KR102638011B1 - (meth)acrylic copolymer, resin composition, antifouling paint composition, and method for producing (meth)acrylic copolymer - Google Patents

Abstract

(식 중, X는 -O-, -S- 또는 -NR¹⁴-를 나타내고, R¹⁴는 수소 원자 또는 알킬기를 나타내고, R¹ 및 R²는 각각 수소 원자 또는 탄소수 1 내지 10의 알킬기를 나타내고, R³ 및 R⁵는 각각 탄소수 1 내지 20의 알킬기, 시클로알킬기 또는 아릴기를 나타내고, R⁴ 및 R⁶은 각각 탄소수 1 내지 10의 알킬렌기를 나타낸다.)The (meth)acrylic copolymer of the first aspect of the present invention has at least one type of structure (I) represented by the following formula (1), the following formula (2), or the following formula (3), and a polysiloxane group.

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

Description

(meth)acrylic copolymer, resin composition, antifouling paint composition, and method for producing (meth)acrylic copolymer

The present invention relates to (meth)acrylic copolymers, resin compositions, antifouling paint compositions, and methods for producing (meth)acrylic copolymers.

This application claims priority based on Japanese Patent Application No. 2015-202407, filed in Japan on October 13, 2015, the contents of which are incorporated herein by reference.

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. The coating film obtained from a self-polishing type antifouling paint exhibits an antifouling effect over a long period of time by gradually dissolving the coating film surface in seawater and renewing the surface (self-polishing), and by constantly exposing the antifouling component to the coating film surface.

As a self-polishing type antifouling paint, for example, a vinyl polymer having a hemiacetal ester group and/or a hemiketal ester group in the side chain and an antifouling agent are combined (Patent Document 1), and (meth) having a silicon-containing group and a divalent metal atom. ) One using an acrylic copolymer (Patent Documents 2 to 3) has been proposed. The polymer used in these antifouling paints has hydrolyzability, and the coating film containing it exhibits self-polishing properties.

Japanese Patent Publication No. 4-103671 International Publication No. 2004/081121 International Publication No. 2011/046086

The antifouling paint film using the vinyl polymer described in Patent Document 1 does not have sufficient antifouling properties.

Antifouling paint films using the (meth)acrylic copolymers described in Patent Documents 2 to 3 also do not have sufficient antifouling properties. There is also the problem of low water resistance.

The object of the present invention is to provide an antifouling paint composition capable of forming a coating film with excellent antifouling properties and water resistance, a (meth)acrylic copolymer and a resin composition suitable for obtaining the antifouling paint composition, and a method for producing the (meth)acrylic copolymer. It is about providing.

The present invention has the following aspects.

[1] A (meth)acrylic copolymer having at least one type of structure (I) represented by the following formula (1), the following formula (2), or the following formula (3) and a polysiloxane group.

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

[2] The (meth)acrylic copolymer according to [1], which has a structural unit derived from the following monomer (m1) and a structural unit derived from the following monomer (m2).

Monomer (m1): A monomer having an ethylenically unsaturated bond with at least one type of the above structure (I).

Monomer (m2): A monomer having an ethylenically unsaturated bond with the polysiloxane group.

[3] A resin composition containing the (meth)acrylic copolymer according to [1] or [2].

[4] The resin composition according to [3], wherein the decomposition rate of the structure (I) in the (meth)acrylic copolymer after storage at 40°C for 30 days is 20% or less.

[5] The resin composition according to [3] or [4], further comprising at least one member selected from the group consisting of a compound that reacts with an acid, a basic compound, an acidic compound, and a dehydrating agent.

[6] The compound that reacts with the acid is at least one compound selected from the group consisting of a compound represented by the following formula (31), a compound represented by the following formula (32), and a compound represented by the following formula (33) B), the resin composition described in [5].

^{( Wherein , _} represents an atom or an alkyl group with 1 to 10 carbon atoms, R ⁹ and R ¹¹ each represent an alkyl group, cycloalkyl group or aryl group with 1 to 20 carbon atoms, R ¹⁰ represents a single bond or an alkylene group with 1 to 9 carbon atoms, R ¹² represents an alkylene group having 1 to 9 carbon atoms.)

[7] The resin composition according to any one of [3] to [6], further comprising silicone oil.

[8] An antifouling paint composition comprising the resin composition according to any one of [3] to [7].

[9] The antifouling paint composition according to [8], further comprising an antifouling agent.

[10] The antifouling agents include cuprous oxide, pyridinetriphenylborane, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4-bromo-2-(4-chlorophenyl)- The antifouling paint composition according to [9], comprising at least one member selected from the group consisting of 5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile and medetomidine.

[11] The antifouling paint composition according to any one of [8] to [10], further comprising a thermoplastic resin other than the (meth)acrylic copolymer.

[12] A method for producing a (meth)acrylic copolymer, wherein a (meth)acrylic copolymer is obtained by polymerizing a monomer mixture containing the following monomer (m1) and the following monomer (m2).

Monomer (m1): A monomer having at least one type of structure (I) represented by the following formula (1), the following formula (2), or the following formula (3) and an ethylenically unsaturated bond.

Monomer (m2): A monomer having a polysiloxane group and an ethylenically unsaturated bond.

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

According to the present invention, an antifouling paint composition capable of forming a coating film with excellent antifouling properties and water resistance, a (meth)acrylic copolymer and a resin composition suitable for obtaining the antifouling paint composition, and a method for producing the (meth)acrylic copolymer. can be provided.

The definitions of terms below apply throughout this specification and claims.

“(Meth)acrylic-based copolymer” means a copolymer in which at least part of the structural units are structural units derived from a (meth)acrylic-based monomer. The (meth)acrylic copolymer may further have structural units derived from monomers other than the (meth)acrylic monomer (for example, vinyl monomers such as styrene).

“Structural unit” means a structural unit derived from a monomer formed by polymerizing a 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 having polymerizability (polymerizable monomer).

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

“(Meth)acryloyl group” is a general term for acryloyl group and methacryloyl group. “(Meth)acrylate” is a general term for acrylate and methacrylate. “(Meth)acrylic acid” is a general term for acrylic acid and methacrylic acid. “(Meth)acrylonitrile” is a general term for acrylonitrile and methacrylonitrile. “(Meth)acrylamide” is a general term for acrylamide and methacrylamide.

“Volatile organic compound (VOC)” means an organic compound (volatile organic compound) that easily volatilizes at room temperature and pressure. In addition, normal temperature and normal pressure refers to 10°C to 30°C and 1000Pa to 1050Pa.

[(meth)acrylic copolymer]

The first aspect of the present invention is a (meth)acrylic copolymer (hereinafter referred to as It is also called “copolymer (A)”).

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

The structure (I) and the polysiloxane group that the polymer (A) has may be one type or two or more types, respectively.

Structure (I) and the polysiloxane group may each be contained in the structural unit of the copolymer (A), may be contained in the terminal of the main chain, or may be contained in both sides. From the viewpoint of antifouling properties, it is preferable that it is included in at least a structural unit.

When structure (I) and the polysiloxane group are each contained in a structural unit, it is preferable that structure (I) and the polysiloxane group are contained in different structural units.

The copolymer (A) includes a structural unit (hereinafter also referred to as “structural unit (u1)”) derived from monomer (m1) having structure (I) and an ethylenically unsaturated bond (polymerizable carbon-carbon double bond), A copolymer having a structural unit (hereinafter also referred to as “structural unit (u2)”) derived from a monomer (m2) having a polysiloxane group and an ethylenically unsaturated bond is preferable.

The number of structural units (u1) and structural units (u2) in the copolymer (A) may be one or two or more.

The copolymer (A), in addition to the structural unit (u1) and the structural unit (u2), has structural units other than the structural unit (u1) and the structural unit (u2) (hereinafter also referred to as “structural unit (u3)”) You may have more.

At least part of the structural units of the copolymer (A) are structural units derived from (meth)acrylic monomers. The ratio of structural units derived from (meth)acrylic monomers to the total (100% by mass) of all structural units in the copolymer (A) is preferably 20 to 100% by mass, and more preferably 40 to 100% by mass.

When the copolymer (A) has a structural unit (u1) and a structural unit (u2), either the structural unit (u1) or the structural unit (u2) may include a structural unit derived from a (meth)acrylic monomer, Both may contain structural units derived from (meth)acrylic monomers.

When the copolymer (A) has a structural unit (u1), a structural unit (u2), and a structural unit (u3), any one of the structural unit (u1), the structural unit (u2), and the structural unit (u3) is (meth ) It may contain a structural unit derived from an acrylic monomer, and two or three types may contain structural units derived from a (meth)acrylic monomer.

(Structure (I))

Structure (I) is represented by the above formula (1), the above formula (2), or the above formula (3). In each formula, among the singlet lines extending from the carbon atom of the carbonyl group, the line that is not bonded to the oxygen atom represents a bond hand.

In formulas (1) to ( ³ ),

In formula (1), the alkyl group having 1 to 10 carbon atoms for R ¹ and R ² includes, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, 2 -Ethylhexyl group, etc. can be mentioned.

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. Combinations, combinations of hydrogen atoms with hydrogen atoms, combinations of long-chain alkyl groups with long-chain alkyl groups, 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 the alkyl group, decyl group, dodecyl group, and tetradecyl group listed above as the alkyl group having 1 to 10 carbon atoms. The alkyl group for R ³ preferably has 1 to 10 carbon atoms.

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 a cycloalkyl group having 1 to 10 carbon atoms is preferable.

The alkyl group, cycloalkyl group or aryl group may be substituted by a substituent selected from the group consisting of cycloalkyl group, aryl group, alkoxy group, alkanoyloxy group, aralkyl group and acetoxy group. When substituted by a substituent, the number of substituents may be 1 or 2 or more.

As substituents, cycloalkyl groups and aryl groups are the same as those described above. 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.

In formula (2), 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 number of carbon atoms of the alkylene group in R ⁴ is preferably 2 to 7, and more preferably 3 to 4.

The alkylene group may be substituted by a substituent selected from the group consisting of cycloalkyl group, aryl group, alkoxyl group, alkanoyloxy group, aralkyl group, and acetoxy group. When substituted by a substituent, the number of substituents may be 1 or 2 or more. Specific examples of the substituent that may be substituted on the alkylene group include the same substituents listed as R ³ .

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

R ⁶ is the same as R ⁴ in formula (2), and the preferred embodiments are also the same.

(polysiloxane group)

A polysiloxane group is a group having Si-O-Si bonds. Examples of the polysiloxane group include a divalent polysiloxane group represented by the following formula (i) or (ii), a monovalent polysiloxane group represented by the following formula (iii) or (iv), and an organopolysiloxane that constitutes the skeleton. and trivalent or higher polysiloxane groups excluding three or more organic groups bonded to silicon atoms.

In formula (i), n is 3 to 80, and R ^1b to R ^1e each represent an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group.

In formula (ii), r and s each represent 0 to 20, and R ^2b to R ^2k each represent an alkyl group.

In formula (iii), x represents 3 to 80, and R ^3b to R ^3f each represent an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group.

In formula (iv), R ^4b to R ^4d each represent an alkyl group, -(OSiR ⁵¹ R ⁵² ) _y -OSiR ⁵³ R ⁵⁴ R ⁵⁵ (where y is an integer of 0 to 20, and R ⁵¹ to R ⁵⁵ represent an alkyl group) ), or R ⁵⁶ -(OC ₂ H ₄ )y _' -OR ⁵⁷ (where y' is an integer of 1 to 20, and R ⁵⁶ and R ⁵⁷ each represent an alkyl group).

In the above formula (i), n is the average degree of polymerization of the polysiloxane structure. If n is more than the lower limit of the above range, the antifouling effect tends to be expressed in the coating film even when the antifouling paint composition containing the copolymer (A) does not contain an antifouling agent, and if n is less than the upper limit of the above range, this The monomer having a polysiloxane group is compatible with monomer (m1) and the like, and the resulting copolymer (A) has good solvent solubility. n is preferably 5 to 50, and more preferably 8 to 40.

