WO2015156073A1 - Antifouling coating material composition and coated article coated with same - Google Patents

Antifouling coating material composition and coated article coated with same Download PDF

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Publication number
WO2015156073A1
WO2015156073A1 PCT/JP2015/056975 JP2015056975W WO2015156073A1 WO 2015156073 A1 WO2015156073 A1 WO 2015156073A1 JP 2015056975 W JP2015056975 W JP 2015056975W WO 2015156073 A1 WO2015156073 A1 WO 2015156073A1
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WIPO (PCT)
Prior art keywords
acid
group
antifouling
polyester resin
meth
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PCT/JP2015/056975
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French (fr)
Japanese (ja)
Inventor
拓真 島田
力 川村
堅次 宮川
Original Assignee
関西ペイント株式会社
Ｎｋｍコーティングス株式会社
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Application filed by 関西ペイント株式会社, Ｎｋｍコーティングス株式会社 filed Critical 関西ペイント株式会社
Priority to CN201580018441.7A priority Critical patent/CN106164189B/en
Priority to JP2016512637A priority patent/JP6755176B2/en
Priority to KR1020167027085A priority patent/KR102470397B1/en
Publication of WO2015156073A1 publication Critical patent/WO2015156073A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to an antifouling paint composition and a coated article formed by coating the antifouling paint composition, and more specifically, an antifouling paint capable of forming an antifouling coating film capable of maintaining excellent antifouling properties for a long period of time.
  • the present invention relates to a composition and a coated article obtained by coating the composition on an object.
  • Such a trialkylsilyl ester group-containing resin has different coating rate depending on the structure of the trialkylsilyl ester group.
  • an antifouling paint composition using a tri-n-butylsilyl ester group-containing resin has a high dissolution rate of the obtained coating film, and it is difficult to maintain the antifouling performance of the coating film for a long period of time.
  • the antifouling coating composition using a triorganosilyl ester group-containing resin in which a branched alkyl group is bonded to a silicon atom has a slow dissolution rate of the resulting coating film. There was a problem of easy adhesion.
  • Patent Documents 1 to 3 methods for controlling the dissolution rate of the coating film by adding rosin or a rosin derivative have been studied.
  • the amount of rosin or rosin derivative used is small, there is a problem that the solubility of the coating film in seawater cannot be sufficiently obtained and the antifouling effect is difficult to be sustained.
  • the amount of rosin or rosin derivative used is large, the dissolution rate of the coating film increases and the antifouling effect is improved, but the physical properties and adhesiveness of the coating film decrease, and the antifouling effect can be maintained for a long time. There was a tendency that coating film defects such as coating film peeling, blistering and cracking were likely to occur.
  • An object of the present invention is to provide an antifouling paint composition capable of maintaining an excellent antifouling property over a long period of time and capable of forming an antifouling coating film that is less susceptible to coating film defects such as coating film peeling, blistering, and cracks And a coated article formed by coating the antifouling coating composition on an object to be coated such as a fishing net, a ship, a structure such as the ocean or the bay.
  • the present inventors have intensively studied to achieve the above object, and the coating film obtained from the antifouling coating composition containing the specific polyester resin and the silyl ester group-containing resin has a coating film dissolution rate in the ocean.
  • the coating film obtained from the antifouling coating composition containing the specific polyester resin and the silyl ester group-containing resin has a coating film dissolution rate in the ocean.
  • the paint film has excellent physical properties such as being able to control the antifouling property over a long period of time.
  • coating film defects such as coating film peeling, blistering, and cracks are less likely to occur during navigation or berthing.
  • the present invention has been completed based on such findings.
  • the present invention provides the following antifouling paint composition and a coated article obtained by coating the antifouling paint composition on an article to be coated.
  • Item 1 An antifouling paint composition comprising a polyester resin (A), a silyl ester group-containing resin (B) and an antifouling agent (C), wherein the silyl ester group-containing resin (B) is represented by the general formula (I): R 5 —CH ⁇ C (R 4 ) —COO—SiR 1 R 2 R 3 (I) [In the formula (I), R 4 represents a hydrogen atom or a methyl group, R 1 , R 2 and R 3 each independently represents a hydrocarbon group, and R 5 represents a hydrogen atom or R 6 —O—CO— ( R 6 represents an organic group or a silyl group represented by —SiR 7 R 8 R 9 , and R 7 , R 8 and R 9 each independently represents a hydrocarbon group.
  • the mass ratio of the polyester resin (A) to the silyl ester group-containing resin (B) is in the range of 3/97 to 80/20, and the antifouling agent (C) content is the polyester resin (
  • the antifouling coating composition wherein the antifouling coating composition is in the range of 50 to 500% by mass based on the total mass of A) and the silyl ester group-containing resin (B).
  • Item 2. The antifouling coating composition according to Item 1, wherein the acid value of the polyester resin (A) is in the range of 0 to 120 KOHmg / g. Item 3. Item 3.
  • Item 4. Item 4. The antifouling paint composition according to any one of Items 1 to 3, wherein a mass ratio of the polyester resin (A) to the silyl ester group-containing resin (B) is in the range of 7/93 to 60/40. object. Item 5. In the silyl ester group-containing resin (B), the mass ratio (b1) / (b2) between the monomer (b1) and the monomer (b2) is in the range of 20/80 to 70/30. 5. The antifouling paint composition according to any one of items 1 to 4. Item 6. Item 6. A coated article obtained by coating the object to be coated with the antifouling coating composition according to any one of Items 1 to 5.
  • the antifouling paint composition of the present invention is capable of maintaining a superior antifouling property over a long period of time, and forms a coating film in which coating film defects such as coating film peeling, blistering and cracking are unlikely to occur. Can do.
  • the antifouling paint composition of the present invention is an antifouling paint composition comprising a polyester resin (A), a silyl ester group-containing resin (B) and an antifouling agent (C), wherein the silyl ester group-containing resin (B ) Is represented by the general formula (I): R 5 —CH ⁇ C (R 4 ) —COO—SiR 1 R 2 R 3 (I) [In the formula (I), R 4 represents a hydrogen atom or a methyl group, R 1 , R 2 and R 3 each independently represents a hydrocarbon group, and R 5 represents a hydrogen atom or R 6 —O—CO— ( R 6 represents an organic group or a silyl group represented by —SiR 7 R 8 R 9 , and R 7 , R 8 and R 9 each independently represents a hydrocarbon group.
  • the mass ratio of the polyester resin (A) to the silyl ester group-containing resin (B) is in the range of 3/97 to 80/20, and the content of the antifouling agent (C) is the polyester resin. It is characterized by being in the range of 50 to 500% by mass based on the total mass of (A) and the silyl ester group-containing resin (B).
  • the antifouling coating composition of the present invention will be described in detail.
  • polyester resin (A) used in the antifouling coating composition of the present invention is produced by using an acid component (a1) and an alcohol component (a2) as main raw materials by esterification and / or transesterification of these components. can do.
  • the acid component (a1) can use the acid component normally used for manufacture of a polyester resin.
  • acid components include alicyclic polybasic acids, aliphatic polybasic acids, aromatic polybasic acids, aromatic monocarboxylic acids, aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and these Examples include esterified products, anhydrides, and halides.
  • an alicyclic polybasic acid is a compound having one or more alicyclic structures (mainly 4 to 6 membered rings) and two or more carboxyl groups in one molecule, and acid anhydrides of the compounds, Esterified products and halides can be used.
  • alicyclic polybasic acids examples include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-cyclohexene-1,2-dicarboxylic acid, 3 -Cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, tetrahydromethylphthalic acids, 3-methyl-1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, Alicyclic polycarboxylic acids such as 1,2,4-cyclohexanetricarboxylic acid and 1,3,5-cyclohexanetricarboxylic acid; anhydrides of these alicyclic polycarboxylic acids; Examples include lower alkyl esterified compounds, which may be used alone or in combination of two or more. Can.
  • aliphatic polybasic acid generally, an aliphatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aliphatic compound, a halide of the aliphatic compound, and the like can be used.
  • aliphatic polybasic acids include succinic acid, malonic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid.
  • Aliphatic polycarboxylic acids such as brassic acid, octadecanedioic acid and citric acid; anhydrides of these aliphatic polyvalent carboxylic acids; halogenation of these aliphatic polyvalent carboxylic acids and the like. Alternatively, two or more kinds can be used in combination.
  • An aromatic polybasic acid generally comprises an aromatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aromatic compound, an esterified product of the aromatic compound, and a halide of the aromatic compound. Can be used.
  • aromatic polybasic acid having two carboxyl groups in one molecule examples include aromatic polybasic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and 4,4′-biphenyldicarboxylic acid. And anhydrides of these aromatic polycarboxylic acids.
