WO2018097260A1 - Polymère, composition de résine, composition de matériau de revêtement antisalissure, procédé de production de polymère, procédé de formation d'une structure pour stabiliser un carbamate sur la surface d'un film de revêtement et procédé pour régénérer une structure de stabilisation d'un carbamate sur la surface d'un film de revêtement - Google Patents

Polymère, composition de résine, composition de matériau de revêtement antisalissure, procédé de production de polymère, procédé de formation d'une structure pour stabiliser un carbamate sur la surface d'un film de revêtement et procédé pour régénérer une structure de stabilisation d'un carbamate sur la surface d'un film de revêtement Download PDF

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Publication number
WO2018097260A1
WO2018097260A1 PCT/JP2017/042272 JP2017042272W WO2018097260A1 WO 2018097260 A1 WO2018097260 A1 WO 2018097260A1 JP 2017042272 W JP2017042272 W JP 2017042272W WO 2018097260 A1 WO2018097260 A1 WO 2018097260A1
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Prior art keywords
group
substituent
polymer
alkylene
phenylene
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PCT/JP2017/042272
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English (en)
Japanese (ja)
Inventor
健雄 須賀
西出　宏之
匠 勝間田
佳奈 谷口
中村　淳一
知一 岩崎
Original Assignee
学校法人早稲田大学
三菱ケミカル株式会社
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Priority claimed from JP2017118169A external-priority patent/JP7026343B2/ja
Application filed by 学校法人早稲田大学, 三菱ケミカル株式会社 filed Critical 学校法人早稲田大学
Priority to CN201780071939.9A priority Critical patent/CN110062771A/zh
Priority to EP17873484.4A priority patent/EP3546487A4/fr
Priority to KR1020197014412A priority patent/KR20190073453A/ko
Publication of WO2018097260A1 publication Critical patent/WO2018097260A1/fr
Priority to JP2018218655A priority patent/JP2019094494A/ja
Priority to US16/398,319 priority patent/US20190276682A1/en

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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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • 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
    • C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to a polymer, a resin composition, an antifouling coating composition, a method for producing the polymer, a method for producing a structure for stabilizing carbamate on the surface of the coating film, and a structure for stabilizing carbamate on the surface of the coating film.
  • This application claims priority based on Japanese Patent Application No. 2016-229585 filed in Japan on November 25, 2016 and Japanese Patent Application No. 2017-118169 filed on June 15, 2017 in Japan. Is hereby incorporated by reference.
  • 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.
  • the antifouling paint those containing a film-forming resin and an antifouling agent are generally used.
  • an antifouling effect can be obtained by imparting super hydrophilicity to the surface of a substrate.
  • Patent Document 1 a polymer containing a structural unit derived from a non-crosslinked vinyl monomer and a structural unit represented by a specific general formula and having a quaternary ammonium salt structure or a betaine structure is used as an active ingredient.
  • An antimicrobial composition is described. It has been reported that by treating the surface of a fishing net or the like using this antibacterial composition, adhesion of contaminants such as aonori in water can be suppressed.
  • Non-Patent Document 1 a polymer brush formed by growing a zwitterionic polymer chain such as poly (phosphobetaine) or poly (sulfobetaine) from the surface of a Si substrate inhibits adhesion of various marine organisms, and is excellent. It has been reported to exhibit antifouling properties.
  • This polymer brush is formed by surface-initiated atom transfer radical polymerization on a Si substrate.
  • the polymer of Patent Document 1 has a quaternary ammonium salt structure or a betaine structure and has high hydrophilicity. Therefore, the coating film of this polymer is also highly hydrophilic and has low water resistance. For example, the coating film tends to collapse or peel off in seawater.
  • the polymer brush of Non-Patent Document 1 is considered to hardly peel off from the substrate because the end is bonded to the substrate. However, this polymer brush is difficult to manufacture and is difficult to apply to a large area substrate.
  • patent document 2 it is not examined about making a zwitterionic polymer into a coating film by coating. Such a coating film is considered to have low water resistance, like the polymer coating film of Patent Document 1, due to the high hydrophilicity of the zwitterionic polymer.
  • An object of the present invention is to provide a polymer, a resin composition and an antifouling coating composition that can form a coating film having both antifouling properties due to super hydrophilicity and water resistance, a method for producing the polymer, and the heavy
  • An object of the present invention is to provide a method for producing a structure for stabilizing carbamate on the surface of a coating film using a coalescence and a method for regenerating a structure for stabilizing carbamate on the surface of the coating film.
  • the polymer according to [1], wherein the structure that reacts with CO 2 and stabilizes the formed carbamate is represented by the following formula (I-1).
  • L 1 is an alkylene group or a phenylene group which may have a substituent, and may be linear or branched.
  • alkylene group and phenylene group may have are alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, hydroxyl group, amide group, halogen, allyl group, epoxy group, alkoxy group, siloxy group Or a group exhibiting hydrophilicity or ionicity.
  • R 1 is an alkylene group which may have a substituent, or a group containing —O— or —S— between the carbon atoms of the alkylene group
  • R 2 to R 4 each independently represents a hydrogen atom, a substituent optionally may alkyl group has, or an alkoxy group or a phenyl group, or one is hydrogen atom, or an alkyl group optionally having a substituent of R 2 ⁇ R 4, alkoxy group or a phenyl group
  • the other two may have a substituent together, a group containing —O— or —N— between the carbon atoms of the alkylene group, a phenylene group, or a substituent. It forms one of the heterocyclic rings.
  • L 1 is an alkylene group or phenylene group having no substituent
  • at least one of R 2 to R 4 is an alkyl group, an alkoxy group or a phenyl group which may have a substituent.
  • the polymer according to [1], wherein the structure that reacts with CO 2 and stabilizes the formed carbamate is represented by the following formula (I-2) and / or formula (I-3).
  • L 2 is an alkylene group or a phenylene group which may have a substituent, and may be linear or branched.
  • the substituents that the alkylene group and phenylene group may have are alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, hydroxyl group, amide group, halogen, allyl group, epoxy group, alkoxy group, siloxy group Or a group exhibiting hydrophilicity or ionicity.
  • R 1 is an alkylene group which may have a substituent, or a group containing —O— or —S— between the carbon atoms of the alkylene group
  • R 5 is a hydrogen atom or a substituent.
  • R 6 to R 8 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, or a phenyl group, or R 6 to R 8 integrally have a substituent.
  • R 9 to R 10 are an alkylene group which may have a substituent, a group containing —O— or —S— between the carbon atoms of the alkylene group, or L 2 , R 9 and R 10 are combined with each other. To form any of the heterocyclic rings which may have a substituent.
  • R 11 to R 12 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group or a phenyl group, or R 11 to R 12 integrally have a substituent.
  • a good alkylene group, a group containing —O— or —N— between carbon atoms of the alkylene group, or a phenylene group is formed.
  • Z ⁇ is a counter anion.
  • L 1 is an alkylene group or a phenylene group which may have a substituent, and may be linear or branched.
  • alkylene group and phenylene group may have are alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, hydroxyl group, amide group, halogen, allyl group, epoxy group, alkoxy group, siloxy group Or a group exhibiting hydrophilicity or ionicity.
  • R 1 is an alkylene group which may have a substituent, or a group containing —O— or —S— between the carbon atoms of the alkylene group
  • R 2 to R 4 each independently represents a hydrogen atom, a substituent optionally may alkyl group has, or an alkoxy group or a phenyl group, or one is hydrogen atom, or an alkyl group optionally having a substituent of R 2 ⁇ R 4, alkoxy group or a phenyl group
  • the other two may have a substituent together, a group containing —O— or —N— between the carbon atoms of the alkylene group, a phenylene group, or a substituent. It forms one of the heterocyclic rings.
