monoacrylate.

(Production Example 3) Synthesis of Trimethylolpropane Monomethacrylate

In addition to the amount of the trimethylolpropane, methyl acrylate (acrylate) of the production example 2, the amount of the intermediate obtained in the step (1), and the amount of the intermediate obtained in the step (2), as shown in Table 1, In the same manner as in Production Example 2, trimethylolpropane monomethacrylate was synthesized in the same manner as in the above description. The amount of the triol and the amount thereof to be added, the intermediate obtained in the step (1), the amount thereof, the intermediate obtained in the step (2), and the amount thereof are shown in Table 1.

(Production Example 4) 1 of the production example of the hydrophobic monomer represented by the formula (1)

In a reaction vessel equipped with a stirrer and a cooling tube, 28.4 g of 16-methylhexadecanoic acid (manufactured by Sigma-Aldrich Co., Ltd.) and 35.7 g of sulfinium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 200 ml of benzene were weighed and mixed. . After refluxing for 4 hours while stirring, purification by vacuum distillation was carried out to obtain 16-methylheptadecyl chloride.

In a reaction vessel equipped with a stirring device, 16.0 g of glyceryl monomethacrylate (manufactured by Nippon Oil & Fats Co., Ltd.) and 30.0 g of triethylamine were dissolved in 300 ml of tetrahydrofuran. The obtained solution was ice-cooled, and while stirring, a solution obtained by dissolving 60.6 g of the above-mentioned 16-methylhexadecane chloride in 100 ml of tetrahydrofuran was added dropwise thereto over 2 hours. After completion of the dropwise addition, the resulting white precipitate was filtered, and tetrahydrofuran and triethylamine were removed from the filtrate using a rotary evaporator to give a product. It was confirmed by NMR measurement that the obtained compound is a hydrophobic monomer (hydrophobic monomer 1) which is an essential constituent unit of the copolymer of the present invention represented by the following formula (29).

Hydrophobic monomer 1

(Production Example 5) 2 of the production examples of the hydrophobic monomer represented by the formula (1)

In a reaction vessel equipped with a stirrer and a cooling tube, 25.6 g of 2-hexadecetic acid (manufactured by Sigma-Aldrich Co., Ltd.), 35.7 g of sulfite chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 200 ml of benzene were weighed and stirred. After refluxing for 4 hours while stirring, purification by vacuum distillation was carried out to obtain 2-hexadecyl chloride.

In a reaction vessel equipped with a stirring device, 16.0 g of glyceryl monomethacrylate (manufactured by Nippon Oil & Fats Co., Ltd.) and 30.0 g of triethylamine were dissolved in 300 ml of tetrahydrofuran. The obtained solution was ice-cooled, and while stirring, a solution obtained by dissolving 55.0 g of the above-mentioned 2-pyridyl chloride in 100 ml of tetrahydrofuran was added dropwise thereto over 2 hours. After completion of the dropwise addition, the resulting white precipitate was filtered, and tetrahydrofuran and triethylamine were removed from the filtrate using a rotary evaporator to give a product. It was confirmed by NMR measurement that the obtained compound is a hydrophobic monomer (hydrophobic monomer 2) which is an essential constituent unit of the copolymer of the present invention represented by the following formula (30).

Hydrophobic monomer 2

(Production Example 6) 3 of the production example of the hydrophobic monomer represented by the formula (1)

In a reaction vessel equipped with a stirrer and a cooling tube, 28.4 g of 9-methylheptadecanoic acid (manufactured by Sigma-Aldrich Co., Ltd.) and 35.7 g of sulfinium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 200 ml of benzene were weighed and mixed. . After refluxing for 4 hours while stirring, purification by vacuum distillation was carried out to obtain 9-methylheptadecyl chloride.

