KR20230161936A - Compounds, polymers and antifouling paint compositions - Google Patents

Abstract

A polymer containing a structural unit derived from a compound, wherein the compound has a weight average molecular weight of 10,000 or less, contains two or more structural units containing a hydrolyzable substituent, has a radical polymerizable group at the terminal, and the para After hydrolysis treatment by heating and stirring the compound in an aqueous toluenesulfonic acid solution, neutralization titration was performed with 0.5 mol/L potassium hydroxide solution (ethanol solution), and 0.5 mol/L hydroxide used was used until the light red color of the indicator continued for 30 seconds. A polymer having a solid acid value calculated from the amount of potassium solution of 10 mgKOH/g or more.

Description

Compounds, polymers and antifouling paint compositions

The present invention relates to compounds, polymers and antifouling paint compositions.

This application claims priority based on Japanese Patent Application No. 2021-058983, filed in Japan on March 31, 2021, and uses the content herein.

It is known that marine structures and ships are coated with antifouling paint for the purpose of preventing corrosion of parts in contact with seawater and adhesion of marine organisms that cause a decrease in navigation speed.

As an antifouling paint, a self-polishing type antifouling paint is known. Self-polishing type antifouling paint typically contains a hydrolyzable resin and an antifouling agent. The coating film obtained from this antifouling paint exhibits an antifouling effect over a long period of time as the surface of the coating film is gradually dissolved in seawater and the surface is renewed (self-polished), and the antifouling component is always exposed to the surface of the coating film.

As a self-polishing type antifouling paint, for example, a hydrolyzable paint containing a 1-(alkyloxy) ester group-containing resin as a main component (Patent Documents 1 to 3) or a hydrolyzable paint containing a triorganosilyloxycarbonyl group as a main component. Type paints (Patent Documents 4 and 5) have been proposed. When a film using the paint is immersed in seawater, the functional group is hydrolyzed to form resin acid, which dissolves in seawater to exhibit an antifouling effect.

Japanese Patent Publication No. 4-103671 Japanese Patent Publication No. 5-230280 Japanese Patent No. 6760061 Publication Japanese Patent Publication No. 8-269390 Japanese Patent No. 6579413 Publication

Hydrolysis of the triorganosilyloxycarbonyl group is accelerated in (weakly) basic aqueous solutions such as seawater, while the hydrolysis of the 1-(alkyloxy) ester group is not accelerated in basic aqueous solutions. For this reason, in the prior art, the dissolution stability of the coating film containing a 1-(alkyloxy) ester group in seawater was not sufficient, and a decrease in self-polishing properties was observed due to a decrease in the dissolution rate.

Although the antifouling paint compositions of Patent Documents 1 to 3 have improved coating film solubility to some extent, the antifouling effect may not be sufficient in some cases.

One object of the present invention is to provide a compound and polymer from which an antifouling paint composition capable of forming a coating film with excellent antifouling properties is obtained, and an antifouling paint composition capable of forming a coating film with excellent antifouling properties. Additionally, one object of the present invention is to provide a compound and polymer from which an antifouling paint composition capable of forming a coating film with excellent solubility is obtained, and an antifouling coating composition capable of forming a coating film with excellent solubility.

The present invention has the following aspects.

[1] A polymer containing structural units derived from a compound,

The compound has a weight average molecular weight of 10000 or less, contains two or more structural units containing a hydrolyzable substituent, and has a radical polymerizable group at the terminal,

After performing hydrolysis treatment by heating and stirring the compound in an aqueous solution of p-toluenesulfonic acid, neutralization titration was performed with 0.5 mol/L potassium hydroxide solution (ethanol solution), and the 0.5 solution used was used until the light red color of the indicator continued for 30 seconds. A polymer having a solid acid value calculated from the amount of mol/L potassium hydroxide solution of 10 mgKOH/g or more.

[2] The polymer according to [1], wherein the ratio of structural units derived from the above compound is 5% by mass or more relative to the total mass of the polymer.

[3] A polymer obtained by copolymerizing a compound containing a polymerizable monomer unit containing a substituent represented by formula (1), formula (2), or formula (3).

^{( Wherein , _} , R ³ and R ⁵ each represent an alkyl group, cycloalkyl group or aryl group having 1 to 20 carbon atoms, R ⁴ represents an alkylene group having 1 to 10 carbon atoms, and R ⁶ represents an alkylene group having 2 to 10 carbon atoms.)

[4] The polymer according to [3], wherein the ratio of structural units derived from the compound is 10% by mass or more and 90% by mass or less with respect to the total mass of the polymer.

[5] A compound represented by the following formula (MM-1).

(In ^formula (MM-1 ^{) ,} X ¹ to , an aryl group, a heterocyclic group, or a substituent including formula (7), (8) or (9), and two or more of Y ¹ to Y ⁿ represent formula (7), (8) or (9). It is a substituent that contains, n represents a natural number of 3 or more, and Z represents a terminal group.)

( ^In formula ( ⁷ ), (8 ⁾ or ( ⁹ ), represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ³ and R ⁵ each independently represent an alkyl group, cycloalkyl group or aryl group having 1 to 20 carbon atoms, and R ⁴ represents an alkylene group having 1 to 10 carbon atoms. , R ⁶ represents an alkylene group having 2 to 10 carbon atoms.)

[6] The compound according to [5], wherein the terminal group is a hydrogen atom or a group derived from a radical polymerization initiator.

[7] The compound according to [5] or [6], wherein the weight average molecular weight is 2,000 or more and 1,000,000 or less.

[8] Any one of [5] to [7], wherein the ratio of monomer units containing formula (7), (8), or (9) to the mass of the entire compound is 9 mass% or more and 80 mass% or less. Compounds described in .

[9] The ratio of the structural unit based on the monomer (M) to the mass of the entire compound is preferably 1 mass% or more and 60 mass% or less, more preferably 20 mass% or more and 60 mass% or less, 25 The compound according to any one of [5] to [8], where the mass% is more preferably 55% by mass or less.

[10] The compound of any of [5] to [9], wherein the monomer (M) is a monomer represented by the following formula (M1-1), (M1-2), or (M1-3).

^{( wherein , _} represents an alkyl group of 1 to 10 carbon atoms, R ³ and R ⁵ each independently represent an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 4 to 8 carbon atoms, or an aryl group of 6 to 20 carbon atoms, and R ⁴ represents an alkyl group of 1 to 10 carbon atoms. represents an alkylene group, R ⁶ represents an alkylene group having 2 to 10 carbon atoms, and Q represents CH ₂ =CH-COO-, or CH ₂ =C(CH ₃ )-COO-.)

[11] The compound of any of [5] to [10], wherein the monomer (M) is at least one type selected from monomers represented by the following structural formula.

[12] It is preferable that the monomer (a) contains a structural unit based on monomer (a), and that the monomer (a) is a (meth)acrylic monomer; A compound represented by the following formula (a1) is more preferable; It is a compound represented by the following formula (a1), wherein R ⁴¹ in formula (a1) is a hydrogen atom or a methyl group, R ⁴² is COOR ⁴⁵ , R ⁴⁵ is an alkyl group with 1 to 5 carbon atoms, an alkoxyalkyl group with 3 to 5 carbon atoms, Alternatively, compounds containing a cycloalkyl group having 3 to 6 carbon atoms are more preferable; It is a compound represented by the following formula (a1), wherein R ⁴¹ in formula (a1) is a hydrogen atom or a methyl group, R ⁴² is COOR ⁴⁵ , and R ⁴⁵ is an alkyl group with 1 to 3 carbon atoms, or an alkoxyalkyl group with 3 to 5 carbon atoms. The compound of any of [5] to [11], wherein a phosphorus compound is particularly preferred.

CH ₂ =CR ⁴¹ R ⁴² (a1)

(Wherein, R ⁴¹ represents a hydrogen atom, a methyl group or a hydroxymethyl group, R ⁴² represents OR ⁴³ , a halogen atom, COR ⁴⁴ , COOR ⁴⁵ , CN, CONR ⁴⁶ R ⁴⁷ or R ⁴⁸ , and R ⁴³ to R ⁴⁷ each independently represents a hydrogen atom, a branched or straight-chain alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 18 carbon atoms, or a heterocyclic group with 5 to 18 carbon atoms, and R ⁴⁸ represents an aryl group with 6 to 18 carbon atoms or a heteroaryl group with 6 to 18 carbon atoms.)

[13] The ratio of structural units based on the monomer (M) to the total (100 mol%) of all structural units constituting the compound is preferably 10 to 40 mol%, and more preferably 20 to 30 mol%. Preferred are the compounds of any of [5] to [12].

[14] The ratio of the total number of substituents represented by the above formulas (7), (8) and (9) to the total number of Y ¹ to Y ⁿ (100 mol%) is preferably 10 to 40 mol%. , more preferably 20 to 30 mol%, of the compound of any of [5] to [13].

[15] Any of [5] to [14] in which the weight average molecular weight is preferably 2,000 to 1,000,000, more preferably 2,500 to 100,000, more preferably 3,000 to 10,000, and even more preferably 4,000 to 6,000. compound of things.

[16] The solid acid value is preferably 30 mgKOH/g or more and 180 mgKOH/g or less, more preferably 40 mgKOH/g or more and 150 mgKOH/g or less, and even more preferably 50 mgKOH/g or more and 120 mgKOH/g or less, [5] to [15] ] Any of the compounds.

[17] The glass transition temperature (Tg) is preferably -10°C or higher and 90°C or lower, more preferably 10°C or higher and 90°C or lower, and even more preferably 30°C or higher and 90°C or lower, among [5] to [16]. Compound of which.

[18] The compound of any of [5] to [17], wherein the molecular weight dispersion is preferably 1.0 or more and 4.0 or less, more preferably 1.0 or more and 3.5 or less, and even more preferably 1.0 or more and 3.0 or less.

[19] The compound of any of [5] to [18], wherein the solubility parameter (sp) is preferably 5.0 or more and 12.0 or less, more preferably 6.0 or more and 11.0 or less, and even more preferably 7.0 or more and 10.0 or less.

[20] A polymer containing a structural unit based on the compound according to any one of [5] to [19].

[21] The polymer according to [20], wherein the ratio of structural units based on the compound is 90% by mass or less relative to the total mass of the polymer.

[22] The above polymer was subjected to hydrolysis treatment by heating and stirring in an aqueous solution of p-toluenesulfonic acid, followed by neutralization titration with 0.5 mol/L potassium hydroxide solution (ethanol solution) until the light red color of the indicator continued for 30 seconds. The polymer according to any one of [1] to [4], [20] and [21], wherein the solid acid value calculated from the amount of 0.5 mol/L potassium hydroxide solution used is 150 mgKOH/g or less.

[23] The polymer according to any one of [1] to [4] and [20] to [22], which is a (meth)acrylic polymer.

[24] The ratio of structural units based on the above compound to the total of all structural units constituting the polymer is preferably 10 mass% or more and 60 mass% or less, and more preferably 15 mass% or more and 50 mass% or less, The polymer according to any one of [1] to [4] and [20] to [23] is more preferably 20 mass% or more and 40 mass% or less.

[25] It is preferable that the monomer (a) contains a structural unit based on monomer (a), and that the monomer (a) is a (meth)acrylic monomer; A compound represented by the following formula (a1) is more preferable; It is a compound represented by the following formula (a1), wherein R ⁴¹ in formula (a1) is a hydrogen atom or a methyl group, R ⁴² is COOR ⁴⁵ , R ⁴⁵ is an alkyl group with 1 to 5 carbon atoms, an alkoxyalkyl group with 3 to 5 carbon atoms, Alternatively, compounds containing a cycloalkyl group having 3 to 6 carbon atoms are more preferable; It is a compound represented by the following formula (a1), wherein R ⁴¹ in formula (a1) is a hydrogen atom or a methyl group, R ⁴² is COOR ⁴⁵ , and R ⁴⁵ is an alkyl group with 1 to 3 carbon atoms, or an alkoxyalkyl group with 3 to 5 carbon atoms. The polymer of any of [1] to [4] and [20] to [24], with phosphorus compounds being particularly preferred.

