CN116601243A - Copolymer for antifouling paint composition and antifouling paint composition - Google Patents

Copolymer for antifouling paint composition and antifouling paint composition Download PDF

Info

Publication number
CN116601243A
CN116601243A CN202180075626.7A CN202180075626A CN116601243A CN 116601243 A CN116601243 A CN 116601243A CN 202180075626 A CN202180075626 A CN 202180075626A CN 116601243 A CN116601243 A CN 116601243A
Authority
CN
China
Prior art keywords
monomer
acrylate
meth
copolymer
coating film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202180075626.7A
Other languages
Chinese (zh)
Inventor
冈永都
安井拓也
松木崇
和久英典
小林慧
伊藤基道
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Kasei Co Ltd
Original Assignee
Nitto Kasei Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Kasei Co Ltd filed Critical Nitto Kasei Co Ltd
Publication of CN116601243A publication Critical patent/CN116601243A/en
Pending legal-status Critical Current

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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (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
    • 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
    • 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
    • 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
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups
    • 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
    • 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
    • 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
    • C09D7/61—Additives non-macromolecular 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
    • 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

Abstract

Provided is an antifouling paint composition which can exhibit excellent performance without deteriorating the dissolution stability of a coating film or causing abnormality of the coating film such as peeling or cracking even if repeated application of an antifouling coating film is performed. According to the present invention, there is provided a copolymer for an antifouling paint composition, which is obtained by copolymerizing a monomer mixture comprising a monomer (a) represented by a general formula (1), a monomer (b) represented by a general formula (2), and a monomer (c) other than the monomer (a) and the monomer (b) and copolymerizable with the monomer (a) and the monomer (b), wherein the ratio of the monomer (a) in the monomer mixture is 25 to 60% by mass, and the molecular weight distribution (Mw/Mn) of the copolymer is 5.0 or more, and the copolymer does not contain sulfur atoms.

