JP6907727B2 - Method for manufacturing resin composition for antifouling paint and antifouling coating film - Google Patents

Description

The present invention relates to a resin composition for an antifouling paint and a method for producing an antifouling coating film.

A coating film is formed on the seawater contact surface of marine structures and ships with an antifouling paint for the purpose of preventing corrosion and preventing the adhesion of marine organisms that cause a decrease in navigation speed. Antifouling paints include elution type (self-polishing) paints in which the surface of the formed coating film is gradually dissolved in seawater and surface renewal (self-polishing), non-eluting type paints in which the coating film is not renewed It has been known. For example, in Patent Document 1, as a non-eluting antifouling coating composition, a cured coating film having a specific microheterogeneous structure is formed of at least two kinds of resins that are incompatible with each other and insoluble in seawater. Has been proposed.
In addition, it is desirable that the coating film formed on the seawater contact surface of a ship has the ability to reduce underwater friction and low resistance for the purpose of reducing frictional resistance from seawater during navigation, improving fuel efficiency and saving energy. Is done. In response to such a requirement, for example, Patent Document 2 proposes an underwater friction reducing coating film in which the contact angle of the film surface with water and the surface roughness are set to predetermined values.

Japanese Unexamined Patent Publication No. 10-60317 Japanese Unexamined Patent Publication No. 2003-277691

However, the conventional antifouling coating film does not always have sufficient antifouling property.
An object of the present invention is to provide a resin composition for an antifouling paint capable of forming an antifouling coating film having excellent antifouling properties, and a method for producing the antifouling coating film.

In order to solve the above problems, the present invention provides the following [1] to [8].
[1] A resin composition for an antifouling coating material containing an amphipathic polymer, wherein the average surface roughness (Q) of the coating film made of the resin composition for the antifouling coating material is 1 nm <(Q) in water. Q) Resin composition for antifouling paint with <10 nm.
[2] The resin composition for an antifouling coating material according to [1], wherein the outer surface of the coating film has an underwater contact angle of 120 to 144 ° and a indentation elastic modulus of 15 to 2900 MPa.
[3] The amphipathic polymer contains a structural unit derived from a macromonomer having a radically polymerizable group and a structural unit derived from a (meth) acrylic monomer other than the macromonomer [1] or [1] or [ 2] Resin composition for antifouling paint.
[4] The resin composition for an antifouling paint according to [3], wherein the macromonomer is represented by the following formula (1).

(In the formula, R is a hydrogen atom, an alkyl group having an unsubstituted or substituent, an alicyclic group having an unsubstituted or substituent, an aryl group having an unsubstituted or substituent, an unsubstituted or substituent. Indicates a heteroaryl group having, or an unsubstituted or non-aromatic heterocyclic group having a substituent, and a plurality of Rs may be the same or different, respectively, and X is a hydrogen atom or a methyl group, and a plurality of Rs are used. X may be the same or different, where Z is the end group and n is a natural number of 2 to 10,000.)
[5] The amphipathic polymer contains a hydrophobic part containing a structural unit derived from the macromonomer and a hydrophilic part containing a structural unit derived from the (meth) acrylic monomer, [3] or [4] The resin composition for an antifouling paint.
[6] The resin composition for an antifouling paint according to any one of [1] to [5], wherein the amphipathic polymer is insoluble.
[7] The resin composition for an antifouling coating material according to any one of [1] to [6], which further contains a solvent.
[8] A method for producing an antifouling coating film, which comprises a step of forming a coating film on the surface of the object to be coated using the resin composition for antifouling paint according to any one of [1] to [7].

According to the resin composition for an antifouling paint of the present invention, an antifouling coating film having excellent antifouling properties can be obtained.
According to the method for producing an antifouling coating film of the present invention, an antifouling coating film having excellent antifouling properties can be obtained.

6 is a scanning probe microscope image of a coating film formed by using the resin composition for an antifouling paint of Example 1.

The definitions of the following terms apply throughout the specification and claims.
The "amphipathic polymer" means a polymer containing a hydrophilic part and a hydrophobic part in the molecule. The hydrophilic part means a polymer having a property of being easily dissolved in water or being easily compatible with water, and the hydrophobic part is meaning a polymer having a property of being difficult to be dissolved in water or being difficult to be compatible with water.
"(Meta) acrylic monomer" means a monomer having a (meth) acryloyl group.
"(Meta) acryloyl group" is a general term for acryloyl group and methacryloyl group.
"(Meta) acrylate" is a general term for acrylate and methacrylate.
"(Meta) acrylic acid" is a general term for acrylic acid and methacrylic acid.
"~" Indicating a numerical range means that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

Hereinafter, suitable embodiments for carrying out the present invention will be described. It should be noted that the embodiments described below show an example of typical embodiments of the present invention, and the scope of the present invention is not narrowly interpreted by this.
The resin composition for an antifouling paint of the present embodiment (hereinafter, also simply referred to as a resin composition) contains an amphipathic polymer.

<Aphiphile polymer>
The amphipathic polymer of the present embodiment has a structural unit derived from a macromonomer (hereinafter, also referred to as “macromonomer (a)”) and a monomer other than the macromonomer (a) (hereinafter, “monomer (b)). ”), And includes.

The amphoteric polymer is typically a block copolymer in which a polymer chain composed of a structural unit derived from the macromonomer (a) and a polymer chain composed of a structural unit derived from the monomer (b) are bonded. , Or a graft copolymer structure in which a polymer chain composed of a structural unit derived from the macromonomer (a) and a polymer chain composed of a structural unit derived from the monomer (b) are bonded.
In the block copolymer or graft copolymer, the polymer chain composed of the structural unit derived from the macromonomer (a) is the hydrophobic part, and the polymer chain composed of the structural unit derived from the monomer (b) is the hydrophilic part. The polymer chain composed of the structural unit derived from the macromonomer (a) is the hydrophilic part, and the polymer chain composed of the structural unit derived from the monomer (b) is the hydrophobic part. May be good.

In the amphipathic polymer, the content of the structural unit derived from the macromonomer (a) is preferably 5 to 95% by mass with respect to the total of all the structural units constituting the amphipathic polymer. When the content of the structural unit derived from the macromonomer (a) is within the above range, the antifouling property of the formed coating film is more excellent.
In the present embodiment, the total of all the structural units constituting the amphipathic polymer is equal to the total of the content of the structural units derived from the macromonomer (a) and the structural units derived from the monomer (b).

[Macromonomer (a)]
The macromonomer (a) has a radically polymerizable group or an addition-reactive functional group such as a hydroxyl group, an isocyanate group, an epoxy group, a carboxy group, an amino group, an amide group, a thiol group, or an acid anhydride group. And so on.

When the macromonomer (a) has a radically polymerizable group, the macromonomer (a) and the monomer (b) can be copolymerized by radical polymerization to produce the amphoteric polymer of the present embodiment.
When the macromonomer (a) has a radically polymerizable group, the macromonomer (a) may have one or more radically polymerizable groups, and preferably has one radically polymerizable group. ..

When the macromonomer (a) has an addition-reactive functional group, the monomer (b) usually has a functional group capable of reacting with the addition-reactive functional group of the macromonomer (a). An amphipathic polymer can be produced by reacting the polymerizable functional group derived from the monomer (b) with the addition-reactive functional group of the macromonomer (a).
When the macromonomer (a) has an addition-reactive functional group, the macromonomer (a) may have one or more addition-reactive functional groups that are the same or different, and the addition-reactive functional group may be used. It is preferable to have one.

Examples of the combination of the addition-reactive functional group of the macromonomer (a) and the functional group capable of reacting with the functional group include the following combinations.
A combination of a hydroxyl group and a carboxy 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 amino group, a combination of a carboxy group and an epoxy group, an amino group and a carboxy group. Combination of amide group and carboxy group, combination of thiol group and epoxy group.

Further, the macromonomer (a) may have either a radically polymerizable group or a functional group, or may have both a radically polymerizable group and a functional group.
When the macromonomer (a) contains both a radically polymerizable group and a functional group, the functional group added to the polymer unit composed of the monomer (b) or the radically polymerizable group copolymerizing with the monomer (b). There may be two or more functional groups or radically polymerizable groups other than any of the above.

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

As the radically polymerizable group of the macromonomer (a), a group having an ethylenically unsaturated bond is preferable. Examples of the group having an ethylenically unsaturated bond, _{e.g., CH 2 = C (COOR)} -CH 2 -, ( meth) acryloyl group, 2- (hydroxymethyl) acryloyl group, a vinyl group, and the like.
Here, R is a hydrogen atom, an alkyl group having an unsubstituted or substituent, an alicyclic group having an unsubstituted or substituent, an aryl group having an unsubstituted or substituent, an unsubstituted or substituent. Shows a heteroaryl group having, or a non-aromatic heterocyclic group having an unsubstituted or substituent.

Examples of the unsubstituted alkyl group in R include a branched or linear alkyl group having 1 to 22 carbon atoms. Specific examples of branched or linear alkyl groups having 1 to 22 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, i-butyl group and pentyl group. Group (amyl group), i-pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, i-octyl group, nonyl group, i-nonyl group, decyl group, i-decyl group, undecyl group, dodecyl Examples thereof include a group (lauryl group), a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group (stearyl group), an i-octadecyl group, a nonadecil group, an icosyl group and a docosyl group.

The unsubstituted alicyclic group in R may be a monocyclic group or a polycyclic group, 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. Examples include a group and an adamantyl group.

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 device 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 an oxygen atom-containing heterocyclic group such as a tetrahydrofuryl group and a tetrahydropyranyl group, a γ-butyrolactone group, an ε-caprolactone group, a pyrrolidinyl group and a pyrrolidone group. Examples thereof include a nitrogen atom-containing heterocyclic group such as a morpholino group.

Substituents in R (alkyl groups having substituents, alicyclic groups having substituents, aryl groups having substituents, heteroaryl groups having substituents, non-aromatic heterocyclic groups having substituents, respectively. (Substituents in) include, for example, 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 , -CONR. ^{Included is at least one selected from the group consisting of 15} R ¹⁶ , halogen atoms, allyl groups, epoxy groups, siloxy groups, and groups exhibiting hydrophilicity or ionicity.
Here, R ^{11 to} R ¹⁶ are independently hydrogen atoms, an alkyl group having an unsubstituted or substituent, an alicyclic group having an unsubstituted or substituent, or an aryl having an unsubstituted or substituent. Indicates a group.

Examples of the alkyl group and the aryl group in the above-mentioned substituent include those similar to the above-mentioned unsubstituted alkyl group and unsubstituted aryl group, respectively.
As R ^{11 of −COOR 11} in the above substituent, a hydrogen atom or an unsubstituted alkyl group is preferable. That is, -COOR ¹¹ is preferably a carboxy group or an alkoxycarbonyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group.
The ^{R 12} in ^{-OR 12} in the above substituents, hydrogen atom or an unsubstituted alkyl group. That is, -OR ¹² is preferably a hydroxy group or an alkoxy group. Examples of the alkoxy group include an alkoxy group having 1 to 12 carbon atoms, and specific examples thereof include a methoxy group.

^{Examples of -NR 13} R ¹⁴ in the above-mentioned substituent include an amino group, a monomethylamino group, a dimethylamino group and the like.
Examples of the -CONR ¹⁵ R ¹⁶ in the above substituent include a carbamoyl group (-CONH ₂ ), an N-methylcarbamoyl group (-CONHCH ₃ ), and an N, N-dimethylcarbamoyl group (dimethylamide group: -CON (CH _3). ) ₂ ) and the like.

