CN112135884A - Antifouling coating composition - Google Patents
Antifouling coating composition Download PDFInfo
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- CN112135884A CN112135884A CN201980032999.9A CN201980032999A CN112135884A CN 112135884 A CN112135884 A CN 112135884A CN 201980032999 A CN201980032999 A CN 201980032999A CN 112135884 A CN112135884 A CN 112135884A
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- acrylate
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- antifouling
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- 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
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- 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
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- 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
- C09D7/20—Diluents or solvents
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- 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 coating composition which can form a coating film having improved cracking resistance, adhesion, and flexibility. According to the present invention, there is provided an antifouling paint composition comprising a polymer a, a component B, and an antifouling agent, wherein the polymer a is a copolymer of a monomer (a) and an ethylenically unsaturated monomer (B) other than the monomer (a), the monomer (a) is represented by general formula (1), and the component B is a paraffin mineral oil containing an aromatic hydrocarbon.
Description
[ technical field ] A method for producing a semiconductor device
The present invention relates to antifouling coating compositions.
[ background of the invention ]
Aquatic fouling organisms such as barnacles, serpula, common mussels, sea grass bugs, sea squirts, enteromorpha, sea lettuce, and sludge are attached to aquatic structures such as ships (particularly ship bottom parts), fishing nets, fishing net accessories, and power generation conduits, thereby causing problems such as functional damage and appearance damage of the ships.
To prevent such problems, a technique of exerting antifouling performance for a long time has been disclosed: an antifouling coating film formed by applying an antifouling coating composition to a ship or the like gradually releases an antifouling agent from the antifouling coating film (patent document 1).
[ Prior art documents ]
[ patent document ]
[ patent document 1 ] Japanese patent laid-open No. 2000-17203
[ summary of the invention ]
[ problem to be solved by the invention ]
The effect of the above antifouling paint depends mainly on the thickness of the coating film. Since water pressure is often applied to the bow, stern, draft, and the like during the travel of the ship, the coating film may be thick. Thereby easily causing cracking, breaking or peeling of the coating film.
The present invention has been made in view of such circumstances, and provides an antifouling coating composition capable of forming a coating film having improved cracking resistance, adhesion, and flexibility.
[ MEANS FOR SOLVING PROBLEMS ] to solve the problems
According to the present invention, there is provided an antifouling paint composition comprising a polymer a, a component B, and an antifouling agent, wherein the polymer a is a copolymer of a monomer (a) and an ethylenically unsaturated monomer (B) other than the monomer (a), the monomer (a) is represented by general formula (1), and the component B is a paraffin mineral oil containing an aromatic hydrocarbon.
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that a composition comprising a polymer a, a component B, and an antifouling agent can solve the above problems, and have completed the present invention.
[ detailed description ] embodiments
The present invention will be specifically described below.
1. Antifouling coating composition
The antifouling paint composition of the present invention comprises a polymer A, a component B, and an antifouling agent.
1-1. Polymer A
The polymer A is a copolymer of a monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a). Polymer a comprises monomer units derived from monomers (a) and (b).
< monomer (a) >
The monomer (a) is a triorganosilyl (meth) acrylate monomer represented by the general formula (1).
[ CHEM 1 ]
(in the formula, R1Represents hydrogen or methyl, R2～R4Are the same or different and each represents a branched alkyl group having 3 to 8 carbon atoms or a phenyl group)
As R2～R4Examples of the branched alkyl group having 3 to 8 carbon atoms include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1-methylpentyl group, 1-dimethylpropyl group, 1-dimethylbutyl group, tert-hexyl group, cyclohexyl group, 1-dimethylpentyl group, 1-methylhexyl group, 1-dimethylhexyl group, 1-methylheptyl group, 2-methylbutyl group, 2-ethylbutyl group, 2-dimethylpropyl group, cyclohexylmethyl group, 2-ethylhexyl group, 2-propylpentyl group, and 3-methylpentyl group. As R2～R4Preferably isopropyl, sec-butyl, tert-butylButyl, phenyl, and 2-ethylhexyl. Isopropyl and 2-ethylhexyl are particularly preferred.