Description

Copolymer for antifouling paint composition and antifouling paint composition
Technical Field
The present invention relates to a copolymer for an antifouling paint composition and an antifouling paint composition.
Background
Aquatic fouling organisms such as barnacles, dragon worms, perna mussels, pergola, sea squirts, sea sedge, sea lettuce, and sludge cause problems such as functional impairment and appearance impairment of ships and the like due to attachment of aquatic structures such as industrial equipment such as ships (especially ship bottom parts), nets, accessories for the nets, and the like, and water pipes for power generation.
In order to prevent such a problem, a technique of forming an antifouling coating film by applying an antifouling coating composition to a ship or the like, and slowly releasing an antifouling agent from the antifouling coating film to thereby exert antifouling performance for a long period of time has been widely known (patent document 1).
[ Prior Art literature ]
[ patent literature ]
Japanese patent application laid-open No. 2000-17203
Disclosure of Invention
Technical problem to be solved by the invention
However, even if the technique of patent document 1 is adopted, it is necessary to repeat coating (recoating) in order to exert long-term antifouling performance for 5 years or more, but after sailing after long-term contact with seawater, there is a possibility that adhesion may be lowered due to flooding into the antifouling coating film and deterioration of the coating film. In particular, even in the case of the paint of the same composition, there is a possibility that the surface of the old paint film tends to be hydrophilized due to deterioration caused by contact with seawater for a long period of time, and the paint film formed of the paint may be in a state different from the original property, and the performance of the paint film formed of the paint repeatedly applied thereto may be affected.
The present invention has been made in view of such circumstances, and provides a copolymer for an antifouling paint composition, which can exhibit excellent performance without deteriorating the dissolution stability of a coating film or causing abnormality of the coating film such as peeling or cracking even when repeated coating of an antifouling coating film is performed.
Means for solving the problems
According to the present invention, there is provided a copolymer for an antifouling paint composition, which is obtained by copolymerizing a monomer mixture comprising a monomer a represented by the general formula (1), a monomer b represented by the general formula (2), and a monomer c other than the monomer a and the monomer b, which is copolymerizable with the monomer a and the monomer b, wherein the ratio of the monomer a in the monomer mixture is 25 to 60% by mass, and the molecular weight distribution (Mw/Mn) of the copolymer is 5.0 or more, and the copolymer does not contain sulfur atoms.
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by controlling the molecular weight distribution (Mw/Mn) of a copolymer containing a specific component, and have completed the present invention.
Detailed Description
The present invention will be specifically described below.
1. Antifouling coating composition
The antifouling paint composition of the present invention contains the copolymer a.
1-1. Copolymer A
The copolymer a is obtained by copolymerizing a monomer mixture comprising a monomer a, a monomer b, and a monomer c. Copolymer a is a triorganosilyl (meth) acrylate-containing copolymer. The method for synthesizing the monomers a to c and the copolymer A will be specifically described below. In the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid, and "(meth) acrylate" means acrylate or methacrylate.
< monomer a >)
The monomer a is a triorganosilyl (meth) acrylate monomer represented by the general formula (1).
[ chemical formula 1 ]
(wherein R is 1 Is hydrogen or methyl, R 2 ～R 4 Respectively identical or different and represents a branched alkyl group having 3 to 8 carbon atoms or a phenyl group)
R 2 ～R 4 For example, 3, 4, 5, 6, 7, 8, or may be in a range between any 2 values exemplified herein. Examples of the branched alkyl group include isopropyl, isopropenyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpropyl, 1-methylbutyl, 1-methylpentyl, 1-dimethylpropyl, 1-dimethylbutyl, tert-hexyl (the xyl), cyclohexyl, 1-dimethylpentyl, 1-methylhexyl, 1-dimethylhexyl, 1-methylheptyl, 2-methylbutyl, 2-ethylbutyl, 2-dimethylpropyl, cyclohexylmethyl, 2-ethylhexyl, 2-propylpentyl, 3-methylpentyl and the like. As R 2 ～R 4 Preferably identical or different and respectively isopropyl, isopropenyl, sec-butyl, tert-butyl, phenyl and 2-ethylhexyl, particularly preferably isopropyl and 2-ethylhexyl.
As the monomer a, a monomer having a monomer group, examples thereof include triisopropylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, diisopropylisopropylsilyl (meth) acrylate, diisopropylsilyl (meth) acrylate, diisopropylbutylsilyl (meth) acrylate, diisopropylsec-butylsilyl (meth) acrylate, diisopropylisopropylisopropylsilyl (meth) acrylate, isopropyldiisobutylsilyl (meth) acrylate, isopropyldi-sec-butylsilyl (meth) acrylate, tert-butyldiisobutylsilyl (meth) acrylate, tert-butyldiisobutyldiisopropylsilyl (meth) acrylate, tert-butyldiisopropylsilyl (meth) acrylate, tert-butyldiphenylsilyl (meth) acrylate, diisopropylsilyl (meth) acrylate, tricyclohexylsilyl (meth) acrylate, triisopropylsilyl (1, 1-dimethylpentyl (meth) acrylate, 2-dimethylpropylsilyl (meth) acrylate Tricyclohexylmethylsilyl (meth) acrylate, diisopropylcyclohexylmethylsilyl (meth) acrylate, tri-2-ethylhexyl silyl (meth) acrylate, tri-2-propylpentylsilyl (meth) acrylate, and the like. Preferred examples thereof include triisopropylsilyl (meth) acrylate, tri-sec-butylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, and tri-2-ethylhexyl silyl (meth) acrylate. These monomers a may be used alone or in combination of 2 or more.
< monomer b >)
Monomer b is represented by chemical formula (2).
[ chemical formula 2 ]
(wherein R is 5 Is hydrogen or methyl, R 6 Is a hydrocarbon group having 2 to 9 carbon atoms and having an oxygen atom. )
Monomer b is at R 6 And a monomer partially containing an oxygen atom and copolymerizable with the monomer a.
R 6 For example, the carbon number of (2), 3, 4, 5, 6, 7, 8, 9, or any number between 2 exemplified herein. As R 6 Examples of the hydrocarbon group(s) of (a) include aliphatic hydrocarbon groups (e.g., alkyl groups) substituted with a substituent having an oxygen atom (e.g., hydroxy group, alkoxy group)) Or an aromatic hydrocarbon group having an aromatic ring containing an oxygen atom.
Examples of the monomer b include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, diethylene glycol monomethyl (meth) acrylate, propylene glycol monomethyl (meth) acrylate, oligo (ethylene glycol) methyl ether (meth) acrylate, oligo (ethylene glycol) ethyl ether (meth) acrylate, epoxypropyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like.
From the viewpoint of dissolution stability, the monomer b preferably has an ether bond. From the viewpoint of physical properties of the coating film, the monomer b is more preferably 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, or 2- (2-ethoxyethoxy) ethyl (meth) acrylate. The monomer b may be used alone or in combination of two or more as the monomer component of the copolymer A.
< monomer c >)
The monomer c is a monomer other than the monomer a and the monomer b, and is copolymerizable with the monomer a and the monomer b. The monomers c are preferably ethylenically unsaturated monomers.
Examples of the monomer c include (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, zinc (meth) acrylate, copper (meth) acrylate, zinc versatate, copper versatate (meth) acrylate, zinc naphthenate (meth) acrylate, copper naphthenate (meth) acrylate, zinc stearate (meth) acrylate, and copper rosin acrylate
The method comprises the steps of carrying out a first treatment on the surface of the Vinyl compounds such as vinyl chloride, vinylidene chloride, (meth) acrylonitrile, vinyl acetate, vinyl alcohol, butyl vinyl ether, isobutyl vinyl ether, lauryl vinyl ether, N-vinylpyrrolidone, and vinylsulfonic acid
The method comprises the steps of carrying out a first treatment on the surface of the Aromatic compounds such as styrene, vinyl toluene, alpha-methylstyrene, vinyl benzenesulfonic acid, and vinyl benzoate
The method comprises the steps of carrying out a first treatment on the surface of the Dibasic acid dialkyl ester compounds such as dimethyl maleate, dibutyl maleate and dimethyl fumarate
The method comprises the steps of carrying out a first treatment on the surface of the Unsaturated monocarboxylic acid compounds such as (meth) acrylic acid and 2-carboxyethyl (meth) acrylate
The method comprises the steps of carrying out a first treatment on the surface of the Compounds having zwitterionic structures such as oxyethyl phosphorylcholine (meth) acrylate, 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propane-1-sulfonic acid, and 3- [ (3-acrylamidopropyl) dimethylammonium ] propionate
The method comprises the steps of carrying out a first treatment on the surface of the An oligomer or polymer having an unsaturated group such AS AA-6 (manufactured by east Asia Synthesis (strand), AS-6 (manufactured by east Asia Synthesis (strand)), terminal methacryloyl polystyrene), silaplane FM-0711 (manufactured by JNC (strand), single terminal methacryloxypolydimethylsiloxane), KF-2012 (manufactured by Xinyue chemical industry (strand), single terminal methacryloxypolydimethylsiloxane).
Among them, aromatic compounds, and (meth) acrylic esters are particularly preferable, and styrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, zinc naphthenate, zinc rosin (meth) acrylate hydrogenated, zinc rosin (meth) acrylate, copper naphthenate, copper rosin (meth) acrylate hydrogenated.
The monomer c may be used alone or in combination of two or more as the monomer component of the above copolymer a. As the monomer c, triorganosilyl (meth) acrylate other than the monomer a may be contained. The ratio of the triorganosilyl (meth) acrylate other than the monomer a in the monomer mixture is preferably 10 mass% or less. Examples of the triorganosilyl (meth) acrylate other than the monomer a include trimethylsilyl (meth) acrylate and triethylsilyl (meth) acrylate.
