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    • 专利摘要:
    COPOLYMER FOR AN ANTI-FOULING COATING COMPOSITION, ANTI-FOULING COATING COMPOSITION, METHOD FOR PRODUCTION OF A COPOLYMER AND COATED OBJECT. The object of the present invention is to provide a copolymer that can make possible an antifouling paint composition used for forming an environmentally safe antifouling paint film having a high water resistance paint film, which does not show paint film defects such as cracking over time in sea water, and maintains stable antifouling performance and paint film solubility. The present invention can provide a copolymer for an antifouling paint composition, containing a copolymer (A) having, in a side chain, a group represented by the chemical formula (1) and having, at the end, at least one of a group represented by the chemical formula (2) and a group represented by the chemical formula (3).
    公开号:BR112015026458B1
    申请号:R112015026458-1
    申请日:2014-04-16
    公开日:2022-02-01
    发明作者:Hidenori Waku
    申请人:Nitto Kasei Co., Ltd；
    IPC主号:
    专利说明:

    Technical Field
    [0001] The present invention relates to an antifouling coating composition, a copolymer for the antifouling coating composition and a method of producing the composition and/or the copolymer, and a coated object having, on its surface , an antifouling coating film formed using the composition. Previous Art
    [0002] Aquatic fouling organisms such as barnacles, barnacles, common mussels, Bugula neritina, ascidians, green algae, sea lettuce, and slimes adhere to ships (especially on the bottom of ships), fishing implements such as fishing nets and accessories of fishing nets, and structures submerged in sea water such as aqueducts for power plant installation, lead to dysfunction, damaged appearance, and other problems of ships and so on.
    [0003] Once a conventional organic copolymer containing tin was banned, copolymers containing the triorganosilyl group, which have low toxicity and are environmentally friendly, were developed and used for antifouling coating compositions (Patent Literature 1).
    [0004] These copolymers can typically be produced by polymerization using a general purpose polymerization initiator such as t-butylperoxy-2-ethyl hexanoate or AIBN, etc. Copolymers having an average molecular weight (Mw) of 10,000 to 100,000 have often been used.
    [0005] The triorganosilyl ester copolymer produced by polymerization using the above general purpose polymerization initiator can be used for an antifouling coating composition. In this case, an antifouling coating film formed using the antifouling coating composition dissolves in seawater at a constant rate during the initial step. However, the coating film dissolution rate gradually increases. After a long period has elapsed, the rate of dissolution of the coating film becomes very large. Unfortunately, it is therefore difficult to design a coating material. In view of the foregoing, the present invention is an antifouling coating material which exerts the property of stable dissolution of the coating film in the long term through the use of rosin, a rosin derivative or a metal salt thereof, in addition to the copolymer containing triorganosilyl ester (Patent Literature 2).
    [0006] Although the antifouling coating material can exert the stable dissolution property of the coating film in the long term, defects in the coating film, such as cracking, occur in the coating film after long-term immersion in water. from the sea. This problem is evident when the low molecular weight copolymer, in particular, is used.
    [0007] Hitherto, a solution containing the copolymer used for the antifouling coating composition has generally been produced using a batch reaction apparatus equipped with a stainless steel reaction tank, an outer jacket, an inner coil, a condenser, a mixer, etc. In this batch reaction apparatus, the temperature is controlled by a cooling fluid flowing through the outer shell and inner coil. When the production of the copolymer is repeated continuously, a gel material derived from the copolymer, insoluble in a solvent, adheres and accumulates inside the reaction tank. Because of this problem, when the copolymer is produced, it takes extra effort and time to wash the inside of the reaction tank. Consequently, there is a big problem in terms of productivity. Furthermore, it has been difficult to control the heat generation during polymerization as the gel material adhered to the internal coil causes a decrease in the cooling capacity.
    [0008] As a method for washing to remove adhered gel material derived from the copolymer, there is disclosed a method for washing a batch reaction apparatus using a highly concentrated alkaline solution (15 to 30% by weight) in high pressure (Patent Literature 3). However, because the highly concentrated alkali is brought into contact with a stainless steel reaction tank under conditions of high temperature and high pressure, the reaction tank is corroded and metal atoms are mixed into a copolymer solution, and the copolymer so it is colored. Furthermore, there is such a problem that due to the reaction tank being subjected to successive washings, the reaction tank is damaged and its life is shortened.
    [0009] Further, as a method for washing to remove a gel material derived from a thermoplastic acrylic copolymer, there is disclosed a method for washing a stainless steel reaction tank by using an aqueous washing solution containing a hydroxide alkali metal (from 1 to less than 15% by weight) and at least one monohydric alcohol (from 3 to 50% or less by weight; the number of carbon atoms is 2 or 3) (Patent Literature 4). This method, however, is performed under mild conditions such as normal pressure and still does not provide a complete solution to the problems. In addition, a washing work step to remove the gel material is still required. Therefore, this method does not lead to an increase in the productivity of the copolymer.
    [0010] Further, as a method of suppressing the generation of a gel material by itself, a batch reaction apparatus having an external circulating cooler is disclosed (Patent Literature 5). Although gel material is not generated in, for example, an internal coil of a reaction tank, gel material is generated in the external circulating cooler. Consequently, washing work is still required. This method also does not lead to an increase in the productivity of the copolymer.
    [0011] As described above, unfortunately, the copolymer produced by polymerization using a commonly used polymerization initiator such as t-butylperoxy-2-ethyl hexanoate or AIBN gives the coating film poor properties such as coating film defects ( e.g. cracks) in seawater after a given period of immersion in seawater. In addition, due to the poor properties of the coating film, the long-term stable dissolution property and anti-fouling performance of the coating film cannot be maintained. In addition, there is another manufacturing problem, such as low productivity caused by the generation of the gel material. List of Citations Patent Literature Patent Literature 1: JP-A-Hei 7-102193 Patent Literature 2: JP-A-Hei 10-30071 Patent Literature 3: JP-A-2001-96248 Patent Literature 4: JP -A-2012-5952 Patent Literature 5: JP-B-3941027 Summary of the invention Technical problem
    [0012] The object of the present invention is to provide a copolymer that allows an antifouling coating composition used for the formation of an environmentally friendly antifouling coating film. The antifouling coating composition gives the coating film increased water resistance and can maintain the stable dissolution ability and antifouling performance of the coating film without causing the coating film defects such as cracking during use. long-term in seawater. Furthermore, another object of the present invention is to provide an efficient method for producing the copolymer. Solution to the Problem
    [0013] One aspect of the present invention provides a copolymer for an antifouling coating composition comprising a copolymer (A) having, in a side chain, a group represented by the chemical formula (1) and having, at the end, at least one of a group represented by the chemical formula (2) and a group represented by the chemical formula (3). Chemical formulas (1) to (3) are described below.