  • Examples of the aromatic polybasic acid having 3 or more carboxyl groups in one molecule include trivalent aromatic polyvalent carboxylic acids and tetravalent aromatic polyvalent carboxylic acids.
  • Examples of the trivalent aromatic polyvalent carboxylic acid include trimellitic acids such as trimellitic acid, trimellitic anhydride, trimellitic acid alkyl ester, trimellitic acid halide; hemimertic acid, hemimellitic anhydride, hemi Hemimellitic acids such as alkyl melicates and halides of hemimellitic acid; trimesic acids such as trimesic acid, trimesic acid alkyl esters and trimesic acid halides; various naphthalene tricarboxylic acids having different bonding positions of carboxyl groups to aromatic rings and their Anhydrous; various anthractricarboxylic acids with different bonding positions of carboxyl groups to aromatic rings and their anhydrides; various biphenyltricarboxylic acids with different bonding positions of carboxy
  • examples of tetravalent aromatic polyvalent carboxylic acids include pyromellitic acids such as pyromellitic acid, pyromellitic dianhydride, pyromellitic acid alkyl ester, and pyromellitic halide; merophanic acid and melophanic dianhydride. And melophanoic acids such as melophanic acid alkyl ester and merophanic acid halide; and planitic acids such as prehnitic acid, prenic acid anhydride, prenic acid alkyl ester, and planitic acid halide. Said aromatic polybasic acid can be used individually or in combination of 2 or more types.
  • the acid component (a1) used in the production of the polyester resin (A) may be a monocarboxylic acid such as an aromatic monocarboxylic acid, an aliphatic monocarboxylic acid, or an alicyclic monocarboxylic acid.
  • the aromatic monocarboxylic acid include benzoic acid, methylbenzoic acid, ethylbenzoic acid, pt-butylbenzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, Biphenyl carboxylic acid etc. are mentioned.
  • aliphatic monocarboxylic acid examples include acetic acid, lactic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, dodecanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid.
  • alicyclic monocarboxylic acid examples include cyclohexanecarboxylic acid, cyclopentanecarboxylic acid, cycloheptanecarboxylic acid, 4-ethylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, 4-laurylcyclohexanecarboxylic acid, and the like. These can be used alone or in combination of two or more.
  • the acid component (a1) used in the production of the polyester resin (A) may contain an esterified product such as a glycerin ester of the monocarboxylic acid.
  • esterified product such as a glycerin ester of the monocarboxylic acid.
  • examples of glycerin esters of monocarboxylic acids include coconut oil, cottonseed oil, hemp seed oil, rice bran oil, fish oil, tall oil, soybean oil, linseed oil, tung oil, rapeseed oil, castor oil, dehydrated castor oil, safflower oil, and the like. Can be mentioned.
  • the acid component (a1) used for manufacture of a polyester resin (A) contains an aromatic polybasic acid from a viewpoint of antifouling property long-term maintenance,
  • the content is acid. Based on the total number of moles of component (a1), it is at least 30 mol%, preferably at least 50 mol%, more preferably at least 70 mol%.
  • the alcohol component (a2) can use the alcohol component normally used for manufacture of a polyester resin.
  • an alcohol component those containing dihydric alcohols such as alicyclic diols, aliphatic diols, aromatic diols and / or trihydric or higher polyhydric alcohols are preferable, for example, ethylene glycol, diethylene glycol, Triethylene glycol, tetraethylene glycol, pentaethylene glycol, 1,2-propylene glycol, di-1,2-propylene glycol, tri-1,2-propylene glycol, 1,2-butylene glycol, 2, 3-butylene glycol, 1,2-hexanediol, 1,2-dihydroxycyclohexane, 3-ethoxypropane-1,2-diol, 3-phenoxypropane-1,2-diol, neopentyl glycol, 2-methyl -1,3-propanediol, 2-methyl-2,4-pen Diol, 3-methyl-1
  • the production method of the polyester resin (A) is not particularly limited, and a normal method can be adopted.
  • the polyester resin (A) comprises one or more acid components (a1) and one or more alcohol components (a2) in a nitrogen stream at a temperature of 150 to 250 ° C. It can manufacture by making it react for 10 hours and performing esterification reaction and / or transesterification. In the esterification reaction and / or transesterification reaction, the acid component (a1) and the alcohol component (a2) may be added at once, or may be added in several portions. The above reaction may be performed in the presence of a known organic solvent.
  • the polyester resin (A) may be obtained by first synthesizing a carboxyl group-containing polyester resin and then esterifying a part of the carboxyl groups in the carboxyl group-containing polyester resin using the alcohol component (a2). be able to. Furthermore, the polyester resin (A) can be obtained by first synthesizing a hydroxyl group-containing polyester resin and then reacting the hydroxyl group-containing polyester resin with the acid anhydride.
  • a catalyst can be used to promote the reaction.
  • catalysts include dibutyltin oxide, antimony trioxide, iron acetate, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, tetraisopropyl titanate, zinc borate, zinc chloride,
  • Known catalysts include zinc sulfate, zinc naphthenate, lead borate, lead acetate, manganese acetate, aluminum acetate, aluminum chloride and the like.
  • the polyester resin (A) is produced by an esterification reaction and / or transesterification of each of these components using the acid component (a1) and the alcohol component (a2) as main raw materials.
  • a known organic and / or inorganic compound may be included as a component, and amidation reaction, urethanization reaction, imidization It may be produced with a known chemical reaction such as a reaction, a carbonate reaction, a urea reaction.
  • the reaction intermediate or reaction product is converted into an organic acid zinc, organic acid copper, zinc chloride, copper chloride, hydroxylation.
  • Metal compounds such as zinc, copper hydroxide, zinc oxide, copper oxide, fatty acids, fats and oils, mono- or polyisocyanate compounds, mono- or polyamine compounds having nitrogen to which hydrogen atoms are bonded, epoxy compounds, acrylic resins, vinyl ester resins, etc.
  • the modified polyester resin obtained by making it react may be sufficient.
  • the constituent components derived from the acid component (a1) and the alcohol component (a2) are preferably 80 mol% or more of the total components of the resin, and 90 mol% or more. It is more preferable.
  • the resin acid value of the polyester resin (A) is preferably in the range of 0 to 120 mgKOH / g, from the viewpoint of maintaining the antifouling property of the obtained coating film over a long period, and is preferably 0 to 95 mgKOH / g. g is more preferable, and a range of 0 to 45 mgKOH / g is particularly preferable.
  • the weight average molecular weight of the polyester resin (A) is preferably 15,000 or less from the viewpoint of the antifouling property of the obtained coating film and the antifouling property over a long period of time. It is more preferably within the range of ⁇ 7000, and particularly preferably within the range of 500 to 4,000.
  • the weight average molecular weight is a value obtained by converting the weight average molecular weight measured by gel permeation chromatograph (“HLC8120GPC” manufactured by Tosoh Corporation) based on the weight average molecular weight of polystyrene.
  • the weight average molecular weight was measured using four columns (trade names “TSKgel G-4000H ⁇ L”, “TSKgel G-3000H ⁇ L”, “TSKgel G-2500H ⁇ L”, and “TSKgel G-2000H ⁇ L” ( All of them are manufactured by Tosoh Corporation), and can be carried out under the conditions of mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: RI.
  • the antifouling coating composition of the present invention further contains a silyl ester group-containing resin (B) in addition to the polyester resin (A).
  • the silyl ester group-containing resin (B) is a monomer (b1) represented by the following general formula (I) and having a polymerizable unsaturated group and a triorganosilyl ester group (hereinafter referred to as “monomer ( b1) ”)) and one or more monomers (b2) having a polymerizable unsaturated group other than the monomer (b1).
  • R 5 CH ⁇ C (R 4 ) —COO—SiR 1 R 2 R 3 (I)
  • R 4 represents a hydrogen atom or a methyl group
  • R 1 , R 2 and R 3 each independently represents a hydrocarbon group
  • R 5 represents a hydrogen atom or R 6 —O—CO—
  • R 6 represents an organic group or a silyl group represented by —SiR 7 R 8 R 9
  • R 7 , R 8 and R 9 each independently represents a hydrocarbon group.
  • the Mw of the silyl ester group-containing resin (B) used in the antifouling paint composition of the present invention is less than 1,000, the dissolution rate of the coating film obtained from the antifouling paint composition increases, The physical properties of the film are inferior, and blisters and cracks are likely to occur. Moreover, when Mw of the said silyl ester group containing resin (B) exceeds 150,000, the melt
  • the monomer (b1) is represented by the following general formula (I-1) when R 5 in the formula (I) is a hydrogen atom.
