Compounds, polymers and antifouling coating compositions

Abstract

A polymer comprising constituent units from a compound having a weight-average molecular weight of 10,000 or less, comprising two or more constituent units containing hydrolyzable substituents, and having a terminal free radical polymerizable group, wherein the compound is subjected to hydrolysis treatment by heating and stirring in an aqueous solution of p-toluenesulfonic acid, and then neutralized and titrated with a 0.5 mol / L potassium hydroxide solution (ethanol solution), and the solid acid value calculated from the amount of 0.5 mol / L potassium hydroxide solution used until the pale red color of the indicator lasts for 30 seconds is 10 mg KOH / g or more.

Description

Technical Field

[0001] This invention relates to compounds, polymers, and antifouling coating compositions.

[0002] This application claims priority based on Japanese Patent Application No. 2021-058983, filed in Japan on March 31, 2021, the contents of which are incorporated herein by reference. Background Technology

[0003] Antifouling coatings are known to be applied to marine structures and ships to prevent corrosion of parts in contact with seawater and to prevent marine organisms from attaching and causing a decrease in sailing speed.

[0004] As an antifouling coating, self-grinding antifouling coatings are known. Self-grinding antifouling coatings typically contain a hydrolyzable resin and an antifouling agent. The coating film obtained from this antifouling coating undergoes surface renewal (self-grinding) by gradually dissolving in seawater, while the antifouling components are always exposed on the coating surface, thus maintaining a long-term antifouling effect.

[0005] As self-grinding antifouling coatings, for example, hydrolyzable coatings with resins containing 1-(alkoxy) ester groups as the main component have been proposed (Patent Documents 1-3), and hydrolyzable coatings with triorganosilyloxycarbonyl groups as the main component have been proposed (Patent Documents 4 and 5). When a coating film using the above coatings is immersed in seawater, the above functional groups are hydrolyzed to form resin acids, which dissolve in seawater, thereby exhibiting an antifouling effect.

[0006] Prior technology documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 4-103671

[0009] Patent Document 2: Japanese Patent Application Publication No. 5-230280

[0010] Patent Document 3: Japanese Patent No. 6760061

[0011] Patent Document 4: Japanese Patent Application Publication No. 8-269390

[0012] Patent Document 5: Japanese Patent No. 6579413 Summary of the Invention

[0013] The hydrolysis of the three organosilyloxycarbonyl groups is accelerated in (weakly) alkaline aqueous solutions such as seawater, while the hydrolysis of the 1-(alkoxy)ester groups is not accelerated in alkaline aqueous solutions. Therefore, in the prior art, the solubility stability of coatings containing 1-(alkoxy)ester groups in seawater is not sufficient, and a decrease in self-grinding properties has been found due to the reduced dissolution rate.

[0014] Although the antifouling coating compositions in Patent Documents 1-3 improve the solubility of the coating film to some extent, their antifouling effect is sometimes insufficient.

[0015] One object of the present invention is to provide compounds and polymers that can form antifouling coating compositions with excellent antifouling properties, and antifouling coating compositions that can form antifouling coating compositions with excellent antifouling properties. Another object of the present invention is to provide compounds and polymers that can form antifouling coating compositions with excellent solubility, and antifouling coating compositions that can form antifouling coating compositions with excellent solubility.

[0016] The present invention has the following aspects.

[0017] [1] A polymer comprising building blocks derived from a compound,

[0018] The above compounds have a weight-average molecular weight of less than 10,000, contain two or more constituent units with hydrolyzable substituents, and have a terminal radical polymerizable group.

[0019] After hydrolysis of the above compound by heating and stirring in an aqueous solution of p-toluenesulfonic acid, the compound was neutralized and titrated with 0.5 mol / L potassium hydroxide solution (ethanol solution). The solid acid value, calculated from the amount of 0.5 mol / L potassium hydroxide solution used until the pale red color of the indicator lasted for 30 seconds, was ≥10 mg KOH / g.

[0020] [2] According to the polymer described in [1], wherein the proportion of constituent units from the above-mentioned compound is 5% by mass or more relative to the total mass of the polymer.

[0021] [3] A polymer is obtained by copolymerizing a compound containing a polymeric monomer unit having a substituent represented by formula (1), formula (2) or formula (3).

[0022]

[0023] (In the formula, X represents -O-, -S-, or -NR) 11 -, R 11 R represents a hydrogen atom or an alkyl group. 1 and R 2 R represents either hydrogen atoms or alkyl groups having 1 to 10 carbon atoms. 3 and R 5 R represents alkyl, cycloalkyl, or aryl groups with 1 to 20 carbon atoms, respectively. 4 R represents an alkylene group having 1 to 10 carbon atoms. 6 (representing alkylene groups with 2 to 10 carbon atoms)

[0024] [4] According to the polymer described in [3], the proportion of the constituent units of the above-mentioned compound relative to the total mass of the polymer is 10% to 90% by mass.

[0025] [5] A compound represented by the following formula (MM-1).

[0026]

[0027] (In formula (MM-1), X) 1 ~X n Each independently represents a hydrogen atom, a methyl group, or a hydroxymethyl group, R and Y. 1 ~Y n Each independently represents a hydrogen atom, alkyl group, cycloalkyl group, aryl group, heterocyclic group, or substituent containing formula (7), (8), or (9), Y 1 ~Y n Two or more of them are substituents that include formulas (7), (8) or (9), where n represents a natural number of 3 or more, and Z represents a terminal group.

[0028]

[0029] In equations (7), (8), or (9), X represents -O-, -S-, or -NR. 11 -, R 11 R represents a hydrogen atom or an alkyl group. 1 and R 2 Each independently represents an alkyl group having 1 to 10 hydrogen atoms or carbon atoms, R 3 and R 5 Each independently represents an alkyl, cycloalkyl, or aryl group having 1 to 20 carbon atoms, R 4 R represents an alkylene group having 1 to 10 carbon atoms. 6 (representing alkylene groups with 2 to 10 carbon atoms)

[0030] [6] According to the compound described in [5], wherein the terminal group is a hydrogen atom or a group derived from a free radical polymerization initiator.

[0031] [7] The compound according to [5] or [6], wherein the weight-average molecular weight is 2,000 to 1,000,000.

[0032] [8] The compound according to any one of [5] to [7], wherein the proportion of the monomeric unit comprising formula (7), (8) or (9) to the total mass of the above compound is 9% to 80% by mass.

[0033] [9] The compound according to any one of [5] to [8], wherein, relative to the total mass of the compound, the proportion of the constituent units based on the monomer (M) is preferably 1% to 60% by mass, more preferably 20% to 60% by mass, and even more preferably 25% to 55% by mass.

[0034]

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

[0035]

[0036] (In the formula, X represents -O-, -S-, or -NR) 11 -, R 11 R represents an alkyl group having 1 to 9 hydrogen atoms or carbon atoms. 1 and R 2 Each independently represents an alkyl group having 1 to 10 hydrogen atoms or carbon atoms, R 3 and R 5 Each can independently represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R 4 R represents an alkylene group having 1 to 10 carbon atoms. 6 Q represents an alkylene group with 2 to 10 carbon atoms, where Q represents CH2=CH-COO- or CH2=C(CH3)-COO-.

[0037]

[11] The compound according to any one of [5] to

[10] , wherein the monomer (M) is selected from at least one monomer represented by the following structural formula.

[0038]

[0039]

[12] The compound according to any one of [5] to

[11] , wherein it comprises a constituent unit based on monomer (a), wherein the monomer (a) is preferably a (meth)acrylic acid monomer; more preferably a compound represented by the following formula (a1); and even more preferably a compound represented by the following formula (a1), namely R in formula (a1). 41 R is a hydrogen atom or a methyl group. 42 For COOR 45 R 45 Compounds that are alkyl groups having 1 to 5 carbon atoms, alkoxyalkyl groups having 3 to 5 carbon atoms, or cycloalkyl groups having 3 to 6 carbon atoms; particularly preferred are compounds represented by the following formula (a1), i.e., R in formula (a1). 41 R is a hydrogen atom or a methyl group. 42 For COOR 45 R 45Compounds that are alkyl groups having 1 to 3 carbon atoms or alkoxyalkyl groups having 3 to 5 carbon atoms.

[0040] CH2=CR 41 R 42 (a1)

[0041] (where R is in the formula) 41 R represents a hydrogen atom, a methyl group, or a hydroxymethyl group. 42 OR 43 Halogen atoms, COR 44 COOR 45 CN, CONR 46 R 47 or R 48 R 43 ~R 47 Each of these groups independently represents a hydrogen atom, a branched or straight-chain alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 18 carbon atoms, or a heterocyclic group with 5 to 18 carbon atoms. R 48 (This refers to aryl groups with 6 to 18 carbon atoms or heteroaryl groups with 6 to 18 carbon atoms)

[0042]

[13] The compound according to any one of [5] to

[12] , wherein the proportion of the constituent unit based on the monomer (M) to the total (100 mol%) of all constituent units constituting the compound is preferably 10 to 40 mol%, more preferably 20 to 30 mol%.

[0043]

[14] The compound according to any one of [5] to

[13] , wherein the total number of substituents represented by the above formulas (7), (8) and (9) is relative to Y. 1 ~Y n The proportion of the total amount (100 mol%) is preferably 10 to 40 mol%, more preferably 20 to 30 mol%.

[0044]

[15] The compound according to any one of [5] to

[14] , wherein the weight-average molecular weight is preferably 2,000 to 1,000,000, more preferably 2,500 to 100,000, even more preferably 3,000 to 10,000, and even more preferably 4,000 to 6,000.

[0045]

[16] The compound according to any one of [5] to

[15] , wherein the solid acid value is preferably 30 mg KOH / g to 180 mg KOH / g, more preferably 40 mg KOH / g to 150 mg KOH / g, and even more preferably 50 mg KOH / g to 120 mg KOH / g.

[0046]

[17] The compound according to any one of [5] to

[16] , wherein the glass transition temperature (Tg) is preferably -10°C to 90°C, more preferably 10°C to 90°C, and even more preferably 30°C to 90°C.

[0047]

[18] The compound according to any one of [5] to

[17] , wherein the molecular weight dispersion is preferably 1.0 to 4.0, more preferably 1.0 to 3.5, and even more preferably 1.0 to 3.0.

[0048]

[19] The compound according to any one of [5] to

[18] , wherein the solubility parameter (sp) is preferably 5.0 to 12.0, more preferably 6.0 to 11.0, and even more preferably 7.0 to 10.0.

[0049]

[20] A polymer comprising a building block based on any one of [5] to

[19] .

[0050]

[21] According to the polymer of

[20] , wherein the proportion of the constituent units of the compound is 90% by mass or less relative to the total mass of the polymer.

[0051]

[22] The polymer according to any one of [1] to [4],

[20] and

[21] , wherein after the above polymer is subjected to hydrolysis treatment by heating and stirring in an aqueous solution of p-toluenesulfonic acid, it is neutralized and titrated with a 0.5 mol / L potassium hydroxide solution (ethanol solution), and the solid acid value calculated from the amount of 0.5 mol / L potassium hydroxide solution used until the pale red color of the indicator lasts for 30 seconds is less than 150 mg KOH / g.

[0052]

[23] The polymer according to any one of [1] to [4] and

[20] to

[22] is a (meth)acrylic polymer.

[0053]

[24] According to any of the polymers [1] to [4] and

[20] to

[23] , wherein the ratio of the constituent units based on the above compounds to the total of all constituent units constituting the polymer is preferably 10% to 60% by mass, more preferably 15% to 50% by mass, and even more preferably 20% to 40% by mass.

[0054]

[25] The polymer according to any one of [1] to [4] and

[20] to

[24] , wherein it comprises a constituent unit based on monomer (a), wherein the monomer (a) is preferably a (meth)acrylic acid monomer; more preferably a compound represented by the following formula (a1); and even more preferably a compound represented by the following formula (a1), namely R in formula (a1). 41 R is a hydrogen atom or a methyl group. 42For COOR 45 R 45 Compounds that are alkyl groups having 1 to 5 carbon atoms, alkoxyalkyl groups having 3 to 5 carbon atoms, or cycloalkyl groups having 3 to 6 carbon atoms; particularly preferred are compounds represented by the following formula (a1), i.e., R in formula (a1). 41 R is a hydrogen atom or a methyl group. 42 For COOR 45 R 45 It is an alkyl group having 1 to 3 carbon atoms or an alkoxyalkyl group having 3 to 5 carbon atoms.

[0055] CH2=CR 41 R 42 (a1)

[0056] (where R is in the formula) 41 R represents a hydrogen atom, a methyl group, or a hydroxymethyl group. 42 OR 43 Halogen atoms, COR 44 COOR 45 CN, CONR 46 R 47 or R 48 R 43 ~R 47 Each of these groups independently represents a hydrogen atom, a branched or straight-chain alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 18 carbon atoms, or a heterocyclic group with 5 to 18 carbon atoms. R 48 (This refers to aryl groups with 6 to 18 carbon atoms or heteroaryl groups with 6 to 18 carbon atoms)

[0057]

[26] According to the polymer described in

[25] , the ratio of the constituent unit based on the monomer (a) to the total of all constituent units constituting the polymer is preferably 40% to 90% by mass, more preferably 50% to 85% by mass, and even more preferably 60% to 80% by mass.