Examples of the monomer (a) include triisopropylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tri-sec-butylsilyl (meth) acrylate, triisopentylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, diisopropylphenylsilyl (meth) acrylate, diisopropylisobutylsilyl (meth) acrylate, diisopropyl sec-butylsilyl (meth) acrylate, diisopropyl isopentylsilyl (meth) acrylate, isopropyl diisobutylsilyl (meth) acrylate, isopropyl di-sec-butylsilyl (meth) acrylate, tert-butyldiisobutylsilyl (meth) acrylate, tert-butyldiisopentylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, triisobutyldiisopentylsilyl (meth) acrylate, triisobutylsilyl (, T-butyldiphenylsilyl (meth) acrylate, diisopropylt-hexylsilyl (meth) acrylate, diisopropylcyclohexylsilyl (meth) acrylate, tricyclohexylsilyl (meth) acrylate, tri-1, 1-dimethylpentylsilyl (meth) acrylate, tri-2, 2-dimethylpropylsilyl (meth) acrylate, tricyclohexylsilyl (meth) acrylate, diisopropylcyclohexylmethylsilyl (meth) acrylate, tri-2-ethylhexylsilyl (meth) acrylate, tri-2-propylpentylsilyl (meth) acrylate, and the like. Preferred examples thereof include triisopropylsilyl (meth) acrylate, tri-sec-butylsilyl (meth) acrylate, tert-butyldiphenylsilyl (meth) acrylate, and tri-2-ethylhexylsilyl (meth) acrylate. These monomers (a) may be used alone or in combination of 2 or more.
< monomer (b) >
The monomer (b) is an ethylenically unsaturated monomer other than the monomer (a), and examples thereof include (meth) acrylates, vinyl compounds, aromatic compounds, and dialkyl ester compounds of dibasic acids. In the present specification, (meth) acrylate means acrylate or methacrylate.
Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, propylene glycol monomethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and mixtures thereof, Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- [2- (2-hydroxyethoxy) ethoxy ] ethyl methacrylate, mono (2- (meth) acryloyloxyethyl) succinate, N- (3-dimethylaminopropyl) (meth) acrylamide, 2- [2- (2-methoxyethoxy) ethoxy ] ethyl (meth) acrylate, N' -dimethyl (meth) acrylamide, 2- (2-methoxyethoxy) ethyl (meth) acrylate, meth) acrylic acid, hydroxypropyl acrylate, 2- (acetoacetoxy) ethyl methacrylate, 2- (2-hydroxyethoxy) ethyl methacrylate, N-vinyl-2-pyrrolidone, and mixtures thereof, Acrylic esters such as 2- [2- (2-ethoxyethoxy) ethoxy ] ethyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, N-isopentylacrylamide, 2- (dimethylamino) ethyl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, 4-hydroxybutyl acrylate, tetrahydrofurfuryl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2- [2- (2-ethoxyethoxy) ethoxy ] ethyl methacrylate, N' -diethylacrylamide, and 3-methoxybutyl acrylate.
Examples of the vinyl compound include vinyl compounds having functional groups such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyric acid, butyl vinyl ether, lauryl vinyl ether, and N-vinylpyrrolidone.
Examples of the aromatic compound include styrene, vinyltoluene, and α -methylstyrene.
Examples of the dialkyl ester compound of the dibasic acid include dimethyl maleate, dibutyl maleate, and dimethyl fumarate.
In the present invention, these monomers (b) may be used alone or in combination of two or more. In particular, from the viewpoint of the coating film properties, (meth) acrylic acid esters are preferred as the monomer (b), and particularly from the viewpoint of crack resistance, methyl methacrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like are more preferred.
The monomer (a) in the polymer A is preferably 5 to 75% by mass, more preferably 30 to 60% by mass.
The content of the monomer (a) is specifically, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75% by mass, and may be in the range between any 2 numerical values exemplified herein.
When the polymer A in the above range is used as the coating composition of the present invention, the coating film solubility is particularly excellent.
The weight average molecular weight (Mw) of the polymer A is preferably 5000 to 300000. This is because when the molecular weight is less than 5000, the coating film of the antifouling paint becomes brittle and peeling or cracking is likely to occur, and when it exceeds 300000, the viscosity of the polymer solution increases and handling becomes difficult. Specifically, the Mw is, for example, 5000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, and 300000, and may be in a range of any 2 values exemplified herein.
An example of a method for measuring Mw is Gel Permeation Chromatography (GPC).
