WO2016190242A1 - 防汚塗料組成物、防汚塗膜、防汚基材、防汚基材の製造方法および防汚塗料組成物の貯蔵方法 - Google Patents
防汚塗料組成物、防汚塗膜、防汚基材、防汚基材の製造方法および防汚塗料組成物の貯蔵方法 Download PDFInfo
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- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
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- A01N59/20—Copper
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- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/24—Cyanogen or compounds thereof, e.g. hydrogen cyanide, cyanic acid, cyanamide, thiocyanic acid
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- C08K3/34—Silicon-containing compounds
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
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- C08K5/54—Silicon-containing compounds
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L43/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L43/04—Homopolymers or copolymers of monomers containing silicon
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- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C09D193/00—Coating compositions based on natural resins; Coating compositions based on derivatives thereof
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Definitions
- the present invention relates to an antifouling coating composition and use thereof, and more specifically, an antifouling agent that contains a silyl ester-based (co) polymer as a film-forming component and can be used to prevent substrate contamination by aquatic organisms.
- the present invention relates to a coating composition, an antifouling coating film using the antifouling coating composition, an antifouling substrate, a method for producing the antifouling substrate, and a method for storing the antifouling coating composition.
- antifouling paints for ships, underwater structures, etc. which are intended to prevent fouling caused by aquatic organisms in the sea, include hydrolyzable resins for imparting film renewability to antifouling paints, A method of combining antifouling agents having the above physiological activity is widely used.
- a silyl ester (co) polymer is widely used as a resin having particularly suitable renewability.
- JP-T-2002-535255 Patent Document 1 shows that medetomidine is useful as a drug for preventing marine organism contamination on a solid surface.
- Patent Document 2 combines these, and an antifouling paint composition that exhibits excellent antifouling performance even in marine areas exposed to high fouling loads, ships under navigation conditions, underwater structures, etc.
- a coating composition containing a silyl ester copolymer having a structural unit derived from triisopropylsilyl acrylate, medetomidine, calcined gypsum, and the like is also disclosed (Examples 10 and 11). ).
- the antifouling paint composition disclosed in Patent Document 2 has a unique paint viscosity presumed to be accompanied by decomposition of the silyl ester copolymer by coexistence of the silyl ester copolymer and medetomidine. It has been found that there is a problem that it is difficult to stably store the coating composition for a long period of time due to the rise or solidification of the coating. More specifically, the coating composition of Comparative Example 3 described later containing a silyl acrylate copolymer has a shelf life of 6 months or longer, whereas Comparative Example described later in which medetomidine was added to this coating composition. The shelf life of one paint composition was found to be less than one month.
- the present invention is an antifouling paint composition used for preventing the substrate from being damaged by aquatic organisms, comprising a silyl ester-based (co) polymer and medetomidine,
- An object of the present invention is to provide an antifouling coating composition that can form an antifouling coating film exhibiting excellent antifouling properties over a long period of time and has good storage stability, and uses thereof.
- the gist of the present invention is as follows.
- the silyl ester-based (co) polymer (A) is represented by the general formula (I): R 1 —CH ⁇ CH—COO— (SiR 2 R 3 O) n —SiR 4 R 5 R 6 ...
- R 2 , R 3 , R 4 , R 5 and R 6 are each independently a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom
- R 1 is a hydrogen atom or R 7 —O—C ⁇ O
- R 7 is a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom
- R 8 R 9 R 10 Si wherein R 8 , R 9 and R 10 are each independently a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom.
- n is 0 or an integer of 1 or more.
- An antifouling paint composition having a structural unit derived from the monomer (a) represented by
- the component (C) includes the dehydrating agent (c1), and the dehydrating agent (c1) includes at least one component selected from the group consisting of hydrolyzable group-containing organosilanes, zeolites, and orthoesters.
- silyl ester-based (co) polymer (A) further has a structural unit derived from an unsaturated monomer (b) that can be copolymerized with the monomer (a).
- the antifouling paint composition as described in any one of.
- the unsaturated monomer (b) is an alkyl (meth) acrylate, a monomer represented by the following general formula (II), an alkoxyalkyl (meth) acrylate, a hydroxyalkyl (meth) acrylate, a metal ester group-containing (
- R 11 CH ⁇ C (CH 3 ) —COO— (SiR 12 R 13 O) n —SiR 14 R 15 R 16 ...
- R 12 , R 13 , R 14 , R 15 and R 16 are each independently a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom
- R 11 is a hydrogen atom or R 17 —O—C ⁇ O
- R 17 is a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom
- R 18 R 19 R 20 A silyl group represented by Si (wherein R 18 , R 19 and R 20 each independently represents a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom).
- n is 0 or an integer of 1 or more.
- the unsaturated monomer includes methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, triisopropylsilyl methacrylate, 2-methoxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
- Antifouling agent (E) other than medetomidine (B) is cuprous oxide, rhodan copper, copper, copper pyrithione, zinc pyrithione, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H -Pyrrol-3-carbonitrile, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, borane-nitrogen base adduct, N, N-dimethyl-N '-(3,4 Dichlorophenyl) urea, N- (2,4,6-trichlorophenyl) maleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-1,3,5-triazine, 2,4,5,6 -Tetrachloroisophthalonitrile, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, chloromethyl
- An antifouling substrate comprising a substrate and the antifouling coating film according to the above [22] provided on the surface of the substrate.
- a method for producing an antifouling substrate comprising a step of attaching a film to the substrate.
- a storage method for an antifouling paint composition wherein the antifouling paint composition according to the above [21] is filled in a container and stored.
- the antifouling coating composition of the present invention By using the antifouling coating composition of the present invention, it is possible to form an antifouling coating film that exhibits excellent antifouling properties over a long period of time. Furthermore, the antifouling coating composition of the present invention can be stored stably for a long period of time.
- the weight used as a reference in defining the content of the component is a component that can constitute a dry coating film excluding the volatile component when the component includes a volatile component such as a solvent for dilution. That is, the weight of “solids”. Solid content means the residue when a component or composition containing a volatile component such as a solvent is dried at 105 ° C. in a hot air dryer for 3 hours to volatilize the solvent.
- (co) polymer” is a term that collectively refers to a polymer and a copolymer
- (meth) acrylate” is a term that collectively refers to acrylate and methacrylate.
- the antifouling coating composition of the present invention contains a silyl ester (co) polymer (A), medetomidine (B), and a specific component (C).
- the silyl ester (co) polymer (A) has the general formula (I): R 1 —CH ⁇ CH—COO— (SiR 2 R 3 O) n —SiR 4 R 5 R 6 A structural unit derived from the monomer (a) represented by the formula (also referred to as “component unit”, “structural unit”, “repeating unit”, etc.), and optionally copolymerized with the monomer (a) And a (co) polymer having a structural unit derived from an unsaturated monomer (b).
- the “component unit derived from X” means that if X is represented by A 1 A 2 C ⁇ CA 3 A 4 (C ⁇ C is a polymerizable carbon-carbon double bond), for example, It is a structural unit represented by a formula.
- R 2 , R 3 , R 4 , R 5 and R 6 are each independently a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom, Examples include a linear, branched, or cyclic alkyl group, an aryl group, and the like in which a heteroatom such as an oxygen atom may be interposed between the bond between a carbon atom and a carbon atom.
- R 2 , R 3 , R 4 , R 5 and R 6 are preferably methyl because the silyl ester (co) polymer (A) is hydrolyzed at an appropriate rate in the antifouling coating film according to the present invention.