CH ₂ =CR ⁴¹ R ⁴² (a1)

(Wherein, R ⁴¹ represents a hydrogen atom, a methyl group or a hydroxymethyl group, R ⁴² represents OR ⁴³ , a halogen atom, COR ⁴⁴ , COOR ⁴⁵ , CN, CONR ⁴⁶ R ⁴⁷ or R ⁴⁸ , and R ⁴³ to R ⁴⁷ each independently represents a hydrogen atom, a branched or straight-chain alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 18 carbon atoms, or a heterocyclic group with 5 to 18 carbon atoms, and R ⁴⁸ represents an aryl group with 6 to 18 carbon atoms or a heteroaryl group with 6 to 18 carbon atoms.)

[26] The ratio of the structural units based on the monomer (a) to the total of all structural units constituting the polymer is preferably 40% by mass or more and 90% by mass or less, and 50% by mass or more and 85% by mass or less. More preferably, the polymer described in [25] is more preferably 60% by mass or more and 80% by mass or less.

[27] The polymer includes structural units based on the monomer (M) in addition to structural units based on the monomer (M) included in the structural units based on the compound,

Structural units based on the monomer (M) relative to the sum of all structural units constituting the polymer (however, excluding structural units based on the monomer (M) contained in the structural units based on the above compound) The ratio is preferably 60 mass% or less and 0 mass% or more, more preferably 45 mass% or less and 0 mass% or more, and even more preferably 30 mass% or less and 0 mass% or more, [1] to [4] and [20. ] to [26].

[28] The solid acid value is preferably 20 mgKOH/g or more and 150 mgKOH/g or less, more preferably 30 mgKOH/g or more and 90 mgKOH/g or less, and even more preferably 30 mgKOH/g or more and 60 mgKOH/g or less, [1] to [4. ] and the polymer of any of [20] to [27].

[29] The glass transition temperature (Tg) is preferably -10°C or higher and 70°C or lower, more preferably 0°C or higher and 50°C or lower, and even more preferably 10°C or higher and 30°C or lower, [1] to [4], and The polymer of any of [20] to [28].

[30] The weight average molecular weight (Mw) is preferably 2,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 9,000 to 20,000, [1] to [4] and [20] to [29]. A polymer of any of the following.

[31] Any of [1] to [4] and [20] to [30], where the molecular weight dispersion is preferably 1.0 or more and 4.0 or less, more preferably 1.0 or more and 3.5 or less, and even more preferably 1.0 or more and 3.0 or less. polymer of things.

[32] Among [1] to [4] and [20] to [31], the solubility parameter (sp) is preferably 5.0 or more and 12.0 or less, more preferably 6.0 or more and 11.0 or less, and even more preferably 7.0 or more and 10.0 or less. Polymer of which.

[33] An antifouling paint composition containing the compound according to any one of [5] to [19].

[34] An antifouling paint composition comprising the polymer according to any one of [1] to [4] and [20] to [32].

[35] A compound having a weight average molecular weight of 10,000 or less, containing two or more structural units containing a hydrolyzable substituent, and having a radical polymerizable group at the terminal,

Polymerizing monomers having an ethylenically unsaturated group (however, the above compounds are excluded),

Method for producing (meth)acrylic copolymer.

According to one aspect of the present invention, a compound and a polymer from which an antifouling paint composition capable of forming a coating film with excellent antifouling properties can be obtained, and an antifouling paint composition capable of forming a coating film with excellent antifouling properties can be provided. In addition, according to one aspect of the present invention, it is possible to provide a compound and a polymer from which an antifouling paint composition capable of forming a coating film with excellent solubility is obtained, and an antifouling paint composition capable of forming a coating film with excellent solubility.

In this specification, “structural unit” means a structural unit derived from the monomer formed by polymerizing the monomer, or a structural unit in which a part of the structural unit is converted into a different structure by processing the polymer.

“Monomer” means a compound (polymerizable monomer) that has polymerizability.

“(meth)acrylic monomer” means a monomer having a (meth)acryloyl group.

“(meth)acryloyl group” means an acryloyl group or a methacryloyl group. The same applies to “(meth)acrylate”, “(meth)acrylic acid”, and “(meth)acrylamide”.

〔compound〕

The compound (hereinafter also referred to as “compound (MM)”) related to one aspect of the present invention has a structural unit based on monomer (M) (hereinafter also referred to as “monomer (M) unit”) of 2 It is a compound containing the above and having a radical polymerizable group at the terminal.

Compound (MM) is a structural unit (hereinafter also referred to as “monomer (a) unit”) based on a monomer (hereinafter also referred to as “monomer (a)”) other than the compound (MM) and monomer (M). ) is preferably further included.

Compound (MM) can be used as a monomer for producing polymers, and is also called a macro monomer.

<Monomer (M) unit>

The monomer (M) unit has hydrolyzability.

“Having hydrolyzability” means that a decomposition product derived from the monomer (M) is obtained through a reaction between a structural unit based on the monomer (M) and water. It is known that the compound according to one aspect of the present invention containing a monomer (M) unit can be hydrolyzed when subjected to hydrolysis treatment in an aqueous solution of p-toluenesulfonic acid, for example, by heating and stirring under conditions of 70°C or higher for 1 hour or more. indicates. Whether or not the monomer (M) unit has been hydrolyzed can be confirmed by identifying the functional group (carboxy group, etc.) generated by hydrolysis.

The monomer (M) unit preferably contains a structure that can be hydrolyzed when the above hydrolysis treatment is performed on the compound (MM). Examples of structures that can be hydrolyzed when the hydrolysis treatment is performed include structures represented by any of formulas (1) to (6). Hereinafter, the structure expressed by formula (1) is also described as “structure (1)”, and structures expressed by other formulas may also be described similarly. These structures are hydrolyzed when the above hydrolysis treatment is performed to generate carboxyl groups.

Among the above, structures represented by any of formulas (1) to (3) are preferable because they can be used in combination with cuprous oxide and hydrolysis is accelerated under acidic conditions.

-COO-M-OCO- (5)

-COO-MR ¹⁰ (6)

^{( Wherein , _} , R ³ and R ⁵ each independently represent an alkyl group, cycloalkyl group or aryl group having 1 to 20 carbon atoms, R ⁴ represents an alkylene group having 1 to 10 carbon atoms, and R ⁶ is an alkylene group having 2 to 10 carbon atoms. group, R ⁷ to R ⁹ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, M represents Zn, Cu, Mg or Ca, and R ¹⁰ represents an organic acid other than a (meth)acryloyloxy group. indicates the residue.)

In formula (1), X may be any of -O- (etheric oxygen atom), -S- (sulfide sulfur atom), or -NR ¹¹ -. The alkyl group of R ¹¹ preferably has 1 to 10 carbon atoms. As X, -O- is preferable.

Examples of the alkyl group having 1 to 10 carbon atoms for R ¹ and R ² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, and 2-ethylhexyl. I can hear it.

The number of carbon atoms of the alkyl group in R ¹ and R ² is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 or 2.

Preferred combinations of R ¹ and R ² include a combination of a hydrogen atom and a methyl group, a combination of a methyl group and a methyl group, a combination of a hydrogen atom and an alkyl group having 2 to 10 carbon atoms (hereinafter also referred to as a “long-chain alkyl group”), and a methyl group and a long-chain alkyl group. A combination of , a combination of a hydrogen atom with a hydrogen atom, a combination of a long-chain alkyl group and a long-chain alkyl group, etc. Among these, the combination of a hydrogen atom and a methyl group is preferable from the viewpoint of hydrolyzability.

Examples of the alkyl group having 1 to 20 carbon atoms for R ³ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, 2-ethylhexyl, decyl, and dodecyl. Examples include actual group and tetradecyl group.

The cycloalkyl group is preferably a cycloalkyl group having 4 to 8 carbon atoms, and examples include cyclohexyl group and cyclopentyl group.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples include a phenyl group and a naphthyl group.

As R ³ , an alkyl group or cycloalkyl group having 1 to 10 carbon atoms is preferable.

The alkyl group, cycloalkyl group, and aryl group for R ³ may each have a substituent. When having a substituent, the number of substituents may be 1 or 2 or more. Examples of the substituent include cycloalkyl group, aryl group, alkoxy group, alkanoyloxy group, aralkyl group, and acetoxy group.

Among the substituents, the cycloalkyl group and the aryl group may be the same as the cycloalkyl group and aryl group for R ³ , respectively. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, etc. Examples of the alkanoyloxy group include ethanoyloxy group. Examples of the aralkyl group include benzyl group.

X in formula (2) is the same as X in formula (1), and the preferred embodiment is also the same.

Examples of the alkylene group having 1 to 10 carbon atoms for R ⁴ include methylene group, ethylene group, propylene group, butylene group, and hexylene group. The alkylene group preferably has 2 to 7 carbon atoms, and more preferably 3 to 4 carbon atoms.

The alkylene group may have a substituent. When having a substituent, the number of substituents may be 1 or 2 or more. Substituents that the alkylene group may have include those similar to the substituents for R ³ .

X in formula (3) is the same as X in formula (1), and the preferred embodiment is also the same.

R ⁵ is the same as R ³ in formula (1), and the preferred embodiment is also the same.

Examples of the alkylene group having 2 to 10 carbon atoms for R ⁶ include ethylene group, propylene group, butylene group, and hexylene group. The alkylene group preferably has 2 to 7 carbon atoms, and more preferably 3 to 4 carbon atoms.

Hydrocarbon groups for R ⁷ to R ⁹ in formula (4) include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Alkyl groups such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, and tetradecyl group; Cycloalkyl groups such as cyclohexyl groups; Aryl groups such as phenyl group and naphthyl group can be mentioned.

The alkyl group, cycloalkyl group, and aryl group may each have a substituent.

Examples of substituents that the alkyl group may have include a halogen atom, an acyl group, a nitro group, and an amino group. Examples of substituents that a cycloalkyl group or aryl group may have include a halogen atom, an alkyl group, an acyl group, a nitro group, and an amino group. The number of carbon atoms of the alkyl group as a substituent is preferably about 1 to 18.

R ⁷ to R ⁹ may be the same or different from each other.

Since a coating film showing a stable polishing rate (polishing speed) can be obtained and antifouling performance can be stably maintained for a long period of time, it is preferable that at least one of R ⁷ to R ⁹ is an isopropyl group, and it is particularly preferable that all of them are isopropyl groups. .

In formula (5), M is preferably Zn or Cu.

In formula (6), M is preferably Zn or Cu.

The organic acid residue of R ¹⁰ refers to the portion remaining after removing one proton from the organic acid (for example, the portion remaining after removing the proton from the carboxyl group of carboxylic acid), and is ionicly bonded to M in place of this proton.

As the organic acid, carboxylic acids are preferable, such as monochloroacetic acid, monofluoroacetic acid, acetic acid, propionic acid, octylic acid, versatic acid, isostearic acid, palmitic acid, cresotic acid, α-naphthoic acid, and β- Naphthoic acid, benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinolinecarboxylic acid, nitrobenzoic acid, nitronaphthalenecarboxylic acid, pyruvic acid, naphthenic acid, abietic acid, hydrogen Monocarboxylic acids, such as added abietic acid, etc. are mentioned.

As R ¹⁰ , a fatty acid residue (aliphatic monocarboxylic acid residue) having 1 to 20 carbon atoms is preferable because a highly durable coating film that can prevent cracks and peeling over a long period of time is obtained.

As the monomer (M), at least one structure selected from the group consisting of structure (1), structure (2), structure (3), structure (4), structure (5), and structure (6), and radical polymerization Monomers containing sexual groups are preferred.

The monomer (M) is preferably a monofunctional monomer having one radical polymerizable group because the viscosity of the polymer containing structural units based on the compound (MM) is lowered when dissolved in an organic solvent.

Examples of the radical polymerizable group include those similar to the radical polymerizable group of compound (MM).

As the radical polymerizable group, a group containing an ethylenically unsaturated bond (polymerizable carbon-carbon double bond) is preferable. When the monomer (M) contains an ethylenically unsaturated bond, the monomer (M) unit has a structure in which the ethylenically unsaturated bond of the monomer (M) is cleaved to form a single bond.

As the radical polymerizable group, (meth)acryloyl group is particularly preferable. That is, it is especially preferable that compound (MM) is a (meth)acrylic monomer.

The monomer (M) is a monomer containing at least one structure selected from the group consisting of structure (1), structure (2), and structure (3) and a radical polymerizable group (hereinafter also referred to as “monomer (M1)” ), a monomer containing structure (4) and a radical polymerizable group (hereinafter also referred to as “monomer (M2)”), a monomer containing structure (5) and a radical polymerizable group (hereinafter referred to as “monomer (M3)” )”) or a monomer containing structure (6) and a radical polymerizable group (hereinafter also described as “monomer (M4)”) is more preferable.