The ratio of the monomer a in the monomer mixture is preferably from 25 to 60% by mass, more preferably from 35 to 50% by mass, from the viewpoint of maintaining stable coating film solubility. The ratio is, for example, 25, 30, 35, 40, 45, 50, 55, 60 mass%, or may be in a range between any 2 values exemplified herein.
The ratio of the monomer b in the monomer mixture is preferably 5 to 55% by mass, more preferably 5 to 50% by mass, and even more preferably 5 to 45% by mass, from the viewpoint of balance between the hydrophobicity and hydrophilicity of the copolymer. The ratio is specifically, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 mass%, and may be in a range between any 2 values exemplified herein.
The weight average molecular weight (Mw) of the copolymer A is preferably 5000 to 300000. This is because when the weight average molecular weight (Mw) is less than 5000, the coating film of the antifouling paint is fragile and peeling or cracking is likely to occur, whereas when it exceeds 300000, the viscosity of the copolymer solution increases, making handling difficult.
The Mw is specifically, for example, 5000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000, and may be within a range between any 2 values exemplified herein.
When the molecular weight distribution (Mw/Mn) of the copolymer of the present invention is 5.0 or more, the crystallinity is relaxed, and the initial solubility of the dried coating film or the adhesion is improved. From the viewpoint of remarkably exhibiting the above-described effects and production efficiency, it is preferably 5.0 to 20.0, more preferably 6.0 to 12.0.Mw/Mn is, for example, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, 14.0, 15.0, 16.0, 17.0, 18.0, 19.0, 20.0, and may be within a range between any 2 values exemplified herein.
The polymerization method for producing such a (meth) acrylic resin having a wide molecular weight distribution is not particularly limited, and a copolymer having a molecular weight distribution (Mw/Mn) of 5.0 or more cannot be obtained by a usual radical polymerization method in which a polymerization is carried out by dropping almost all of the initiator and a monomer mixture in 1 stage together, and the concentration of the initiator and the concentration of the monomer in the polymerization reaction system are not greatly different.
In the series of polymerization steps, a method of stepwise changing the concentration of the initiator or monomer by a dropping method or a single shot addition (shot addition) method, a method of stepwise changing the polymerization temperature, a method of using 2 or more kinds of appropriately selected initiators, a method of mixing 2 or more kinds of copolymers having the same composition and different molecular weights, which are produced respectively, a method of appropriately adding a chain transfer agent in a proper amount, a method of appropriately adding a polyfunctional monomer in a proper amount, or a proper combination of these methods are preferable. In one example, at the beginning of the polymerization, the polymerization is performed in a state where the concentration of the polymerization initiator is very low, whereby a component having a very high molecular weight is produced, and then the concentration of the polymerization initiator is increased to produce a low molecular weight component, whereby the molecular weight distribution can be enlarged. Further, for example, the molecular weight distribution of the polymer produced can be increased by adding a chain transfer agent after the middle stage of polymerization to reduce the molecular weight of the polymer produced. According to such a method, the molecular weight distribution can be enlarged by increasing the component having a very high molecular weight or the component having a very low molecular weight.
By performing the production method having the above-described characteristics, it is easy to synthesize a copolymer having a molecular weight distribution (Mw/Mn) of 5.0 or more. The difference between the initiator concentration and the monomer concentration may be selected to be an arbitrary amount ratio at an arbitrary stage, but in view of temperature control during the polymerization reaction, particularly from the viewpoint of heat generation control, it is preferable to make the initiator concentration low and the monomer concentration high at an initial stage of the polymerization.
Examples of the method for measuring Mw and Mn include gel permeation chromatography (GPC method). The molecular weight distribution (Mw/Mn) can be calculated using the values of Mw and Mn measured by the above-described method.
Copolymer a may be any of a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer.
The copolymer a can be obtained, for example, by polymerizing a monomer mixture composed of the monomer a and the monomer b and the monomer c in the presence of a polymerization initiator.
Examples of the polymerization initiator used in the polymerization reaction include peroxides such as 2, 2-Azobisisobutyronitrile (AIBN), 2-azobis-2-methylbutyronitrile (AMBN), and dimethyl 2, 2-azobisisobutyrate, dibenzoyl peroxide, m-toluoyl peroxide, m-methylbenzoyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, t-butyl peroctoate, t-butyl peroxy 2-ethylhexanoate, 1, 3-tetramethylbutyl peroxy-2-ethylhexanoate, 1, 3-tetramethylbutyl peroxyneodecanoate, and nyer BMT-K40 (manufactured by japan fat and oil).
Among them, AIBN, AMBN, dibenzoyl peroxide, m-toluoyl peroxide, m-methylbenzoyl peroxide, t-butyl peroctoate, and 1, 3-tetramethylbutyl peroxy-2-ethylhexanoate are particularly preferably used. The polymerization initiator may be used alone or in combination of 2 or more. The kind of the polymerization initiator used is preferably selected in consideration of the polymerization temperature. The amount of the polymerization initiator to be used may be appropriately determined depending on the kind of the monomer, the ratio thereof, and the like.
The molecular weight of the copolymer A can be adjusted by appropriately setting the amount of the polymerization initiator to be used. As described above, in the polymerization step, the concentration of the initiator in each stage or the type of the initiator may be adjusted to adjust the molecular weight distribution (Mw/Mn).
The molecular weight of the copolymer a may be adjusted by adding a suitable amount of a chain transfer agent or a polyfunctional monomer in a proper manner, and the amount of the initiator may be suppressed by using these additives. From this viewpoint, preferable chain transfer agents include, for example, an α -methylstyrene dimer (manufactured by Japanese fat & oil Co., ltd.; NOFMER MSD), 1, 4-naphthoquinone, 2-hydroxy-1, 4-naphthoquinone, QUINO POWER QS-10 (manufactured by Kawasaki chemical industry Co., ltd.), and the like.
When the sulfur atom is contained as a component of the copolymer a, the physical properties (crack resistance) are deteriorated, and therefore, the use of a thiol chain transfer agent should be avoided. Further, the odor peculiar to the mercapto group-containing or disulfide-containing compound is a problem, and is not preferable in terms of production.
Examples of the chain transfer agent of the thiol system include monofunctional thiol compounds such as n-butylthiol, n-octylthiol, t-octylthiol, n-dodecylthiol, t-dodecylthiol, tridecylthiol, tetradecylthiol, hexadecylthiol, β -mercaptopropionic acid, and 2-ethylhexyl thioglycolate, 2-functional thiol compounds such as both terminal mercapto-modified polysiloxanes (manufactured by the Xinyue chemical industry (strand; X-22-167B)), side chain multifunctional mercapto-modified polysiloxanes having side chains modified with mercapto groups (the Xinyue chemical industry (strand); KF-2001, KF-2004), and the like.
Examples of the polyfunctional monomer include 1, 2-ethylene glycol di (meth) acrylate, 1, 2-propylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethylene oxide addition bisphenol a di (meth) acrylate, ethylene oxide addition bisphenol F di (meth) acrylate, propylene oxide addition bisphenol a di (meth) acrylate, propylene oxide addition bisphenol F di (meth) acrylate, and the like.
Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and non-aqueous dispersion polymerization. Among them, solution polymerization or non-aqueous dispersion polymerization is particularly preferable in that the copolymer a can be obtained simply and accurately.
In the polymerization reaction, an organic solvent may be used as needed. Examples of the organic solvent include aromatic hydrocarbon solvents such as xylene and toluene
The method comprises the steps of carrying out a first treatment on the surface of the Aliphatic hydrocarbon solvents such as hexane, heptane, octane, and mineral spirits; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate and methoxypropyl acetate
The method comprises the steps of carrying out a first treatment on the surface of the Alcohol solvents such as isopropyl alcohol, butanol, propylene glycol monomethyl ether, and the like; ether solvents such as dioxane, diethyl ether and dibutyl ether
The method comprises the steps of carrying out a first treatment on the surface of the Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.
Among them, aliphatic hydrocarbon solvents, ester solvents, alcohol solvents, and aromatic hydrocarbon solvents are particularly preferable, and mineral spirits, butyl acetate, isobutyl acetate, butanol, propylene glycol monomethyl ether, toluene, and xylene are more preferable. These solvents may be used alone or in combination of 2 or more.
The reaction temperature in the polymerization reaction may be appropriately set depending on the kind of the polymerization initiator, and is usually 60 to 150℃and preferably 70 to 140 ℃.
The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon.
1-2 antifouling agent
Examples of the stain-proofing agent include inorganic agents and organic agents.