- Group, an alkyl group such as an ethyl group, an isopropyl group and a sec-butyl group, and more preferably an isopropyl group.
- R 1 is a hydrogen atom or R 7 —O—C ⁇ O (where R 7 is a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom, or R 8 R 9 R 10 Si (wherein R 8 , R 9 and R 10 are each independently a silyl group represented by a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom). Yes, preferably a hydrogen atom.
- Examples of the monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom as R 7 , R 8 , R 9 and R 10 are each independently a hetero atom such as an oxygen atom and a carbon atom.
- Examples include a linear, branched, or cyclic alkyl group that may be interposed between bonds with a carbon atom, and an aryl group, and an isopropyl group is preferable.
- n is 0 or an integer of 1 or more, preferably 0. The upper limit value of n may be 1,000, for example.
- Examples of the monomer (a) represented by the formula (I) include trimethylsilyl acrylate, triethylsilyl acrylate, tri-n-propylsilyl acrylate, triisopropylsilyl acrylate, tri-n-butylsilyl acrylate, triisobutyl.
- Examples include silyl acrylate, tri-sec-butyl silyl acrylate, tri 2-ethylhexyl silyl acrylate, trialkyl silyl acrylates such as butyl diisopropyl silyl acrylate, and 1-acryloyloxynonamethyl tetrasiloxane.
- Examples of the unsaturated monomer (b) that can be copolymerized with the monomer (a) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth).
- the silyl ester (co) polymer (A) is preferably hydrolyzed at an appropriate rate, so that it is preferably an alkyl group, and more preferably an isopropyl group.
- R 11 is a hydrogen atom or R 17 —O—C ⁇ O (where R 17 is a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom, or R 18 R 19 R 20 Si (Wherein R 18 , R 19 and R 20 each independently represents a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom). Yes, preferably a hydrogen atom.
- Examples of the monovalent organic group having 1 to 20 carbon atoms that may have a heteroatom as R 17 , R 18 , R 19 and R 20 include, for example, a heteroatom such as an oxygen atom, Examples thereof include linear, branched, and cyclic alkyl groups and aryl groups that may be interposed between these bonds, and preferably an isopropyl group.
- n is 0 or an integer of 1 or more, preferably 0.
- the upper limit value of n may be 1,000, for example.
- silyl methacrylate is more preferably 2-methoxyethyl (meth) as the unsaturated monomer (b). It contains structural units derived from acrylate, particularly preferably contains 1 to 30% by weight of structural units derived from 2-methoxyethyl (meth) acrylate, and this range may be 1 to 40% by weight.
- the structural unit derived from the monomer (a) is usually 10 to 100% by weight, preferably 10 to 90% by weight, more preferably 30 to 80%.
- the structural units contained by weight and derived from the unsaturated monomer (b) contain the remaining amount, that is, usually 0 to 90% by weight, preferably 10 to 90% by weight, more preferably 20 to 70% by weight. It is desirable in terms of excellent surface renewal sustainability of the antifouling coating film according to the present invention (however, the amount of all structural units in the silyl ester (co) polymer (A) is 100% by weight) To do.)
- the number average molecular weight Mn (polystyrene conversion value.
- the measuring method is a method described in the column of Examples described later or a method equivalent thereto) of the silyl ester-based (co) polymer (A). It is usually 1,000 to 200,000, preferably 1,000 to 100,000 in view of viscosity, storage stability and physical properties of the coating film.
- the content of the silyl ester (co) polymer (A) in the antifouling coating composition of the present invention is preferably 0.1 to 99% by weight, more preferably 5 to 5% in the composition in terms of solid content. 90% by weight, particularly preferably 10 to 80% by weight.
- the silyl ester (co) polymer (A) can be prepared by (co) polymerizing the monomer (a) and optionally the unsaturated monomer (b) by a known polymerization method.
- Each content (weight) of the structural unit derived from the monomer (a) and the structural unit derived from the unsaturated monomer (b) contained in the silyl ester-based (co) polymer (A) ) Ratio tends to coincide with the ratio of the charged amount (weight) of the monomer (a) and the unsaturated monomer (b) subjected to the polymerization reaction.
- Medetomidine is ( ⁇ ) -4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole.
- the content of medetomidine (B) in the antifouling coating composition of the present invention is preferably 0.001 to 10% by weight in 100% by weight of the antifouling coating composition (solid content). Further, the content of medetomidine (B) in the antifouling coating composition of the present invention is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the silyl ester (co) polymer (A), The amount is more preferably 0.02 to 20 parts by weight, still more preferably 0.04 to 10 parts by weight. When the content of medetomidine (B) is within this range, the antifouling coating film obtained from the antifouling coating composition of the present invention exhibits excellent antifouling properties.
- the antifouling coating composition of the present invention comprises at least one component (C) selected from the group consisting of a dehydrating agent (c1) and rosins (c2).
- the dehydrating agent (c1) may be either organic or inorganic, or a combination thereof.
- organic dehydrating agents include hydrolyzable group-containing organosilanes, orthoesters such as orthoformate alkyl esters, orthoboric acid, isocyanates, etc., preferably hydrolyzable group-containing organosilanes or orthoformate alkyl esters, Preferably, hydrolyzable group-containing organosilane is used.
- the hydrolyzable group-containing organosilane is preferably a compound represented by the following general formula (III).
- R 10 n SiY (4-n) (III) is independently a hydrocarbon group having 1 to 6 carbon atoms (eg, methyl group, ethyl group), and Y is independently a hydrolyzable group (eg, methoxy group, ethoxy group, N) is an integer of 0 to 3.
- hydrolyzable group-containing organosilane commercially available ones can be used, for example, “ethyl silicate 28” (manufactured by Colcoat Co.) as tetraethylorthosilicate, and “KBM-13” (Shin-Etsu Chemical Co., Ltd.) as alkyltrialkoxysilane. Etc.).
- ethyl silicate 28 manufactured by Colcoat Co.
- KBM-13 Shin-Etsu Chemical Co., Ltd.
- inorganic dehydrating agent examples include zeolite, alumina, silica and the like, and zeolite is preferable.
- zeolite what is marketed by the general name of "Molecular sieve" can be used.
- the dehydrating agent (c1) When these are included as the dehydrating agent (c1), good paint storage stability can be obtained.
- the component (C) is a dehydrating agent (c1) selected from hydrolyzable group-containing organosilane, zeolite and orthoester
- the content of the dehydrating agent (c1) in the antifouling coating composition of the present invention is:
- the amount is preferably 0.01 to 200 parts by weight, more preferably 1 to 50 parts by weight, and 100 parts by weight of the medetomidine (B) with respect to 100 parts by weight of the silyl ester-based (co) polymer (A).
- it is preferably 1 to 100,000 parts by weight, more preferably 10 to 10,000 parts by weight.
- the blending amount of the dehydrating agent (c1) is within this range, good paint storage stability can be obtained.
- rosins (c2) examples include rosins such as gum rosin, wood rosin and tall oil rosin, hydrogenated rosin, disproportionated rosin, rosin derivatives such as rosin metal salts, and pine tar.
- the content of the rosin (c2) in the antifouling coating composition of the present invention is based on 100 parts by weight of the silyl ester (co) polymer (A).
- the amount is preferably 0.01 to 500 parts by weight, more preferably 1 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, and preferably 1 to 100 parts by weight of the medetomidine (B). ⁇ 50,000 parts by weight.