    [0014] The present inventor has addressed the problem of developing an antifouling coating composition that can maintain the stable dissolution property and antifouling performance of a coating film without causing defects in the coating film, such as cracking, during long-term use in seawater. The present inventor analyzed various materials and found that the use of the above copolymer allowed for significantly better water resistance of the clear coating film. Furthermore, with regard to the antifouling coating composition using the copolymer, not only did the strength of the initial coating film (a stage before immersion in seawater) increase, but there were also no defects of the coating film ( e.g. a crack) in the antifouling coating film after immersion in sea water for a certain period. These surprising results were obtained.
    [0015] Most surprisingly, no gel material was generated, for example, in a reaction tank during the fabrication of copolymer (A) above. This makes it possible to efficiently produce copolymer (A) without a washing step. Advantageous Effects of the Invention
    [0016] The present invention provides a copolymer that enables an antifouling coating composition used to form an environmentally friendly antifouling coating film. The antifouling coating composition gives the coating film increased water resistance and can keep the dissolving ability and antifouling performance of the coating film stable without causing the coating film defects, such as cracking, during long-term use in seawater. Furthermore, no gel material was generated in, for example, a reaction tank. Collectively, an efficient method for producing the copolymer is provided. Brief Description of Drawings
    [0017] Figure 1 - Figures 1(a) and (b) each show an NMR spectrum obtained with respect to a copolymer of Production Example 1. FIG. 1(a) shows a spectrum with respect to "13C-DEPT135". FIG. 1(b) shows a spectrum with respect to "13C-single pulse with 1H decoupling".
    [0018] Figure 2 - Figure 2 is an enlarged view of the spectrum region between 43 and 49 nm in Figures 1(a) and (b). Description of Forms of Achievement
    [0019] Hereinafter, the present invention will be explained in detail. Copolymer (A)
    [0020] A copolymer (A) according to the present invention has, in a side chain, a group represented by the chemical formula (1) and having, at the terminus, at least one of a group represented by the chemical formula (2) and a group represented by the chemical formula (3). The copolymer (A) preferably has, at the end, either the group represented by the chemical formula (2) or the group represented by the chemical formula (3), but can have, at the end, either. Chemical formula (1):
    (wherein R1, R2, and R3 are the same or different from each other and each represents a C3-6 alkyl group branched at an α-position or a phenyl group). Chemical formula (2):
    Chemical formula (3):

    [0021] Examples of the C3-6 alkyl group branched at the α-position include an isopropyl group, s-butyl group, t-butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1-methylpentyl group, 1,1-dimethylpropyl group , 1,1-dimethylbutyl group, and t-hexyl group.
    [0022] In particular, the present invention allows the formation of an antifouling coating film that is unlikely to cause coating film defects and is excellent in water resistance, by selecting specific groups for R1, R2, and R3. . From this point of view, R1 , R2 , and R3 are the same or different from each other and each is preferably an isopropyl group, s-butyl group, t-butyl group, or phenyl group and more preferably an isopropyl group. Copolymer Synthesis (A)
    [0023] The copolymer (A), for example, can be produced by polymerizing a mixture of the monomer described below (a) and monomer (b), using a 1,1,3,3-tetramethyl-butylperoxy-2 polymerization initiator. -ethyl hexanoate or 1,1,3,3-tetramethyl butylperoxy neodecanoate. The molecular weight of copolymer A can be adjusted by appropriately selecting the amount of polymerization initiator used. If necessary, a chain transfer agent, etc., can be used. Monomer
    [0024] Monomer (a) is an ethylenically unsaturated monomer (a) having a group represented by the chemical formula (1) above.
    [0025] Examples of the monomer (a) include tri-isopropylsilyl methacrylate, tri-s-butylsilyl methacrylate, triphenylsilyl methacrylate, diisopropyl s-butylsilyl methacrylate, diisopropyl t-butylsilyl methacrylate, di- isopropyl t-hexylsilyl methacrylate, di-isopropyl phenylsilyl methacrylate, isopropyl di-s-butylsilyl methacrylate, isopropyl diphenylsilyl methacrylate, diphenyl t-hexylsilyl methacrylate, t-butyldiphenylsilyl methacrylate, bis(triisopropylsilyl) maleate, bis(triisopropylsilyl) maleate triisopropylsilyl methyl, triisopropylsilyl ethyl maleate, triisopropylsilyl n-butyl maleate, triisopropylsilyl isobutyl maleate, triisopropylsilyl t-butyl maleate, triisopropylsilyl n-pentyl maleate, tri-isopentyl maleate - isopropylsilyl, 2-ethylhexyl triisopropylsilyl maleate, cyclohexyl triisopropylsilyl maleate, bis(triisopropylsilyl) fumarate, triisopropylsilyl methyl fumarate, tri-isoethyl fumarate propylsilyl, triisopropylsilyl n-butyl fumarate, triisopropylsilyl isobutyl fumarate, triisopropylsilyl n-pentyl fumarate, triisopropylsilyl isopentyl fumarate, 2-ethylhexyl triisopropylsilyl fumarate, cyclohexyl fumarate triisopropylsilyl.
    [0026] From the point of view that, in particular, defects in the coating film are unlikely to occur and that an antifouling coating film having excellent water resistance can be produced, triisopropylsilyl methacrylates, methacrylate of tri-s-butylsilyl, t-butyldiphenylsilyl methacrylate and tri-isopropylsilyl isopentyl maleate. More preferred are triisopropylsilyl methacrylates, triisopropylsilyl isopentyl maleate. These ethylenically unsaturated monomers (a) are used alone or in combination. Monomer (b)
    [0027] Monomer (b) is an ethylenically unsaturated monomer copolymerizable with monomer (a). Examples of the monomer (b) include: methacrylic esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate , 2-methoxyethyl acrylate, 2-methoxypropyl acrylate, 4-methoxybutyl acrylate, 2-ethoxyethyl methacrylate, ethylene glycol monomethyl methacrylate, propylene glycol monomethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylate dimethylaminoethyl, diethylaminoethyl methacrylate, benzyl methacrylate, phenyl methacrylate and the like; vinyl compounds such as vinyl chloride, vinylidene chloride, methacrylonitrile, vinyl acetate, vinyl butyl ether, vinyl lauryl ether, n-vinyl pyrrolidone and the like; aromatic compounds such as styrene, vinyl toluene, α-methyl styrene and the like; and maleic compounds such as dimethyl maleate, diethyl maleate and the like. Among them, in particular, methacrylic esters are preferred, and methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, 2-ethylhexyl methacrylate and 2-methoxyethyl acrylate are most preferred. Examples of the monomer (b) can be used alone or in combination as a monomer component of the copolymer (A).
    [0028] The content of monomer (a) in the mixture is preferably from about 20 to 70% by weight, and more preferably from about 20 to 60% by weight. When the content of monomer (a) is about 20 to 70% by weight, the coating film formed using the resulting antifouling coating composition can exhibit stable dissolving property, and can maintain an antifouling effect for a long time. long period of time.