Examples of the halogen atom in the above-mentioned 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 above substituent include an alkali salt of a carboxy group or an alkali salt of a sulfo group, a poly (alkylene oxide) group such as a polyethylene oxide group and a polypropylene oxide group, and a quaternary ammonium base. Cationic substituents can be mentioned.

As R, an alkyl group having an unsubstituted or substituent, or an alicyclic group having an unsubstituted or substituent is preferable, and an unsubstituted alkyl group or a fat having an alkyl group as an unsubstituted or substituent is preferable. A cyclic group is more preferred.
Among the above, due to the availability, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclo Propyl group, cyclobutyl group, isobornyl group and adamantyl group are preferable, and methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, isobornyl group and The adamantyl group is more preferred.

The macromonomer (a) preferably has two or more structural units derived from a monomer having a radically polymerizable group (hereinafter, also referred to as “monomer (aa1)”).
As the radically polymerizable group contained in the monomer (aa1), a group having an ethylenically unsaturated bond is preferable as in the radical polymerizable group preferably possessed by the macromonomer (a).

As the monomer (aa1), for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic T-butyl acid, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, ( Isononyl (meth) acrylate, decyl (meth) acrylate, isodecil (meth) acrylate, lauryl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, ( Phenyl acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfurfryl (meth) acrylate, isobornyl (meth) acrylate, 3,5,5-trimethylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, terpene acrylate and its derivatives, hydrogenated rosin acrylate and its derivatives, docosyl (meth) acrylate Such as hydrocarbon group-containing (meth) acrylic acid ester;
2-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, A hydroxyl group-containing (meth) acrylic acid ester such as glycerol (meth) acrylate;
(Meta) acrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxy Propylphthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, crotonic acid , Phthalic acid, maleic acid, itaconic acid, citraconic acid, monomethyl maleate, monoethyl maleate, monooctyl maleate, monomethyl itaconic acid, monoethyl itaconic acid, monobutyl itaconic acid, monooctyl itaconic acid, monomethyl fumarate, monoethyl fumarate , Monobutyl fumarate, monooctyl fumarate, monoethyl citraconic acid and other carboxy group-containing vinyl monomers;
Vinyl anhydride group-containing vinyl monomers such as maleic anhydride and itaconic anhydride;
Unsaturated dicarboxylic acid diester monomers such as dimethylmalate, dibutylmalate, dimethylfumarate, dibutylfumarate, dibutylitaconate, diperfluorocyclohexylfumarate;
Epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, and 3,4-epoxybutyl (meth) acrylate;
Amino group-containing (meth) acrylic acid ester-based vinyl monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate;
(Meta) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-isopropylacrylamide, hydroxyethyl acrylamide, N-methoxymethyl (meth) ) Vinyl-based monomers containing amide groups such as acrylamide, N-butoxymethyl (meth) acrylamide, diacetoneacrylamide, maleic acid amide, and maleimide;
Vinyl-based monomers such as styrene, α-methylstyrene, vinyltoluene, (meth) acrylonitrile, vinyl chloride, vinyl acetate, and vinyl propionate;
Divinylbenzene, ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di ( Meta) 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-Nonandiol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, trimethylpropantri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, allyl ( Polyfunctional vinyl-based monomers such as meth) acrylate, triallyl cyanurate, diallyl maleate, polypropylene glycol diallyl ether, and N, N'-methylenebis (meth) acrylamide;
(Meta) Heterocyclic monomers such as acryloyl morpholine, vinylpyrrolidone, vinylpyridine, and vinylcarbazole;
Polyethylene glycol (meth) acrylate, Polypropylene glycol (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, n-butoxyethyl (meth) acrylate, isobutoxyethyl (meth) acrylate , (Meta) t-butoxyethyl acrylate, (meth) ethoxyethoxyethyl acrylate, phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, (meth) Acetoxyethyl acrylate, "Placel FM" (caprolactone-added monomer manufactured by Daicel Chemical Co., Ltd., trade name), "Blemmer PME-100" (methoxypolyethylene glycol methacrylate manufactured by Nichiyu Co., Ltd. (ethylene glycol chain is 2). (Things), trade name), "Blemmer PME-200" (Nichiyu Co., Ltd. methoxypolyethylene glycol methacrylate (those with 4 ethylene glycol chains), trade name), "Blemmer PME-400" (Nichiyu (Nichiyu) Methoxypolyethylene glycol methacrylate manufactured by Nichiyu Co., Ltd. (the chain of ethylene glycol is 9), trade name), "Blemmer 50 POEP-800B" (Octoxy polyethylene glycol-polypropylene glycol-methacrylate (chain of ethylene glycol) manufactured by Nichiyu Co., Ltd. Is 8 and the chain of propylene glycol is 6), trade name), "Blemmer 20 ANEP-600" (Nonylphenoxy (ethylene glycol-polypropylene glycol) monoacrylate manufactured by Nichiyu Co., Ltd., trade name), " Blemmer AME-100 (manufactured by Nichiyu Co., Ltd., trade name), "Blemmer AME-200" (manufactured by Nichiyu Co., Ltd., trade name) and "Blemmer 50 AOEP-800B" (manufactured by Nichiyu Co., Ltd., product) Name) and other glycol ester-based monomers,
3- (Meta) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane , Silane coupling agent-containing monomer such as vinyltriethoxysilane,
Trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tri-n-propylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, tri-n-amylsilyl (meth) acrylate, tri-n-hexylsilyl (Meta) acrylate, tri-n-octylsilyl (meth) acrylate, tri-n-dodecylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, tri-p-methylphenylsilyl (meth) acrylate, tribenzylsilyl (Meta) acrylate, triisopropylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tri-s-butylsilyl (meth) acrylate, tri-2-methylisopropylsilyl (meth) acrylate, tri-t-butylsilyl (meth) acrylate ) Acrylic, ethyldimethylsilyl (meth) acrylate, n-butyldimethylsilyl (meth) acrylate, diisopropyl-n-butylsilyl (meth) acrylate, n-octyldi-n-butylsilyl (meth) acrylate, diisopropylstearylsilyl (meth) acrylate , Dicyclohexylphenylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, lauryldiphenylsilyl (meth) acrylate, triisopropylsilylmethylmalate, triisopropylsilylamylmalate, tri-n-butylsilyl-n-butylmalate , T-Butyldiphenylsilylmethylmalate, t-butyldiphenylsilyl-n-butylmalate, triisopropylsilylmethylfumarate, triisopropylsilylamylfumarate, tri-n-butylsilyl-n-butylfumarate, t-butyldiphenyl Cyril methyl fumarate, t-butyldiphenylsilyl-n-butyl fumarate, silaplane FM-0711 (manufactured by JNC Co., Ltd., trade name), silaplane FM-0721 (manufactured by JNC Co., Ltd., trade name), sila Plain FM-0725 (manufactured by JNC Co., Ltd., trade name), Silaplane TM-0701 (manufactured by JNC Co., Ltd., trade name), Silaplane TM-0701T (manufactured by JNC Co., Ltd., trade name), X-22 -174ASX (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name), X-22-174BX (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name), KF-2012 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name), X -22-2426 (Shinetsu) Organosilyl group-containing monomers other than silane coupling agent-containing monomers such as Gakukogyo Co., Ltd., trade name), X-22-2404 (Shin-Etsu Chemical Co., Ltd., trade name);
Halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene, etc.
2-Isocyanatoethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluorophenyl (meth) acrylate, 2- (perfluorobutyl) Ethyl (meth) 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, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate , 1H, 1H, 5H-octafluoropentyl (meth) methacrylate, 1H, 1H, 2H, 2H-tridecafluorooctyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H , 1H, 3H-hexafluorobutyl (meth) acrylate, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl (meth) acrylate and other fluorine-containing monomers (excluding halogenated olefins) ),
A single having an acetal structure such as 1-butoxyethyl (meth) acrylate, 1- (2-ethylhexyloxy) ethyl (meth) acrylate, 1- (cyclohexyloxy) ethyl methacrylate, 2-tetrahydropyranyl (meth) acrylate. Quantum,
Examples thereof include 4-methacryloyloxybenzophenone and -2-isocyanatoethyl (meth) acrylate.
One of these monomers may be used alone, or two or more of these monomers may be used in combination.

It is preferable that the macromonomer (a) has a radically polymerizable group and has two or more structural units represented by the following formula (AA) (hereinafter, also referred to as “constituent unit (AA)”).

(In the formula, 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 , and R ^{3 to} R ⁷ are independently hydrogen atoms, alkyl groups having unsubstituted or substituents, alicyclic groups having unsubstituted or substituents, aryl groups having unsubstituted or substituents, and unsubstituted or substituents, respectively. Heteroaryl group with unsubstituted or substituent, non-aromatic heterocyclic group with unsubstituted or substituent, aralkyl group with unsubstituted or substituent, alkalinel group with unsubstituted or substituent, or unsubstituted Alternatively, an organosilyl group having a substituent is shown, and the allowable substituents thereof are a carboxy group, an alkoxycarbonyl group, an epoxy group, a hydroxy group, an alkoxy group, a primary amino group, a secondary amino group, and a tertiary amino, respectively. It is at least one selected from the group consisting of a group, an isocyanato group, a sulfo group and a halogen, and R ⁸ represents an aryl group having an unsubstituted or substituent or a heteroaryl group having an unsubstituted or substituent. The substituents allowed for these are carboxy group, alkoxycarbonyl group, epoxy group, hydroxy group, alkoxy group, primary amino group, secondary amino group, tertiary amino group, isocyanato group, sulfo group and unsubstituted group, respectively. Alternatively, it is at least one selected from the group consisting of an alkyl group having a substituent, an aryl group having an unsubstituted or substituent, an alkenyl-containing group having an unsubstituted or substituent, and a halogen.)

A hydrogen atom and a methyl group are preferable as ^{R 1} , and COOR ⁵ is preferable ^{as R 2.}
The unsubstituted alkyl group, unsubstituted alicyclic group, unsubstituted aryl group, unsubstituted heteroaryl group, and unsubstituted non-aromatic heterocyclic group of ^{R 3 to} R ^{7 are the above-mentioned R, respectively.} Examples thereof include an unsubstituted alkyl group, an unsubstituted alicyclic group, an unsubstituted aryl group, an unsubstituted heteroaryl group, and an unsubstituted non-aromatic heterocyclic group in the above.

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

Examples of the unsubstituted organosilyl group of R ^{3 to} R ^{7 include −SiR 17} R ¹⁸ R ¹⁹ (where R ^{17 to} R ¹⁹ are each independently unsubstituted or an alkyl group having a substituent, unsubstituted or substituted. An alicyclic group having a substituent, or an aryl group having an unsubstituted or substituent is shown.).
Examples of the alkyl group having an unsubstituted or substituent in R ^{17 to} R ¹⁹ include the same as described above, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-amyl group, n. -Hexyl group, n-octyl group, n-dodecyl group, stearyl group, lauryl group, isopropyl group, isobutyl group, s-butyl group, 2-methylisopropyl group, benzyl group and the like can be mentioned.
Examples of the alicyclic group having an unsubstituted or substituent in R ^{17 to} R ¹⁹ include the same as described above, and examples thereof include a cyclohexyl group.
Examples of the aryl group having an unsubstituted or substituent in R ^{17 to} R ¹⁹ include the same as described above, and examples thereof include a phenyl group and p-methylphenyl.
R ^{17 to} R ¹⁹ may be the same or different from each other.

