WO2019230675A1 - 防汚塗料組成物 - Google Patents
防汚塗料組成物 Download PDFInfo
- Publication number
- WO2019230675A1 WO2019230675A1 PCT/JP2019/020988 JP2019020988W WO2019230675A1 WO 2019230675 A1 WO2019230675 A1 WO 2019230675A1 JP 2019020988 W JP2019020988 W JP 2019020988W WO 2019230675 A1 WO2019230675 A1 WO 2019230675A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- meth
- acrylate
- compound
- carbon atoms
- Prior art date
Links
Classifications
-
- 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
- C09D5/1668—Vinyl-type 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
- 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
- C09D133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
-
- 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
-
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
-
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
-
- 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
- C08F8/14—Esterification
-
- 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
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C09D193/00—Coating compositions based on natural resins; Coating compositions based on derivatives thereof
- C09D193/04—Rosin
-
- 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
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
-
- 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
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
-
- 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
- C09D5/1687—Use of special additives
-
- 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
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; DRIERS (SICCATIVES); TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
-
- 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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
-
- 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
- C08F2810/00—Chemical modification of a polymer
- C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
Definitions
- the present invention relates to an antifouling coating composition.
- This application claims priority based on Japanese Patent Application No. 2018-105921 filed in Japan on June 1, 2018, the contents of which are incorporated herein 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.
- Self-polishing antifouling paints are known as antifouling paints. Coating films obtained from self-polishing antifouling paints have a coating surface that gradually dissolves in seawater and is renewed (self-polishing). Demonstrate the soiling effect.
- a self-polishing antifouling paint a hydrolyzable resin is used, for example, a vinyl polymer having a hemiacetal ester group or a hemiketal ester group in the side chain (Patent Document 1), an organic silyl group.
- VOC volatile organic compounds
- Japanese Patent Laid-Open No. 4-103671 Japanese Patent Laid-Open No. 10-30071 Japanese Patent Laid-Open No. 11-116858 JP 2001-226440 A Japanese Patent Laid-Open No. 2005-082725
- Patent Documents 1 to 5 have high paint viscosity and poor paintability. Furthermore, the antifouling coating film using the vinyl polymer described in Patent Document 1 does not have sufficient antifouling properties. In addition, the antifouling coating film using the (meth) acrylic copolymer described in Patent Documents 2 to 5 has low water resistance and cracks with time. There are problems such as low.
- An object of the present invention is to provide an antifouling coating composition that can form a coating film excellent in antifouling property and water resistance, has good storage stability, has a low viscosity when the VOC content is reduced, and has good paintability. Is to provide.
- An antifouling paint composition comprising: (Wherein Ra, Rb and Rc represent a hydrocarbon group having 1 to 40 carbon atoms, X represents —O—, —S— or —NR 14 —, R 14 represents a hydrogen atom or an alkyl group, R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 3 and R 5 each represents an alkyl group, cycloalkyl group or aryl group having 1 to 20 carbon atoms, and R 4 And R 6 each represents an alkylene group having 1 to 10 carbon atoms.) [2] The antifouling coating composition according to [1], wherein Ra, Rb and Rc of the compound (A) are cyclic hydrocarbon residues derived from rosin.
- R 21 represents a hydrogen atom or an alkyl group
- R 15 and R 16 each represents a hydrogen atom or an alkyl having 1 to 10 carbon atoms.
- R 17 and R 19 are each an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, or an aryl group, and R 18 and R 20 are each an alkylene group having 1 to 10 carbon atoms.
- -COO-M-OCO (7) -COO-MR 13 (8) (In the formula, M represents Zn, Cu, Mg, or Ca, and R 13 represents an organic acid residue other than the (meth) acryloyloxy group.)
- the antifouling paint composition according to any one of [1] to [3], further comprising 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. Stuff.
- the compound that reacts with an acid is at least one compound (Y3) selected from the group consisting of compounds represented by the following formula (31), the following formula (32), and the following formula (33)
- Y3 The antifouling paint composition according to item 4.
- R 21 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.
- the antifouling agent cuprous oxide, pyridine triphenylborane, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4-bromo-2- (4-chlorophenyl)-
- the antifouling paint composition according to [6] comprising at least one selected from the group consisting of 5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile and medetomidine.
- an antifouling coating composition that can form a coating film excellent in antifouling property and water resistance, has good storage stability, and has good paintability when the VOC content is reduced.
- Cyclic hydrocarbon residue derived from rosin refers to the remainder of the cyclic hydrocarbon skeleton of various resin acids contained in rosin used as a raw material, excluding one or more carboxyl groups present on the skeleton.
- a cyclic hydrocarbon group of “Volatile organic compound (VOC)” means an organic compound that readily volatilizes at normal temperature and pressure. The normal temperature and normal pressure are 10 ° C. to 30 ° C. and 1000 Pa to 1050 Pa.
- the antifouling coating composition of the present invention comprises at least one compound (A) selected from the group consisting of compounds represented by the following formula (1), the following formula (2) and the following formula (3), and a vinyl type A copolymer (B).
- Ra, Rb and Rc represent a hydrocarbon group having 1 to 40 carbon atoms
- X represents —O—, —S— or —NR 14 —
- R 14 represents a hydrogen atom or an alkyl group
- R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
- R 3 and R 5 each represent an alkyl group, cycloalkyl group or aryl group having 1 to 20 carbon atoms
- R 4 And R 6 each represents an alkylene group having 1 to 10 carbon atoms.
- examples of the hydrocarbon group of Ra, Rb, and Rc include a linear hydrocarbon group, a branched hydrocarbon group, and a cyclic hydrocarbon group.
- examples of the straight chain and branched hydrocarbon groups include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, pentyl groups, hexyl groups, 2-ethylhexyl groups, lauryl groups, and stearyl groups. Is mentioned. Further, it may be a hydrocarbon residue derived from a fatty acid such as linoleic acid or versatic acid, and a hydrocarbon residue derived from versatic acid is preferred.
- the number of carbon atoms is 1 to 40, preferably 1 to 20, more preferably 3 to 18, and still more preferably 5 to 15.
- Cyclic hydrocarbon groups include cyclohexyl groups, cyclopentyl groups, phenyl groups, naphthyl groups, hydrocarbon residues derived from carboxylic acids such as trimethylisobutenylcyclohexene carboxylic acid and salicylic acid, and cyclic hydrocarbon residues derived from rosin. Groups and the like.
- the hydrocarbon group for Ra, Rb and Rc is more preferably a cyclic hydrocarbon group from the viewpoint of antifouling properties, water resistance and physical properties of the coating film. Most preferred are cyclic hydrocarbon residues derived from rosin. Examples of the rosin include the rosins described below.
- X may be any of —O— (etheric oxygen atom), —S— (sulfide sulfur atom), —NR 14 —, and preferably —O—. .
- 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 even 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, tetradecyl groups and the like 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.
- Compound (A) is a hydrolyzable carboxy group-protected compound, which suppresses cross-linking with copper and zinc-derived metal elements in the paint and suppresses the paint viscosity compared to non-protected compounds. And excellent paintability.
- the antifouling property tends to be improved, but water enters the coating film, resulting in a decrease in water resistance and generation of cracks.
- the compound (A) protected with a carboxy group is excellent in water resistance and antifouling property over a long period of time because water penetration into the coating film can be moderately suppressed.
- Compound (A) can be synthesized by reacting the carboxy group of compound (A0) having a carboxy group with compound (Y1).
- Examples of the compound (A0) include naphthenic acid, trimethylisobutenylcyclohexene carboxylic acid, stearic acid, salicylic acid, linoleic acid, versatic acid, gum rosin, wood rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin and the like. Examples include rosins.
- rosin known ones can be used.
- natural rosin gaum rosin, tall oil rosin, wood rosin, etc.
- rosin obtained by stabilizing the natural rosin by a known method hydrogenated rosin, disproportionated rosin, etc.
- various modified rosins using the natural rosin Rosin (referred to as ⁇ , ⁇ -unsaturated carboxylic acid-modified rosin) obtained by Diels-Alder reaction of ⁇ , ⁇ -unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, fumaric acid, etc., polymerized rosin Etc.).
- the rosin is preferably natural rosin, hydrogenated rosin or disproportionated rosin.
- the rosin may contain resin acids described later, and may contain impurities and impurities.
- impurities and impurities in the present invention, those purified by a known method (for example, recrystallization method) can also be used.
- Examples of the resin acid contained in the rosin include monobasic resin acids (abietic acid, neoabietic acid, parastrinic acid, levopimaric acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, pimaric acid, isopimaric acid, sandaracopimal.
- monobasic resin acids abietic acid, neoabietic acid, parastrinic acid, levopimaric acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, pimaric acid, isopimaric acid, sandaracopimal.
- Dibasic resin acids dimers of the above-mentioned monobasic resin acids, acrylopimaric acid, etc.); tribasic resin acids (fumaropimaric acid, etc.); monobasic resin acids having an anhydrous ring (maleopimaric acid, etc.), other Examples thereof include polybasic resin acids (acrylic pimaric acid, maleopimaric acid, dimers of fumaropimaric acid, etc.), resin acids obtained by hydrogenating these, and the like.
- Examples of the compound (Y1) include compounds represented by the following formula (31), the following formula (32), and the following formula (33).
- X represents —O—, —S— or —NR 14 —
- 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 (1) is CH 2 R 7
- R 2 is R 8
- R 3 is 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 (1), respectively.
- Examples of the compound represented by the formula (31) include a 1-alkenylalkyl ether in which X in the formula (31) is —O—, and a 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
- Compound (A) is obtained by maintaining compound (A0) and compound (Y1) at a reaction temperature of 40 to 150 ° C. in the presence or absence of an acidic catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid, etc. It can be obtained by reacting for 30 hours.
- an acidic catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid, etc. It can be obtained by reacting for 30 hours.
- the vinyl copolymer (B) is a copolymer polymerized from a monomer having a vinyl group, and is an acrylic copolymer, a vinyl chloride copolymer, a styrene copolymer, a vinyl acetate copolymer, a vinyl ether. A copolymer etc. are mentioned.
- chlorinated polyolefin such as chlorinated polyethylene and chlorinated polypropylene
- polyvinyl ether such as chlorinated polyethylene and chlorinated polypropylene
- polyvinyl ether such as chlorinated polyethylene and chlorinated polypropylene
- polyvinyl ether such as chlorinated polyethylene and chlorinated polypropylene
- polyvinyl ether such as chlorinated polyethylene and chlorinated polypropylene
- polyvinyl ether such as chlorinated polyethylene and chlorinated polypropylene
- polyvinyl ether such as vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl propionate copolymer, vinyl chloride-isobutyl vinyl ether copolymer
- Vinyl chloride copolymers such as vinyl chloride-isopropyl vinyl ether copolymer and vinyl chloride-ethyl vinyl ether copolymer
- chlorinated paraffin chlorinated rubber
- the vinyl copolymer (B) has a structural unit (hereinafter referred to as “structural unit”) having at least one structure (I) represented by the following formula (4), the following formula (5) or the following formula (6). u1) "), a structural unit having a triorganosilyloxycarbonyl group (hereinafter also referred to as” structural unit (u2) "), and a structure represented by the following formula (7) or the following formula (8)
- a (meth) acrylic copolymer having at least one structural unit selected from the group consisting of structural units having at least one type of III) hereinafter also referred to as “structural unit (u3)
- structural unit (u3) A (meth) acrylic copolymer having at least one structural unit selected from the group consisting of structural units having at least one type of III)
- each formula of the single lines extending from the carbon atom of the carbonyl group, the line not bonded to the oxygen atom represents a bond.
- R 15 , R 16 and R 17 are the same as R 1 , R 2 and R 3 in the formula (1), respectively, and the preferred embodiments are also the same.
- R 18 is the same as R 4 in formula (2), and the preferred embodiment is also the same.
- R 19 and R 20 are the same as R 5 and R 6 in formula (3), respectively.
- X and —NR 21 — are the same as formulas (1) to (3) and —NR 14 —, and the preferred embodiments are also the same.
- the vinyl copolymer (B) further includes other structural units (hereinafter also referred to as “structural unit (u4)”) other than the structural unit (u1), the structural unit (u2), and the structural unit (u3). You may have.
- 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 vinyl copolymer (B) 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 21 —
- R 21 represents a hydrogen atom Alternatively, it represents 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), wherein the carboxy group is substituted with the structure (I) or an alkyl ester group. Type).
- Structure in R X (I) is as defined above.
- 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.
- alkyl group for R X1 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 triorganosilyloxycarbonyl group.
- Examples of the triorganosilyloxycarbonyl group include a group represented by the following formula (II). —COO—SiR 41 R 42 R 43 (II)
- R 41 to R 43 each represent a hydrocarbon group having 1 to 20 carbon atoms.
- Examples of the hydrocarbon group in R 41 to R 43 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group.
- cycloalkyl group and the aryl group may have a substituent.
- substituents include a halogen atom, an alkyl group, an acyl group, a nitro group, and an amino group.
- the alkyl group as a substituent preferably has about 1 to 18 carbon atoms.
- R 41 to R 43 may be the same or different. It is preferable that at least one of R 41 to R 43 is an isopropyl group in that a coating film exhibiting a stable polishing rate (polishing rate) can be obtained and the antifouling performance can be stably maintained for a long period of time. An isopropyl group is particularly preferred.
- the structural unit (u2) is typically a monomer (m2) having a triorganosilyloxycarbonyl group.
- 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 monomer (m2) is preferably a monofunctional monomer having one ethylenically unsaturated bond from the viewpoint of lowering the viscosity when the vinyl copolymer (B) is dissolved in a solvent.