  • L 1 is an alkylene group or phenylene group having no substituent
  • at least one of R 2 to R 4 is an alkyl group, an alkoxy group or a phenyl group which may have a substituent.
  • L 2 is an alkylene group or a phenylene group which may have a substituent, and may be linear or branched.
  • the substituents that the alkylene group and phenylene group may have are alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, hydroxyl group, amide group, halogen, allyl group, epoxy group, alkoxy group, siloxy group Or a group exhibiting hydrophilicity or ionicity.
  • R 1 is an alkylene group which may have a substituent, or a group containing —O— or —S— between the carbon atoms of the alkylene group
  • R 5 is a hydrogen atom or a substituent.
  • R 6 to R 8 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, or a phenyl group, or R 6 to R 8 integrally have a substituent.
  • R 9 to R 10 are an alkylene group which may have a substituent, a group containing —O— or —S— between the carbon atoms of the alkylene group, or L 2 , R 9 and R 10 are combined with each other. To form any of the heterocyclic rings which may have a substituent.
  • R 11 to R 12 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group or a phenyl group, or R 11 to R 12 integrally have a substituent.
  • a good alkylene group, a group containing —O— or —N— between carbon atoms of the alkylene group, or a phenylene group is formed.
  • Z ⁇ is a counter anion.
  • a resin composition comprising the polymer according to any one of [1] to [7].
  • An antifouling paint composition comprising the resin composition according to [8].
  • the antifouling paint composition according to [9] further comprising an antifouling agent.
  • 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 [10] comprising at least one selected from the group consisting of 5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile and medetomidine.
  • Monomer (m1) A monomer having the structure (I).
  • L 1 is an alkylene group or a phenylene group which may have a substituent, and may be linear or branched.
  • the substituents that the alkylene group and phenylene group may have are alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, hydroxyl group, amide group, halogen, allyl group, epoxy group, alkoxy group, siloxy group Or a group exhibiting hydrophilicity or ionicity.
  • R 1 is an alkylene group which may have a substituent, or a group containing —O— or —S— between the carbon atoms of the alkylene group
  • R 2 to R 4 each independently represents a hydrogen atom, a substituent optionally may alkyl group has, or an alkoxy group or a phenyl group, or one is hydrogen atom, or an alkyl group optionally having a substituent of R 2 ⁇ R 4, alkoxy group or a phenyl group
  • the other two may have a substituent together, a group containing —O— or —N— between the carbon atoms of the alkylene group, a phenylene group, or a substituent. It forms one of the heterocyclic rings.
  • L 1 is an alkylene group or phenylene group having no substituent
  • at least one of R 2 to R 4 is an alkyl group, an alkoxy group or a phenyl group which may have a substituent.
  • L 2 is an alkylene group or a phenylene group which may have a substituent, and may be linear or branched.
  • the substituents that the alkylene group and phenylene group may have are alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, hydroxyl group, amide group, halogen, allyl group, epoxy group, alkoxy group, siloxy group Or a group exhibiting hydrophilicity or ionicity.
  • R 5 is a hydrogen atom, an optionally substituted alkyl group, an alkoxy group or a phenyl group.
  • R 6 to R 8 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, or a phenyl group, or R 6 to R 8 integrally have a substituent.
  • R 9 to R 10 are an alkylene group which may have a substituent, a group containing —O— or —S— between the carbon atoms of the alkylene group, or L 2 , R 9 and R 10 are combined with each other. To form any of the heterocyclic rings which may have a substituent.
  • R 11 to R 12 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group or a phenyl group, or R 11 to R 12 integrally have a substituent.
  • a good alkylene group, a group containing —O— or —N— between carbon atoms of the alkylene group, or a phenylene group is formed.
  • Z ⁇ is a counter anion.
  • Polymer (A) A polymer having the structure (I) represented by the following formula (I-1) and / or (I-2) and / or (I-3).
  • Polymer (A0) A polymer having an epoxy group.
  • Compound (1) A compound capable of reacting with an epoxy group.
  • L 1 is an alkylene group or a phenylene group which may have a substituent, and may be linear or branched.
  • alkylene group and phenylene group may have are alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, hydroxyl group, amide group, halogen, allyl group, epoxy group, alkoxy group, siloxy group Or a group exhibiting hydrophilicity or ionicity.
  • R 1 is an alkylene group which may have a substituent, or a group containing —O— or —S— between the carbon atoms of the alkylene group
  • R 2 to R 4 each independently represents a hydrogen atom, a substituent optionally may alkyl group has, or an alkoxy group or a phenyl group, or one is hydrogen atom, or an alkyl group optionally having a substituent of R 2 ⁇ R 4, alkoxy group or a phenyl group
  • the other two may have a substituent together, a group containing —O— or —N— between the carbon atoms of the alkylene group, a phenylene group, or a substituent. It forms one of the heterocyclic rings.
  • L 1 is an alkylene group or phenylene group having no substituent
  • at least one of R 2 to R 4 is an alkyl group, an alkoxy group or a phenyl group which may have a substituent.
  • L 2 is an alkylene group or a phenylene group which may have a substituent, and may be linear or branched.
  • the substituents that the alkylene group and phenylene group may have are alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, hydroxyl group, amide group, halogen, allyl group, epoxy group, alkoxy group, siloxy group Or a group exhibiting hydrophilicity or ionicity.
  • R 5 is a hydrogen atom, an optionally substituted alkyl group, an alkoxy group or a phenyl group.
  • R 6 to R 8 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, or a phenyl group, or R 6 to R 8 integrally have a substituent.
  • R 9 to R 10 are an alkylene group which may have a substituent, a group containing —O— or —S— between the carbon atoms of the alkylene group, or L 2 , R 9 and R 10 are combined with each other. To form any of the heterocyclic rings which may have a substituent.
  • R 11 to R 12 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group or a phenyl group, or R 11 to R 12 integrally have a substituent.
  • a good alkylene group, a group containing —O— or —N— between carbon atoms of the alkylene group, or a phenylene group is formed.
  • Z ⁇ is a counter anion.
  • a polymer, a resin composition and an antifouling coating composition that can form a coating film having both antifouling properties due to super hydrophilicity and water resistance, an antifouling coating composition, a method for producing the polymer, and the heavy It is possible to provide a method for producing a structure for stabilizing carbamate on the surface of the coating film and a method for regenerating the structure for stabilizing carbamate on the surface of the coating film using the coalescence.
  • the “(meth) acrylic polymer” means a polymer 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).
  • “Polymer” is meant to include both single polymers and copolymers.
  • “(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.
  • a first aspect of the present invention is a polymer having a structure that stabilizes a carbamate formed in the presence of water and satisfying the following formula (1).
  • the surface of the coating film containing the polymer (A) is reacted with CO 2 in the presence of water to stabilize the carbamate formed. Generate.
  • the contact angle in water after reacting with CO 2 in the presence of water on the surface of the coating film is greater than the contact angle in water before reacting with CO 2 in the presence of water on the surface of the coating film containing the polymer.
  • water contact angle after the reaction with CO 2 may, it is preferably higher than 10 degrees than water contact angle before reacting with CO 2
  • water contact angle after the reaction with CO 2 is 140 Is more preferably 150 degrees or more, further preferably 160 degrees or more, and particularly preferably 165 degrees or more.
  • Water contact angle after the reaction with CO 2 is by high 10 degrees or more than water contact angle before reacting with CO 2, the initial water resistance is good, the compatibility between water resistance and stain resistance Is possible.
  • Water contact angle after the reaction with CO 2 is improved antifouling property by greater than 140 degrees, by higher than 160 degrees, further antifouling performance improvement is expected.