Among these, monomer (M1) is particularly preferable because it can be used in combination with cuprous oxide and hydrolysis is accelerated under acidic conditions.

Examples of the monomer (M1) include monomers represented by the following formulas (M1-1), (M1-2), or (M1-3).

₍ ^{Wherein ,} _{_ _} ^_ _{_ =} ^{C (} _{CH 2} ^R indicates.)

In Q, CH ₂ =CH-COO- is an acryloyloxy group, and CH ₂ =C(CH ₃ )-COO- is a methacryloyloxy group.

CH(CH ₃ )=CH-COO- is a crotonoyloxy group (the ethylenically unsaturated bond is trans) or an isocrotonoyloxy group (the ethylenically unsaturated bond is cis).

^CHR The ethylenically unsaturated bond is in the trans form.

^The alkyl ester group in ^R R ^X1 represents an alkyl group. As the alkyl group for ^R

^When _{Q is} ^CHR _{_} ^_ _{_} ^_ It is preferable that it is a structure or an alkyl ester group. For example ^, in the case ^of a compound represented ^by the formula (M1-1), ^R

^CH _{2 =} C ₍ CH ₂ ^R It is a time of ilok. ^R

As Q, CH ₂ =CH-COO- or CH(CH ₃ )=CH-COO- is preferable.

Specific examples of monomer (M1) include those shown below.

<Monomer (a) unit>

The monomer (a) may be copolymerized with the monomer (M), and examples include compounds having a radical polymerizable group (however, compound (MM) and monomer (M) are excluded). As the radically polymerizable group contained in the monomer (a), a group having an ethylenically unsaturated bond is preferable.

As monomer (a), various things can be used, for example,

Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, Isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate , hexadecyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, Isobornyl (meth)acrylate, 3,5,5-trimethylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, Hydrocarbon group-containing (meth)acrylic acid esters such as terpene acrylate and its derivatives, hydrogenated rosin acrylate and its derivatives, and docosyl (meth)acrylate;

2-hydroxyethyl (meth)acrylic acid, 2-hydroxypropyl (meth)acrylic acid, 2-hydroxybutyl (meth)acrylic acid, 3-hydroxybutyl (meth)acrylic acid, 4-hydroxybutyl (meth)acrylic acid, Hydroxyl group-containing (meth)acrylic acid esters such as glycerol (meth)acrylate;

(meth)acrylic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxypropylhexahydrophthalic acid, 2-(meth)acryloyloxyethylphthalic acid, 2-(meth) Acryloyloxypropylphthalic acid, 2-(meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyloxypropylmaleic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth) Acryloyloxypropylsuccinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, monomethyl maleate, monoethyl maleate, monooctyl maleate, monomethyl itaconate, monoethyl itaconate, mono itaconic acid. Carboxyl group-containing vinyl monomers such as butyl, monooctyl itaconate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monooctyl fumarate, and monoethyl citraconic acid;

vinyl monomers containing acid anhydride groups such as maleic anhydride and itaconic anhydride;

Unsaturated dicarboxylic acid diester monomers such as dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, dibutyl itaconate, and diperfluorocyclohexyl fumarate;

Epoxy group-containing vinyl monomers such as glycidyl (meth)acrylate, α-ethylacrylate glycidyl, and 3,4-epoxybutyl (meth)acrylate;

Amino group-containing vinyl monomers such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate;

(meth)acrylamide, N-t-butyl (meth)acrylamide, N-methylol (meth)acrylamide, N-isopropylacrylamide, hydroxyethyl acrylamide, N-methoxymethyl (meth)acrylamide, N - Vinyl monomers containing amide groups such as butoxymethyl (meth)acrylamide, diacetone acrylamide, maleic acid amide, and maleimide;

Vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, (meth)acrylonitrile, 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 Rate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate , neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol Tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, allyl(meth)acrylate, triallyl cyanurate, diallyl maleate, polypropylene glycol diallyl ether, N,N'-methylenebis( multifunctional vinyl monomers such as meth)acrylamide;

Acryloylmorpholine, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, n-butoxyethyl (meth)acrylate, (meth)acrylate Isobutoxyethyl acrylate, t-butoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, 3-methoxy (meth)acrylate Butyl, acetoxyethyl (meth)acrylate, “Flaxel FM” (caprolactone addition monomer manufactured by Daicel Chemical Co., Ltd., brand name), “Blemmer PME-100” (methoxypolyethylene glycol manufactured by Nichiyu Co., Ltd.) Methacrylate (ethylene glycol chain number 2), brand name), “Blemmer PME-200” (Methoxypolyethylene glycol methacrylate (ethylene glycol chain number 4) manufactured by Nichiyu Co., Ltd., brand name ), “Blemmer PME-400” (Methoxypolyethylene glycol methacrylate (ethylene glycol chain is 9) manufactured by Nichiyu Co., Ltd., brand name), “Blemmer 50POEP-800B” (Nichiyu Co., Ltd.) Octoxypolyethylene glycol-polypropylene glycol-methacrylate (the chain of ethylene glycol is 8 and the chain of propylene glycol is 6), brand name) and “Blemmer 20ANEP-600” (Nonyl, manufactured by Nichiyu Co., Ltd. Phenoxy (ethylene glycol-polypropylene glycol) monoacrylate, brand name), “Blemmer AME-100” (manufactured by Nichiyu Co., Ltd., brand name), “Blemmer AME-200” (manufactured by Nichiyu Co., Ltd., brand name) and “Blemmer 50AOEP-800B” (manufactured by Nichiyu Co., Ltd., brand name), Silaplane FM-0711 (manufactured by JNC Co., Ltd., brand name), Silaplane FM-0721 (manufactured by JNC Co., Ltd., brand name), Silaplane FM-0725 (manufactured by JNC Corporation, brand name), Silaplane TM-0701 (manufactured by JNC Corporation, brand name), Silaplane TM-0701T (manufactured by JNC Corporation, brand name), X-22-174ASX (manufactured by Shin-Etsu Chemical Industries, Ltd., brand name), X-22-174DX (manufactured by Shin-Etsu Chemical Industries, Ltd., brand name), (meth)acrylic acid ester containing an ether group or ester group in the side group, such as do.);

Halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and chlorotrifluoroethylene;

(Meth)acrylic acid 2-isocyanatoethyl 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-pentafluorophenyl (meth)acrylate, 2-(purple Fluorobutyl)ethyl (meth)acrylate, 3-(perfluorobutyl)-2-hydroxypropyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 3-perfluoro Rohexyl-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-tridecafluor Looctyl (meth)acrylate, 1H-1-(trifluoromethyl)trifluoroethyl (meth)acrylate, 1H,1H,3H-hexafluorobutyl (meth)acrylate, 1,2,2, Fluorine-containing monomers such as 2-tetrafluoro-1-(trifluoromethyl)ethyl (meth)acrylate (however, halogenated olefins are excluded);

4-methacryloyloxybenzophenone, (meth)acrylic acid-2-isocyanatoethyl, etc. are mentioned. These monomers may be used individually or in combination of two or more types.

It is preferable that at least part of the monomer (a) is a (meth)acrylic monomer.

As the monomer (a), a compound represented by the following formula (a1) is preferable.

CH ₂ =CR ⁴¹ R ⁴² (a1)

(Wherein, R ⁴¹ represents a hydrogen atom, a methyl group or a hydroxymethyl group, and R ⁴² represents OR ⁴³ , a halogen atom, COR ⁴⁴ , COOR ⁴⁵ , CN, CONR ⁴⁶ R ⁴⁷ or R ^48. R ⁴³ to R ⁴⁷ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and R ⁴⁸ represents an aryl group or a heteroaryl group.)

Examples of the alkyl group for R ⁴³ to R ⁴⁷ include branched or straight-chain alkyl groups having 1 to 20 carbon atoms. Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, i-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, de Examples include syl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and icosyl group.

The cycloalkyl group for R ⁴³ to R ⁴⁷ may be monocyclic or polycyclic, and examples include cycloalkyl groups having 3 to 20 carbon atoms. Specific examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, bicyclo[2.2.1]heptyl group, cyclooctyl group, and adamantyl group.

Examples of the aryl group for R ⁴³ to R ⁴⁷ include an aryl group having 6 to 18 carbon atoms. Specific examples of the aryl group include phenyl group and naphthyl group.

Examples of the heterocyclic group for R ⁴³ to R ⁴⁷ include heterocyclic groups having 5 to 18 carbon atoms. Specific examples of heterocyclic groups include oxygen atom-containing heterocyclic groups such as γ-butyrolactone group and ε-caprolactone group, nitrogen atom-containing heterocyclic groups such as pyridyl group, carbazolyl group, pyrrolidinyl group, and pyrrolidone group. Examples include summoning group, morpholino group, etc.

In R ⁴³ to R ⁴⁷ , the alkyl group, cycloalkyl group, aryl group, and heterocyclic group may each have a substituent.

Substituents that the alkyl group may have include, for example, aryl group, -COOR ⁵¹ , cyano group, -OR ⁵² , -NR ⁵³ R ⁵⁴ , -CONR ⁵⁵ R ⁵⁶ , halogen atom, allyl group, epoxy group, siloxy group and hydrophilic group. Or at least one type selected from the group consisting of groups showing ionic properties.

Substituents that a cycloalkyl group, an aryl group, or a heterocyclic group may have include, for example, an alkyl group, an aryl group, -COOR ⁵¹ , a cyano group, -OR ⁵² , -NR ⁵³ R ⁵⁴ , -CONR ⁵⁵ R ⁵⁶ , and a halogen atom. , allyl group, epoxy group, siloxy group, and hydrophilic or ionic group.

Among the above substituents, the alkyl group and the aryl group include those similar to the alkyl group and aryl group for R ⁴³ to R ⁴⁷ , respectively.

In -COOR ⁵¹ , -OR ⁵² , -NR ⁵³ R ⁵⁴ , -CONR ⁵⁵ R ⁵⁶ , R ⁵¹ to R ⁵⁶ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. The alkyl group, cycloalkyl group, and aryl group for R ⁵¹ to R ⁵⁶ may be the same as the alkyl group, cycloalkyl group, and aryl group for R, respectively.

R ⁵¹ of -COOR ⁵¹ is preferably a hydrogen atom or an alkyl group. That is, -COOR ⁵¹ is preferably a carboxyl group or an alkoxycarbonyl group. Examples of the alkoxycarbonyl group include methoxycarbonyl group.

As R ⁵² of -OR ⁵² , a hydrogen atom or an alkyl group is preferable. That is, -OR ⁵² 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 a methoxy group is a specific example.

Examples of -NR ⁵³ R ⁵⁴ include amino group, monomethylamino group, and dimethylamino group.

Examples of -CONR ⁵⁵ R ⁵⁶ include carbamoyl group (-CONH ₂ ), N-methylcarbamoyl group (-CONHCH ₃ ), N,N-dimethylcarbamoyl group (dimethylamide group: -CON(CH ₃ ) ₂ ) can be mentioned.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of hydrophilic or ionic groups include alkali salts of carboxyl groups or alkali salts of sulfoxy groups, poly(alkylene oxide) groups such as polyethylene oxide groups and polypropylene oxide groups, and quaternary ammonium bases. A cationic substituent may be mentioned.

R ⁴³ to R ⁴⁷ are preferably an alkyl group or a cycloalkyl group. As the cycloalkyl group, a cycloalkyl group without a substituent or a cycloalkyl group with an alkyl group as a substituent is preferable.

As R ⁴³ to R ⁴⁷ , methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group and octyl group are more preferable due to ease of availability. , methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, isobornyl group and adamantyl group are more preferable.

The aryl group at R ⁴⁸ may be the same as the aryl group at R ⁴³ to R ⁴⁷ .

Examples of heteroaryl groups include pyridyl groups and carbazolyl groups.

The aryl group and heteroaryl group may each have a substituent. Substituents include carboxylic acid group, carboxylic acid ester group, epoxy group, hydroxy group, alkoxy group, primary amino group, secondary amino group, tertiary amino group, isocyanato group, sulfonic acid group, halogen atom, allyl group, etc. .

The carboxylic acid ester group, alkoxy group, primary amino group, secondary amino group, tertiary amino group, alkyl group, aryl group, and halogen atom may be the same as above.

As the monomer (a), a (meth)acrylic monomer is preferable, and a compound in which R ⁴¹ in formula (a1) is a hydrogen atom or a methyl group and R ⁴² is COOR ⁴⁵ is preferable.

As R ⁴⁵ , an alkyl group or a cycloalkyl group is preferable. As the cycloalkyl group, a cycloalkyl group without a substituent or a cycloalkyl group with an alkyl group as a substituent is preferable.

R ⁴⁵ is preferably a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, or octyl group due to ease of availability, and methyl group, Ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, isobornyl group, or adamantyl group is more preferable.

<Ratio of each constituent unit>

The ratio of the monomer (M) unit to the mass of the entire compound (MM) is preferably 1 mass% or more and 80 mass% or less, more preferably 20 mass% or more and 60 mass% or less, and 25 mass% or more and 50 mass%. The following is more preferable. If the ratio of monomer (M) units is more than the above lower limit, the hydrolyzability of the compound (MM) is improved and the antifouling property of the coating film tends to be more excellent, and if the ratio of the monomer (M) unit is less than the above upper limit, the crack resistance of the coating film tends to be more excellent.

The ratio of the monomer (M1) unit to the total of 100 mol% of all structural units constituting the compound (MM) is preferably 10 to 40 mol%, and more preferably 20 to 30 mol%. If the ratio of the monomer (M1) unit is more than the above lower limit, the hydrolyzability of the monomer (M1) unit is improved and the antifouling property of the coating film tends to be more excellent, and if the ratio of the monomer (M1) unit is less than the above upper limit, the crack resistance of the coating film tends to be more excellent. .

<Radical polymerization group>

As the radical polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of groups containing ethylenically unsaturated bonds include CH ₂ =C(COOR)-CH ₂ -, (meth)acryloyl group, 2-(hydroxymethyl)acryloyl group, vinyl group, etc. there is.

In CH ₂ =C(COOR)-CH ₂ -, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or a 1-alkyloxy group.

Examples of the 1-alkyloxy group include groups represented by the following formula (7), (8), or (9).

(In the formula, R ¹ to R ⁶ are the same as above.)

The amount of radical polymerizable groups contained in the compound (MM) is preferably 0.1 to 1.5 per molecule. If it is 0.1 or more, antifouling properties will be good, and if it is 1.5 or less, the viscosity of the polymer-containing composition is sufficiently low, and a coating composition with low VOC can be obtained.

Examples of the alkyl group include branched or straight-chain alkyl groups having 1 to 20 carbon atoms. Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, i-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, de Examples include syl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and icosyl group.

The cycloalkyl group may be monocyclic or polycyclic, and examples include cycloalkyl groups having 3 to 20 carbon atoms. Specific examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, bicyclo[2.2.1]heptyl group, cyclooctyl group, and adamantyl group.

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

Examples of heterocyclic groups include heterocyclic groups having 5 to 18 carbon atoms. Specific examples of heterocyclic groups include oxygen atom-containing heterocyclic groups such as γ-butyrolactone group and ε-caprolactone group, nitrogen atom-containing heterocyclic groups such as pyridyl group, carbazolyl group, pyrrolidinyl group, and pyrrolidone group. Examples include summoning group, morpholino group, etc.

In R, the alkyl group, cycloalkyl group, aryl group, and heterocyclic group may each have a substituent.

Substituents include, for example, an alkyl group (except for cases where R is an alkyl group having a substituent), aryl group, -COOR ⁵¹ , cyano group, -OR ⁵² , -NR ⁵³ R ⁵⁴ , -CONR ⁵⁵ R ⁵⁶ , and at least one selected from the group consisting of a halogen atom, an allyl group, an epoxy group, a siloxy group, and a hydrophilic or ionic group.

Among the above substituents, the alkyl group and the aryl group are the same as the alkyl group and aryl group for R, respectively.

In -COOR ⁵¹ , -OR ⁵² , -NR ⁵³ R ⁵⁴ , -CONR ⁵⁵ R ⁵⁶ , R ⁵¹ to R ⁵⁶ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. The alkyl group, cycloalkyl group, and aryl group for R ⁵¹ to R ⁵⁶ may be the same as the alkyl group, cycloalkyl group, and aryl group for R, respectively.

R ⁵¹ of -COOR ⁵¹ is preferably a hydrogen atom or an alkyl group. That is, -COOR ⁵¹ is preferably a carboxyl group or an alkoxycarbonyl group. Examples of the alkoxycarbonyl group include methoxycarbonyl group.

As R ⁵² of -OR ⁵² , a hydrogen atom or an alkyl group is preferable. That is, -OR ⁵² 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 a methoxy group is a specific example.

Examples of -NR ⁵³ R ⁵⁴ include amino group, monomethylamino group, and dimethylamino group.

Examples of -CONR ⁵⁵ R ⁵⁶ include carbamoyl group (-CONH ₂ ), N-methylcarbamoyl group (-CONHCH ₃ ), N,N-dimethylcarbamoyl group (dimethylamide group: -CON(CH ₃ ) ₂ ) can be mentioned.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of hydrophilic or ionic groups include alkali salts of carboxyl groups or alkali salts of sulfoxy groups, poly(alkylene oxide) groups such as polyethylene oxide groups and polypropylene oxide groups, and quaternary ammonium bases. A cationic substituent may be mentioned.

As R, an alkyl group or a cycloalkyl group is preferable. As the cycloalkyl group, a cycloalkyl group without a substituent or a cycloalkyl group with an alkyl group as a substituent is preferable.

As R, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group and octyl group are preferable due to ease of availability, and methyl group, ethyl group, More preferred are n-propyl group, i-propyl group, n-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, isobornyl group and adamantyl group.

In one aspect of the compound (MM), a main chain portion containing 2 or more monomer (M) units and 1 or more monomer (a) units, or 3 or more monomer (M) units, and one end or both of the main chain portion Examples include compounds containing a radical polymerizable group bonded to the terminal of . When a radical polymerizable group is bonded to one terminal of the main chain portion, a terminal group other than the radical polymerizable group is bonded to the other terminal.

As the compound (MM), a compound represented by the following formula (MM-1) is preferable from the viewpoint of productivity and coating film performance.

(In the ^{formula ,} X ^{1 to} , a heterocyclic group, or a substituent represented by the following formula (7), (8) or (9), and two or more of Y ¹ to Y ⁿ are represented by the following formula (7), (8) or (9) is a substituent, n represents a natural number of 3 or more, and Z represents a terminal group.)

(Wherein, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group with 1 to 10 carbon atoms, and R ³ and R ⁵ each independently represent an alkyl group with 1 to 20 carbon atoms or a cycloalkyl group with 4 to 8 carbon atoms. Or represents an aryl group having 6 to 20 carbon atoms, R ⁴ represents an alkylene group having 1 to 10 carbon atoms, and R ⁶ represents an alkylene group having 2 to 10 carbon atoms.)

The dotted line in formula (MM-1) represents the state in which the monomer units are polymerized. When n is 3, among the methylene groups bonded to the carbon atom to ^which X ² is bonded, a methylene group located on the side opposite to the carbon atom to ^which The carbon atom to which ⁿ is bonded is directly bonded. ^{When n} is 4 or more ^, the methylene group bonded to the carbon atom bonded ^to COOY ⁱ )-CH ₂ -, i represents a natural number of 3 or more (n-1) or less.) are combined through.

In formula (MM-1), R and Y ¹ to Y ⁿ include an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, and a structure represented by the formula (7), (8) or (9). The substituents include the same alkyl group, cycloalkyl group, aryl group, heterocyclic group, and 1-alkyloxy group for R of CH ₂ =C(COOR)-CH ₂ - described above, respectively.

The ratio of the number of 1-alkyloxy groups to the total number of Y ¹ to Y ⁿ is preferably 10 to 40 mol%, and more preferably 20 to 30 mol%. If the ratio of 1-alkyloxy groups is more than the above lower limit, the hydrolyzability of compound (MM) is improved and the antifouling property of the coating film tends to be more excellent, and if the ratio of the 1-alkyloxy group is less than the above upper limit, the crack resistance of the coating film tends to be more excellent.

n is preferably a value such that the weight average molecular weight of the compound represented by formula (MM-1) is 2000 or more and 1,000,000 or less. A more preferable range of the weight average molecular weight is as described later.

Z may be the same as the terminal group of a polymer obtained by known radical polymerization, and examples include a hydrogen atom, a group derived from a radical polymerization initiator, and a radical polymerizable group. Among these, a group derived from a hydrogen atom or a radical polymerization initiator is preferable because side reactions do not proceed.

Compound (MM) preferably has a solid acid value of 10 mgKOH/g or more and 180 mgKOH/g or less, more preferably 20 mgKOH/g or more and 150 mgKOH/g or less, as measured after subjecting the compound (MM) to the above hydrolysis treatment, and 30 mgKOH/g. It is more preferable that it is more than g and less than 120 mgKOH/g. When the solid acid value of the compound (MM) is equal to or higher than the above lower limit, the hydrolyzability of the compound (MM) is improved and the antifouling property of the coating film is more excellent. If the solid acid value of the compound (MM) is less than the above upper limit value, the crack resistance of the coating film is more excellent.

The solid acid value is measured by the method described in the Examples described later.

The glass transition temperature (Tg) of the compound (MM) is preferably -10°C or higher and 90°C or lower, more preferably 10°C or higher and 90°C or lower, and even more preferably 30°C or higher and 90°C or lower. If the glass transition temperature of the compound (MM) is above the lower limit, the coating film hardness is more excellent, and if it is below the above upper limit, the coating film solubility is more excellent.

The glass transition temperature is calculated by the method described in the Examples described later.

The weight average molecular weight (Mw) of the compound (MM) is preferably 2,000 to 1,000,000, more preferably 2,500 to 100,000, more preferably 3,000 to 10,000, and even more preferably 4,000 to 10,000. If the weight average molecular weight of the compound (MM) is more than the above lower limit, the coating film hardness is more excellent, and if the weight average molecular weight of the compound (MM) is less than the above upper limit, the coating film solubility is more excellent.

The molecular weight dispersion of the compound (MM) is preferably 1.0 or more and 4.0 or less, more preferably 1.0 or more and 3.5 or less, and still more preferably 1.0 or more and 3.0 or less. Molecular weight dispersion is the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

The weight average molecular weight and number average molecular weight are measured by gel filtration chromatography (GPC) using polystyrene as a reference material.

The solubility parameter (sp) of the compound (MM) is preferably 5.0 or more and 12.0 or less, more preferably 6.0 or more and 11.0 or less, and even more preferably 7.0 or more and 10.0 or less. If the solubility parameter of the compound (MM) is more than the above lower limit, the coating film solubility is more excellent, and if the solubility parameter of the compound (MM) is less than the above upper limit, the water resistance is more excellent.

The solubility parameter is a measure of solubility. The larger the value of the solubility parameter, the higher the polarity, and the smaller the value, the lower the polarity. In the present invention, the solubility parameter is obtained by Fedors' estimation method. Specifically, it is calculated by the following formula.

δ(sp)=(ΣEcoh/ΣV) ^1/2

In the formula, ΣEcoh represents the cohesive energy (cal/mol) and ΣV represents the molar molecular volume (cm3/mol).

ΣEcoh and ΣV can be known values, for example, values described in Robert F. FEDORS, "POLYMER ENGINEERING AND SCIENCE", February, 1974, Vol. 14, No. 2, pages 147 to 154.

<Method for producing compounds>

As a method for producing the compound (MM), for example, (i) a method of polymerizing a monomer mixture containing the monomer (M) using a cobalt chain transfer agent, (ii) a method of polymerizing the monomer mixture containing the monomer (M) , a method of polymerizing using an α-substituted unsaturated compound such as α-methylstyrene dimer as a chain transfer agent, (iii) polymerizing a monomer mixture containing monomer (M) units, and chemically bonding a radical polymerizable group to the obtained polymer. method, (iv) polymerizing a monomer mixture containing the monomer (M), and thermally decomposing the obtained polymer.

Among these, method (i) is preferable as a method for producing compound (MM) because the number of production steps is small and a catalyst with a high chain transfer constant is used. Additionally, compound (MM) when produced using a cobalt chain transfer agent has a structure represented by the above formula (MM-1).

In the method (i), examples of the method for polymerizing the monomer mixture include aqueous dispersion polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. When solution polymerizing the obtained compound (MM) with other monomers, the solution polymerization method is preferable because purification is unnecessary.

