JP6926863B2 - Methods for manufacturing polymers for antifouling paints, resin compositions, antifouling paints, coating films, and polymers for antifouling paints - Google Patents

Description

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

It is known that marine structures and ships are coated with antifouling paint for the purpose of preventing the adhesion of marine organisms that cause corrosion of parts in contact with seawater and slowdown of navigation speed.
Antifouling paints include an elution type (self-polishing type) in which the surface of the coating film to be formed gradually dissolves in seawater and the surface is renewed (self-polishing), and a non-eluting type in which the coating film has high water resistance and the surface is not renewed. It has been known.

As a resin material used for self-polishing antifouling coating material, Patent Document 1 describes a reaction product of an inorganic metal compound and a carboxy group-containing radically polymerizable monomer (metal-containing monomer) and other radically polymerizable non-polymerizable materials. A resin composition copolymerized with a saturated monomer is described. The metal-containing polymer contained in such a resin composition has hydrolyzability, and the coating film containing the metal-containing polymer exhibits self-polishing property.

Japanese Unexamined Patent Publication No. 2002-012630

From the viewpoint of environmental protection, it is desired that the antifouling paint has little influence on living organisms, but this point is not always sufficient for the coating film formed from the conventional paint composition.
An object of the present invention is an antifouling paint polymer, a resin composition, an antifouling paint, and a coating film formed by using these, which can form a coating film exhibiting excellent antifouling property while suppressing the influence on living organisms. An object of the present invention is to provide a method for producing a polymer for an antifouling paint and an antifouling material.

The present invention has the following aspects.
[1] A polymer for antifouling coating material containing a structural unit (C) derived from the monomer (c) represented by the following formula (c1).
R ^21- O-R ^22- NC ... (c1)
In formula (c1), R ²¹ is a monovalent group having a reactive double bond, R ²² is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, and a substituted or unsubstituted alkynylene. It is a divalent group selected from a group, and the divalent group may contain one or more selected from the following hetero atom, the following hetero atomic group, and the following cyclic divalent group in the chain.
Heteroatom: One or more selected from = N-, -O- and -S-.
Heteroatom group: One or more selected from epoxy, -N (R ²³ )-, -CO-, -SO- and -SO _2-. R ²³ is a hydrogen atom, a hydroxy group, or a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkynyl group, a heterocycloalkyl group, an alkoxy group, a cycloalkoxy group, or a hetero. Cycloalkoxy group, aryl group, heteroaryl group, arylalkyl group, heteroarylalkyl group, aryloxy group, arylalkyloxy group, arylalkenyloxy group, heteroaryloxy group, heteroarylalkyloxy group, aryl condensed cycloalkyl group Alternatively, it is an aryl-condensed heterocycloalkyl group.
Cyclic divalent group: substituted or unsubstituted cycloalkylene group, substituted or unsubstituted cycloalkenylene group, substituted or unsubstituted cycloalkynylene group, substituted or unsubstituted arylene group and substituted or unsubstituted heteroarylene group One or more selected from.

[2] The polymer for antifouling paint according to [1], ^{wherein R 21} in the formula (c1) is a (meth) acryloyl group.
[3] The structural unit (C) is derived from a structural unit derived from the monomer (c2) represented by the following formula (c2) or a monomer (c3) represented by the following formula (c3). The polymer for antifouling paint of [2], which contains the structural unit to be used.

[4] A structural unit (A) derived from the macromonomer (a) and a structural unit (B) derived from a monomer (b) that is not a macromonomer (however, excluding the monomer (c)). , A polymer for an antifouling coating according to any one of [1] to [3], which comprises a structural unit (C) derived from the monomer (c).
[5] The solubility parameter of the monomer (aa) constituting the macromonomer (a) is ^{less than 18.5 (J / cm 3} ) ^1/2 , and the solubility parameter of the monomer (b) is 18. .5 (J / cm ³ ) ^1/2 or more, the polymer for antifouling paint of [4].
[6] The antifouling agent of [4] or [5], wherein the macromonomer (a) is a macromonomer having a radically polymerizable group and having two or more structural units represented by the following formula (AA). Polymer for paint.

(In the formula, R ¹ is a hydrogen atom, a methyl group or CH ₂ OH, R ² is an 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, substituted or unsubstituted alkyl groups, substituted or unsubstituted alicyclic groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted non-substituted. aromatic heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkaryl group, or a substituted or represents an unsubstituted organosilyl group, R ⁸ is a substituted or unsubstituted aryl group, or a substituted Alternatively, it indicates an unsubstituted heteroaryl group.)
[7] The polymer for antifouling coating material according to any one of [4] to [6], wherein the macromonomer (a) is a macromonomer represented by the following formula (1).

(In the formula, R is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted heteroaryl group. It is a non-aromatic heterocyclic group, and a plurality of Rs may be the same or different, X is a hydrogen atom or a methyl group, and a plurality of Xs may be the same or different. Often, Z is the terminal group and n is a natural number of 2 to 10,000.)
[8] A resin composition containing the polymer for antifouling paint according to any one of the above [1] to [7].
[9] An antifouling paint containing the resin composition of the above [8].
[10] A coating film formed by using the resin composition of [8] or the antifouling paint of [9].
[11] An antifouling coating material that polymerizes a monomer mixture containing the monomer (c) represented by the formula (c1) and a monomer copolymerizable with the monomer (c). How to make a polymer for.

[12] An antifouling material represented by the above formula (c1).
[13] The antifouling material of [12], ^{wherein R 21} in the formula (c1) is a (meth) acryloyl group.
[14] An antifouling material represented by the formula (c2) or the formula (c3).

According to the present invention, a polymer for an antifouling paint, a resin composition, an antifouling paint, and a coating film formed by using these, which can form a coating film exhibiting excellent antifouling property while suppressing the influence on living organisms. A method for producing a polymer for an antifouling paint and an antifouling material can be provided.

The definitions of the following terms apply throughout the specification and claims.
"(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.

Hereinafter, embodiments of the present invention will be described. The following embodiments are merely exemplary to illustrate the invention and are not intended to limit the invention to this embodiment alone. The present invention can be implemented in various aspects as long as it does not deviate from the gist thereof.

[Polymer for antifouling paint]
The polymer for antifouling coating material of the present embodiment contains a structural unit (C) derived from the monomer (c) represented by the formula (c1) described later.
The antifouling coating polymer of the present embodiment has a structural unit (C) derived from the monomer (c) and another configuration derived from the monomer (d) copolymerizable with the monomer (c). It is preferably a copolymer containing the unit (D). The copolymer may be a random copolymer, a block copolymer, or a graft copolymer.

(Constituent unit (C))
The structural unit (C) is a structural unit derived from the monomer (c) represented by the following formula (c1).
R ^21- O-R ^22- NC ... (c1)
In formula (c1), R ²¹ is a monovalent group having a reactive double bond, R ²² is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, and a substituted or unsubstituted alkynylene. It is a divalent group selected from a group, and the divalent group may contain one or more selected from a hetero atom, a hetero atomic group, and a cyclic divalent group in the chain.

The monovalent group having a reactive double bond as ^{R 21 is preferably a radically polymerizable group.} Examples thereof include (meth) acryloyl group and vinyl group. A (meth) acryloyl group is preferred in terms of transparency.

The alkylene group as R ²² may be linear or branched. The number of carbon atoms is preferably 1 to 5.
The alkenylene group as R ²² may be linear or branched. The number of carbon atoms is preferably 2-5. Those having one double bond are preferable.
The alkynylene group as R ²² may be linear or branched. The number of carbon atoms is preferably 2-5. Those having one triple bond are preferable.

The ^{heteroatom contained in the chain of R 22} is one or more selected from = N-, -O- and -S-.

The heteroatom group contained in the chain of ^{R 22} is one or more selected from ^{epoxy groups, -N (R 23} )-, -CO-, -SO- and -SO _2-.
-N (R 23) ^- in R ²³ is a hydrogen atom, hydroxy group, or a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, cycloalkynyl group, a heterocycloalkyl group, Alkoxy group, cycloalkoxy group, heterocycloalkoxy group, aryl group, heteroaryl group, arylalkyl group, heteroarylalkyl group, aryloxy group, arylalkyloxy group, arylalkenyloxy group, heteroaryloxy group, heteroarylalkyl It is an oxy group, an aryl-condensed cycloalkyl group, or an aryl-condensed heterocycloalkyl group.