  • the underwater contact angle is the contact angle between the coating film surface and air in water.
  • the second aspect of the present invention is a polymer in which the structure that reacts with CO 2 to stabilize the carbamate formed is represented by the following formula (I-1).
  • L 1 is an alkylene group or a phenylene group which may have a substituent, and may be linear or branched.
  • the substituents that the alkylene group and phenylene group may have are alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, hydroxyl group, amide group, halogen, allyl group, epoxy group, alkoxy group, siloxy group Or a group exhibiting hydrophilicity or ionicity.
  • R 1 is an alkylene group which may have a substituent, or a group containing —O— or —S— between the carbon atoms of the alkylene group
  • R 2 to R 4 each independently represents a hydrogen atom, a substituent optionally may alkyl group has, or an alkoxy group or a phenyl group, or one is hydrogen atom, or an alkyl group optionally having a substituent of R 2 ⁇ R 4, alkoxy group or a phenyl group
  • the other two may have a substituent together, a group containing —O— or —N— between the carbon atoms of the alkylene group, a phenylene group, or a substituent. It forms one of the heterocyclic rings.
  • L 1 is an alkylene group or phenylene group having no substituent
  • at least one of R 2 to R 4 is an alkyl group, an alkoxy group or a phenyl group which may have a substituent.
  • the third aspect of the present invention is a polymer in which the structure that reacts with CO 2 to stabilize the carbamate is represented by the following formula (I-2) and / or (I-3).
  • L 2 is an alkylene group or a phenylene group which may have a substituent, and may be linear or branched.
  • the substituents that the alkylene group and phenylene group may have are alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, hydroxyl group, amide group, halogen, allyl group, epoxy group, alkoxy group, siloxy group Or a group exhibiting hydrophilicity or ionicity.
  • R 1 is an alkylene group which may have a substituent, or a group containing —O— or —S— between the carbon atoms of the alkylene group
  • R 5 is a hydrogen atom or a substituent.
  • R 6 to R 8 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, or a phenyl group, or R 6 to R 8 integrally have a substituent. Forms one of the good heterocycles.
  • R 9 to R 10 are an alkylene group which may have a substituent, a group containing —O— or —S— between the carbon atoms of the alkylene group, or L 2 , R 9 and R 10 are combined with each other.
  • R 11 to R 12 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group or a phenyl group, or R 11 to R 12 integrally have a substituent.
  • a good alkylene group, a group containing —O— or —N— between carbon atoms of the alkylene group, or a phenylene group is formed.
  • Z ⁇ is a counter anion.
  • a fourth aspect of the present invention is a polymer having the structural formula (I) represented by the following formula (I-1).
  • L 1 is an alkylene group or a phenylene group which may have a substituent, and may be linear or branched.
  • the substituents that the alkylene group and phenylene group may have are alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, hydroxyl group, amide group, halogen, allyl group, epoxy group, alkoxy group, siloxy group Or a group exhibiting hydrophilicity or ionicity.
  • R 1 is an alkylene group which may have a substituent, or a group containing —O— or —S— between the carbon atoms of the alkylene group
  • R 2 to R 4 each independently represents a hydrogen atom, a substituent optionally may alkyl group has, or an alkoxy group or a phenyl group, or one is hydrogen atom, or an alkyl group optionally having a substituent of R 2 ⁇ R 4, alkoxy group or a phenyl group
  • the other two may have a substituent together, a group containing —O— or —N— between the carbon atoms of the alkylene group, a phenylene group, or a substituent. It forms one of the heterocyclic rings.
  • L 1 is an alkylene group or phenylene group having no substituent
  • at least one of R 2 to R 4 is an alkyl group, an alkoxy group or a phenyl group which may have a substituent.
  • a fifth aspect of the present invention is a polymer having the structural formula (I) represented by the following formula (I-2) and / or formula (I-3).
  • L 2 is an alkylene group or a phenylene group which may have a substituent, and may be linear or branched.
  • the substituents that the alkylene group and phenylene group may have are alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, hydroxyl group, amide group, halogen, allyl group, epoxy group, alkoxy group, siloxy group Or a group exhibiting hydrophilicity or ionicity.
  • R 1 is an alkylene group which may have a substituent, or a group containing —O— or —S— between the carbon atoms of the alkylene group
  • R 5 is a hydrogen atom or a substituent.
  • R 6 to R 8 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, or a phenyl group, or R 6 to R 8 integrally have a substituent. Forms one of the good heterocycles.
  • R 9 to R 10 are an alkylene group which may have a substituent, a group containing —O— or —S— between the carbon atoms of the alkylene group, or L 2 , R 9 and R 10 are combined with each other.
  • R 11 to R 12 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group or a phenyl group, or R 11 to R 12 integrally have a substituent.
  • a good alkylene group, a group containing —O— or —N— between carbon atoms of the alkylene group, or a phenylene group is formed.
  • Z ⁇ is a counter anion.
  • L 1 and L 2 preferably have 1 to 10 carbon atoms.
  • R 1 is preferably (CR 13 R 14 ) n .
  • R 13 and R 14 are each independently a hydrogen atom or an alkyl group which may have a substituent, and n is preferably an integer of 1 to 10. When n is 2 or more, n R 11 and n R 12 may be the same or different.
  • the alkyl group of R 13 and R 14 preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • Examples of the substituent that the alkyl group may have include the same substituents that the alkylene group may have.
  • the (CR 13 R 14) n, those both R 13 and R 14 are hydrogen atoms, i.e. (CH 2) n is preferable.
  • n is preferably an integer of 1 to 10, particularly preferably 2 or 3.
  • a reaction occurs in which structure (I) becomes a zwitterionic structure or a dicationic structure.
  • n is 2 or 3
  • the ratio of the zwitterionic structure to the total of the zwitterionic structure and the dicationic structure generated from the structure (I) tends to increase.
  • the alkyl group of R 2 to R 4 may be linear or branched.
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a 2-ethylhexyl group.
  • the alkoxy group may be linear or branched.
  • the alkoxy group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, 2-ethylhexyloxy group and the like.
  • Examples of the substituent that the alkyl group, alkoxy group, and phenyl group of R 2 to R 4 may have include an alkyl group, an aryl group, a carboxyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group, an amide group, and a halogen atom.
  • examples of the alkyl group and alkoxy group include the same groups as described above.
  • Examples of the aryl group include a phenyl group and a naphthyl group.
  • the alkoxy group in the alkoxycarbonyl group is the same as described above.
  • Examples of the alkoxycarbonyl group include a methoxycarbonyl group.
  • Examples of the amide group include a carbamoyl group (—CONH 2 ), an N-methylcarbamoyl group (—CONHCH 3 ), and an N, N-dimethylcarbamoyl group (dimethylamide group: —CON (CH 3 ) 2 ).
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • hydrophilic or ionic group examples include cationic substitution such as alkali salt of carboxy group or alkali salt of sulfoxy group, poly (alkylene oxide) group such as polyethylene oxide group and polypropylene oxide group, and quaternary ammonium base. Groups.
  • Two of R 2 to R 4 may together form an alkylene group, a group containing —O— between the carbon atoms of the alkylene group, or a phenylene group. Each of these groups may have a substituent. Examples of the substituent include the same substituents that the alkylene group, alkoxy group, and phenyl group may have. Examples of the alkylene group formed by combining R 2 or R 3 and R 4 and a group containing —O— between the carbon atoms of the alkylene group are the same as those for R 1, and preferred embodiments are also the same. . When R 2 and R 3 are combined to form an alkylene group, examples of this alkylene group include (CR 15 R 16 ) m .