    [0029] Generally, the copolymer produced using another polymerization initiator has an average molecular weight (Mw) preferably from 10,000 to 100,000. The copolymer (A) produced using 1,1,3,3-tetramethylbutylperoxy-2-ethyl hexanoate or 1,1,3,3-tetramethylbutylperoxide neodecanoate as the polymerization initiator has an average molecular weight (Mw), which may be less, preferably from 3,000 to 100,000 and more preferably from 3,000 to 70,000. When the Mw is 3,000 to 100,000, the coating films are not brittle and have an adequate dissolution rate, so that a desired anti-fouling effect can be effectively exerted. When the copolymer has an average molecular weight (Mw) of 3,000 to 12,000, the viscosity of the antifouling coating composition can conveniently be lowered such that the amount of a solvent used can be significantly reduced at the time of using the composition as a a coating material. An example of the method for measuring Mw is gel permeation chromatography (GPC).
    [0030] Copolymer A can be any of a random copolymer, alternating copolymer, periodic copolymer, and block copolymer between monomer (a) and monomer (b). Copolymer A, for example, can be produced by polymerizing monomer (a) and monomer (b) in the presence of a polymerization initiator of 1,1,3,3-tetramethylbutylperoxy-2-ethyl hexanoate or sodium neodecanoate. 1,1, 3,3-tetramethyl butylperoxide. When such a polymerization initiator is used, the terminus of a generated polymer chain has a group represented by chemical formula (2) and/or chemical formula (3).
    [0031] Examples of polymerization methods include solution polymerization, batch polymerization, emulsion polymerization and suspension polymerization. Among them, solution polymerization is preferable as it allows copolymer A to be prepared easily and accurately.
    [0032] In the polymerization reaction, an organic solvent can be added if necessary. Examples of the organic solvent include: aromatic hydrocarbon based solvents (eg xylene, toluene); aliphatic hydrocarbon based solvents (eg hexane, heptane); ester-based solvents (e.g. ethyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate); alcohol-based solvents (eg isopropyl alcohol, butyl alcohol); ether-based solvents (e.g., dioxane, diethyl ether, dibutyl ether); and ketone-based solvents (e.g., methyl ethyl ketone, methyl isobutyl ketone). Among these, solvents based on aromatic hydrocarbons are preferred, and xylene is particularly preferred. These solvents can be used alone or in combination.
    [0033] The reaction temperature in the polymerization reaction is usually from 70 to 140 °C and preferably from 80 to 120 °C. The reaction time required for the polymerization reaction can be suitably selected depending on the reaction temperature, etc., and is usually about 4 to 8 hours. The polymerization reaction is preferably carried out under an inert gas atmosphere (eg nitrogen gas, argon gas).
    [0034] The amount of copolymer (A) in the composition of the present invention is not particularly limited, and is usually from 2 to 50% by mass and preferably from 4 to 25% by mass in relation to the solids content of the composition of the present invention. invention. When the amount of copolymer (A) is 4 to 25% by mass, suitable dissolution rate and coating film properties in seawater can be achieved. Furthermore, the long-term stable surface renewal can remain constant and a desired antifouling effect can be effectively exerted. In addition, the coating film can exert excellent coating performance.
    [0035] The antifouling coating composition of the present invention may further contain, if necessary, an antifouling, a release modifier, a plasticizing agent, and/or other resin, etc., in addition to the copolymer (A). The addition can improve the antifouling effect. antifouling
    [0036] There is no limitation for antifoulings as they have a deadly or repellent effect against aquatic fouling organisms. Examples may include inorganic and organic anti-scalants.
    [0037] Examples of inorganic anti-scalants include cuprous oxide, copper thiocyanate (general name: copper rhodanide), cupronickel, and copper powder. Among them, cuprous oxide and copper rhodanide are particularly preferred.
    [0038] Examples of the organic anti-scalants include: organic copper compounds such as copper 2-mercaptopyridine-N-oxide (general name: copper pyrithione) and the like; organic zinc compounds, such as zinc 2-mercaptopyridine-N-oxide (generic name: zinc pyrithione), zinc ethylene bis(dithiocarbamate) (generic name: zineb), zinc bis(dimethyldithiocarbamate) (generic name: ziram ), dizinc bis(dimethyldithiocarbamate)ethylene-bis(dithiocarbamate) (generic name: polycarbamate) and the like; organic boron compounds such as pyridine-triphenylborane, 4-isopropyl pyridyldiphenylmethylborane, 4-phenyl-pyridyl-diphenylborane, triphenylborane-n-octadecyl amine, triphenyl[3-(2-ethylhexyloxy)propylamine]borane and the like; maleimide compounds such as 2,4,6-trichloromaleimide, N-(2,6-diethylphenyl)-2,3-dichloromaleimide and the like; and 4,5-dichloro-2-n-octyl-3-isothiazolone (general name: Sea-Nine 211), 3,4-dichlorophenyl-NN-dimethylurea (general name: diuron), 2-methylthio-4-t- butylamino-6-cyclopropylamino-s-triazine (general name: Irgarol 1051), 2,4,5,6-tetrachloroisophthalonitrile (general name: chlorothalonyl), N-dichlorofluoromethylthio-N',N'-dimethyl-Np-tolylsulfamide (general name: general: tolylfluanid), N-dichloromethylthio-N',N'-dimethyl-N-phenylsulfamide (general name: dichlofluanid), 2-(4-thiazolyl)benzimidazole (generic name: thiabendazole), 3-(benzo[b]thien -2-yl)-5,6-dihydro-1,4,2-oxathiazine-4-oxide (general name: betoxazin), 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyl pyrrole (generic name: ECONEA 028), etc. Among them, particularly preferred are zinc pyrithione, copper pyrithione, pyridine-triphenylborane, 4-isopropyl-pyridyl-diphenylmethylborane, betoxazine, zineb, Sea-Nine 211, and Irgarol 1051. More preferred are copper pyrithione, zinc, pyridine-triphenylborane, and betoxazine.
    [0039] As an anti-scalant, preferred are copper oxide, copper rhodanide, zinc pyrithione, copper pyrithione, pyridine-triphenylborane, 4-isopropyl-pyridyl-diphenylmethylborane, betoxazine, zineb, Sea-Nine 211, Irgarol 1051, tolylfluanid, and dichlofluanid. More preferred are copper oxide, copper pyrithione, zinc pyrithione, pyridine-triphenylborane, and Sea-Nine 211.
    [0040] These antifoulings can be used alone or in combination.
    [0041] The amount of antifouling in the composition of the present invention is not particularly limited, and is usually from 0.1 to 75% by mass, and preferably from 1 to 60% by mass in relation to the solids content of the composition of the composition. present invention. When the amount of antifouling is less than 0.1% by mass, a sufficient antifouling effect may not be obtained. When the amount of antifouling is more than 75% by mass, the coating film obtained is fragile, and the adhesion of the coating film to the coated object is poor, and therefore, the coating film is not sufficient to exhibit the Function as an anti-fouling coating film. Release Modifier
    [0042] Examples of the release modifier include rosin, a rosin derivative and a metal salt thereof, monocarboxylic acid and a salt thereof, and an alicyclic hydrocarbon resin.
