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WO2017065172A1 - Copolymère (méth)acrylique, composition de résine, composition de matériau de revêtement antisalissure, et procédé de production de copolymère (méth)acrylique - Google Patents

Copolymère (méth)acrylique, composition de résine, composition de matériau de revêtement antisalissure, et procédé de production de copolymère (méth)acrylique Download PDF

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Publication number
WO2017065172A1
WO2017065172A1 PCT/JP2016/080250 JP2016080250W WO2017065172A1 WO 2017065172 A1 WO2017065172 A1 WO 2017065172A1 JP 2016080250 W JP2016080250 W JP 2016080250W WO 2017065172 A1 WO2017065172 A1 WO 2017065172A1
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Prior art keywords
group
monomer
meth
copolymer
resin composition
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English (en)
Japanese (ja)
Inventor
匠 勝間田
佳奈 谷口
中村　淳一
正敏 浦
良啓 加門
学文 浅井
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Mitsubishi Chemical Corp
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Mitsubishi Rayon Co Ltd
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Priority to CN201680058764.3A priority Critical patent/CN108137751B/zh
Priority to JP2016565365A priority patent/JPWO2017065172A1/ja
Priority to KR1020187011051A priority patent/KR102638011B1/ko
Priority to JP2017072718A priority patent/JP6922349B2/ja
Publication of WO2017065172A1 publication Critical patent/WO2017065172A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions

Definitions

  • the present invention relates to a (meth) acrylic copolymer, a resin composition, an antifouling coating composition, and a method for producing a (meth) acrylic copolymer.
  • This application claims priority based on Japanese Patent Application No. 2015-202407 for which it applied to Japan on October 13, 2015, and uses the content here.
  • antifouling paints are applied to offshore structures and ships for the purpose of preventing adhesion of marine organisms that cause corrosion of a portion in contact with seawater and a decrease in navigation speed.
  • Self-polishing antifouling paints are known as antifouling paints.
  • the coating film obtained from the self-polishing antifouling paint has a coating surface that gradually dissolves in seawater and is renewed (self-polishing). Demonstrate the dirt effect.
  • a self-polishing antifouling paint for example, a combination of a vinyl polymer having a hemiacetal ester group and / or a hemiketal ester group in the side chain and an antifouling agent (Patent Document 1), a silicon-containing group and 2 There have been proposed (Patent Documents 2 to 3) using a (meth) acrylic copolymer having a valent metal atom.
  • the polymer used for these antifouling paints has hydrolyzability, and the coating film containing the polymer exhibits self-polishing properties.
  • the antifouling coating film using the vinyl polymer described in Patent Document 1 has insufficient antifouling properties.
  • the antifouling coating film using the (meth) acrylic copolymer described in Patent Documents 2 to 3 also has insufficient antifouling properties. There is also a problem of low water resistance.
  • An object of the present invention is to provide an antifouling coating composition capable of forming a coating film excellent in antifouling property and water resistance, and a (meth) acrylic copolymer and a resin composition suitable for obtaining the antifouling coating composition And a method for producing the (meth) acrylic copolymer.
  • X represents —O—, —S— or —NR 14 —
  • R 14 represents a hydrogen atom or an alkyl group
  • R 1 and R 2 represent a hydrogen atom or an alkyl having 1 to 10 carbon atoms, respectively.
  • R 3 and R 5 each represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or an aryl group, and R 4 and R 6 each represents an alkylene group having 1 to 10 carbon atoms.
  • Monomer (m1) A monomer having at least one of the structures (I) and an ethylenically unsaturated bond.
  • Monomer (m2) A monomer having the polysiloxane group and an ethylenically unsaturated bond.
  • a resin composition comprising the (meth) acrylic copolymer according to [1] or [2].
  • the compound that reacts with the acid is selected from the group consisting of a compound represented by the following formula (31), a compound represented by the following formula (32), and a compound represented by the following formula (33).
  • An antifouling paint composition comprising the resin composition according to any one of [3] to [7]. [9] The antifouling paint composition according to [8], further comprising an antifouling agent. [10] The antifouling agent is cuprous oxide, pyridine triphenylborane, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4-bromo-2- (4-chlorophenyl)- The antifouling coating composition according to [9], comprising at least one selected from the group consisting of 5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile and medetomidine.
  • the antifouling coating composition according to any one of [8] to [10], further comprising a thermoplastic resin other than the (meth) acrylic copolymer.
  • Production of a (meth) acrylic copolymer by polymerizing a monomer mixture containing the following monomer (m1) and the following monomer (m2) to obtain a (meth) acrylic copolymer Method.
  • Monomer (m1) A monomer having at least one structure (I) represented by the following formula (1), the following formula (2) or the following formula (3) and an ethylenically unsaturated bond.
  • Monomer (m2) A monomer having a polysiloxane group and an ethylenically unsaturated bond.
  • R 14 represents a hydrogen atom or an alkyl group
  • R 1 and R 2 represent a hydrogen atom or an alkyl having 1 to 10 carbon atoms, respectively.
  • R 3 and R 5 each represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or an aryl group
  • R 4 and R 6 each represents an alkylene group having 1 to 10 carbon atoms.
  • an antifouling coating composition capable of forming a coating film excellent in antifouling properties and water resistance, a (meth) acrylic copolymer and a resin composition suitable for obtaining the antifouling coating composition And a method for producing the (meth) acrylic copolymer.
  • the “(meth) acrylic copolymer” means a copolymer in which at least a part of the structural unit is a structural unit derived from a (meth) acrylic monomer.
  • the (meth) acrylic polymer may further have a structural unit derived from a monomer other than the (meth) acrylic monomer (for example, a vinyl monomer such as styrene).
  • Structural unit means a structural unit derived from a monomer formed by polymerizing monomers, or a structural unit in which a part of the structural unit is converted to another structure by treating the polymer.
  • Means. “Monomer” means a polymerizable compound (polymerizable monomer).
  • (Meth) acrylic monomer means a monomer having a (meth) acryloyl group.
  • (Meth) acryloyl group is a general term for an acryloyl group and a methacryloyl group.
  • (Meth) acrylate is a general term for acrylate and methacrylate.
  • (Meth) acrylic acid is a general term for acrylic acid and methacrylic acid.
  • (Meth) acrylonitrile” is a general term for acrylonitrile and methacrylonitrile.
  • (Meth) acrylamide” is a general term for acrylamide and methacrylamide.
  • Volatile organic compound (VOC)” means an organic compound (volatile organic compound) that easily volatilizes at normal temperature and pressure. The normal temperature and normal pressure are 10 ° C. to 30 ° C. and 1000 Pa to 1050 Pa.
  • a first aspect of the present invention is a (meth) acryl having at least one structure (I) represented by the following formula (1), the following formula (2) or the following formula (3) and a polysiloxane group.
  • a copolymer hereinafter also referred to as “copolymer (A)”.
  • R 14 represents a hydrogen atom or an alkyl group
  • R 1 and R 2 represent a hydrogen atom or an alkyl having 1 to 10 carbon atoms, respectively.
  • R 3 and R 5 each represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or an aryl group
  • R 4 and R 6 each represents an alkylene group having 1 to 10 carbon atoms.
  • the structure (I) and polysiloxane group possessed by the copolymer (A) may each be one kind or two or more kinds.
  • Each of the structure (I) and the polysiloxane group may be contained in the constituent unit of the copolymer (A), may be contained at the end of the main chain, or may be contained in both of them. In terms of antifouling properties, it is preferably contained in at least a structural unit.
  • the structure (I) and the polysiloxane group are each contained in a structural unit, the structure (I) and the polysiloxane group are preferably contained in different structural units.
  • the copolymer (A) includes a structural unit derived from the monomer (m1) having the structure (I) and an ethylenically unsaturated bond (polymerizable carbon-carbon double bond) (hereinafter referred to as “structural unit (u1) And a structural unit derived from the monomer (m2) having a polysiloxane group and an ethylenically unsaturated bond (hereinafter also referred to as “structural unit (u2)”). Is preferred.
  • Each of the structural unit (u1) and the structural unit (u2) of the copolymer (A) may be one kind or two or more kinds.
  • the copolymer (A) includes other structural units other than the structural unit (u1) and the structural unit (u2) (hereinafter referred to as “structural unit (u3)”). May also be included.
  • At least a part of the structural units of the copolymer (A) is a structural unit derived from a (meth) acrylic monomer.
  • the ratio of the structural unit derived from the (meth) acrylic monomer to the total (100% by weight) of all the structural units in the copolymer (A) is preferably 20 to 100% by weight, more preferably 40 to 100% by weight. preferable.
  • the copolymer (A) has the structural unit (u1) and the structural unit (u2), one of the structural unit (u1) and the structural unit (u2) is derived from the (meth) acrylic monomer
  • These structural units may be included, and both may include a structural unit derived from a (meth) acrylic monomer.
  • any one of the structural unit (u1), the structural unit (u2), and the structural unit (u3) 1 type may contain the structural unit derived from a (meth) acrylic-type monomer, and 2 or 3 types may contain the structural unit derived from a (meth) acrylic-type monomer.
  • the structure (I) is represented by the formula (1), the formula (2), or the formula (3).
  • the line not bonded to the oxygen atom represents a bond.
  • (1) ⁇ (3), X is, -O- (etheric oxygen atom), - S- (sulfide sulfur atom), - NR 14 - may be any of, -O- is preferable .
  • examples of the alkyl group having 1 to 10 carbon atoms in R 1 and R 2 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, 2- An ethylhexyl group etc. are mentioned.
  • the number of carbon atoms of the alkyl group in R 1 and R 2 is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 or 2.
  • R 1 and R 2 include a combination of a hydrogen atom and a methyl group, a combination of a methyl group and a methyl group, a hydrogen atom and an alkyl group having 2 to 10 carbon atoms (hereinafter also referred to as “long-chain alkyl group”). .), A combination of a methyl group and a long chain alkyl group, a combination of a hydrogen atom and a hydrogen atom, a combination of a long chain alkyl group and a long chain alkyl group, and the like. Among these, a combination of a hydrogen atom and a methyl group is preferable in terms of hydrolyzability.
  • Examples of the alkyl group having 1 to 20 carbon atoms in R 3 include the alkyl groups, decyl groups, dodecyl groups, and tetradecyl groups mentioned above as the alkyl groups having 1 to 10 carbon atoms.
  • the number of carbon atoms of the alkyl group in R 3 is preferably 1-10.
  • the cycloalkyl group is preferably a cycloalkyl group having 4 to 8 carbon atoms, and examples thereof include a cyclohexyl group and a cyclopentyl group.
  • As the aryl group an aryl group having 6 to 20 carbon atoms is preferable, and examples thereof include a phenyl group and a naphthyl group.
  • R 3 is preferably an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group.