  • R 15 and R 16 are each independently a hydrogen atom or an alkyl group which may have a substituent, and m is preferably an integer of 2 to 10. m R 15 and m R 16 may be the same or different from each other. Examples of the alkyl group for R 15 and R 16 include the same alkyl groups as those for R 13 and R 14 . m is preferably an integer of 2 to 10, particularly preferably an integer of 2 to 6.
  • the alkyl group, alkoxy group or phenyl group which may have a substituent of R 5 to R 12 has a substituent in R 2 to R 4 , respectively. It is the same as the alkyl group, alkoxy group or phenyl group which may be present.
  • Z ⁇ include Br ⁇ , I ⁇ , BF 4 ⁇ , PF 6 — and the like. Of these, Br ⁇ and I ⁇ are preferable in terms of imparting hydrophilicity and antibacterial properties.
  • At least one of R 2 to R 4 is preferably a hydrogen atom.
  • at least one of R 5 , R 11 and R 12 is preferably a hydrogen atom. Since the hydrogen atom is bonded to the nitrogen atom in the structure (I), the reaction in which the structure (I) becomes a zwitterionic structure easily proceeds.
  • Examples of the structure (I-1) further include structures of the following formulas (I-1-a) and (I-1-b).
  • L 1 is an alkylene group or a phenylene group which may have a substituent, and may be linear or branched.
  • the substituents that the alkylene group and phenylene group may have are alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, hydroxyl group, amide group, halogen, allyl group, epoxy group, alkoxy group, siloxy group Or a group exhibiting hydrophilicity or ionicity.
  • R 1 is an alkylene group which may have a substituent, or a group containing —O— or —S— between the carbon atoms of the alkylene group.
  • Preferred examples of the structure (I-2) further include structures of the following formulas (I-2-a) to (I-2-e).
  • L 2 is an alkylene group or a phenylene group which may have a substituent, and may be linear or branched.
  • the substituents that the alkylene group and phenylene group may have are alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, hydroxyl group, amide group, halogen, allyl group, epoxy group, alkoxy group, siloxy group Or a group exhibiting hydrophilicity or ionicity.
  • R 1 is an alkylene group which may have a substituent, or a group containing —O— or —S— between the carbon atoms of the alkylene group.
  • Examples of the structure (I-3) further include structures of the following formulas (I-3-a) to (I-3-f).
  • L 1 is an alkylene group or a phenylene group which may have a substituent, and may be linear or branched.
  • the substituents that the alkylene group and phenylene group may have are alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, hydroxyl group, amide group, halogen, allyl group, epoxy group, alkoxy group, siloxy group Or a group exhibiting hydrophilicity or ionicity.
  • R 1 is an alkylene group which may have a substituent, or a group containing —O— or —S— between the carbon atoms of the alkylene group.
  • L 2 is an alkylene group or a phenylene group which may have a substituent, and may be linear or branched.
  • the substituents that the alkylene group and phenylene group may have are alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, hydroxyl group, amide group, halogen, allyl group, epoxy group, alkoxy group, siloxy group Or a group exhibiting hydrophilicity or ionicity.
  • R 32 is an alkyl group
  • R 33 to R 35 are a hydrogen atom or an alkyl group.
  • R 32 to R 35 are a hydrogen atom or an alkyl group.
  • R 32 to R 34 are a hydrogen atom or a phenyl group, and R 42 is a hydrogen atom or an alkyl group.
  • R 32 to R 36 are a hydrogen atom or a phenyl group, and R 42 is a hydrogen atom or an alkyl group.
  • R 32 to R 34 are an alkyl group or a phenyl group.
  • n and Z ⁇ are the same as described above.
  • the structure (I) of the polymer (A) may be one type or two or more types. For example, it may have any structure of formula (I-1) and / or formula (I-2) and / or formula (I-3).
  • the structure (I) may be contained in the structural unit of the polymer (A), may be contained at the ends of the main chain, may be contained between the main chains, or may be contained in any of them. From the viewpoint of antifouling properties, it is preferable that the structure (I) is contained at least in the structural unit. That is, the polymer (A) is preferably a polymer having a structural unit having the structure (I) (hereinafter also referred to as “structural unit (u1)”).
  • the structural unit (u1) only needs to have the structure (I), and the structure of the portion other than the structure (I) is not particularly limited.
  • the structure of the portion other than the structure (I) can be appropriately selected from structural units possessed by various known resins (polymers). Examples of such resins include vinyl polymers such as (meth) acrylic polymers and styrene polymers, novolak polymers, acrylamide polymers, polybutadiene polymers, and cellulose polymers. It is done.
  • the structural unit (u1) include structural units of the following formulas (u1-1) to (u1-3). Of these, the structural unit of the formula (u1-1) is preferable from the viewpoint of the solvent solubility of the polymer and the durability of the coating film.
  • R 21 to R 23 are each a hydrogen atom or a methyl group
  • W 1 to W 3 are each the structure (I).
  • the structural unit (u1) is not particularly limited, but may be a structural unit formed by polymerization of the monomer (m1) having the structure (I), and may be an epoxy group or an isocyanate group in the polymer.
  • a structural unit formed by converting a structural unit having a functional group such as the above structure (I) may be used.
  • the method for converting the epoxy group into the structure (I) will be described in detail in the production method ( ⁇ ) described later.
  • a polymer having an isocyanate group is added with a triamine compound such as diethyleneamine or an alcohol having a diamine skeleton such as 2- (2-aminoethylamino) ethanol.
  • Examples of the monomer (m1) having the structure (I) include epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate, glycidyl ⁇ -ethyl acrylate, and 3,4-epoxybutyl (meth) acrylate. And a monomer obtained by a reaction between the diamine compound and a diamine compound (for example, a compound (1) described later).
  • the content of the structural unit (u1) in the polymer (A) is preferably 1% by mass or more, more preferably 15% by mass or more, and more preferably 30% by mass or more with respect to the total of all the structural units (100% by mass). preferable.
  • An upper limit is not specifically limited, 100 mass% may be sufficient.
  • Content (mass%) of the structural unit (u1) in a polymer (A) 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 polymer (A) may further include another structural unit other than the structural unit (u1) (hereinafter also referred to as “structural unit (u2)”).
  • the structural unit (u2) is not particularly limited as long as it is a structural unit not having the structure (I), and can be appropriately selected from the structural units possessed by various known resins as described above.
  • the polymer (A) is a vinyl polymer such as a (meth) acrylic polymer
  • examples of the structural unit (u2) include structural units derived from the following monomer (m2).
  • the structural unit derived from the monomer (m2) has a structure in which the ethylenically unsaturated bond (polymerizable carbon-carbon double bond) of the monomer (m2) is cleaved to form a single bond.
  • Monomer (m2) A vinyl monomer having an ethylenically unsaturated bond and having no structure (I).
  • Examples of the monomer (m2) 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
  • Tertiary amino group-containing vinyl monomers Tertiary amino group-containing vinyl monomers; heterocyclic basic monomers such as vinyl pyrrolidone, vinyl pyridine and vinyl carbazole; trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tri-n-propyl Silyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, tri-n-amylsilyl (meth) acrylate, tri-n-hexylsilyl (meth) acrylate, tri-n-octylsilyl (meth) acrylate, tri- n-dodecylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, tri-p-methylphenylsilyl (meth) acrylate, tribenzylsilyl (meth) acrylate, triisopropylsilyl (meth
  • 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, the various monomers mentioned above as examples of the monomer (m2) can be used (however, the macromonomer is excluded). Specific examples of the macromonomer include monomers disclosed in International Publication No. 2013/108880.
  • Examples of the (meth) acrylate having at least one selected from the group consisting of 1- (alkyloxy) ester group, 1- (alkylthio) ester group and 1- (dialkylamino) ester group include, for example, WO2016 / And monomers disclosed in No. 167360.