The alkyl group and the alkoxy group in R ^1b to R ^1e each preferably have 1 to 18 carbon atoms. Substituents in the substituted phenyl group and substituted phenoxy group include an alkyl group and an alkoxy group.

R ^1b to R ^1e are each preferably an alkyl group having 1 to 18 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

In the above formula (ii), r and s are each the average degree of polymerization of the polysiloxane structure. When r and s are each below the above upper limit, the monomer having the polysiloxane group is compatible with the monomer (m1) and the like, and the resulting copolymer (A) has good solvent solubility. r and s are each preferably 10 or less, and more preferably 5 or less.

The alkyl group for R ^2b to R ^2k is preferably an alkyl group having 1 to 18 carbon atoms, and examples include methyl group, ethyl group, n-propyl group, and n-butyl group. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

In the above formula (iii), x is the average degree of polymerization of the polysiloxane structure. If x is more than the lower limit of the above range, the antifouling effect tends to be expressed in the coating film even when the antifouling paint composition containing the copolymer (A) does not contain an antifouling agent, and if x is less than the upper limit of the above range, The monomer having a polysiloxane group is compatible with monomer (m1) and the like, and the resulting copolymer (A) has good solvent solubility. x is preferably 5 to 50, and more preferably 8 to 40.

The alkyl group and the alkoxy group in R ^3b to R ^3f each preferably have 1 to 18 carbon atoms. Substituents in the substituted phenyl group and substituted phenoxy group include an alkyl group and an alkoxy group.

R ^3b to R ^3f are each preferably an alkyl group having 1 to 18 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

In the formula (iv), the alkyl group for R ^4b to R ^4d is preferably an alkyl group having 1 to 18 carbon atoms, and examples include methyl group, ethyl group, n-propyl group, and n-butyl group. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

y is the average degree of polymerization of the polysiloxane structure, and y' is the average degree of polymerization of the polyether structure. If y and y' are below the above upper limit, the monomer having the polysiloxane group is compatible with the monomer (m1) and the like, and the resulting copolymer (A) has good solvent solubility. Each of y and y' is preferably 10 or less, and more preferably 5 or less.

Examples of the alkyl group for R ⁵¹ to R ⁵⁷ include the same alkyl groups as R ^4b to R ^4d , and the preferred embodiments are the same.

(Configuration unit (u1))

The structural unit (u1) has a structure in which the ethylenically unsaturated bond of the monomer (m1) is cleaved to form a single bond.

The monomer (m1) is preferably a monofunctional monomer having one ethylenically unsaturated bond because the viscosity of the copolymer (A) is lowered when the copolymer (A) is dissolved in a solvent.

Examples of the monomer (m1) include compounds represented by the following formula (11), compounds represented by the following formula (12), and compounds represented by the following formula (13).

(In the formula, Z is CH ₂ =CH-COO-, CH ₂ =C(CH ₃ )-COO-, CHR ^X =CH-COO-, CH ₂ =C(CH ₂ ^R _{2 =} ^{CR _ _ _} Represents an alkyl group, and R ¹ to R ⁶ have the same meaning as above.)

For Z, 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 structure (I) in ^{R R} For example ^, in the case of a compound ^represented by formula ( ¹¹ ), ^R

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

CH _{2 =} C _{( CH} ^{2 R R}

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

Examples of the monomer (m1) include those shown below.

(Configuration Unit (u2))

The structural unit (u2) has a structure in which the ethylenically unsaturated bond of the monomer (m2) is cleaved to form a single bond.

The number of polysiloxane groups and ethylenically unsaturated bonds that the monomer (m2) has in the molecule is not particularly limited, and may be one or two or more.

As the monomer (m2), from the viewpoint of antifouling properties, a monomer having a divalent polysiloxane group and an ethylenically unsaturated bond-containing group bonded to both ends thereof (hereinafter also referred to as "double-terminal polysiloxane macromonomer"), and a monovalent polysiloxane group at one end thereof. A monomer (hereinafter also referred to as “single-terminated polysiloxane macromonomer”) having a bonded ethylenically unsaturated bond-containing group is preferable. These may be used either individually or in combination.

Examples of both terminal polysiloxane macromonomers include monomers represented by the following formula (m2-1) or (m2-2).

Examples of the one-terminal polysiloxane macromonomer include monomers represented by the following formula (m2-3) or (m2-4).

Therefore, the monomer (m2) includes a monomer represented by the following formula (m2-1), a monomer represented by the formula (m2-2), a monomer represented by the formula (m2-3), and a monomer represented by the formula (m2-4) At least one type selected from the group consisting of monomers is preferred.

In the formula (m2-1), R ^1a and R ^1f are each a hydrogen atom or a methyl group, k and p are each an integer of 2 to 5, l and q are each an integer of 0 to 50, and m and o are each an integer of 2 to 5. , n is 3 to 80, and R ^1b to R ^1e each represent an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group.

In the formula (m2-2), R ^2a and R ^2l are each a hydrogen atom or a methyl group, k' and p' are each an integer of 2 to 5, l' and q' are each an integer of 0 to 50, and m' and o' are each an integer. Each is an integer of 2 to 5, r and s are each 0 to 20, and R ^2b to R ^2k each represent an alkyl group.

In formula (m2-3), R ^3a is a hydrogen atom or a methyl group, u is an integer of 2 to 5, v is 0 to 50, w is an integer of 2 to 5, x is 3 to 80, and R ^3b to R ^3f are Each represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group.

In formula (m2-4), R ^4a is a hydrogen atom or a methyl group, u' is an integer of 2 to 5, v' is an integer of 0 to 50, w' is an integer of 2 to 5, R ^4b to R ^4d are each an alkyl group, -(OSiR ⁵¹ R ⁵² ) _y -OSiR ⁵³ R ⁵⁴ R ⁵⁵ (where y is an integer from 0 to 20 and R ⁵¹ to R ⁵⁵ represent an alkyl group), or R ⁵⁶ -(OC ₂ H ₄ ) _y' - OR ⁵⁷ (where y' is an integer from 1 to 20, and R ⁵⁶ and R ⁵⁷ each represent an alkyl group).

In formula (m2-1), l and q are the average degree of polymerization of the polyether structure. When l and q are 50 or less, the water resistance of the coating film tends to be good. In particular, a value of 30 or less is preferable because it has excellent recoating properties with the old coating film. l and q may be 0, but are preferably larger than 0 because recoating properties with the old coating film tend to improve. l and q are preferably 3 to 25, and more preferably 5 to 20.

k and p are integers from 2 to 5, and 2 or 3 is preferable in terms of cost. It is also possible to use k and p of 2 and 3 in combination.

m and o are integers from 2 to 5, and 2 or 3 is preferred.

n and R ^1b to R ^1e are the same as n and R ^1b to R ^1e in the formula (i), respectively, and the preferred embodiments are the same.

In addition, R ^1a to R ^1f , k, l, m, n, o, p and q are each independent, and if the same symbol exists within or between molecules, they may be different.

Specific examples of the monomer represented by the formula (m2-1) include those in which l and q are 0, such as FM-7711, FM-7721, and FM-7725 (above, brand names) manufactured by Chisso Corporation and Toray/Dow Corning Corporation. Examples include F2-311-02 (brand name). Examples of those in which l and q are greater than 0 include F2-354-04 (brand name) manufactured by Toray and Dow Corning.

The monomer represented by the formula (m2-1) may be used individually or in combination of multiple types.

In formula (m2-2), l' and q' are the average degree of polymerization of the polyether structure. When l' and q' are 50 or less, the water resistance of the coating film tends to be good. In particular, a value of 30 or less is preferable because it has excellent recoating properties with the old coating film. l' and q' may be 0, but are preferably larger than 0 because recoating properties with the old coating film tend to improve. l' and q' are preferably 3 to 25, and more preferably 5 to 20.

k' and p' are integers from 2 to 5, and 2 or 3 is preferred in terms of cost. It is also possible to use k' and p' of 2 and 3 in combination.

m' and o' are integers from 2 to 5, and 2 or 3 is preferred.

r, s and R ^2b to R ^2k are the same as r, s and R ^2b to R ^2k in formula (ii), respectively, and their preferred embodiments are the same.

In addition, R ^2a to R ^2l , k', l', m', n', o', p', q', r and s are each independent, and when the same symbol exists in or between molecules , they may be different.

Specific examples of the monomer represented by the formula (m2-2) include those in which l' and q' are 0, such as F2-312-01 (trade name) manufactured by Toray Dow Corning Co., Ltd. Examples of those in which l' and q' are greater than 0 include F2-312-04 (brand name) manufactured by Toray and Dow Corning.

The monomer represented by the formula (m2-2) may be used individually or in combination of multiple types.

In formula (m2-3), v is the average degree of polymerization of the polyether structure. When v is 50 or less, the water resistance of the coating film tends to be good. In particular, a value of 30 or less is preferable because it has excellent recoating properties with the old coating film. v may be 0, but is preferably larger than 0 because recoating properties with the old coating film tend to improve. v is preferably 3 to 25, and more preferably 5 to 20.

u is an integer of 2 to 5, and 2 or 3 is preferable in terms of cost. It is also possible to use u of 2 and u of 3 together.

w is an integer of 2 to 5, preferably 2 or 3.

x and R ^3b to R ^3f are the same as x and R ^3b to R ^3f in formula (iii), respectively, and the preferred embodiments are the same.

In addition, R ^3a to R ^3f , u, v, w and x are each independent, and if the same symbol exists within or between molecules, they may be different.

Specific examples of the monomer represented by the formula (m2-3) include those in which v is 0, such as FM-0711, FM-0721, and FM-0725 (above, brand names) manufactured by Chisso Corporation, and those manufactured by Shin-Etsu Chemical. Examples include X-24-8201, X-22-174DX, and X-22-2426 (above, brand names). Examples of those with v greater than 0 include F2-254-04 and F2-254-14 (brand name) manufactured by Toray and Dow Corning.

The monomer represented by the formula (m2-3) may be used individually or in combination of multiple types.

In formula (m2-4), v' is the average degree of polymerization of the polyether structure. When v' is 50 or less, the water resistance of the coating film tends to be good. In particular, a value of 30 or less is preferable because it has excellent recoating properties with the old coating film. v' may be 0, but is preferably larger than 0 because recoating properties with the old coating film tend to improve. v' is preferably 3 to 25, and more preferably 5 to 20.

u' is an integer of 2 to 5, and 2 or 3 is preferable in terms of cost. It is also possible to use both u' of 2 and u' of 3.

w' is an integer of 2 to 5, and 2 or 3 is preferable.

R ^4b to R ^4d are each the same as R ^4b to R ^4d in formula (iv) above, and their preferred embodiments are the same.

In addition, R ^4a to R ^4d , u', v', w', y and y' are each independent, and if the same symbol exists within or between molecules, they may be different.

Specific examples of the monomer represented by the formula (m2-4) include those in which v' is 0, such as TM-0701 (trade name) manufactured by Chisso Corporation, X-22-2404 (brand name) manufactured by Shin-Etsu Chemical Corporation, Examples include F2-250-01 and F2-302-01 (above, brand names) manufactured by Toray and Dow Corning. Examples of those with v' greater than 0 include F2-302-04 (brand name) manufactured by Toray and Dow Corning.

The monomer represented by the formula (m2-4) may be used individually or in combination of multiple types.

It is preferable that the structural unit (u2) contains only structural units derived from a single-terminated polysiloxane macromonomer from the viewpoint of crack resistance and adhesion to the substrate.

From the viewpoint of recoating properties, the structural unit (u2) preferably contains a structural unit derived from a double-terminal polysiloxane macromonomer and a structural unit derived from a single-terminal polysiloxane macromonomer.

