CN111868184A - Copolymer for antifouling paint composition, and antifouling paint composition containing same - Google Patents
Copolymer for antifouling paint composition, and antifouling paint composition containing same Download PDFInfo
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- CN111868184A CN111868184A CN201980020125.1A CN201980020125A CN111868184A CN 111868184 A CN111868184 A CN 111868184A CN 201980020125 A CN201980020125 A CN 201980020125A CN 111868184 A CN111868184 A CN 111868184A
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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
- 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
- C09D133/10—Homopolymers or copolymers of methacrylic acid 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
- 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
-
- 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
- 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
Abstract
The present invention addresses the problem of providing an antifouling coating composition which has good storage stability of the coating material, and which can provide an antifouling coating film that does not cause film abnormalities (whitening, peeling, cracking, etc.) in seawater over a long period of time, and which has sustained and stable film solubility and antifouling effect. The present invention provides a copolymer for an antifouling paint composition, which is obtained by copolymerizing a mixture of a monomer (a) and a polymerizable unsaturated monomer (b) other than the monomer (a), wherein the monomer (a) is represented by general formula (1), the monomer (b) contains 2-methoxyethyl methacrylate, the content of the monomer (a) is 5 to 45 mass% based on the total mass of the monomer (a) and the monomer (b), and the content of the 2-methoxyethyl methacrylate is 55 to 95 mass% based on the total mass of the monomer (a) and the monomer (b).
Description
[ technical field ] A method for producing a semiconductor device
The present invention relates to a copolymer for an antifouling paint composition, and an antifouling paint composition containing the copolymer.
[ 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. In particular, ships increase losses by a decrease in speed or an increase in oil consumption due to an increase in resistance.
Therefore, a method of preventing damage, in which an antifouling coating film is formed by applying an antifouling coating material containing a triorganosilyl group-containing copolymer as a carrier to the surface of an underwater structure such as a marine vessel (particularly a ship bottom part), a fishery tool such as a fishing net or a fishing net attachment, or a power generation conduit, has been widely used.
The triorganosilyl-containing copolymer has a triorganosilyl ester moiety hydrolyzed in seawater, and the copolymer gradually dissolves in seawater to renew the surface of the coating film, thereby exerting an antifouling effect.
As a triorganosilyl group-containing copolymer, a triorganosilyl group-containing copolymer obtained by copolymerizing a triorganosilyl group-containing monomer comprising a branched alkyl group or an aryl group such as triisopropylsilyl or tert-butyldiphenylsilyl with an alkoxyalkyl (meth) acrylate such as 2-methoxyethyl (meth) acrylate has been proposed (patent documents 1 to 4).
However, since the storage stability of the antifouling paint using the triorganosilyl group-containing copolymer as a carrier is poor, it has been proposed to use a paint in which a dehydrating agent such as ethyl silicate or anhydrite is mixed (patent documents 5 to 6), but this is not sufficient, and there is a problem that the storage stability is poor when the humidity during the production of the paint is high.
Further, these triorganosilyl group-containing copolymers have the following problems: the initial dissolution of the coating film is insufficient, and the coating film may whiten or fouling organisms may adhere during the assembly period or the initial parking period.
[ Prior art documents ]
[ patent document ]
[ patent document 1 ] Japanese patent laid-open No. Hei 7-102193
[ patent document 2 ] Japanese patent laid-open No. 2001-226440
[ patent document 3 ] Japanese patent laid-open No. 2005-82725
[ patent document 4 ] Japanese patent application 2016-062432 publication
[ patent document 5 ] Japanese patent laid-open No. Hei 7-18216
[ patent document 6 ] Japanese patent laid-open No. 9-48948
[ summary of the invention ]
[ problem to be solved by the invention ]
The present invention addresses the problem of providing an antifouling coating composition which has good storage stability of the coating material, and which can provide an antifouling coating film that does not cause film abnormalities (whitening, peeling, cracking, etc.) in seawater over a long period of time, and which has sustained and stable film solubility and antifouling effect.