In a reaction vessel equipped with a stirring device, 16.0 g of glyceryl monomethacrylate (manufactured by Nippon Oil & Fats Co., Ltd.) and 30.0 g of triethylamine were dissolved in 300 ml of tetrahydrofuran. The obtained solution was ice-cooled, and while stirring, a solution obtained by dissolving 60.6 g of the above-mentioned 9-methylhexadecane chloride in 100 ml of tetrahydrofuran was added dropwise thereto over 2 hours. After completion of the dropwise addition, the resulting white precipitate was filtered, and tetrahydrofuran and triethylamine were removed from the filtrate using a rotary evaporator to give a product. It was confirmed by NMR measurement that the obtained compound is a hydrophobic monomer (hydrophobic monomer 3) which is an essential constituent unit of the copolymer of the present invention represented by the following formula (31).

Hydrophobic monomer 3

<2> Synthesis of the copolymer of the present invention (1) Synthesis of copolymers of Example 1 and Comparative Example 1

In a flask equipped with a nitrogen introduction tube, a cooler, and a stirring device, 24.0 g of a hydrophobic monomer 1 (Production Example 4) and methoxypolyethylene glycol (23) methacrylate (manufactured by Nippon Oil Co., Ltd.) were weighed. In the product name "Blenmer PME-1000", 90.0 g, 300 ml of isopropyl alcohol, and 300 ml of a phosphate buffer solution (pH 6.8) (manufactured by NACALAI TESQUE Co., Ltd.) were stirred and mixed. Nitrogen substitution was carried out for 1 hour while stirring. To the solution, 2.0 g of ammonium persulfate was dissolved in 20 ml of the solution, and stirring was continued while carrying out a reaction at 65 ° C for 10 hours (copolymer of Comparative Example 1 which was reacted for 16 hours under the same conditions). After completion of the reaction, the pH was adjusted to 7.0 using an aqueous sodium hydroxide solution, and isopropyl alcohol was removed by a rotary evaporator to obtain an aqueous solution of the copolymer of Example 1 (treated under the same conditions to obtain an aqueous solution of the copolymer of Comparative Example 1). .

The weight average molecular weight (in terms of polystyrene) of the copolymer of Example 1 was 61,000 when it was determined by GPC. Further, when measured by NMR, the mass ratio of the constituent unit (a) to the constituent unit (b) was about 3:7.

On the other hand, the weight average molecular weight of the copolymer of Comparative Example 1 was 122,500, and the mass ratio of the constituent unit (a) to the constituent unit (b) was about 3:7.

(2) Synthesis of copolymers of Examples 2 to 8

A copolymer having a structure, a weight average molecular weight, and a molar ratio of the structural unit (a) and the structural unit (b) shown in Table 2 was synthesized by the same method as the above (1). The weight average molecular weight of the copolymer is adjusted by changing the reaction time. Further, the molar ratio of the constituent unit (a) and the constituent unit (b) can be adjusted by adjusting the molar ratio of the amount of the hydrophobic monomer to the hydrophilic monomer added to the reaction liquid.

Further, Examples 2 to 6 are copolymers synthesized using the hydrophobic monomer 1. Further, Example 7 is a copolymer synthesized using the hydrophobic monomer 2, and Example 8 is a copolymer synthesized using the hydrophobic monomer 3.

<Test Example 1>

A 2% by mass aqueous solution of the copolymers of Examples 1 to 6 and Comparative Example 1 was prepared. Each of the aqueous copolymer solutions was applied to the skin of three sensory evaluators, and the evaluation was made on the basis of the following criteria. The results are shown in Table 3.

‧Feeling

◎...has a very strong sense of elasticity

○...has a strong sense of elasticity

△...has a sense of elasticity

×...not very elastic

As shown in Table 3, when the copolymers of Examples 1 to 6 and the Comparative Example 1 having the same structure as the unit (a) were compared, the aqueous solutions of the copolymers of Examples 1 to 6 were compared with the aqueous solution of the copolymer of Comparative Example 1. , has a strong sense of elasticity. In particular, the copolymers of the present invention of Examples 1, 5 and 6 have a very strong elastic feeling.

The above results show that a copolymer having a weight average molecular weight of 20,000 to 110,000, particularly preferably 57,000 to 66,000, of the constituent unit (a) and the constituent unit (b) has a good elastic feeling.