- Examples of the monomer (m2) include a monomer represented by the following formula (m2-1), a monomer represented by the following formula (m2-2), and the like. Among these, the monomer represented by the formula (m2-1) is preferable.
- CH 2 C (R 44 ) —COO—SiR 41 R 42 R 43 (m2-1)
- CH (COOR 45 ) C (R 44 ) —COO—SiR 41 R 42 R 43 ...
- R 41 to R 43 are as defined above, R 44 represents a hydrogen atom or a methyl group, and R 45 represents an alkyl group.
- Specific examples of the monomer represented by the formula (m2-1) include the following. Trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tri-n-propylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, tri-n-amylsilyl (meth) acrylate, tri-n-hexylsilyl (Meth) acrylate, tri-n-octylsilyl (meth) acrylate, tri-n-dodecylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, tri-p-methylphenylsilyl (meth) acrylate, tribenzylsilyl (Meth) acrylate, tri
- examples of the alkyl group for R 45 include alkyl groups having 1 to 5 carbon atoms.
- Specific examples of the compound represented by the formula (m2-2) include those shown below. Triisopropylsilylmethyl malate, triisopropylsilylamyl malate, tri-n-butylsilyl-n-butylmalate, t-butyldiphenylsilylmethylmalate, t-butyldiphenylsilyl-n-butylmalate, triisopropylsilylmethyl fumarate, Triisopropylsilyl amyl fumarate, tri-n-butylsilyl-n-butyl fumarate, t-butyldiphenylsilylmethyl fumarate, t-butyldiphenylsilyl-n-butyl fumarate, etc.
- the structural unit (u3) has a structure in which the ethylenically unsaturated bond of the monomer (m3) is cleaved to form a single bond.
- the structural unit (u3) has at least one structure (III) selected from the group consisting of structures represented by the following formula (7) or (8).
- -COO-M-OCO (7) -COO-MR 13 (8) In the formula, M represents Zn, Cu, Mg, or Ca, and R 13 represents an organic acid residue other than the (meth) acryloyloxy group.)
- M Zn or Cu is preferable.
- the organic acid residue of R 13 refers to the remaining part obtained by removing one proton from the organic acid (for example, the remaining part obtained by removing the proton from the carboxy group of the carboxylic acid), and ion-bonded to M instead of this proton. ing.
- a carboxylic acid is preferable. 1,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinolinecarboxylic acid, nitrobenzoic acid, nitronaphthalenecarboxylic acid, pyruvic acid, naphthenic acid, abietic acid, hydrogenated abietic acid and other monocarboxylic acids Etc.
- R 13 is preferably a fatty acid residue having 1 to 20 carbon atoms (aliphatic monocarboxylic acid residue) from the viewpoint of obtaining a highly durable coating film that can prevent cracking and peeling for a long period of time.
- the structural unit (u3) is a monomer (m3) having the structure (III).
- the monomer (m3) having the structure (III) for example, a monomer in which a vinyl group having an unsubstituted or substituted group is bonded to both ends of the group represented by the formula (7), the formula (8) ), A monomer having an unsubstituted or substituted vinyl group bonded to one end (the side opposite to the R 13 side).
- Examples of the monomer having the vinyl group bonded to both ends of the group represented by the formula (7) include a monomer represented by the following formula (m3-1) (hereinafter referred to as “monomer (m3-1)”. ) ").).
- a monomer represented by the following formula (m3-2) (hereinafter referred to as “monomer (m3-2) ) ").
- (CH 2 C (R 31 ) —COO) 2 M (m3-1)
- CH 2 C (R 31 ) -COO-MR 32 (m3-2)
- M represents Zn, Cu, Mg or Ca
- R 31 represents a hydrogen atom or a methyl group
- R 32 represents an organic acid residue other than a (meth) acryloyloxy group.
- M and R 32 are the same as described above, and the preferred embodiments are also the same.
- zinc (meth) acrylate and copper (meth) acrylate are preferred because the transparency of the vinyl copolymer (B) tends to be high and the color tone of the coating film containing the vinyl copolymer (B) tends to be beautiful.
- Examples of the monomer (m3-2) include monochloro magnesium acetate (meth) acrylate, monochloro calcium acetate (meth) acrylate, monochloro zinc acetate (meth) acrylate, monochloro copper acetate (meth) acrylate; monofluoro magnesium acetate (meta) ) Acrylate, calcium monofluoroacetate (meth) acrylate, zinc monofluoroacetate (meth) acrylate, copper monofluoroacetate (meth) acrylate; magnesium acetate (meth) acrylate, calcium acetate (meth) acrylate, zinc acetate (meth) acrylate , Copper acetate (meth) acrylate; magnesium propionate (meth) acrylate, calcium propionate (meth) acrylate, zinc propionate (meth) acrylate, copper propionate (meta Acrylate; Magnesium octylate (meth) acrylate, Calcium o
- a zinc-containing monomer in which M is Zn is preferable because the transparency of the copolymer (A-2) tends to be high and the color tone of the coating film containing the copolymer (A-2) tends to be beautiful. Furthermore, from the viewpoint of durability of the obtained coating film, fatty acid zinc (meth) acrylate (M in formula (m3-2) is Zn, R32 is a fatty acid residue), or fatty acid copper (meth) acrylate ( More preferably, M in the formula (m3-2) is Cu and R32 is a fatty acid residue.
- Monomer (m3) is a monomer (m3-1) and monomer (m3-2) from the standpoint that the self-polishing property of the resulting coating film is maintained over a long period of time and good antifouling properties are obtained. It is preferable to include both.
- a combination of the monomer (m3-1) and the monomer (m3-2) a combination of zinc (meth) acrylate and fatty acid zinc (meth) acrylate, or (meth) acrylic acid copper and fatty acid copper (Meth) acrylate is preferred.
- this ratio is 90/10 or less, the coating film is excellent in crack resistance and adhesion, and when it is 10/90 or more, the coating tends to have a low viscosity.
- the monomer (m3-1) is, for example, an inorganic metal compound containing a metal element corresponding to M in the formula (m3-1) and (meth) acrylic acid, a diluent such as an organic solvent, or ethylenic It is obtained by a method of reacting in a reactive diluent having a polymerizable unsaturated group such as an unsaturated monomer.
- the mixture containing the metal-containing polymerizable monomer obtained by this method is excellent in compatibility with organic solvents and other monomers and can be easily polymerized.
- the reaction is preferably performed in the presence of water, and the water content in the reaction product is preferably in the range of 0.01 to 30% by mass.
- the inorganic metal compound include metal oxides, hydroxides, and chlorides selected from Zn, Cu, Mg, and Ca.
- the monomer (m3-2) includes, for example, an inorganic metal compound containing a metal element corresponding to M in the formula (m3-2), (meth) acrylic acid, and an organic acid residue in the formula (32). and an organic acid corresponding to R 32, obtainable by a method of reacting in a reactive diluent having a polymerizable unsaturated group such as a diluent or ethylenically unsaturated monomers such as an organic solvent.
- the inorganic metal compound include those similar to the inorganic metal compound for obtaining the monomer (m3-1).
- the monomer mixture containing the monomer (m3-1) and the monomer (m3-2) is, for example, a metal element corresponding to M in the formulas (m3-1) to (m3-2).
- the amount of the organic acid corresponding to R 32 is preferably 0.01 to 3 times the mole, more preferably 0.01 to 0.95 times the mole, relative to the inorganic metal compound, More preferably, the molar ratio is ⁇ 0.7 times.
- the content of the organic acid is 0.01 times mol or more, solid precipitation is suppressed in the production process of the monomer mixture, and self-polishing properties and crack resistance of the resulting coating film are better. It becomes.
- the amount is 3 times or less, the antifouling property of the resulting coating film tends to be maintained for a longer period.
- the structural unit (u4) is a structural unit other than the structural unit (u1), the structural unit (u2), and the structural unit (u3).
- the structural unit (u4) has an ethylenically unsaturated bond, and the ethylenically unsaturated bond of the monomer (m4) not containing the structure (I), the triorganosilyloxycarbonyl group and the structure (III) Has a structure in which a single bond is cleaved.
- Examples of the monomer (m4) include the following.
- Substituted or unsubstituted alkyl (meth) acrylate [for example, 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 (m4) can be used (however, excluding the macromonomer).
- the monomers (m1) to (m3) it is possible to use various monomers mentioned above in combination.
- a macromonomer the monomer currently disclosed by international publication 2013/108880 is mentioned, for example.
- the monomer (m4) is a monofunctional monomer having one ethylenically unsaturated bond from the viewpoint that when the vinyl copolymer (B) is dissolved in a solvent, it tends to have a low viscosity even at a high solid content. It is particularly preferable that the ethylenically unsaturated bond is derived from an acryloyl group. That is, the monomer (m4) is particularly preferably a monofunctional monomer having one acryloyl group.
- the hydrophobic group-containing (meth) acrylic acid It is preferable to include a structural unit derived from an ester monomer.
- the hydrophobic group-containing (meth) acrylic acid ester monomer alkyl (meth) acrylate is preferable.
- the structural unit (u4) preferably contains a structural unit derived from an oxyethylene group-containing (meth) acrylic acid ester monomer from the viewpoint of improving the solubility and crack resistance of the coating film to be formed.
- a compound represented by the following formula (4-1) is preferable.
- Z 1- (CH 2 CH 2 O) n R 22 (4-1) (In the formula, Z 1 represents an acryloyloxy group or a methacryloyloxy group, R 22 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 units (u1) to (u3) in the vinyl copolymer (B) is preferably 1 to 99% by weight, preferably 2 to 90% by weight, based on the total (100% by weight) of all the structural units. More preferred is 5 to 70% by mass.
- the content of the structural units (u1) to (u3) is not less than the lower limit of the above range, the self-polishing property of the coating film to be formed is more excellent. If the content of the structural units (u1) to (u3) is less than or equal to the upper limit of the above range, the formed coating film has appropriate hydrolyzability, maintains self-polishing properties over a long period of time, and has an antifouling effect. Is better.
- the content of the structural unit (u4) is preferably 1 to 99% by mass, more preferably 10 to 98% by mass, and still more preferably 30 to 95% by mass with respect to the total (100% by mass) of all the structural units.
- the structural unit of the vinyl copolymer (B) preferably includes 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 mass%) of all the structural units in the vinyl copolymer (B) is preferably 20 to 100 mass%, preferably 40 to 100 mass%. Is more preferable.
- the content of this structural unit is 1 to 80 relative to the total of all the structural units. % By mass is preferable, and 5 to 40% 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 vinyl copolymer (B) is a structural unit derived from a monomer (m4) other than an 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, more preferably 10 to 80% by mass with respect to the total of all the structural units.
- the content of this structural unit is within the above range, the flexibility and crack resistance / peeling resistance of the coating film to be formed become higher, and the antifouling effect becomes more excellent.
- 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), the structural unit (u3), and the structural unit (u4) 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 weight average molecular weight (Mw) of the vinyl copolymer (B) is preferably 1,000 to 100,000, more preferably 2,000 to 80,000, and further preferably 3,000 to 60,000. If the weight average molecular weight of the vinyl copolymer (B) is not more than the upper limit of the above range, the viscosity of the solution in which the vinyl copolymer (B) is dissolved in the solvent becomes lower, and the antifouling paint composition is obtained. It is easy to obtain one with high solid content and low viscosity. 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 vinyl copolymer (B) is preferably 500 to 50,000, more preferably 1,000 to 40,000.
- the polydispersity (Mw / Mn) of the vinyl copolymer (B) 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 vinyl copolymer (B) are each measured by gel filtration chromatography (GPC) using polystyrene as a reference resin.
- Method for producing vinyl copolymer (B) As a method for producing the vinyl copolymer (B), for example, known polymerization methods 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-methylbutyronitrile), 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.
- Examples of the method for producing the vinyl copolymer (B) having the structure (I) include the following production methods ( ⁇ ) and ( ⁇ ).
- Production method ( ⁇ ) A method of polymerizing a monomer mixture containing the monomer (m1).
- Production method ( ⁇ ) A monomer mixture containing a monomer (m0) having an ethylenically unsaturated bond and a carboxy group is polymerized to obtain a copolymer (B0) having a carboxy group.
- the monomer mixture used in the production method ( ⁇ ) includes the monomer (m1) and may further include the monomers (m2) to (m4).
- Each of the monomers (m1) to (m4) can 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 a method of reacting (addition reaction) the monomer (m0) and the compound (Y2).
- Examples of the compound (Y2) include the same as the compound (Y1).
- R 1 in the formula (11) is CH 2 R 7
- R 2 is R 8
- R 3 as the monomer (m1). Is obtained wherein R 9 is R 9 .
- 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.
- R 5 in the formula (13) is R 11 and R 6 is CH 2 -R 12 as the monomer (m1). A compound is obtained.
- R 11 is the same as R 5 .
- R 12 is the same as R 6 except that the number of carbon atoms is 9 or less.
- the monomer (m1) can be obtained by reacting the monomer (m0) and the compound (Y2) at a reaction temperature of 40 to 150 ° C. for 5 to 30 hours.
- An acidic catalyst such as hydrochloric acid, sulfuric acid or phosphoric acid may be used.
- the target monomer can be collect
- a monomer mixture containing the monomer (m0) is polymerized to obtain a copolymer (B0) having a carboxy group.
- the monomer mixture may further contain monomers (m1) to (m4).
- the monomers (m0) to (m4) are the same as described above.
- the preferable range of the monomer (m0) in the monomer mixture is the same as the preferable range of the content of the monomer (m1) in the monomer mixture in the production method ( ⁇ ).