The alkyl group as R ²³ may be linear or branched. The number of carbon atoms is preferably 1 to 5.
The alkenyl group as R ²³ may be linear or branched. The number of carbon atoms is preferably 1 to 5. Those having one double bond are preferable.
The alkynyl group as R ²³ may be linear or branched. The number of carbon atoms is preferably 1 to 5. Those having one triple bond are preferable.
The cycloalkyl group as R ²³ is a saturated alicyclic hydrocarbon. The number of carbon atoms is preferably 3 to 6. Examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
The cycloalkenyl group as R ²³ is a group in which one or more CC single bonds of the cycloalkyl are replaced with double bonds. The number of carbon atoms is preferably 3 to 6. Examples thereof include cyclobutenyl, cyclopentenyl, cyclohexenyl and the like.
The cycloalkynyl group as R ²³ is a group in which one or more CC single bonds of the cycloalkyl are replaced with triple bonds. The number of carbon atoms is preferably 3 to 6. Cyclobutynyl, cyclopentinyl, cyclohexynyl and the like can be exemplified.

In ^{the heterocycloalkyl group as R 23} , one or more carbon atoms of the cycloalkyl group, cycloalkenyl group or cycloalkynyl group are independently nitrogen atoms (N), sulfur atoms (S) and oxygen atoms (S). It is a group substituted with a heteroatom selected from O). Substitutions with N or S include substitutions with N-oxide or S-oxide or dioxide, respectively. Examples thereof include pyrrolidinyl group, tetrahydrofuranyl group, dihydrofuranyl group, tetrahydrothienyl group, tetrahydropyranyl group, dihydropyranyl group, tetrahydrothiopyranyl group, piperidinyl group, morpholinyl group, thiomorpholinyl group, piperazinyl group and the like.

The alkoxy group as R ²³ may be linear or branched. The number of carbon atoms is preferably 1 to 5.
The cycloalkoxy group as R ²³ is a group in which the hydrogen atom of the hydroxy group is substituted with the cycloalkyl group, cycloalkenyl group or cycloalkynyl group. The number of carbon atoms is preferably 3 to 6. Examples thereof include a cyclopropoxy group, a cyclobutoxy group, a cyclopentoxy group and the like.
The heterocycloalkoxy group as R ²³ is a group in which the hydrogen atom of the hydroxy group is substituted with the heterocycloalkyl group.
The aryl group as R ²³ preferably has 6 to 15 carbon atoms. Examples thereof include a phenyl group, a biphenyl group, a naphthyl group, an anthrasenyl group and the like.

In ^{the heteroaryl group as R 23} , one or more carbon atoms of the aryl group are independently replaced with heteroatoms selected from nitrogen atom (N), sulfur atom (S) and oxygen atom (O). It is a base that has been made. Substitutions with N or S include substitutions with N-oxide or S-oxide or dioxide, respectively. Furanyl group, thienyl (thiophenyl) group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, thiazolyl group, oxazolyl group, isooxazolyl group, oxadiazolyl group, thiadiazolyl group, isothiazolyl group, pyridyl group, pyridazinyl group Examples thereof include a group, a pyrimidinyl group, a quinolinyl group, an isoquinolinyl group, an indolyl group and the like.
The arylalkyl group as R ²³ is a group in which one of the hydrogen atoms of the alkyl group is substituted with the aryl group. The number of carbon atoms is preferably 7 to 16. Examples thereof include a benzyl group, a 1-phenethyl group, a 2-phenethyl group and the like.
The heteroarylalkyl group as R ²³ is a group in which one of the hydrogen atoms of the alkyl group is substituted with the heteroaryl group. Examples thereof include indole-3-ylmethyl groups.

The ^{aryloxy group as R 23} is a group in which the hydrogen atom of the hydroxy group is substituted with the aryl group. The number of carbon atoms is preferably 6 to 15. Examples thereof include a phenoxy group, a biphenyloxy group, a naphthyloxy group, and an anthryloxy (anthrasenyloxy) group.
The arylalkyloxy group as R ²³ is a group in which the hydrogen atom of the hydroxy group is substituted with the arylalkyl group. The number of carbon atoms is preferably 7 to 16. Examples thereof include a benzyloxy group, a 1-phenethyloxy group, a 2-phenethyloxy group and the like.
The ^{arylalkenyloxy group as R 23} is a group in which the hydrogen atom of the hydroxy group is substituted with the arylalkenyl group. The number of carbon atoms is preferably 8 to 17. Examples include styryloxy groups.
The heteroaryloxy group as R ²³ is a group in which the hydrogen atom of the hydroxy group is substituted with the heteroaryl group. Franyloxy group, thienyloxy (thiophenyloxy) group, pyrrolyloxy group, imidazolyloxy group, pyrazolyloxy group, triazolyloxy group, tetrazolyloxy group, thiazolyloxy group, oxazolyloxy group, isooxazolyloxy group, Oxaziazolyloxy group, thiadiazolyloxy group, isothiazolyloxy group, pyridyloxy group, pyridazinyloxy group, pyrazinyloxy group, pyrimidinyloxy group, quinolinyloxy group, isoquinolinyloxy group, indolyloxy group Etc. can be exemplified.
The heteroarylalkyloxy group as R ²³ is a group in which the hydrogen atom of the hydroxy group is substituted with the heteroarylalkyl group.

The aryl-condensed cycloalkyl group as R ²³ is a condensed ring group formed by condensing the aryl group and the cycloalkyl group. Examples thereof include a benzocyclobutenyl group, an indanyl group, and a tetrahydronaphthyl group.
The aryl-condensed heterocycloalkyl group as R ²³ is a condensed ring group formed by condensing the aryl group and the heterocycloalkyl group. Examples thereof include 2,3-dihydroindrill group, 1,2,3,4-tetrahydroquinolinyl group and the like.

The cyclic divalent group contained in the chain of R ²² is a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted cycloalkenylene group, a substituted or unsubstituted cycloalkynylene group, a substituted or unsubstituted arylene group. And one or more selected from substituted or unsubstituted heteroarylene groups.
The cycloalkylene group as the cyclic divalent group is a divalent group obtained by removing one hydrogen atom from the cycloalkyl group.
The cycloalkenylene group as the cyclic divalent group is a divalent group obtained by removing one hydrogen atom from the cycloalkenylene group.
The cycloalkynylene group as the cyclic divalent group is a divalent group obtained by removing one hydrogen atom from the cycloalkynylene group.
The arylene group as the cyclic divalent group is a divalent group obtained by removing one hydrogen atom from the aryl group.
The heteroarylene group as the cyclic divalent group is a divalent group obtained by removing one hydrogen atom from the heteroaryl group.

As ^{the substituent of R 22,} the substituent of R ²³ , or the substituent of the cyclic divalent group, a halogen atom, a cyano group, an isocyano group, -NZ ¹ Z ² , -OZ ¹ , -SZ ¹ , -C ( = O) -Z ¹ , -C (= NH) -Z ¹ , alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, cycloalkynyl group, aryl group, heteroaryl group, heterocycloalkyl group, An example is one or more monovalent groups selected from the group consisting of an arylalkyl group, a heteroarylalkyl group, an aryl-condensed cycloalkyl group, and an aryl-condensed heterocycloalkyl group. The substituents may be further substituted with a monovalent group selected from the group.
Z ¹ and Z ² are independently hydrogen atom, hydroxy group, substituted or unsubstituted amino group, alkyl group, alkoxy group, alkynyl group, cycloalkyl group, cycloalkoxy group, cycloalkynyl group, heterocyclo. Alkoxy group, alkoxy group, cycloalkoxy group, heterocycloalkoxy group, aryl group, heteroaryl group, arylalkyl group, heteroarylalkyl group, aryloxy group, arylalkyloxy group, arylalkenyloxy group, heteroaryloxy group, Heteroarylalkyloxy group,
Examples thereof include an aryl condensed cycloalkyl group, an aryl condensed heterocycloalkyl group, and an acyl group.

Preferred R ²² includes a substituted or unsubstituted alkylene group having 2 to 15 carbon atoms, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, and an acyl group. When these have a substituent, preferred substituents include a hydroxy group, an amino group, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group and an acyl group.

The structural unit (C) is derived from the structural unit (C2) derived from the monomer (c2) represented by the following formula (c2) or the monomer (c3) represented by the following formula (c3). It is preferable to include a structural unit (C3). Both may be included.
The total of the structural unit (C2) and the structural unit (C3) is preferably 0.1 to 100% by mass, more preferably 1 to 100% by mass, based on the total of the structural units (C) in the polymer for antifouling paint. ..

(Structural unit (D))
The structural unit (D) is a structural unit derived from the monomer (d) copolymerizable with the monomer (c). The monomer (d) preferably has a radically polymerizable group, and examples thereof 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 alkoxyallylized 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 and (meth) 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 itacone, monoethyl itaconate, Monobutyl itaconate, monooctyl itaconate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monooctyl fumarate, monoethyl citraconic acid, monohydroxyethyl tetrahydrophthalate (meth) acrylate, monohydroxypropyl tetrahydrophthalate (meth) Acrylic, monohydroxybutyl (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, monohydroxypropyl (meth) phthalate, monohydroxyethyl succinate (meth) acrylate, monohydroxypropyl succinate (meth) ) Carboxy group-containing ethylenically unsaturated compounds such as acrylate, monohydroxyethyl maleate (meth) acrylate, monohydroxypropyl maleate (meth) acrylate;
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.

