JP6915276B2 - Antifouling paint, coating film, and underwater friction reduction method - Google Patents

Description

The present invention relates to a polymer for an insoluble antifouling paint, a resin composition, an antifouling paint, a coating film, a method for reducing friction in water, and a method for producing a polymer for an insoluble antifouling paint.
This application applies to Japanese Patent Application No. 2015-238670 filed in Japan on December 7, 2015, Japanese Patent Application No. 2016-136502 filed in Japan on July 11, 2016, and Japan on July 15, 2016. Claim the priority based on Japanese Patent Application No. 2016-139981 filed in the above, and the contents thereof are incorporated herein by reference.

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.
Known 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 is not surface-renewed. There is.
As a non-eluting antifouling coating material, for example, one which is composed of at least two kinds of resins which are incompatible with each other and insoluble in seawater to form a cured coating film having a specific microheterogeneous structure has been proposed (Patented). Document 1).

On the other hand, a ship receives frictional resistance from seawater while sailing. From the viewpoint of reducing fuel consumption and energy saving, it is desired that the coating film provided on the portion of the ship in contact with seawater has a performance of reducing frictional resistance.
In response to such demands, for example, a coating composition (Patent Document 2) containing a composite particle composed of a specific organic polymer substance and a specific dispersant and having a specific particle size and a resin binder, or a film surface. An underwater friction-reducing coating film (Patent Document 3) in which the contact angle with water and the surface roughness of the above are set to predetermined values has been proposed.

Japanese Patent No. 10-60317 Japanese Patent No. 2007-169628 Japanese Unexamined Patent Publication No. 2003-277691

However, the effect of reducing the frictional resistance of the coating film formed from the conventional coating composition is not yet sufficient.

An object of the present invention is a polymer for an insoluble antifouling paint capable of forming a coating film having a small frictional resistance with an aqueous liquid such as seawater, a resin composition, an antifouling paint, a coating film formed by using these, and underwater. It is an object of the present invention to provide a method for reducing friction and a method for producing a polymer for an insoluble antifouling coating material.

The present invention has the following aspects.

（式中、Ｒ^１は水素原子、メチル基又はＣＨ_２ＯＨであり、Ｒ^２はＯＲ^３、ハロゲン原子、ＣＯＲ^４、ＣＯＯＲ^５、ＣＮ、ＣＯＮＲ^６Ｒ^７又はＲ^８であり、Ｒ^３〜Ｒ^７はそれぞれ独立に、水素原子、非置換の若しくは置換基を有するアルキル基、非置換の若しくは置換基を有する脂環式基、非置換の若しくは置換基を有するアリール基、非置換の若しくは置換基を有するヘテロアリール基、非置換の若しくは置換基を有する非芳香族の複素環式基、非置換の若しくは置換基を有するアラルキル基、非置換の若しくは置換基を有するアルカリール基、又は非置換の若しくは置換基を有するオルガノシリル基を示し、これらに許容される置換基はそれぞれ、カルボキシル基、アルコキシカルボニル基、エポキシ基、ヒドロキシ基、アルコキシ基、１級アミノ基、２級アミノ基、３級アミノ基、イソシアナト基、スルホ基及びハロゲンからなる群から選ばれる少なくとも１種であり、Ｒ^８は非置換の若しくは置換基を有するアリール基、又は非置換の若しくは置換基を有するヘテロアリール基を示し、これらに許容される置換基はそれぞれ、カルボキシル基、アルコキシカルボニル基、エポキシ基、ヒドロキシ基、アルコキシ基、１級アミノ基、２級アミノ基、３級アミノ基、イソシアナト基、スルホ基、非置換の若しくは置換基を有するアルキル基、非置換の若しくは置換基を有するアリール基、非置換の若しくは置換基を有するアルケニル含有基及びハロゲンからなる群から選ばれる少なくとも１種である。）
［４］前記単量体（ｂ）が脂肪族単量体である、［１］〜［３］のいずれか一項に記載の非溶解性防汚塗料用ポリマー。
［５］ガラス転移点が１０℃以上である、［１］〜［４］のいずれか一項に記載の非溶解性防汚塗料用ポリマー。
［６］前記マクロモノマー（ａ）が、下記式（１）で表されるマクロモノマーである、［１］〜［５］のいずれか一項に記載の非溶解性防汚塗料用ポリマー。

（式中、Ｒは水素原子、非置換の若しくは置換基を有するアルキル基、非置換の若しくは置換基を有する脂環式基、非置換の若しくは置換基を有するアリール基、非置換の若しくは置換基を有するヘテロアリール基、又は非置換の若しくは置換基を有する非芳香族の複素環式基であり、複数のＲはそれぞれ同一であっても異なっていてもよく、Ｘは水素原子又はメチル基であり、複数のＸはそれぞれ同一であっても異なっていてもよく、Ｚは末端基であり、ｎは２〜１０，０００の自然数である。）[1] Containing a structural unit (A) derived from the macromonomer (a) and a structural unit (B) derived from the monomer (b) that is not a macromonomer.
The solubility parameter of the monomer (aa) constituting the macromonomer (a) is less than ^{18.5 (J / cm 3} ) ^1/2.
A polymer for insoluble antifouling coating material, wherein the solubility parameter of the monomer (b) is 18.5 (J / cm ³ ) ^{1/2 or more.}
[2] The contact angle of the surface of the formed coating film by the captive bubble method is 120 ° or more and 144 ° or less, and the indentation elastic modulus of the formed coating film is 15 MPa or more and 2900 MPa or less [1]. ] Described polymer for non-soluble antifouling paint.
[3] The macromonomer according to [1] or [2], 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). Non-soluble antifouling paint polymer.

(In the formula, R ¹ is a hydrogen atom, a methyl group or CH ₂ OH, R ² is OR ³ , a halogen atom, COR ⁴ , COOR ⁵ , CN, CONR ⁶ R ⁷ or R ⁸ , and R ^{3 to} R ⁷ are independently hydrogen atoms, alkyl groups having unsubstituted or substituents, alicyclic groups having unsubstituted or substituents, aryl groups having unsubstituted or substituents, and unsubstituted or substituents, respectively. Heteroaryl group with unsubstituted or substituent, non-aromatic heterocyclic group with unsubstituted or substituent, aralkyl group with unsubstituted or substituent, alkalinel group with unsubstituted or substituent, or unsubstituted Alternatively, an organosilyl group having a substituent is shown, and the allowable substituents thereof are a carboxyl group, an alkoxycarbonyl group, an epoxy group, a hydroxy group, an alkoxy group, a primary amino group, a secondary amino group, and a tertiary amino, respectively. It is at least one selected from the group consisting of a group, an isocyanato group, a sulfo group and a halogen, and R ⁸ represents an aryl group having an unsubstituted or substituent or a heteroaryl group having an unsubstituted or substituent. The substituents allowed for these are carboxyl group, alkoxycarbonyl group, epoxy group, hydroxy group, alkoxy group, primary amino group, secondary amino group, tertiary amino group, isocyanato group, sulfo group, and unsubstituted. Alternatively, it is at least one selected from the group consisting of an alkyl group having a substituent, an aryl group having an unsubstituted or substituent, an alkenyl-containing group having an unsubstituted or substituent, and a halogen.)
[4] The polymer for an insoluble antifouling coating material according to any one of [1] to [3], wherein the monomer (b) is an aliphatic monomer.
[5] The polymer for an insoluble antifouling coating material according to any one of [1] to [4], which has a glass transition point of 10 ° C. or higher.
[6] The polymer for an insoluble antifouling coating material according to any one of [1] to [5], wherein the macromonomer (a) is a macromonomer represented by the following formula (1).

(In the formula, R is a hydrogen atom, an alkyl group having an unsubstituted or substituent, an alicyclic group having an unsubstituted or substituent, an aryl group having an unsubstituted or substituent, an unsubstituted or substituent. A heteroaryl group having a Yes, the plurality of Xs may be the same or different, where Z is a terminal group and n is a natural number of 2 to 10,000.)