  • CH 2 C (R 4 ) —COO—SiR 1 R 2 R 3 (I-1)
  • R 4, R 1, R 2 and R 3 in the formula (I-1) is the same as R 4, R 1, R 2 and R 3 in each of the formula (I).
  • the hydrocarbon group in R 1 , R 2 and R 3 in the formula (I) or the formula (I-1) is a linear or branched alkyl group having 1 to 10 carbon atoms, or any Are preferably substituted or unsubstituted phenyl groups, and each hydrocarbon group may be the same or different.
  • an alkyl group having 1 to 5 carbon atoms is preferable, and an alkyl group such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an s-butyl group, a t-butyl group, and an isopropyl group is particularly preferable.
  • Examples of the monomer represented by the formula (I-1) include, for example, trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, Examples include (meth) acrylic acid trialkylsilyl such as (meth) acrylic acid triisopropylsilyl. Among these, solubility of the obtained coating film, durability of antifouling performance, resistance to occurrence of blisters and cracks. In view of the above, triisopropylsilyl (meth) acrylate is preferred.
  • R 5 in the formula (I) is “R 6 —O—CO—” (where R 6 represents an organic group or a silyl group represented by —SiR 7 R 8 R 9).
  • R 7 , R 8 and R 9 each independently represents a hydrocarbon group.), It is represented by the following general formula (I-2).
  • R 4 in the formula (I-2), R 1, R 2 and R 3 are each the formula (I) or the formula (I-1) R 4 in, R 1, R 2 and R 3 Is the same.
  • the organic group represented by R 6 is a linear or branched alkyl group having 1 to 10 carbon atoms. Cycloalkyl group, unsaturated alkyl group, aralkyl group and the like.
  • linear or branched alkyl group having 1 to 10 carbon atoms examples include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, isobutyl group, n-butyl group, s- Examples include butyl group, t-butyl group, 2-methylbutyl group, 2-ethylbutyl group, pentyl group, 3-methylpentyl group, hexyl group, heptyl group, octyl group and the like.
  • Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • Examples of the unsaturated alkyl group include 2-propenyl group, 2-butenyl group, 3-butenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group and the like.
  • aralkyl group examples include a benzyl group, a phenethyl group, and a phenylpropyl group.
  • said alkyl group, cycloalkyl group, unsaturated alkyl group, and aralkyl group may have a substituent.
  • a substituent include an alkoxy group and an acyl group.
  • the number of substituents, the position of substitution and the like are not particularly limited as long as the effects of the present invention are not hindered.
  • Examples of the monomer represented by the formula (I-2) include maleic acid diester compounds and fumaric acid diester compounds (formula (I-2)).
  • R 4 is a hydrogen atom).
  • the hydrocarbon group in R 7 , R 8 and R 9 in the formula (I), the formula (I-1) or the formula (I-2) is linear or branched having 1 to 10 carbon atoms. It is preferably an alkyl group having a chain, or a phenyl group substituted or unsubstituted by an arbitrary substituent, and each hydrocarbon group may be the same or different. Among them, an alkyl group having 1 to 5 carbon atoms is preferable, and an alkyl group such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an s-butyl group, a t-butyl group, and an isopropyl group is particularly preferable.
  • the monomer (b1) is preferably an isopropylsilyl group-containing unsaturated monomer from the viewpoints of solubility of the resulting coating film, durability of the antifouling performance, difficulty in generating blisters and cracks, and the like.
  • isopropylsilyl group-containing unsaturated monomers examples include triisopropylsilyl (meth) acrylate, triisopropylsilyl 4-pentenoate, bis (triisopropylsilyl) maleate, methyltriisopropylsilyl maleate, Ethyl triisopropylsilyl maleate, n-butyltriisopropylsilyl maleate, isobutyltriisopropylsilyl maleate, t-butyltriisopropylsilyl maleate, n-pentyltriisopropylsilyl maleate, isopentyltriisopropylsilyl maleate, malein 2-ethylhexyl triisopropylsilyl acid, cyclohexyl triisopropylsilyl maleate, bis (triisopropylsilyl) fumarate, methyltriisopropylsilyl fuma
  • the silyl ester group-containing resin (B) is obtained by copolymerizing the monomer (b1) and the monomer (b2) at a mass ratio (b1) / (b2) within the range of 20/80 to 70/30. What was obtained was preferable, and was obtained by copolymerizing the monomer (b1) and the monomer (b2) at a mass ratio (b1) / (b2) within the range of 30/70 to 60/40. More preferred.
  • the mass ratio (b1) / (b2) is smaller than 20/80, the dissolution rate of the resulting coating film is slow and the antifouling performance may be inferior, and the mass ratio (b1) / (b2) is 70 / When it is larger than 30, the solubility of the resulting coating film is increased, but it may be difficult to maintain the antifouling effect over a long period of time.
  • Examples of the monomer (b2) copolymerizable with the monomer (b1) (or the monomer (b1-1) and / or (b1-2)) include, for example, methyl (meth) acrylate, (meta ) Ethyl acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, etc.
  • (Meth) alkyl acrylates (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 2-methoxypropyl, (meth) acrylic acid 4-methoxybutyl, (meth) acrylic acid 2-ethoxyethyl etc.
  • Alkoxyalkyl acrylates ethylene glycol monomethyl (meth) acrylate, having a polyoxyethylene chain in which one molecular end is an alkoxy group
  • metal Acrylates (meth) acrylates having a polyoxypropylene chain with one molecular terminal being an alkoxy group
  • acrylic acid alkylene glycol monomethyls such as (meth) acrylic acid propylene glycol monomethyl
  • acrylic acid 2-hydroxy ⁇ -caprolactone modified product of ethyl, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monoester of (meth) acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms, allyl alcohol Hydroxyl group-containing monomers such as (meth) acrylates such as (meth) acrylates having a polyoxyethylene chain having a hydroxyl group at the molecular terminal; (meth) acrylonitriles, (meth)
  • the monomer (b2) include vinyl ester compounds such as vinyl propionate and vinyl acetate; (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, and croton.
  • carboxyl group-containing monomers such as ⁇ -carboxyethyl (meth) acrylate; glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxy Epoxy group-containing monomers such as cyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether; 2- (meth) acrylamide-2-methylpropanesulfonic acid, allylsulfonic acid, styrenesulfonic acid , Sul Sulfonic acid group-containing monomers such as foethyl (meth) acrylate and sodium salts or ammonium salts thereof; monomers having a phosphoric acid group such as 2- (meth) acryloyloxyethyl
  • the monomers (b2) exemplified above can be used alone or in combination of two or more.
  • the monomers (b2) exemplified above in particular, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( Preference is given to 2-methoxyethyl (meth) acrylate and 2-methoxypropyl (meth) acrylate.
  • (meth) acrylate means acrylate or methacrylate
  • (meth) acrylic acid means acrylic acid or methacrylic acid
  • (Meth) acryloyl means acryloyl or methacryloyl
  • (meth) acrylamide means acrylamide or methacrylamide.
  • the silyl ester group-containing resin (B) can be produced by a known polymerization method.
  • the silyl ester group-containing resin (B) may be any type of copolymer as long as it is a known copolymer such as a random copolymer, a graft copolymer, a gradient structure copolymer, or a block copolymer. It may be a coalescence.
  • the silyl ester group-containing resin (B) can be obtained, for example, by copolymerizing the monomer (b1) and the monomer (b2) in the presence of a radical polymerization initiator.
  • radical polymerization initiator examples include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis-2-methylbutyronitrile, and dimethyl-2.
  • Azo compounds such as 2,2'-azobisisobutyrate; diacyl peroxide compounds such as dibenzoyl peroxide, di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dilauryl peroxide T-butyl peroxide compounds such as di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, t-butyl peroctoate; t-amylperoxy-2-ethyl Hexanoate, t-amyl peroxyacetate, t- T-amyl peroxides such as milperoxy isononanoate, t-amyl peroxybenzo
  • AIBN 2,2′-azo
  • the molecular weight of the silyl ester group-containing resin (B) can be adjusted by appropriately setting the amount of the polymerization initiator used.
  • Examples of the polymerization method for obtaining the silyl ester group-containing resin (B) include a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, and a suspension polymerization method.
  • the solution polymerization method is particularly preferable in that the silyl ester group-containing resin (B) can be synthesized easily and accurately.
  • an organic solvent may be used as necessary.
  • organic solvents 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.
  • Solvents include alcohol solvents such as isopropyl alcohol and butyl alcohol; ether solvents such as dioxane, diethyl ether and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.
  • aromatic hydrocarbon solvents are preferable, and xylene is particularly preferable. These solvents can be used alone or in combination of two or more.