The polymer a may be any of a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer of the monomer (a) and the monomer (b).
The polymer a can be obtained, for example, by polymerizing the monomer (a) and the monomer (b) in the presence of a polymerization initiator.
Examples of the polymerization initiator include azo compounds such as 2,2' -azobisisobutyronitrile, 2' -azobis (2-methylbutyronitrile), 2' -azobis (2, 4-dimethylvaleronitrile), dimethyl 2,2' -azobisisobutyrate, and 2,2' -azobis (N-butyl-2-methylpropionamide); peroxides such as benzoyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, t-butyl peroxy2-ethylhexanoate, t-hexyl peroxy2-ethylhexanoate, di-t-hexyl peroxide, t-butyl peroxy2-ethylhexyl monocarbonate, di-t-butyl peroxide, 1,3, 3-tetramethylbutyl peroxyneodecanoate, t-amyl peroxyneodecanoate, t-hexyl peroxypivalate, t-amyl peroxypivalate, and 1,1,3, 3-tetramethylbutyl peroxy2-ethylhexanoate. These polymerization initiators may be used alone or in combination of 2 or more. As the above-mentioned polymerization initiator, 2 '-azobisisobutyronitrile, 2' -azobis (2-methylbutyronitrile), 2 '-azobis (2, 4-dimethylvaleronitrile), dimethyl 2,2' -azobisisobutyrate and 1,1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate are particularly preferable. The molecular weight of the copolymer a can be adjusted by appropriately setting the amount of the polymerization initiator to be used.
Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and nonaqueous dispersion polymerization. Among them, solution polymerization and nonaqueous dispersion polymerization are particularly preferable in terms of enabling the polymer a to be obtained easily and with good precision.
In the polymerization reaction, an organic solvent may be used as needed. The organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbon solvents such as xylene and toluene; an aliphatic hydrocarbon solvent; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate, and the like; alcohol solvents such as isopropyl alcohol, butyl alcohol, and propylene glycol monomethyl ether; ether solvents such as dioxane, diethyl ether, and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.
Among them, butyl acetate, isobutyl acetate, butanol, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, toluene, and xylene are particularly preferable. These solvents may be used alone or in combination of 2 or more.
The reaction temperature of the polymerization reaction may be suitably set according to the kind of the polymerization initiator, and is usually 50 to 160 ℃, preferably 60 to 150 ℃.
The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon.
1-2. Component B
The component B is a paraffin mineral oil containing aromatic hydrocarbon.
Mineral oils are fractions of purified petroleum oils and are composed of paraffins, naphthenes, aromatic hydrocarbons, and the like. The ring analysis (n-d-m method) by astm d3238 is composed of the number of paraffin carbon atoms (% CP), the number of naphthene carbon atoms (% CN), and the number of aromatic carbon atoms (% CA), and a mineral oil having a% CP of 50% or more is referred to as a paraffinic mineral oil. The% CP is, for example, 50 to 95%, specifically, for example, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95%, and may be in a range between any 2 values exemplified herein.
The component B is a paraffin mineral oil containing aromatic hydrocarbons, and the content of the aromatic hydrocarbons is 0.1 to 20%, preferably 0.1 to 15%, more preferably 0.3 to 12%, and still more preferably 8 to 12% by ring analysis (n-d-m method) using ASTM D3238. Specific examples of the% CA include 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2,3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20, and may be in a range between any 2 values exemplified herein.
The aniline point of the component B is preferably 80 to 123 ℃, more preferably 80 to 120 ℃, and still more preferably 80 to 110 ℃ from the viewpoint of not causing coating film abnormality. Specifically, the value is, for example, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123 ℃, and may be in a range between any 2 values exemplified herein. The aniline point is a value measured according to JIS K2256.
As the component B, commercially available products include, for example, Cosmo Pure Safety 10M, Cosmo Pure Safety22, Cosmo Pure Safety32, Cosmo Pure Safety 46, Cosmo Pure Safety68, Cosmo Pure Safety 100, Cosmo Pure Safety 150, Cosmo Neutral 100, Cosmo Neutral150, Cosmo Neutral 350, Cosmo Neutral 500, Cosmo Neutral700, Cosmo SP10, Cosmo SP15, and Cosmo SP83 (trade name, product name, manufactured by Cosmo oil LUICANTS corporation).