[ MEANS FOR SOLVING PROBLEMS ] to solve the problems
The present invention provides a copolymer for an antifouling paint composition, which is obtained by copolymerizing a mixture of a monomer (a) and a polymerizable unsaturated monomer (b) other than the monomer (a), wherein the monomer (a) is represented by general formula (1), the monomer (b) contains 2-methoxyethyl methacrylate, the content of the monomer (a) is 5 to 45 mass% based on the total mass of the monomer (a) and the monomer (b), and the content of the 2-methoxyethyl methacrylate is 55 to 95 mass% based on the total mass of the monomer (a) and the monomer (b).
As a result of earnest studies, the present inventors have found that when a copolymer (a) obtained by adding a specific amount of 2-methoxyethyl methacrylate to a monomer (b) copolymerizable with a monomer (a) having a specific structure is used as a carrier, an antifouling coating composition can be obtained which has excellent storage stability of the coating even when produced under high humidity conditions, does not cause coating film abnormalities such as whitening, peeling, and cracking in seawater for a long period of time, and has stable coating film solubility and antifouling effect for a long period of time.
[ 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 copolymer (A) for an antifouling paint composition and an antifouling agent (B).
1-1. Copolymer (A) for antifouling paint composition
The copolymer (A) for an antifouling paint composition is a triorganosilyl group-containing copolymer obtained by copolymerizing a mixture of a monomer (a) and a monomer (b). The copolymer (a) contains monomer units derived from the monomers (a) to (b).
< monomer (a) >
The monomer (a) is a triorganosilyl methacrylate monomer and is represented by the general formula (1).
[ CHEM 1 ]
(in the formula, R1Is methyl, R2、R3、R4Is selected from branched alkyl groups having 3 to 8 carbon atoms and phenyl groups, which may be the same or different)
In the present invention, examples of the monomer (a) represented by the general formula (1) include triisopropylsilyl methacrylate, triisobutylsilyl methacrylate, tri-sec-butylsilyl methacrylate, triisopentylsilyl methacrylate, tri (2-ethylhexyl) silyl methacrylate, triphenylsilyl methacrylate, diisopropylisobutylsilyl methacrylate, diisopropylisopentylsilyl methacrylate, diisopropyl (2-ethylhexyl) silyl methacrylate, diisopropylphenylsilyl methacrylate, diisopropylcyclohexylsilyl methacrylate, tert-butyldiisopropylsilyl methacrylate, tert-butyldiisobutylsilyl methacrylate, tert-butyldiisopentylsilyl methacrylate, and the like, T-butyldiphenylsilyl methacrylate and the like are preferable, and t-butyldiphenylsilyl methacrylate and triisopropylsilyl methacrylate are preferable, and triisopropylsilyl methacrylate is particularly preferable. These monomers are used singly or in combination.
< monomer (b) >
The monomer (b) is a polymerizable unsaturated monomer other than the monomer (a), and is copolymerizable with the monomer (a). In the present invention, the monomer (b) is required to contain 2-methoxyethyl methacrylate, and the monomer (b) contains a specific amount of 2-methoxyethyl methacrylate, so that the coating composition obtained exhibits the following technical effects: the storage stability is very good, the coating film does not cause coating film abnormality such as whitening, peeling, cracking and the like for a long time, and the coating film solubility and the antifouling effect are continuously stable.
The monomer (b) may contain only 2-methoxyethyl methacrylate or may contain a monomer other than 2-methoxyethyl methacrylate. Examples of the monomer other than 2-methoxyethyl methacrylate include the following monomers.
● triorganosilyl acrylates such as triisopropylsilyl acrylate, triisobutylsilyl acrylate, tri-sec-butylsilyl acrylate, triisopentylsilyl acrylate, tri (2-ethylhexyl) silyl acrylate, triphenylsilyl acrylate, diisopropylisobutylsilyl acrylate, diisopropylisopentylsilyl acrylate, diisopropyl (2-ethylhexyl) silyl acrylate, diisopropylphenylsilyl acrylate, diisopropylcyclohexylsilyl acrylate, tert-butyldiisopropylsilyl acrylate, tert-butyldiisobutylsilyl acrylate, tert-butyldiisopentylsilyl acrylate, and tert-butyldiphenylsilyl acrylate.