[0058]

[27] The polymer according to any one of [1] to [4] and

[20] to

[26] , wherein the polymer, in addition to the monomer-based (M) constituent units included in the constituent units of the compound, also includes constituent units based on the monomer (M).

[0059] The ratio of monomer-based constituent units (excluding monomer-based constituent units included in the constituent units based on the above-mentioned compound) to the total of all constituent units constituting the above-mentioned polymer is preferably 60% to 0% by mass, more preferably 45% to 0% by mass, and even more preferably 30% to 0% by mass.

[0060]

[28] The polymer according to any one of [1] to [4] and

[20] to

[27] , wherein the solid acid value is preferably 20 mg KOH / g to 150 mg KOH / g, more preferably 30 mg KOH / g to 90 mg KOH / g, and even more preferably 30 mg KOH / g to 60 mg KOH / g.

[0061]

[29] The polymer according to any one of [1] to [4] and

[20] to

[28] , wherein the glass transition temperature (Tg) is preferably -10°C to 70°C, more preferably 0°C to 50°C, and even more preferably 10°C to 30°C.

[0062]

[30] The polymer according to any one of [1] to [4] and

[20] to

[29] , wherein the weight-average molecular weight (Mw) is preferably 2,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 9,000 to 20,000.

[0063]

[31] The polymer according to any one of [1] to [4] and

[20] to

[30] , wherein the molecular weight dispersion is preferably 1.0 to 4.0, more preferably 1.0 to 3.5, and even more preferably 1.0 to 3.0.

[0064]

[32] The polymer according to any one of [1] to [4] and

[20] to

[31] , wherein the solubility parameter (sp) is preferably 5.0 to 12.0, more preferably 6.0 to 11.0, and even more preferably 7.0 to 10.0.

[0065]

[33] An antifouling coating composition comprising any one of the compounds described in [5] to

[19] .

[0066]

[34] An antifouling coating composition comprising any one of the polymers described in [1] to [4] and

[20] to

[32] .

[0067]

[35] A method for manufacturing a (meth)acrylic acid copolymer, wherein a compound having a weight average molecular weight of 10,000 or less, comprising two or more constituent units containing hydrolyzable substituents and having free radical polymerizable groups at the ends, is polymerized with a monomer having an olefinic unsaturated group (wherein, the above-mentioned compound is not included).

[0068] According to one aspect of the present invention, compounds and polymers capable of forming antifouling coating compositions with excellent antifouling properties, as well as antifouling coating compositions capable of forming antifouling coating compositions with excellent antifouling properties, can be provided. Additionally, according to one aspect of the present invention, compounds and polymers capable of forming antifouling coating compositions with excellent solubility, as well as antifouling coating compositions capable of forming antifouling coating compositions with excellent solubility, can be provided. Detailed Implementation

[0069] In this specification, "constituent unit" refers to a constituent unit derived from the aforementioned monomers through polymerization of the monomers, or a constituent unit obtained by processing the polymer to convert a portion of the constituent unit into other structures.

[0070] "Monomer" refers to a compound that has polymerizability (polymerizable monomer).

[0071] "(Meth)acrylic monomers" refers to monomers containing a (meth)acryloyl group.

[0072] "(Methacryl)acryloyl" indicates acryloyl or methacryloyl. The same applies to "(meth)acrylate", "(meth)acrylic acid", and "(meth)acrylamide".

[0073] [Compound]

[0074] One aspect of the compound of the present invention (hereinafter also referred to as "compound (MM)") is a compound comprising two or more monomer (M) based constituent units (hereinafter also referred to as "monomer (M) units") and having a free radical polymerizable group at the end.

[0075] The compound (MM) preferably further comprises a constituent unit (hereinafter also referred to as "monomer (a)") based on a monomer (hereinafter also referred to as "monomer (a)") other than the compound (MM) and the monomer (M).

[0076] Compounds (MMs) can be used as monomers for manufacturing polymers, also known as macromonomers.

[0077] <M-unit>

[0078] The monomer (M) unit is hydrolyzable.

[0079] "Hydrolyticity" means that the reaction of the constituent unit of monomer (M) with water yields decomposition products derived from monomer (M). A compound of one aspect of the invention containing the monomer (M) unit indicates that it can be hydrolyzed when subjected to a hydrolysis treatment in an aqueous solution of p-toluenesulfonic acid, for example, under conditions of heating and stirring at 70°C or higher for more than 1 hour. Whether the monomer (M) unit has been hydrolyzed can be confirmed by identifying the functional groups (carboxyl groups, etc.) generated by the hydrolysis.

[0080] The monomer (M) unit preferably includes a structure that can be hydrolyzed when the compound (MM) is subjected to the above-described hydrolysis treatment. For example, structures represented by any of formulas (1) to (6) can be cited as structures capable of hydrolysis during the above-described hydrolysis treatment. Hereinafter, the structure represented by formula (1) will also be referred to as "structure (1)", and structures represented by other formulas will sometimes be described similarly. These structures undergo hydrolysis during the above-described hydrolysis treatment to generate a carboxyl group.

[0081] Of the above, from the perspective of being able to be used in conjunction with cuprous oxide and to accelerate hydrolysis under acidic conditions, the structure represented by any one of formulas (1) to (3) is preferred.

[0082]

[0083] -COO-M-OCO-(5)

[0084] -COO-M-R 10 (6)

[0085] (In the formula, X represents -O-, -S-, or -NR) 11 -, R 11 R represents a hydrogen atom or an alkyl group. 1 and R 2 Each independently represents an alkyl group having 1 to 10 hydrogen atoms or carbon atoms, R 3 and R 5 Each independently represents an alkyl, cycloalkyl, or aryl group having 1 to 20 carbon atoms, R 4 R represents an alkylene group having 1 to 10 carbon atoms. 6 R represents an alkylene group having 2 to 10 carbon atoms. 7 ~R 9 Each group independently represents a hydrocarbon group with 1 to 20 carbon atoms, where M represents Zn, Cu, Mg, or Ca, and R represents... 10 (Indicates organic acid residues other than (meth)acryloyloxy)

[0086] In formula (1), X can be -O- (ether oxygen atom), -S- (thioether sulfur atom), or -NR-. 11 Any one of them. R 11 The alkyl group preferably has 1 to 10 carbon atoms. X is preferably -O-.

[0087] As R 1 and R 2 Alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, 2-ethylhexyl, etc.

[0088] R 1 and R 2The alkyl group in the alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3, and even more preferably 1 or 2.

[0089] As R 1 and R 2 Preferred combinations include combinations of hydrogen atoms and methyl groups, combinations of methyl groups with methyl groups, combinations of hydrogen atoms and alkyl groups having 2 to 10 carbon atoms (hereinafter also referred to as "long-chain alkyl groups"), combinations of methyl groups with long-chain alkyl groups, combinations of hydrogen atoms with hydrogen atoms, and combinations of long-chain alkyl groups with long-chain alkyl groups. Among these, the combination of hydrogen atoms and methyl groups is preferred from the perspective of hydrolysis.

[0090] As R 3 Alkyl groups having 1 to 20 carbon atoms include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, etc.

[0091] As a cycloalkyl group, a cycloalkyl group with 4 to 8 carbon atoms is preferred, such as cyclohexyl and cyclopentyl.

[0092] As an aryl group, aryl groups with 6 to 20 carbon atoms are preferred, such as phenyl and naphthyl groups.

[0093] As R 3 Preferably, alkyl or cycloalkyl groups have 1 to 10 carbon atoms.

[0094] R 3 The alkyl, cycloalkyl, and aryl groups in the compound can each have substituents. When substituents are present, the number of substituents can be one or more. Examples of substituents include cycloalkyl, aryl, alkoxy, alkanoyloxy, aralkyl, and acetoxy groups.

[0095] Among the substituents, cycloalkyl and aryl groups can be listed as having a relationship with R. 3 The same group as cycloalkyl and aryl in the compound. Examples of alkoxy groups include methoxy, ethoxy, propoxy, and butoxy. Examples of alkanoyloxy groups include acetoxy. Examples of aralkyl groups include benzyl.

[0096] X in equation (2) is the same as X in equation (1), and the preferred method is also the same.

[0097] As R 4 The alkylene group having 1 to 10 carbon atoms is, for example, methylene, ethylene, propylene, butylene, and hexane. The alkylene group preferably has 2 to 7 carbon atoms, more preferably 3 to 4.

[0098] Alkyl groups can have substituents. When substituents are present, the number of substituents can be one or more. Examples of substituents that can be present in alkyl groups include those related to R. 3 The substituents are the same groups as those in the original text.

[0099] X in equation (3) is the same as X in equation (1), and the preferred method is also the same.

[0100] R 5 R in equation (1) 3 Similarly, the preferred method is also the same.

[0101] As R 6 The alkylene group having 2 to 10 carbon atoms is, for example, ethylene, propyleneene, butylene, and hexaneene. The alkylene group preferably has 2 to 7 carbon atoms, more preferably 3 to 4.

[0102] As R in equation (4) 7 ~R 9 The hydrocarbon groups in the name include, for example, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl and other alkyl groups; cyclohexyl and other cycloalkyl groups; and aryl groups such as phenyl and naphthyl.

[0103] Alkyl, cycloalkyl, and aryl groups can each have substituents.

[0104] Substituents that can be present in an alkyl group include, for example, halogen atoms, acyl groups, nitro groups, and amino groups. Substituents that can be present in a cycloalkyl or aryl group include, for example, halogen atoms, alkyl groups, acyl groups, nitro groups, and amino groups. The number of carbon atoms in the alkyl group that is the substituent is preferably about 1 to 18.

[0105] R 7 ~R 9 They can be the same as or different from each other.

[0106] From the perspective of obtaining a coating film with a stable polishing rate (grinding speed) and maintaining anti-fouling performance stably over a long period of time, R is preferred. 7 ~R 9 At least one of them is isopropyl, and preferably all of them are isopropyl.

[0107] In equation (5), Zn or Cu is preferred as M.

[0108] In equation (6), Zn or Cu is preferred as M.

[0109] R 10The organic acid residue refers to the remainder obtained by removing one proton from an organic acid (e.g., the remainder obtained by removing a proton from the carboxyl group of a carboxylic acid), which is ionically bonded to M to replace that proton.

[0110] As an organic acid, carboxylic acids are preferred, such as monochloroacetic acid, monofluoroacetic acid, acetic acid, propionic acid, octanoic acid, tert-carbonic acid (Versatic Acid), isostearic acid, palmitic acid, cresolic acid, α-naphthoic acid, β-naphthoic acid, benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinoline carboxylic acid, nitrobenzoic acid, nitronaphthoic acid, pyruvic acid, naphthenic acid, rosin acid, hydrogenated rosin acid, and other monocarboxylic acids.

[0111] As R 10 From the perspective of obtaining a durable coating that can prevent cracking and peeling over a long period of time, fatty acid residues (aliphatic monocarboxylic acid residues) with 1 to 20 carbon atoms are preferred.

[0112] As a monomer (M), it is preferred to be a monomer containing at least one structure selected from structure (1), structure (2), structure (3), structure (4), structure (5) and structure (6) and a free radical polymerizable group.

[0113] From the perspective of reducing the viscosity when a polymer containing a compound-based (MM) constituent unit is dissolved in an organic solvent, the monomer (M) is preferably a monofunctional monomer having a free radical polymerizable group.

[0114] As a free radical polymerizable group, the same group as the free radical polymerizable group possessed by compound (MM) can be cited.

[0115] As a free radical polymerizable group, it is preferable to have a group containing an olefinic unsaturated bond (polymerizable carbon-carbon double bond). When the monomer (M) contains an olefinic unsaturated bond, the monomer (M) unit has a structure in which the olefinic unsaturated bond of the monomer (M) is broken into a single bond.

[0116] As a free radical polymerizable group, (meth)acryloyl group is particularly preferred. That is, the compound (MM) is particularly preferred to be a (meth)acrylic acid monomer.

[0117] As a monomer (M), more preferably a monomer (hereinafter also referred to as "monomer (M1)") comprising at least one structure selected from structure (1), structure (2) and structure (3) and a free radical polymerizable group, a monomer (hereinafter also referred to as "monomer (M2)") comprising structure (4) and a free radical polymerizable group, a monomer (hereinafter also referred to as "monomer (M3)") comprising structure (5) and a free radical polymerizable group, or a monomer (hereinafter also referred to as "monomer (M4)") comprising structure (6) and a free radical polymerizable group.

[0118] Among these, monomer (M1) is particularly preferred from the perspective of its ability to be used in conjunction with cuprous oxide and to accelerate hydrolysis under acidic conditions.

[0119] As a monomer (M1), for example, monomers represented by the following formulas (M1-1), (M1-2) or (M1-3) can be cited.