  • the reaction temperature in the copolymerization reaction may be appropriately set according to the type of the polymerization initiator and the like, and is usually a temperature in the range of 70 to 160 ° C., preferably a temperature in the range of 80 to 140 ° C.
  • the reaction time in the copolymerization reaction may be appropriately set according to the reaction temperature, the type of polymerization initiator, and the like, and is usually about 4 to 8 hours.
  • the copolymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen gas or argon gas.
  • the antifouling coating composition of the present invention further contains an antifouling agent (C) in addition to the polyester resin (A) and the silyl ester group-containing resin (B).
  • an antifouling agent (C) in addition to the polyester resin (A) and the silyl ester group-containing resin (B).
  • a conventionally well-known thing can be used as antifouling agent (C).
  • the antifouling agent (C) include inorganic compounds, organic compounds containing metals, and organic compounds not containing metals.
  • the inorganic compound examples include copper compounds such as cuprous oxide, copper powder, copper thiocyanate, copper carbonate, copper chloride, and copper sulfate, zinc sulfate, zinc oxide, nickel sulfate, and copper-nickel alloy.
  • Examples of the organic compound containing the above metal include organic copper compounds, organic nickel compounds, and organic zinc compounds.
  • manneb, manceb, propineb, and the like can also be used.
  • Examples of the organic copper compound include copper oxine, copper pyrithione, copper nonylphenol sulfonate, copper bis (ethylenediamine) -bis (dodecylbenzenesulfonate), copper acetate, copper naphthenate, bis (pentachlorophenolic acid) copper, and the like.
  • Examples of the organic nickel compound include nickel acetate and nickel dimethyldithiocarbamate.
  • Examples of the organic zinc compound include zinc acetate, zinc carbamate, zinc dimethyldithiocarbamate, zinc pyrithione, and zinc ethylenebisdithiocarbamate.
  • organic compound containing no metal examples include N-trihalomethylthiophthalimide, dithiocarbamic acid, N-arylmaleimide, 3-substituted amino-1,3-thiazolidine-2,4-dione, and dithiocyano compounds. And triazine compounds.
  • N-trihalomethylthiophthalimide examples include N-trichloromethylthiophthalimide and N-fluorodichloromethylthiophthalimide.
  • dithiocarbamic acid examples include bis (dimethylthiocarbamoyl) disulfide, ammonium N-methyldithiocarbamate, ethylenebis (dithiocarbamic acid) ammonium, and milneb.
  • N-arylmaleimide examples include N- (2,4,6-trichlorophenyl) maleimide, N-4-tolylmaleimide, N-3-chlorophenylmaleimide, N- (4-n-butylphenyl) maleimide, N- (anilinophenyl) maleimide, N- (2,3-xylyl) maleimide, 2,3-dichloro-N- (2 ', 6'-diethylphenyl) maleimide, 2,3-dichloro-N- (2 And '-ethyl-6'-methylphenyl) maleimide.
  • 3-substituted amino-1,3-thiazolidine-2,4-dione examples include 3-benzylideneamino-1,3-thiazolidine-2,4-dione, 3- (4-methylbenzylideneamino)- 1,3-thiazolidine-2,4-dione, 3- (2-hydroxybenzylideneamino) -1,3-thiazolidine-2,4-dione, 3- (4-dimethylaminobenzylideneamino) -1,3-thiazoline -2,4-dione, 3- (2,4-dichlorobenzylideneamino) -1,3-thiazolidine-2,4-dione, and the like.
  • dithiocyano compound examples include dithiocyanomethane, dithiocyanoethane, and 2,5-dithiocyanothiophene.
  • triazine compound examples include 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine.
  • the antifouling agent (C) can be used alone or in combination of two or more of the compounds exemplified above.
  • the antifouling agent (C) is preferably cuprous oxide from the viewpoint of exhibiting stable antifouling performance among the compounds exemplified above, and in particular, cuprous oxide and copper pyrithione are used in combination. It is preferable to do.
  • the antifouling paint composition of the present invention is an antifouling paint composition comprising the polyester resin (A), the silyl ester group-containing resin (B) and the antifouling agent (C), wherein the polyester resin (A ) And the silyl ester group-containing resin (B) in a range of 3/97 to 80/20, and the antifouling agent (C) is contained in the polyester resin (A) and the resin. It is characterized by being in the range of 50 to 500% by mass based on the total mass with the silyl ester group-containing resin (B).
  • the mass ratio of the polyester resin (A) to the silyl ester group-containing resin (B) is in the range of 3/97 to 80/20, preferably in the range of 7/93 to 60/40. More preferably, it is within the range of 10/90 to 40/60.
  • the mass ratio of the polyester resin (A) to the silyl ester group-containing resin (B) is in the range of 3/97 to 80/20, the antifouling coating film obtained by the antifouling coating composition of the present invention Excellent antifouling performance can be maintained over a long period of time, and coating film defects such as coating film peeling, blistering and cracking are less likely to occur in the antifouling coating film.
  • the mass ratio of the polyester resin (A) and the silyl ester group-containing resin (B) is smaller than 3/97 or larger than 80/20, the antifouling performance of the obtained coating film is maintained for a long time. May be difficult to do.
  • the content of the antifouling agent (C) is in the range of 50 to 500% by mass based on the total mass of the polyester resin (A) and the silyl ester group-containing resin (B), preferably 250 Within the range of ⁇ 400 mass%. If the content of the antifouling agent (C) is less than 50% by mass, it may be difficult to maintain the antifouling performance of the resulting coating film for a long period of time, and the antifouling agent (C) When there is more content than 500 mass%, the physical property of the coating film obtained may fall and malfunctions, such as peeling and a swelling, may generate
  • the antifouling coating composition of the present invention comprises, in addition to the above-mentioned polyester resin (A), silyl ester group-containing resin (B) and antifouling agent (C), pigments, dyes, dehydrating agents, plasticizers, and alteration agents.
  • Sagging agent used in general coating compositions such as resins other than the polyester resin (A) or the silyl ester group-containing resin (B), organic acids, solvents, etc.
  • Various components can be blended as necessary. These components can be used alone or in combination of two or more.
  • pigments examples include color pigments such as bengara, talc, titanium oxide, yellow iron oxide, silica, calcium carbonate, barium sulfate, calcium oxide, carbon black, naphthol red, phthalocyanine blue, talc, silica, mica, clay,
  • extender pigments include calcium carbonate, kaolin, alumina white, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, and zinc sulfide.
  • the content of the pigment in the antifouling coating composition is preferably in the range of 0.05 to 1000% by mass based on the total mass of the polyester resin (A) and the silyl ester group-containing resin (B). More preferably, it is in the range of 1 to 500% by mass.
  • the above dehydrating agent is a component that contributes to improving the storage stability of the paint.
  • dehydrating agents include inorganic gypsum, hemihydrate gypsum (calcined gypsum), synthetic zeolite-based adsorbents (trade name “Molecular Sieve”, etc.), and other orthoesters ( (Methyl orthoformate, methyl orthoacetate, orthoborate, etc.), silicates, isocyanates, and the like can also be used.
  • orthoesters (Methyl orthoformate, methyl orthoacetate, orthoborate, etc.), silicates, isocyanates, and the like
  • anhydrous gypsum and hemihydrate gypsum (calcined gypsum) which are inorganic dehydrating agents are preferable.
  • These dehydrating agents may be used alone or in combination of two or more.
  • the content of the dehydrating agent in the antifouling coating composition can be adjusted as appropriate, but is 0 to 100 mass based on the total mass of the polyester resin (A) and the silyl ester group-containing resin (B). %, Preferably in the range of 0.5 to 25% by mass.
  • the plasticizer is a component that contributes to improving the crack resistance and water resistance of the resulting antifouling coating film.
  • plasticizers include tricresyl phosphate, dioctyl phthalate, chlorinated paraffin, liquid paraffin, n-paraffin, chlorinated paraffin, polybutene, terpene phenol, tricresyl phosphate (TCP), polyvinylethyl. Examples include ether. These plasticizers may be used alone or in combination of two or more.
  • the content of the plasticizer in the antifouling coating composition can be appropriately adjusted, but is 0.5 to 10 mass based on the total mass of the polyester resin (A) and the silyl ester group-containing resin (B). %, Preferably 1 to 5% by mass.
  • antioxidants examples include 2,6-di-tert-butyl-4-methylphenol.
  • alteration agent examples include organic waxes (polyethylene wax, oxidized polyethylene wax, polyamide wax, amide wax, hydrogenated castor oil wax, etc.), organic clay compounds (Al, Ca, Zn amine salts, stears). Rate salts, lecithin salts, alkyl sulfonates, etc.), bentonite, synthetic fine silica and the like. These alteration agents may be used alone or in combination of two or more.