Substituents in R ^{3 to} R ⁷ (alkyl group having substituent, alicyclic group having substituent, aryl group having substituent, heteroaryl group having substituent, non-aromatic heterocycle having substituent) Of the substituents in each of the formula group, the aralkyl group having a substituent, the alkalinel group having a substituent, and the organosilyl group having a substituent), an alkyl group, an aryl group, a heteroaryl group, and a non-aromatic heterocycle Examples of the formula group, the aralkyl group, and the alkaline group are the same as described above.
Examples of the alkoxycarbonyl group include an alkyl group in which R ^{11 of -COOR 11} is unsubstituted or has a substituent, an alicyclic group having an unsubstituted or substituent, or an aryl group having an unsubstituted or substituent. There is a group that is.
Examples of the alkoxy group include a group in which R ^{12 of −OR 12} is an unsubstituted alkyl group.
As the secondary amino group, R ^{13 of the -NR 13} R ¹⁴ is a hydrogen atom, R ¹⁴ is an alkyl group having an unsubstituted or substituent, an alicyclic group having an unsubstituted or substituent, or an unsubstituted group. Or a group which is an aryl group having a substituent.
The tertiary amino group, an alkyl group having R ¹³ and R ¹⁴ are each unsubstituted or substituted group of the -NR ¹³ R ^14, unsubstituted or cycloaliphatic radical having a substituent, or an unsubstituted or Examples thereof include a group which is an aryl group having a substituent.
Examples of the alkyl group having an unsubstituted or substituent, the aryl group having an unsubstituted or substituent, and the halogen atom are the same as described above.

Unsubstituted aryl groups in R ^8, unsubstituted heteroaryl group, a heterocyclic group of the non-aromatic unsubstituted respectively, are the same as those described above.
Substituents on R ⁸ of (aryl group having a substituent, a heteroaryl group having a substituent, the substituent in each Non-aromatic heterocyclic groups having a substituent), an alkoxycarbonyl group, an alkoxy group, a primary Examples of the amino group, the secondary amino group, the tertiary amino group, the alkyl group having an unsubstituted or substituent, the aryl group having an unsubstituted or substituent, and the halogen atom are the same as described above.
Examples of the unsubstituted alkenyl-containing group include an allyl group and the like.
Examples of the substituent in the alkenyl-containing group having a substituent include the same as the substituent in R ^{3 to} R ⁷ .

The structural unit (AA) is a structural 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) acrylates [eg, methyl (meth) acrylates, ethyl (meth) acrylates, n-propyl (meth) acrylates, i-propyl (meth) acrylates, n-butyl (meth) acrylates, i -Butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 1-methyl-2-methoxyethyl ( Meta) acrylate, 3-methoxybutyl (meth) acrylate, 3-methyl-3-methoxybutyl (meth) acrylate], substituted or unsubstituted aralkyl (meth) acrylate [eg, benzyl (meth) acrylate, m-methoxyphenyl] Ethyl (meth) acrylate, p-methoxyphenyl ethyl (meth) acrylate], substituted or unsubstituted aryl (meth) acrylate [eg, phenyl (meth) acrylate, m-methoxyphenyl (meth) acrylate, p-methoxyphenyl (eg) Meta) acrylate, o-methoxyphenyl ethyl (meth) acrylate], alicyclic (meth) acrylate [eg, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate], halogen atom-containing (meth) acrylate [eg, trifluoro Hydrophobic group-containing (meth) acrylic acid ester monomer such as ethyl (meth) acrylate, perfluorooctyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate];
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate , Phenoxyethyl (meth) acrylate, 2- (2-ethylhexaoxy) ethyl (meth) acrylate and other oxyethylene group-containing (meth) acrylic acid ester monomers;
Hydroxyl-containing (meth) acrylic acid ester monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerol (meth) acrylate;
Terminal alkoxyallylated polyethers such as methoxypolyethylene glycol allyl ether, methoxypolyethylene glycol allyl ether, butoxypolyethylene glycol allyl ether, butoxypolypropylene glycol allyl ether, methoxypolyethylene glycol-polypropylene glycol allyl ether, butoxypolyethylene glycol-polypropylene glycol allyl ether. Quantitative;
Epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, and 3,4-epoxybutyl (meth) acrylate;
Primary or secondary amino group-containing vinyl monomers such as butylaminoethyl (meth) acrylate and (meth) acrylamide;
Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl Tertiary amino group-containing vinyl monomer such as (meth) acrylamide;
Heterocyclic basic monomers such as vinylpyrrolidone, vinylpyridine, and vinylcarbazole;
Trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tri-n-propylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, tri-n-amylsilyl (meth) acrylate, tri-n-hexylsilyl (Meta) acrylate, tri-n-octylsilyl (meth) acrylate, tri-n-dodecylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, tri-p-methylphenylsilyl (meth) acrylate, tribenzylsilyl (Meta) acrylate, triisopropylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tri-s-butylsilyl (meth) acrylate, tri-2-methylisopropylsilyl (meth) acrylate, tri-t-butylsilyl (meth) acrylate ) Acrylate, ethyldimethylsilyl (meth) acrylate, n-butyldimethylsilyl (meth) acrylate, diisopropyl-n-butylsilyl (meth) acrylate, n-octyldi-n-butylsilyl (meth) acrylate, diisopropylstearylsilyl (meth) acrylate , Dicyclohexylphenylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, lauryldiphenylsilyl (meth) acrylate and other organosilyl group-containing vinyl monomers;
Methacrylate, acrylic acid, vinyl benzoic acid, monohydroxyethyl (meth) acrylate of tetrahydrophthalate, monohydroxypropyl (meth) acrylate of tetrahydrophthalate, monohydroxybutyl (meth) acrylate of tetrahydrophthalate, monohydroxyethyl phthalate (meth) ) Acrylate, monohydroxypropyl phthalate (meth) acrylate, monohydroxyethyl succinate (meth) acrylate, monohydroxypropyl succinate (meth) acrylate, monohydroxyethyl maleate (meth) acrylate, monohydroxypropyl maleate (meth) ) Carboxy group-containing ethylenically unsaturated monomer such as acrylate;
Cyano group-containing vinyl monomers such as acrylonitrile and methacrylonitonyl;
Vinyl ether monomers such as alkyl vinyl ethers [eg, ethyl vinyl ethers, propyl vinyl ethers, butyl vinyl ethers, hexyl vinyl ethers, 2-ethylhexyl vinyl ethers, etc.], cycloalkyl vinyl ethers [eg, cyclohexyl vinyl ethers, etc.];
Vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene;
Halogenated olefins such as vinyl chloride and vinyl fluoride; etc.

When the macromonomer (a) is a macromonomer having a radically polymerizable group and having two or more structural units (AA), the macromonomer (a) is a structural unit other than the structural unit (AA). May further have. Examples of other structural units include structural units derived from the monomers that do not correspond to _{CH 2} = CR ¹ R ² among the monomers listed as examples of the above-mentioned monomer (aa1).

From the viewpoint of recoatability, the macromonomer (a) is a hydrophobic group-containing (meth) acrylic acid ester monomer, an oxyethylene group-containing (meth) acrylic acid ester monomer, and a hydroxyl group-containing (meth) acrylic acid ester single amount. Body, terminal alkoxyallylated polyether monomer, epoxy group-containing vinyl monomer, primary or secondary amino group-containing vinyl monomer, tertiary amino group-containing vinyl monomer, heterocyclic base One or more simple monomers selected from a sex monomer, a carboxy group-containing ethylenically unsaturated monomer, a cyano group-containing vinyl monomer, a vinyl ether monomer, a vinyl ester monomer, and an aromatic vinyl monomer. It is preferably a structural unit derived from a monomer.

In the macromonomer (a), the monomer forming the structural unit (AA) or another structural unit includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate. , (Meta) isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, (meth) Octyl acrylate, (meth) lauryl acrylate, (meth) stearyl acrylate, (meth) isostearyl acrylate (meth) hexadecyl acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, (meth) acrylic Phenyl acid acid, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 3,5,5-trimethylcyclohexyl (meth) acrylate, (meth) Carbonation of dicyclopentanyl acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, terpene acrylate and its derivatives, hydrogenated rosin acrylate and its derivatives, docosyl (meth) acrylate, etc. Hydrogen group-containing (meth) acrylic acid ester; 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ( Hydroxyl-containing (meth) acrylic acid esters such as 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerol (meth) acrylate; (meth) acrylic acid, 2- (meth) acryloyloxyethyl hexa. Hydrophthalic acid, 2- (meth) acrylic oxypropylhexahydrophthalic acid, 2- (meth) acrylic oxyethyl phthalic acid, 2- (meth) acrylic oxypropyl phthalic acid, 2- (meth) acrylic oxyethyl maleic acid, 2- (Meta) acrylic oxypropyl maleic acid, 2- (meth) acrylic oxyethyl succinic acid, 2- (meth) acrylic oxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, itacone Carboxy group-containing vinyl monomer such as monomethyl acid; Acid anhydride group-containing vinyl monomer such as maleic anhydride and itaconic acid anhydride; (meth) glycylic acid acrylate Epoxy group-containing vinyl-based monomers such as zill, glycidyl α-ethyl acrylate, and (meth) acrylate 3,4-epoxybutyl; containing amino groups such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate. (Meta) Acrylate-based vinyl monomer; (meth) acrylamide, N-t-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-isopropylacrylamide, hydroxyethyl acrylamide, N-methoxymethyl Vinyl-based monomers containing amide groups such as (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide, maleic acid amide, maleimide, etc .; styrene, α-methylstyrene, vinyltoluene, (meth) acrylonitrile , Vinyl chloride, vinyl acetate, vinyl propionate and other vinyl-based monomers; divinylbenzene, ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, Triethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, Trimethylol propantri (meth) acrylate, Allyl (meth) acrylate, N, N'- Polyfunctional vinyl-based monomers such as methylenebis (meth) acrylamide; acryloylmorpholin, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethyl (meth) acrylate, ethoxy (meth) acrylate Ethyl, n-butoxyethyl (meth) acrylate, isobutoxyethyl (meth) acrylate, t-butoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) ) Nonylphenoxyethyl acrylate, 3-methoxybutyl (meth) acrylate, acetoxyethyl (meth) acrylate, "Placel FM" (caprolactone-added monomer manufactured by Daicel Chemical Co., Ltd., trade name), "Blemmer PME-100" (Nichiyu Co., Ltd. methoxypolyethylene glycol methacrylate (the chain of ethylene glycol is 2), trade name), "Blemmer PME-200" (Nippon Oil Co., Ltd. methoxypolyethylene glycol methacrylate (the chain of ethylene glycol) (4), trade name), "Blemmer PME-400" (Nichiyu Co., Ltd. methoxypolyethylene glycol methacrylate (those with 9 ethylene glycol chains), trade name), "Blemmer 50 POEP-800B" ( Octoxypolyethylene glycol-polypropylene glycol-methacrylate (with 8 ethylene glycol chains and 6 propylene glycol chains), trade name) and "Blemmer 20 ANEP-600" (Nichiyu (Nichiyu) Nonylphenoxy (ethylene glycol-polypropylene glycol) monoacrylate manufactured by Nichiyu Co., Ltd., "Blemmer AME-100" (manufactured by Nichiyu Co., Ltd., product name), "Blemmer AME-200" (manufactured by Nichiyu Co., Ltd.) , Product name) and "Blemmer 50 AOEP-800B" (manufactured by Nichiyu Co., Ltd., product name), Silaplane FM-0711 (manufactured by JNC Co., Ltd., product name), Silaplane FM-0721 (manufactured by JNC Co., Ltd.) , Product name), Silaplane FM-0725 (manufactured by JNC Co., Ltd., product name), Silaplane TM-0701 (manufactured by JNC Co., Ltd., product name), Silaplane TM-0701T (manufactured by JNC Co., Ltd., product name) Name), X-22-174DX (manufactured by Shinetsu Chemical Industry Co., Ltd., product name), X-22-2426 (manufactured by Shinetsu Chemical Industry Co., Ltd., product name), X-22-2475 (manufactured by Shinetsu Chemical Industry Co., Ltd., product name) ), Trade name), 2-isocyanatoethyl (meth) acrylate, and the like.