In the method (iii) above, a method of chemically bonding a radical polymerizable group to a polymer includes, for example, replacing the halogen group of a polymer having a halogen group with a compound having a radically polymerizable carbon-carbon double bond. Method, reacting a vinyl monomer having an acid group with a vinyl polymer having an epoxy group, reacting a vinyl polymer having an epoxy group with a vinyl monomer having an acid group, reacting a vinyl polymer having a hydroxyl group with a diisocyanate compound. A method of producing a vinyl polymer having an isocyanate group and reacting this vinyl polymer with a vinyl monomer having a hydroxyl group may be used, and it may be produced by any method.

When the monomer (M) is monomer (M1), in the methods (i) to (iv) above, a monomer (m1) containing a carboxyl group and a radical polymerizable group is used instead of the monomer (M), and after polymerization, Compound (MM) can also be produced by converting the carboxyl group of the obtained polymer into structure (1), (2) or (3).

Examples of the monomer (m1) include (meth)acrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, monomethyl maleate, and monomethyl fumarate.

Methods for converting the carboxyl group of a polymer into structure (1), (2) or (3) include, for example, a polymer, a compound represented by the formula (11) below, a compound represented by the formula (12) below, and A method of reacting (addition reaction) with at least one alkenyl compound selected from the group consisting of compounds represented by formula (13) can be cited.

^{( Wherein , _} Each independently represents an alkyl group, a cycloalkyl group, or an aryl group having 1 to 20 carbon atoms, R ¹⁴ represents a single bond or an alkylene group having 2 to 9 carbon atoms, and R ¹⁶ represents an alkylene group having 1 to 9 carbon atoms. )

When a compound represented by formula (11) is used as an alkenyl compound, a compound in formula (1) wherein R ¹ is CH ₂ R ¹¹ , R ² is R ¹² , and R ³ is R ¹³ is obtained.

In formula (11), the alkyl group having 1 to 9 carbon atoms for R ¹¹ is the same as the alkyl group having 1 to 10 carbon atoms for R ¹ except that the alkyl group has 9 or less carbon atoms. R ¹² and R ¹³ are the same as R ² and R ³ , respectively.

Examples of the compound represented by formula (11) include alkyl vinyl ether (e.g., ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether), cyclo Vinyl ethers such as alkyl vinyl ether (for example, cyclohexyl vinyl ether); 1-propenyl ethers such as ethyl-1-propenyl ether; 1-butenyl ethers such as ethyl-1-butenyl ether; etc. can be mentioned. Among these, vinyl ethers and 1-propenyl ethers are preferable.

When a compound represented by formula (12) is used as an alkenyl compound, a compound in which R ⁴ in the formula (2) is CH ₂ -R ¹⁴ is obtained.

In formula (12), the alkylene group having 1 to 9 carbon atoms in R ¹⁴ is the same as that of R ⁴ except that the alkylene group has 9 or less carbon atoms.

Examples of the compound represented by formula (12) include dihydrofurans such as 2,3-dihydrofuran and 5-methyl-2,3-dihydrofuran; dihydropyrans such as 3,4-dihydro-2H-pyran and 5,6-dihydro-4-methoxy-2H-pyran; etc. can be mentioned.

When a compound represented by formula (13) is used as an alkenyl compound, a compound in which R ⁵ in the formula (3) is R ¹⁵ and R ⁶ is CH ₂ -R ¹⁶ is obtained.

In formula (13), R ¹⁵ is the same as R ⁵ . R ¹⁶ is the same as R ⁶ except that the number of carbon atoms is 9 or less.

Examples of compounds represented by formula (13) include 1-methoxy-1-cyclopentene, 1-methoxy-1-cyclohexene, 1-methoxy-1-cycloheptene, and 1-ethoxy-1. -1-alkoxy-1-cycloalkylenes such as cyclopentene, 1-ethoxy-1-cyclohexene, 1-butoxy-1-cyclopentene, and 1-butoxy-1-cyclohexene; 1-alkoxy-1-cycloalkylenes containing a substituent such as 1-ethoxy-3-methyl-1-cyclohexene; etc. can be mentioned.

The reaction between the polymer and the alkenyl compound proceeds under relatively mild conditions. For example, the target product is obtained by maintaining the reaction temperature at 40 to 100°C and reacting for 5 to 10 hours in the presence or absence of an acidic catalyst such as hydrochloric acid, sulfuric acid, or phosphoric acid. After completion of the reaction, the target polymer can be recovered by performing reduced pressure distillation under predetermined conditions.

Compound (MM) is made into a polymer containing Compound (MM) units by polymerizing Compound (MM) alone or with other monomers (monomer (a), monomer (M)). The coating film containing this polymer increases solubility in seawater and the like by hydrolyzing the compound (MM) unit in seawater, etc., and exhibits an antifouling effect. Additionally, this coating film has excellent initial solubility compared to the case where monomer (M) is used instead of compound (MM).

The reasons for exhibiting the above effect are considered as follows.

Generally, the rate of the hydrolysis reaction is limited until the first hydrolysis begins.

A polymer obtained by polymerizing a compound (MM) does not contain a monomer (M) unit as a structural unit constituting the main chain of the polymer, or even if the proportion of monomer (M) units among the structural units constituting the main chain of the polymer is small, Two or more monomer (M) units are present in the side chain portion of the compound (MM) unit. Therefore, it is thought that the density of hydrolysis reaction sites increases locally in the coating film, the initial hydrolysis is promoted due to the proximity effect, and the initial solubility is improved.

If the monomer (M) unit is not included as a structural unit constituting the main chain of the polymer, or the ratio of the monomer (M) unit is small among the structural units constituting the main chain of the polymer, the crack resistance of the coating film is improved.

Compound (MM) may be polymerized in advance and blended into the antifouling paint composition as a polymer, or may be blended into the antifouling paint composition as compound (MM).

The use of compound (MM) is not limited to antifouling paint compositions, and can be used for other purposes, such as antifogging paint compositions.

〔polymer〕

The polymer (hereinafter also referred to as “polymer (A)”) related to one aspect of the present invention includes a structural unit based on compound (MM) (hereinafter also referred to as “compound (MM) unit”). It is a polymer that

The polymer (A) may further contain a monomer (a) unit in addition to the compound (MM) unit.

The polymer (A) may further contain a monomer (M) unit in addition to the compound (MM) unit, or in addition to the compound (MM) unit and the monomer (a) unit.

The ratio of the compound (MM) unit to the total of all structural units constituting the polymer (A) is preferably 5 mass% or more and 90 mass% or less, preferably 10 mass% or more and 60 mass% or less, and 15 mass%. 50 mass% or less is more preferable, and 20 mass% or more and 40 mass% or less is further preferable. If the ratio of the compound (MM) unit is more than the above lower limit, the initial solubility of the coating film containing the polymer (A) is more excellent, and the effect of preventing adhesion of marine organisms, etc. is likely to be expressed from the initial stage of immersing the coating film in seawater, etc. . If the ratio of compound (MM) units is below the above upper limit, the crack resistance of the coating film is more excellent.

The ratio of the monomer (a) unit to the total of all structural units constituting the polymer (A) is preferably 40% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 85% by mass or less, and 60% by mass. % or more and 80 mass% or less is more preferable. If the ratio of monomer (a) units is more than the above lower limit, the crack resistance of the coating film is more excellent, and if it is less than the above upper limit, the ratio of compound (MM) units can be sufficiently high, and the solubility of the coating film is more excellent.

The ratio of the monomer (M) unit to the total of all structural units constituting the polymer (A) is preferably 60% by mass or less, more preferably 45% by mass or less, further preferably 30% by mass or less, and 0. It may be mass%.

The monomer (M) unit here is a monomer (M) unit other than the monomer (M) unit included in the compound (MM) unit. If the ratio of monomer (M) units is below the above upper limit, the crack resistance of the coating film containing the polymer (A) is more excellent.

However, the sum of the ratio of the compound (MM) unit, the ratio of the monomer (a) unit, and the ratio of the monomer (M) unit to the sum of all structural units constituting the polymer (A) does not exceed 100% by mass. .

The polymer (A) is preferably a (meth)acrylic polymer from the viewpoint of hydrolysis and crack resistance.

“(meth)acrylic polymer” refers to a polymer in which at least part of the structural units constituting the polymer is a structural unit based on a (meth)acrylic monomer (hereinafter also referred to as a “(meth)acrylic monomer unit”). . The (meth)acrylic polymer may further contain a structural unit based on a monomer other than the (meth)acrylic monomer (for example, a vinyl monomer such as styrene).

When the polymer (A) contains only compound (MM) units, it is preferred that at least a portion of the compound (MM) units are (meth)acrylic monomer units. When the polymer (A) contains a compound (MM) unit and a monomer (a) unit, it is preferable that at least a part of the compound (MM) unit and the monomer (a) unit are (meth)acrylic monomers. When the polymer (A) comprises compound (MM) units and monomer (a) units and monomer (M) units, at least some of the compound (MM) units, monomer (a) units and monomer (M) units are (meth ) It is preferable that it is an acrylic monomer.

The ratio of the (meth)acrylic monomer unit to the total of all structural units constituting the polymer (A) is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, It is especially preferable that it is 100 mass%. That is, it is particularly preferable that all structural units constituting the polymer (A) are (meth)acrylic monomer units.

The solid acid value of the polymer (A) measured after subjecting the polymer (A) to the above hydrolysis treatment is preferably 20 mgKOH/g or more and 150 mgKOH/g or less, more preferably 30 mgKOH/g or more and 90 mgKOH/g or less, and 30 mgKOH It is more preferable that it is more than /g and less than 60mgKOH/g. If the solid acid value of the polymer (A) is more than the above lower limit, the solubility of the coating film is more excellent, and if it is less than the above upper limit, the crack resistance of the coating film is more excellent.

The glass transition temperature (Tg) of the polymer (A) is preferably -10°C or higher and 70°C or lower, more preferably 0°C or higher and 50°C or lower, and even more preferably 10°C or higher and 30°C or lower. If the glass transition temperature of the polymer (A) is equal to or higher than the above lower limit, the hardness of the coating film is superior, and if the glass transition temperature of the polymer (A) is equal to or lower than the upper limit, the solubility of the coating film is superior.

The weight average molecular weight (Mw) of the polymer (A) is preferably 2,000 or more and 100,000 or less, more preferably 5,000 or more and 50,000 or less, and even more preferably 9,000 or more and 20,000 or less. If the weight average molecular weight of the polymer (A) is more than the above lower limit, the coating film hardness is more excellent, and if the weight average molecular weight of the polymer (A) is less than the above upper limit, the coating film solubility is more excellent.

The molecular weight dispersion of the polymer (A) is preferably 1.0 or more and 4.0 or less, more preferably 1.0 or more and 3.5 or less, and still more preferably 1.0 or more and 3.0 or less.

The solubility parameter (sp) of the polymer (A) is preferably 5.0 or more and 12.0 or less, more preferably 6.0 or more and 11.0 or less, and even more preferably 7.0 or more and 10.0 or less. If the solubility parameter of the polymer (A) is more than the above lower limit, the solubility of the coating film is more excellent, and if it is less than the above upper limit, water resistance is more excellent.

<Method for producing polymer>

Examples of the method for producing polymer (A) include polymerizing a monomer mixture containing compound (MM).

The monomer mixture may further contain monomer (a).

The monomer mixture may further contain a monomer (M).

The composition of the monomer mixture, that is, the type of monomer constituting the monomer mixture, and the ratio (mass %) of each monomer to the mass of the entire monomer mixture are the composition of the polymer (A), that is, the proportion of each monomer unit constituting the polymer (A). The same applies to the type and the ratio (mass %) of each monomer unit to the total of all structural units constituting the polymer (A).

As a method for polymerizing the monomer mixture, for example, known polymerization methods such as solution polymerization method, suspension polymerization method, bulk polymerization method, and emulsion polymerization method can be applied. From the viewpoint of productivity and coating film performance, the solution polymerization method is preferable. The solvent used in solution polymerization is not particularly limited, and general organic solvents can be used.

Polymerization may be performed by a known method using a known polymerization initiator. For example, there is a method of reacting the monomer mixture in the presence of a radical polymerization initiator at a reaction temperature of 60 to 180°C (further 60 to 120°C) for 4 to 14 hours (further 5 to 10 hours). During polymerization, if necessary, a chain transfer agent may be used.

