JP2009179797A - Composition comprising reactive silyl group-containing copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound having excellent antifouling and water repellent properties, moreover, stable against water. <P>SOLUTION: A composition comprising a copolymer and water is provided. In the composition, the copolymer includes a reactive silyl group-containing (meth)acrylate ester (A), (meth)acrylic acid or an ester thereof (B), a siloxane-containing (meth)acrylate ester (C), and an amine-containing (meth)acrylate ester (D) as constituent monomers, wherein the content of the monomer (A) is ≥0.1 mass% to <25.0 mass%, and is produced by solution polymerization, and the copolymer concentration in the composition is equal to or less than a specific amount. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a composition containing a reactive silyl group-containing copolymer, and particularly to an improvement in applicability thereof to a preparation.

  Conventionally, as a method of imparting water repellency and antifouling properties to a certain material, a method of forming a film by treating a resin, a silicone compound or the like is used. Among these, recently, in order to improve the durability of the silicone film, a specific proportion of reactive silyl groups are contained in the silicone compound, and a crosslinking reaction between the silicones proceeds by hydrolysis to form a film. Research of technology is performed (for example, refer to patent documents 1 to 4). And since these silicone compounds can form a strong film on hair, skin, fibers, etc., for the purpose of imparting water repellency and antifouling properties, hair cosmetics, makeup cosmetics, or repellents are provided. It is applied to liquid medicine.

Japanese Patent Laid-Open No. 11-12412 Japanese Patent Laid-Open No. 11-43415 JP-A-11-302129 Japanese Patent Laid-Open No. 11-302140

  However, the silicone compound of the above prior art is excellent in water repellency and antifouling properties, but has a very high reactivity with water, and the crosslinking reaction proceeds. During the coexistence of, it could not exist stably. For this reason, in the preparation using such a silicone compound, the presence of water is contraindicated, and the formulation type is limited to those containing no water. On the other hand, in recent years, preparations containing a large amount of an organic solvent have a tendency to be avoided from the viewpoint of impact on the human body and the environment. Under such circumstances, it has been expected to develop a compound capable of imparting excellent water repellency and antifouling property even in a preparation having a high water content (cosmetics, hair treatment agent, clothing treatment agent). In view of the above, an object of the present invention is to provide a compound having excellent antifouling properties and water repellency and further stable in water.

  In order to achieve the above object, the present inventors have intensively studied on improving the composition of the silicone copolymer so that a crosslinked product can be formed and stability can be maintained even in a preparation containing water. went. As a result, by adjusting the content of the reactive silyl group in the copolymer to a low level, the crosslinking reaction does not proceed even if water is mixed in the copolymer, and therefore the preparation contains a large amount of water. It has been found that even when doing this, it can be kept stable. That is, in the copolymer having a (meth) acrylic acid ester having a reactive silyl group as a constituent monomer, the content of the constituent monomer is 0.1% by mass or more and less than 25.0% by mass in the total amount of the copolymer. Can be stably present in the presence of water, and by applying a preparation containing the copolymer and water to the material to be treated, the material to be treated has good water repellency, The inventors have found that antifouling properties can be imparted and have completed the present invention.

（一般式（Ｉ）中、Ｒ_１は水素原子あるいはメチル基、Ｒ_２は炭素数１〜６のアルキレン基、Ｒ_３、Ｒ_４、Ｒ_５は、このうちの少なくとも１つが官能基自身もしくはその加水分解物が共重合体分子間を架橋しうる反応性官能基、このうちの反応性官能基を除く他は非反応性官能基を意味する。）

（一般式（II）中、Ｒ_６は水素原子あるいはメチル基、Ｒ_７は水素原子、炭素数１〜１８のアルキル基、炭素数1〜１８のフッ化アルキル基、エチレンオキシド（１〜５０モル）、プロピレンオキシド（１〜５０モル）、エチレンオキシドとプロピレンオキシドの共重合体（１〜５０モル、ランダムあるいはブロック）、あるいはこれらのアルキレンオキシドの末端ＯＨ基が炭素数1〜１８のアルキル基のものを意味する。）

（一般式（III）中、Ｒ_８は水素原子あるいはメチル基、Ｒ_９は炭素数１〜６のアルキレン基を意味する。Ｘは下記一般式（IV）〜（VI）の何れかで表される基を意味する。）

（一般式（IV）中、Ｒ_１０は炭素数１〜６のアルキル基を意味する。）

（一般式（V）中、Ｒ_１１及びＲ_１１’は炭素数１〜６のアルキル基、ｘ_１は正の整数を意味する。）

（一般式（VI）中、Ｒ_８、Ｒ_９は前記定義の通りである。Ｒ_１２は炭素数１〜６のアルキル基、ｘ_２は正の整数を意味する。）

（一般式（VII）中、Ｒ_１３は水素原子あるいはメチル基、Ｒ_１４は炭素数１〜６のアルキレン基を意味する。Ｙは−Ｎ^＋（Ｒ_１５）_３又は−Ｎ（Ｒ_１５）_２で示される基であり、Ｒ_１５は炭素数１〜６のアルキル基を意味する。）
（数１）
Ｘ＝｛Ａ／（Ａ＋Ｂ）｝×１００
（ただし、Ａは組成物中の前記共重合体の質量（ｇ）、Ｂは組成物中の全溶媒の質量（ｇ）を表す。）
（数２）
Ｘ´＝７５０／（Ｃ×Ｄ）
（ただし、Ｃは組成物中に含まれる共重合体中のモノマー（Ａ）の割合（質量％）、Ｄは組成物中に含まれる全溶媒中の水の割合（質量％）を表す。） That is, the first subject of the present invention is a monomer (A) represented by the following general formula (I), a monomer (B) represented by the following general formula (II), a monomer represented by the following general formula (III) ( C) and a copolymer having the monomer (D) represented by the following general formula (VII) as a constituent monomer, the proportion of the monomer (A) is 0.1% by mass or more and less than 25.0% by mass in the copolymer And contains a copolymer produced by solution polymerization and water, and the copolymer concentration X in the composition represented by the following formula 1 is X ′% by mass or less represented by the following formula 2. It is a composition characterized by the above-mentioned.

(In general formula (I), R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 1 to 6 carbon atoms, R ₃ , R ₄ , and R ₅ are at least one of the functional group itself or its Reactive functional groups that the hydrolyzate can crosslink between the copolymer molecules means non-reactive functional groups other than reactive functional groups.

(In general formula (II), R ₆ is a hydrogen atom or a methyl group, R ₇ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 18 carbon atoms, ethylene oxide (1 to 50 mol)) , Propylene oxide (1 to 50 mol), copolymers of ethylene oxide and propylene oxide (1 to 50 mol, random or block), or those having terminal OH groups of these alkylene oxides having 1 to 18 carbon atoms. means.)

(In the general formula (III), R ₈ represents a hydrogen atom or a methyl group, and R ₉ represents an alkylene group having 1 to 6 carbon atoms. X is represented by any one of the following general formulas (IV) to (VI)). Meaning a group.)

(In general formula (IV), R ₁₀ represents an alkyl group having 1 to 6 carbon atoms.)

(In the general formula (V), R ₁₁ and R ₁₁ ′ represent an alkyl group having 1 to 6 carbon atoms, and x ₁ represents a positive integer.)

(In general formula (VI), R ₈ and R ₉ are as defined above. R ₁₂ represents an alkyl group having 1 to 6 carbon atoms, and x ₂ represents a positive integer.)