Preferred specific examples of other structural units include the following monomer-derived structural units.
Triisopropylsilylmethylmalate, triisopropylsilylamylmalate, tri-n-butylsilyl-n-butylmalate, t-butyldiphenylsilylmethylmalate, t-butyldiphenylsilyl-n-butylmalate, triisopropylsilylmethylfumarate, Organosilyl group-containing vinyl monomers such as triisopropylsilylamyl fumarate, tri-n-butylsilyl-n-butylfumarate, t-butyldiphenylsilylmethyl fumarate, t-butyldiphenylsilyl-n-butylfumarate;
An acid anhydride group-containing vinyl monomer such as maleic anhydride and itaconic anhydride;
Crotonic acid, fumaric acid, itaconic acid, maleic acid, citraconic acid, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monomethyl itaconic acid, monoethyl itaconic acid, monobutyl itaconic acid, monooctyl itaconic acid, fumal Carboxy group-containing ethylenically unsaturated monomers such as monomethyl acid, monoethyl fumarate, monobutyl fumarate, monooctyl fumarate, and monoethyl citraconate;
Unsaturated dicarboxylic acid diester monomers such as dimethylmalate, dibutylmalate, dimethylfumarate, dibutylfumarate, dibutylitaconate, diperfluorocyclohexylfumarate;
Halogenated olefins such as vinylidene chloride, vinylidene fluoride, and chlorotrifluoroethylene;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, trimethylpropantri (meth) acrylate, pentaerythritol Polyfunctional monomers such as tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, allyl methacrylate, triallyl cyanurate, diallyl maleate, and polypropylene glycol diallyl ether.

In the macromonomer (a), the structural unit derived from the (meth) acrylic monomer preferably occupies 50% by mass or more of the total mass (100% by mass) of the structural units constituting the macromonomer (a). , 70% by mass or more is more preferable. The upper limit is not particularly limited and may be 100% by mass.
As the structural unit derived from the (meth) acrylic monomer, a structural unit in which R ¹ in the formula (AA) is a hydrogen atom or a methyl group and R ² is COOR ⁵ is preferable.

As the macromonomer (a), a macromonomer in which a radically polymerizable group is introduced at the end of a main chain containing two or more structural units (AA) is preferable.
Those having the structure of the following formula (a2) are preferable.
_{In addition, "..." connecting CH 2} = C (COOR) -CH ₂ and Z in the formula (a2) indicates a main chain portion including two or more structural units (AA).

(In the formula, R is the same as R described above, and Z is a terminal group.)

As R in the formula (a2), include those the same as ^{R 5} in the formula (AA), preferable embodiments thereof are also the same.

Z is the terminal group of the macromonomer (a).
Examples of Z include a hydrogen atom, a group derived from a radical polymerization initiator, a radically polymerizable group, and the like, as in the case of a known terminal group of a polymer obtained by radical polymerization.

As the macromonomer (a), those represented by the following formula (1) are particularly preferable.

(In the formula, R is the same as R described above, a plurality of Rs may be the same or different, X is a hydrogen atom or a methyl group, a plurality of Xs may be the same or different, and Z is. It is a terminal group, and n is a natural number of 2 to 10,000.)

The R in the formula (1) is the same as the R ⁵ in the formula (AA). The Z in the formula (1) is the same as the Z in the formula (a2).

When the structural unit derived from the macromonomer (a) is contained in the hydrophobic part of the amphoteric polymer, R in the formula (1) is an alkyl group, an alicyclic group, an aryl group, from the viewpoint of hydrophobicity. It is preferably a heteroaryl group or a non-aromatic heterocyclic group, more preferably an alkyl group or an alicyclic group, and particularly preferably an alkyl group.
When the structural unit derived from the macromonomer (a) is contained in the hydrophilic portion of the amphipathic polymer, R in the formula (1) is preferably a hydrogen atom from the viewpoint of hydrophilicity.

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

The ratio of the structural unit (AA) to the total (100% by mass) of all the structural units constituting the macromonomer (a) is preferably 40% by mass or more, more preferably 50% by mass or more from the viewpoint of coating film performance. , 100% by mass is particularly preferable.

When the structural unit derived from the macromonomer (a) is contained in the hydrophobic part of the amphipathic polymer, the structural unit (AA) constituting the macromonomer (a) is of the formula (AA) from the viewpoint of hydrophobicity. A structural unit in which R ^{3 to} R ⁷ are an alkyl group, an alicyclic group, an aryl group, a heteroaryl group or a non-aromatic heterocyclic group (hereinafter, also referred to as “constituent unit (AA1)”). It is preferable to include it. As the structural unit (AA1), those in which R ^{3 to} R ⁷ in the formula (AA) are alkyl groups or alicyclic groups are preferable, and those in which R ^{3 to} R ⁷ are alkyl groups are more preferable.
The ratio of the structural unit (AA1) to the total (100% by mass) of all the structural units constituting the macromonomer (a) forming the hydrophobic portion is preferably 70% by mass or more, more preferably 90% by mass or more. 100% by mass is particularly preferable.

When the structural unit derived from the macromonomer (a) is contained in the hydrophilic part of the amphipathic polymer, the structural unit (AA) constituting the macromonomer (a) is of the formula (AA) from the viewpoint of hydrophilicity. It is preferable to include a structural unit in which R ^{3 to} R ⁷ are hydrogen atoms (hereinafter, also referred to as “constituent unit (AA2)”). In particular, those in which R ² is a carboxy group are preferable.
The ratio of the structural unit (AA2) to the total (100% by mass) of all the structural units constituting the macromonomer (a) forming the hydrophilic portion is preferably 70% by mass or more, more preferably 90% by mass or more. 100% by mass is particularly preferable.

[Monomer (b)]
The monomer (b) is a monomer other than the macromonomer (a). The monomer (b) preferably has a radical polymerization group. Examples of the monomer (b) include the following.

Substituted or unsubstituted alkyl (meth) acrylates [eg, methyl (meth) acrylates, ethyl (meth) acrylates, n-propyl (meth) acrylates, i-propyl (meth) acrylates, n-butyl (meth) acrylates, i -Butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 1-methyl-2-methoxyethyl ( Meta) acrylate, 3-methoxybutyl (meth) acrylate, 3-methyl-3-methoxybutyl (meth) acrylate], substituted or unsubstituted aralkyl (meth) acrylate [eg, benzyl (meth) acrylate, m-methoxyphenyl] Ethyl (meth) acrylate, p-methoxyphenyl ethyl (meth) acrylate], substituted or unsubstituted aryl (meth) acrylate [eg, phenyl (meth) acrylate, m-methoxyphenyl (meth) acrylate, p-methoxyphenyl (eg) Meta) acrylate, o-methoxyphenyl ethyl (meth) acrylate], alicyclic (meth) acrylate [eg, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate], trifluoroethyl (meth) acrylate, perfluorooctyl ( Hydrophobic group-containing (meth) acrylates such as meta) acrylates and perfluorocyclohexyl (meth) acrylates;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate , Phenoxyethyl (meth) acrylate, 2- (2-ethylhexaoxy) ethyl (meth) acrylate and other oxyethylene group-containing (meth) acrylates;
Hydroxy group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerol (meth) acrylate;
Terminal alkoxyallylated polyether compounds such as methoxypolyethylene glycol allyl ether, methoxypolyethylene glycol allyl ether, butoxypolyethylene glycol allyl ether, butoxypolyethylene glycol allyl ether, methoxypolyethylene glycol-polypropylene glycol allyl ether, butoxypolyethylene glycol-polypropylene glycol allyl ether ;
Epoxy group-containing vinyl compounds such as glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, and 3,4-epoxybutyl (meth) acrylate;
Primary or secondary amino group-containing vinyl compounds such as butylaminoethyl (meth) acrylate, (meth) acrylamide, hydroxyethyl acrylamide;
Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, dimethyl Tertiary amino group-containing vinyl compounds such as aminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide;
Heterocyclic basic vinyl compounds such as vinylpyrrolidone, vinylpyridine and vinylcarbazole;
Trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tri-n-propylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, tri-n-amylsilyl (meth) acrylate, tri-n-hexylsilyl (Meta) acrylate, tri-n-octylsilyl (meth) acrylate, tri-n-dodecylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, tri-p-methylphenylsilyl (meth) acrylate, tribenzylsilyl (Meta) acrylate, triisopropylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tri-s-butylsilyl (meth) acrylate, tri-2-methylisopropylsilyl (meth) acrylate, tri-t-butylsilyl (meth) acrylate ) Acrylic, ethyldimethylsilyl (meth) acrylate, n-butyldimethylsilyl (meth) acrylate, diisopropyl-n-butylsilyl (meth) acrylate, n-octyldi-n-butylsilyl (meth) acrylate, diisopropylstearylsilyl (meth) acrylate , Dicyclohexylphenylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, lauryldiphenylsilyl (meth) acrylate, triisopropylsilylmethylmalate, triisopropylsilylamylmalate, tri-n-butylsilyl-n-butylmalate , T-Butyldiphenylsilylmethylmalate, t-butyldiphenylsilyl-n-butylmalate, triisopropylsilylmethylfumarate, triisopropylsilylamylfumarate, tri-n-butylsilyl-n-butylfumarate, t-butyldiphenyl Organosilyl group-containing vinyl compounds such as silylmethyl fumarate and t-butyldiphenylsilyl-n-butyl fumarate;
Acid anhydride group-containing vinyl compounds such as maleic anhydride and itaconic anhydride;
(Meta) acrylic acid, crotonic acid, vinyl benzoic acid, fumaric acid, itaconic acid, maleic acid, citraconic acid, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monomethyl itaconic acid, monoethyl itaconic acid, Monobutyl itaconic acid, monooctyl itaconic acid, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monooctyl fumarate, monoethyl citraconate, monohydroxyethyl tetrahydrophthalate (meth) acrylate, monohydroxypropyl tetrahydrophthalate (meth) Acrylate, monohydroxybutyl (meth) tetrahydrophthalate, monohydroxyethyl phthalate (meth) acrylate, monohydroxypropyl (meth) phthalate, monohydroxyethyl succinate (meth) acrylate, monohydroxypropyl succinate (meth) ) A carboxy group-containing ethylenically unsaturated compound such as acrylate, monohydroxyethyl (meth) acrylate of maleate, and monohydroxypropyl (meth) acrylate of maleate;
Unsaturated dicarboxylic acid diesters such as dimethylmalate, dibutylmalate, dimethylfumarate, dibutylfumarate, dibutylitaconate, diperfluorocyclohexylfumarate;
Cyano group-containing vinyl compounds such as acrylonitrile and methacrylonitonyl;
Vinyl ether compounds such as alkyl vinyl ethers [eg, ethyl vinyl ethers, propyl vinyl ethers, butyl vinyl ethers, hexyl vinyl ethers, 2-ethylhexyl vinyl ethers, etc.], cycloalkyl vinyl ethers [eg, cyclohexyl vinyl ethers, etc.];
Vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene;
Halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, trimethylpropantri (meth) acrylate, pentaerythritol Polyfunctional compounds such as tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, allyl methacrylate, triallyl cyanurate, diallyl maleate, and polypropylene glycol diallyl ether.
These can be used by appropriately selecting one kind or two or more kinds as needed.