1-3. Antifouling agent
Examples of the antifouling agent include inorganic agents and organic agents.
Examples of the inorganic reagent include cuprous oxide, copper thiocyanate (common 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, cuprous oxide is more preferably surface-treated with glycerin, sucrose, stearic acid, lauric acid, lysine, mineral oil, or the like.
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-NINE211), 3, 4-dichlorophenyl-N-dimethylurea (common name: diuron), 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine (common name: Irgarol1051), 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (common name: ECONEA28), 4- [1- (2,3-dimethylphenyl) ethyl ] -1H-imidazole (common name: medetomidine), and the like.
These antifouling agents may be used in 1 kind or in combination of 2 or more kinds.
1-4. Other additives
The resin for an antifouling paint of the present invention may be added with a resin component other than the polymer a, an elution regulator, a plasticizer, a pigment, a dye, an antifoaming agent, a dehydrating agent, a thixotropic agent, an organic solvent, and the like as necessary to form an antifouling paint.
Examples of the other resin component include a polymer P.
The polymer P is a polymer obtained by polymerizing the monomer (b). The monomer (b) is any ethylenically unsaturated monomer other than the monomer (a). The composition of the monomer (b) used for polymerization of the polymer P may be the same as or different from that of the monomer (b) used for polymerization of the polymer a.
In the present invention, two or more monomers (b) may be used alone, and from the viewpoint of compatibility with the polymer a, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and benzyl (meth) acrylate are preferable.
The polymerization method, initiator, solvent, temperature, other conditions, method for measuring Mw, and the like can be applied to the methods described in the description of the polymer a.
The content of the polymer P in the composition of the present invention is not particularly limited, and the content ratio of the polymer P to the polymer a is usually 0.1 to 9.0, preferably 0.1 to 4.0 in terms of solid content by mass ratio (polymer P/polymer a).
Examples of the elution regulators include rosin, rosin derivatives, naphthenic acids, cycloalkenylcarboxylic acids, bicycloalkenylcarboxylic acids, versatic acids, trimethylisobutenylcyclohexene carboxylic acids, metal salts thereof, monocarboxylic acids and salts thereof, and the above alicyclic hydrocarbon resins. These may be used alone or in combination of 2 or more.
Examples of the rosin derivatives include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin.
Examples of the alicyclic hydrocarbon resin include Quinton1500, 1525L, 1700 (trade name, manufactured by Nippon Zeon corporation), and the like, which are commercially available products.
Among them, rosin derivatives, naphthenic acids, versatic acids, trimethylisobutenylcyclohexene carboxylic acids or metal salts of these are preferred.
Examples of the plasticizer include phosphoric acid esters, phthalic acid esters, adipic acid esters, sebacic acid esters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, t-nonyl pentasulfide, vaseline, polybutene, tris (2-ethylhexyl) trimellitate, silicone oil, and chlorinated paraffin. These may be used alone or in combination of 2 or more.
Examples of the dehydrating agent include silicates such as calcium sulfate, synthetic zeolite adsorbents, orthoesters, tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides and carbodiimides. 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 by, for example, mixing and dispersing a mixed solution containing the polymer a, the component B, the antifouling agent, other additives, and the like in a dispersing machine.
The mixed solution is preferably prepared by dissolving or dispersing various materials such as the polymer a, the component B, and the antifouling agent in a solvent.
As the dispersing machine, for example, a dispersing machine usable as a fine pulverizer is preferably used. For example, a commercially available homogenizer, sand mill, bead mill, etc. can be used. Further, the mixed liquid may be mixed and dispersed by a device in which glass beads for dispersion are mixed and added to a container equipped with a stirrer.
3. Antifouling treatment method, antifouling coating film, and coated article
The antifouling treatment method of the present invention is a method for forming an antifouling coating film on the surface of a coating film-formed article by using the above antifouling coating composition. According to the antifouling treatment method of the present invention, the antifouling coating film is gradually dissolved from the surface and the surface of the coating film is constantly renewed, whereby the adhesion of aquatic fouling organisms can be prevented.
Examples of the coating film-formed article include ships (particularly ship bottoms), fishery equipment, underwater structures, and the like.
The thickness of the antifouling coating film may be appropriately set depending on the type of the coating film-formed product, the ship's speed, the seawater temperature, and the like. For example, when the coating material is a ship bottom, the thickness of the antifouling coating film is usually 50 to 700. mu.m, preferably 100 to 600. mu.m.