[7] A resin composition containing the polymer for insoluble antifouling coating material according to any one of [1] to [6].
[8] The resin composition according to [7], further comprising a solvent.
[9] The resin composition according to [7] or [8], which has a viscosity at 25 ° C. of 5 × 10 ^{4 mPa · s or less.}
[10] An antifouling coating material containing the resin composition according to any one of [7] to [9].
[11] A coating film formed by using the resin composition according to any one of [7] to [9] or the antifouling paint according to [10].
[12] The step of forming a coating film on the surface of the object to be coated by using the resin composition according to any one of [7] to [9] or the antifouling paint according to [10] is included. , Underwater friction reduction method.

[13] The insolubility prevention according to any one of [1] to [6] by polymerizing a monomer mixture containing the macromonomer (a) and a monomer (b) that is not a macromonomer. A method for producing a non-soluble antifouling paint polymer, which obtains a polymer for stain paint.
A method for producing a polymer for an insoluble antifouling coating material, wherein the macromonomer (a) is a macromonomer having a radically polymerizable group.
[14] The method for producing a polymer for an insoluble antifouling coating according to [13], wherein the macromonomer having a radically polymerizable group is produced by a suspension polymerization method.
[15] The method for producing a polymer for an insoluble antifouling coating according to [14], wherein the monomer mixture is polymerized by a solution polymerization method.

According to the present invention, a polymer for an insoluble antifouling paint capable of forming a coating film having a small frictional resistance with an aqueous liquid such as seawater, a resin composition, an antifouling paint, a coating film formed by using these, and underwater. A method for reducing friction and a method for producing a polymer for an insoluble antifouling paint 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 non-soluble antifouling paint]
The polymer for non-soluble antifouling coating material of the present invention includes a structural unit derived from a macromonomer (hereinafter, also referred to as “macromonomer (a)”) (hereinafter, also referred to as “constituent unit (A)”). The macromonomer (a) contains a structural unit (hereinafter, also referred to as “constituent unit (B)”) derived from a monomer that is not a macromonomer (hereinafter, also referred to as “monomer (b)”). The solubility parameter of the monomer (hereinafter, also referred to as “monomer (aa)”) constituting the above is less than 18.5, and the solubility parameter of the monomer (b) is 18.5 or more.

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

(Constituent unit (A))
The structural unit (A) is a structural unit derived from the macromonomer (a) described later.
The macromonomer (a) 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 preferably 15.0 or more and less than 18.5, and more 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 is "(J / cm ³ ) ^{1 /. 2} ”, but the unit may be omitted in this specification.

但し、式（２）において、原子団の凝集エネルギー及びモル体積の値は表１に示す値を用いた。-Solubility parameter In the present invention, 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 equation (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 formula (3).}

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

When the macromonomer (a) has a radically polymerizable group, the macromonomer (a) and the monomer (b) are copolymerized by radical polymerization to produce the insoluble antifouling coating polymer of the present invention. be able to.
When the macromonomer (a) has a radically polymerizable group, the macromonomer (a) may have one or more radically polymerizable groups, and preferably has one radically polymerizable group. ..

When the macromonomer (a) has an addition-reactive functional group, the monomer (b) usually has a functional group capable of reacting with the addition-reactive functional group of the macromonomer (a). The polymer for insoluble antifouling coating material of the present invention is produced by reacting the polymerizable functional group derived from the monomer (b) with the addition-reactive functional group of the macromonomer (a). Can be done.
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.
Combination of hydroxyl group and carboxyl group or acid anhydride group, combination of isocyanate group and hydroxyl group or thiol group, combination of epoxy group and amino group, combination of carboxyl group and epoxy group, combination of amino group and carboxyl group Combination of amide group and carboxyl 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, it is copolymerized with the polymer unit composed of the monomer (b) and the functional group to be added, or the monomer (b). There may be two or more functional groups other than any of the radically polymerizable groups or radically polymerizable groups.

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

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

Examples of the unsubstituted alkyl group in R include a branched or linear alkyl group having 1 to 22 carbon atoms. Specific examples of 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 device having 4 to 18 carbon atoms include a pyridyl group and a carbazolyl group.

Examples of the unsubstituted heterocyclic group in R include a heterocyclic group having 4 to 18 carbon atoms. Specific examples of the heterocyclic group having 4 to 18 carbon atoms include an oxygen atom-containing heterocyclic group such as a tetrahydrofuryl group and a tetrahydropyranyl group, a γ-butyrolactone group, an ε-caprolactone group, a pyrrolidinyl group and a pyrrolidone group. Examples thereof include a nitrogen atom-containing heterocyclic group such as a morpholino group.

Substituents in R (alkyl groups having substituents, alicyclic groups having substituents, aryl groups having substituents, heteroaryl groups having substituents, non-aromatic heterocyclic groups having substituents, respectively. (Substituents in) include, for example, an alkyl group (except when R is an alkyl group having a substituent), an aryl group, -COOR ¹¹ , a cyano group, -OR ¹² , -NR ¹³ R ¹⁴ , -CONR. ^{Included is at least one selected from the group consisting of 15} R ¹⁶ , halogen atoms, allyl groups, epoxy groups, siloxy groups, and groups exhibiting hydrophilicity or ionicity.
Here, R ^{11 to} R ¹⁶ are each independently a hydrogen atom, an alkyl group having an unsubstituted or substituent, an alicyclic group having an unsubstituted or substituent, or an aryl having an unsubstituted or substituent. Indicates a group.

Examples of the alkyl group and the aryl group in the above-mentioned substituent include those similar to the above-mentioned unsubstituted alkyl group and unsubstituted aryl group, respectively.
As R ^{11 of −COOR 11} in the above substituent, a hydrogen atom or an unsubstituted alkyl group is preferable. That is, -COOR ¹¹ is preferably a carboxyl 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 carboxyl group or an alkali salt of a sulfo group, a poly (alkylene oxide) group such as a polyethylene oxide group and a polypropylene oxide group, and a quaternary ammonium base. Cationic substituents can be mentioned.