As the monomer (b), a (meth) acrylic monomer is preferable in terms of copolymerizability with the macromonomer (a). As the (meth) acrylic monomer, at least one selected from the group consisting of (meth) acrylic acid, (meth) acrylate, and substituted or unsubstituted (meth) acrylamide is preferable.

When the structural unit derived from the monomer (b) is contained in the hydrophilic part of the amphipathic polymer and the monomer (b) is a (meth) acrylate, the (meth) acrylate has the following formula from the viewpoint of hydrophilicity. The compound represented by (b-1) is preferable.
CH ₂ = CX-C (= O) -O- (R ²² O) _m R ²¹ (b-1)
(In the formula, X is a hydrogen atom or a methyl group,
R ²¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group.
R ²² is an alkylene group having 2 to 10 carbon atoms.
m is an integer of 1 to 15. )

The alkyl group having 1 to 10 carbon atoms in R ²¹ may be branched or linear, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a t-butyl group. , I-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.
Examples of the aryl group include an aryl group having 6 to 18 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group.
As R ²¹ , a hydrogen atom or a methyl group is preferable, and a hydrogen atom is particularly preferable, from the viewpoint of hydrophilicity. That is, it is particularly preferable that the terminal is a hydroxy group.
As R ²² , an ethylene group is preferable from the viewpoint of hydrophilicity.
For m, an integer of 1 to 10 is preferable, an integer of 1 to 5 is more preferable, an integer of 1 to 3 is further preferable, and 1 or 2 is particularly preferable.

When the structural unit derived from the monomer (b) is contained in the hydrophobic part of the amphipathic polymer and the monomer (b) is a (meth) acrylate, the (meth) acrylate is described above from the viewpoint of hydrophobicity. Hydrophobic group-containing (meth) acrylates are preferred. Of these, the compound represented by the following formula (b-2) is preferable.
CH ₂ = CX-C (= O) -OR ²³ (b-2)
(In the formula, X is a hydrogen atom or a methyl group,
R ²³ is an alkyl group, an alicyclic group or an aryl group. )
Examples of the alkyl group, alicyclic group, and aryl group in ^{R 23} include those similar to the alkyl group, alicyclic group, and aryl group in ^{R 5 in the above formula (AA), and the preferred embodiments are also the same.} be.

As the substituted or unsubstituted (meth) acrylamide, a compound represented by the following formula (b-3) is preferable.
CH ₂ = CX-C (= O) -NR ²⁴ R ²⁵ (b-3)
(In the formula, X is a hydrogen atom or a methyl group,
R ²⁴ and R ²⁵ are independently hydrogen atoms, alkyl groups, hydroxyalkyl groups, or -R ^26- NR ²⁷ R ²⁸ . R ²⁶ is an alkylene group, and R ²⁷ and R ²⁸ are independent hydrogen atoms or alkyl groups, respectively. )

Examples ^{of the alkyl group in R 24} , R ²⁵ , R ²⁷ and R ²⁸ are the same as those in ^{R 6} and R ⁷ in the above formula (AA), respectively. It is preferable that R ²⁴ , R ²⁵ , R ²⁷ and R ²⁸ are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms.
As ^{the alkylene group of R 26,} an alkylene group having 2 to 4 carbon atoms is preferable.
Specific examples of −R ²⁶ −NR ²⁷ R ²⁸ include dimethylaminoethyl group, diethylaminoethyl group, butylaminoethyl group, dibutylaminoethyl group, dimethylaminopropyl group, diethylaminopropyl group, dimethylaminobutyl group and the like. ..

[Preferable Aspects of Amphiphilic Polymer (I)]
Preferred embodiments of the amphipathic polymer include the following amphipathic polymer (I).
Amphiphile polymer (I): a hydrophobic portion containing a structural unit derived from the macromonomer (a), a hydrophilic portion containing a structural unit derived from a (meth) acrylic monomer other than the macromonomer (a), and the like. Amphiphilic polymer containing.

As the macromonomer (a) forming the hydrophobic portion of the amphipathic polymer (I), the structural unit derived from the macromonomer (a) is the hydrophobicity of the amphipathic polymer in the description of the macromonomer (a). The same as the macromonomer (a) mentioned as preferable when it is contained in the part is preferable.

The (meth) acrylic monomer other than the macromonomer (a) forming the hydrophilic portion of the amphoteric polymer (I) can be appropriately selected from, for example, the above-mentioned monomer (b), and the (meth) acrylic acid. , (Meta) acrylates, particularly at least one selected from the group consisting of (meth) acrylates having a hydroxy group and substituted or unsubstituted (meth) acrylamides are preferred.
The hydrophilic part of the amphipathic polymer (I) is hydrophilic such as a hydroxy group, a carboxy group,-(R ²² O) _m R ²¹ , -NR ²⁴ R ^25, etc. as a constituent unit derived from the (meth) acrylic monomer. It preferably contains a structural unit derived from a (meth) acrylic monomer having a group. -(R ²² O) _m R ^{21 and -NR 24} R ²⁵ are the same as- (R ²² O) _m R ^{21 in} the above formula (b-1) and -NR ²⁴ R ²⁵ in the above formula (b-3), respectively. The same is true.
Examples of the (meth) acrylic monomer having a hydrophilic group include (meth) acrylic acid, a (meth) acrylate having a hydroxy group, a compound represented by the formula (b-1), and the formula (b-3). At least one selected from the group consisting of the represented compounds is preferred.
The content of the structural unit derived from the (meth) acrylic monomer having a hydrophilic group is preferably 40% by mass or more, more preferably 70% by mass or more, based on the total of all the structural units constituting the hydrophilic part. It may be 100% by mass.

The hydrophilic portion of the amphipathic polymer (I) may further contain a structural unit derived from a (meth) acrylic monomer having no hydrophilic group, as long as the hydrophilicity of the hydrophilic portion is not impaired. Examples of the (meth) acrylic monomer having no hydrophilic group include a compound represented by the above formula (b-2).
The hydrophilic portion of the amphipathic polymer (I) may further contain structural units derived from other monomers other than the macromonomer (a) and the (meth) acrylic monomer, as long as the coating film performance is not impaired. As the other monomer, for example, it can be appropriately selected from the above-mentioned monomer (b).

The content of the hydrophobic portion with respect to the amphipathic polymer (I) is preferably 5 to 90% by mass, more preferably 20 to 70% by mass, and 30 to 60% by mass with respect to the total mass of the amphipathic polymer (I). % Is more preferable. When the content of the hydrophobic portion is within the above range, the antifouling property of the formed coating film is more excellent.
The total mass of the amphipathic polymer is equal to the sum of the hydrophobic part and the hydrophilic part.

[Preferable embodiment of amphipathic polymer (II)]
Another preferred embodiment of the amphipathic polymer is the following amphipathic polymer (II).
Amphiphile polymer (II): Parents containing a hydrophilic part containing a structural unit derived from a macromonomer (a) and a hydrophobic part containing a structural unit derived from a (meth) acrylic monomer other than the macromonomer. Medial polymer.

As the macromonomer (a) forming the hydrophilic part of the amphipathic polymer (II), the structural unit derived from the macromonomer (a) is the hydrophilicity of the amphipathic polymer in the description of the macromonomer (a). The same as the macromonomer (a) mentioned as preferable when it is contained in the part is preferable.

The (meth) acrylic monomer other than the macromonomer (a) forming the hydrophobic portion of the amphipathic polymer (II) can be appropriately selected from the above-mentioned monomers (b), and (meth) acrylate is preferable. ..
The hydrophobic part does not have a hydrophilic group such ^{as the above-mentioned hydroxy group, carboxy group,-(R 22} O) _m R ²¹ , -NR ²⁴ R ^25, etc. as a constituent unit derived from the (meth) acrylic monomer (meth). ) It is preferable to contain a structural unit derived from an acrylic monomer.
As the (meth) acrylic monomer having no hydrophilic group, the compound represented by the above formula (b-2) is preferable.
The content of the structural unit derived from the (meth) acrylic monomer having no hydrophilic group is preferably 70% by mass or more, more preferably 90% by mass or more, based on the total of all the structural units constituting the hydrophobic portion. , 100% by mass.

The hydrophobic portion of the amphipathic polymer (II) may further contain a structural unit derived from the (meth) acrylic monomer having a hydrophilic group as long as the hydrophobicity of the hydrophobic portion is not impaired.
The hydrophobic portion of the amphipathic polymer (II) may further contain a structural unit derived from the monomer (b) other than the (meth) acrylic monomer, as long as the coating film performance is not impaired. As the other monomer, for example, it can be appropriately selected from the above-mentioned monomer (b).
The content of the hydrophilic part in the amphipathic polymer (II) is preferably 10 to 95% by mass, more preferably 30 to 80% by mass, and 40 to 70% by mass with respect to the total mass of the amphipathic polymer (II). % Is more preferable. When the content of the hydrophilic portion is within the above range, the antifouling property of the formed coating film is more excellent.

<Characteristics of amphipathic polymer>
The weight average molecular weight (Mw) of the amphipathic polymer is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000. When the weight average molecular weight of the amphipathic polymer is at least the lower limit of the above range, the coating film performance is excellent. When the weight average molecular weight is not more than the upper limit of the above range, the coatability is excellent.
The weight average molecular weight of the amphoteric polymer is measured by gel permeation chromatography (GPC) using polystyrene as a reference resin.

<Manufacturing method of amphipathic polymer>
The amphipathic polymer of the present embodiment can be produced, for example, by polymerizing the following monomer mixture.

(1) Monomer mixture The monomer mixture contains a macromonomer (a) and a monomer (b).
The macromonomer (a) is preferably a macromonomer having a radically polymerizable group.
When producing the amphipathic polymer (I) or (II) described above, at least a (meth) acrylic monomer is used as the monomer (b), and if necessary, a monomer other than the (meth) acrylic monomer is used. (B) may be further used.

The content of the macromonomer (a) in the monomer mixture is preferably 5 to 95% by mass with respect to the total mass of the monomer mixture (total mass of all monomers). That is, the amphipathic polymer is preferably obtained by polymerizing a monomer mixture containing the macromonomer (a) in an amount of 5 to 95% by mass (charged amount) with respect to the total mass of all the monomers.
When the amphoteric polymer is the amphoteric polymer (I), the content of the macromonomer (a) is more preferably 5 to 90% by mass with respect to the total mass of the monomer mixture (total mass of all monomers). 20 to 70% by mass is more preferable, and 30 to 60% by mass is particularly preferable.
When the amphoteric polymer is the amphoteric polymer (II), the content of the macromonomer (a) is more preferably 10 to 95% by mass with respect to the total mass of the monomer mixture (total mass of all monomers). 30 to 80% by mass is more preferable, and 40 to 70% by mass is particularly preferable.
When the content of the macromonomer (a) is within the above range, the antifouling property of the coating film formed by using the obtained amphipathic polymer is more excellent.
The total of the macromonomer (a) and the monomer (b) is 100% by mass.

When the amphipathic polymer is an amphipathic polymer (I), 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, more preferably 70% by mass or more, and more preferably 100% by mass, based on the total mass of the monomers other than the macromonomer (a). It may be% by mass.
When the amphipathic polymer is an amphipathic polymer (II), the monomer mixture preferably contains the (meth) acrylic monomer having no hydrophilic group. The content of the (meth) acrylic monomer having no hydrophilic group in the monomer mixture is preferably 70% by mass or more, more preferably 90% by mass or more, based on the total mass of the monomers other than the macromonomer (a). It may be 100% by mass.