  • the polymer (A) is preferably a (meth) acrylic polymer or a novolac polymer from the viewpoint of the durability of the coating film, and a (meth) acrylic polymer from the viewpoint of the solvent solubility of the polymer. Particularly preferred is a polymer.
  • a (meth) acrylic polymer at least a part of the structural unit of the polymer (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 mass) of all the structural units in the polymer (A) is preferably 20 to 100% by mass, more preferably 40 to 100% by mass. .
  • the structural unit (u1) includes a structural unit derived from a (meth) acrylic monomer (for example, the structural unit of the formula (u1-1)). preferable.
  • the polymer (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 a (meth) acrylic monomer.
  • a structural unit may be included, and both may include a structural unit derived from a (meth) acrylic monomer.
  • Examples of the polymer (A) that is a novolak polymer include a polymer containing the structural unit of the formula (u1-3).
  • the number average molecular weight (Mn) of the polymer (A) is preferably 1,000 to 500,000, more preferably 2,000 to 200,000.
  • the weight average molecular weight (Mw) of the polymer (A) is preferably from 2,000 to 1,500,000, more preferably from 3,000 to 300,000. If Mn or Mw of a polymer (A) is below the upper limit of the said range, the solvent solubility of a polymer will be more excellent. If Mn or Mw is not less than the lower limit of the above range, the durability of the coating film is more excellent.
  • the degree of dispersion (Mw / Mn) of the polymer (A) is preferably 1.1 to 99.9, and more preferably 1.5 to 9.9.
  • Mn and Mw of the polymer (A) are values in terms of standard polystyrene, which are measured by gel filtration chromatography (GPC).
  • Examples of the method for producing the polymer (A) include the following production methods ( ⁇ ) and ( ⁇ ). However, the manufacturing method of a polymer (A) is not limited to these.
  • the monomer mixture may further contain a monomer other than the monomer (m1).
  • the other monomer may be any monomer that does not have the structure (I) and can be copolymerized with the monomer (m1).
  • the monomer (m1) is a monomer having an ethylenically unsaturated bond
  • the other monomers are usually monomers having an ethylenically unsaturated bond.
  • the said monomer (m2) is mentioned, for example.
  • the preferable range of the content (mass%) (charge amount) of the monomer constituting the monomer mixture is the same as the preferable range of the content corresponding to the monomer.
  • the content of the monomer (m1) is preferably 1% by mass or more, preferably 15% by mass or more, and more preferably 30% by mass or more with respect to the total mass (100% by mass) of the monomer mixture.
  • Each of the monomer (m1) and the monomer (m2) can be purchased as a commercial product, and can be appropriately synthesized using a known method.
  • 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. For example, a method of reacting the above monomer mixture in the presence of a radical polymerization 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 polymerization initiator known ones can be used. For example, 2,2-azobis (isobutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (2 -Methylbutyronitrile), benzoyl peroxide, cumene hydroperoxide, lauryl peroxide, di-t-butyl peroxide, t-butylperoxy-2-ethylhexanoate and the like.
  • the content of the radical 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 monomer mixture.
  • 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.
  • Examples of the compound (1) include compounds represented by the following formula (1-1) and / or (1-2) and / or (1-3).
  • R 1 to R 12 are as defined above, and X is a hydrogen atom or an organic group having a functional group capable of reacting with an epoxy group.
  • Examples of the functional group capable of reacting with the epoxy group include a primary amino group, a secondary amino group, a primary alkylene alcohol group, a secondary alkylene alcohol group, a primary alkylene thiol group, and a secondary alkylene thiol group.
  • X is an organic group having a primary amino group or a secondary amino group
  • the primary amino group or the secondary amino group in the organic group may be in a salt state.
  • Specific examples of the compound (1) include N, N-diethylethylenediamine, N- (tert-butoxycarbonyl) -N′-methylethylenediamine, aminoethylpyridinium bromide / hydrobromide, and the like.
  • Each of the polymer (A0) and the compound (1) can be purchased as a commercial product, or can be appropriately synthesized using a known method.
  • a homopolymer or copolymer of an epoxy group-containing vinyl monomer can be obtained by polymerizing a monomer mixture containing an epoxy group-containing vinyl monomer.
  • the monomer mixture may further contain a monomer other than the epoxy group-containing vinyl monomer. Polymerization of the monomer mixture can be carried out in the same manner as in the production method ( ⁇ ).
  • the reaction (addition reaction) between the epoxy group of the polymer (A0) and the compound (1) can be carried out by a conventional method.
  • the reaction conditions may be 1 to 3 hours at 70 ° C. with addition of a catalyst such as triethylamine.
  • the epoxy group of the polymer (A0) is converted into a group having the structure (I).
  • the epoxy group is —CH (OH) —CH 2 —NR 4 —R 1 —NR 2 R 3 Become. Thereby, a polymer (A) is obtained.
  • a coating film having both antifouling property due to super hydrophilicity and water resistance can be formed.
  • CO 2 reacts with the surface of the coating film containing the polymer (A) in the presence of water, a zwitterionic structure as a structure that stabilizes the carbamate in which the structure (I) is formed on the coating film surface; Reaction to form a cation structure occurs.
  • a dicationic structure When a hydrogen atom is bonded to the nitrogen atom to which R 5 and R 11 are bonded, a dicationic structure is obtained.
  • the hydrophilicity of the coating film surface increases, the surface tension decreases, and the wettability increases.
  • higher hydrophilicity is exhibited as compared to the case where only the dication structure is formed. For example, it can exhibit super hydrophilicity with an air contact angle of 160 ° or more in water.
  • the surface of the coating film containing the polymer (A) in water or seawater is changed to a structure that stabilizes the carbamate in which the structure (I) is formed as described above, and super hydrophilicity is expressed.
  • the coating film in this state is difficult for marine organisms or the like to adhere to the surface, and exhibits an excellent antifouling effect even when it does not contain an antifouling agent.
  • the structure (I) does not change in the portion other than the surface of the coating film, the hydrophilicity is lower than that of the surface and it is hardly affected by water. This portion can sufficiently ensure the water resistance of the coating film. For example, the coating film is unlikely to collapse or peel off in seawater.
  • the structure (I) exposed on the surface of the coating thereby reacts with CO 2 in the presence of water and changes to a zwitterionic structure, which again becomes super Hydrophilicity is expressed. Therefore, even if the coating film surface collapses or peels off, the super hydrophilicity is restored.
  • the resin composition containing the polymer (A) and the coating film of the antifouling coating composition also have the same effects as described above.
  • the polymer (A) is suitable for an antifouling coating composition.
  • the use of the polymer (A) is not limited to this, and it can be used for uses other than the antifouling coating composition, for example, an antifogging coating composition.
  • the resin composition of the present invention contains the polymer (A).
  • the polymer (A) contained in the resin composition of the present invention may be one type or two or more types.
  • content of the polymer (A) in the resin composition of this invention is not specifically limited, 3 mass% or more is preferable with respect to the whole quantity except the solvent of a resin composition, 10 mass% or more is more preferable, 20 A mass% or more is particularly preferred.
  • content of the polymer (A) is not less than the lower limit, an antifouling coating composition having sufficiently high hydrophilicity can be easily obtained.
  • the upper limit of content of a polymer (A) is not specifically limited, 100 mass% may be sufficient.
  • the resin composition of the present invention can contain an organic solvent.
  • the organic solvent is not particularly limited.
  • an aromatic solvent such as anisole, toluene or xylene
  • an ether solvent such as propylene glycol monomethyl ether-2-acetate
  • a ketone solvent such as methyl isobutyl ketone
  • n-butyl acetate And ester solvents such as Any of these may be used alone or in combinations of two or more.