- the rosin (c2) is contained in such a proportion, good storage stability of the antifouling coating composition is obtained, and good antifouling property of the antifouling coating film is obtained.
- Various components can be blended.
- inorganic and organic antifouling agents can be used.
- the amount of the antifouling agent (E) other than medetomidine can be adjusted as appropriate, and is, for example, 0.01 to 1,000 parts by weight per 100 parts by weight of the silyl ester (co) polymer (A).
- the antifouling coating composition of the present invention contains the monocarboxylic acid compound (F), the surface renewability and water resistance of the antifouling coating film obtained from the antifouling coating composition can be improved.
- the monocarboxylic acid compound (F) includes a saturated or unsaturated aliphatic hydrocarbon group having 10 to 20 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a substituted product thereof. Is preferred. Among them, trimethylisobutenylcyclohexene carboxylic acid compound, versatic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, abietic acid, neoabietic acid, pimaric acid, dehydroabietic acid, 12-hydroxystearic acid or naphthenic acid Acids and their salts (eg, metal salts) are desirable.
- trimethylisobutenylcyclohexenecarboxylic acid examples include a reaction product of 2,6-dimethylocta-2,4,6-triene and methacrylic acid, which is 1,2,3-trimethyl-5- ( 2-Methylprop-1-en-1-yl) cyclohex-3-en-1-carboxylic acid and 1,4,5-trimethyl-2- (2-methylprop-1-en-1-yl) cyclohex-3-
- the main component (85% or more) is ene-1-carboxylic acid.
- the amount of the monocarboxylic acid compound (F) can be adjusted as appropriate, and is, for example, 0.01 to 1,000 parts by weight, preferably 1 with respect to 100 parts by weight of the silyl ester (co) polymer (A). ⁇ 500 parts by weight.
- coloring pigment (G) examples include inorganic pigments such as petals, titanium white (titanium oxide), and yellow iron oxide, and organic pigments such as carbon black, naphthol red, and phthalocyanine blue. These color pigments can be used singly or in combination of two or more.
- the color pigment may further contain various colorants such as dyes.
- the blending amount of the color pigment (G) can be adjusted as appropriate, and is, for example, 0.05 to 125 parts by weight with respect to 100 parts by weight of the silyl ester (co) polymer (A).
- the extender pigment (H) has a small refractive index and is transparent and does not hide the coated surface when kneaded with oil or varnish.
- extender pigments (H) include talc, mica, clay, potash feldspar, zinc oxide, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, and sulfide.
- Examples thereof include zinc, and zinc oxide, talc, mica, clay, calcium carbonate, kaolin, barium sulfate, calcium sulfate, and potassium feldspar are preferable.
- These extender pigments can be used alone or in combination of two or more.
- the amount of the extender pigment (H) can be adjusted as appropriate, and is, for example, 0.5 to 250 parts by weight with respect to 100 parts by weight of the silyl ester (co) polymer (A).
- the plasticizer (I) is a component that contributes to improvement of crack resistance and water resistance of the antifouling coating film and suppression of discoloration.
- the plasticizer (I) include n-paraffin, chlorinated paraffin, terpene phenol, tricresyl phosphate (TCP), polyvinyl ethyl ether, etc. Among them, chlorinated paraffin and terpene phenol are preferable, Chlorinated paraffin is particularly preferred.
- These plasticizers can be used alone or in combination of two or more.
- n-paraffin examples include “n-paraffin” manufactured by Nippon Petrochemical Co., Ltd.
- chlorinated paraffin examples include “Toyoparax A-40 / A-50 / A-70 /” manufactured by Tosoh Corporation.
- a product such as “A-145 / A-150” can be used.
- the blending amount of the plasticizer (I) can be adjusted as appropriate, and is, for example, 1 to 5% by weight based on the total solid content in the antifouling coating composition.
- the wrinkle modifier (J) is a component that contributes to sagging-preventing properties and settling prevention of the paint.
- the alteration agent (J) include organic bentonite, stearate of Al, Ca or Zn, lecithin, alkyl sulfonate, polyethylene wax, oxidized polyethylene wax, amide wax, hydrogenated castor oil wax, amide wax / oxidized.
- a polyethylene wax composite system may be mentioned.
- These alteration agents can be used alone or in combination of two or more.
- the blending amount of the habit modifier (J) can be adjusted as appropriate, and is, for example, 0.25 to 50 parts by weight with respect to 100 parts by weight of the silyl ester (co) polymer (A).
- the antifouling coating composition of the present invention may contain one or two or more other resins (K) as required in addition to the silyl ester (co) polymer (A) described above. Good.
- the blending amount of the other resins (K) can be appropriately adjusted, and is, for example, 0.01 to 1,000 parts by weight with respect to 100 parts by weight of the silyl ester (co) polymer (A).
- Solvent (L) The various components constituting the antifouling paint composition of the present invention are dissolved or dispersed in a solvent as in the case of a normal antifouling paint composition.
- aliphatic solvents aromatic solvents (xylene, toluene, etc.), ketone solvents (MIBK, cyclohexanone, etc.), ester solvents, ether solvents (propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.
- Commonly used solvents for antifouling paints such as alcohol solvents (isopropyl alcohol and the like) can be used.
- the blending amount of the solvent (L) can be adjusted as appropriate, for example, such that the total solid content of the antifouling coating composition is 20 to 90% by weight. Also good.
- the antifouling paint composition of the present invention can be prepared using the same apparatus, means, etc. as those of known general antifouling paints.
- the (co) polymer (A) ((co) polymer (A) is composed of (co) polymer (A) Solution (the solution obtained when the (co) polymer (A) was prepared)), medetomidine (B), component (C), and other additives and other components as necessary May be added to the solvent all at once or sequentially, followed by stirring and mixing.
- the antifouling coating composition of the present invention since the antifouling coating composition of the present invention has high storage stability, the component containing the silyl ester (co) polymer (A) and the component containing medetomidine (B) should be stored separately. In addition, it can also be stored as a one-component paint containing a silyl ester (co) polymer (A), medetomidine (B) and component (C).
- the antifouling coating film of the present invention comprises the solid content of the antifouling coating composition of the present invention.
- the antifouling coating film of the present invention is formed from the antifouling coating composition of the present invention.
- the antifouling coating composition contains a solvent (L)
- the antifouling coating composition of the present invention applied on a substrate is used.
- the soil coating composition can be formed by, for example, natural drying or curing using a drying means such as a heater (that is, removing the solvent (L)).
- the antifouling base material of the present invention comprises a base material and the antifouling coating film of the present invention formed on the surface of the base material. Is also an antifouling object or an object to be coated.) Is applied or impregnated using a coating means such as air spray, airless spray, brush, roller, etc.
- a coating means such as air spray, airless spray, brush, roller, etc.
- the resulting coating composition is naturally dried (ie, dried at a temperature of about room temperature) or dried and cured using a drying means such as a heater to form an antifouling coating on the substrate. Can be manufactured.
- the antifouling substrate of the present invention forms an antifouling coating film on the surface of the temporary substrate from the antifouling coating composition of the present invention, and the antifouling coating film is peeled off from the temporary substrate for antifouling. It can also be manufactured by sticking it to the substrate. At this time, an antifouling coating film may be affixed on the substrate via an adhesive layer.
- the base material is not particularly limited, but is preferably a base material that comes into contact with seawater or fresh water.