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

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

As the monomer (aa1), for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic T-butyl acid, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, ( Isononyl (meth) acrylate, decyl (meth) acrylate, isodecil (meth) acrylate, lauryl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, ( Phenyl acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfurfryl (meth) acrylate, isobornyl (meth) acrylate, 3,5,5-trimethylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, terpene acrylate and its derivatives, hydrogenated rosin acrylate and its derivatives, docosyl (meth) acrylate Such as hydrocarbon group-containing (meth) acrylic acid ester;
2-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, A hydroxyl group-containing (meth) acrylic acid ester such as glycerol (meth) acrylate;
(Meta) Acrylic Acid, 2- (Meta) Acryloyloxyethyl Hexahydrophthalic Acid, 2- (Meta) Acryloyloxypropyl Hexahydrophthalic Acid, 2- (Meta) Acryloyloxyethyl Phthalic Acid, 2- (Meta) 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 itaconate, monoethyl itaconate, monobutyl itaconate, monooctyl itaconate, monomethyl fumarate, monoethyl fumarate , Monobutyl fumarate, monooctyl fumarate, monoethyl citraconic acid and other carboxyl 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. (ethylene glycol chain is 2). (Things), trade name), "Blemmer PME-200" (Nichiyu Co., Ltd. methoxypolyethylene glycol methacrylate (those with 4 ethylene glycol chains), trade name), "Blemmer PME-400" (Nichiyu (Nichiyu) Methoxypolyethylene glycol methacrylate manufactured by Nichiyu Co., Ltd. (the chain of ethylene glycol is 9), trade name), "Blemmer 50 POEP-800B" (Octoxy polyethylene glycol-polypropylene glycol-methacrylate (chain of ethylene glycol) manufactured by Nichiyu Co., Ltd. Is 8 and the chain of propylene glycol is 6), trade name), "Blemmer 20 ANEP-600" (Nonylphenoxy (ethylene glycol-polypropylene glycol) monoacrylate manufactured by Nichiyu Co., Ltd., trade name), " Blemmer AME-100 (manufactured by Nichiyu Co., Ltd., trade name), "Blemmer AME-200" (manufactured by Nichiyu Co., Ltd., trade name) and "Blemmer 50 AOEP-800B" (manufactured by Nichiyu Co., Ltd., product) Name) and other glycol ester-based monomers,
3- (Meta) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane , Silane coupling agent-containing monomer such as vinyltriethoxysilane,
Trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tri-n-propylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, tri-n-amylsilyl (meth) acrylate, tri-n-hexylsilyl (Meta) acrylate, tri-n-octylsilyl (meth) acrylate, tri-n-dodecylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, tri-p-methylphenylsilyl (meth) acrylate, tribenzylsilyl (Meta) acrylate, triisopropylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tri-s-butylsilyl (meth) acrylate, tri-2-methylisopropylsilyl (meth) acrylate, tri-t-butylsilyl (meth) acrylate ) Acrylic, ethyldimethylsilyl (meth) acrylate, n-butyldimethylsilyl (meth) acrylate, diisopropyl-n-butylsilyl (meth) acrylate, n-octyldi-n-butylsilyl (meth) acrylate, diisopropylstearylsilyl (meth) acrylate , Dicyclohexylphenylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, lauryldiphenylsilyl (meth) acrylate, triisopropylsilylmethylmalate, triisopropylsilylamylmalate, tri-n-butylsilyl-n-butylmalate , T-Butyldiphenylsilylmethylmalate, t-butyldiphenylsilyl-n-butylmalate, triisopropylsilylmethylfumarate, triisopropylsilylamylfumarate, tri-n-butylsilyl-n-butylfumarate, t-butyldiphenyl Cyril methyl fumarate, t-butyldiphenylsilyl-n-butyl fumarate, silaplane FM-0711 (manufactured by JNC Co., Ltd., trade name), silaplane FM-0721 (manufactured by JNC Co., Ltd., trade name), sila Plain FM-0725 (manufactured by JNC Co., Ltd., trade name), Silaplane TM-0701 (manufactured by JNC Co., Ltd., trade name), Silaplane TM-0701T (manufactured by JNC Co., Ltd., trade name), X-22 -174ASX (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name), X-22-174BX (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name), KF-2012 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name), X -22-2426 (Shinetsu) Organosilyl group-containing monomers other than silane coupling agent-containing monomers such as Gakukogyo Co., Ltd., trade name), X-22-2404 (Shin-Etsu Chemical Co., Ltd., trade name);
Halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene, etc.
2-Isocyanatoethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluorophenyl (meth) acrylate, 2- (perfluorobutyl) Ethyl (meth) acrylate, 3- (perfluorobutyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate , 3- (Perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate , 1H, 1H, 5H-octafluoropentyl (meth) methacrylate, 1H, 1H, 2H, 2H-tridecafluorooctyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H , 1H, 3H-hexafluorobutyl (meth) acrylate, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl (meth) acrylate and other fluorine-containing monomers (excluding halogenated olefins) ),
A single having an acetal structure such as 1-butoxyethyl (meth) acrylate, 1- (2-ethylhexyloxy) ethyl (meth) acrylate, 1- (cyclohexyloxy) ethyl methacrylate, 2-tetrahydropyranyl (meth) acrylate. Quantum,
Examples thereof include 4-methacryloyloxybenzophenone and -2-isocyanatoethyl (meth) acrylate.
One of these monomers may be used alone, or two or more of these monomers may be used in combination.

（式中、Ｒ^１は水素原子、メチル基又はＣＨ_２ＯＨであり、Ｒ^２はＯＲ^３、ハロゲン原子、ＣＯＲ^４、ＣＯＯＲ^５、ＣＮ、ＣＯＮＲ^６Ｒ^７又はＲ^８であり、Ｒ^３〜Ｒ^７はそれぞれ独立に、水素原子、非置換の若しくは置換基を有するアルキル基、非置換の若しくは置換基を有する脂環式基、非置換の若しくは置換基を有するアリール基、非置換の若しくは置換基を有するヘテロアリール基、非置換の若しくは置換基を有する非芳香族の複素環式基、非置換の若しくは置換基を有するアラルキル基、非置換の若しくは置換基を有するアルカリール基、又は非置換の若しくは置換基を有するオルガノシリル基を示し、これらに許容される置換基はそれぞれ、カルボキシル基、アルコキシカルボニル基、エポキシ基、ヒドロキシ基、アルコキシ基、１級アミノ基、２級アミノ基、３級アミノ基、イソシアナト基、スルホ基及びハロゲンからなる群から選ばれる少なくとも１種であり、Ｒ^８は非置換の若しくは置換基を有するアリール基、又は非置換の若しくは置換基を有するヘテロアリール基を示し、これらに許容される置換基はそれぞれ、カルボキシル基、アルコキシカルボニル基、エポキシ基、ヒドロキシ基、アルコキシ基、１級アミノ基、２級アミノ基、３級アミノ基、イソシアナト基、スルホ基、非置換の若しくは置換基を有するアルキル基、非置換の若しくは置換基を有するアリール基、非置換の若しくは置換基を有するアルケニル含有基及びハロゲンからなる群から選ばれる少なくとも１種である。）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 ⁷ are independently hydrogen atoms, alkyl groups having unsubstituted or substituents, alicyclic groups having unsubstituted or substituents, aryl groups having unsubstituted or substituents, and unsubstituted or substituents, respectively. Heteroaryl group with unsubstituted or substituent, non-aromatic heterocyclic group with unsubstituted or substituent, aralkyl group with unsubstituted or substituent, alkalinel group with unsubstituted or substituent, or unsubstituted Alternatively, an organosilyl group having a substituent is shown, and the allowable substituents thereof are a carboxyl group, an alkoxycarbonyl group, an epoxy group, a hydroxy group, an alkoxy group, a primary amino group, a secondary amino group, and a tertiary amino, respectively. It is at least one selected from the group consisting of a group, an isocyanato group, a sulfo group and a halogen, and R ⁸ represents an aryl group having an unsubstituted or substituent or a heteroaryl group having an unsubstituted or substituent. The substituents allowed for these are carboxyl group, alkoxycarbonyl group, epoxy group, hydroxy group, alkoxy group, primary amino group, secondary amino group, tertiary amino group, isocyanato group, sulfo group, and unsubstituted. Alternatively, it is at least one selected from the group consisting of an alkyl group having a substituent, an aryl group having an unsubstituted or substituent, an alkenyl-containing group having an unsubstituted or substituent, and a halogen.)

A hydrogen atom and a methyl group are preferable as ^{R 1} , and COOR ⁵ is preferable ^{as R 2.}

The unsubstituted alkyl group, unsubstituted alicyclic group, unsubstituted aryl group, unsubstituted heteroaryl group, and unsubstituted non-aromatic heterocyclic group of ^{R 3 to} R ^{7 are the above-mentioned R, respectively.} Examples thereof include an unsubstituted alkyl group, an unsubstituted alicyclic group, an unsubstituted aryl group, an unsubstituted heteroaryl group, and an unsubstituted non-aromatic heterocyclic group in the above.