[0120]

[0121] (where X and R are in the formula) 1 ~R 6 With X and R mentioned above 1 ~R 6 The meanings are the same; Q represents CH2=CH-COO-, CH2=C(CH3)-COO-, and CHR. X =CH-COO-、CH2=C(CH2R) X )-COO- or CH2=CR X -CH2COO-, R X (representing the above structures (1), (2), (3) or alkyl ester groups)

[0122] In Q, CH2=CH-COO- is an acryloxy group, and CH2=C(CH3)-COO- is a methacryloyloxy group.

[0123] CH(CH3)=CH-COO- is a crotonyloxy group (the olefinic unsaturated bond is trans) or an isocrotyloxy group (the olefinic unsaturated bond is cis).

[0124] CHR X =CH-COO- is a maleic oxy group (cis-type olefinic unsaturated bond) or fumarooxy group (trans-type olefinic unsaturated bond) in which the carboxyl group is replaced by a maleic oxy group (cis-type olefinic unsaturated bond) or a fumarooxy group (trans-type olefinic unsaturated bond) in which the carboxyl group is replaced by a maleic oxy group (cis-type olefinic unsaturated bond) or

[0125] R X The alkyl ester group in it is composed of -COOR X1 Indicates. R X1 Indicates alkyl group. As R X1 Alkyl groups, preferably alkyl groups having 1 to 6 carbon atoms, and particularly preferably methyl groups.

[0126] In Q, CHR X =CH-COO-、CH2=C(CH2R) X )-COO- or CH2=CR X In the case of -CH2COO-, R in Q X Preferably, it has the same structure as the group bonded to Q, or it is an alkyl ester group. For example, in the case of compounds represented by formula (M1-1), R in Q...X The preferred structure is (1)(-CR) 1 R 2 -XR 3 ) or alkyl ester group.

[0127] CH2=C(CH2R X )-COO- or CH2=CR X -CH2COO- is an itaconicoyloxy group in which the carboxyl group is replaced with a structure (1), structure (2), structure (3) or an alkyl ester group. R X With the above R X same.

[0128] As for Q, CH2=CH-COO- or CH(CH3)=CH-COO- are preferred.

[0129] As a specific example of a monomer (M1), the following examples can be cited.

[0130]

[0131] <Single (a) unit>

[0132] As monomer (a), any compound capable of copolymerizing with monomer (M) is acceptable; for example, compounds having radical polymerizable groups can be cited (excluding compounds (MM) and monomer (M)). Preferably, the radical polymerizable groups of monomer (a) are groups having olefinic unsaturated bonds.

[0133] As monomer (a), various monomers can be used, for example:

[0134] Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, hexadecyl (meth)acrylate, nonyl (meth)acrylate, (meth)acrylate Isononyl acrylate, phenyl acrylate, benzyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 3,5,5-trimethylcyclohexyl acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, dicyclopentenoxyethyl acrylate, terpene acrylates or their derivatives, hydrogenated rosin acrylates or their derivatives, docosyl acrylate and other (meth)acrylates containing hydrocarbon groups;

[0135] 2-Hydroxyethyl methacrylate, 2-Hydroxypropyl methacrylate, 2-Hydroxybutyl methacrylate, 3-Hydroxybutyl methacrylate, 4-Hydroxybutyl methacrylate, glyceryl methacrylate, and other hydroxyl-containing methacrylates.

[0136] Vinyl monomers containing carboxyl groups, including (meth)acrylic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxypropyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, monomethyl maleate, monoethyl maleate, monooctyl maleate, monomethyl itaconic acid, monoethyl itaconic acid, monobutyl itaconic acid, monooctyl itaconic acid, monomethyl fumaric acid, monoethyl fumaric acid, monobutyl fumaric acid, monooctyl fumaric acid, and monoethyl citraconic acid.

[0137] Vinyl monomers containing anhydride groups, such as maleic anhydride and itaconic anhydride;

[0138] Dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, dibutyl itaconic acid, diperfluorocyclohexyl fumarate and other unsaturated dicarboxylic acid diester monomers.

[0139] Vinyl monomers containing epoxy groups, such as glycidyl methacrylate, α-ethyl glycidyl methacrylate, and 3,4-epoxybutyl methacrylate.

[0140] Vinyl monomers containing amino groups, such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate;

[0141] Vinyl monomers containing amide groups, such as (meth)acrylamide, N-tert-butyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-isopropylacrylamide, hydroxyethylacrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, diacetone acrylamide, maleamide, and maleimide.

[0142] Vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, (meth)acrylonitrile, vinyl acetate, and vinyl propionate;

[0143] Divinylbenzene, ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, allyl acrylate, triallyl cyanurate, diallyl maleate, polypropylene glycol diallyl ether, N,N'-methylenebis(meth)acrylamide and other multifunctional vinyl monomers;

[0144] Acryloylmorpholine, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, n-butoxyethyl methacrylate, isobutoxyethyl methacrylate, tert-butoxyethyl methacrylate, ethoxyethyl methacrylate, phenoxyethyl methacrylate, nonylphenoxyethyl methacrylate, 3-methoxybutyl methacrylate, acetoxyethyl methacrylate, "PLACCEL FM" (caprolactone addition monomer manufactured by Daicel Chemical Co., Ltd., trade name), "BLEMMER PME-100" (methoxy polyethylene glycol methacrylate (a substance with a 2-chain ethylene glycol) manufactured by Nippon Oil Co., Ltd., trade name), "BLEMMER PME-200" (methoxy polyethylene glycol methacrylate (a substance with a 4-chain ethylene glycol) manufactured by Nippon Oil Co., Ltd., trade name), "BLEMMER PME-400 (Nippon Oil Co., Ltd. methoxy polyethylene glycol methacrylate (a substance with a 9-chain ethylene glycol), trade name), BLEMMER 50POEP-800B (Nippon Oil Co., Ltd. octyloxy polyethylene glycol-polypropylene glycol-methacrylate (a substance with an 8-chain ethylene glycol and a 6-chain propylene glycol), trade name), BLEMMER20ANEP-600 (Nippon Oil Co., Ltd. nonylphenoxy (ethylene glycol-polypropylene glycol) monoacrylate, trade name), BLEMMER AME-100 (Nippon Oil Co., Ltd., trade name), BLEMMER AME-200 (Nippon Oil Co., Ltd., trade name), BLEMMER 50AOEP-800B (Nippon Oil Co., Ltd., trade name), Silaplane FM-0711 (JNC Co., Ltd., trade name), Silaplane FM-0721 (manufactured by JNC Corporation, trade name), Silaplane FM-0725 (manufactured by JNC Corporation, trade name), Silaplane TM-0701 (manufactured by JNC Corporation, trade name), Silaplane TM-0701T (manufactured by JNC Corporation, trade name), X-22-174ASX (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name), X-22-174DX (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name), X-22-2426 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name), X-22-2475 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name) and other (meth)acrylates with ether or ester groups as side groups (excluding monomer (M));

[0145] Halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and trifluorochloroethylene;

[0146] 2-Isocyanate ethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluorophenyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, 3-(perfluorobutyl)-2-hydroxypropyl methacrylate, 2-(perfluorohexyl)ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl methacrylate, 2-(perfluoro)acrylate 2,3,3-Tetrafluoropropyl ester, (meth)acrylic acid 1H,1H,5H-octafluoropentyl ester, (meth)methacrylic acid 1H,1H,5H-octafluoropentyl ester, (meth)acrylic acid 1H,1H,2H,2H-tridecylfluorooctyl ester, (meth)acrylic acid 1H-1-(trifluoromethyl)trifluoroethyl ester, (meth)acrylic acid 1H,1H,3H-hexafluorobutyl ester, (meth)acrylic acid 1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl ester, etc., fluorine-containing monomers (excluding haloalkenes);

[0147] 4-Methacryloxybenzophenone, ethyl 2-isocyanate (meth)acrylate, etc. These monomers can be used alone or in combination of two or more.

[0148] At least a portion of monomer (a) is preferably a (meth)acrylic acid monomer.

[0149] As monomer (a), the preferred compound is one represented by the following formula (a1).

[0150] CH2=CR 41 R 42 (a1)

[0151] (where R is in the formula) 41 R represents a hydrogen atom, a methyl group, or a hydroxymethyl group. 42 OR 43 Halogen atoms, COR 44 COOR 45 CN, CONR 46 R 47 or R 48 R 43 ~R 47 Each independently represents a hydrogen atom, alkyl, cycloalkyl, aryl, or heterocyclic group, R 48 (Indicates aryl or heteroaryl)

[0152] As R 43 ~R 47Alkyl groups, for example, can be branched or straight-chain alkyl groups having 1 to 20 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl.

[0153] As R 43 ~R 47 The cycloalkyl group can be monocyclic or polycyclic, for example, cycloalkyl groups with 3 to 20 carbon atoms. Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclic [2.2.1]heptyl, cyclooctyl, and adamantyl.

[0154] As R 43 ~R 47 The aryl group in the aryl group can be exemplified by aryl groups having 6 to 18 carbon atoms. Specific examples of aryl groups include phenyl and naphthyl groups.

[0155] As R 43 ~R 47 The heterocyclic group in the group can be exemplified by heterocyclic groups having 5 to 18 carbon atoms. Specific examples of heterocyclic groups include heterocyclic groups containing oxygen atoms such as γ-butyrolactone and ε-caprolactone, heterocyclic groups containing nitrogen atoms such as pyridyl, carbazole, pyrrolylalkyl, and pyrrolidone, and morpholino.

[0156] R 43 ~R 47 In this context, alkyl, cycloalkyl, aryl, and heterocyclic groups can each have substituents.

[0157] Substituents that can be present in an alkyl group include, for example, those selected from aryl, -COOR, etc. 51 , cyano, -OR 52 、-NR 53 R 54 -CONR 55 R 56 At least one of the following: halogen atom, allyl group, epoxy group, silyloxy group, and group exhibiting hydrophilic or ionic properties.

[0158] Substituents that can be present as cycloalkyl, aryl, or heterocyclic groups include, for example, those selected from alkyl, aryl, and -COOR groups. 51 , cyano, -OR 52 、-NR 53 R 54 -CONR 55 R 56At least one of the following: halogen atom, allyl group, epoxy group, silyloxy group, and group exhibiting hydrophilic or ionic properties.

[0159] Among the substituents mentioned above, alkyl and aryl groups can be listed as having the same meaning as R. 43 ~R 47 The same group as alkyl and aryl in it.

[0160] -COOR 51 -OR 52 、-NR 53 R 54 -CONR 55 R 56 In the middle, R 51 ~R 56 Each can independently represent a hydrogen atom, alkyl group, cycloalkyl group, or aryl group. R 51 ~R 56 The alkyl, cycloalkyl, and aryl groups in R can be the same as the alkyl, cycloalkyl, and aryl groups in R.

[0161] As -COOR 51 R 51 Preferably, it contains hydrogen atoms or alkyl groups. That is, -COOR 51 Carboxyl or alkoxycarbonyl groups are preferred. For example, methoxycarbonyl can be cited as an alkoxycarbonyl group.

[0162] As -OR 52 R 52 Preferably, it contains hydrogen atoms or alkyl groups. That is, -OR 52 Hydroxyl or alkoxy groups are preferred. Examples of alkoxy groups include those with 1 to 12 carbon atoms, and methoxy groups are specific examples.

[0163] As -NR 53 R 54 Examples include amino, monomethylamino, and dimethylamino.

[0164] As -CONR 55 R 56 Examples include carbamoyl (-CONH2), N-methylcarbamoyl (-CONHCH3), and N,N-dimethylcarbamoyl (dimethylamido: -CON(CH3)2).

[0165] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0166] Examples of groups that exhibit hydrophilicity or ionicity include, for example, alkali metal salts of carboxyl groups or alkali metal salts of sulfonyl groups, poly(olefin) groups such as poly(olefin) groups and quaternary ammonium groups.

[0167] As R 43 ~R 47 Preferably, it is an alkyl or cycloalkyl group. As a cycloalkyl group, it is preferred to be a cycloalkyl group without substituents or a cycloalkyl group with alkyl as a substituent.

[0168] As R 43 ~R 47 From the perspective of ease of acquisition, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl and octyl are more preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, isobornyl and adamantyl are even more preferred.

[0169] R 48 Aryl groups in R can be cited as examples. 43 ~R 47 The same aryl group as the aryl group in the text.

[0170] Examples of heteroaryl groups include pyridyl and carbazolyl.

[0171] Aryl and heteroaryl groups can each have substituents. Examples of substituents include carboxylic acid groups, carboxylic acid ester groups, epoxy groups, hydroxyl groups, alkoxy groups, primary amino groups, secondary amino groups, tertiary amino groups, isocyanate groups, sulfonic acid groups, halogen atoms, and allyl groups.

[0172] Examples of carboxylic acid ester groups, alkoxy groups, primary amino groups, secondary amino groups, tertiary amino groups, alkyl groups, aryl groups, and halogen atoms can be given as above.

[0173] As monomer (a), it is preferably a (meth)acrylic acid monomer, and R in formula (a1) is preferred. 41 It is a hydrogen atom or a methyl group and R 42 For COOR 45 Compounds.