Examples of the inorganic reagent include cuprous oxide, copper thiocyanate (general name: rhodamine copper), and copper powder. Among them, cuprous oxide and rhodamine copper are particularly preferable, and from the viewpoint of long-term stability during storage, surface treatment of cuprous oxide with glycerin, sucrose, stearic acid, lauric acid, lecithin, mineral oil, or the like is more preferable.
Examples of the organic reagent include 2-mercaptopyridine-N-copper oxide (common name: copper pyrithione), 2-mercaptopyridine-N-zinc oxide (common name: zinc pyrithione), zinc ethylenebisdithiocarbamate (common name: zineb), 4, 5-dichloro-2-N-octyl-3-isothiazolone (common name: SEA-NINE 211), 3, 4-dichlorophenyl-N-dimethylurea (common name: diuron), 2-methylsulfanyl-4-t-butylamino-6-cyclopropylamino-s-triazine (common name: irgarol 1051), 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (common name: ECONEA 28), and 4- [1- (2, 3-dimethylphenyl) ethyl ] -1H-imidazole (common name: medetomidine). These antifouling agents may be used in combination of 1 or 2 or more.
The content of the stain-proofing agent in the composition of the present invention is not particularly limited, but is usually 0.1 to 60.0% by mass in terms of solid content. The content of the antifouling agent is, for example, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 mass%, and may be in a range between any 2 values exemplified herein.
1-3 other additives
The resin for an antifouling paint of the present invention may be used as an antifouling paint by adding components other than the copolymer a and the antifouling agent, for example, a dissolution regulator, a plasticizer, a pigment, a dye, an antifoaming agent, a dehydrating agent, a thixotropic agent, an organic solvent, and the like, as required.
Examples of the elution control agent include monocarboxylic acids and salts thereof, and alicyclic hydrocarbon resins such as rosin, rosin derivatives, naphthenic acids, cycloalkenyl carboxylic acids, bicycloalkenyl carboxylic acids, versatic acids, trimethylisobutenyl cyclohexene carboxylic acids, and metal salts thereof. These may be used alone or in combination of 2 or more.
Among them, rosin derivatives, naphthenic acid, tertiary carbonic acid, trimethylisobutenyl cyclohexene carboxylic acid or metal salts of these are preferable.
Examples of the rosin derivatives include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin.
Examples of the plasticizer include paraffin plasticizers such as liquid paraffin and chlorinated paraffin, vegetable oil plasticizers such as linseed oil, epoxidized linseed oil, soybean oil and epoxidized soybean oil, alicyclic ester plasticizers such as di-n-octyl phthalate, di-2-ethylhexyl phthalate, isononyl phthalate, diisodecyl phthalate, diisononyl 2, 5-furandicarboxylate, di-2-ethylhexyl isophthalate, aromatic diester plasticizers such as di-2-ethylhexyl terephthalate, aromatic triester plasticizers such as tributyl trimellitate, tri-2-ethylhexyl trimellitate, aromatic tetraester plasticizers such as tetra-2-ethylhexyl trimesic acid, alicyclic ester plasticizers such as di-2-ethylhexyl 4-cyclohexene-1, 2-dicarboxylate, diisononyl 1, 2-cyclohexanedicarboxylate, alicyclic ester plasticizers such as diisononyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate, di-2-butoxyethyl adipate, diisononyl adipate, fatty acid esters such as di-2-ethylhexyl azelate, tributyl citrate, tri-2-ethylhexyl citrate, tri-acetyl-2-hydroxyethyl benzoate, diethyl-butyrate, diethyl-glycol, diethyl-butyrate, diethyl-glycerin-diethyl-butyrate, and the like,
Phosphate plasticizers such as trimethyl phosphate and tricresyl phosphate,
Polyvinyl alkyl ether plasticizers such as Lutolal M40 and Lutolal A25, polyester plasticizers,
Camphor, terpene phenols, tertiary nonyl pentasulfide, and the like. These may be used singly or in combination of 2 or more.
Among them, paraffin, vegetable oil, aliphatic ester, and aromatic ester are preferable from the viewpoint of easy chiral access, and among them, chlorinated paraffin, liquid paraffin, epoxidized soybean oil, acetyltriethyl citrate, acetyltributyl citrate, acetyltri-2-ethylhexyl citrate, diisononyl phthalate, diisodecyl phthalate, diisononyl 1, 2-cyclohexanedicarboxylate, di-2-ethylhexyl terephthalate, and tri-2-ethylhexyl trimellitate are more preferable from the viewpoint of cost, and chlorinated paraffin and liquid paraffin are preferable.
The content of the plasticizer in the composition of the present invention is not particularly limited, but is usually 0.01 to 30% by mass in terms of solid content, and from the viewpoints of paint viscosity and coating film hardness, it is preferably 0.05 to 25% by mass, more preferably 0.1 to 20% by mass.
Examples of the copolymer or resin component other than the copolymer a include (meth) acrylic resins, polyester resins, vinyl resins, petroleum resins, metal-containing resins, dipole-ion-containing compound resins, silicone resins, alicyclic hydrocarbon resins, and the like, other than the copolymer a.
Examples of the alicyclic hydrocarbon resin include Quinton1500, 1525L, 1700 (trade name, manufactured by Nippon Zeon corporation) and the like.
Examples of the dehydration agent include synthetic zeolite adsorbents, silicates such as orthoesters, tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides and carbodiimidazoles. These may be used alone or in combination of 2 or more.
2. Method for producing antifouling paint composition
The antifouling paint composition of the present invention can be produced, for example, by mixing and dispersing a mixed solution containing the copolymer a and other additives and the like by a dispersing machine.
As the above-mentioned mixed solution, a mixed solution in which various materials such as a copolymer and an antifouling agent are dissolved or dispersed in a solvent is preferable.
As the dispersing machine, for example, a dispersing machine usable as a fine pulverizer is preferably used. For example, a commercially available homogenizer, a sand mill, a bead mill, or the like can be used. The mixed solution may be mixed and dispersed by a device in which glass beads for mixing and dispersing are added to a container provided with a stirrer.
3. Method for antifouling treatment, antifouling coating film, and coated article
The method for treating an antifouling coating according to the present invention is a method for forming an antifouling coating film on the surface of a coated film-formed article by using the above-mentioned antifouling coating composition. According to the method of the present invention, the antifouling coating film gradually dissolves from the surface and the surface of the coating film is always updated, whereby adhesion of aquatic fouling organisms can be prevented.
Examples of the coating film-forming material include ships (particularly, bottoms of ships), fishing gear, underwater structures, and the like.
The thickness of the antifouling coating film may be appropriately set according to the type of the coating film-formed article, the sailing speed of the ship, the sea water temperature, and the like. For example, when the object to be coated is the bottom of a ship, the thickness of the antifouling coating film is usually 50 to 700. Mu.m, preferably 100 to 600. Mu.m.
Examples
The features of the present invention will be further clarified by examples and the like shown below. However, the present invention is not limited to the examples and the like.
The% in each of the production examples, examples and comparative examples represents mass%. The viscosity is a measured value at 25℃and is determined by an E-type viscometer. The weight average molecular weight (Mw) is a value (polystyrene equivalent) obtained by GPC. The conditions for GPC are as follows.
HLC-8320GPC manufactured by Tosoh Co., ltd
guardcolumn···TSKgel SuperHZ-L
Column TSKgel SuperHZM-M2 roots
Flow rate 0.35mL/min
Detector RI
Column constant temperature bath temperature 40 DEG C
Eluent. THF
Calibration curve is drawn using standard substances Pick top (Mp) 1044000, 728000, 364000, 206000, 107100, 46380, 27060, 12980, 6660, 2790, 1300, 1140, 162 manufactured by Agilent technologies Co., ltd
Calibration curve Cheng Huizhi was used to 3 th power based on the Mp value and elution time of the standard substance.
Analytical software EcoSEC Version 2.02, ecoSEC DaTa Analysis Version1.14
Analysis conditions in the obtained RI chromatogram, a flat and stable portion in the base line immediately before and immediately after elution of the polymer was connected by a straight line, and the polymer was detected and analyzed. However, when it is measured that peaks of monomers or impurities derived from monomers (oligomers and the like) remaining in the production process overlap with polymer peak portions, the polymer portions and the monomer portions are separated from the impurity portions by vertically dividing the polymer portions into the most concave portions in the overlapping portions with the polymers, and only the molecular weight (Mw and Mn) and the molecular weight distribution (Mw/Mn) of the polymer portions are calculated.
The heating residual component was according to JIS K5601-1-2: 1999 (ISO 3251:1993) "coating composition test method-heating residual composition" measured value.
1. Preparation example of copolymer solution
Copolymer solutions A-1 to A-8 containing copolymer A and copolymer solutions B-1 to B-6 containing copolymers other than copolymer A were obtained according to the methods shown in production examples 1 to 8 and comparative production examples 1 to 6. The heating residual components, weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), and viscosity of each of the obtained copolymer solutions were measured and are shown in tables 1 to 3.
[ Table 1 ]
[ Table 2 ]
[ Table 3 ]
Production example 1 (production of copolymer solution A-1) >
A flask equipped with a thermometer, reflux condenser, stirrer and dropping funnel was prepared. The raw materials were charged and all polymerization reactions were carried out under a nitrogen atmosphere.