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

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

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

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

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

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

From the viewpoint of recoatability, the macromonomer (a) is a hydrophobic group-containing (meth) acrylic acid ester monomer, an oxyethylene group-containing (meth) acrylic acid ester monomer, and a hydroxyl group-containing (meth) acrylic acid ester single amount. Body, terminal alkoxyallylated polyether monomer, epoxy group-containing vinyl monomer, primary or secondary amino group-containing vinyl monomer, tertiary amino group-containing vinyl monomer, heterocyclic base One or more simple monomers selected from a sex monomer, a carboxy group-containing ethylenically unsaturated monomer, a cyano group-containing vinyl monomer, a vinyl ether monomer, a vinyl ester monomer, and an aromatic vinyl monomer. It is preferably a 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 Phenyl acid acid, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 3,5,5-trimethylcyclohexyl (meth) acrylate, (meth) Carbonation of dicyclopentanyl acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, terpene acrylate and its derivatives, hydrogenated rosin acrylate and its derivatives, docosyl (meth) acrylate, etc. Hydrogen group-containing (meth) acrylic acid ester; 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ( Hydroxyl-containing (meth) acrylic acid esters such as 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerol (meth) acrylate; (meth) acrylic acid, 2- (meth) acryloyloxyethyl hexa. Hydrophthalic acid, 2- (meth) acrylic oxypropylhexahydrophthalic acid, 2- (meth) acrylic oxyethyl phthalic acid, 2- (meth) acrylic oxypropyl phthalic acid, 2- (meth) acrylic oxyethyl maleic acid, 2- (Meta) acrylic oxypropyl maleic acid, 2- (meth) acrylic oxyethyl succinic acid, 2- (meth) acrylic oxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, itacone Carboxyl group-containing vinyl monomer such as monomethyl acid; Acid anhydride group-containing vinyl monomer such as maleic anhydride and itaconic acid anhydride; (meth) acrylic acid grease Epoxy group-containing vinyl-based monomers such as sidyl, 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 monomers; divinylbenzene, ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, Triethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, Trimethylol propantri (meth) acrylate, Allyl (meth) acrylate, N, N'- Polyfunctional vinyl-based monomers such as methylenebis (meth) acrylamide; acryloylmorpholin, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethyl (meth) acrylate, ethoxy (meth) acrylate Ethyl, n-butoxyethyl (meth) acrylate, isobutoxyethyl (meth) acrylate, t-butoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) ) Nonylphenoxyethyl acrylate, 3-methoxybutyl (meth) acrylate, acetoxyethyl (meth) acrylate, "Placel FM" (caprolactone-added monomer manufactured by Daicel Chemical Co., Ltd., trade name), "Blemmer PME-100" (Nichiyu Co., Ltd. methoxypolyethylene glycol methacrylate (chain of ethylene glycol is 2), trade name), "Blemmer PME-200" (Nichiyu Co., Ltd. methoxypolyethylene glycol methacrylate (chain of ethylene glycol) (4), trade name), "Blemmer PME-400" (Nichiyu Co., Ltd. methoxypolyethylene glycol methacrylate (those with 9 ethylene glycol chains), trade name), "Blemmer 50 POEP-800B" (Octoxy Polyethylene Glycol-Polypropylene Glycol-methacrylate (ethylene glycol chain 8 and propylene glycol chain 6), trade name) and "Blemmer 20 ANEP-600" (Nippon Oil Co., Ltd.) Nonylphenoxy (ethylene glycol-polypropylene glycol) monoacrylate manufactured by Nichiyu Co., Ltd. (trade name), "Blemmer AME-100" (manufactured by Nichiyu Co., Ltd., product name), "Blemmer AME-200" (Nichiyu Co., Ltd.) (Product, product name) and "Blemmer 50AOEP-800B" (manufactured by Nichiyu Co., Ltd., product name), Silaplane FM-0711 (manufactured by JNC Co., Ltd., product name), Silaplane FM-0721 (JNC Co., Ltd.) , Product name), Silaplane FM-0725 (manufactured by JNC Co., Ltd., product name), Silaplane TM-0701 (manufactured by JNC Co., Ltd., product name), Silaplane TM-0701T (manufactured by JNC Co., Ltd., Product name), X-22-174DX (manufactured by Shinetsu Chemical Industry Co., Ltd., product name), X-22-2426 (manufactured by Shinetsu Chemical Industry Co., Ltd., product name), X-22-2475 (manufactured by Shinetsu Chemical Industry Co., Ltd., product name) 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 group-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.
Those having the structure of the following formula (a2) are preferable.
_{In addition, "..." connecting CH 2} = C (COOR) -CH ₂ and Z in the formula (a2) indicates a main chain portion including two or more structural units (AA).

（式中、Ｒは前述のＲと同様であり、Ｚは末端基である。）

(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.

（式中、Ｒは前述のＲと同様であり、複数のＲはそれぞれ同じでも異なってもよく、Ｘは水素原子又はメチル基であり、複数のＸはそれぞれ同じでも異なってもよく、Ｚは末端基であり、ｎは２〜１０，０００の自然数である。）

(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 insoluble antifouling coating polymer, 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 insoluble antifouling coating polymer, R in the formula (1) is preferably a hydrogen atom from the viewpoint of hydrophilicity.

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

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

When the structural unit derived from the macromonomer (a) is contained in the hydrophobic part of the polymer for insoluble antifouling coating material, 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 part of the polymer for insoluble antifouling coating material, 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, it is preferable that R is a carboxyl group.
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.
The monomer (b) has a solubility parameter of 18.5 or more. The solubility parameter of the monomer (b) is preferably 18.5 or more and 47 or less, and more 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 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 alkoxyallylated polyether compounds such as methoxypolyethylene glycol allyl ether, methoxypolyethylene glycol allyl ether, butoxypolyethylene glycol allyl ether, butoxypolyethylene glycol allyl ether, methoxypolyethylene glycol-polypropylene glycol allyl ether, butoxypolyethylene glycol-polypropylene glycol allyl ether ;
Epoxy group-containing vinyl compounds such as glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, and 3,4-epoxybutyl (meth) acrylate;
Primary or secondary amino group-containing vinyl compounds such as butylaminoethyl (meth) acrylate 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 itaconic acid, monoethyl itaconic acid, Monobutyl itaconic acid, monooctyl itaconic acid, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monooctyl fumarate, monoethyl citraconate, monohydroxyethyl tetrahydrophthalate (meth) acrylate, monohydroxypropyl tetrahydrophthalate (meth) Acrylic, monohydroxybutyl (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, monohydroxypropyl (meth) phthalate, monohydroxyethyl succinate (meth) acrylate, monohydroxypropyl succinate (meth) ) A carboxy group-containing ethylenically unsaturated compound such as acrylate, monohydroxyethyl (meth) acrylate of maleate, and monohydroxypropyl (meth) acrylate of maleate;
Unsaturated dicarboxylic acid diesters such as dimethylmalate, dibutylmalate, dimethylfumarate, dibutylfumarate, dibutylitaconate, diperfluorocyclohexylfumarate;
Cyano group-containing vinyl compounds such as acrylonitrile and methacrylonitonyl;
Vinyl ether compounds such as alkyl vinyl ethers [eg, ethyl vinyl ethers, propyl vinyl ethers, butyl vinyl ethers, hexyl vinyl ethers, 2-ethylhexyl vinyl ethers, etc.], cycloalkyl vinyl ethers [eg, cyclohexyl vinyl ethers, etc.];
Vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene;
Halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, trimethylpropantri (meth) acrylate, pentaerythritol Polyfunctional compounds such as tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, allyl methacrylate, triallyl cyanurate, diallyl maleate, and polypropylene glycol diallyl ether.
These can be used by appropriately selecting one type or two or more types as required.

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 macromonomer (a), and (meth) acrylic acid, (meth) acrylate and substituted or unsubstituted. More preferably, at least one selected from the group consisting of (meth) acrylamide.

When the monomer (b) is a (meth) acrylate and the structural unit derived from the monomer (b) is contained in the hydrophilic part of the insoluble antifouling coating polymer, the monomer (b) From the viewpoint of hydrophilicity, a 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 (meth) acrylate is contained in the hydrophobic part of the polymer for insoluble antifouling coating material, 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. ..

(Preferable Aspects (I) of Polymers for Non-Soluble Antifouling Paints)
Preferred embodiments of the non-soluble antifouling paint polymer of the present invention include the following non-soluble antifouling paint polymer (I).
Insoluble antifouling coating polymer (I): Hydrophilic part containing a constituent unit derived from a macromonomer (a) and a hydrophilic portion containing a constituent unit derived from a (meth) acrylic monomer that is not a macromonomer. Polymer for non-soluble antifouling paint including parts.

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

As the (meth) acrylic monomer other than the macromonomer (a) forming the hydrophilic portion of the non-soluble antifouling coating polymer (I), for example, among the above-mentioned monomers (b), it is appropriate. At least one selected from the group consisting of (meth) acrylic acid, (meth) acrylate, particularly (meth) acrylate having a hydroxy group, and substituted or unsubstituted (meth) acrylamide is preferable.
The hydrophilic part of the non-soluble antifouling coating polymer (I) has a carboxyl group, − (R ^b2 O) _m R ^b3 , and −NR ^b4 R ^{b5 as a constituent unit derived from the (meth) acrylic monomer.} It is preferable to contain a structural unit derived from a (meth) acrylic monomer having a hydrophilic group such as. -(R ^b2 O) _m R ^b3 and -NR ^b4 R ^b5 are the same ^{as-(R b2} O) _m R ^{b3 in the above formula (b-1) and -NR b4} R ^b5 in the above formula (b-3), respectively. Is.
The (meth) acrylic monomer having a hydrophilic group includes (meth) acrylic acid, a compound represented by the formula (b-1), and a compound represented by the formula (b-3). At least one selected from is preferable.
The content of the structural unit derived from the (meth) acrylic monomer having a hydrophilic group may occupy 40% by mass or more of the total (100% by mass) of all the structural units constituting the hydrophilic part. It is more preferable to occupy 70% by mass or more, and it may be 100% by mass.