(In the general formula (VII), R ₁₃ represents a hydrogen atom or a methyl group, R ₁₄ represents an alkylene group having 1 to 6 carbon atoms. Y represents —N ⁺ (R ₁₅ ) ₃ or —N (R ₁₅ ) _2. And R ₁₅ means an alkyl group having 1 to 6 carbon atoms.)
(Equation 1)
X = {A / (A + B)} × 100
(However, A represents the mass (g) of the copolymer in the composition, and B represents the mass (g) of the total solvent in the composition.)
(Equation 2)
X ′ = 750 / (C × D)
(However, C represents the proportion (mass%) of the monomer (A) in the copolymer contained in the composition, and D represents the proportion (mass%) of water in the total solvent contained in the composition.)

  In the composition, the copolymer is preferably a copolymer having a hydrophilic monomer as a constituent monomer. In the composition, it is preferable that the solvent is a volatile solvent.

  Moreover, the water repellent according to the present invention comprises the above composition. The cosmetic according to the present invention is characterized by comprising the above composition. Moreover, the hair treatment agent concerning this invention consists of the said composition. The skin cosmetic according to the present invention is characterized by comprising the above composition. In addition, the pack cosmetic according to the present invention is characterized by comprising the above composition. The processing method according to the present invention is characterized in that the copolymer molecules are crosslinked by heating or natural drying after the composition is applied to a material to be processed.

  When the copolymer according to the present invention is applied to a material to be treated, the solvent is volatilized by heating or natural drying, and the copolymer is crosslinked, thereby forming a strong crosslinked film on the surface. In addition, it is possible to impart good water repellency and antifouling property to the material to be treated, and furthermore, it can exist stably against water, acid and alkali, so it is highly stable against humidity, pH, etc. A formulation can be obtained. Further, the copolymer according to the present invention can be stably blended in a preparation containing water, and therefore, it can be used as a safer preparation with a relatively reduced amount of organic solvent. it can.

It is a figure which shows an example of the crosslinking reaction of the copolymer concerning this invention. It is explanatory drawing of the crosslinking reaction of the copolymer concerning this invention.

Hereinafter, preferred embodiments of the present invention will be described.
The monomer (A) represented by the general formula (I) is an ester of acrylic acid or methacrylic acid containing at least one reactive functional group in the reactive silyl group —SiR ₃ R ₄ R ₅ . In the general formula (I), R ₁ is a hydrogen atom or a methyl group. R ₂ means an alkylene group having 1 to 6 carbon atoms, preferably a propylene group. At least one of R ₃ , R ₄ , and R ₅ forms siloxane-bonded Si—O—Si by dehydration condensation of the functional group itself or a hydrolyzate of the functional group. It is a reactive functional group capable of crosslinking between copolymer molecules, and examples thereof include a hydrogen atom, a hydroxyl group, an alkoxy group, a halogen atom, an acyloxy group, and an amino group. From the viewpoints of the safety of by-products generated by decomposition and the reactivity of the crosslinking reaction described later, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms is preferable, and a methoxy group or an ethoxy group is particularly preferable.

In the monomer (A) represented by the general formula (I), R ₃ , R ₄ and R ₅ may be the same or different, and at least one of R ₃ , R ₄ and R ₅ is The reactive functional group may be trifunctional, bifunctional, or monofunctional. In the case of the bifunctional or monofunctional, R ₃ , R ₄ , and R _{5 each} include a non-reactive functional group such as a lower alkyl group such as a methyl group or an ethyl group in addition to the reactive functional group. It can have as long as it does not affect the crosslinking reaction. In the copolymer of the present invention, one or more of the above monomers (A) can be used as a constituent monomer.

  The monomer (A) represented by the general formula (I) has a reactive silyl group as described above, and crosslinks the copolymer molecules by forming the siloxane bond, thereby forming a crosslinked film. Form. And by performing such a crosslinking reaction on a to-be-processed material, durable high water repellency and antifouling property can be exhibited.

  As a monomer composition of the copolymer of this invention, the ratio of the monomer (A) in a copolymer is 0.1 to 25.0 mass% in a copolymer. When the proportion of the monomer (A) is 0.1% by mass or less, the number of cross-linking reaction sites is small, and the cross-linking reaction does not substantially occur or is slight. The effect may not be sufficiently exhibited. On the other hand, when the proportion of the monomer (A) is 25.0% by mass or more, there are too many crosslinking reaction sites, and the crosslinking reaction proceeds due to the presence of water, resulting in gelation. Alternatively, there is a concern about the stability of the copolymer in the presence of water because it produces an insoluble precipitate.

Furthermore, the copolymer of the present invention may have one or more kinds selected from the monomer (B) represented by the general formula (II) as a constituent monomer.
The monomer (B) represented by the general formula (II) is an ester of acrylic acid or methacrylic acid. In the general formula (II), R ₆ is a hydrogen atom or a methyl group, R ₇ is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, or a C 1-18 carbon atom. Fluorinated alkyl group, ethylene oxide (1 to 50 mol), propylene oxide (1 to 50 mol), copolymer of ethylene oxide and propylene oxide (1 to 50 mol, random or block), and terminal OH of these ethylene oxide and propylene oxide The group means an alkyl-capped group, preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group. In the copolymer of the present invention, one or more of the above monomers (B) can be used as a constituent monomer.

Monomer (B) represented by the general formula (II) contributes to the water repellency of the cross-linked film comprising a monomer (A), when R ₇ is hydrogen or ethylene oxide is highly water soluble, R ₇ is In the case of a long-chain alkyl group, the water repellency is increased due to the hydrophobicity. Therefore, the properties of the crosslinked film can be adjusted by balancing the composition of both. In addition, the monomer (B) can suppress flaking and stickiness of the crosslinked film. In the copolymer of the present invention, the proportion of the monomer (B) in the copolymer is preferably 1% by mass or more, and more preferably 10% by mass or more, but the monomer (B) in the copolymer When the ratio of the monomer is increased, the ratio of the other monomer inevitably decreases, and since the copolymer becomes hardly soluble in the alcohol solvent, the ratio of the monomer (B) is at most 75% by mass, Preferably it is 60 mass% or less.

Furthermore, the copolymer of the present invention may have one or more kinds selected from monomers (C) represented by the general formula (III) as constituent monomers.
The monomer (C) represented by the general formula (C) is a siloxane-containing (meth) acrylic ester. In the general formula (III), R ₈ is a hydrogen atom or a methyl group. R ₉ is an alkylene group having 1 to 6 carbon atoms, preferably an ethylene group, a propylene group or a 2-hydroxypropylene group. X means a siloxane represented by any one of the general formulas (IV) to (VI). In the general formulas (IV) to (VI), R ₁₀ , R ₁₁ , R ₁₁ ′, and R _{12 each} represent a linear or branched alkyl group having 1 to 6 carbon atoms or a phenyl group. In each of the general formulas, there are a plurality of R ₁₀ , R ₁₁ and R _12, but these may be the same or different. R ₁₀ , R ₁₁ and R ₁₂ are preferably methyl groups. R ₁₁ 'is preferably a butyl group. When X is the general formula (V) or the general formula (VI), the molecular weight of the monomer (C) is 1,000 to 100,000, preferably 2,000 to 20,000. In the copolymer of the present invention, one or more of the above monomers (C) can be used as a constituent monomer.

  The monomer (C) represented by the general formula (C) has a siloxane portion, thereby significantly increasing the water repellency of the crosslinked film and giving the fiber a smooth finish. And flaking can be suppressed. In the copolymer of the present invention, the proportion of the monomer (C) in the copolymer is preferably 1% by mass or more, more preferably 5% by mass or more in the copolymer. If the proportion is too large, the proportion of other monomers will be relatively lowered, and the water resistance tends to decrease. Therefore, the proportion of monomer (C) is at most 70% by mass, preferably 60% by mass. It is as follows.