300g of xylene was charged into the flask, and 100g was charged into the dropping funnel. A monomer mixture was prepared by mixing 300g of triisopropylsilyl methacrylate, 105g of 2-methoxyethyl acrylate, 10g of 2-ethoxyethyl acrylate, 25g of 2-methoxyethyl methacrylate, 55g of methyl methacrylate and 5g of 2-ethylhexyl acrylate in a separate vessel. Half of the monomer mixture was charged into the flask, and the other half was charged into the dropping funnel [ the ratio of the distribution of the monomer mixture (initial charge of flask amount/total amount) =0.5 ].
Next, 0.3g of 2,2' -Azobisisobutyronitrile (AIBN) as a polymerization initiator was charged into the flask, 50g of 1, 3-tetramethylbutyl peroxy-2-ethylhexanoate (manufactured by Japanese fat and oil (stock); PEROCTA O) was charged into the dropping funnel, and the solutions in the flask and the dropping funnel were each thoroughly mixed (the concentration of the polymerization initiator in the mixed solution in the flask was lower than the concentration of the polymerization initiator in the mixed solution in the dropping funnel).
The mixture in the flask was heated to 85.+ -. 5 ℃ and stirred for 1 hour (polymerization reaction in stage 1). The viscosity of the solution in the flask after heating and stirring for 1 hour was increased compared with the initial state immediately after the temperature reached 85 ℃.
Then, the mixture in the flask was kept at 85.+ -. 5 ℃ and the mixture in the dropping funnel was dropped thereto over 1 hour, followed by stirring (polymerization reaction in stage 2) at the same temperature for 1 hour.
As a final step of the polymerization reaction, 1g of 1, 3-tetramethylbutyl peroxy-2-ethylhexanoate (manufactured by Japanese fat and oil (stock); PEROCTA O) was added 3 times every 1 hour to polymerize a minute amount of the remaining monomer, thereby completing the polymerization reaction.
After stopping the heating apparatus and leaving to cool to room temperature, 100g of xylene was added and mixed to obtain a copolymer solution A-1.
Production examples 2 to 7 (production of copolymer solutions A-2 to A-7) >, respectively
Under the conditions of the distribution ratio of the monomer mixture and the reaction temperature shown in tables 1 to 2, the same amounts of the monomers, the polymerization initiator, the chain transfer agent, the organic solvent and the like as described in the same tables were used, and polymerization was carried out in the same manner as in production example 1 to obtain copolymer solutions A-2 to A-7. The chain transfer agent in the amounts shown in the table was mixed with the respective monomers and used as a part of the monomer mixture. The heating residual components, weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), and viscosity of each of the obtained copolymer solutions were measured and are described in the same table.
Production example 8 (production of copolymer solution A-8) >
A flask equipped with a thermometer, reflux condenser, stirrer and dropping funnel was prepared. The raw materials were charged and all polymerization reactions were carried out under a nitrogen atmosphere.
All of the monomer mixture composed of the monomers described in production example 8 of table 2 was charged into the flask [ the ratio of the distribution of the monomer mixture (initial charge flask amount/total amount) =1.0 ].
Then, 300g of xylene was charged into the flask. 5g of 1, 3-tetramethylbutylperoxy-2-ethylhexanoate (manufactured by Japanese fat and oil (Kogaku) Co.; PEROCTA O) and 100g of xylene were charged into the dropping funnel, and the mixture was thoroughly mixed (105 g of the total was charged into the dropping funnel).
The temperature of the mixture in the flask was slowly raised to stabilize the temperature at 85.+ -. 5 ℃. The mixed solution in the dropping funnel was added to the solution in the flask stirred at 85±5 ℃ in order of 5g, 10g, 55g and 35g for each hour, and polymerization was carried out (the step of stirring for 1 hour after adding a proper amount of the mixed solution in the dropping funnel at one time, including stirring for 1 hour after the last 35g addition, was repeated, and a total of 4 hours was required).
Since heat generation occurs immediately after the single shot addition, the setting of the cooling device for the heater Wen is operated at a timing and is always maintained at 85±5 ℃. After the completion of the single shot addition step of the mixed solution in all the dropping funnels, 1g of 1, 3-tetramethylbutyl peroxy-2-ethylhexanoate (manufactured by Japanese fat and oil (stock); PEROCTA O) was added 3 times per 1 hour as a final step of the polymerization reaction in order to polymerize a minute amount of the residual monomer.
After the heating apparatus was stopped and left to cool to room temperature, 100g of xylene was added and mixed to obtain copolymer solution A-8.
Comparative production example 1 (production of copolymer solution B-1) >)
A flask equipped with a thermometer, reflux condenser, stirrer and dropping funnel was prepared. The raw materials were charged and all polymerization reactions were carried out under a nitrogen atmosphere.
380g of xylene was charged into the flask and the temperature was raised to 85.+ -. 5 ℃. 300g of triisopropylsilyl methacrylate, 105g of 2-methoxyethyl acrylate, 10g of 2-ethoxyethyl acrylate, 25g of 2-methoxyethyl methacrylate, 55g of methyl methacrylate, 5g of 2-ethylhexyl acrylate, 8g of 1, 3-tetramethylbutyl peroxy-2-ethylhexanoate (manufactured by Japanese fat and oil (stock); PEROCTA O) as a polymerization initiator, and 30g of xylene were charged into a dropping funnel and mixed.
Then, xylene was dropped into the flask under heating and mixing (a monomer mixture having a constant concentration of a polymerization initiator was dropped at a constant rate and polymerization was performed) at 85.+ -. 5 ℃ over 2 hours. Then, the mixture was heated and stirred at the same temperature for 1 hour.
As a final step of the polymerization reaction, 1g of 1, 3-tetramethylbutyl peroxy-2-ethylhexanoate (manufactured by Japanese fat and oil (stock); PEROCTA O) was added 3 times every 1 hour to polymerize a minute amount of the remaining monomer, thereby completing the polymerization reaction. Then, 90g of xylene was added thereto and mixed to obtain a copolymer solution B-1.
Comparative production example 2 (production of copolymer solution B-2) >)
Polymerization was carried out in the same manner as in comparative production example 1 using the amounts of the monomer, the polymerization initiator, the organic solvent, and the like described in the same table under the conditions of the reaction temperature, etc., as shown in Table 2, to obtain a copolymer solution B-2.
Comparative production examples 3 to 6 (production of copolymer solutions B-3 to B6 >)
Under the conditions of the distribution ratio of the monomer mixture and the reaction temperature shown in Table 3, the same amounts of the monomers, the polymerization initiator, the chain transfer agent, the organic solvent and the like as described in the same table were used, and polymerization was carried out in the same manner as in production example 1 to obtain copolymer solutions B-3 to B-6. The amounts of the chain transfer agents described in table 3 were mixed together with the respective monomers as part of the monomer mixture.
2. Other production examples
Production example 9 (production of rosin Zinc salt solution) >)
240g of a resin rosin (WW) produced in China and 360g of xylene were placed in a flask equipped with a thermometer, a reflux condenser and a stirrer, and 120g of zinc oxide was added to form zinc salts from all resin acids in the rosin, and the mixture was dehydrated under reduced pressure at 70 to 80℃for 3 hours. Subsequently, a xylene solution (brown transparent liquid, solid content 50%) of the rosin zinc salt was obtained by cooling and filtering. The heating residual component of the obtained solution was 50.4%.
Production example 10 (production of trimethylisobutenyl cyclohexene carboxylic acid solution) >
320g of alloocimene, 175g of methacrylic acid and 0.17g of MEHQ0.17g were placed in a flask equipped with a thermometer, a reflux condenser and a stirrer, and the flask was heated and stirred at 35 to 45℃for 24 hours. Then, the unreacted raw material was distilled off under reduced pressure to obtain 73g of trimethylisobutenyl cyclohexene carboxylic acid having brown consistency. To this was added xylene as a solution of trimethylisobutenyl cyclohexene carboxylic acid (solid content 50%).
3. Examples 1 to 15 and comparative examples 1 to 6 (production of coating compositions)
The components shown in tables 4 to 6 were mixed with the ratios (mass%) shown in these tables, and mixed and dispersed with glass beads having diameters of 1.5 to 2.5mm, to prepare coating compositions.
[ Table 4 ]
[ Table 5 ]
[ Table 6 ]
The specific components in the table are as follows.
Plasticizer >
Chlorinated paraffin: trade name "Paraffin Chlorinated (Cl: 40%)" (manufactured by Wako pure chemical industries, ltd.)
Liquid paraffin: trade name "Cosomosp-32Cosmo White P200" (manufactured by Cosmo Petroleum LUBRICANTS)
E-2000H: epoxidized soybean oil, trade name "Sansosizer E-2000H" (manufactured by New Japanese physicochemical (Strand))
Lutona a25: trade name "Lutonal" (registered trademark) a25 "(manufactured by BASF corporation)
JP120: ethylene glycol benzoate, trade name "JP 120" ((stock) J.PLUS manufacture)
DINP: diisononyl phthalate: trade name "diisononyl phthalate" (manufactured by Wako pure chemical industries, ltd.)
DINCH: diisononyl 1, 2-cyclohexanedicarboxylate: trade name "HEXAMOL" (registered trademark) DINCH (registered trademark) (manufactured by BASF corporation)
DEHT: di-2-ethylhexyl terephthalate: trade name "Bis (2-ethylxyl) terephthalate" (manufactured by SIGMA-ALDRICH Co., ltd.)
TOTM: tri-2-ethylhexyl trimellitate: trade name "Tris (2-ethylhexyl) Trimellitate" (manufactured by tokyo chemical Co., ltd.)
ATBC: acetyl tributyl citrate: trade name "tributyll O-Acetylcitate" (manufactured by Tokyo chemical Co., ltd.)
< antifouling Agents >
Cuprous oxide: trade name "NC-301" (manufactured by Nissan chemco (Co.))
Rhodamine copper: trade name "copper (I) thiocyanate" (manufactured by SIGMA-ALDRICH)
Copper pyrithione: trade name "Copper Omadine" (manufactured by Arch Chemicals (Inc.))
Zinc pyrithione: trade name "Zinc Omadine" (manufactured by Arch Chemicals)
Zineb: trade name "Zineb" (manufactured by SIGMA-ALDRICH Co., ltd.)