When the structural unit (u2) includes a structural unit derived from a double-terminal polysiloxane macromonomer and a structural unit derived from a single-terminal polysiloxane macromonomer, their ratio is: structural unit derived from both terminal polysiloxane macromonomer/structural unit derived from single-terminal polysiloxane macromonomer. Constituent unit = 1/99 to 80/20 (molar ratio) is preferable, and 3/97 to 60/40 is more preferable. If the ratio of structural units derived from polysiloxane macromonomers at both ends is 80/20 or less, a coating film with excellent crack resistance and adhesion to the substrate tends to be obtained. If the ratio of structural units derived from polysiloxane macromonomers at both ends is 1/99 or more, the formed coating film tends to have better long-term antifouling properties and recoating properties.

(Configuration Unit (u3))

The structural unit (u3) is a structural unit other than the structural unit (u1) and the structural unit (u2). That is, it is a structural unit that does not contain structure (I) and a polysiloxane group.

Examples of the structural unit (u3) include a structural unit derived from a monomer (m3) that has an ethylenically unsaturated bond and does not contain structure (I) and a polysiloxane group. This structural unit has a structure in which the ethylenically unsaturated bond of the monomer (m3) is cleaved to form a single bond.

Examples of the monomer (m3) include the following.

Substituted or unsubstituted alkyl (meth)acrylate [e.g., methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n- Butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate , behenyl (meth)acrylate, 1-methyl-2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 3-methyl-3-methoxybutyl (meth)acrylate] , substituted or unsubstituted aralkyl (meth)acrylate [e.g., benzyl (meth)acrylate, m-methoxyphenylethyl (meth)acrylate, p-methoxyphenylethyl (meth)acrylate], Substituted or unsubstituted aryl (meth)acrylate [e.g., phenyl (meth)acrylate, m-methoxyphenyl (meth)acrylate, p-methoxyphenyl (meth)acrylate, o-methoxyphenyl ethyl (meth)acrylate], alicyclic (meth)acrylate [e.g., isobornyl (meth)acrylate, cyclohexyl (meth)acrylate], trifluoroethyl (meth)acrylate, perfluoroethyl Hydrophobic group-containing (meth)acrylic acid ester monomers such as looctyl (meth)acrylate and perfluorocyclohexyl (meth)acrylate;

2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, butoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth) ) (meth)acrylic acid ester monomers containing oxyethylene groups such as acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, and 2-(2-ethylhexaoxy)ethyl (meth)acrylate. ;

hydroxyl group-containing (meth)acrylic acid ester monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerol (meth)acrylate;

Methoxypolyethylene glycol allyl ether, methoxypolypropylene glycol allyl ether, butoxypolyethylene glycol allyl ether, butoxypolypropylene glycol allyl ether, methoxypolyethylene glycol-polypropylene glycol allyl ether, butoxypolyethylene glycol-polypropylene glycol allyl terminal alkoxyallylated polyether monomers such as ether;

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

vinyl monomers containing primary or secondary amino groups such as butylaminoethyl (meth)acrylate and (meth)acrylamide;

Dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, dimethylaminoethyl Vinyl monomers containing tertiary amino groups such as (meth)acrylamide and dimethylaminopropyl (meth)acrylamide;

Heterocyclic basic monomers such as vinylpyrrolidone, vinylpyridine, and vinylcarbazole;

Trimethylsilyl (meth)acrylate, triethylsilyl (meth)acrylate, tri-n-propylsilyl (meth)acrylate, tri-n-butylsilyl (meth)acrylate, tri-n-amylsilyl (meth) Acrylate, tri-n-hexylsilyl (meth)acrylate, tri-n-octylsilyl (meth)acrylate, tri-n-dodecylsilyl (meth)acrylate, triphenylsilyl (meth)acrylate, tri -p-methylphenylsilyl(meth)acrylate, tribenzylsilyl(meth)acrylate, triisopropylsilyl(meth)acrylate, triisobutylsilyl(meth)acrylate, tri-s-butylsilyl(meth)acrylate Rate, tri-2-methylisopropylsilyl (meth)acrylate, tri-t-butylsilyl (meth)acrylate, ethyldimethylsilyl (meth)acrylate, n-butyldimethylsilyl (meth)acrylate, diiso Propyl-n-butylsilyl (meth)acrylate, n-octyldi-n-butylsilyl (meth)acrylate, diisopropylstearylsilyl (meth)acrylate, dicyclohexylphenylsilyl (meth)acrylate, t-Butyldiphenylsilyl(meth)acrylate, lauryldiphenylsilyl(meth)acrylate, triisopropylsilylmethyl maleate, triisopropylsilylamyl maleate, tri-n-butylsilyl-n-butylmaleate ate, t-butyldiphenylsilylmethyl maleate, t-butyldiphenylsilyl-n-butylmaleate, triisopropylsilylmethyl fumarate, triisopropylsilylamyl fumarate, tri-n-butylsilyl-n- Organosilyl group-containing vinyl monomers such as butyl fumarate, t-butyldiphenylsilylmethyl fumarate, and t-butyldiphenylsilyl-n-butyl fumarate;

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

Methacrylic acid, acrylic acid, crotonic acid, vinylbenzoic acid, fumaric acid, itaconic acid, maleic acid, citraconic acid, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monomethyl itaconic acid, itaconic acid Monoethyl itaconate, monobutyl itaconate, monooctyl itaconate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monooctyl fumarate, monoethyl citraconic acid, monohydroxyethyl (meth)acrylate tetrahydrophthalate, Tetrahydrophthalate monohydroxypropyl (meth)acrylate, tetrahydrophthalate monohydroxy butyl (meth)acrylate, phthalate monohydroxyethyl (meth)acrylate, phthalate monohydroxypropyl (meth)acrylate, succinic acid mono Carboxyl group-containing ethylenically unsaturated products such as hydroxyethyl (meth)acrylate, monohydroxypropyl (meth)acrylate succinate, monohydroxyethyl (meth)acrylate maleate, and monohydroxypropyl (meth)acrylate maleate. monomer;

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

Cyano group-containing vinyl monomers such as acrylonitrile and methacrylonitrile;

Alkyl vinyl ethers [e.g., ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, 2-ethylhexyl vinyl ether, etc.], cycloalkyl vinyl ethers [e.g., cyclohexyl vinyl ether, etc.], etc. vinyl ether monomer;

Vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate;

Aromatic vinyl monomers such as styrene, vinyl toluene, and α-methylstyrene;

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

Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethyl Allpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, allyl methacrylate, triallyl cyanurate, diallyl maleate, polypropylene glycol diallyl Polyfunctional monomers such as ether;

macro monomer; etc.

These can be used by appropriately selecting one type or two or more types as needed.

Examples of the macromonomer include compounds having an ethylenically unsaturated bond-containing group and two or more structural units derived from a monomer containing an ethylenically unsaturated bond-containing group. Two or more structural units of the macromonomer may be the same or different.

Examples of the ethylenically unsaturated bond-containing group include CH ₂ =C(COOR)-CH ₂ -, (meth)acryloyl group, 2-(hydroxymethyl)acryloyl group, and vinyl group. Here, R represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted heterocyclic group. Substituents include, for example, an alkyl group (except for cases where R is an alkyl group having a substituent), aryl group, -COOR ⁶¹ , cyano group, -OR ⁶² , -NR ⁶³ R ⁶⁴ , -CONR ⁶⁵ R ⁶⁶ , halogen. At least one type selected from the group consisting of atoms, allyl groups, epoxy groups, siloxy groups, and hydrophilic or ionic groups can be mentioned. Here, R ⁶¹ to R ⁶⁶ each independently represent a hydrogen atom, an alkyl group, an alicyclic group, or an aryl group.

As the monomer having an ethylenically unsaturated bond-containing group, for example, various monomers listed above can be used as examples of the monomer (m3) (however, macro monomers are excluded).

Specific examples of the macromonomer include monomers disclosed in International Publication No. 2013/108880.

The monomer (m3) is preferably a monofunctional monomer having one ethylenically unsaturated bond because it is easy to make the copolymer (A) low in viscosity even if the solid content is high when the copolymer (A) is dissolved in a solvent. It is particularly preferable if it is derived from this acryloyl group. That is, the monomer (m3) is particularly preferably a monofunctional monomer having one acryloyl group.

The structural unit (u3) is derived from a hydrophobic group-containing (meth)acrylic acid ester monomer in that the flexibility and/or crack resistance and peeling resistance of the formed coating film and long-term self-polishing properties can be maintained in a good balance. It is desirable to include structural units.

As the hydrophobic group-containing (meth)acrylic acid ester monomer, alkyl (meth)acrylate is preferable.

The structural unit (u3) preferably contains a structural unit derived from an oxyethylene group-containing (meth)acrylic acid ester monomer from the viewpoint of solubility and crack resistance of the formed coating film.

As the oxyethylene group-containing (meth)acrylic acid ester monomer, a compound represented by the following formula (3-1) is preferable.

(In the formula, Z ¹ represents an acryloyloxy group or a methacryloyloxy group, R ²¹ represents a hydrogen atom, an alkyl group or an aryl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 15.)

In formula (3-1), when Z ¹ is an acryloyloxy group or a methacryloyloxy group, the hydrolysis rate tends to be faster in the case of an acryloyloxy group, and can be arbitrarily selected depending on the dissolution rate. You can.

The alkyl group and aryl group having 1 to 10 carbon atoms for R ²¹ may be the same as those listed for R ¹ and R ³ above, respectively.

From the viewpoint of water resistance and crack resistance, n is preferably an integer of 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and especially preferably 1 or 2.

(Content of each constituent unit)

The content of the structural unit (u1) in the copolymer (A) is preferably 1 to 80% by mass, more preferably 10 to 70% by mass, and 20 to 20% by mass, based on the total (100% by mass) of all structural units. 60 mass% is more preferable. If the content of the structural unit (u1) is more than the lower limit of the above range, the self-polishing properties of the formed coating film are more excellent. If the content of the structural unit (u1) is below the upper limit of the above range, the formed coating film has appropriate hydrolyzability, maintains self-polishing properties over a long period of time, and has a more excellent antifouling effect.

The content of the structural unit (u2) in the copolymer (A) is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, and 10 to 10% by mass, based on the total (100% by mass) of all structural units. 60 mass% is more preferable. If the content of the structural unit (u2) is more than the lower limit of the above range, the resulting coating film has better antifouling properties. If the content of the structural unit (u2) is below the upper limit of the above range, the crack resistance is more excellent.

In the copolymer (A), the content of structural units derived from both terminal polysiloxane macromonomers is preferably 30% by mass or less, and more preferably 25% by mass or less, based on the total (100% by mass) of all structural units. , 20% by mass or less is more preferable. If the content of the structural units derived from the polysiloxane macromonomers at both ends is below the above upper limit, a copolymer tends to be obtained without gelation due to crosslinking during production of the copolymer (A). Additionally, the viscosity of the solution of copolymer (A) tends to decrease.

The content of the structural unit (u3) is preferably 0 to 98% by mass, more preferably 5 to 85% by mass, and still more preferably 10 to 70% by mass, relative to the total (100% by mass) of all structural units.

When the copolymer (A) has a structural unit derived from an oxyethylene group-containing (meth)acrylic acid ester monomer, the content of this structural unit is preferably 1 to 80% by mass, and 5 to 60%, relative to the total of all structural units. The mass % is more preferable, and 20 to 50 mass % is more preferable. If the content of this structural unit is more than the lower limit of the above range, the hydrophilicity of the formed coating film becomes higher and the self-polishing property becomes more excellent. If the content of this structural unit is below the upper limit of the above range, the formed coating film has appropriate hydrolyzability, maintains self-polishing properties over a long period of time, and has a more excellent antifouling effect.

When the copolymer (A) has a structural unit derived from a monomer (m3) other than the oxyethylene group-containing (meth)acrylic acid ester monomer, such as a hydrophobic group-containing (meth)acrylic acid ester monomer, the content of this structural unit is the total composition. 1 to 90% by mass is preferable, and 10 to 80% by mass is more preferable relative to the total of the units. If the content of this structural unit is within the above range, the flexibility and crack resistance and peeling resistance of the formed coating film will be higher, and the antifouling effect will be more excellent. If the content of this structural unit is below the upper limit of the above range, the formed coating film has appropriate hydrolyzability, maintains self-polishing properties over a long period of time, and has a more excellent antifouling effect.

In addition, the total of the structural unit (u1), the structural unit (u2), and the structural unit (u3) is 100% by mass.

The content (mass %) of each structural unit in the copolymer can be measured by known methods such as gas chromatography, high-performance liquid chromatography, and nuclear magnetic resonance spectroscopy.

The copolymer (A) is preferably a copolymer obtained by polymerizing a monomer mixture containing the monomer (m1) and the monomer (m2). In such a copolymer, a monomer mixture containing a monomer (m0) and a monomer (m2) having an ethylenically unsaturated bond and a carboxyl group is polymerized to obtain a copolymer (A0) having a carboxyl group, and the carboxyl group of this copolymer (A0) is obtained. Compared to the copolymer obtained by converting to structure (I), water resistance is more excellent.

The monomer mixture preferably contains 1 to 80 mass% of monomer (m1), 1 to 80 mass% of monomer (m2), and 0 to 98 mass% of monomer (m3). The content of each monomer is a ratio to the total amount of the monomer mixture. The more preferable content range of each monomer is the same as the preferable content range of the structural unit derived from each monomer.

The weight average molecular weight (Mw) of the copolymer (A) is preferably 2,000 to 100,000, more preferably 3,000 to 80,000, and still more preferably 5,000 to 60,000.

If the weight average molecular weight of the copolymer (A) is below the upper limit of the above range, the viscosity of a solution obtained by dissolving the copolymer (A) in a solvent becomes lower, and it is easy to obtain an antifouling paint composition with high solid content and low viscosity. In addition, the formed coating film has excellent antifouling properties. If the weight average molecular weight is more than the lower limit of the above range, the hardness and durability of the formed coating film are more excellent.

The number average molecular weight (Mn) of the copolymer (A) is preferably 1,000 to 50,000, and more preferably 2,000 to 40,000.

The polydispersity (Mw/Mn) of the copolymer (A) is preferably 1.5 to 5.0, and more preferably 2.2 to 3.0.

The weight average molecular weight and number average molecular weight of the copolymer (A) are each measured by gel filtration chromatography (GPC) using polystyrene as a reference resin.

(Method for producing copolymer (A))

Examples of the production method of the copolymer (A) include the following production methods (α) and (β).

Manufacturing method (α): A method of polymerizing a monomer mixture containing monomer (m1) and monomer (m2).

Manufacturing method (β): Polymerize a monomer mixture containing a monomer (m0) having an ethylenically unsaturated bond and a carboxyl group and a monomer (m2) to obtain a copolymer (A0) having a carboxyl group, and this copolymer (A0) Method for converting the carboxyl group of to structure (I).

「Manufacturing method (α)」

Monomer mixture:

The monomer mixture used in the production method (α) contains at least a monomer (m1) and a monomer (m2), and may further contain a monomer (m3).

The content of monomer (m1) in the monomer mixture is preferably 1 to 80% by mass with respect to the total mass (100% by mass) of all monomers. That is, the copolymer (A) is preferably obtained by polymerizing a monomer mixture containing 1 to 80% by mass (input amount) of monomer (m1) relative to the total mass of all monomers. The content of the monomer (m1) is more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass. If the content of the monomer (m1) is more than the lower limit of the above range, the self-polishing properties of the formed coating film are more excellent. If the content of the monomer (m1) is below the upper limit of the above range, the formed coating film has appropriate hydrolyzability, maintains self-polishing properties over a long period of time, and has a more excellent antifouling effect.

The content of the monomer (m2) in the monomer mixture is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, and even more preferably 10 to 60% by mass, based on the total mass of all monomers. If the content of monomer (m2) is more than the lower limit of the above range, the resulting coating film has better antifouling properties. If the content of the monomer (m2) is below the upper limit of the above range, the crack resistance is more excellent.

The content of both terminal polysiloxane macromonomers in the monomer mixture is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less, based on the total mass of all monomers. If the content of the polysiloxane macromonomer at both ends is below the above upper limit, gelation due to crosslinking does not proceed during polymerization of the monomer mixture, and a copolymer tends to be obtained. Additionally, the viscosity of the resulting solution of copolymer (A) tends to decrease.

The content of monomer (m3) in the monomer mixture is preferably 0 to 98% by mass, more preferably 5 to 85% by mass, and even more preferably 10 to 70% by mass, relative to the total mass of all monomers.

When the monomer mixture contains an oxyethylene group-containing (meth)acrylic acid ester monomer, the content of this monomer is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, based on the total mass of all monomers. 20 to 50 mass% is more preferable. If the content of this monomer is more than the lower limit of the above range, the hydrophilicity of the formed coating film becomes higher and the self-polishing property becomes more excellent. If the content of this structural unit is below the upper limit of the above range, the formed coating film has appropriate hydrolyzability, maintains self-polishing properties over a long period of time, and has a more excellent antifouling effect.

When the monomer mixture contains a monomer (m3) other than the oxyethylene group-containing (meth)acrylic acid ester monomer, such as a hydrophobic group-containing (meth)acrylic acid ester monomer, the content of this monomer is 1 to 1 with respect to the total mass of all monomers. 90 mass% is preferable, and 10 to 80 mass% is more preferable.

In addition, the total of monomer (m1), monomer (m2), and monomer (m3) (including the case where monomer (m3) is not contained) is set to 100% by mass.

Monomer (m1), monomer (m2), and monomer (m3) can each be purchased commercially, or can be synthesized appropriately using known methods.

Monomer (m1) can be synthesized by converting the carboxyl group of monomer (m0), which has an ethylenically unsaturated bond and a carboxyl group, into structure (I).

Examples of the monomer (m0) include (meth)acrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, monomethyl maleate, and monomethyl fumarate.

As a method of converting the carboxyl group of monomer (m0) into structure (I), for example, monomer (m0), a compound represented by the following formula (31), a compound represented by the following formula (32), and a compound represented by the following formula (33) ), a method of reacting (addition reaction) with at least one compound (B) selected from the group consisting of compounds represented by ). Compound (B) may be used individually or in combination of two or more types.

^{( Wherein , _} represents an atom or an alkyl group with 1 to 10 carbon atoms, R ⁹ and R ¹¹ each represent an alkyl group, cycloalkyl group or aryl group with 1 to 20 carbon atoms, R ¹⁰ represents a single bond or an alkylene group with 1 to 9 carbon atoms, R ¹² represents an alkylene group having 1 to 9 carbon atoms.)

When a compound represented by the formula (31) is used as the compound (B), as the monomer (m1), a compound in the formula (11) wherein R ¹ is CH ₂ R ⁷ , R ² is R ⁸ , and R ³ is R ⁹ This is obtained.

In formula (31), the alkyl group having 1 to 9 carbon atoms for R ⁷ 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 ⁸ and R ⁹ are the same as R ² and R ³ in the above formula (11), respectively.

Examples of the compound represented by formula (31) include 1-alkenyl alkyl ether where X in formula (31) is -O-, 1-alkenyl alkyl sulfide where X in formula (31) is -S-, and 1-alkenyldialkylamine wherein X in formula (31) is -NR ¹⁴ -. Examples of 1-alkenyl alkyl ether include alkyl vinyl ether (e.g., ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether), and cycloalkyl vinyl ether. Vinyl ethers such as (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. Examples of 1-alkenyl alkyl sulfide include 1-(ethenylthio)ethane, 1-(ethenylthio)propane, 1-(ethenylthio)butane, 2-(ethenylthio)butane, 1- 1-alkenyl alkyl sulfides such as (ethenylthio)-2-methylpropane, 1-(propylthio)-1-propene, and 2-(propylthio)-1-propene; etc. can be mentioned. Examples of 1-alkenyl dialkylamine include N,N-dimethyletheneamine, N-methyl-N-ethylethenamine, N,N-diethylethenamine, N-vinylpyrrolidine, etc. -Alkenyl dialkylamines, etc. can be mentioned.

Among these, 1-alkenyl alkyl ether is preferable, and vinyl ethers and 1-propenyl ethers are more preferable.

When the compound represented by the formula (32) is used as the compound (B), a compound in which R ⁴ in the formula (12) is CH ₂ -R ¹⁰ is obtained as the monomer (m1).

In formula (32), the alkylene group having 1 to 9 carbon atoms in R ¹⁰ 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 (32) 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; Dihydrothiophenes such as 2,3-dihydrothiophene; Dihydrothiopyrans such as 3,4-dihydro-2H-thiopyran; Dihydropyrroles such as 2,3-dihydro-1-methylpyrrole; Tetrahydropyridines such as 1,2,3,4-tetrahydro-1-methylpyridine; etc. can be mentioned.

Among these, dihydrofurans and dihydropyranes are preferable, and dihydropyrans are more preferable.

When a compound represented by the formula (33) is used as the compound (B), a compound in which R ⁵ in the formula (13) is R ¹¹ and R ⁶ is CH ₂ -R ¹² is obtained as the monomer (m1).

In formula (33), R ¹¹ is the same as R ⁵ . R ¹² is the same as R ⁶ except that the number of carbon atoms is 9 or less.

Compounds represented by formula (33) include, for example, 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; 1-(alkylthio)-1-cycloalkylenes such as 1-(methylthio)-1-cyclopentene and 1-(methylthio)-1-cyclohexene; 1-(1-pyrrolidinyl)-1-cycloalkylenes such as 1-(1-pyrrolidinyl)-1-cyclopentene and 1-(1-pyrrolidinyl)-1-cyclohexene; etc. can be mentioned.

Compound (B) can be purchased commercially or synthesized appropriately.

The reaction between monomer (m0) and compound (B) proceeds under relatively mild conditions. For example, the target product can be 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 monomer can be recovered by performing reduced pressure distillation under predetermined conditions.

Polymerization of monomer mixture:

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. The solution polymerization method is preferable in terms of productivity and film performance.

Polymerization may be performed by a known method using a known polymerization initiator. For example, a method of reacting the above monomer mixture in the presence of a radical initiator at a reaction temperature of 60 to 120° C. for 4 to 14 hours is included. During polymerization, a chain transfer agent may be used as needed.

As the radical initiator, known ones can be used, for example, 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2 -methylbutyronitrile), benzoyl peroxide, cumene hydroperoxide, lauryl peroxide, di-t-butyl peroxide, t-butyl peroxy-2-ethylhexanoate, etc.

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, and examples include mercaptans such as n-dodecyl mercaptan, thioglycolic acid esters such as octyl thioglycolate, α-methylstyrene dimer, and terpinolene. 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.

As a solvent used in solution polymerization, for example, general organic solvents such as toluene, xylene, methyl isobutyl ketone, and n-butyl acetate can be used.

「Manufacturing method (β)」

In the production method (β), first, a monomer mixture containing the monomer (m0) and the monomer (m2) is polymerized to obtain a copolymer (A0) having a carboxyl group. The monomer mixture may further contain monomer (m3).

Monomer (m0), monomer (m2), and monomer (m3) are the same as above.

The preferable range of the content of each monomer (m0) and monomer (m2) in the monomer mixture is the same as the preferable range of the content of each monomer (m1) and monomer (m2) in the monomer mixture in the production method (α). The preferred content range of the oxyethylene group-containing (meth)acrylic acid ester monomer and other monomers (m3) is also the same as above.

Polymerization of the monomer mixture can be performed in the same manner as the production method (α).

Next, the carboxyl group of copolymer (A0) is converted to structure (I) to obtain copolymer (A).

As a method of converting the carboxyl group of the copolymer (A0) into structure (I), for example, a method of reacting (addition reaction) the copolymer (A0) with the above compound (B) is included.

The reaction between the copolymer (A0) and the compound (B) can be carried out in the same manner as the reaction between the monomer (m0) and the compound (B).

(action effect)

Since the copolymer (A) has a structure (I) in which the carboxyl group is protected by a specific group, it can be hydrolyzed in seawater or the like. Therefore, the coating film containing the copolymer (A) exhibits self-polishing properties in seawater or the like. That is, the copolymer (A) has structure (I) and is not soluble in seawater in this state, but when structure (I) is hydrolyzed by contact with seawater, carboxyl groups, etc. are generated and dissolved in seawater. . The surface of the coating film gradually dissolves in seawater and the surface is renewed (self-polishing).

Additionally, because the copolymer (A) has a polysiloxane group, it is difficult for marine organisms or other contaminants to attach to the surface of the coating film. Therefore, the coating film containing the copolymer (A) exhibits an excellent antifouling effect even when it does not contain an antifouling agent. When an antifouling agent is included, since the surface of the coating film is renewed, the antifouling agent is always exposed to the surface of the coating film, and the antifouling effect of the antifouling agent is stably exhibited over a long period of time.

Additionally, since the copolymer (A) has structure (I) as the hydrolyzable structure, the water resistance of the coating film is excellent compared to the case where a copolymer having a structure containing a divalent metal as the hydrolyzable structure is used. In particular, these effects become more excellent by combining polysiloxane groups in structure (I). This is thought to be due to the polysiloxane group reducing the hydrophilicity of the coating film and thereby suppressing swelling and excessive dissolution of the coating film. Because the water resistance of the coating film is excellent, an excellent antifouling effect is exhibited stably over a long period of time.

The hardness of the coating film is sufficiently high, and damage or peeling of the coating film that causes a decrease in the antifouling effect is unlikely to occur. In this regard as well, an excellent antifouling effect is exhibited stably over a long period of time.

A coating film of a resin composition or antifouling paint composition containing the copolymer (A) also exhibits an effect equivalent to the above.

Additionally, the copolymer (A) can be made into a solution with high solid content and low viscosity when an organic solvent is added. If the resin composition containing the copolymer (A) and the organic solvent has a high solid content and low viscosity, an antifouling paint composition with coating suitability can be obtained without additional addition of an organic solvent to the resin composition during production of the antifouling paint composition. You can. Additionally, when adding an antifouling agent, etc., the antifouling agent, etc. can be mixed well even without adding an organic solvent. Therefore, an antifouling paint composition with a low VOC content can be obtained.

Therefore, copolymer (A) is suitable for use in antifouling paint compositions.

[Resin composition]

A second aspect of the present invention is a resin composition containing the above copolymer (A). The number of copolymers (A) contained in the resin composition of this form may be one, or two or more types may be used.

The content of the copolymer (A) in the resin composition of this form is not particularly limited, but is preferably 45% by mass or more, more preferably 50% by mass or more, and even more preferably 55% by mass or more relative to the total amount of the resin composition. 60 mass% or more is particularly preferable, and 64 mass% or more is most preferable. If the content of the copolymer (A) is more than the above lower limit, an antifouling paint composition with a low VOC content can be easily obtained.

The upper limit of the content of the copolymer (A) is not particularly limited and may be 100% by mass. When the resin composition contains a solvent, the viscosity of the resin composition measured with a type B viscometer at 25°C is preferably less than 5,000 mPa·s (more preferably less than 3,000 mPa·s), and the copolymer ( Although it also varies depending on the weight average molecular weight of A), glass transition temperature, presence or absence of a crosslinked structure, etc., 80 mass% or less is preferable, and 85 mass% or less is more preferable.

It is preferable that the resin composition of this form further contains at least one type selected from the group consisting of compounds that react with acids, basic compounds, acidic compounds, and dehydrating agents. Thereby, the storage stability of the resin composition or the antifouling paint composition containing it is improved.

In the case of copolymer (A), structure (I) may unintentionally decompose during storage. When structure (I) is decomposed, carboxylic acid is produced. As a result, the glass transition temperature of the copolymer (A) increases, or the carboxylic acid and other components in the paint form a crosslinked structure, and the viscosity of the solution of the copolymer (A) or the paint containing it increases. Additionally, as free carboxylic acid is produced, the dissolution stability in organic solvents and water resistance decrease. Additionally, the generated carboxylic acid catalytically promotes the hydrolysis reaction as an acid, thereby further decomposing structure (I). By containing a compound that reacts with an acid in the resin composition, when the structure (I) in the copolymer (A) is decomposed to produce carboxylic acid, the carboxylic acid is captured by the compound that reacts with the acid, thereby improving storage stability.

Additionally, in high pH areas or low pH areas, decomposition of structure (I) is accelerated, thereby reducing storage stability. In a high pH range, storage stability decreases due to a decrease in the reactivity between compound (B) and carboxylic acid. By adjusting the pH of the resin composition by adding a basic compound or an acidic compound, decomposition of structure (I) can be suppressed and a decrease in storage stability can be suppressed.

Additionally, moisture promotes the decomposition (hydrolysis) of structure (I). By containing a dehydrating agent in the resin composition, moisture in the resin composition can be captured and a decrease in storage stability can be suppressed.

Compounds that react with acids include the above-mentioned compound (B), basic compounds, and compounds having an epoxy group.

Examples of basic compounds include dimethylamine, diethylamine, trimethylamine, triethylamine, aniline, and pyridine.

Compounds containing an epoxy group include 2-ethyloxirane, 2,3-dimethyloxirane, 2,2-dimethyloxirane, glycidyl (meth)acrylate, glycidyl α-ethylacrylate, and (meth)acrylic acid 3. , 4-epoxybutyl, etc. can be mentioned.

As a compound that reacts with acid, compound (B) is preferable from the viewpoint of storage stability. As the compound (B), among those listed above, 1-alkenyl alkyl ether in which Vinyl ethers such as isobutyl vinyl ether are more preferable.

Examples of basic compounds for pH adjustment include the same basic compounds as those described above.

As acidic compounds, abietic acid, neoavietic acid, palustric acid, pimaric acid, isopimaric acid, levopimaric acid, dextropimaric acid, sandaracopimaric acid, acetic acid, propionic acid, butyric acid, and lauric acid. , stearic acid, linoleic acid, oleic acid, chloroacetic acid, fluoroacetic acid, etc.

Examples of dehydrating agents include silicate-based, isocyanate-based, orthoester-based, inorganic-based, etc. More specifically, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, orthoboric acid ester, tetraethyl orthosilicate, anhydrous gypsum, calcined gypsum, synthetic zeolite (molecular sieve), etc. Molecular sieves are particularly preferred.

These additives can be used individually or in combination of two or more.

Examples of combinations of two or more additives include a combination of compound (B) and a dehydrating agent, a combination of compound (B), an acidic compound and a dehydrating agent, a combination of compound (B), a basic compound, an acidic compound and a dehydrating agent, and a combination of a basic compound and a dehydrating agent. etc. can be mentioned.

When the resin composition contains compound (B), the content of compound (B) in the resin composition is preferably 20 mol% or more, and 30 to 1000 mol% relative to the structure (I) of the copolymer (A). It is more preferable, and 40 to 800 mol% is still more preferable. If the content of compound (B) is within the above range, the effect of improving storage stability is more excellent.

When the resin composition contains a basic compound or/and an acidic compound, the content of the basic compound or/and the acidic compound in the resin composition is a basic compound at a concentration such that the pH measured in water is 2 to 12 from the viewpoint of storage stability. The amount is preferable, and the amount of the basic compound at a concentration such that the pH is 6 to 9 is more preferable.

Here, the pH measured in water is specifically a value measured by adding a basic compound to water. The pH is the value at 23°C.

When the resin composition contains a dehydrating agent, the content of the dehydrating agent in the resin composition is preferably 0.1 to 40% by mass, more preferably 1 to 20% by mass, based on the total mass of the resin composition. If the content of the dehydrating agent is more than the lower limit of the above range, storage stability is more excellent. If the content of the dehydrating agent is below the upper limit of the above range, the dissolution stability is good.

<Silicone oil>

It is preferable that the resin composition of the present invention further contains silicone oil. When the resin composition contains silicone oil, the resulting coating film has better antifouling properties.

Examples of silicone oils include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil, and modified silicone oils. Modified silicone oil is a silicone oil in which organic groups other than methyl groups and phenyl groups (hereinafter also referred to as “modified groups”) are introduced into some of the silicon atoms of straight silicone oil. Examples of the modifying group include chlorophenyl group, methylstyrene group, long-chain alkyl group (e.g., alkyl group having 2 to 18 carbon atoms), polyether group, carbinol group, aminoalkyl group, epoxy group, (meth)acryloyl group, etc. there is. These silicone oils can be used individually or in combination of two or more types. Among the above-mentioned silicone oils, polyether-modified silicone oils having a polyether group as a modified group are preferable from the viewpoint of anti-fouling properties.

As silicone oil, a commercially available product can be used. Commercially available silicone oils include, for example, "KF-96", "KF-50", "KF-54", "KF-56", and "KF-6016" (above, Shinetsu Chemical Co., Ltd. ), “TSF451” (manufactured by Momentive Performance Materials), “Fluid47” (manufactured by Ronnefranc, France), “SH200”, “SH510”, “SH550”, “SH710”, “DC200”, Examples include “ST-114PA” and “FZ209” (manufactured by Toray and Dow Corning).

When the resin composition contains silicone oil, the content of silicone oil in the resin composition is preferably 0.1 to 40% by mass, more preferably 1 to 20% by mass, relative to the total mass of the resin composition. If the content of silicone oil is more than the lower limit of the above range, the antifouling property is more excellent. If the content of silicone oil is below the upper limit of the above range, the dissolution stability is more excellent.

<Organic solvent>

It is preferable that the resin composition of this form contains an organic solvent. When the resin composition contains an organic solvent, the coating suitability of the antifouling paint composition using the resin composition, the water resistance of the formed coating film, the film forming properties, etc. are superior.

The organic solvent is not particularly limited as long as it can dissolve the copolymer (A), and examples include hydrocarbon solvents such as toluene and xylene; Ether-based solvents such as the above compound (B) and propylene glycol monomethyl ether-2-acetate; Ketone-based solvents such as methyl isobutyl ketone; Ester solvents such as n-butyl acetate; etc. can be mentioned. These can be used individually or in combination of two or more.

The content of the organic solvent in the resin composition of this form is preferably 60% by mass or less, more preferably 50% by mass or less, and 45% by mass relative to the total amount of the resin composition from the viewpoint of reducing the VOC content of the antifouling paint composition. % or less is more preferable, and 40 mass% or less is especially preferable.

The content of the organic solvent is preferably such that the viscosity of the resin composition measured with a type B viscometer at 25°C is below the preferred upper limit described later, and the weight average molecular weight, glass transition temperature, and presence or absence of a crosslinked structure of the copolymer (A) Although it varies depending on the case, 15 mass% or more is preferable, and 20 mass% or more is more preferable.

Additionally, the compound (B) can also function as an organic solvent. Therefore, when the resin composition contains compound (B), the content of compound (B) is included in the content of the organic solvent.

<Other ingredients>

The resin composition of this form may further contain components other than the copolymer (A), an acid-reactive compound, a basic compound, an acidic compound, a dehydrating agent, silicone oil, and an organic solvent.

Examples of other components include the same components as the other components in the antifouling paint composition described later.

The content of other components is preferably 200% by mass or less relative to the copolymer (A), and may be 0% by mass.

<Solid content>

The solid content of the resin composition of this form is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and especially preferably 60% by mass or more. If the solid content of the resin composition is more than the lower limit of the above range, the VOC content of the antifouling paint composition is sufficiently low.

The upper limit of the solid content of the resin composition is not particularly limited and may be 100% by mass. When the resin composition contains an organic solvent, from the viewpoint of the viscosity of the resin composition, 85% by mass or less is preferable, and 80% by mass or less is more preferable.

The solid content of the resin composition is measured by the measurement method described in the Examples described later.

<Viscosity>

When the resin composition of this form contains a solvent, the viscosity of this resin composition measured with a type B viscometer at 25°C (hereinafter also referred to as “type B viscosity”) is preferably less than 5000 mPa·s, and is 3000 mPa·s. Less than is more preferable, less than 2,000 mPa·s is more preferable, and less than 1,000 mPa·s is particularly preferable.

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

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

The resin composition preferably has a viscosity of at least 50% by mass of solid content below the above preferred 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 type B viscosity at 25°C is 100 mPa·s or more.

Therefore, the type B viscosity at 25°C of the resin composition is preferably 100 mPa·s or more and less than 5,000 mPa·s, more preferably 100 mPa·s or more and less than 3,000 mPa·s, and 100 mPa·s or more and less than 2,000 mPa·s. This is more preferable, and 100 mPa·s or more and less than 1,000 mPa·s are particularly preferable.

The viscosity of the resin composition can be adjusted by the solid content of the resin composition (content of copolymer (A) and other components), weight average molecular weight of copolymer (A), glass transition temperature, presence or absence of crosslinked structure, etc. For example, the smaller the solid content, especially the copolymer (A) content, the lower the viscosity tends to be. Additionally, the smaller the weight average molecular weight of the copolymer (A) or the lower the glass transition temperature, the lower the viscosity tends to be.

<Decomposition rate of structure (I)>

In the resin composition of this form, the decomposition rate of structure (I) in copolymer (A) after storage at 40°C for 30 days is preferably 20% or less, more preferably 7% or less, and still more preferably 4% or less. It is particularly preferable that it is 3% or less, and it is most preferable that it is 2% or less. If the decomposition rate of structure (I) after storing the resin composition at 40°C for 30 days is below the above upper limit, the storage stability of the resin composition or the antifouling paint composition containing the same is excellent. Additionally, when the resin composition contains an organic solvent, the dissolution stability of the copolymer (A) in the organic solvent is also excellent. The lower the decomposition rate, the more preferable it is, and the lower limit may be 0%.

The decomposition rate of structure (I) after storage at 40°C for 30 days can be reduced to 20% or less by, for example, containing a compound that reacts with acid, a basic compound, an acidic compound, a dehydrating agent, etc. in the resin composition.

In measuring the decomposition rate of structure (I), storage of the resin composition refers to putting the resin composition in a glass bottle, sealing it, and leaving it in a shielded environment in a drying room.

The decomposition rate of structure (I) is calculated from the measured solid acid value (a) of the resin composition (after storage at 40°C for 30 days) to the theoretical solid acid value (b) when all of structure (I) contained in the copolymer (A) is not decomposed. ) is defined as the following value divided by the theoretical solid acid value (c) when all the structures (I) included in the copolymer (A) are decomposed.

(Decomposition rate) = {(measured solid acid value (a)) - (theoretical solid acid value (b))}/(theoretical solid acid value (c)) × 100

The measured solid acid value is explained in the acid value measurement section described later.

The theoretical solid acid value can be calculated with the following formula.

(Theoretical solid acid value)=Σ(561×100/Mw _i ×w _i )

w _i represents the mass fraction of monomer i having an acid functional group among the monomers constituting the copolymer (A), and Mw _i represents the molecular weight of the monomer having an acid functional group. The acid functional group is a functional group such as carboxylic acid.

The acid value when decomposed is calculated by treating it as a monomer having an acid functional group.

The acid value when not decomposed is calculated by treating it as a monomer without an acid functional group.

(Method for producing resin composition)

The resin composition of this form can be manufactured using a known method. For example, a copolymer (A) is produced by the above-mentioned production method (α) or (β), and if necessary, a compound that reacts with an acid, a basic compound, an acidic compound, a dehydrating agent, an organic A resin composition can be prepared by mixing solvents, other components, etc.

When the resin composition of this form contains compound (B), the timing of mixing compound (B) may be during production of copolymer (A) or after production of copolymer (A), and is not particularly limited. . For example, in the above production method (α), compound (B) may coexist during polymerization of the monomer mixture, or compound (B) may be added after completion of polymerization. In the above production method (β), after completion of polymerization of the monomer mixture, when compound (B) is reacted with the resulting copolymer (A0) to obtain copolymer (A), the copolymer (A0) is obtained in an equivalent amount relative to the carboxyl group of the copolymer (A0). Excess compound (B) may be added so that unreacted compound (B) remains. Since a part of Compound (B) is radically polymerized when Compound (B) is coexisted during the polymerization reaction, a method of adding Compound (B) after completion of polymerization is preferable.

The resin composition of this form can be used as is or mixed with an antifouling agent, etc. as needed to make an antifouling paint composition.

The resin composition of this form can also be used for antifogging paint compositions other than antifouling paint compositions.

(action effect)

Since the resin composition of this form contains the copolymer (A), the coating film containing the resin composition of this form exhibits self-polishing properties in seawater or the like as described above. In addition, even when it does not contain an antifouling agent, it exhibits an excellent antifouling effect and has excellent water resistance. This coating film has sufficiently high hardness.

Additionally, the resin composition of this form can be in the form of a solution with high solid content and low viscosity. Therefore, by using the resin composition of this form, an antifouling paint composition with a low VOC content can be obtained.

Additionally, when the resin composition of this form contains, in addition to the copolymer (A), at least one member selected from the group consisting of a compound that reacts with an acid, a basic compound, an acidic compound, and a dehydrating agent, the resin composition exhibits excellent storage stability. It can manifest. For example, the decomposition rate of structure (I) in copolymer (A) after storage at 40°C for 30 days can be 20% or less. Additionally, when the resin composition further contains an organic solvent, an increase in the viscosity of the resin composition over time can be suppressed. The copolymer (A) in the resin composition also has excellent dissolution stability in organic solvents.

Therefore, the resin composition of this form is suitable for use as an antifouling paint composition.

[Antifouling paint composition]

A third aspect of the present invention is an antifouling paint composition containing the resin composition of the second aspect. Accordingly, the antifouling paint composition of this form contains the above copolymer (A).

From the viewpoint of storage stability of the antifouling paint composition, it is preferable that the antifouling paint composition further contains at least one member selected from the group consisting of compounds that react with acids, basic compounds, acidic compounds, and dehydrating agents. Compounds that react with acids, basic compounds, acidic compounds, and dehydrating agents may be the same as those described above. The preferred content is also the same.

It is preferable that the antifouling paint composition of this form further contains silicone oil from the viewpoint of antifouling properties of the coating film. Silicone oils include the same ones as above. The preferred content is also the same.

The antifouling paint composition of this form may contain an organic solvent. Organic solvents include the same ones as above.

The antifouling paint composition of this form may further include an antifouling agent.

The antifouling paint composition of this form may further contain components other than the copolymer (A), an acid-reactive compound, a basic compound, an acidic compound, a dehydrating agent, silicone oil, an organic solvent, and an antifouling agent.

When the antifouling paint composition contains compounds that react with acids, basic compounds, acidic compounds, dehydrating agents, silicone oil, organic solvents, other components, etc., these components may be derived from the above resin composition, respectively, or may be not derived from the resin composition ( blended during the production of the antifouling paint composition) may be used, or a mixture thereof may be used.

<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 benzothiazole-based agents. Compounds, maleimide-based compounds, pyridine-based compounds, etc. can be mentioned. These can 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-dimethyl Dichlorophenylurea, zinc ethylene bisdithiocarbamate, rhodan copper, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, N-(fluorodichloromethylthio)phthalimide , N,N'-dimethyl-N'-phenyl-(N-fluorodichloromethylthio)sulfamide, 2-pyridinethiol-1-oxide zinc salt (also known as "zinc pyrithione"), tetramethylthiuram Disulfide, Cu-10% Ni solid solution alloy, 2,4,6-trichlorophenylmaleimide 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, 3-iodo-2-propylene Nylbutylcarbamate, diiodomethylparatrilsulfone, bisdimethyldithiocarbamoylzincethylenebisdithiocarbamate, phenyl(bispyridyl)bismuth dichloride, 2-(4-thiazolyl)-benz Examples include imidazole, medetomidine, and pyridine triphenylborane.

Antifouling agents include, among those mentioned above, copper cuprous oxide, pyridinetriphenylborane, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and 4-bromo-2-in terms of antifouling properties. At least one member selected from the group consisting of (4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (hereinafter also referred to as “antifouling agent (b1)”) and medetomidine. It is desirable to include.

When combining cuprous oxide and antifouling agent (b1), the mixing ratio (mass ratio) is preferably cuprous oxide/antifouling agent (b1) = 80/20 to 99/1, and more preferably 90/10 to 99/1. .

At least one selected from the group consisting of cuprous oxide, pyridine triphenylborane, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, antifouling agent (b1), and medetomidine, Other antifouling agents may be combined.

When the antifouling paint composition contains an antifouling agent, the content of the antifouling agent in the antifouling paint composition is not particularly limited, but is preferably 10 to 200 parts by mass, and more preferably 50 to 150 parts by mass, based on 100 parts by mass of the copolymer (A). do. If the content of the antifouling agent is more than the lower limit of the above range, the antifouling effect of the formed coating film is more excellent. If the content of the antifouling agent is below the upper limit of the above range, the physical properties of the coating film are excellent.

<Other ingredients>

Examples of other components include polymers other than copolymer (A). Other polymers are, for example, polymers that do not have structure (I).

Examples of other polymers include thermoplastic resins (thermoplastic polymers) other than copolymer (A). The antifouling paint composition of this form preferably contains a thermoplastic resin other than the copolymer (A). When the antifouling paint composition contains a thermoplastic resin other than the copolymer (A), the physical properties of the coating film, such as crack resistance and water resistance, are improved.

Thermoplastic resins other than copolymer (A) 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. ; 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 has the effect of improving 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 thermoplastic resin other than the copolymer (A) in the antifouling paint composition 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 copolymer (A). If the content of the thermoplastic resin other than the copolymer (A) is more than the lower limit of the above range, the coating film physical properties such as crack resistance and water resistance are more excellent, and if the content of the thermoplastic resin other than the copolymer (A) is less than the upper limit of the above range, the hydrolysis property is more excellent.

The antifouling paint composition of this type contains silicone compounds such as dimethylpolysiloxane (excluding silicone oil) and fluorine-containing compounds such as fluorinated hydrocarbons for the purpose of providing lubricity to the surface of the coating film and preventing attachment of living things. You can do it.

The antifouling paint composition of this form contains various pigments, antifoaming 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 control agents. etc. may be included.

Pigments include zinc oxide, talc, silica, barium sulfate, potash feldspar, aluminum hydroxide, magnesium carbonate, mica, carbon black, Bengala, titanium oxide, phthalocyanine blue, kaolin, gypsum, etc. In particular, zinc oxide or talc is preferable.

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 phthalate 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 plasticizers such as epoxy soybean oil and octyl epoxy stearate; 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, TCP is preferable among those mentioned above.

The VOC content of the antifouling paint composition of this form is preferably 410 g/L or less, more preferably 400 g/L or less, and still more preferably 380 g/L or less.

The VOC content is calculated from the following formula using the values of specific gravity and solid content (heated residue) of the antifouling paint composition.

VOC content (g/L) = Specific gravity of the composition × 1000 × (100 - solid content) / 100

The specific gravity of the antifouling paint composition is calculated by filling the antifouling paint composition in a specific gravity cup with a capacity of 100 mL at 25°C and measuring the mass.

The solid content (heated residue) of the antifouling paint composition is measured by the method described in the Examples described later.

The VOC content can be adjusted depending on the organic solvent content.

The solid content of the antifouling paint composition of this form is preferably 55 to 100% by mass, more preferably 60 to 90% by mass, and still more preferably 65 to 80% by mass.

If the solid content of the antifouling paint composition is more than the lower limit of the above range, the VOC content is sufficiently low. If the solid content is below the upper limit of the above range, the viscosity of the antifouling paint composition is likely to be lowered.

The type B viscosity at 25°C of the antifouling paint composition of this form is preferably less than 5,000 mPa·s, more preferably less than 3,000 mPa·s, and still more preferably less than 1,000 mPa·s. If the 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 of the antifouling paint composition is not particularly limited, but from the viewpoint of the coating film physical properties, 100 mPa·s or more is preferable.

The viscosity of the antifouling paint composition can be adjusted by the viscosity of the resin composition, the amount of organic solvent added to the resin composition, etc.

The antifouling paint composition of this form can be prepared by preparing the resin composition of this form as described above, adding an antifouling agent, other components, and an organic solvent as necessary, and mixing them.

The antifouling paint composition of this type 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 of this form can be formed on the surface of the substrate directly or through a base coating film.

The base coating film can be formed using a wash primer, a chlorinated rubber-based or epoxy-based primer, or an intermediate coating.

Formation of the coating film can be performed by a known method. For example, the antifouling paint composition can be applied to 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 dried to form a coating film.

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 through 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))

0.50 g of the measurement sample (resin composition or antifouling paint composition) was measured and taken on an aluminum dish, 3 mL of toluene was added with a dropper, spread evenly on the bottom of the dish, and pre-drying was performed. Pre-drying is a process for spreading the measurement sample over the entire plate to facilitate volatilization of the solvent in the main drying. In preliminary drying, the measurement sample and toluene were heated and dissolved in a water bath at 70 to 80°C and evaporated to dryness. After preliminary drying, main drying was performed for 2 hours in a hot air dryer at 105°C. The solid content (heated residue) was determined from the mass of the measurement sample before preliminary drying (mass before drying) and the mass after main drying (mass after drying) using the following equation.

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

(Type B viscosity)

The viscosity of the measurement sample was measured with a type B viscometer at 25°C, and the value was expressed as type B viscosity.

(Gardner viscosity)

The measurement 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 viscous tube serving as the reference tube and the viscous tube containing the sample are simultaneously immersed in the water bath. 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.

(Decomposition rate of structure (I) after storage at 40℃ for 30 days)

100 g of the prepared resin composition was placed in a 150 mL glass bottle, sealed, and left in a dry room under a shielded environment at 40°C for 30 days. After that (after storage at 40°C for 30 days), the solid acid value (a) of the resin composition was measured in the following procedure, and the decomposition rate (%) was calculated using the following formula. The theoretical solid acid values (b) and (c) are each as described above.

Decomposition rate (%) = {(measured solid acid value (a)) - (theoretical solid acid value (b))}/(theoretical solid acid value (c)) × 100

(Measured solid acid value)

Approximately 4.0 g of the sample (resin composition) was precisely weighed (A(g)) in a beaker, and 50 mL of toluene/95% ethanol solution was added at a ratio of 50/50. After stirring in an airtight container for 5 minutes, using a Hiranuma automatic titrator (AUTO TITRATOR COM-1600), 0.5 mol/L potassium hydroxide solution (ethanol solution), and the maximum slope of the titration curve was used as the end point (titer = B (mL), titer of KOH solution = f). A blank measurement was performed in the same manner (appropriate amount = C (mL)) and calculated according to the following formula.

Measured solid acid value (mgKOH/g)={(B-C)×0.5×56.11×f}/A/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 polymer were measured using gel permeation chromatography (GPC) (HLC-8220, manufactured by Tosoh Corporation). The columns used were TSKgelα-M (manufactured by Tosoh Corporation, 7.8 mm x 30 cm) and TSKguardcolumnα (manufactured by Tosoh Corporation, 6.0 mm x 4 cm). The calibration curve was prepared using F288/F1/F28/F80/F40/F20/F2/A1000 (manufactured by Tosoh Corporation, standard polystyrene) and styrene monomer.

(VOC content)

The VOC content of the antifouling paint composition was calculated from the following formula.

VOC content (g/L) = Specific gravity of the composition × 1000 × (100 - solid content) / 100

The method for measuring solid content is as described above. The specific gravity was calculated by filling the antifouling paint composition in a specific gravity cup with a capacity of 100 mL at 25°C and measuring the mass.

(Painting aptitude)

The smoothness of the coating film after painting was visually confirmed, and coating suitability was evaluated based on the following criteria.

○: The coating film is smooth.

×: Stripes remain in the coating film.

(Paint viscosity change rate)

The type B viscosity (type B viscosity before storage) (mPa·s) of the prepared antifouling paint composition was measured. This antifouling paint composition was placed in a 150 mL glass bottle and stored at 40°C for 30 days. After that, the type B viscosity (type B viscosity after storage at 40°C for 30 days) (mPa·s) of the antifouling paint composition was measured, and the paint viscosity change rate (%) was calculated using the following formula.

Paint viscosity change rate (%) = Type B viscosity after storage at 40℃ for 30 days/Type B viscosity before storage × 100

(Coat film hardness)

The resin composition was applied on a glass substrate with a 500 µm applicator, dried at 25°C for one week to form a coating film, and a test plate was obtained. For the coating film of this test plate, the Martens hardness (HM) was measured using an ultramicro hardness meter (manufactured by Fischer Instruments Co., Ltd., brand name: HM2000). The measurement conditions were dQRST(F)/dt = constant, F (test force) = 10 mN/10 seconds, C (maximum load creep time) = 5 seconds, maximum indentation load of 10 mN, and maximum indentation depth of 6 μm. Martens hardness (HM) was measured at three different locations on the same coating film, their average value was taken as the coating film hardness, and evaluated based on the following criteria.

◎: Coating film hardness is 10.0N/mm ² or more.

○: Coating film hardness is 5.0 N/mm ² or more and less than 10.0 N/mm ² .

△: Coating film hardness is 1.2 N/mm ² or more and less than 5.0 N/mm ² .

×: Coating film hardness is less than 1.2N/mm ² .

(Water resistance of the coating film of the resin composition)

The resin composition was applied on a glass substrate with a 500 µm applicator, dried at room temperature for one week to form a coating film, and a test plate was obtained. After immersing this test panel in sterilized filtered seawater for 1 month, the test panel was dried at room temperature of 20°C for 1 week. Regarding the degree of whitening, the surface of the coating film of the test panel was visually observed. Evaluation was performed based on the following standards.

◎: Almost no whitening is observed.

○: Very little whitening is observed.

△: Slight whitening is observed.

×: Considerable whitening is observed.

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

A test plate was produced by applying the antifouling paint composition on a glass plate to a dry film thickness of 120 μm. After the test panel was immersed in sterilized filtered seawater for 3 months, the test panel was dried at room temperature of 20°C for 1 week, and the surface of the coating film was observed. Evaluation was performed based on the following standards.

◎: Cracks and peeling are not completely observed.

○: Cracks are partially observed.

△: Cracks and peeling are observed in some areas.

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

(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 so that the dry film thickness was 200 to 300 μm, dried to form a film, and a test plate was obtained. After this test panel was left to stand in the sea within the Seto Inland Sea for 6 months, the ratio of the area to which marine organisms adhered to the total area of the coating film (area to which marine organisms adhered) 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 film consumption test)

The antifouling paint composition was applied to a hard vinyl chloride plate of 50 mm This test plate was installed on a rotating drum installed in seawater and rotated at a peripheral speed of 7.7 m/s (15 knots). This state was maintained for 6 months, and the film thickness (μm) of the coating film 3 months and 6 months after installation was measured. From the measured film thickness, the depleted film thickness (120 ㎛ - measured film thickness) was calculated after 3 months and 6 months, and the value was used as the degree of depletion (after 3 months and 6 months).

The ratio of wasting (㎛) after 3 months to the wasting (㎛) after 6 months (after 3 months/after 6 months) was calculated. The closer this ratio is to 2.0, the less the change in the consumption of the coating film over time is preferable.

The meaning of the abbreviations used in each example below is as follows.

Monomer (M1): 1-butoxyethyl methacrylate (synthetic product synthesized in Production Example M1 described later).

Monomer (M2): 1-isobutoxyethyl methacrylate (synthetic product synthesized in Production Example M2 described later).

Monomer (M3): 1-(cyclohexyloxy)ethyl methacrylate (synthetic product synthesized in Production Example M3 described later).

Monomer (M4): 1-(2-ethylhexyloxy)ethyl methacrylate (synthetic product synthesized in Production Example M4 described later).

Monomer (M5): 2-tetrahydropyranyl methacrylate (synthetic product synthesized in Production Example M5 described later).

FM-0711: Brand name, manufactured by Chisso Co., Ltd. (one-terminal polysiloxane macromonomer in the above formula (m2-3) where v=0, R ^3a to R ^3f =methyl group, w=3, x=10).

X-24-8201: Product name, manufactured by Shin-Etsu Chemical Co., Ltd. (v = 0, R ^3a to R ^3f = methyl group, w = 3, x = 25 in the above formula (m2-3)).

FM-0721: Brand name, manufactured by Chisso Co., Ltd. (v=0 in the above formula (m2-3), R ^3a to R ^3f =methyl group, w=3, x=65).

X-22-174DX: Product name, manufactured by Shin-Etsu Chemical Co., Ltd. (v = 0 in the above formula (m2-3), R ^3a to R ^3f = methyl group, w = 3, reactor equivalent weight 4600 g/mol).

FM-7711: Brand name, manufactured by Chisso Co., Ltd. (l and q = 0, m and o = 3 in the above formula (m2-1), R ^1a to R ^1f = methyl group, n = 10).

FM-7721: Brand name, manufactured by Chisso Co., Ltd. (l and q = 0, m and o = 3 in the above formula (m2-1), R ^1a to R ^1f = methyl group, n = 65).

MMA: Methyl methacrylate.

EA: ethyl acrylate.

2-MTA: 2-methoxyethyl acrylate.

2-MTMA: 2-methoxyethyl methacrylate.

MAA: Methacrylic acid.

TIPX: Triisopropylsilyl acrylate.

Monomer (N1): Ethylenically unsaturated monomer mixture containing a divalent metal (synthetic product synthesized in Production Example N1 described later).

AIBN: 2,2'-azobisisobutyronitrile.

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

Nopmer MSD: Product name, Nichiyu Co., Ltd., α-methylstyrene dimer.

Additive (a): Dispalon (registered trademark) 4200-20 (manufactured by Kusumoto Kasei Co., Ltd., polyethylene oxide wax).

Additive (b): Dispalon A603-20X (manufactured by Kusumoto Kasei Co., Ltd., polyamide wax).

Additive (c): Toyopalax (registered trademark) 150 (manufactured by Tosoh Co., Ltd., chlorinated paraffin).

KF-6016: Product name, manufactured by Shinetsu Chemical Co., Ltd., polyether-modified silicone oil.

ST-114PA: Product name, manufactured by Toray and Dow Corning, polyether-modified silicone oil.

FZ209: Product name, Toray/Dow Corning, methylphenyl silicone oil.

KF-56: Product name, manufactured by Shin-Etsu Chemical Co., Ltd., methylphenyl silicone oil.

Antifouling agent (1): 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile.

Antifouling agent (2): Pyridinetriphenylborane (manufactured by Hokko Chemical Industry Co., Ltd., brand name: PK).

Antifouling agent (3): 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (manufactured by Rohm & Haas, trade name: Cinine (211)).

[Production Example M1]

150.2 parts (1.5 mol) of butyl vinyl ether, 0.24 parts of hydroquinone, and 0.47 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 350 parts of a 20% by mass aqueous potassium carbonate solution. 0.06 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 166.9 parts (0.91 mol) of 1-butoxyethyl methacrylate (monomer (M1)) with a boiling point of 70°C/5 torr (667 Pa).

[Production Example M2]

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 (monomer (M2)) with a boiling point of 60°C/3 torr.

[Production Example M3]

138.8 parts (1.1 mol) of cyclohexyl vinyl ether, 0.28 parts of hydroquinone, and 0.53 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. 220.4 parts (2.5 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. 0.06 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 160.0 parts (0.75 mol) of 1-(cyclohexyloxy)ethyl methacrylate (monomer (M3)) with a boiling point of 92°C/5 torr.

[Production Example M4]

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 (monomer (M4)) with a boiling point of 99°C/3torr.

[Production Example M5]

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 reacted 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 (monomer (M5)) with a boiling point of 76°C/3 torr.

[Production Example N1]

85.4 parts of PGM (propylene glycol methyl ether) and 40.7 parts of zinc oxide were added to a reaction vessel equipped with a stirrer, temperature regulator, and dropping funnel, and the temperature was raised to 75°C while stirring. Subsequently, a mixture containing 43.1 parts of methacrylic acid, 36.1 parts of acrylic acid, and 5 parts of water was added dropwise at a constant rate over 3 hours from the dropping funnel. After further stirring for 2 hours, 36 parts of PGM was added, and a transparent divalent metal atom-containing monomer mixture (monomer (N1)) with a solid content of 44.8% by mass was obtained.

[Production Example B-1]

75 parts of xylene was added to a reaction vessel equipped with a stirrer, temperature regulator, and dropping device, and the temperature was raised to 90°C while stirring. Subsequently, a mixture containing 25 parts of monomer (M2), 20 parts of FM-0711, 35 parts of MMA, 20 parts of EA, and 1.6 parts of AMBN as an initiator was added dropwise at a constant rate over 4 hours from the dropping funnel. After the dropwise addition was completed, 10 parts of xylene was added, and then 2.0 parts of AMBN and 4.0 parts of xylene were added dropwise at a constant rate over 30 minutes. After further stirring for 2 hours, 6.7 parts of isobutyl vinyl ether, 1.3 parts of xylene, and 3 parts of butyl acetate were added to obtain a resin composition B-1 containing a copolymer with a solid content of 51% by mass.

[Production Examples B-2 to B-4, B-11 to B-26, B-32 to B-33]

The types and amounts of monomers and initiators, and the types and amounts of additives (compound (B), basic compound, acidic compound, dehydrating agent) added after polymerization are shown in Tables 1 to 3, and the theoretical solid content is 50% by mass. Resin compositions B-2 to B-4, B-11 to B-26, and B-32 to B-33 were prepared in the same manner as in Production Example B-1, except that the amount of xylene after completion of dropping was adjusted according to the amount of additives. was manufactured.

[Production Examples B-5 to B-10, B-34, B-35]

The type and amount of monomer and initiator, and the type and amount of additives (compound (B), basic compound, acidic compound, dehydrating agent) added after polymerization are as shown in Table 1 or Table 3, and the amount of xylene at the end of dropwise addition. Resin compositions B-5 to B-10, B-34, B were prepared in the same manner as in Production Example B-1, except that omitted and the initial amount of xylene was adjusted according to the amount of additives so that the theoretical solid content was 65% by mass. -35 was prepared.

[Production Examples B-28 to B-31]

The types and amounts of monomers and initiators, and the types and amounts of additives (compound (B), basic compound, acidic compound, dehydrating agent) added after polymerization are as shown in Table 3, and the amount of xylene at the end of dropping is omitted. , Resin compositions B-28 to B-31 were produced in the same manner as Production Example B-1, except that the initial amount of xylene was adjusted according to the amount of additives so that the theoretical solid content was 55% by mass.

[Production Example B-27]

44.4 parts of propylene glycol monomethyl ether acetate was added to a reaction vessel equipped with a stirrer, a temperature regulator, and a dropping device, and the temperature was raised to 90°C while stirring. Subsequently, a mixture containing 30 parts of After the dropwise addition was completed, 2.0 parts of AMBN and 2.0 parts of xylene were added dropwise at a constant rate over 30 minutes. After stirring for 2 hours, 67 parts of isobutyl vinyl ether was added dropwise at a constant rate over 30 minutes, and then stirred for another 15 hours. As a result, the carboxyl group in the

[Production Example B-36]

15 parts of PGM (propylene glycol methyl ether), 65 parts of xylene, and 4 parts of ethyl acrylate were added to a reaction vessel equipped with a stirrer, temperature regulator, and dropping funnel, and the temperature was raised to 100°C while stirring. Subsequently, from the dropping funnel, 24 parts of MMA, 11.3 parts of EA, 50 parts of FM-071, 23.9 parts of monomer (N1), 10 parts of xylene, 1.2 parts of nopmer MSD, 2.5 parts of AIBN, 1 part of AMBN The transparent mixture containing 1 part was added dropwise at a constant rate over 6 hours. After the dropwise addition was completed, 9 parts of xylene were added, then 0.5 part of t-butylperoctoate and 10 parts of xylene were added 4 times at 30-minute intervals, and after stirring for 1 hour, 10.1 parts of xylene were added to obtain a solid content of 45 mass. Resin composition B-36 containing % copolymer was obtained.

Tables 1 to 3 show the properties of the obtained resin compositions B-1 to B-36 (solid content (mass %), type B viscosity, Gardner viscosity, decomposition rate of structure (I) after storage at 40°C for 30 days, included in each resin composition. The evaluation results of the number average molecular weight (Mn) and weight average molecular weight (Mw) of the resulting copolymer and the performance (water resistance, coating film hardness) of the coating film formed from each resin composition were described.

In addition, Production Examples B-1 to B-31 are examples, and Production Examples B-32 to B-36 are comparative examples.

In Tables 1 to 3, the values written in the monomer and initiator columns represent the input amount (parts). Regarding the input amount of monomer (N1), the value shown in parentheses is the input amount in solid content, and the value written above is the input amount in the total amount including the solvent.

Regarding resin composition B-35, since it was adhesive, the coating film hardness could not be measured.

[Examples 1 to 34, Comparative Examples 1 to 5]

According to the formulations shown in Tables 4 to 8, each component was mixed with a high-speed disper to obtain an antifouling paint composition.

The evaluation results of the obtained antifouling paint composition for paint properties (solids content, B-type viscosity, VOC content), coating suitability, paint viscosity change rate, and film performance (stationary antifouling property, water resistance, film consumption test) are shown in Tables 4 to 8.

In Tables 4 to 8, the values written in the composition column represent the blending amount (parts). The compounding amount of the resin composition is the amount of the entire resin composition.

The antifouling paint compositions of Examples 1 to 34 had high solid content and low viscosity, and had good coating suitability. In addition, the viscosity change during storage was small, and from the results of Production Examples B-1, B-5 to B-9, it could be judged that the decomposition rate of structure (I) during storage was low, and storage stability was excellent.

In addition, the coating films of the antifouling paint compositions of Examples 1 to 34 were excellent in stationary antifouling properties and water resistance. This can also be confirmed from the results of Production Examples B-1 to B-31. Additionally, this coating film had an appropriate wear rate.

On the other hand, the coating film of the antifouling paint composition of Comparative Example 1 using a resin composition containing a copolymer with structure (I) and no polysiloxane group had poor stationary antifouling property and water resistance.

The coating film of the antifouling paint composition of Comparative Example 2 containing a copolymer with a higher ratio of structure (I) than that of Comparative Example 1 had improved stationary antifouling property, but decreased water resistance.

The coating film of the antifouling paint composition of Comparative Example 3 containing a copolymer (having a structural unit derived from TIPX) having a triorganosilyloxycarbonyl group as a hydrolyzable structure had poor stationary antifouling property. Additionally, from the results of Production Example B-35, it can be judged that this coating film has a significantly low coating film hardness and is therefore insufficient as a film strength.

From Comparative Example 3, the antifouling paint composition of Comparative Example 5, which includes a copolymer with an increased proportion of triorganosilyloxycarbonyl groups and a lowered proportion of polysiloxane groups, improved the paint viscosity change rate, but the stationary antifouling property of the coating film was still poor. It was poor. Additionally, from the results of Production Example B-34, it can be determined that this coating film has a low coating film hardness and is therefore insufficient in terms of film strength.

The coating film of the antifouling paint composition of Comparative Example 4 containing a copolymer having a structure containing a divalent metal as a hydrolyzable structure had poor water resistance. Additionally, this antifouling paint composition had high viscosity and poor coating suitability.

The (meth)acrylic copolymer and resin composition of the present invention can be used in antifouling paint compositions, antifogging paint compositions, etc., respectively, and can be particularly suitably used in antifouling paint compositions.

Claims (12)

At least one type of structure (I) represented by the following formula (1), the following formula (2), or the following formula (3), and a structure (I) represented by the following formula (i), the following formula (ii), or the following formula (iii) An antifouling paint composition comprising a resin composition comprising a (meth)acrylic copolymer having a polysiloxane group.

^{( Wherein , _} R ³ and R ⁵ each represent an alkyl group, cycloalkyl group or aryl group having 1 to 20 carbon atoms, R ⁴ and R ⁶ each represent an alkylene group having 1 to 10 carbon atoms, n represents 3 to 80, and R ^1b to R ^1e each represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group or a substituted phenoxy group, r and s each represent 0 to 20, R ^2b to R ^2k each represent an alkyl group, and x represents 3 to 80. and R ^3b to R ^3f each represent an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group.) The antifouling paint composition according to claim 1, wherein the (meth)acrylic copolymer has structural units derived from the following monomer (m1) and structural units derived from the following monomer (m2).
Monomer (m1): A monomer having an ethylenically unsaturated bond with at least one type of the above structure (I).
Monomer (m2): A monomer having an ethylenically unsaturated bond with the polysiloxane group. The antifouling paint composition according to claim 1, wherein the decomposition rate of the structure (I) in the (meth)acrylic copolymer after storage at 40°C for 30 days is 20% or less. The antifouling paint composition according to claim 1, further comprising at least one member selected from the group consisting of a compound that reacts with an acid, a basic compound, an acidic compound, and a dehydrating agent. The method according to claim 4, wherein the compound that reacts with the acid is at least one selected from the group consisting of a compound represented by the following formula (31), a compound represented by the following formula (32), and a compound represented by the following formula (33) An antifouling paint composition, which is a compound (B) of the species.

^{( Wherein , _} represents an atom or an alkyl group with 1 to 10 carbon atoms, R ⁹ and R ¹¹ each represent an alkyl group, cycloalkyl group or aryl group with 1 to 20 carbon atoms, R ¹⁰ represents a single bond or an alkylene group with 1 to 9 carbon atoms, R ¹² represents an alkylene group having 1 to 9 carbon atoms.) The antifouling paint composition according to claim 1, further comprising silicone oil. The antifouling paint composition according to claim 1, further comprising an antifouling agent. The method of claim 7, wherein the antifouling agent is copper cuprous oxide, pyridine triphenylborane, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4-bromo-2-(4- An antifouling paint composition comprising at least one member selected from the group consisting of chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile and medetomidine. The antifouling paint composition according to claim 1, further comprising a thermoplastic resin other than the (meth)acrylic copolymer. A method for producing an antifouling paint composition containing a resin composition containing a (meth)acrylic copolymer,
A method for producing an antifouling paint composition, wherein a (meth)acrylic copolymer is obtained by polymerizing a monomer mixture containing the following monomer (m1) and the following monomer (m2).
Monomer (m1): A monomer having at least one type of structure (I) represented by the following formula (1), the following formula (2), or the following formula (3) and an ethylenically unsaturated bond.
Monomer (m2): A monomer having a polysiloxane group and an ethylenically unsaturated bond represented by the following formula (i), (ii), or (iii).

^{( Wherein , _} R ³ and R ⁵ each represent an alkyl group, cycloalkyl group or aryl group having 1 to 20 carbon atoms, R ⁴ and R ⁶ each represent an alkylene group having 1 to 10 carbon atoms, n represents 3 to 80, and R ^1b to R ^1e each represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group or a substituted phenoxy group, r and s each represent 0 to 20, R ^2b to R ^2k each represent an alkyl group, and x represents 3 to 80. and R ^3b to R ^3f each represent an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group.) delete delete