[ examples ] A method for producing a compound
The following examples and the like are provided to further clarify the features of the present invention. However, the present invention is not limited to these examples.
In each of the production examples, examples and comparative examples,% represents mass%. The weight average molecular weight (Mw) is a value (polystyrene equivalent) obtained by GPC. The GPC conditions were as follows.
Device HLC-8220GPC, made by Tosoh corporation
Column TSKgel SuperHZM-M (available from Tosoh Co., Ltd.) 2
Flow 0.35mL/min
Detector. RI
Column thermostatic bath temperature 40 DEG C
Eluent THF
The heating residual component was measured according to JIS K5601-1-2: 1999(ISO 3251:1993) "coating composition test method-heating residual composition" determination of values.
Production example 1 (production of Polymer A solution A-1) >
40g of xylene (initial solvent) was charged into a four-neck flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel, nitrogen gas was introduced, and stirring was carried out while maintaining 88 ℃. A mixture of the monomers (a) and (b) shown in Table 1 and 0.8g (initially added) of 1,1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate as a polymerization initiator was added dropwise while maintaining 88 ℃ for 3 hours. Then, after stirring at 88 ℃ for 1 hour, 0.2g of 1,1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate was added every 1 hour (post-addition) 3 times, and after stirring at the same temperature for 2 hours, 60g of xylene (diluting solvent) was added and cooled to room temperature to obtain a polymer a solution a-1. The residual heating components and Mw of A-1 are shown in Table 1.
< production examples 2 to 10 (production of Polymer A solutions A-2 to A-7 and Polymer solutions P-1 to P-3) >
Using the monomers, polymerization initiators and solvents shown in Table 1, polymerization reactions were carried out at respective reaction temperatures in the same manner as in production example 1 to obtain polymer A solutions A-2 to A-7 and polymer solutions P-1 to P-3. The heating residue contents and Mw of A-2 to A-7 and P-1 to P-3 are shown in Table 1. The numerical values in the table are mass%.
[ TABLE 1 ]
Production example 11 (production of rosin zinc salt solution) >
240g of Chinese gum rosin (WW) and 360g of xylene were charged into a flask equipped with a thermometer, a reflux condenser and a stirrer, and 120g of zinc oxide was added thereto to convert all resin acids in the rosin into zinc salts, followed by reflux dehydration at 70 to 80 ℃ for 3 hours under reduced pressure. After that, the mixture was cooled and filtered to obtain a xylene solution of zinc rosin salt (dark brown transparent liquid, solid content: 50%). The heating residual component of the resulting solution was 50.2%.
Production example 12 (production of hydrogenated rosin Zinc salt solution) >
A flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 240g of HYPALE CH (hydrogenated gum rosin) and 360g of xylene, and further with 120g of zinc oxide to convert all resin acids in the rosin into zinc salts, and reflux dehydration was carried out at 70 to 80 ℃ under reduced pressure for 3 hours. Then, the mixture was concentrated, cooled and filtered to obtain a xylene solution (a concentrated brown liquid, a solid content of 65%) of the hydrogenated rosin zinc salt. The heating residual component of the resulting solution was 65.1%.
< examples 1 to 27 and comparative examples 1 to 12 (production of coating composition) >)
The components shown in tables 2 to 7 were mixed at the ratios (mass%) shown in these tables, and the mixture was dispersed in glass beads having a diameter of 1.5 to 2.5mm to prepare a coating composition.
[ TABLE 2 ]
TABLE 2
[ TABLE 3 ]
TABLE 3
[ TABLE 4 ]
TABLE 4
[ TABLE 5 ]
TABLE 5
[ TABLE 6 ]
TABLE 6
[ TABLE 7 ]
TABLE 7
The components B, stain-proofing agents and other additives in the tables are specifically as follows.