SeaNine: trade name "Sea Nine211"4, 5-dichloro-2-n-octyl-3- (2H) isothiazolone (30% solid xylene solution, manufactured by Robin Hasi Co., ltd.)
Econea: trade name "Econea 028"2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP)
mecytomidine: trade name "4- (1- (2, 3-Dimethylphenyl) ethyl) -1H-imidozole (manufactured by Wako pure chemical industries, ltd.)
< dissolution regulator >)
Rosin zinc salt solution: the solution produced in production example 9 was used
Hydrogenated rosin solution: a50% solid xylene solution under the trade name "HYPALE CH" (manufactured by Sichuan chemical Co., ltd.)
Rosin solution: solid content 50% xylene solution of Chinese gum rosin (WW)
High rosin: trade name "harrtall R-WW" (manufactured by Harima chemical industry (strand))
NT-RMZ: use is made of a zinc salt solution of hydrogenated rosin: the trade name "NT-RMZ" (manufactured by Nikko Chemie Co., ltd.). The solid content was 65%.
Cyclohexene carboxylic acid solution: trimethyl isobutenyl cyclohexene carboxylic acid solution (prepared in preparation example 10)
< other additives, solvents >
Iron oxide red: trade name "TODA COLOR EP-13D" (manufactured by Mintian Pigment (R) stock)
Talc: trade name "CROWNTALC 3S" (manufactured by Songcun industry (stock))
Zinc oxide: trade name "Zinc oxide 2" (manufactured by ordinary chemical industry (Strand))
Titanium oxide: trade name "FR-41" (manufactured by Guhe mechanical metals (strands))
Tetraethoxysilane: trade name "Tetraethyl Orthosilicate" (manufactured by tokyo chemical industry (stock))
Anhydrous gypsum: trade name "D-1" (manufactured by Noritake co., ltd. (stock))
Aliphatic amide thixotropic agents: trade name "DISPARONA 603-20X" (manufactured by Nanye chemical Co., ltd.)
Modified alcohol: trade name "CLEAN ACE High" (manufactured by Jinjin pharmaceutical industry (Stra))
4. Evaluation
Test panels (second test panels) each having a dried coating film were prepared from the coating compositions of examples and comparative examples, and test examples 1 to 3 were carried out by the following procedure. The results are shown in tables 4 to 6.
< preparation of second test plate >
First, a rust-preventive coating material (epoxy vinyl-based A/C) was applied to a titanium plate (71X 100mm, thickness: 0.5 mm) so that the thickness after drying was about 100. Mu.m, and dried to form a rust-preventive coating film. Next, the coating compositions obtained in examples and comparative examples were applied to the above-mentioned coating films, respectively, so that the thickness after drying was about 400 μm. The test plate was dried at 40℃for 3 days to obtain a test plate (hereinafter, referred to as a first test plate) having a dried coating film composed of the coating compositions obtained in examples and comparative examples.
The first test plate was fixed to a rotary drum described later so as to be in contact with seawater, and the rotary drum was rotated at a speed of 20 knots. The sea water temperature is kept at 25 ℃ and the pH is kept at 8.0-8.2, and the sea water is replaced every week.
During 24 months, the first test plate, which was mounted on a rotary drum and rotated in a state of being in contact with seawater, was removed, and after the seawater adhering to the surface of the coating film was gently washed off with pure water, it was dried at 40℃for 3 days. A coating material having the same composition as the coating material composition used in the preparation of the first test plate was applied to the surface of the coating film remaining on the test plate so that the thickness after drying was about 300. Mu.m.
The test plate was dried at 40℃for 3 days to obtain a test plate (second test plate) having a new dried coating film.
< related to Rotary Drum device >)
The rotary drum is a device in which a drum rotated by a motor is installed at the center of a water tank (diameter 515mm, height 440 mm), and a cooling device for maintaining the temperature of seawater constant and a pH automatic controller for maintaining the pH of seawater constant are installed. The rotating drum is provided with a test plate, and the coating film coated on the test plate is contacted with seawater and rotates at a certain speed, so that the device can simulate the behavior of the coating film coated on the bottom of the ship when the ship sails at sea.
Test example 1 (measurement of dissolved amount of coating film after recoating) >
The second test plate having a coating film composed of the coating composition described in each example and comparative example was fixed to a rotating drum apparatus after measuring the film thickness by a laser focus displacement meter, and the rotating drum was rotated at a speed of 20 knots. The sea water temperature is kept at 25 ℃ and the pH is kept at 8.0-8.2, and the sea water is replaced every week.
The rotating drum was removed from the test plate every 6 months after the start of the test, and the residual film thickness was measured each time by a laser focus displacement meter.
The coating compositions described in examples and comparative examples were subjected to calculation of the dissolved coating thickness from the difference between the initial coating film thickness and the film thickness of each 6 months after the start of the test in each of the above-described tests, to obtain the average dissolved amount (. Mu.m/month) of each period.
The stability of dissolution behavior was evaluated by classifying according to the following criteria.
A: an average dissolution amount (μm/month) per 1 month of 5 or more and less than 15
B: an average dissolution amount (μm/month) per 1 month of 2 or more and less than 5
C: the average dissolution amount (μm/month) per 1 month is 15 or more
X: an average dissolution amount (μm/month) per 1 month of less than 2
-: all the coating films dissolved, or peeled off, within 6 months.
Test example 2 (test for confirming physical properties of coating film)
Test example 1 the test panels after 24 months dissolution test were dried, and the surfaces of the respective coating films were visually observed to evaluate the state of the coating films. The evaluation was performed by the following method.
And (3) the following materials: completely free of abnormality
O: capillary cracks were observed at less than 10% of the total surface area of the coating film
Delta: capillary cracks were observed at 10% to 30% of the total surface area of the coating film
X: capillary cracks were observed at 30% or more of the total surface area of the coating film
X×: film abnormality such as large cracks, bubbles, peeling (peeling of only a part of the film surface or edge), peeling (peeling of the entire film, state of no test film remaining) and the like were observed
Test example 3 (adhesion)
The test plate after 24-month dissolution test in test example 1 was dried, and the adhesion of the coating film was measured by a cross-cut test according to JISK 5600-5-6. The dicing blade was used to cut out 3 mm-spaced 6×6 cut-in openings in the member, and after the tape was peeled off from the member, the remaining dicing portions were visually observed and evaluated by the following criteria. The peeling of the individual layers was not classified according to the peeling criteria, and the state of the coating film attached to the adhesive tape and peeled from the test sheet was evaluated according to the following criteria for the peeling of all the primer anticorrosive layers, the peeling of the old anti-contamination coating film, and the partial peeling of the repeated coating film.
And (3) the following materials: any mesh was not peeled off.
And (2) the following steps: there was slight film peeling at the intersection of the cuts, but the peeling was clearly not more than 5% in the area of the test portion.
Delta: the coating film is peeled off at the intersections along the lines of the cuts. The peeling was 5% or more and less than 35% in the test part area.
X: the coating film is peeled off partially or entirely along the edges of the slit. The peeling was 35% or more in the test part area.
-: at the stage of the cross-cut test, peeling occurred at 35% or more of the test part area.
< test JI fruit >
Test examples 1 to 3 were simulation tests for evaluating the performance of a coating film obtained by further coating an old coating film whose surface was polished in seawater for 24 months with a coating material of the same composition, and evaluating various performances of the obtained dry coating film, and for a ship bottom antifouling coating material of an actual ship, the coating film was repeatedly coated with a ship bottom antifouling coating film at the time of repair.
In test example 1, the antifouling paint composition described in this example was found to have good and stable long-term coating film solubility (examples in tables 4 and 6) without change in dissolution behavior or the like within 24 months after repeated application.
In test example 2, the antifouling paint composition described in this example was free from occurrence of coating abnormality such as cracking or blisters within 24 months after repeated coating, and high coating physical properties were confirmed (examples in tables 4 and 6).
Further, test example 3 shows that the antifouling paint composition according to the present example was polished in seawater for a certain period of time, and after the surface properties were changed, the paint-coated article of the same composition was repeatedly applied, and the adhesion was high (table 4 and table 6).
From these results, it can be seen that the high coating film properties (coating film solubility, coating film physical properties, adhesion) after repeated coating of the old coating film, which are characteristic of the present invention, are achieved by including the copolymer a having a specific composition and a specific molecular weight distribution (Mw/Mn) (examples of table 4, and comparative examples of table 5).
Further, in the scope of the present invention, when the copolymer a is contained appropriately, the effects of the present invention can be exhibited even if the compounding amount or kind of the antifouling agent, the pigment component, the elution regulator component and the like are changed (see table 6).