  • the content of the discoloring agent in the antifouling coating composition can be appropriately adjusted. For example, the content is 0.25 based on the total mass of the polyester resin (A) and the silyl ester group-containing resin (B). Within the range of ⁇ 50 mass%.
  • the antifouling coating composition of the present invention contains one or more other resins as necessary in addition to the polyester resin (A) and the silyl ester group-containing resin (B) as described above.
  • resins include acrylic resins having no silyl ester group, acrylic silicone resins, epoxy resins, fluororesins, polybutene resins, silicone rubbers, urethane resins, polyamide resins, and vinyl chloride-based resins.
  • Examples include copolymer resins, chlorinated rubber, chlorinated olefin resins, styrene / butadiene copolymer resins, ketone resins, ethylene-vinyl acetate copolymer resins, vinyl chloride resins, alkyd resins, coumarone resins, terpene phenol resins, petroleum resins, etc. .
  • the antifouling coating composition of the present invention may contain a known rosin compound.
  • rosin compounds include rosin, rosin derivatives, rosin metal salts, and the like.
  • the rosin include tall rosin, gum rosin, and wood rosin.
  • the rosin derivative include hydrogenated rosin, maleated rosin obtained by reacting rosin and maleic anhydride, formylated rosin, and polymerized rosin.
  • the rosin metal salt include zinc chloride, calcium rosinate, copper rosinate, magnesium rosinate, and other reactants of metal compounds and rosin. These rosin compounds can be used alone or in combination of two or more.
  • the usage-amount of the said rosin type compound is not specifically limited, 50 mass% or less is preferable on the basis of the total mass of polyester resin (A) and silyl ester group containing resin (B), and 30 mass% or less. Is more preferable.
  • the antifouling coating composition of the present invention comprises an aliphatic solvent, an aromatic solvent (xylene, toluene, etc.), a ketone solvent (methyl isobutyl ketone, cyclohexanone, etc.), an ester solvent, an ether solvent (propylene glycol monomethyl ether, propylene glycol monomethyl ether).
  • An organic solvent generally used as a solvent for an antifouling paint such as an acetate solvent or the like, or an alcohol solvent (such as isopropyl alcohol) can be blended.
  • the blending amount of the organic solvent can be adjusted as appropriate. For example, the blending amount is such that the total solid content of the antifouling coating composition is in the range of 20 to 90% by mass. You may add further according to property etc.
  • the antifouling paint composition of the present invention can be prepared by the same method as known antifouling paint compositions.
  • the polyester resin (A), the silyl ester group-containing resin (B), the antifouling agent (C), and, if necessary, the organic solvent and additives are added to the stirring tank at once or sequentially. , Stirring and mixing.
  • the coated article of the present invention is an article in which the surface of a base material is coated with the antifouling paint composition of the present invention.
  • the coated article includes at least a step of applying or impregnating the antifouling coating composition to the surface of the substrate one or more times, and a step of drying the antifouling coating composition covering the surface of the substrate. It can obtain by the manufacturing method containing.
  • the base material examples include a base material that is in contact with seawater or fresh water (for example, constantly or intermittently), specifically, an underwater structure; a ship outer plate or a ship bottom; a water conduit or a cooling pipe of a power plant; Examples include aquaculture or stationary fishing nets, fishing gear, or floats used in them; fishing net accessories such as ropes.
  • the film thickness of the coating film obtained from the antifouling coating composition of the present invention can be appropriately adjusted in consideration of the consumption rate (dissolution rate) of the coating film, for example, the film per coating time
  • the thickness ( ⁇ m) may be 30 to 250 ⁇ m / time, preferably about 75 to 150 ⁇ m / time, and may be applied twice or more as necessary.
  • the antifouling paint composition of the present invention is applied to the surface of the base material after applying a primer, an anticorrosive paint, and, if necessary, a binder paint to the surface by brushing, spraying, roller coating, dipping or the like. It may be painted. Further, the antifouling coating composition of the present invention may be overcoated on the surface of an existing antifouling coating film. Although the coating film can be dried at room temperature, it may be dried by heating at a temperature up to about 100 ° C. if necessary.
  • polyester resin (A) Production of polyester resin (A1)
  • a 2 L reactor equipped with a thermometer, a stirrer and a rectifying tower 527.2 parts of PA, 267.2 parts of NPG, 269.7 parts of DEG were charged, and the temperature of the reactor contents was raised to 160 ° C.
  • the temperature was raised from 160 ° C. to 230 ° C. in 3 hours, and the content temperature was maintained at 230 ° C. for 2 hours.
  • the rectification column was replaced with a water separator, and about 50.0 parts of xylene was added to the reactor.
  • the polycondensation was carried out while removing the condensed water by azeotropically distilling water and xylene.
  • PA phthalic anhydride
  • iPA isophthalic acid
  • AD isophthalic acid
  • HHPA adipic acid
  • HHPA hexahydrophthalic anhydride
  • EG ethylene glycol
  • PG propylene glycol
  • NPG propylene glycol
  • 1,6-hexane Diol BEPG
  • 1,4-cyclohexanedimethanol DEG
  • diethylene glycol, TEG triethylene glycol, tetraEG
  • tetraethylene glycol, DPG dipropylene Glycol, TMP
  • Production Example 13 Production of Polyester Resin (A13)
  • a 2 L reactor equipped with a thermometer, a stirrer, and a rectifying tower was charged with 377.8 parts iPA, 364.2 parts BEPG, and 227.6 parts TEG.
  • the temperature of the reactor contents was raised to 160 ° C.
  • the temperature was raised from 160 ° C. to 230 ° C. in 3 hours, and the content temperature was maintained at 230 ° C. for 2 hours.
  • the rectification column was replaced with a water separator, and about 50.0 parts of xylene was added to the reactor.
  • the polycondensation was carried out while removing the condensed water by azeotropically distilling water and xylene.
  • the content temperature was cooled to 160 ° C. Further, 112.3 parts of PA was added and maintained at 160 ° C. for 1 hour for addition reaction (half esterification), and then cooling was started. After cooling to 130 ° C., xylene was added and diluted to obtain a resin solution of a polyester resin (A13) having a solid content of 70%.
  • silyl ester group-containing resin (B) (Production Example 18) Production of silyl ester group-containing resin (B1) After charging 40 parts of xylene into a flask equipped with a stirrer, the liquidus temperature was maintained at 140 ° C. A mixture of each unit amount of each unsaturated monomer described in 2 and 1 part of a peroxide-based polymerization initiator “Perbutyl I” (trade name, manufactured by NOF Corporation) was placed into a flask. Dropped over time. After completion of the dropping, the temperature was maintained for 30 minutes. Next, a mixture of 10 parts of xylene and 1 part of “Perbutyl I” was added dropwise over 20 minutes.
  • a resin solution was prepared by adding xylene to the flask so that the solid content concentration of the produced resin was 50% by mass, and a resin solution of the silyl ester group-containing resin (B1) was obtained.

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Abstract

The purpose of the present invention is to provide: an antifouling coating material composition which is capable of forming an antifouling coating film that is able to maintain excellent antifouling properties for a long period of time and is not susceptible to the occurrence of coating film defects such as coating film separation, blisters and cracks; and a coated article which is obtained by coating an object to be coated such as a fishing net, a boat or ship, or a structure in the ocean or on the gulf coast with the antifouling coating material composition. The present invention provides: an antifouling coating material composition which contains (A) a specific polyester resin, (B) a silyl ester group-containing resin and (C) an antifouling agent; and a coated article which is coated with the composition.

Description

防汚塗料組成物、及びそれを塗装してなる塗装物品Antifouling paint composition and coated article obtained by coating the same
　本発明は、防汚塗料組成物、及びそれを塗装してなる塗装物品に関し、さらに詳しくは、優れた防汚性を長期間維持することが可能な防汚塗膜を形成し得る防汚塗料組成物、及びそれを被塗物に塗装してなる塗装物品に関する。 The present invention relates to an antifouling paint composition and a coated article formed by coating the antifouling paint composition, and more specifically, an antifouling paint capable of forming an antifouling coating film capable of maintaining excellent antifouling properties for a long period of time. The present invention relates to a composition and a coated article obtained by coating the composition on an object.