As the macromonomer (a) and the monomer (b), those produced by a known method may be used, or commercially available ones may be used.
Examples of the method for producing the macromonomer (a) include the following methods (α1), (α2), (α3), (α4) and the like.
(Α1): A method of polymerizing a monomer component containing a monomer forming a structural unit (AA) using a cobalt chain transfer agent.
(Α2): A method of polymerizing a monomer component containing a monomer forming a structural unit (AA) using an α-substituted unsaturated compound such as α-methylstyrene dimer as a chain transfer agent.
(Α3): A method in which a monomer component containing a monomer forming a structural unit (AA) is polymerized, and a radical polymerizable group is chemically bonded to the obtained polymer.
(Α4): A method of polymerizing a monomer component containing a monomer forming a structural unit (AA) and thermally decomposing the obtained polymer.
The monomer component may further contain monomers forming other building blocks, if desired.

In the methods (α1) to (α4), examples of the method for polymerizing the monomer component include a massive 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. The aqueous dispersion polymerization method is preferable, and the suspension polymerization method is particularly preferable, because the recovery step is simple. When the macromonomer (a) is produced by the suspension polymerization method, it is easy to handle.
The polymerization may be carried out by a known method using a known radical polymerization initiator. For example, a method of reacting the above-mentioned monomer component in the presence of a radical initiator at a reaction temperature of 60 to 120 ° C. for 4 to 14 hours can be mentioned. During polymerization, methods (α1) and (α2) use predetermined chain transfer agents. In methods (α3) and (α4), chain transfer agents may be used, if desired.

Known radical polymerization initiators can be used, for example, 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (2-). Azo compounds such as methylbutyronitrile); benzoyl peroxide, cumenehydroperoxide, lauryl peroxide, di-t-butyl peroxide, t-butylperoxy-2-ethylhexanoate, 1,1,3,3 -Organic peroxides such as tetramethylbutylperoxy-2-ethylhexanoate; etc. Only one of these polymerization initiators may be used alone, or two or more thereof may be used in combination.

In the method (α3), as a method of chemically bonding a radically polymerizable group to the polymer, for example, the halogen group of the polymer having a halogen group is replaced with a compound having a radically polymerizable carbon-carbon double bond. A method of reacting a vinyl-based monomer having an acid group with a vinyl-based polymer having an epoxy group, a method of reacting a vinyl-based polymer having an epoxy group with a vinyl-based monomer having an acid group, and a hydroxyl group. Examples thereof include a method of reacting a vinyl-based polymer having a diisocyanate compound with a diisocyanate compound to obtain a vinyl-based polymer having an isocyanate group, and reacting the vinyl-based polymer with a vinyl-based monomer having a hydroxyl group. It doesn't matter.
As a method for producing the macromonomer (a), a method using a cobalt chain transfer agent (α1) is preferable in that a catalyst having a small number of production steps and a high chain transfer constant is used. In particular, in the method (α1), it is preferable to carry out the polymerization of the monomer component by the suspension polymerization method.
The macromonomer (a) produced using a cobalt chain transfer agent has the structure of the above formula (a2).

(2) Polymerization of Monomer Mixture As a polymerization method of the monomer mixture, for example, a known polymerization method such as a solution polymerization method, a suspension polymerization method, a massive polymerization method, and an emulsion polymerization method can be applied. The solution polymerization method is preferable in terms of the productivity of the amphipathic polymer and the coating film performance of the coating film formed by using the obtained amphipathic polymer.
The polymerization may be carried out by a known method using a known radical polymerization initiator. For example, a method of reacting the above-mentioned monomer mixture in the presence of a radical initiator at a reaction temperature of 60 to 120 ° C. for 4 to 14 hours can be mentioned. At the time of polymerization, a chain transfer agent may be used if necessary.

Known radical polymerization initiators can be used, for example, 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (2-). Azo compounds such as methylbutyronitrile); benzoyl peroxide, cumenehydroperoxide, lauryl peroxide, di-t-butyl peroxide, t-butyl peroxy-2-ethylhexanoate, 1,1,3,3-tetra Organic peroxides such as methylbutylperoxy-2-ethylhexanoate; and the like.
As the chain transfer agent, known ones can be used, and examples thereof include mercaptans such as n-dodecyl mercaptan, thioglycolic acid esters such as octyl thioglycolate, α-methylstyrene dimer, and tarpinolene.
As the solvent used in the solution polymerization, general organic solvents such as toluene, xylene, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, n-butyl acetate and ethyl 3-ethoxypropionate can be used.

<Resin composition for antifouling paint>
The resin composition for antifouling paint contains one or more amphipathic polymers. Further, it is preferable to contain a solvent. When a solvent is contained, the coating suitability, the water resistance of the formed coating film, the film forming property, and the like are more excellent.
The resin composition for an antifouling paint is typically a non-eluting type resin composition in which the coating film to be formed does not dissolve in an aqueous liquid such as seawater.

The content of the amphipathic polymer in the resin composition is not particularly limited, but is preferably 5 to 85% by mass, more preferably 10 to 80% by mass, and 30 to 75% by mass with respect to the total mass of the resin composition. Is more preferable, and 55 to 75% by mass is particularly preferable. When the content of the amphipathic polymer is not more than the above upper limit value, a coating film having excellent water resistance, coating film hardness and the like can be obtained. When the content of the amphipathic polymer is at least the above lower limit value, a resin composition having a low VOC content can be easily obtained.

[solvent]
The solvent is not particularly limited as long as it can dissolve the amphipathic polymer.
For example, monovalent alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; polyhydric alcohols such as ethylene glycol and 1,2-propylene glycol; ketones such as acetone, methyl ethyl ketone, acetyl acetone and butyl acetate; methyl ethyl ether and dioxane. Ethers such as: ethylene glycol monomethyl ether (also known as methyl cellosolve), ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol. Glycol ethers such as dimethyl ether and dipropylene glycol monopropyl ether; glycol acetates such as ethylene glycol monoacetate, ethylene glycol diacetate and ethylene glycol monomethyl ether acetate; aliphatic hydrocarbons such as n-pentane and n-hexane. Aromatic hydrocarbons such as toluene, xylene, solvent naphtha; and the like. Any one of these can be used alone or in combination of two or more.

The content of the solvent in the resin composition is preferably 15 to 99% by mass, more preferably 20 to 90% by mass, still more preferably 25 to 75% by mass, based on the total mass of the resin composition. When the content of the solvent is at least the above lower limit value, a coating film having excellent water resistance can be obtained. When the solvent content is not more than the above upper limit value, a resin composition having a low VOC content can be easily obtained.

The resin composition may further contain other components (amphipathic polymer, components unavoidable in the production of the amphipathic polymer, and components other than the solvent).
The content of the other components is preferably 200 parts by mass or less, and may be 0 parts by mass with respect to 100 parts by mass of the amphipathic polymer.

[Anti-fouling agent]
The resin composition may contain an antifouling agent as another component.
Examples of the antifouling agent include an inorganic antifouling agent, an organic antifouling agent, and the like, and one type or two or more types can be appropriately selected and used depending on the required performance.
Examples of the antifouling agent include copper-based antifouling agents such as cuprous oxide, thiocyan copper, and copper powder, compounds of other metals (lead, zinc, nickel, etc.), amine derivatives such as diphenylamine, nitrile compounds, and benzothiazole. Examples thereof include based compounds, maleimide based compounds, and pyridine based compounds. These can be used alone or in combination of two or more.

More specifically, as an antifouling agent, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, Manganese ethylenebisdithiocarbamate, zinc dimethyldithio Carbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, zincethylenebisdithiocarbamate , Rodin copper, 4,5-dichloro-2-noctyl-3 (2H) isothiazolone, N- (fluorodichloromethylthio) phthalimide, N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide , 2-Pyridoxythiol-1-oxide zinc salt, tetramethylthiuram disulfide, Cu-10% Ni solid solution alloy, 2,4,6-trichlorophenylmaleimide 2,3,5,6-tetrachloro-4- ( Methylsulfonyl) pyridine, 3-iodo-2-propinylbutylcarbamate, diiodomethylparatrisulfone, bisdimethyldithiocarbamoylzincethylenebisdithiocarbamate, phenyl (bispyridyl) bismasdichloride, 2- (4-thiazolyl) -benzoimidazole , Medetomidin, pyridine-triphenylboran and the like.

Among the above, the antifouling agent includes cuprous oxide, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3 carbonitrile (hereinafter, "antifouling agent (1)). It is preferable that at least one selected from the group consisting of (also referred to as) and medetomidine is contained.
When the cuprous oxide and the antifouling agent (1) are combined, the blending ratio (mass ratio) is preferably cuprous oxide / antifouling agent (1) = 80/20 to 99/1, and 90/10 to 99 /. 1 is more preferable.
One or both of the cuprous oxide and the antifouling agent (1) may be combined with other antifouling agents other than these.

When the resin composition contains an antifouling agent, the content of the antifouling agent in the resin composition is not particularly limited, but is preferably 10 to 200 parts by mass, preferably 50 to 200 parts by mass, based on 100 parts by mass of the amphipathic polymer. More preferably, 150 parts by mass. When the content of the antifouling agent is at least the lower limit of the above range, the antifouling effect of the formed coating film is more excellent. When the content of the antifouling agent is not more than the upper limit of the above range, the physical characteristics of the coating film are excellent.

[Other resins]
The resin composition may contain a resin other than the amphipathic polymer as another component.
As the other resin, a thermoplastic resin (hereinafter, also simply referred to as a thermoplastic resin) is preferable. When the resin composition contains a thermoplastic resin, the physical characteristics of the coating film such as crack resistance and water resistance are improved.
Examples of thermoplastic resins include chlorinated paraffins; chlorinated polyolefins such as rubber chloride, chlorinated polyethylene, and chlorinated polypropylene; polyvinyl ethers; polypropylene sebacates; partially hydrogenated terphenyls; polyvinyl acetates; (meth) acrylic acids. Methyl-based copolymer, (meth) ethyl acrylate-based copolymer, (meth) propyl acrylate-based copolymer, (meth) butyl acrylate-based copolymer, (meth) cyclohexyl acrylate-based copolymer, etc. Poly (meth) acrylic acid alkyl ester; polyether polyol; alkyd resin; polyester resin; vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl propionate copolymer, vinyl chloride-isobutyl vinyl ether copolymer, vinyl chloride -Vinyl chloride resins such as isopropyl vinyl ether copolymers and vinyl chloride-ethyl vinyl ether copolymers; silicone oils; waxes; fats and oils other than waxes that are solid at room temperature, fats and oils that are liquid at room temperature such as castor oil, and their purified products; Vaseline; liquid paraffin; rosin, hydrogenated rosin, naphthenic acid, fatty acids and divalent metal salts thereof; and the like. Examples of the wax include animal-derived wax such as beeswax; plant-derived wax; semi-synthetic wax such as amide-based wax; and synthetic wax such as polyethylene oxide-based wax. Only one kind of these thermoplastic resins may be used alone, or two or more kinds thereof may be used in combination.
Chlorinated paraffin is preferable because it functions as a plasticizer and has an effect of improving crack resistance and peel resistance of the coating film.
Organic waxes such as semi-synthetic wax and synthetic wax are preferable, and polyethylene wax and polyethylene oxide are preferable in that they function as a settling inhibitor and an anti-dripping agent and can improve the storage stability and pigment dispersibility of the resin composition. Wax and polyethylene wax are more preferable.