  • the content of the organic solvent in the resin composition of the present invention is preferably 90% by mass or less, more preferably 80% 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 preferred.
  • the content of the organic solvent is preferably such that the viscosity measured by a B-type viscometer at 25 ° C. of the resin composition is not more than the preferred upper limit described later, and the weight average molecular weight of the polymer (A), the glass transition temperature. Depending on the presence or absence of a crosslinked structure, etc., it is preferably 20% by mass or more, more preferably 30% by mass or more.
  • the resin composition of this invention may further contain other components other than a polymer (A) and an organic solvent.
  • the other components include the same components as the other components in the antifouling coating composition described later. 20 mass parts or less are preferable with respect to 100 mass parts of polymers (A), and content of another component may be 0 mass parts.
  • the viscosity of the resin composition measured with a B-type viscometer at 25 ° C. (hereinafter also referred to as “B-type viscosity”) is as follows. 4000 mPa ⁇ s or less is preferable, and 2000 mPa ⁇ s or less is more preferable. If the B-type viscosity of the resin composition is not more than the above upper limit value, an antifouling agent or the like can be blended or coated without adding a solvent for dilution to the resin composition, and the VOC content An antifouling coating composition with a low content can be obtained.
  • the lower limit of the B-type viscosity is not particularly limited. From the viewpoint of suppressing the sagging of the paint during coating, it is preferably 100 mPa ⁇ s or more.
  • the resin composition of the present invention can be produced using a known method.
  • the polymer composition (A) is produced by the production method ( ⁇ ) or ( ⁇ ) described above, and if necessary, the resin composition is obtained by blending the obtained polymer (A) with an organic solvent, other components and the like. Can be prepared.
  • the resin composition of the present invention can be used as it is or mixed with an antifouling agent or the like as necessary to obtain an antifouling paint composition.
  • the antifouling coating composition of the present invention contains the resin composition. Therefore, the antifouling coating composition of the present invention contains the polymer (A).
  • the antifouling coating composition of the present invention may further contain an antifouling agent.
  • the antifouling coating composition of the present invention may further contain an organic solvent. Examples of the organic solvent are the same as described above.
  • the antifouling coating composition of the present invention may further contain other components other than the polymer (A), the antifouling agent and the organic solvent. When the antifouling coating composition contains an organic solvent, other components, etc., these components may be derived from the resin composition or not derived (mixed at the time of manufacturing the antifouling coating composition). Or a mixture thereof.
  • Anti-fouling 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 polymer (A). It is preferably 50 to 150 parts by mass.
  • the content of the antifouling agent is at least 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 polymers other than the polymer (A).
  • the other polymer is a polymer having no structure (I).
  • examples of other polymers include thermoplastic resins (thermoplastic polymers) other than the polymer (A).
  • the antifouling coating composition of the present invention preferably contains a thermoplastic resin other than the polymer (A). When the antifouling coating composition contains a thermoplastic resin other than the polymer (A), the coating film properties such as crack resistance and water resistance are improved.
  • thermoplastic resin other than the polymer (A) examples include chlorinated paraffin; chlorinated polyolefin such as chlorinated rubber, chlorinated polyethylene and chlorinated polypropylene; polyvinyl ether; polypropylene sebacate; partially hydrogenated terphenyl; Vinyl; (meth) methyl acrylate copolymer, (meth) ethyl acrylate copolymer, (meth) propyl acrylate copolymer, (meth) butyl acrylate copolymer, (meth) acryl Poly (meth) acrylic acid alkyl esters such as acid cyclohexyl copolymers; polyether polyols; alkyd resins; polyester resins; vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl propionate copolymers, vinyl chloride-isobutyl Vinyl ether copolymer, vinyl chloride-isopropyl vinyl ether Vinyl chloride resins such as vinyl copo
  • 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 polymer (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 polymer (A). 1 to 10 parts by mass is more preferable. If the content of the thermoplastic resin other than the polymer (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 it is not more than the upper limit of the above range, it is hydrophilic. More excellent.
  • the antifouling coating composition of the present invention may contain a silicon compound such as dimethylpolysiloxane, a fluorine-containing compound such as fluorinated hydrocarbon, etc. for the purpose of imparting lubricity to the coating film surface and preventing biological adhesion. Good.
  • the antifouling paint 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 antifouling coating composition is preferably 1 to 10% by mass with respect to the total mass of the antifouling coating composition, and 1 to 5% by mass. % Is more preferable. 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 the content of the silicone oil is not more than the upper limit of the above range, the recoatability is more excellent.
  • the antifouling coating composition of the present invention may further contain a crosslinking agent.
  • a crosslinking agent By including a crosslinking agent, the coating film can be cured and the water resistance, strength, and the like can be further increased.
  • a catalyst When the crosslinking agent is included, a catalyst may be further included in order to increase the crosslinking reactivity.
  • a crosslinking agent the compound which has 2 or more of functional groups which react with the amino group of structure (I) is mentioned, for example. Examples of such functional groups include epoxy groups, amino groups, mercapto groups, acrylic groups, carboxyl groups, and acid anhydride groups.
  • crosslinking agent examples include bisphenol A glycidyl ether oligomer, diethylenetriamine, trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane triacrylate, pyromellitic anhydride, and the like.
  • catalyst examples include 2,4,6-tris (dimethylaminomethyl) phenol, diazabicycloundecene, 2-ethyl-4-methylimidazole, triphenylphosphine and the like.
  • the antifouling paint composition of the present invention comprises various pigments, cross-linking agents, dehydrating agents, antifoaming agents, leveling agents, pigment dispersants (for example, anti-settling agents), anti-sagging agents, matting agents, UV absorbers, oxidation agents.
  • An inhibitor, a heat resistance improver, a slip agent, an antiseptic, a plasticizer, a viscosity control agent, and the like may be included. These additives can be used alone or in combination of two or more.
  • pigment examples include zinc oxide, talc, silica, barium sulfate, potassium feldspar, aluminum hydroxide, magnesium carbonate, mica, carbon black, dial, titanium oxide, phthalocyanine blue, kaolin, gypsum and the like.
  • zinc oxide and talc are preferable.
  • dehydrating agent examples include silicate-based, isocyanate-based, orthoester-based, and inorganic-based materials.
  • methyl orthoformate ethyl orthoformate, methyl orthoacetate, orthoborate ester, tetraethyl orthosilicate, anhydrous gypsum, calcined gypsum, synthetic zeolite (molecular sieve) and the like can be mentioned.
  • Molecular sieve is particularly preferable.
  • thermoplastic resins examples include bentonite-based, finely divided silica-based, stearate salt, lecithin salt, alkyl sulfonate, 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.
  • TCP tricresyl phosphate
  • TCP triary
  • organic tin plasticizers such as dioctyltin laurate and dibutyltin laurate
  • trioctyl trimellitic acid triacetylene and the like
  • the solid content of the antifouling coating composition of the present invention is preferably 10 to 100% by mass, more preferably 30 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.
  • the solid content (heating residue) is measured by the following measuring method. Weigh 0.50 g of the sample to be measured (antifouling paint composition) on an aluminum dish, add 3 mL of toluene with a dropper, spread evenly on the bottom of the dish, and perform preliminary drying. Pre-drying is a process for extending the measurement sample over the entire dish and facilitating volatilization of the solvent in the main drying.
  • the B-type viscosity at 25 ° C. is preferably 4000 mPa ⁇ s or less, and more preferably 2000 mPa ⁇ s or less. If the B-type viscosity of the antifouling coating composition is less than or equal to 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 antifouling coating composition of the present invention can be prepared by preparing the resin composition of the present invention as described above, adding an antifouling agent, an organic solvent, other components and the like as necessary, and mixing them. .