The hydrophilic portion of the non-soluble antifouling coating polymer (I) contains a structural unit derived from the (meth) acrylic monomer having no hydrophilic group as long as the hydrophilicity of the hydrophilic portion is not impaired. Further may be included. Examples of the (meth) acrylic monomer having no hydrophilic group include a compound represented by the above formula (b-2).
The hydrophilic portion of the non-soluble antifouling coating polymer (I) is derived from a monomer other than the macromonomer (a) and the (meth) acrylic monomer as long as the coating film performance is not impaired. Additional building blocks may be included. As the other monomer, for example, it can be appropriately selected from the above-mentioned monomer (b).

The content of the hydrophobic portion in the insoluble antifouling coating polymer (I) accounts for 5 to 90% by mass with respect to the total mass (100% by mass) of the insoluble antifouling coating polymer (I). It is preferable that it occupies 20 to 70% by mass, more preferably 30 to 60% by mass. When the content of the hydrophobic portion is within the above range, the effect of reducing the frictional resistance of the formed coating film is more excellent.
The total mass of the non-soluble antifouling coating polymer is equal to the total of the hydrophobic part and the hydrophilic part.

(Preferable Aspects of Non-Soluble Antifouling Paint Polymers (II))
Another preferred embodiment of the insoluble antifouling coating polymer of the present invention is the following insoluble antifouling coating polymer (II).
Insoluble antifouling coating polymer (II): Hydrophobic part containing a hydrophilic part containing a structural unit derived from a macromonomer (a) and a hydrophobic part containing a structural unit derived from a (meth) acrylic monomer other than the macromonomer. Polymer for non-soluble antifouling paint including parts.

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

The (meth) acrylic monomer other than the macromonomer (a) forming the hydrophobic portion of the non-soluble antifouling coating polymer (II) is appropriately selected from the above-mentioned monomers (b). Yes, (meth) acrylate is preferred.
The hydrophobic part does not have a hydrophilic group such ^{as the above-mentioned carboxyl group,-(R b2} O) _m R ^b3 , -NR ^b4 R ^b5 , as a constituent unit derived from the (meth) acrylic monomer (meth). It preferably contains a structural unit derived from an acrylic monomer.
As the (meth) acrylic monomer having no hydrophilic group, the compound represented by the above formula (b-2) is preferable.
The content of the structural unit derived from the (meth) acrylic monomer having no hydrophilic group occupies 70% by mass or more with respect to the total (100% by mass) of all the structural units constituting the hydrophobic portion. It is preferable that it occupies 90% by mass or more, and it may be 100% by mass.

The hydrophobic portion of the non-soluble antifouling coating polymer (II) further contains a structural unit derived from the (meth) acrylic monomer having a hydrophilic group as long as the hydrophobicity of the hydrophobic portion is not impaired. But it may be.
The hydrophobic portion of the non-soluble antifouling coating polymer (II) further contains a structural unit derived from the monomer (b) other than the (meth) acrylic monomer as long as the coating film performance is not impaired. But it may be. As the other monomer, for example, it can be appropriately selected from the above-mentioned monomer (b).

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

(Content of each structural unit)
In the insoluble antifouling coating polymer of the present invention, the content of the structural unit (A) derived from the macromonomer (a) in the total of all the constituent units constituting the insoluble antifouling coating polymer is. 5 to 95% by mass is preferable with respect to 100% by mass of the total of all the constituent units constituting the polymer for non-soluble antifouling coating.
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.
The total of all the structural units constituting the polymer for insoluble antifouling coating is the content of the structural unit (A) derived from the macromonomer (a) and the structural unit derived from the monomer (b). Is equal to the sum of.

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

The glass transition point of the polymer for non-soluble antifouling coating material of the present invention 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 non-soluble antifouling coating polymer of the present invention 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.

In the insoluble antifouling coating polymer of the present invention, the hydrophobic part and the hydrophilic part are incompatible. Therefore, when forming a coating film containing this insoluble antifouling coating polymer, the hydrophobic portion and the hydrophilic portion can be phase-separated to obtain a coating film having a micro or nano-uniform structure. .. The region composed of the hydrophobic portion has a lower affinity with an aqueous liquid such as seawater than the region in which the hydrophobic portion and the hydrophilic portion exist without phase separation. Further, the region composed of the hydrophilic portion has a higher affinity with an aqueous liquid such as seawater than the region in which the hydrophobic portion and the hydrophilic portion exist without phase separation, and the coating film surface details. A layer of water (Water Trap Layer) in which the flow is constrained can be formed. Since the region consisting of the hydrophobic part and the hydrophilic part exists on the surface of the coating film, the frictional resistance with the aqueous liquid becomes smaller.

In the present invention, "insoluble" means, for example, that the coating film residual ratio required below is 33% or more and 99% or less. The coating film residual ratio is preferably 50% or more and 99% or less, more preferably 75% or more and 99% or less, further preferably 80% or more and 99% or less, and particularly preferably 90% or more and 99% or less.

(Remaining rate test of coating film)
A resin composition for an antifouling paint was applied to a hard vinyl chloride plate having a size of 50 mm × 50 mm × 2 mm (thickness) with an applicator so as to have a dry film thickness of 120 μm to prepare a test plate. These test plates were attached to a rotating drum installed in seawater and rotated at a peripheral speed of 7.7 m / s (15 knots). One month later, the test plate was taken out and the film thickness was measured. The coating film residual rate is calculated by the following formula:
It is obtained from the coating film residual ratio (%) = residual film thickness (μm) after 1 month / initial film thickness 120 (μm) × 100.

(Manufacturing method of polymer for non-soluble antifouling paint)
The polymer for non-soluble antifouling coating material of the present invention can be produced, for example, by polymerizing the following monomer mixture.

-Monomer mixture The monomer mixture contains a macromonomer (a) and a monomer (b) that is not a macromonomer. The macromonomer (a) is preferably a macromonomer having a radically polymerizable group.
When producing the above-mentioned polymer (I) for insoluble antifouling paint or polymer (II) for insoluble antifouling paint, at least (meth) acrylic monomer is used as the monomer (b). If necessary, a monomer (b) other than the (meth) acrylic monomer may be further used.

The content of the macromonomer (a) in the monomer mixture is preferably 5 to 95% by mass with respect to the total mass of the monomer mixture (total mass of all monomers: 100% by mass). That is, the non-soluble antifouling coating polymer is obtained by polymerizing a monomer mixture containing macromonomer (a) in an amount of 5 to 95% by mass (charged amount) with respect to the total mass of all the monomers. Is preferable.
When the polymer for insoluble antifouling paint is the polymer (I) for insoluble antifouling paint, the content of the macromonomer (a) is the total mass of the monomer mixture (total mass of all monomers: From 100% by mass), 5 to 90% by mass is more preferable, 20 to 70% by mass is further preferable, and 30 to 60% by mass is particularly preferable.
When the polymer for insoluble antifouling paint is the polymer for insoluble antifouling paint (II), the content of the macromonomer (a) is the total mass of the monomer mixture (total mass of all monomers: From 100% by mass), 10 to 95% by mass is more preferable, 30 to 80% by mass is further preferable, and 40 to 70% by mass is particularly preferable.
When the content of the macromonomer (a) is within the above range, the effect of reducing the frictional resistance of the coating film formed by using the obtained polymer for non-soluble antifouling coating material is more excellent.
The total of the macromonomer (a) and the monomer (b) is 100% by mass.