    [0043] Examples of rosin include pine oil rosin, gum rosin and wood rosin. Examples of the rosin derivative include hydrogenated rosin, disproportionate rosin, maleinized rosin, formylated rosin, and polymerized rosin. A reaction product of a metal compound with rosin can be used as a metal salt of rosin or a metal salt of the rosin derivative. Examples of metallic rosin salt include a zinc (or copper) salt of gum rosin, a zinc (or copper) salt of wood rosin, and a zinc (or copper) salt of pine oil rosin. Examples of the metal salt of the rosin derivative include a zinc (or copper) salt of hydrogenated rosin, a zinc (or copper) salt of disproportionate rosin, a salt of zinc (or copper) of maleinized rosin, a salt of zinc ( or copper) of formylated rosin, and a zinc (or copper) salt of polymerized rosin.
    [0044] Examples of the monocarboxylic acid include C5-30 fatty acid, synthetic fatty acid and naphthenic acid. Examples of a monocarboxylic acid salt include copper salts, zinc salts, magnesium salts and calcium salts.
    [0045] Examples of commercially available alicyclic hydrocarbon resin include Quintone 1500, 1525L, and 1700 (product name; manufactured by ZEON CORPORATION).
    [0046] In order to give the composition of the present invention a suitably facilitated elution property, the composition preferably contains at least one member selected from the group consisting of rosin, a rosin derivative, and a metal salt thereof, as a release modifier. . In order to improve breaking strength and water resistance, the composition more preferably contains a copper or zinc salt of rosin or a copper or zinc salt of a rosin derivative.
    [0047] The amount of the release modifying agent in the composition of the present invention is generally from 1 to 400 parts by mass and preferably from 5 to 350 parts by mass with respect to 100 parts by mass of the copolymer (A). When the release modifier is less than 1 part by mass, the effect of preventing attachment of aquatic fouling organisms, in particular during framing, cannot be expected. plasticizer
    [0048] By adding plasticizer in the antifouling coating composition of the present invention, it is possible to improve the plasticity of the composition and, as a result, it is possible to form a suitable strong coating film.
    [0049] Examples of the plasticizer include: phosphate esters such as tricresyl phosphate, trioctyl phosphate, triphenyl phosphate and the like; phthalate esters such as dibutyl phthalate, dioctyl phthalate and the like; adipate esters such as dibutyl adipate, dioctyl adipate and the like; sebacate esters such as dibutyl sebacate, dioctyl sebacate and the like; epoxidized and fatty oils such as soybean oil epoxidized, linseed oil epoxidized and the like; alkyl vinyl ether polymers, such as a methyl vinyl ether polymer, an ethyl vinyl ether polymer, and the like; similar polyalkylene glycols; and t-nonylpentasulfide, petroleum jelly, polybutene, tris(2-ethyl hexyl) trimellitate, silicone oil, liquid paraffin and chlorinated paraffin. These plasticizers can be used alone or in combination.
    [0050] The amount of plasticizer in the composition of the present invention is usually from 0.1 to 100 parts by mass and preferably from 0.5 to 90 parts by mass with respect to 100 parts by mass of the copolymer (A). other resin
    [0051] Another resin is added to the antifouling coating composition of the present invention. This makes it possible to reduce the cost without impairing the effects of the present invention. Furthermore, a synergistic effect with the resin properties can be obtained.
    [0052] Examples of another resin include a methacrylic resin, an alkyd resin, a polyester resin, a chlorinated rubber resin and a vinyl resin.
    [0053] The other resin can be added to the composition of the present invention to such a degree that the proper dissolution rate and properties of the coating film in seawater are not impaired. Their amount is from 1 to 300 parts by mass and preferably from 10 to 250 parts by mass with respect to 100 parts by mass of the copolymer (A). Other Additives
    [0054] In addition, the antifouling coating composition of the present invention, if necessary, may include a pigment, a dye, an antifoam agent, an anti-sag agent, a dispersant, an anti-settling agent, a dehydrating agent and/or an organic solvent to such a degree that the proper dissolution rate and properties of the coating film in seawater are not impaired.
    [0055] Example pigment includes zinc oxide, red iron oxide, talc, titanium oxide, silica, calcium carbonate, barium sulfate, calcium oxide and magnesium oxide. They can be used individually or in combination.
    [0056] Examples of the dye include various types of organic dyes soluble in an organic solvent.
    [0057] Examples of the defoaming agent include a silicone resin-based defoaming agent and an acrylic resin-based defoaming agent.
    [0058] Examples of the anti-sag agent, dispersing agent or anti-settling agent include fatty acid starch wax and oxidized polyethylene.
    [0059] Examples of the dehydrating agent include an adsorbent based on synthetic zeolite, orthoesters, silicates such as tetraethoxysilane, and isocyanates. They can be used individually or in combination.
    [0060] Examples of organic solvents include solvents such as an aliphatic solvent, an aromatic solvent, a ketone-based solvent, an ester-based solvent, and an ether-based solvent, which are commonly used in anti-coating material. -encrustation. They can be used individually or in combination. Method for Producing the Antifouling Coating Composition
    [0061] The antifouling coating composition of the present invention can be manufactured, for example, by mixing and dispersing a mixed solution containing the copolymer (A) and, for example, an antifouling, a release modifier, a plasticizer and/or other resin through the use of a disperser.
    [0062] The mixed solution is preferably obtained by dissolving or dispersing various materials (for example, the copolymer (A) and an antifouling, a release modifier, a plasticizer and/or other resin) in a solvent. As the solvent, a solvent identical or similar to the above organic solvent can be used.
    [0063] As a disperser, for example, one that can be used properly can be a micro-spray. For example, a commercially available homo mixer, sand mill, ball mill, or the like can be used. In addition, the mixed solution can be mixed and dispersed using a vessel equipped with an agitator containing glass beads for mixing and dispersing. Antifouling Treatment, Antifouling Coating Film and Coated Object
    [0064] The antifouling treatment of the present invention is characterized in that an antifouling coating film is formed using the above explained antifouling coating composition on the surface of an object that is subjected to the coating. The antifouling treatment of the present invention can prevent the adhesion of aquatic fouling organisms by gradually dissolving the surface of the antifouling coating film such that the surface of the coating film is continuously renewed. After dissolution of the coating film, fouling can be continuously displayed by coating the composition.
    [0065] Examples of objects on which the coating film can be formed include ships (especially ship bottoms), fishing implements, and structures submerged in seawater. Examples of fishing implements include fishing nets for use in aquaculture or fixed net and fishing net accessories such as ropes and floats attached to fishing nets. Examples of structures submerged in seawater include power plant aqueducts, bridges and port facilities.