- water supply / drainage ports of various power plants thermal power, nuclear power
- bay roads submarine tunnels
- Equipment or underwater structures such as sludge diffusion prevention membranes used in various marine or river civil engineering works such as canals or waterways, ship outer plates (especially from the draft section of the ship to the bottom of the ship), fishing materials (ropes, fishing nets, etc.) , Floats or buoys).
- Examples of the material of these base materials include steel, aluminum, wood, FRP, etc. for ship outer plates, natural or synthetic fibers for fish nets, etc., and synthetic resin for floats, buoys, etc. As long as it is a base material that is in water and requires antifouling properties, the material is not particularly limited.
- the surface of these base materials is usually the surface of the primer-treated base material after the primer such as a rust preventive paint is primed on the surface of the steel base material as described above.
- the antifouling paint composition (antifouling paint) of the present invention is applied once or a plurality of times and applied or impregnated (impregnation is carried out particularly when the substrate is a fish net or the like).
- the antifouling paint composition When the antifouling paint composition is cured to form an antifouling coating film, it has characteristics that prevent the attachment of aquatic organisms such as blue seaweeds, barnacles, aonori, cell plastics, oysters, and chrysanthemum insects over a long period of time (antifouling properties, particularly static It is excellent in antifouling property, and the antifouling component can be gradually released over a long period of time.
- the base material surface may be primed or may have a layer formed from various binder paints.
- the antifouling coating composition is applied to the surface of the base material a plurality of times (also referred to as thick coating). The thickness is about 100 to 600 ⁇ m.) Then, the obtained antifouling substrate exhibits a good balance of not only excellent antifouling properties but also moderate flexibility and excellent crack resistance.
- the antifouling coating composition of the present invention may be directly applied to the surface, or the substrate
- the surface of the substrate may be impregnated with the antifouling coating composition of the present invention when the substrate is a fish net or the like, and when the substrate is a steel sheet fabric, the substrate surface is coated with a rust preventive or primer. May be applied in advance to form an undercoat layer, and then the antifouling paint composition of the present invention may be applied to the surface of the undercoat layer.
- the thickness of the antifouling coating film of the present invention formed by a single coating operation is not particularly limited, but is about 30 to 250 ⁇ m, for example, when the substrate is a ship outer plate or an underwater structure. .
- the underwater structure having the antifouling coating film of the present invention can maintain the function of the underwater structure for a long period because it can prevent adhesion of aquatic organisms over a long period of time.
- the fish net having the antifouling coating film of the present invention is less likely to cause environmental pollution, and can prevent clogging of the net because it can prevent adhesion of aquatic organisms.
- Solid content refers to the heating residue when the reaction mixture, paint or uncured coating film containing resin and solvent, etc. is dried at 105 ° C. in a hot air dryer for 3 hours to volatilize the solvent, etc. Say.
- the solid content usually includes a resin component, a pigment, and the like, and becomes a coating film forming component.
- Examples 1 to 34, Comparative Examples 1 to 6 Manufacture of antifouling paint composition
- Table 2 including solutions (A-1 to A-4), medetomidine (B), dehydrating agent (c1), rosins (c2), and the like, containing the silyl ester copolymers obtained in Preparation Examples 1 to 4