< ingredient B >
Cosmos p 83: % CP67.2,% CN32.5,% CA0.3,% aniline point 119.0 deg.C
Cosmos p 15: % CP67.1,% CN31.6,% CA1.3, aniline point 102.0 deg.C
Cosmo Neutral 700: % CP66.8,% CN25.3,% CA7.9, aniline point 110.1 deg.C
Cosmo Neutral 150: % CP68.3,% CN27.7,% CA4.0, aniline point 104.9 deg.C
Cosmo Pure security 68: % CP63.1,% CN27.7,% CA9.2, aniline point 99.5 deg.C
Cosmo Pure security 32: % CP64.0,% CN25.7,% CA10.3, aniline point 93.4 deg.C
Cosmo Pure security 22: % CP62.1,% CN28.3,% CA9.6, aniline point 88.8 deg.C
Cosmo Pure security 10: % CP59.0,% CN30.3,% CA10.7, aniline point 81.6 deg.C
Moresco white P-350P: % CP70,% CN30,% CA0, aniline point 122 deg.C
Moresco white P-260: % CP70,% CN30,% CA0, aniline point 118.0 deg.C
Moresco white P-100: % CP70,% CN30,% CA0, aniline point 108.2 deg.C
< antifouling agent >
Cuprous oxide (trade name: NC-301) (manufactured by NISSHIN CHEMCO Co., Ltd.)
Copper pyrithione: trade name "hopper Omadine" (manufactured by LONZA corporation)
Zinc pyrithione (trade name "Zinc Omadine" (manufactured by LONZA corporation)
Copper thiocyanate (I): trade name "copper (I) thiocyanate" (manufactured by Wako pure chemical industries, Ltd.)
Zineb trade name "Zineb" (manufactured by SIGMA-ALDRICH Co., Ltd.)
DCOIT: 4, 5-dichloro-2-n-octyl-3-isothiazolone (manufactured by Beijing Kanghua chemical Co., Ltd.)
Econea.trade name "Econea 028" 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP)
Medetomidine: (+ -) -4- (1- (2, 3-dimethyl) ethyl) -1H-imidazol (manufactured by Wako pure chemical industries, Ltd.)
< other additives >
TOYOPARAX a 40S: chlorinated paraffin, chlorine content 40.5% (manufactured by DONG CAO CO Co., Ltd.)
Sansosizer E-2000H: epoxidized soybean oil (made by Xinri basis physics and chemistry)
Rosin zinc salt solution: using the one manufactured in manufacturing example 11
Gum rosin solution-a 50% xylene solution of the solid content of gum rosin (WW) produced in China
Hydrogenated gum rosin solution (50% xylene solution of solid content) trade name HYPALE CH (manufactured by KAKIRA CHEMICAL CO., LTD.).
Hydrogenated rosin zinc salt solution: using the one manufactured in manufacturing example 12
Iron oxide pellet: the trade name "Tiedan gold jade" (manufactured by Senguo Shuichi industries Co., Ltd.)
Talc: trade name "Talc MS" (manufactured by Nippon Talc Co., Ltd.)
Zinc oxide: trade name "Zinc oxide 2" (manufactured by Zhengsui chemical industry Co., Ltd.)
Titanium oxide trade name "FR-41" (manufactured by Guhe mechanical Metal Co., Ltd.)
Ethyl silicate 28: tetraethoxysilane: trade name "Ethyl silicate 28" (manufactured by COLCOAT corporation)
Semi-hydrated gypsum: "NP 3D" (manufactured by Noritake Co., Ltd.)
DISPARLON A603-20X: amide thixotropic agent: trade name "DISPARLON A603-20X" (manufactured by NAKAI CHEMICAL CO., LTD.)
DISPARLON 4200-20: oxidized polyethylene thixotropic agent: trade name "DISPARLON 4200-20" (manufactured by NAKAI CHENJIAO Kabushiki Kaisha)
The following tests were carried out on the coating compositions of examples and comparative examples.
< test example 1 (test for physical Properties of coating film) >
A rotating drum having a diameter of 515mm and a height of 440mm was installed at the center of the water tank and rotated by a motor. In addition, a cooling device for keeping the temperature of the seawater constant and a pH automatic controller for keeping the pH of the seawater constant are installed.
Test panels were prepared as follows.
First, a rust preventive coating (epoxy vinyl A/C) was applied to a titanium plate (71X 100X 0.5mm) to a thickness of about 100 μm after drying, and dried to form a rust preventive coating film. Next, test plates were prepared by applying the coating compositions obtained in examples and comparative examples so that the dry film thicknesses were about 100 μm and about 200 μm, and drying them at 40 ℃ for 3 days. 4 identical test panels were prepared for each coating composition.