<Test Example 2>

In the same manner as in Test Example 1, the copolymers of Examples 7 and 8 were also evaluated for the elastic feeling. As a result, it was found that the copolymers of Examples 7 and 8 also had a feeling of elasticity.

This result shows that a copolymer having a elastic feeling can be obtained even if various changes are made to the structure of the constituent unit (a).

<Test Example 3>

0.5% by mass of Sansan gum was added to the 2% by mass aqueous solution of the copolymer of Example 1 or the copolymer of Comparative Example 1 to prepare a gelatinous cosmetic. This gel-like cosmetic was applied to the skin of three specialized sensory evaluators similar to Test Example 1, and evaluated for a non-sticky feeling, a feeling of elasticity, and a moist feeling. The evaluation was carried out on the basis of the following evaluation criteria based on the feeling of use when the skin was coated with an emulsion (reference cosmetic) containing trimethylolpropane triisostearate. The average value of the evaluation values by the three evaluators is shown in Table 4 and FIG.

‧Evaluation criteria

4 points... better than the touch of the benchmark cosmetic ingredients

3 points... the same level of touch as the benchmark cosmetic ingredients

2 points... close to the touch of the benchmark cosmetic ingredients, but slightly worse

1 point... worse than the touch of the reference cosmetic raw materials

0 points... quite poor compared to the touch of the reference cosmetic raw materials

As shown in Table 4 and Fig. 1, the gel-like cosmetic of Example 1 was significantly stronger than the gel-like cosmetic of Comparative Example 1, and was also excellent in no stickiness or moist feeling.

As a result, the copolymer comprising the constituent unit (a) having a weight average molecular weight of 20,000 to 110,000 and the constituent unit (b) was obtained, and the elastic feeling was first, and the feeling of stickiness and moistness was also good.

The emulsified composition was produced by stirring and mixing the components of the following Tables 5 to 7.

Further, in the present embodiment, as the water-soluble copolymer of the emulsifier of the present invention, methacrylic acid methacrylate using a hydrophobic monomer of diisostearic acid methacrylate and a hydrophilic monomer is used. The ester PEG-23 was copolymerized with an average molecular weight of 61,000 (glyceryl diisostearate methacrylate/methoxy methacrylate PEG-23) copolymer in a mass ratio of about 3:7.

Further, as the water-soluble copolymer, PEG/PPG-60/11 glycerin (ADEKANOL M-3228) using polyoxypropylene (degree of polymerization 60) and polyoxyethylene (average degree of polymerization 11) and glycerol ether was used. Compositions (Comparative Examples 2, 4, and 6) were produced.

Further, an emulsified composition (Comparative Examples 3, 5, and 7) was produced using polyoxyethylene hardened castor oil as a surfactant.

3-component phase diagram of the blending ratio of glyceryl diisostearate methacrylate/methoxypropionate PEG-23 copolymer of Examples 9 to 31 with squalane and water Shown in Figure 2.

Blending ratio of (glyceryl diisostearate methacrylate/methyl propyl methacrylate PEG-23) copolymer of Examples 32-62 with tris(octanoic acid/capric acid) glyceride and water The three component phases of the drawing are shown in Fig. 3.

Three-component phase diagram of the blend ratio of (glyceryl diisostearate methacrylate/methyl propyl methacrylate PEG-23) copolymer of Examples 63-89 and bismuth and water Shown in Figure 4.

The emulsified compositions of Examples 9 to 89 showed a stable emulsified form even after storage for 3 months at room temperature. That is, by using a (glyceryl diisostearate methacrylate/methacrylate PEG-23) copolymer, even in the use of a non-polar hydrocarbon oil of squalane, a polar hydrocarbon oil of three In the case of any of the oils of octanoic acid/capric acid glyceride and decyl ketone oil, a stable emulsified composition can also be produced.

On the other hand, the compositions of Comparative Examples 2, 4 and 6 containing PEG/PPG-60/11 glycerol containing a water-soluble copolymer could not be emulsified even if stirred and mixed, and immediately separated into an oil phase after production. water box.

This result shows that a water-soluble copolymer of an emulsifier according to the present invention can produce a stable emulsified composition using various oil agents.