[0174] As R 45 Preferably, it is an alkyl or cycloalkyl group. As a cycloalkyl group, it is preferred to be a cycloalkyl group without substituents or a cycloalkyl group with alkyl as a substituent.

[0175] As R 45 For ease of acquisition, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl or octyl are preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, isobornyl or adamantyl are more preferred.

[0176] <Proportions of each constituent unit>

[0177] The mass ratio of monomer (M) units to the total mass of compound (MM) is preferably 1% to 80% by mass, more preferably 20% to 60% by mass, and even more preferably 25% to 50% by mass. If the proportion of monomer (M) units is above the lower limit mentioned above, there is a tendency for the hydrolyticity of compound (MM) to be improved and the antifouling properties of the coating to be better; if it is below the upper limit mentioned above, there is a tendency for the crack resistance of the coating to be better.

[0178] The proportion of monomer (M1) units relative to the total 100 mol% of all constituent units constituting the compound (MM) is preferably 10 to 40 mol%, more preferably 20 to 30 mol%. If the proportion of monomer (M1) units is above the lower limit mentioned above, there is a tendency for improved hydrolytic properties of monomer (M1) units and better antifouling properties of the coating film; if it is below the upper limit mentioned above, there is a tendency for better crack resistance of the coating film.

[0179] <Free radical polymerizable groups>

[0180] As a free radical polymerizable group, it is preferable to have a group containing an olefinic unsaturated bond. Examples of groups containing an olefinic unsaturated bond include CH2=C(COOR)-CH2-, (meth)acryloyl, 2-(hydroxymethyl)acryloyl, vinyl, etc.

[0181] In CH2=C(COOR)-CH2-, R represents a hydrogen atom, alkyl, cycloalkyl, aryl, heterocyclic group, or 1-alkoxy group.

[0182] As a 1-alkoxy group, for example, the group represented by the following formulas (7), (8) or (9) can be cited.

[0183]

[0184] (where R is in the formula) 1 ~R 6 With the above R 1 ~R 6 (Same meaning)

[0185] As for the amount of free radical polymerizable groups introduced into the compound (MM), it is preferable to have 0.1 to 1.5 per molecular chain. If it is 0.1 or more, the antifouling properties become good, and if it is 1.5 or less, the viscosity of the composition containing the polymer is low enough to obtain a coating composition with low VOCs.

[0186] Examples of alkyl groups include branched or straight-chain alkyl groups having 1 to 20 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl.

[0187] As a cycloalkyl group, it can be monocyclic or polycyclic, for example, cycloalkyl groups with 3 to 20 carbon atoms can be mentioned. Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclic [2.2.1]heptyl, cyclooctyl and adamantyl.

[0188] Examples of aryl groups include those with 6 to 18 carbon atoms. Specific examples of aryl groups include phenyl and naphthyl groups.

[0189] Examples of heterocyclic groups include, for example, heterocyclic groups with 5 to 18 carbon atoms. Specific examples of heterocyclic groups include heterocyclic groups containing oxygen atoms such as γ-butyrolactone and ε-caprolactone, heterocyclic groups containing nitrogen atoms such as pyridyl, carbazole, pyrrolylalkyl, and pyrrolidone, and morpholinoyl.

[0190] In R, alkyl, cycloalkyl, aryl, and heterocyclic groups can each have substituents.

[0191] As substituents, examples include those selected from alkyl groups (excluding cases where R is an alkyl group with a substituent), aryl groups, and -COOR groups. 51 , cyano, -OR 52 、-NR 53 R 54 -CONR 55 R 56 At least one of the following: halogen atom, allyl group, epoxy group, silyloxy group, and group exhibiting hydrophilic or ionic properties.

[0192] Among the substituents mentioned above, alkyl and aryl groups can be the same as the alkyl and aryl groups in R.

[0193] -COOR 51 -OR 52 、-NR 53 R 54 -CONR 55 R 56 In the middle, R 51 ~R 56 Each can independently represent a hydrogen atom, alkyl group, cycloalkyl group, or aryl group. R 51 ~R 56The alkyl, cycloalkyl, and aryl groups in R can be the same as the alkyl, cycloalkyl, and aryl groups in R.

[0194] As -COOR 51 R 51 Preferably, it contains hydrogen atoms or alkyl groups. That is, -COOR 51 Carboxyl or alkoxycarbonyl groups are preferred. For example, methoxycarbonyl can be cited as an alkoxycarbonyl group.

[0195] As -OR 52 R 52 Preferably, it contains hydrogen atoms or alkyl groups. That is, -OR 52 Hydroxyl or alkoxy groups are preferred. Examples of alkoxy groups include those with 1 to 12 carbon atoms, and methoxy groups are specific examples.

[0196] As -NR 53 R 54 Examples include amino, monomethylamino, and dimethylamino.

[0197] As -CONR 55 R 56 Examples include carbamoyl (-CONH2), N-methylcarbamoyl (-CONHCH3), and N,N-dimethylcarbamoyl (dimethylamido: -CON(CH3)2).

[0198] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0199] Examples of groups that exhibit hydrophilicity or ionicity include, for example, alkali metal salts of carboxyl groups or alkali metal salts of sulfonyl groups, poly(olefin) groups such as poly(olefin) groups and quaternary ammonium groups.

[0200] R is preferably an alkyl or cycloalkyl group. As a cycloalkyl group, a cycloalkyl group without substituents or a cycloalkyl group with alkyl substituents is preferred.

[0201] As R, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, and octyl are preferred for ease of acquisition, and methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, isobornyl, and adamantyl are more preferred.

[0202] As a type of compound (MM), examples include a main chain portion consisting of two or more monomer (M) units and one or more monomer (a) units, or consisting of three or more monomer (M) units, and a free radical polymerizable group bonded to one or both ends of the main chain portion. In the case where the free radical polymerizable group is bonded to one end of the main chain portion, a terminal group other than the free radical polymerizable group is bonded to the other end.

[0203] From the perspective of productivity and coating performance, the compound represented by the following formula (MM-1) is preferred as the compound (MM).

[0204]

[0205] (where X) 1 ~X n Each independently represents a hydrogen atom, a methyl group, or a hydroxymethyl group, R and Y. 1 ~Y n Each of the following groups independently represents a hydrogen atom, alkyl group, cycloalkyl group, aryl group, heterocyclic group, or substituent shown in formula (7), (8), or (9) below, Y 1 ~Y n Two or more of the substituents are represented by the following formulas (7), (8) or (9), where n represents a natural number of 3 or more, and Z represents a terminal group.

[0206]

[0207] (where R is in the formula) 1 and R 2 Each independently represents an alkyl group having 1 to 10 hydrogen atoms or carbon atoms, R 3 and R 5 Each can independently represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R 4 R represents an alkylene group having 1 to 10 carbon atoms. 6 (representing alkylene groups with 2 to 10 carbon atoms)

[0208] The dashed line in equation (MM-1) represents the state of monomer unit polymerization. When n is 3, the state is located at the bonded to X. 2 The methylene group of the bonded carbon atom with X 1 The methylene group (where X is on the opposite side of the bonded carbon atom) 2 The methylene group on the right side of the bonded carbon atom (and X) n The bonded carbon atoms are directly bonded. When n is 4 or higher, the atom bonded to X is located at... 2 The methylene group of the bonded carbon atom with X 1The methylene group on the opposite side of the bonded carbon atom is bonded to X. n The bonded carbon atoms are composed of one or more monomer units (-CX). i (COOY i )-CH2-, where i represents a natural number from 3 to (n-1)) bond.

[0209] In equation (MM-1), R and Y 1 ~Y n The alkyl, cycloalkyl, aryl, heterocyclic groups and substituents containing the structures represented by formulas (7), (8) or (9) above can be examples of the same groups as the alkyl, cycloalkyl, aryl, heterocyclic groups and 1-alkoxy groups in R of CH2=C(COOR)-CH2- above.

[0210] The number of 1-alkoxy groups relative to Y 1 ~Y n The proportion of the total amount is preferably 10 to 40 mol%, more preferably 20 to 30 mol%. If the proportion of 1-alkoxy groups is above the lower limit of the above-mentioned value, there is a tendency for the hydrolyticity of the compound (MM) to be improved and the antifouling properties of the coating to be better. If it is below the upper limit of the above-mentioned value, there is a tendency for the coating to have better crack resistance.

[0211] The preferred value for n is the weight-average molecular weight of the compound represented by formula (MM-1) in the range of 2,000 to 1,000,000. More preferred ranges for weight-average molecular weight are described below.

[0212] Z can be the same as the terminal group of a polymer obtained by known free radical polymerization, for example, a hydrogen atom, a group from a free radical polymerization initiator, a free radical polymerizable group, etc. Among these, from the perspective of not causing side reactions, a hydrogen atom or a group from a free radical polymerization initiator is preferred.

[0213] For compound (MM), the solid acid value measured after the above-described hydrolysis treatment of compound (MM) is preferably 10 mg KOH / g to 180 mg KOH / g, more preferably 20 mg KOH / g to 150 mg KOH / g, and even more preferably 30 mg KOH / g to 120 mg KOH / g. If the solid acid value of compound (MM) is above the lower limit of the above-described value, the hydrolyticity of compound (MM) is improved and the antifouling properties of the coating film are better; if it is below the upper limit of the above-described value, the crack resistance of the coating film is better.

[0214] The solid acid value was determined using the method described in the examples below.

[0215] The glass transition temperature (Tg) of the compound (MM) is preferably -10°C to 90°C, more preferably 10°C to 90°C, and even more preferably 30°C to 90°C. If the glass transition temperature of the compound (MM) is above the lower limit mentioned above, the coating film hardness is better; if it is below the upper limit mentioned above, the coating film solubility is better.

[0216] The glass transition temperature is calculated using the method described in the examples below.

[0217] The weight-average molecular weight (Mw) of compound (MM) is preferably 2,000 to 1,000,000, more preferably 2,500 to 100,000, even more preferably 3,000 to 10,000, and even more preferably 4,000 to 10,000. If the weight-average molecular weight of compound (MM) is above the lower limit above, the coating film hardness is better; if it is below the upper limit above, the coating film solubility is better.

[0218] The molecular weight dispersion of compound (MM) is preferably 1.0 to 4.0, more preferably 1.0 to 3.5, and even more preferably 1.0 to 3.0. Molecular weight dispersion is the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (Mw / Mn).

[0219] Weight-average molecular weight and number-average molecular weight were determined by gel permeation chromatography (GPC) using polystyrene as a reference.

[0220] The solubility parameter (sp) of compound (MM) is preferably 5.0 to 12.0, more preferably 6.0 to 11.0, and even more preferably 7.0 to 10.0. If the solubility parameter of compound (MM) is above the lower limit value mentioned above, the coating film has better solubility; if it is below the upper limit value mentioned above, the water resistance is better.

[0221] The solubility parameter is a measure of solubility; a larger value indicates higher polarity, and a smaller value indicates lower polarity. In this invention, the solubility parameter is obtained using the Fedors extrapolation method. Specifically, it is calculated using the following formula.

[0222] δ(sp)=(ΣEcoh / ΣV) 1 / 2

[0223] In the formula, ΣEcoh represents the condensation energy (cal / mol), and ΣV represents the molar volume (cm³). 3 / mol).

[0224] ΣEcoh and ΣV can use known values, such as those described in Robert F. Fedors, “Polymer Engineering and Science”, February, 1974, Vol. 14, No. 2, pp. 147–154.

[0225] <Methods for manufacturing compounds>

[0226] Examples of methods for manufacturing the compound (MM) include: (i) a method of polymerizing a monomer mixture containing monomer (M) using a cobalt chain transfer agent; (ii) a method of polymerizing a monomer mixture containing monomer (M) using an α-substituted unsaturated compound such as α-methylstyrene dimer as a chain transfer agent; (iii) a method of polymerizing a monomer mixture containing monomer (M) units and chemically bonding free radical polymerizable groups to the resulting polymer; and (iv) a method of polymerizing a monomer mixture containing monomer (M) and thermally decomposing the resulting polymer.

[0227] Of these, method (i) is preferred as a method for manufacturing compound (MM) from the perspective of having fewer manufacturing steps and using a catalyst with a high chain transfer constant. It should be noted that the compound (MM) manufactured using a cobalt chain transfer agent has the structure represented by the above formula (MM-1).

[0228] In the method described in (i) above, examples of methods for polymerizing monomer mixtures include bulk polymerization, solution polymerization, and aqueous dispersion polymerization methods such as suspension polymerization and emulsion polymerization. When the obtained compound (MM) is solution polymerized with other monomers, solution polymerization is preferred from the perspective of eliminating the need for purification.

[0229] In the method described in (iii) above, as a method for chemically bonding free radical polymerizable groups to a polymer, examples include: a method of manufacturing a polymer by replacing the halogen groups of a polymer having halogen groups with a compound having a carbon-carbon double bond that has free radical polymerizable properties; a method of reacting an acidic vinyl monomer with an epoxy group of a vinyl polymer; a method of reacting an epoxy group of a vinyl polymer with an acidic vinyl monomer; a method of reacting a hydroxyl-containing vinyl polymer with a diisocyanate compound to obtain a vinyl polymer with an isocyanate group, and then reacting the vinyl polymer with a hydroxyl-containing vinyl monomer, etc., which can be manufactured by any of these methods.