　近年、海洋汚染が懸念される有機錫含有共重合体に替わる防汚塗料用樹脂として、海水中で加水分解するエステル結合を重合体の側鎖に導入した防汚塗料用樹脂が、各種検討されている。中でも、トリアルキルシリルエステル基含有樹脂を用いた防汚塗料組成物は、トリアルキルシリルエステル部分が海水中で加水分解されるため、前記防汚塗料組成物から得られる塗膜が表面より徐々に海水中に溶解する性質を有し、防汚塗料用樹脂として実用化に至っている。 In recent years, various antifouling paint resins in which ester bonds that hydrolyze in seawater have been introduced into the side chains of the polymer have been studied as substitutes for antifouling paints that replace organic tin-containing copolymers that are a concern for marine pollution. ing. Among them, in the antifouling paint composition using the trialkylsilyl ester group-containing resin, since the trialkylsilyl ester portion is hydrolyzed in seawater, the coating film obtained from the antifouling paint composition is gradually from the surface. It has the property of dissolving in seawater and has been put to practical use as a resin for antifouling paints.
　このようなトリアルキルシリルエステル基含有樹脂は、トリアルキルシリルエステル基の構造により、塗膜の溶解速度が異なる。例えば、トリ－ｎ－ブチルシリルエステル基含有樹脂を用いた防汚塗料組成物は、得られる塗膜の溶解速度が速いため、塗膜の防汚性能を長期間維持することが困難であった。一方、ケイ素原子に分岐アルキル基が結合したトリオルガノシリルエステル基含有樹脂を用いた防汚塗料組成物は、得られる塗膜の溶解速度が遅いため、海水温度の低い海域では、水棲汚損生物が付着しやすいという問題があった。そこで、後者の防汚塗料組成物においては、ロジン又はロジン誘導体を添加することによって塗膜の溶解速度を制御する方法が検討されている（特許文献１～３）。しかしながら、このような方法においても、ロジン又はロジン誘導体の使用量が少ないと、海水中における塗膜の溶解性が十分に得られず、防汚効果が持続しにくいという問題があった。一方、ロジン又はロジン誘導体の使用量が多いと、塗膜の溶解速度が大きくなり、防汚効果は向上するが、塗膜の物性や接着性が低下してしまい、防汚効果の長期維持が困難となり、塗膜剥離、ブリスター、クラックなどの塗膜欠陥が発生し易い傾向があった。 Such a trialkylsilyl ester group-containing resin has different coating rate depending on the structure of the trialkylsilyl ester group. For example, an antifouling paint composition using a tri-n-butylsilyl ester group-containing resin has a high dissolution rate of the obtained coating film, and it is difficult to maintain the antifouling performance of the coating film for a long period of time. . On the other hand, the antifouling coating composition using a triorganosilyl ester group-containing resin in which a branched alkyl group is bonded to a silicon atom has a slow dissolution rate of the resulting coating film. There was a problem of easy adhesion. Therefore, in the latter antifouling coating composition, methods for controlling the dissolution rate of the coating film by adding rosin or a rosin derivative have been studied (Patent Documents 1 to 3). However, even in such a method, if the amount of rosin or rosin derivative used is small, there is a problem that the solubility of the coating film in seawater cannot be sufficiently obtained and the antifouling effect is difficult to be sustained. On the other hand, if the amount of rosin or rosin derivative used is large, the dissolution rate of the coating film increases and the antifouling effect is improved, but the physical properties and adhesiveness of the coating film decrease, and the antifouling effect can be maintained for a long time. There was a tendency that coating film defects such as coating film peeling, blistering and cracking were likely to occur.
特開平１０－３００７１号公報Japanese Patent Laid-Open No. 10-30071 特開２００２－５３７９７号公報JP 2002-53797 A 特開２０１１－２６３５７号公報JP 2011-26357 A
　本発明の目的は、長期間に亘って優れた防汚性を維持することができ、塗膜剥離、ブリスター、クラックなどの塗膜欠陥が発生し難い防汚塗膜を形成できる防汚塗料組成物、及び該防汚塗料組成物を漁網、船舶、海洋や湾岸等の構造物などの被塗物に塗装してなる塗装物品を提供することである。 An object of the present invention is to provide an antifouling paint composition capable of maintaining an excellent antifouling property over a long period of time and capable of forming an antifouling coating film that is less susceptible to coating film defects such as coating film peeling, blistering, and cracks And a coated article formed by coating the antifouling coating composition on an object to be coated such as a fishing net, a ship, a structure such as the ocean or the bay.
　本発明者らは、前記目的を達成するべく鋭意検討を行い、特定のポリエステル樹脂及びシリルエステル基含有樹脂を含む防汚塗料組成物により得られた塗膜は、海洋中への塗膜溶解速度を制御することができるとともに、長期間に亘って優れた防汚性を維持することができるといった塗膜の物性に優れるため、上述の防汚塗料組成物を船舶の船底部に塗装した場合に、航行又は停泊中に塗膜剥離、ブリスター、クラックなどの塗膜欠陥が発生し難くなることを見出した。本発明は、かかる知見に基づいて完成されたものである。 The present inventors have intensively studied to achieve the above object, and the coating film obtained from the antifouling coating composition containing the specific polyester resin and the silyl ester group-containing resin has a coating film dissolution rate in the ocean. When the above-mentioned antifouling paint composition is applied to the bottom of a ship, the paint film has excellent physical properties such as being able to control the antifouling property over a long period of time. The present inventors have found that coating film defects such as coating film peeling, blistering, and cracks are less likely to occur during navigation or berthing. The present invention has been completed based on such findings.
　本発明は、以下の防汚塗料組成物、及び該防汚塗料組成物を被塗物に塗装してなる塗装物品を提供するものである。
項１．　ポリエステル樹脂（Ａ）、シリルエステル基含有樹脂（Ｂ）及び防汚剤（Ｃ）を含む防汚塗料組成物であって、前記シリルエステル基含有樹脂（Ｂ）が、一般式（Ｉ）：
Ｒ5－ＣＨ＝Ｃ（Ｒ4）－ＣＯＯ－ＳｉＲ1Ｒ2Ｒ3・・・（Ｉ）
［式（Ｉ）中、Ｒ4は水素原子又はメチル基を示し、Ｒ1、Ｒ2及びＲ3はそれぞれ独立に炭化水素基を示し、Ｒ5は水素原子又はＲ6－Ｏ－ＣＯ－（ただし、Ｒ6は有機基又は－ＳｉＲ7Ｒ8Ｒ9で表されるシリル基を示し、Ｒ7、Ｒ8及びＲ9はそれぞれ独立に炭化水素基を示す。）を示す。］で表される単量体（ｂ１）の１種又は２種以上と、前記単量体（ｂ１）以外の単量体（ｂ２）の１種又は２種以上との共重合体からなり、前記ポリエステル樹脂（Ａ）と前記シリルエステル基含有樹脂（Ｂ）との質量比が３／９７～８０／２０の範囲内であり、かつ、前記防汚剤（Ｃ）含有量が前記ポリエステル樹脂（Ａ）と前記シリルエステル基含有樹脂（Ｂ）との合計質量を基準として５０～５００質量％の範囲内であることを特徴とする、前記防汚塗料組成物。
項２．　前記ポリエステル樹脂（Ａ）の酸価が０～１２０ＫＯＨｍｇ／ｇの範囲内である、項１に記載の防汚塗料組成物。
項３．　前記ポリエステル樹脂（Ａ）の重量平均分子量が１５０００以下である、項１又は２に記載の防汚塗料組成物。
項４．　前記ポリエステル樹脂（Ａ）と前記シリルエステル基含有樹脂（Ｂ）との質量比が７／９３～６０／４０の範囲内である、項１～３のいずれか一項に記載の防汚塗料組成物。
項５．　前記シリルエステル基含有樹脂（Ｂ）は、前記単量体（ｂ１）と前記単量体（ｂ２）との質量比（ｂ１）／（ｂ２）が２０／８０～７０／３０の範囲内である、項１～４のいずれか一項に記載の防汚塗料組成物。
項６．　項１～５のいずれか一項に記載の防汚塗料組成物を被塗物に塗装してなる塗装物品。 The present invention provides the following antifouling paint composition and a coated article obtained by coating the antifouling paint composition on an article to be coated.
Item 1. An antifouling paint composition comprising a polyester resin (A), a silyl ester group-containing resin (B) and an antifouling agent (C), wherein the silyl ester group-containing resin (B) is represented by the general formula (I):
R 5 —CH═C (R 4 ) —COO—SiR 1 R 2 R 3 (I)
[In the formula (I), R 4 represents a hydrogen atom or a methyl group, R 1 , R 2 and R 3 each independently represents a hydrocarbon group, and R 5 represents a hydrogen atom or R 6 —O—CO— ( R 6 represents an organic group or a silyl group represented by —SiR 7 R 8 R 9 , and R 7 , R 8 and R 9 each independently represents a hydrocarbon group. And a copolymer of one or more monomers (b1) and one or more monomers (b2) other than the monomer (b1), The mass ratio of the polyester resin (A) to the silyl ester group-containing resin (B) is in the range of 3/97 to 80/20, and the antifouling agent (C) content is the polyester resin ( The antifouling coating composition, wherein the antifouling coating composition is in the range of 50 to 500% by mass based on the total mass of A) and the silyl ester group-containing resin (B).