Further, as shown in Tables 5 to 7, the content of the (glyceryl diisostearate methacrylate/methacrylate PEG-23) copolymer is not less than 1 to 30% by mass. An emulsified composition can also be produced.

Further, as shown in Tables 5 to 7, the emulsified composition can be produced even in the case where the content of the oil phase is from 10 to 70% by mass.

Examples 9 to 89 and Comparative Examples 3, 5, and 7 were applied to the skin in an appropriate amount. As a result, the emulsified compositions of Examples 9 to 89 had no irritating feeling compared with the emulsified compositions of Comparative Examples 3, 5, and 7, and had less stickiness.

This result shows that the emulsified composition emulsified by the water-soluble copolymer of the emulsifier of the present invention has a good feeling of use compared to a general emulsified composition which is emulsified by a surfactant.

In particular, the emulsified composition of the example having a content of (glyceryl diisostearate methacrylate/methacrylate PEG-23) copolymer of 15% by mass, more preferably 1% by mass, has More excellent use.

<Manufacturing Example 7>

The facial cleansers of Examples 90 to 92 and Comparative Examples 8 and 9 were produced according to the formulations shown below. That is, by heating each of the components of α and β to 80° C., β is added to α with stirring, stirred, and cooled to obtain a facial cleanser.

Further, as the water-soluble copolymer, a methacrylic acid methacrylate PEG-23 which is a hydrophobic monomer and a hydrophilic monomer is used, which is about 3:7. A copolymer of (glyceryl diisostearate methacrylate/methoxy methacrylate PEG-23) having an average molecular weight of 61,000 in an ear copolymerization.

<Test Example 4>

The skilled evaluator used the facial cleansing creams of Examples 90 to 92 and Comparative Examples 8 and 9 to wash the face, and used the foaming property and the foam quality during use, and the skin without feeling tight and non-sticky after washing the face. The feeling was evaluated based on the following evaluation criteria. The results are shown in Table 8.

‧foaming

◎... very good foaming

○...good blistering

△... weak foaming

×...no blistering

‧ foam quality

◎...very dense foam quality

○...a dense foam quality

△...not too dense

△...not dense

‧ no tension

◎...no tightness

○... almost no tension

△...has a tight feeling

×...has a strong sense of tension

‧No stickiness

◎...no sticky feeling

○... almost no sticky feeling

△...has a sticky feeling

×...has a strong sticky feeling

As shown in Table 8, the facial cleanser of Comparative Example 8 had a strong feeling of tightness on the skin after washing the face. On the other hand, the facial cleansing creams of Examples 90 to 92 had almost no feeling of tightness after washing the face.

This result shows that the (glycerol diisostearate methacrylate/methacrylate PEG-23) copolymer can reduce the tightness of the skin caused by the fatty acid soap.

Further, in the facial cleanser of Comparative Example 9 containing a water-soluble polymer carboxymethylcellulose instead of (glyceryl diisostearate methacrylate/methoxy methacrylate PEG-23) copolymer There is no good foaming property to see the advantages of fatty acid soap. On the other hand, the facial cleansers of Examples 90 to 92 showed good foaming properties.

The result shows that according to the (glyceryl diisostearate methacrylate/methacrylate PEG-23) copolymer, it does not hinder the good foaming property of the fatty acid soap, and can reduce the skin after use. Tightness.

Further, as shown in Table 8, the facial cleansing creams of Examples 91 and 92 exhibited more excellent foaming properties than the facial cleanser of Comparative Example 8.

As a result, the foaming property of the fatty acid soap can be improved by setting the content of the (glyceryl diisostearate methacrylate/methoxy methacrylate PEG-23) copolymer to 0.8% by mass or more.

Further, as shown in Table 8, the facial cleanser of Comparative Example 9 had a strong sticky feeling on the skin after washing the face. On the other hand, the facial cleansers of Examples 90 to 92 showed little stickiness after washing the face.

The result shows that according to the (glyceryl diisostearate methacrylate/methacrylate PEG-23) copolymer, it does not cause stickiness and can reduce the skin of the skin cleansing agent after use. Tightness.