When the polymer for insoluble antifouling paint is the polymer (I) for insoluble antifouling paint, the monomer mixture preferably contains the (meth) acrylic monomer having the hydrophilic group. The content of the (meth) acrylic monomer having a hydrophilic group in the monomer mixture is 40% by mass or more with respect to the total mass (100% by mass) of the monomers other than the macromonomer (a). It is preferably 70% by mass or more, and may be 100% by mass.

When the polymer for insoluble antifouling paint is the polymer for insoluble antifouling paint (II), the monomer mixture preferably contains the (meth) acrylic monomer having no hydrophilic group. The content of the (meth) acrylic monomer having no hydrophilic group in the monomer mixture is 70% by mass or more with respect to the total mass (100% by mass) of the monomers other than the macromonomer (a). Is preferable, 90% by mass or more is more preferable, and it may be 100% by mass.

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

In the methods (α1) to (α4), examples of the method for polymerizing the monomer component include a massive polymerization method, a solution polymerization method, and an aqueous dispersion polymerization method. Examples of the aqueous dispersion polymerization method include a suspension polymerization method and an emulsion polymerization method. The aqueous dispersion polymerization method is preferable, and the suspension polymerization method is particularly preferable, because the recovery step is simple. When the macromonomer (a) is produced by the suspension polymerization method, it is easy to handle.
The polymerization may be carried out by a known method using a known radical polymerization initiator. For example, a method of reacting the above-mentioned monomer component in the presence of a radical initiator at a reaction temperature of 60 to 120 ° C. for 4 to 14 hours can be mentioned. 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 non-soluble antifouling paint and the coating performance of the coating film formed by using the obtained polymer for non-soluble antifouling paint.
The polymerization may be carried out by a known method using a known radical polymerization initiator. For example, a method of reacting the above-mentioned monomer mixture in the presence of a radical initiator at a reaction temperature of 60 to 120 ° C. for 4 to 14 hours can be mentioned. At the time of polymerization, a chain transfer agent may be used if necessary.

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

[Resin composition]
The resin composition of the present invention contains the above-mentioned polymer for insoluble antifouling coating material of the present invention. The resin composition of the present invention preferably further contains a solvent.
The polymer for an insoluble antifouling coating contained in the resin composition may be one kind or two or more kinds. The above-mentioned polymer for non-soluble antifouling paint is preferably used as a resin for antifouling paint.

The content of the non-soluble antifouling coating polymer in the resin composition of the present invention is not particularly limited, but is preferably 5 to 85% by mass with respect to the total mass (100% by mass) of the resin composition. , 10 to 80% by mass, more preferably 30 to 75% by mass, and particularly preferably 55 to 75% by mass.
If the content of the polymer for non-soluble 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 more than the lower limit value, the VOC content is small. An antifouling paint 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 of the present invention 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 a polymer for insoluble antifouling paint, for example, monovalent alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; ethylene glycol, 1,2-propylene glycol and the like. Polyhydric 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 Glycol ethers such as propylene glycol monon-propyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether and dipropylene glycol monopropyl ether; glycols such as ethylene glycol monoacetate, ethylene glycol diacetate and ethylene glycol monomethyl ether acetate. Acetates; 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 of the present invention preferably occupies 15 to 95% by mass, more preferably 20 to 90% by mass, based on the total mass (100% by mass) of the resin composition. It is more preferable to occupy 25 to 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 of the present invention may further contain components other than the insoluble antifouling coating polymer.
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 insoluble antifouling coating material.

The viscosity of the resin composition of the present invention 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 4,000 mPa · s. The following is even more preferable, 3,000 mPa · s or less is even more preferable, and 2,000 mPa · s or less is particularly preferable.
If the viscosity of the resin composition of the present invention 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 of the present invention 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 insoluble antifouling coating polymer.

The method for producing the resin composition of the present invention is not particularly limited. For example, a monomer mixture of macromonomer (a) and monomer (b) is polymerized by a solution polymerization method to obtain a polymerization product containing an insoluble antifouling coating polymer and a solvent, and if necessary. Therefore, it can be prepared by adding a solvent or other components to the obtained polymerization product.

The resin composition of the present invention can be used as it is or, if necessary, mixed with an antifouling agent or the like to obtain an antifouling paint.
The resin composition of the present invention can be used not only for antifouling paints but also for antifogging 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 non-soluble antifouling paint of the present invention.
The antifouling paint of the present invention may further contain an antifouling agent, and may further contain other components other than the insoluble antifouling paint polymer of the present invention 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 of the present invention may further contain a solvent. Examples of the solvent include the same as described above. When the antifouling paint contains a solvent, the solvent may be derived from the resin composition of the present invention or may not be derived (blended at the time of manufacturing the antifouling paint). It may be both of them.

By applying the resin composition of the present invention to a portion of a marine structure or ship that comes into contact with seawater to form a coating film, corrosion of this portion by seawater and adhesion of marine organisms that cause a decrease in navigation speed are suppressed. can. The antifouling coating material of the present invention is typically a non-eluting antifouling coating material in which the formed coating film 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-pyrrole-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 (pyrythion zinc), 2-pyridinethiol-1-oxide copper salt (pyrythion 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, zinc pyrithione, copper pyrithione 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 10 to 10 parts by mass with respect to 100 parts by mass of the insoluble antifouling paint polymer of the present invention. 200 parts by mass is preferable, and 50 to 150 parts by mass is more preferable.
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 insoluble antifouling coating polymer of the present invention.
As the other resin, a thermoplastic resin other than the insoluble antifouling coating polymer of the present invention is preferable. When the antifouling paint contains a thermoplastic resin other than the polymer for the non-soluble 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 non-soluble antifouling coating of the present invention include chlorinated paraffin; chlorinated polyolefin such as rubber chloride, chlorinated polyethylene and chlorinated polypropylene; polyvinyl ether; polypropylene sevacate; partial water. Addition terphenyl; polyvinyl 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 coalesced (meth) acrylic acid cyclohexyl-based copolymer; polyether polyol; alkyd resin; polyester resin; vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl propionate co-weight Vinyl chloride-based resins such as coalesced vinyl chloride-isobutylvinyl ether copolymers, vinyl chloride-isopropylvinyl ether copolymers, vinyl chloride-ethylvinyl ether copolymers; silicone oils; waxes; fats and oils other than waxes that are solid at room temperature, castor oil Such as fats and oils liquid at room temperature and their purified products; Vaseline; liquid paraffin; rosin, hydrogenated rosin, naphthenic acid, fatty acids and divalent metal salts thereof; and the like. Examples of the wax include animal-derived wax such as beeswax; plant-derived wax; semi-synthetic wax such as amide-based wax; and synthetic wax such as polyethylene oxide-based wax. Only one kind of these thermoplastic resins may be used alone, or two or more kinds thereof may be used in combination.
Chlorinated paraffin is preferable because it functions as a plasticizer and has an effect of improving crack resistance and peel resistance of the coating film.
Organic waxes such as semi-synthetic wax and synthetic wax are preferable 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 polyamide wax are more preferable.

When the antifouling paint contains a thermoplastic resin other than the insoluble antifouling paint polymer of the present invention, the content of the thermoplastic resin other than the insoluble antifouling paint polymer of the present invention in the antifouling paint is Although not particularly limited, 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 insoluble antifouling coating polymer of the present invention.
When the content of the thermoplastic resin other than the non-soluble antifouling paint polymer of the present invention in the antifouling paint is at least the above lower limit value, the coating film physical properties such as crack resistance and water resistance are more excellent, and the above upper limit value. If the following, the flexibility and water absorption are more excellent.

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-settling 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 pigments include zinc oxide, talc, silica, barium sulfate, potassium feldspar, aluminum hydroxide, magnesium carbonate, mica, carbon black, petals, titanium oxide, phthalocyanine blue, kaolin, and plaster. 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 coating material of the present invention 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 coating material of the present invention 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.

Further, the coating film formed by using the resin composition of the present invention or the antifouling paint has a small frictional resistance with an aqueous liquid such as seawater. Therefore, by forming a coating film on the surface of the object to be coated using the resin composition of the present invention or the antifouling paint, the frictional resistance of the surface with the aqueous liquid can be reduced.
For example, by applying the resin composition or antifouling paint of the present invention to a portion that receives frictional resistance from seawater during navigation of a ship to form a coating film, the frictional resistance with seawater during navigation is reduced and fuel consumption is reduced. It is possible to reduce the amount of water and save energy.