[0230] When the monomer (M) is monomer (M1), the compound (MM) can also be manufactured by replacing the monomer (M) with a monomer (m1) containing a carboxyl group and a free radical polymerizable group in the methods described in (i) to (iv) above, and by converting the carboxyl group of the obtained polymer into the structure (1), (2) or (3) after polymerization.

[0231] Examples of monomers (m1) include (meth)acrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, monomethyl maleate, and monomethyl fumarate.

[0232] As a method for converting the carboxyl group of a polymer to structure (1), (2) or (3), for example, a method of reacting the polymer with at least one alkenyl compound selected from the compounds represented by formula (11), formula (12) and formula (13) below (addition reaction) can be cited.

[0233]

[0234] (In the formula, X has the same meaning as X above, R) 11 R represents an alkyl group having 1 to 9 hydrogen atoms or carbon atoms. 12 R represents an alkyl group having 1 to 10 hydrogen atoms or carbon atoms. 13 and R 15 Each independently represents an alkyl, cycloalkyl, or aryl group having 1 to 20 carbon atoms, R 14 R represents a single bond or an alkylene group having 2 to 9 carbon atoms. 16 (representing alkylene groups with 1 to 9 carbon atoms)

[0235] If the compound represented by formula (11) is used as an alkenyl compound, then R in the above formula (1) can be obtained. 1 CH2R 11 R 2 For R 12 R 3 For R 13 Compounds.

[0236] In equation (11), R 11 Alkyl groups with 1 to 9 carbon atoms, except those with 9 or fewer carbon atoms, are related to R. 1 The same applies to alkyl groups with 1 to 10 carbon atoms. 12 R 13 respectively with R 2 R 3 same.

[0237] Examples of compounds represented by formula (11) include, for example, alkyl vinyl ethers (e.g., ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether), cycloalkyl vinyl ethers (e.g., cyclohexyl vinyl ether), 1-propenyl ethers such as ethyl-1-propenyl ether, and 1-butenyl ethers such as ethyl-1-butenyl ether. Among these, vinyl ethers and 1-propenyl ethers are preferred.

[0238] If the compound represented by formula (12) is used as an alkenyl compound, then R in formula (2) above can be obtained. 4 CH2-R 14 Compounds.

[0239] In equation (12), R 14 Alkyl groups with 1 to 9 carbon atoms, except those with 9 or fewer carbon atoms, are related to R. 4 same.

[0240] Examples of compounds represented by formula (12) include dihydrofurans such as 2,3-dihydrofuran and 5-methyl-2,3-dihydrofuran; and dihydropyrans such as 3,4-dihydro-2H-pyran and 5,6-dihydro-4-methoxy-2H-pyran.

[0241] If the compound represented by formula (13) is used as an alkenyl compound, then R in formula (3) above can be obtained. 5 For R 15 R 6 CH2-R 16 Compounds.

[0242] In equation (13), R 15 With R 5 Similarly. R 16 Except for those with 9 or fewer carbon atoms, and R 6 same.

[0243] Examples of compounds represented by formula (13) include 1-alkoxy-1-cyclopentene, 1-methoxy-1-cyclohexene, 1-methoxy-1-cycloheptene, 1-ethoxy-1-cyclopentene, 1-ethoxy-1-cyclohexene, 1-butoxy-1-cyclopentene, 1-butoxy-1-cyclohexene, and other 1-alkoxy-1-cycloolefins; and 1-alkoxy-1-cycloolefins containing substituents, such as 1-ethoxy-3-methyl-1-cyclohexene.

[0244] The reaction between the polymer and the alkenyl compound is carried out under relatively mild conditions. For example, the target compound can be obtained by reacting at a reaction temperature of 40–100°C for 5–10 hours in the presence or absence of acidic catalysts such as hydrochloric acid, sulfuric acid, or phosphoric acid. After the reaction is complete, the target polymer can be recovered by vacuum distillation under specified conditions.

[0245] Compound (MM) is a polymer containing compound (MM) units, prepared by polymerizing compound (MM) alone or with other monomers (monomer (a), monomer (M)). The coating containing this polymer exhibits improved solubility in seawater and the like due to the hydrolysis of compound (MM) units in seawater, thus demonstrating an antifouling effect. Furthermore, this coating shows superior initial solubility compared to cases where monomer (M) is used instead of compound (MM).

[0246] The reasons for achieving the above-mentioned effects are as follows.

[0247] Generally speaking, the rate-limited nature of hydrolysis reactions is until the initial hydrolysis begins.

[0248] Even if the polymer obtained by polymerizing compound (MM) does not contain monomer (M) units as the main building blocks of the polymer chain, or if the proportion of monomer (M) units in the main building blocks of the polymer chain is small, there are still two or more monomer (M) units in the side chain portion of the compound (MM) unit. Therefore, it is believed that the density of hydrolysis reaction sites in the coating film is locally increased, which promotes the initial hydrolysis through the proximity effect, thereby improving the initial solubility.

[0249] If the polymer does not contain monomer (M) units as the building blocks of the polymer main chain, or if the proportion of monomer (M) units in the building blocks of the polymer main chain is low, the crack resistance of the coating is improved.

[0250] The compound (MM) can be prepolymerized and incorporated into the antifouling coating composition in polymer form, or the compound (MM) can be directly incorporated into the antifouling coating composition.

[0251] The use of compound (MM) is not limited to antifouling coating compositions, but can also be used for other purposes, such as antifog coating compositions.

[0252] 〔polymer〕

[0253] One aspect of the polymer of the present invention (hereinafter also referred to as "polymer (A)") is a polymer comprising compound (MM) based constituent units (hereinafter also referred to as "compound (MM) units").

[0254] In addition to compound (MM) units, polymer (A) may further contain monomer (a) units.

[0255] In addition to compound (MM) units, or in addition to compound (MM) units and monomer (a) units, polymer (A) may further contain monomer (M) units.

[0256] The proportion of compound (MM) units relative to the total number of constituent units constituting polymer (A) is preferably 5% to 90% by mass, more preferably 10% to 60% by mass, more preferably 15% to 50% by mass, and even more preferably 20% to 40% by mass. If the proportion of compound (MM) units is above the lower limit mentioned above, the coating containing polymer (A) exhibits superior initial solubility and readily demonstrates an effect of preventing the adhesion of marine organisms from the initial stage of immersion in seawater or the like. If the proportion of compound (MM) units is below the upper limit mentioned above, the coating exhibits superior crack resistance.

[0257] The proportion of monomer (a) units relative to the total number of constituent units constituting polymer (A) is preferably 40% to 90% by mass, more preferably 50% to 85% by mass, and even more preferably 60% to 80% by mass. If the proportion of monomer (a) units is above the lower limit mentioned above, the crack resistance of the coating film is better; if it is below the upper limit mentioned above, the proportion of compound (MM) units can be sufficiently increased, and the solubility of the coating film is better.

[0258] The proportion of monomer (M) units relative to the total of all constituent units constituting polymer (A) is preferably 60% by mass or less, more preferably 45% by mass or less, even more preferably 30% by mass or less, and may also be 0% by mass.

[0259] The monomer (M) unit here refers to monomer (M) units other than those contained in the compound (MM) unit. If the proportion of monomer (M) units is below the upper limit mentioned above, the coating containing the polymer (A) exhibits superior crack resistance.

[0260] Of which, relative to the total of all constituent units constituting polymer (A), the total proportion of compound (MM) units, monomer (a) units, and monomer (M) units does not exceed 100 by mass.

[0261] From the perspectives of hydrolysis resistance and crack resistance, polymer (A) is preferably a (meth)acrylic acid polymer.

[0262] "(Meth)acrylate polymer" means a polymer in which at least a portion of the constituent units of the polymer are based on (meth)acrylate monomers (hereinafter also referred to as "(meth)acrylate monomer units"). (Meth)acrylate polymers may further include constituent units based on monomers other than (meth)acrylate monomers (e.g., vinyl monomers such as styrene).

[0263] When polymer (A) is composed solely of compound (MM) units, at least a portion of the compound (MM) units is preferably a (meth)acrylic acid monomer unit. When polymer (A) is composed of compound (MM) units and monomer (a) units, at least a portion of the compound (MM) units and monomer (a) units is preferably a (meth)acrylic acid monomer. When polymer (A) is composed of compound (MM) units, monomer (a) units, and monomer (M) units, at least a portion of the compound (MM) units, monomer (a) units, and monomer (M) units is preferably a (meth)acrylic acid monomer.

[0264] The proportion of (meth)acrylic monomer units relative to the total number of constituent units constituting polymer (A) is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 100% by mass. That is, it is particularly preferred that all constituent units constituting polymer (A) are (meth)acrylic monomer units.

[0265] For polymer (A), the solid acid value measured after the above-mentioned hydrolysis treatment of polymer (A) is preferably 20 mg KOH / g to 150 mg KOH / g, more preferably 30 mg KOH / g to 90 mg KOH / g, and even more preferably 30 mg KOH / g to 60 mg KOH / g. If the solid acid value of polymer (A) is above the lower limit of the above-mentioned value, the coating film has better solubility; if it is below the upper limit of the above-mentioned value, the coating film has better crack resistance.

[0266] The glass transition temperature (Tg) of polymer (A) is preferably -10°C to 70°C, more preferably 0°C to 50°C, and even more preferably 10°C to 30°C. If the glass transition temperature of polymer (A) is above the lower limit of the above-mentioned value, the coating film has better hardness; if it is below the upper limit of the above-mentioned value, the coating film has better solubility.

[0267] The weight-average molecular weight (Mw) of polymer (A) is preferably 2,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 9,000 to 20,000. If the weight-average molecular weight of polymer (A) is above the lower limit above, the coating film has better hardness; if it is below the upper limit above, the coating film has better solubility.

[0268] The molecular weight dispersion of polymer (A) is preferably 1.0 to 4.0, more preferably 1.0 to 3.5, and even more preferably 1.0 to 3.0.

[0269] The solubility parameter (sp) of polymer (A) is preferably 5.0 to 12.0, more preferably 6.0 to 11.0, and even more preferably 7.0 to 10.0. If the solubility parameter of polymer (A) is above the lower limit value mentioned above, the solubility of the coating film is better, and if it is below the upper limit value mentioned above, the water resistance is better.

[0270] <Methods for manufacturing polymers>

[0271] As a method for manufacturing polymer (A), for example, a method for polymerizing a mixture of monomers containing compound (MM) can be cited.

[0272] The monomer mixture may further contain monomer (a).

[0273] The monomer mixture may further contain monomers (M).

[0274] The composition of the monomer mixture, i.e., the types of monomers constituting the monomer mixture and the mass ratio (mass%) of each monomer relative to the total of the monomer mixture, is the same as the composition of the polymer (A), i.e., the types of monomer units constituting the polymer (A) and the total mass ratio (mass%) of each monomer unit relative to all the constituent units constituting the polymer (A).

[0275] Polymerization methods for monomer mixtures can include, for example, known polymerization methods such as solution polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. From the perspectives of productivity and coating performance, solution polymerization is preferred. There are no particular limitations on the solvent used in solution polymerization; common organic solvents can be used.

[0276] Polymerization can be carried out using known polymerization initiators and known methods. For example, a method can be described by reacting a monomer mixture in the presence of a free radical polymerization initiator at a reaction temperature of 60–180°C (moreover, 60–120°C) for 4–14 hours (moreover, 5–10 hours). Chain transfer agents may also be used during polymerization as needed.

[0277] As a free radical polymerization initiator, known polymerization initiators can be used, such as azo compounds like 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylpentanonitrile), and 2,2-azobis(2-methylbutyronitrile); and organic peroxides such as lauroyl peroxide, benzoyl peroxide, cumene peroxide, lauroyl peroxide, di-tert-butyl peroxide, and tert-butyl peroxide-2-ethylhexanoate.

[0278] There is no particular limitation on the content of the polymerization initiator; it can be set appropriately. Typically, it is about 0.1 to 20 parts by mass relative to 100 parts by mass of the polymerizable monomer.

[0279] As chain transfer agents, known chain transfer agents can be used, such as thiols like n-dodecyl mercaptan, thioglycolates like octyl mercaptoacetate, α-methylstyrene dimers, and terpinene.

[0280] 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 relative to 100 parts by mass of the polymerizable monomer.

[0281] Polymer (A) is used, for example, in antifouling coating compositions. The coating film of an antifouling coating composition containing polymer (A) exhibits antifouling effects due to improved solubility in seawater and the like, achieved through the hydrolysis of compound (MM) units in seawater. Furthermore, this coating film exhibits superior initial solubility compared to cases where monomer (M) is used instead of compound (MM).

[0282] In particular, if the proportion of monomer (M) units to the total of all constituent units constituting polymer (A) is less than 30% by mass, the coating film also exhibits excellent crack resistance.

[0283] It should be noted that the use of polymer (A) is not limited to antifouling coating compositions, but can also be used for other purposes, such as antifog coating compositions.