  • the alkyl group, cycloalkyl group or aryl group may be substituted with a substituent selected from the group consisting of a cycloalkyl group, an aryl group, an alkoxy group, an alkanoyloxy group, an aralkyl group and an acetoxy group.
  • a substituent selected from the group consisting of a cycloalkyl group, an aryl group, an alkoxy group, an alkanoyloxy group, an aralkyl group and an acetoxy group.
  • the number of substituents may be one or two or more.
  • Examples of the cycloalkyl group and aryl group as substituents are the same as those described above.
  • Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • Examples of the alkanoyloxy group include an ethanoyloxy group.
  • the aralkyl group include
  • examples of the alkylene group having 1 to 10 carbon atoms in R 4 include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.
  • the alkylene group in R 4 preferably has 2 to 7 carbon atoms, and more preferably 3 to 4 carbon atoms.
  • the alkylene group may be substituted with a substituent selected from the group consisting of a cycloalkyl group, an aryl group, an alkoxyl group, an alkanoyloxy group, an aralkyl group, and an acetoxy group. When substituted by a substituent, the number of substituents may be one or two or more. Specific examples of the substituent that may be substituted on the alkylene group include the same substituents as those described for R 3 .
  • R 5 is the same as R 3 in formula (1), and the preferred embodiment is also the same.
  • R 6 is the same as R 4 in formula (2), and the preferred embodiment is also the same.
  • the polysiloxane group is a group having a Si—O—Si bond.
  • Examples of the polysiloxane group include a divalent polysiloxane group represented by the following formula (i) or (ii), a monovalent polysiloxane group represented by the following formula (iii) or (iv), and organopolysiloxane. Examples thereof include trivalent or higher polysiloxane groups in which three or more organic groups bonded to silicon atoms constituting the skeleton are removed from siloxane.
  • n 3 to 80
  • R 1b to R 1e each represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group.
  • r and s each represent 0 to 20, and R 2b to R 2k each represents an alkyl group.
  • x represents 3 to 80
  • R 3b to R 3f each represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group.
  • R 4b to R 4d are each an alkyl group, — (OSiR 51 R 52 ) y —OSiR 53 R 54 R 55 (where y is an integer of 0 to 20, and R 51 to R 55 are alkyl) Or R 56 — (OC 2 H 4 ) y ′ —OR 57 (where y ′ is an integer of 1 to 20, and R 56 and R 57 each represents an alkyl group).
  • n is the average degree of polymerization of the polysiloxane structure. If n is not less than the lower limit of the above range, even if the antifouling coating composition containing the copolymer (A) does not contain an antifouling agent, the antifouling effect tends to develop in the coating film, If it is below the upper limit of the above range, the monomer having the polysiloxane group is compatible with the monomer (m1) and the like, and the solvent solubility of the resulting copolymer (A) is good. . n is preferably from 5 to 50, more preferably from 8 to 40.
  • the alkyl group and alkoxy group in R 1b to R 1e each preferably have 1 to 18 carbon atoms.
  • Examples of the substituent in the substituted phenyl group and the substituted phenoxy group include an alkyl group and an alkoxy group.
  • R 1b to R 1e are each preferably an alkyl group having 1 to 18 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
  • r and s are the average degree of polymerization of the polysiloxane structure. If r and s are each less than or equal to the upper limit, the monomer having a polysiloxane group is compatible with the monomer (m1) and the like, and the solvent solubility of the resulting copolymer (A) is high. It is good. r and s are each preferably 10 or less, and more preferably 5 or less.
  • the alkyl group in R 2b to R 2k is preferably an alkyl group having 1 to 18 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
  • x is the average degree of polymerization of the polysiloxane structure. If x is not less than the lower limit of the above range, even if the antifouling coating composition containing the copolymer (A) does not contain an antifouling agent, the antifouling effect tends to be exhibited in the coating film, If it is below the upper limit of the above range, the monomer having the polysiloxane group is compatible with the monomer (m1) and the like, and the solvent solubility of the resulting copolymer (A) is good. . n is preferably from 5 to 50, more preferably from 8 to 40.
  • the number of carbon atoms of the alkyl group and alkoxy group in R 3b to R 3f is preferably 1 to 18, respectively.
  • Examples of the substituent in the substituted phenyl group and the substituted phenoxy group include an alkyl group and an alkoxy group.
  • R 3b to R 3f are each preferably an alkyl group having 1 to 18 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
  • the alkyl group in R 4b to R 4d is preferably an alkyl group having 1 to 18 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. . Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
  • y is the average degree of polymerization of the polysiloxane structure
  • y ′ is the average degree of polymerization of the polyether structure.
  • y and y ′ are not more than the above upper limit values, the monomer having the polysiloxane group is compatible with the monomer (m1) and the like, and the solvent solubility of the resulting copolymer (A) is high. It is good.
  • y and y ′ are each preferably 10 or less, and more preferably 5 or less.
  • Examples of the alkyl group for R 51 to R 57 include the same alkyl groups as those for R 4b to R 4d , and preferred embodiments thereof are also the same.
  • the structural unit (u1) has a structure in which the ethylenically unsaturated bond of the monomer (m1) is cleaved to form a single bond.
  • the monomer (m1) is preferably a monofunctional monomer having one ethylenically unsaturated bond from the viewpoint of lowering the viscosity when the copolymer (A) is dissolved in a solvent.
  • Examples of the monomer (m1) include a compound represented by the following formula (11), a compound represented by the following formula (12), a compound represented by the following formula (13), and the like.
  • R X represents the structure (I) or an alkyl ester group
  • X represents —O—, —S— or —NR 14 —
  • R 14 represents a hydrogen atom Or an alkyl group
  • R 1 to R 6 are as defined above.
  • CH 2 ⁇ CH—COO— is an acryloyloxy group
  • CH 2 ⁇ C (CH 3 ) —COO— is a methacryloyloxy group.
  • CH (CH 3 ) ⁇ CH—COO— is a crotonoyloxy group (ethylenically unsaturated bond is trans-type) or an isocrotonoyloxy group (ethylenically unsaturated bond is cis-type).
  • CHR X CH-COO- is a maleoyloxy group (ethylenically unsaturated bond is cis type) or a fumaroyloxy group (ethylenically unsaturated bond is trans Type).
  • R X preferably has the same structure as the group to which Z is bonded.
  • R X is preferably a group represented by —CR 1 R 2 —OR 3 .
  • the alkyl ester group in R X is represented by —COOR X1 .
  • R X1 represents an alkyl group.
  • an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is particularly preferable.
  • CH 2 ⁇ C (CH 2 R X ) —COO— or CH 2 ⁇ CR X —CH 2 COO— is an itaconoyloxy group in which the carboxy group is substituted with the structure (I) or an alkyl ester group.
  • R X is the same as described above.
  • Z is preferably CH 2 ⁇ CH—COO— or CH (CH 3 ) ⁇ CH—COO—.
  • Examples of the monomer (m1) include those shown below.
  • the structural unit (u2) has a structure in which the ethylenically unsaturated bond of the monomer (m2) is cleaved to form a single bond.
  • the number of polysiloxane groups and ethylenically unsaturated bonds that the monomer (m2) has in the molecule is not particularly limited, and may be one or two or more.
  • the monomer (m2) a monomer having a divalent polysiloxane group and an ethylenically unsaturated bond-containing group bonded to both ends thereof (hereinafter referred to as “both terminal polysiloxane” is used as the monomer (m2).
  • a monomer having a monovalent polysiloxane group and an ethylenically unsaturated bond-containing group bonded to one end thereof (hereinafter also referred to as “one-end polysiloxane macromonomer”) is preferable. . Any one of these may be used alone or in combination.
  • Examples of the both-end polysiloxane macromonomer include monomers represented by the following formula (m2-1) or (m2-2).
  • Examples of the one-end polysiloxane macromonomer include monomers represented by the following formula (m2-3) or (m2-4).
  • the monomer (m2) a monomer represented by the following formula (m2-1), a monomer represented by the formula (m2-2), and a formula (m2-3) At least one selected from the group consisting of a monomer and a monomer represented by the formula (m2-4) is preferable.
  • R 1a and R 1f are each a hydrogen atom or a methyl group
  • k and p are each an integer of 2 to 5
  • l and q are each 0 to 50
  • m and o are each 2 to 5
  • An integer, n is 3 to 80
  • R 1b to R 1e are each an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group.
  • Formula (m2-2) in each R 2a and R 2l is a hydrogen atom or a methyl group
  • k 'and p' are each an integer of 2 ⁇ 5, l 'and q' respectively 0 ⁇ 50
  • m 'and o' Each represents an integer of 2 to 5
  • r and s each represent 0 to 20
  • R 2b to R 2k each represents an alkyl group.
  • R 3a is a hydrogen atom or a methyl group
  • u is an integer of 2 to 5
  • v is 0 to 50
  • w is an integer of 2 to 5
  • x is 3 to 80
  • R 3b to R 3f Represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group or a substituted phenoxy group, respectively.
  • R 4a is a hydrogen atom or a methyl group
  • u ′ is an integer of 2 to 5
  • v ′ is 0 to 50
  • w ′ is an integer of 2 to 5
  • R 4b to R 4d are each alkyl.
  • l and q are the average degree of polymerization of the polyether structure. If l and q are 50 or less, the water resistance of the coating film tends to be good. In particular, it is preferably 30 or less because of excellent recoatability with the old coating film. l and q may be 0, but are preferably larger than 0 because recoatability with the old coating film tends to be good. l and q are preferably from 3 to 25, and more preferably from 5 to 20. k and p are integers of 2 to 5, and 2 or 3 is preferable from the viewpoint of inexpensiveness. It is also possible to use those having k and p of 2 and 3. m and o are integers of 2 to 5, and 2 or 3 is preferable.
  • n and R 1b ⁇ R 1e are each similar to n and R 1b ⁇ R 1e of the formula (i), preferable embodiments thereof are also the same.
  • R 1a to R 1f , k, l, m, n, o, p, and q are independent of each other, and may be different when the same symbol exists in or between molecules.
  • the monomer represented by the formula (m2-1) include, for example, FM-7711, FM-7721, FM-7725 (trade names, manufactured by Chisso Corporation) where l and q are 0. And F2-311-02 (trade name) manufactured by Toray Dow Corning. Examples of those in which l and q are larger than 0 include F2-354-04 (trade name) manufactured by Toray Dow Corning.
  • the monomer represented by the formula (m2-1) one type may be used alone, or a plurality of types may be used in combination.
  • l ′ and q ′ are the average degree of polymerization of the polyether structure. If l ′ and q ′ are 50 or less, the water resistance of the coating film tends to be good. In particular, it is preferably 30 or less because of excellent recoatability with the old coating film. l ′ and q ′ may be 0, but are preferably larger than 0 because recoatability with the old coating film tends to be good. l ′ and q ′ are preferably 3 to 25, and more preferably 5 to 20. k ′ and p ′ are integers of 2 to 5, and 2 or 3 is preferable from the viewpoint of low cost. It is also possible to use a combination of k ′ and p ′ of 2 and 3.