● (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl acrylate, 2-methoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, polyethylene glycol methyl ether (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate.
● metal side chains of (meth) acrylic acid such as zinc (meth) carbonate (meth) acrylate, magnesium (meth) carbonate (meth) acrylate, copper (meth) acrylate, magnesium (meth) acrylate, zinc (meth) acrylate, magnesium laurate (meth) acrylate, copper (meth) acrylate laurate, zinc (meth) acrylate, magnesium stearate (meth) acrylate, copper (meth) acrylate, and zinc (meth) acrylate.
● 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.
● aromatic compounds such as styrene, vinyl toluene and alpha-methyl styrene.
● dialkyl ester compounds of unsaturated dibasic acids such as dimethyl malate, dibutyl malate, and dimethyl fumarate.
One or more monomers other than 2-methoxyethyl methacrylate that can be copolymerized are used, and (meth) acrylates are preferred, and methyl (meth) acrylate is particularly preferred.
The mass ratio of the content of 2-methoxyethyl methacrylate in the monomer (b) is preferably 0.75 to 0.95, more preferably 0.8 to 0.95, and specifically, for example, 0.75, 0.8, 0.85, 0.9, and 0.95, and may be in the range of any 2 values exemplified herein.
< Synthesis of copolymer (A) >
The copolymer (A) used in the antifouling paint of the present invention can be obtained by copolymerizing a mixture of the monomer (a) and the monomer (b). The copolymerization is carried out, for example, in the presence of a polymerization initiator.
The content of the monomer (a) in the mixture is 5 to 45% by mass, preferably 10 to 40% by mass, and more preferably 15 to 35% by mass. When the content of the monomer (a) is 5 to 45% by mass, the obtained antifouling paint composition has very good paint stability, and the coating film does not cause any abnormality such as whitening, peeling, cracking, etc. in seawater for a long period of time, and can maintain stable coating film solubility and antifouling performance from the initial stage. Specifically, the content is, for example, 5, 10, 15, 20, 25, 30, 35, 40, or 45 mass%, and may be in a range between any 2 values exemplified herein.
The content of 2-methoxyethyl methacrylate in the mixture is 55 to 95% by mass, preferably 60 to 90% by mass, and more preferably 60 to 85% by mass. When the content of 2-methoxyethyl methacrylate is 55 to 95% by mass, the coating film formed from the obtained antifouling paint composition has good coating film solubility and antifouling effect in seawater from the initial stage, does not cause coating film abnormalities such as whitening, peeling, and cracking, and can maintain stable coating film solubility and antifouling effect for a long period of time. Specifically, the content is, for example, 55, 60, 65, 70, 75, 80, 85, 90, or 95% by mass, and may be in a range between any 2 values exemplified herein.
The total content of the monomer (a) and 2-methoxyethyl methacrylate is 60 mass% or more, preferably 70 mass% or more, and more preferably 80 mass% or more, based on the total mass of the monomer (a) and the monomer (b). When the amount is within the above range, the coating film can be stably dissolved for a long period of time without causing film defects such as whitening, peeling, and cracking, and an excellent antifouling effect can be exhibited. Specifically, the content is, for example, 60, 65, 70, 75, 80, 85, 90, 95, 100 mass%, and may be in a range between any 2 values exemplified herein.
The weight average molecular weight of the copolymer of the present invention 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 copolymer 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.
Examples of the polymerization initiator include azo compounds such as 2,2' -Azobisisobutyronitrile (AIBN), 2' -azobis-2-methylbutyronitrile, and dimethyl 2,2' -azobisisobutyrate; peroxides such as benzoyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexanoate, and 1,1,3, 3-tetramethylbutyl peroxy-2-ethylhexanoate. These polymerization initiators may be used alone or in combination of 2 or more. As the polymerization initiator, 2' -azobisisobutyronitrile and 1,1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate are particularly preferable.