[0284] [Antifouling coating composition (1)]

[0285] An antifouling coating composition of one aspect of the present invention (hereinafter also referred to as "antifouling coating composition (1)") comprises the polymer (A) described above.

[0286] The antifouling coating composition (1) may further contain organic solvents.

[0287] The antifouling coating composition (1) may further include an antifouling agent.

[0288] The antifouling coating composition (1) may further contain other ingredients.

[0289] <Organic Solvents>

[0290] Examples of organic solvents include monohydric alcohols such as methanol, ethanol, and isopropanol; polyhydric alcohols such as ethylene glycol and 1,2-propanediol; ketones such as acetone, methyl ethyl ketone, acetylacetone, and methyl isobutyl ketone; and methyl ethyl ether, diethyl ethyl ketone, methyl ethyl ketone, diethyl ... Alkane and other ether solvents; glycol ether solvents such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol mono-n-propyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, dipropylene glycol monopropyl ether, etc.; glycol acetate solvents such as ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc.; other ester solvents such as n-butyl acetate, ethyl 3-ethoxypropionate, etc.; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, etc.; aromatic hydrocarbon solvents such as toluene, xylene, and naphthol. These organic solvents can be used individually or in combination of two or more.

[0291] As an organic solvent, an organic solvent capable of dissolving polymer (A) is preferred.

[0292] The content of organic solvents is set according to the solid components of the antifouling coating composition.

[0293] Antifouling agent

[0294] As antifouling agents, inorganic antifouling agents and organic antifouling agents can be used, and one or more types can be selected appropriately according to the required performance.

[0295] Examples of antifouling agents include, for example, 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; benzothiazole compounds; maleimide compounds; and pyridine compounds. These antifouling agents can be used alone or in combination of two or more.

[0296] As antifouling agents, more specifically, examples include 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carboxylonitrile, ethylene bis(dithiocarbamate)manganese, zinc dimethyl dithiocarbamate, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N,N-dimethyldichlorophenylurea, ethylene bis(dithiocarbamate)zinc, cuprous thiocyanate, 4,5-dichloro-2-n-octyl-3(2H)isothiazolinone, N-(fluorodichloromethylthio)phthalimide, and N,N'-dimethyl... Examples of such products include: 2-pyridinethiol-1-zinc oxide salt, tetramethylthiuram disulfide, Cu-10%Ni solid solution alloy, 2,4,6-trichlorophenylmaleimide, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, 3-iodo-2-propynyl butylcarbamate, diiodomethyl-p-tolyl sulfone, bis(dimethyldithiocarbamate)ethylene bis(dithiocarbamate)zinc disulfide, phenyl(bispyridyl)bismuth dichloride, 2-(4-thiazolyl)-benzimidazole, metoprimidine, pyridine-triphenylborane, etc.

[0297] Of the above, the antifouling agent preferably includes cuprous oxide and copper pyrithione.

[0298] When the antifouling agent contains cuprous oxide and copper pyrithione, their mass ratio is preferably cuprous oxide / copper pyrithione = 80 / 20 to 99 / 1, more preferably 90 / 10 to 99 / 1.

[0299] There is no particular limitation on the content of the antifouling agent, but it is preferably 10 to 200 parts by weight relative to 100 parts by weight of polymer (A), and more preferably 50 to 150 parts by weight. If the content of the antifouling agent is above the lower limit mentioned above, the antifouling effect of the formed coating film is better, and if it is below the upper limit mentioned above, the self-scraping property is better.

[0300] <Other Ingredients>

[0301] The antifouling coating composition (1) may contain polymers other than polymer (A).

[0302] Other polymers include, for example, other thermoplastic resins (thermoplastic polymers) besides polymer (A).

[0303] The antifouling coating composition (1) preferably contains other thermoplastic resins. If the antifouling coating composition (1) contains other thermoplastic resins, the coating properties such as crack resistance and water resistance are improved.

[0304] Other thermoplastic resins include, for example, chlorinated paraffin; chlorinated polyolefins such as chlorinated rubber, chlorinated polyethylene, and chlorinated polypropylene; polyvinyl ether; polypropylene sebate; partially hydrogenated terphenyl; polyvinyl acetate; poly(meth)acrylate copolymers, poly(meth)acrylate copolymers, poly(meth)acrylate copolymers, poly(meth)acrylate copolymers, poly(meth)acrylate copolymers, poly(meth)acrylate cyclohexyl ester copolymers, etc.; polyether polyols; alkyd resins; polyester resins; vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl propionate copolymers, vinyl chloride-isobutyl vinyl ether copolymers, vinyl chloride-isopropyl vinyl ether copolymers, vinyl chloride-ethyl vinyl ether copolymers, etc.; silicone oils; waxes; oils other than waxes that are solid at room temperature, oils such as castor oil that are liquid at room temperature, and their purified products; petrolatum; liquid paraffin; rosin, hydrogenated rosin, naphthenic acids, fatty acids, and their divalent metal salts, etc. Examples of waxes include animal-derived waxes such as beeswax; plant-derived waxes; semi-synthetic waxes such as amide-based waxes; and synthetic waxes such as oxidized polyethylene-based waxes. These thermoplastic resins can be used alone or in combination with two or more.

[0305] Chlorinated paraffin is preferred from the perspective of its function as a plasticizer and its effect on improving the crack resistance and peel resistance of the coating film.

[0306] From the perspective of acting as an anti-settling agent and anti-sagging agent, and improving the storage stability and pigment dispersibility of the antifouling coating composition, semi-synthetic waxes, synthetic waxes and other organic waxes are preferred, and polyethylene waxes, oxidized polyethylene waxes and polyamide waxes are more preferred.

[0307] There is no particular limitation on the content of other thermoplastic resins, but it is preferably 0.1 to 50 parts by weight, more preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of polymer (A). If the content of other thermoplastic resins is above the lower limit mentioned above, the coating properties such as crack resistance and water resistance are better; if it is below the upper limit mentioned above, the hydrolytic properties are better.

[0308] When the antifouling coating composition (1) comprises a polymer (A) containing a compound (MM) unit comprising at least one structure selected from structures (1), (2), and (3), the antifouling coating composition (1) preferably comprises at least one alkenyl compound selected from the compounds represented by formula (11), formula (12), and formula (13). By including an alkenyl compound in the antifouling coating composition, the storage stability of the antifouling coating composition is improved.

[0309] As alkenyl compounds, vinyl ethers such as butyl vinyl ether and isobutyl vinyl ether are preferred from the perspective of improving storage stability.

[0310] The content of the alkenyl compound is preferably 20 mol% or more, more preferably 30 to 1000 mol%, and even more preferably 40 to 800 mol%, relative to the total of structures (1), (2) and (3) in polymer (A) of 100 mol%. If the content of the alkenyl compound is within the above range, the storage stability is even better.

[0311] For the purpose of imparting lubricity to the coating surface and preventing biofouling, the antifouling coating composition (1) may also contain silicon compounds such as dimethyl polysiloxane and organosilicon oil, and fluorinated compounds such as fluorinated hydrocarbons.

[0312] The antifouling coating composition (1) may contain various pigments, dehydrating agents, defoamers, leveling agents, pigment dispersants (e.g., antisettling agents), anti-sagging agents, matting agents, ultraviolet absorbers, antioxidants, heat resistance improvers, slip agents, preservatives, plasticizers, viscosity control agents, etc.

[0313] Examples of pigments include zinc oxide, talc, silicon dioxide, barium sulfate, potassium feldspar, aluminum hydroxide, magnesium carbonate, mica, carbon black, Bengal red, titanium dioxide, phthalocyanine blue, kaolin, and gypsum. Zinc oxide and talc are particularly preferred.

[0314] Examples of dehydrating agents include silicate esters, isocyanates, orthoesters, and inorganic agents. More specifically, examples include methyl orthoformate, ethyl orthoformate, methyl orthoacetate, orthoborates, tetraethyl orthosilicate, anhydrous gypsum, calcined gypsum, and synthetic zeolites (molecular sieves). Molecular sieves are particularly preferred. Moisture can be replenished and storage stability improved by including dehydrating agents in the antifouling coating composition.

[0315] Examples of anti-settling and anti-sagging agents other than thermoplastic resins include bentonite-based, micronized silica-based, stearates, lecithin salts, and alkyl sulfonates.

[0316] Examples of plasticizers other than thermoplastic resins include phthalate plasticizers such as dioctyl phthalate, dimethyl phthalate, dicyclohexyl phthalate, and diisodecyl phthalate; aliphatic diester 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 epoxidized soybean oil and epoxidized octyl stearate; organotin plasticizers such as dioctyltin laurate and dibutyltin laurate; and trioctyl trimellitate and triacetylene. Including plasticizers in antifouling coating compositions can improve the crack resistance and peel resistance of the coating film. Among the above-mentioned plasticizers, TCP is preferred.

[0317] The antifouling coating composition (1) may contain water.

[0318] The moisture content of the antifouling coating composition (1) is preferably 15% by mass or less, more preferably 10% by mass or less. There is no particular limitation on the lower limit, and it can be 0% by mass. The moisture content is the ratio of water to the total mass of the antifouling coating composition (1). If the moisture content is below the upper limit mentioned above, the coating film formed by the antifouling coating composition (1) exhibits superior water resistance and drying properties.

[0319] The solid content of the antifouling coating composition (1) relative to the total mass of the antifouling coating composition (1) is preferably 40 to 90% by mass, more preferably 50 to 80% by mass, and even more preferably 60 to 70% by mass.

[0320] The antifouling coating composition (1) preferably has a B-type viscosity of less than 5000 mPa·s, more preferably less than 4000 mPa·s, even more preferably less than 3000 mPa·s, and particularly preferably less than 2000 mPa·s, as measured by a B-type viscometer at 25°C. If the B-type viscosity of the antifouling coating composition is below the above-mentioned upper limit, it is easy to apply.

[0321] The lower limit of the type B viscosity of the antifouling coating composition at 25°C is not particularly limited, but from the perspective of suppressing coating sagging during coating, it is preferably 100 mPa·s or more, more preferably 200 mPa·s or more, further preferably 300 mPa·s or more, and particularly preferably 1000 mPa·s or more.

[0322] The antifouling coating composition (1) can be prepared by preparing a polymer (A) and mixing it with an organic solvent, an antifouling agent, and other ingredients as needed.

[0323] The antifouling coating composition (1) can be used to form a coating (antifouling coating) on ​​the surface of a substrate such as ships, various fishing nets, port facilities, oil spill containment, bridges, seabed bases and other underwater structures.

[0324] The coating obtained using the antifouling coating composition (1) can be formed directly or through a base coating on the surface of a substrate. The base coating can be formed using etching primers, chlorinated rubber-based coatings, epoxy-based coatings, or intermediate coatings.

[0325] The coating film can be formed by known methods. For example, the antifouling coating composition (1) can be applied to the substrate surface or a base coating film on the substrate by brush coating, spraying, roller coating, dip coating, etc., and then dried to form a coating film.

[0326] The coating amount of the antifouling coating composition (1) can generally be set to achieve a thickness of 10 to 400 μm based on the dry film thickness.

[0327] The coating can usually be dried at room temperature, or heated as needed.

[0328] [Antifouling coating composition (2)]

[0329] Another aspect of the present invention provides an antifouling coating composition (hereinafter also referred to as "antifouling coating composition (2)") comprising the above-described compound (MM).

[0330] The antifouling coating composition (2) may further include monomer (a).

[0331] The antifouling coating composition (2) may further include monomers (M).

[0332] The antifouling coating composition (2) may further include a free radical polymerization initiator.

[0333] The antifouling coating composition (2) may further contain organic solvents.

[0334] The antifouling coating composition (2) may further include an antifouling agent.

[0335] The antifouling coating composition (2) may further contain other ingredients.

[0336] Monomer (a), monomer (M), free radical polymerization initiator, organic solvent, antifouling agent, and other components can be exemplified by the same examples as above.

[0337] The proportion of compound (MM) relative to the total of compound (MM), monomer (a), and monomer (M) is preferably 10% to 60% by mass, more preferably 15% to 50% by mass, and even more preferably 20% to 40% by mass. If the proportion of compound (MM) is above the lower limit mentioned above, the initial solubility of the coating film is superior, and it readily exhibits an effect of preventing the adhesion of marine organisms from the initial stage of immersion in seawater or the like. If the proportion of compound (MM) is below the upper limit mentioned above, the crack resistance of the coating film is superior.

[0338] The ratio of monomer (a) to compound (MM), monomer (a) and monomer (M) is preferably 40% to 90% by mass, more preferably 50% to 85% by mass, and even more preferably 60% to 80% by mass. If the ratio of monomer (a) is above the lower limit mentioned above, the crack resistance of the coating film is better, and if it is below the upper limit mentioned above, the ratio of compound (MM) can be sufficiently increased.

[0339] The proportion of monomer (M) relative to the compound (MM), monomer (a), and monomer (M) is preferably 60% by mass or less, more preferably 45% by mass or less, even more preferably 30% by mass or less, and may also be 0% by mass. If the proportion of monomer (M) is below the above-mentioned upper limit, the crack resistance of the coating film is more excellent.