As a radical polymerization initiator, known ones can be used, for example, 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis. Azo compounds such as (2-methylbutyronitrile); Organic peroxides such as lauryl peroxide, benzoyl peroxide, cumene hydroperoxide, lauryl peroxide, di-t-butyl peroxide, and t-butyl peroxy-2-ethylhexanoate; etc. can be mentioned.

The content of the polymerization initiator is not particularly limited and can be set appropriately. Typically, it is about 0.1 to 20 parts by mass per 100 parts by mass of the polymerizable monomer.

As the chain transfer agent, known ones can be used, for example, mercaptans such as n-dodecyl mercaptan, thioglycolic acid esters such as octyl thioglycolate, α-methylstyrene dimer, terpinolene, etc. there is.

The content of the chain transfer agent is not particularly limited and can be set appropriately. Typically, it is about 0.0001 to 10 parts by mass per 100 parts by mass of the polymerizable monomer.

Polymer (A) is used, for example, in antifouling paint compositions. The coating film of the antifouling paint composition containing the polymer (A) exhibits an antifouling effect by increasing solubility in seawater and the like as the compound (MM) unit is hydrolyzed in seawater. Additionally, this coating film has excellent initial solubility compared to the case where monomer (M) is used instead of compound (MM).

In particular, if the ratio of the monomer (M) unit to the total of all structural units constituting the polymer (A) is 30% by mass or less, the crack resistance of the coating film is also excellent.

In addition, the use of polymer (A) is not limited to antifouling paint compositions, and can be used for other purposes, such as antifogging paint compositions.

[Antifouling paint composition (1)]

The antifouling paint composition (hereinafter also referred to as “antifouling paint composition (1)”) according to one aspect of the present invention contains the polymer (A) described above.

The antifouling paint composition (1) may further contain an organic solvent.

The antifouling paint composition (1) may further contain an antifouling agent.

The antifouling paint composition (1) may further contain other components.

<Organic solvent>

Examples of organic solvents include monohydric alcohol-based solvents such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; polyhydric alcohol-based solvents such as ethylene glycol and 1,2-propylene glycol; Ketone-based solvents such as acetone, methyl ethyl ketone, acetylacetone, and methyl isobutyl ketone; Ether-based solvents such as methyl ethyl ether and dioxane; Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, dipropylene glycol monopropyl ether glycol ether-based solvents such as; Glycol acetate-based solvents such as ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate; Other ester solvents such as n-butyl acetate and ethyl 3-ethoxypropionate; Aliphatic hydrocarbon solvents such as n-pentane and n-hexane; Aromatic hydrocarbon solvents such as toluene, xylene, and solvent naphtha; etc. can be mentioned. These organic solvents may be used individually or in combination of two or more types.

As an organic solvent, one capable of dissolving the polymer (A) is preferable.

The content of the organic solvent is set according to the solid content of the antifouling paint composition.

<Antifouling agent>

Antifouling agents include inorganic antifouling agents and organic antifouling agents, and one or two or more types can be appropriately selected and used depending on the required performance.

Examples of antifouling agents include copper-based antifouling agents such as cuprous oxide, copper thiocyanate, and copper powder, compounds of other metals (lead, zinc, nickel, etc.), amine derivatives such as diphenylamine, nitrile compounds, and benzothia. Sol-based compounds, maleimide-based compounds, pyridine-based compounds, etc. can be mentioned. These antifouling agents may be used individually or in combination of two or more types.

As an antifouling agent, more specifically, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, manganese ethylene bisdithiocarbamate. , zinc dimethyldithiocarbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N,N- Dimethyldichlorophenylurea, zinc ethylenebisdithiocarbamate, copper rhodanide, 4,5-dichloro-2-noctyl-3(2H)isothiazolone, N-(fluorodichloromethylthio)phthalimide, N,N'-dimethyl-N'-phenyl-(N-fluorodichloromethylthio)sulfamide, 2-pyridinethiol-1-oxide zinc salt, tetramethylthiuram disulfide, Cu-10% Ni solid solution alloy , 2,4,6-trichlorophenylmaleimide, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, 3-iodo-2-propynylbutylcarbamate, diiodo Methylparatrisulfone, bisdimethyldithiocarbamoylzincethylenebisdithiocarbamate, phenyl(bispyridyl)bismuth dichloride, 2-(4-thiazolyl)-benzimidazole, medetomidine, pyridine- Triphenylborane, etc. can be mentioned.

Among those mentioned above, the antifouling agent preferably contains cuprous oxide and copper pyrithione.

When the antifouling agent contains cuprous oxide and copper pyrithione, their mass ratio is preferably cuprous oxide/copper pyrithione = 80/20 to 99/1, and more preferably 90/10 to 99/1.

The content of the antifouling agent is not particularly limited, but is preferably 10 to 200 parts by mass, and more preferably 50 to 150 parts by mass, per 100 parts by mass of the polymer (A). If the content of the antifouling agent is more than the above lower limit, the antifouling effect of the formed coating film is more excellent, and if the content of the antifouling agent is less than the above upper limit, the self-polishing properties are more excellent.

<Other ingredients>

The antifouling paint composition (1) may contain a polymer other than the polymer (A).

Examples of other polymers include thermoplastic resins (thermoplastic polymers) other than polymer (A).

The antifouling paint composition (1) preferably contains another thermoplastic resin. When the antifouling paint composition (1) contains another thermoplastic resin, the physical properties of the coating film, such as crack resistance and water resistance, are improved.

Other thermoplastic resins include, for example, chlorinated paraffin; Chlorinated polyolefins such as chlorinated rubber, chlorinated polyethylene, and chlorinated polypropylene; polyvinyl ether; polypropylene sebacate; Partially hydrogenated terphenyl; polyvinyl acetate; Poly(meth)acrylate-based copolymer, ethyl (meth)acrylate-based copolymer, propyl (meth)acrylate-based copolymer, butyl (meth)acrylate-based copolymer, and cyclohexyl (meth)acrylate-based copolymer. ) Acrylic acid alkyl ester; polyetherpolyol; alkyd resin; polyester resin; Vinyl chloride-based resins such as vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl propionate copolymer, vinyl chloride-isobutyl vinyl ether copolymer, vinyl chloride-isopropyl vinyl ether copolymer, and vinyl chloride-ethyl vinyl ether copolymer. ; silicone oil; wax; Oils and fats that are solid at room temperature other than wax, fats and oils that are liquid at room temperature such as castor oil, and their refined products; vaseline; liquid paraffin; Rosin, hydrogenated rosin, naphthenic acid, fatty acids and divalent metal salts thereof; etc. can be mentioned. Examples of wax include animal-derived waxes such as beeswax; waxes of plant origin; Semi-synthetic waxes such as amide waxes; Synthetic waxes such as polyethylene oxide waxes, etc. can be mentioned. These thermoplastic resins may be used individually, or two or more types may be used in combination.

Chlorinated paraffin is preferable because it functions as a plasticizer and improves the crack resistance and peeling resistance of the coating film.

Since it functions as an anti-settling agent or anti-flow agent and improves the storage stability and pigment dispersibility of the antifouling paint composition, organic waxes such as semi-synthetic wax and synthetic wax are preferable, and polyethylene wax, polyethylene oxide wax, and polyamide wax are preferable. It is more desirable.

The content of the other thermoplastic resin is not particularly limited, but is preferably 0.1 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the polymer (A). If the content of the other thermoplastic resin is more than the above lower limit, the coating film physical properties such as crack resistance and water resistance are more excellent, and if the content of the other thermoplastic resin is less than the above upper limit, the hydrolysis property is more excellent.

The antifouling paint composition (1) contains a polymer (A) containing a compound (MM) unit containing at least one structure selected from the group consisting of structure (1), structure (2), and structure (3). In this case, the antifouling paint composition (1) is at least one alkenyl selected from the group consisting of a compound represented by the formula (11), a compound represented by the formula (12), and a compound represented by the formula (13). It is preferable to include a compound. When the antifouling paint composition contains an alkenyl compound, the storage stability of the antifouling paint composition is improved.

As the alkenyl compound, vinyl ethers such as butyl vinyl ether and isobutyl vinyl ether are preferable because they have a more excellent storage stability improvement effect.

The content of the alkenyl compound is preferably 20 mol% or more, more preferably 30 to 1000 mol%, based on a total of 100 mol% of structure (1), structure (2), and structure (3) in the polymer (A). , 40 to 800 mol% is more preferable. If the content of the alkenyl compound is within the above range, storage stability is more excellent.

The antifouling paint composition (1) may contain silicone compounds such as dimethylpolysiloxane and silicone oil, fluorine-containing compounds such as fluorinated hydrocarbons, etc. for the purpose of providing lubricity to the surface of the coating film and preventing attachment of living things.

The antifouling paint composition (1) includes various pigments, dehydrating agents, anti-foaming agents, leveling agents, pigment dispersants (e.g. anti-settling agents), anti-flow agents, matting agents, ultraviolet absorbers, antioxidants, heat resistance improvers, slip agents, preservatives, plasticizers, and viscosity agents. It may contain a control agent, etc.

Pigments include zinc oxide, talc, silica, barium sulfate, orthite, aluminum hydroxide, magnesium carbonate, mica, carbon black, Bengala, titanium oxide, phthalocyanine blue, kaolin, gypsum, etc. In particular, zinc oxide and talc are preferred.

Examples of dehydrating agents include silicate-based, isocyanate-based, orthoester-based, inorganic-based, etc. More specifically, examples include methyl orthoformate, ethyl orthoformate, methyl orthoacetate, orthoboron ester, tetraethyl orthosilicate, anhydrous gypsum, calcined gypsum, and synthetic zeolite (molecular sieve). In particular, molecular sieves are preferred. By containing a dehydrating agent in the antifouling paint composition, moisture can be replenished and storage stability can be improved.

Examples of anti-settling agents and anti-flow agents other than thermoplastic resins include bentonite-based, finely divided silica-based, stearate salts, lecithin salts, and alkyl sulfonates.

Examples of plasticizers other than thermoplastic resins include phthalic acid ester plasticizers such as dioctyl phthalate, dimethyl phthalate, dicyclohexyl phthalate, and diisodecyl phthalate; Aliphatic dibasic acid ester plasticizers such as isobutyl adipate and dibutyl sebacate; Glycol ester plasticizers such as diethylene glycol dibenzoate and pentaerythritol alkyl ester; Phosphate ester plasticizers such as tricresyl phosphate (TCP), triaryl phosphate, and trichloroethyl phosphate; Epoxy-based plasticizers such as epoxy soybean oil and octyl epoxystearate; Organic tin plasticizers such as dioctyltin laurylate and dibutyltin laurylate; Trioctyl trimellitate, triacetylene, etc. can be mentioned. By containing a plasticizer in the antifouling paint composition, the crack resistance and peeling resistance of the coating film can be improved. As a plasticizer, among those mentioned above, TCP is preferable.

The antifouling paint composition (1) may contain water.

The moisture content of the antifouling paint composition (1) is preferably 15% by mass or less, and more preferably 10% by mass or less. The lower limit is not particularly limited and may be 0 mass%. The water content is the ratio of water to the total mass of the antifouling paint composition (1). When the moisture content is below the above upper limit, the water resistance and drying properties of the coating film formed from the antifouling paint composition (1) are more excellent.

The solid content of the antifouling paint composition (1) is preferably 40 to 90% by mass, more preferably 50 to 80% by mass, and still more preferably 60 to 70% by mass, relative to the total mass of the antifouling paint composition (1).

The type B viscosity of the antifouling paint composition (1) measured with a type B viscometer at 25°C is preferably less than 5,000 mPa·s, more preferably less than 4,000 mPa·s, and even more preferably less than 3,000 mPa·s. , less than 2,000 mPa·s is particularly preferable. If the type B viscosity of the antifouling paint composition is below the above upper limit, it is easy to paint.

The lower limit of the B-type viscosity at 25°C of the antifouling paint composition is not particularly limited, but in terms of suppressing paint dripping during painting, 100 mPa·s or more is preferable, 200 mPa·s or more is more preferable, and 300 mPa·s. More than this is more preferable, and 1,000 mPa·s or more is especially preferable.

Antifouling paint composition (1) can be prepared by preparing polymer (A) and mixing it with an organic solvent, antifouling agent, or other components as needed.

The antifouling paint composition (1) can be used to form a coating film (antifouling coating film) on the surface of a substrate such as underwater structures such as ships, various fishing nets, port facilities, oil fences, bridges, and underwater bases.

