TW201730284A - Polymer for insoluble antifouling coating material, resin composition, antifouling coating material, coating film, method for reducing underwater friction, and process for producing polymer for insoluble antifouling coating material - Google Patents

Abstract

Provided are: a polymer for insoluble antifouling coating materials which comprises a constituent unit (A) derived from a macromonomer (a) and a constituent unit (B) derived from a monomer (b) that is not a macromonomer, the macromonomer (a) being constituted of a monomer (aa) having a solubility parameter less than 18.5 (J/cm3)1/2, the monomer (b) having a solubility parameter of 18.5 (J/cm3)1/2 or greater, and the polymer being capable of forming coating films that have low resistance of friction with aqueous liquids such as seawater; a resin composition; an antifouling coating material; coating films formed from the resin composition and the antifouling coating material; a method for reducing underwater friction; and a process for producing the polymer for insoluble antifouling coating materials.

Description

Polymer for non-soluble antifouling paint, resin composition, antifouling paint, coating film, method for reducing friction in water, and method for producing polymer for non-soluble antifouling paint

The present invention relates to a polymer for a non-soluble antifouling coating, a resin composition, an antifouling coating, a coating film, a method for reducing friction in water, and a method for producing a polymer for an insoluble antifouling coating. Japanese Patent Application No. 2015-238670 filed in Japan on December 7, 2015, Japanese Patent Application No. 2016-136502 filed on July 11, 2016 in Japan, and July 2016 The priority of Japanese Patent Application No. 2016-139981, filed on Jan. 5, the entire content of

It is known that in marine structures or ships, antifouling coatings are applied in order to prevent corrosion of the portion in contact with seawater caused by the adhesion of organisms in the sea or a decrease in the speed of navigation. As the antifouling paint, it is known that the surface of the formed coating film is gradually dissolved in seawater to perform surface renewal (self-polishing), a dissolution type (self-polishing type), and a non-dissolving type in which the coating film is not surface-updated. As the non-dissolving type antifouling paint, for example, a hard coat film comprising at least two kinds of resins which are incompatible with each other and insoluble in seawater and which form a specific microscopic Heterogeneous Structure is proposed (Patent Document 1).

On the other hand, the ship receives frictional resistance from seawater during navigation. From the viewpoint of reduction in fuel consumption or energy saving, it is desirable to reduce the frictional resistance of the coating film provided on the ship's seawater contact portion. With respect to such a request, for example, a coating composition containing a composite particle containing a specific organic polymer substance and a specific dispersing agent and having a specific particle diameter, and a resin binder is proposed (Patent Document 2); or The contact angle of the film surface with respect to water and the surface roughness of the coating are set to a predetermined value to reduce the coating film in water (Patent Document 3). [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2003-277691.

[Problems to be Solved by the Invention] However, the effect of reducing the frictional resistance of the coating film formed from the conventional coating composition is not sufficient.

It is an object of the present invention to provide a polymer for a non-soluble antifouling coating, a resin composition, an antifouling paint, a coating film formed using the coating film, and a coating film which can form a coating film having a small frictional resistance with an aqueous liquid such as seawater. A method for producing a friction reducing method and a polymer for a non-soluble antifouling coating. [Means for solving the problem]

The present invention has the following aspects.

[1] A polymer for an insoluble antifouling coating comprising a constituent unit derived from a macromonomer (a) (A) and a constituent unit derived from a monomer (b) which is not a macromonomer (B) The solubility parameter of the monomer (aa) constituting the macromonomer (a) is less than 18.5 (J/cm ³ ) ^1/2 , and the solubility parameter of the monomer (b) is 18.5 (J/cm ^{3 ).} ) ^1/2 or more. [2] The polymer for an insoluble antifouling coating according to [1], wherein a contact angle of a surface of the coating film formed by a captive bubble method is 120° or more and 144° or less. Further, the formed coating film has an indentation modulus of elasticity of 15 MPa or more and 2900 MPa or less. [3] The polymer for an insoluble antifouling coating according to [1], wherein the macromonomer (a) is a radical polymerizable group and has two or more of the following formulas; (AA) The macromonomer of the constituent unit shown, [Chemical 1] ・・・(AA) (wherein R ¹ is a hydrogen atom, a methyl group or CH ₂ OH, R ² is OR ³ , a halogen atom, COR ⁴ , COOR ⁵ , CN, CONR ⁶ R ⁷ or R ⁸ , R ³ ～R ⁷ each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, Substituted or substituted heteroaryl, unsubstituted or substituted non-aromatic heterocyclic group, unsubstituted or substituted aralkyl group, unsubstituted or substituted An alkaryl group, or an unsubstituted or substituted organoalkylene group, wherein the substituents allowed in the above are selected from the group consisting of a carboxyl group, an alkoxycarbonyl group, an epoxy group, a hydroxyl group, and an alkoxy group. At least one of the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, an isocyanate group, a sulfo group, and a halogen, and R ⁸ represents an unsubstituted or substituted aryl group, or An unsubstituted or substituted heteroaryl group, wherein the substituents allowed in the above are each selected from a carboxyl group, Oxycarbonyl, epoxy, hydroxy, alkoxy, primary amine, secondary amine, tertiary amine, isocyanato, sulfo, unsubstituted or substituted alkyl, unsubstituted At least one of the group consisting of a substituted or substituted aryl group, an unsubstituted or substituted alkenyl group-containing group, and a halogen group). [4] The polymer for an insoluble antifouling coating according to any one of [1] to [3] wherein the monomer (b) is an aliphatic monomer. [5] The polymer for an insoluble antifouling coating according to any one of [1] to [4] wherein the glass transition point is 10 ° C or higher. [6] The polymer for an insoluble antifouling coating according to any one of [1] to [5] wherein the macromonomer (a) is a macromonomer represented by the following formula (1) , [Chemical 2] (wherein R is a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, unsubstituted Or a heteroaryl group having a substituent or a non-aromatic heterocyclic group having an unsubstituted or substituted group, and a plurality of R groups may be the same or different, and X is a hydrogen atom or a methyl group, and a plurality of X may be They may be the same or different, Z is a terminal group, and n is a natural number of 2 to 10,000.

[7] A resin composition comprising the polymer for an insoluble antifouling coating according to any one of [1] to [6]. [8] The resin composition according to [7], which further comprises a solvent. [9] The resin composition according to [7] or [8], wherein the viscosity at 25 ° C is 5 × 10 ⁴ mPa·s or less. [10] An antifouling coating comprising the resin composition according to any one of [7] to [9]. [11] A coating film formed by using the resin composition according to any one of [7] to [9] or the antifouling paint according to [10]. [12] A method of reducing the friction in the water, comprising: using the resin composition according to any one of [7] to [9], or the antifouling paint according to [10] on the surface of the object to be coated A step of forming a coating film.

[13] A method for producing a polymer for an insoluble antifouling coating, which comprises polymerizing a monomer mixture comprising the macromonomer (a) and a monomer (b) which is not a macromonomer to obtain [ The polymer for a non-soluble antifouling coating according to any one of [6], wherein the macromonomer (a) is a macromonomer having a radical polymerizable group. [14] The method for producing a polymer for an insoluble antifouling coating according to [13], wherein the macromonomer having a radical polymerizable group is produced by a suspension polymerization method. [15] The method for producing a polymer for an insoluble antifouling coating according to [14], wherein the monomer mixture is polymerized by a solution polymerization method. [Effects of the Invention]

According to the present invention, it is possible to provide a polymer for a non-soluble antifouling paint, a resin composition, an antifouling paint, a coating film formed using the coating film, and a coating film which can form a coating film having a small frictional resistance with an aqueous liquid such as seawater. A method for producing a friction reducing method and a polymer for a non-soluble antifouling coating.

The definitions of the following terms can be applied to this specification and the scope of the patent application. The "(meth)acrylic monomer" means a monomer having a (meth)acrylonitrile group. "(Meth) propylene fluorenyl group" is a general term for propylene fluorenyl group and methacryl fluorenyl group. "(Meth)acrylate" is a generic term for acrylate and methacrylate. "(Meth)acrylic acid" is a generic term for acrylic acid and methacrylic acid.

Hereinafter, embodiments of the present invention will be described. The following embodiments are merely illustrative of the invention and are not intended to limit the invention only. The present invention can be implemented in various aspects as long as the gist of the invention is not exceeded.

[Polymer for non-soluble antifouling paint] The polymer for the non-soluble antifouling paint of the present invention contains a constituent unit derived from a macromonomer (hereinafter also referred to as "macromonomer (a)") (hereinafter, It is also called "constituting unit (A)") and a constituent unit derived from a monomer which is not a giant monomer (hereinafter also referred to as "monomer (b)") (hereinafter, also referred to as "constituting unit (B)" In the above, the solubility parameter of the monomer constituting the macromonomer (a) (hereinafter also referred to as "monomer (aa)") is less than 18.5, and the solubility parameter of the monomer (b) is 18.5 or more.

The polymer for an insoluble antifouling coating of the present invention has a structure of a block copolymer and/or a graft copolymer. Further, the polymer for a non-soluble antifouling paint of the present invention is typically an amphiphilic polymer containing a hydrophilic portion and a hydrophobic portion in a molecule. In the amphiphilic polymer, the polymer chain composed of the structural unit (A) derived from the macromonomer (a) may be a hydrophobic portion, and the constituent unit derived from the monomer (b) (B) The polymer chain formed is a hydrophilic portion. Alternatively, the polymer chain composed of the constituent unit derived from the macromonomer (a) may be a hydrophilic portion, and the polymer chain composed of the constituent unit derived from the monomer (b) may be a hydrophobic portion.

(Structural unit (A)) The constituent unit (A) is a constituent unit derived from a giant monomer (a) to be described later. In the macromonomer (a), the solubility parameter of the monomer (aa) constituting the macromonomer (a) is less than 18.5. The solubility parameter of the monomer (aa) constituting the macromonomer (a) is preferably 15.0 or more and less than 18.5, more preferably 16.0 or more and less than 18.4. When the solubility parameter of the monomer (aa) constituting the macromonomer (a) is at least the above lower limit value, the storage stability of the coating material is excellent, and when it is at most the above upper limit value, the coating film is adhered to the substrate. Excellent sex.

The solubility parameter (Sp value) is a measure of solubility. In the present specification, the Sp value is a value calculated from the measured value in the following manner, and has a unit "(J/cm ³ ) ^1/2 ", but Units are omitted from the description.

- Solubility parameter In the present invention, the solubility parameter (Sp value) is by Robert F. Fedor ("Polymer Engineering and Science", February 1974, Vol. 14, No. 2, (Fr. F. Fedor) The value estimated by the Fedors method described in Robert F. Fedors (pp. 147-154). The value of the solubility parameter can be calculated by the following formula (2). [Expression 1] ・・・(2) In the formula (2), the values of the cohesive energy and the molar volume of the atomic group are the values shown in Table 1.

[Table 1]

For example, in the case of polymethyl methacrylate (PMMA), the monomer unit (MMA) is represented by the following formula and contains 2 CH ₃ and CH ₂ = 1, = C< It is one atomic group having one COO. Therefore, the Sp value of the MMA unit is calculated to be 18.27 (J/cm ³ ) ^1/2 from the following formula (3). [Chemical 3] [Expression 2] ・・・(3)

Examples of the macromonomer (a) include a radically polymerizable group or an addition reactive functional group such as a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an amine group, a guanamine group, a thiol group or an acid anhydride group. Wait.

In the case where the macromonomer (a) has a radical polymerizable group, the macromonomer (a) and the monomer (b) can be copolymerized by radical polymerization to produce the non-dissolving antifouling of the present invention. Polymer for coatings. In the case where the macromonomer (a) has a radical polymerizable group, the macromonomer (a) may have one or more radical polymerizable groups, and preferably has one radical polymerizable group.

When the macromonomer (a) has an addition-reactive functional group, the monomer (b) usually has a functional group reactive with an addition-reactive functional group possessed by the macromonomer (a). The polymerizable functional group derived from the monomer (b) can be reacted with an addition-reactive functional group possessed by the macromonomer (a) to produce a polymer for an insoluble antifouling coating of the present invention. In the case where the macromonomer (a) has an addition-reactive functional group, the macromonomer (a) may have the same or different one or more addition-reactive functional groups, preferably having an addition-reactive functional group. base.

The combination of the addition-reactive functional group which the macromonomer (a) has and the functional group which can react with the said functional group is the following combination, for example. a combination of a hydroxyl group and a carboxyl group or an acid anhydride group, a combination of an isocyanate group and a hydroxyl group or a thiol group, a combination of an epoxy group and an amine group, a combination of a carboxyl group and an epoxy group, a combination of an amine group and a carboxyl group, a mercapto group and a carboxyl group. Combination, a combination of a thiol group and an epoxy group.

Further, the macromonomer (a) may have either a radical polymerizable group or a functional group, or may have both a radical polymerizable group and a functional group. When the macromonomer (a) contains both a radical polymerizable group and a functional group, a functional group added to the polymer unit containing the monomer (b) or a monomer (b) is added. The functional group other than any of the polymerizable radical polymerizable groups or the radical polymerizable group may be two or more.

The macromonomer (a) preferably has a radical polymerizable group, and more preferably has a radical polymerizable group copolymerizable with the monomer (b).

The radical polymerizable group which the macromonomer (a) has is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include CH ₂ =C(COOR)-CH ₂ -, (meth)acrylonyl group, 2-(hydroxymethyl)propenyl group, vinyl group and the like. Here, R represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, and an unsubstituted one. Or a heteroaryl group having a substituent or a non-aromatic heterocyclic group having an unsubstituted or substituted group.