[0340] There is no particular limitation on the content of the antifouling agent, but it is preferably 10 to 200 parts by mass relative to the total of 100 parts by mass of the compound (MM), monomer (a), and monomer (M), and more preferably 50 to 150 parts by mass. If the content of the antifouling agent is above the lower limit mentioned above, the antifouling effect of the formed coating film is better, and if it is below the upper limit mentioned above, the self-scraping property is better.

[0341] The content of other thermoplastic resins in other components is not particularly limited, but is preferably 0.1 to 50 parts by mass relative to the total of 100 parts by mass of compound (MM), monomer (a), and monomer (M), and more preferably 0.1 to 10 parts by mass. If the content of other thermoplastic resins is above the lower limit mentioned above, the coating properties such as crack resistance and water resistance are better; if it is below the upper limit mentioned above, the hydrolytic properties are better.

[0342] When the antifouling coating composition (2) contains alkenyl compounds from other components, the content of the alkenyl compound is preferably 20 mol% or more, more preferably 30 to 1000 mol%, and even more preferably 40 to 800 mol%, relative to the total of structures (1), (2), and (3) in the compound (MM) of 100 mol%. If the content of the alkenyl compound is within the above range, the storage stability is even better.

[0343] The moisture content of the antifouling coating composition (2) is preferably 15% by mass or less, more preferably 10% by mass or less. There is no particular limitation on the lower limit, and it may also be 0% by mass. If the moisture content is below the aforementioned upper limit, the coating film formed by the antifouling coating composition (2) exhibits superior water resistance and drying properties.

[0344] The solid content of the antifouling coating composition (2) relative to the total mass of the antifouling coating composition (2) is preferably 40-90% by mass, more preferably 50-80% by mass, and even more preferably 60-70% by mass.

[0345] The B-type viscosity of the antifouling coating composition (2), measured using a B-type viscometer at 25°C, is preferably less than 5000 mPa·s, more preferably less than 4000 mPa·s, even more preferably less than 3000 mPa·s, and particularly preferably less than 2000 mPa·s. If the B-type viscosity of the antifouling coating composition is below the above-mentioned upper limit, it is easier to apply.

[0346] The lower limit of the type B viscosity of the antifouling coating composition at 25°C is not particularly limited, but from the perspective of suppressing coating sagging during coating, it is preferably 100 mPa·s or more, more preferably 200 mPa·s or more, further preferably 300 mPa·s or more, and particularly preferably 1000 mPa·s or more.

[0347] The antifouling coating composition (2) can be prepared by preparing a compound (MM) and mixing it with monomer (a), monomer (M), organic solvent, antifouling agent, and other components as needed.

[0348] The antifouling coating composition (2) can be used, like the antifouling coating composition (1), to form a coating (antifouling film) on the surface of substrates such as ships, various fishing nets, port facilities, oil spill containment fences, bridges, seabed bases and other underwater structures.

[0349] The coating obtained using the antifouling coating composition (2) can be formed directly or through a base coating on the surface of the substrate. The base coating can be formed using etching primers, chlorinated rubber-based coatings, epoxy-based coatings, intermediate coatings, etc.

[0350] The coating can be formed using known methods. For example, the antifouling coating composition (2) can be applied to the substrate surface or a base coating on the substrate by brush coating, spraying, roller coating, dip coating, etc., and then dried to form a coating.

[0351] The coating amount of an antifouling coating composition can generally be set to achieve a thickness of 10 to 400 μm based on the dry film thickness.

[0352] The coating can usually be dried at room temperature, or it can be dried by heating as needed.

[0353] Example

[0354] The present invention will now be described in more detail using examples and comparative examples, but the invention is not limited to these examples in any way. It should be noted that parts in the examples refer to parts by mass.

[0355] The evaluation in the embodiments was performed using the methods shown below.

[0356] (Solid components (residual components after heating))

[0357] Weigh 0.50 g of the test sample (a solution polymer of compound (MM) or a composition containing the polymer) into an aluminum dish (test mass (g)). Add 3 mL of toluene using a dropper, spreading it evenly at the bottom of the dish. Heat the test sample in a water bath at 70–80 °C to dissolve it and allow it to evaporate to dryness. Then, dry it in a hot air dryer at 105 °C for 2 hours. Calculate the solid content (residual content after heating) from the mass of the test sample (test mass (g)) and the mass after drying (mass after drying (g)) using the following formula.

[0358] Solid content (mass%) = (mass after drying (g) / mass measured (g)) × 100

[0359] (glass transition temperature (Tg))

[0360] The glass transition temperature (Tg) of a compound (MM) or polymer is a value obtained by converting the absolute temperature (K) calculated by the following formula into degrees Celsius (°C).

[0361] 1 / Tg=Σ(wi / Tg i )

[0362] In the above formula, wi represents the mass fraction of monomer i constituting the compound (MM) or polymer, and Tg i This indicates the glass transition temperature of the homopolymer of monomer i that constitutes the compound (MM) or polymer.

[0363] In the above formula, Tg and Tg iThis is a value expressed in absolute temperature (K). Additionally, Tg... i The value is as recorded in the "Polymer Handbook Fourth Edition".

[0364] (Solid acid value)

[0365] Accurately weigh approximately 2.5 mmol (A(g)) of the sample (solution polymer of compound (MM) or a composition containing the polymer) into a beaker. Add a trace amount of phenolphthalein and 5 mL of 0.476 wt% p-toluenesulfonic acid aqueous solution, and 50 mL of a 50 / 50 mixture of toluene / 95% ethanol solution. After stirring at 70°C for 60 minutes, perform neutralization titration with a 0.5 mol / L potassium hydroxide solution (ethanol solution) with a factor (f) of 1.003 at 20°C (prepared by Kishida Chemicals). The endpoint is defined as the period when the pale red color of the indicator persists for 30 seconds. (Titration volume = B(mL), potency of KOH solution = f). Calculate the solid acid value using the following formula.

[0366] Solid acid value (mgKOH / g) = {(B×0.5-0.125)×56.11×f} / (A×resin solid content)

[0367] (Weight-average molecular weight (Mw), Number-average molecular weight (Mn))

[0368] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the compounds (MM) or polymers were determined using gel permeation chromatography (GPC) (Tosoh Corporation, HLC-8220). Columns used were TSKgelα-M (Tosoh Corporation, 7.8 mm × 30 cm) and TSKguardcolumnα (Tosoh Corporation, 6.0 mm × 4 cm). Standard curves were prepared using F288 / F1 / 28 / F80 / F40 / F20 / F2 / A1000 (Tosoh Corporation, standard polystyrene) and styrene monomer.

[0369] (Solubility parameter (sp))

[0370] The solubility parameter (sp) of a compound (MM) or polymer is obtained using the Fedors extrapolation method, as shown below. Specifically, it is calculated using the following formula.

[0371] δ(sp)=(ΣEcoh / ΣV) 1 / 2

[0372] In the formula, ΣEcoh represents the condensation energy (cal / mol), and ΣV represents the molar volume (cm³). 3 / mol).

[0373] (Viscosity of the composition containing the polymer)

[0374] Place the sample up to the indicator line in a dried Gardner bubble viscosity tube (hereinafter also referred to as "viscosity tube") and plug it with a cork. After taking the sample, vertically immerse the viscosity tube in a constant temperature water bath adjusted to the specified temperature (25.0±0.1℃) for at least 2 hours to keep the sample at a constant temperature. Rotate the viscosity tube (used as a reference tube) and the viscosity tube containing the sample 180° simultaneously. Compare the rising speed of the sample foam with that of the reference tube to determine the viscosity (Gardner viscosity).

[0375] The viscosity (hereinafter also referred to as "Gardner viscosity") of the composition containing the polymer, as measured at 25°C using a Gardner bubble viscometer, is Z or less, preferably W or less, and more preferably V or less.

[0376] If the viscosity (Type B viscosity or Gardner viscosity) of the polymer-containing composition is below the above-mentioned upper limit, a coating composition with low VOC content can be obtained even without further adding organic solvents for dilution to the polymer-containing composition, or by applying antifouling agents, etc.

[0377] The viscosity of the polymer-containing composition is preferably below the above-mentioned upper limit when the solid content is at least 45% by mass.

[0378] There is no particular limitation on the lower limit of the viscosity of the resin composition. From the perspective of suppressing paint sagging during coating, a Gardner viscosity of B or higher at 25°C is preferred.

[0379] (Stillness prevents staining)

[0380] The antifouling coating composition was applied with a brush to a pre-coated rust-preventive coating on a sandblasted steel plate to a dry film thickness of 200–300 μm, and then dried to form a coating film, resulting in a test plate. After the test plate was left to stand in Sanhe Bay for 6 months, the ratio of the area with attached marine organisms to the total area of ​​the coating film (the area with attached marine organisms) was investigated, and the antifouling performance was evaluated based on the following criteria.

[0381] ◎: The attachment area of ​​marine organisms is less than 10%.

[0382] ○: The attachment area of ​​marine organisms is more than 10% but less than 20%.

[0383] △: The attachment area of ​​marine organisms is more than 20% but less than 40%.

[0384] ×: The attachment area of ​​marine organisms exceeds 40%.

[0385] (Coating consumption rate)

[0386] The antifouling coating composition was applied to a 50mm × 50mm × 2mm rigid vinyl chloride plate using a coating applicator to achieve a dry film thickness of 120μm. The plate was then dried to form a coating film, resulting in a test plate. This test plate was mounted on a rotating drum placed in seawater and rotated at a circumferential speed of 7.7m / s (15 knots). This condition was maintained for 3 months, and the film thickness (μm) after 3 months was measured. The film thickness consumed each month was recorded as the consumption rate (μm / M).

[0387] (Crack resistance of the coating film of the antifouling coating composition)

[0388] The antifouling coating composition was applied to a 50mm × 50mm × 2mm rigid vinyl chloride plate using a coating applicator to achieve a dry film thickness of 120μm. The plate was then dried to form a coating film, resulting in a test plate. This test plate was mounted on a rotating drum placed in seawater and rotated at a circumferential speed of 7.7m / s (15 knots). This condition was maintained for 3 months, and the coating surface was observed after 3 months. Crack resistance was evaluated using the following benchmarks.

[0389] ◎: No cracks or peeling can be observed at all.

[0390] ○: Cracks were observed in some areas.

[0391] △: Cracks and peeling were observed in some areas.

[0392] ×: Cracks and peeling were observed on the entire surface.

[0393] The materials used in the following examples are as described below.

[0394] MMA: Methyl methacrylate.

[0395] EA: Ethyl acrylate.

[0396] BA: n-Butyl acrylate.

[0397] X-22-174ASX: A polymerizable monomer containing polysiloxane blocks, manufactured by Shin-Etsu Chemical Co., Ltd.

[0398] MTMA: 2-Methoxyethyl methacrylate.

[0399] MTA: 2-Methoxyethyl Acrylate.

[0400] PERBUTYL O: tert-butyl peroxide 2-ethylhexanoate (Nippon Oil Co., Ltd. "PERBUTYL O (registered trademark)").

[0401] AMBN: 2,2'-azobis(2-methylbutyronitrile).

[0402] AIBN: 2,2'-azobisisobutyronitrile.

[0403] IBVE: Isobutyl vinyl ether.

[0404] EHVE: 2-Ethylhexylvinyl ether.

[0405] DHP: 3,4-dihydro-2H-pyran.

[0406] Additive (1): Chlorinated paraffin (TOYOPARAX 150 manufactured by Tosoh Corporation).

[0407] Additive (2): Oxidized polyethylene wax (DISPARLON 4200-20 manufactured by Kusumoto Chemical Co., Ltd.).

[0408] 50% Rosin: 50% xylene dilution of rosin (Arakawa Chemical Industry Co., Ltd. "China Rosin (Registered Trademark)").

[0409] <Manufacturing of Monomer M (IBEMA)>

[0410] 90.1 parts (0.9 mol) of isobutyl vinyl ether, 0.14 parts (0.14 mol) of hydroquinone, and 0.28 parts (0.28 mol) of phenothiazine were stirred and mixed at room temperature until homogeneous. 51.7 parts (0.6 mol) of methacrylic acid were added dropwise while blowing air (10 ml / min) to maintain the temperature of the reaction solution below 60°C. After the addition, the temperature of the reaction solution was increased to 80°C, and the reaction was allowed to proceed for 6 hours. 158.7 parts (1.8 mol) of tert-butyl methyl ether were added to the reaction solution and mixed. The organic phase was washed once with 200 parts (w / w) of 20% potassium carbonate aqueous solution. 0.03 parts (w / w) of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxy radical were added to the organic phase, and the low-boiling components were distilled off using an evaporator. The resulting residue was subjected to vacuum distillation to obtain 97.5 parts (0.52 mol) of 1-isobutoxyethyl methacrylate (IBEMA) with a boiling point of 60°C / 3 torr.