Further, the copolymer of the present invention may further have one or more kinds selected from the monomers (D) represented by the general formula (VII) as constituent monomers.
The monomer (D) represented by the general formula (VII) is an amine-containing (meth) acrylic acid ester monomer. In the general formula (VII), R ₁₃ is a hydrogen atom or a methyl group. R ₁₄ means an alkylene group having 1 to 6 carbon atoms, preferably an ethylene group or a propylene group. Y is a group represented by —N ⁺ (R ₁₅ ) ₃ or —N (R ₁₅ ) ₂ , and R ₁₅ represents an alkyl group having 1 to 6 carbon atoms. In the case of -N ⁺ (R ₁₅ ) ₃ group, it may be a salt having a counter ion of halogen, organic acid or the like. In the copolymer of the present invention, one or more of the above monomers (D) can be used as a constituent monomer. The monomer (D) represented by the general formula (VII) has a hydrophilic amine moiety, which gives a smooth feeling to the fiber as well as a smooth feeling. In addition, since there exists a tendency for the hydrophilicity of a film to become high and to become inferior in water repellency by the amine part which a monomer (D) has when there are too many ratios of a monomer (D), the ratio of a monomer (D) is It is 1-100 mass% with respect to the total weight of the monomer (A), monomer (B), and monomer (C) in a copolymer, Preferably it is the range of 5-50 mass%.

The copolymer of the present invention can further have a hydrophilic monomer as a constituent monomer.
The hydrophilic monomer is a monomer having a hydrophilic group as typified by, for example, an amide group, a sulfuric acid group, a sulfonic acid group, a carboxylic acid group, a hydroxyl group, or an oxyethylene group. In the copolymer of the present invention, one or more of the above hydrophilic monomers can be used as a constituent monomer. By including the hydrophilic monomer in the copolymer composition, the dissolved state can be stably obtained even in a preparation containing a large amount of water, and the function as a copolymer can be sufficiently exhibited. If the ratio of the hydrophilic monomer is too large, the hydrophilicity of the film tends to be high and the water repellency tends to be poor. Therefore, the ratio of the hydrophilic monomer is based on the total weight of other monomers in the copolymer. It is 1-100 mass% with respect to it, Preferably it is the range of 5-50 mass%.

Examples of the hydrophilic monomer include acrylamide, methacrylamide, methylacrylamide, methylmethacrylamide, dimethylmethacrylamide, ethylacrylamide, ethylmethacrylamide, diethylmethacrylamide, N-isopropylacrylamide, 2-acrylamide-2-methylpropanesulfonic acid. N-vinylpyrrolidone, ε-caprolactam, vinyl alcohol, maleic anhydride, hydroxyethyl methacrylate, ethylene oxide, polydiallyldimethylammonium and the like.
In addition, as long as the effect of this invention is not impaired, it is also possible to have monomers other than the above as a constituent monomer of the copolymer of this invention.

  The copolymer according to the present invention can be obtained by polymerizing the above monomers using a known solution polymerization method. For example, the copolymer of this invention can be obtained by melt | dissolving in a solvent with the monomer composition which calculates | requires each monomer, adding a radical polymerization initiator under nitrogen atmosphere, and stirring with heating.

  As the solvent used in the polymerization, any solvent can be used as long as it can dissolve or suspend the monomer and does not contain water. For example, methanol, ethanol, propyl alcohol, Alcohol solvents such as isopropyl alcohol and butyl alcohol, hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane and liquid paraffin, ether solvents such as dimethyl ether, diethyl ether and tetrahydrofuran, and ketone solvents such as acetone and methyl ethyl ketone In addition to ester solvents such as methyl acetate, ethyl acetate, and butyl acetate, chloride solvents such as methylene chloride, chloroform, and carbon tetrachloride, dimethylformamide, diethylformamide, dimethylsulfoxide, dioxane, etc. It is. Two or more of these solvents may be mixed and used. Usually, it is suitable to select a solvent having a boiling point higher than the starting temperature of the polymerization initiator to be used.

  The polymerization initiator is not particularly limited as long as it has the ability to initiate radical polymerization. For example, peroxides such as benzoyl peroxide, azobisisobutyronitrile, 2,2′-azobis (isobutyric acid) ) In addition to azo compounds such as dimethyl, persulfuric acid polymerization initiators such as potassium persulfate and ammonium persulfate may be mentioned. In addition, it can superpose | polymerize by photochemical reaction, radiation irradiation, etc. irrespective of these polymerization initiators. The polymerization temperature is not less than the polymerization start temperature of each polymerization initiator. For example, in the case of a peroxide-based polymerization initiator, it may be usually about 70 ° C.

  The polymerization time is not particularly limited, but is usually 2 to 24 hours. When it is desired to obtain a relatively high molecular weight polymer, it is desirable to react for about one day. If the reaction time is too short, unreacted monomers may remain and the molecular weight may be relatively small. The average molecular weight of the copolymer of the present invention is not particularly limited, and a desired effect can be exhibited as long as it has a degree of polymerization higher than that of an oligomer. However, when the degree of polymerization becomes small, the speed of the crosslinking reaction described later decreases, and when the degree of polymerization is too large, the viscosity becomes high and the coating property and workability are poor, so the average molecular weight is 2,000 to 150. About 1,000,000.

Preferable examples of the copolymer according to the present invention include a copolymer represented by the following general formula (VIII) and a copolymer represented by the following general formula (IX).

なお、一般式（VIII）及び一般式（IX）中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９、Ｒ_１３、Ｒ_１４、Ｘ，Ｙは前記定義の通りである。ｎ、ｍ、ｌ、ｐはそれぞれモノマー（Ａ）、モノマー（Ｂ）、モノマー（Ｃ）、モノマー（Ｄ）のモル比を表す。なお、モノマー（Ａ）のモル比ｎは、モノマー（Ａ）の割合が共重合体全量中の０．１質量％以上２５質量％未満となるように調整される。

In general formula (VIII) and general formula (IX), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₃ , R ₁₄ , X, Y is as defined above. n, m, l, and p represent the molar ratio of the monomer (A), the monomer (B), the monomer (C), and the monomer (D), respectively. The molar ratio n of the monomer (A) is adjusted so that the proportion of the monomer (A) is 0.1% by mass or more and less than 25% by mass in the total amount of the copolymer.

  The copolymer of the present invention thus obtained has a reactive silyl group derived from the monomer (A). For this reason, when the reactive silyl group undergoes dehydration condensation, the copolymers of the present invention are crosslinked to form a crosslinked product. And by performing such a crosslinking reaction on a to-be-processed object, the crosslinked body film | membrane of a copolymer is formed in the surface, and durable high water repellency and antifouling property can be exhibited.

  Moreover, the crosslinked body film | membrane by the copolymer of this invention exhibits glueing property, a wrinkle extension, a wrinkle prevention effect with respect to a fiber material, and is excellent in the usability | use_condition. Moreover, while exhibiting firmness and firmness to the hair, it exhibits excellent shampoo resistance such that the effect is maintained without being lost even after repeated shampooing. In addition, for colored hair, discoloration during shampooing is suppressed, and the effect of significantly improving dyeing durability is provided. In addition, it protects against nails, skin, eyebrows, wrinkles, etc., and the film is very difficult to remove even with water or detergent. Excellent. Further, when used as a pack cosmetic, it has a feature that the skin plug, old stratum corneum, dirt and the like are removed together with the pack film, and the usability is very good.