The molecular weight of the triorganosilyl ester-containing copolymer can be adjusted by appropriately setting the amount of the polymerization initiator used.
Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization. Among them, solution polymerization is particularly preferable in that the copolymer (a) can be obtained easily and with high accuracy.
In the polymerization reaction, an organic solvent may be used as necessary. Examples of the organic solvent include aromatic hydrocarbon solvents such as xylene, ethylbenzene, and toluene. And aliphatic hydrocarbon solvents such as hexane and heptane. Ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and methoxypropyl acetate. Alcohol solvents such as isopropyl alcohol and butyl alcohol. Ether solvents such as dioxane, diethyl ether, and dibutyl ether. Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Among them, an aromatic hydrocarbon solvent is particularly preferable, and xylene is more preferable. These solvents may be used alone or in combination of 2 or more.
The reaction temperature of the polymerization reaction is usually 70 to 120 ℃ and may be appropriately set depending on the kind of the polymerization initiator, and is preferably 70 to 100 ℃. The reaction time of the polymerization reaction may be appropriately set depending on the reaction temperature, and is usually about 4 to 8 hours.
The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon.
1-2. Antifouling agent (B)
Examples of the stain-proofing agent (B) 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-copper N-oxide (common name: copper pyrithione), 2-mercaptopyridine-zinc N-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 combination of 1 or more than 2.
The content of the antifouling agent in the composition of the present invention is not particularly limited, and is usually 0.1 to 75% by mass, preferably 1 to 60% by mass in the solid content of the composition of the present invention. When the content of the antifouling agent is less than 0.1% by mass, a sufficient antifouling effect may not be obtained. When the content of the antifouling agent exceeds 75% by mass, the formed coating film is weak and the adhesion to the object to be coated is also weak, and the function as an antifouling coating film cannot be exhibited.
1-3. Other additives
The resin for an antifouling paint of the present invention may further contain, as required, a dissolution-adjusting agent, a plasticizer, a pigment, a dye, a defoaming agent, a dehydrating agent, a thixotropic agent, and an organic solvent as an antifouling paint.
Examples of the dissolution-controlling agent include rosin, rosin derivatives, naphthenic acids, cycloalkenylcarboxylic acids, bicycloalkenylcarboxylic acids, versatic acids, trimethylisobutenylcyclohexene carboxylic acids, metal salts thereof, monocarboxylic acids and salts thereof, and 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, product name of Nippon Zeon corporation) and the like as commercially available products.
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, liquid paraffin, and chlorinated paraffin. These may be used alone or in combination of 2 or more.
Examples of the dehydrating agent include synthetic zeolite adsorbents, silicates such as 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 copolymer, the antifouling agent, and other additives in a dispersing machine.
The mixed solution is preferably a solution in which various materials such as a copolymer and an antifouling agent are dissolved or dispersed in a solvent.
As the above-mentioned disperser, for example, a disperser usable as a fine pulverizer can be preferably used. For example, a commercially available homogenizer, sand mill, bead mill, etc. can be used. The mixed solution may be mixed and dispersed by using a device in which glass beads for mixing and dispersing are added to a container equipped with a stirrer.
3. Method of antifouling processing, 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, reference examples, and comparative examples,% represents mass%.
The heating residual component was a value obtained by heating at 125 ℃ for 1 hour in accordance with JIS K5601-1-2 (ISO 3251).
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 unit of the amount of each component in the table is g.