  • m ′ and o ′ are integers of 2 to 5, with 2 or 3 being preferred.
  • r, s and R 2b ⁇ R 2k are similar to each r in formula (ii), s and R 2b ⁇ R 2k, preferable embodiments thereof are also the same.
  • R 2a to R 2l , k ′, l ′, m ′, n ′, o ′, p ′, q ′, r, and s are independent of each other, and the same code exists in or between molecules. If so, they may be different.
  • the monomer represented by the formula (m2-2) include, for example, F2-212-01 (trade name) manufactured by Toray Dow Corning Co., Ltd., where l ′ and q ′ are 0. It is done. Examples of those in which l ′ and q ′ are greater than 0 include F2-212-04 (trade name) manufactured by Toray Dow Corning. As the monomer represented by the formula (m2-2), one type may be used alone, or a plurality of types may be used in combination.
  • v is the average degree of polymerization of the polyether structure. If v is 50 or less, the water resistance of the coating film tends to be good. In particular, it is preferably 30 or less because of excellent recoatability with the old coating film. v may be 0, but it is preferably larger than 0 because recoatability with the old coating film tends to be good. v is preferably from 3 to 25, more preferably from 5 to 20. u is an integer of 2 to 5, and 2 or 3 is preferable from the viewpoint of low cost. It is also possible to use a combination of u 2 and 3. w is an integer of 2 to 5, and 2 or 3 is preferable.
  • R 3b ⁇ R 3f are each same as x and R 3b ⁇ R 3f of the formula (iii), a preferable embodiment thereof is also the same.
  • R 3a to R 3f , u, v, w, and x are independent of each other, and may be different when the same symbol exists in or between molecules.
  • the monomer represented by the formula (m2-3) include, for example, FM-0711, FM-0721, FM-0725 (trade name) manufactured by Chisso Corporation, where v is 0. X-24-8201, X-22-174DX, X-22-2426 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. and the like can be mentioned.
  • Examples of v greater than 0 include F2-254-04, F2-254-14 (trade name) manufactured by Toray Dow Corning.
  • the monomer represented by the formula (m2-3) one type may be used alone, or a plurality of types may be used in combination.
  • v ′ is the average degree of polymerization of the polyether structure. If v 'is 50 or less, the water resistance of the coating film tends to be good. In particular, it is preferably 30 or less because of excellent recoatability with the old coating film. v ′ may be 0, but is preferably larger than 0 because recoatability with the old coating film tends to be good. v ′ is preferably from 3 to 25, more preferably from 5 to 20.
  • u ′ is an integer of 2 to 5, and 2 or 3 is preferable from the viewpoint of low cost. It is possible to use a combination of u ′ of 2 and 3.
  • w ′ is an integer of 2 to 5, preferably 2 or 3.
  • R 4b ⁇ R 4d is the same as R 4b ⁇ R 4d of each of the formula (iv), preferable embodiments thereof are also the same.
  • R 4a to R 4d , u ′, v ′, w ′, y, and y ′ are each independent, and they may be different when the same symbol exists in or between molecules.
  • the monomer represented by the formula (m2-4) include those having v ′ of 0, TM-0701 (trade name) manufactured by Chisso Corporation, and X-22-2 manufactured by Shin-Etsu Chemical Co., Ltd. 2404 (trade name), F2-250-01 manufactured by Toray Dow Corning, F2-302-01 (above, trade name), and the like.
  • Examples of v 'greater than 0 include F2-302-04 (trade name) manufactured by Toray Dow Corning.
  • the monomer represented by the formula (m2-4) one type may be used alone, or a plurality of types may be used in combination.
  • the structural unit (u2) is preferably composed of only a structural unit derived from a single-terminal polysiloxane macromonomer in terms of crack resistance and adhesion to a substrate.
  • the structural unit (u2) preferably includes a structural unit derived from a polysiloxane macromonomer at both ends and a structural unit derived from a polysiloxane macromonomer at one end in terms of recoatability.
  • the structural unit (u2) includes a structural unit derived from a polysiloxane macromonomer at both ends and a structural unit derived from a polysiloxane macromonomer at one end
  • the structural unit (u3) is a structural unit other than the structural unit (u1) and the structural unit (u2). That is, the structural unit does not contain the structure (I) and the polysiloxane group.
  • structural unit (u3) structural units derived from the monomer (m3) having an ethylenically unsaturated bond and not containing the structure (I) and the polysiloxane group can be mentioned.
  • Such a structural unit has a structure in which the ethylenically unsaturated bond of the monomer (m3) is cleaved to form a single bond.
  • Examples of the monomer (m3) include the following.
  • Substituted or unsubstituted alkyl (meth) acrylate [eg, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i -Butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 1-methyl-2-methoxyethyl ( Meth) acrylate, 3-methoxybutyl (meth) acrylate, 3-methyl-3-methoxybutyl (meth) acrylate], substituted or unsubstituted aralkyl (me
  • Examples of the macromonomer include compounds having two or more structural units derived from monomers having an ethylenically unsaturated bond-containing group and having an ethylenically unsaturated bond-containing group. Two or more structural units of the macromonomer may be the same or different.
  • Examples of the ethylenically unsaturated bond-containing group include CH 2 ⁇ C (COOR) —CH 2 —, (meth) acryloyl group, 2- (hydroxymethyl) acryloyl group, vinyl group and the like.
  • R represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted group.
  • the substituent include an alkyl group (except when R is an alkyl group having a substituent), an aryl group, —COOR 61 , a cyano group, —OR 62 , —NR 63 R 64 , —CONR 65.
  • Examples thereof include at least one selected from the group consisting of R 66 , a halogen atom, an allyl group, an epoxy group, a siloxy group, and a group exhibiting hydrophilicity or ionicity.
  • R 61 to R 66 each independently represent a hydrogen atom, an alkyl group, an alicyclic group, or an aryl group.
  • the monomer having an ethylenically unsaturated bond-containing group for example, various monomers mentioned above as examples of the monomer (m3) can be used (excluding the macromonomer). Specific examples of the macromonomer include monomers disclosed in International Publication No. 2013/108880.
  • the monomer (m3) is a monofunctional monomer having one ethylenically unsaturated bond from the viewpoint that when the copolymer (A) is dissolved in a solvent, it is easy to have a low viscosity even at a high solid content.
  • the ethylenically unsaturated bond is particularly preferably derived from an acryloyl group. That is, the monomer (m3) is particularly preferably a monofunctional monomer having one acryloyl group.
  • the structural unit (u3) has a hydrophobic group-containing (meta) property in that the flexibility or / and crack / peeling resistance of the coating film to be formed and the long-term self-polishing property can be improved in a good balance.
  • the hydrophobic group-containing (meth) acrylic acid ester monomer alkyl (meth) acrylate is preferable.
  • the structural unit (u3) preferably includes a structural unit derived from an oxyethylene group-containing (meth) acrylic acid ester monomer in terms of solubility and crack resistance of the coating film to be formed.
  • a compound represented by the following formula (3-1) is preferable.
  • Z 1- (CH 2 CH 2 O) n R 21 (3-1) (In the formula, Z 1 represents an acryloyloxy group or a methacryloyloxy group, R 21 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group, and n represents an integer of 1 to 15)
  • n is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably an integer of 1 to 3, and particularly preferably 1 or 2, from the viewpoint of water resistance and crack resistance.
  • the content of the structural unit (u1) in the copolymer (A) is preferably 1 to 80% by weight, more preferably 10 to 70% by weight, and more preferably 20 to 60% with respect to the total (100% by weight) of all the structural units. More preferred is mass%. If content of a structural unit (u1) is more than the lower limit of the said range, the self-polishing property of the coating film formed will be more excellent. If the content of the structural unit (u1) is less than or equal to the upper limit of the above range, the formed coating film has moderate hydrolyzability, maintains self-polishing properties over a long period of time, and has a better antifouling effect. It will be a thing.
  • the content of the structural unit (u2) in the copolymer (A) is preferably 1 to 80% by weight, more preferably 5 to 70% by weight, with respect to the total (100% by weight) of all the structural units. More preferred is mass%. If content of a structural unit (u2) is more than the lower limit of the said range, the antifouling property of the coating film formed will be more excellent. If content of a structural unit (u2) is below the upper limit of the said range, crack resistance will be more excellent.
  • the content of the structural unit derived from the polysiloxane macromonomer at both terminals is preferably 30% by mass or less, more preferably 25% by mass or less, based on the total of all the structural units (100% by mass). 20 mass% or less is more preferable. If the content of the structural unit derived from the polysiloxane macromonomer at both ends is not more than the above upper limit value, the copolymer tends to be obtained without proceeding to gelation by crosslinking during the production of the copolymer (A). Moreover, it exists in the tendency for the viscosity of the solution of a copolymer (A) to become low.
  • the content of the structural unit (u3) is preferably 0 to 98% by weight, more preferably 5 to 85% by weight, and even more preferably 10 to 70% by weight with respect to the total of all the structural units (100% by weight).
  • the content of the structural unit is 1 to 80% by mass relative to the total of all the structural units. 5 to 60% by mass is more preferable, and 20 to 50% by mass is more preferable.
  • the content of the structural unit is not less than the lower limit of the above range, the hydrophilicity of the formed coating film becomes higher and the self-polishing property becomes more excellent. If the content of this structural unit is less than or equal to the upper limit of the above range, the formed coating film has moderate hydrolyzability, maintains self-polishing properties over a long period of time, and has a better antifouling effect. Become.
  • the copolymer (A) has a structural unit derived from a monomer (m3) other than the oxyethylene group-containing (meth) acrylate monomer, such as a hydrophobic group-containing (meth) acrylate monomer.
  • the content of the structural unit is preferably 1 to 90% by mass and more preferably 10 to 80% by mass with respect to the total of all the structural units.
  • the flexibility and crack resistance / peeling resistance of the coating film to be formed become higher, and the antifouling effect becomes more excellent. If the content of this structural unit is less than or equal to the upper limit of the above range, the formed coating film has moderate hydrolyzability, maintains self-polishing properties over a long period of time, and has a better antifouling effect. Become.
  • the total of the structural unit (u1), the structural unit (u2), and the structural unit (u3) is 100% by mass.
  • Content (mass%) of each structural unit in a copolymer can be measured by well-known methods, such as a gas chromatography, a high performance liquid chromatography, and a nuclear magnetic resonance spectrum method.
  • the copolymer (A) is preferably a copolymer obtained by polymerizing a monomer mixture containing the monomer (m1) and the monomer (m2).
  • a monomer mixture containing a monomer (a0) having an ethylenically unsaturated bond and a carboxy group and a monomer (m2) is polymerized to obtain a copolymer having a carboxy group.