    [0066] The antifouling coating film can be formed by applying the antifouling coating composition to the surface (fully or partially) of an object on which the coating film is to be formed.
    [0067] Examples of the coating method include brush coating, spray coating, dip coating, flow coating, and spin coating. These coating methods can be used alone or in combination.
    [0068] The coating composition is dried after application. The drying temperature can be room temperature. Drying time can be suitably selected depending on coating film thickness, etc.
    [0069] The antifouling coating film produced using the above antifouling coating composition according to an embodiment of the present invention can exhibit adequate dissolution rate and coating film properties in seawater. Furthermore, the long-term stable surface renewal can remain constant and a desired antifouling effect can be effectively exerted. Furthermore, the coating film can advantageously exert excellent coating performance.
    [0070] The thickness of the antifouling coating film can be properly selected depending on the types of object on which the coating film is to be formed, the sailing speed of a ship, the temperature of sea water, etc. For example, when the object on which a coating film is formed is a ship's bottom, the thickness of the antifouling coating film is generally 50 to 500 μm, and preferably 100 to 400 μm.
    [0071] The antifouling coating film of the present invention has adequate hardness. Specifically, the antifouling coating film of the present invention has sufficient hardness not to cause defects in the coating film, such as cold flow.
    [0072] The coated object of the present invention has the antifouling coating film on its surface. The coated object of the present invention may have the antifouling coating film over the entire surface thereof or over a partial surface thereof.
    [0073] The coated object of the present invention is provided with a coating film having long-term stable surface renewal and excellent coating performance, due to the proper dissolution rate and the properties of the coating film in seawater being improved. . Therefore, the coated object can preferably be applied to the above ships (in particular, the bottom of the ship), fishing implements, structures submerged in sea water, etc. For example, when the antifouling coating film is formed on the bottom surface of the ship, the antifouling coating film gradually dissolves from the surface, so that the surface of the coating film is always renewed. This prevents the adhesion of aquatic fouling organisms. Furthermore, the rate of hydrolysis of the antifouling coating film is desirably controlled. Thus, ships benefit from the anti-fouling effect for a long period of time. Furthermore, even when ships are not moving, for example during mooring, rigging, etc., the adhesion and accumulation of aquatic fouling organisms is poorly observed and the antifouling effect is exhibited for a long time.
    [0074] In addition, the surface of the anti-fouling coating film is basically free from cracking or peeling even after a long period of time. Therefore, it is not necessary to completely remove the existing coating film before forming a new coating film. Thus, by directly coating the antifouling coating film composition, the antifouling coating film can be formed effectively. This makes it possible to continuously maintain the antifouling effect in a simple and inexpensive way. Examples
    [0075] Examples, etc., and other illuminating features of the present invention are illustrated below. The present invention, however, is not limited to these Examples.
    [0076] In each of the Production Examples, Production Comparative Examples and Comparative Examples, "%" means "% by mass". Viscosity was determined at 25°C using a Brookfield viscometer. The average molecular weight (Mw) was determined by gel permeation chromatography (GPC) (using a polystyrene standard). GPC was performed under the following conditions: Equipment: HLC-8220 GPC; Tosoh Corporation Pre-column: TSK Super HZ-L guard column (manufactured by Tosoh Corporation) Column: TSK-gel Super HZM-M 4.6 mm I.D. 15 cm (manufactured by Tosoh Corporation); two columns connected in series Flow rate: 0.35 mL/min Detector: RI Column thermostat temperature: 40 °C Developer solvent: THF (special grade chemical; manufactured by Wako Pure Chemical Industries, Ltd.) Sample concentration: 10 g/L Input quantity: 3 μl
    [0077] Viscosity was determined with a Brookfield rotary viscometer at 25°C in accordance with JIS7117-1.
    [0078] The non-volatile content was determined by heating for 1 hour at 125 °C.
    [0079] The amounts of each component presented in the Tables are represented in grams. Production of Copolymer Solution Production Example 1 (Production of Copolymer Solution A-1)
    [0080] Initially, 170 g of xylene was loaded into a stainless steel reaction tank equipped with a thermometer, a cooler, an agitator and a drip funnel. Then, a mixture of 270 g of triisopropylsilyl methacrylate, 50 g of methyl methacrylate, 130 g of 2-methoxyethyl methacrylate, 30 g of 2-methoxyethyl acrylate, 20 g of n-butyl acrylate, and 2 g of 1,1,3,3-tetramethylbutylperoxy-2-ethyl hexanoate (initially added) was added dropwise into the reaction tank over a period of 2 hours, while nitrogen gas was injected and the mixture was stirred at 85 ± 5 °C. Then, after the resulting reaction solution was stirred at the above temperature for 1 hour, 1 g of 1,1,3,3-tetramethylbutylperoxy-2-ethyl hexanoate (subsequently added) was added three times at 1 hour intervals. to complete the polymerization reaction. After that, 330 g of xylene was added and dissolved to produce the A-1 copolymer solution.
    [0081] Table 1 shows the viscosity, non-volatile content, Mw, and glass transition temperature of A-1. Production Examples 2 to 22 and Comparative Production Examples 1 to 11 (Production of Copolymer Solutions A-2 to A-22 and B-1 to B-11)
    [0082] Polymerization reactions were carried out according to the same procedure as in Production Example 1, using the monomers, polymerization initiators, and solvents shown in Tables 1 to 3. Copolymer solutions A-2 to A- 22 and B-1 to B-11 were thus obtained. Tables 1 to 3 show the viscosity, non-volatile content, Mw, and glass transition temperature of each of these copolymer solutions.
    [0083] When 1,1,3,3-tetramethylbutylperoxy-2-ethyl hexanoate or 1,1,3,3-tetramethylbutylperoxide neodecanoate was used among the polymerization initiators shown in Tables 1 to 3, the end of the polymer chain had a group represented by the chemical formula (2) and/or a group represented by the chemical formula (3). However, when a polymerization initiator other than those mentioned above is used, the terminus of the polymer chain has a group having another structure. This terminal structure difference appears to cause a difference between the evaluation results relative to Test Examples 2 to 4.
    [0084] The terminus of each of the copolymers obtained in Production Examples 1 to 22 was determined by measuring a spectrum with respect to the 13C single pulse with 1H decoupling and a spectrum at 13C-DEPT135.
    [0085] NMR analysis was performed under the following conditions. Equipment: ECX400; JEOL RESONANCE Inc. Probe: ROYAL probe Rotation angle: 30 degrees Pulse hold time: 20 sec Number of integrations: 10,000 times
    [0086] Figures 1(a) and (b) each show an NMR spectrum obtained with respect to the copolymer of Production Example 1. FIG. 1(a) shows a spectrum with respect to "13C-DEPT135". FIG. 1(b) shows a spectrum with respect to the "13C single pulse with 1H decoupling". Comparison between Figures 1(a) and 1(b) reveals that a group of signals between 44 ppm and 49 ppm was assigned to a quaternary carbon. In addition, the spectrum obtained was analyzed using the "Prediction" function of the ACD software (ie, the NMR analysis software marketed by FUJITSU Inc.). As shown in FIG. 2 , each of the peaks at or near 47 ppm and each of the peaks at or near 45 ppm includes a plurality of peaks. The peak at 47.07 ppm was found to be attributed to chemical formula (2). The peak at 44.97 ppm was found to be attributed to chemical formula (3). Note that it is postulated that the peaks assigned to neither of the chemical formulas (2) nor (3) are assigned to a quaternary carbon present in the main chain of the copolymer. The NMR spectrum of each of the copolymers of Production Examples 2 to 22 was analyzed under the same conditions. Likewise, the analysis demonstrated the peaks attributed to chemical formulas (2) and (3). [Table 1]











    [0087] Product name "VeoVa 9": C9 vinyl ester (manufactured by Momentive Inc.)
    [0088] Product name "Nyper BMT-K40": a mixture of di-(2-methyl benzoyl peroxide), benzoyl peroxide (3-methyl benzoyl), and dibenzoyl peroxide (manufactured by NOF CORPORATION)
    [0089] Note that the stabilizers shown in Table 4 were added to various monomers shown in Tables 1 to 3 and the resulting mixtures were used. [Table 4] Table 4 (Stabilizer)

    Test Example 1 (Repeated Production Test)
    [0090] Batch production of each of copolymer solutions A-1 to A-22 was repeated 300 times as obtained in Production Examples 1 to 22. Gel materials were visually unrecognizable on the inside wall of the reaction tank , etc.
    [0091] The production of each of the copolymer solutions B-1 to B-11 was repeated as obtained in Comparative Production Examples 1 to 11. Gel materials were observed on the inside wall of the reaction tank, etc. Tables 1 to 3 show the number of batches in which gel materials were observed.
    [0092] This demonstrates that production according to the method of the present invention does not result in the generation of gel materials even if the production is repeated. Example 2 (Water Resistance Test)
    [0093] Each of the copolymers (A-1 to A-22 and B-1 to B-11) as obtained in Production Examples 1 to 22 and Comparative Production Examples 1 to 11 was applied onto a dark glass surface ( 100 x 200 x 2 mm) to form a dry film with a thickness of about 100 μm. The applied coating was dried for 3 days at 50°C, such that a test piece was prepared with the dry film having a thickness of about 100 μm. The test piece was immersed in natural seawater at 35°C for 6 months. Then, the condition of the coating film was visually inspected.
    [0094] A: The coating film does not change. B: The coating film becomes cloudy. C: the coating film turns white. D: The coating film is swollen.
    [0095] The results are shown in Tables 1 to 3.
    [0096] It can be seen from Tables 1 to 3 that the dry films formed using the copolymers (A-1 to A-22) as obtained in Production Examples 1 to 22 of the present invention have excellent water resistance. Production of Coating Compositions Examples 1 to 22 and Comparative Examples 1 to 11 (Production of Coating Compositions)
    [0097] The components indicated in Tables 5 to 7 were mixed in the proportions (% by mass) shown in Tables 5 to 7, and were mixed and dispersed together with glass spheres with a diameter of 1.5 to 2.5 mm to produce the coating compositions.
    [0098] Solution containing a zinc salt of gum pitch: the one prepared in Production Example 23 was used.
    [0099] Solution containing a hydrogenated pitch zinc salt: the one prepared in Production Example 24 was used.
    [00100] Gum Pitch-Containing Solution: A xylene solution containing, as a solids content, about 60% Gum Pitch (WW) made in China.
    [00101] Solution containing hydrogenated rosin: a xylene solution containing, as a solids content, about 60% "Highpale CH" (product name).
    [00102] Epoxidized Soybean Oil: Product name "Sansocizer E-2000H" (manufactured by New Japan Chemical Co., Ltd.).
    [00103] Chlorinated Paraffin: Product name "TOYOPARAX 150" (manufactured by Tosoh Corporation).
    [00104] Acrylic polymer: product name "UP-1000" (with a viscosity: 1000 mPa^s, Mw: 3000, Tg: -77 °C, and solid content: >98%) (Manufactured by TOAGOSEI CO, LTD).
    [00105] Styrene Acrylic Polymer: Product name "UF-5022" (flakes; with an Mw: 14,000, Tg: 75 °C, and solid content: >96%) (Manufactured by TOAGOSEI CO, LTD.) .
    [00106] Cuprous oxide: Product name "NC-301", with an average particle size of 3 μm (manufactured by Nissin Chemco, Ltd.)
    [00107] Copper pyrithione: Product name "copper Omadine" (manufactured by Arch Chemicals, Inc.).
    [00108] 4,5-Dichloro-2-n-octyl-4-isothiazoline-3-one: product name "Sea-Nine 211" (Rohm & Haas, Inc.) with a solid content of 30% by weight .
    [00109] Red Iron Oxide: Product name "TODA COLOR EP-13D" (manufactured by Toda Pigment Corp.).
    [00110] Talc: Product name "Crown Talc 3S" (manufactured by MATSUMURA Industries Co., Ltd.).
    [00111] Zinc Oxide: Product name "Type II Zinc Oxide" (manufactured by Seido Chemical Industry Co., Ltd.).
    [00112] Titanium Oxide: Product name "FR-41" (manufactured by FURUKAWA CO., LTD.).
    [00113] Tetraethoxysilane: a special grade chemical, manufactured by Kishida Chemical Co., Ltd.
    [00114] Starch-based fatty acid thixotropic agent: product name "Dispalon A603-20X" (manufactured by Kusumoto Chemicals, Ltd.). Production Example 23 (Production of xylene solution containing gum rosin zinc salt)
    [00115] Initially, 240 g of Chinese-made gum pitch (WW) and 240 g of xylene were added to a 1 liter flask equipped with a thermometer, a reflux condenser, and a stirrer, and 120 g were further added. of zinc oxide to these, such that all the resin acids in the gum pitch formed zinc salts. Then, the mixture was dehydrated under reflux at 70 to 80°C for 3 hours. Thereafter, the mixture was cooled and filtered to obtain the xylene solution containing a zinc salt of gum rosin (a clear dark brown solution; solids content: about 60%). The resulting xylene solution had a non-volatile content of 60.5%. Production Example 24 (Production of xylene solution containing Hydrogenated Pitch Zinc Salt)
    [00116] Initially, 240 g of Highpale CH (hydrogenated pitch) and 240 g of xylene were added to a 1 liter flask equipped with a thermometer, a reflux condenser, and a stirrer, and 120 g of sodium oxide were added. zinc to these, such that all the resin acids in the hydrogenated pitch formed zinc salts. Then, the mixture was dehydrated under reflux at 70 to 80°C for 3 hours. Thereafter, the mixture was cooled and filtered to obtain the xylene solution containing a hydrogenated pitch zinc salt (a clear dark brown solution; solids content: about 60%). The resulting xylene solution had a non-volatile content of 60.6%.Table 5







    Test Example 3 (Rotating Test)
    [00117] A tank was provided having, in the center thereof, a rotating drum having a diameter of 515 mm and a height of 440 mm to allow the rotation of the drum by means of a motor. The tank was also provided with a cooling device to keep the seawater temperature constant, and an automatic pH controller to keep the seawater pH constant.
    [00118] Two test plates were prepared for each coating composition according to the following method.
    [00119] First, an anti-corrosion coating film was formed by applying an anti-corrosion coating material (an epoxy vinyl based A/C) onto a titanium plate (71 x 100 x 0.5 mm) so so that the thickness after drying could be about 100 μm, followed by drying. Each of the anti-fouling coating compositions obtained in Examples 1 to 22 and Comparative Examples 1 to 11 was applied on the anti-fouling coating film so that the thickness after drying could be about 300 μm. The applied coating was dried for 3 days at 40°C, so that the test plate was prepared having the dry coating film with a thickness of about 300 μm.
    [00120] One of the test plates thus prepared was fixed to the rotating drum of the rotating apparatus of the aforementioned equipment and was placed to be in contact with sea water, and the rotating drum was rotated at a speed of 10.2889 m/ sec (20 knots). During the test, the seawater temperature was maintained at 25 °C and the pH at 8.0 to 8.2; sea water was replaced once a week.
    [00121] The initial coating film thickness and the remaining coating film thickness, as measured every 3 months from the start of the test, were determined using a laser focus shift meter for each breadboard, and the dissolved coating film thickness was calculated from the difference between them to give the amount of coating film dissolution per month (μm/m0s). The measurement was carried out for 24 months and the amount of dissolution of the coating film was calculated every 12 months.
    [00122] After the rotary test was completed (after 24 months), the test plate was dried, and the surface of each coating film was visually inspected to assess the condition of the coating film.
    [00123] The status has been evaluated as follows: A: no defects are observed. B: fine cracks were slightly observed. C: Fine cracks are observed on the entire surface of the coating film. D: Defects are observed in the coating film, such as large cracks, blisters or flaking.
    [00124] The results are shown in Tables 5 to 7. It can be seen from Tables 5 to 7 that the coating films formed using the coating compositions of the present invention (Examples 1 to 22) are dissolved in seawater in an amount of about 2 to 5μm per month (annual average). Furthermore, coating films formed using the coating compositions of the present invention are excellent in water resistance, and fine cracks or cracks do not develop. In this way, the anti-fouling effect can be maintained for a long time. Coating films formed using the coating compositions of Examples 4 to 5, 9 to 11, 15 to 16 and 20 to 22 developed neither cracks nor fine cracks, although low molecular weight copolymers were used.
    [00125] In contrast, coating films formed using the coating compositions of Comparative Examples 1 to 11 developed coating film defects, such as cracking or peeling, after a long period of time had elapsed, due to copolymers being used. low molecular weight. That is, the above coating films cannot exhibit the anti-fouling effect for a long time. Test Example 4 (Anti-fouling Test)
    [00126] Each of the coating compositions obtained in Examples 1 to 22 and Comparative Examples 1 to 11 was applied to both surfaces of a rigid vinyl chloride board (100 x 200 x 2 mm) in such a way that the thickness of a dry coating film could be about 200 μm. The applied coating was dried for 3 days at room temperature (25°C), such that the test plate was prepared having the dry coating film with a thickness of about 200 μm. This test plate was immersed 1.5 m below sea level in Owase City, Mie Prefecture, Japan, and the fouling test plate was examined for 12 months, due to the objects adhering.
    [00127] The surface condition of the coating film was visually evaluated according to the criteria below: A: fouling organisms such as crustaceans and algae do not adhere, and the sludge hardly adheres. B: fouling organisms such as crustaceans and algae do not adhere, and sludge adheres finely (to the extent that the surface of the coating film is observable) and sludge can be removed when gently brushing. C: fouling organisms such as crustaceans and algae do not adhere, but sludge adheres densely (insofar as the surface of the coating film is not observable) and the sludge cannot be removed even when cleaned heavily with a brush. D: Encrusting organisms such as crustaceans and algae adhere.
    [00128] The results are shown in Tables 5 to 7. It can be seen from Tables 5 to 7 that fouling organisms such as crustaceans or algae do not adhere and the sludge hardly adheres to the coating films formed using the coating compositions of the present invention (Examples 1 to 22).
    [00129] In contrast, fouling organisms such as crustaceans, algae, and/or sludge adhere, after 12 months of immersion, to coating films formed using the coating compositions of Comparative Examples 1 to 11.
    权利要求:
    Claims (6)
    [0001]
    1. COPOLYMER FOR AN ANTI-FOULING COATING COMPOSITION, characterized in that it comprises a copolymer (A) having, in a side chain, a group represented by the chemical formula (1) and having, at the end, at least one of a group represented by the chemical formula (2) and a group represented by the chemical formula (3), where the chemical formula (1) is
    [0002]
    2. COPOLYMER FOR AN ANTI-FOULING COATING COMPOSITION according to claim 1, characterized in that the copolymer (A) has, at the terminal, both the group represented by the chemical formula (2) and the group represented by the chemical formula (3).
    [0003]
    3. ANTI-FOOTING COATING COMPOSITION characterized in that it comprises the copolymer according to any one of claims 1 or 2 and an anti-fouling.
    [0004]
    4. ANTI-FOULING COATING COMPOSITION according to claim 3, characterized in that it further comprises a selected rosin release modifier, a rosin derivative and a metal salt thereof, monocarboxylic acid and a salt thereof, and a resin of alicyclic hydrocarbon.
    [0005]
    5. METHOD FOR PRODUCTION OF A COPOLYMER of an antifouling coating composition, characterized in that it comprises the steps of: polymerizing an ethylenically unsaturated monomer (a) having a group represented by the chemical formula (1) and an ethylenically unsaturated monomer (b) being different from monomer (a) and copolymerizable with monomer (a) in the presence of a polymerization initiator of 1,1,3,3-tetramethylbutylperoxy-2-ethyl hexanoate or 1,1,3-neodecanoate ,3-tetramethyl butylperoxide, wherein the chemical formula (1) is
    [0006]
    6. COATED OBJECT characterized in that it has, on its surface, an antifouling coating film formed using the antifouling coating composition according to any one of claims 3 or 4.
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    同族专利:
    公开号 | 公开日
    ZA201507759B|2016-12-21|
    JP5747198B2|2015-07-08|
    CN105209561A|2015-12-30|
    HK1212722A1|2016-06-17|
    US20160068688A1|2016-03-10|
    CN105209561B|2019-02-12|
    ES2791750T3|2020-11-05|
    US9624385B2|2017-04-18|
    EP2990450B1|2020-02-19|
    BR112015026458A2|2017-07-25|
    EP2990450A1|2016-03-02|
    JPWO2014175140A1|2017-02-23|
    WO2014175140A1|2014-10-30|
    KR20160002881A|2016-01-08|
    KR102239172B1|2021-04-09|
    SG11201507231SA|2015-10-29|
    EP2990450A4|2016-12-28|
    RU2617351C1|2017-04-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3941027A|1975-05-08|1976-03-02|Lockheed Aircraft Corporation|Fastener system for structural members|
    JP2790021B2|1993-09-30|1998-08-27|日本油脂株式会社|Paint composition|
    JP3874486B2|1996-04-17|2007-01-31|Ｂａｓｆコーティングスジャパン株式会社|Paint composition|
    JP3941027B2|1998-03-30|2007-07-04|関西ペイント株式会社|Batch reactor and polymer production method using the same|
    DE60016112T2|1999-08-27|2005-11-03|Rohm And Haas Co.|Process for the purification of reactors|
    US6722377B1|1999-08-27|2004-04-20|Rohm And Haas Company|Process for cleaning reactors|
    KR20010096248A|2000-04-18|2001-11-07|구자홍|Sensing device for sensing abnormal air conditioner using acoustic emmision|
    EP1260513A1|2001-05-22|2002-11-27|Sigma Coatings B.V.|Process for the preparation of trialkylsilylated carboxylate monomers, the obtained trialkylsilylated carboxylate monomers and their use in antifouling coatings|
    US7553481B2|2002-03-15|2009-06-30|Api Corporation|Underwater antifouling coating composition with excellent storage stability|
    US7297727B2|2002-05-28|2007-11-20|Arkema Inc.|Triarylsilylacryloyl-containing polymers for marine coating compositions|
    US20030225184A1|2002-05-30|2003-12-04|Aubart Mark Anthony|Triarylsilylacryloyl-containing polymers for marine coating compositions|
    JP2007084783A|2005-08-24|2007-04-05|Nippon Shokubai Co Ltd|Curable composition and cured product|
    JP2008291250A|2007-04-27|2008-12-04|Kuraray Co Ltd|Method for producing acrylate-styrene copolymer|
    WO2009001619A1|2007-06-22|2008-12-31|Nitto Kasei Co., Ltd.|Antifouling coating composition, process for producing the composition, antifouling coating film formed from the composition, coated object having the coating film on surface, and method of antifouling treatment by formation of the coating film|
    JP4521589B2|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|
    KR101241747B1|2008-12-19|2013-03-15|닛토 가세이 가부시끼 가이샤|Antifouling coating composition, antifouling coating film formed using the composition, coated object having the coating film on the surface, and method of antifouling treatment by formation of the coating film|
    JP2011175724A|2010-01-26|2011-09-08|Showa Denko Kk|Curing composition for transfer material, and pattern forming method|
    JP5295176B2|2010-05-26|2013-09-18|東洋インキＳｃホールディングス株式会社|Method for producing composition for light scattering film, and light scattering film using the same|
    JP2012005952A|2010-06-24|2012-01-12|Nippon Shokubai Co Ltd|Method of cleaning reaction vessel|
    US8374018B2|2010-07-09|2013-02-12|Crossbar, Inc.|Resistive memory using SiGe material|
    JP4769331B1|2010-08-25|2011-09-07|日東化成株式会社|Antifouling paint composition, copolymer for antifouling paint composition, and coated article having antifouling coating film formed on the surface using the composition|
    US9139741B2|2010-11-25|2015-09-22|Mitsubishi Rayon Co., Ltd.|Antifouling paint composition and antifouling paint|
    CN102718919B|2012-06-29|2014-12-03|华南理工大学|Hydrolyzing-speed-controllable anti-pollution estersil material as well as preparation method and application thereof|US10913861B2|2013-05-10|2021-02-09|Stopaq B.V.|Pipe and pipe support protection process and composition therefor|
    EP3330331B1|2015-07-31|2020-09-02|Chugoku Marine Paints, Ltd.|Antifouling coating material composition, antifouling coating film, antifouling substrate, rosin compound for antifouling coating material composition, and method for manufacturing antifouling coating material composition|
    WO2017051922A1|2015-09-25|2017-03-30|三菱レイヨン株式会社|acrylic copolymer, polymer solution, polymer-containing composition, antifouling coating composition, and method for producing acrylic copolymer|
    CN108307625B|2015-11-30|2020-10-16|中国涂料株式会社|Antifouling composite coating film, antifouling substrate, and method for producing antifouling substrate|
    CN108368376B|2015-11-30|2021-01-01|中国涂料株式会社|Antifouling coating composition, antifouling coating film, antifouling substrate, and method for producing antifouling substrate|
    CN108603069A|2016-01-29|2018-09-28|中国涂料株式会社|Antifouling paint compositions, film and the base material with film|
    US10208198B2|2016-06-10|2019-02-19|Ppg Coatings Europe B.V.|Solventborne binder for an intumescent coating|
    CN111164164A|2017-10-04|2020-05-15|日东化成株式会社|Antifouling coating composition and coated article having antifouling coating film formed on surface thereof|
    KR20200073248A|2017-10-23|2020-06-23|헴펠 에이/에스|Self-polishing type anti-pollution coating composition comprising alkoxysilane|
    GB201718891D0|2017-11-15|2017-12-27|Jotun As|Antifouling composition|
    GB201718899D0|2017-11-15|2017-12-27|Jotun As|Antifouling coating composition|
    JP2021105069A|2018-04-12|2021-07-26|日東化成株式会社|Antifouling coating composition|
    CN111886305A|2018-04-20|2020-11-03|日东化成株式会社|Copolymer for antifouling paint composition, and antifouling paint composition comprising same|
    CN111886304B|2018-04-20|2022-02-01|日东化成株式会社|Antifouling coating composition|
    KR20210002585A|2018-04-20|2021-01-08|닛토 가세이 가부시끼 가이샤|Antifouling paint composition|
    JP6472562B1|2018-07-03|2019-02-20|日本ペイントマリン株式会社|Vehicle resin for antifouling paint composition and antifouling paint composition containing the same|
    GB201813454D0|2018-08-17|2018-10-03|Jotun As|Antifouling composition|
    CN110437689A|2019-08-09|2019-11-12|江苏海晟涂料有限公司|A kind of low-surface-energy environment-friendly type marine antifouling coating|
    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: C09D 143/04 (2006.01), C08F 230/08 (2006.01), C09D |
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    优先权:
    申请号 | 申请日 | 专利标题
    JP2013091623|2013-04-24|
    JP2013-091623|2013-04-24|
    PCT/JP2014/060831|WO2014175140A1|2013-04-24|2014-04-16|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|
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