The monomer (d) is preferably an aliphatic monomer from the viewpoint of weather resistance of the coating material. The aliphatic monomer means a monomer having no aromatic ring.

^{When R 21 of the} monomer (c) is a (meth) acryloyl group, the monomer (d) has a (meth) acryloyl group in terms of copolymerizability with the monomer (c). A monomer is preferable, and at least one selected from the group consisting of (meth) acrylic acid, (meth) acrylate and substituted or unsubstituted (meth) acrylamide is more preferable.

(Content of constituent unit (C))
By including the constituent unit (C) in the resin component forming the coating film, it is possible to improve the antifouling property of the coating film while suppressing the influence on living organisms. It is thought that this is because it exerts a repellent effect on living things.
The structural unit (C) is preferably 0.1 to 90% by mass, more preferably 1 to 80% by mass, based on all the structural units constituting the polymer for antifouling coating material. When it is at least the above lower limit value, the effect of adding the constituent unit (C) is sufficiently exhibited, and when it is at least the above upper limit value, the film forming property is more excellent.

<Anti-fouling material>
The compound represented by the formula (c1) is useful as a repellent material having a repellent effect on living organisms, and is suitable as an antifouling material for preventing the adhesion of living organisms.
For example, it can exert a repellent effect against aquatic organisms such as barnacles, mussels, and bryozoa.
Since the compound represented by the formula (c1) has a reactive double bond, it is suitable as a monomer. For example, it is suitable as a monomer that imparts a repellent effect to living organisms to an antifouling coating film or a polymer for an antifouling coating film that forms an antifouling coating film.
Alternatively, the compound represented by the formula (c1) may be added to the antifouling paint without polymerizing. The compound represented by the formula (c1) can also be used as an antifouling material that prevents the adhesion of organisms by reacting with the components in the coating film after forming a coating film with an antifouling paint containing the compound. be.

<Polymer for antifouling paint having a structural unit derived from macromonomer>
The copolymer containing the structural unit (C) and the other structural unit (D) has a structural unit (A) derived from the macromonomer (a) and a monomer that is not a macromonomer in that the water resistance of the coating film is increased. It is preferable to include the structural unit (B) derived from (b) (however, excluding the monomer (c)).
A copolymer containing the structural unit (A), the structural unit (B), and the structural unit (C) (hereinafter, also referred to as an antifouling coating polymer (P)) is typically hydrophilic and hydrophobic. It is an amphipathic polymer containing a moiety in the molecule.
In the amphipathic polymer, the polymer chain composed of the structural unit (A) derived from the macromonomer (a) is the hydrophobic part, and the structural unit (B) and the monomer derived from the monomer (b). The polymer chain composed of the structural unit (C) derived from (c) may be a hydrophilic portion. Alternatively, the polymer chain composed of the structural unit derived from the macromonomer (a) is the hydrophilic part, and the polymer chain composed of the monomer (b) and the structural unit derived from the monomer (c) is hydrophobic. It may be a sex part.
The solubility parameter of the monomer constituting the macromonomer (a) (hereinafter, also referred to as “monomer (aa)”) is less than 18.5, and the solubility parameter of the monomer (b) is 18.5. The above is preferable.

(Constituent unit (A))
The structural unit (A) is a structural unit derived from the macromonomer (a) described later.
The macromonomer (a) preferably has a solubility parameter of less than 18.5 for the monomer (aa) constituting the macromonomer (a). The solubility parameter of the monomer (aa) constituting the macromonomer (a) is more preferably 15.0 or more and less than 18.5, and further preferably 16.0 or more and less than 18.4.
When the solubility parameter of the monomer (aa) constituting the macromonomer (a) is not less than the lower limit value, the storage stability of the paint is excellent, and when it is not more than the upper limit value, the coating film adheres to the substrate. Excellent in sex.

The solubility parameter (Sp value) is a measure of solubility, and in the present specification, the Sp value is a value calculated from the measured value as follows, and the unit "(J / cm ³ ) ^{1 /. 2} ”, but the unit may be omitted in this specification.

-Solubility parameter In this specification, the solubility parameter (Sp value) is described in "POLYMER ENGINEERING AND SCIENCE, February, 1974, Vol. 14, No. 2, Robert F. Fedors (pages 147 to 154)". It is a value estimated by the Fedors method. The value of the solubility parameter can be calculated by the following formula (2).
However, in the formula (2), the values shown in Table 1 were used as the values of the aggregation energy and the molar volume of the atomic group.

For example, in the case of polymethylmethacrylate (PMMA), the monomer unit (MMA) is represented by the following formula, CH ₃ is 2, CH ₂ = is 1, = C <is 1, and COO is 1. It consists of atomic groups. Therefore, the Sp value of the MMA unit is calculated as ^{18.27 (J / cm 3} ) ^{1/2 from the following equation (3).}

The macromonomer (a) has a radically polymerizable group or an addition-reactive functional group such as a hydroxy 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), the monomer (b) and the monomer (c) are copolymerized by radical polymerization to obtain a polymer for antifouling coating (P). ) Can be manufactured.
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) and the monomer (c) are usually capable of reacting with the addition-reactive functional group of the macromonomer (a). It has a functional group. The polymerizable functional group derived from the monomer (b) and the polymerizable functional group derived from the monomer (c) are reacted with the addition-reactive functional group of the macromonomer (a) to prevent the reaction. A polymer (P) for stain coating can be produced.
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 hydroxy group and a carboxy group or an acid anhydride group, a combination of an isocyanate group and a hydroxy 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 or monomer added to the polymer unit composed of the monomer (b) and the monomer (c). There may be two or more functional groups or radically polymerizable groups other than any of the radically polymerizable groups copolymerizing with (b) and the monomer (c).

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

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, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted non-substituted group. Indicates an aromatic heterocyclic group.

Examples of the unsubstituted alkyl group in R include a branched or linear alkyl group having 1 to 22 carbon atoms. Specific examples of the branched or linear alkyl group having 1 to 22 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an i-butyl group, and a 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 group having 4 to 18 carbon atoms include a pyridyl group and a carbazolyl group.

Examples of the unsubstituted heterocyclic group in R include a heterocyclic group having 4 to 18 carbon atoms. Specific examples of the heterocyclic group having 4 to 18 carbon atoms include 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 independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted aryl group, respectively.

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, a substituted or unsubstituted alkyl group or a substituted or unsubstituted alicyclic group is preferable, and an unsubstituted alkyl group or an alicyclic group having an alkyl group as an unsubstituted or substituent is more preferable. ..
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, Hydroxy 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;
An acid anhydride group-containing vinyl monomer 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. (with 2 ethylene glycol chains), product Name), "Blemmer PME-200" (Nichiyu Co., Ltd. methoxypolyethylene glycol methacrylate (the chain of ethylene glycol is 4), trade name), "Blemmer PME-400" (Nichiyu Co., Ltd. methoxypolyethylene glycol methacrylate) (The chain of ethylene glycol is 9), trade name), "Blemmer 50 POEP-800B" (Octoxy polyethylene glycol-polypropylene glycol-methacrylate (manufactured by Nichiyu Co., Ltd.) (the chain of ethylene glycol 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., product) Name), glycol ester-based monomers such as "Blemmer AME-200" (manufactured by Nichiyu Co., Ltd., trade name) and "Blemmer 50 AOEP-800B" (manufactured by Nichiyu Co., Ltd., trade name),
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) ) 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 Cyrilmethylfumarate, t-butyldiphenylsilyl-n-butylfumarate, Cyraplane FM-0711 (JNC, trade name), Cyraplane FM-0721 (JNC, trade name), Cyraplane FM-0725 (JNC, product name), Silaplane TM-0701 (JNC, product name), Silaplane TM-0701T (JNC, product name), X-22-174ASX (Shinetsu Chemical Industry, product) Name), X-22-174BX (manufactured by Shinetsu Chemical Industry Co., Ltd., product name), KF-2012 (manufactured by Shinetsu Chemical Industry Co., Ltd., product name), X-22-2426 (manufactured by Shinetsu Chemical Industry Co., Ltd., product name), X -22- Organosilyl group-containing monomers other than silane coupling agent-containing monomers such as 2404 (manufactured by 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. Dimer,
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.

The macromonomer (a) preferably 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 ^{Each of 7} is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted non-substituted group. It represents an aromatic heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkalinel group, or a substituted or unsubstituted organosilyl group, and the allowable substituents thereof are the carboxy group, respectively. ^{R 8} is at least one selected from the group consisting of an alkoxycarbonyl group, an epoxy group, a hydroxy group, an alkoxy group, a primary amino group, a secondary amino group, a tertiary amino group, an isocyanato group, a sulfo group and a halogen. It represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and the allowable substituents thereof are a carboxy group, an alkoxycarbonyl group, an epoxy group, a hydroxy group, an alkoxy group, and a primary amino group, respectively. At least selected from the group consisting of a secondary amino group, a tertiary amino group, an isocyanato group, a sulfo group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl-containing group and a halogen. It is one kind.)