A coating film using the antifouling paint composition (1) can be formed on the surface of the substrate directly or through an underlying coating film. The base coating film can be formed using a wash primer, a chlorinated rubber-based or epoxy-based primer, or an intermediate paint.

Formation of the coating film can be performed by a known method. For example, a coating film can be formed by applying the antifouling paint composition (1) on the surface of the substrate or the base coating film on the substrate by means of brush application, spray application, roller application, or dip coating, and then drying it.

The application amount of the antifouling paint composition (1) can generally be set to an amount that results in a thickness of 10 to 400 μm as a dry coating film.

Drying of the coating film can usually be performed at room temperature, and heat drying may be performed as needed.

[Antifouling paint composition (2)]

An antifouling paint composition (hereinafter also referred to as “antifouling paint composition (2)”) related to another aspect of the present invention contains the above-described compound (MM).

The antifouling paint composition (2) may further contain monomer (a).

The antifouling paint composition (2) may further contain a monomer (M).

The antifouling paint composition (2) may further contain a radical polymerization initiator.

The antifouling paint composition (2) may further contain an organic solvent.

The antifouling paint composition (2) may further contain an antifouling agent.

The antifouling paint composition (2) may further contain other components.

Monomer (a), monomer (M), radical polymerization initiator, organic solvent, antifouling agent, and other components may be the same as above.

The ratio of compound (MM) to the total of compound (MM), monomer (a), and monomer (M) is preferably 10 mass% or more and 60 mass% or less, and more preferably 15 mass% or more and 50 mass% or less. , 20% by mass or more and 40% by mass or less are more preferable. If the ratio of the compound (MM) is more than the above lower limit, the initial solubility of the coating film is superior, and the effect of preventing adhesion of marine organisms and the like is likely to be exhibited from the initial stage of immersing the coating film in seawater or the like. If the ratio of the compound (MM) is below the above upper limit, the crack resistance of the coating film is more excellent.

The ratio of monomer (a) to the total of compound (MM), monomer (a), and monomer (M) is preferably 40% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 85% by mass or less. , 60% by mass or more and 80% by mass or less are more preferable. If the ratio of monomer (a) is more than the above lower limit, the crack resistance of the coating film is more excellent, and if the ratio of monomer (a) is less than the above upper limit, the ratio of compound (MM) can be sufficiently high.

The ratio of monomer (M) to the total of compound (MM), monomer (a), and monomer (M) is preferably 60% by mass or less, more preferably 45% by mass or less, and even more preferably 30% by mass or less. Also, it may be 0 mass%. If the ratio of monomer (M) is below the above upper limit, the crack resistance of the coating film is more excellent.

The content of the antifouling agent is not particularly limited, but is preferably 10 to 200 parts by mass, more preferably 50 to 150 parts by mass, based on a total of 100 parts by mass of the compound (MM), monomer (a), and monomer (M). If the content of the antifouling agent is more than the above lower limit, the antifouling effect of the formed coating film is more excellent, and if the content of the antifouling agent is less than the above upper limit, the self-polishing properties are more excellent.

The content of the other thermoplastic resin among the other components is not particularly limited, but is preferably 0.1 to 50 parts by mass, and is preferably 0.1 to 10 parts by mass based on a total of 100 parts by mass of the compound (MM), monomer (a), and monomer (M). desirable. If the content of the other thermoplastic resin is more than the above lower limit, the coating film physical properties such as crack resistance and water resistance are more excellent, and if the content of the other thermoplastic resin is less than the above upper limit, the hydrolysis property is more excellent.

When the antifouling paint composition (2) contains an alkenyl compound among other components, the content of the alkenyl compound is 100 mol% of the total of structure (1), structure (2), and structure (3) in the compound (MM). 20 mol% or more is preferable, 30 to 1000 mol% is more preferable, and 40 to 800 mol% is still more preferable. If the content of the alkenyl compound is within the above range, storage stability is more excellent.

The moisture content of the antifouling paint composition (2) is preferably 15% by mass or less, and more preferably 10% by mass or less. The lower limit is not particularly limited and may be 0 mass%. When the moisture content is below the above upper limit, the water resistance and drying properties of the coating film formed from the antifouling paint composition (2) are more excellent.

The solid content of the antifouling paint composition (2) is preferably 40 to 90% by mass, more preferably 50 to 80% by mass, and even more preferably 60 to 70% by mass, relative to the total mass of the antifouling paint composition (2).

The type B viscosity of the antifouling paint composition (2) measured with a type B viscometer at 25°C is preferably less than 5,000 mPa·s, more preferably less than 4,000 mPa·s, and even more preferably less than 3,000 mPa·s. , less than 2,000 mPa·s is particularly preferable. If the type B viscosity of the antifouling paint composition is below the above upper limit, it is easy to paint.

The lower limit of the B-type viscosity at 25°C of the antifouling paint composition is not particularly limited, but in terms of suppressing paint dripping during painting, 100 mPa·s or more is preferable, 200 mPa·s or more is more preferable, and 300 mPa·s. More than this is more preferable, and 1,000 mPa·s or more is especially preferable.

The antifouling paint composition (2) can be prepared by preparing the compound (MM) and mixing it with monomer (a), monomer (M), organic solvent, antifouling agent, and other components as needed.

The antifouling paint composition (2), like the antifouling paint composition (1), can be used to form a coating film (antifouling film) on the surface of a substrate such as underwater structures such as ships, various fishing nets, port facilities, oil fences, bridges, and underwater bases. You can.

A coating film using the antifouling paint composition (2) can be formed on the surface of the substrate directly or through an underlying coating film. The base coating film can be formed using a wash primer, a chlorinated rubber-based or epoxy-based primer, or an intermediate paint.

Formation of the coating film can be performed by a known method. For example, a coating film can be formed by applying the antifouling paint composition (2) on the surface of the substrate or an underlying coating film on the substrate by means of brush application, spray application, roller application, or dip coating and drying.

The application amount of the antifouling paint composition can generally be set to an amount that provides a thickness of 10 to 400 μm as a dry coating film.

Drying of the coating film can usually be performed at room temperature, and heat drying may be performed as needed.

Example

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is in no way limited by these examples. In addition, parts in the examples represent mass parts.

Evaluation in the examples was performed by the method shown below.

(Solids (heated residue))

Weigh 0.50 g of the measurement sample (solution polymerization product of compound (MM) or polymer-containing composition) on an aluminum dish (measured mass (g)), add 3 mL of toluene using a dropper, and spread evenly on the bottom of the dish. The measurement sample was heated and dissolved in a water bath at 70 to 80°C and evaporated to dryness. After that, drying was performed for 2 hours in a hot air dryer at 105°C. From the mass of the measurement sample (measured mass (g)) and the mass after drying (mass after drying (g)), the solid content (heating residue) was calculated using the following equation.

Solid content (mass%) = mass after drying (g) / measured mass (g) × 100

(Glass transition temperature (Tg))

The glass transition temperature (Tg) of a compound (MM) or polymer is a value calculated by converting the absolute temperature (K) into degrees Celsius (°C) calculated from the formula below.

1/Tg=Σ(wi/Tg _i )

In the above formula, wi represents the mass fraction of monomer i constituting the compound (MM) or the polymer, and Tg _i represents the glass transition temperature of the homopolymer of the compound (MM) or monomer i constituting the polymer.

Tg and Tg _i in the above formula are values expressed in absolute temperature (K). In addition, Tg _i is a value described in “POLYMER HANDBOOK FOURTH EDITION”.

(solid acid value)

Approximately 2.5 mmol of the sample (solution polymerization product or polymer-containing composition of the compound (MM)) was precisely weighed in a beaker (A(g)), and a trace amount of phenolphthalein and 5 mL of a 0.476 wt% aqueous solution of paratoluenesulfonic acid, toluene/95 50 mL of % ethanol solution = 50/50 mixed solution was added. After stirring at 70°C for 60 minutes, neutralization titration was performed with 0.5 mol/L potassium hydroxide solution (ethanol solution) manufactured by Kishida Chemical with a factor (f) of 1.003 at 20°C, and the light red color of the indicator continued for 30 seconds. The end point was when it was done. (Titer = B (mL), titer of KOH solution = f). The solid acid value was calculated according to the formula below.

Solid acid value (mgKOH/g)={(B×0.5-0.125)×56.11×f}/(A×resin solid content)

(Weight average molecular weight (Mw), number average molecular weight (Mn))

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

(Solubility parameter (sp))

The solubility parameter (sp) of the compound (MM) or polymer was obtained by Fedors' estimation method using the following formula. Specifically, it was calculated using the following formula.

δ(sp)=(ΣEcoh/ΣV) ^1/2

In the formula, ΣEcoh represents the cohesive energy (cal/mol) and ΣV represents the molar molecular volume (cm3/mol).

(Viscosity of polymer-containing composition)

The sample was placed in a dried Gardner bubble viscosity tube (hereinafter simply referred to as a “viscosity tube”) up to the indicator line of the viscosity tube and stopped with a cork. The viscous tube from which the sample was collected is vertically immersed in a constant temperature water bath adjusted to the specified temperature (25.0 ± 0.1°C) for at least 2 hours to keep the sample at a constant temperature, and the viscosity tube serving as the reference tube and the viscous tube containing the sample are simultaneously The viscosity (Gardner viscosity) was determined by rotating the sample by 180° and comparing the rate of bubble rise of the sample with a reference tube.

The viscosity of the polymer-containing composition measured with a Gardner bubble viscometer at 25°C (hereinafter also referred to as “Gardner viscosity”) is Z or less, preferably W or less, and more preferably V or less.

If the viscosity (B-type viscosity or Gardner viscosity) of the polymer-containing composition is below the above upper limit, antifouling agents, etc. can be mixed or painted without further adding an organic solvent for dilution to the polymer-containing composition, and a paint with a low VOC content can be applied. A composition is obtained.

The polymer-containing composition preferably has a viscosity of at least 45% by mass of solid content below the above preferable upper limit.

The lower limit of the viscosity of the resin composition is not particularly limited. In terms of suppressing paint dripping during painting, it is preferable that the Gardner viscosity at 25°C is B or higher.

(political anti-fouling)

The antifouling paint composition was applied with a brush to a sandblasted steel plate to which an antirust paint had been previously applied to a dry film thickness of 200 to 300 μm, dried to form a film, and a test plate was obtained. After this test panel was left standing in Mikawa Bay for 6 months, the ratio of the area to which marine organisms adhered to the total area of the coating film (area of marine organisms attached) was examined, and the standing antifouling property was evaluated based on the following criteria.

◎: The adhesion area of seawater organisms is 10% or less.

○: The adhesion area of seawater organisms is more than 10% and 20% or less.

△: The adhesion area of marine organisms is more than 20% and 40% or less.

×: The adhesion area of seawater organisms exceeds 40%.

(Coat consumption)

The antifouling paint composition was applied to a 50 mm x 50 mm x 2 mm hard vinyl chloride plate using an applicator to a dry film thickness of 120 µm, dried to form a coating film, and a test plate was obtained. This test plate was installed on a rotating drum installed in seawater and rotated at a circumferential speed of 7.7 m/s (15 knots). The state was maintained for 3 months, the film thickness (μm) of the coating film after 3 months was measured, and the film thickness consumed per month was defined as the rate of consumption (μm/M).

(Crack resistance of the coating film of the antifouling paint composition)

The antifouling paint composition was applied to a 50 mm x 50 mm x 2 mm hard vinyl chloride plate using an applicator to a dry film thickness of 120 µm, dried to form a coating film, and a test plate was obtained. This test plate was installed on a rotating drum installed in seawater and rotated at a circumferential speed of 7.7 m/s (15 knots). This state was maintained for 3 months, the surface of the coating film was observed after 3 months, and crack resistance was evaluated based on the following standards.

◎: No cracks or peeling are observed at all.

○: Cracks are partially observed.

△: Cracks and peeling are observed in some areas.

×: Cracks and peeling are observed on the entire surface.

The materials used in each example below are as follows.

MMA: Methyl methacrylate.

EA: ethyl acrylate.

BA: n-butylacrylate.

X-22-174ASX: Polysiloxane block-containing polymerizable monomer manufactured by Shin-Etsu Chemical Co., Ltd.

MTMA: 2-methoxyethyl methacrylate.

MTA: 2-methoxyethyl acrylate.

Perbutyl O: t-butylperoxy-2-ethylhexanoate (“Perbutyl O (registered trademark)” manufactured by Nichiyu Co., Ltd.).