Claims (2)

1. A copolymer for an antifouling paint composition, which is obtained by copolymerizing a monomer mixture comprising a monomer a, a monomer b and a monomer c, characterized in that,
the monomer a is represented by the general formula (1),
the monomer b is represented by the general formula (2),
the monomer c is a monomer other than the monomer a and the monomer b, which is copolymerizable with the monomer a and the monomer b,
The ratio of the monomer a in the monomer mixture is 25 to 60 mass%,
the copolymer has a molecular weight distribution (Mw/Mn) of 5.0 or more,
the above-mentioned copolymers do not contain a sulfur atom,
[ chemical formula 1 ]
Wherein R is 1 Is hydrogen or methyl, R 2 ～R 4 Respectively the same or different and represents a branched alkyl group or phenyl group having 3 to 8 carbon atoms,
[ chemical formula 2 ]
Wherein R is 5 Is hydrogen or methyl, R 6 Is a hydrocarbon group having 2 to 9 carbon atoms and having an oxygen atom.
2. An antifouling paint composition comprising a copolymer for an antifouling paint composition and an antifouling agent, characterized in that,
the copolymer for an antifouling paint composition according to claim 1.
CN202180075626.7A 2020-11-10 2021-11-04 Copolymer for antifouling paint composition and antifouling paint composition Pending CN116601243A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2020-187164 2020-11-10
JP2020187164 2020-11-10
PCT/JP2021/040527 WO2022102493A1 (en) 2020-11-10 2021-11-04 Copolymer for antifouling coating compositions, and antifouling coating composition