Further, as shown in Table 8, the facial cleansing creams of Examples 90 and 91 were more excellent in stick-slip feeling than the facial cleanser of Example 92.

The result is that when the content of the (glyceryl diisostearate methacrylate/methacrylate PEG-23) copolymer is 3% by mass or less, the stickiness is not generated and can be reduced. The tightness of the skin after use of the skin cleanser.

<Manufacturing Example 8>

The gel washes of Examples 93 to 96 and Comparative Examples 10 to 12 were obtained by stirring and mixing the components shown in Table 9.

<Test Example 5>

In the same manner as in Test Example 4, the skilled evaluator used a gel cleanser to wash the face, and the cleaning power and the skin to be used at the time of use. The tension and the feeling of the skin after washing the face were evaluated by the following evaluation criteria (the evaluation criteria for no tightness were the same as in Test Example 4). The results are shown in Table 9.

‧cleaning power

◎...the cleaning power is very strong

○...strong cleaning power

△...weak cleaning power

×...the cleaning power is very weak

‧Expansion to the skin

◎...very easy to extend

○...easy extension

△...not easy to extend

×...very easy to extend

As shown in Table 9, the gel facial cleansing agents of Comparative Examples 10 and 11 had a strong feeling of tightness on the skin after washing the face. On the other hand, the facial cleansing creams of Examples 93 to 96 were hardly stretched after washing the face. sense.

This result shows that the (glycerol diisostearate methacrylate/methacrylate PEG-23) copolymer can reduce the tightness of the skin caused by the nonionic surfactant.

Further, as shown in Table 9, the gel facial cleansing creams of Examples 94 and 95 had a better effect of reducing the feeling of tightness of the skin after use than the gel facial cleanser of Example 93.

This result shows that the content of the (glyceryl diisostearate methacrylate/methacrylate PEG-23) copolymer is 0.7% by mass or more, and the skin after use can be more effectively reduced. Tightness.

Further, as shown in Table 9, the gel facial cleansing creams of Examples 93 to 96 had better cleaning power than the gel facial cleansing creams of Comparative Examples 10 to 12.

This result shows that the cleaning power of the skin cleansing agent containing the nonionic surfactant can be improved according to the (glyceryl diisostearate methacrylate/methacrylate PEG-23) copolymer.

Further, the gel facial cleanser of Example 95 had better cleaning power than the gel facial cleansing agents of Examples 93 and 94.

This result shows that the content of the (glyceryl diisostearate methacrylate/methacrylate PEG-23) copolymer is 2% by mass or more, and the inclusion of the nonionic surfactant can be improved. The cleansing power of skin cleansers.

Further, as shown in Table 9, the gel facial cleanser of Example 94 had a better spreadability to the skin than the gel facial cleansing creams of Examples 93 and 95.

This result shows that when the content of the (glyceryl diisostearate methacrylate/methacrylate PEG-23) copolymer is 0.6 to 3% by mass, the use of the gel facial cleanser can be improved. The ease of stretching on the skin.

Further, the gel facial cleanser of Example 91 had the same content as the non-ionic surfactant of the gel facial cleanser of Example 93, but the type thereof was different. However, as shown in Table 9, these two gel facial cleansing creams showed the same effect in terms of cleansing power, ease of stretching to the skin, and no tightness.

The results show that the skin cleanser contains (glyceryl diisostearate methacrylate / methacrylate PEG-23) copolymer resulting in The advantageous effect is not affected by the type of surfactant contained in the skin cleansing agent.

The results of Test Examples 4 and 5 show that according to the present invention, the feeling of tightness of the skin after use of the skin cleansing agent can be reduced.

Moreover, according to the present invention, it is shown that the foaming property, the foaming quality and the cleansing power which are not damaged, and the skin cleansing agent which does not impair the ease of stretching of the skin, or the like, are not adversely affected, or It can improve the tightness of the skin after use while improving the aforementioned effects.

<Manufacturing Example 9>

According to the formulation shown in Table 10, the water-based sunscreen cosmetics of Examples 98 to 103 and Comparative Examples 13 to 15 were produced by the following methods.

The mixture of the oil phase components was prepared by mixing and heating to dissolve (I), and the titanium oxide fine particles were hydrophobized by dispersing the disperser.

Next, (I) was added to the heated (II), and emulsified by a homogenizer. After emulsification, by adding (III) and (IV), it is cooled while stirring and mixing to produce a sunscreen cosmetic.

Further, in the present embodiment, as the water-soluble copolymer of the component (A), methacrylic acid methacrylate containing a hydrophobic monomer and glyceryl methacrylate of a hydrophilic monomer is used. PEG-23, a copolymer of an average molecular weight of 61000 (glyceryl diisostearate methacrylate/methoxy methacrylate PEG-23) copolymerized at a molar ratio of about 3:7.

<Test Example 6>

The water-based sunscreen cosmetics of Examples 97 to 102 and Comparative Examples 13 to 15 which were prepared were evaluated for the emulsification stability and the non-sticky feeling and moisturizing feeling at the time of use, and were evaluated according to the following criteria. The results are shown in Table 10.

‧Emulsifying stability (state at the time of storage at room temperature for 1 month)

◎...There is no way to confirm the separation of the oil phase

○...It is almost impossible to confirm the separation of the oil phase

△...oil film on the surface of the preparation

×... Clearly observe the separation of the oil phase

‧No sticky feeling

◎... completely non-sticky

○... almost no sticky feeling

△...has a sticky feeling

×... quite sticky

‧ moisturizing

◎...the moist feeling is very strong

○...weak feeling

△...weak moisture

×...weakness is very weak

As shown in Table 10, the water-based sunscreen cosmetics of Examples 97 to 102 containing all of the components (A) to (D) had good emulsion stability, no stickiness, and a moisturizing feeling.

On the other hand, the sunscreen cosmetic of Comparative Example 13 which did not contain the component (A) had a strong sticky feeling. Further, in Comparative Example 14 which did not contain the component (B) The sunscreen cosmetic and the sunscreen cosmetic of Comparative Example 15 which did not contain the component (C) were inferior in emulsion stability.

These results show that the water-based sunscreen cosmetics containing the components (A) to (D) have excellent emulsion stability and no stickiness, and have moisturizing properties.

Further, as shown in Table 10, the sunscreen cosmetic of Example 97 containing sodium stearyl lactate as the component (C) was compared with the sunscreen cosmetic of Example 100 containing sodium cocoyl sulphate as the component (C). Emulsification stability is preferred.

This result shows an oil-in-water type sunscreen cosmetic containing sodium decyl lactate as the component (C), and has excellent emulsion stability.

Further, as shown in Table 10, the sunscreen cosmetic of Example 97 containing tributyl glycerol monoglyceride-10 as the component (B) was compared with the composition comprising polyglyceryl tristearate-10 as a component (B). The sunscreen cosmetic of Example 101 was excellent in emulsion stability.

This result shows that an oil-in-water type sunscreen cosmetic containing octaaryl polyglycerol ester-10 as the component (B) has excellent emulsion stability.

Further, as shown in Table 10, the sunscreen cosmetic of Example 97 containing the sodium polyacrylate-coated particulate titanium dioxide as the ultraviolet scattering agent of the component (D) was moisturized as compared with the sunscreen cosmetic of Example 102 which did not contain the coated particulate titanium oxide. Excellent feeling.

This result shows that an ultraviolet ray scattering agent containing a surface treatment by sodium polyacrylate, that is, an underwater oil type sunscreen cosmetic containing a water-dispersible ultraviolet ray scattering agent as the component (D), has an excellent moisturizing feeling.

Further, in the sunscreen cosmetics of Example 102, compared with the sunscreen cosmetics of Examples 98 and 99 in which the content of the component (B) was 0.3% by mass and 7% by mass, respectively, the emulsion stability and the non-stickiness were compared. Excellent.

The result shows that the content of the component (B) is preferably 0.5% by mass or more from the viewpoint of the improvement of the emulsification stability, and is preferably 5% by mass or less from the viewpoint of suppressing the feeling of stickiness.