- the components shown in Table 3 were mixed uniformly in the proportions shown in Tables 2 and 3 (the values in the table indicate parts by weight) using a paint shaker to produce an antifouling paint composition. The evaluation was performed.
- the antifouling paint composition of the above Example was stored at room temperature, the paint state was confirmed every month, and the elapsed months up to the month immediately before the paint was gelled or solidified was evaluated as the shelf life. .
- Viscosity stability The antifouling coating compositions of Examples and Comparative Examples were stored at 50 ° C. for 2 weeks, and the viscosities immediately after storage were compared. A value obtained by dividing the difference in viscosity numerical values before and after storage by the viscosity before storage was determined as “viscosity increase rate (%)”, and the viscosity stability of the antifouling coating composition was evaluated based on this value. Note that “ ⁇ ” in Table 2 indicates that the measurement was not performed because the shelf life was extremely short. The viscosity was measured for each composition under a temperature condition of 23 ° C. with a Stormer viscometer (manufacturer: Dazai Equipment Co., Ltd., product name: Stormer viscometer, model: 691).
- Sand blasted steel sheet (length 300mm x width 100mm x thickness 3.2mm) and epoxy-type anticorrosive paint (epoxy AC paint, trade name "Banno 500", manufactured by China Paint Co., Ltd.) have a dry film thickness of 150 ⁇ m.
- a vinyl binder paint (trade name “Sylvax SQ-K”, manufactured by China Paint Co., Ltd.) was applied so that the dry film thickness was 40 ⁇ m.
- the antifouling paint composition produced according to the above example was applied once so that the dry film thickness was 100 ⁇ m and dried at room temperature for 7 days to prepare a test plate with an antifouling coating film. The above three coatings were performed once a day.
- test plate prepared as described above was immersed in Tokyo Bay for 3 months in the summer, and the area of the antifouling coating with the barnacles attached (hereinafter also referred to as “barnacles attached area”). It was measured. Then, according to the above [Evaluation Criteria for Static Antifouling Property by Barnacle Adhesive Area], the static antifouling property of the antifouling coating film was evaluated. The results are as shown in Tables 2 and 3.
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Abstract
Description
一方、たとえば特表2002-535255号公報(特許文献1)には、メデトミジンが固体表面における海洋生物汚染を阻止する薬剤として有用であることが示されている。
シリルエステル系(共)重合体(A)、メデトミジン(B)、ならびに脱水剤(c1)およびロジン類(c2)からなる群から選ばれる少なくとも一つの成分(C)を含み、
前記シリルエステル系(共)重合体(A)が、一般式(I):
R1-CH=CH-COO-(SiR2R3O)n-SiR4R5R6
・・・(I)
[式(I)中、R2、R3、R4、R5およびR6は、それぞれ独立にヘテロ原子を有してもよい炭素数1~20の1価の有機基であり、
R1は水素原子またはR7-O-C=O(ただし、R7は水素原子、ヘテロ原子を有してもよい炭素数1~20の1価の有機基またはR8R9R10Si(ただし、R8、R9およびR10は、それぞれ独立にヘテロ原子を有してもよい炭素数1~20の1価の有機基である。)で表されるシリル基である。)であり、
nは0または1以上の整数である。]
で表される単量体(a)から誘導される構造単位を有する防汚塗料組成物。
前記成分(C)が前記脱水剤(c1)を含み、前記脱水剤(c1)が加水分解性基含有オルガノシラン、ゼオライトおよびオルトエステルからなる群から選ばれる少なくとも一つの成分を含む上記[1]に記載の防汚塗料組成物。
前記脱水剤(c1)が前記加水分解性基含有オルガノシランを含む上記[2]に記載の防汚塗料組成物。
前記脱水剤(c1)が前記ゼオライトを含む上記[2]または[3]に記載の防汚塗料組成物。
前記脱水剤(c1)が前記オルトエステルを含む上記[2]~[4]のいずれか一つに記載の防汚塗料組成物。
前記成分(C)が前記ロジン類(c2)を含む上記[1]~[5]のいずれか一つに記載の防汚塗料組成物。
前記メデトミジン(B)が、防汚塗料組成物の固形分100重量%の中に0.001~10重量%の割合で含まれている上記[1]~[6]のいずれか一つに記載の防汚塗料組成物。
前記脱水剤(c1)が、前記シリルエステル系(共)重合体(A)100重量部に対して0.01~200重量部の割合で含まれている上記[1]~[7]のいずれか一つに記載の防汚塗料組成物。
前記脱水剤(c1)が、前記メデトミジン(B)100重量部に対して1~100,000重量部の割合で含まれている上記[1]~[8]のいずれか一つに記載の防汚塗料組成物。
前記ロジン類(c2)が、前記シリルエステル系(共)重合体(A)100重量部に対して0.01~500重量部の割合で含まれている上記[1]~[9]のいずれか一つに記載の防汚塗料組成物。
前記ロジン類(c2)が、前記メデトミジン(B)100重量部に対して1~50,000重量部の割合で含まれている上記[1]~[10]のいずれか一つに記載の防汚塗料組成物。
前記一般式(I)において、R4、R5およびR6がすべてイソプロピル基である上記[1]~[11]のいずれか一つに記載の防汚塗料組成物。
前記シリルエステル系(共)重合体(A)が、前記単量体(a)と共重合し得る不飽和単量体(b)から誘導される構造単位をさらに有する上記[1]~[12]のいずれか一つに記載の防汚塗料組成物。