- the preferred range of the content of the oxyethylene group-containing (meth) acrylic acid ester monomer and other monomers (m4) is the same as described above. Polymerization of the monomer mixture can be carried out in the same manner as in the production method ( ⁇ ).
- the vinyl copolymer (B) is obtained by converting the carboxy group of the copolymer (B0) into the structure (I).
- Examples of the method for converting the carboxy group of the copolymer (B0) into the structure (I) include a method of reacting (addition reaction) the copolymer (B0) and the compound (Y2).
- the reaction between the copolymer (B0) and the compound (Y2) can be carried out in the same manner as the reaction between the monomer (m0) and the compound (Y2).
- a copolymer vinyl copolymer (B) having the structure (III) for example, a copolymer vinyl copolymer (B) is produced by the following production method ( ⁇ ) or ( ⁇ ) and necessary. Depending on the method, an organic solvent may be added. Among these, from the viewpoint of water resistance, a method in which the vinyl copolymer (B) is produced by the production method ( ⁇ ) and an organic solvent is added as necessary is preferable.
- Production method ( ⁇ ) A method of polymerizing a monomer mixture containing the monomer (m3).
- a method for converting the carboxy group of the copolymer (B0 ′) into the structure (III) for example, The method of making a copolymer (B0 ') and organic acid metal salts, such as copper acetate and zinc acetate, react is mentioned.
- the metal of the organic acid metal salt corresponds to M.
- the reaction between the copolymer (B0 ′) and the organic acid metal salt is carried out, for example, by raising the temperature to the reflux temperature and removing the distillate of an organic acid such as acetic acid, water and an organic solvent, and the same amount of organic
- the reaction can be carried out by continuing the reaction for 10 to 20 hours while replenishing the solvent.
- the vinyl copolymer (B) Since the vinyl copolymer (B) has at least one of the structure (I), triorganosilyloxycarbonyl group and structure (III) in which the carboxy group is protected by a specific group, It can be hydrolyzed. Therefore, the coating film containing the vinyl copolymer (B) exhibits self-polishing properties in seawater or the like. That is, since the vinyl copolymer (B) is protected with a specific group, it does not dissolve in seawater in this state, but when a specific group 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 vinyl copolymer (B) can be made into a solution having a high solid content and a low viscosity when an organic solvent is added. If the resin composition containing the vinyl copolymer (B) and the organic solvent has a high solid content and a low viscosity, it is not necessary to add an organic solvent to the resin composition when the antifouling coating composition is produced. An antifouling coating composition having paintability can be obtained. 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.
- the antifouling paint composition of the present invention is an antifouling paint composition comprising the compound (A) and a vinyl copolymer (B).
- the compound (A) contained in the antifouling coating composition of the present invention may be one type or two or more types. Although content of the compound (A) in the antifouling coating composition of this invention is not specifically limited, 1 mass% or more is preferable with respect to the whole quantity of an antifouling coating composition, and 3 mass% or more is more preferable.
- the vinyl copolymer (B) contained in the antifouling coating composition of the present invention may be one type or two or more types.
- the content of the vinyl copolymer (B) in the antifouling coating composition of this embodiment is not particularly limited, but is preferably 5% by mass or more and more preferably 10% by mass or more with respect to the total amount of the resin composition. .
- the content ratio of the compound (A) to the vinyl copolymer (B) in the antifouling coating composition is preferably 0.1 / 99.9 to 70/30, more preferably 90/10 to 40/60. If it is the said content ratio, it can suppress a viscosity and is excellent in coating property, and can improve water resistance and antifouling property.
- the antifouling coating composition of the present invention preferably further 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.
- a compound that reacts with an acid, a basic compound, an acidic compound, and a dehydrating agent preferably further 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.
- the viscosity of the paint increases.
- free carboxylic acid is generated, 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 reacted with the compound that reacts with the acid. Captured and improved storage stability. Further, in the high pH region and the low pH region, the storage stability is lowered by promoting the decomposition of the structure (I).
- the storage stability also decreases due to a decrease in the reactivity between the compound that reacts with the acid and the carboxylic acid.
- adjusting the pH of the resin composition by adding a basic compound or an acidic compound, decomposition of the structure (I) can be suppressed, and a decrease in storage stability can be suppressed.
- moisture promotes decomposition (hydrolysis) of the structure (I).
- a dehydrating agent in the resin composition, moisture in the resin composition can be captured and deterioration in storage stability can be suppressed.
- Examples of the compound that reacts with an acid include the compound (Y3), a basic compound, and a compound having an epoxy group.
- Examples of the compound (Y3) include the same compounds (Y1) and (Y2).
- the compound that reacts with an acid the compound (Y3) is preferable.
- 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.
- the compound that reacts with the acid is preferably the compound (Y3) from the viewpoint of storage stability.
- the compound (Y3) is preferably a 1-alkenyl alkyl ether in which X in the formula (31) is —O— in terms of more excellent storage stability. More preferred are vinyl ethers such as vinyl ether and isobutyl vinyl ether.
- Examples of the basic compound for adjusting the pH include those similar to the basic compound.
- 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 may be used individually by 1 type, and may be used in combination of 2 or more type.
- combinations of two or more additives include a combination of a compound (Y3) and a dehydrating agent, a combination of a compound (Y3), an acidic compound and a dehydrating compound (Y3), a basic compound, an acidic compound and a dehydrating agent. And a combination of a basic compound and a dehydrating agent.
- the content of the compound (Y3) in the antifouling paint composition is 20 moles relative to the structure (I) of the vinyl copolymer (B). % Or more, preferably 30 to 1000 mol%, more preferably 40 to 800 mol%. If content of a compound (Y3) is in the said range, the improvement effect of storage stability will be more excellent.
- the content of the basic compound or acidic compound in the antifouling coating composition is such that the pH measured in water is 2 from the viewpoint of storage stability.
- the amount of basic compound at a concentration of ⁇ 12 is preferred, and the amount of basic compound at a concentration of pH 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, and preferably 1 to 20% by mass with respect to the total mass of the resin composition. More preferred. 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 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 oil examples 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 Co., Ltd.).
- the content of silicone oil in the resin composition is preferably 0.1 to 40% by mass, and preferably 1 to 20% by mass with respect to the total mass of the resin composition. More preferred. 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 antifouling coating composition of the present invention preferably contains an organic solvent.
- the organic solvent is not particularly limited as long as it can dissolve the vinyl copolymer (B).
- hydrocarbon solvents such as toluene and xylene; the compound (Y3), propylene glycol monomethyl ether-2-acetate And ether solvents such as methyl isobutyl ketone, ester solvents such as n-butyl acetate, and the like. Any of these may be used alone or in combinations of two or more.
- Antifouling agent examples include inorganic antifouling agents and organic antifouling agents, and one or two or more 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 may be used individually by 1 type and may be used in combination of 2 or more type.
- 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.
- the antifouling coating composition of this embodiment preferably contains a thermoplastic resin other than the vinyl copolymer (B).
- the coating film properties such as crack resistance and water resistance are improved.
- thermoplastic resins other than the vinyl copolymer (B) include alkyd resins; polyester resins, chlorinated paraffins; waxes; oils and fats that are liquid at room temperature, such as solid oils and castor oils other than wax, and their Purified product; petrolatum; liquid paraffin; rosin, hydrogenated rosin, naphthenic acid, fatty acid and divalent metal salts thereof.
- the wax include animal-derived waxes such as beeswax; plant-derived waxes; semi-synthetic waxes such as amide waxes; synthetic waxes such as oxidized polyethylene waxes. These thermoplastic resins may be used alone or in combination of two or more.
- Chlorinated paraffin is preferable because it functions as a plasticizer and an effect of improving crack resistance and peel resistance of the coating film is obtained.
- Organic waxes such as semi-synthetic wax and synthetic wax are preferred because 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 vinyl copolymer (B) in the antifouling coating composition is not particularly limited, but is 0.1 to 50 masses per 100 mass parts of the vinyl copolymer (B). Part is preferable, and 0.1 to 10 parts by mass is more preferable. If the content of the thermoplastic resin other than the vinyl copolymer (B) is equal to or higher than the lower limit of the above range, the coating film properties such as crack resistance and water resistance are more excellent, and should be equal to or lower than the upper limit of the above range. In this case, the hydrolyzability is more excellent.
- the antifouling coating composition of the present invention is provided with a silicone compound such as dimethylpolysiloxane (excluding silicone oil), a fluorinated hydrocarbon 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)
- a fluorinated hydrocarbon for the purpose of imparting lubricity to the coating surface and preventing the adhesion of organisms.
- Fluorine-containing compounds such as
- the antifouling paint composition of the present invention comprises various pigments, antifoaming agents, leveling agents, pigment dispersants (for example, 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. In particular, zinc oxide and talc are preferable.
- Examples of the anti-settling agent and the anti-sagging agent other than the thermoplastic resin 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.
- phthalate plasticizers such as dioctyl phthalate, dimethyl phthalate, dicyclohexyl phthalate, and diisodecyl phthalate
- aliphatic dibasic ester plasticizers such as isobutyl a
- organic tin plasticizers such as dioctyltin laurate and dibutyltin laurate
- trioctyl trimellitic acid triacetylene and the like.
- the content of the organic solvent in the antifouling coating composition of the present invention is preferably 60% by mass or less, and preferably 50% by mass with respect to the total amount of the resin composition, from the viewpoint of reducing the VOC content of the antifouling coating composition.
- the following is more preferable, 45% by mass or less is further preferable, and 40% by mass or less is particularly preferable.
- the content of the organic solvent is preferably such that the viscosity measured with a B-type viscometer at 25 ° C.
- the weight average of the vinyl copolymer (B) Although it varies depending on the molecular weight, glass transition temperature, presence or absence of a crosslinked structure, etc., it is preferably 15% by mass or more, more preferably 20% by mass or more.
- the compound (Y3) can also function as an organic solvent. Therefore, when a resin composition contains a compound (Y3), content of a compound (Y3) is contained in content of an organic solvent.
- the viscosity of the resin composition measured with a B-type viscometer at 25 ° C. is less than 5000 mPa ⁇ s. Is preferably less than 4000 mPa ⁇ s, more preferably less than 3,000 mPa ⁇ s, and particularly preferably less than 2,000 mPa ⁇ s.
- the viscosity of the antifouling coating composition is determined based on the solid content of the resin composition (contents of the vinyl copolymer (B) and other components), the weight average molecular weight of the vinyl copolymer (B), the glass transition temperature, It can be adjusted by the presence or absence of a crosslinked structure. For example, the lower the solid content, particularly the content of the vinyl copolymer (B), the lower the viscosity. Moreover, there exists a tendency for it to become low viscosity, so that the weight average molecular weight of a vinyl-type copolymer (B) is small or a glass transition temperature is low.
- the solid content of the antifouling coating composition of the present invention is preferably 55 to 100% by mass, more preferably 60 to 90% by mass, and further 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 of the antifouling coating composition of the present invention at 25 ° C. 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 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 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 on the surface of a substrate or a base coating on a substrate by means of brush coating, spray coating, roller coating, submersion coating, etc., 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 then plugged with a cork stopper.
- the viscosity tube from which the sample was collected was immersed in a constant temperature water bath adjusted to the specified temperature (25.0 ⁇ 0.1 ° C) for 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). The columns used were TSKgel ⁇ -M (Tosoh Corp., 7.8 mm ⁇ 30 cm) and TSKguardcolumn ⁇ (Tosoh Corp., 6.0 mm ⁇ 4 cm).
- a calibration curve was prepared using F288 / F1 / 28 / F80 / F40 / F20 / F2 / A1000 (manufactured by Tosoh Corporation, standard polystyrene) and a styrene monomer.
- the antifouling paint composition was applied to a hard vinyl chloride plate of 50 mm ⁇ 50 mm ⁇ 2 mm with an applicator so as to have a dry film thickness of 120 ⁇ m, and dried to form a coating film, thereby obtaining a test plate.
- This test plate was attached to a rotating drum installed in seawater and rotated at a peripheral speed of 7.7 m / s (15 knots). The state was maintained for 6 months, and the surface of the coating film after 6 months 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. ⁇ : Some cracks and peeling are observed ⁇ : Cracks and peeling are observed on the entire surface
- 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 Mikawa Bay for 6 months, the ratio of the area where marine organisms adhered to the total area of the paint film (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 with an applicator so as to have a dry film thickness of 120 ⁇ m, and dried to form a coating film, thereby obtaining a test plate.
- This test plate was attached to a rotating drum installed in seawater and rotated at a peripheral speed of 7.7 m / s (15 knots). The state was maintained for 6 months, the film thickness ( ⁇ m) of the coating film after 6 months was measured, and the consumed film thickness per month was defined as the degree of wear ( ⁇ m / M).
- IBMA 1-isobutoxyethyl methacrylate (synthetic product synthesized in Production Example M1 described later).
- MMA methyl methacrylate.
- EA ethyl acrylate.
- BA Butyl acrylate.
- CHMA cyclohexyl methacrylate.
- 2-MTMA 2-methoxyethyl methacrylate.
- MAA methacrylic acid.
- TIPSA triisopropylsilyl acrylate.
- TIPSSMA triisopropylsilyl methacrylate.
- AMBN 2,2′-azobis (2-methylbutyronitrile).
- NOFMER MSD trade name, manufactured by NOF Corporation, ⁇ -methylstyrene dimer.
- Antifouling agent (1) 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile.
- Antifouling agent (2) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (Rohm and Haas, trade name: Cine Nine 211).
- Table 1 shows the properties (solid content (mass%), B-type viscosity, Gardner viscosity, number average molecular weight (Mn) of the copolymer contained in each resin composition of the obtained resin compositions B-1 to B-6. ) And weight average molecular weight (Mw)) results.