< production example 1 (production of copolymer P-1) >
A2000 ml flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was charged with a mixed solution of 400g of xylene, which was stirred under a nitrogen atmosphere and heated to 85. + -. 2 ℃ and held at 85. + -. 2 ℃ for 1 hour, and then, 5g of triisopropylsilyl methacrylate 175g, 2-methoxyethyl methacrylate 300g, methyl methacrylate 25g, 1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate (PERCATA O, manufactured by NOF corporation) was added dropwise. After dropping, 0.5g of 1,1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate was added 3 times per hour at 85. + -. 2 ℃ to terminate the polymerization reaction, and then the mixture was cooled by raising the temperature to 110 ℃ and maintaining the temperature for 30 minutes, and 100g of xylene was added at 90 ℃ or lower to dissolve the mixture, thereby obtaining a copolymer solution P-1. P-1 had a heating residual component of 49.7% and a weight average molecular weight of 52000.
< production examples 2 to 8, reference examples 1 to 12 >
Using the organic solvents, monomers and polymerization initiators shown in tables 1 to 2, copolymer solutions P-2 to P-8 and comparative copolymer solutions H-1 to H-12 were obtained by copolymerization in the same manner as in production example 1. The residual components after heating and the weight average molecular weight of each of the obtained copolymer solutions were measured. The results are shown in tables 1 to 2.
[ TABLE 1 ]
TABLE 1
[ TABLE 2 ]
< examples 1 to 12, comparative examples 1 to 12 >
Antifouling paint compositions were prepared by mixing the copolymer solutions P-1 to P-8 obtained in production examples 1 to 8 and reference examples 1 to 12 and the copolymer solutions H-1 to H-12 obtained in comparative examples, as shown in tables 3 to 4.
(method for producing coating composition)
The antifouling paint compositions of examples 1 to 12 and comparative examples 1 to 12 were prepared by mixing and dispersing the compositions in an air stream having a humidity of 90% or more by operating 2 humidifiers for 1 hour using a small bench sander for experiment (using glass beads having a diameter of 1.5 to 2.5 mm), and then divided into 2 tin cans of 100ml, and the paint of one tin can was used for various tests of coating film, and the paint of the other tin can was used for evaluation of storage stability.
(evaluation of storage stability of coating)
After measuring the viscosity of the paint charged into one tin can, the paint was sealed and stored in a thermostat at 45 ℃ for 3 months, and then the viscosity of the paint was measured by a type B viscometer.
The storage stability of the coating material was evaluated by the following method.
Very good: the viscosity change of the coating is less than 500 mPa.s/25 ℃ (hardly thickening)
O: viscosity of the coating changes to 500-5000 mPa & s/25 ℃ (slightly thickened)
And (delta): the viscosity of the coating changes to 5000 mPa.s/25 ℃ or higher (greatly increased in thickness)
X: viscosity change to undetectable (gel or solid)
The results are shown in tables 3 and 4.
(measurement of hardness of coating film)
The coating film hardness of the coating material was measured by a Pendulum (Pendulum) hardness tester.
Each paint sample was coated on a release sheet (100X 200X 2mm) to a thickness of about 100 μm after drying, and after drying at 40 ℃ for 1 day, the hardness of the coating film was measured in a room at 25 ℃ by a pendulum hardness tester. The value is a count.
The results are shown in tables 3 and 4.
(rotation test)
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) so that the thickness after drying was about 100 μm, and dried to form a rust preventive coating film. Next, the coating compositions obtained in examples 1 to 12 and comparative examples 1 to 12 were applied to the rust inhibitive coating film so that the thickness after drying was about 300. mu.m. The resulting coated article was dried at 40 ℃ for 3 days to prepare a test sheet having a dried coating film with a thickness of about 300. mu.m.
The test plate 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 once per week.
● measurement of dissolved amount of coating film
The residual film thickness of each test plate at the initial stage and every 1 month after the start of the test was measured by a shape measuring laser microscope VK-X100 manufactured by KEYENCE, K.K., and the dissolved film thickness was calculated from the difference, thereby obtaining the dissolved amount of the film (μm/month) per 1 month.
The results are shown in tables 3 and 4.
● Observation of surface State of coating film
When the residual film thickness after 6 months of the spin test was measured, the surface state of each coating film was evaluated by observing the surface of each coating film with the naked eye and a microscope.
The surface state of the coating film was evaluated according to the following criteria.