前記不飽和単量体(b)が、アルキル(メタ)アクリレート、下記一般式(II)で表される単量体、アルコキシアルキル(メタ)アクリレート、ヒドロキシアルキル(メタ)アクリレート、金属エステル基含有(メタ)アクリレートおよびオルガノシロキサン基含有(メタ)アクリレートからなる群から選ばれる少なくとも1種の不飽和単量体を含む上記[13]に記載の防汚塗料組成物。
R11-CH=C(CH3)-COO-(SiR12R13O)n-SiR14R15R16
・・・(II)
[式(II)中、R12、R13、R14、R15およびR16は、それぞれ独立にヘテロ原子を有してもよい炭素数1~20の1価の有機基であり、
R11は、水素原子またはR17-O-C=O(ただし、R17は水素原子、ヘテロ原子を有してもよい炭素数1~20の1価の有機基またはR18R19R20Si(ただし、R18、R19およびR20は、それぞれ独立にヘテロ原子を有してもよい炭素数1~20の1価の有機基である。)で表されるシリル基を示す。)であり、
nは0または1以上の整数である。]
前記不飽和単量体が、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレート、トリイソプロピルシリルメタクリレート、2-メトキシエチル(メタ)アクリレートおよび2-ヒドロキシエチル(メタ)アクリレートからなる群から選ばれる少なくとも1種の不飽和単量体である上記[14]に記載の防汚塗料組成物。
前記シリルエステル系(共)重合体(A)が、前記単量体(a)から誘導される構造単位を40~80重量%含む上記[13]~[15]のいずれか一つに記載の防汚塗料組成物。
前記メデトミジン(B)が、前記シリルエステル系(共)重合体(A)100重量部に対して0.001~50重量部の割合で含まれている上記[1]~[16]のいずれか一項に記載の防汚塗料組成物。
さらに前記メデトミジン(B)以外の防汚剤(E)を含む上記[1]~[17]のいずれか一項に記載の防汚塗料組成物。
前記メデトミジン(B)以外の防汚剤(E)が、亜酸化銅、ロダン銅、銅、銅ピリチオン、ジンクピリチオン、4-ブロモ-2-(4-クロロフェニル)-5-(トリフルオロメチル)-1H-ピロール-3-カルボニトリル、4,5-ジクロロ-2-n-オクチル-4-イソチアゾリン-3-オン、ボラン-窒素系塩基付加物、N,N-ジメチル-N'-(3,4-ジクロロフェニル)尿素、N-(2,4,6-トリクロロフェニル)マレイミド、2-メチルチオ-4-tert-ブチルアミノ-6-シクロプロピルアミノ-1,3,5-トリアジン、2,4,5,6-テトラクロロイソフタロニトリル、ビスジメチルジチオカルバモイルジンクエチレンビスジチオカーバメート、クロロメチル-n-オクチルジスルフィド、N,N'-ジメチル-N'-フェニル-(N-フルオロジクロロメチルチオ)スルファミド、テトラアルキルチウラムジスルフィド、ジンクジメチルジチオカーバメート、ジンクエチレンビスジチオカーバメート、2,3-ジクロロ-N-(2',6'-ジエチルフェニル)マレイミド、および2,3-ジクロロ-N-(2'-エチル-6'-メチルフェニル)マレイミドからなる群から選ばれる少なくとも1種の防汚剤である上記[18]に記載の防汚塗料組成物。
さらにモノカルボン酸化合物(F)を含む上記[1]~[19]のいずれか一項に記載の防汚塗料組成物。
1液型塗料である上記[1]~[20]のいずれか一項に記載の防汚塗料組成物。
上記[1]~[21]のいずれか一つに記載の防汚塗料組成物から形成される防汚塗膜。
基材と、該基材の表面に設けられた上記[22]に記載の防汚塗膜とを有する防汚基材。
海水または真水と接触する上記[23]に記載の防汚基材。
前記基材が、水中構造物、船舶外板または漁具である上記[24]に記載の防汚基材。
基材の表面に、上記[1]~[21]のいずれか一つに記載の防汚塗料組成物を塗布するかもしくは含浸させる工程と、該工程により前記基材に塗布された、もしくは含浸された前記防汚塗料を硬化させる工程とを備えるか、または
前記防汚塗料組成物から塗膜を形成し、この塗膜を硬化させて防汚塗膜を形成する工程と、前記防汚塗膜を基材に貼付する工程とを備える
防汚基材の製造方法。
防汚塗料組成物の貯蔵方法であって、上記[21]に記載の防汚塗料組成物を容器に充填して貯蔵する貯蔵方法。
なお、本発明において成分の含有量を規定する際の基準となる重量は、成分が希釈用溶剤等の揮発性成分を含む場合には、揮発性成分を除いた乾燥塗膜を構成しうる成分、すなわち「固形分」の重量である。固形分とは、溶剤等の揮発成分が含まれた成分ないし組成物を、105℃で熱風乾燥機中で3時間乾燥して溶剤等を揮散させたときの残分をいう。また、「(共)重合体」は、重合体および共重合体を総称する語句であり、「(メタ)アクリレート」は、アクリレートおよびメタクリレートを総称する語句である。
本発明の防汚塗料組成物は、シリルエステル系(共)重合体(A)、メデトミジン(B)、および特定の成分(C)を含有する。
シリルエステル系(共)重合体(A)は、一般式(I):
R1-CH=CH-COO-(SiR2R3O)n-SiR4R5R6
で表される単量体(a)から誘導される構造単位(「成分単位」、「構成単位」、「繰り返し単位」などともいう。)と、任意に、単量体(a)と共重合し得る不飽和単量体(b)から誘導される構造単位とを有する(共)重合体である。なお"Xから誘導される成分単位"とは、XをA1A2C=CA3A4(C=Cは、重合性炭素-炭素二重結合である。)と表すならば、たとえば下式で表される構造単位である。
nは0または1以上の整数であり、好ましくは0である。nの上限値は、たとえば1,000であってもよい。
フェニル(メタ)アクリレート;
ベンジル(メタ)アクリレート;
メトキシメチル(メタ)アクリレート、2-メトキシエチル(メタ)アクリレート、エトキシメチル(メタ)アクリレート、2-エトキシエチル(メタ)アクリレート、4-メトキシブチル(メタ)アクリレート、メトキシプロピル(メタ)アクリレート、エトキシプロピル(メタ)アクリレート、プロポキシエチル(メタ)アクリレート、2-ブトキシエチル(メタ)アクリレート、イソブトキシブチルジグリコール(メタ)アクリレート、フェノキシエチル(メタ)アクリレート等のアルコキシアルキル(メタ)アクリレート;
ヒドロキシメチル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、2-ヒドロキシ-3-フェノキシプロピル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレート;
亜鉛(メタ)アクリレート、亜鉛ジ(メタ)アクリレート、銅(メタ)アクリレート、銅ジ(メタ)アクリレート等の金属エステル基含有(メタ)アクリレート;
オルガノシロキサン基含有(メタ)アクリレート、および
一般式(II):
R11-CH=C(CH3)-COO-(SiR12R13O)n-SiR14R15R16
[式(II)中、R12、R13、R14、R15およびR16は、それぞれ独立にヘテロ原子を有してもよい炭素数1~20の1価の有機基であり、たとえば、酸素原子などのヘテロ原子が炭素原子と炭素原子との結合間に介在しても良い、直鎖状、分岐鎖状、環状のアルキル基、アリール基などが挙げられる。本発明に係る防汚塗膜においてシリルエステル系(共)重合体(A)が適切な速度で加水分解することから、好ましくはアルキル基であり、さらに好ましくはイソプロピル基である。
で表される単量体が好ましく、中でも、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレート、2-メトキシエチル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、トリイソプロピルシリルメタクリレートがさらに好ましい。貯蔵安定性に特に優れた防汚塗料組成物を製造できることから、シリルエステル系(共)重合体(A)は、より好ましくは不飽和単量体(b)としての2-メトキシエチル(メタ)アクリレートから誘導される構造単位を含み、特に好ましくは2-メトキシエチル(メタ)アクリレートから誘導される構造単位を1~30重量%含み、この範囲は1~40重量%としてもよい。
シリルエステル系(共)重合体(A)に含まれる、前記単量体(a)から誘導される構造単位および前記不飽和単量体(b)から誘導される構造単位の各含有量(重量)の比率は、重合反応に供される前記単量体(a)および前記不飽和単量体(b)の仕込み量(重量)の比率に一致する傾向にある。
メデトミジンは、(±)-4-[1-(2,3-ジメチルフェニル)エチル]-1H-イミダゾールである。
本発明の防汚塗料組成物は、脱水剤(c1)およびロジン類(c2)からなる群から選ばれる少なくとも一つの成分(C)を含む。
脱水剤(c1)は、有機系、無機系のいずれかまたはそれらを組み合わせて用いて良い。
R10 nSiY(4-n) …(III)
上記一般式(III)において、R10は独立に炭素原子数1~6の炭化水素基(たとえば、メチル基、エチル基)であり、Yは独立に加水分解性基(たとえば、メトキシ基、エトキシ基)であり、nは0~3の整数である。
このようなゼオライトとしては、「モルキュラーシーブ」の一般名称で市販されているものを用いることができる。