The mechanism of action that produces such effects is considered as follows. FIG. 1 schematically shows an example of the crosslinking reaction of the copolymer according to the present invention. That is, the copolymer according to the present invention has a reactive silyl group -SiR ₃ R ₄ R ₅ derived from the monomer (A). This reactive silyl group is easily hydrolyzed with water, acid, alkali, or the like to form a hydroxysilyl group —Si (OH) _n (n = 1 to 3). Here, FIG. 1 shows a case of a trifunctional silyl group (n = 3). Such hydroxysilyl groups react with other hydroxysilyl groups to form stable siloxane-bonded Si-O-Si, and as a result, a crosslinked copolymer in which the copolymer molecules are crosslinked in a three-dimensional network. It becomes. In this way, the copolymer molecules of the present invention are cross-linked, and the cross-linked product forms a film excellent in water repellency and washing resistance by covering the material to be treated firmly and uniformly in a network. Inferred.

  Here, the copolymer having a reactive silyl group in the prior art is hydrolyzed into a hydroxysilyl group in the presence of water, and at the same time, a crosslinking reaction between the hydroxysilyl groups proceeds, resulting in gelation or insolubility. In the presence of water, it could not exist stably (FIG. 2 (a)). On the other hand, the copolymer of the present invention is adjusted even when the water content is contained by adjusting the ratio of the monomer (A) as low as 0.1% by mass or more and less than 25.0% by mass in the total amount of the copolymer. Further, since the distance between the hydroxysilyl groups after hydrolysis is sufficiently large, they can exist stably in the dispersion medium without proceeding with the crosslinking reaction (FIG. 2B). And, in the copolymer of the present invention, after coating, the dispersion medium is volatilized by heating or natural drying, the distance between the hydroxysilyl groups of the copolymer is reduced, and dehydration condensation, that is, a crosslinking reaction occurs. This is the first time a film is formed. In addition, the copolymer according to the present invention is stable without causing a crosslinking reaction even in the presence of an acid or an alkali for the same reason.

  Thus, the copolymer according to the present invention is stable because the crosslinking reaction does not proceed even in the presence of water, acid, and alkali. For this reason, the composition comprising the copolymer according to the present invention is less susceptible to external influences such as humidity and pH, and has a very good temporal stability compared to conventional silicone copolymers. In addition, the composition comprising the copolymer according to the present invention can be blended with these water, acid, and alkali, and therefore has a wide range of application to formulations and the like.

The copolymer according to the present invention is preferably made into a composition in the state of coexisting with water. That is, a preparation containing a large amount of an organic solvent is not preferable from the viewpoint of impact on the human body and the environment, and a preparation using water is particularly preferable for a preparation such as cosmetics used directly on the human body. The conventional reactive silicone copolymer could not exist stably because the crosslinking reaction proceeds due to coexistence with water, but the copolymer according to the present invention is in a coexistence state with water. Can also exist stably.
In a composition in which such a copolymer of the present invention and water are blended, the blending amount of water is preferably 80% by mass or less. If the blending amount of water is more than 80% by mass, the copolymer may become difficult to dissolve in the solvent and precipitate.

In the composition of the present invention, it is preferable that the copolymer concentration X represented by the following formula 5 is X ′% by mass or less represented by the following formula 6.
(Equation 3)
X = {A / (A + B)} × 100
(However, A shows the mass (g) of the copolymer contained in a composition, and B shows the mass (g) of all the solvents in a composition.)
(Equation 4)
X ′ = 750 / (C × D)
(However, C represents the proportion (mass%) of the monomer (A) in the copolymer contained in the composition, and D represents the proportion (mass%) of water in the total solvent contained in the composition.)
In the composition according to the present invention, when the copolymer concentration X defined in the formula 5 is greater than X ′% by mass defined in the formula 6, a crosslinking reaction occurs in the composition. In some cases, the appearance, applicability, extensibility, usability, etc. may be inferior.

  That is, normally, the copolymer of the present invention can be stably present in a state dispersed in a solvent without causing a crosslinking reaction, but the solvent is reduced due to volatilization or the like, and a certain amount of copolymer When the coalescence concentration is exceeded, the crosslinking reaction begins to occur due to the approaching of the hydroxysilyl group that is the crosslinking reaction site in the copolymer. Here, the concentration of the copolymer that can be stably dispersed without causing crosslinking in the composition depends on the proportion of the monomer (A) in the copolymer and the proportion of water in all the solvents in the composition. Therefore, it can be obtained in advance by the equation (6). Therefore, in the composition according to the present invention, the copolymer concentration X represented by the formula 5 is X ′ mass% represented by the formula 6 depending on the ratio of the monomer (A) in each copolymer. It is preferable to adjust so that it may become the following.

  Even in the case of a composition containing the copolymer and other components of the solvent in the composition, the copolymer concentration X defined in the present invention is as defined in the formula 5. It is defined only by the mass of the copolymer and the mass of the solvent. That is, the copolymer concentration X defined in the present invention must always be defined in the relationship between the copolymer and the solvent, and in a composition containing multiple components, the copolymer concentration is a normal mass. When the% concentration is used, the relationship between the copolymer concentration X and X ′ described above may not be established.

  In the composition of the present invention, it is preferable that the solvent contained in the composition is a volatile solvent. If a non-volatile solvent is used, the dispersion medium cannot be volatilized by heating or natural drying, and it is difficult to form a film. As volatile solvents, in addition to water, aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, ether solvents, alcohol solvents, C 1-4 aliphatic C1-C4 alcohols, ethyl cellosolve And sorbent solvents such as butylcellsolve, and volatile organic solvents such as dioxane, methyl acetate and dimethylformamide. From the viewpoint of safety, it is particularly preferable to use water alone or as a mixed solvent with these volatile organic solvents. Among these volatile organic solvents, preferred from the viewpoints of toxicity and safety are aliphatic and divalent alcohols such as methanol, ethanol, isopropanol, and propylene glycol. Particularly, from the viewpoint of safety, ethanol is ethanol. Isopropanol is preferred.

  As the material to be treated in the present invention, monofilaments, spun yarns, random fibers, textile materials in any form of woven fabric and final product, and the epidermis of hair, skin, nails, wrinkles and eyebrows are suitable. In addition to these, it is also possible to process other materials that require water repellency and antifouling properties, such as glass plates, glass products, metal plates, and metal products.

  The treatment method of the material to be treated using the composition according to the present invention is characterized in that the composition of the present invention is applied to the material to be treated and then crosslinked between the copolymer molecules by heating or natural drying. To do. That is, after applying the composition of the present invention, the dispersion medium is volatilized by heating or natural drying, etc., and dehydration condensation is performed by reducing the distance between the hydroxysilyl groups between the copolymers in the composition to form a crosslinked product. To do. Specifically, in clothing such as shirts, the composition is sprayed before ironing, and then ironed or steam ironed. In hair, the composition is sprayed or applied and then driered. A method is mentioned as a suitable method.

The dosage form of the composition concerning this invention is not specifically limited, What kind of thing may be sufficient if it is a form which can exhibit the effect of this invention. For example, liquid, emulsion, cream, gel, mist, spray, aerosol, mousse and the like can be mentioned.
The water-containing composition according to the present invention may contain other components as long as the effects of the present invention are not impaired. Examples include surfactants, ultraviolet absorbers, pH adjusters, preservatives, antioxidants, chelating agents, thickeners, film forming agents, oil components, polymer compounds, and propellants. In addition, it is also possible to mix | blend an acid and an alkali in a composition with the copolymer of this invention as mentioned above. If a coloring material such as a pigment or a pigment is blended, it is possible to form a water-resistant colored film, and blending an ultraviolet absorber can prevent the material to be treated from fading.