- Examples 1 to 8, Comparative Examples 1 to 4 According to the formulation shown in Table 2, each component was mixed with a rocking shaker to obtain an antifouling paint composition. Evaluation results of coating properties (solid content, B-type viscosity), coating suitability, coating viscosity change rate, coating film performance (stationary antifouling property, water resistance, coating film consumption test) of the obtained antifouling coating composition Is shown in Table 2.
- the compounding quantity of a resin composition is the quantity of the whole resin composition.
- the antifouling coating compositions of Examples 1 to 8 had a low viscosity even at a high solid content, and good paintability.
- the coating films of the antifouling coating compositions of Examples 1 to 8 were excellent in static antifouling properties and water resistance. Further, this coating film had an appropriate degree of wear.
- Comparative Examples 1 to 4 using the antifouling coating composition not having the compound (A) had a solid content equivalent to that of the resin composition having the compound (A) and had a measured B-type viscosity. The viscosity was high and high. Due to the high viscosity, the coating suitability is poor and is not suitable for a low VOC paint.
- the antifouling paint composition of the present invention can be suitably used for antifouling paint applications.
Abstract
Description
本願は、2018年6月1日に、日本に出願された特願2018-105921号に基づき優先権を主張し、その内容をここに援用する。
防汚塗料として、自己研磨型の防汚塗料が知られている。自己研磨型の防汚塗料から得られる塗膜は、塗膜表面が徐々に海水に溶解して表面更新(自己研磨)され、塗膜表面に常に防汚成分が露出することにより、長期にわたって防汚効果を発揮する。
自己研磨型の防汚塗料として、加水分解型の樹脂が使用されており、例えば、側鎖にヘミアセタールエステル基又はヘミケタールエステル基を有するビニル重合体(特許文献1)、有機シリル基を有するビニル重合体がある。また、防汚性向上や溶解性の向上等の目的でこれらの加水分解型樹脂にロジンがブレンドされることもある(特許文献2~5)。また、近年、環境等への影響から、揮発性有機化合物(Volatile Organic Compound;以下、「VOC」ともいう。)の低減が重要になっており、これらの自己研磨型の防汚塗料についてもVOCの低減が検討されている。
溶剤の含有量を減らした場合、特許文献1~5は塗料粘度が高く塗装性が不良である。さらに、特許文献1に記載のビニル重合体を用いた防汚塗料の塗膜は、防汚性が充分ではない。また、特許文献2~5に記載の(メタ)アクリル系共重合体を用いた防汚塗料の塗膜は、耐水性が低く経時でクラックが生じることや特許文献3では、塗料の貯蔵安定性が低い等の課題がある。
[1] 下記式(1)、下記式(2)及び下記式(3)で表される化合物からなる群から選ばれる少なくとも1種の化合物(A)と、ビニル系共重合体(B)とを含む防汚塗料組成物。
[2] 前記化合物(A)のRa、Rb及びRcが、ロジンに由来する環式炭化水素残基である[1]に記載の防汚塗料組成物。
[3] 前記ビニル系共重合体(B)が、下記式(4)、下記式(5)又は下記式(6)で表される構造(I)の少なくとも1種を有する構成単位(u1)、トリオルガノシリルオキシカルボニル基を有する構成単位(u2)、及び下記式(7)又は下記式(8)で表される構造(III)の少なくとも1種を有する構成単位(u3)からなる群から選ばれ
る少なくとも1種の構成単位を有する(メタ)アクリル系共重合体である[1]または[2]に記載の防汚塗料組成物。
-COO-M-OCO ・・・(7)
-COO-M-R13 ・・・(8)
(式中、MはZn、Cu,Mg又はCaを示し、R13は(メタ)アクリロイルオキシ基以外の有機酸残基を示す。)
[4] 酸と反応する化合物、塩基性化合物、酸性化合物及び脱水剤からなる群から選ばれる少なくとも1種をさらに含む、[1]~[3]のいずれか一項に記載の防汚塗料組成物。
[5] 酸と反応する化合物が、下記式(31)、下記式(32)、及び下記式(33)で表される化合物からなる群から選ばれる少なくとも1種の化合物(Y3)である[4]に記載の防汚塗料組成物。
[6] 防汚剤をさらに含む、[1]~[5]のいずれかに記載の防汚塗料組成物。
[7] 前記防汚剤として、亜酸化銅、ピリジントリフェニルボラン、4,5-ジクロロ-2-n-オクチル-4-イソチアゾリン-3-オン、4-ブロモ-2-(4-クロロフェニル)-5-(トリフルオロメチル)-1H-ピロール-3-カルボニトリル及びメデトミジンからなる群から選ばれる少なくとも1種を含む、[6]の防汚塗料組成物。
「ロジンに由来する環式炭化水素残基」とは、原料として用いるロジンに含まれる各種樹脂酸が有する環式炭化水素骨格において、当該骨格上に存在するカルボキシル基の一つ以上を除いた残りの環式炭化水素基をいう。
「揮発性有機化合物(VOC)」とは、常温常圧で容易に揮発する有機化合物を意味する。なお、常温常圧とは、10℃~30℃、1000Pa~1050Paをいう。
本発明の防汚塗料組成物は、下記式(1)、下記式(2)及び下記式(3)で表される化合物からなる群から選ばれる少なくとも1種の化合物(A)と、ビニル系共重合体(B)とを含む。
環式炭化水素基としては、シクロヘキシル基、シクロペンチル基、フェニル基、ナフチル基及び、トリメチルイソブテニルシクロヘキセンカルボン酸、サリチル酸等のカルボン酸由来の炭化水素残基、ロジンに由来する環式炭化水素残基等が挙げられる。
前記Ra、Rb及びRcの炭化水素基としては、防汚性、耐水性、塗膜物性の観点で環式炭化水素基がより好ましく。ロジンに由来する環式炭化水素残基が最も好ましい。ロジンとしては後述のロジンが挙げられる。
R1及びR2におけるアルキル基の炭素数は、1~4が好ましく、1~3がより好ましく、1又は2がさらに好ましい。
シクロアルキル基としては、炭素数4~8のシクロアルキル基が好ましく、例えばシクロヘキシル基、シクロペンチル基等が挙げられる。
アリール基としては、炭素数6~20のアリール基が好ましく、例えばフェニル基、ナフチル基等が挙げられる。
R3としては、炭素数1~10のアルキル基、シクロアルキル基が好ましい。
置換基としてのシクロアルキル基、アリール基はそれぞれ、前記と同様のものが挙げられる。アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等が挙げられる。アルカノイルオキシ基としては、エタノイルオキシ基等が挙げられる。アラルキル基としては、ベンジル基等が挙げられる。
R4におけるアルキレン基の炭素数は、2~7が好ましく、3~4がより好ましい。
前記アルキレン基は、シクロアルキル基、アリール基、アルコキシル基、アルカノイルオキシ基、アラルキル基及びアセトキシ基からなる群から選ばれる置換基により置換されていてもよい。置換基により置換されている場合、置換基の数は1つでもよく2つ以上でもよい。アルキレン基に置換してもよい置換基の具体例としては、R3で挙げた置換基と同様のものが挙げられる。
R6は、式(2)中のR4と同様であり、好ましい態様も同様である。
化合物(A0)としては、例えば、ナフテン酸、トリメチルイソブテニルシクロヘキセンカルボン酸、ステアリン酸、サリチル酸、リノール酸、バーサチック酸等やガムロジン、ウッドロジン、トール油ロジン、水添ロジン、不均化ロジン等のロジン類が挙げられる。
式(31)中、R7における炭素数1~9のアルキル基は、炭素数が9以下である以外は、R1における炭素数1~10のアルキル基と同様である。
R8、R9はそれぞれ、前記式(1)におけるR2、R3と同様である。
これらのなかでは、1-アルケニルアルキルエーテルが好ましく、ビニルエーテル類、1-プロペニルエーテル類がより好ましい。
式(32)中、R10における炭素数1~9のアルキレン基は、炭素数が9以下である以外は、R4と同様である。
これらのなかでは、ジヒドロフラン類、ジヒドロピラン類が好ましく、ジヒドロピラン類がより好ましい。
式(33)中、R11は、R5と同様である。R12は、炭素数が9以下である以外は、R6と同様である。
ビニル系共重合体(B)は、ビニル基を有する単量体から重合される共重合体であり、アクリル共重合体、塩化ビニル共重合体、スチレン共重合体、酢酸ビニル共重合体、ビニルエーテル共重合体等が挙げられる。例えば、塩素化ポリエチレン、塩素化ポリプロピレン等の塩素化ポリオレフィン;ポリビニルエーテル;ポリ酢酸ビニル、塩化ビニル-酢酸ビニル共重合体、塩化ビニル-プロピオン酸ビニル共重合体、塩化ビニル-イソブチルビニルエーテル共重合体、塩化ビニル-イソプロピルビニルエーテル共重合体、塩化ビニル-エチルビニルエーテル共重合体等の塩化ビニル共重合体;塩素化パラフィン;塩化ゴム、;ポリエーテルポリオール、(メタ)アクリル酸エステル共重合体等が挙げられる。
も1種を有する構成単位(以下、「構成単位(u3)」ともいう)からなる群から選ばれる少なくとも1種の構成単位を有する(メタ)アクリル系共重合体が好ましい。
式(4)中、R15、R16、R17はそれぞれ、前記式(1)におけるR1、R2、R3と同様であり、好ましい態様も同様である。式(5)中、R18は前記式(2)におけるR4と同様であり、好ましい態様も同様である。式(6)中、R19、R20はそれぞれ、前記式(3)におけるR5、R6と同様である。式(4)~(6)中、X及び-NR21-は、式(1)~(3)及び-NR14-と同様であり、好ましい態様も同様である。
-COO-M-R13 ・・・(8)
式中、MはZn、Cu,Mg又はCaを示し、R13は(メタ)アクリロイルオキシ基以外の有機酸残基を示す。
ビニル系共重合体(B)は、前記構成単位(u1)、構成単位(u2)及び構成単位(u3)以外の他の構成単位(以下、「構成単位(u4)」ともいう。)をさらに有するものであってもよい。
構成単位(u1)は、単量体(m1)のエチレン性不飽和結合が開裂して単結合となった構造を有する。
単量体(m1)は、ビニル系共重合体(B)を溶剤に溶解したときの粘度が低くなる点から、エチレン性不飽和結合を1つ有する単官能単量体であることが好ましい。
単量体(m1)としては、例えば、下記式(11)で表される化合物、下記式(12)で表される化合物、下記式(13)で表される化合物等が挙げられる。
CH(CH3)=CH-COO-は、クロトノイルオキシ基(エチレン性不飽和結合がトランス型)又はイソクロトノイルオキシ基(エチレン性不飽和結合がシス型)である。
CHRX=CH-COO-は、カルボキシ基が構造(I)又はアルキルエステル基に置換された、マレイノイルオキシ基(エチレン性不飽和結合がシス型)又はフマロイルオキシ基(エチレン性不飽和結合がトランス型)である。
RXにおける構造(I)は前記と同様である。RXは、Zが結合した基と同じ構造を有することが好ましい。例えば式(11)で表される化合物の場合、RXは、-CR1R2-OR3で表される基であることが好ましい。
RXにおけるアルキルエステル基は、-COORX1で表される。RX1はアルキル基を示す。RX1のアルキル基としては、炭素数1~6のアルキル基が好ましく、メチル基が特に好ましい。
CH2=C(CH2RX)-COO-又はCH2=CRX-CH2COO-は、カルボキシ基が構造(I)又はアルキルエステル基に置換されたイタコノイルオキシ基である。RXは前記と同様である。
Zとしては、CH2=CH-COO-又はCH(CH3)=CH-COO-が好ましい。
構成単位(u2)は、トリオルガノシリルオキシカルボニル基を有する。トリオルガノシリルオキシカルボニル基としては、例えば、下記式(II)で表される基が挙げられる。
-COO-SiR41R42R43 ・・・(II)
式(II)中、R41~R43はそれぞれ、炭素数1~20の炭化水素基を示す。
R41~R43における炭化水素基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基等の炭素数1~20のアルキル基;シクロヘキシル基等のシクロアルキル基;フェニル基、ナフチル基等のアリール基等が挙げられる。
シクロアルキル基、アリール基はそれぞれ、置換基を有していてもよい。置換基としては、例えばハロゲン原子、アルキル基、アシル基、ニトロ基、アミノ基等が挙げられる。置換基としてのアルキル基の炭素数は、1~18程度が好ましい。
R41~R43はそれぞれ同一でもよく異なってもよい。
安定したポリッシングレート(研磨速度)を示す塗膜が得られ、防汚性能を長期間安定して維持できる点で、R41~R43のうち少なくとも1つがイソプロピル基であることが好ましく、全てがイソプロピル基であることが特に好ましい。
構成単位(u2)は、典型的には、トリオルガノシリルオキシカルボニル基を有する単量体(m2)である。