  • the antifouling paint composition of the present invention is used to form a coating film (antifouling coating 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. Can be used.
  • the coating film using the antifouling coating composition of the present invention 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 primer such as a chlorinated rubber or an epoxy, 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. By setting the amount to be the thickness, the durability of the coating film is improved.
  • the coating film can be usually dried at room temperature, and may be heat-dried as necessary.
  • Method 1 CO is coated on the surface of the coating film containing the polymer (A) in the presence of water. 2 is reacted to produce a structure that stabilizes the carbamate.
  • a reaction occurs in which the structure (I) stabilizes the carbamate on the surface of the coating film, For example, a zwitterionic structure is generated.
  • the coating film containing the polymer (A) can be formed, for example, in the same manner as the coating film using the above-described antifouling coating composition of the present invention.
  • the resin composition of the present invention may be used.
  • the method of reacting with CO 2 on the surface of the coating film in the presence of water include a method of immersing the coating film in water in which CO 2 is dissolved (for example, seawater), and a state in which the coating film is immersed in water. And a method of bubbling CO 2 in water, a method of immersing in carbonated water, and the like.
  • the saturated CO 2 concentration in water generally, 25 ° C., is 300ppm approximately at atmospheric pressure.
  • the condition for contacting CO 2 with the surface of the coating film in the presence of water may be, for example, 0 to 50 ° C. for 1 minute or longer.
  • bubbling CO 2 may be bubbled example 1 mL / min or more.
  • the presence of water includes water containing water and water vapor.
  • Method 2 the structure for stabilizing the carbamate formed on the surface of the coating film by Method 1 is removed.
  • the surface of the coating film is reacted with CO 2 in the presence of water to regenerate the structure that stabilizes the carbamate.
  • the surface on which the zwitterionic structure is formed is highly hydrophilic and therefore susceptible to water, and the zwitterionic structure may be removed by causing the surface to collapse or peel in water or the like.
  • Examples of the method for reacting CO 2 on the surface of the coating film in the presence of water include the same methods as those described in Method 1.
  • the conditions for reacting CO 2 on the surface of the coating film in the presence of water may be the same as those mentioned in Method 1.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polymer were measured by the GPC measurement method under the following conditions. Measurement was performed using gel permeation chromatography (GPC) (HLC-8320 manufactured by Tosoh Corporation). A tetrahydrofuran solution was prepared so that the macromonomer was 0.2% by mass. The measurement was performed under the conditions of flow rate: 0.35 ml / min, eluent: tetrahydrofuran (stabilizer BHT), column temperature: 40 ° C. The weight average molecular weight (Mw) or number average molecular weight (Mn) was calculated in terms of standard polystyrene.
  • GPC gel permeation chromatography
  • ⁇ Production Example 1 Production of Dispersant 1>
  • a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 900 parts of deionized water, 60 parts of sodium 2-sulfoethyl methacrylate, 10 parts of potassium methacrylate and 12 parts of methyl methacrylate (MMA) are stirred.
  • the temperature was raised to 50 ° C. while the inside of the polymerization apparatus was replaced with nitrogen. Thereto was added 0.08 part of 2,2′-azobis (2-methylpropionamidine) dihydrochloride as a polymerization initiator, and the temperature was further raised to 60 ° C.
  • MMA was continuously added dropwise at a rate of 0.24 part / minute for 75 minutes using a dropping pump.
  • the reaction solution was held at 60 ° C. for 6 hours and then cooled to room temperature to obtain Dispersant 1 having a solid content of 10% by mass as a transparent aqueous solution.
  • the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension containing the polymer.
  • the aqueous suspension was filtered through a nylon filter cloth having an opening of 45 ⁇ m, and the filtrate was washed with deionized water, dehydrated, and dried at 40 ° C. for 16 hours to obtain a macromonomer (1).
  • the number average molecular weight of the macromonomer (1) was 3000, and the weight average molecular weight was 7000.
  • polymer P1 amine polymer of white powder having an epoxy group opened.
  • the quantitative ring opening of the epoxy group was supported by 1 H-NMR.
  • Polymer P2 supported the ring opening of the epoxy group quantitatively by 1 H-NMR. Soluble in acetone, ethyl acetate and chloroform, insoluble in hexane diethyl ether and water. 1.50 g of the polymer P2 was dissolved in 14.90 g of trifluoroacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), deprotected and subjected to precipitation purification to 360 g of diethyl ether to obtain a white powder polymer P3. The progress of deprotection was supported by 1 H-NMR, 13 C-NMR, and 19 F-NMR.
  • This antifouling coating composition was bar-coated on a PET substrate and heated at room temperature for 24 hours and at 80 ° C. for 3 hours to prepare cured films of Examples 1 to 9.
  • a coating film was prepared without using an amine polymer.
  • a coating film using polyallylamine (PAA) manufactured by Nitto Bo Medical Co., Ltd.
  • PAA polyallylamine
  • the underwater contact angle was measured for the coating films (cured films or coating films) of Examples 1 to 9 and Comparative Examples 1 and 2. Moreover, each coating film was immersed in 1M NaCl aqueous solution, CO 2 bubbling was performed at a bubbling amount of 10 mL / min for 15 minutes, and the contact angle in water was measured again. The results before and after CO 2 bubbling for 15 minutes are shown in Tables 1-3.
  • Example 10 On the surface of the cured film after performing CO 2 bubbling for 15 minutes in Example 6 with a continuous load type surface property measuring instrument Heidon TYPE: 22 (manufactured by Shinto Kagaku Co., Ltd.), a polishing film (manufactured by Sankyo Rikagaku Co., Ltd.) , # 4000) was reciprocated 2000 times with a load of 450 g (4.4 N) to wear the surface of the cured film by 1.8 ⁇ m. As a result, the underwater contact angle of the surface decreased from 169 degrees to 158 degrees.
  • this cured film was immersed in a 1M NaCl aqueous solution and CO 2 was bubbled at a bubbling amount of 10 mL / min for 15 minutes. As a result, the contact angle in water was recovered to 168 degrees.
  • the cross section of the cured film of Example 6 after the CO 2 bubbling treatment was cut out by a microtome method, and element distribution analysis was performed using a two-dimensional high-resolution secondary ion mass spectrometer (NanoSIMS 50L, manufactured by AMETEC Corporation's Cameca). Since an increase in carbon relative concentration and a decrease in nitrogen relative concentration were observed in the thickness region, the thickness at which the structure for stabilizing carbamate was generated (regenerated) was estimated to be 1 ⁇ m.
  • ⁇ Synthesis Example 7 Synthesis of Polymer P50> A reaction vessel equipped with a stirrer, a temperature controller, and a dropping funnel was charged with 47 parts of xylene and 3 parts of n-butyl acetate and heated to 90 ° C. while stirring. Subsequently, from the dropping funnel, 60.5 parts of methyl methacrylate (MMA), 9.5 parts of ethyl acrylate (EA), 30 parts of glycidyl methacrylate (GMA), 20 parts of xylene, 2,2-azobis (2-methylbutyrate) A mixture of 0.8 part of (ronitrile) (AMBN) was added dropwise at a constant rate over 4 hours.
  • MMA methyl methacrylate
  • EA ethyl acrylate
  • GMA glycidyl methacrylate
  • AMBN 2,2-azobis (2-methylbutyrate
  • MMA methyl methacrylate
  • EA ethyl acrylate
  • GMA glycidyl methacrylate
  • X-22-174ASX silicone macromer manufactured by Shin-Etsu Chemical Co., Ltd.