[0411] <Manufacturing of Monomer M (EHEMA)>

[0412] 171.9 parts (1.1 mol) of 2-ethylhexyl vinyl ether, 0.32 parts of hydroquinone, and 0.61 parts of phenothiazine were stirred and mixed until homogeneous at room temperature. 86.1 parts (1.0 mol) of methacrylic acid were added dropwise while blowing air (10 ml / min) to maintain the temperature of the reaction solution below 60°C. After the addition, the temperature of the reaction solution was increased to 80°C, and the reaction was allowed to proceed for 5 hours. 264.5 parts (3.0 mol) of tert-butyl methyl ether were added to the reaction solution and mixed. The organic phase was washed once with 135 parts of a 20% (w / w) potassium carbonate aqueous solution. 0.07 parts of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxy radical were added to the organic phase, and the low-boiling components were distilled off using an evaporator. The residue was subjected to vacuum distillation to obtain 207.0 parts (0.85 mol) of 1-(2-ethylhexyloxy)ethyl methacrylate (EHEMA) with a boiling point of 99°C / 3 torr.

[0413] <Manufacturing of Monomer M (THPMA)>

[0414] 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 and mixed until homogeneous at room temperature. 51.7 parts (0.6 mol) of methacrylic acid (MAA) were added dropwise while blowing air (10 ml / min) to maintain the temperature of the reaction solution below 60°C. After the addition, the temperature of the reaction solution was increased to 80°C, and the reaction was allowed to proceed for 12 hours. 158.7 parts (1.8 mol) of tert-butyl methyl ether were added to the reaction solution and mixed. The organic phase was washed once with 200 parts of 20% potassium carbonate aqueous solution. 0.03 parts of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxy radical were added to the organic phase, and the low-boiling components were distilled off using an evaporator. The residue was subjected to vacuum distillation to obtain 75.7 parts (0.44 mol) of 2-tetrahydropyranyl methacrylate (THPMA) with a boiling point of 76°C / 3 torr.

[0415] <Manufacturing of Chain Transfer Agents>

[0416] In a synthesis apparatus equipped with a stirrer, under a nitrogen atmosphere, 1.00 g of cobalt(II) acetate tetrahydrate, 1.93 g of diphenylethylene dioxime, and 80 mL of diethyl ether pre-deoxygenated by nitrogen bubbling were added, and the mixture was stirred at room temperature for 30 minutes. Then, 10 mL of boron trifluoride diethyl ether complex was added, and the mixture was stirred further for 6 hours. The mixture was filtered, the solid was washed with diethyl ether, and dried under vacuum for 15 hours to obtain 2.12 g of chain transfer agent 1 (bis[(difluoroboryl)diphenylethylene dioxime]cobalt(II); CoPhBF) as a reddish-brown solid.

[0417] <Manufacturing of Compound (MM)>

[0418] (Manufacturing Example 1)

[0419] In a polymerization apparatus equipped with a stirrer, cooling pipe, and thermometer, 50 parts xylene, 16 parts MMA, 4 parts IBEMA, and 0.007 parts chain transfer agent 1 were charged and stirred. The mixture was heated to 90°C under a nitrogen atmosphere. Next, a mixture of 16 parts IBEMA, 64 parts MMA, and 3.2 parts AMBN was added dropwise at a constant rate over 3 hours. The mixture was further heated and stirred at 90°C for 1 hour. 30 minutes after the addition was complete, 16.6 parts xylene and 0.2 parts AMBN were added dropwise at a constant rate over 30 minutes, maintaining the temperature at 90°C for 90 minutes. The reaction mixture was then cooled to 40°C to obtain a solution of compound (MM1).

[0420] (Manufacturing Examples 2-6)

[0421] The feed amounts (parts) of monomer, initiator and chain transfer agent are shown in Table 1. Otherwise, solutions of compounds (MM1 to MM6) are obtained in the same manner as in Manufacturing Example 1.

[0422] Table 1 shows the solid composition of the obtained compound (MM) solutions, the Tg of each compound (MM1 to MM6), the solid acid value, Mw, Mn and sp.

[0423] [Table 1]

[0424]

[0425] <Preparation of Compositions Containing Polymers>

[0426] (Manufacturing Example 7)

[0427] 17.0 parts of xylene were charged into a reaction vessel equipped with a stirrer, temperature controller, and dropping funnel. Under a nitrogen atmosphere, the mixture was heated to 90°C while stirring. Then, over 3 hours, a mixture consisting of 50 parts of the solid components of the MM1 solution obtained in Manufacturing Example 1, 15 parts of MTA, 21 parts of EA, 14 parts of BA, and 7.5 parts of AMBN was added dropwise at a constant rate using a dropping funnel. Thirty minutes after the addition was complete, 7.8 parts of xylene, 2.1 parts of butyl acetate, and 7.5 parts of AMBN were added dropwise at a constant rate over 30 minutes, maintaining the temperature at 90°C for 90 minutes. Then, 6.7 parts of isobutyl vinyl ether were added, and the reaction mixture was cooled to 40°C to obtain a polymer-containing composition A-1 in solution form.

[0428] (Manufacturing Examples 8-13)

[0429] The feed amounts (parts) of the monomer and the initiator AIBN are shown in Tables 2 and 3. Otherwise, the polymer-containing compositions A-2 to A-13 in solution form are manufactured in the same manner as in Manufacturing Example 7.

[0430] In Tables 2 and 3, the amount of compound (MM) is the amount converted from solid components.

[0431] Tables 2 and 3 show the solid composition of the polymer-containing compositions (A-1 to A-13), the Tg of the polymer contained in each polymer-containing composition, the solid acid value, Mw, Mn and sp.

[0432] [Table 2]

[0433]

[0434] [Table 3]

[0435]

[0436] <Preparation and Evaluation of Antifouling Coating Compositions>

[0437] According to the composition shown in Tables 4 and 5, after loading each material into a metal can, add 70g of glass beads, mix with a stirring rod, and further disperse using a shaker to obtain the antifouling coating composition.

[0438] In Tables 4 and 5, the values ​​listed in the composition column indicate the amount (parts) of the composition. The amount of the composition containing the polymer is the total amount of the composition containing the polymer.

[0439] Tables 4 and 5 show the theoretical solids content and evaluation results (static antifouling performance, film consumption rate, and crack resistance) of the obtained antifouling coating compositions. The theoretical solids content is a value calculated from the solids content of each material incorporated into the antifouling coating composition.

[0440] [Table 4]

[0441]

[0442] [Table 5]

[0443]

[0444] The antifouling coating compositions of Examples 1-12, obtained using compounds (MM) containing monomeric M units (macromonomers), exhibit excellent static antifouling properties. Furthermore, they have a suitable consumption rate. In particular, the antifouling coating compositions of Examples 1-3, obtained using polymers that do not contain monomeric M units as constituent units based on monomers other than compounds (MM), or even if they do contain monomeric M units as constituent units based on monomers other than compounds (MM), the proportion of these monomeric M units relative to all constituent units is 6.5% by mass or less, also exhibit excellent crack resistance.

[0445] On the other hand, the antifouling coating composition of Comparative Example 1, obtained using a macromolecular monomer that does not contain monomer M units, exhibits poor static antifouling properties. Furthermore, it has low consumption.

[0446] Industrial availability

[0447] According to one aspect of the present invention, compounds and polymers capable of forming antifouling coating compositions with excellent antifouling properties, as well as antifouling coating compositions capable of forming antifouling coating compositions with excellent antifouling properties, can be provided. Additionally, according to one aspect of the present invention, compounds and polymers capable of forming antifouling coating compositions with excellent solubility, as well as antifouling coating compositions capable of forming antifouling coating compositions with excellent solubility, can be provided.

Claims

1. A polymer comprising building blocks derived from a compound, The compound has a weight-average molecular weight of less than 10,000, contains two or more constituent units comprising hydrolyzable substituents represented by formula (1), (2), or (3), and has a radical polymerizable group at the end. After hydrolysis of the compound by heating and stirring in an aqueous solution of p-toluenesulfonic acid, a neutralization titration was performed using a 0.5 mol / L potassium hydroxide solution (i.e., an ethanol solution). The solid acid value, calculated from the amount of 0.5 mol / L potassium hydroxide solution used until the indicator remained pale red for 30 seconds, was 10 mg KOH / g or higher. The proportion of the constituent units containing hydrolyzable substituents represented by formula (1), (2), or (3) relative to the total mass of the compound was 20% to 60% by mass. The proportion of constituent units containing hydrolyzable substituents represented by formula (1), (2), or (3), other than the constituent units based on the compound, to the total number of constituent units constituting the polymer is 6.5% by mass or less. The proportion of the constituent units of the compound relative to the total mass of the polymer is 10% to 90% by mass. After hydrolysis of the polymer by heating and stirring in an aqueous solution of p-toluenesulfonic acid, neutralization titration was performed using a 0.5 mol / L potassium hydroxide solution (i.e., an ethanol solution). The solid acid value, calculated from the amount of 0.5 mol / L potassium hydroxide solution used until the indicator remained pale red for 30 seconds, was 30 mg KOH / g to 60 mg KOH / g. , In the formula, X represents -O-, -S-, or -NR. 11 -, R 11 R represents a hydrogen atom or an alkyl group. 1 and R 2 R represents either hydrogen atoms or alkyl groups having 1 to 10 carbon atoms. 3 and R 5 R represents alkyl, cycloalkyl, or aryl groups with 1 to 20 carbon atoms, respectively. 4 R represents an alkylene group having 1 to 10 carbon atoms. 6 Indicates alkylene groups having 2 to 10 carbon atoms.

2. A polymer comprising building blocks based on compounds represented by the following formula (MM-1), The proportion of constituent units containing hydrolyzable substituents represented by formula (7), (8), or (9) relative to the total mass of the compound is 9% to 80% by mass. The proportion of constituent units containing hydrolyzable substituents represented by formula (7), (8), or (9), other than the constituent units based on the compound, to the total number of constituent units constituting the polymer is 6.5% by mass or less. The proportion of the constituent units of the compound relative to the total mass of the polymer is 5% to 90% by mass. After hydrolysis of the polymer by heating and stirring in an aqueous solution of p-toluenesulfonic acid, neutralization titration was performed using a 0.5 mol / L potassium hydroxide solution (i.e., an ethanol solution). The solid acid value, calculated from the amount of 0.5 mol / L potassium hydroxide solution used until the indicator remained pale red for 30 seconds, was 30 mg KOH / g to 60 mg KOH / g. , In formula (MM-1), X 1 ~X n Each independently represents a hydrogen atom, a methyl group, or a hydroxymethyl group, R and Y. 1 ~Y n Each independently represents a hydrogen atom, alkyl group, cycloalkyl group, aryl group, heterocyclic group, or substituent containing formula (7), (8), or (9), Y 1 ~Y n Two or more of them are substituents that include formulas (7), (8) or (9), where n represents a natural number of 3 or more, and Z represents a terminal group. , In equations (7), (8), or (9), R 1 and R 2 Each independently represents an alkyl group having 1 to 10 hydrogen atoms or carbon atoms, R 3 and R 5 Each independently represents an alkyl, cycloalkyl, or aryl group having 1 to 20 carbon atoms, R 4 R represents an alkylene group having 1 to 10 carbon atoms. 6 Indicates alkylene groups having 2 to 10 carbon atoms.

3. The polymer according to claim 2, wherein, The terminal group is a hydrogen atom or a group derived from a free radical polymerization initiator.

4. The polymer according to claim 2, wherein, The weight-average molecular weight of the compound is 2,000 to 1,000,000.

5. The polymer according to any one of claims 1 to 4, wherein it is a (meth)acrylic polymer.

6. An antifouling coating composition comprising the polymer according to any one of claims 1 to 4.

7. A method for manufacturing a (meth)acrylic acid copolymer, comprising polymerizing a compound having a weight-average molecular weight of 10,000 or less, comprising two or more hydrolyzable substituents represented by formula (1), formula (2) or formula (3) and having a free radical polymerizable group at the end, with a monomer having an olefinic unsaturated group, wherein, The monomer does not include the compound. The proportion of constituent units containing hydrolyzable substituents represented by formula (1), (2), or (3) relative to the total mass of the compound is 20% to 60% by mass. The proportion of constituent units containing hydrolyzable substituents represented by formula (1), (2), or (3), other than the constituent units based on the compound, to the total number of constituent units constituting the polymer is 6.5% by mass or less. The proportion of the constituent units of the compound relative to the total mass of the polymer is 5% to 90% by mass. After hydrolysis of the polymer by heating and stirring in an aqueous solution of p-toluenesulfonic acid, neutralization titration was performed using a 0.5 mol / L potassium hydroxide solution (i.e., an ethanol solution). The solid acid value, calculated from the amount of 0.5 mol / L potassium hydroxide solution used until the indicator remained pale red for 30 seconds, was 30 mg KOH / g to 60 mg KOH / g. , In the formula, X represents -O-, -S-, or -NR. 11 -, R 11 R represents a hydrogen atom or an alkyl group. 1 and R 2 R represents either hydrogen atoms or alkyl groups having 1 to 10 carbon atoms. 3 and R 5 R represents alkyl, cycloalkyl, or aryl groups with 1 to 20 carbon atoms, respectively. 4 R represents an alkylene group having 1 to 10 carbon atoms. 6 Indicates alkylene groups having 2 to 10 carbon atoms.

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