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 independently substituted or unsubstituted alkyl groups, substituted or unsubstituted, respectively. An alicyclic group or a substituted or unsubstituted aryl group is shown.).
Examples of the substituted or unsubstituted alkyl group in R ^{17 to} R ¹⁹ include the same as described above, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl. Examples thereof include a group, an n-octyl group, an n-dodecyl group, a stearyl group, a lauryl group, an isopropyl group, an isobutyl group, an s-butyl group, a 2-methylisopropyl group and a benzyl group.
Examples of the substituted or unsubstituted alicyclic group in R ^{17 to} R ¹⁹ include the same group as described above, and examples thereof include a cyclohexyl group.
Examples of the substituted or unsubstituted aryl group 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 a group in which R ^{11 of -COOR 11} is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted aryl group.
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 a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted aryl group. There is a group.
The tertiary amino group, the -NR ¹³ R ¹⁴ R ¹³ and R ¹⁴ are each a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted group is an aryl group Can be mentioned.
Examples of the substituted or unsubstituted alkyl group, the substituted or unsubstituted aryl group, 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 substituted or unsubstituted alkyl group, the substituted or unsubstituted aryl group, 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 alkoxyallylized polyethers 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, etc. Quantitative body;
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;
Methacrylic acid, 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 (meth) phthalate, 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 monomer-derived structural unit.

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 Phenylate 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" (Japan) Aburasha made methoxy polyethylene glycol methacrylate (as a chain of ethylene glycol is 2), trade name), those "BLEMMER PME-200" (manufactured by NOF Corporation methoxy polyethylene glycol methacrylate (ethylene glycol chain is 4 ), Product name), "Blemmer PME-400" (Nichiyu Co., Ltd. methoxypolyethylene glycol methacrylate (the chain of ethylene glycol is 9), product name), "Blemmer 50 POEP-800B" (Nichiyu Co., Ltd. Octoxy) Polyethylene glycol-polypropylene glycol-methacrylate (ethylene glycol chain is 8 and propylene glycol chain is 6), trade name) and "Blemmer 20 ANEP-600" (Nonylphenoxy (ethylene glycol-polypropylene) manufactured by Nichiyu Co., Ltd. Glycol) monoacrylate, product name), "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" (Nichiyu Co., Ltd.) Silaplane FM-0711 (JNC, product name), Silaplane FM-0721 (JNC, product name), Silaplane FM-0725 (JNC, product name), Sila Plain TM-0701 (manufactured by JNC, product name), Silaplane TM-0701T (manufactured by JNC, product name), X-22-174DX (manufactured by Shinetsu Chemical Industry Co., Ltd., product name), X-22-2426 (Shinetsu) Examples thereof include X-22-2475 (manufactured by Shinetsu Kagaku Kogyo Co., Ltd., 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;
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-containing ethylenically unsaturated monomers such as monomethyl acid, monoethyl fumarate, monobutyl fumarate, monooctyl fumarate, and monoethyl citraconic acid;
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, and one having a structure of the following formula (a2) is 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.)
Examples of the R in the formula (a2) include those similar to the R in the formula (AA), and the preferred embodiment is 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 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 antifouling coating polymer (P), R in the formula (1) is an alkyl group or an alicyclic group from the viewpoint of hydrophobicity. , Aryl group, heteroaryl group or non-aromatic heterocyclic group is preferable, alkyl group or alicyclic group is more preferable, and alkyl group is particularly preferable.
When the structural unit derived from the macromonomer (a) is contained in the hydrophilic portion of the antifouling coating polymer (P), 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 antifouling coating polymer (P), the structural unit (AA) constituting the macromonomer (a) is considered from the viewpoint of hydrophobicity. A structural unit in which R in the formula (AA) is 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 in the formula (AA) is an alkyl group or an alicyclic group are preferable, and those in which R is an alkyl group 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 portion of the polymer (P) for antifouling coating, the structural unit (AA) constituting the macromonomer (a) is considered from the viewpoint of hydrophilicity. It is preferable to include a structural unit in which R in the formula (AA) is a hydrogen atom (hereinafter, also referred to as “constituent unit (AA2)”). In particular, those in which R 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.

(Constituent unit (B))
The structural unit (B) is a structural unit derived from a monomer (b) that is not a macromonomer. However, the monomer (b) does not contain the monomer (c) described later.
The monomer (b) preferably has a solubility parameter of 18.5 or more. The solubility parameter of the monomer (b) is more preferably 18.5 or more and 47 or less, and further preferably 18.6 or more and 30 or less.
When the solubility parameter of the monomer (b) is at least the lower limit value, the compatibility between the macromonomer and the solvent is good, and when it is at least the upper limit value, the water resistance is good.

The monomer (b) preferably has a radically polymerizable group, and the compounds listed above as examples of the monomer (d) can be exemplified. As these compounds, one kind or two or more kinds can be appropriately selected and used as needed.
Of these, aliphatic monomers are preferable from the viewpoint of weather resistance of the paint. The aliphatic monomer means a monomer having no aromatic ring.

As the monomer (b), a (meth) acrylic monomer is preferable from the viewpoint of copolymerizability with the monomer (c) and the macromonomer (a), and (meth) acrylic acid and (meth). More preferably, at least one selected from the group consisting of acrylates and substituted or unsubstituted (meth) acrylamides.

When the monomer (b) is a (meth) acrylate and the structural unit derived from the monomer (b) is contained in the hydrophilic portion of the antifouling coating polymer (P), the monomer (b) From the viewpoint of antifouling property, the compound represented by the following formula (b-1) is preferable.
CH ₂ = CX-C (= O) -O- (R ^b2 O) _m R ^b1 (b-1)
In formula (b-1), X is a hydrogen atom or a methyl group, R ^b1 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group, and R ^b2 is an alkylene group having 2 to 10 carbon atoms. And m is an integer of 1 to 15.

The alkyl group having 1 to 10 carbon atoms in R ^b1 may be 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 in R ^b1 include an aryl group having 6 to 18 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group.
As R ^b1 , 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 ^b2 , 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 (meth) acrylate is contained in the hydrophobic portion of the polymer (P) for antifouling paint, the (meth) acrylate includes the above-mentioned hydrophobic group-containing (meth) acrylate from the viewpoint of hydrophobicity. preferable. Of these, the compound represented by the following formula (b-2) is preferable.
CH ₂ = CX-C (= O) -OR ^b3 (b-2)
In formula (b-2), X is a hydrogen atom or a methyl group, and R ^b3 is an alkyl group, an alicyclic group or an aryl group.

^Examples of the alkyl group, alicyclic group, and aryl group in R b3 include those similar to the alkyl group, alicyclic group, and aryl group in R in the above formula (AA), and the preferred embodiment is also the same.

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

^Examples of the alkyl group in R ^b4 , R ^b5 , R ^b7 and R b8 are the same as the alkyl group in R in the above formula (AA). It is preferable that R ^b4 , R ^b5 , R ^b7 and R ^b8 are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms.
As ^{the alkylene group of R b6,} an alkylene group having 2 to 4 carbon atoms is preferable.
Specific examples of −R ^b6 −NR ^b7 R ^b8 include dimethylaminoethyl group, diethylaminoethyl group, butylaminoethyl group, dibutylaminoethyl group, dimethylaminopropyl group, diethylaminopropyl group, dimethylaminobutyl group and the like. ..

(Contents of constituent units (A), (B), (C))
In the polymer (P) for antifouling paint, a single amount with respect to a total of 100 parts by mass of the structural unit (A) derived from the macromonomer (a) and the structural unit (B) derived from the monomer (b). The structural unit (C) derived from the body (c) is preferably 3 to 15 parts by mass, more preferably 3 to 10 parts by mass. When it is at least the above lower limit value, the effect of adding the constituent unit (C) is sufficiently exhibited, and when it is at least the above upper limit value, the film forming property is more excellent.

In the antifouling paint polymer (P), the content of the structural unit (A) derived from the macromonomer (a) is the total structural unit (however, the structural unit (C)) constituting the antifouling paint polymer (P). 5 to 95% by mass is preferable with respect to 100% by mass of the total (excluding).
When the content of the structural unit (A) derived from the macromonomer (a) is within the above range, the effect of reducing the frictional resistance of the formed coating film is more excellent. For example, by forming a coating film that has the effect of reducing frictional resistance on the part that receives frictional resistance from seawater while the ship is sailing, the frictional resistance with seawater during navigation is reduced, and fuel consumption and energy saving can be achieved. It becomes.
The total of all the structural units (excluding the structural unit (C)) constituting the polymer (P) for antifouling coating is the content of the structural unit (A) derived from the macromonomer (a) and a single amount. Equal to the sum with the building block (B) derived from the body (b).