The content of the thermoplastic resin in the resin composition is not particularly limited, but is preferably 0.1 to 50 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the amphipathic polymer. When the content of the thermoplastic resin is at least the lower limit of the above range, the physical properties of the coating film such as crack resistance and water resistance are more excellent, and when it is at least the upper limit of the above range, the flexibility and water absorption are more excellent. Excellent.

The resin composition may contain a silicon compound such as dimethylpolysiloxane or silicone oil, a fluorine-containing compound such as a fluorinated hydrocarbon, or the like for the purpose of imparting lubricity to the surface of the coating film and preventing the adhesion of organisms.

Resin compositions include various pigments, dehydrating agents, defoaming agents, leveling agents, pigment dispersants (for example, anti-settling agents), anti-dripping agents, matting agents, ultraviolet absorbers, antioxidants, heat resistance improvers, etc. Additives such as slip agents, preservatives, plasticizers and viscosity control agents may be included.
Examples of pigments include zinc oxide, talc, silica, barium sulfate, potassium feldspar, aluminum hydroxide, magnesium carbonate, mica, carbon black, petals, titanium oxide, phthalocyanine blue, kaolin, gypsum and the like. In particular, zinc oxide and talc are preferable.
Examples of the dehydrating agent include silicate-based, isocyanate-based, orthoester-based, and inorganic-based dehydrating agents. More specifically, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, orthoboron ester, tetraethyl orthosilicate, anhydrous gypsum, gypsum, synthetic zeolite (molecular sieve) and the like can be mentioned. By incorporating a dehydrating agent in the antifouling coating composition, moisture can be supplemented and storage stability can be improved.

Examples of the sedimentation inhibitor and the dripping inhibitor other than the thermoplastic resin include bentonite-based, fine silica-based, stearate salt, lecithin salt, alkyl sulfonate and the like.

Examples of plasticizers other than thermoplastic resins include phthalate-based plasticizers such as dioctylphthalate, dimethylphthalate, dicyclohexylphthalate, and diisodecylphthalate; aliphatic dibasic acid ester-based plasticizers such as isobutyl adipate and dibutyl sebacate. Glycolester plasticizers such as diethylene glycol dibenzoate and pentaerythritol alkyl ester; Phthalate plasticizers such as tricresyl phosphate (TCP), triaryl phosphate, trichloroethyl phosphate; epoxy soybean oil, octyl epoxy stearate, etc. Epoxy plasticizers; organic tin plasticizers such as dioctyl tin laurylate and dibutyl tin laurylate; trioctyl trimellitic acid, triacetylene and the like. By including a plasticizer in the antifouling coating composition, the crack resistance and peeling resistance of the coating film can be enhanced. Among the above, TCP is preferable as the plasticizer.

The VOC content of the resin composition is preferably 420 g / L or less, more preferably 400 g / L or less, and even more preferably 380 g / L or less.
"VOC" means an organic compound (volatile organic compound) that easily volatilizes at normal temperature and pressure. The VOC content is calculated from the following formula using the specific gravity of the resin composition and the value of the heating residue. The VOC content can be adjusted by the content of the solvent.
VOC content (g / L) = specific gravity of resin composition x 1000 x (100-heat residue) / 100

The specific gravity of the resin composition is calculated by filling a specific gravity cup having a capacity of 100 mL with the resin composition at 25 ° C. and measuring the mass.
The heating residue (solid content) of the resin composition is determined by the following method.
Weigh 0.50 g of the measurement sample (resin composition) on an aluminum dish, add 3 mL of toluene with a dropper, spread it evenly on the bottom of the dish, and perform pre-drying. Pre-drying is a process in which the measurement sample is spread over the entire dish to facilitate the volatilization of the solvent in the main drying. In the pre-drying, the measurement sample and toluene are heated and dissolved in a water bath at 70 to 80 ° C., and evaporated to dryness. After the pre-drying, the main drying is performed for 2 hours in a hot air dryer at 105 ° C. From the mass of the measurement sample before pre-drying (mass before drying) and the mass after main drying (mass after drying), the heating residue (solid content) is calculated by the following formula.
Heating residue (solid content) = mass after drying (g) / mass before drying (g) x 100 (%)

The heating residue (solid content) of the resin composition is preferably 45 to 85% by mass, more preferably 55 to 80% by mass, and even more preferably 60 to 75% by mass. When the heating residue of the resin composition is equal to or higher than the lower limit of the above range, the VOC content is sufficiently low. When the heating residue is not more than the upper limit of the above range, the viscosity of the resin composition can be easily lowered.

The viscosity of the resin composition measured by a B-type viscometer at 25 ° C. is preferably less than 5,000 mPa · s, more preferably less than 4,000 mPa · s, further preferably less than 3,000 mPa · s, 2, Less than 000 mPa · s is particularly preferable. When the viscosity of the resin composition is not more than the above upper limit value, it is easy to paint.
The lower limit of the viscosity of the resin composition is not particularly limited, but 1,000 mPa · s or more is preferable from the viewpoint of suppressing paint sagging during painting.
The viscosity of the resin composition can be adjusted by the amount of solvent added or the like.

<Manufacturing method of resin composition for antifouling paint>
The method for producing the resin composition is not particularly limited. The amphipathic polymer and any other component may be mixed to form a solid resin composition, or the amphipathic polymer, the solvent and any other component may be mixed to form a liquid resin composition.
The liquid resin composition can be used as it is or diluted with a solvent to produce an antifouling coating film. The solid resin composition can be mixed with a solvent and used for producing an antifouling coating film.

<Coating film>
The coating film made of the resin composition (hereinafter, also simply referred to as a coating film) has an average surface roughness (Q) of 1 nm <(Q) <10 nm in water on the outer surface. The average surface roughness (Q) is a value measured by the method described in Examples, and represents the degree of unevenness formed on the outer surface in a state where the coating film is immersed in water and sufficiently swollen.
The lower limit of the average surface roughness (Q) is preferably 2 nm or more, more preferably 3 nm or more, further preferably 3.5 nm or more, and particularly preferably 4 nm or more. The upper limit of the average surface roughness (Q) is preferably 9.9 nm or less, more preferably 9.5 nm or less.
When the average surface roughness (Q) is within the above range, the antifouling property is excellent. For example, it has excellent antifouling properties against adherent larvae (Cyprus larvae).

The average surface roughness (Q) of the coating film in water can be adjusted by the phase separation structure. For example, in a composition in which the water absorption rate in the vicinity of the surface layer is non-uniform, the average surface roughness (Q) tends to be large, and in a composition in which the water absorption rate in the vicinity of the surface layer is similar, the average surface roughness (Q) is small. Tend.
For example, when the amphipathic polymer contains a hydrophobic part containing a structural unit derived from the macromonomer (a) and a hydrophilic part containing a structural unit derived from the monomer (b), the hydrophilic part is hydrophilic. If the monomer (b) is selected so that is higher, the average surface roughness (Q) is increased, and if the monomer (b) is selected so that the hydrophilicity of the hydrophilic portion is lower, the average surface roughness (Q) is increased. Tends to be smaller.

The reason why unevenness is formed on the outer surface when the coating film is immersed in water is considered as follows.
In the amphipathic polymer, the hydrophobic part and the hydrophilic part are incompatible. Therefore, when forming a coating film containing an amphipathic polymer, the hydrophobic portion and the hydrophilic portion can be phase-separated to obtain a coating film having a micro or nanoheterogeneous structure. Examples of the micro or nanonon-uniform structure include a sea-island structure, a cylinder structure, a lamellar structure, a co-continuous structure, and the like.
The region composed of the hydrophobic portion has a lower affinity with an aqueous liquid such as seawater and a lower water absorption rate than the region in which the hydrophobic portion and the hydrophilic portion exist without phase separation. Further, the region composed of the hydrophilic portion has a higher affinity with an aqueous liquid such as seawater and a higher water absorption rate than the region in which the hydrophobic portion and the hydrophilic portion exist without phase separation. Since the region consisting of the hydrophobic part and the hydrophilic part exists on the surface of the coating film, the water absorption rate becomes non-uniform, and unevenness is formed on the outer surface in a state where the coating film is immersed in water and sufficiently swollen. It is thought that.

The water contact angle of the outer surface of the coating film is preferably 120 to 144 °, more preferably 125 to 142 °, and even more preferably 130 to 140 °. When the underwater contact angle is at least the above lower limit value, the frictional resistance with the aqueous liquid on the outer surface of the coating film is sufficiently small, so that the friction reducing effect by providing the coating film is excellent. If it exceeds the above upper limit value, the frictional resistance with the aqueous liquid becomes large, and there is a possibility that the friction reducing effect by providing the coating film cannot be sufficiently obtained.
The underwater contact angle of the outer surface of the coating film means the contact angle of air that comes into contact with the outer surface of the coating film in a state where the coating film is immersed in water. The underwater contact angle is measured by the method described in the examples.
The water contact angle of the outer surface of the coating film can be adjusted by adjusting the proportion of the hydrophilic portion of the amphipathic polymer and the like. For example, the more hydrophilic parts of an amphipathic polymer, the larger the water contact angle tends to be.

The indentation elastic modulus of the outer surface of the coating film is preferably 15 to 2900 MPa, more preferably 30 to 2800 MPa, still more preferably 35 to 2700 MPa. When the indentation elastic modulus is at least the above lower limit value, the tackiness of the coating film surface is small, so that the handleability is good. When it is not more than the above upper limit value, the shape-following production of the coating film becomes good.
The indentation elastic modulus of the outer surface of the coating film is measured by the method described in Examples described later.
The indentation elastic modulus of the outer surface of the coating film can be adjusted by the glass transition temperature (Tg) of the amphipathic polymer or the like. For example, the higher the glass transition temperature (Tg) of the amphipathic polymer, the higher the indentation modulus tends to be.

The water absorption rate of the coating film is preferably 20% or more, and more preferably 25% or more. When the water absorption rate is at least the above lower limit value, a water layer in which the flow is constrained is easily formed on the surface of the coating film, and the friction reducing effect by providing the coating film is excellent.
The water absorption rate of the coating film is a value obtained by a measuring method based on JIS K 7209: 2000 plastic-water absorption rate.
The water absorption rate of the coating film can be adjusted by adjusting the proportion of the hydrophilic portion of the amphipathic polymer and the like. For example, the more hydrophilic parts of an amphipathic polymer, the higher the water absorption rate tends to be.

The coating film preferably has a micro or nano non-uniform structure, and irregularities corresponding to the micro or nano non-uniform structure are formed on the surface of the coating film.
For example, when the resin composition contains a solvent, the above-mentioned coating film can be formed by using a solvent as the solvent, which is difficult to be compatible with either the hydrophobic portion or the hydrophilic portion and is easily compatible with the other. This is because when the coating film is formed, the parts that are difficult to be compatible with the solvent form an aggregate to fix the structure, and the parts that are easy to be compatible with the solvent protrude in the volatilization direction (upward) of the solvent by solvation. It is considered that the part that is not compatible with the solvent is a concave part and the part that is easily compatible with the solvent is a convex part. The compatibility between the solvent and the hydrophobic part or the hydrophilic part can be judged from the SP value (solubility parameter).

<Manufacturing method of antifouling coating film>
The method for producing a coating film using the resin composition for an antifouling paint is not particularly limited, and a known method can be used. For example, a coating film can be formed by adding a solvent to the resin composition as needed, applying it to the surface of the object to be coated by means such as brush coating, spray coating, roller coating, and dipping coating, and drying it. ..
Drying after application of the resin composition can usually be carried out at room temperature, and heat drying may be carried out if necessary.