Examples of the present invention are given below, but the present invention is not limited thereto.
First, the evaluation method used in the present invention will be described.
Water Resistance Stability Various copolymers were added with water at various concentrations to 10% by mass ethanol solution, and allowed to stand for 1 month. The degree of gelation was visually judged to evaluate the stability.
◎… No change at all ○… Almost no change △… Some gelation.
X: Complete gelation is observed.

A 10% water / ethanol solution of each water repellent copolymer was sprayed onto a cotton shirt and allowed to air dry. A few drops of water were dropped on this shirt, and the water repellency was evaluated by visual judgment. Evaluation criteria A: Very good.
○: Good.
Δ: Slightly poor
X: Defect.

Antifouling property One drop of coffee liquid was dropped on a shirt treated in the same manner as in the above water repellency test, and the degree of soil adhesion after wiping with a separate cloth was visually determined to evaluate the antifouling property.
Evaluation criteria A: Very good.
○: Good.
Δ: Slightly poor
X: Defect.

Smoothness 2 g of a 10 mass% water / ethanol solution of each copolymer was applied to one piece of cotton (10 g) and air dried. The smoothness of this fabric was sensory-evaluated by touch with 20 professional panels.
Evaluation criteria A: 15 or more responded as good.
○: 10 to 14 people answered that it was good.
(Triangle | delta): Five to nine people answered that it was favorable.
X: Less than 4 responded as good.

Sensation of slimness The sense of slimness of the treated fabric in the same manner as in the smoothness test described above was sensory-evaluated by touch by 20 professional panels.
Evaluation criteria A: 15 or more responded as good.
○: 10 to 14 people answered that it was good.
(Triangle | delta): Five to nine people answered that it was favorable.
X: Less than 4 responded as good.

Dispersion stability Copolymer / water / ethanol solutions with various copolymer concentrations were prepared, the gelation state was visually judged, and the stability was evaluated.
◎… No change at all ○… Almost no change △… Some gelation.
X: Complete gelation is observed.

Next, the structure of each monomer used in the present invention is shown below.
Monomer A1:

Monomer B1:

Monomer B2:

Monomer C1:

Monomer C2:

Monomer C3:

Monomer D1:

The method for synthesizing the copolymer according to the present invention will be described below.
Synthesis example Copolymer 1 3-methacryloxypropyltrimethoxysilane (monomer A1) 0.5 g (2 mmol), methyl methacrylate (monomer B1) 4.75 g (47.5 mmol), butyl methacrylate (monomer B2) 75 g (35.4 mmol) was dissolved in 100 ml of ethanol, heated and stirred at 70 ° C. for 1 hour under a nitrogen stream, then added with 0.05 g of potassium persulfate and allowed to react overnight to complete the copolymerization reaction. The reaction solution was cooled to room temperature and concentrated under reduced pressure. The residue was dissolved in 10 ml of ethanol and added to 500 ml of n-hexane. The precipitate was collected to obtain the desired copolymer.
In addition, in the NMR spectrum data (solvent CDCl ₃ or DMSO-d ₆ ) of the obtained copolymer, a peak of a CH ₂ ═C hydrogen atom derived from a raw material monomer found in the vicinity of _{6 to} 7 ppm is not observed, This confirmed the production of the copolymer. In the present invention, the formation of the copolymer was confirmed in the same manner for other copolymers.

The present inventors prepared various copolymers according to the synthesis method shown above, and evaluated them.
The amount present inventors monomer (A) is first of all, to produce a variety of copolymers 1-5 was varied the amount of the monomer (A), the stability to water of each copolymer Was evaluated. Tables 1 and 2 show the results of water resistance stability tests at 37 ° C. and 50 ° C., respectively.

  As shown in Tables 1 and 2, Copolymers 1 to 3 containing 5.0 to 20.0% by mass of monomer (A) with respect to the total amount of monomers are excellent in water resistance stability and coexist with water. It was stable for a long time. On the other hand, in the copolymer 5 which mix | blended 50 mass% of monomers (A), the stability with respect to water was bad and gelled. This is presumably because the hydroxysilyl group of the monomer (A) caused a condensation reaction in the presence of water to form a crosslinked product. Further, in the copolymer 4 having a monomer (A) content of 25% by mass, gelation tends to start to occur at a high temperature (50 ° C.). Therefore, in the copolymer according to the present invention, in order for the hydroxysilyl group of the monomer (A) to exist so as not to form a crosslinked product, the ratio of the monomer (A) in the copolymer is: It became clear that it was necessary to be less than 25% by mass.

表３に示されるように、モノマー（Ａ）の割合が少ない共重合体１〜３においても、撥水性、防汚性について良好な結果を示した。 Furthermore, the present inventors evaluated the water repellency and antifouling property of the copolymers 1 to 3 according to the present invention. The results are shown in Table 3.

As shown in Table 3, also in the copolymers 1 to 3 having a small proportion of the monomer (A), good results were shown for water repellency and antifouling property.

Copolymer monomer composition Hereinafter, the present inventors further examined the composition of a suitable monomer of the copolymer according to the present invention.
Monomers (A) to (C)
The present inventors evaluated the copolymers 6 to 9 containing the monomers (A), (B), and (C). The results are shown in Table 4.

  As shown in Table 4, the copolymers 6 to 9 composed of the monomers (A) to (C) are very excellent in water repellency and antifouling properties, and are copolymerized from the monomers (A) and (B). Compared with the coalescence 1-3, it gave a smooth feeling of use. From this, by using the monomer (C) in the copolymer, it is possible to obtain a copolymer that is excellent in water repellency and antifouling properties and that gives a smooth feel to the fibers. Further, it was shown that the same effect can be obtained when the monomer (C) is any of the monomers C1, C2, and C3. In the case of the copolymer composed of the monomer (A) and the monomer (C), the stickiness is remarkably difficult to use, so the monomer (B) suppresses the stickiness and has an appropriate film property. It was suggested to give.

表５に示されるように、モノマー（Ａ）〜（Ｄ）からなる共重合体１０、１１は、モノマー（Ｄ）を用いることにより、更に繊維に対してぬめり感を与え、しっとりした感触を付与することができることが明らかとなった。 Monomer (D)
Furthermore, the present inventors evaluated the copolymers 10 and 11 containing the monomer (D). The results are shown in Table 5.

As shown in Table 5, the copolymers 10 and 11 composed of the monomers (A) to (D) give a slimy feeling to the fibers and give a moist feel by using the monomer (D). It became clear that it could be done.

Hydrophilic monomer Furthermore, by further detailed examination by the present inventors, the copolymer according to the present invention includes a hydrophilic monomer in the composition, so that a dissolved state can be stably obtained even in a preparation rich in water. It was revealed that the function as a copolymer can be sufficiently exhibited. That is, when the copolymer according to the present invention is allowed to coexist with a large amount of water, the copolymer itself becomes difficult to dissolve in a solvent, and insoluble precipitation may occur. In such a case, by including the hydrophilic monomer as described above in the copolymer composition, it is possible to stably exist in a state dispersed in a solvent containing a large amount of water.

Following copolymer concentration in the composition, the present inventors have found that when using copolymers according to the present invention as a composition, was examined preferred copolymer concentration (wt%).
The inventors first prepared a composition in which the copolymer 7 (the ratio of the monomer (A): 10% by mass) was dispersed as a copolymer in a solvent of water: alcohol = 60: 40. The dispersion stability was tested when the copolymer concentration (% by mass) was changed. The results are shown in Table 6.

  As shown in Table 6, when copolymer 7 (ratio of monomer (A): 10% by mass) was used, the copolymer concentration in the composition was 1.5% by mass or more. Gelation occurs and the composition cannot exist stably. This is because the hydroxysilyl groups of the monomer (A) between the copolymer molecules cannot be sufficiently separated due to dispersion in the solvent, and a condensation reaction has occurred in part to form a crosslinked product. Conceivable. That is, in the composition of the present invention, when the copolymer 7 having a monomer (A) ratio of 10% by mass is dispersed in a solvent having a water ratio of 60% by mass, the copolymer concentration is 1 It became clear that it was necessary to adjust so that it might become 25 mass% or less.

  Here, as described above, the inventors of the present invention have the gelation of the composition, that is, the progress of the crosslinking reaction, related to the distance between the hydroxysilyl groups of the monomer (A) in the copolymer molecule. Therefore, the copolymer concentration at which the crosslinking reaction starts was considered to depend on the proportion of the monomer (A) in the copolymer in the composition and the proportion of water in the solvent. Thus, the dispersion stability of the composition when the ratio of the monomer (A) in the copolymer and the blending ratio of water was changed was tested in the same manner as in the above test.

1. Relationship Between Copolymer Concentration in Composition and Ratio of Monomer (A) As the copolymer, the copolymer 1 (the ratio of the monomer (A): 5% by mass) was used, and water: alcohol = 60: 40. A composition dispersed in the above solvent was prepared, and the dispersion stability when the copolymer concentration (% by mass) was changed was tested. The results are shown in Table 7.

  As shown in Table 7, when the copolymer 1 having a monomer (A) ratio of 5% by mass was used and the copolymer concentration in the composition exceeded 2.5% by mass, the composition was It became clear that it could not exist stably. From the test results, in the case of the composition using the copolymer 7 in which the proportion of the monomer (A) is 10% by mass under the same conditions, the stable copolymer concentration is 1.25% by mass or less. In view of these results, the copolymer concentration capable of being stably dispersed in the composition is considered to depend on the proportion of the monomer (A) in the copolymer.

2. Relationship Between Copolymer Concentration in Composition and Water Blending Ratio in Solvent The copolymer 7 (monomer (A) ratio: 10% by mass) was used as a copolymer, and water: alcohol = 50: 50. A composition dispersed in the above solvent was prepared, and the dispersion stability when the copolymer concentration (% by mass) was changed was tested. The results are shown in Table 8.

  As shown in Table 8, when the blending ratio of water is 50% by mass, the composition cannot exist stably when the concentration of the copolymer 7 in the composition exceeds 1.5% by mass. It became clear. From the above test results, when the copolymer 7 was used and the blending ratio of water was 60% by mass, the stable copolymer concentration was 1.25% by mass or less. It is considered that the concentration of the dispersible copolymer depends on the blending ratio of water.

As described above, the concentration of the stable copolymer in the composition according to the present invention depends on both the proportion of the monomer (A) in the copolymer and the water blending proportion in the solvent. Conceivable. The present inventors have examined in more detail the relationship between the copolymer concentration, the ratio of the monomer (A) in the copolymer, and the water blending ratio in the solvent. As a result, the monomer in the copolymer In the composition in which the ratio of (A) is C mass% and the water blending ratio in the solvent is D mass%, the copolymer concentration in the composition is larger than X ′ mass% obtained from the following formula 7. Then, it became clear that it could not be stably dispersed.
(Equation 5)
X ′ = 750 / (C × D)
(However, C represents the proportion (mass%) of the monomer (A) in the copolymer contained in the composition, and D represents the proportion (mass%) of water in the total solvent contained in the composition.)

  That is, in the composition of the present invention in which the proportion of the monomer (A) in the copolymer is C mass% and the proportion of water in the solvent is D mass%, the copolymer concentration is determined by the above formula 7. When it is larger than X ′% by mass, a crosslinking reaction is initiated in the composition, and this causes gelation of the system, so that the composition cannot be kept stable. Therefore, in order to keep the composition according to the present invention stable, the copolymer concentration in the composition is determined according to the proportion of the monomer (A) of the copolymer and the blending proportion of water in the total solvent. It is necessary to adjust so that it may become X 'mass% or less calculated | required from said Formula 7, It is preferable to adjust beforehand in this way.

In addition, in the said test, since it tested using the copolymer single component solution, the copolymer density | concentration was shown as the mass%, However, The above relationship is applied in the composition containing multiple components. For this purpose, it is necessary to use a copolymer concentration calculated according to the formula shown in the following equation (8).
(Equation 6)
X = {A / (A + B)} × 100
(However, A shows the mass (g) of the copolymer contained in a composition, B shows the mass (g) of the solvent in a composition.)
That is, it is considered that the copolymer concentration defined in the present invention must always be defined in the relationship between the copolymer and the solvent. For this reason, in the composition concerning this invention, it is suitable that the copolymer density | concentration X shown by said Formula 8 is below X 'calculated | required by said Formula 7.

Examples of suitable synthesis of the copolymer according to the present invention are shown below.
Synthesis Example 1 3-Methacryloxypropyltrimethoxysilane 0.5 g (2 mmol), methyl methacrylate 4.5 g (45 mmol), butyl methacrylate 4.5 g (34 mmol), methacryloxyethyltri (trimethylsiloxy) silane 0.5 g (1.5 mmol) was dissolved in 100 ml of ethanol and heated and stirred at 70 ° C. for 1 hour under a nitrogen stream. Then, 0.05 g of potassium persulfate was added and reacted overnight to complete the copolymerization reaction. The reaction solution was cooled to room temperature and concentrated under reduced pressure. The residue was dissolved in 10 ml of ethanol and added to 500 ml of n-hexane. The precipitate was collected to obtain the desired copolymer.

Synthesis Example 2 3-methacryloxypropyltrimethoxysilane 0.5 g (2 mmol), methyl methacrylate 4.0 g (40 mmol), butyl methacrylate 4.0 g (30 mmol), methacryloxyethyltri (trimethylsiloxy) silane 0.5 g (1.5 mmol) and 1.0 g (6.4 mmol) of acryloxyethyldiethylamine were dissolved in 100 ml of ethanol, heated and stirred at 70 ° C. for 1 hour under a nitrogen stream, and 0.05 g of potassium persulfate was added to react overnight. To complete the copolymerization reaction. The reaction solution was cooled to room temperature and concentrated under reduced pressure. The residue was dissolved in 10 ml of ethanol and added to 500 ml of n-hexane. The precipitate was collected to obtain the desired copolymer.

Synthesis Example 3 3-Methacryloxypropyltrimethoxysilane 0.5 g (2 mmol), methyl methacrylate 3.5 g (35 mmol), butyl methacrylate 3.5 g (26 mmol), acryloxyethyl diethylamine 1.0 g (6.4 mmol) , 0.5 g (1.5 mmol) of methacryloxyethyltri (trimethylsiloxy) silane and 1.0 g (14.3 mmol) of acrylamide were dissolved in 100 ml of ethanol and heated and stirred at 70 ° C. for 1 hour under a nitrogen stream. 0.05 g of potassium sulfate was added and reacted overnight to complete the copolymerization reaction. The reaction solution was cooled to room temperature and concentrated under reduced pressure. The residue was dissolved in 10 ml of ethanol and added to 500 ml of n-hexane. The precipitate was collected to obtain the desired copolymer.

Synthesis Example 4 3-methacryloxypropyldimethoxymethylsilane 1.0 g (4 mmol), methyl methacrylate 3.5 g (30 mmol), butyl methacrylate 3.5 g (26 mmol), acryloxyethyl diethylamine 1.0 g (6.4 mmol) , 0.5 g (1.5 mmol) of methacryloxyethyltri (trimethylsiloxy) silane and 0.5 g of methoxypolyethoxyethyl methacrylate were dissolved in 100 ml of ethanol and heated and stirred at 70 ° C. for 1 hour under a nitrogen stream. 0.05 g of potassium sulfate was added and reacted overnight to complete the copolymerization reaction. The reaction solution was cooled to room temperature and concentrated under reduced pressure. The residue was dissolved in 10 ml of ethanol and added to 500 ml of n-hexane. The precipitate was collected to obtain the desired copolymer.

Synthesis Example 5 3-methacryloxypropylmethoxydimethylsilane 1.0 g (4 mmol), methyl methacrylate 3.5 g (30 mmol), butyl methacrylate 3.5 g (26 mmol), acryloxyethyl diethylamine 1.0 g (6.4 mmol) , 0.5 g (1.5 mmol) of methacryloxyethyltri (trimethylsiloxy) silane and 0.5 g (3.8 mmol) of hydroxyethyl methacrylate were dissolved in 100 ml of ethanol, and the mixture was heated and stirred at 70 ° C. for 1 hour under a nitrogen stream. Thereafter, 0.05 g of potassium persulfate was added and reacted overnight to complete the copolymerization reaction. The reaction solution was cooled to room temperature and concentrated under reduced pressure. The residue was dissolved in 10 ml of ethanol and added to 500 ml of n-hexane. The precipitate was collected to obtain the desired copolymer.

Below, the suitable compounding example of the copolymer concerning this invention is shown. In addition, all compounding quantities are represented by mass%.
Formulation Example 1 Hairpack mass%
(1) Methylpolysiloxane 2.0
(2) Cetanol 3.0
(3) Behenyl alcohol 3.0
(4) Glycerin 4.0
(5) Diglycerin 2.0
(6) Cetyl 2-ethylhexanoate 1.0
(7) Glycerin monostearate 1.0
(8) Stearyltrimethylammonium chloride 2.0
(9) Citric acid 0.1
(10) Hydrolyzed marine collagen 0.05
(11) Oil-soluble plant protein 0.05
(12) Amino-modified polysiloxane (Toray Dow SM8702C) 1.0
(13) High molecular weight polysiloxane (n = 4000) 0.5
(14) Copolymer 7 0.5
(15) Paraben 0.2
(16) Perfume proper amount (17) Purified water remaining amount

Formulation Example 2 Hair Finish Spray Stock Solution / LPG = 55/45
Stock solution mass%
(1) Methylphenylpolysiloxane 0.5
(2) Residual amount of ethanol (3) 1,3-butylene glycol 0.5
(4) Liquid lanolin 0.2
(5) Cetyl 2-ethylhexanoate 0.5
(6) Lauric acid diethanolamide 0.5
(7) Pyroglutamic acid isostearic acid POE hydrogenated castor oil 0.2
(8) Paraben 0.2
(9) 2-Ethylhexyl paramethoxycinnamate 0.5
(10) Copolymer 6 1.0
(11) Oil-soluble plant protein 0.02
(12) Hydrolyzed marine collagen 0.02
(13) Hydrolyzed eggshell membrane 0.02
(14) Perfume appropriate amount (15) Purified water 10.0

Formulation Example 3 Hair Spray Stock Solution / LPG = 50/50
Stock solution mass%
(1) Liquid paraffin 6.0
(2) Methylpolysiloxane 3.0
(3) Methylphenylpolysiloxane 2.0
(4) Residual amount of ethanol (5) Oil-soluble plant protein 0.03
(6) Decyltetradecanol 6.0
(7) Cetyl 2-ethylhexanoate 3.0
(8) Copolymer 6 1.0

Formulation Example 4 Foam set stock solution / LPG = 90/10
Stock solution mass%
(1) Propylene glycol 10.0
(2) Yuka Former SM (Mitsubishi Chemical Corporation) 5.0
(3) Copolymer 6 0.5
(4) Polyoxyethylene (60) hydrogenated castor oil 1.0
(5) POE monolaurate (20) sorbitan 1.0
(6) Diisostearyl malate 2.0
(7) Dimethylpolysiloxane 1.0
(8) Myristic acid 4.0
(9) Triethanolamine 2.0
(10) Purified water balance

Formulation Example 5 Rinse mass%
(1) Liquid paraffin 1.0
(2) Methylpolysiloxane 3.0
(3) Cetanol 1.0
(4) Octyldodecanol 3.0
(5) Oil-soluble plant protein 0.1
(6) Propylene glycol 5.0
(7) Polyoxyethylene hydrogenated castor oil 0.5
(8) Polyoxyethylene stearyl ether 0.5
(9) Alkyltrimethylammonium chloride 1.5
(10) Citric acid 0.1
(11) Potassium chloride 0.5
(12) Copolymer 7 0.5
(13) Phenoxyethanol 0.3
(14) Pyrithione zinc solution (50%) 0.01
(15) Hydrolyzed marine collagen 0.1
(16) Purified water remaining amount (17) Perfume appropriate amount

Formulation Example 6 Cream mass%
(1) Vaseline 2.0
(2) Methylpolysiloxane 3.0
(3) Cetanol 2.0
(4) Glycerin 3.0
(5) 1,3-butylene glycol 5.0
(6) Hardened oil 2.0
(7) Stearic acid 2.0
(8) Glyceryl tri-2-ethylhexanoate 3.5
(9) Polyoxyethylene glyceryl isostearate 0.7
(10) Glycerin monostearate 2.3
(11) Potassium hydroxide 0.15
(12) Sodium hexametaphosphate 0.01
(13) Sodium hyaluronate 0.1
(14) Ascorbic acid phosphate magnesium 2.0
(15) Paraben 0.3
(16) Carboxyvinyl polymer 0.05
(17) Copolymer 8 0.5
(18) Hydrolyzed marine collagen 0.1
(19) Oil-soluble plant protein 0.1
(20) Purified water remaining amount (21) Perfume appropriate amount

Formulation Example 7 Gel mass%
(1) Ethanol 5.0
(2) Glycerin 8.0
(3) Polyoxyethylene methyl glucoside 4.0
(4) POE (12) lauryl ether 1.0
(5) Lauryldimethylamine oxide 0.3
(6) Potassium hydroxide 0.5
(7) Hydrolyzed marine collagen 1.0
(8) L-ascorbic acid-2-glucoside 2.0
(9) Paraben 0.3
(10) Carboxyvinyl polymer 0.6
(11) Copolymer 7 0.5
(12) Purified water remaining amount (13) Perfume appropriate amount

Formulation Example 8 Whitening cream mass%
(1) Liquid paraffin 5.0
(2) Vaseline 1.0
(3) Methylpolysiloxane 2.0
(4) Ethanol 3.0
(5) Cetanol 0.5
(6) Glycerin 6.0
(7) 1,3-butylene glycol 6.0
(8) Polyethylene glycol 1500 1.0
(9) Hardened oil 2.0
(10) Cetyl 2-ethylhexanoate 4.0
(11) Polyoxyethylene glyceryl isostearate 1.0
(12) Polyoxyethylene glycerol monostearate 1.0
(13) Potassium hydroxide 0.1
(14) Sodium metaphosphate 0.02
(15) Arginine hydrochloride 0.1
(16) DL-α-tocopherol acetate 0.1
(17) Oil-soluble plant protein 0.5
(18) Rosemary extract 1.0
(19) Sodium hyaluronate 0.2
(20) Arbutin 5.0
(21) Phenoxyethanol 0.3
(22) Edetate trisodium 0.05
(23) 2-Ethylhexyl paramethoxycinnamate 1.0
(24) Xanthan gum 0.1
(25) Copolymer 9 0.5
(26) Remaining amount of purified water (27) Appropriate amount of perfume

Formulation Example 9 Hair Manicure Mass%
(1) Benzyl alcohol 10.0
(2) N-methylpyrrolidone 15.0
(3) Citric acid 3.0
(4) Hydrolyzed marine collagen 0.1
(5) Xanthan gum 1.0
(6) Copolymer 10 0.5
(7) Acid dye 0.8

Formulation Example 10 O / W Sun Protector Mass%
(1) Dimethylpolysiloxane 3.0
(2) Dioctyl succinate 3.0
(3) Octylmethoxycinnamate 7.0
(4) Carboxybonyl polymer 0.3
(5) PEMULEN TR-2 ^TM (Goodrich) 0.1
(6) Copolymer 10 0.5
(7) Glycerin 10.0
(8) Hardened castor oil 0.5
(9) Fine particle silica 0.5
(10) Preservative appropriate amount (11) pH adjuster appropriate amount (12) Fragrance appropriate amount (13) Remaining amount of ion-exchanged water

Formulation Example 11 W / O sunscreen mass%
(1) Dimethylpolysiloxane 5.0
(2) Decamethylcyclopentasiloxane 20.0
(3) Polyoxyethylene methyl polysiloxane copolymer 4.0
(4) 1,3-butylene glycol 5.0
(5) Cetyl octanoate 7.0
(6) Sorbitan sesquiisostearate 0.5
(7) Dextrin palmitate-treated fine zinc oxide 10.0
(8) Fine particle titanium oxide 5.0
(9) Dimethyl distearyl ammonium hectorite 1.0
(10) Spherical polymethyl methacrylate resin 4.0
(11) Copolymer 10 1.0
(12) Preservative appropriate amount (13) pH adjuster appropriate amount (14) Fragrance appropriate amount (15) Ion-exchanged water remaining amount

Formulation Example 12 Hair Cream Mass%
(1) Dimethylpolysiloxane 5.0
(2) Isoparaffin 7.0
(3) Ethanol 5.0
(4) Glycerin 5.0
(5) Polyoxypropylene decaglyceryl ether 2.0
(6) Isostearic acid 1.0
(7) Hardened castor oil 0.5
(8) Imidazolium betaine 3.0
(9) Xanthan gum 0.5
(10) Copolymer 11 0.5
(11) Preservative appropriate amount (12) pH adjuster appropriate amount (13) Fragrance appropriate amount (14) Residual amount of ion-exchange water

Formulation Example 13 Hair Treatment Mass%
(1) Dimethylpolysiloxane 3.0
(2) Amino-modified silicone 0.6
(3) Polyoxyethylene methyl polysiloxane copolymer 0.5
(4) Ethanol 10.0
(5) Propylene glycol 6.0
(6) Xanthan gum 0.1
(7) Carboxyvinyl polymer 0.3
(8) PEMULEN TR-2 ^TM (Goodrich) 0.1
(9) Copolymer 7 0.5
(10) Preservative appropriate amount (11) pH adjuster appropriate amount (12) Fragrance appropriate amount (13) Remaining amount of ion-exchanged water

Formulation Example 14 Mascara mass%
(1) Light isoparaffin 7.0
(2) Methylpolysiloxane (5000 mPa) 2.0
(3) Decamethylcyclopentasiloxane 12.0
(4) 1,3-butylene glycol 4.0
(5) Dioleic acid polyethylene glycol 1.0
(6) Polyglyceryl diisostearate 4.0
(7) Paraben appropriate amount (8) Black iron oxide 7.0
(9) Bentonite 0.5
(10) Dimethyl distearyl ammonium hectorite 5.0
(11) Heavy liquid isoparaffin 5.0
(12) Polyvinyl acetate 8.0
(13) Polyvinyl alcohol 2.0
(14) Copolymer 11 1.0
(15) Nylon fiber 6.0
(16) Trimethylsiloxysilicic acid 2.0
(17) Residual amount of purified water

Claims (9)

In the monomer (A) represented by the following general formula (I), the monomer (B) represented by the following general formula (II), the monomer (C) represented by the following general formula (III), and the following general formula (VII) In the copolymer having the monomer (D) shown as a constituent monomer, the proportion of the monomer (A) is 0.1% by mass or more and less than 25.0% by mass in the copolymer, and the copolymer produced by solution polymerization Coalescence,
Containing water,
A composition having a copolymer concentration X in the composition represented by the following formula 1 of X ′% by mass or less represented by the following formula 2.

(In general formula (I), R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 1 to 6 carbon atoms, R ₃ , R ₄ , and R ₅ are at least one of the functional group itself or its Reactive functional groups that the hydrolyzate can crosslink between the copolymer molecules means non-reactive functional groups other than reactive functional groups.

(In general formula (II), R ₆ is a hydrogen atom or a methyl group, R ₇ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 18 carbon atoms, ethylene oxide (1 to 50 mol)) , Propylene oxide (1 to 50 mol), copolymers of ethylene oxide and propylene oxide (1 to 50 mol, random or block), or those having terminal OH groups of these alkylene oxides having 1 to 18 carbon atoms. means.)

(In the general formula (III), R ₈ represents a hydrogen atom or a methyl group, and R ₉ represents an alkylene group having 1 to 6 carbon atoms. X is represented by any one of the following general formulas (IV) to (VI)). Meaning a group.)

(In general formula (IV), R ₁₀ represents an alkyl group having 1 to 6 carbon atoms.)

(In the general formula (V), R ₁₁ and R ₁₁ ′ represent an alkyl group having 1 to 6 carbon atoms, and x ₁ represents a positive integer.)

(In general formula (VI), R ₈ and R ₉ are as defined above. R ₁₂ represents an alkyl group having 1 to 6 carbon atoms, and x ₂ represents a positive integer.)

(In the general formula (VII), R ₁₃ represents a hydrogen atom or a methyl group, R ₁₄ represents an alkylene group having 1 to 6 carbon atoms. Y represents —N ⁺ (R ₁₅ ) ₃ or —N (R ₁₅ ) _2. And R ₁₅ means an alkyl group having 1 to 6 carbon atoms.)
(Equation 1)
X = {A / (A + B)} × 100
(However, A represents the mass (g) of the copolymer in the composition, and B represents the mass (g) of the total solvent in the composition.)
(Equation 2)
X ′ = 750 / (C × D)
(However, C represents the proportion (mass%) of the monomer (A) in the copolymer contained in the composition, and D represents the proportion (mass%) of water in the total solvent contained in the composition.) 2. The composition according to claim 1, wherein the copolymer is a copolymer further having a hydrophilic monomer as a constituent monomer. 3. The composition according to claim 1 or 2, wherein the solvent is a volatile solvent. A water repellent comprising the composition according to any one of claims 1 to 3. A cosmetic comprising the composition according to any one of claims 1 to 3. A hair treatment agent comprising the composition according to any one of claims 1 to 3. A skin cosmetic comprising the composition according to any one of claims 1 to 3. A pack cosmetic comprising the composition according to any one of claims 1 to 3. A material to be treated using the composition, wherein the copolymer molecule is crosslinked by heating or natural drying after applying the composition according to any one of claims 1 to 3 to the material to be treated. Processing method.

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