JP2006131886A - Surface treating agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface treating agent which enables imparting excellent hydrophobicity to a powder and improving wash-down properties. <P>SOLUTION: The surface treating agent comprises a polymer containing a monomer (A) represented by formula (1) (wherein R<SP>1</SP>is hydrogen or a 1-3C alkyl group; R<SP>2</SP>is a 4-22C alkylene group; X<SP>1</SP>is an -NH- group or oxygen; and M<SP>1</SP>is hydrogen or a monovalent inorganic or organic cation) as a constituting monomer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to imparting hydrophobicity to surface treatment agents, particularly cosmetic powders, and improving wash-out properties.

  In cosmetics, in particular, makeup cosmetics, the aesthetic effect that makes a person look beautiful is natural, and the sustainability of the effect, that is, the longevity of makeup is also required as one of the extremely important performances. For this reason, in the development of cosmetic bases, improvement of makeup retention has become an important issue. In the field of makeup cosmetics, oily bases are often used so that makeup collapse does not occur due to moisture such as sweat, tears or saliva. When the powder is blended, separation from the base is likely to occur, and the hydrophilic powder flows out due to moisture, which is a major cause of makeup collapse. Because of these problems, conventionally, when powders are blended in cosmetics, it has been widely practiced to blend hydrophobic powders that have been previously hydrophobized.

  Many methods are known for hydrophobizing cosmetic powders, such as higher fatty acids, higher alcohols, hydrocarbons, triglycerides, esters, silicone oils, silicone resins such as silicone resins, or fluorine compounds. A method of applying hydrophobicity to the powder by coating the surface of the hydrophilic powder is used. Among them, since the hydrophobic treatment of powder using silicones as a surface treatment agent can impart particularly excellent hydrophobicity, many methods have been established so far (for example, Patent Document 1, Patent Document 1). 2). In recent years, a method of using a copolymer of acrylic acid or an acrylic ester as a powder surface treatment agent is also known (see, for example, Patent Document 3).

  On the other hand, in cosmetics, its washability is also required as one of the important performances. However, when the above-described conventional hydrophobized powder is blended, it can improve makeup durability, but it can be easily washed away with water even if soap is used because of its excellent hydrophobicity. Can not. For this reason, oil-based washing-off preparations are widely used, but this oil-based preparation needs to be washed away with soap or the like, which places a heavy burden on the user. Further, when a hydrophilic powder is blended for the purpose of facilitating washing off, as described above, makeup collapse is likely to occur, resulting in inferior makeup. For this reason, it is a very difficult task to satisfy both performances at the same time, being able to maintain its effect for a long time while applying makeup, while being able to wash off easily when removing makeup. Met.

JP-A-60-16397 JP-A-62-177070 JP-A-8-337514

  The present invention has been made in view of the above-described problems, and its object is to provide a surface treatment agent that imparts excellent hydrophobicity to powder and improves its wash-out property. It is to provide.

  As a result of the inventors' diligent research in view of the above-mentioned problems, the surface treatment of the powder with a polymer containing an acrylic derivative having a specific structure as a constituent monomer is focused on the pH-responsive hydrophobic-hydrophilic change. When used as an agent, it became clear that the hydrophobicity-hydrophilicity of the treated powder changed dramatically with respect to pH change. That is, the powder treated with the surface treatment agent exhibits excellent hydrophobicity in an acidic to neutral region where general cosmetics are used, while it has an appropriate basic environment with soapy water or the like. The surface of the powder changes to hydrophilic. As a result, when the treated powder is blended in the cosmetic, it can be easily washed away with water using soap or the like, despite having excellent makeup. Thus, the present inventors have found that by treating the surface of the powder with the surface treatment agent, excellent hydrophobicity is imparted to the powder, and the washing property is remarkably improved. The present invention has been completed.

（式中、Ｒ^１は水素又は炭素数１〜３のアルキル基、Ｒ^２は炭素数４〜２２のアルキレン基、Ｘ^１は−ＮＨ−基又は酸素原子、Ｍ^１は水素又は１価の無機又は有機カチオンを表す。）
また、前記表面処理剤において、前記モノマー（Ａ）を構成モノマー全量中７０モル％以上含有するポリマーからなることが好適である。 That is, the surface treating agent according to the present invention is characterized by comprising a polymer containing a monomer (A) represented by the following general formula (1) as a constituent monomer.

(In the formula, R ¹ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ² is an alkylene group having 4 to 22 carbon atoms, X ¹ is an —NH— group or an oxygen atom, M ¹ is hydrogen or a monovalent inorganic group. Or represents an organic cation.)
The surface treatment agent preferably comprises a polymer containing 70 mol% or more of the monomer (A) in the total amount of the constituent monomers.

（式中、Ｒ^３は水素又は炭素数１〜３のアルキル基、Ｒ^４は炭素数１〜４のアルキレン基、Ｘ^２は−ＮＨ−基又は酸素原子、Ｍ^２は水素又は１価の無機又は有機カチオンを表す。） Moreover, it is suitable that the surface treatment agent further comprises a polymer containing a monomer (B) represented by any one of the following general formulas (2) to (7) as a constituent monomer.

(Wherein R ³ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ⁴ is an alkylene group having 1 to ⁴ carbon atoms, X ² is an —NH— group or an oxygen atom, and M ² is hydrogen or a monovalent inorganic group. Or represents an organic cation.)

（式中、Ｒ^５は水素又は炭素数１〜３のアルキル基、Ｒ^６は炭素数１〜１０のアルキル基、フッ化アルキル基、アミノアルキル基、又はヒドロキシアルキル基、Ｘ^３は−ＮＨ−基又は酸素原子を表す。）

(Wherein R ⁵ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ⁶ is an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group, an aminoalkyl group, or a hydroxyalkyl group, and X ³ is —NH—. Represents a group or an oxygen atom.)

（式中、Ｒ^７は水素又は炭素数１〜３のアルキル基、Ｒ^８は炭素数１〜４のアルキレン基、Ｒ^９は同一又は異なっていてもよい水素又は炭素数１〜４のアルキル基、Ｘ^４は−ＮＨ−基又は酸素原子、Ｙ⁻は１価の有機又は無機アニオンを表す。）

(Wherein R ⁷ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ⁸ is an alkylene group having 1 to 4 carbon atoms, R ⁹ is the same or different hydrogen or alkyl group having 1 to 4 carbon atoms. X ⁴ represents an —NH— group or an oxygen atom, and Y ⁻ represents a monovalent organic or inorganic anion.)

（式中、Ｒ^１０は水素又は炭素数１〜３のアルキル基、Ｒ^１１は炭素数１〜４のアルキレン基、Ｒ^１２は水素又は炭素数１〜４のアルキル基、Ｘ^５は−ＮＨ−基又は酸素原子、ｌは１〜１００の整数を表す。）

Wherein R ¹⁰ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ¹¹ is an alkylene group having 1 to 4 carbon atoms, R ¹² is hydrogen or an alkyl group having 1 to 4 carbon atoms, and X ⁵ is —NH—. Group or oxygen atom, l represents an integer of 1 to 100)

（式中、Ｒ^１３は水素又は炭素数１〜３のアルキル基、Ｒ^１４は同一又は異なっていてもよい水素又は炭素数１〜４のアルキル基、Ｒ^１５は水素又は炭素数１〜４のアルキル基、Ｘ^６は−ＮＨ−基又は酸素原子、ｍは１〜１００の整数を表す。）

(Wherein R ¹³ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ¹⁴ is hydrogen which may be the same or different, or an alkyl group having 1 to 4 carbon atoms, and R ¹⁵ is hydrogen or one having 1 to 4 carbon atoms. An alkyl group, X ⁶ represents an —NH— group or an oxygen atom, and m represents an integer of 1 to 100.)

（式中、Ｒ^１６は水素又は炭素数１〜３のアルキル基、Ｒ^１７は炭素数１〜４のアルキレン基、Ｘ^７は−ＮＨ−基又は酸素原子、Ｍ^３は水素１価の無機又は有機カチオン、ｎは１〜１００の整数を表す。）

(Wherein R ¹⁶ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ¹⁷ is an alkylene group having 1 to 4 carbon atoms, X ⁷ is an —NH— group or an oxygen atom, and M ³ is a monovalent inorganic hydrogen or Organic cation, n represents an integer of 1 to 100)

  In the surface treatment agent, the ratio of the monomer (A) to the monomer (B) is preferably (A) :( B) = 70: 30 to 99.9: 0.1 in molar ratio. It is.