Very good performance that no abnormal condition exists
Observation of slight capillary cracking
Delta, hairline cracks were observed over the entire coating film
Film coating abnormality such as cracking, bubbling or peeling was observed
The results are shown in tables 3 and 4.
● whitening of coating film
When the residual film thickness after 6 months of the spin test was measured, the presence or absence of whitening on the surface of each coating film was visually evaluated.
The evaluation of the presence or absence of whitening on the coating film surface with the naked eye was carried out according to the following criteria.
O: the color of the surface of the coating film hardly changes
And (delta): the color of the coating film surface is slightly whitened
X: the color of the entire coating film was clearly whitened
The results are shown in tables 3 and 4.
● measurement of L value of coating film
The L value (brightness) of the coating film before the spin test and the residual coating film after 6 months of the spin test were measured by a colorimeter. The Color Meter ZE6000 manufactured by Nippon Denshoku industries Co., Ltd was used as the colorimeter. The L value (luminance) is defined in JIS Z8781-4 (formula for calculating CIE method). Since white is 100 and black is 0 in the L value (brightness), when the surface of the coating film is whitened, the coating film becomes bright and the number of L values increases.
(antifouling test (static immersion test))
Each of the antifouling paints obtained in examples 1 to 12 and comparative examples 1 to 12 was applied to both surfaces of a rigid polyvinyl chloride plate (100X 200X 2mm) so that the thickness of the dried coating film was about 200 μm. The test panel was immersed 1.5m below the sea surface of the eagle city, caucasian prefecture, triple prefecture, observed for 12 months and evaluated for fouling by attached organisms. The evaluation was carried out by visually observing the state of the surface of the coating film, and was judged according to the following criteria.
Excellent in that fouling organisms such as shellfish and algae are not attached and sludge is hardly generated.
O rating that no fouling organisms such as shellfish and algae are attached and sludge is attached thinly (the degree of coating film surface is visible), and the sludge can be removed by lightly wiping with a brush.
And a scale in which fouling organisms such as shellfish and algae are not attached, but sludge is attached to a large extent such that the film surface is not clearly visible, and cannot be removed even by strongly wiping with a brush.
The results are shown in tables 3 and 4, respectively, for the degree of fouling organisms such as shellfish and algae.
[ TABLE 3 ]
TABLE 3
[ TABLE 4 ]
TABLE 4
The antifouling agents, pigments and other additives shown in tables 3 and 4 are as follows.
< antifouling agent >
Cuprous oxide (NC-301 average particle size 3 μm manufactured by NISSHIN CHEMCO Co., Ltd.)
Copper pyrithione (Copper Omadine, manufactured by Arch Chemicals Co., Ltd.)
< pigment >
Iron oxide pellet (manufactured by Toda Pigment, TODA COLOR EP-13D)
Talc (Songcun industrial manufacturing, CROWNTALC 3S)
Zinc oxide (manufactured by the same chemical Co., Ltd., Zinc oxide 2 kinds (trade name))
Titanium oxide (made of metal of gulhe machine, FR-41)
< other additives >
Tetraethoxysilane (KiSHIDA CHEMICAL MAKING, CHEMICAL)
Rosin zinc salt (50% xylene solution)
Paraffin chloride (product name "EMPARA A-40S" manufactured by Tosoh corporation)
DISPARLON A603-20X (NANOFAMILY FABRICATION, fatty acid amide thixotropic agent)
As can be seen from tables 3 and 4: the coating compositions (examples 1 to 12) of the present invention were excellent in storage stability, and the amount of the formed coating film dissolved in seawater was kept high, and fouling organisms such as shellfish and algae were not attached and sludge was hardly attached in the antifouling test. The dried coating film after 6 months of the spin test was satisfactory without any abnormality such as whitening, cracking, and peeling.
On the contrary, the coating materials produced by the coating compositions of comparative examples 1 to 6 or 10 to 12 were inferior to those of the examples in storage stability, and the coating films formed by the coating materials were apt to be whitened.