(Characteristics of polymer for antifouling paint)
The weight average molecular weight (Mw) of the polymer for antifouling coating is preferably 3,000 to 1,000,000, more preferably 5,000 to 500,000.
When the weight average molecular weight of the polymer for antifouling coating is not less than the lower limit value, the coating film performance is excellent, and when it is not more than the upper limit value, the coatability is excellent.
The weight average molecular weight of the polymer for antifouling coating is measured by gel permeation chromatography (GPC) using polystyrene as a reference resin.

The glass transition point of the polymer for antifouling coating is preferably 10 ° C. or higher, more preferably 10 ° C. or higher and 60 ° C. or lower, and further preferably 15 ° C. or higher and 50 ° C. or lower.
When the glass transition point of the antifouling coating polymer is at least the lower limit value, the coatability is excellent, and when it is at least the upper limit value, the coating film performance is excellent.

(Manufacturing method of polymer for antifouling paint)
The antifouling coating polymer can be produced, for example, by polymerizing the following monomer mixture.

-Monomer mixture The monomer mixture contains a monomer (c) and a monomer (d) copolymerizable with the monomer (c).
By using the macromonomer (a) and the monomer (b) as the monomer (d), a polymer for an antifouling coating material containing a structural unit (A), a structural unit (B), and a structural unit (C). (P) is obtained.

When the monomer mixture is composed of a macromonomer (a), a monomer (b) and a monomer (c), the content of the macromonomer (a) in the monomer mixture is the monomer mixture. , 5 to 95% by mass is preferable with respect to the total mass excluding the monomer (c) (total mass of the macromonomer (a) and the monomer (b): 100% by mass). That is, the polymer for antifouling paint polymerizes 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 excluding the monomer (c). It is preferable that the product is obtained by allowing the mixture to be obtained.
When the content of the macromonomer (a) is within the above range, the water resistance of the coating film formed by using the obtained polymer for antifouling paint is more excellent.

As the macromonomer (a), the monomer (b) and the monomer (c), 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. At the time of polymerization, in the methods (α1) and (α2), a predetermined chain transfer agent is used. In the methods (α3) and (α4), 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-butylperoxy-2-ethylhexanoate, 1,1,3,3 -Organic radicals 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 polymer 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 polymer having an acid group. Examples thereof include a method of reacting a vinyl polymer having a hydroxyl group with a diisocyanate compound to obtain a vinyl polymer having an isocyanate group, and then reacting the vinyl polymer with a vinyl monomer having a hydroxyl group. It may be manufactured by any method.

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).

-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 polymer for antifouling paint and the coating film performance of the coating film formed by using the obtained polymer for antifouling paint.
The polymerization is preferably 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 radicals such as methylbutylperoxy-2-ethylhexanoate; and the like.
Known chain transfer agents can be used, and examples thereof include mercaptans such as n-dodecyl mercaptan, thioglycolic acid esters such as octyl thioglycolate, α-methylstyrene dimer, and turpinolene.
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]
The resin composition of the present invention contains the polymer for antifouling paint of the present invention. The resin composition of the present invention preferably further contains a solvent.
The polymer for antifouling coating contained in the resin composition may be one kind or two or more kinds. The polymer for antifouling paint of the present invention is suitably used as a resin for antifouling paint.

The content of the polymer for antifouling coating in the resin composition is not particularly limited, but is preferably 5 to 85% by mass, preferably 10 to 80% by mass, based on the total mass (100% by mass) of the resin composition. Is more preferable, 30 to 75% by mass is further preferable, and 55 to 75% by mass is particularly preferable.
If the content of the polymer for antifouling paint is not more than the upper limit value, a coating film having excellent water resistance, coating film hardness, etc. can be obtained, and if it is not more than the lower limit value, the antifouling paint having a low VOC content is obtained. Can be easily obtained.
The term "VOC" means an organic compound (volatile organic compound) that easily volatilizes at normal temperature and pressure.

The resin composition preferably contains a solvent. When the resin composition contains a solvent, the coating suitability, the water resistance of the formed coating film, the film forming property, and the like are more excellent.
The solvent is not particularly limited as long as it can dissolve the polymer for antifouling paint, for example, monovalent alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; and polyvalent such as ethylene glycol and 1,2-propylene glycol. Alcohols; Ketones such as acetone, methyl ethyl ketone, acetyl acetone, butyl acetate; Ethers such as methyl ethyl ether and dioxane; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Glycol ethers such as mono n-propyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether and dipropylene glycol monopropyl ether; glycol acetates such as ethylene glycol monoacetate, ethylene glycol diacetate and ethylene glycol monomethyl ether acetate; Examples thereof include aliphatic hydrocarbons such as n-pentane and n-hexane; aromatic hydrocarbons such as toluene, xylene and 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 preferably occupies 15 to 95% by mass, more preferably 20 to 90% by mass, and 25 to 50% by mass, based on the total mass (100% by mass) of the resin composition. It is more preferable to occupy 70% by mass, and particularly preferably to occupy 25 to 45% by mass.
When the solvent content is at least the lower limit value, a coating film having excellent water resistance can be obtained, and when the solvent content is at least the upper limit value, a resin composition having a low VOC content can be easily obtained.

The resin composition may further contain components other than the polymer for antifouling paint.
Examples of other components include those similar to other components in antifouling paints described later.
The content of 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 polymer for antifouling coating.

The viscosity of the resin composition measured by a B-type viscometer at 25 ° C. ^{is preferably 5 × 10 4} mPa · s or less, more preferably 5,000 mPa · s or less, and further preferably 4,000 mPa · s or less. Preferably, it is even more preferably 3,000 mPa · s or less, and particularly preferably 2,000 mPa · s or less.
If the viscosity of the resin composition measured by a B-type viscometer at 25 ° C. is equal to or less than the upper limit, coating is easy.
The lower limit of the viscosity of the resin composition measured by a B-type viscometer at 25 ° C. 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 the solvent added to the polymer for antifouling paint and the like.

The method for producing the resin composition is not particularly limited. For example, when the monomer mixture is composed of a macromonomer (a), a monomer (b) and a monomer (c), the monomer mixture is polymerized by a solution polymerization method to polymerize a polymer for antifouling coating (P). ) And a polymerization product containing a solvent, and if necessary, it can be prepared by adding a solvent or other components to the obtained polymerization product.

The resin composition can be used as it is as an antifouling paint and exhibits a repellent effect on living organisms. Alternatively, if necessary, it can be mixed with an antifouling agent or the like to obtain an antifouling paint.
The resin composition can be used not only for antifouling paints but also for antifog paints and the like.

[Anti-fouling paint]
The antifouling coating material of the present invention contains the resin composition of the present invention. Therefore, the antifouling paint of the present invention includes the polymer for antifouling paint of the present invention.
The antifouling paint may further contain an antifouling agent, and may further contain other components other than the antifouling paint polymer and the antifouling agent.
The other components may be derived from the resin composition of the present invention, may not be derived (blended at the time of manufacturing the antifouling paint), or may be both of them. ..
The antifouling paint may further contain a solvent. Examples of the solvent include the same as described above. If the antifouling paint contains a solvent, the solvent may or may not be derived from the resin composition (blended during the manufacture of the antifouling paint) or both. It may be.

By applying the resin composition of the present invention to a portion of an offshore structure or ship that comes into contact with seawater to form a coating film, the effect on living organisms is suppressed, and the cause of corrosion and a decrease in navigation speed in this portion due to seawater. It is possible to suppress the adhesion of marine organisms.
In particular, the antifouling paint containing the polymer (P) for antifouling paint is typically a non-eluting type antifouling paint in which the coating film to be formed does not dissolve in an aqueous liquid such as seawater.

(Anti-fouling agent)
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 system compounds, maleimide compounds, pyridine compounds such as pyrithion zinc and pyrithion copper.

More specifically, as an antifouling agent, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrol-3-carbonitrile, Manganese ethylene bisdithiocarbamate, 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-n-octyl-3 (2H) -isothiazolone, N- (fluorodichloromethylthio) phthalimide, N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) ) Sulfamide, 2-pyridinethiol-1-oxide zinc salt (pyrithione zinc), 2-pyridinethiol-1-oxide copper salt (pyrithione copper), tetramethylthiuram disulfide, Cu-10% Ni solid solution alloy, 2, 4,6-Trichlorophenylmaleimide 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 3-iodo-2-propynylbutylcarbamate, diiodomethylparatrilsulfone, bisdimethyldithiocarbamoylzincethylenebis Examples thereof include dithiocarbamate, phenyl (bispyridyl) bismas dichloride, 2- (4-thiazolyl) -benzoimidazole, medetomidin, pyridine-triphenylborane and the like.