One of the test plates thus produced was fixed to a rotary drum of a rotary apparatus of the above apparatus so as to be in contact with seawater, and the rotary drum was rotated at a speed of 20 knots. During the period, the temperature of the seawater is kept at 25 ℃, the pH value is kept at 8.0-8.2, and the seawater is replaced every two weeks.
After the test plates having a dry film thickness of about 100 μm and about 200 μm after 3 months and 6 months of the spin test were dried, the surface of each coating film was visually observed to evaluate the state of the coating film. Evaluation was carried out by the following method.
Very good: completely free of abnormality
O: hairline cracks were observed at less than 10% of the total area of the coating surface
And (delta): the hairline cracks are observed in 10-30% of the total area of the coating surface
X: the hairline cracks were observed in the coating film surface in an amount of 30% or more of the total area
X: coating film abnormalities such as large cracks, bubbles, peeling (peeling of only a part of the surface or edge of the coating film), peeling (peeling of the entire coating film, leaving no test coating film) and the like were observed
< test example 2 (test for adhesion of coating film) >
The adhesion test of the coating film was carried out in accordance with JIS K-5600-5-6. Specifically, after drying a test plate having a dry film thickness of about 100 μm and about 200 μm after 3 months and 6 months of the spin test, 6 wounds up to the bottom were put in a grid pattern with 6 cuts each in length and width to form a 25-piece square grid pattern with a side of 3 mm. A tape having a width of 24mm manufactured by Nichiban, Inc. was attached to the lattice pattern so that air bubbles would not enter, and the tape was strongly rubbed with a fingertip. The tape was peeled off by holding one end of the tape at a time, and the adhesion state of the coating film was visually checked.
Very good: the number of the stripped lattices is 22-25
Good: 16 to 21 stripped lattices
And (delta): 11 to 15 stripped lattices
X: 0 to 10 stripped lattices
< test example 3 (bendability test of coating film) >
After the test plates having a dry film thickness of about 100 μm and about 200 μm after 3 months and 6 months of the spin test were dried, they were bent to 90 degrees, and the state of the coating film was visually confirmed.
Very good: almost no cracking or peeling was observed
O: small cracks, peelings were observed
And (delta): moderate cracking and peeling was observed
X: large cracks and peelings were observed
< fruit JI in test >
From the results of test examples 1 to 3, it was confirmed that the cracking resistance of the coating film was improved, the adhesion of the coating film was improved, and the flexibility of the coating film was improved.
Claims (1)
1. An antifouling paint composition comprising a polymer A, a component B and an antifouling agent, wherein the antifouling paint composition is characterized in that,
the polymer A is a copolymer of a monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a),
the monomer (a) is represented by the general formula (1),
the component B is a paraffin-based mineral oil containing aromatic hydrocarbon,
[ CHEM 1 ]
In the formula (1), R1Represents hydrogen or methyl, R2～R4Are the same or different and represent a branched alkyl group having 3 to 8 carbon atoms or a phenyl group.
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| PCT/JP2019/018879 WO2019221047A1 (en) | 2018-05-18 | 2019-05-13 | Antifouling coating material composition |
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| KR (1) | KR20210013111A (en) |
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| JP4064100B2 (en) * | 2001-12-13 | 2008-03-19 | 日東化成株式会社 | Anti-fouling composition for fishing nets, fishing nets coated with the anti-fouling composition for fishing nets, and anti-fouling method for fishing nets using the anti-fouling composition for fishing nets |
| JP2010031074A (en) * | 2008-07-25 | 2010-02-12 | Cci Corp | Coating composition |
| JP4812895B1 (en) * | 2010-11-10 | 2011-11-09 | 日東化成株式会社 | Antifouling paint composition, fishing net to which the paint composition is applied, fishing net equipment and underwater construction |
| JP5691102B2 (en) * | 2013-08-26 | 2015-04-01 | 日東化成株式会社 | Fishing net antifouling coating composition, copolymer for fishing net antifouling coating composition, fishing net, fishing net tool or underwater structure having antifouling coating film formed using the composition on the surface |
| WO2017164283A1 (en) * | 2016-03-25 | 2017-09-28 | 中国塗料株式会社 | Antifouling coating composition, antifouling coating film, antifouling substrate and method for producing same |
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