Examples of the unsubstituted alkyl group in R include a branched alkyl group having 1 to 22 carbon atoms or a linear alkyl group. Specific examples of the branched alkyl group or the linear alkyl group having 1 to 22 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a t-butyl group, an isobutyl group, and a pentyl group. (amyl), isoamyl, hexyl, heptyl, 2-ethylhexyl, octyl, isooctyl, decyl, isodecyl, decyl, isodecyl, undecyl, dodecyl Lauryl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl (stearyl), iso-octadecyl, nonadecyl, Eicosyl and behenyl and the like.

The unsubstituted alicyclic group in R may be a monocyclic ring or a polycyclic ring, and examples thereof include an alicyclic group having 3 to 20 carbon atoms. The alicyclic group is preferably a saturated alicyclic group, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a bicyclo[2.2.1]heptyl group, and a cyclooctyl group. And adamantyl and the like.

Examples of the unsubstituted aryl group in R include an aryl group having 6 to 18 carbon atoms. Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group and a naphthyl group.

Examples of the unsubstituted heteroaryl group in R include a heteroaryl group having 4 to 18 carbon atoms. Specific examples of the heteroaryl group having 4 to 18 carbon atoms include a pyridyl group and a carbazolyl group.

Examples of the unsubstituted heterocyclic group in R include a heterocyclic group having 4 to 18 carbon atoms. Specific examples of the heterocyclic group having 4 to 18 carbon atoms include a heterocyclic group having an oxygen atom such as a tetrahydrofuranyl group or a tetrahydropyranyl group, a γ-butyrolactone group, an ε-caprolactone group, and a pyrrole group. a heterocyclic group containing a nitrogen atom such as a pyridyl group, a pyrrolidinyl group or a morpholinyl group.

As a substituent in R (alkyl group having a substituent, alicyclic group having a substituent, aryl group having a substituent, heteroaryl group having a substituent, non-aromatic heterocyclic group having a substituent The substituent in each) may, for example, be selected from an alkyl group (except when R is an alkyl group having a substituent), an aryl group, -COOR ¹¹ , a cyano group, -OR ¹² , -NR ¹³ R ¹⁴ , - At least one of the group consisting of CONR ¹⁵ R ¹⁶ , a halogen atom, an allyl group, an epoxy group, a decyloxy group, and a group exhibiting hydrophilicity or ionicity. Here, R ¹¹ to R ¹⁶ each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, or an unsubstituted or substituted group. Aryl.

The alkyl group and the aryl group in the substituent may be the same as the unsubstituted alkyl group or the unsubstituted aryl group, respectively. R ¹¹ of -COOR ¹¹ in the substituent is preferably a hydrogen atom or an unsubstituted alkyl group. That is, -COOR ^{11 is} preferably a carboxyl group or an alkoxycarbonyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group. R ¹² of -OR ¹² in the substituent is preferably a hydrogen atom or an unsubstituted alkyl group. That is, -OR ^{12 is} preferably a hydroxyl group or an alkoxy group. Examples of the alkoxy group include alkoxy groups having 1 to 12 carbon atoms, and specific examples thereof include a methoxy group.

Examples of -NR ¹³ R ¹⁴ in the substituent include an amine group, a monomethylamino group, a dimethylamino group and the like. As -CONR ¹⁵ R ¹⁶ in the substituent, for example, an amine-methyl group (-CONH ₂ ), an N-methylamine-methyl group (-CONHCH ₃ ), and an N,N-dimethylamine formamidine can be cited. A group (dimethylammonium group: -CON(CH ₃ ) ₂ ) or the like.

Examples of the halogen atom in the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the group exhibiting hydrophilicity or ionicity in the substituent include an alkali salt of a carboxyl group or an alkali salt of a sulfo group, a poly(alkylene oxide) such as a polyethylene oxide group or a polypropylene oxide group. a cationic substituent such as a quaternary ammonium salt group.

R is preferably an unsubstituted or substituted alkyl group, or an unsubstituted or substituted alicyclic group, more preferably an unsubstituted alkyl group, or an unsubstituted or alkyl group. An alicyclic group as a substituent. Among them, in terms of easiness of obtaining, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and ring are preferred. Propyl, cyclobutyl, isobornyl and adamantyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, iso Borneol base and adamantyl.

The macromonomer (a) is preferably a constituent unit having two or more monomers derived from a radical polymerizable group (hereinafter also referred to as "monomer (aa1)"). The radical polymerizable group of the monomer (aa1) is preferably a group having an ethylenically unsaturated bond, similarly to the preferred radical polymerizable group of the macromonomer (a).

Examples of the monomer (aa1) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid. N-butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Ester, octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylate Anthracene ester, lauryl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, phenyl (meth)acrylate, (A) Benzyl acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, 3,5,5-trimethylcyclohexane (meth)acrylate Ester, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, terpene acrylate or its derivative, hydrogenated rosin acrylate Or its derivatives, Hydrocarbyl-containing (meth) acrylate such as behenyl acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate a hydroxyl group-containing (meth) acrylate such as ester, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate or glyceryl (meth)acrylate; (meth)acrylic acid, hexahydrogen 2-(Methyl)propenyloxyethyl phthalate, 2-(meth)acryloxypropyl hexahydrophthalate, 2-(methyl)propenyloxy phthalate Ethyl ester, 2-(methyl)propenyl propyl propyl phthalate, 2-(methyl) propylene methoxyethyl maleate, 2-(methyl) propylene maleate醯-propyl propyl ester, 2-(methyl) propylene methoxyethyl succinate, 2-(methyl) propylene methoxy propyl succinate, crotonic acid, fumaric acid, maleic acid Acid, itaconic acid, citraconic acid, monomethyl maleate, monoethyl maleate, monooctyl maleate, monomethyl itaconate, monoethyl itaconate , itaconic acid monobutyl ester, itaconic acid monooctyl ester, fumaric acid monomethyl ester, fumaric acid monoethyl a carboxyl group-containing vinyl monomer such as an ester, a butyl fumarate, a monooctyl fumarate or a monoethyl citrate; an acid anhydride group-containing ethylene such as maleic anhydride or itaconic anhydride Monomer; dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, dibutyl itaconate, fubutene Unsaturated dicarboxylic acid diester monomer such as diperfluorocyclohexyl diacid; glycidyl (meth)acrylate, glycidyl α-ethyl acrylate, 3,4-epoxy butyl (meth)acrylate An epoxy group-containing vinyl monomer such as an ester; an amine group-containing (meth) acrylate-based ethylene such as dimethylaminoethyl (meth)acrylate or diethylaminoethyl (meth)acrylate Monomer; (methyl) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N- Hydroxymethyl (meth) acrylamide, N-isopropyl acrylamide, hydroxyethyl acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl ( Methyl) acrylamide, diacetone acrylamide, maleic acid, cis A vinyl monomer containing a guanamine group such as butylene diimide; ethylene such as styrene, α-methylstyrene, vinyl toluene, (meth)acrylonitrile, vinyl chloride, vinyl acetate or vinyl propionate Monomer; divinylbenzene, ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1 , 6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, Polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1 , 10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, (methyl) Multifunctional such as allyl acrylate, triallyl cyanurate, diallyl maleate, polypropylene glycol diallyl ether, N, N'-methylene bis(methyl) acrylamide Vinyl monomer; (methyl)propenyl morpholine a heterocyclic monomer such as vinyl pyrrolidine copper, vinyl pyridine or vinyl oxazole; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethyl (meth)acrylate, Ethoxyethyl (meth)acrylate, n-butoxyethyl (meth)acrylate, isobutoxyethyl (meth)acrylate, tert-butoxyethyl (meth)acrylate, (A) Ethyl ethoxyethoxyethyl acrylate, phenoxyethyl (meth) acrylate, decyl phenoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ( Ethyl methoxyethyl methacrylate, "Placcel FM" (caprolactone addition monomer manufactured by Daicel Chemical Co., Ltd., trade name), "Blanmo" Blemmer) PME-100" (Nippon Oil Co., Ltd. methoxy polyethylene glycol methacrylate (two chains of ethylene glycol), trade name), "Blemmer PME-200" (Nippon Oil Co., Ltd. produced methoxy polyethylene glycol methacrylate (four chains of ethylene glycol), trade name), "Blemmer PME-400" (Nippon Oil ( Manufacturing Methoxy polyethylene glycol methacrylate (ethylene glycol chain of 9), trade name), "Blemmer 50POEP-800B" (Nippon Oil Co., Ltd.) Glycol-polypropylene glycol-methacrylate (8-chain of ethylene glycol and 6 chains of propylene glycol), trade name), Blemmer 20ANEP-600 (manufactured by Nippon Oil Co., Ltd.) Nonylphenoxy (ethylene glycol-polypropylene glycol) monoacrylate, trade name), Blemmer AME-100 (manufactured by Nippon Oil Co., Ltd., trade name), Blemmer ) AME-200" (manufactured by Nippon Oil Co., Ltd., trade name) and "Blemmer 50AOEP-800B" (manufactured by Nippon Oil Co., Ltd., trade name) and other glycol ester monomers; 3-( Methyl) propylene methoxy propyl trimethoxy decane, 3-(methyl) propylene methoxy propyl methyl diethoxy decane, 3-(methyl) propylene methoxy propyl triethoxy a monomer containing a decane coupling agent such as decane, 3-propenyloxypropyltrimethoxydecane, ethylene trimethoxydecane or ethylene triethoxysilane; (meth)acrylic acid trimethyldecane ester, (A) Triethyl decyl acrylate, tri-n-propyl decyl (meth) acrylate, tri-n-butyl decyl (meth) acrylate, tri-n-pentyl decyl (meth) acrylate, (A) Tris-n-hexyl decyl acrylate, tri-n-octyl decyl (meth) acrylate, tri-n-dodecyl decyl (meth) acrylate, triphenyl decyl (meth) acrylate, ( Tri-p-methylphenyl decyl methacrylate, tribenzyl decyl (meth) acrylate, triisopropyl decyl (meth) acrylate, triisobutyl decyl (meth) acrylate, ( Tri-t-butyl decyl methacrylate, tris-2-methylisopropyl decyl (meth) acrylate, tri-tert-butyl decyl (meth) acrylate, (meth) acrylate Dimethyl decyl ester, n-butyl dimethyl methacrylate (meth) acrylate, diisopropyl n-butyl decyl (meth) acrylate, n-octyl di-n-butyl (meth) acrylate a decyl ester, diisopropyl stearyl methacrylate (meth) acrylate, dicyclohexyl phenyl decyl (meth) acrylate, tert-butyl diphenyl decyl (meth) acrylate, (methyl) Acrylic month Diphenyl decyl ester, triisopropyl decyl methyl maleate, triisopropyl decyl amyl maleate, tri-n-butyl decyl-n-butyl maleate Ester, tert-butyl diphenyl decyl methyl ester of maleic acid, tert-butyl diphenyl decyl-n-butyl maleate, triisopropyl sulfonyl methacrylate Ester, triisopropyl decyl amyl methacrylate, tri-n-butyl decyl-n-butyl fumarate, tert-butyl diphenyl decyl methyl methacrylate, Tert-butyl diphenyl decyl-n-butyl methacrylate, Silaplane FM-0711 (manufactured by JNC, trade name), Silaplane FM-0721 (manufactured by JNC), Silaplane FM-0725 (manufactured by JNC), SilaplaneTM-0701 (manufactured by JNC) Name), SilaplaneTM-0701T (manufactured by JNC), X-22-174ASX (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), X-22-174BX (Shin-Etsu Chemical) Industry Manufacture, trade name), KF-2012 (Shin-Etsu Chemical Co., Ltd., trade name), X-22-2426 (Shin-Etsu Chemical Co., Ltd., trade name), X-22-2404 (Shin-Etsu Chemical Industry ( a product containing a decane coupling agent other than a monomer containing a decane coupling agent; a halogenated olefin such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride or chlorotrifluoroethylene; 2-ethyl isocyanate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-pentafluorophenyl (meth)acrylate, (A) 2-(perfluorobutyl)ethyl acrylate, 3-(perfluorobutyl)-2-hydroxypropyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 3-Perfluorohexyl-2-hydroxypropyl (meth)acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl (meth)acrylate, 2,2, (meth)acrylic acid 3,3-tetrafluoropropyl ester, (meth)acrylic acid 1H, 1H, 5H-octafluoropentyl ester, (meth)methacrylic acid 1H, 1H, 5H-octafluoropentyl ester, (meth)acrylic acid 1H, 1H, 2H, 2H-tridecafluorooctyl ester, 1H-1-(trifluoromethyl)trifluoroethyl (meth)acrylate, 1H,1H,3H-hexafluorobutyl (meth)acrylate, a fluorine-containing monomer such as 1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl (meth)acrylate (excluding a halogenated olefin); 1-butoxy B (meth)acrylate Ester, 1-(2-ethylhexyloxy)ethyl (meth)acrylate, 1-(cyclohexyloxy)ethyl methacrylate, 2-tetrahydropyranyl (meth)acrylate, etc. A monomer having an aldehyde structure; 4-methylpropenyloxybenzophenone, ethyl 2-isocyanate (meth)acrylate, and the like. These monomers may be used alone or in combination of two or more.

The macromonomer (a) preferably contains a radical polymerizable group and has two or more constituent units represented by the following formula (AA) (hereinafter also referred to as "constituting unit (AA)"). [Chemical 4] ・・・(AA) (wherein R ¹ is a hydrogen atom, a methyl group or CH ₂ OH, R ² is OR ³ , a halogen atom, COR ⁴ , COOR ⁵ , CN, CONR ⁶ R ⁷ or R ⁸ , R ³ ～R ⁷ each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, Substituted or substituted heteroaryl, unsubstituted or substituted non-aromatic heterocyclic group, unsubstituted or substituted aralkyl group, unsubstituted or substituted An alkaryl group, or an unsubstituted or substituted organoalkylene group, wherein the substituents permitted in the above are each selected from the group consisting of a carboxyl group, an alkoxycarbonyl group, an epoxy group, a hydroxyl group, an alkoxy group, and a primary amino group. At least one of the group consisting of a secondary amine group, a tertiary amino group, an isocyanate group, a sulfo group, and a halogen, and R ⁸ represents an unsubstituted or substituted aryl group, or an unsubstituted group. Or a heteroaryl group having a substituent, wherein the substituents allowed in the above are each selected from a carboxyl group, an alkoxycarbonyl group, and a ring. Oxyl, hydroxy, alkoxy, primary amine, secondary amine, tertiary amine, isocyanato, sulfo, unsubstituted or substituted alkyl, unsubstituted or substituted At least one of the group consisting of an aryl group, an unsubstituted or substituted alkenyl group, and a halogen)

R ^{1 is} preferably a hydrogen atom or a methyl group, and R ^{2 is} preferably COOR ⁵ .

R ³ to R ⁷ unsubstituted alkyl, unsubstituted alicyclic, unsubstituted aryl, unsubstituted heteroaryl, unsubstituted non-aromatic heterocyclic group, respectively Listed as the unsubstituted alkyl group in the R, the unsubstituted alicyclic group, the unsubstituted aryl group, the unsubstituted heteroaryl group, the unsubstituted non-aromatic heterocyclic group By.

Examples of the unsubstituted aralkyl group of R ³ to R ⁷ include a benzyl group and a phenylethyl group.

Examples of the unsubstituted organodecylalkyl group of R ³ to R ⁷ include -SiR ¹⁷ R ¹⁸ R ¹⁹ (wherein, R ¹⁷ to R ¹⁹ each independently represent an unsubstituted or substituted alkyl group, Unsubstituted or substituted alicyclic group, or unsubstituted or substituted aryl group). Examples of the unsubstituted or substituted alkyl group in R ¹⁷ to R ¹⁹ include the same as those described above, and examples thereof include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, and a hexyl group. Base, n-octyl, n-dodecyl, stearyl, lauryl, isopropyl, isobutyl, t-butyl, 2-methylisopropyl, benzyl, and the like. Examples of the unsubstituted or substituted alicyclic group in R ¹⁷ to R ¹⁹ include the same as those described above, and examples thereof include a cyclohexyl group. Examples of the unsubstituted or substituted aryl group in R ¹⁷ to R ¹⁹ include the same as those described above, and examples thereof include a phenyl group and a p-methylphenyl group. R ¹⁷ to R ¹⁹ may be the same or different.

Substituent in R ³ to R ⁷ (alkyl group having a substituent, alicyclic group having a substituent, aryl group having a substituent, heteroaryl group having a substituent, non-aromatic heterocyclic ring having a substituent An alkyl group, an aryl group, a heteroaryl group or a non-aromatic heterocyclic ring in the group of a substituent, an arylalkyl group having a substituent, an alkylaryl group having a substituent, a substituent in each of an organic decyl group having a substituent The formula, the aralkyl group, and the alkaryl group may be the same as those described above. As the alkoxycarbonyl group, for example, R ¹¹ of the -COOR ¹¹ is an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, or an unsubstituted or A group of an aryl group having a substituent. As the alkoxy group, R ¹² -OR ¹² include the unsubstituted alkyl group. The secondary amine group may, for example, be an alkyl group, an unsubstituted or substituted alicyclic group wherein R ¹³ of the -NR ¹³ R ¹⁴ is a hydrogen atom, R ¹⁴ is an unsubstituted or substituted group. Or a group of an unsubstituted or substituted aryl group. As the tertiary amino group, R ¹³ and R ^{14 of} the -NR ¹³ R ¹⁴ are each an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, or A group of an unsubstituted or substituted aryl group. The unsubstituted or substituted alkyl group, the unsubstituted or substituted aryl group, and the halogen atom may be respectively the same as those described above.

The unsubstituted aryl group, the unsubstituted heteroaryl group, and the unsubstituted non-aromatic heterocyclic group in R ⁸ may be the same as those described above, respectively. Alkoxycarbonyl group, alkoxy group in the substituent in R ⁸ (the substituent in the aryl group, the heteroaryl group having a substituent, the substituent in each of the non-aromatic heterocyclic groups having a substituent) a primary amino group, a secondary amino group, a tertiary amino group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, and a halogen atom may be exemplified by the same . Examples of the unsubstituted alkenyl group-containing group include an allyl group and the like. The substituent in the alkenyl group-containing group having a substituent may be the same as the substituent in R ³ to R ⁷ .

The constituent unit (AA) is a constituent unit derived from CH ₂ =CR ¹ R ² . Specific examples of CH ₂ =CR ¹ R ² include the following. Substituted or unsubstituted alkyl (meth)acrylate [eg, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate , n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, ( Stearic acid methyl methacrylate, behenyl alcohol (meth) acrylate, 1-methyl-2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ( 3-methyl-3-methoxybutyl methacrylate], substituted or unsubstituted arylalkyl (meth) acrylate [eg, benzyl (meth) acrylate, (meth) acrylate Methoxyphenylethyl ester, p-methoxyphenylethyl (meth)acrylate], substituted or unsubstituted aryl (meth)acrylate [eg, phenyl (meth) acrylate, (A) Methyl phenyl acrylate, p-methoxyphenyl (meth) acrylate, o-methoxy phenyl ethyl (meth) acrylate], alicyclic (meth) acrylate [eg, ( Isobornyl (meth)acrylate, cyclohexyl (meth)acrylate], a (meth) acrylate containing a halogen atom [for example, trifluoroethyl (meth) acrylate, perfluorooctyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate] or the like having a hydrophobic group ( Methyl) acrylate monomer; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, butoxy Diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, (Oxy) vinyl (meth) acrylate monomer such as 2-(2-ethylhexyloxy)ethyl (meth)acrylate; 2-hydroxyethyl (meth) acrylate, (meth) acrylate 2 a hydroxyl group-containing (meth) acrylate monomer such as hydroxypropyl ester, 4-hydroxybutyl (meth) acrylate or glyceryl (meth) acrylate; methoxypolyethylene glycol allyl ether, methoxy group Polypropylene glycol allyl ether, butoxy polyethylene glycol allyl ether, butoxy polypropylene glycol allyl ether, methoxy polyethylene glycol-polypropylene glycol allyl ether, butoxy polyethylene glycol-polypropylene glycol Terminal alkoxyallyl polyethers such as allyl ether ; an epoxy group-containing ethylene monomer such as glycidyl (meth)acrylate, glycidyl α-ethyl acrylate, 3,4-epoxybutyl (meth)acrylate; butyl (meth)acrylate An ethylene monomer containing a primary or secondary amine group such as an aminoethyl ester or a (meth)acrylamide; a dimethylaminoethyl (meth)acrylate; and a diethylamino (meth)acrylate Ethyl ester, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, dimethylaminoethyl ( a vinyl monomer containing a tertiary amino group such as methacrylamide or dimethylaminopropyl (meth) acrylamide; a heterocyclic alkaline monomer such as vinylpyrrolidone, vinylpyridine or vinylcarbazole Benzyl (meth) acrylate, triethyl decyl (meth) acrylate, tri-n-propyl decyl (meth) acrylate, tri-n-butyl decyl (meth) acrylate, Tri-n-pentyl decyl (meth) acrylate, tri-n-hexyl decyl (meth) acrylate, tri-n-octyl decyl (meth) acrylate, tri-n-dodecyl (meth) acrylate Decyl ester, (a ) Triphenyl decyl acrylate, tri-p-methylphenyl decyl (meth) acrylate, tribenzyl decyl (meth) acrylate, triisopropyl decyl (meth) acrylate, (methyl) Triisobutyl decyl acrylate, tri-t-butyl decyl (meth) acrylate, tris-2-methylisopropyl decyl (meth) acrylate, tri-tertiary butyl (meth) acrylate Decyl ester, ethyl dimethyl methacrylate (meth) acrylate, n-butyl dimethyl methacrylate (meth) acrylate, diisopropyl butyl butyl methacrylate, (methyl) N-octyldi-n-butyl decyl acrylate, diisopropyl stearyl methacrylate, dicyclohexyl phenyl decyl (meth) acrylate, tert-butyl (meth) acrylate A vinyl group-containing vinyl monomer such as phenyl decyl ester or lauryl diphenyl decyl (meth) acrylate; methacrylic acid, acrylic acid, ethylene benzoic acid, tetrahydrophthalic acid monohydroxyl (meth) acrylate Ethyl ester, monohydroxypropyl tetrahydrophthalate (meth) acrylate, monohydroxybutyl tetrahydrophthalate, (meth) acrylate Monohydroxyethyl phthalate, monohydroxypropyl phthalate phthalate, monohydroxyethyl methacrylate succinate, monohydroxypropyl succinate (meth) acrylate, (methyl) a carboxyl group-containing ethylenically unsaturated monomer such as acrylic acid maleic acid monohydroxyethyl ester or (meth)acrylic acid maleic acid monohydroxypropyl ester; a cyano group-containing vinyl monomer such as acrylonitrile or methacrylonitrile; Alkyl vinyl ether [eg, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, 2-ethylhexyl vinyl ether, etc.], cycloalkyl vinyl ether [eg, cyclohexyl vinyl ether) Etc. vinyl ether monomer; vinyl acetate monomer such as vinyl acetate, vinyl propionate, vinyl butyrate or vinyl benzoate; aromatic vinyl monomer such as styrene, vinyl toluene or α-methylstyrene ; halogenated olefins such as vinyl chloride and vinyl fluoride.

When the macromonomer (a) is a macromonomer having a radical polymerizable group and having two or more constituent units (AA), the macromonomer (a) may further have a constituent unit (AA) Other constituent units. The other constituent unit is, for example, a constituent unit derived from a monomer which is not equivalent to CH ₂ =CR ¹ R ² among the monomers exemplified as the monomer (aa1).

From the viewpoint of recoatability, the macromonomer (a) is preferably derived from a (meth) acrylate monomer selected from a hydrophobic group, an oxyethylene group-containing (meth) acrylate monomer, a hydroxyl group-containing (meth) acrylate monomer, a terminal alkoxyallyylated polyether monomer, an epoxy group-containing ethylene monomer, a primary or secondary amine group-containing ethylene monomer, and three Amino-based ethylene monomer, heterocyclic basic monomer, carboxyl group-containing ethylenically unsaturated monomer, cyano group-containing ethylene monomer, vinyl ether monomer, vinyl ester monomer, aromatic vinyl monomer A constituent unit of one or more monomers.

In the macromonomer (a), among the monomers forming the constituent unit (AA) or other constituent units, for example, methyl (meth)acrylate, ethyl (meth)acrylate, or n-propyl (meth)acrylate may be mentioned. Ester, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, (A) Ethyl hexyl acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cetyl (meth) acrylate , (meth) methacrylate, isodecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydro (meth) acrylate Anthracene ester, isobornyl (meth)acrylate, 3,5,5-trimethylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate , hydrocarbyl-containing (meth)acrylic acid dicyclopentenyloxyethyl ester, terpene acrylate or its derivative, hydrogenated rosin acrylate or its derivative, behenyl (meth) acrylate Propylene Ester; 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (methyl) a hydroxyl group-containing (meth) acrylate such as 3-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate or glyceryl (meth) acrylate; (meth)acrylic acid, hexahydrophthalic acid 2 -(Meth) propylene methoxyethyl ester, 2-(methyl) propylene methoxy propyl hexaphthalate, 2-(methyl) propylene methoxyethyl phthalate, o-benzene 2-(methyl)propenyl propyl propyl dicarboxylate, 2-(methyl) propylene methoxyethyl maleate, 2-(methyl) propylene methoxy propyl maleate , 2-(methyl) propylene methoxyethyl succinate, 2-(methyl) propylene methoxy propyl succinate, crotonic acid, fumaric acid, maleic acid, itaconic acid a carboxyl group-containing vinyl monomer such as maleic acid monomethyl ester or itaconic acid monomethyl ester; an acid anhydride group-containing vinyl monomer such as maleic anhydride or itaconic anhydride; and (meth)acrylic acid shrinkage Glyceryl ester, α-ethyl methacrylate, 3,4-epoxy butyl (meth)acrylate An epoxy group-containing vinyl monomer; an amino group-containing (meth) acrylate-based vinyl group such as dimethylaminoethyl (meth)acrylate or diethylaminoethyl (meth)acrylate Monomer; (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-isopropyl acrylamide, hydroxyethyl Acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide, maleimide, maleene A vinyl monomer containing a guanamine group such as a quinone imine; an ethylene monomer such as styrene, α-methylstyrene, vinyl toluene, (meth)acrylonitrile, vinyl chloride, vinyl acetate or vinyl propionate Divinylbenzene, ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol Alcohol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, (meth)acrylic acid Propionate, N, N'-methylene bis(methyl) acrylamide, etc. Energy vinyl monomer; propylene decylmorpholine, (meth)acrylic acid polyethylene glycol ester, (meth)acrylic acid polypropylene glycol ester, (meth)acrylic acid methoxyethyl ester, (meth)acrylic acid Oxyethyl ester, n-butoxyethyl (meth)acrylate, isobutoxyethyl (meth)acrylate, tert-butoxyethyl (meth)acrylate, ethoxylate (meth)acrylate Ethoxyethyl ester, phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, acetamidine (meth)acrylate Oxyethyl Ether, "Placcel FM" (Caprolactone Addition Monomer manufactured by Daicel Chemical Co., Ltd., trade name), "Blemmer PME-100" (Nippon Oil Co., Ltd. produced methoxy polyethylene glycol methacrylate (two chains of ethylene glycol), trade name), "Blemmer PME-200" (Nippon Oil (shares) Manufactured methoxy polyethylene glycol methacrylate (four chains of ethylene glycol), trade name), "Blemmer PME-400" (Nippon Oil Co., Ltd.) Polyethylene glycol methyl Acrylate (ethylene glycol chain of 9), trade name), "Blemmer 50POEP-800B" (Nippon Oil Co., Ltd. octyloxy polyethylene glycol-polypropylene glycol-methacrylic acid) Ester (ethylene glycol chain is 8 and propylene glycol chain is 6), trade name) and "Blemmer 20ANEP-600" (Nippon Oil Co., Ltd.) - Polypropylene glycol) monoacrylate, trade name), "Blemmer AME-100" (manufactured by Nippon Oil Co., Ltd., trade name), "Blemmer AME-200" (Nippon Oil ( (manufacturing, trade name) and "Blemmer 50AOEP-800B" (manufactured by Nippon Oil Co., Ltd., trade name), Silaplane FM-0711 (manufactured by JNC) ), Silaplane FM-0721 (made by JNC), Silaplane FM-0725 (made by JNC), Silaplane ) TM-0701 (manufactured by JNC), SilaplaneTM-0701T (manufactured by JNC), X-22-174DX (letter) Manufactured by the chemical industry (stock), trade name), X-22-2426 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), X-22-2475 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), (methyl) ) 2-ethyl isocyanate or the like.

Preferred specific examples of the other constituent units include constituent units derived from the following monomers. Triisopropyl decyl methylene maleate, triisopropyl decyl amyl maleate, tri-n-butyl decyl-n-butyl maleate, maleic acid Third butyl diphenyl decyl methyl ester, tert-butyl diphenyl decyl-n-butyl maleate, triisopropyl decyl methyl methacrylate, fumaric acid Triisopropyl decyl amyl amyl ester, tri-n-butyl decyl-n-butyl fumarate, tert-butyl diphenyl decyl methyl ester of fumaric acid, third derivative of fumaric acid An ethylene monomer containing an alkyl group such as butyl diphenyl decyl-n-butyl ester; an acid anhydride group-containing ethylene monomer such as maleic anhydride or itaconic anhydride; crotonic acid, fumaric acid, and clothing Kang acid, maleic acid, citraconic acid, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, clothing Monomethyl coconate, monoethyl itaconate, monobutyl itaconate, monooctyl itaconate, monomethyl fumarate, monoethyl fumarate, fumaric acid Monobutyl ester, monooctyl fumarate, monoethyl citrate a carboxyl group-containing ethylenically unsaturated monomer; dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, itaconic acid Unsaturated dicarboxylic acid diester monomer such as butyl ester or diperfluorocyclohexyl fumarate; halogenated olefin such as vinylidene chloride, vinylidene fluoride or chlorotrifluoroethylene; ethylene glycol di(methyl) Acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(a) Acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10 -decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, allyl methacrylate A polyfunctional monomer such as triallyl cyanurate, diallyl maleate or polypropylene glycol diallyl ether.

In the total mass (100% by mass) of the constituent units of the macromonomer (a), the macromonomer (a) preferably contains 50% by mass or more of the constituent unit derived from the (meth)acrylic monomer. More preferably, it accounts for 70% by mass or more. The upper limit is not particularly limited and may be 100% by mass.

The constituent unit derived from the (meth)acrylic monomer is preferably a constituent unit in which R ¹ in the formula (AA) is a hydrogen atom or a methyl group, and R ² is COOR ⁵ .

The macromonomer (a) is preferably a macromonomer having a radical polymerizable group introduced at a terminal end of a main chain comprising two or more constituent units (AA), and preferably having a structure of the following formula (a2) By. In addition, "・・" which connects CH ₂ =C(COOR)-CH ₂ and Z in the formula (a2) represents a main chain portion including two or more constituent units (AA).

[Chemical 5] (wherein R is the same as R, and Z is a terminal group)

The R in the formula (a2) may be the same as R in the formula (AA), and the preferred embodiment is also the same.

Z is the terminal group of the macromonomer (a). Z is, for example, a hydrogen atom, a radical derived from a radical polymerization initiator, a radical polymerizable group, and the like, in the same manner as the terminal group of the polymer obtained by a known radical polymerization.

The macromonomer (a) is particularly preferably represented by the following formula (1).

[Chemical 6] (wherein R is the same as R, and a plurality of R's may be the same or different, X is a hydrogen atom or a methyl group, and a plurality of X's may be the same or different, Z is a terminal group, and n is 2 to 10,000. Natural number)

R in the formula (1) is the same as R in the formula (AA). Z in the formula (1) is the same as Z in the formula (a2).

In the case where the constituent unit derived from the macromonomer (a) is contained in the hydrophobic portion of the polymer for the non-soluble antifouling coating material, R in the formula (1) is preferably an alkane from the viewpoint of hydrophobicity. The alicyclic group, the aryl group, the heteroaryl group or the non-aromatic heterocyclic group is more preferably an alkyl group or an alicyclic group, and particularly preferably an alkyl group. When the constituent unit derived from the macromonomer (a) is contained in the hydrophilic portion of the polymer for the non-soluble antifouling coating material, R in the formula (1) is preferably hydrogen from the viewpoint of hydrophilicity. atom.

The number average molecular weight (Mn) of the macromonomer (a) is preferably from 300 to 100,000, more preferably from 500 to 50,000, still more preferably from 1,000 to 35,000. When the number average molecular weight of the macromonomer (a) is at least the above lower limit value, the coating film performance is more excellent, and when it is at most the above upper limit value, the coating property is more excellent. The number average molecular weight of the macromonomer (a) can be determined by gel permeation chromatography (GPC) using polystyrene as a reference resin.

In terms of the coating film performance, the proportion of the constituent unit (AA) in the total (100% by mass) of all the constituent units constituting the giant monomer (a) is preferably 40% by mass or more, more preferably 50%. More than or equal to 100% by mass.

When the constituent unit derived from the macromonomer (a) is contained in the hydrophobic portion of the polymer for the non-soluble antifouling coating material, the constituent unit constituting the giant monomer (a) from the viewpoint of hydrophobicity (AA) is preferably a constituent unit containing an alkyl group, an alicyclic group, an aryl group, a heteroaryl group or a non-aromatic heterocyclic group in the formula (AA) (hereinafter, also referred to as "constituting unit" AA1)"). The constituent unit (AA1) is preferably one in which the R in the formula (AA) is an alkyl group or an alicyclic group, and more preferably R is an alkyl group. The ratio of the constituent unit (AA1) in the total (100% by mass) of all the constituent units constituting the giant monomer (a) forming the hydrophobic portion is preferably 70% by mass or more, and more preferably 90% by mass or more. Especially preferred is 100% by mass.

When the constituent unit derived from the macromonomer (a) is contained in the hydrophilic portion of the polymer for the non-soluble antifouling coating material, the constituent unit constituting the giant monomer (a) from the viewpoint of hydrophilicity (AA) is preferably a structural unit containing R in the formula (AA) as a hydrogen atom (hereinafter also referred to as "constituting unit (AA2)"). It is especially preferred that R is a carboxyl group. The proportion of the total amount (100% by mass) of all the constituent units constituting the macromonomer (a) forming the hydrophilic portion in the constituent unit (AA2) is preferably 70% by mass or more, and more preferably 90% by mass or more. Especially preferred is 100% by mass.

(Structural unit (B)) The constituent unit (B) is a constituent unit derived from the monomer (b) which is not a macromonomer. The solubility parameter of the monomer (b) is 18.5 or more. The solubility parameter of the monomer (b) is preferably 18.5 or more and 47 or less, more preferably 18.6 or more and 30 or less. When the solubility parameter of the monomer (b) is at least the above lower limit value, the compatibility between the macromonomer and the solvent is good, and when it is at most the above upper limit value, the water resistance is good.

The monomer (b) preferably has a radical polymerizable group, and examples thereof include the following. Substituted or unsubstituted alkyl (meth)acrylate [eg, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate , n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, ( Stearic acid methyl methacrylate, behenyl alcohol (meth) acrylate, 1-methyl-2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ( 3-methyl-3-methoxybutyl methacrylate], substituted or unsubstituted arylalkyl (meth) acrylate [eg, benzyl (meth) acrylate, (meth) acrylate Methoxyphenylethyl ester, p-methoxyphenylethyl (meth)acrylate], substituted or unsubstituted aryl (meth)acrylate [eg, phenyl (meth) acrylate, (A) Methyl phenyl acrylate, p-methoxyphenyl (meth) acrylate, o-methoxy phenyl ethyl (meth) acrylate], alicyclic (meth) acrylate [eg, ( Isobornyl (meth)acrylate, cyclohexyl (meth)acrylate], (meth)acrylate containing a hydrophobic group such as trifluoroethyl (meth)acrylate, perfluorooctyl (meth)acrylate or perfluorocyclohexyl (meth)acrylate; 2-methyl (meth)acrylate Oxyethyl ester, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, butoxydiethylene glycol (meth) acrylate, methoxy triethyl Glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, 2-(2-ethylhexyloxy) (meth) acrylate (Oxy) vinyl (meth) acrylate such as ethyl ester; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (A) Hydroxy-containing (meth) acrylate such as glyceryl acrylate; methoxypolyethylene glycol allyl ether, methoxypolypropylene glycol allyl ether, butoxy polyethylene glycol allyl ether, butoxy a terminal alkoxyallyl polyether compound such as polypropylene glycol allyl ether, methoxy polyethylene glycol-polypropylene glycol allyl ether, butoxy polyethylene glycol-polypropylene glycol allyl ether; (methyl) Glycidyl acrylate, α-ethyl acrylate An epoxy group-containing vinyl compound such as glyceride or 3,4-epoxybutyl (meth)acrylate; a primary amino group such as butylaminoethyl (meth)acrylate or (meth)acrylamide Or a secondary amine-based vinyl compound; dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, (A) Dimethylaminobutyl acrylate, dibutylaminoethyl (meth)acrylate, N,N-dimethyl(meth)acrylamide, dimethylaminoethyl (methyl) a vinyl compound containing a tertiary amino group such as acrylamide or dimethylaminopropyl (meth) acrylamide; a heterocyclic alkaline vinyl compound such as vinylpyrrolidone, vinylpyridine or vinylcarbazole; Trimethyl decyl acrylate, triethyl decyl (meth) acrylate, tri-n-propyl decyl (meth) acrylate, tri-n-butyl decyl (meth) acrylate, (methyl) Tri-n-pentyl decyl acrylate, tri-n-hexyl decyl (meth) acrylate, tri-n-octyl decyl (meth) acrylate, tri-n-dodecyl decyl (meth) acrylate, ( Methyl) propylene Triphenyl decyl ester, tri-p-methylphenyl decyl (meth) acrylate, tribenzyl decyl (meth) acrylate, triisopropyl decyl (meth) acrylate, (meth) acrylate Isobutyl decyl ester, tri-t-butyl decyl (meth) acrylate, tris-2-methylisopropyl decyl (meth) acrylate, tri-tert-butyl decyl (meth) acrylate , (Ethyl dimethyl methacrylate), n-butyl dimethyl methacrylate, diisopropyl-n-butyl decyl (meth) acrylate, (meth) acrylate Octyl di-n-butyl decyl ester, diisopropyl stearyl methacrylate (meth) acrylate, dicyclohexyl phenyl decyl (meth) acrylate, tert-butyl diphenyl (meth) acrylate矽alkyl ester, lauryl diphenyl decyl (meth) acrylate, triisopropyl decyl methyl maleate, triisopropyl decyl amyl maleate, maleic acid - n-butyl decyl-n-butyl ester, tert-butyl diphenyl decyl methyl ester of maleic acid, tert-butyl diphenyl decyl-n-butyl maleate, anti-butene Triisopropyl sulfonate Methyl ester, triisopropyl decyl amyl glutamate, tri-n-butyl decyl-n-butyl fumarate, tert-butyl diphenyl sulfonyl alkyl fumarate a vinyl compound containing an alkyl group such as an ester, a butyl fumarate or a butyl butyl butyl acrylate; an acid anhydride group-containing vinyl compound such as maleic anhydride or itaconic anhydride; (methyl) Acrylic acid, crotonic acid, ethylene benzoic acid, fumaric acid, itaconic acid, maleic acid, citraconic acid, maleic acid monomethyl ester, maleic acid monoethyl ester, cis-butane Monobutyl succinate, monooctyl maleate, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, monooctyl itaconate, fumarate Methyl ester, monoethyl fumarate, monobutyl methacrylate, monooctyl fumarate, monoethyl citrate, monohydroxyl tetrahydrophthalate Ethyl ester, monohydroxypropyl tetrahydrophthalate (meth) acrylate, monohydroxybutyl methacrylate (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, ( Methyl acrylate Monohydroxypropyl phthalate, monohydroxyethyl succinate (succinic acid), monohydroxypropyl succinate (meth) acrylate, monohydroxyethyl (meth) acrylate, (methyl) a carboxyl group-containing ethylenically unsaturated compound such as acrylic acid maleic acid monohydroxypropyl ester; dimethyl maleate, dibutyl maleate, dimethyl fumarate, and anti-butyl An unsaturated dicarboxylic acid diester such as dibutyl phthalate, dibutyl itaconate or diperfluorocyclohexyl fumarate; a cyano group-containing vinyl compound such as acrylonitrile or methacrylonitrile; Vinyl ether [for example, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, 2-ethylhexyl vinyl ether, etc.], cycloalkyl vinyl ether [e.g., cyclohexyl vinyl ether, etc.] Vinyl ether compound; vinyl acetate compound such as vinyl acetate, vinyl propionate, vinyl butyrate or vinyl benzoate; aromatic vinyl compound such as styrene, vinyl toluene or α-methylstyrene; vinyl chloride, partial Halogenated olefin such as vinyl chloride, vinyl fluoride, vinylidene fluoride or chlorotrifluoroethylene; Acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di Methyl) acrylate, 1,6-hexanediol di(meth) acrylate, neopentyl glycol di(meth) acrylate, 1,9-nonanediol di(meth) acrylate, 1, 10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, methacrylic acid allyl A polyfunctional compound such as an ester, triallyl cyanurate, diallyl maleate or polypropylene glycol diallyl ether. These visual needs are suitably selected to use one or two or more.

Among them, from the viewpoint of weather resistance of the coating material, an aliphatic monomer is preferred. The aliphatic monomer refers to a monomer which does not have an aromatic ring.

In terms of copolymerization with the macromonomer (a), the monomer (b) is preferably a (meth)acrylic monomer, more preferably selected from (meth)acrylic acid or (meth)acrylic acid. At least one of the group consisting of an ester and a substituted or unsubstituted (meth) acrylamide.

When the monomer (b) is a (meth) acrylate and the constituent unit derived from the monomer (b) is contained in the hydrophilic portion of the polymer for the non-soluble antifouling coating, from the viewpoint of hydrophilicity In other words, the monomer (b) is preferably a compound represented by the following formula (b-1). CH ₂ =CX-C(=O)-O-(R ^b2 O) _m R ^b1 (b-1) In the formula (b-1), X is a hydrogen atom or a methyl group, and R ^b1 is a hydrogen atom and a carbon number. An alkyl group or an aryl group of 1 to 10, R ^b2 is an alkylene group having 2 to 10 carbon atoms, and m is an integer of 1 to 15.

The alkyl group having 1 to 10 carbon atoms in R ^b1 may be a branched or straight chain, and specific examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, and a t-butyl group. Isobutyl, pentyl, hexyl, heptyl, octyl, decyl and decyl groups. Examples of the aryl group in R ^b1 include an aryl group having 6 to 18 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group. From the viewpoint of hydrophilicity, R ^{b1 is} preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. That is, it is particularly preferred that the terminal is a hydroxyl group. From the viewpoint of hydrophilicity, R ^{b2 is} preferably an ethyl group. m is preferably an integer of from 1 to 10, more preferably an integer of from 1 to 5, still more preferably an integer of from 1 to 3, still more preferably 1 or 2.

When the structural unit derived from the (meth) acrylate is contained in the hydrophobic portion of the polymer for the non-soluble antifouling coating material, the (meth) acrylate is preferably the above from the viewpoint of hydrophobicity. A hydrophobic group-containing (meth) acrylate. Among them, a compound represented by the following formula (b-2) is preferred. CH ₂ =CX-C(=O)-OR ^b3 (b-2) In the formula (b-2), X is a hydrogen atom or a methyl group, and R ^b3 is an alkyl group, an alicyclic group or an aryl group.

The alkyl group, the alicyclic group, and the aryl group in R ^b3 may be the same as those of the alkyl group, the alicyclic group or the aryl group of R in the formula (AA), and the preferred embodiment is also the same.

The substituted or unsubstituted (meth) acrylamide is preferably a compound represented by the following formula (b-3). CH ₂ =CX-C(=O)-NR ^b4 R ^b5 (b-3) In the formula (b-3), X is a hydrogen atom or a methyl group, and R ^b4 and R ^b5 are each independently a hydrogen atom or an alkyl group. Or -R ^b6 -NR ^b7 R ^b8 . R ^b6 is an alkylene group, and R ^b7 and R ^b8 are each independently a hydrogen atom or an alkyl group.

The alkyl group in R ^b4 , R ^b5 , R ^b7 and R ^b8 may be the same as the alkyl group of R in the formula (AA), respectively. R ^b4 , R ^b5 , R ^b7 and R ^b8 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkylene group of R ^b6 is preferably an alkylene group having 2 to 4 carbon atoms. Specific examples of -R ^b6 -NR ^b7 R ^b8 include dimethylaminoethyl, diethylaminoethyl, butylaminoethyl, dibutylaminoethyl, and dimethylamine. Propyl, diethylaminopropyl, dimethylaminobutyl and the like.

(Preparation of the polymer for the non-soluble antifouling paint (I)) The preferred embodiment of the polymer for the non-soluble antifouling paint of the present invention includes the following polymerization for the non-soluble antifouling paint. (I). The polymer (I) for an insoluble antifouling coating material comprises: a hydrophobic portion containing a constituent unit derived from the macromonomer (a), and a (meth)acrylic monomer derived from a non-macro monomer. A polymer for an insoluble antifouling coating constituting a hydrophilic portion of the unit.

The macromonomer (a) which forms the hydrophobic portion of the polymer (I) for the non-soluble antifouling coating is preferably derived from the macromonomer (a) in the description of the macromonomer (a). The constituent unit contained in the hydrophobic portion of the polymer for the non-soluble antifouling coating is preferably the same as the macromonomer (a).

The (meth)acrylic monomer other than the macromonomer (a) which forms the hydrophilic portion of the polymer (I) for the non-soluble antifouling paint can be suitably selected from the monomer (b), for example. It is preferably selected from the group consisting of (meth)acrylic acid, (meth) acrylate, especially a (meth) acrylate having a hydroxyl group, and a substituted or unsubstituted (meth) acrylamide. At least one of them. The hydrophilic portion of the polymer (I) for the non-soluble antifouling paint preferably contains a (meth)acrylic acid derived from a hydrophilic group having a carboxyl group, -(R ^b2 O) _m R ^b3 or -NR ^b4 R ^b5 The constituent unit of the monomer is a constituent unit derived from a (meth)acrylic monomer. -(R ^b2 O) _m R ^b3 and -NR ^b4 R ^b5 are respectively -(R ^b2 O) _m R ^b3 in the formula (b-1), -NR ^{b4 in} the formula (b-3) R ^{b5 is the} same. The (meth)acrylic monomer having a hydrophilic group is preferably selected from the group consisting of (meth)acrylic acid, the compound represented by the formula (b-1), and the compound represented by the formula (b-3). At least one of the group consisting of. The content of the constituent unit derived from the (meth)acrylic monomer having a hydrophilic group is preferably 40% by mass or more, more preferably 40% by mass or more, based on the total of all the constituent units constituting the hydrophilic portion (100% by mass). It accounts for 70% by mass or more, and may also be 100% by mass.

The hydrophilic portion of the polymer (I) for the non-soluble antifouling paint may further contain a (meth)acrylic monomer derived from the non-hydrophilic portion in the range of the hydrophilicity of the hydrophilic portion. Form the unit. The (meth)acrylic monomer having no such hydrophilic group may, for example, be a compound represented by the above formula (b-2). The hydrophilic portion of the polymer (I) for the non-soluble antifouling coating may further include other monomers other than the macromonomer (a) and the (meth)acrylic monomer in the range of non-destructive coating properties. The constituent unit of the body. As the other monomer, for example, it can be suitably selected from the monomer (b).

The content of the hydrophobic portion in the polymer (I) for the non-soluble antifouling coating is preferably 5 by mass based on the total mass (100% by mass) of the polymer (I) for the non-soluble antifouling coating. From 8% to 90% by mass, more preferably from 20% by mass to 70% by mass, and still more preferably from 30% by mass to 60% by mass. When the content of the hydrophobic portion is within the above range, the effect of reducing the frictional resistance of the formed coating film is more excellent. Further, the total mass of the polymer for the non-soluble antifouling coating is equal to the total of the hydrophobic portion and the hydrophilic portion.

(Preferred Aspect (II) of Polymer for Non-Soluble Antifouling Coating) As a preferred aspect of the polymer for insoluble antifouling coating of the present invention, the following non-dissolving antifouling is exemplified Polymer for coating (II). The polymer (II) for an insoluble antifouling coating material comprises a hydrophilic portion containing a constituent unit derived from the macromonomer (a) and a (meth)acrylic monomer derived from a macromonomer. A polymer for an insoluble antifouling coating constituting a hydrophobic portion of the unit.

The macromonomer (a) which forms the hydrophilic portion of the polymer (II) for an insoluble antifouling coating is preferably derived from a macromonomer in the description of the macromonomer (a). The constituent unit is the same as the macromonomer (a) which is preferably included in the hydrophilic portion of the polymer for the non-soluble antifouling coating.

The (meth)acrylic monomer other than the macromonomer (a) which forms the hydrophobic portion of the polymer (II) for the non-soluble antifouling paint can be appropriately selected from the monomer (b). Jia (meth) acrylate. The hydrophobic portion preferably contains a constituent unit derived from a (meth)acrylic monomer having no hydrophilic group such as a carboxyl group, -(R ^b2 O) _m R ^b3 or -NR ^b4 R ^b5 as a source (a A structural unit of an acrylic monomer. The (meth)acrylic monomer having no such hydrophilic group is preferably a compound represented by the above formula (b-2). The content of the constituent unit derived from the (meth)acrylic monomer having no such hydrophilic group is preferably 70% by mass or more, and more preferably 70% by mass or more, based on the total of all the constituent units constituting the hydrophobic portion (100% by mass). Jia is 90% by mass or more, and may also be 100% by mass.

The hydrophobic portion of the polymer (II) for an insoluble antifouling coating may further include the composition derived from the (meth)acrylic monomer having a hydrophilic group in the range of the hydrophobicity of the non-decomposable hydrophobic portion. unit. The hydrophobic portion of the polymer (II) for the non-soluble antifouling paint may further contain a constituent unit derived from the monomer (b) other than the (meth)acrylic monomer in the range of the non-destructive coating film performance. As the other monomer, for example, it can be suitably selected from the monomer (b).

The content of the hydrophilic portion in the polymer (II) for the non-soluble antifouling paint is preferably 10% by mass based on the total mass (100% by mass) of the polymer (II) for the non-soluble antifouling paint. 95% by mass, more preferably 30% by mass to 80% by mass, and further preferably 40% by mass to 70% by mass. When the content of the hydrophilic portion is within the above range, the effect of reducing the frictional resistance of the formed coating film is further excellent.

(content of each constituent unit) The polymer for the non-soluble antifouling paint of the present invention is derived from a macromonomer (100 mass%) based on 100% by mass of all the constituent units constituting the polymer for the non-solubility antifouling paint. The content of the constituent unit (a) of a) in the total of all the constituent units constituting the polymer for the non-soluble antifouling coating material is preferably from 5% by mass to 95% by mass. When the content of the structural unit (A) derived from the macromonomer (a) is within the above range, the effect of reducing the frictional resistance of the formed coating film is further excellent. In addition, the total of all the constituent units constituting the polymer for the non-soluble antifouling coating is equal to the total of the constituent unit (A) derived from the macromonomer (a) and the constituent unit derived from the monomer (b). .

(Characteristics of Polymer for Non-Soluble Antifouling Coating) The weight average molecular weight (Mw) of the polymer for insoluble antifouling coating of the present invention is preferably 3,000 to 1,000,000, more preferably 5,000 to 500,000. When the weight average molecular weight of the polymer for the non-soluble antifouling coating material is at least the above lower limit value, the coating film performance is excellent, and when it is at most the above upper limit value, the coating property is excellent. The weight average molecular weight of the polymer for the non-soluble antifouling coating can be measured by gel filtration chromatography (GPC) using polystyrene as a reference resin.

The glass transition point of the polymer for insoluble antifouling paint of the present invention is preferably 10 ° C or more, more preferably 10 ° C or more and 60 ° C or less, and still more preferably 15 ° C or more and 50 ° C or less. When the glass transition point of the polymer for a non-soluble antifouling coating material of the present invention is at least the above lower limit value, the coating property is excellent, and when it is at most the above upper limit value, the coating film performance is excellent.

In the polymer for a non-soluble antifouling coating of the present invention, the hydrophobic portion is incompatible with the hydrophilic portion. Therefore, when the coating film containing the polymer for the non-soluble antifouling coating is formed, the hydrophobic portion is separated from the hydrophilic portion, whereby a coating film having a microscopic heterostructure or a nano-heterostructure can be obtained. The affinity of the region containing the hydrophobic portion to the aqueous liquid such as seawater is lower than the region where the hydrophobic portion and the hydrophilic portion are not separated from each other. In addition, the affinity of the region containing the hydrophilic portion and the aqueous liquid such as seawater is higher than the region where the hydrophobic portion and the hydrophilic portion are not separated from each other, and a water layer which is restricted in the surface of the coating film can be formed. (Water Trap Layer). Since the region including the hydrophobic portion and the hydrophilic portion exists on the surface of the coating film, the frictional resistance with the aqueous liquid is further reduced.

In the present invention, the "non-solubility" is, for example, a coating film residual ratio determined in the following manner of 33% or more and 99% or less. The coating film residual ratio is preferably 50% or more and 99% or less, more preferably 75% or more and 99% or less, further preferably 80% or more and 99% or less, and particularly preferably 90% or more and 99% or less.

(Residual Rate Test of Coating Film) The resin composition for an antifouling coating was applied to a hard vinyl chloride sheet of 50 mm × 50 mm × 2 mm (thickness) by a coater so that the dry film thickness was 120 μm. , making a test board. The test panels were mounted on a rotating drum set in seawater and rotated at a peripheral speed of 7.7 m/s (15 knots). The test plate was taken out after one month, and the film thickness was measured. The coating film residual ratio was determined according to the following formula: coating film residual ratio (%) = residual film thickness (μm) after one month / initial film thickness 120 (μm) × 100.

(Method for Producing Polymer for Non-Soluble Antifouling Coating) The polymer for insoluble antifouling coating of the present invention can be produced, for example, by polymerizing a monomer mixture described below.

• Monomer mixture The monomer mixture contains a macromonomer (a) and a monomer (b) which is not a macromonomer. The macromonomer (a) is preferably a macromonomer having a radical polymerizable group. In the case of producing the polymer (I) for the non-soluble antifouling paint or the polymer (II) for the non-soluble antifouling paint, at least (meth)acrylic acid can be used as the monomer (b). Further, a monomer (b) other than the (meth)acrylic monomer may be used as needed.

The content of the macromonomer (a) in the monomer mixture is preferably from 5% by mass to 95% by mass based on the total mass of the monomer mixture (the total mass of all the monomers: 100% by mass). In other words, the polymer for the non-soluble antifouling coating material is preferably a monomer mixture containing 5% by mass to 95% by mass of the macromonomer (a) in terms of the total mass of all the monomers. Winner. In the case where the polymer for the non-soluble antifouling coating is the polymer (I) for the non-soluble antifouling coating, the total mass (the total mass of all the monomers: 100% by mass) with respect to the total mass of the monomer mixture, the giant single The content of the body (a) is more preferably from 5% by mass to 90% by mass, still more preferably from 20% by mass to 70% by mass, even more preferably from 30% by mass to 60% by mass. In the case where the polymer for the non-soluble antifouling coating is the polymer (II) for the non-soluble antifouling coating, the total mass (the total mass of all the monomers: 100% by mass) with respect to the total mass of the monomer mixture, the giant single The content of the body (a) is more preferably from 10% by mass to 95% by mass, still more preferably from 30% by mass to 80% by mass, even more preferably from 40% by mass to 70% by mass. When the content of the macromonomer (a) is within the above range, the coating film formed using the obtained polymer for a non-soluble antifouling coating material is more excellent in the friction resistance reducing effect. Further, the total of the macromonomer (a) and the monomer (b) was 100% by mass.

In the case where the polymer for the non-soluble antifouling coating is the polymer (I) for the non-soluble antifouling coating, the monomer mixture preferably contains the (meth)acrylic monomer having a hydrophilic group. The content of the (meth)acrylic monomer having a hydrophilic group in the monomer mixture is preferably 40% by mass or more based on the total mass (100% by mass) of the monomers other than the macromonomer (a). More preferably, it is 70 mass% or more, and may be 100 mass%.

In the case where the polymer for the non-soluble antifouling coating is the polymer (II) for the non-soluble antifouling coating, the monomer mixture preferably contains a (meth)acrylic monomer which does not have the hydrophilic group. The content of the (meth)acrylic monomer having no such hydrophilic group in the monomer mixture is preferably 70% by mass or more based on the total mass (100% by mass) of the monomers other than the macromonomer (a). More preferably, it is 90% by mass or more, and may be 100% by mass.

The macromonomer (a) and the monomer (b) can be produced by a known method, or a commercially available one can be used. Examples of the method for producing the macromonomer (a) include the following methods (α1), methods (α2), methods (α3), and methods (α4). (α1): A method of polymerizing a monomer component containing a monomer forming a constituent unit (AA) using a cobalt chain transfer agent. (α2): A method of polymerizing a monomer component containing a monomer forming the structural unit (AA) using an α-substituted unsaturated compound such as α-methylstyrene dimer as a chain transfer agent. (α3): A method of polymerizing a monomer component containing a monomer forming the constituent unit (AA) to chemically bond a radical polymerizable group to the obtained polymer. (α4): A method of polymerizing a monomer component containing a monomer forming the structural unit (AA) to thermally decompose the obtained polymer. The monomer component may further contain monomers forming other constituent units as needed.

In the method (α1) to the method (α4), examples of the polymerization method of the monomer component include a bulk polymerization method, a solution polymerization method, and an aqueous dispersion polymerization method. Examples of the aqueous dispersion polymerization method include a suspension polymerization method and an emulsion polymerization method. In terms of a simple recovery step, a water-based dispersion polymerization method is preferred, and a suspension polymerization method is preferred. If the macromonomer (a) is produced by a suspension polymerization method, the operation is easy. The polymerization can be carried out by a known method using a known radical polymerization initiator. For example, a method of allowing the monomer component to react in the presence of a radical initiator at a reaction temperature of 60 to 120 ° C for 4 to 14 hours is exemplified. In the polymerization, a predetermined chain transfer agent can be used in the method (α1) and the method (α2). A chain transfer agent can be used as needed in the method (α3) and the method (α4).

As the radical polymerization initiator, a known one can be used, and examples thereof include 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), and 2,2- Azo compound such as azobis(2-methylbutyronitrile); benzamidine peroxide, cumene hydroperoxide, lauryl peroxide, di-tert-butyl peroxide, peroxy-2- An organic peroxide such as tert-butyl ethylhexanoate or 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate. These polymerization initiators may be used alone or in combination of two or more.

In the method (α3), as a method of chemically bonding the radical polymerizable group to the polymer, for example, a halogen group of a polymer having a halogen group is replaced by a compound having a radical polymerizable carbon-carbon double bond. In the method of producing a method in which a vinyl-based monomer having an acid group is reacted with an ethylene-based polymer having an epoxy group, a vinyl-based polymer having an epoxy group is reacted with a vinyl-based monomer having an acid group. A method of reacting a vinyl polymer having a hydroxyl group with a diisocyanate compound to obtain an ethylene-based polymer having an isocyanate group, and reacting the vinyl polymer with a vinyl monomer having a hydroxyl group, etc., by any method To manufacture.

The method for producing the macromonomer (a) is preferably a method (α1) using a cobalt chain transfer agent in terms of a catalyst having a small number of production steps and a high chain transfer constant. Particularly in the method (α1), it is preferred to carry out the polymerization of the monomer component by a suspension polymerization method. Further, the macromonomer (a) in the case of production using a cobalt chain transfer agent has the structure of the above formula (a2).

- Polymerization of the monomer mixture As the polymerization method of the monomer mixture, for example, a known polymerization method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, or an emulsion polymerization method can be applied. The solution polymerization method is preferred in terms of the productivity of the polymer for the non-soluble antifouling coating material and the coating film properties of the coating film formed by using the polymer for the non-soluble antifouling coating obtained. The polymerization can be carried out by a known method using a known radical polymerization initiator. For example, a method of reacting the monomer mixture in the presence of a radical initiator at a reaction temperature of 60 to 120 ° C for 4 hours to 14 hours can be mentioned. A chain transfer agent may be used as needed during the polymerization.

As the radical polymerization initiator, a known one can be used, and examples thereof include 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), and 2,2- Azo compound such as azobis(2-methylbutyronitrile); benzamidine peroxide, cumene hydroperoxide, lauryl peroxide, di-tert-butyl peroxide, peroxy-2- An organic peroxide such as tert-butyl ethylhexanoate or 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate. As the chain transfer agent, a known one may be used, and examples thereof include mercaptans such as n-dodecyl mercaptan and thioglycolate such as octyl thioglycolate, α-methylstyrene dimer, and hydrazine. Oleene and the like. As the solvent to be used in the solution polymerization, for example, toluene, xylene, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, n-butyl acetate, ethyl 3-ethoxypropionate, or the like can be used. Organic solvents.

[Resin Composition] The resin composition of the present invention contains the above-described polymer for an insoluble antifouling paint of the present invention. The resin composition of the present invention preferably further contains a solvent. The polymer for the non-soluble antifouling coating contained in the resin composition may be one type or two or more types. The polymer for the non-soluble antifouling coating can be preferably used as a resin for an antifouling coating.

The content of the polymer for the non-soluble antifouling coating material in the resin composition of the present invention is not particularly limited, and is preferably from 5% by mass to 85% by mass based on the total mass (100% by mass) of the resin composition. It is preferably from 10% by mass to 80% by mass, more preferably from 30% by mass to 75% by mass, even more preferably from 55% by mass to 75% by mass. When the content of the polymer for the non-soluble antifouling coating material is at most the above upper limit value, a coating film having excellent water resistance and coating film hardness can be obtained, and if it is at least the lower limit value, the VOC content can be easily obtained. Antifouling coating. In addition, "VOC" means an organic compound (Volatile Organic Compound) which is easily volatilized under normal temperature and normal pressure.

The resin composition of the present invention preferably contains a solvent. When the resin composition contains a solvent, the coating property is more excellent in water resistance, film formability, and the like of the formed coating film. The solvent is not particularly limited as long as it is a polymer for dissolving the non-soluble antifouling coating, and examples thereof include monohydric alcohols such as methanol, ethanol, and isopropyl alcohol; and ethylene glycol and 1,2-propanediol. Alcohols; ketones such as acetone, methyl ethyl ketone, acetamidine acetone, butyl acetate; ethers such as methyl ethyl ether and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol single Glycol ethers such as methyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, dipropylene glycol monopropyl ether; ethylene glycol; Glycol acetates such as monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate; aliphatic hydrocarbons such as n-pentane and n-hexane; toluene, xylene, and solvent oil ( An aromatic hydrocarbon such as Solvent naphtha). These may be used alone or in combination of two or more.

The content of the solvent in the resin composition of the present invention is preferably from 15% by mass to 95% by mass, more preferably from 20% by mass to 90% by mass, based on the total mass (100% by mass) of the resin composition. Jia is from 25% by mass to 70% by mass, and particularly preferably from 25% by mass to 45% by mass. When the content of the solvent is at most the lower limit value, a coating film having excellent water resistance can be obtained. When the content is at most the above upper limit, a resin composition having a small VOC content can be easily obtained.

The resin composition of the present invention may further contain other components than the polymer for the non-soluble antifouling coating. The other component is, for example, the same as the other components in the antifouling paint to be described later. The content of the other component is preferably 200 parts by mass or less, and may be 0 parts by mass, based on 100 parts by mass of the polymer for the non-soluble antifouling coating material.

The viscosity of the resin composition of the present invention measured by a Brookfield viscometer at 25 ° C is preferably 5 × 10 ⁴ mPa·s or less, more preferably 5,000 mPa·s or less, and still more preferably 4,000 mPa·s or less. More preferably, it is 3,000 mPa·s or less, and particularly preferably 2,000 mPa·s or less. When the viscosity of the resin composition of the present invention measured by a B-type viscosity meter at 25 ° C is at most the above upper limit value, coating is easy. The lower limit of the viscosity of the resin composition of the present invention measured by a B-type viscosity meter at 25 ° C is not particularly limited, and is preferably 1,000 mPa·s or more in terms of suppressing the sag of the coating material during coating. The viscosity of the resin composition can be adjusted according to the amount of addition of the solvent to the polymer for the non-soluble antifouling coating or the like.

The method for producing the resin composition of the present invention is not particularly limited. For example, it can be prepared by polymerizing a monomer mixture of the macromonomer (a) and the monomer (b) by a solution polymerization method to obtain a polymerization product comprising a polymer for a non-soluble antifouling coating material and a solvent. And, if necessary, formulating a solvent or other ingredients in the obtained polymerization product.

The resin composition of the present invention can be directly or optionally mixed with an antifouling agent or the like to prepare an antifouling paint. The resin composition of the present invention can be used in an antifogging paint or the like in addition to an antifouling paint.

[Antifouling Coating Material] The antifouling coating material of the present invention contains the resin composition of the present invention. Therefore, the antifouling paint of the present invention comprises the polymer for a non-dissolving antifouling paint of the present invention. The antifouling paint of the present invention may further contain an antifouling agent, and may further contain other components other than the polymer for insoluble antifouling paint of the present invention and the antifouling agent. The other components may be those derived from the resin composition of the present invention, or may be those not derived from the composition (as formulated in the case of producing an antifouling paint), or may be both of them. The antifouling coating of the present invention may further comprise a solvent. The solvent is the same as the above. In the case where the antifouling coating contains a solvent, the solvent may be derived from the resin composition of the present invention, or may be derived from the composition (in the case of preparing an antifouling coating), or may be Both of these.

In the marine structure or the ship, by coating the resin composition of the present invention on a portion in contact with seawater and forming a coating film, it is possible to suppress corrosion caused by seawater in the portion or adhesion of marine organisms which cause a decrease in navigation speed. . The antifouling paint of the present invention is typically a non-dissolving antifouling paint in which the formed coating film is not dissolved in an aqueous liquid such as seawater.

(Antifouling agent) The antifouling agent may, for example, be an inorganic antifouling agent or an organic antifouling agent, and one or two or more kinds may be appropriately selected depending on the required properties. Examples of the antifouling agent include copper antifouling agents such as cuprous oxide, copper thiocyanate, and copper powder; compounds of other metals (such as lead, zinc, and nickel), amine derivatives such as diphenylamine, and nitrile compounds. A benzothiazole compound, a maleimide compound, a pyrithione or a pyridinium compound such as pyrithione.

As the antifouling agent, more specifically, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, manganese ethylene bisdithio Urethane, zinc dimethyl dithiocarbamate, 2-methylthio-4-tributylamino-6-cyclopropylamino-s-triazine, 2,4 ,5,6-tetrachloroisoindolonitrile, N,N-dimethyldichlorophenylurea, zinc ethylene bisdithiocarbamate, copper thiocyanate, 4,5-dichloro-2- N-octyl-3(2H)-isothiazolone, N-(fluorodichloromethylthio)phthalimide, N,N'-dimethyl-N'-phenyl-(N- Fluorodichloromethylthio)thioguanamine, 2-pyridinethiol-1-oxide zinc oxide (zinc pyrithione), 2-pyridine thiol-1-oxide copper salt (copper sulphide), tetrasulfide tetrasulfide Kiryulam, Cu-10%Ni solid solution alloy, 2,4,6-trichlorophenylmethyleneimine, 2,3,5,6-tetrachloro-4-(methylsulfonyl) Pyridine, 3-iodo-2-propynylbutylcarbamate, diiodomethyl-p-tolylhydrazine, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamic acid Ester, phenyl (bipyridyl) ruthenium dichloride, 2-(4-thiazolyl)-benzimidazole, medetomidine, pyridine triphenyl borane, and the like.

In terms of good antifouling performance, it is preferred to comprise a material selected from the group consisting of cuprous oxide, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-. At least one of the group consisting of nitrile, pyridyltriphenylborane, zinc pyrithione, copper pyrithione and medetomidine.

In addition, it may also be selected from the group consisting of cuprous oxide, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, zinc pyrithione, copper pyrithione. And at least two of the group consisting of medetomidine.

In the case where the antifouling paint contains an antifouling agent, the content of the antifouling agent in the antifouling paint is not particularly limited, and is preferably 10 parts by mass based on 100 parts by mass of the polymer for the non-soluble antifouling paint of the present invention. The parts by mass are -200 parts by mass, more preferably 50 parts by mass to 150 parts by mass. When the content of the antifouling agent is at least the above lower limit value, the antifouling effect of the formed coating film is more excellent, and when it is at most the above upper limit value, the coating film physical properties are excellent.

(Other components) Examples of the other components include other resins other than the polymer for the non-soluble antifouling paint of the present invention. The other resin is preferably a thermoplastic resin other than the polymer for the non-soluble antifouling coating of the present invention. When the antifouling paint contains a thermoplastic resin other than the polymer for insoluble antifouling paint of the present invention, the physical properties of the coating film such as crack resistance and water resistance are improved.

Examples of the thermoplastic resin other than the polymer for the non-soluble antifouling paint of the present invention include chlorinated paraffin; chlorinated polyolefin such as chlorinated rubber, chlorinated polyethylene, and chlorinated polypropylene; polyvinyl ether; and polypropylene. Sebacate; partially hydrogenated terphenyl; polyvinyl acetate; methyl (meth) acrylate copolymer, ethyl (meth) acrylate copolymer, propyl (meth) acrylate copolymer Poly(meth)acrylic acid alkyl ester such as butyl (meth)acrylate copolymer or cyclohexyl (meth)acrylate copolymer; polyether polyol; alkyd resin; polyester resin; vinyl chloride -vinyl acetate copolymer, vinyl chloride-vinyl propionate copolymer, vinyl chloride-isobutyl vinyl ether copolymer, vinyl chloride-isopropyl vinyl ether copolymer, vinyl chloride-ethyl vinyl ether Vinyl chloride resin such as copolymer; eucalyptus oil; wax; solid oil at room temperature other than wax, liquid oil at room temperature such as castor oil and purified products thereof; petrolatum; mobile paraffin; rosin, hydrogenated rosin, naphthenic acid , fatty acids and these divalent metal salts. Examples of the wax include animal-derived waxes such as beeswax; plant-derived waxes; semi-synthetic waxes such as guanamine-based waxes; and synthetic waxes such as oxidized polyethylene-based waxes. These thermoplastic resins may be used alone or in combination of two or more. A chlorinated paraffin is preferred in that it functions as a plasticizer and can obtain an effect of improving the crack resistance or peeling resistance of the coating film. It is preferable to use an organic wax such as a semi-synthetic wax or a synthetic wax in terms of a function as a sedimentation preventing agent or a sag preventing agent and an effect of improving the storage stability or the pigment dispersibility of the antifouling coating. It is a polyethylene wax, an oxidized polyethylene wax, or a polyamide wax.

In the case where the antifouling paint contains a thermoplastic resin other than the polymer for the non-soluble antifouling paint of the present invention, the antifouling paint has no content of the thermoplastic resin other than the polymer for the non-soluble antifouling paint of the present invention. In particular, it is preferably 0.1 parts by mass to 50 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, per 100 parts by mass of the polymer for the non-soluble antifouling coating material of the present invention. When the content of the thermoplastic resin other than the polymer for the non-soluble antifouling paint of the present invention in the antifouling paint is at least the above lower limit, the coating property such as crack resistance or water resistance is more excellent. When it is less than the upper limit, it is more excellent in flexibility or water absorbability.

The antifouling paint of the present invention may contain a fluorene compound such as dimethyl polysiloxane or eucalyptus oil or a fluorinated compound such as a fluorinated hydrocarbon as a component for the purpose of imparting lubricity to the surface of the coating film and preventing adhesion of the living body. .

The antifouling paint of the present invention may also contain various pigments, dehydrating agents, antifoaming agents, leveling agents, pigment dispersing agents (such as sedimentation inhibitors), sag prevention agents, matting agents, ultraviolet absorbers, antioxidants, and heat resistance. Enhancers, slip agents, preservatives, plasticizers, viscosity control agents, etc. as other ingredients.

Examples of the pigment include zinc oxide, talc, cerium oxide, barium sulfate, potassium feldspar, aluminum hydroxide, magnesium carbonate, mica, carbon black, red iron oxide, titanium oxide, phthalocyanine blue, kaolin, gypsum, and the like. It is especially preferred to be zinc oxide or talc.

Examples of the dehydrating agent include a citrate type, an isocyanate type, an orthoester type, and an inorganic type. More specifically, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, orthoborate, tetraethyl orthosilicate, anhydrite, calcined gypsum, synthetic zeolite (molecular sieve), and the like can be given. By containing a dehydrating agent in the antifouling coating, it is possible to make up the moisture and improve the storage stability.

Examples of the sedimentation preventing agent or the sag preventing agent other than the thermoplastic resin include bentonite-based, fine-powdered cerium oxide-based, stearic acid, lecithin, and alkylsulfonate.

Examples of the plasticizer other than the thermoplastic resin include phthalic acid such as dioctyl phthalate, dimethyl phthalate, dicyclohexyl phthalate, and diisononyl phthalate. Acid ester plasticizer; aliphatic dibasic acid ester plasticizer such as isobutyl adipate or dibutyl sebacate; glycol ester such as diethylene glycol dibenzoate or pentaerythritol alkyl ester Plasticizer; phosphate ester plasticizer such as tricresyl phosphate (TCP), triaryl phosphate, trichloroethyl phosphate, etc.; epoxy plasticizer such as epoxy soybean oil or octyl epoxy stearate ; an organic tin-based plasticizer such as dioctyltin laurate or dibutyltin laurate; trioctyl trimellitate, triacetylene, and the like. By including a plasticizer in the antifouling paint, the crack resistance or peeling resistance of the coating film can be improved. Among them, the plasticizer is preferably TCP.

(Characteristics of Antifouling Coating) The VOC content of the antifouling coating of the present invention is preferably 420 g/L or less, more preferably 400 g/L or less, and still more preferably 380 g/L or less. The VOC content can be calculated from the following formula using the specific gravity of the antifouling paint and the value of the heating residual component. The VOC content can be adjusted depending on the content of the solvent. VOC content (g/L) = specific gravity of the composition × 1000 × (100 - heating residual component) / 100

The specific gravity of the antifouling paint can be calculated by filling the anti-fouling paint in a 100 cc specific gravity cup at 25 ° C and measuring the mass. The heating residual component (solid content) of the antifouling paint can be obtained by the following method. 0.50 g of a measurement sample (antifouling paint) was weighed in an aluminum vessel, and 3 mL of toluene was added by a pipette pipe and uniformly spread on the bottom of the vessel, and pre-dried. The pre-drying is a treatment in which the measurement sample is entirely extended in the vessel and is used to volatilize the solvent easily in the main drying. In the pre-drying, the measurement sample and the toluene were heated and dissolved in a water bath at 70 ° C to 80 ° C, and evaporated to dryness. After pre-drying, it was subjected to formal drying for 2 hours using a hot air dryer at 105 °C. The heating residual component (solid content) was determined from the mass before the pre-drying (the mass before drying) and the mass after the main drying (the mass after drying) by the following formula. Heating residual components (solid content) = mass after drying (g) / mass before drying (g) × 100 (%)

The heating residual component (solid content) of the antifouling paint of the present invention is preferably from 45% by mass to 85% by mass, more preferably from 55% by mass to 80% by mass, even more preferably from 60% by mass to 75% by mass. When the heating residual component of the antifouling paint is at least the lower limit of the above range, the VOC content is sufficiently lowered. When the heating residual component is at most the upper limit of the above range, the viscosity of the antifouling coating is easily lowered.

The antifouling paint of the present invention can be prepared by preparing the resin composition of the present invention, adding an antifouling agent or other components, a solvent, and mixing as needed.

Further, the coating film formed by using the resin composition or the antifouling paint of the present invention has a small frictional resistance with an aqueous liquid such as seawater. Therefore, by using the resin composition of the present invention or the antifouling paint to form a coating film on the surface of the object to be coated, the frictional resistance with the aqueous liquid on the surface can be lowered. For example, by coating the resin composition or the antifouling paint of the present invention on a part of a ship that receives frictional resistance from seawater during navigation and forming a coating film, the frictional resistance with seawater during navigation is reduced, thereby realizing Reduced fuel consumption or energy saving.

[Coating film] The coating film of the present invention is formed by using the above-described resin composition or antifouling paint of the present invention, and comprises the polymer for insoluble antifouling paint of the present invention. The thickness of the coating film is not particularly limited. For the purpose of antifouling or friction reduction with an aqueous liquid, it is typically from 10 μm to 400 μm.

The contact angle by the captive bubble method of the outer surface of the coating film formed of the polymer for insoluble antifouling paint of the present invention is preferably 120° or more and 144° or less, more preferably 125° or more. 140° or less, and further preferably 130° or more and 135° or less. When the contact angle of the outer surface of the coating film formed of the polymer for insoluble antifouling paint of the present invention by the captive bubble method is at least the lower limit value, the water content on the outer surface of the coating film is Since the frictional resistance of the liquid is sufficiently small, the friction reducing effect by the coating film is excellent, and when it is at most the above upper limit, the water resistance is excellent. In the present specification, the contact angle of the outer surface of the coating film refers to the contact angle of air which is in contact with the outer surface of the coating film in a state where the coating film is immersed in water. The contact angle in water can be measured by the method described in the examples. The contact angle of the outer surface of the coating film can be adjusted according to the ratio of the hydrophilic portion of the polymer for the non-soluble antifouling coating or the like. For example, the more the hydrophilic portion of the polymer for the non-soluble antifouling coating, the larger the contact angle tends to be.

The indentation elastic modulus of the outer surface of the coating film formed of the polymer for insoluble antifouling paint of the present invention is preferably 15 MPa or more and 2,900 MPa or less, more preferably 30 MPa or more and 2,000 MPa or less, and further preferably 50. MPa or more and 1,500 MPa or less. When the indentation elastic modulus of the outer surface of the coating film formed of the polymer for a non-soluble antifouling coating material of the present invention is at least the lower limit value, the surface of the coating film has less viscosity, and therefore the workability is improved. When it is below the upper limit, the hardness of the coating film is improved, and the abrasion resistance is improved. The indentation elastic modulus of the outer surface of the coating film can be measured by the method described in the examples. The indentation modulus of elasticity of the outer surface of the coating film can be adjusted according to the glass transition temperature (Tg) of the polymer for the non-soluble antifouling coating or the like. For example, the larger the glass transition temperature (Tg) of the polymer for the non-soluble antifouling coating, the greater the indentation elastic modulus.

The water absorption of the coating film of the present invention is preferably 5% or more and 70% or less, more preferably 5% or more and 50% or less, and still more preferably 5% or more and 45% or less. When the water absorption is equal to or higher than the lower limit value, it is easy to form a water layer that is restricted from flowing on the surface of the coating film, and the friction reducing effect by providing the coating film is excellent, and when it is at most the upper limit value, the coating film is formed. Excellent water resistance. The water absorption rate of the coating film can be measured by the method described in the examples below. The water absorption rate of the coating film can be adjusted according to the ratio of the hydrophilic portion of the polymer for the non-soluble antifouling coating material and the like. For example, the more the hydrophilic portion of the polymer for the non-soluble antifouling coating material, the higher the water absorption rate tends to be.

The coating film of the present invention preferably has a microscopic heterostructure or a nanoheterostructure. As described above, the hydrophobic portion of the polymer for a non-soluble antifouling paint of the present invention is incompatible with the hydrophilic portion, so that when the coating film containing the polymer for the non-soluble antifouling coating is formed, the hydrophobic portion is made The hydrophilic portion is phase-separated, whereby a coating film having a microscopic heterostructure or a nano-heterostructure can be obtained. The affinity of the region containing the hydrophobic portion to the aqueous liquid such as seawater is lower than the region containing the hydrophilic portion or the region where the hydrophobic portion and the hydrophilic portion are not separated from each other. Since the region containing the hydrophobic portion exists on the surface of the coating film, the frictional resistance with the aqueous liquid is further reduced. Examples of the microscopic heterostructure or the nanoheterostructure include a sea-island structure, a cylindrical structure, a layered structure, and a co-continuous structure.

The method for forming the coating film is not particularly limited, and it can be carried out by a known method. For example, in the case where the resin composition or the antifouling coating contains a polymer and a solvent for the non-soluble antifouling coating, the resin composition or the anti-foaming coating can be applied by brush coating, spray coating, roll coating, dip coating, or the like. The stain coating is applied to the surface of the object to be coated and dried to form a coating film. The object to be coated is not particularly limited, and examples thereof include a ship, a fishing net, a harbor facility, a petroleum fence, a bridge, an underwater structure (a seabed base, etc.). A base coating film may also be provided on the surface of the object to be coated. The base coating film can be formed, for example, by using a primer such as a rust primer, a chlorinated rubber or an epoxy, an intermediate coat, or the like. The coating amount of the resin composition or the antifouling paint can be set in accordance with the thickness of the formed coating film. The drying after application of the resin composition or the antifouling paint can be usually carried out at room temperature, and can also be dried by heating as needed. [Examples]

Hereinafter, the present invention will be described in further detail by way of examples and comparative examples, but the invention is not limited by the examples. Further, the parts in the examples mean parts by mass. The evaluation in the examples was carried out by the method shown below.

(Weight average molecular weight (Mw), number average molecular weight (Mn)) The measurement was carried out by gel permeation chromatography (GPC) (HLC-8220, manufactured by Tosoh Co., Ltd.). The column was made of TSKgel α-M (manufactured by Tosoh Corporation, 7.8 mm × 30 cm), TSK guard column α (manufactured by Tosoh Corporation, 6.0 mm × 4 cm). The calibration curve was prepared using F288/F1/28/F80/F40/F20/F2/A1000 (manufactured by Tosoh Corporation, standard polystyrene) and styrene monomer.

(Torque Value) The torque value was evaluated using a double cylindrical resistance measuring device. The double-cylinder type resistance measuring device is such that a coating film of a sample to be measured is formed on one of the two cylinders, and water is placed between the two cylinders, and one of the circles is measured in the state. The torque value when the barrel is rotated. Specifically, the obtained resin composition was applied to a cylindrical drum made of stainless steel (SUS) having a diameter of 9.6 cm and a height of 12.8 cm, and dried at room temperature to form a coating film. The cylindrical drum on which the coating film was formed was rotated in artificial seawater, and the torque value at a measurement temperature of 23 ° C and 1000 rpm was measured using a UTM II torque meter (manufactured by UNIPULSE). Cm). The value is set as the torque value of the resin composition. The water is pure water, and artificial seawater is prepared using MARINE ART Hi (manufactured by Tomita Pharmaceutical Co., Ltd., trade name). The smaller the torque value, the smaller the frictional resistance of the coating film of the resin composition under artificial seawater.

(DR rate) The DR rate was calculated using the following formula. The higher the DR ratio, the more excellent the effect of reducing the frictional resistance.

[Expression 3]

G: dimensionless torque, T: torque value of resin composition (g·cm), ρ: density of artificial seawater 997.794 kg/m ³ , ν: dynamic viscosity of artificial seawater 9.6×10 ^-7 m ² /s, L : The height of the cylindrical drum made of SUS was 0.128 m, G _{Comparative Example 1} : The dimensionless torque of Comparative Example 1, G _Example : The dimensionless torque of the example.

(Water absorption rate) The water absorption rate of the coating film was measured in accordance with the method for determining the plastic-water absorption rate according to Japanese Industrial Standard JIS K7209:2000.

(Contact angle by bubble trapping method) A sample was applied onto a glass slide of 76 mm × 26 mm × 1 mm (thickness) so that the dry film thickness was 200 μm to prepare a test plate. The contact angle measurement of the water in the coating film was carried out by using an automatic contact angle meter DM-301 (manufactured by Kyowa Interface Science Co., Ltd., trade name), and using a bubble trapping method in which water was brought into contact with the surface of the test plate in water. The greater the contact angle in water, the higher the hydrophilicity of the substrate surface.

(Indentation Elasticity Coefficient) A test piece was prepared by applying a sample to a glass slide of 76 mm × 26 mm × 1 mm (thickness) so that the dry film thickness was 200 μm. Using a micro hardness tester HM-2000 (manufactured by Fischer Instruments, trade name), Vickers indenter, load 7 mN/100 s, creeping 60 s, R=0.4 mN/ The indentation modulus of elasticity of the test plate was measured under the measurement conditions of 100 s.

Production Example 1 900 parts of deionized water, 60 parts of 2-sulfoethyl methacrylate, 10 parts of potassium methacrylate, and methyl methacrylate (Methyl methacrylate) were placed in a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer. 12 parts of MMA) were stirred and heated to 50 ° C while being subjected to nitrogen substitution in the polymerization apparatus. 0.08 part of 2,2'-azobis(2-methylpropylindole) dihydrochloride as a polymerization initiator was added thereto, and the temperature was further raised to 60 °C. After the temperature was raised, the MMA was continuously added dropwise at a rate of 0.24 parts/min for 75 minutes using a drip pump. The reaction solution was kept at 60 ° C for 6 hours, and then cooled to room temperature to obtain a dispersant 1 having a solid content of 10% by mass as a transparent aqueous solution.

Next, 145 parts of deionized water, 0.1 part of sodium sulfate, and 0.25 parts of dispersing agent 1 (solid content: 10% by mass) were placed in a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, and stirred to obtain a uniform aqueous solution. Next, 100 parts of MMA, 0.0016 parts of bis[(difluoroboroboryl)diphenylglyoxime]cobalt (II) as a chain transfer agent, and 0.1 part of "Piketta" as a polymerization initiator were added. Perocta)O" (registered trademark) (1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, manufactured by Nippon Oil Co., Ltd.), and made into an aqueous suspension. Next, the inside of the polymerization apparatus was purged with nitrogen, and the temperature was raised to 80 ° C to carry out a reaction for 4 hours. Further, in order to increase the polymerization rate, the temperature was raised to 90 ° C and maintained for 2 hours. Thereafter, the reaction liquid was cooled to 40 ° C to obtain an aqueous suspension containing a macromonomer. The aqueous suspension was filtered, and the filtrate was washed with deionized water, dehydrated, and dried at 40 ° C for 16 hours to obtain a macromonomer (MM1). The macromonomer (MM1) had a number average molecular weight of 7,200.

Example A1 Into a flask equipped with a cooling tube, 50 parts of a macromonomer (MM1) produced in Production Example 1 and 2-hydroxylethyl acrylate (HEA) were added (Osaka Organic Chemical Industry Co., Ltd.) (manufacturing) 50 parts of a monomer solution of methyl cellosolve (manufactured by Kanto Chemical Co., Ltd., special grade) as a solvent, and nitrogen substitution by nitrogen bubbling. Then, 2,2'-azobisisobutyronitrile (2,2'-azobis) as a radical polymerization initiator was heated while the monomer composition was heated to maintain the internal temperature at 70 °C. (isobutyronitrile), AIBN) 0.4 parts (Wako Pure Chemicals Co., Ltd., and light grade) were added to the monomer composition, and maintained for 4 hours, followed by raising the temperature to 80 ° C for 1 hour to complete the polymerization. Then, the polymerization reaction was cooled to room temperature, and reprecipitation was carried out using a large amount of diisopropyl ether (pure chemical). The polymer precipitated by reprecipitation was recovered and vacuum-dried at 50 ° C and 50 mmHg (6.67 kPa) or less for one night to obtain a polymer for an insoluble antifouling coating. The polymer for the non-soluble antifouling coating had a weight average molecular weight of 72,000. Next, 25 parts of the polymer for the non-soluble antifouling paint and 75 parts of the methyl cellosolve were blended into a glass container, and stirred at room temperature for 2 hours with a stirrer to obtain a polymerization containing the non-soluble antifouling paint. A resin composition of a substance and a solvent. The obtained resin composition was applied onto a glass substrate so that the thickness after drying became 200 μm or more, and dried at room temperature to form a coating film. The water contact angle and the indentation modulus of the coating film were 135° and 448 MPa, respectively. In addition, the torque value is 585 g·cm.

(Preparation of the antifouling evaluation sample) The obtained resin composition was spin-coated on an acrylic plate (5 cm × 5 cm × 1 mm) so that the thickness after drying became 200 μm or more, and it was made at room temperature. It is dried to form a coating film. The coating film was placed on the bottom surface of a polypropylene container (8 cm × 8 cm × 4.5 cm), and 100 ml of seawater and 100 individuals of the attached larvae (adenosperm larvae) were placed. After being applied to the test seawater by shaking at a temperature of 22 ° C ± 2 ° C at room temperature of 2 ° C ± 2 ° C, the larvae adhered to the coating film after 7 days of counting under a stereoscopic microscope. The number of abnormal individuals (adhesion rate), and the number of dead individuals (mortality). The adhesion rate and mortality of the coating film were 1% and 2%, respectively.

Example A2 to Example A5, Example B1 to Example B4, Comparative Example A1 to Comparative Example A3, and Comparative Example B1 to Comparative Example B2 were the same as Example 1 except that they were changed to the monomers or solvents described in the Table. Each of the polymers for the non-soluble antifouling coating was obtained, and each evaluation was carried out in the same manner as in Example 1. Further, in Comparative Example 1, an existing ship bottom paint (LR1672 manufactured by Mitsubishi Rayon Co., Ltd.) was used as a resin composition. The ship bottom paint is a dissolution type antifouling paint containing a copolymer of a hydrophobic monomer and a metal-containing monomer as a resin component.

The types and amounts (parts by mass) of the monomers and solvents used in the production of the polymer or resin composition for the non-soluble antifouling paint are shown in the table, and the respective evaluation results are shown.

In addition, the abbreviation in the table indicates the following meaning. MMA: Methyl methacrylate, manufactured by Mitsubishi Rayon Co., Ltd. HEA: 2-hydroxyethyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. AE400: Blemmer AE400, manufactured by Nippon Oil Co., Ltd. NIPAM: N-isopropyl acrylamide, manufactured by KJ Chemical Co., Ltd. MEA: 2-methoxyethyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd. HEMA: 2-hydroxyethyl methacrylate, manufactured by Tokyo Chemical Industry Co., Ltd. PE350: Blemmer PE350, manufactured by Nippon Oil Co., Ltd. HEAA: 2-hydroxyethyl acrylamide, manufactured by KJ Chemical Co., Ltd. DMAAm: dimethyl methacrylate, manufactured by KJ Chemical Co., Ltd. PME400: Blemmer PME400, manufactured by Nippon Oil Co., Ltd. PEA: 2-phenoxyethyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd. AcSi: 3-(trimethoxydecyl)propyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd. MCS: Methyl cellosolve. BA: butyl acetate.

[Table 2]

[table 3]

The coating films of Examples A1 to A5 had higher water contact angles or indentation elastic coefficients than the coating films of Comparative Example A1. Further, it was confirmed that the coating films of Examples B1 to B4 form a phase separation structure, and therefore the antifouling property is excellent.

Since the coating films of Comparative Example A2 and Comparative Example A3 did not have a macromonomer, they did not have a microscopic heterostructure or a nanoheterostructure, and the torque values were higher than those of the coating films of Examples A1 to A5. From the results of the torque value and the DR ratio, it was confirmed that the coating films of Examples A1 to A5 were superior in the effect of reducing the frictional resistance with the aqueous liquid as compared with the coating film of Comparative Example A1. On the other hand, it was confirmed that the coating film of Comparative Example B1 and Comparative Example B2 had a low water contact angle and was inferior in antifouling property.

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no

Claims (15)

A polymer for a non-soluble antifouling coating comprising a constituent unit (A) derived from a macromonomer (a) and a constituent unit (B) derived from a monomer (b) which is not a macromonomer, and comprises The solubility parameter of the monomer (aa) of the macromonomer (a) is less than 18.5 (J/cm ³ ) ^1/2 , and the solubility parameter of the monomer (b) is 18.5 (J/cm ³ ) ^1/2 the above. The polymer for an insoluble antifouling coating according to the first aspect of the invention, wherein a contact angle of a surface of the coating film formed by a captive bubble method is 120° or more and 144° or less. Further, the formed coating film has an indentation modulus of elasticity of 15 MPa or more and 2900 MPa or less. The polymer for a non-soluble antifouling coating according to the first or second aspect of the invention, wherein the macromonomer (a) is a radical polymerizable group and has two or more of the following formulas; (AA) the macromonomers constituting the unit, (A) In the formula, R ¹ is a hydrogen atom, a methyl group or a CH ₂ OH, R ² is OR ³ , a halogen atom, COR ⁴ , COOR ⁵ , CN, CONR ⁶ R ⁷ or R ⁸ , R ³ ～ R ⁷ each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, and an unsubstituted group. Or substituted heteroaryl, unsubstituted or substituted non-aromatic heterocyclic group, unsubstituted or substituted aralkyl group, unsubstituted or substituted alkane An aryl group, or an unsubstituted or substituted organoalkylene group, wherein the substituents permitted in the above are each selected from the group consisting of a carboxyl group, an alkoxycarbonyl group, an epoxy group, a hydroxyl group, an alkoxy group, a primary amine group, At least one of the group consisting of a secondary amino group, a tertiary amino group, an isocyanate group, a sulfo group, and a halogen, and R ⁸ represents an unsubstituted or substituted aryl group, or an unsubstituted or a heteroaryl group having a substituent selected from the group consisting of a carboxyl group, an alkoxycarbonyl group, and an epoxy group, respectively. Base, hydroxyl, alkoxy, primary amine, secondary amine, tertiary amine, isocyanato, sulfo, unsubstituted or substituted alkyl, unsubstituted or substituted At least one of the group consisting of an aryl group, an unsubstituted or substituted alkenyl group, and a halogen. The polymer for a non-soluble antifouling coating according to any one of claims 1 to 3, wherein the monomer (b) is an aliphatic monomer. The polymer for a non-soluble antifouling coating according to any one of claims 1 to 4, wherein the glass transition point is 10 ° C or higher. The polymer for a non-soluble antifouling coating according to any one of the preceding claims, wherein the macromonomer (a) is a macromonomer represented by the following formula (1) , Wherein R is a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, unsubstituted Or a heteroaryl group having a substituent or a non-aromatic heterocyclic group having an unsubstituted or substituted group, and a plurality of R groups may be the same or different, and X is a hydrogen atom or a methyl group, and a plurality of X may be respectively The same or different, Z is a terminal group, and n is a natural number of 2 to 10,000. A resin composition comprising the polymer for a non-soluble antifouling coating according to any one of the first to sixth aspects of the invention. The resin composition according to claim 7, which further comprises a solvent. The resin composition according to claim 7 or 8, wherein the viscosity at 25 ° C is 5 × 10 ⁴ mPa·s or less. An antifouling coating comprising the resin composition according to any one of claims 7 to 9. A coating film formed by using the resin composition according to any one of claims 7 to 9 or the antifouling paint according to claim 10 of the patent application. A method for reducing friction in water, which comprises applying the resin composition according to any one of claims 7 to 9 or the antifouling paint according to claim 10 of the patent application. The step of forming a coating film on the surface of the object. A method for producing a polymer for a non-soluble antifouling coating, which comprises polymerizing a monomer mixture comprising the macromonomer (a) and a monomer (b) which is not a macromonomer, as obtained in the patent application scope The polymer for a non-soluble antifouling coating according to any one of the items 1 to 6, wherein the macromonomer (a) is a macromonomer having a radical polymerizable group. The method for producing a polymer for an insoluble antifouling coating according to claim 13, wherein the macromonomer having a radical polymerizable group is produced by a suspension polymerization method. The method for producing a polymer for an insoluble antifouling coating according to claim 14, wherein the monomer mixture is polymerized by a solution polymerization method.