構成単位(u2)は、単量体(m2)のエチレン性不飽和結合が開裂して単結合となった構造を有する。
単量体(m2)は、ビニル系共重合体(B)を溶剤に溶解したときの粘度が低くなる点から、エチレン性不飽和結合を1つ有する単官能単量体であることが好ましい。
単量体(m2)としては、例えば、下記式(m2-1)で表される単量体、下記式(m2-2)で表される単量体等が挙げられる。これらの中でも前記式(m2-1)で表される単量体が好ましい。
CH2=C(R44)-COO-SiR41R42R43 ・・・(m2-1)
CH(COOR45)=C(R44)-COO-SiR41R42R43 ・・・(m
2-2)
(式中、R41~R43は前記と同義であり、R44は水素原子またはメチル基を示し、R45はアルキル基を示す。)
前記式(m2-1)で表される単量体の具体例として、以下に示すものが挙げられる。トリメチルシリル(メタ)アクリレート、トリエチルシリル(メタ)アクリレート、トリ-n-プロピルシリル(メタ)アクリレート、トリ-n-ブチルシリル(メタ)アクリレート、トリ-n-アミルシリル(メタ)アクリレート、トリ-n-ヘキシルシリル(メタ)アクリレート、トリ-n-オクチルシリル(メタ)アクリレート、トリ-n-ドデシルシリル(メタ)アクリレート、トリフェニルシリル(メタ)アクリレート、トリ-p-メチルフェニルシリル(メタ)アクリレート、トリベンジルシリル(メタ)アクリレート、トリイソプロピルシリル(メタ)アクリレート、トリイソブチルシリル(メタ)アクリレート、トリ-s-ブチルシリル(メタ)アクリレート、トリ-2-メチルイソプロピルシリル(メタ)アクリレート、トリ-t-ブチルシリル(メタ)アクリレート、エチルジメチルシリル(メタ)アクリレート、n-ブチルジメチルシリル(メタ)アクリレート、ジイソプロピル-n-ブチルシリル(メタ)アクリレート、n-オクチルジ-n-ブチルシリル(メタ)アクリレート、ジイソプロピルステアリルシリル(メタ)アクリレート、ジシクロヘキシルフェニルシリル(メタ)アクリレート、t-ブチルジフェニルシリル(メタ)アクリレート、ラウリルジフェニルシリル(メタ)アクリレート等。
前記式(m2-2)中、R45におけるアルキル基としては、例えば炭素数1~5のアルキル基が挙げられる。
前記式(m2-2)で表される化合物の具体例として、以下に示すものが挙げられる。トリイソプロピルシリルメチルマレート、トリイソプロピルシリルアミルマレート、トリ-n-ブチルシリル-n-ブチルマレート、t-ブチルジフェニルシリルメチルマレート、t-ブチルジフェニルシリル-n-ブチルマレート、トリイソプロピルシリルメチルフマレート、トリイソプロピルシリルアミルフマレート、トリ-n-ブチルシリル-n-ブチルフマレート、t-ブチルジフェニルシリルメチルフマレート、t-ブチルジフェニルシリル-n-ブチルフマレート等。
構成単位(u3)は、単量体(m3)のエチレン性不飽和結合が開裂して単結合となった構造を有する。
構成単位(u3)は、下記式(7)又は(8)で表される構造からなる群から選ばれる少なくとも1種の構造(III)を有する。
-COO-M-OCO ・・・(7)
-COO-M-R13 ・・・(8)
(式中、MはZn、Cu、Mg又はCaを示し、R13は(メタ)アクリロイルオキシ基以外の有機酸残基を示す。)
Mとしては、ZnまたはCuが好ましい。
R13の有機酸残基は、有機酸からプロトン1つを除いた残りの部分(例えばカルボン酸のカルボキシ基からプロトンを除いた残りの部分)をいい、このプロトンの代わりにMとイオン結合している。
有機酸としては、カルボン酸が好ましく、例えばモノクロル酢酸、モノフルオロ酢酸、酢酸、プロピオン酸、オクチル酸、バーサチック酸、イソステアリン酸、パルミチン酸、クレソチン酸、α-ナフトエ酸、β-ナフトエ酸、安息香酸、2,4,5-トリクロロフェノキシ酢酸、2,4-ジクロロフェノキシ酢酸、キノリンカルボン酸、ニトロ安息香酸、ニトロナフタレンカルボン酸、ピルビン酸、ナフテン酸、アビエチン酸、水添アビエチン酸等のモノカルボン酸等が挙げられる。
R13としては、長期にわたりクラックや剥離を防止できる耐久性の高い塗膜が得られる点で、炭素数1~20の脂肪酸残基(脂肪族モノカルボン酸残基)が好ましい。
構造(III)を有する単量体(m3)としては、例えば、式(7)で表される基の両末端に、非置換又は置換基を有するビニル基が結合した単量体、式(8)で表される基の片末端(R13側とは反対側)に、非置換又は置換基を有するビニル基が結合した単量体等が挙げられる。
式(7)で表される基の両末端に前記ビニル基が結合した単量体として、例えば下記式(m3-1)で表される単量体(以下、「単量体(m3-1)」ともいう。)が挙げられる。
式(8)で表される基の片末端に前記ビニル基が結合した単量体として、例えば下記式(m3-2)で表される単量体(以下、「単量体(m3-2)」ともいう。)が挙げられる。
(CH2=C(R31)-COO)2M ・・・(m3-1)
CH2=C(R31)-COO-M-R32 ・・・(m3-2)
式中、MはZn、Cu、Mg又はCaを示し、R31は水素原子又はメチル基を示し、R32は(メタ)アクリロイルオキシ基以外の有機酸残基を示す。
M及びR32はそれぞれ前記と同様であり、好ましい態様も同様である。
単量体(m3-1)としては、例えばアクリル酸亜鉛[(CH2=CHCOO)2Zn]、メタクリル酸亜鉛[(CH2=C(CH3)COO)2Zn]、アクリル酸銅[(CH2=CHCOO)2Cu]、メタクリル酸銅[(CH2=C(CH3)COO)2Cu]、アクリル酸マグネシウム[(CH2=CHCOO)2Mg]、メタクリル酸マグネシウム[(CH2=C(CH3)COO)2Mg]、アクリル酸カルシウム[(CH2=CHCOO)2Ca]、メタクリル酸カルシウム[(CH2=C(CH3)COO)2Ca]等が挙られる。これらはいずれか1種を単独で用いてもよく2種以上を組み合わせて用いてもよい。
中でも、ビニル系共重合体(B)の透明性が高くなり、これを含む塗膜の色調が美しくなる傾向にある点から、(メタ)アクリル酸亜鉛、(メタ)アクリル酸銅が好ましい。
中でも、共重合体(A-2)の透明性が高くなり、これを含む塗膜の色調が美しくなる傾向にある点から、MがZnである亜鉛含有単量体が好ましい。さらに、得られる塗膜の耐久性の点から、脂肪酸亜鉛(メタ)アクリレート(式(m3-2)中のMがZn、R32が脂肪酸残基であるもの)、又は脂肪酸銅(メタ)アクリレート(式(m3-2)中のMがCu、R32が脂肪酸残基であるもの)がより好ましい。
単量体(m3)は、得られる塗膜の自己研磨性が長期にわたり維持され、良好な防汚性が得られる点から、単量体(m3-1)及び単量体(m3-2)の両方を含むことが好ましい。
単量体(m3-1)と単量体(m3-2)との組み合わせとしては、(メタ)アクリル酸亜鉛と脂肪酸亜鉛(メタ)アクリレートとの組み合わせ、又は(メタ)アクリル酸銅と脂肪酸銅(メタ)アクリレートが好ましい。
ビニル系共重合体(B)が単量体(m3-1)単位及び単量体(m、3-2)単位の両方を有する場合、ビニル系共重合体(B)中の単量体(m3-1)単位と単量体(m3-2)単位との比率(モル比)は、単量体(m3-1)単位/単量体(m3-2)単位=10/90~90/10が好ましく、20/80~80/20がより好ましく、30/70~70/30がさらに好ましい。この比率が90/10以下であると、塗膜の耐クラック性や密着性が優れ、10/90以上であると、塗料が低粘度化しやすい傾向にある。
単量体(m3-1)は、例えば、式(m3-1)中のMに対応する金属元素を含む無機金属化合物と、(メタ)アクリル酸とを、有機溶剤等の希釈剤またはエチレン性不飽和単量体等の重合性不飽和基を有する反応性希釈剤中で反応させる方法により得られる。この方法で得られる金属含有重合性単量体を含有する混合物は、有機溶剤や他の単量体との相溶性に優れ、重合を容易に行うことができる。前記反応は、水の存在下で行うことが好ましく、反応物中の水の含有量を0.01~30質量%の範囲とすることが好ましい。前記無機金属化合物としては、例えばZn、Cu、Mg及びCaから選ばれる金属の酸化物、水酸化物、塩化物等が挙げられる。
その際、R32に対応する有機酸の使用量は、無機金属化合物に対して0.01~3倍モルであることが好ましく、0.01~0.95倍モルがより好ましく、0.1~0.7倍モルがさらに好ましい。この有機酸の含有量が0.01倍モル以上であると、この単量体混合物の製造工程において固体の析出が抑制されると共に、得られる塗膜の自己研磨性、耐クラック性がより良好となる。3倍モル以下であると、得られる塗膜の防汚性がより長期間維持される傾向にある。
構成単位(u4)は、構成単位(u1)、構成単位(u2)及び構成単位(u3)以外の他の構成単位である。前記構成単位(u4)は、エチレン性不飽和結合を有し、前記構造(I)、トリオルガノシリルオキシカルボニル基及び前記構造(III)を含まない単量体(m4)のエチレン性不飽和結合が開裂して単結合となった構造を有する。
置換又は非置換のアルキル(メタ)アクリレート[例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、i-プロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、i-ブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、ベヘニル(メタ)アクリレート、1-メチル-2-メトキシエチル(メタ)アクリレート、3-メトキシブチル(メタ)アクリレート、3-メチル-3-メトキシブチル(メタ)アクリレート]、置換又は非置換のアラルキル(メタ)アクリレート[例えば、ベンジル(メタ)アクリレート、m-メトキシフェニルエチル(メタ)アクリレート、p-メトキシフェニルエチル(メタ)アクリレート]、置換又は非置換のアリール(メタ)アクリレート[例えば、フェニル(メタ)アクリレート、m-メトキシフェニル(メタ)アクリレート、p-メトキシフェニル(メタ)アクリレート、o-メトキシフェニルエチル(メタ)アクリレート]、脂環式(メタ)アクリレート[例えば、イソボルニル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート]、トリフルオロエチル(メタ)アクリレート、パーフルオロオクチル(メタ)アクリレート、パーフルオロシクロヘキシル(メタ)アクリレート等の疎水基含有(メタ)アクリル酸エステル単量体;
2-メトキシエチル(メタ)アクリレート、2-エトキシエチル(メタ)アクリレート、2-ブトキシエチル(メタ)アクリレート、ブトキシジエチレングリコール(メタ)アクリレート、メトキシトリエチレングリコール(メタ)アクリレート、メトキシポリエチレングリコール(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、2-(2-エチルヘキサオキシ)エチル(メタ)アクリレート等のオキシエチレン基含有(メタ)アクリル酸エステル単量体;
2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、グリセロール(メタ)アクリレート等の水酸基含有(メタ)アクリル酸エステル単量体;
メトキシポリエチレングリコールアリルエーテル、メトキシポリプロピレングリコールアリルエーテル、ブトキシポリエチレングリコールアリルエーテル、ブトキシポリプロピレングリコールアリルエーテル、メトキシポリエチレングリコール-ポリプロピレングリコールアリルエーテル、ブトキシポリエチレングリコール-ポリプロピレングリコールアリルエーテル等の末端アルコキシアリル化ポリエーテル単量体;
(メタ)アクリル酸グリシジル、α-エチルアクリル酸グリシジル、(メタ)アクリル酸3,4-エポキシブチル等のエポキシ基含有ビニル単量体;
ブチルアミノエチル(メタ)アクリレート、(メタ)アクリルアミド等の第一級又は第二級アミノ基含有ビニル単量体;
ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、ジメチルアミノプロピル(メタ)アクリレート、ジメチルアミノブチル(メタ)アクリレート、ジブチルアミノエチル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリルアミド、ジメチルアミノプロピル(メタ)アクリルアミド等の第三級アミノ基含有ビニル単量体;
ビニルピロリドン、ビニルピリジン、ビニルカルバゾール等の複素環系塩基性単量体;
無水マレイン酸、無水イタコン酸等の酸無水物基含有ビニル単量体;
メタクリル酸、アクリル酸、クロトン酸、ビニル安息香酸、フマル酸、イタコン酸、マレイン酸、シトラコン酸、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノブチル、マレイン酸モノオクチル、イタコン酸モノメチル、イタコン酸モノエチル、イタコン酸モノブチル、イタコン酸モノオクチル、フマル酸モノメチル、フマル酸モノエチル、フマル酸モノブチル、フマル酸モノオクチル、シトラコン酸モノエチル、テトラヒドロフタル酸モノヒドロキシエチル(メタ)アクリレート、テトラヒドロフタル酸モノヒドロキシプロピル(メタ)アクリレート、テトラヒドロフタル酸モノヒドロキシブチル(メタ)アクリレート、フタル酸モノヒドロキシエチル(メタ)アクリレート、フタル酸モノヒドロキシプロピル(メタ)アクリレート、コハク酸モノヒドロキシエチル(メタ)アクリレート、コハク酸モノヒドロキシプロピル(メタ)アクリレート、マレイン酸モノヒドロキシエチル(メタ)アクリレート、マレイン酸モノヒドロキシプロピル(メタ)アクリレート等のカルボキシ基含有エチレン性不飽和単量体;
ジメチルマレート、ジブチルマレート、ジメチルフマレート、ジブチルフマレート、ジブチルイタコネート、ジパーフルオロシクロヘキシルフマレート等の不飽和ジカルボン酸ジエステル単量体;
アクリロニトリル、メタクリロニトニル等のシアノ基含有ビニル単量体;
アルキルビニルエーテル[例えば、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、ヘキシルビニルエーテル、2-エチルヘキシルビニルエーテル等]、シクロアルキルビニルエーテル[例えば、シクロヘキシルビニルエーテル等]等のビニルエーテル単量体;
酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、安息香酸ビニル等のビニルエステル単量体;
スチレン、ビニルトルエン、α-メチルスチレン等の芳香族ビニル単量体;
塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、クロロトリフルオロエチレン等のハロゲン化オレフィン;
エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、アリルメタクリレート、トリアリルシアヌレート、マレイン酸ジアリル、ポリプロピレングリコールジアリルエーテル等の多官能単量体;
マクロモノマー;等。
これらは1種又は2種以上を必要に応じて適宜選択して使用することができる。
エチレン性不飽和結合含有基としては、例えば、CH2=C(COOR)-CH2-、(メタ)アクリロイル基、2-(ヒドロキシメチル)アクリロイル基、ビニル基等が挙げられる。ここで、Rは水素原子、非置換の若しくは置換基を有するアルキル基、非置換の若しくは置換基を有する脂環式基、非置換の若しくは置換基を有するアリール基又は非置換の若しくは置換基を有する複素環基を示す。置換基としては、例えば、アルキル基(ただしRが置換基を有するアルキル基である場合を除く。)、アリール基、-COOR61、シアノ基、-OR62、-NR63R64、-CONR65R66、ハロゲン原子、アリル基、エポキシ基、シロキシ基、及び親水性又はイオン性を示す基からなる群から選択される少なくとも1種が挙げられる。ここで、R61~R66はそれぞれ独立に、水素原子、アルキル基、脂環式基又はアリール基を示す。
エチレン性不飽和結合含有基を有する単量体としては、例えば、単量体(m4)の例として前記で挙げた各種の単量体を用いることができ(ただしマクロモノマーを除く。)、単量体(m1)~(m3)の例として前記で挙げた各種の単量体を併用することも可能である。
マクロモノマーとしては、例えば、国際公開第2013/108880号に開示されている単量体が挙げられる。
疎水基含有(メタ)アクリル酸エステル単量体としては、アルキル(メタ)アクリレートが好ましい。
オキシエチレン基含有(メタ)アクリル酸エステル単量体としては、下記式(4-1)で表される化合物が好ましい。
Z1-(CH2CH2O)nR22 (4-1)
(式中、Z1はアクリロイルオキシ基又はメタクリロイルオキシ基を示し、R22は水素原子、炭素数1~10のアルキル基、又はアリール基を示し、nは1~15の整数を示す。)
R22における炭素数1~10のアルキル基、アリール基はそれぞれ前記R1、R3で挙げたものと同様のものが挙げられる。
nは、耐水性、耐クラック性の点から、1~10の整数が好ましく、1~5の整数がより好ましく、1~3の整数がさらに好ましく、1又は2が特に好ましい。
ビニル系共重合体(B)における構成単位(u1)~(u3)の含有量は、全構成単位の合計(100質量%)に対し、1~99質量%が好ましく、2~90質量%がより好ましく、5~70質量%がさらに好ましい。構成単位(u1)~(u3)の含有量が前記範囲の下限値以上であれば、形成される塗膜の自己研磨性がより優れる。構成単位(u1)~(u3)の含有量が前記範囲の上限値以下であれば、形成される塗膜が適度な加水分解性を有し、長期にわたって自己研磨性が維持され、防汚効果がより優れたものとなる。
共重合体中の各構成単位の含有量(質量%)は、ガスクロマトグラフィー、高速液体クロマトグラフィー、核磁気共鳴スペクトル法等の公知の方法により測定できる。
ビニル系共重合体(B)の重量平均分子量が前記範囲の上限値以下であれば、ビニル系共重合体(B)を溶剤に溶解した溶液の粘度がより低くなり、防汚塗料組成物として高固形分低粘度のものを得やすい。また、形成される塗膜の防汚性が優れる。重量平均分子量が前記範囲の下限値以上であれば、形成される塗膜の硬度、耐久性がより優れる。
ビニル系共重合体(B)の多分散度(Mw/Mn)は、1.5~5.0が好ましく、2.2~3.0がより好ましい。
ビニル系共重合体(B)の重量平均分子量及び数平均分子量はそれぞれ、ゲルろ過クロマトグラフィー(GPC)により、ポリスチレンを基準樹脂として測定される。
ビニル系共重合体(B)の製造方法としては、例えば、溶液重合法、懸濁重合法、塊状重合法、乳化重合法などの公知の重合方法が適用できる。生産性、塗膜性能の点で溶液重合法が好ましい。
重合は、公知の重合開始剤を用いて、公知の方法で行えばよい。例えば、上記した単量体混合物をラジカル開始剤の存在下に60~120℃の反応温度で4~14時間反応させる方法が挙げられる。重合の際、必要に応じて、連鎖移動剤を用いてもよい。
重合開始剤の含有量は、特に限定されず、適宜設定することができる。典型的には、重合性単量体100質量部に対して0.1~20質量部程度である。
連鎖移動剤の含有量は、特に限定されず、適宜設定することができる。典型的には、重合性単量体100質量部に対して0.0001~10質量部程度である。
製造方法(α):単量体(m1)を含む単量体混合物を重合する方法。
製造方法(β):エチレン性不飽和結合とカルボキシ基とを有する単量体(m0)を含む単量体混合物を重合し、カルボキシ基を有する共重合体(B0)を得て、この共重合体(B0)のカルボキシ基を構造(I)に変換する方法。
単量体混合物:
製造方法(α)で用いられる単量体混合物は、単量体(m1)の単量体を含み、単量体(m2)~(m4)をさらに含んでもよい。
単量体(m1)は、エチレン性不飽和結合とカルボキシ基とを有する単量体(m0)のカルボキシ基を構造(I)に変換することにより合成できる。
単量体(m0)としては、例えば(メタ)アクリル酸、クロトン酸、イソクロトン酸、マレイン酸、フマル酸、イタコン酸、マレイン酸モノメチル、フマル酸モノメチル等が挙げられる。
式(31)中、R7における炭素数1~9のアルキル基は、炭素数が9以下である以外は、R1における炭素数1~10のアルキル基と同様である。
R8、R9はそれぞれ、前記式(11)におけるR2、R3と同様である。
式(32)中、R10における炭素数1~9のアルキレン基は、炭素数が9以下である以外は、R4と同様である。
式(33)中、R11は、R5と同様である。R12は、炭素数が9以下である以外は、R6と同様である。
製造方法(β)では、まず、単量体(m0)を含む単量体混合物を重合し、カルボキシ基を有する共重合体(B0)を得る。単量体混合物は、単量体(m1)~(m4)をさらに含んでもよい。
単量体(m0)~(m4)はそれぞれ前記と同様である。
単量体混合物中の単量体(m0)の好ましい範囲は、製造方法(α)における単量体混合物中の単量体(m1)の含有量の好ましい範囲と同様である。オキシエチレン基含有(メタ)アクリル酸エステル単量体やその他の単量体(m4)の含有量の好ましい範囲も前記と同様である。
単量体混合物の重合は、製造方法(α)と同様にして行うことができる。
共重合体(B0)のカルボキシ基を構造(I)に変換する方法としては、例えば共重合体(B0)と、前記化合物(Y2)とを反応(付加反応)させる方法が挙げられる。
共重合体(B0)と化合物(Y2)との反応は、前記単量体(m0)と化合物(Y2)との反応と同様にして行うことができる。
造方法(γ)又は(δ)により共重合体ビニル系共重合体(B)を製造し、必要に応じて有機溶剤を添加する方法が挙げられる。これらのうち、耐水性の点では、製造方法(γ)によりビニル系共重合体(B)を製造し、必要に応じて有機溶剤を添加する方法が好ましい。
製造方法(γ):単量体(m3)を含む単量体混合物を重合する方法。
製造方法(δ):エチレン性不飽和結合及びカルボキシ基を有する単量体(m0)を含む単量体混合物(δ1)を重合し、カルボキシ基を有する共重合体(B0’)を得て、この共重合体(B0’)のカルボキシ基を構造(III)に変換する方法。
共重合体(B0’)のカルボキシ基を構造(III)に変換する方法としては、例えば、
共重合体(B0’)と、酢酸銅、酢酸亜鉛等の有機酸金属塩とを反応させる方法が挙げられる。有機酸金属塩の金属は前記Mに対応する。
水中等で加水分解可能である。そのためビニル系共重合体(B)を含む塗膜は、海水中等で自己研磨性を示す。すなわち、ビニル系共重合体(B)は、特定の基で保護されているため、この状態では海水に溶解しないが、海水との接触により特定の基が加水分解すると、カルボキシ基等が生成し、海水に溶解する。塗膜表面が徐々に海水に溶解して表面更新(自己研磨)される。
また、ビニル系共重合体(B)は、有機溶剤を加えたときに、高固形分低粘度の溶液状とすることができる。ビニル系共重合体(B)と有機溶剤とを含む樹脂組成物が高固形分低粘度であれば、防汚塗料組成物の製造時に、この樹脂組成物にさらに有機溶剤を加えなくても、塗装適性を有する防汚塗料組成物を得ることができる。また、防汚剤等を加える場合に、有機溶剤を加えなくても防汚剤等と良好に混合できる。そのため、VOC含有量が少ない防汚塗料組成物を得ることができる。
本発明の防汚塗料組成物は、前記化合物(A)とビニル系共重合体(B)とを含む防汚塗料組成物である。
本発明の防汚塗料組成物中の化合物(A)の含有量は、特に限定されないが、防汚塗料組成物の全量に対して1質量%以上が好ましく、3質量%以上がより好ましい。
本発明の防汚塗料組成物に含まれるビニル系共重合体(B)は1種でもよく2種以上でもよい。本態様の防汚塗料組成物中のビニル系共重合体(B)の含有量は、特に限定されないが、樹脂組成物の全量に対して5質量%以上が好ましく、10質量%以上がより好ましい。防汚塗料組成物における化合物(A)の含有量とビニル系共重合体(B)の含有量比は、好ましくは、0.1/99.9~70/30、より好ましくは90/10~40/60である。上記含有量比であれば、粘度を抑え塗装性に優れ、耐水性、防汚性を向上できる。
ビニル系共重合体(B)においては、貯蔵中に構造(I)が意図せずに分解してしまうことがある。構造(I)が分解すると、カルボン酸が生成する。これによって、ビニル系共重合体(B)のガラス転移温度が上昇したり、カルボン酸と塗料中の他成分とが架橋構造を形成し、ビニル系共重合体(B)の溶液やこれを含む塗料の粘度が上昇したりする。また、フリーのカルボン酸が生成することにより、有機溶剤に対する溶解安定性や耐水性が低下する。また発生したカルボン酸が酸として触媒的に加水分解反応を促進させることにより、構造(I)のさらなる分解が進行する。樹脂組成物に酸と反応する化合物を含有させることにより、ビニル系共重合体(B)中の構造(I)が分解してカルボン酸が生成したときに、酸と反応する化合物によってカルボン酸が捕捉され、貯蔵安定性が向上する。
また、高pH領域や低pH領域では、構造(I)の分解が促進されることにより貯蔵安定性が低下する。高pH領域では、酸と反応する化合物とカルボン酸との反応性が低下することによっても貯蔵安定性が低下する。塩基性化合物又は酸性化合物の添加によって樹脂組成物のpHを調整することで、構造(I)の分解を抑制し、貯蔵安定性の低下を抑制することができる。
また、水分は、構造(I)の分解(加水分解)を促進する。樹脂組成物に脱水剤を含有させることにより、樹脂組成物中の水分を捕捉し、貯蔵安定性の低下を抑制することができる。
塩基性化合物としては、ジメチルアミン、ジエチルアミン、トリメチルアミン、トリエチルアミン、アニリン、ピリジン等が挙げられる。
エポキシ基を含有する化合物としては、2-エチルオキシラン、2,3-ジメチルオキシラン、2,2-ジメチルオキシラン、(メタ)アクリル酸グリシジル、α-エチルアクリル酸グリシジル、(メタ)アクリル酸3,4-エポキシブチル等が挙げられる。
酸と反応する化合物としては、貯蔵安定性の観点で、化合物(Y3)が好ましい。化合物(Y3)としては、前記で挙げたもののなかでも、貯蔵安定性の向上効果がより優れる点で、前記式(31)中のXが-O-である1-アルケニルアルキルエーテルが好ましく、ブチルビニルエーテルやイソブチルビニルエーテル等のビニルエーテル類がより好ましい。
酸性化合物としては、アビエチン酸、ネオアビエチン酸、パラストリン酸、ピマル酸、イソピマル酸、レボピマル酸、デキストロピマル酸、サンダラコピマル酸、酢酸、プロピオン酸、酪酸、ラウリル酸、ステアリン酸、リノール酸、オレイン酸、クロル酢酸、フルオロ酢酸等が挙げられる。
2種以上の添加剤の組み合わせ例としては、化合物(Y3)と脱水剤との組み合わせ、化合物(Y3)と酸性化合物と脱水剤との組み合わせ化合物(Y3)と塩基性化合物と酸性化合物と脱水剤との組み合わせ、塩基性化合物と脱水剤との組み合わせ等が挙げられる。
ここで、水中で測定されるpHとは、具体的には、水中に塩基性化合物を添加することにより測定される値である。前記pHは、23℃における値である。
本発明の防汚塗料組成物は、シリコーンオイルをさらに含むことが好ましい。防汚塗料組成物がシリコーンオイルを含むと、形成される塗膜の防汚性がより優れる。
シリコーンオイルとしては、例えば、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、メチルハイドロジェンシリコーンオイル等のストレートシリコーンオイル、変性シリコーンオイル等が挙げられる。変性シリコーンオイルは、ストレートシリコーンオイルのケイ素原子の一部にメチル基及びフェニル基以外の有機基(以下「変性基」ともいう。)が導入されたシリコーンオイルである。変性基としては、例えばクロロフェニル基、メチルスチレン基、長鎖アルキル基(例えば炭素数2~18のアルキル基)、ポリエーテル基、カルビノール基、アミノアルキル基、エポキシ基、(メタ)アクリロイル基等が挙げられる。これらのシリコーンオイルはいずれか1種を単独で、または2種以上を組み合わせて用いることができる。シリコーンオイルとしては、上記の中でも、防汚性の観点で、変性基としてポリエーテル基を有するポリエーテル変性シリコーンオイルが好ましい。
本発明の防汚塗料組成物は、有機溶剤を含むことが好ましい。防汚塗料組成物が有機溶剤を含むと、これを用いた防汚塗料組成物の塗工適性、形成される塗膜の耐水性、成膜性等がより優れる。
有機溶剤としては、ビニル系共重合体(B)を溶解できるものであれば特に限定されず、例えばトルエン、キシレン等の炭化水素系溶剤;前記化合物(Y3)、プロピレングリコールモノメチルエーテル-2-アセタート等のエーテル系溶剤;メチルイソブチルケトン等のケトン系溶剤;酢酸n-ブチル等のエステル系溶剤;等が挙げられる。これらはいずれか1種を単独で、又は2種以上を組み合わせて用いることができる。
防汚剤としては、無機防汚剤、有機防汚剤等が挙げられ、要求性能に応じて1種又は2種以上を適宜選択して使用することができる。
防汚剤としては、例えば、亜酸化銅、チオシアン銅、銅粉末等の銅系防汚剤、他の金属(鉛、亜鉛、ニッケル等)の化合物、ジフェニルアミン等のアミン誘導体、ニトリル化合物、ベンゾチアゾール系化合物、マレイミド系化合物、ピリジン系化合物等が挙げられる。これらは、1種を単独で使用してもよいし、2種以上を組み合わせて使用してもよい。