  By treating the surface of the powder with the surface treating agent according to the present invention, excellent hydrophobicity can be imparted to the powder, and the washing-off property can be remarkably improved.

Hereinafter, preferred embodiments of the present invention will be described in detail.
In addition, the surface treating agent concerning this invention consists of a polymer which contains the monomer (A) shown by the said General formula (1) as a structural monomer, It is characterized by the above-mentioned.
The monomer (A) represented by the general formula (1) is a compound in which a fatty acid is added in acrylic acid or alkyl-substituted acrylic acid, or acrylamide or alkyl-substituted acrylamide. In the general formula (1), R ¹ is hydrogen or an alkyl group having 1 to 3 carbon atoms. When R ¹ is an alkyl group, it may be linear or branched. R ¹ is preferably hydrogen or a methyl group. In the general formula (1), ^{R 2} is an alkylene group having 4 to 22 carbon atoms. The alkylene group may be linear or branched. Examples of R ² include an octylene group having 8 carbon atoms, an 11 undecylene group, and a 12 dodecylene group. R ² may include an aromatic ring or a carbon-carbon double bond in the structure, and may be, for example, a vinylene group, a methylphenylene group, a vinylphenylene group, or the like. In the general formula (1), X ¹ is a —NH— group or an oxygen atom, and particularly preferably a —NH— group. In the general formula (1), M ¹ is hydrogen or a monovalent inorganic or organic cation. The monovalent inorganic or organic cation is not particularly limited as long as it can form a salt of a carboxylic acid, and examples of the monovalent inorganic cation include sodium ion, potassium ion, lithium ion, and the like. Examples of the organic cation include ammonium ion, monoethanolammonium ion, triethanolammonium ion, and the like. Regarding M ¹ , after polymer production, it is reversibly converted into a carboxylic acid (M ¹ = hydrogen) or sodium salt (M ¹ = sodium) form using an appropriate amount of dilute hydrochloric acid or dilute sodium hydroxide solution. It is also possible.

  Examples of the monomer (A) used in the present invention include 11-methacrylamidoundecanoic acid, 8-acrylamidooctanoic acid, 12-acrylamidododecanoic acid, 12-methacrylamideamidododecanoic acid, 3- {4-[(methacryloxy) methyl. ] Phenyl} acrylic acid and the like. In the polymer of the present invention, one or more of the monomers (A) can be used as a constituent monomer.

  In the polymer according to the present invention, the monomer (A) is preferably contained in an amount of 70 mol% or more based on the total amount of the constituent monomers. When the monomer (A) is less than 70 mol%, the hydrophobic-hydrophilic adjustment effect is small, and the desired performance may not be imparted to the powder. Further, the monomer (A) is particularly preferably 90 mol% or more. In addition, in the polymer concerning this invention, the said monomer (A) may occupy the whole quantity of a structural monomer.

Moreover, as a polymer of this invention, the monomer (B) shown in any one of the said general formula general formula (2)-(7) can be used suitably as structural monomers other than the said monomer (A). .
The monomer represented by the general formula (2) is a compound in which an alkylsulfonic acid is added in acrylic acid or alkyl-substituted acrylic acid, or acrylamide or alkyl-substituted acrylamide. In general formula (2), ^{R 3} is an alkyl group having 1 to 3 carbon hydrogen or carbon. When R ³ is an alkyl group, it may be linear or branched. R ³ is preferably hydrogen or a methyl group. In the general formula (2), ^{R 4} is an alkylene group having 1 to 4 carbon atoms. The alkylene group may be linear or branched. Examples of R ⁴ include a methylene group, an ethylene group, and a propylene group, and an ethylene group and a propylene group are particularly preferable. In the general formula (2), ^{X 2} is an -NH- group or an oxygen atom, and particularly preferably -NH- group. In the general formula (2), M ² is hydrogen or a monovalent inorganic or organic cation. Any monovalent inorganic or organic cation may be used as long as it can form a sulfonic acid salt. Examples of the monovalent inorganic cation include sodium ion, potassium ion, lithium ion, and the like. Examples of the organic cation include ammonium ion, monoethanolammonium ion, triethanolammonium ion, and the like. Regarding M ² , after the production of the polymer, it is reversibly converted into a sulfonic acid (M ² = hydrogen) or sodium salt (M ² = sodium) form using an appropriate amount of dilute hydrochloric acid or dilute sodium hydroxide solution. It is also possible.

  Examples of the monomer represented by the general formula (2) include 2-acrylamido-2-methylpropanesulfonic acid, potassium 3-methacryloxypropanesulfonate, and the like.

The monomer represented by the general formula (3) is acrylic acid, alkyl-substituted acrylic acid, or an alkyl adduct of acrylamide or alkyl-substituted acrylamide. In the general formula (3), R ⁵ is hydrogen or an alkyl group having 1 to 3 carbon atoms, and when R ⁵ is an alkyl group, it may be linear or branched. R ⁵ is preferably hydrogen or a methyl group. In the general formula (3), R ⁶ represents an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group containing one or more fluorine atoms, an aminoalkyl group containing one or more amino groups, or one or more hydroxyl groups. It is a hydroxyalkyl group containing. These alkyl groups may be linear or branched. When R ⁶ is an alkyl group, examples thereof include a methyl group, an ethyl group, a pentyl group, an octyl group, a decyl group, a 2-ethylhexyl group, and the like, and particularly preferably a 2-ethylhexyl group. When R ⁶ is a fluorinated alkyl group, examples thereof include a trifluoromethyl group, a trifluoroethyl group, a tetrafluoropropyl group, and the like, and particularly preferably a trifluoroethyl group and a tetrafluoropropyl group. When R ⁶ is an aminoalkyl group, examples thereof include an aminoethyl group, an aminopropyl group, and an N, N-dimethylaminoethyl group, and an N, N-dimethylaminoethyl group is particularly preferable. When R ⁶ is a hydroxyalkyl group, examples thereof include a hydroxyethyl group, a hydroxypropyl group, a dihydroxypropyl group, and the like, and particularly preferably a hydroxyethyl group. In the general formula (3), ^{X 3} is an -NH- group or an oxygen atom.

  Examples of the monomer represented by the general formula (3) include 2-ethylhexyl acrylate, 2,2,2-trifluoropropyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, and acrylic acid 2 -(N, N-dimethylamino) ethyl, 2-dimethylaminoethyl methacrylate, N-hydroxyethyl acrylate, glycerol monomethacrylate and the like.

The monomer represented by the general formula (4) is acrylic acid, alkyl-substituted acrylic acid, or acrylamide or alkyl ammonium salt adduct of alkyl-substituted acrylamide. In the general formula (4), R ⁷ is hydrogen or an alkyl group having 1 to 3 carbon atoms, and when R ⁷ is an alkyl group, it may be linear or branched. R ⁷ is preferably hydrogen or a methyl group. In the general formula (4), ^{R 8} is an alkylene group having 1 to 4 carbon atoms. The alkylene group may be linear or branched. Examples of R ⁸ include a methylene group, an ethylene group, and a propylene group, and an ethylene group and a propylene group are particularly preferable. R ⁹ is hydrogen or an alkyl group having 1 to 4 carbon atoms which may be the same or different. When R ⁹ is an alkyl group, it may be linear or branched. R ⁹ is preferably hydrogen or a methyl group. In the general formula (4), X ⁴ is a —NH— group or an oxygen atom. Y < ^- > is a monovalent organic or inorganic anion and may be any as long as it can form a quaternary ammonium salt. Y ^- as, for example, as, for example, chloride ion, fluoride ion, a monovalent inorganic anions such as iodide ions or sulfate ions, acetate ion, benzenesulfonate ion, a monovalent or phosphoric acid ions Of organic anions.

  Examples of the monomer represented by the general formula (4) include N, N-dimethylaminoethyl acrylate methyl chloride, N, N-dimethylaminoacrylamide methyl chloride and the like.

The monomer represented by the general formula (5) is acrylic acid, alkyl-substituted acrylic acid, or (poly) alkylene oxide adduct of acrylamide or alkyl-substituted acrylamide. In the general formula (5), R ¹⁰ is hydrogen or an alkyl group having 1 to 3 carbon atoms, and when R ¹⁰ is an alkyl group, it may be linear or branched. R ¹⁰ is preferably hydrogen or a methyl group. In the general formula (5), R ¹¹ is an alkylene group having 1 to 4 carbon atoms, and the alkylene group may be linear or branched. Examples of R ¹¹ include a methylene group, an ethylene group, and a propylene group, and an ethylene group and a propylene group are particularly preferable. R ¹² is hydrogen or an alkyl group having 1 to 4 carbon atoms, and examples thereof include hydrogen, a methyl group, and an ethyl group. R ¹² is preferably a methyl group. In the general formula (5), ^{X 5} is an -NH- group or an oxygen atom. L is the number of added moles of alkylene oxide and is an integer of 1 to 100.

  Examples of the monomer represented by the general formula (5) include methoxypolyethylene glycol methacrylate.

The monomer represented by the general formula (6) is acrylic acid, alkyl-substituted acrylic acid, or (poly) siloxane adduct of acrylamide or alkyl-substituted acrylamide. In the general formula (6), R ¹³ is hydrogen or an alkyl group having 1 to 3 carbon atoms, and when R ¹³ is an alkyl group, it may be linear or branched. R ¹³ is preferably hydrogen or a methyl group. Moreover, in General formula (6), R <^14> is the same or different hydrogen or a C1-C4 alkyl group. When R ¹⁴ is an alkyl group, it may be linear or branched. R ¹⁴ is preferably hydrogen or a methyl group. R ¹⁵ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and examples thereof include hydrogen, a methyl group, and an ethyl group. R ¹⁵ is preferably hydrogen or a methyl group. In the general formula (6), ^{X 6} is an -NH- group or an oxygen atom. M is the added mole number of siloxane and is an integer of 1 to 100.

  Examples of the monomer represented by the general formula (6) include methacryloxy group-modified silicone.

The monomer represented by the general formula (7) is acrylic acid, alkyl-substituted acrylic acid, or alkyl phosphoric acid (salt) adduct of acrylamide or alkyl-substituted acrylamide. In the general formula (7), R ¹⁶ is hydrogen or an alkyl group having 1 to 3 carbon atoms, and when R ¹⁶ is an alkyl group, it may be linear or branched. R ¹⁶ is preferably hydrogen or a methyl group. In the general formula (7), R ¹⁷ is an alkylene group having 1 to 4 carbon atoms, and the alkylene group may be linear or branched. Examples of R ¹⁷ include a methylene group, an ethylene group, and a propylene group, and an ethylene group and a propylene group are particularly preferable. In the general formula (7), X ⁷ is an —NH— group or an oxygen atom. N is the number of added moles of alkylene oxide, and is an integer of 1 to 100. In the general formula (7), M ³ is hydrogen or a monovalent inorganic or organic cation. The monovalent inorganic or organic cation is not particularly limited as long as it can form a salt of phosphoric acid, and examples of the monovalent inorganic cation include sodium ion, potassium ion, lithium ion, and the like. Examples of the organic cation include ammonium ion, monoethanolammonium ion, triethanolammonium ion, and the like. Regarding M ³ , after polymer production, it is reversibly converted into phosphoric acid (M ³ = hydrogen) or sodium salt (M ³ = sodium) form using an appropriate amount of dilute hydrochloric acid or dilute sodium hydroxide solution. It is also possible.

  Examples of the monomer represented by the general formula (7) include 2-methacryloxyethyl phosphoric acid.

In the polymer of the present invention, one or more of the monomers (B) represented by any one of the general formulas (2) to (7) can be used as a constituent monomer.
Moreover, in the polymer concerning this invention, it is suitable that the said monomer (B) is contained 1-30 mol% in the structural monomer whole quantity. If the monomer (B) is less than 1 mol%, the effect of the blending cannot be obtained, and if it exceeds 30 mol%, the content of the monomer (A) is relatively reduced, and the desired performance with respect to the powder. May not be granted.

  Moreover, the polymer of this invention can also contain monomers other than the said monomer (A) and (B) as a structural monomer, if it is a range which does not impair the effect of this invention. Content should just be the range of 30 mol% or less of a constituent monomer whole quantity, for example, can contain about 1-20 mol%. Examples of such monomers include acrylamide, methacrylamide, N-vinylpyrrolidone, ε-caprolactam, vinyl alcohol, maleic anhydride, diallyldimethylammonium chloride, styrene, and the like.

  The polymer of the present invention can be obtained by polymerizing various monomers containing the above monomers using a known polymerization method. For example, homogeneous solution polymerization method, heterogeneous solution polymerization method, emulsion polymerization method, reverse phase emulsion polymerization method, bulk polymerization method, suspension polymerization method, precipitation polymerization method and the like can be used. For example, in the case of the homogeneous solution polymerization method, the polymer of the present invention can be obtained by dissolving various monomers in a solvent, adding a radical polymerization initiator under a nitrogen atmosphere, and stirring with heating. The polymer of the present invention can also be obtained by post-modification in which a functional group is added to polyacrylic acid or polyacrylamide.

  As a solvent used in the polymerization, any solvent can be used as long as it can dissolve or suspend various monomers 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 Solvents, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, chloride solvents such as methylene chloride, chloroform, carbon tetrachloride, dimethylformamide, diethylformamide, dimethylsulfoxide, dioxane, etc. And the like. Two or more of these solvents may be used in combination. 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, peroxide such as benzoyl peroxide, azobisisobutyronitrile (AIBN), 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, the temperature may usually be about 50 to 70 ° C.

  The polymerization time is not particularly limited, but is usually about 30 minutes to 24 hours. When it is desired to obtain a polymer having a relatively high molecular weight, it is desirable to react for about 24 hours. 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 polymer of the present invention is not particularly limited, and the target effect can be exhibited as long as it has a polymerization degree equal to or higher than that of the oligomer, but the average molecular weight is preferably about 3000 to 100,000. In addition, a copolymer in which various monomers are randomly added is usually obtained by mixing two or more monomers and performing polymerization.

The surface treating agent according to the present invention is characterized by comprising the polymer obtained as described above.
The polymer of the present invention has a carboxyl group derived from the monomer (A) in the polymer side chain, and this carboxyl group is a hydrophobic carboxylic acid (—COOH) or base under acidic to neutral conditions. Change to hydrophilic carboxylate ion (—COO ⁻ M ⁺ ). For this reason, the treated powder obtained by treating the surface of the powder with this polymer exhibits a pH-responsive hydrophobic-hydrophilic change such as hydrophobicity in an acidic to neutral environment and hydrophilicity in a basic environment. It seems that it comes to show.
And when such treated powders are blended in cosmetics, soaps and the like are used in spite of being excellent in cosmetics to show hydrophobicity in the acidic to neutral regions where cosmetics are usually used. When used in an appropriate basic environment, the surface of the powder changes to hydrophilic, so that it can be easily washed away with water.

  In addition, the monomer (B) is hardly affected by pH and exhibits stable hydrophilic or hydrophobic properties over a wide pH range. Therefore, by appropriately adjusting the monomer ratio of the monomer (A) and the monomer (B) in the constituent monomers to produce a polymer, the hydrophobic-hydrophilic balance imparted to the powder is suitably adjusted. Is possible. For example, the hydrophilicity can be enhanced by combining the monomer (A) with the monomer of the general formula (2) as the monomer (B), and conversely, the monomer of the general formula (6) as the monomer (B). The hydrophobicity can be increased by combining them. Further, by using an appropriate amount of the monomer (B), the adsorptivity of the polymer to the powder can be enhanced.

  When the surface treating agent according to the present invention is used for a cosmetic powder, the ratio of the monomer (A) to the monomer (B) is (A) :( B) = 70: 30 to 99 in terms of molar ratio. .9: It is preferable to adjust to be 0.1. When the ratio of the monomer (A) is less than 70:30, the treated powder is biased toward hydrophilicity, so that sufficient hydrophobicity may not be imparted, while the ratio of the monomer (A) is 99. .9: When the ratio is more than 0.1, it is difficult for the polymer to be adsorbed on the surface of the powder, which may adversely affect the stability of the powder.

  Although the surface treatment agent according to the present invention may be used for any type, it can be suitably used particularly for cosmetic powders. Examples of such powders include silicic acid, silicic anhydride, magnesium silicate, talc, kaolin, mica, bentonite, titanium-coated mica, bismuth oxychloride, zirconium oxide, magnesium oxide, zinc oxide, titanium dioxide, and oxidation. Inorganic powders such as aluminum, calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, iron oxide, ultramarine, bitumen, chromium oxide, chromium hydroxide, carbon black and composites thereof, polyamide, polyester, polyethylene, Polypropylene, polystyrene, polyurethane, vinyl resin, epoxy resin, polycarbonate resin, divinylbenzene / styrene copolymer, copolymer comprising two or more monomers of the above compounds, celluloid, acetylcellulose, cellulose, polysaccharide, Protein, CI Pigment Yellow, CI Pigment Orange, organic powders such as CI Pigment Green and the like. Also, the shape of the powder may be any shape such as a plate shape, a lump shape, a scale shape, a sphere shape, a porous sphere shape, and the particle size is not particularly limited.

  The surface treatment agent according to the present invention may be used by an ordinary treatment method, and the method is not particularly limited. For example, when the powder is treated with the surface treatment agent according to the present invention, the surface treatment agent is dissolved in an appropriate solvent such as ethyl alcohol, and the powder is mixed and stirred in this solution. A method of distilling off or a method in which a surface treatment agent dissolved in a non-volatile oil such as a higher alcohol is directly mixed and stirred. Further, when the powder treated with the surface treatment agent according to the present invention is blended in the cosmetic, the surface treatment agent may be directly mixed and stirred in the powder base during the production process of the cosmetic.

  In addition, when processing powder with the surface treating agent concerning this invention, it is necessary to pay attention to the zeta potential of the powder. Here, the zeta potential of the powder is the difference between the potential on the outermost surface (sliding surface) of the layer that moves in close contact with the solid phase and the potential inside the solution when the solid and liquid phases move relative to each other. It is shown. When the solution is near neutral, the zeta potential of titanium oxide, silica, etc. is negative, and on the contrary, the zeta potential of zinc oxide, alumina, etc. is positive. When processing a powder with a positive zeta potential, such as zinc oxide or alumina, the carboxylic acid sites important for pH responsiveness will be offset by the positive charge on the surface of the powder when processed in the usual way. The surface-treated powder thus obtained may not exhibit pH responsiveness. In order to impart pH responsiveness to such a powder, a negatively charged inorganic substance or organic substance such as silica or polystyrene sulfonic acid is previously treated on the powder surface, and the zeta potential on the powder surface is increased. It needs to turn negative. As such a treatment method, for example, a method in which powder is dispersed in a water glass solution and an acid is dropped to deposit silica on the surface, or after the powder is dispersed in a polystyrene sulfonic acid aqueous solution, The method of volatilizing water is mentioned.

  When the surface treatment agent according to the present invention is processed into powder, the coating amount of the polymer with respect to the powder is, by mass ratio, polymer: powder = 3: 97 to 40:60, more preferably 5:95 to 30: 70. When the amount of polymer coating is less than 3:97, desired performance may not be imparted to the powder. When the amount of coating is larger than 40:60, the feeling of use when used as a cosmetic, etc. May have an adverse effect.

Examples of the present invention are given below, but the present invention is not limited thereto.
First, a method for synthesizing the polymer of the present invention will be described.

Synthesis Example 1 11: Methacrylamidoundecanoic acid (MAU) homopolymer

11-methacrylamidoundecanoic acid sodium (NaMAU) 5.244 g (18 mmol), azobisisobutyronitrile 7.4 mg (0.045 mmol), a mixed solvent of methanol 32.4 mL and water 3.6 mL (methanol / water = 9/1). Degassing was carried out by bubbling argon for 30 minutes, and the container was covered with a septum and polymerized by heating at 60 ° C. for 12 hours. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of ether, and the precipitate was collected by suction filtration. This precipitate was dissolved in water, dialyzed against pure water for 1 week, and freeze-dried to obtain 2.64 g of NaMAU homopolymer (yield: 50.40%).
1.10 g of the recovered NaMAU homopolymer was dissolved in water, and the pH was adjusted to 4 with hydrochloric acid. This solution was dialyzed against water at pH 5 for 1 week and freeze-dried to obtain 0.97 g of 11-methacrylamideamidecanoic acid (MAU) homopolymer.

Synthesis Example 2 11-methacrylamidoundecanoic acid (MAU) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (MAU / AMPS = 95/5)

Sodium 11-methacrylamide undecanoate (NaMAU) 4.9823 g (17.1 mmol), 2-acrylamido-2-methylpropanesulfonic acid (AMPS) 186.5 mg (0.9 mmol), sodium hydroxide 39.6 mg (0. 99 mmol) and 7.4 mg (0.045 mmol) of azobisisobutyronitrile were dissolved in a mixed solvent (methanol / water = 9/1) of 32.4 mL of methanol and 3.6 mL of water. Degassing was carried out by bubbling argon for 30 minutes, and the container was covered with a septum and polymerized by heating at 60 ° C. for 12 hours. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of ether, and the precipitate was collected by suction filtration. The precipitate was dissolved in water, dialyzed against pure water for 1 week, and freeze-dried to obtain 2.78 g of random NaMAU / AMPS copolymer (95/5) (yield: 53 71%).
The recovered NaMAU / AMPS copolymer (1.54 g) was dissolved in water, and the pH was adjusted to 4 using hydrochloric acid. This solution was dialyzed against water at pH 5 for 1 week and freeze-dried to obtain 0.97 g of random MAU / AMPS copolymer (95/5).

Next, the powder surface treatment method using the surface treatment agent of the present invention will be described.
Powder processing example 1
In 500 mL of ethanol, 45 g of the polymer prepared in Synthesis Examples 1 and 2 and 15 g of stearic acid were dissolved. In this solution, 240 g of titanium oxide was mixed and dispersed, and ethanol was volatilized by an evaporator. The obtained massive substance was pulverized to obtain a surface-treated powder.
The obtained treated powder was mixed and dissolved in a pH 5 and pH 10 buffer solution at a ratio of powder: solution = 1: 100. The powder was separated from this solution by centrifugation, and the remaining solution was removed by drying. When the coverage of the surface treatment agent was measured by elemental analysis on the obtained powder, the polymer was 15% by mass and stearic acid was 5% by mass in the total amount of the powder.

Examples 1-1 to 1-4, Comparative Examples 1-1 to 1-4
In order to examine the characteristics of the surface-treated powder that has been surface-treated with the polymer of the present invention, the present inventors surface-treated with various polymers in accordance with Synthesis Examples 1 and 2 and Powder Treatment Example 1. Titanium oxide powder was produced, and the water solubility of the treated powder under acidic (pH 5) and basic (pH 10) conditions was evaluated. Further, as a comparative example, the same test was performed using silicones and acrylic acid / acrylic acid ester copolymers which are conventional hydrophobizing surface treatment agents. The evaluation results are shown in Table 1 and FIGS. The evaluation method is as follows.

0.1 g of titanium oxide powder surface-treated with various water-soluble surface treatment agents of the treated powder is placed in a vial together with 30 mL of various pH buffered aqueous solutions of pH 5 and pH 10, and after mixing and stirring for 1 minute with a magnetic stirrer, static value The state of the solution was confirmed.
○: The powder was uniformly dissolved in water to form a cloudy solution.
X: The powder did not dissolve in water and separated on the water surface.

  As shown in Table 1 and FIGS. 1 and 2, the treated powders of Examples 1-1 to 1-4 surface-treated with the MAU homopolymer of the present invention and the MAU / AMPS copolymer were subjected to pH 5 acidic conditions. Was not dissolved in water at all, and the powder was found to exhibit excellent hydrophobicity. On the other hand, when the basic condition was pH 10, it was revealed that the treated powder was uniformly dissolved in water and the powder changed to hydrophilic. That is, when the treated powder treated with the polymer of the present invention is blended in cosmetics, it exhibits excellent hydrophobicity in the acidic to neutral range where general cosmetics are used, so it is excellent in cosmetics. Regardless, it is considered that when the surface of the powder is made hydrophilic when soap or the like is used to make it an appropriate basic environment, it can be easily washed away with water.

  In contrast, the treated powders of Comparative Examples 1-1 to 1-4 that have been surface-treated with silicones and acrylic acid / acrylic acid ester copolymers that have been conventionally used as hydrophobizing agents for cosmetic powders. The body was unable to dissolve in water at all under acidic conditions at pH 5 and basic conditions at pH 10. From this, when the powder treated with the conventional surface treatment agent is blended in cosmetics, even if the cosmetic durability can be improved, excellent hydrophobicity is maintained even under basic conditions. Therefore, it is difficult to wash away with soapy water.

Synthesis Example 3 : 3- {4-[(methacryloxy) methyl] phenyl} acrylic acid (MMPA) homopolymer

1) Synthesis of MMPA monomer 2.46 g (15 mmol) of 4-hydroxycinnamic acid and 0.005 g of butylhydroxytoluene were dissolved in 25 g of acetone, 1.57 g (15 mmol) of methacryloyl chloride was added dropwise, and the mixture was stirred at room temperature for 3 hours. did. After completion of the reaction, 1.67 g of triethylamine was added dropwise to the solution, 100 g of 0.015N dilute hydrochloric acid solution was further added, and the precipitate was collected by suction filtration. The precipitate was washed with water and dried under reduced pressure at 30 ° C. to obtain 2.09 g of MMPA monomer (yield: 60%). In addition, the production | generation of the MMPA monomer was confirmed by the NMR analysis about a product. The NMR analysis results are shown in FIG.

2) Polymerization of MMPA monomer 2.01 g (9 mmol) of the MMPA monomer obtained above was dissolved in 100 g of tetrahydrofuran and bubbled with nitrogen for 40 minutes. Next, a solution prepared by dissolving 0.038 g (0.23 mmol) of azobisisobutyronitrile in 10 g of tetrahydrofuran was dropped, and after bubbling with nitrogen for 10 minutes, the mixture was stirred and polymerized at 60 ° C. for 24 hours. After completion of the polymerization reaction, the reaction solution was concentrated with an evaporator, and ethyl acetate was added to remove the precipitate. The mixture was concentrated again with an evaporator and dried under reduced pressure at 30 ° C. to obtain 1.64 g of MMPA homopolymer (yield 82%).

Powder processing example 2
1 g of MMPA homopolymer produced in Synthesis Example 3 was dissolved in 50 mL of tetrahydrofuran. 9 g of titanium oxide was mixed and dispersed in this solution, and tetrahydrofuran was volatilized by an evaporator. The obtained massive substance was pulverized to obtain a surface-treated powder.

Example 1-5
The inventors of the present invention manufactured titanium oxide powder surface-treated with MMPA homopolymer according to the above powder treatment example 2, and the obtained treated powder in pH 5 and pH 10 buffer solution, powder: solution = The mixture was dispersed at a ratio of 1: 100, and the water solubility of the treated powder was evaluated under acidic (pH 5) and basic (pH 10) conditions. The results are shown in FIG.

  As shown in FIG. 4, the treated powder of Example 1-5 surface-treated with the MMPA homopolymer of the present invention was not dissolved in water at all under acidic conditions of pH 5, whereas the treated powder of pH 10 When the basic condition was adopted, it was confirmed that the treated powder was uniformly dissolved in water, and the powder was changed from hydrophobic to hydrophilic due to pH change.

  Subsequently, the inventors performed infrared spectroscopic measurement of the MMPA polymer of Synthesis Example 3 under the conditions of untreated and 1M NaOH solution treatment. The results are shown in FIG.

As shown in FIG. 5, the MMPA homopolymer of the present invention shows a peak of carboxylic acid (—COOH) under untreated conditions, whereas the carboxylic acid peak disappears under the conditions of 1M NaOH solution treatment. It was confirmed that a peak of rate ion (—COO ⁻ ) appeared. And from this result, the polymer of the present invention is converted to a hydrophobic carboxylic acid under acidic to neutral conditions, and to a hydrophilic carboxylate ion under basic conditions, whereby a pH-responsive hydrophobic- It is thought to show hydrophilicity changes.

Example 2-1
Subsequently, the present inventors attempted to prepare a cosmetic containing a powder surface-treated with the polymer of the present invention and evaluated it.
Surface-treated powder 2-1
In 1000 mL of ethanol, 34.5 g of MAU / AMPS copolymer (MAU / AMPS = 95/5) produced according to Synthesis Example 2 and 34.5 g of stearic acid were dissolved. In this solution, 85 g of talc, 50.8 g of sericite, 10 g of titanium oxide, 6 g of nylon powder, 0.4 g of black iron oxide, 5.8 g of yellow iron oxide, and 2 g of bengara were mixed and dispersed, and ethanol was volatilized by an evaporator. . The obtained massive substance was pulverized to obtain surface-treated powder 2-1.

Powder type foundation content (mass%)
(1) Surface-treated powder 2-1 86.6
(2) Liquid paraffin 4.0
(3) Octyl dodecyl myristate 3.0
(4) Sorbitan isostearate 3.0
(5) Octyldodecanol 3.0
(6) Preservative 0.1
(7) Bactericide 0.1
(8) Antioxidant 0.1
(9) Fragrance 0.1
(Production Method) In addition to (2) to (6) in which (1) and (7) to (9) were dissolved by heating, they were mixed with a Henschel mixer to obtain a powder type foundation.
The powder-type foundation obtained as described above was excellent in long-lasting makeup and could be easily washed away with water using soap.

  Hereinafter, the present invention will be described in more detail with reference to other examples, but the present invention is not limited thereto. The molecular weight was calculated using size exclusion chromatography HLC-8220 GPC (manufactured by Tosoh Corporation). As the column, Shodex Asahipak GF-7M HQ (manufactured by Showa Denko KK) was used, and methanol containing 100 mM lithium perchlorate was used as the mobile phase. Polyethylene oxide is used as the standard substance, and the obtained weight average molecular weight is in terms of polyethylene oxide.

Example 3-1 : 11-methacrylamidoundecanoic acid (MAU) homopolymer 11-methacrylamidoundecanoic acid (MAU) 75.0 g (278.49 mmol), azobisisobutyronitrile (manufactured by Nacalai Tesque) 0.31 g (1.89 mmol) was dissolved in 224.69 g of methanol. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of ethyl acetate, and the precipitate was collected by suction filtration. After drying under reduced pressure, 45.6 g of MAU homopolymer was obtained (yield: 60.8%). The weight average molecular weight was 66000.

Example 3-2 : 11-methacrylamidoundecanoic acid (MAU) homopolymer 11-methacrylamidoundecanoic acid (MAU) 75.0 g (278.49 mmol), azobisisobutyronitrile (manufactured by Nacalai Tesque) 0.93 g (5.66 mmol) was dissolved in 224.07 g of methanol. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of ethyl acetate, and the precipitate was collected by suction filtration. After drying under reduced pressure, 64.9 g of MAU homopolymer was obtained (yield: 86.5%). The weight average molecular weight was 61000.

Example 3-3 : 12-methacrylamide dodecanoic acid (MAD) homopolymer 12-methacrylamide dodecanoic acid (MAD) 40.0 g (141.34 mmol), azobisisobutyronitrile (manufactured by Nacalai Tesque) 0.58 g (3.53 mmol) was dissolved in 120.0 g of methanol. Azobisisobutyronitrile was recrystallized from methanol in accordance with a conventional method. Degassing was carried out by bubbling argon for 60 minutes, and the container was covered with a septum and polymerized by heating at 60 ° C. for 20 hours. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of diethyl ether, and the precipitate was collected by suction filtration. After drying under reduced pressure, 124.15 g of MAD homopolymer was obtained (yield: 60.4%). The weight average molecular weight was 33,000.

Example 3-4 : 12-acrylamide dodecanoic acid (AAD) homopolymer 12-acrylamide dodecanoic acid (AAD) 40.0 g (148.70 mmol), azobisisobutyronitrile (manufactured by Nacalai Tesque) 0.61 g (3 .71 mmol) was dissolved in 360.0 g of methanol. Azobisisobutyronitrile was recrystallized from methanol in accordance with a conventional method. Degassing was carried out by bubbling argon for 60 minutes, and the container was covered with a septum and polymerized by heating at 60 ° C. for 20 hours. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of diethyl ether, and the precipitate was collected by suction filtration. After drying under reduced pressure, 27.51 g of AAD homopolymer was obtained (yield: 68.8%). The weight average molecular weight was 44,000.

Example 3-5 : 11-methacrylamidoundecanoic acid (MAU) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (99/1)
11-methacrylamidoundecanoic acid (MAU) 74.23 g (275.63 mmol), 2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich Japan) 0.77 g (3.72 mmol), hydroxylated Sodium 0.15 g (3.72 mmol) and azobisisobutyronitrile (manufactured by Nacalai Tesque) 0.93 g (5.66 mmol) were dissolved in methanol 233.92 g. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of diethyl ether, and the precipitate was collected by suction filtration. After drying under reduced pressure, 52.0 g of random MAU / AMPS copolymer (99/1) was obtained (yield: 69.2%). The weight average molecular weight was 56000.

Example 3-6 : 11-methacrylamidoundecanoic acid (MAU) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (99/1)
11-methacrylamidoundecanoic acid (MAU) 74.23 g (275.63 mmol), 2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich Japan) 0.77 g (3.72 mmol), hydroxylated 0.15 g (3.72 mmol) of sodium and 1.55 g (9.44 mmol) of azobisisobutyronitrile (manufactured by Nacalai Tesque) were dissolved in 223.30 g of methanol. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of ethyl acetate, and the precipitate was collected by suction filtration. After drying under reduced pressure, 52.3 g of random MAU / AMPS copolymer (99/1) was obtained (yield: 69.6%). The weight average molecular weight was 36000.

Example 3-7 : 11-methacrylamidoundecanoic acid (MAU) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (99/1)
11-methacrylamidoundecanoic acid (MAU) 74.23 g (275.63 mmol), 2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich Japan) 0.77 g (3.72 mmol), hydroxylated 0.15 g (3.72 mmol) of sodium and 3.10 g (18.88 mmol) of azobisisobutyronitrile (manufactured by Nacalai Tesque) were dissolved in 236.75 g of methanol. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of ethyl acetate, and the precipitate was collected by suction filtration. After drying under reduced pressure, 60.1 g of random MAU / AMPS copolymer (99/1) was obtained (yield: 80.0%). The weight average molecular weight was 21,000.

Example 3-8 : 11-methacrylamidoundecanoic acid (MAU) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (90/10)
11-methacrylamidoundecanoic acid (MAU) 18.42 g (68.41 mmol), 2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich Japan) 1.58 g (7.60 mmol), hydroxylated 0.31 g (7.60 mmol) of sodium and 0.31 g (1.89 mmol) of azobisisobutyronitrile (manufactured by Nacalai Tesque) were dissolved in 59.4 g of methanol. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of ethyl acetate, and the precipitate was collected by suction filtration. After drying under reduced pressure, 17.8 g of random MAU / AMPS copolymer (90/10) was obtained (yield: 87.9%). The weight average molecular weight was 92,000.

Example 3-9 : 11-methacrylamidoundecanoic acid (MAU) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (99/1)
11-methacrylamidoundecanoic acid (MAU) was dissolved in chloroform and passed through Inhibitor Remover, Disposable Column (manufactured by ALDRICH) to remove the polymerization inhibitor contained in MAU. 19.85 g (73.69 mmol) of MAU from which the polymerization inhibitor was removed, 0.15 g (0.74 mmol) of 2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich Japan), sodium hydroxide 03 g (0.74 mmol) and azobisisobutyronitrile (manufactured by Nacalai Tesque) 0.06 g (0.37 mmol) were dissolved in 59.91 g of methanol. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of ethyl acetate, and the precipitate was collected by suction filtration. After drying under reduced pressure, 17.33 g of random MAU / AMPS copolymer (99/1) was obtained (yield: 86.6%). The weight average molecular weight was 740000.

Example 3-10 : 11-methacrylamidoundecanoic acid (MAU) / 3-methacryloxypropane potassium sulfonate copolymer (90/10)
11-methacrylamidoundecanoic acid (MAU) 18.15 g (67.41 mmol), potassium 3-methacryloxypropanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.85 g (7.49 mmol), azobisisobutyronitrile (Nacalai) Tesque) 0.31 g (1.89 mmol) was dissolved in methanol 59.69 g. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of ethyl acetate, and the precipitate was collected by suction filtration. After drying under reduced pressure, 18.47 g of random MAU / 3-methacryloxypropane potassium sulfonate copolymer (90/10) was obtained (yield: 92.4%). The weight average molecular weight was 240,000.

Example 3-11 : 12-methacrylamidododecanoic acid (MAD) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (99/1)
12.85 g (70.14 mmol) of 12-methacrylamide dodecanoic acid (MAD), 0.15 g (0.72 mmol) of 2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich Japan), hydroxylation 0.028 g (0.70 mmol) of sodium and 0.29 g (1.77 mmol) of azobisisobutyronitrile (manufactured by Nacalai Tesque) were dissolved in 60.0 g of methanol. Azobisisobutyronitrile was recrystallized from methanol in accordance with a conventional method. Degassing was carried out by bubbling argon for 60 minutes, and the container was covered with a septum and polymerized by heating at 60 ° C. for 20 hours. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of diethyl ether, and the precipitate was collected by suction filtration. After drying under reduced pressure, 13.5 g of random MAD / AMPS copolymer (99/1) was obtained (yield: 67.5%). The weight average molecular weight was 49000.

Example 3-12 : 12-methacrylamidododecanoic acid (MAD) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (90/10)
12.50 g (65.37 mmol) of 12-methacrylamide dodecanoic acid (MAD), 1.50 g (7.24 mmol) of 2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich Japan), hydroxylation Sodium 0.29 g (7.25 mmol) and azobisisobutyronitrile (manufactured by Nacalai Tesque) 0.30 g (1.83 mmol) were dissolved in methanol 60.0 g. Azobisisobutyronitrile was recrystallized from methanol in accordance with a conventional method. Degassing was carried out by bubbling argon for 60 minutes, and the container was covered with a septum and polymerized by heating at 60 ° C. for 20 hours. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of diethyl ether, and the precipitate was collected by suction filtration. After drying under reduced pressure, 15.2 g of random MAD / AMPS copolymer (90/10) was obtained (yield: 75.1%). The weight average molecular weight was 50000.

Example 3-13 : 12-methacrylamidododecanoic acid (MAD) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (80/20)
12.90 g (59.72 mmol) of 12-methacrylamide dodecanoic acid (MAD), 3.10 g (14.96 mmol) of 2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich Japan), hydroxylation 0.60 g (1.50 mmol) of sodium and 0.31 g (1.89 mmol) of azobisisobutyronitrile (manufactured by Nacalai Tesque) were dissolved in 60.0 g of methanol. Azobisisobutyronitrile was recrystallized from methanol in accordance with a conventional method. Degassing was carried out by bubbling argon for 60 minutes, and the container was covered with a septum and polymerized by heating at 60 ° C. for 20 hours. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of ethyl acetate, and the precipitate was collected by suction filtration. After drying under reduced pressure, 16.1 g of random MAD / AMPS copolymer (80/20) was obtained (yield: 78.6%). The weight average molecular weight was 95,000.

Example 3-14 : 12-methacrylamidododecanoic acid (MAD) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (70/30)
12.22 g (53.78 mmol) of 12-methacrylamide dodecanoic acid (MAD), 4.78 g (23.06 mmol) of 2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich Japan), hydroxylation 0.92 g (23.0 mmol) of sodium and 0.32 g (1.95 mmol) of azobisisobutyronitrile (manufactured by Nacalai Tesque) were dissolved in 60.0 g of methanol. Azobisisobutyronitrile was recrystallized from methanol in accordance with a conventional method. Degassing was carried out by bubbling argon for 60 minutes, and the container was covered with a septum and polymerized by heating at 60 ° C. for 20 hours. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of ethyl acetate, and the precipitate was collected by suction filtration. After drying under reduced pressure, 19.0 g of random MAD / AMPS copolymer (70/30) was obtained (yield: 91.6%). The weight average molecular weight was 108,000.

Example 3-15 : 12-methacrylamidododecanoic acid (MAD) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (60/40)
12.44 g (47.49 mmol) of 12-methacrylamide dodecanoic acid (MAD), 6.56 g (31.65 mmol) of 2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich Japan), hydroxylation 1.27 g (31.75 mmol) of sodium and 0.32 g (1.95 mmol) of azobisisobutyronitrile (manufactured by Nacalai Tesque) were dissolved in 60.0 g of methanol. Azobisisobutyronitrile was recrystallized from methanol in accordance with a conventional method. Degassing was carried out by bubbling argon for 60 minutes, and the container was covered with a septum and polymerized by heating at 60 ° C. for 20 hours. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of ethyl acetate, and the precipitate was collected by suction filtration. After drying under reduced pressure, 20.05 g of random MAD / AMPS copolymer (60/40) was obtained (yield: 95.4%). The weight average molecular weight was 129000.

Example 3-16 : 12-methacrylamidododecanoic acid (MAD) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (50/50)
12-methacrylamide decanoic acid (MAD) 11.55 g (40.81 mmol), 2-acrylamido-2-methylpropane sulfonic acid (AMPS: Sigma-Aldrich Japan) 8.45 g (40.77 mmol), hydroxylated 1.63 g (40.75 mmol) of sodium and 0.33 g (1.97 mmol) of azobisisobutyronitrile (manufactured by Nacalai Tesque) were dissolved in 60.0 g of methanol. Azobisisobutyronitrile was recrystallized from methanol in accordance with a conventional method. Degassing was carried out by bubbling argon for 60 minutes, and the container was covered with a septum and polymerized by heating at 60 ° C. for 20 hours. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of ethyl acetate, and the precipitate was collected by suction filtration. After drying under reduced pressure, 20.95 g of random MAD / AMPS copolymer (50/50) was obtained (yield: 98.4%). The weight average molecular weight was 176000.

Example 3-17 : 11-methacrylamidoundecanoic acid (MAU) / 2-ethylhexyl acrylate copolymer (90/10)
11.-methacrylamidoundecanoic acid (MAU) 18.59 g (69.02 mmol), 2-ethylhexyl acrylate (manufactured by Sigma-Aldrich Japan) 1.41 g (7.67 mmol), azobisisobutyronitrile (Nacalai Tesque) 0.31 g (1.89 mmol) was dissolved in 59.69 g of methanol. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, a yellow candy-like substance was obtained. 80 g of methanol was added to this and dissolved. The obtained solution was dropped into a large excess of ethyl acetate, and the precipitate was collected by suction filtration. After drying under reduced pressure, 13.01 g of random MAU / 2-ethylhexyl acrylate copolymer (90/10) was obtained (yield: 65.0%). The weight average molecular weight was 560000.

Example 3-18 : 11-methacrylamidoundecanoic acid (MAU) / acrylic acid 2,2,2-trifluoroethyl copolymer (90/10)
11-methacrylamidoundecanoic acid (MAU) 18.80 g (69.82 mmol), 2,2,2-trifluoroethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.20 g (7.76 mmol), azobisisobutyro Nitrile (Nacalai Tesque) 0.32 g (1.95 mmol) was dissolved in methanol 59.68 g. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of ethyl acetate, and the precipitate was collected by suction filtration. After drying under reduced pressure, 9.02 g of random MAU / acrylic acid 2,2,2-trifluoroethyl copolymer (90/10) was obtained (yield: 45.1%). The weight average molecular weight was 35000.

Example 3-19 : 11-methacrylamidoundecanoic acid (MAU) / methacrylic acid 2,2,3,3-tetrafluoropropyl copolymer (90/10)
11-methacrylamidoundecanoic acid (MAU) 18.47 g (68.60 mmol), 2,2,3,3-tetrafluoropropyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.53 g (7.62 mmol), azobisiso 0.31 g (1.89 mmol) of butyronitrile (manufactured by Nacalai Tesque) was dissolved in 59.69 g of methanol. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of diethyl ether, and the precipitate was collected by suction filtration. After drying under reduced pressure, 16.15 g of random MAU / methacrylic acid 2,2,3,3-tetrafluoropropyl copolymer (90/10) was obtained (yield: 80.8%). The weight average molecular weight was 220,000.

Example 3-20 : 11-methacrylamidoundecanoic acid (MAU) / acrylic acid 2- (N, N-dimethylamino) ethyl copolymer (90/10)
11-methacrylamidoundecanoic acid (MAU) 18.88 g (70.12 mmol), 2- (N, N-dimethylamino) ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.12 g (7.79 mmol), azobisiso 0.32 g (1.95 mmol) of butyronitrile (manufactured by Nacalai Tesque) was dissolved in 59.68 g of methanol. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the solution was dried under reduced pressure and dissolved in 60 g of dimethylformamide. The obtained solution was dropped into a large excess of diethyl ether, and the precipitate was collected by suction filtration. After drying under reduced pressure, 5.22 g of random MAU / acrylic acid 2- (N, N-dimethylamino) ethyl copolymer (90/10) was obtained (yield: 26.1%). The weight average molecular weight was 130,000.

Example 3-21 : 11-methacrylamidoundecanoic acid (MAU) / methacrylic acid 2-dimethylaminoethyl ester copolymer (90/10)
11-methacrylamidoundecanoic acid (MAU) 18.78 g (69.74 mmol), methacrylic acid 2-dimethylaminoethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.22 g (7.75 mmol), azobisisobutyronitrile (Nacalai) 0.32 g (1.95 mmol) manufactured by Tesque Corporation was dissolved in 59.68 g of methanol. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the solution was dried under reduced pressure and dissolved in 60 g of dimethylformamide. The obtained solution was dropped into a large excess of diethyl ether, and the precipitate was collected by suction filtration. After drying under reduced pressure, 7.78 g of random MAU / methacrylic acid 2-dimethylaminoethyl ester copolymer (90/10) was obtained (yield: 38.9%). The weight average molecular weight was 250,000.

Example 3-22 : 12-methacrylamido dodecanoic acid (MAD) / N-hydroxyethylacrylamide (HEAA) copolymer (90/10)
12.14-methacrylamidododecanoic acid (MAD) 19.14 g (67.63 mmol), N-hydroxyethylacrylamide (HEAA: manufactured by Kojin Co., Ltd.) 0.86 g (7.51 mmol), azobisisobutyronitrile (Nacalai Tesque) 0.33 g (1.97 mmol) was dissolved in 60.0 g of methanol. Azobisisobutyronitrile was recrystallized from methanol in accordance with a conventional method. Degassing was carried out by bubbling argon for 60 minutes, and the container was covered with a septum and polymerized by heating at 60 ° C. for 20 hours. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of diethyl ether, and the precipitate was collected by suction filtration. After drying under reduced pressure, 16.90 g of MAD / HEAA copolymer (90/10) was obtained (yield: 84.5%).

Example 3-23 : 11-methacrylamidoundecanoic acid (MAU) / N, N-dimethylaminoethyl acrylate methyl chloride copolymer (90/10)
11-methacrylamidoundecanoic acid (MAU) 18.52 g (68.77 mmol), N, N-dimethylaminoethyl acrylate methyl chloride (manufactured by Kojin Co., Ltd.) 1.48 g (7.64 mmol), azobisisobutyronitrile ( 0.31 g (1.89 mmol) (manufactured by Nacalai Tesque) was dissolved in 59.69 g of methanol. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the obtained solution was dropped into a large excess of acetone, and the precipitate was collected by suction filtration. After drying under reduced pressure, 9.43 g of random MAU / N, N-dimethylaminoethyl acrylate methyl chloride copolymer (90/10) was obtained (yield: 47.2%). The weight average molecular weight was 68,000.

Example 3-24 : 11-methacrylamidoundecanoic acid (MAU) / N, N-dimethylaminopropylacrylamidomethyl chloride copolymer (90/10)
11-methacrylamidoundecanoic acid (MAU) 18.43 g (68.43 mmol), N, N-dimethylaminopropylacrylamide methyl chloride (manufactured by Kojin) 1.57 g (7.60 mmol), azobisisobutyronitrile ( 0.31 g (1.89 mmol) (manufactured by Nacalai Tesque) was dissolved in 59.69 g of methanol. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the obtained solution was dropped into a large excess of acetone, and the precipitate was collected by suction filtration. After drying under reduced pressure, 9.60 g of random MAU / N, N-dimethylaminopropylacrylamide methyl chloride copolymer (90/10) was obtained (yield: 48.0%). The weight average molecular weight was 42,000.

Example 3-25 : 11-methacrylamidoundecanoic acid (MAU) / methoxypolyethylene glycol monomethacrylate copolymer (90/10)
11-methacrylamidoundecanoic acid (MAU) 17.96 g (66.67 mmol), methoxypolyethylene glycol monomethacrylate (Blenmer PME-200: manufactured by NOF Corporation) 2.04 g (7.41 mmol), azobisisobutyronitrile ( 0.30 g (1.83 mmol) (manufactured by Nacalai Tesque) was dissolved in 59.70 g of methanol. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the obtained solution was dropped into a large excess of ethyl acetate, and the precipitate was collected by suction filtration. After drying under reduced pressure, 9.69 g of random MAU / methoxypolyethylene glycol monomethacrylate copolymer (90/10) was obtained (yield: 48.5%). The weight average molecular weight was 110,000.

Example 3-26 : 11-methacrylamidoundecanoic acid (MAU) / methoxypolyethylene glycol monomethacrylate copolymer (99/1)
11-methacrylamidoundecanoic acid (MAU) 19.80 g (73.50 mmol), methoxypolyethylene glycol monomethacrylate (Blenmer PME-200: manufactured by NOF Corporation), 0.20 g (0.74 mmol), azobisisobutyronitrile ( 0.30 g (1.83 mmol) (manufactured by Nacalai Tesque) was dissolved in 59.70 g of methanol. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the obtained solution was dropped into a large excess of ethyl acetate, and the precipitate was collected by suction filtration. After drying under reduced pressure, 10.28 g of random MAU / methoxypolyethylene glycol monomethacrylate copolymer (99/1) was obtained (yield: 51.4%). The weight average molecular weight was 34,000.

Example 3-27 : 11-methacrylamidoundecanoic acid (MAU) / methacryloxy group-modified silicone copolymer (90/10)
11-methacrylamidoundecanoic acid (MAU) 14.16 g (52.57 mmol), methacryloxy group-modified silicone (FM-0711: manufactured by Chisso) 5.84 g (5.84 mmol), azobisisobutyronitrile (Nacalai Tesque) 0.24 g (1.46 mmol) was dissolved in a mixed solution of 30 g of methanol and 30 g of chloroform. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, it was dried under reduced pressure and dissolved in 100 g of tetrahydrofuran. The obtained solution was dropped into a large excess of n-hexane, and the precipitate was collected by suction filtration. After drying under reduced pressure, 12.15 g of random MAU / methacryloxy group-modified silicone copolymer (90/10) was obtained (yield: 60.8%). The weight average molecular weight was 53,000.

Example 3-28 : 11-methacrylamidoundecanoic acid (MAU) / 2-methacryloxyethyl phosphate copolymer (90/10)
11-methacrylamidoundecanoic acid (MAU) 18.40 g (68.32 mmol), 2-methacryloxyethyl phosphoric acid (Phosmer M: Unichemical Co., Ltd.) 1.60 g (7.59 mmol), sodium hydroxide 0.30 g ( 7.59 mmol) and 0.31 g (1.89 mmol) of azobisisobutyronitrile (manufactured by Nacalai Tesque) were dissolved in a mixed solvent of 75 g of methanol and 25 g of ion-exchanged water. Nitrogen was bubbled for 60 minutes for deaeration, and the vessel was covered with a septum and heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, a gel product was obtained. After drying under reduced pressure, 6.0 g of the dried product was added to 200 g of methanol, and the mixture was sufficiently stirred, and insoluble materials were removed by filtration. The obtained solution was dropped into a large excess of ethyl acetate, and the precipitate was collected by suction filtration. After drying under reduced pressure, 2.01 g of random MAU / 2-methacryloxyethyl phosphate copolymer (90/10) was obtained. The weight average molecular weight was 190,000.

It is a photograph figure of pH5 buffer solution of the surface treatment powder processed with various surface treating agents (MAU homopolymer and MAU / AMPS copolymer) concerning the present invention. It is a photograph figure of pH10 buffer solution of the surface treatment powder processed with various surface treating agents (MAU homopolymer and MAU / AMPS copolymer) concerning the present invention. It is a NMR measurement result about the surface treating agent (MMPA homopolymer) concerning this invention. It is a photograph figure of pH5 buffer solution and pH10 buffer solution of the surface treatment powder processed with the surface treating agent (MMPA homopolymer) concerning the present invention. It is an infrared spectroscopic measurement result in each condition of the untreated and 1M NaOH solution treatment about the surface treating agent (MMPA homopolymer) concerning the present invention.

Claims (4)

A surface treatment agent comprising a polymer containing a monomer (A) represented by the following general formula (1) as a constituent monomer.

(In the formula, R ¹ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ² is an alkylene group having 4 to 22 carbon atoms, X ¹ is an —NH— group or an oxygen atom, M ¹ is hydrogen or a monovalent inorganic group. Or represents an organic cation.)   2. The surface treatment agent according to claim 1, comprising a polymer containing 70 mol% or more of the monomer (A) in the total amount of the constituent monomers. The surface treatment agent according to claim 1 or 2, further comprising a polymer containing the monomer (B) represented by any one of the following general formulas (2) to (7) as a constituent monomer. Agent.

(Wherein R ³ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ⁴ is an alkylene group having 1 to ⁴ carbon atoms, X ² is an —NH— group or an oxygen atom, and M ² is hydrogen or a monovalent inorganic group. Or represents an organic cation.)

(Wherein R ⁵ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ⁶ is an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group, an aminoalkyl group, or a hydroxyalkyl group, and X ³ is —NH—. Represents a group or an oxygen atom.)

(Wherein R ⁷ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ⁸ is an alkylene group having 1 to 4 carbon atoms, R ⁹ is the same or different hydrogen or alkyl group having 1 to 4 carbon atoms. X ⁴ represents an —NH— group or an oxygen atom, and Y ⁻ represents a monovalent organic or inorganic anion.)

Wherein R ¹⁰ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ¹¹ is an alkylene group having 1 to 4 carbon atoms, R ¹² is hydrogen or an alkyl group having 1 to 4 carbon atoms, and X ⁵ is —NH—. Group or oxygen atom, l represents an integer of 1 to 100)

(Wherein R ¹³ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ¹⁴ is hydrogen which may be the same or different, or an alkyl group having 1 to 4 carbon atoms, and R ¹⁵ is hydrogen or one having 1 to 4 carbon atoms. An alkyl group, X ⁶ represents an —NH— group or an oxygen atom, and m represents an integer of 1 to 100.)

(Wherein R ¹⁶ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ¹⁷ is an alkylene group having 1 to 4 carbon atoms, X ⁷ is an —NH— group or an oxygen atom, and M ³ is hydrogen or a monovalent inorganic group. Or an organic cation, n represents an integer of 1 to 100.)   The surface treating agent according to claim 3, wherein a ratio of the monomer (A) to the monomer (B) is (A) :( B) = 70: 30 to 99.9: 0.1 in terms of molar ratio. A surface treatment agent comprising a polymer.

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