Copper oxide, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, pyridine-triphenylborane, pyrithione in terms of good antifouling performance. It preferably contains at least one selected from the group consisting of zinc, pyrithione copper and medetomidin.

Also, at least 2 selected from the group consisting of cuprous oxide, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, pyrithione zinc, pyrithione copper and medetomidine. Seeds may be combined.

When the antifouling paint contains an antifouling agent, the content of the antifouling agent in the antifouling paint is not particularly limited, but is preferably 10 to 200 parts by mass with respect to 100 parts by mass of the polymer for the antifouling paint. More preferably, 50 to 150 parts by mass.
When the content of the antifouling agent is not less than the lower limit value, the antifouling effect of the formed coating film is more excellent, and when it is not more than the upper limit value, the physical characteristics of the coating film are excellent.

(Other ingredients)
Examples of other components include resins other than the polymer for antifouling coatings of the present invention.
As the other resin, a thermoplastic resin other than the polymer for antifouling paint of the present invention is preferable. When the antifouling paint contains a thermoplastic resin other than the polymer for the antifouling paint of the present invention, the physical properties of the coating film such as crack resistance and water resistance are improved.

Examples of the thermoplastic resin other than the polymer for antifouling coating of the present invention include chlorinated paraffin; chlorinated polyolefin such as rubber chloride, chlorinated polyethylene, and chlorinated polypropylene; polyvinyl ether; polypropylene sebacate; partially hydrogenated terphenyl. Vinyl acetate; (meth) methyl acrylate-based copolymer, (meth) ethyl acrylate-based copolymer, (meth) propyl acrylate-based copolymer, (meth) butyl acrylate-based copolymer, ( Poly (meth) acrylic acid alkyl ester such as meta) cyclohexyl acrylate copolymer; polyether polyol; alkyd resin; polyester resin; vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl propionate copolymer, chloride Vinyl chloride-based resins such as vinyl-isobutylvinyl ether copolymers, vinyl chloride-isopropylvinyl ether copolymers, vinyl chloride-ethylvinyl ether copolymers; silicone oils; waxes; Liquid fats and oils and their purified products; Vaseline; liquid paraffins; 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 in that they function as anti-settling agents and anti-sagging agents and can improve the storage stability and pigment dispersibility of antifouling paints, and polyethylene wax and polyethylene oxide. Wax and polyethylene wax are more preferable.

When the antifouling paint contains a thermoplastic resin other than the polymer for antifouling paint of the present invention, the content of the thermoplastic resin other than the polymer for antifouling paint in the antifouling paint is not particularly limited, but the antifouling paint 0.1 to 50 parts by mass is preferable, and 0.1 to 10 parts by mass is more preferable with respect to 100 parts by mass of the polymer for use.
When the content of the thermoplastic resin other than the polymer for antifouling paint in the antifouling paint is at least the above lower limit value, the physical properties of the coating film such as crack resistance and water resistance are more excellent, and when it is at least the above upper limit value, it is possible. It has better flexibility and water absorption.

The antifouling coating material of the present invention contains silicon compounds such as dimethylpolysiloxane and silicone oil, and fluorinated hydrocarbons as other components for the purpose of imparting lubricity to the coating film surface and preventing the adhesion of organisms. It may contain a fluorine compound or the like.

The antifouling paint of the present invention has various pigments, a dehydrating agent, a defoaming agent, a leveling agent, a pigment dispersant (for example, an anti-sedimenting agent), an anti-dripping agent, a matting agent, an ultraviolet absorber, and an oxidation as other components. It may contain an inhibitor, a heat resistance improver, a slip agent, a preservative, a plasticizer, a viscosity control agent and the like.

Examples of the pigment 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, orthoboric acid ester, tetraethyl orthosilicate, anhydrous gypsum, gypsum, synthetic zeolite (molecular sieve) and the like can be mentioned. By including a dehydrating agent in the antifouling paint, 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 paint, the crack resistance and peeling resistance of the coating film can be improved. Among the above, TCP is preferable as the plasticizer.

(Characteristics of antifouling paint)
The VOC content of the antifouling coating material of the present invention is preferably 420 g / L or less, more preferably 400 g / L or less, and even more preferably 380 g / L or less.
The VOC content is calculated from the following formula using the specific gravity of the antifouling paint 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 composition x 1000 x (100-heat residue) / 100

The specific gravity of the antifouling paint is calculated by filling a specific gravity cup having a capacity of 100 mL with the antifouling paint at 25 ° C. and measuring the mass.
The heating residue (solid content) of the antifouling paint is determined by the following method.
Weigh 0.50 g of the measurement sample (antifouling paint) 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.
Residual heating (solid content) = mass after drying (g) / mass before drying (g) x 100 (%)

The heating residue (solid content) of the antifouling paint 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 antifouling paint 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 antifouling paint can be easily lowered.

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

The coating film formed by using the resin composition of the present invention or the antifouling paint is excellent in antifouling property. Therefore, for example, by forming a coating film using the resin composition of the present invention or the antifouling paint on a portion of a ship in contact with seawater, adhesion of marine organisms can be suppressed.

[Coating film]
The coating film of the present invention is formed by using the above-mentioned resin composition of the present invention or the antifouling paint, and contains the polymer for the antifouling paint of the present invention.
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 water contact angle of the outer surface of the coating film formed from the polymer for antifouling coating material of the present invention by the captive bubble method is preferably 120 ° or more and 170 ° or less, and 125 ° or more and 170 ° or less. More preferably, it is more preferably 130 ° or more and 170 ° or less.
When the underwater contact angle by the captive bubble method of the outer surface of the coating film formed from the polymer for antifouling coating material of the present invention is within the above range, the outer surface of the coating film is excellent in antifouling property. Further, if it 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, and if it is at least the above upper limit value, it is water resistant. Excellent in sex.
In the present specification, 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 indentation elastic modulus of the outer surface of the coating film formed from the polymer for antifouling coating material of the present invention is preferably 15 MPa or more and 2,900 MPa or less, more preferably 30 MPa or more and 2,000 MPa or less, and 50 MPa or more. It is more preferably 1,500 MPa or less.
When the indentation elastic modulus of the outer surface of the coating film formed from the polymer for antifouling coating material of the present invention is at least the above lower limit value, the tack property of the coating film surface is small, so that the handleability is good and at least the above upper limit value. If this is the case, the hardness of the coating film is increased, so that the wear resistance is improved.
The indentation elastic modulus of the outer surface of the coating film is measured by the method described in Examples.
The indentation elastic modulus of the outer surface of the coating film can be adjusted by the glass transition temperature (Tg) of the antifouling coating polymer. For example, the larger the glass transition temperature (Tg) of the antifouling coating polymer, the higher the indentation elastic modulus tends to be.

The water absorption rate of the coating film of the present invention is preferably 5% or more and 70% or less, more preferably 5% or more and 50% or less, and further preferably 5% or more and 45% or less.
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. Has excellent water resistance.
The water absorption rate of the coating film is measured by the method described in Examples described later.
The higher the content of the structural unit (C) in the coating film, the higher the water absorption rate tends to be.

The coating film of the present invention preferably has a micro or nano non-uniform structure.
In the antifouling paint polymer (P), the hydrophobic part and the hydrophilic part are incompatible with each other. Therefore, when the coating film containing the antifouling paint polymer (P) is formed, the hydrophobic part and the hydrophilic part are formed. It is possible to obtain a coating film having a micro or nano-uniform structure by phase-separating with and. The region consisting of the hydrophobic part has a lower affinity with an aqueous liquid such as seawater than the region consisting of the hydrophilic part or the region where the hydrophobic part and the hydrophilic part exist without phase separation. .. Since the region composed of the hydrophobic portion exists on the surface of the coating film, the frictional resistance with the aqueous liquid becomes smaller.
Examples of the micro or nanoheterogeneous structure include a sea-island structure, a cylinder structure, a lamellar structure, a co-continuous structure, and the like.

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 addition, the part in an Example represents a mass part.
The evaluation in the examples was performed by the method shown below.

(Weight average molecular weight (Mw), number average molecular weight (Mn))
Measurements were made using gel permeation chromatography (GPC) (HLC-8220, manufactured by Tosoh Corporation). As the column, TSKgelα-M (manufactured by Tosoh Co., Ltd., 7.8 mm × 30 cm) and TSKguardcolumnα (manufactured by Tosoh Co., Ltd., 6.0 mm × 4 cm) were used. The calibration curve was prepared using F288 / F1 / 28 / F80 / F40 / F20 / F2 / A1000 (manufactured by Tosoh Corporation, standard polystyrene) and styrene monomer.