亜酸化銅と防汚剤(b1)とを組み合わせる場合、配合比率(質量比)は、亜酸化銅/防汚剤(b1)=80/20~99/1が好ましく、90/10~99/1がより好ましい。
亜酸化銅、ピリジントリフェニルボラン、4,5-ジクロロ-2-n-オクチル-4-イソチアゾリン-3-オン、防汚剤(b1)及びメデトミジンからなる群から選ばれる少なくとも1種と、その他の防汚剤とを組み合わせてもよい。
他の成分としては、ビニル系共重合体(B)以外の熱可塑性樹脂等が挙げられる。本態様の防汚塗料組成物は、ビニル系共重合体(B)以外の熱可塑性樹脂を含むことが好ましい。防汚塗料組成物がビニル系共重合体(B)以外の熱可塑性樹脂を含むと、耐クラック性や耐水性等の塗膜物性が向上する。
可塑剤として機能し、塗膜の耐クラック性や耐剥離性の向上効果が得られることから、塩素化パラフィンが好ましい。
沈降防止剤やたれ防止剤として機能し、防汚塗料組成物の貯蔵安定性や顔料分散性の向上効果が得られることから、半合成ワックス、合成ワックス等の有機系ワックスが好ましく、ポリエチレンワックス、酸化ポリエチレンワックス、ポリアマイドワックスがより好ましい。
熱可塑性樹脂以外の沈降防止剤やたれ防止剤としては、ベントナイト系、微粉シリカ系、ステアレート塩、レシチン塩、アルキルスルホン酸塩等が挙げられる。
有機溶剤の含有量は、防汚塗料組成物の25℃にてB型粘度計で測定される粘度が後述する好ましい上限値以下となる量が好ましく、ビニル系共重合体(B)の重量平均分子量、ガラス転移温度、架橋構造の有無等によっても異なるが、15質量%以上が好ましく、20質量%以上がより好ましい。
なお、前記化合物(Y3)は、有機溶剤としても機能し得る。したがって、樹脂組成物が化合物(Y3)を含む場合、化合物(Y3)の含有量は有機溶剤の含有量に含まれる。
本発明の防汚塗料組成物が溶剤を含む場合、この樹脂組成物の25℃にてB型粘度計で測定される粘度(以下、「B型粘度」ともいう。)は、5000mPa・s未満が好ましく、4000mPa・s未満がより好ましく、3,000mPa・s未満がさらに好ましく、2,000mPa・s未満が特に好ましい。
防汚塗料組成物の固形分が前記範囲の下限値以上であれば、VOC含有量が充分に低くなる。固形分が前記範囲の上限値以下であれば、防汚塗料組成物の粘度を低くしやすい。
防汚塗料組成物のB型粘度の下限は特に限定されないが、塗膜物性の点では、100mPa・s以上が好ましい。
防汚塗料組成物の粘度は、樹脂組成物の粘度、樹脂組成物への有機溶剤の添加量等によって調整できる。
本発明の防汚塗料組成物を用いた塗膜は、基材表面に、直接に、又は下地塗膜を介して形成することができる。
下地塗膜としては、ウオッシュプライマー、塩化ゴム系やエポキシ系等のプライマー、中塗り塗料等を用いて形成できる。
塗膜の形成は、公知の方法により行うことができる。例えば、基材表面又は基材上の下地塗膜の上に、防汚塗料組成物を、刷毛塗り、吹き付け塗り、ローラー塗り、沈漬塗り等の手段で塗布し、乾燥することにより塗膜を形成できる。
防汚塗料組成物の塗布量は、一般的には乾燥塗膜として10~400μmの厚さになる量に設定できる。
塗膜の乾燥は、通常、室温で行うことができ、必要に応じて加熱乾燥を行ってもよい。
実施例中の評価は、以下に示す方法で行った。
測定試料(樹脂組成物又は防汚塗料組成物)0.50gをアルミニウム製の皿に測りとり(測定質量)、トルエン3mLをスポイトで加えて皿の底に一様に広げ、70~80℃の水浴上で測定試料を加熱溶解させ、蒸発乾固させた。その後、105℃の熱風乾燥機で2時間の乾燥を行った。測定試料の質量(測定質量)と、乾燥後の質量(乾燥後質量)とから、以下の式により固形分(加熱残分)を求めた。
固形分(質量%)=乾燥後質量/測定質量×100
測定試料の粘度を25℃においてB型粘度計で測定し、その値をB型粘度として示した。
乾燥したガードナー気泡粘度管(以下、単に粘度管ともいう。)に測定試料を粘度管の指示線まで入れコルク栓で栓をした。試料を採取した粘度管を、規定の温度(25.0±0.1℃)に調節した恒温水槽中に2時間垂直に浸漬して試料を恒温にし、基準管となる粘度管と試料を入れた粘度管を同時に180°回転させ、試料のアワ上昇速度を基準管と比較することで粘度(ガードナー粘度)を決定した。
重合体の重量平均分子量(Mw)及び数平均分子量(Mn)は、ゲル透過クロマトグラフィー(GPC)(東ソー(株)製、HLC-8220)を用いて測定した。カラムはTSKgelα-M(東ソー(株)製、7.8mm×30cm)、TSKguardcolumnα(東ソー(株)製、6.0mm×4cm)を使用した。検量線は、F288/F1/28/F80/F40/F20/F2/A1000(東ソー(株)製、標準ポリスチレン)、及びスチレン単量体を使用して作成した。
塗装後の塗膜の平滑性を目視で確認し、以下の基準で塗装適性を評価した。
○:塗膜が平滑である。
△:塗膜に部分的にスジが残る。
×:塗膜にスジが残る。
製造した防汚塗料組成物のB型粘度(貯蔵前B型粘度)(mPa・s)を測定した。この防汚塗料組成物を、150mlのガラス瓶に入れ、40℃で30日間保管した。その後、防汚塗料組成物のB型粘度(40℃30日間貯蔵後B型粘度)(mPa・s)を測定し、下記式により塗料粘度変化率(%)を算出した。
塗料粘度変化率(%)=40℃30日間貯蔵後B型粘度/貯蔵前B型粘度×100
防汚塗料組成物を、50mm×50mm×2mmの硬質塩化ビニル板に、乾燥膜厚120μmになるようにアプリケーターで塗布し、乾燥して塗膜を形成し、試験板を得た。この試験板を、海水中に設置した回転ドラムに取り付け、周速7.7m/s(15ノット)で回転させた。その状態を6カ月間維持し、6カ月後の塗膜表面を観察した。評価は以下の基準で行った。
◎:クラック及び剥離が全く観察されない。
○:クラックが部分的に観察される。
△:一部にクラック、剥離が観察される
×:クラック、剥離が全面に観察される
防汚塗料組成物を、予め防錆塗料を塗布してあるサンドブラスト鋼板に、乾燥膜厚が200~300μmになるように刷毛で塗布し、乾燥して塗膜を形成し、試験板を得た。この試験板を、三河湾内で6ヶ月間静置した後、塗膜の全面積に対する海中生物が付着した面積の割合(海中生物の付着面積)を調べ、以下の基準で静置防汚性を評価した。
◎:海水生物の付着面積が10%以下。
○:海水生物の付着面積が10%超20%以下。
△:海水生物の付着面積が20%超40%以下。
×:海水生物の付着面積が40%超。
防汚塗料組成物を、50mm×50mm×2mmの硬質塩化ビニル板に、乾燥膜厚120μmになるようにアプリケーターで塗布し、乾燥して塗膜を形成し、試験板を得た。この試験板を、海水中に設置した回転ドラムに取り付け、周速7.7m/s(15ノット)で回転させた。その状態を6カ月間維持し、6カ月後の塗膜の膜厚(μm)を測定し、1ヵ月あたりの消耗膜厚を消耗度(μm/M)とした。
IBEMA:1-イソブトキシエチルメタクリレート(後述する製造例M1で合成した合成品)。
MMA:メチルメタクリレート。
EA:エチルアクリレート。
BA:ブチルアクリレート。
CHMA:シクロヘキシルメタクリレート。
2-MTMA:2-メトキシエチルメタクリレート。
MAA: メタクリル酸。
TIPSA:トリイソプロピルシリルアクリレート。
TIPSMA:トリイソプロピルシリルメタクリレート。
ノフマーMSD:商品名、日油株式会社製、α-メチルスチレンダイマー。
添加剤(a):ディスパロン(登録商標)4200-20(楠本化成(株)製、酸化ポリエチレンワックス)。
添加剤(b):ディスパロンA603-20X(楠本化成(株)製、ポリアマイドワックス)。
添加剤(c):トヨパラックス(登録商標)150(東ソー(株)製、塩素化パラフィン)。
KF-6016:商品名、信越化学工業(株)製、ポリエーテル変性シリコーンオイル。
防汚剤(1):4-ブロモ-2-(4-クロロフェニル)-5-(トリフルオロメチル)-1H-ピロール-3-カルボニトリル。
防汚剤(2):4,5-ジクロロ-2-n-オクチル-4-イソチアゾリン-3-オン(ロームアンドハース社製、商品名:シーナイン211)。
イソブチルビニルエーテル90.1部(0.9mol)、ヒドロキノン0.14部、フェノチアジン0.28部を室温で撹拌して均一になるまで混合した。空気(10ml/min)を吹込みながら、メタクリル酸51.7部(0.6mol)を、反応液の温度が60℃以下を保つようにして滴下した。滴下後、反応液の温度を80℃まで上げて、6時間反応させた。反応液にt-ブチルメチルエーテル158.7部(1.8mol)を加えて混合し、有機相を20質量%炭酸カリウム水溶液200部で1回洗浄した。有機相に4-ベンゾイルオキシ-2,2,6,6-テトラメチルピペリジン-N-オキシル0.03部を加え、エバポレータにより低沸分を留出させた。得られた残渣を減圧蒸留して、沸点60℃/3torrの1-イソブトキシエチルメタクリレート(IBEMA)97.5部(0.52mol)を得た。
撹拌機、温度調整機、滴下装置を備えた反応容器に、キシレン100部にロジン100部を溶解させた液を仕込み、撹拌しながら120℃に昇温した。イソブチルビニルエーテル66.2部を30分間で添加して、6時間撹拌後、固形分が48.8質量%の化合物A-1を得た。
撹拌機、温度調整機、滴下装置を備えた反応容器に、キシレン100部にロジン100部を溶解させた液を仕込み、撹拌しながら120℃に昇温した。2-エチルヘキシルビニルエーテル103.4部を30分間で添加して、6時間撹拌後、固形分が49.2質量%の化合物A-2を得た。
撹拌機、温度調整機、滴下装置を備えた反応容器に、キシレン100部にバーサチック酸100部を溶解させた液を仕込み、撹拌しながら120℃に昇温した。イソブチルビニルエーテル117部を30分間で添加して、6時間撹拌後、固形分が49.0質量%の化合物A-3を得た。
撹拌機、温度調整機、滴下装置を備えた反応容器に、工業キシレン50部を仕込み、撹拌しながら90℃に昇温した。続いて、滴下ロートから単量体(M1)の25部、MMAの24部、EAの36部、MTMAの15部、開始剤としてAMBNの1.9部からなる混合物を4時間かけて等速滴下した。滴下終了30分後、キシレン9.9部とAMBN2.0部を30分かけて等速滴下した。さらに2時間撹拌した後、イソブチルビニルエーテル6.7部を添加し、固形分が60質量%のビニル系共重合体(B)を含む樹脂組成物B-1を得た。
単量体及び開始剤の種類及び仕込み量、並びに重合後に添加する添加剤の種類及び量を表1に示すようにし、理論固形分が60質量%となるように、添加剤量に応じて、滴下終了後のキシレン量を調整したこと以外は製造例B-1と同様にして、ビニル系共重合体(B)を含む樹脂組成物B-2~B-5を製造した。
撹拌機、温度調整機、滴下装置を備えた反応容器に、プロピレングリコールモノメチルエーテルアセテート76.7部を仕込み、撹拌しながら90℃に昇温した。続いて、滴下ロートからMAAの11.6部、MMAの24部、EAの36部、MTMAの15部、開始剤としてAMBNの1.9部からなる混合物を4時間かけて等速滴下した。滴下終了後、30分後、キシレン9.9部とAMBN2.0部を30分かけて等速滴下した。さらに2時間撹拌した後110℃に昇温し、イソブチルビニルエーテル26.8部を30分かけて等速滴下した後、さらに6時間撹拌した。これにより、共重合体中のカルボキシ基とイソブチルビニルエーテルとを反応させて、固形分が50.1質量%のビニル系共重合体(B)を含む樹脂組成物B-6を得た。
表2に示す配合に従い、各成分をロッキングシェーカーにより混合して、防汚塗料組成物を得た。
得られた防汚塗料組成物の塗料性状(固形分、B型粘度)、塗装適性、塗料粘度変化率、塗膜性能(静置防汚性、耐水性、塗膜消耗度試験)の評価結果を表2に示す。
また、実施例1~8の防汚塗料組成物の塗膜は、静置防汚性及び耐水性に優れていた。また、この塗膜は適切な消耗度を有していた。
一方、化合物(A)を有していない防汚塗料組成物を用いた比較例1~4は、化合物(A)を有している樹脂組成物に比べ固形分同等でB型粘度測定値が高く高粘度であった。高粘度に起因して塗装適性が悪く、低VOC塗料に適していない。
Claims (7)
- 前記化合物(A)のRa、Rb及びRcがロジンに由来する環式炭化水素残基である、請求項1に記載の防汚塗料組成物。
- 前記ビニル系共重合体(B)が下記式(4)、下記式(5)又は下記式(6)で表される構造(I)の少なくとも1種を有する構成単位(u1)、トリオルガノシリルオキシカルボニル基を有する構成単位(u2)、及び下記式(7)又は下記式(8)で表される構造(III)の少なくとも1種を有する構成単位(u3)からなる群から選ばれる少なくとも1種の構成単位を有する(メタ)アクリル系共重合体である、請求項1又は2に記載の防汚塗料組成物。
-COO-M-OCO ・・・(7)
-COO-M-R13 ・・・(8)
(式中、MはZn、Cu、Mg又はCaを示し、R13は(メタ)アクリロイルオキシ基以外の有機酸残基を示す。) - 酸と反応する化合物、塩基性化合物、酸性化合物及び脱水剤からなる群から選ばれる少なくとも1種をさらに含む、請求項1~3のいずれか一項に記載の防汚塗料組成物。
- 防汚剤をさらに含む、請求項1~5のいずれか一項に記載の防汚塗料組成物。
- 前記防汚剤として、亜酸化銅、ピリジントリフェニルボラン、4,5-ジクロロ-2-n-オクチル-4-イソチアゾリン-3-オン、4-ブロモ-2-(4-クロロフェニル)-5-(トリフルオロメチル)-1H-ピロール-3-カルボニトリル及びメデトミジンからなる群から選ばれる少なくとも1種を含む、請求項6に記載の防汚塗料組成物。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020207034095A KR102528764B1 (ko) | 2018-06-01 | 2019-05-28 | 방오 도료 조성물 |
EP19812177.4A EP3805327A4 (en) | 2018-06-01 | 2019-05-28 | ANTI-FOULING PAINT COMPOSITION |
JP2019530850A JP7413781B2 (ja) | 2018-06-01 | 2019-05-28 | 防汚塗料組成物 |
SG11202011912RA SG11202011912RA (en) | 2018-06-01 | 2019-05-28 | Antifouling paint composition |
CN201980035261.8A CN112166162B (zh) | 2018-06-01 | 2019-05-28 | 防污涂料组合物 |