  • the water resistance is more excellent.
  • the monomer mixture is preferably composed of 1 to 80% by mass of monomer (m1), 1 to 80% by mass of monomer (m2), and 0 to 98% by mass of monomer (m3). .
  • the content of each monomer is a ratio with respect to the total amount of the monomer mixture.
  • the range of the more preferable content of each monomer is the same as the range of the preferable content of the structural unit derived from each monomer.
  • the weight average molecular weight (Mw) of the copolymer (A) is preferably from 2,000 to 100,000, more preferably from 3,000 to 80,000, and even more preferably from 5,000 to 60,000. If the weight average molecular weight of the copolymer (A) is less than or equal to the upper limit of the above range, the viscosity of the solution obtained by dissolving the copolymer (A) in a solvent will be lower, and the anti-fouling coating composition will have a low high solid content. Viscosity is easy to obtain. Moreover, the antifouling property of the coating film formed is excellent. If a weight average molecular weight is more than the lower limit of the said range, the hardness and durability of the coating film formed will be more excellent.
  • the number average molecular weight (Mn) of the copolymer (A) is preferably 1,000 to 50,000, more preferably 2,000 to 40,000.
  • the polydispersity (Mw / Mn) of the copolymer (A) is preferably 1.5 to 5.0, more preferably 2.2 to 3.0.
  • the weight average molecular weight and the number average molecular weight of the copolymer (A) are each measured by gel filtration chromatography (GPC) using polystyrene as a reference resin.
  • Production method of copolymer (A) examples include the following production methods ( ⁇ ) and ( ⁇ ).
  • the monomer mixture used in the production method ( ⁇ ) includes at least the monomer (m1) and the monomer (m2), and may further include the monomer (m3).
  • the content of the monomer (m1) in the monomer mixture is preferably 1 to 80% by mass with respect to the total mass (100% by mass) of all monomers. That is, the copolymer (A) is obtained by polymerizing a monomer mixture containing 1 to 80% by mass (charge amount) of the monomer (m1) with respect to the total mass of all monomers. Preferably there is.
  • the content of the monomer (m1) is more preferably 10 to 70% by mass, and further preferably 20 to 60% by mass. If content of a monomer (m1) is more than the lower limit of the said range, the self-polishing property of the coating film formed will be more excellent.
  • the formed coating film has moderate hydrolyzability, maintains self-polishing properties over a long period of time, and has a better antifouling effect. It will be.
  • the content of the monomer (m2) in the monomer mixture is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, and more preferably 10 to 60% by mass with respect to the total mass of all monomers. Further preferred. If content of a monomer (m2) is more than the lower limit of the said range, the antifouling property of the coating film formed will be more excellent. If content of a monomer (m2) is below the upper limit of the said range, crack resistance will be more excellent.
  • the content of the polysiloxane macromonomer at both ends in the monomer mixture is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less based on the total mass of all monomers. If the content of the both-end polysiloxane macromonomer is not more than the above upper limit value, a copolymer tends to be obtained without proceeding to gelation by crosslinking during polymerization of the monomer mixture. Moreover, it exists in the tendency for the viscosity of the solution of the obtained copolymer (A) to become low.
  • the content of the monomer (m3) in the monomer mixture is preferably 0 to 98% by mass, more preferably 5 to 85% by mass, and more preferably 10 to 70% by mass with respect to the total mass of all monomers. Further preferred.
  • the content of this monomer is preferably 1 to 80% by mass relative to the total mass of all monomers, It is more preferably 5 to 60% by mass, and further preferably 20 to 50% by mass. If the content of this monomer is not less than the lower limit of the above range, the hydrophilicity of the formed coating film becomes higher and the self-polishing property becomes more excellent. If the content of this structural unit is less than or equal to the upper limit of the above range, the formed coating film has moderate hydrolyzability, maintains self-polishing properties over a long period of time, and has a better antifouling effect. Become.
  • the monomer mixture contains a monomer (m3) other than the oxyethylene group-containing (meth) acrylate monomer, such as a hydrophobic group-containing (meth) acrylate monomer, this monomer
  • the content of is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, based on the total mass of all monomers.
  • the total of the monomer (m1), the monomer (m2), and the monomer (m3) (including the case where the monomer (m3) is not included) is 100% by mass.
  • the monomer (m1), the monomer (m2), and the monomer (m3) can each be purchased as a commercial product, or can be appropriately synthesized using a known method.
  • the monomer (m1) can be synthesized by converting the carboxy group of the monomer (m0) having an ethylenically unsaturated bond and a carboxy group into the structure (I).
  • Examples of the monomer (m0) include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, monomethyl maleate, monomethyl fumarate, and the like.
  • Examples of the method for converting the carboxy group of the monomer (m0) into the structure (I) include, for example, the monomer (m0), a compound represented by the following formula (31), and the following formula (32). Examples include a method of reacting (addition reaction) a compound and at least one compound (B) selected from the group consisting of the compound represented by the following formula (33). You may use a compound (B) individually or in combination of 2 or more types.
  • R 14 represents a hydrogen atom or an alkyl group
  • R 7 represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms
  • R 8 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 9 and R 11 each represents an alkyl group, a cycloalkyl group or an aryl group having 1 to 20 carbon atoms
  • R 10 represents a single bond Or an alkylene group having 1 to 9 carbon atoms
  • R 12 represents an alkylene group having 1 to 9 carbon atoms.
  • R 1 in the formula (11) is CH 2 R 7
  • R 2 is R 8
  • R 3 is A compound of R 9 is obtained.
  • the alkyl group having 1 to 9 carbon atoms in R 7 is the same as the alkyl group having 1 to 10 carbon atoms in R 1 except that it has 9 or less carbon atoms.
  • R 8 and R 9 are the same as R 2 and R 3 in the formula (11), respectively.
  • Examples of the compound represented by the formula (31) include 1-alkenylalkyl ether in which X in the formula (31) is —O—, and 1-alkenylalkyl in which X in the formula (31) is —S—. Examples thereof include sulfides and 1-alkenyldialkylamines in which X in the formula (31) is —NR 14 —.
  • 1-alkenyl alkyl ethers examples include vinyl ethers such as alkyl vinyl ethers (eg, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether) and cycloalkyl vinyl ethers (eg, cyclohexyl vinyl ether).
  • alkyl vinyl ethers eg, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether
  • cycloalkyl vinyl ethers eg, cyclohexyl vinyl ether
  • 1-propenyl ethers such as ethyl-1-propenyl ether
  • 1-butenyl ethers such as ethyl-1-butenyl ether; and the like.
  • Examples of 1-alkenylalkyl sulfide include 1- (ethenylthio) ethane, 1- (ethenylthio) propane, 1- (ethenylthio) butane, 2- (ethenylthio) butane, 1- (ethenylthio) -2-methylpropane, 1 1-alkenyl alkyl sulfides such as-(propylthio) -1-propene and 2- (propylthio) -1-propene;
  • Examples of 1-alkenyldialkylamines include 1-alkenyldialkylamines such as N, N-dimethylethenamine, N-methyl-N-ethylethenamine, N, N-diethylethenamine, and N-vinylpyrrolidine. . Of these, 1-alkenyl alkyl ether is preferable, and vinyl ethers and 1-propenyl ethers are more preferable.
  • Examples of the compound represented by the formula (32) include dihydrofurans such as 2,3-dihydrofuran and 5-methyl-2,3-dihydrofuran; 3,4-dihydro-2H-pyran, 5,6 Dihydropyrans such as dihydro-4-methoxy-2H-pyran; dihydrothiophenes such as 2,3-dihydrothiophene; dihydrothiopyrans such as 3,4-dihydro-2H-thiopyran; 2,3-dihydro- Dihydropyrroles such as 1-methylpyrrole; tetrahydropyridines such as 1,2,3,4-tetrahydro-1-methylpyridine; and the like. Of these, dihydrofurans and dihydropyrans are preferable, and dihydropyrans are more preferable.
  • Examples of the compound represented by the formula (33) include 1-methoxy-1-cyclopentene, 1-methoxy-1-cyclohexene, 1-methoxy-1-cycloheptene, 1-ethoxy-1-cyclopentene, 1-ethoxy- 1-alkoxy-1-cycloalkylenes such as 1-cyclohexene, 1-butoxy-1-cyclopentene, 1-butoxy-1-cyclohexene; 1-alkoxy having substituents such as 1-ethoxy-3-methyl-1-cyclohexene 1-cycloalkylenes; 1- (alkylthio) -1-cycloalkylenes such as 1- (methylthio) -1-cyclopentene and 1- (methylthio) -1-cyclohexene; 1- (1-pyrrolidinyl) -1- 1- (1-pyrrolidinyl) such as cyclopentene, 1- (1-pyrrolidinyl) -1-cyclohexene 1-cycloalkylene ethers; and the like.
  • the reaction between the monomer (m0) and the compound (B) proceeds under relatively mild conditions.
  • the desired product can be obtained by carrying out the reaction for 5 to 10 hours while maintaining the reaction temperature at 40 to 100 ° C. in the presence or absence of an acidic catalyst such as hydrochloric acid, sulfuric acid or phosphoric acid.
  • an acidic catalyst such as hydrochloric acid, sulfuric acid or phosphoric acid.
  • the objective monomer can be recovered by distillation under reduced pressure under predetermined conditions.
  • Polymerization of monomer mixture for example, a known polymerization method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method can be applied.
  • the solution polymerization method is preferable in terms of productivity and coating film performance.
  • the polymerization may be performed by a known method using a known polymerization initiator. For example, a method of reacting the above monomer mixture in the presence of a radical initiator at a reaction temperature of 60 to 120 ° C. for 4 to 14 hours can be mentioned. In the polymerization, a chain transfer agent may be used as necessary.
  • radical initiator known ones can be used, for example, 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (2-methyl). Butyronitrile), benzoyl peroxide, cumene hydroperoxide, lauryl peroxide, di-t-butyl peroxide, t-butylperoxy-2-ethylhexanoate and the like.
  • the content of the polymerization initiator is not particularly limited and can be set as appropriate. Typically, it is about 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
  • chain transfer agent known ones can be used, and examples thereof include mercaptans such as n-dodecyl mercaptan, thioglycolic acid esters such as octyl thioglycolate, ⁇ -methylstyrene dimer, terpinolene and the like.
  • the content of the chain transfer agent is not particularly limited and can be set as appropriate. Typically, the amount is about 0.0001 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
  • a general organic solvent such as toluene, xylene, methyl isobutyl ketone, n-butyl acetate can be used.
  • a monomer mixture containing the monomer (m0) and the monomer (m2) is polymerized to obtain a copolymer (A0) having a carboxy group.
  • the monomer mixture may further contain a monomer (m3).
  • the monomer (m0), monomer (m2), and monomer (m3) are the same as described above.
  • the preferable ranges of the contents of the monomer (m0) and the monomer (m2) in the monomer mixture are the monomer (m1) and the monomer in the monomer mixture in the production method ( ⁇ ).
  • M2 It is the same as the preferable range of each content.
  • the copolymer (A) is obtained by converting the carboxy group of the copolymer (A0) into the structure (I).
  • Examples of the method for converting the carboxy group of the copolymer (A0) into the structure (I) include a method in which the copolymer (A0) and the compound (B) are reacted (addition reaction).
  • the reaction between the copolymer (A0) and the compound (B) can be carried out in the same manner as the reaction between the monomer (m0) and the compound (B).
  • the copolymer (A) Since the copolymer (A) has a structure (I) in which a carboxy group is protected by a specific group, it can be hydrolyzed in seawater or the like. Therefore, the coating film containing the copolymer (A) exhibits self-polishing properties in seawater or the like. That is, the copolymer (A) has the structure (I) and does not dissolve in seawater in this state, but when the structure (I) is hydrolyzed by contact with seawater, a carboxy group or the like is generated, Dissolves in seawater. The coating surface gradually dissolves in seawater and is renewed (self-polishing).
  • the copolymer (A) since the copolymer (A) has a polysiloxane group, marine organisms and other dirt are difficult to adhere to the surface of the coating film. Therefore, the coating film containing the copolymer (A) exhibits an excellent antifouling effect even when the antifouling agent is not included. When the antifouling agent is included, the surface of the coating film is renewed, so that the antifouling agent is always exposed on the surface of the coating film, and the antifouling effect by the antifouling agent is stably exhibited over a long period of time.
  • the coating (A) is more coated than the case of using a copolymer having a structure containing a divalent metal as the hydrolyzable structure.
  • by combining a polysiloxane group with the structure (I) these effects become more excellent. This is considered to be due to the fact that the hydrophilicity of the coating film is lowered by the polysiloxane group, thereby suppressing the swelling and excessive dissolution of the coating film. Since the water resistance of the coating film is excellent, an excellent antifouling effect is stably exhibited over a long period of time.
  • the coating film has a sufficiently high hardness and is unlikely to cause damage or peeling of the coating film that causes a decrease in the antifouling effect. Also from this point, the excellent antifouling effect is stably exhibited over a long period of time.
  • the resin composition containing the copolymer (A) and the coating film of the antifouling coating composition also have the same effects as described above. Further, the copolymer (A) can be made into a solution having a high solid content and a low viscosity when an organic solvent is added.
  • the resin composition containing the copolymer (A) and the organic solvent has a high solid content and a low viscosity, it is possible to apply paint without adding an organic solvent to the resin composition at the time of producing the antifouling coating composition. It is possible to obtain an antifouling paint composition having Further, when an antifouling agent or the like is added, it can be mixed well with the antifouling agent or the like without adding an organic solvent. Therefore, an antifouling paint composition having a low VOC content can be obtained. Therefore, the copolymer (A) is suitable for an antifouling coating composition.
  • the second aspect of the present invention is a resin composition containing the copolymer (A).
  • the copolymer (A) contained in the resin composition of this embodiment may be one type or two or more types.
  • content of the copolymer (A) in the resin composition of this aspect is not specifically limited, 45 mass% or more is preferable with respect to the whole quantity of a resin composition, 50 mass% or more is more preferable, 55 mass% The above is more preferable, 60% by mass or more is particularly preferable, and 64% by mass or more is most preferable. If content of a copolymer (A) is more than the said lower limit, an antifouling paint composition with little VOC content can be obtained easily.
  • the upper limit of content of a copolymer (A) is not specifically limited, 100 mass% may be sufficient.
  • an amount is preferably such that the viscosity of the resin composition measured with a B-type viscometer at 25 ° C.
  • the copolymer (A) is less than 5,000 mPa ⁇ s (more preferably less than 3,000 mPa ⁇ s), although it varies depending on the weight average molecular weight, glass transition temperature, presence or absence of a crosslinked structure, etc., the copolymer (A) is preferably 80% by mass or less, more preferably 85% by mass or less.
  • the resin composition of this embodiment further includes at least one selected from the group consisting of a compound that reacts with an acid, a basic compound, an acidic compound, and a dehydrating agent.
  • the storage stability of the resin composition and the antifouling coating composition containing the resin composition is improved.
  • the structure (I) may be unintentionally decomposed during storage.
  • structure (I) decomposes a carboxylic acid is produced.
  • the glass transition temperature of the copolymer (A) is increased, or the carboxylic acid and other components in the coating form a crosslinked structure. Or rise.
  • dissolution stability and water resistance in an organic solvent are reduced.
  • the generated carboxylic acid catalyzes the hydrolysis reaction as an acid, whereby the structure (I) is further decomposed.
  • the carboxylic acid is captured by the compound that reacts with the acid.
  • Storage stability is improved. Further, in the high pH region and the low pH region, the storage stability is lowered by promoting the decomposition of the structure (I). In the high pH region, the storage stability also decreases due to a decrease in the reactivity between the compound (B) and the carboxylic acid.
  • Examples of the compound that reacts with an acid include the aforementioned compound (B), a basic compound, and a compound having an epoxy group.
  • Examples of the basic compound include dimethylamine, diethylamine, trimethylamine, triethylamine, aniline, pyridine and the like.
  • Examples of the compound containing an epoxy group include 2-ethyloxirane, 2,3-dimethyloxirane, 2,2-dimethyloxirane, glycidyl (meth) acrylate, glycidyl ⁇ -ethylacrylate, and (meth) acrylic acid 3,4. -Epoxybutyl and the like.
  • the compound that reacts with the acid is preferably the compound (B) from the viewpoint of storage stability.
  • the compound (B) is preferably a 1-alkenyl alkyl ether in which X in the formula (31) is —O— in that the effect of improving storage stability is more excellent. More preferred are vinyl ethers such as vinyl ether and isobutyl vinyl ether.
  • Acidic compounds include abietic acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, levopimaric acid, dextropimaric acid, sandaracopimaric acid, acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, linoleic acid, oleic acid Chloroacetic acid, fluoroacetic acid and the like.
  • Examples of the dehydrating agent include silicate type, isocyanate type, ortho ester type, and inorganic type. More specifically, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ortho boron ester, tetraethyl orthosilicate, anhydrous gypsum, calcined gypsum, synthetic zeolite (molecular sieve) and the like can be mentioned. Molecular sieve is particularly preferable.
  • additives can be used alone or in combination of two or more.
  • combinations of two or more additives include a combination of a compound (B) and a dehydrating agent, a combination of a compound (B), an acidic compound and a dehydrating agent, a compound (B), a basic compound, an acidic compound and a dehydrating agent.
  • the content of the compound (B) in the resin composition is 20 mol% or more based on the structure (I) of the copolymer (A). Preferably, it is 30 to 1000 mol%, more preferably 40 to 800 mol%. If content of a compound (B) is in the said range, the improvement effect of storage stability will be more excellent.
  • the content of the basic compound or / and acidic compound in the resin composition is such that the pH measured in water is 2 from the viewpoint of storage stability.
  • An amount of basic compound at a concentration of ⁇ 12 is preferred, and an amount of basic compound at a concentration of 6 ⁇ 9 is more preferred.
  • the pH measured in water is specifically a value measured by adding a basic compound in water.
  • the pH is a value at 23 ° C.
  • the content of the dehydrating agent in the resin composition is preferably 0.1 to 40% by mass, more preferably 1 to 20% by mass with respect to the total mass of the resin composition. . If content of a dehydrating agent is more than the lower limit of the said range, storage stability will be more excellent. If content of a dehydrating agent is below the upper limit of the said range, melt
  • the resin composition of the present invention preferably further contains silicone oil.
  • silicone oil examples include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil, and modified silicone oils.
  • the modified silicone oil is a silicone oil in which an organic group other than a methyl group and a phenyl group (hereinafter also referred to as “modified group”) is introduced into a part of silicon atoms of a straight silicone oil.
  • the modifying group examples include a chlorophenyl group, a methylstyrene group, a long chain alkyl group (for example, an alkyl group having 2 to 18 carbon atoms), a polyether group, a carbinol group, an aminoalkyl group, an epoxy group, a (meth) acryloyl group, and the like. Is mentioned. These silicone oils can be used alone or in combination of two or more. Among the above, as the silicone oil, a polyether-modified silicone oil having a polyether group as a modifying group is preferable from the viewpoint of antifouling properties.
  • silicone oils Commercially available products can be used as the silicone oil.
  • examples of commercially available silicone oils include “KF-96”, “KF-50”, “KF-54”, “KF-56”, “KF-6016” (above, manufactured by Shin-Etsu Chemical Co., Ltd.), “ “TSF451” (made by Momentive Performance Materials), “Fluid47” (made by Rhone Plan (France)), “SH200”, “SH510”, “SH550”, “SH710", “DC200”, “ST-114PA” ",” FZ209 “(manufactured by Toray Dow Corning).
  • the content of the silicone oil in the resin composition is preferably 0.1 to 40% by mass, more preferably 1 to 20% by mass with respect to the total mass of the resin composition. . If the content of the silicone oil is not less than the lower limit of the above range, the antifouling property is more excellent. If content of silicone oil is below the upper limit of the said range, melt
  • the resin composition of this embodiment preferably contains an organic solvent.
  • the organic solvent is not particularly limited as long as it can dissolve the copolymer (A).
  • hydrocarbon solvents such as toluene and xylene; the compound (B), propylene glycol monomethyl ether-2-acetate, etc.
  • the content of the organic solvent in the resin composition of this embodiment is preferably 60% by mass or less, and preferably 50% by mass or less, based on the total amount of the resin composition, from the viewpoint of reducing the VOC content of the antifouling coating composition. More preferably, it is more preferably 45% by mass or less, and particularly preferably 40% by mass or less.
  • the content of the organic solvent is preferably such that the viscosity measured with a B-type viscometer at 25 ° C.
  • the weight average molecular weight of the copolymer (A), glass transition Although it varies depending on the temperature and the presence or absence of a crosslinked structure, it is preferably 15% by mass or more, and more preferably 20% by mass or more.
  • the compound (B) can also function as an organic solvent. Therefore, when a resin composition contains a compound (B), content of a compound (B) is contained in content of an organic solvent.
  • the resin composition of this embodiment may further contain other components other than the copolymer (A), a compound that reacts with an acid, a basic compound, an acidic compound, a dehydrating agent, silicone oil, and an organic solvent.
  • other components include the same components as the other components in the antifouling coating composition described later.
  • the content of other components is preferably 200% by mass or less, and may be 0% by mass with respect to the copolymer (A).
  • the solid content of the resin composition of this embodiment is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 60% by mass or more.
  • the VOC content of the antifouling coating composition is sufficiently low.
  • the upper limit of the solid content of the resin composition is not particularly limited, and may be 100% by mass.
  • the content is preferably 85% by mass or less, and more preferably 80% by mass or less from the viewpoint of the viscosity of the resin composition.
  • the solid content of the resin composition is measured by the measurement method described in Examples described later.
  • the viscosity of the resin composition measured with a B-type viscometer at 25 ° C. is preferably less than 5000 mPa ⁇ s. It is more preferably less than 3000 mPa ⁇ s, even more preferably less than 2,000 mPa ⁇ s, and particularly preferably less than 1,000 mPa ⁇ s.
  • the viscosity (hereinafter also referred to as “Gardner viscosity”) measured by a Gardner bubble viscometer at 25 ° C. of the resin composition is preferably W or less, and more preferably V or less.
  • the viscosity (B-type viscosity or Gardner viscosity) of the resin composition is less than or equal to the above upper limit, an antifouling agent or the like may be blended or applied without adding a solvent for dilution to the resin composition.
  • an antifouling coating composition having a low VOC content can be obtained.
  • the resin composition has a viscosity at a solid content of at least 50% by mass, not more than the preferable upper limit.
  • the lower limit of the viscosity of the resin composition is not particularly limited. From the viewpoint of suppressing the sagging of the paint during coating, the B-type viscosity at 25 ° C. is preferably 100 mPa ⁇ s or more.
  • the B-type viscosity at 25 ° C. of the resin composition is preferably 100 mPa ⁇ s or more and less than 5,000 mPa ⁇ s, more preferably 100 mPa ⁇ s or more and less than 3,000 mPa ⁇ s, and more preferably 100 mPa ⁇ s or more and 2,000 mPa ⁇ s. Less than s is more preferable, and 100 mPa ⁇ s or more and less than 1,000 mPa ⁇ s is particularly preferable.
  • the viscosity of the resin composition depends on the solid content of the resin composition (contents of the copolymer (A) and other components), the weight average molecular weight of the copolymer (A), the glass transition temperature, the presence or absence of a crosslinked structure, and the like. Can be adjusted. For example, the lower the solid content, particularly the content of the copolymer (A), the lower the viscosity. Moreover, there exists a tendency for it to become low viscosity, so that the weight average molecular weight of a copolymer (A) is small or a glass transition temperature is low.
  • the decomposition rate of the structure (I) in the copolymer (A) after storage at 40 ° C. for 30 days is preferably 20% or less, and preferably 7% or less. More preferably, it is 4% or less, more preferably 3% or less, and most preferably 2% or less. If the decomposition rate of the structure (I) after storing the resin composition at 40 ° C. for 30 days is not more than the above upper limit value, the storage stability of the resin composition and the antifouling coating composition containing the resin composition is excellent. Moreover, when a resin composition contains the organic solvent, it is excellent also in the melt stability with respect to the organic solvent of a copolymer (A).
  • the decomposition rate is preferably as low as possible, and the lower limit may be 0%.
  • the decomposition rate of structure (I) after storage at 40 ° C. for 30 days can be reduced to 20% or less, for example, by adding a compound that reacts with an acid, a basic compound, an acidic compound, a dehydrating agent, or the like to the resin composition.
  • the storage of the resin composition means that the resin composition is sealed in a glass bottle and left in a dry environment in a shielded environment.
  • the decomposition rate of the structure (I) is determined when the structure (I) contained in the copolymer (A) is not completely decomposed from the measured solid acid value (a) of the resin composition (after storage at 40 ° C. for 30 days). It is defined as the following value obtained by dividing the value obtained by subtracting the theoretical solid acid value (b) by the theoretical acid value (c) when the structure (I) contained in the copolymer (A) is completely decomposed.
  • (Decomposition rate) ⁇ (Measured solid acid value (a)) ⁇ (Theoretical solid acid value (b)) ⁇ / (Theoretical solid acid value (c)) ⁇ 100
  • the measured solid acid value will be described later in the item of acid value measurement.
  • the theoretical solid acid value can be calculated by the following formula.
  • (Theoretical solid acid value) ⁇ (561 ⁇ 100 / Mw i ⁇ w i )
  • w i represents the mass fraction of the monomer i with acid functionality of the monomers constituting the copolymer (A)
  • Mw i represents the molecular weight of a monomer having an acid functional group .
  • the acid functional group is a functional group such as carboxylic acid.
  • the acid value at the time of decomposition is calculated as a monomer having an acid functional group.
  • the acid value when not decomposed is calculated as a monomer having no acid functional group.
  • the resin composition of this embodiment can be produced using a known method.
  • the copolymer (A) is produced by the production method ( ⁇ ) or ( ⁇ ) described above, and if necessary, the obtained copolymer (A) can be reacted with an acid, a basic compound, an acidic compound.
  • a resin composition can be prepared by blending a compound, a dehydrating agent, an organic solvent, other components, and the like.
  • blends a compound (B) may be the time of manufacture of a copolymer (A), and after manufacture of a copolymer (A). There may be, and it is not specifically limited.
  • the compound (B) may coexist during the polymerization of the monomer mixture, or the compound (B) may be added after the polymerization is completed.
  • the copolymer (A0) is obtained by reacting the produced copolymer (A0) with the compound (B) to obtain the copolymer (A0).
  • the compound (B) exceeding the equivalent amount with respect to the carboxy group of) may be added so that the unreacted compound (B) remains.
  • a method of adding the compound (B) after the completion of the polymerization is preferable.
  • the resin composition of this embodiment can be used as it is or mixed with an antifouling agent or the like as necessary to obtain an antifouling coating composition.
  • the resin composition of this embodiment can also be used for an antifogging paint composition and the like.
  • the coating film containing the resin composition of this embodiment exhibits self-polishing properties in seawater or the like as described above. Moreover, even when it does not contain an antifouling agent, it exhibits an excellent antifouling effect and is excellent in water resistance.
  • This coating film has a sufficiently high hardness.
  • the resin composition of this aspect can be made into the solution form of a high solid content low viscosity. Therefore, by using the resin composition of this embodiment, an antifouling paint composition having a low VOC content can be obtained.
  • the resin composition of this embodiment contains at least one selected from the group consisting of a compound that reacts with an acid, a basic compound, an acidic compound, and a dehydrating agent, in addition to the copolymer (A).
  • the resin composition can exhibit excellent storage stability.
  • the decomposition rate of the structure (I) in the copolymer (A) after storage at 40 ° C. for 30 days can be reduced to 20% or less.
  • the resin composition further contains an organic solvent, the increase in the viscosity of the resin composition over time can be suppressed. It is excellent also in the dissolution stability with respect to the organic solvent of the copolymer (A) in a resin composition. Therefore, the resin composition of this embodiment is suitable for an antifouling coating composition.
  • the third aspect of the present invention is an antifouling paint composition containing the resin composition of the second aspect. Therefore, the antifouling coating composition of this embodiment contains the copolymer (A).
  • the antifouling coating composition of this embodiment further comprises at least one selected from the group consisting of a compound that reacts with an acid, a basic compound, an acidic compound, and a dehydrating agent, from the viewpoint of the storage stability of the antifouling coating composition. It is preferable. Examples of the compound that reacts with an acid, a basic compound, an acidic compound, and a dehydrating agent are the same as those described above. The preferable content is also the same.
  • the antifouling coating composition of this embodiment further contains silicone oil from the viewpoint of the antifouling property of the coating film.
  • silicone oil are the same as described above.
  • the preferable content is also the same.
  • the antifouling paint composition of this embodiment may contain an organic solvent. Examples of the organic solvent are the same as described above.
  • the antifouling coating composition of this embodiment may further contain an antifouling agent.
  • the antifouling paint composition of this embodiment further comprises other components other than the copolymer (A), a compound that reacts with an acid, a basic compound, an acidic compound, a dehydrating agent, a silicone oil, an organic solvent, and an antifouling agent. But you can.
  • the antifouling paint composition contains a compound that reacts with an acid, a basic compound, an acidic compound, a dehydrating agent, a silicone oil, an organic solvent, other components, etc.
  • these components are derived from the resin composition, respectively. It may be, may not be derived (mixed at the time of manufacture of the antifouling paint composition), or a mixture thereof.
  • Antifouling agent examples include inorganic antifouling agents, organic antifouling agents, and the like, and one or more types can be appropriately selected and used according to the required performance.
  • Antifouling agents include, for example, copper-based antifouling agents such as cuprous oxide, thiocyanic copper and copper powder, compounds of other metals (lead, zinc, nickel, etc.), amine derivatives such as diphenylamine, nitrile compounds, benzothiazole Compounds, maleimide compounds, pyridine compounds, and the like. These can be used individually by 1 type or in combination of 2 or more types.
  • an antifouling agent 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, Manganese ethylene bisdithiocarbamate, zinc dimethyldithio Carbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, zinc ethylenebisdithiocarbamate Rhodan copper, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, N- (fluorodichloromethylthio) phthalimide, N, N′-dimethyl-N′-phenyl- (N-fluorodichloro Methylthio) sulfamide, 2-pyridinethiol-1-oxide zinc salt Also referred to
  • the antifouling agent includes cuprous oxide, pyridine triphenylborane, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4-bromo-2 in terms of antifouling properties.
  • the content of the antifouling agent in the antifouling coating composition is not particularly limited, but is 10 to 200 parts by mass with respect to 100 parts by mass of the copolymer (A). Part is preferable, and 50 to 150 parts by weight is more preferable.
  • the content of the antifouling agent is not less than the lower limit of the above range, the antifouling effect of the formed coating film is more excellent.
  • the content of the antifouling agent is not more than the upper limit of the above range, the coating film properties are excellent.
  • Examples of other components include other polymers than the copolymer (A).
  • Another polymer is a polymer which does not have structure (I), for example.
  • examples of other polymers include thermoplastic resins (thermoplastic polymers) other than the copolymer (A).
  • thermoplastic resins thermoplastic polymers
  • the antifouling coating composition of this embodiment contains a thermoplastic resin other than the copolymer (A).
  • the coating film properties such as crack resistance and water resistance are improved.
  • thermoplastic resin other than the copolymer (A) examples include chlorinated paraffin; chlorinated polyolefin such as chlorinated rubber, chlorinated polyethylene, and chlorinated polypropylene; polyvinyl ether; polypropylene sebacate; partially hydrogenated terphenyl; Vinyl acetate; (meth) methyl acrylate copolymer, (meth) ethyl acrylate copolymer, (meth) propyl acrylate copolymer, (meth) butyl acrylate copolymer, (meth) Poly (meth) acrylic acid alkyl ester such as cyclohexyl acrylate copolymer; polyether polyol; alkyd resin; polyester resin; vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl propionate copolymer, vinyl chloride- Isobutyl vinyl ether copolymer, vinyl chloride-isopropyl vinyl ester Vinyl chloride resins
  • the wax examples include animal-derived waxes such as beeswax; plant-derived waxes; semi-synthetic waxes such as amide waxes; synthetic waxes such as oxidized polyethylene waxes.
  • animal-derived waxes such as beeswax
  • plant-derived waxes such as plant-derived waxes
  • semi-synthetic waxes such as amide waxes
  • synthetic waxes such as oxidized polyethylene waxes.
  • thermoplastic resins may be used alone or in combination of two or more. Chlorinated paraffin is preferable in that it functions as a plasticizer and can improve the crack resistance and peel resistance of the coating film.
  • Organic waxes such as semi-synthetic wax and synthetic wax are preferred in that they function as an anti-settling agent and an anti-sagging agent, and an effect of improving the storage stability and pigment dispersibility of the antifouling coating composition is obtained. Oxidized polyethylene wax and polyamide wax are more preferred.
  • the content of the thermoplastic resin other than the copolymer (A) in the antifouling coating composition is not particularly limited, but is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the copolymer (A). 0.1 to 10 parts by mass is more preferable. If the content of the thermoplastic resin other than the copolymer (A) is not less than the lower limit of the above range, the coating film properties such as crack resistance and water resistance are more excellent, and if not more than the upper limit of the above range, More hydrolyzable.
  • the antifouling paint composition of this embodiment is provided with a silicone compound such as dimethylpolysiloxane (excluding silicone oil), fluorinated hydrocarbons for the purpose of imparting lubricity to the coating surface and preventing the adhesion of organisms.
  • a silicone compound such as dimethylpolysiloxane (excluding silicone oil), fluorinated hydrocarbons for the purpose of imparting lubricity to the coating surface and preventing the adhesion of organisms.
  • fluorine-containing compounds such as
  • the antifouling coating composition of this embodiment is composed of various pigments, antifoaming agents, leveling agents, pigment dispersants (eg anti-settling agents), anti-sagging agents, matting agents, ultraviolet absorbers, antioxidants, and improved heat resistance. Agents, slip agents, preservatives, plasticizers, viscosity control agents and the like may be included.
  • Examples of the pigment include zinc oxide, talc, silica, barium sulfate, potassium feldspar, aluminum hydroxide, magnesium carbonate, mica, carbon black, petal, titanium oxide, phthalocyanine blue, kaolin, gypsum and the like.
  • zinc oxide and talc are preferable.
  • anti-settling agents and anti-sagging agents other than thermoplastic resins include bentonite-based, finely divided silica-based, stearate salts, lecithin salts, alkyl sulfonates, and the like.
  • plasticizers other than thermoplastic resins include phthalate plasticizers such as dioctyl phthalate, dimethyl phthalate, dicyclohexyl phthalate, and diisodecyl phthalate; aliphatic dibasic ester plasticizers such as isobutyl adipate and dibutyl sebacate ; Glycol ester plasticizers such as diethylene glycol dibenzoate and pentaerythritol alkyl ester; phosphate ester plasticizers such as tricresyl phosphate (TCP), triaryl phosphate and trichloroethyl phosphate; epoxy soybean oil, octyl epoxy stearate, etc.
  • phthalate plasticizers such as dioctyl phthalate, dimethyl phthalate, dicyclohexyl phthalate, and diisodecyl phthalate
  • aliphatic dibasic ester plasticizers such as isobutyl
  • organic tin plasticizers such as dioctyltin laurate and dibutyltin laurate
  • trioctyl trimellitic acid triacetylene and the like.
  • the VOC content of the antifouling coating composition of this embodiment is preferably 410 g / L or less, more preferably 400 g / L or less, and even more preferably 380 g / L or less.
  • the VOC content is calculated from the following formula using the specific gravity of the antifouling paint composition and the value of the solid content (heating residue).
  • VOC content (g / L) specific gravity of composition ⁇ 1000 ⁇ (100 ⁇ solid content) / 100
  • the specific gravity of the antifouling coating composition is calculated by filling the antifouling coating composition in a specific gravity cup having a capacity of 100 mL at 25 ° C. and measuring the mass.
  • the solid content (heating residue) of the antifouling coating composition is measured by the method described in Examples described later.
  • VOC content can be adjusted with content of an organic solvent.
  • the solid content of the antifouling coating composition of this embodiment is preferably 55 to 100% by mass, more preferably 60 to 90% by mass, and even more preferably 65 to 80% by mass. If the solid content of the antifouling coating composition is at least the lower limit of the above range, the VOC content will be sufficiently low. If solid content is below the upper limit of the said range, it will be easy to make the viscosity of an antifouling coating composition low.
  • the B type viscosity at 25 ° C. of the antifouling coating composition of this embodiment is preferably less than 5,000 mPa ⁇ s, preferably less than 3,000 mPa ⁇ s, and more preferably less than 1,000 mPa ⁇ s. If the viscosity of the antifouling coating composition is not more than the above upper limit value, coating is easy.
  • the lower limit of the B-type viscosity of the antifouling coating composition is not particularly limited, but is preferably 100 mPa ⁇ s or more in terms of physical properties of the coating film.
  • the viscosity of the antifouling coating composition can be adjusted by the viscosity of the resin composition, the amount of organic solvent added to the resin composition, and the like.
  • the antifouling coating composition of this embodiment can be prepared by preparing the resin composition of this embodiment as described above, adding an antifouling agent, other components, and an organic solvent as necessary, and mixing them.
  • the antifouling paint composition of this aspect is for forming a paint film (antifouling paint film) on the surface of a base material such as an underwater structure such as a ship, various fishing nets, a port facility, an oil fence, a bridge, and a submarine base.
  • a coating film using the antifouling coating composition of this embodiment can be formed on the substrate surface directly or via a base coating film.
  • the undercoat film can be formed using a wash primer, a chlorinated rubber-based or epoxy-based primer, an intermediate coating, or the like.
  • the coating film can be formed by a known method.
  • an antifouling coating composition is applied to the surface of a substrate or a base coating on the substrate by means of brush coating, spray coating, roller coating, immersion coating, or the like, and dried to dry the coating film.
  • the coating amount of the antifouling coating composition can generally be set to an amount that results in a dry coating film thickness of 10 to 400 ⁇ m.
  • the coating film can be usually dried at room temperature, and may be heat-dried as necessary.
  • B type viscosity The viscosity of the measurement sample was measured with a B-type viscometer at 25 ° C., and the value was shown as the B-type viscosity.
  • a measurement sample was put in a dried Gardner bubble viscosity tube (hereinafter also simply referred to as a viscosity tube) up to the indication line of the viscosity tube, and the tube was stoppered with a cork stopper.
  • the viscosity tube from which the sample was collected was immersed vertically in a constant temperature water bath adjusted to a specified temperature (25.0 ⁇ 0.1 ° C) for at least 2 hours to make the sample constant temperature.
  • the viscosity tube was rotated 180 ° at the same time, and the viscosity (Gardner viscosity) was determined by comparing the milling speed of the sample with the reference tube.
  • Weight average molecular weight (Mw), number average molecular weight (Mn) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured using gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8220). TSKgel ⁇ -M (Tosoh Corp., 7.8 mm ⁇ 30 cm) and TSKguardcolumn ⁇ (Tosoh Corp., 6.0 mm ⁇ 4 cm) were used as columns.
  • a calibration curve was prepared using F288 / F1 / 28 / F80 / F40 / F20 / F2 / A1000 (manufactured by Tosoh Corporation, standard polystyrene) and a styrene monomer.
  • VOC content The VOC content of the antifouling coating composition was calculated from the following formula.
  • VOC content (g / L) specific gravity of composition ⁇ 1000 ⁇ (100 ⁇ solid content) / 100
  • the method for measuring the solid content is as described above.
  • the specific gravity was calculated by filling a specific gravity cup having a capacity of 100 mL with an antifouling paint composition at 25 ° C. and measuring the mass.
  • Martens hardness was measured at three different locations of the same coating film, and the average value thereof was defined as the coating film hardness, which was evaluated according to the following criteria.
  • ⁇ film hardness is 10.0 N / mm 2 or more
  • the coating film hardness is 5.0 N / mm 2 or more 10.0 N / mm less than 2.
  • ⁇ Coating film hardness of 1.2 N / mm 2 or more 5.0 N / mm less than 2.
  • X The coating film hardness is less than 1.2 N / mm 2 .
  • the resin composition On the glass substrate, the resin composition was applied with a 500 ⁇ m applicator and dried at room temperature for 1 week to form a coating film to obtain a test plate. After immersing this test plate in sterilized filtered seawater for one month, the test plate was dried at room temperature of 20 ° C. for one week. About the whitening degree, the coating-film surface of this test plate was observed visually. Evaluation was performed according to the following criteria. A: Almost no whitening is observed. ⁇ : Slight whitening is observed. ⁇ : Some whitening is observed. X: Fair whitening is observed.
  • a test plate was prepared by applying an antifouling coating composition on a glass plate substrate so that the dry film thickness was 120 ⁇ m. After immersing the test plate in sterilized filtered seawater for 3 months, the test plate was dried at room temperature of 20 ° C. for 1 week, and the surface of the coating film was observed. Evaluation was performed according to the following criteria. (Double-circle): A crack and peeling are not observed at all. ⁇ : Cracks are partially observed. (Triangle
  • the antifouling paint composition was applied to a sandblasted steel sheet to which a rust preventive paint had been applied in advance with a brush so that the dry film thickness was 200 to 300 ⁇ m, and dried to form a coating film to obtain a test plate. . After leaving this test plate in the Seto Inland Sea for 6 months, the ratio of the area where marine organisms adhered to the total area of the coating (the area where marine organisms adhered) was examined. evaluated.
  • ⁇ The adhesion area of seawater organisms is more than 10% and 20% or less.
  • X The adhesion area of seawater organisms exceeds 40%.
  • the antifouling paint composition was applied to a hard vinyl chloride plate of 50 mm ⁇ 50 mm ⁇ 2 mm (thickness) with an applicator so as to have a dry film thickness of 120 ⁇ m, dried to form a coating film, and a test plate was obtained. .
  • the test plate was attached to a rotating drum installed in seawater and rotated at a peripheral speed of 7.7 m / s (15 knots). This state was maintained for 6 months, and the film thickness ( ⁇ m) of the coating film was measured after 3 months and 6 months after installation.
  • the consumable film thickness 120 ⁇ m—measured film thickness
  • the value was defined as the degree of wear (after 3 months and 6 months).
  • the ratio of the degree of wear after 3 months ( ⁇ m) to the degree of wear after 6 months ( ⁇ m) (after 3 months / 6 months) was calculated. The closer this ratio is to 2.0, the smaller the change in the degree of wear of the coating film over time, which is preferable.
  • Monomer (M1) 1-butoxyethyl methacrylate (synthetic product synthesized in Production Example M1 described later).
  • Monomer (M2) 1-isobutoxyethyl methacrylate (synthetic product synthesized in Production Example M2 described later).