成分(C)が加水分解性基含有オルガノシラン、ゼオライトおよびオルトエステルから選択される脱水剤(c1)である場合、本発明の防汚塗料組成物中の脱水剤(c1)の含有量は、前記シリルエステル系(共)重合体(A)100重量部に対して、好ましくは0.01~200重量部であり、さらに好ましくは1~50重量部であり、前記メデトミジン(B)100重量部に対して、好ましくは1~100,000重量部であり、さらに好ましくは10~10,000重量部である。脱水剤(c1)の配合量がこの範囲にあると良好な塗料貯蔵安定性が得られる。
本発明の防汚塗料組成物には、前述した成分の他に、メデトミジン(B)以外の防汚剤(E)、モノカルボン酸化合物(F)、着色顔料(G)、体質顔料(H)、可塑剤(I)、搖変剤(J)、シリルエステル系(共)重合体(A)以外の樹脂類(K)、溶剤(L)等、一般的な塗料組成物に用いられている各種成分を配合することができる。
本発明の防汚塗料組成物がメデトミジン(B)以外の防汚剤(E)を含むことで、防汚塗料組成物から得られる防汚塗膜の防汚性能をさらに向上させることができる。
メデトミジン以外の防汚剤(E)の配合量は、適宜調整でき、例えば、シリルエステル系(共)重合体(A)100重量部に対して0.01~1,000重量部である。
本発明の防汚塗料組成物がモノカルボン酸化合物(F)を含むことで、防汚塗料組成物から得られる防汚塗膜の表面更新性および耐水性を向上させることができる。
着色顔料(G)としては、例えば、弁柄、チタン白(酸化チタン)、黄色酸化鉄等の無機系顔料や、カーボンブラック、ナフトールレッド、フタロシアニンブルー等の有機系顔料が挙げられる。これらの着色顔料は、1種単独で、または2種以上組み合わせて用いることができる。なお、着色顔料には、さらに染料等の各種着色剤が含まれていてもよい。
着色顔料(G)の配合量は、適宜調整でき、例えば、シリルエステル系(共)重合体(A)100重量部に対して0.05~125重量部である。
体質顔料(H)は、屈折率が小さく、油やワニスと混練した場合に透明で被塗面を隠さないような顔料である。体質顔料(H)としては、例えば、タルク、マイカ、クレー、カリ長石、酸化亜鉛、炭酸カルシウム、カオリン、アルミナホワイト、ホワイトカーボン、水酸化アルミニウム、炭酸マグネシウム、炭酸バリウム、硫酸バリウム、硫酸カルシウム、硫化亜鉛等が挙げられ、なかでも、酸化亜鉛、タルク、マイカ、クレー、炭酸カルシウム、カオリン、硫酸バリウム、硫酸カルシウム、カリ長石が好ましい。これらの体質顔料は、1種単独で、または2種以上組み合わせて用いることができる。
体質顔料(H)の配合量は、適宜調整でき、例えば、シリルエステル系(共)重合体(A)100重量部に対して0.5~250重量部である。
可塑剤(I)は、防汚塗膜の耐クラック性や耐水性の向上および変色の抑制に寄与する成分である。可塑剤(I)としては、例えば、n-パラフィン、塩素化パラフィン、テルペンフェノール、トリクレジルフォスフェート(TCP)、ポリビニルエチルエーテル等が挙げられ、なかでも、塩素化パラフィン、テルペンフェノールが好ましく、塩素化パラフィンが特に好ましい。これらの可塑剤は、1種単独で、または2種以上組み合わせて用いることができる。前記n-パラフィンとしては、日本石油化学(株)製「n-パラフィン」等の商品を、前記塩素化パラフィンとしては、東ソー(株)製「トヨパラックス A-40/A-50/A-70/A-145/A-150」等の商品を使用できる。
可塑剤(I)の配合量は、適宜調整でき、例えば、防汚塗料組成物中の全固形分に対して1~5重量%である。
搖変剤(J)は、塗料のタレ止め性および沈降防止に寄与する成分である。搖変剤(J)としては、例えば、有機ベントナイト、Al、CaまたはZnのステアレート、レシチン、アルキルスルホン酸塩、ポリエチレンワックス、酸化ポリエチレンワックス、アマイドワックス、水素添加ヒマシ油ワックス、アマイドワックス/酸化ポリエチレンワックス複合系が挙げられる。これらの搖変剤は、1種単独で、または2種以上組み合わせて用いることができる。
搖変剤(J)の配合量は、適宜調整でき、例えば、シリルエステル系(共)重合体(A)100重量部に対して0.25~50重量部である。
本発明の防汚塗料組成物は、前述のシリルエステル系(共)重合体(A)以外にも、必要に応じて1種または2種以上のその他の樹脂類(K)を含んでいてもよい。
その他の樹脂類(K)の配合量は、適宜調整でき、例えば、シリルエステル系(共)重合体(A)100重量部に対して0.01~1,000重量部である。
本発明の防汚塗料組成物を構成する各種成分は、通常の防汚塗料組成物と同様、溶剤に溶解もしくは分散している。本発明では、脂肪族系溶剤、芳香族系溶剤(キシレン、トルエン等)、ケトン系溶剤(MIBK、シクロヘキサノン等)、エステル系溶剤、エーテル系溶剤(プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等)、アルコール系溶剤(イソプロピルアルコール等)等、防汚塗料用の溶剤として一般的なものを用いることができる。
溶剤(L)の配合量は、適宜調整でき、例えば、防汚塗料組成物の全固形分率が20~90重量%となるような割合であり、作業性に応じて塗装時にさらに添加してもよい。
本発明の防汚塗料組成物は、公知の一般的な防汚塗料と同様の装置、手段等を用いて調製することができる。例えば、あらかじめシリルエステル系(共)重合体(A)を調製した後、この(共)重合体(A)((共)重合体(A)の態様としては、(共)重合体(A)の溶液((共)重合体(A)を調製した際に得られた溶液)が挙げられる。)と、メデトミジン(B)、成分(C)と、必要に応じてその他の添加剤等の成分とを、一度にまたは順次溶剤に添加して、撹拌、混合して製造すれば良い。
本発明の防汚塗膜は、本発明の防汚塗料組成物の固形分からなる。本発明の防汚塗膜は、本発明の防汚塗料組成物から形成され、たとえば防汚塗料組成物が溶剤(L)を含む場合であれば、基材上に塗布された本発明の防汚塗料組成物を、たとえば自然乾燥またはヒーター等の乾燥手段を用いて硬化させて(すなわち、前記溶剤(L)を除去して)、形成することができる。
本発明の防汚塗膜を有する水中構造物は、長期間に亘って水棲生物の付着を防止できることに起因して、水中構造物の機能を長期間維持できる。また、本発明の防汚塗膜を有する魚網は、環境汚染のおそれが少ない上に、水棲生物の付着を防止できることに起因して網目の閉塞を防止できる。
<シリルエステル系(共)重合体溶液の粘度>
シリルエステル系(共)重合体溶液の25℃における粘度は、E型粘度計(東機産業(株)製)により測定した。
固形分とは、樹脂および溶剤等が含まれた、反応混合物、塗料または未硬化塗膜等を105℃で熱風乾燥機中で3時間乾燥して溶剤等を揮散させたときの加熱残分をいう。固形分は、通常は樹脂分さらには顔料等を含み、塗膜形成成分となる。
シリルエステル系(共)重合体の数平均分子量(Mn)、重量平均分子量(Mw)を下記条件でGPC(ゲルパーミエーションクロマトグラフィー)を用いて測定した。
GPC条件
装置 :「HLC-8120GPC」(東ソー(株)製)
カラム :「SuperH2000+H4000」(東ソー(株)製、6mm(内径)、各15cm(長さ))
溶離液 :テトラヒドロフラン(THF)
流速 :0.500ml/min
検出器 :RI
カラム恒温槽温度 :40℃
標準物質 :ポリスチレン
サンプル調製法 :各製造例で調製された重合体溶液に少量の塩化カルシウムを加えて脱水した後、メンブレムフィルターで濾過して得られた濾物をGPC測定サンプルとした。
攪拌機、コンデンサー、温度計、滴下装置、窒素導入管および加熱冷却ジャケットを備えた反応容器にキシレン54重量部を仕込み、窒素気流下で85℃±5℃の温度条件下に加熱し攪拌を行った。同温度を保持しつつ滴下装置より、前記反応容器内にトリイソプロピルシリルアクリレート60重量部、メチルメタクリレート40重量部からなるモノマー混合物、および2,2'-アゾビスイソブチロニトリル0.75重量部を2時間かけて滴下した。その後、同温度で2時間攪拌を行った後、2,2'-アゾビスイソブチロニトリル0.4重量部を加え、更に同温度で4時間攪拌を行い、キシレン44重量部を加えて、無色透明のシリルエステル系共重合体溶液(A-1)を得た。
使用された原料の量、ならびに溶液(A-1)およびこれに含まれるシリルエステル系共重合体の特性値を表1に示す。
製造例1において使用されたモノマー混合物のかわりに、表1に示される組成を有するモノマー混合物を使用し、キシレンと2,2'-アゾビスイソブチロニトリルの添加量を適宜調整したことを除いては、製造例1と同様にして、シリルエステル系共重合体を含むシリルエステル系共重合体溶液(A-2)~(A-4)を調製した。
使用された原料の量、ならびに溶液(A-2)~(A-4)およびこれらに含まれるシリルエステル系共重合体の特性値を表1に示す。
(防汚塗料組成物の製造)
前記製造例1~4により得られたシリルエステル系共重合体を含む溶液(A-1~A-4)、メデトミジン(B)、脱水剤(c1)、ロジン類(c2)など、表2、3に示す成分を表2、3に示す割合(表中の数値は重量部を示す。)で、ペイントシェーカーを用いて均一に混合することにより、防汚塗料組成物を製造し、下記の方法によりその評価を行った。