Publications (1)

Publication Number Publication Date
CN116601243A true CN116601243A (en) 2023-08-15

Family

ID=81601262

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202180075626.7A Pending CN116601243A (en) 2020-11-10 2021-11-04 Copolymer for antifouling paint composition and antifouling paint composition

Country Status (4)

Country Link
JP (1) JPWO2022102493A1 (en)
KR (1) KR20230098837A (en)
CN (1) CN116601243A (en)
WO (1) WO2022102493A1 (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109906254A (en) * 2016-11-09 2019-06-18 中国涂料株式会社 Antifouling paint compositions, antifouling coat, the substrate with antifouling coat and its manufacturing method and anti-fouling method

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3693501B2 (en) 1998-07-06 2005-09-07 日東化成株式会社 Antifouling paint composition
KR102340452B1 (en) * 2017-06-01 2021-12-16 주고꾸 도료 가부시키가이샤 Laminated antifouling coating film, substrate with laminated antifouling coating film and manufacturing method thereof, coating kit for forming laminated antifouling coating film, upper layer antifouling coating composition, and antifouling method
KR102656962B1 (en) * 2018-07-27 2024-04-11 주고꾸 도료 가부시키가이샤 Antifouling paint composition, antifouling film, antifouling film attachment base material, manufacturing method thereof, and repair method
GB201813454D0 (en) * 2018-08-17 2018-10-03 Jotun As Antifouling composition
JP7323980B2 (en) * 2019-03-20 2023-08-09 関西ペイント株式会社 antifouling paint composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109906254A (en) * 2016-11-09 2019-06-18 中国涂料株式会社 Antifouling paint compositions, antifouling coat, the substrate with antifouling coat and its manufacturing method and anti-fouling method

Also Published As

Publication number Publication date
WO2022102493A1 (en) 2022-05-19
KR20230098837A (en) 2023-07-04
JPWO2022102493A1 (en) 2022-05-19

Similar Documents

Publication Publication Date Title
EP2990450B1 (en) Antifouling paint composition, copolymer for antifouling paint composition and method for manufacturing same, and painted object having on surface antifouling paint film formed using said composition
EP2975095B1 (en) Antifouling coating composition, antifouling coating film formed using said composition, and coated article having antifouling coating film on surface
CN116490575A (en) Antifouling coating composition
CN111886304B (en) Antifouling coating composition
CN116601243A (en) Copolymer for antifouling paint composition and antifouling paint composition
CN111868184B (en) Copolymer for antifouling paint composition and antifouling paint composition comprising the same
EP3783073B1 (en) Antifouling coating composition
JP2022107656A (en) Bilayer anti-fouling coating film, coated object having on surface the coating film
CN116981742A (en) Antifouling coating composition
EP3783074B1 (en) Copolymer for antifouling coating composition and antifouling coating composition containing said copolymer
CN111902497A (en) Antifouling coating composition
EP3693421A1 (en) Antifouling paint composition and coated article having antifouling coating formed using said composition on surface
JP7287648B2 (en) antifouling paint composition
JP6624666B1 (en) Antifouling paint composition
CN111836863A (en) Antifouling coating composition
CN117015579A (en) Antifouling coating composition
JP7351504B2 (en) Antifouling paint composition
WO2023145634A1 (en) Antifouling coating material composition
WO2020189414A1 (en) Antifouling coating composition
CN117255833A (en) Antifouling coating composition
CN117062880A (en) Antifouling coating composition
CN117120560A (en) Antifouling coating composition
CN117062881A (en) Antifouling coating composition
CN117015578A (en) Antifouling coating composition
JP2021105069A (en) Antifouling coating composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination