WO2018092668A1 - Composition de revêtement antisalissure et objet revêtu portant, sur sa surface, un film de revêtement antisalissure formé à partir de ladite composition - Google Patents

Composition de revêtement antisalissure et objet revêtu portant, sur sa surface, un film de revêtement antisalissure formé à partir de ladite composition Download PDF

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Publication number
WO2018092668A1
WO2018092668A1 PCT/JP2017/040377 JP2017040377W WO2018092668A1 WO 2018092668 A1 WO2018092668 A1 WO 2018092668A1 JP 2017040377 W JP2017040377 W JP 2017040377W WO 2018092668 A1 WO2018092668 A1 WO 2018092668A1
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Prior art keywords
coating film
antifouling
meth
group
antifouling coating
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PCT/JP2017/040377
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English (en)
Japanese (ja)
Inventor
大輔 三富
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日東化成株式会社
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Application filed by 日東化成株式会社 filed Critical 日東化成株式会社
Priority to KR1020197016916A priority Critical patent/KR102517197B1/ko
Priority to CN201780070266.5A priority patent/CN109952351B/zh
Priority to JP2018551591A priority patent/JP6954649B2/ja
Publication of WO2018092668A1 publication Critical patent/WO2018092668A1/fr

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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
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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

Definitions

  • the present invention relates to an antifouling coating composition and a coated article having an antifouling coating film formed using the composition on the surface.
  • Aquatic fouling organisms such as barnacles, cell plastics, blue mussels, scallops, sea squirts, blue sea breams, blue sea breams, slime, etc., become submarine structures such as ships (especially ship bottoms), fishing nets, fishing net accessories, etc.
  • Adhering causes problems such as damage to the functions of the ship and the like, and the appearance. Since the ban on the use of conventionally used organotin-containing copolymers, triorganosilyl group-containing copolymers with low toxicity and low environmental impact have been developed and used in antifouling paints (Patent Document 1). .
  • the coating film dissolves at a constant rate in seawater for a long period of time, but the coating film dissolution rate generally tends to be low.
  • the ship is normally operated and has a navigation speed above a certain level, but in situations where the ship's berthing period is prolonged or the navigation speed is reduced due to the recent global economic downturn, The problem that the coating film dissolution rate became too low and the antifouling effect was not sufficiently exhibited came to arise.
  • Various proposals have been made to solve the above problems.
  • an antifouling coating (Patent Documents 2 to 4) containing a highly hydrophilic triorganosilyl ester-containing copolymer using a highly hydrophilic monomer as a constituent monomer of the triorganosilyl ester-containing copolymer,
  • Antifouling paints containing a large amount of dissolution aids such as rosin compounds have been proposed (Patent Documents 5 to 7).
  • the proposed antifouling paint cannot sufficiently improve the dissolution rate of the coating film, and as an adverse effect of excessively increasing the hydrophilicity, the coating film dissolves in a relatively short period of time after being immersed in seawater. Have stopped, or caused deterioration of coating film properties such as cracks.
  • the present invention includes a triorganosilyl ester-containing copolymer capable of maintaining a high coating film dissolution rate in seawater for a long period of time and maintaining stable antifouling performance without causing coating film abnormalities such as cracks.
  • An object is to provide an antifouling paint composition.
  • (A) (a) general formula (1): (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 , R 3, and R 4 are the same or different and each represents an alkyl group or a phenyl group branched from the ⁇ -position of 3 to 6 carbon atoms.
  • An antifouling paint composition is provided.
  • the inventor added a siloxane compound (B) having a specific structure to the triorganosilyl ester-containing copolymer (A) having a specific structure, thereby providing physical properties of the coating film (particularly crack resistance).
  • the present inventors have found that an unexpected effect of significantly improving the coating film dissolution rate, particularly the coating film dissolution rate from the initial stage, can be obtained without impairing the above.
  • the siloxane compound (B) also has an advantageous characteristic that the coating film hardness is not lowered as compared with other coating film dissolution aids.
  • the antifouling coating composition which can form the antifouling coating film which is excellent in storage stability and maintains high antifouling performance over a long period of time is provided.
  • Antifouling paint composition comprises the above triorganosilyl ester-containing copolymer (A) and the above siloxane compound (B).
  • the copolymer (A) of the present invention is obtained by copolymerization of the monomer (a) and the monomer (b).
  • a method for synthesizing the monomer (a), the monomer (b), the copolymer (A), and the like will be specifically described.
  • Examples of the alkyl group branched at the ⁇ -position having 3 to 6 carbon atoms include, for example, isopropyl group, s-butyl group, t-butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1-methylpentyl group, 1, Examples thereof include 1-dimethylpropyl group, 1,1-dimethylbutyl group, texyl group and the like.
  • R 2 , R 3, and R 4 it is possible to form an antifouling coating film that hardly causes coating film abnormality and is excellent in water resistance.
  • R 2 , R 3 and R 4 are the same or different and are preferably an isopropyl group, a s-butyl group, a t-butyl group and a phenyl group, and preferably an isopropyl group. More preferred.
  • Examples of the monomer (a) include triisopropylsilyl (meth) acrylate, tris-butylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, diisopropyl s-butylsilyl (meth) acrylate, (Meth) acrylic acid diisopropyl t-butylsilyl, (meth) acrylic acid diisopropyl texylsilyl, (meth) acrylic acid diisopropylphenylsilyl, (meth) acrylic acid isopropyl dis-butylsilyl, (meth) acrylic acid isopropyl diphenylsilyl, ( Examples thereof include diphenyl hexylsilyl (meth) acrylate and t-butyldiphenylsilyl (meth) acrylate.
  • trimethyacrylic acid triisopropylsilyl, tris-butylsilyl (meth) acrylate, and (meth) acrylic acid are less likely to cause coating film abnormalities and can form antifouling coatings with excellent water resistance.
  • t-Butyldiphenylsilyl is preferred, and triisopropylsilyl (meth) acrylate is more preferred.
  • These (meth) acrylic acid triorganosilyl ester monomers are used alone or in combination of two or more.
  • the monomer (b) is an ethylenically unsaturated monomer copolymerizable with the monomer (a).
  • (meth) acrylic acid esters are particularly preferred.
  • Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (meth) acrylic acid 2-Ethylhexyl and 2-methoxyethyl acrylate are more preferred.
  • the exemplified monomer (b) can be used alone or in combination of two or more as the monomer component of the copolymer (A).
  • Synthetic copolymer (A) of copolymer (A) is obtained by polymerizing a mixture of monomer (a) and monomer (b).
  • the content of the monomer (a) in the mixture is preferably about 20 to 70% by weight, and more preferably about 30 to 60% by weight.
  • the weight average molecular weight (Mw) of the copolymer (A) is preferably 10,000 to 100,000, particularly preferably 20,000 to 70,000.
  • the coating film When the Mw is 10,000 to 100,000, the coating film does not become brittle, and the coating film is moderately dissolved, so that a desired antifouling effect can be effectively exhibited.
  • the method for measuring Mw include gel permeation chromatography (GPC).
  • the copolymer (A) is a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer of the monomer (a) and the monomer (b). It may be.
  • the copolymer (A) can be obtained, for example, by polymerizing the monomer (a) and the monomer (b) in the presence of a polymerization initiator.
  • polymerization initiator used in the polymerization reaction examples include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis-2-methylbutyronitrile, dimethyl-2,2 ′.
  • -Azo compounds such as azobisisobutyrate, benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy 2-ethylhexanoate, Examples thereof include peroxides such as 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate and 1,1,3,3-tetramethylbutylperoxyneodecanoate.
  • polymerization initiators can be used alone or in combination of two or more.
  • examples of the polymerization initiator include AIBN, tert-butylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate or 1,1,3. 1,3-tetramethylbutylperoxyneodecanoate is preferred.
  • the molecular weight of the copolymer A can be adjusted by appropriately setting the amount of the polymerization initiator used. At this time, a chain transfer agent such as mercaptan or ⁇ -methylstyrene dimer can also be used.
  • polymerization method examples include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like.
  • solution polymerization is particularly preferable in that the copolymer (A) can be obtained easily and accurately.
  • an organic solvent may be used as necessary.
  • the organic solvent include aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and methoxypropyl acetate; isopropyl
  • examples include alcohol solvents such as 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.
  • an aromatic hydrocarbon solvent is particularly preferable, and xylene is more preferable. These solvents can be used alone or in combination of two or more.
  • the reaction temperature in the polymerization reaction may be appropriately set according to the kind of the polymerization initiator and the like, and is usually 70 to 140 ° C., preferably 80 to 120 ° C.
  • the reaction time in the polymerization reaction may be appropriately set according to the reaction temperature and the like, and is usually about 4 to 8 hours.
  • the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen gas or argon gas.
  • the content of the copolymer (A) in the composition of the present invention is not particularly limited, but is usually 2 to 50% by mass, preferably 4 to 25% by mass, based on the solid content of the composition of the present invention.
  • the content of the copolymer (A) is 4% by mass to 25% by mass, an appropriate coating film dissolution rate and coating film properties in seawater can be obtained, and stable surface renewability can be maintained over a long period of time. A desired antifouling effect can be exhibited effectively. Moreover, the recoat performance which was excellent in the coating film can be exhibited.
  • the siloxane compound (B) of the present invention is a siloxane compound having an alkoxy group having 1 to 4 carbon atoms and a siloxane skeleton, and the number of Si atoms in the siloxane skeleton is 5 to 100.
  • the number of Si atoms of the siloxane compound (B) is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85. , 90, 95, 100, and may be within a range between any two of the numerical values exemplified here.
  • Each Si in the siloxane skeleton preferably has at least one alkoxy group having 1 to 4 carbon atoms bonded thereto.
  • Each Si in the siloxane skeleton has a plurality of substituents (terminal Si is three substituents, and other Si is two substituents). All of the plurality of substituents are preferably alkoxy groups having 1 to 4 carbon atoms. Two of the plurality of substituents may be an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an alkoxy group having 1 to 4 carbon atoms.
  • the siloxane skeleton may be linear, branched or cyclic.
  • the siloxane compound (B) may contain one kind of compound having a linear, branched or cyclic siloxane skeleton, or may be a mixture containing plural kinds.
  • alkoxy group having 1 to 4 carbon atoms examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy group, and preferably methoxy and ethoxy groups. Furthermore, an ethoxy group is preferable.
  • alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl, etc., preferably methyl, ethyl It is a group.
  • the siloxane compound (B) may include a compound represented by the following general formula (2).
  • R 5 examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl group, and the like, preferably methyl and ethyl group. More preferably, it is an ethyl group.
  • R 6 includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl, phenyl group, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy , T-butoxy group and the like, preferably methyl, ethyl, phenyl, methoxy and ethoxy groups.
  • the siloxane compound (B) of the present invention may be produced, for example, by partially hydrolytic condensation of an organosilicate, or a commercially available product may be used.
  • organosilicate include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraisobutoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyl Tripropoxysilane, methyltriisopropoxysilane, methyltrin-butoxysilane, methyltriisobutoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, phenyltrin-butoxysilane, Trifunctional
  • Examples of commercially available siloxane compounds (B) include MKC silicate MS56, MKC silicate MS57, MKC silicate MS56S (all of which are trade names manufactured by Mitsubishi Chemical Corporation), methyl silicate 53A, ethyl silicate 40, and ethyl silicate.
  • the method for blending the siloxane compound (B) of the present invention into the coating composition is not particularly limited, and it may be blended at the coating dispersion step or at the final step. Alternatively, it may be added to the paint and mixed immediately before painting.
  • the siloxane compound (B) of the present invention is contained in an amount of 0.2 to 5% by mass, particularly preferably 0.5 to 2% by mass in the solid content of the composition of the present invention.
  • the content of the siloxane compound (B) is within the above range, the effect of promoting the dissolution rate of the coating film in the initial stage (before immersion in seawater) is remarkable, and the antifouling coating film after being immersed in seawater for a certain period of time No coating film abnormalities (cracks, etc.) occur.
  • the content ratio of the copolymer (A) and the siloxane compound (B) is, in terms of solid content, a mass ratio (the copolymer (A) / the condensate (B)) of 1 to 75, The effect of promoting the dissolution rate of the coating film in the initial stage (before immersion in seawater) is remarkably exhibited, and when the content ratio is 2.5 to 30, the effect is further exhibited.
  • an antifouling agent (C) In addition to the copolymer (A) and the siloxane compound (B), an antifouling agent (C), an elution regulator (D), and a plasticizer (E ), Other resins (F) and the like can be blended. Thereby, the more outstanding antifouling effect can be exhibited.
  • the antifouling agent (C) is not particularly limited as long as it is a substance having a killing or repelling action against marine fouling organisms.
  • medical agent are mentioned.
  • inorganic agents include cuprous oxide, copper thiocyanate (generic name: rhodan copper), cupronickel, copper powder, and the like. Of these, cuprous oxide and rhodan copper are particularly preferred.
  • organic agents examples include organic copper compounds such as 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione), 2-mercaptopyridine-N-oxide zinc (generic name: zinc pyrithione), zinc ethylenebisdithiocarbamate.
  • organic copper compounds such as 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione), 2-mercaptopyridine-N-oxide zinc (generic name: zinc pyrithione), zinc ethylenebisdithiocarbamate.
  • Organic boron compounds such as triphenylborane, 4-isopropylpyridyl-diphenylmethylborane, 4-phenylpyridyl-diphenylborane, triphenylboron-n-octadecylamine, triphenyl [3- (2-ethylhexyloxy) propylamine] boron ;
  • Maleimide compounds such as 2,4,6-trichloromaleimide and N- (2,6diethylphenyl) 2,3-dichloromaleimide; other 4,4-dichloro-2-n-octyl-3-isothiazolone (generic name) :
  • zinc pyrithione, copper pyrithione, pyridine / triphenylborane, 4-isopropylpyridyl-diphenylmethylborane, betoxazine, dineb, cineine 211 and irgarol 1051 are preferable, and copper pyrithione, zinc pyrithione, pyridine / triphenylborane and betoxazine are more preferable. preferable.
  • Antifouling agents (C) include cuprous oxide, rhodan copper, zinc pyrithione, copper pyrithione, pyridine triphenylborane, 4-isopropylpyridyl-diphenylmethylborane, betoxazine, dinebu, cineine 211 and irgarol 1051, trifluanid, diclofluaniani And cuprous oxide, copper pyrithione, zinc pyrithione, pyridine triphenylborane and betoxazine are more preferred. These antifouling agents can be used alone or in combination of two or more.
  • the content of the antifouling agent (C) in the composition of the present invention is not particularly limited, but 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. is there.
  • medical agent (C) is less than 0.1 mass%, there exists a possibility that sufficient antifouling effect may not be acquired.
  • content of the antifouling agent (C) exceeds 75% by mass, the formed coating film is fragile, and further, the adhesion to the coating film formation is weak, and the function as an antifouling coating film is sufficient. I can't do it.
  • the elution regulator (D) include rosin, rosin derivatives and their metal salts, monocarboxylic acids and salts thereof, or alicyclic hydrocarbon resins.
  • the rosin include tall oil rosin, gum rosin, and wood rosin.
  • the rosin derivative include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin.
  • the metal salt of rosin and the metal salt of rosin derivative a reaction product of a metal compound and rosin can be used.
  • Examples of the metal salt of rosin include gum rosin zinc (or copper) salt, wood rosin zinc (or copper) salt, Examples include tall oil rosin zinc (or copper) salt.
  • metal salts of rosin derivatives hydrogenated rosin zinc (or copper) salt, disproportionated rosin zinc (or copper) salt, maleated rosin zinc (or copper) salt, formylated rosin zinc (or copper) salt, polymerization
  • Examples of the monocarboxylic acid include fatty acids having about 5 to 30 carbon atoms, synthetic fatty acids, and naphthenic acids.
  • Examples of the monocarboxylic acid salt include a copper salt, a zinc salt, a magnesium salt, and a calcium salt.
  • Examples of the alicyclic hydrocarbon resin include Quinton 1500, 1525L, 1700 (trade name, manufactured by Nippon Zeon Co., Ltd.) and the like as commercially available products.
  • the composition of the present invention is at least selected from the group consisting of rosin, rosin derivatives, and metal salts thereof, as an elution regulator (D) in that it can impart moderate elution promoting properties to the composition of the present invention. It is preferable to contain one, and it is particularly preferable to contain a copper salt or a zinc salt of rosin or a rosin derivative from the viewpoint of improving crack resistance and water resistance.
  • the content of the elution regulator (D) in the composition of the present invention is usually 1 to 80 parts by mass, preferably 10 to 50 parts by mass with respect to 100 parts by mass of the copolymer (A).
  • the elution control agent (D) is less than 1 part by mass, the effect of preventing the adhesion of varicella-fouling organisms, particularly the effect of preventing the attachment of varicella-fouling organisms during the outfitting period cannot be expected.
  • the content of the elution regulator (D) exceeds 80 parts by mass, defects such as cracks and peeling are likely to occur in the coating film, and there is a possibility that the effect of preventing the adhesion of waterpox fouling organisms may not be exhibited sufficiently.
  • the content of the elution regulator (D) is, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 with respect to 100 parts by mass of the copolymer (A). , 60, 65, 70, 75, 80 parts by mass, and may be within the range of any two numerical values exemplified here.
  • plasticizer (E) By including the plasticizer (E) in the antifouling coating composition of the present invention, the plasticity of the composition can be improved, and as a result, a tough coating film can be suitably formed.
  • the plasticizer (E) include phosphate esters such as tricresyl phosphate, trioctyl phosphate and triphenyl phosphate, phthalates such as dibutyl phthalate and dioctyl phthalate, dibutyl adipate, dioctyl adipate and the like.
  • Adipic acid esters such as dibutyl sebacate and dioctyl sebacate, epoxidized oils and fats such as epoxidized soybean oil and epoxidized linseed oil, alkyl vinyl ether polymers such as methyl vinyl ether polymer and ethyl vinyl ether polymer Polymers, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, t-nonyl pentasulfide, petrolatum, polybutene, trimellitic acid tris (2-ethylhexyl), liquid paraffin And chlorinated paraffin. These can be used alone or in combination of two or more.
  • the content of the plasticizer (E) in the composition of the present invention is usually 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the copolymer (A).
  • ⁇ Other resins (F)> By containing the other resin (F) in the antifouling coating composition of the present invention, the cost can be reduced without impairing the effects of the present invention, and a synergistic effect with the physical properties of the resin (F). Can be obtained.
  • the other resin (F) include (meth) acrylic resin, alkyd resin, polyester resin, chlorinated rubber resin, vinyl resin and the like.
  • Other resin (F) in the composition of this invention can be contained in the range by which the moderate coating-film dissolution rate and coating-film physical property in seawater are not impaired,
  • the content is a copolymer ( A) 1 to 200 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight.
  • the antifouling coating composition of the present invention contains, as necessary, pigments, dyes, antifoaming agents, anti-sagging agents, dispersants, anti-settling agents, dehydrating agents, organic solvents, etc. It can be added within a range where the coating film dissolution rate and coating film physical properties are not impaired.
  • the antifouling paint composition of the present invention is prepared, for example, by mixing and dispersing a mixed liquid containing a siloxysan compound (B) using a disperser or a siloxane compound (B). It can manufacture by adding and mixing a siloxane compound (B) at the last process, after mixing and dispersing the liquid mixture containing other than using a disperser. Or you may manufacture by adding and mixing a siloxysan compound (B) just before coating.
  • the contents of the copolymer (A) and the siloxane compound (B) in the mixed solution are the contents of the copolymer (A) and the siloxane compound (B) in the antifouling coating composition, and What is necessary is just to adjust suitably so that it may become a content rate.
  • the disperser for example, one that can be used as a fine pulverizer can be suitably used.
  • a commercially available homomixer, sand mill, bead mill or the like can be used.
  • the mixed solution may be mixed and dispersed using a container provided with a stirrer to which glass beads for mixing and dispersing are added.
  • Antifouling treatment method, antifouling coating film , and coated article forms an antifouling coating film on the surface of a coating film-forming article using the antifouling coating composition.
  • the antifouling coating film gradually dissolves from the surface and the coating film surface is constantly renewed, thereby preventing the adhesion of chickenpox fouling organisms.
  • the antifouling effect can be exhibited continuously by overcoating the said composition. Examples of the coating film formation include ships (particularly ship bottoms), fishing equipment, underwater structures, and the like.
  • the fishery tools include aquaculture or stationary fishing nets, fishing net accessories such as floats and ropes used in the fishing nets, and the like.
  • Examples of the underwater structure include a power plant conduit, a bridge, a port facility, and the like.
  • the antifouling coating film can be formed by applying the antifouling coating composition to the surface (entirely or partly) of the coating film forming article.
  • Examples of the application method include brush coating, spraying, dipping, flow coating, and spin coating. These may be used alone or in combination of two or more. After application, dry.
  • the drying temperature may be room temperature. What is necessary is just to set drying time suitably according to the thickness etc. of a coating film.
  • the antifouling coating film of the present invention formed using the antifouling coating composition exhibits an appropriate coating film dissolution rate and coating film properties in seawater, and can maintain a stable surface renewability over a long period of time.
  • the desired antifouling effect can be effectively exhibited.
  • it has the advantage that the outstanding recoat performance of a coating film can be exhibited.
  • What is necessary is just to set the thickness of an antifouling coating film suitably according to the kind of coating-film formation thing, the navigation speed of a ship, seawater temperature, etc.
  • the thickness of the antifouling coating film is usually 50 to 500 ⁇ m, preferably 100 to 400 ⁇ m.
  • the antifouling coating film of the present invention has an appropriate hardness. That is, the antifouling coating film of the present invention has a hardness that does not cause coating film abnormality such as cold flow.
  • the coated article of the present invention has the antifouling coating film on the surface.
  • the coated product of the present invention may have the antifouling coating film on the entire surface or a part thereof. Since the coated product of the present invention has a coating film excellent in long-term stable surface renewability and recoatability by improving an appropriate coating film dissolution rate and coating film properties in seawater, In particular, it can be suitably used as ship bottoms), fishing equipment, underwater structures and the like.
  • the antifouling coating film when the antifouling coating film is formed on the ship bottom surface of the ship, the antifouling coating film gradually dissolves from the surface, and the coating film surface is constantly renewed, thereby preventing adhesion of waterpox fouling organisms. it can. Moreover, the hydrolysis rate of the antifouling coating film is suitably suppressed. Therefore, the ship can maintain antifouling performance for a long period of time. For example, even in a stationary state such as during berthing or during outfitting, there is little adhesion and accumulation of Minamata fouling organisms, and the antifouling effect can be exhibited for a long period of time.
  • the antifouling coating on the surface is basically free from cracks or peeling. Therefore, it is not necessary to perform another operation such as forming a coating film after the coating film is completely removed. Therefore, an antifouling coating film can be suitably formed by directly overcoating the antifouling coating film composition. Thereby, it is possible to easily and continuously maintain the antifouling performance at a low cost.
  • % In each production example, comparative production example, example and comparative example represents mass%.
  • the viscosity is a measured value at 25 ° C., and is a value determined by a B-type viscometer.
  • the weight average molecular weight (Mw) is a value (polystyrene conversion value) determined by GPC.
  • the conditions of GPC are as follows. Equipment: HLC-8220GPC manufactured by Tosoh Corporation Column: TSKgel SuperHZM-M (Tosoh Corporation) 2 flow rate: 0.35 mL / min Detector ... RI Column thermostatic chamber temperature: 40 ° C Eluent: THF
  • the heating residue is a value obtained by heating at 125 ° C. for 1 hour.
  • the unit of the compounding quantity of each component in Table 1 is g.
  • a triorganosilyl ester-containing copolymer solution A-1 was obtained by adding and dissolving 300 g of xylene.
  • the viscosity of the obtained copolymer solution was 450 cps / 25 ° C., the heating residue was 49.8%, and the Mw was 51,000.
  • Production Example 2 (Production of copolymer solution A-2) A flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel was charged with 170 g of xylene and stirred at 85 ⁇ 5 ° C. in a nitrogen atmosphere, with 300 g of triisopropylsilyl acrylate, 130 g of methyl methacrylate, and mecrylic acid. A mixture of 20 g of 2-methoxyethyl, 20 g of n-butyl acrylate, 30 g of i-butyl methacrylate and 4 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added over 2 hours.
  • Production Example 3 (Production of copolymer solution A-3) A flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was charged with 200 g of xylene and stirred at 85 ⁇ 5 ° C. in a nitrogen atmosphere, while 270 g of triisopropylsilyl methacrylate, 160 g of methyl methacrylate, acrylic acid A mixed solution of 20 g of n-butyl, 50 g of n-butyl methacrylate and 6 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added dropwise over 2 hours.
  • Triorganosilyl ester-containing copolymer solution A-3 was obtained by adding and dissolving 300 g of xylene.
  • the viscosity of the obtained copolymer solution was 440 cps / 25 ° C., the heating residue was 50.3%, and the Mw was 50,500.
  • Production Example 4 (Production of copolymer solution A-4) A flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel was charged with 350 g of xylene and stirred at 85 ⁇ 5 ° C.
  • Examples 1 to 6 and Comparative Examples 1 to 7 Manufacture of coating compositions
  • the components shown in Table 1 were blended in the proportions (mass%) shown in Table 1, and mixed and dispersed with glass beads having a diameter of 1.5 to 2.5 mm to produce a coating composition.
  • the details of each component in Table 1 are as follows.
  • Gum rosin zinc salt solution used in Production Example 5
  • Gum rosin solution Chinese gum rosin (WW) about 60% solid content xylene solution
  • Cuprous oxide Trade name “NC-301” (manufactured by Nisshin Chemco) Copper pyrithione: Trade name “Copper Omagine” (manufactured by Arch Chemical Co., Ltd.) Bengala: Trade name “TODA COLOR EP-13D” (manufactured by Toda Pigment Corporation)
  • Talc Trade name “Crown Talc 3S” (Matsumura Sangyo Co., Ltd.)
  • Zinc oxide Trade name “Zinc oxide 2 types” (manufactured by Shodo Chemical Co., Ltd.) Titanium oxide: Trade name “FR-41” (Furukawa Machine Metal Co., Ltd.)
  • Fatty acid amide thixotropic agent Trade name “Disparon A603-20X” (manufactured by Enomoto Kasei Co., Ltd
  • Test Example 1 (Rotary test) A rotating drum having a diameter of 515 mm and a height of 440 mm was attached to the center of the water tank so that it could be rotated by a motor. In addition, a cooling device for keeping the temperature of the seawater constant and an automatic pH controller for keeping the pH of the seawater constant were attached. A test plate was prepared according to the following method. First, on a titanium plate (75 x 150 x 0.5 mm), a rust preventive paint (epoxy vinyl A / C) is applied so that the thickness after drying is about 100 ⁇ m and dried to form a rust preventive coating. did.
  • a rust preventive paint epoxy vinyl A / C
  • the coating compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 7 were applied on the rust preventive coating so that the thickness after drying was about 300 ⁇ m.
  • the obtained coated material was dried at 40 ° C. for 3 days to prepare a test plate having a dry coating film having a thickness of about 300 ⁇ m.
  • One of the produced test plates was fixed to the rotating drum of the rotating device of the apparatus so as to contact seawater, and the rotating drum was rotated at a speed of 20 knots. Meanwhile, the temperature of the seawater was kept at 25 ° C. and the pH was kept at 8.0 to 8.2, and the seawater was changed every week.
  • each test plate is measured with a laser focus displacement meter at the initial stage and every 3 months after the start of the test, and the dissolved film thickness is calculated from the difference ( ⁇ m / month ) In addition, the said measurement was performed for 24 months and the said coating-film melt
  • Test example 2 (antifouling test) The coating compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 7 were applied on both sides of a hard PVC plate (100 ⁇ 200 ⁇ 2 mm) so that the thickness as a dry coating film was about 200 ⁇ m. The obtained coated material was dried at room temperature (25 ° C.) for 3 days to prepare a test plate having a dry coating film having a thickness of about 200 ⁇ m. This test plate was immersed in 1.5 m below the sea surface in Owase City, Mie Prefecture, and the test plate was observed for contamination by deposits after 12 months and 24 months. Evaluation was performed by visually observing the state of the coating film surface, and was judged according to the following criteria.
  • A There is no adhesion of fouling organisms such as shellfish and algae, and there is almost no slime.
  • ⁇ Level at which fouling organisms such as shellfish and algae do not adhere, and slime is thin (appreciable to the surface of the paint film) but can be gently wiped with a brush. [Delta]: No fouling organisms such as shellfish and algae adhere, but the slime is so thick that the surface of the coating cannot be seen and cannot be removed even if wiped with a brush.
  • ⁇ Level at which fouling organisms such as shellfish and algae adhere
  • Example 1 the coating films formed using the coating compositions of the present invention (Examples 1 to 6) were more effective in seawater than the coating films formed using the coating compositions of Comparative Examples 1 to 7.
  • the dissolved amount is maintained high in any period, and the state of the dried coating film after the end of the rotary test (after 24 months) is generally good without causing large cracks.
  • the coating films formed using the coating compositions of Comparative Examples 1 to 7 have a low dissolution amount in seawater as a whole, or some of the dissolution amount disappears after the latter half. In some cases, cracks occur in the coating film or in the antifouling test, it is impossible to prevent the attachment of fouling organisms over a long period of time, and the performance cannot be balanced.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition de revêtement antisalissure contenant un copolymère d'ester de triorganosilyle, la composition donnant un film de revêtement qui conserve un taux de dissolution élevé dans l'eau de mer pendant une longue période et peut conserver des performances antisalissure stables sans souffrir d'aucune anomalie telle que des craquelures. La composition de revêtement antisalissure selon la présente invention comprend (A) un copolymère d'ester de triorganosilyle obtenu à partir d'un mélange de (a) un monomère (méth)acrylate de triorganosilyle représenté par la formule générale (1) avec (b) un monomère à insaturation éthylénique copolymérisable avec le monomère (méth)acrylate de triorganosilyle et (B) un composé siloxane comprenant un groupe alcoxy C1-4 et un squelette siloxane (le squelette siloxane ayant de 5 à 100 atomes de Si). (Dans la formule (1),R1 représente un atome d'hydrogène ou un groupe méthyle, et R2, R3, et R4 sont identiques ou différents et représentent chacun un groupe alkyle C3-6 ramifié en position α ou un groupe phényle).
PCT/JP2017/040377 2016-11-17 2017-11-09 Composition de revêtement antisalissure et objet revêtu portant, sur sa surface, un film de revêtement antisalissure formé à partir de ladite composition WO2018092668A1 (fr)

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CN201780070266.5A CN109952351B (zh) 2016-11-17 2017-11-09 防污涂料组合物、在表面具有利用该组合物形成的防污涂膜的涂装物
JP2018551591A JP6954649B2 (ja) 2016-11-17 2017-11-09 防汚塗料組成物、該組成物を用いて形成される防汚塗膜を表面に有する塗装物

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