防汚塗料組成物の貯蔵安定性は、下記の貯蔵寿命と粘度安定性の二面から評価した。
前記実施例の防汚塗料組成物を常温にて貯蔵して1カ月経過毎に塗料状態を確認し、塗料がゲル状態化または固形化する直前の月までの経過月数を貯蔵寿命として評価した。
実施例および比較例の防汚塗料組成物を50℃にて2週間貯蔵し、貯蔵直前直後での粘度を比較した。貯蔵前後の粘度数値差を貯蔵前の粘度で除して得た値を「粘度上昇率(%)」として求め、この値に基づいて防汚塗料組成物の粘度安定性を評価した。なお、表2の中の「-」は、貯蔵寿命が極端に短いため測定を実施しなかったことを表す。
粘度は、各組成物を23℃の温度条件下で、それぞれストーマー粘度計(製造元:太佑機材株式会社、製品名:ストーマー粘度計、型式:691)にて測定した。
サンドブラスト処理鋼板(縦300mm×横100mm×厚み3.2mm)に、エポキシ系防錆塗料(エポキシAC塗料、商品名「バンノー500」、中国塗料(株)製)をその乾燥膜厚が150μmとなるように塗布した後、ビニル系バインダー塗料(商品名「シルバックスSQ-K」、中国塗料(株)製)をその乾燥膜厚が40μmとなるように塗布した。続いて、前記実施例により製造した防汚塗料組成物をその乾燥膜厚が100μmとなるように1回塗布し、室温で7日間乾燥させて、防汚塗膜付き試験板を作製した。なお、前記の3回の塗装は1日当たり1回のペースで行った。
0 : フジツボの付着なし
1 : フジツボが部分的に付着
2 : フジツボが全面に付着
Claims (27)
- シリルエステル系(共)重合体(A)、メデトミジン(B)、ならびに脱水剤(c1)およびロジン類(c2)からなる群から選ばれる少なくとも一つの成分(C)を含み、
前記シリルエステル系(共)重合体(A)が、一般式(I):
R1-CH=CH-COO-(SiR2R3O)n-SiR4R5R6
・・・(I)
[式(I)中、R2、R3、R4、R5およびR6は、それぞれ独立にヘテロ原子を有してもよい炭素数1~20の1価の有機基であり、
R1は水素原子またはR7-O-C=O(ただし、R7は水素原子、ヘテロ原子を有してもよい炭素数1~20の1価の有機基またはR8R9R10Si(ただし、R8、R9およびR10は、それぞれ独立にヘテロ原子を有してもよい炭素数1~20の1価の有機基である。)で表されるシリル基である。)であり、
nは0または1以上の整数である。]
で表される単量体(a)から誘導される構造単位を有する防汚塗料組成物。 - 前記成分(C)が前記脱水剤(c1)を含み、前記脱水剤(c1)が加水分解性基含有オルガノシラン、ゼオライトおよびオルトエステルからなる群から選ばれる少なくとも一つの成分を含む請求項1に記載の防汚塗料組成物。
- 前記脱水剤(c1)が前記加水分解性基含有オルガノシランを含む請求項2に記載の防汚塗料組成物。
- 前記脱水剤(c1)が前記ゼオライトを含む請求項2または3に記載の防汚塗料組成物。
- 前記脱水剤(c1)が前記オルトエステルを含む請求項2~4のいずれか一項に記載の防汚塗料組成物。
- 前記成分(C)が前記ロジン類(c2)を含む請求項1~5のいずれか一項に記載の防汚塗料組成物。
- 前記メデトミジン(B)が、防汚塗料組成物の固形分100重量%の中に0.001~10重量%の割合で含まれている請求項1~6のいずれか一項に記載の防汚塗料組成物。
- 前記脱水剤(c1)が、前記シリルエステル系(共)重合体(A)100重量部に対して0.01~200重量部の割合で含まれている請求項1~7のいずれか一項に記載の防汚塗料組成物。
- 前記脱水剤(c1)が、前記メデトミジン(B)100重量部に対して1~100,000重量部の割合で含まれている請求項1~8のいずれか一項に記載の防汚塗料組成物。
- 前記ロジン類(c2)が、前記シリルエステル系共重合体(A)100重量部に対して0.01~500重量部の割合で含まれている請求項1~9のいずれか一項に記載の防汚塗料組成物。
- 前記ロジン類(c2)が、前記メデトミジン(B)100重量部に対して1~50,000重量部の割合で含まれている請求項1~10のいずれか一項に記載の防汚塗料組成物。
- 前記一般式(I)において、R4、R5およびR6がすべてイソプロピル基である請求項1~11のいずれか一項に記載の防汚塗料組成物。
- 前記シリルエステル系(共)重合体(A)が、前記単量体(a)と共重合し得る不飽和単量体(b)から誘導される構造単位をさらに有する請求項1~12のいずれか一項に記載の防汚塗料組成物。
- 前記不飽和単量体(b)が、アルキル(メタ)アクリレート、下記一般式(II)で表される単量体、アルコキシアルキル(メタ)アクリレート、ヒドロキシアルキル(メタ)アクリレート、金属エステル基含有(メタ)アクリレートおよびオルガノシロキサン基含有(メタ)アクリレートからなる群から選ばれる少なくとも1種の不飽和単量体を含む請求項13に記載の防汚塗料組成物。
R11-CH=C(CH3)-COO-(SiR12R13O)n-SiR14R15R16
・・・(II)
[式(II)中、R12、R13、R14、R15およびR16は、それぞれ独立にヘテロ原子を有してもよい炭素数1~20の1価の有機基であり、
R11は、水素原子またはR17-O-C=O(ただし、R17は水素原子、ヘテロ原子を有してもよい炭素数1~20の1価の有機基またはR18R19R20Si(ただし、R18、R19およびR20は、それぞれ独立にヘテロ原子を有してもよい炭素数1~20の1価の有機基である。)で表されるシリル基を示す。)であり、
nは0または1以上の整数である。] - 前記不飽和単量体が、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレート、トリイソプロピルシリルメタクリレート、2-メトキシエチル(メタ)アクリレートおよび2-ヒドロキシエチル(メタ)アクリレートからなる群から選ばれる少なくとも1種の不飽和単量体である請求項14に記載の防汚塗料組成物。
- 前記シリルエステル系(共)重合体(A)が、前記単量体(a)から誘導される構造単位を30~80重量%含む請求項13~15のいずれか一項に記載の防汚塗料組成物。
- 前記メデトミジン(B)が、前記シリルエステル系(共)重合体(A)100重量部に対して0.001~50重量部の割合で含まれている請求項1~16のいずれか一項に記載の防汚塗料組成物。
- さらに前記メデトミジン(B)以外の防汚剤(E)を含む請求項1~17のいずれか一項に記載の防汚塗料組成物。
- 前記メデトミジン(B)以外の防汚剤(E)が、亜酸化銅、ロダン銅、銅、銅ピリチオン、ジンクピリチオン、4-ブロモ-2-(4-クロロフェニル)-5-(トリフルオロメチル)-1H-ピロール-3-カルボニトリル、4,5-ジクロロ-2-n-オクチル-4-イソチアゾリン-3-オン、ボラン-窒素系塩基付加物、N,N-ジメチル-N'-(3,4-ジクロロフェニル)尿素、N-(2,4,6-トリクロロフェニル)マレイミド、2-メチルチオ-4-tert-ブチルアミノ-6-シクロプロピルアミノ-1,3,5-トリアジン、2,4,5,6-テトラクロロイソフタロニトリル、ビスジメチルジチオカルバモイルジンクエチレンビスジチオカーバメート、クロロメチル-n-オクチルジスルフィド、N,N'-ジメチル-N'-フェニル-(N-フルオロジクロロメチルチオ)スルファミド、テトラアルキルチウラムジスルフィド、ジンクジメチルジチオカーバメート、ジンクエチレンビスジチオカーバメート、2,3-ジクロロ-N-(2',6'-ジエチルフェニル)マレイミド、および2,3-ジクロロ-N-(2'-エチル-6'-メチルフェニル)マレイミドからなる群から選ばれる少なくとも1種の防汚剤である請求項18に記載の防汚塗料組成物。
- さらにモノカルボン酸化合物(F)を含む請求項1~19のいずれか一項に記載の防汚塗料組成物。
- 1液型塗料である請求項1~20のいずれか一項に記載の防汚塗料組成物。
- 請求項1~21のいずれか一項に記載の防汚塗料組成物から形成される防汚塗膜。
- 基材と、該基材の表面に設けられた請求項22に記載の防汚塗膜とを有する防汚基材。
- 海水または真水と接触する請求項23に記載の防汚基材。
- 前記基材が、水中構造物、船舶外板または漁具である請求項24に記載の防汚基材。
- 基材の表面に、請求項1~21のいずれか一項に記載の防汚塗料組成物を塗布するかもしくは含浸させる工程と、該工程により前記基材に塗布された、もしくは含浸された前記防汚塗料を硬化させる工程とを備えるか、または
前記防汚塗料組成物から塗膜を形成し、この塗膜を硬化させて防汚塗膜を形成する工程と、前記防汚塗膜を基材に貼付する工程とを備える
防汚基材の製造方法。 - 防汚塗料組成物の貯蔵方法であって、請求項21に記載の防汚塗料組成物を容器に充填して貯蔵する貯蔵方法。
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GB201813454D0 (en) * | 2018-08-17 | 2018-10-03 | Jotun As | Antifouling composition |
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