  • Monomer (M3) 1- (cyclohexyloxy) ethyl methacrylate (synthetic product synthesized in Production Example M3 described later)
  • Monomer (M4) 1- (2-ethylhexyloxy) ethyl methacrylate (synthetic product synthesized in Production Example M4 described later).
  • Monomer (M5) 2-tetrahydropyranyl methacrylate (synthetic product synthesized in Production Example M5 described later).
  • MMA methyl methacrylate.
  • EA ethyl acrylate.
  • 2-MTA 2-methoxyethyl acrylate.
  • 2-MTMA 2-methoxyethyl methacrylate.
  • MAA methacrylic acid.
  • TIPX Triisopropylsilyl acrylate.
  • Monomer (N1) Ethylenically unsaturated monomer mixture containing a divalent metal (synthetic product synthesized in Production Example N1 described later).
  • AIBN 2,2′-azobisisobutyronitrile.
  • AMBN 2,2′-azobis (2-methylbutyronitrile).
  • NOFMER MSD trade name, manufactured by NOF Corporation, ⁇ -methylstyrene dimer.
  • Additive (b) Disparon A603-20X (manufactured by Enomoto Kasei Co., Ltd., polyamide wax).
  • KF-6016 trade name, manufactured by Shin-Etsu Chemical Co., Ltd., polyether-modified silicone oil.
  • ST-114PA trade name, manufactured by Toray Dow Corning, polyether-modified silicone oil.
  • FZ209 Trade name, manufactured by Toray Dow Corning, methylphenyl silicone oil.
  • KF-56 trade name, manufactured by Shin-Etsu Chemical Co., Ltd., methylphenyl silicone oil.
  • Antifouling agent (1) 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile.
  • Antifouling agent (2) pyridine triphenylborane (manufactured by Hokuko Chemical Co., Ltd., trade name: PK).
  • Antifouling agent (3) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (Rohm and Haas, trade name: Cine Nine 211).
  • Tables 1 to 3 show the types and amounts of monomers and initiators, and the types and amounts of additives (compound (B), basic compound, acidic compound, dehydrating agent) added after polymerization.
  • Resin compositions B-2 to B-4 were prepared in the same manner as in Production Example B-1, except that the amount of xylene after the completion of dropping was adjusted according to the amount of additive so that the solid content was 50% by mass.
  • B-11 to B-26 and B-32 to B-35 were produced.
  • Table 3 shows the types and amounts of monomers and initiators, and the types and amounts of additives (compound (B), basic compound, acidic compound, dehydrating agent) to be added after polymerization.
  • compound (B) compound, basic compound, acidic compound, dehydrating agent
  • Tables 1 to 3 show characteristics of the obtained resin compositions B-1 to B-36 (solid content (mass%), B-type viscosity, Gardner viscosity, decomposition rate of structure (I) after storage at 40 ° C. for 30 days) Evaluation of the number average molecular weight (Mn) and weight average molecular weight (Mw) of the copolymer contained in each resin composition, and the performance (water resistance, coating hardness) of the coating film formed from each resin composition The results are listed.
  • Production Examples B-1 to B-31 are examples, and Production Examples B-32 to B-36 are comparative examples.
  • Examples 1 to 34, Comparative Examples 1 to 5 In accordance with the formulations shown in Tables 4 to 8, each component was mixed with a high speed disper to obtain an antifouling coating composition. Coating properties (solid content, B-type viscosity, VOC content), coating suitability, coating viscosity change rate, coating film performance (stationary antifouling property, water resistance, coating film consumption test) of the obtained antifouling coating composition Tables 4 to 8 show the evaluation results.
  • the compounding quantity of a resin composition is the quantity of the whole resin composition.
  • the antifouling paint compositions of Examples 1 to 34 had a low viscosity even at a high solid content, and good paintability. In addition, the viscosity change during storage is small, and it can be judged from the results of Production Examples B-1 and B-5 to B-9 that the decomposition rate of structure (I) during storage is low, and the storage stability is excellent. there were. In addition, the coating films of the antifouling paint compositions of Examples 1 to 34 were excellent in static fouling resistance and water resistance. This can be confirmed from the results of Production Examples B-1 to B-31. Further, this coating film had an appropriate degree of wear.
  • the coating film of the antifouling coating composition of Comparative Example 1 using the resin composition containing the copolymer having the structure (I) and not having the polysiloxane group has a static antifouling property and water resistance. It was inferior.
  • the coating film of the antifouling coating composition of Comparative Example 2 containing a copolymer having a higher structure (I) ratio than that of Comparative Example 1 was improved in static antifouling property but decreased in water resistance.
  • the coating film of the antifouling coating composition of Comparative Example 3 containing a copolymer having a triorganosilyloxycarbonyl group as a hydrolyzable structure (having a constitutional unit derived from TIPX) was inferior in static antifouling properties. .
  • the coating film of the antifouling coating composition of Comparative Example 4 containing a copolymer having a structure containing a divalent metal as a hydrolyzable structure was inferior in water resistance. Moreover, this antifouling paint composition had a high viscosity and was inferior in coating suitability.
  • the (meth) acrylic copolymer and resin composition of the present invention can be used for an antifouling coating composition, an antifogging coating composition, and the like, respectively, and particularly preferably for an antifouling coating composition.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Un copolymère (méth)acrylique, conformément à un mode de réalisation de la présente invention, comporte un groupe polysiloxane et au moins l'une des structures (I) représentées par la formule (1), la formule (2) ou la formule (3). (Dans les formules, X représente -O-, -S- ou -NR14- ; R14 représente un atome d'hydrogène ou un groupe alkyle ; R1 et R2 représentent un atome d'hydrogène ou un groupe alkyle ayant de 1 à 10 atomes de carbone ; R3 et R5 représentent un groupe alkyle ayant de 1 à 20 atomes de carbone, un groupe cycloalkyle ou un groupe aryle ; et R4 et R6 représentent un groupe alkylène ayant de 1 à 10 atomes de carbone.
PCT/JP2016/080250 2015-10-13 2016-10-12 Copolymère (méth)acrylique, composition de résine, composition de matériau de revêtement antisalissure, et procédé de production de copolymère (méth)acrylique Ceased WO2017065172A1 (fr)

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JP2016565365A JPWO2017065172A1 (ja) 2015-10-13 2016-10-12 （メタ）アクリル系共重合体、樹脂組成物、防汚塗料組成物及び（メタ）アクリル系共重合体の製造方法
KR1020187011051A KR102638011B1 (ko) 2015-10-13 2016-10-12 (메트)아크릴계 공중합체, 수지 조성물, 방오 도료 조성물 및 (메트)아크릴계 공중합체의 제조 방법
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JP2018062555A (ja) * 2016-10-12 2018-04-19 三菱ケミカル株式会社 （メタ）アクリル系共重合体、樹脂組成物、防汚塗料組成物および（メタ）アクリル系共重合体の製造方法
WO2018181429A1 (fr) * 2017-03-29 2018-10-04 三菱ケミカル株式会社 Copolymère (méth)acrylique, son procédé de production, composition de résine et composition de peinture antisalissures
WO2019230675A1 (fr) * 2018-06-01 2019-12-05 三菱ケミカル株式会社 Composition de peinture antisalissure
GB202107159D0 (en) 2021-03-23 2021-06-30 Jotun As Monitoring a vessel
WO2021180588A2 (fr) 2020-03-09 2021-09-16 Jotun A/S Robot de nettoyage de coque
WO2021191388A1 (fr) 2020-03-27 2021-09-30 Jotun A/S Composition de revêtement antisalissure
WO2022190755A1 (fr) * 2021-03-11 2022-09-15 Dic株式会社 Résine acrylique insaturée, composition de résine durcissable par rayonnement d'énergie active, produit durci et article
WO2022200430A1 (fr) 2021-03-23 2022-09-29 Jotun A/S Surveillance de la propreté d'une surface immergée d'un objet stationnaire
US11643489B2 (en) 2015-09-25 2023-05-09 Mitsubishi Chemical Corporation (Meth)acrylic copolymer, polymer solution, polymer-containing composition, anti-fouling coating composition, and method for producing (meth)acrylic copolymer
EP3714007B1 (fr) 2017-11-24 2024-08-21 Jotun A/S Composition antisalissures
WO2024227831A1 (fr) 2023-05-04 2024-11-07 Akzo Nobel Coatings International B.V. Composition de revêtement anti-salissures

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JP7686419B2 (ja) * 2020-03-26 2025-06-02 中国塗料株式会社 防汚塗料組成物
CN114716913B (zh) * 2022-03-17 2023-03-03 中国船舶重工集团公司第七二五研究所 一种双亲性防污活性剂及其制备方法
CN118006183A (zh) * 2024-02-18 2024-05-10 蓝海超杰特种材料(青岛)有限公司 一种高透明强粘结聚硅氧烷化合物及其制备方法

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JP2018062555A (ja) * 2016-10-12 2018-04-19 三菱ケミカル株式会社 （メタ）アクリル系共重合体、樹脂組成物、防汚塗料組成物および（メタ）アクリル系共重合体の製造方法
US11414508B2 (en) 2017-03-29 2022-08-16 Mitsubishi Chemical Corporation Resin composition with a (meth)acrylic copolymer, antifouling paint composition, and method for producing same
WO2018181429A1 (fr) * 2017-03-29 2018-10-04 三菱ケミカル株式会社 Copolymère (méth)acrylique, son procédé de production, composition de résine et composition de peinture antisalissures
EP3714007B1 (fr) 2017-11-24 2024-08-21 Jotun A/S Composition antisalissures
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WO2019230675A1 (fr) * 2018-06-01 2019-12-05 三菱ケミカル株式会社 Composition de peinture antisalissure
WO2021180588A2 (fr) 2020-03-09 2021-09-16 Jotun A/S Robot de nettoyage de coque
WO2021191388A1 (fr) 2020-03-27 2021-09-30 Jotun A/S Composition de revêtement antisalissure
WO2022190755A1 (fr) * 2021-03-11 2022-09-15 Dic株式会社 Résine acrylique insaturée, composition de résine durcissable par rayonnement d'énergie active, produit durci et article
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JP7375948B2 (ja) 2021-03-11 2023-11-08 Dic株式会社 不飽和アクリル樹脂、活性エネルギー線硬化性樹脂組成物、硬化物及び物品
GB202107159D0 (en) 2021-03-23 2021-06-30 Jotun As Monitoring a vessel
WO2022200430A1 (fr) 2021-03-23 2022-09-29 Jotun A/S Surveillance de la propreté d'une surface immergée d'un objet stationnaire
WO2022200427A1 (fr) 2021-03-23 2022-09-29 Jotun A/S Surveillance d'un navire
WO2024227831A1 (fr) 2023-05-04 2024-11-07 Akzo Nobel Coatings International B.V. Composition de revêtement anti-salissures

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