US17/104,696 US20210079232A1 (en) | 2018-06-01 | 2020-11-25 | Antifouling paint composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018105921 | 2018-06-01 | ||
JP2018-105921 | 2018-06-01 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US17/104,696 Continuation US20210079232A1 (en) | 2018-06-01 | 2020-11-25 | Antifouling paint composition |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2019230675A1 true WO2019230675A1 (ja) | 2019-12-05 |
Family
ID=68698179
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2019/020988 WO2019230675A1 (ja) | 2018-06-01 | 2019-05-28 | 防汚塗料組成物 |
Country Status (8)
Country | Link |
---|---|
US (1) | US20210079232A1 (ja) |
EP (1) | EP3805327A4 (ja) |
JP (1) | JP7413781B2 (ja) |
KR (1) | KR102528764B1 (ja) |
CN (1) | CN112166162B (ja) |
SG (1) | SG11202011912RA (ja) |
TW (1) | TW202003716A (ja) |
WO (1) | WO2019230675A1 (ja) |
Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04103671A (ja) | 1990-08-24 | 1992-04-06 | Dainippon Ink & Chem Inc | 防汚塗料用組成物 |
JPH06135877A (ja) * | 1992-08-06 | 1994-05-17 | Dainippon Ink & Chem Inc | ヘミアセタールエステル類の製造法 |
JPH1030071A (ja) | 1996-04-17 | 1998-02-03 | Nof Corp | 塗料組成物 |
JPH11116858A (ja) | 1997-10-17 | 1999-04-27 | Nof Corp | 塗料組成物 |
JP2001226440A (ja) | 2000-02-17 | 2001-08-21 | Nippon Paint Co Ltd | 共重合体及び塗料組成物 |
JP2001262076A (ja) * | 2000-03-22 | 2001-09-26 | Nof Corp | ロジン誘導体 |
JP2001261620A (ja) * | 2000-03-22 | 2001-09-26 | Nof Corp | アビエチン酸多官能ビニル(チオ)エーテル誘導体を含有するロジン誘導体 |
JP2005082725A (ja) | 2003-09-09 | 2005-03-31 | Nitto Kasei Co Ltd | 防汚塗料組成物、該防汚塗料組成物が塗布された海中物品類、および該防汚塗料組成物を使用する防汚方法 |
JP2008106047A (ja) * | 2006-09-26 | 2008-05-08 | Arakawa Chem Ind Co Ltd | (メタ)アクリロイル基含有ロジン誘導体およびその製造方法 |
JP2010100821A (ja) * | 2008-09-29 | 2010-05-06 | Arakawa Chem Ind Co Ltd | ロジン系共重合体、活性エネルギー線硬化型樹脂組成物、および硬化物 |
WO2013108880A1 (ja) | 2012-01-18 | 2013-07-25 | 三菱レイヨン株式会社 | ビニル系ポリマーの製造方法およびビニル系ポリマーを含む水性防汚塗料用樹脂組成物 |
WO2016167360A1 (ja) * | 2015-04-16 | 2016-10-20 | 三菱レイヨン株式会社 | 防汚塗料組成物 |
WO2017065172A1 (ja) * | 2015-10-13 | 2017-04-20 | 三菱レイヨン株式会社 | (メタ)アクリル系共重合体、樹脂組成物、防汚塗料組成物及び(メタ)アクリル系共重合体の製造方法 |
WO2018008166A1 (ja) * | 2016-07-05 | 2018-01-11 | 三菱ケミカル株式会社 | 重合体含有組成物および防汚塗料組成物 |
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 |
JP2018105921A (ja) | 2016-12-22 | 2018-07-05 | キヤノン株式会社 | 画像形成装置 |
WO2018181429A1 (ja) * | 2017-03-29 | 2018-10-04 | 三菱ケミカル株式会社 | (メタ)アクリル系共重合体、その製造方法、樹脂組成物及び防汚塗料組成物 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI228132B (en) * | 2001-09-26 | 2005-02-21 | Nof Corp | Soldering flux composition and solder paste |
EP1695956B1 (en) * | 2003-11-27 | 2012-06-20 | Chugoku Marine Paints, Ltd. | Cyclic carboxylic acid compound and use thereof |
SG10201911773YA (en) * | 2015-09-25 | 2020-02-27 | Mitsubishi Chem Corp | (meth)acrylic copolymer, polymer solution, polymer-containing composition, anti-fouling coating composition, and method for producing (meth)acrylic copolymer |
-
2019
- 2019-05-28 EP EP19812177.4A patent/EP3805327A4/en active Pending
- 2019-05-28 WO PCT/JP2019/020988 patent/WO2019230675A1/ja unknown
- 2019-05-28 SG SG11202011912RA patent/SG11202011912RA/en unknown
- 2019-05-28 CN CN201980035261.8A patent/CN112166162B/zh active Active
- 2019-05-28 JP JP2019530850A patent/JP7413781B2/ja active Active
- 2019-05-28 KR KR1020207034095A patent/KR102528764B1/ko active IP Right Grant
- 2019-05-29 TW TW108118516A patent/TW202003716A/zh unknown
-
2020
- 2020-11-25 US US17/104,696 patent/US20210079232A1/en not_active Abandoned
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04103671A (ja) | 1990-08-24 | 1992-04-06 | Dainippon Ink & Chem Inc | 防汚塗料用組成物 |
JPH06135877A (ja) * | 1992-08-06 | 1994-05-17 | Dainippon Ink & Chem Inc | ヘミアセタールエステル類の製造法 |
JPH1030071A (ja) | 1996-04-17 | 1998-02-03 | Nof Corp | 塗料組成物 |
JPH11116858A (ja) | 1997-10-17 | 1999-04-27 | Nof Corp | 塗料組成物 |
JP2001226440A (ja) | 2000-02-17 | 2001-08-21 | Nippon Paint Co Ltd | 共重合体及び塗料組成物 |
JP2001262076A (ja) * | 2000-03-22 | 2001-09-26 | Nof Corp | ロジン誘導体 |
JP2001261620A (ja) * | 2000-03-22 | 2001-09-26 | Nof Corp | アビエチン酸多官能ビニル(チオ)エーテル誘導体を含有するロジン誘導体 |
JP2005082725A (ja) | 2003-09-09 | 2005-03-31 | Nitto Kasei Co Ltd | 防汚塗料組成物、該防汚塗料組成物が塗布された海中物品類、および該防汚塗料組成物を使用する防汚方法 |
JP2008106047A (ja) * | 2006-09-26 | 2008-05-08 | Arakawa Chem Ind Co Ltd | (メタ)アクリロイル基含有ロジン誘導体およびその製造方法 |
JP2010100821A (ja) * | 2008-09-29 | 2010-05-06 | Arakawa Chem Ind Co Ltd | ロジン系共重合体、活性エネルギー線硬化型樹脂組成物、および硬化物 |
WO2013108880A1 (ja) | 2012-01-18 | 2013-07-25 | 三菱レイヨン株式会社 | ビニル系ポリマーの製造方法およびビニル系ポリマーを含む水性防汚塗料用樹脂組成物 |
WO2016167360A1 (ja) * | 2015-04-16 | 2016-10-20 | 三菱レイヨン株式会社 | 防汚塗料組成物 |
WO2017065172A1 (ja) * | 2015-10-13 | 2017-04-20 | 三菱レイヨン株式会社 | (メタ)アクリル系共重合体、樹脂組成物、防汚塗料組成物及び(メタ)アクリル系共重合体の製造方法 |
WO2018008166A1 (ja) * | 2016-07-05 | 2018-01-11 | 三菱ケミカル株式会社 | 重合体含有組成物および防汚塗料組成物 |
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 |
JP2018105921A (ja) | 2016-12-22 | 2018-07-05 | キヤノン株式会社 | 画像形成装置 |
WO2018181429A1 (ja) * | 2017-03-29 | 2018-10-04 | 三菱ケミカル株式会社 | (メタ)アクリル系共重合体、その製造方法、樹脂組成物及び防汚塗料組成物 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3805327A4 |
Also Published As
Publication number | Publication date |
---|---|
KR20210005177A (ko) | 2021-01-13 |
TW202003716A (zh) | 2020-01-16 |
CN112166162B (zh) | 2022-06-28 |
KR102528764B1 (ko) | 2023-05-08 |
JPWO2019230675A1 (ja) | 2021-06-03 |
EP3805327A4 (en) | 2022-01-05 |
JP7413781B2 (ja) | 2024-01-16 |
US20210079232A1 (en) | 2021-03-18 |
EP3805327A1 (en) | 2021-04-14 |
CN112166162A (zh) | 2021-01-01 |
SG11202011912RA (en) | 2020-12-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7006741B2 (ja) | 防汚塗料組成物 | |
JP6369563B2 (ja) | (メタ)アクリル系共重合体、重合体含有組成物、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 | |
KR102638011B1 (ko) | (메트)아크릴계 공중합체, 수지 조성물, 방오 도료 조성물 및 (메트)아크릴계 공중합체의 제조 방법 | |
JP7056648B2 (ja) | 樹脂組成物、その製造方法及び防汚塗料組成物 | |
JP7327605B2 (ja) | (メタ)アクリル系共重合体、その製造方法、樹脂組成物及び防汚塗料組成物 | |
JP6809231B2 (ja) | 重合体含有組成物および防汚塗料組成物 | |
JP6094484B2 (ja) | 防汚塗料用樹脂組成物、防汚塗料および防汚塗膜 | |
JP6866603B2 (ja) | 樹脂組成物、防汚塗料組成物および樹脂組成物の製造方法 | |
JP7413781B2 (ja) | 防汚塗料組成物 | |
JP6922349B2 (ja) | 防汚塗料組成物および防汚塗料組成物の製造方法 | |
WO2022210547A1 (ja) | 化合物、重合体及び防汚塗料組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2019530850 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19812177 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20207034095 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2019812177 Country of ref document: EP Effective date: 20210111 |