(Adhesion rate, mortality rate, swimming rate)
A sample was spin-coated on a 5 cm × 5 cm × 1 mm (thickness) acrylic plate so as to have a dry film thickness of 200 μm, and dried at room temperature to form a coating film, which was used as a test plate.
The test plate was allowed to stand on the bottom surface of a polypropylene container (8 cm × 8 cm × 4.5 cm) so that the coating film was on the upper surface, and 100 ml of seawater and 100 larvae in the adhesion stage (Cyprus larvae) were added. The test seawater was maintained in a state of being moved by horizontal shaking (3 cm round trip 60 times / minute) at room temperature of 22 ± 2 ° C. Seven days after the injection, the number of individuals with attached / transformed larvae attached to the coating film (adhesion rate), the number of dead individuals (mortality rate), and the number of surviving individuals without attachment (swimming rate) are measured under a stereomicroscope. Counted with.
The adhesion rate, the mortality rate, and the swimming rate are the ratios of the number of each individual to the 100 individuals input, and the total of the adhesion rate, the mortality rate, and the swimming rate is 100%.

(Contact angle by the captive bubble method (underwater contact angle))
A sample was spin-coated on a slide glass 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, which was used as a test plate.
The underwater contact angle of the coating film was 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 test plate in water. .. The larger the contact angle in water, the higher the hydrophilicity of the substrate surface.

(Indentation modulus)
A sample was spin-coated on a slide glass 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, which was used as a test plate.
Measurement conditions of Vickers indenter, load 7 mN / 100s, creep 60s, R = 0.4 mN / 100s (s is seconds, R is release speed) with a micro hardness tester HM-2000 (manufactured by Fisher Instruments, trade name). (Represented), the indentation elasticity of the coating film was measured.

Production Example 1 [Synthesis of macromonomer (MM1)]
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 O" (registered trademark) (1,1, 1) as a polymerization initiator. 3,3-Tetramethylbutylperoxy2-ethylhexanoate (manufactured by NOF CORPORATION) 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.
The Sp value of MMA is 18.27 (J / cm ³ ) ^1/2 .

Production Example 2 [Synthesis of monomer (c2) represented by formula (c2)]
In advance, a compound (d2) represented by the following formula (d2) was synthesized by a known method (Polymer, 1990, Vol. 31, Vol. 31, p. 1164-1169).
A three-necked flask equipped with a dropping funnel and a stir bar is thoroughly dried in advance, and 25 g of N- (triethylammoniosulfonyl) methyl carbamate (Burges reagent) (manufactured by Tokyo Kasei Co., Ltd., 105 mmol) is added under a dry air stream. 100 mL of dehydrated THF (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred and dissolved at room temperature. All subsequent reactions were carried out under a dry air stream. Separately, 12.9 g (70 mmol) of compound (d2) was dissolved in 100 mL of ultra-dehydrated THF (manufactured by Wako Pure Chemical Industries, Ltd.) in a dropping funnel, and the mixture was added dropwise to the three-necked flask over 30 minutes at room temperature. After completion of the dropping, the mixture was heated and stirred at 40 ° C. for 2 hours. After cooling to room temperature, 200 mL of water and 100 mL of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the mixture was vigorously stirred for 30 minutes, and then the organic layer and the aqueous layer were separated by a separating funnel. The aqueous layer was further extracted with 100 mL of toluene, and then the combined organic layer was washed twice with 100 mL of water. After adding 10 g of magnesium sulfate to the organic layer and allowing it to stand overnight, the solution obtained by removing magnesium sulfate by vacuum filtration was concentrated by an evaporator (17 Torr, 30 ° C.). The obtained residue was purified by a silica gel column (developing solvent: hexane / acetic acid = 15/1) to obtain 8.2 g of monomer (c2) (yield: 70.4%).

With respect to the obtained monomer (c2), ¹ H-NMR spectrum and ¹³ C-NMR spectrum were measured under the following conditions, and it was confirmed that the target compound was synthesized.
^{1 1} H-NMR (270 MHz, CDCl ₃ ) δ6.22 (1H, = CH), 5.71 (1H, = CH), 4.11 (2H, -CH ₂ ), 1.92 (3H, -CH3) , 1.48 (6H, -CH ₃ )
¹³ _{C-NMR (270 MHz, CDCl 3} ) δ166, 155, 135, 127, 70, 56, 26, 18
< ^{1 1} H-NMR, ¹³ C-NMR measurement conditions>
Equipment: JEOL Ltd. GSX-270 FT-NMR
Frequency: 270MHz
Sample: 10 mg of each compound dissolved in 1 g of deuterated chloroform

Production Example 3 [Synthesis of monomer (c3) represented by formula (c3)]
In advance, a compound (d3) represented by the following formula (d3) was synthesized by a known method (Polymer, 1990, Vol. 31, Vol. 31, p. 1164-1169).
In Production Example 2, 4.7 g of the monomer (c3) was obtained in the same manner as in Production Example 2 except that 11.9 g (70 mmol) of the compound (d3) was used instead of the compound (d2). (Yield 44.0%).
With respect to the obtained monomer (c3), ¹ H-NMR spectrum and ¹³ C-NMR spectrum were measured in the same manner as in Production Example 2, and it was confirmed that the target compound was synthesized.
^{1 1} H-NMR (270 MHz, CDCl ₃ ) δ6.51 (1H, = CH), 6.14 (1H, = CH), 5.91 (1H, = CH), 4.05, (2H, -CH ₂₎ ), 1.47 (6H, -CH ₃ )
¹³ _{C-NMR (270 MHz, CDCl 3} ) δ165, 155, 132, 128, 70, 56, 26

Comparative manufacturing example 1 [Manufacturing of comparative antifouling paint (1)]
[Production of metal-containing monomer mixture (M1)]
85.4 parts of PGM (propylene glycol methyl ether) and 40.7 parts of zinc oxide were placed in a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, and the temperature was raised to 75 ° C. with stirring. Subsequently, a mixture consisting of 43.1 parts of methacrylic acid, 36.1 parts of acrylic acid, and 5 parts of water was added dropwise from the dropping funnel at a constant velocity in 3 hours. After completion of the dropping, the reaction solution became transparent from a milky white state. After further stirring for 2 hours, 36 parts of PGM was added to obtain a transparent metal-containing monomer mixture (M1). The solid content was 44.8%.
[Manufacturing of hydrolyzable antifouling paint resin]
85.4 parts of PGM (propylene glycol methyl ether) and 40.7 parts of zinc oxide were placed in a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, and the temperature was raised to 75 ° C. with stirring. Subsequently, a mixture consisting of 43.1 parts of methacrylic acid, 36.1 parts of acrylic acid, and 5 parts of water was added dropwise from the dropping funnel at a constant velocity in 3 hours. After completion of the dropping, the reaction solution became transparent from a milky white state. After further stirring for 2 hours, 36 parts of PGM was added to obtain a transparent metal-containing monomer mixture (M1). The solid content was 44.8%.
15 parts of PGM (propylene glycol methyl ether), 57 parts of xylene and 4 parts of ethyl acrylate were placed in a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, and the temperature was raised to 100 ° C. with stirring. .. Subsequently, 14.6 parts of methyl methacrylate, 52.6 parts of ethyl acrylate, 7.5 parts of n-butyl acrylate, 47.4 parts of the metal-containing monomer mixture (M1) obtained above, 10 parts of xylene, and a chain from the dropping funnel. Transparent consisting of 1 part of transfer agent (manufactured by Nippon Oil & Fats Co., Ltd., product name: Nofmer MSD), 2.5 parts of AIBN, and 8.5 parts of AMBN (compound name: 2,2'-azobis (2-methylbutyronitrile)). The mixture was added dropwise at a constant velocity in 6 hours. After completion of the addition, 0.5 part of t-butylperoctate and 7 parts of xylene were added dropwise in 30 minutes, and after further stirring for 1 hour and 30 minutes, 6.9 parts of xylene was added. Then, a pale yellow transparent metal-containing resin composition (comparative antifouling coating material (1)) having no insoluble matter was obtained. The antifouling coating material of this example contained a hydrophobic monomer and a metal as resin components. An elution type antifouling coating containing a copolymer with a monomer.

Example 1
In a flask with a cooling tube, 50 parts of the macromonomer (MM1) produced in Production Example 1, 50 parts of 2-hydroxyethyl acrylate (HEA) (manufactured by Osaka Organic Chemical Industries, Ltd.), and the monomer produced in Production Example 2 (c2). ) 5 parts and 250 parts of propylene glycol monomethyl ether (Wako Pure Chemical Industries, Ltd.) as a solvent were 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, 0.1 part (Wako Pure Chemical Industries, Ltd.) Wako Special Grade) manufactured by Yakusha was added to the monomer composition and then retained 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 (manufactured by 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 a polymer for antifouling paint. The weight average molecular weight of the polymer for antifouling paint was 55,000, and the glass transition point was 34 ° C.
Next, 25 parts of the antifouling paint polymer and 75 parts of propylene glycol monomethyl ether 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 antifouling paint polymer and the solvent. ..
Using the obtained resin composition as a sample, a coating film was formed by the above method, and the adhesion rate, mortality rate, swimming rate, underwater contact angle, and indentation elastic modulus were measured.
The table shows the types and amounts (parts by mass) of the monomers and solvents used in the production of the polymer or resin composition for antifouling paint, and the evaluation results.