The coatings produced from the coating compositions of comparative examples 7 to 9 had a low amount of dissolution in seawater, and the prevention of fouling organisms from adhering was insufficient.
Claims (3)
1. A copolymer for an antifouling paint composition, which is obtained by copolymerizing a mixture of a monomer (a) and a polymerizable unsaturated monomer (b) other than the monomer (a),
the monomer (a) is represented by the general formula (1),
the monomer (b) contains 2-methoxyethyl methacrylate,
the content of the monomer (a) is 5 to 45 mass% based on the total mass of the monomer (a) and the monomer (b),
the content of the 2-methoxyethyl methacrylate is 55 to 95% by mass based on the total mass of the monomer (a) and the monomer (b),
[ CHEM 1 ]
In the formula, R1Is methyl, R2、R3、R4Are selected from branched alkyl groups having 3 to 8 carbon atoms and phenyl groups, and are the same or different.
2. The copolymer according to claim 1,
the total content of the monomer (a) and 2-methoxyethyl methacrylate is 70% by mass or more based on the total mass of the monomer (a) and the monomer (b).
3. An antifouling coating composition comprising a copolymer and an antifouling agent,
The copolymer is the copolymer for an antifouling paint composition according to claim 1 or claim 2.
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| JP2018-080026 | 2018-04-18 | ||
| JP2018080026 | 2018-04-18 | ||
| PCT/JP2019/015971 WO2019203154A1 (en) | 2018-04-18 | 2019-04-12 | Copolymer for stain-proof coating compositions, and stain-proof coating composition containing said copolymer |
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| CN105189670A (en) * | 2013-03-15 | 2015-12-23 | 日东化成株式会社 | Antifouling coating composition, antifouling coating film formed using said composition, and coated article having antifouling coating film on surface |
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| JP3261220B2 (en) | 1993-06-30 | 2002-02-25 | 日本油脂ビーエーエスエフコーティングス株式会社 | Underwater antifouling paint composition |
| JP2790021B2 (en) | 1993-09-30 | 1998-08-27 | 日本油脂株式会社 | Paint composition |
| JP3696333B2 (en) | 1995-06-01 | 2005-09-14 | 中国塗料株式会社 | Antifouling coating composition, coating film formed from the antifouling coating composition, antifouling method using the antifouling coating composition, and hull or underwater structure coated with the coating |
| JP3857010B2 (en) | 2000-02-17 | 2006-12-13 | 日本ペイント株式会社 | Copolymer and coating composition |
| JP3914437B2 (en) * | 2000-04-24 | 2007-05-16 | Ｂａｓｆコーティングスジャパン株式会社 | Antifouling paint, antifouling coating film, submerged structure and antifouling method |
| 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 |
| US20030225184A1 (en) * | 2002-05-30 | 2003-12-04 | Aubart Mark Anthony | Triarylsilyl(meth)acryloyl-containing polymers for marine coating compositions |
| JP2005082725A (en) * | 2003-09-09 | 2005-03-31 | Nitto Kasei Co Ltd | Antifouling coating composition and submarine articles coated with the composition, and antifouling method using the composition |
| PL2128208T3 (en) * | 2007-02-27 | 2012-12-31 | Nitto Kasei Co Ltd | Stain-proof coating composition, method for production of the composition, stain-proof coating film formed by using the composition, coated article having the coating film on the surface, and stain-proofing treatment method for forming the coating film |
| JP5142150B2 (en) * | 2008-10-02 | 2013-02-13 | Ｎｋｍコーティングス株式会社 | Copolymer composition, antifouling paint composition, construction method and structure |
| JP4521589B2 (en) * | 2008-12-19 | 2010-08-11 | 日東化成株式会社 | Antifouling paint composition, antifouling coating film formed using the composition, coated product having the coating film on the surface, and antifouling treatment method for forming the coating film |
| JP6217576B2 (en) | 2014-09-19 | 2017-10-25 | 京セラドキュメントソリューションズ株式会社 | Image forming apparatus and screen operation method |
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