  • PGM propylene glycol monomethyl ether
  • AMBN 2,2-azobis (2-methylbutyronitrile
  • MMA methyl methacrylate
  • EA ethyl acrylate
  • GMA glycidyl methacrylate
  • macromonomer (1) 30 parts
  • PMA propylene glycol monomethyl ether acetate
  • AMBN 2,2-azobis (2-methylbutyronitrile
  • ⁇ Synthesis Example 13 Synthesis of Pam + > Dissolve 3.00 g of glycidyl methacrylate (GMA) (manufactured by Tokyo Chemical Industry Co., Ltd.) in 19.90 g of anisole (manufactured by Tokyo Chemical Industry Co., Ltd.) and add 21.7 mg of azobisisobutyronitrile (manufactured by Kanto Chemical Co., Inc.) as an initiator. The mixture was stirred at 2 ° C. for 2 hours for polymerization, precipitated and purified with methanol, and vacuum dried at room temperature to obtain 1.50 g of white powder PGMA (yield 50%).
  • GMA glycidyl methacrylate
  • anisole manufactured by Tokyo Chemical Industry Co., Ltd.
  • azobisisobutyronitrile manufactured by Kanto Chemical Co., Inc.
  • 1.5 g of PGMA was dissolved in 10.00 g of dimethyl sulfoxide (manufactured by Kanto Chemical Co., Inc.), 8.46 g of N- (tert-butoxycarbonyl) -1,2-diaminoethane (manufactured by Tokyo Kasei Co., Ltd.) was added, and 10 g at 80 ° C. was added.
  • the mixture was reacted for a period of time, purified by precipitation to 750 g of diethyl ether, and vacuum dried at room temperature to obtain a yellow viscous liquid Pam-boc.
  • 2 g of Pam-boc was dissolved in 11.79 g of acetonitrile (manufactured by Kanto Chemical Co., Inc.), 11.06 g of iodoethane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.90 g of potassium carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and reacted at 50 ° C. for 12 hours.
  • Example 21 Using the polymer P51, each component was charged into a metal can with the formulation shown below, glass beads were added, and the mixture previously mixed with a stirring rod was dispersed with a rocking shaker to prevent stains. A coating composition was obtained.
  • P51 10 parts
  • Dispalon 4200-20 manufactured by Enomoto Kasei Co., Ltd., sagging inhibitor
  • Pyrithione copper 2.1 parts 30 parts of propylene glycol monomethyl ether (PGM)
  • the reaction solution was mixed with 110.3 g of a saturated aqueous solution in which 10.3 g of sodium hydrogen carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved.
  • a yellow liquid 1 was obtained through dehydration and vacuum drying at room temperature.
  • the identification of the product was supported by FAB-MS and 1 H-NMR. 2.01 g of the obtained yellow liquid 1 was dissolved in 9.95 g of anisole (Tokyo Kasei Co., Ltd.), 11.1 mg of azobisisobutyronitrile (Kanto Chemical Co., Ltd.) was added as an initiator, and the mixture was added at 70 ° C.
  • This antifouling paint composition was bar-coated on a PET substrate and heated at room temperature for 24 hours and at 80 ° C. for 3 hours to prepare cured films of Examples 11 to 21.
  • P11 was used, and as Comparative Example 4, a film using p (AEAEMA) was similarly produced.
  • the underwater contact angle was measured for the coating films (cured films or coating films) of Examples 11 to 21 and Comparative Examples 3 to 4.
  • each coating film was immersed in 1M NaCl aqueous solution, CO 2 bubbling was performed at a bubbling amount of 10 mL / min for 15 minutes, and the contact angle in water was measured again. The results before and after CO 2 bubbling for 15 minutes are shown in Tables 2-3.
  • the coating films of Examples 1 to 20 having the amine polymer having the structure (I) have a high surface water contact angle after CO 2 bubbling. This is considered to have an excellent antifouling function. Moreover, the difference in the underwater contact angle before and after CO 2 addition is high, and the water resistance is also excellent.
  • the polymer and resin composition of the present invention can be used in an antifouling coating composition, and in particular, can exhibit an excellent function that the coating film surface layer becomes hydrophilic and develops antifouling properties due to CO 2 in seawater. This is an industrially very useful invention.

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Abstract

L'invention concerne : un polymère qui est capable de former un film de revêtement qui présente à la fois une résistance à l'eau et des propriétés antisalissure associées à une super-hydrophilie ; une composition de résine ; une composition de matériau de revêtement antisalissure ; un procédé de production du polymère de l'invention ; et un procédé de formation d'une structure de stabilisation d'un carbamate sur la surface d'un film de revêtement et un procédé de régénération d'une structure pour stabiliser un carbamate sur la surface d'un film de revêtement, chacun utilisant le polymère de l'invention. L'invention concerne un polymère qui réagit avec le CO2 en présence d'eau et a une structure permettant de stabiliser un carbamate à produire, et qui respecte la formule (1). (angle de contact dans l'eau après réaction avec le CO2)- (angle de contact dans l'eau avant réaction avec le CO2) ≥ 10 formule (1)
PCT/JP2017/042272 2016-11-25 2017-11-24 Polymère, composition de résine, composition de matériau de revêtement antisalissure, procédé de production de polymère, procédé de formation d'une structure pour stabiliser un carbamate sur la surface d'un film de revêtement et procédé pour régénérer une structure de stabilisation d'un carbamate sur la surface d'un film de revêtement WO2018097260A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201780071939.9A CN110062771A (zh) 2016-11-25 2017-11-24 聚合物、树脂组合物、防污涂料组合物、聚合物的制造方法、在涂膜表面生成使氨基甲酸酯稳定化的结构的方法、在涂膜表面再生使氨基甲酸酯稳定化的结构的方法
EP17873484.4A EP3546487A4 (fr) 2016-11-25 2017-11-24 Polymère, composition de résine, composition de matériau de revêtement antisalissure, procédé de production de polymère, procédé de formation d'une structure pour stabiliser un carbamate sur la surface d'un film de revêtement et procédé pour régénérer une structure de stabilisation d'un carbamate sur la surface d'un film de revêtement
KR1020197014412A KR20190073453A (ko) 2016-11-25 2017-11-24 중합체, 수지 조성물, 방오 도료 조성물, 중합체의 제조 방법, 도막의 표면에 카르바메이트를 안정화시키는 구조를 생성하는 방법, 도막의 표면에 카르바메이트를 안정화시키는 구조를 재생하는 방법
JP2018218655A JP2019094494A (ja) 2016-11-25 2018-11-21 重合体、樹脂組成物、防汚塗料組成物、重合体の製造方法、塗膜の表面にカルバメートを安定化する構造を生成する方法、塗膜の表面にカルバメートを安定化する構造を再生する方法
US16/398,319 US20190276682A1 (en) 2016-11-25 2019-04-30 Polymer, resin composition, antifouling coating material composition, method for producing polymer, method for forming structure for stabilizing carbamate on surface of coating film, and method for regenerating structure for stabilizing carbamate on surface of coating film

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WO2013108880A1 (fr) 2012-01-18 2013-07-25 三菱レイヨン株式会社 Procédé pour la production de polymère vinylique et composition de résine pour peinture antisalissure à base d'eau contenant le polymère vinylique
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JPH04342504A (ja) 1990-10-31 1992-11-30 Otsuka Chem Co Ltd 抗菌性組成物
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WO2013108880A1 (fr) 2012-01-18 2013-07-25 三菱レイヨン株式会社 Procédé pour la production de polymère vinylique et composition de résine pour peinture antisalissure à base d'eau contenant le polymère vinylique
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CN109802331A (zh) * 2019-04-10 2019-05-24 问洋铭 一种高空线路滑动作业平台

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