Further, in the sunscreen cosmetic of Example 97, compared with the content of the component (C) of 0.05% by mass and 1.5% by mass of the sunscreen cosmetics of Examples 98 and 99, the emulsion stability and the non-stickiness were compared. Excellent.

In the result of the improvement of the emulsification stability, the content of the component (C) is preferably 0.07% by mass or more, and is preferably 1% by mass or less from the viewpoint of suppressing the feeling of stickiness.

<Manufacturing Example 10>

As shown in Table 11, the content of the immobilized santillac and the amphiphilic copolymer was changed, and the contents of various 1,3-butanediol (promoting polyol) and glycerol (inhibitory polyol) were changed, and preparation and implementation were carried out. The compositions of the present invention of Examples 103 to 123. The content of 1,3-butanediol and glycerol in each of the examples is based on the relationship between the mass of the tri-sand and the amphiphilic copolymer, as shown in Fig. 5 as a 3-component phase diagram. Representation and adjustment.

Further, as the amphiphilic copolymer, methacrylic acid methacrylate PEG-23 which is a hydrophobic monomer and diisostearate methacrylate is used, and about 3:7 is used. The molar ratio of 61000 (glyceryl diisostearate methacrylate / methacrylate PEG-23) copolymer having an average molecular weight of 61,000.

Further, in the following test examples, in order to facilitate the observation of the sea-island structure by the microscope, the fluorescent probe "NBD-COCl" was chemically introduced (glyceryl diisostearate methacrylate / A methoxy methacrylate PEG-23) copolymer was prepared to prepare a composition.

<Test Example 7> Observation of the island structure of the film

About 0.5 g of the compositions of Examples 103 to 123 were applied to a range of about 1.5 cm × 1.5 cm on a glass slide, and left at 40 ° C for 3 days to evaporate the water in the composition to form on a glass slide. Membrane. The constitution of the films of Examples 103 to 123 thus formed was observed by a conjugated-focus laser scanning microscope.

As a result, any of the compositions forms an island structure. A photomicrograph of the compositions of Examples 105, 106, 108, 111, 113, 114, 115, 119, 120, 122, 123 is shown in Fig. 6.

As shown in Fig. 6, in the compositions of Examples 115, 119 and 120, aggregation of island particles was observed, and many island particles having an average particle diameter of more than 10 μm or island particles having a major axis minor axis ratio of less than 0.5 were observed.

On the other hand, in the compositions of Examples 106 to 114, the aggregation of the island particles was not observed, and the number of fine island particles having an average particle diameter of 1 to 5 μm was 80% or more.

As a result, the total amount of the water-soluble polymer and the amphiphilic copolymer in the total amount of the components shown in the three-component phase diagram of Fig. 5 is 15% by mass or less, and aggregation of the island particles is less likely to occur.

Further, the area ratio of the marine phase to the island phase of the coatings of Examples 103 to 114 in which the number of fine island particles having an average particle diameter of 1 to 5 μm was 80% or more was not observed. 6:4~7:3.

<Test Example 8> Sensory evaluation

The composition of Example 103 was used by a evaluator of 48 people, and the film formed on the skin after application to the skin was moist, sensible, soft, soft, delicate, sticky, and sticky. As shown in the figure, the evaluation is based on 7 points. Further, commercially available lotions and lotions were used as comparison targets. The results are shown in Figure 7.

Further, as a cosmetic, a general substance containing mainly water, and including a polyhydric alcohol, a known water-soluble polymer, a preservative, and an extract is used. Further, as the emulsion, an oil-in-water emulsion cosmetic containing mineral oil, Australian walnut oil or the like as an oil phase component is used.

As shown in Fig. 7, the film formed by applying the composition of Example 103 to the skin has the same moisturizing, elastic feeling, softness, softness, and swelling feeling as the emulsion containing the oil agent. The above is a high evaluation.

Further, as shown in Fig. 7, the film formed of the composition of Example 103 was remarkably low in viscosity compared with the emulsion, and was similar to the lotion.