[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 insoluble 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 contact angle of the outer surface of the coating film formed from the non-soluble antifouling coating polymer of the present invention by the captive bubble method is preferably 120 ° or more and 144 ° or less, and 125 ° or more and 140 ° or less. It is more preferable that the temperature is 130 ° or more and 135 ° or less.
If the contact angle of the outer surface of the coating film formed from the non-soluble antifouling coating polymer of the present invention by the captive bubble method is equal to or greater than the lower limit, it can be regarded as an aqueous liquid on the outer surface of the coating film. Since the frictional resistance of the above is sufficiently small, the effect of reducing friction by providing the coating film is excellent, and if it is not more than the above upper limit value, the water resistance is excellent.
In the present specification, the 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 contact angle of the outer surface of the coating film can be adjusted by adjusting the proportion of the hydrophilic portion of the polymer for insoluble antifouling paint. For example, the more hydrophilic parts of the non-soluble antifouling paint polymer, the larger the contact angle tends to be.

The indentation elastic modulus of the outer surface of the coating film formed from the non-soluble antifouling coating polymer of the present invention is preferably 15 MPa or more and 2,900 MPa or less, and more preferably 30 MPa or more and 2,000 MPa or less. , 50 MPa or more and 1,500 MPa or less is more preferable.
When the indentation elastic modulus of the outer surface of the coating film formed from the non-soluble antifouling coating polymer of the present invention is equal to or higher than the lower limit value, the tackiness of the coating film surface is small, so that the handleability is good. If it is not more than the upper limit value, the hardness of the coating film is increased, so that the abrasion resistance is good.
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 polymer for insoluble antifouling paint. For example, the larger the glass transition temperature (Tg) of the non-soluble 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 water absorption rate of the coating film can be adjusted by the proportion of the hydrophilic portion of the polymer for insoluble antifouling paint. For example, the more hydrophilic parts of the non-soluble antifouling paint polymer, 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.
As described above, since the hydrophobic part and the hydrophilic part of the insoluble antifouling paint polymer of the present invention are incompatible with each other, when forming a coating film containing the insoluble antifouling paint polymer. It is possible to obtain a coating film having a micro or nanoheterogeneous structure by phase-separating the hydrophobic part and the hydrophilic part. 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 nano non-uniform structure include a sea-island structure, a cylinder structure, a lamellar structure, a co-continuous structure, and the like.

The method for forming the coating film is not particularly limited, and a known method can be used. For example, when the resin composition or antifouling paint contains a solvent together with the insoluble antifouling paint polymer, the resin composition or antifouling paint is applied to the surface of the object to be coated by brushing, spraying, roller coating, or submerging. A coating film can be formed by applying by means such as coating and drying.
The object to be coated is not particularly limited, and examples thereof include ships, fishing nets, harbor facilities, booms, bridges, underwater structures (undersea bases, etc.) and the like.
An undercoat may be provided on the surface of the object to be coated. The undercoat film can be formed by using, for example, a wash primer, a chlorinated rubber-based or epoxy-based primer, an intermediate coating film, or the like.
The amount of the resin composition or antifouling paint applied is set according to the thickness of the coating film to be formed.
The drying after the application of the resin composition or the antifouling paint can be usually carried out at room temperature, and heat drying may be carried out if necessary.

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))
Measurement was performed using gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8220). As the column, TSKgelα-M (manufactured by Tosoh Corporation, 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.

(Torque value)
The torque value was evaluated using a double cylindrical resistance measuring device. The double-cylindrical resistance measuring device forms a coating film of the sample to be measured on one surface of two cylinders, and the torque when one cylinder is rotated with water placed between the two cylinders. It measures the value.
Specifically, the obtained resin composition was applied to a stainless steel (SUS) cylindrical drum having a diameter of 9.6 cm and a height of 12.8 cm, and dried at room temperature to form a coating film. The cylindrical drum on which this coating film was formed was rotated in artificial seawater, and the torque value (g · cm) at a measurement temperature of 23 ° C. and 1000 rpm was measured with a UTMIII torque meter (manufactured by UNIpulse Corporation, trade name). The value was taken as the torque value of the resin composition. Pure water was used as the water, and artificial seawater was prepared using Marine Art High (trade name, manufactured by Tomita Pharmaceutical Co., Ltd.). The smaller the torque value, the smaller the frictional resistance due to the resin composition coating film under artificial seawater.

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

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

(Water absorption rate)
The water absorption rate of the coating film was measured in accordance with the Japanese Industrial Standards JIS K 7209: 2000 Plastic-How to determine the water absorption rate.

(Contact angle by the captive bubble method)
A sample was applied to a slide glass of 76 mm × 26 mm × 1 mm (thickness) so as to have a dry film thickness of 200 μm to prepare 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 applied to a slide glass of 76 mm × 26 mm × 1 mm (thickness) so as to have a dry film thickness of 200 μm to prepare a test plate.
With a micro-hardness meter HM-2000 (manufactured by Fisher Instruments, trade name), the indentation elastic modulus of the test plate was measured under the measurement conditions of Vickers indenter, load 7 mN / 100s, creep 60s, R = 0.4 mN / 100s. It was measured.

Manufacturing example 1
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 Nichiyu Co., Ltd.) 0.1 part was added to prepare an aqueous suspension.
Next, the inside of the polymerization apparatus was replaced with nitrogen, the temperature was raised to 80 ° C. and reacted for 4 hours, and in order to further increase the polymerization rate, the temperature was raised to 90 ° C. and held for 2 hours. Then, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension containing a macromonomer. The aqueous suspension was filtered, the filtrate was washed with deionized water, dehydrated and dried at 40 ° C. for 16 hours to give macromonomer (MM1). The number average molecular weight of this macromonomer (MM1) was 7200.

Example A1
In a flask with a cooling tube, 50 parts of macromonomer (MM1) manufactured in Production Example 1, 50 parts of 2-hydroxyethyl acrylate (HEA) (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and methyl cellosolve (Kanto Chemical Co., Ltd.) as a solvent. A monomer composition containing 250 parts (manufactured by Co., Ltd., special grade reagent) was charged, and the inside was replaced with nitrogen by nitrogen bubbling. Next, while the monomer composition was heated and the internal temperature was maintained at 70 ° C., 2,2'-azobisisobutyronitrile (AIBN) as a radical polymerization initiator, 0.4 part (Wako Pure Chemical Industries, Ltd.) Yaku Co., Ltd., Wako Special Grade) was added to the monomer composition and then held for 4 hours, then the temperature was raised to 80 ° C. and held for 1 hour to complete the polymerization. After that, the polymerization reaction product was cooled to room temperature and reprecipitated with a large amount of diisopropyl ether (Junsei Chemical Co., Ltd.). The polymer precipitated by reprecipitation was recovered and vacuum dried overnight at 50 ° C. and 50 mmHg (6.67 kPa) or less to obtain an insoluble antifouling coating polymer. The weight average molecular weight of the non-soluble antifouling coating polymer was 72,000.
Next, 25 parts of the insoluble antifouling paint polymer and 75 parts of methyl cellosolve are mixed in a glass container, and the mixture is stirred with a stirrer for 2 hours at room temperature to form a resin composition containing the insoluble antifouling paint polymer and a solvent. I got something.
The obtained resin composition was applied onto a glass substrate so that the thickness after drying was 200 μm or more, and dried at room temperature to form a coating film. The water contact angle and indentation elastic modulus of this coating film were 135 ° and 448 MPa, respectively. The torque value was 585 g · cm.

(Preparation of antifouling property evaluation sample)
The resin composition obtained above was spin-coated on an acrylic plate (5 cm × 5 cm × 1 mm) so that the thickness after drying was 200 μm or more, and dried at room temperature to form a coating film. This coating film was allowed to stand on the bottom surface of a polypropylene container (8 cm × 8 cm × 4.5 cm), and 100 ml of seawater and 100 larvae in the adhesion stage (Cyprus larvae) were added. The number of individuals in which the adhesion stage larvae adhered to or transformed into the coating film 7 days after the addition, with the test seawater being moved by horizontal shaking (60 round trips of 3 cm / min) at room temperature of 22 ± 2 ° C (adhesion rate). ) And the number of dead individuals (mortality rate) were counted under a stereomicroscope. The adhesion rate and mortality rate of this coating film were 1% and 2%, respectively.