AMBN: 2,2'-azobis(2-methylbutyronitrile).

AIBN: 2,2'-azobisisobutyronitrile.

IBVE: Isobutyl vinyl ether.

EHVE: 2-ethylhexyl vinyl ether.

DHP: 3,4-dihydro-2H-pyran.

Additive (1): Chlorinated paraffin (“Toyopalax (registered trademark) 150” manufactured by Tosoh Corporation).

Additive (2): Polyethylene oxide wax (“Dispalon (registered trademark) 4200-20” manufactured by Kusumoto Kasei Co., Ltd.).

50% rosin: 50 w% xylene dilution of rosin (“Chinese Rosin (registered trademark)” manufactured by Arakawa Chemical Industry Co., Ltd.).

<Preparation of monomer M (IBEMA)>

90.1 parts (0.9 mol) of isobutyl vinyl ether, 0.14 parts of hydroquinone, and 0.28 parts of phenothiazine were stirred at room temperature and mixed until uniform. While blowing air (10 ml/min), 51.7 parts (0.6 mol) of methacrylic acid was added dropwise while maintaining the temperature of the reaction solution below 60°C. After dropwise addition, the temperature of the reaction solution was raised to 80°C and reaction was performed for 6 hours. 158.7 parts (1.8 mol) of t-butylmethyl ether was added to the reaction solution and mixed, and the organic phase was washed once with 200 parts of a 20% by mass aqueous potassium carbonate solution. 0.03 part of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl was added to the organic phase, and the low boiling point component was distilled out by an evaporator. The obtained residue was distilled under reduced pressure to obtain 97.5 parts (0.52 mol) of 1-isobutoxyethyl methacrylate (IBEMA) with a boiling point of 60°C/3 torr.

<Preparation of monomer M (EHEMA)>

171.9 parts (1.1 mol) of 2-ethylhexyl vinyl ether, 0.32 parts of hydroquinone, and 0.61 parts of phenothiazine were stirred at room temperature and mixed until uniform. While blowing air (10 ml/min), 86.1 parts (1.0 mol) of methacrylic acid was added dropwise while maintaining the temperature of the reaction solution below 60°C. After dropwise addition, the temperature of the reaction solution was raised to 80°C and reaction was performed for 5 hours. 264.5 parts (3.0 mol) of t-butylmethyl ether was added to the reaction solution and mixed, and the organic phase was washed once with 135 parts of a 20% by mass aqueous potassium carbonate solution. 0.07 part of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl was added to the organic phase, and the low boiling point component was distilled out by an evaporator. The obtained residue was distilled under reduced pressure to obtain 207.0 parts (0.85 mol) of 1-(2-ethylhexyloxy)ethyl methacrylate (EHEMA) with a boiling point of 99°C/3torr.

<Preparation of monomer M (THPMA)>

75.7 parts (0.9 mol) of 3,4-dihydro-2H-pyran, 0.13 parts of hydroquinone, and 0.26 parts of phenothiazine were stirred at room temperature and mixed until uniform. While blowing air (10 ml/min), 51.7 parts (0.6 mol) of methacrylic acid (MAA) was added dropwise while maintaining the temperature of the reaction solution below 60°C. After dropwise addition, the temperature of the reaction solution was raised to 80°C and reaction was performed for 12 hours. 158.7 parts (1.8 mol) of t-butylmethyl ether was added to the reaction solution and mixed, and the organic phase was washed once with 200 parts of a 20% by mass aqueous potassium carbonate solution. 0.03 part of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl was added to the organic phase, and the low boiling point component was distilled out by an evaporator. The obtained residue was distilled under reduced pressure to obtain 75.7 parts (0.44 mol) of 2-tetrahydropyranyl methacrylate (THPMA) with a boiling point of 76°C/3 torr.

<Manufacture of chain transfer agent>

In a synthesis device equipped with a stirring device, under a nitrogen atmosphere, 1.00 g of cobalt (II) acetate tetrahydrate, 1.93 g of diphenylglyoxime, and 80 mL of diethyl ether previously deoxygenated by nitrogen bubbling were placed, and the mixture was stirred at room temperature. It was stirred for 30 minutes. Subsequently, 10 mL of boron trifluoride diethyl ether complex was added, and the mixture was stirred for further 6 hours. The mixture was filtered, the solid was washed with diethyl ether, and dried under vacuum for 15 hours to obtain 2.12 g of chain transfer agent 1 (bis[(difluoroboryl)diphenylglyoximato]cobalt(II); CoPhBF) as a reddish-brown solid.

<Preparation of compound (MM)>

(Production Example 1)

In a polymerization apparatus equipped with a stirrer, cooling pipe, and thermometer, 50 parts of xylene, 16 parts of MMA, 4 parts of IBEMA, and 0.007 part of chain transfer agent 1 were added, stirred, and heated to 90°C under a nitrogen atmosphere. Next, a mixture containing 16 parts of IBEMA, 64 parts of MMA, and 3.2 parts of AMBN was added dropwise to this solution at a constant rate over 3 hours. Additionally, the mixture was heated and stirred at 90°C for 1 hour. 30 minutes after the end of the dropping, 16.6 parts of xylene and 0.2 part of AMBN were added dropwise at a constant rate over 30 minutes, and maintained at 90°C for 90 minutes. Afterwards, the reaction solution was cooled to 40°C to obtain a solution of compound (MM1).

(Production Examples 2 to 6)

Solutions of compounds (MM1 to MM6) were obtained in the same manner as in Preparation Example 1, except that the input amounts (parts) of the monomer, initiator, and chain transfer agent were as shown in Table 1.

Table 1 shows the solid content of the obtained compound (MM) solution, Tg, solid acid value, Mw, Mn, and sp of each compound (MM1 to MM6).

<Preparation of polymer-containing composition>

(Production Example 7)

17.0 parts of xylene was added to a reaction vessel equipped with a stirrer, temperature regulator, and dropping funnel, and the temperature was raised to 90°C while stirring in a nitrogen atmosphere. Subsequently, from the dropping funnel, a mixture containing 50 parts of the solution of MM1 obtained in Production Example 1 in terms of solid content, 15 parts of MTA, 21 parts of EA, 14 parts of BA, and 7.5 parts of AMBN was poured at a constant speed over 3 hours. Dropped. 30 minutes after the end of dropping, 7.8 parts of xylene, 2.1 parts of butyl acetate, and 7.5 parts of AMBN were added dropwise at a constant rate over 30 minutes, and maintained at 90°C for 90 minutes. After that, 6.7 parts of isobutyl vinyl ether was added and the reaction liquid was cooled to 40°C to obtain solution-like polymer-containing composition A-1.

(Production Examples 8 to 13)

Solution polymer-containing compositions A-2 to A-13 were prepared in the same manner as in Preparation Example 7, except that the input amounts (parts) of AIBN as the monomer and initiator were as shown in Tables 2 and 3.

In Tables 2 and 3, the compounding amount of compound (MM) is the amount in terms of solid content.

Tables 2 and 3 show the solid content of the obtained polymer-containing compositions (A-1 to A-13), Tg, solid acid value, Mw, Mn, and sp of the polymer contained in each polymer-containing composition.

<Preparation and evaluation of antifouling paint composition>

According to the composition shown in Tables 4 and 5, each material was put into a metal can, then 70 g of glass beads were added, mixed with a stirring bar, and further dispersed with a rocking shaker to obtain an antifouling paint composition.

In Tables 4 and 5, the values written in the composition column indicate the blending amount (parts). The compounding amount of the polymer-containing composition is the amount of the entire polymer-containing composition.

Tables 4 and 5 show the theoretical solid content and evaluation results (stationary antifouling property, coating film consumption, and crack resistance) of the obtained antifouling paint composition. The theoretical solid content is a value calculated from the solid content of each material blended in the antifouling paint composition.

The coating films of the antifouling paint compositions of Examples 1 to 12 using the compound (MM) (macromonomer) containing monomer M units had excellent stationary antifouling properties. Additionally, it had an appropriate level of consumption. In particular, the coating film of the antifouling paint composition of Examples 1 to 3 using a polymer as a structural unit based on a monomer other than the compound (MM) that does not contain the monomer M unit or, even if it does contain it, is 6.5% by mass or less with respect to the total structural units. Also, crack resistance was excellent.

On the other hand, the coating film of the antifouling paint composition of Comparative Example 1 using a macromonomer not containing monomer M units had poor stationary antifouling property. Additionally, consumption was low.

According to one aspect of the present invention, a compound and a polymer from which an antifouling paint composition capable of forming a coating film with excellent antifouling properties can be obtained, and an antifouling paint composition capable of forming a coating film with excellent antifouling properties can be provided. In addition, according to one aspect of the present invention, it is possible to provide a compound and a polymer from which an antifouling paint composition capable of forming a coating film with excellent solubility is obtained, and an antifouling paint composition capable of forming a coating film with excellent solubility.

Claims (15)

A polymer containing structural units derived from a compound,
The compound has a weight average molecular weight of 10,000 or less, contains two or more structural units containing a hydrolyzable substituent, and has a radical polymerizable group at the terminal,
After performing hydrolysis treatment by heating and stirring the compound in an aqueous solution of p-toluenesulfonic acid, neutralization titration was performed with 0.5 mol/L potassium hydroxide solution (ethanol solution), and the 0.5 solution used was used until the light red color of the indicator continued for 30 seconds. A polymer having a solid acid value calculated from the amount of mol/L potassium hydroxide solution of 10 mgKOH/g or more. The polymer according to claim 1, wherein the proportion of structural units derived from the compound is 5% by mass or more relative to the total mass of the polymer. A polymer obtained by copolymerizing a compound containing a polymerizable monomer unit containing a substituent represented by formula (1), formula (2), or formula (3).

^{( Wherein , _} , R ³ and R ⁵ each represent an alkyl group, cycloalkyl group or aryl group having 1 to 20 carbon atoms, R ⁴ represents an alkylene group having 1 to 10 carbon atoms, and R ⁶ represents an alkylene group having 2 to 10 carbon atoms.) The polymer according to claim 3, wherein the proportion of structural units derived from the compound is 10% by mass or more and 90% by mass or less with respect to the total mass of the polymer. A compound represented by the following formula (MM-1).

(In ^formula (MM-1 ^{) ,} X ¹ to , an aryl group, a heterocyclic group, or a substituent including formula (7), (8) or (9), and two or more of Y ¹ to Y ⁿ represent formula (7), (8) or (9). It is a substituent that contains, n represents a natural number of 3 or more, and Z represents a terminal group.)

( ^In formula ( ⁷ ), (8 ⁾ or ( ⁹ ), represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ³ and R ⁵ each independently represent an alkyl group, cycloalkyl group or aryl group having 1 to 20 carbon atoms, and R ⁴ represents an alkylene group having 1 to 10 carbon atoms. , R ⁶ represents an alkylene group having 2 to 10 carbon atoms.) The compound according to claim 5, wherein the terminal group is a hydrogen atom or a group derived from a radical polymerization initiator. The compound according to claim 5 or 6, wherein the compound has a weight average molecular weight of 2,000 or more and 1,000,000 or less. The compound according to any one of claims 5 to 7, wherein the ratio of monomer units containing formula (7), (8) or (9) to the mass of the entire compound is 9% by mass or more and 80% by mass or less. . A polymer comprising a structural unit based on the compound according to any one of claims 5 to 7. The polymer according to claim 9, wherein the proportion of structural units based on the compound is 90% by mass or less relative to the total mass of the polymer. The method according to any one of claims 1 to 4, 9, and 10, wherein the polymer is subjected to hydrolysis treatment by heating and stirring in an aqueous solution of p-toluenesulfonic acid, and then added to the polymer in 0.5 mol/L potassium hydroxide solution (ethanol). A polymer having a solid acid value of 150 mgKOH/g or less, calculated from the amount of 0.5 mol/L potassium hydroxide solution used until the light red color of the indicator continues for 30 seconds. The polymer according to any one of claims 1 to 4 and 9 to 11, which is a (meth)acrylic polymer. An antifouling paint composition comprising the compound according to any one of claims 5 to 8. An antifouling paint composition comprising the polymer according to any one of claims 1 to 4 and 9 to 11. A compound having a weight average molecular weight of 10,000 or less, containing two or more structural units containing a hydrolyzable substituent, and having a radical polymerizable group at the terminal,
Polymerizing monomers having an ethylenically unsaturated group (however, the above compounds are excluded),
Method for producing (meth)acrylic copolymer.