As a result, the composition of the present invention can form a film having a tactile sensation such as milk containing an oil agent on the skin regardless of whether or not the aqueous component is used as a main component. In particular, the composition of the present invention can exhibit both moisturizing properties and softness which are difficult to achieve in a cosmetic having a water-soluble component as a main component.

Moreover, this result shows that since the composition of the present invention has an aqueous component as a main component, there are few disadvantages such as a sticky feeling seen in a cosmetic containing an oil agent.

<Manufacturing Example 11>

The compositions of the present invention of Examples 124 and 125 were prepared according to the formulation of Table 12.

The film formed of the compositions of Examples 124 and 125 was observed by a microscope according to the same method as in Test Example 8. As a result, in the same manner as the films of Examples 103 to 114, the aggregation of the island particles was not observed, and the number of fine island particles having an average particle diameter of 1 to 5 μm was 80% or more.

This result shows that even in the case of using polyquaternium-61 and (glyceryl methacrylate-ethyl methacrylate/stearyl methacrylate) copolymer as the amphiphilic copolymer, it can be formed to have good The envelope of the island structure. That is, even in the case of changing an amphiphilic copolymer having a constituent unit derived from a hydrophobic monomer and a constituent unit derived from a hydrophilic monomer, by combining a water-soluble polymer and water, A composition capable of forming a film having a sea-island structure can be prepared.

[Industrial availability]

The copolymer of the present invention for solving the first problem can be applied to cosmetics.

The present invention for solving the second problem can be applied to an emulsified cosmetic.

The present invention for solving the third and fourth problems can be applied to a facial cleanser.

The present invention for solving the fifth problem can be applied to a sunscreen cosmetic.

The present invention for solving the sixth problem can be applied to an oil-free cosmetic.

Claims (9)

A copolymer which is one or two or more kinds of constituent units (a) derived from a hydrophobic monomer represented by the following formula (1) and a hydrophilic sheet represented by the following formula (2) One or more constituent units (b) derived from the body are provided as essential constituent units, and the weight average molecular weight is from 20,000 to 110,000; (In the formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² and R ³ may be the same or different, and represent a carbon number 6 to 22 having a branch structure which does not have a ring structure. Sulfhydryl; X represents a group from which the OH group is desorbed from the triol; (In the formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵ represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R ⁶ represents a hydrogen atom and a carbon number of 6~ An aromatic hydrocarbon group of 10, an aliphatic hydrocarbon group having 1 to 14 carbon atoms or a fluorenyl group having 1 to 12 carbon atoms; and n represents an integer of 6 to 40). The copolymer of claim 1, wherein the mass ratio of the constituent unit (a) to the constituent unit (b) is from 25:75 to 35:65. The copolymer of claim 1 or 2, wherein the molar ratio of the constituent unit (a) to the constituent unit (b) is 35:65 to 46:54. The copolymer according to any one of claims 1 to 3, wherein the hydrophobic monomer is a hydrophobic monomer represented by the following formula (3); (In the formula (3), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁸ and R ⁹ may be the same or different, and represent a branched carbon number of 10 to 22 which does not have a ring structure. A fluorenyl group or a fluorenyl group having 6 to 9 carbon atoms having two or more branches without a ring structure; Y represents a group desorbing an OH group from a triol. The polymer according to any one of claims 1 to 4, wherein the hydrophilic monomer is a hydrophilic monomer represented by the following formula (4); (In the formula (4), R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹¹ represents a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 14 carbon atoms or carbon. The number of thiol groups from 1 to 12; m represents an integer from 6 to 40). The copolymer of any one of claims 1 to 5, wherein the triol is selected from the group consisting of glycerol, trimethylolpropane, and trimethylolethane. The copolymer according to any one of claims 1 to 6, wherein the hydrophobic monomer is a compound represented by the following formula (5); (In the formula (5), R ¹² and R ¹³ may be the same or different and each represents a fluorenyl group having a branched carbon number of 18 which does not have a ring structure. The polymer according to any one of claims 1 to 7, wherein the hydrophilic monomer is a hydrophilic monomer represented by the following formula (6); (In the formula (6), l represents an integer of 6 to 40). A skin external preparation containing the copolymer according to any one of claims 1 to 8.