The object to be coated is not particularly limited, and examples thereof include ships, fishing nets, harbor facilities, booms, bridges, underwater structures (undersea bases, etc.) and the like.
For example, by coating a resin composition on a part of an offshore structure or a ship that comes into contact with seawater and providing an antifouling coating film, it is possible to suppress corrosion of this part due to seawater and adhesion of marine organisms that cause a decrease in navigation speed. ..
An undercoat film is provided on the surface of the object to be coated, and a coating film of the resin composition may be formed on the undercoat film. The undercoat film can be formed by using, for example, a wash primer, a chlorinated rubber-based or epoxy-based primer, an intermediate coating film, or the like.
The coating amount of the resin composition is set according to the thickness of the coating film to be formed.
The thickness of the coating film is not particularly limited. For the purpose of antifouling and reducing friction with aqueous liquids, it is typically 10 to 400 μm.

The coating film formed by using the resin composition of the present embodiment has an average surface roughness (Q) of the outer surface in water in the above range and is excellent in antifouling property. Therefore, by forming a coating film on the surface of the object to be coated using the resin composition of the present embodiment, it is possible to impart excellent antifouling properties to the surface.
Further, when the underwater contact angle of the coating film is within the above range, the frictional resistance between the surface of the coating film and the aqueous liquid can be reduced. For example, by forming a coating film on a portion that receives frictional resistance from seawater during navigation of a ship, frictional resistance with seawater during navigation is reduced, and fuel consumption and energy saving can be reduced.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these examples. In the following, "part" represents "part by mass".
The evaluation in the examples was performed by the method shown below.

(Average surface roughness in water (Q))
The measurement was performed using a scanning probe microscope SPA-400 (manufactured by Hitachi High-Technologies Corporation, trade name). SI-DF3 (manufactured by Hitachi High-Technologies Corporation, trade name) was used as the cantilever, and the shape image of the outer surface of the coating film in water was observed. The measurement range was 1 μm square, the average surface roughness (Ra) was calculated from the obtained shape image, and the obtained value was defined as “average surface roughness (Q) in water”.

Specifically, the procedure was as follows.
The resin composition to be evaluated was coated on a glass substrate so that the thickness after drying was 200 μm or more, and dried at room temperature to form a coating film. The obtained coating film was immersed in water for 12 hours or more, sufficiently absorbed, and then subjected to shape measurement in water. The measurement conditions were dynamic force mode, and the measurement range was 1 μm square. Arithmetic mean surface roughness (Ra) was calculated for the obtained shape image by a method according to JIS B 0601 (2001).

(Underwater contact angle (contact angle by the captive bubble method))
The resin composition to be evaluated was coated on a slide glass having a size of 76 mm × 26 mm × 1 mm (thickness) so as to have a dry film thickness of 200 μm, and dried at room temperature to form a coating film.
The underwater contact angle of the outer surface of the coating film is measured by using an automatic contact angle meter DM-301 (manufactured by Kyowa Interface Science Co., Ltd., trade name) and using the captive bubble method in which air bubbles are brought into contact with the surface of the coating film in water. went. The larger the contact angle in water, the higher the hydrophilicity of the outer surface of the coating film.

(Indentation modulus)
The resin composition to be evaluated was coated on a slide glass having a size of 76 mm × 26 mm × 1 mm (thickness) so as to have a dry film thickness of 200 μm, and dried at room temperature to form a coating film.
Measurement conditions of Vickers indenter, load 7 mN / 100s, creep 60s, R = 0.4 mN / 100s with a micro hardness tester HM-2000 (manufactured by Fisher Instruments, trade name) (“s” is seconds, “R” Represents the release rate), and the indentation elasticity of the coating film was measured.

(Adhesion rate (evaluation of antifouling property))
The resin composition to be evaluated was spin-coated on an acrylic plate (5 cm × 5 cm × 1 mm (thickness)) so that the thickness after drying was 200 μm or more, and dried at room temperature to form a coating film. .. This coating film was allowed to stand on the bottom surface of a polypropylene container (8 cm × 8 cm × 4.5 cm (height)), and 100 ml of seawater and 100 larvae in the adhesion stage (Cyprus larvae) were added. The number of individuals in which the larvae in the adhesion stage adhered to and transformed into the coating film after 7 days, while the seawater in the container was kept in a state of being moved by horizontal shaking (3 cm round trip 60 times / minute) at room temperature 22 ° C ± 2. Adhesion rate) was counted under a stereomicroscope. The ratio of the number of individuals adhering to or metamorphosing to the coating film with respect to the 100 individuals charged was defined as the adhesion rate (%). The lower the adhesion rate, the better the antifouling property.

<Production Example 1: Production of macromonomer>
900 parts of deionized water, 60 parts of 2-sulfoethyl sodium methacrylate, 10 parts of potassium methacrylate and 12 parts of methyl methacrylate (MMA) are placed in a polymerization apparatus equipped with a stirrer, a cooling tube and a thermometer and stirred. The temperature was raised to 50 ° C. while substituting nitrogen in the polymerization apparatus. 0.08 part of 2,2'-azobis (2-methylpropionamidine) dihydrochloride was added as a polymerization initiator, and the temperature was further raised to 60 ° C. After the temperature was raised, MMA was continuously added dropwise at a rate of 0.24 part / min for 75 minutes using a drip pump. The reaction solution was held 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, which is a transparent aqueous solution.

Next, 145 parts of deionized water, 0.1 part of sodium sulfate and 0.25 part of dispersant 1 (solid content 10% by mass) were placed in a polymerization apparatus equipped with a stirrer, a cooling tube and a thermometer and stirred. Then, a uniform aqueous solution was prepared. Next, 100 parts of MMA, 0.0016 parts of bis [(difluoroboryl) diphenylglioxymate] cobalt (II) as a chain transfer agent, and "Perocta О" (registered trademark) (1,1, 1) as a polymerization initiator. 3,3-Tetramethylbutylperoxy2-ethylhexanoate (manufactured by Nichiyu Co., Ltd.) 0.1 part was added to prepare an aqueous suspension.
Next, the inside of the polymerization apparatus was replaced with nitrogen, the temperature was raised to 80 ° C. and reacted for 4 hours, and in order to further increase the polymerization rate, the temperature was raised to 90 ° C. and held for 2 hours. Then, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension containing a macromonomer. The aqueous suspension was filtered, the filtrate was washed with deionized water, dehydrated and dried at 40 ° C. for 16 hours to give macromonomer (MM1). The number average molecular weight of this macromonomer (MM1) was 7200.

<Example 1>
In a flask with a cooling tube, 50 parts of macromonomer (MM1), 50 parts of 2-hydroxyethyl acrylate (HEA) as monomer (b) (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and methyl cellosolve as solvent (Kanto Chemical Co., Ltd. ), Reagent special grade) A monomer composition containing 250 parts was added, and the inside was replaced with nitrogen by nitrogen bubbling. Next, while the monomer composition was heated and the internal temperature was maintained at 70 ° C., 2,2'-azobisisobutyronitrile (AIBN) as a radical polymerization initiator, 0.4 part (Wako Pure Chemical Industries, Ltd.) Co., Ltd., Wako Special Grade) was added to the monomer composition and then held for 4 hours, then the temperature was raised to 80 ° C. and held for 1 hour to complete the polymerization. After that, the polymerization reaction product was cooled to room temperature and reprecipitated with a large amount of diisopropyl ether (Junsei Chemical Co., Ltd.). The polymer precipitated by reprecipitation was recovered and vacuum dried overnight at 50 ° C. and 50 mmHg (6.67 kPa) or less to obtain an amphipathic polymer.

Next, 25 parts of the amphipathic polymer and 75 parts of methyl cellosolve were mixed in a glass container, and the mixture was stirred with a stirrer for 2 hours at room temperature to obtain a resin composition containing the amphipathic polymer and the solvent.
The average surface roughness (Q), contact angle in water, indentation elastic modulus, and adhesion rate in water were measured for the obtained resin composition by the above method. These results are shown in Table 1 (the same applies hereinafter).
FIG. 1 shows a scanning probe microscope image of the coating film taken in the measurement of the average surface roughness (Q).

<Examples 2 to 4, Comparative Examples 1 to 2>
In Example 1, a resin composition was produced in the same manner as in Example 1 except that the monomer (b) was changed as shown in Table 1.
The monomers shown in Table 1 are as follows.
HEMA: 2-hydroxyethyl methacrylate, manufactured by Tokyo Chemical Industry Co., Ltd.
HEAA: 2-Hydroxyethyl acrylamide, manufactured by KJ Chemicals Co., Ltd.
Blemmer 350: Blemmer PE350 (trade name), manufactured by NOF CORPORATION, polyethylene glycol-monomethacrylate, ethylene glycol having an average of 8 chains.
AcSi: 3- (trimethoxysilyl) propyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd.
MMA: Methyl methacrylate, manufactured by Mitsubishi Rayon Co., Ltd.

Examples 1 and 2 are examples in which a (meth) acrylate having a hydroxy group is used as the monomer (b).
Example 3 is an example in which a secondary amino group-containing vinyl compound is used as the monomer (b).
Example 4 is an example in which a (meth) acrylate containing an oxyethylene group is used as the monomer (b).
Comparative Example 1 is an example in which MMA is used instead of the macromonomer (a).
Comparative Example 2 is an example in which an organosilyl group-containing vinyl compound is used as the monomer (b).

It was confirmed that in Examples 1 to 4 in which the average surface roughness (Q) of the coating film in water was within the range of 1 nm <(Q) <10 nm, the adhesion rate was low and the antifouling property was excellent.
On the other hand, it was confirmed that Comparative Example 1 in which the average surface roughness (Q) of the coating film was 10 nm and Comparative Example 2 in which the average surface roughness (Q) was 1 nm had a high adhesion rate and were inferior in antifouling property. rice field.

Claims (6)

A resin composition for an antifouling coating material containing an amphoteric polymer containing a structural unit derived from a macromonomer having a radically polymerizable group and a structural unit derived from a (meth) acrylic monomer other than the macromonomer. The antifouling paint having a water absorption rate of 20% or more and an average surface roughness (Q) of the outer surface in water of 1 nm <(Q) <10 nm of the coating film made of the resin composition for antifouling paint. Resin composition for use. The resin composition for an antifouling paint according to claim 1, wherein the water contact angle of the outer surface of the coating film is 120 to 144 °, and the indentation elastic modulus is 15 to 2900 MPa. The resin composition for an antifouling paint according to claim 1 or 2 , wherein the macromonomer is represented by the following formula (1).

(In the formula, R is a hydrogen atom, an alkyl group having an unsubstituted or substituent, an alicyclic group having an unsubstituted or substituent, an aryl group having an unsubstituted or substituent, an unsubstituted or substituent. Indicates a heteroaryl group having, or an unsubstituted or non-aromatic heterocyclic group having a substituent, and a plurality of Rs may be the same or different, respectively, and X is a hydrogen atom or a methyl group and a plurality of Rs. X may be the same or different, and Z is a group derived from a radical polymerization initiator which is a hydrogen atom, an azo compound or an organic peroxide, or a radical polymerizable group having an ethylenically unsaturated bond , and n is a radical polymerizable group. It is a natural number of 2 to 10,000.) Any of claims 1 to 3, wherein the amphipathic polymer contains a hydrophobic part containing a structural unit derived from the macromonomer and a hydrophilic part containing a structural unit derived from the (meth) acrylic monomer. The resin composition for an antifouling paint according to item 1. The resin composition for an antifouling paint according to any one of claims 1 to 4 , further comprising a solvent. A method for producing an antifouling coating film, which comprises a step of forming a coating film on the surface of an object to be coated using the resin composition for an antifouling paint according to any one of claims 1 to 5.

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