Item 2. Item 2. The antifouling coating composition according to Item 1, wherein the acid value of the polyester resin (A) is in the range of 0 to 120 KOHmg / g.
Item 3. Item 3. The antifouling coating composition according to Item 1 or 2, wherein the polyester resin (A) has a weight average molecular weight of 15000 or less.
Item 4. Item 4. The antifouling paint composition according to any one of Items 1 to 3, wherein a mass ratio of the polyester resin (A) to the silyl ester group-containing resin (B) is in the range of 7/93 to 60/40. object.
Item 5. In the silyl ester group-containing resin (B), the mass ratio (b1) / (b2) between the monomer (b1) and the monomer (b2) is in the range of 20/80 to 70/30. 5. The antifouling paint composition according to any one of items 1 to 4.
Item 6. Item 6. A coated article obtained by coating the object to be coated with the antifouling coating composition according to any one of Items 1 to 5.
　本発明の防汚塗料組成物は、優れた防汚性を長期間に亘って維持可能であり、かつ、塗膜剥離、ブリスター、クラックなどの塗膜欠陥が発生しにくい塗膜を形成することができる。 The antifouling paint composition of the present invention is capable of maintaining a superior antifouling property over a long period of time, and forms a coating film in which coating film defects such as coating film peeling, blistering and cracking are unlikely to occur. Can do.
　本発明の防汚塗料組成物は、ポリエステル樹脂（Ａ）、シリルエステル基含有樹脂（Ｂ）及び防汚剤（Ｃ）を含む防汚塗料組成物であって、前記シリルエステル基含有樹脂（Ｂ）が、一般式（Ｉ）：
Ｒ5－ＣＨ＝Ｃ（Ｒ4）－ＣＯＯ－ＳｉＲ1Ｒ2Ｒ3・・・（Ｉ）
［式（Ｉ）中、Ｒ4は水素原子又はメチル基を示し、Ｒ1、Ｒ2及びＲ3はそれぞれ独立に炭化水素基を示し、Ｒ5は水素原子又はＲ6－Ｏ－ＣＯ－（ただし、Ｒ6は有機基又は－ＳｉＲ7Ｒ8Ｒ9で表されるシリル基を示し、Ｒ7、Ｒ8及びＲ9はそれぞれ独立に炭化水素基を示す。）を示す。］で表される単量体（ｂ１）の１種又は２種以上と、前記単量体（ｂ１）以外の単量体（ｂ２）の１種又は２種以上との共重合体からなり、前記ポリエステル樹脂（Ａ）と前記シリルエステル基含有樹脂（Ｂ）との質量比が３／９７～８０／２０の範囲内であり、かつ、前記防汚剤（Ｃ）の含有量が前記ポリエステル樹脂（Ａ）と前記シリルエステル基含有樹脂（Ｂ）との合計質量を基準として５０～５００質量％の範囲内であることを特徴とする。以下、本発明の防汚塗料組成物について詳細に説明する。 The antifouling paint composition of the present invention is an antifouling paint composition comprising a polyester resin (A), a silyl ester group-containing resin (B) and an antifouling agent (C), wherein the silyl ester group-containing resin (B ) Is represented by the general formula (I):
R 5 —CH═C (R 4 ) —COO—SiR 1 R 2 R 3 (I)
[In the formula (I), R 4 represents a hydrogen atom or a methyl group, R 1 , R 2 and R 3 each independently represents a hydrocarbon group, and R 5 represents a hydrogen atom or R 6 —O—CO— ( R 6 represents an organic group or a silyl group represented by —SiR 7 R 8 R 9 , and R 7 , R 8 and R 9 each independently represents a hydrocarbon group. And a copolymer of one or more monomers (b1) and one or more monomers (b2) other than the monomer (b1), The mass ratio of the polyester resin (A) to the silyl ester group-containing resin (B) is in the range of 3/97 to 80/20, and the content of the antifouling agent (C) is the polyester resin. It is characterized by being in the range of 50 to 500% by mass based on the total mass of (A) and the silyl ester group-containing resin (B). Hereinafter, the antifouling coating composition of the present invention will be described in detail.
　［ポリエステル樹脂（Ａ）］
　本発明の防汚塗料組成物に用いられるポリエステル樹脂（Ａ）は、酸成分（ａ１）とアルコール成分（ａ２）とを主要原料として、これら各成分のエステル化反応及び／又はエステル交換反応によって製造することができる。 [Polyester resin (A)]
The polyester resin (A) used in the antifouling coating composition of the present invention is produced by using an acid component (a1) and an alcohol component (a2) as main raw materials by esterification and / or transesterification of these components. can do.
　酸成分（ａ１）
　本発明において、酸成分（ａ１）は、ポリエステル樹脂の製造に通常使用される酸成分を使用することができる。そのような酸成分としては、例えば、脂環族多塩基酸、脂肪族多塩基酸、芳香族多塩基酸、芳香族モノカルボン酸、脂肪族モノカルボン酸、脂環族モノカルボン酸、並びにこれらの酸のエステル化物、無水物及びハロゲン化物が挙げられる。 Acid component (a1)
In this invention, the acid component (a1) can use the acid component normally used for manufacture of a polyester resin. Examples of such acid components include alicyclic polybasic acids, aliphatic polybasic acids, aromatic polybasic acids, aromatic monocarboxylic acids, aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and these Examples include esterified products, anhydrides, and halides.
　脂環族多塩基酸は、一般に、１分子中に１個以上の脂環式構造（主として４～６員環）と２個以上のカルボキシル基とを有する化合物、並びに該化合物の酸無水物、エステル化物及びハロゲン化物を用いることができる。そのような脂環族多塩基酸としては、例えば、１，２－シクロヘキサンジカルボン酸、１，３－シクロヘキサンジカルボン酸、１，４－シクロヘキサンジカルボン酸、２－シクロヘキセン－１，２－ジカルボン酸、３－シクロヘキセン－１，２－ジカルボン酸、４－シクロヘキセン－１，２－ジカルボン酸、テトラヒドロメチルフタル酸類、３－メチル－１，２－シクロヘキサンジカルボン酸、４－メチル－１，２－シクロヘキサンジカルボン酸、１，２，４－シクロヘキサントリカルボン酸、１，３，５－シクロヘキサントリカルボン酸等の脂環族多価カルボン酸；これら脂環族多価カルボン酸の無水物；これら脂環族多価カルボン酸の低級アルキルエステル化物などが挙げられ、これらは、単独で又は２種以上を組み合わせて使用することができる。 Generally, an alicyclic polybasic acid is a compound having one or more alicyclic structures (mainly 4 to 6 membered rings) and two or more carboxyl groups in one molecule, and acid anhydrides of the compounds, Esterified products and halides can be used. Examples of such alicyclic polybasic acids include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-cyclohexene-1,2-dicarboxylic acid, 3 -Cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, tetrahydromethylphthalic acids, 3-methyl-1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, Alicyclic polycarboxylic acids such as 1,2,4-cyclohexanetricarboxylic acid and 1,3,5-cyclohexanetricarboxylic acid; anhydrides of these alicyclic polycarboxylic acids; Examples include lower alkyl esterified compounds, which may be used alone or in combination of two or more. Can.
　脂肪族多塩基酸は、一般に、１分子中に２個以上のカルボキシル基を有する脂肪族化合物、該脂肪族化合物の酸無水物、該脂肪族化合物のハロゲン化物などを用いることができる。そのような脂肪族多塩基酸としては、例えば、コハク酸、マロン酸、マレイン酸、フマル酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカン二酸、ドデカン二酸、ブラシル酸、オクタデカン二酸、クエン酸等の脂肪族多価カルボン酸；これら脂肪族多価カルボン酸の無水物；これら脂肪族多価カルボン酸のハロゲン化などが挙げられ、これらは、単独で又は２種以上を組み合わせて使用することができる。 As the aliphatic polybasic acid, generally, an aliphatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aliphatic compound, a halide of the aliphatic compound, and the like can be used. Examples of such aliphatic polybasic acids include succinic acid, malonic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid. Aliphatic polycarboxylic acids such as brassic acid, octadecanedioic acid and citric acid; anhydrides of these aliphatic polyvalent carboxylic acids; halogenation of these aliphatic polyvalent carboxylic acids and the like. Alternatively, two or more kinds can be used in combination.