Examples A2 to A5, Examples B1 to B4, Comparative Examples A1 to A3, Comparative Examples B1 to B2
A polymer for an insoluble antifouling coating material was obtained in the same manner as in Example 1 except that the monomer or solvent was changed to the one shown in the table, and each evaluation was carried out in the same manner as in Example 1.
In Comparative Example 1, an existing ship bottom paint (LR1672 manufactured by Mitsubishi Rayon Co., Ltd.) was used as the resin composition. This ship bottom paint is an elution type antifouling paint containing a copolymer of a hydrophobic monomer and a metal-containing monomer as a resin component.

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

The abbreviations in the table have the following meanings.
MMA: Methyl methacrylate, manufactured by Mitsubishi Rayon Co., Ltd.
HEA: 2-Hydroxyethyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.
AE400: Blemmer AE400, manufactured by NOF CORPORATION.
NIPAM: N-isopropylacrylamide, manufactured by KJ Chemicals Co., Ltd.
MEA: 2-Methoxyethyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd.
HEMA: 2-hydroxyethyl methacrylate, manufactured by Tokyo Chemical Industry Co., Ltd.
PE350: Blemmer PE350, manufactured by NOF CORPORATION.
HEAA: 2-Hydroxyethyl acrylamide, manufactured by KJ Chemicals Co., Ltd.
DMAAm: Dimethylacrylamide, manufactured by KJ Chemicals Co., Ltd.
PME400: Blemmer PME400, manufactured by NOF CORPORATION.
PEA: 2-phenoxyethyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd.
AcSi: 3- (trimethoxysilyl) propyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd.
MCS: Methyl cellosolve.
BA: Butyl acetate.

The coating films of Examples A1 to A5 had a higher underwater contact angle or indentation elastic modulus than the coating films of Comparative Example A1.
Further, it was confirmed that the coating films of Examples B1 to B4 have excellent antifouling properties because they form a phase-separated structure.

Since the coating films of Comparative Examples A2 and A3 do not use macromonomers, they do not have a micro or nano-uniform structure, and the torque value is higher than that of the coating films of Examples A1 to A5. rice field.
From the results of the torque value and the DR rate, it was confirmed that the coating films of Examples A1 to A5 were superior in the effect of reducing the frictional resistance with the aqueous liquid as compared with the coating film of Comparative Example A1.
On the other hand, it was confirmed that the coating films of Comparative Example B1 and Comparative Example B2 had a low contact angle in water and were inferior in antifouling property.

Claims (12)

It contains a structural unit (A) derived from the macromonomer (a) and a structural unit (B) derived from the monomer (b) that is not a macromonomer.
The solubility parameter of the monomer (aa) constituting the macromonomer (a) is less than ^{18.5 (J / cm 3} ) ^1/2.
The solubility parameter of the monomer (b) is 18.5 (J / cm ³ ) ^1/2 or more.
Wherein a value estimated respectively, by the Fedors method is the solubility parameter of the solubility parameter and the monomer of the monomer (aa) (b), the non-soluble antifouling paint polymer viewed including the non-soluble anti An antifouling coating material comprising a resin composition having a contact angle of 120 ° or more and 144 ° or less according to a captive bubble method on the surface of a coating film formed of a polymer for stain coating. The antifouling coating material according to claim 1, wherein the indentation elastic modulus of the coating film formed from the non-soluble antifouling coating polymer is 15 MPa or more and 2900 MPa or less. The antifouling coating material according to claim 1 or 2, 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).

(In the formula, R ¹ is a hydrogen atom, a methyl group or CH ₂ OH, R ² is OR ³ , a halogen atom, COR ⁴ , COOR ⁵ , CN, CONR ⁶ R ⁷ or R ⁸ , and R ^{3 to} R ⁷ are independently hydrogen atoms, alkyl groups having unsubstituted or substituents, alicyclic groups having unsubstituted or substituents, aryl groups having unsubstituted or substituents, and unsubstituted or substituents, respectively. Heteroaryl group with unsubstituted or substituent, non-aromatic heterocyclic group with unsubstituted or substituent, aralkyl group with unsubstituted or substituent, alkalinel group with unsubstituted or substituent, or unsubstituted Alternatively, an organosilyl group having a substituent is shown, and the allowable substituents thereof are a carboxyl group, an alkoxycarbonyl group, an epoxy group, a hydroxy group, an alkoxy group, a primary amino group, a secondary amino group, and a tertiary amino, respectively. It is at least one selected from the group consisting of a group, an isocyanato group, a sulfo group and a halogen, and R ⁸ represents an aryl group having an unsubstituted or substituent or a heteroaryl group having an unsubstituted or substituent. The substituents allowed for these are carboxyl group, alkoxycarbonyl group, epoxy group, hydroxy group, alkoxy group, primary amino group, secondary amino group, tertiary amino group, isocyanato group, sulfo group, and unsubstituted. Alternatively, it is at least one selected from the group consisting of an alkyl group having a substituent, an aryl group having an unsubstituted or substituent, an alkenyl-containing group having an unsubstituted or substituent, and a halogen.) The antifouling coating material according to any one of claims 1 to 3, wherein the monomer (b) is an aliphatic monomer. The antifouling paint according to any one of claims 1 to 4, wherein the glass transition point of the non-soluble antifouling paint polymer is 10 ° C. or higher. The antifouling coating material according to any one of claims 1 to 5, wherein the macromonomer (a) is a macromonomer represented by the following formula (1).

(In the formula, R is a hydrogen atom, an alkyl group having an unsubstituted or substituent, an alicyclic group having an unsubstituted or substituent, an aryl group having an unsubstituted or substituent, an unsubstituted or substituent. A heteroaryl group having a Yes, the plurality of Xs may be the same or different, where Z is a terminal group and n is a natural number of 2 to 10,000.) The antifouling coating material according to any one of claims 1 to 6, wherein the resin composition further contains a solvent. The antifouling coating material according to any one of claims 1 to 6, wherein the resin composition has a viscosity at 25 ° C. of 5 × 10 ^{4 mPa · s or less.} A coating film formed by using the antifouling coating material according to any one of claims 1 to 8. It contains a structural unit (A) derived from the macromonomer (a) and a structural unit (B) derived from the monomer (b) that is not a macromonomer.
The solubility parameter of the monomer (aa) constituting the macromonomer (a) is less than ^{18.5 (J / cm 3} ) ^1/2.
The solubility parameter of the monomer (b) is 18.5 (J / cm ³ ) ^1/2 or more.
Wherein a value estimated respectively, by the Fedors method is the solubility parameter of the solubility parameter and the monomer of the monomer (aa) (b), the non-soluble antifouling paint polymer viewed including the non-soluble anti A coating film formed by using a resin composition having a contact angle of 120 ° or more and 144 ° or less by a captive bubble method on the surface of a coating film formed of a polymer for stain coating. An underwater friction reducing method comprising a step of forming a coating film on the surface of an object to be coated using the antifouling paint according to any one of claims 1 to 8. On the surface of the object to be painted,
It contains a structural unit (A) derived from the macromonomer (a) and a structural unit (B) derived from the monomer (b) that is not a macromonomer.
The solubility parameter of the monomer (aa) constituting the macromonomer (a) is less than ^{18.5 (J / cm 3} ) ^1/2.
The solubility parameter of the monomer (b) is 18.5 (J / cm ³ ) ^1/2 or more.
Wherein a value estimated respectively, by the Fedors method is the solubility parameter of the solubility parameter and the monomer of the monomer (aa) (b), the non-soluble antifouling paint polymer viewed including the non-soluble anti Underwater friction reduction including a step of forming a coating film using a resin composition having a contact angle of 120 ° or more and 144 ° or less by a captive bubble method on the surface of a coating film formed of a polymer for stain coating. Method.