Examples 2-16
A polymer for antifouling paint was obtained in the same manner as in Example 1 except that the monomer was changed to the monomer shown in Table 1, a resin composition was prepared, and each evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1
Using the comparative antifouling paint (1) obtained in Comparative Production Example 1 as a sample, each evaluation was carried out in the same manner as in Example 1. The results are shown in Table 2.
Comparative Example 2
Each evaluation was carried out in the same manner as in Example 1 using the existing antifouling paint (2) (product name: New Peraklin Plus, manufactured by Chugoku Marine Paint Co., Ltd.) as a sample. The results are shown in Table 2.
Comparative Example 3
A polymer for antifouling paint was obtained in the same manner as in Example 1 except that the monomer or solvent was changed to the solvent shown in Table 2, a resin composition was prepared, and each evaluation was performed in the same manner as in Example 1. rice field.

The abbreviations in the table have the following meanings.
MMA: Methyl methacrylate, manufactured by Mitsubishi Rayon, Sp value: 18.27 (J / cm ³ ) ^1/2 .
HEA: 2-hydroxyethyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., Sp value: 25.47 (J / cm ³ ) ^1/2 .
MEA: 2-methoxyethyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd., Sp value: 18.55 (J / cm ³ ) ^1/2 .
HEMA: 2-hydroxyethyl methacrylate, manufactured by Tokyo Chemical Industry Co., Ltd., Sp value: 24.67 (J / cm ³ ) ^1/2 .
MCS: Methyl cellosolve.
PGM: Propylene glycol monomethyl ether.

Since the coating films of Examples 1 to 16 had a high swimming rate and a low adhesion rate and mortality rate, it was confirmed that they were excellent in antifouling property due to the repellent effect.

Claims (13)

A structural unit (A) derived from the macromonomer (a), a structural unit (B) derived from a monomer (b) that is not a macromonomer (however, excluding the monomer (c)), and the following formula. (c1) viewed contains a structural unit (C) derived from the monomer (c) represented by,
The solubility parameter of the monomer (aa) constituting the macromonomer (a) is less than ^{18.5 (J / cm 3} ) ^1/2.
A polymer for antifouling paint, wherein the solubility parameter of the monomer (b) is 18.5 (J / cm ³ ) ^1/2 or more.
R ^21- O-R ^22- NC ... (c1)
In formula (c1), R ²¹ is a monovalent group having a reactive double bond, R ²² is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, and a substituted or unsubstituted alkynylene. It is a divalent group selected from a group, and the divalent group may contain one or more selected from the following hetero atom, the following hetero atomic group, and the following cyclic divalent group in the chain.
Heteroatom: One or more selected from = N-, -O- and -S-.
Heteroatom group: One or more selected from epoxy, -N (R ²³ )-, -CO-, -SO- and -SO _2-. R ²³ is a hydrogen atom, a hydroxy group, or a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkynyl group, a heterocycloalkyl group, an alkoxy group, a cycloalkoxy group, or a hetero. Cycloalkoxy group, aryl group, heteroaryl group, arylalkyl group, heteroarylalkyl group, aryloxy group, arylalkyloxy group, arylalkenyloxy group, heteroaryloxy group, heteroarylalkyloxy group, aryl condensed cycloalkyl group Alternatively, it is an aryl-condensed heterocycloalkyl group.
Cyclic divalent group: substituted or unsubstituted cycloalkylene group, substituted or unsubstituted cycloalkenylene group, substituted or unsubstituted cycloalkynylene group, substituted or unsubstituted arylene group and substituted or unsubstituted heteroarylene group One or more selected from. The polymer for an antifouling paint according to claim 1, ^{wherein R 21} in the formula (c1) is a (meth) acryloyl group. The structural unit (C) is a structural unit derived from the monomer (c2) represented by the following formula (c2), or a structural unit derived from the monomer (c3) represented by the following formula (c3). The polymer for antifouling paint according to claim 2.

The macromonomer according to any one of claims 1 to 3, wherein the macromonomer (a) is a macromonomer having a radically polymerizable group and having two or more structural units represented by the following formula (AA). Polymer for antifouling paint.

(In the formula, R ¹ is a hydrogen atom, a methyl group or CH ₂ OH, R ² is an 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, substituted or unsubstituted alkyl groups, substituted or unsubstituted alicyclic groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted non-substituted. aromatic heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkaryl group, or a substituted or represents an unsubstituted organosilyl group, R ⁸ is a substituted or unsubstituted aryl group, or a substituted Alternatively, it indicates an unsubstituted heteroaryl group.) The polymer for antifouling coating material according to any one of claims 1 to 4 , wherein the macromonomer (a) is a macromonomer represented by the following formula (1).

(In the formula, R is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted heteroaryl group. It is a non-aromatic heterocyclic group, and a plurality of Rs may be the same or different, X is a hydrogen atom or a methyl group, and a plurality of Xs may be the same or different. Often, Z is the terminal group and n is a natural number of 2 to 10,000.) A resin composition comprising the polymer for an antifouling coating material according to any one of claims 1 to 5. An antifouling paint containing the resin composition according to claim 6. A coating film formed by using the resin composition according to claim 6 or the antifouling paint according to claim 7. A polymer for antifouling paint that polymerizes a monomer mixture containing a monomer (c) represented by the following formula (c1) and a monomer copolymerizable with the monomer (c). It ’s a manufacturing method ,
The monomer copolymerizable with the monomer (c) contains a macromonomer (a) and a monomer (b) that is not a macromonomer (however, excluding the monomer (c)).
The solubility parameter of the monomer (aa) constituting the macromonomer (a) is less than ^{18.5 (J / cm 3} ) ^1/2.
A method for producing a polymer for an antifouling paint, wherein the solubility parameter of the monomer (b) is 18.5 (J / cm ³ ) ^1/2 or more.
R ^21- O-R ^22- NC ... (c1)
In formula (c1), R ²¹ is a monovalent group having a reactive double bond, R ²² is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, and a substituted or unsubstituted alkynylene. It is a divalent group selected from a group, and the divalent group may contain one or more selected from the following hetero atom, the following hetero atomic group, and the following cyclic divalent group in the chain.
Heteroatom: One or more selected from = N-, -O- and -S-.
Heteroatom group: One or more selected from epoxy, -N (R ²³ )-, -CO-, -SO- and -SO _2-. R ²³ is a hydrogen atom, a hydroxy group, or a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkynyl group, a heterocycloalkyl group, an alkoxy group, a cycloalkoxy group, or a hetero. Cycloalkoxy group, aryl group, heteroaryl group, arylalkyl group, heteroarylalkyl group, aryloxy group, arylalkyloxy group, arylalkenyloxy group, heteroaryloxy group, heteroarylalkyloxy group, aryl condensed cycloalkyl group Alternatively, it is an aryl-condensed heterocycloalkyl group.
Cyclic divalent group: substituted or unsubstituted cycloalkylene group, substituted or unsubstituted cycloalkenylene group, substituted or unsubstituted cycloalkynylene group, substituted or unsubstituted arylene group and substituted or unsubstituted heteroarylene group One or more selected from. R in the formula (c1) ²¹ The method for producing a polymer for an antifouling paint according to claim 9, wherein is a (meth) acryloyl group. The tenth aspect of the present invention, wherein the monomer (c) contains a monomer (c2) represented by the following formula (c2) or a monomer (c3) represented by the following formula (c3). A method for producing a polymer for antifouling paint.

The invention according to any one of claims 9 to 11, wherein the macromonomer (a) is a macromonomer having a radically polymerizable group and having two or more structural units represented by the following formula (AA). A method for producing a polymer for an antifouling paint.

(In the formula, R ¹ Is a hydrogen atom, a methyl group or CH ₂ OH and R ² Is OR ³ , Halogen atom, COR ⁴ , COOR ⁵ , CN, CONR ⁶ R ⁷ Or R ⁸ And R ³ ~ R ⁷ Are independently hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alicyclic groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted non-fragrances, respectively. Indicates a group heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkalil group, or a substituted or unsubstituted organosilyl group, and R ⁸ Indicates a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. ) The method for producing a polymer for an antifouling coating according to any one of claims 9 to 12, wherein the macromonomer (a) is a macromonomer represented by the following formula (1).

(In the formula, R is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted heteroaryl group. It is a non-aromatic heterocyclic group, and a plurality of Rs may be the same or different, X is a hydrogen atom or a methyl group, and a plurality of Xs may be the same or different. Often, Z is the terminal group and n is a natural number of 2 to 10,000.)