　芳香族多塩基酸は、一般に、１分子中に２個以上のカルボキシル基を有する芳香族化合物、並びに該芳香族化合物の酸無水物、該芳香族化合物のエステル化物及び芳香族化合物のハロゲン化物を用いることができる。 An aromatic polybasic acid generally comprises an aromatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aromatic compound, an esterified product of the aromatic compound, and a halide of the aromatic compound. Can be used.
　１分子中に２個のカルボキシル基を有する芳香族多塩基酸としては、例えば、フタル酸、イソフタル酸、テレフタル酸、ナフタレンジカルボン酸、４，４’－ビフェニルジカルボン酸等の芳香族多価カルボン酸；これら芳香族多価カルボン酸の無水物などが挙げられる。 Examples of the aromatic polybasic acid having two carboxyl groups in one molecule include aromatic polybasic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and 4,4′-biphenyldicarboxylic acid. And anhydrides of these aromatic polycarboxylic acids.
　１分子中に３個以上のカルボキシル基を有する芳香族多塩基酸としては、例えば、３価の芳香族多価カルボン酸、４価の芳香族多価カルボン酸などが挙げられる。３価の芳香族多価カルボン酸としては、例えば、トリメリット酸、無水トリメリット酸、トリメリット酸アルキルエステル、トリメリット酸ハロゲン化物等のトリメリット酸類；ヘミメリット酸、無水ヘミメリット酸、ヘミメリット酸アルキルエステル、ヘミメリット酸ハロゲン化物等のヘミメリット酸類；トリメシン酸、トリメシン酸アルキルエステル、トリメシン酸ハロゲン化物等のトリメシン酸類；カルボキシル基の芳香環への結合位置が異なる各種ナフタレントリカルボン酸及びその無水物；カルボキシル基の芳香環への結合位置が異なる各種アントラセントリカルボン酸及びその無水物；カルボキシル基の芳香環への結合位置が異なる各種ビフェニルトリカルボン酸及びその無水物；カルボキシル基の芳香環への結合位置が異なる各種ベンゾフェノントリカルボン酸及びその無水物；エチレンビストリメリット酸及びその無水物などが挙げられる。また、４価の芳香族多価カルボン酸としては、ピロメリット酸、ピロメリット酸二無水物、ピロメリット酸アルキルエステル、ピロメリット酸ハロゲン化物等のピロメリット酸類；メロファン酸、メロファン酸二無水物、メロファン酸アルキルエステル、メロファン酸ハロゲン化物等のメロファン酸類；プレーニト酸（prehnitic acid）、プレーニト酸無水物、プレーニト酸アルキルエステル、プレーニト酸ハロゲン化物等のプレーニト酸類などが挙げられる。上記の芳香族多塩基酸は、単独で又は２種以上を組み合わせて使用することができる。 Examples of the aromatic polybasic acid having 3 or more carboxyl groups in one molecule include trivalent aromatic polyvalent carboxylic acids and tetravalent aromatic polyvalent carboxylic acids. Examples of the trivalent aromatic polyvalent carboxylic acid include trimellitic acids such as trimellitic acid, trimellitic anhydride, trimellitic acid alkyl ester, trimellitic acid halide; hemimertic acid, hemimellitic anhydride, hemi Hemimellitic acids such as alkyl melicates and halides of hemimellitic acid; trimesic acids such as trimesic acid, trimesic acid alkyl esters and trimesic acid halides; various naphthalene tricarboxylic acids having different bonding positions of carboxyl groups to aromatic rings and their Anhydrous; various anthractricarboxylic acids with different bonding positions of carboxyl groups to aromatic rings and their anhydrides; various biphenyltricarboxylic acids with different bonding positions of carboxyl groups to aromatic rings and anhydrides; carboxyl groups to aromatic rings Bonding position is different Seed benzophenone tricarboxylic acid and anhydrides thereof; ethylene bis trimellitic acid and its anhydride. In addition, examples of tetravalent aromatic polyvalent carboxylic acids include pyromellitic acids such as pyromellitic acid, pyromellitic dianhydride, pyromellitic acid alkyl ester, and pyromellitic halide; merophanic acid and melophanic dianhydride. And melophanoic acids such as melophanic acid alkyl ester and merophanic acid halide; and planitic acids such as prehnitic acid, prenic acid anhydride, prenic acid alkyl ester, and planitic acid halide. Said aromatic polybasic acid can be used individually or in combination of 2 or more types.
　本発明において、ポリエステル樹脂（Ａ）の製造に用いられる酸成分（ａ１）は、芳香族モノカルボン酸、脂肪族モノカルボン酸、脂環族モノカルボン酸などのモノカルボン酸を使用してもよい。芳香族モノカルボン酸としては、例えば、安息香酸、メチル安息香酸、エチル安息香酸、ｐ－ｔ－ブチル安息香酸、ナフタレンカルボン酸、サリチル酸、４－メチル安息香酸、３－メチル安息香酸、フェノキシ酢酸、ビフェニルカルボン酸などが挙げられる。また、脂肪族モノカルボン酸としては、例えば、酢酸、乳酸、プロピオン酸、酪酸、オクタン酸、デカン酸、ドデカン酸、カプリル酸、ペラルゴン酸、カプリン酸、ウンデカン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、エライジン酸、ブラシジン酸、リノール酸、リノレン酸、ロジン酸、ヤシ油脂肪酸、綿実油脂肪酸、麻実油脂肪酸、米ぬか油脂肪酸、魚油脂肪酸、トール油脂肪酸、大豆油脂肪酸、アマニ油脂肪酸、桐油脂肪酸、ナタネ油脂肪酸、ヒマシ油脂肪酸、脱水ヒマシ油脂肪酸、サフラワー油脂肪酸等の飽和又は不飽和の脂肪族モノカルボン酸が挙げられ、これらは、単独で又は２種以上を組み合わせて使用することができる。 In the present invention, the acid component (a1) used in the production of the polyester resin (A) may be a monocarboxylic acid such as an aromatic monocarboxylic acid, an aliphatic monocarboxylic acid, or an alicyclic monocarboxylic acid. . Examples of the aromatic monocarboxylic acid include benzoic acid, methylbenzoic acid, ethylbenzoic acid, pt-butylbenzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, Biphenyl carboxylic acid etc. are mentioned. Examples of the aliphatic monocarboxylic acid include acetic acid, lactic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, dodecanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid. , Stearic acid, oleic acid, elaidic acid, brassic acid, linoleic acid, linolenic acid, rosin acid, coconut oil fatty acid, cottonseed oil fatty acid, hemp oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, linseed oil Saturated or unsaturated aliphatic monocarboxylic acids such as fatty acids, tung oil fatty acids, rapeseed oil fatty acids, castor oil fatty acids, dehydrated castor oil fatty acids, safflower oil fatty acids, and the like are used alone or in combination of two or more. Can be used.
　上記脂環族モノカルボン酸としては、例えば、シクロヘキサンカルボン酸、シクロペンタンカルボン酸、シクロヘプタンカルボン酸、４－エチルシクロヘキサンカルボン酸、４－へキシルシクロヘキサンカルボン酸、４－ラウリルシクロヘキサンカルボン酸などが挙げられ、これらは、単独で又は２種以上を組み合わせて使用することができる。 Examples of the alicyclic monocarboxylic acid include cyclohexanecarboxylic acid, cyclopentanecarboxylic acid, cycloheptanecarboxylic acid, 4-ethylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, 4-laurylcyclohexanecarboxylic acid, and the like. These can be used alone or in combination of two or more.
　本発明において、ポリエステル樹脂（Ａ）の製造に用いられる酸成分（ａ１）は、上記モノカルボン酸のグリセリンエステル等のエステル化物を含んでいてもよい。モノカルボン酸のグリセリンエステルとしては、例えば、ヤシ油、綿実油、麻実油、米ぬか油、魚油、トール油、大豆油、アマニ油、桐油、ナタネ油、ヒマシ油、脱水ヒマシ油、サフラワー油などが挙げられる。 In the present invention, the acid component (a1) used in the production of the polyester resin (A) may contain an esterified product such as a glycerin ester of the monocarboxylic acid. Examples of glycerin esters of monocarboxylic acids include coconut oil, cottonseed oil, hemp seed oil, rice bran oil, fish oil, tall oil, soybean oil, linseed oil, tung oil, rapeseed oil, castor oil, dehydrated castor oil, safflower oil, and the like. Can be mentioned.
　また、本発明において、ポリエステル樹脂（Ａ）の製造に用いられる酸成分（ａ１）は、防汚性の長期維持の観点から、芳香族多塩基酸を含むことが好ましく、その含有量は、酸成分（ａ１）の合計モル数を基準として、３０モル％以上、好ましくは５０モル％以上、更に好ましくは７０モル％以上である。 Moreover, in this invention, it is preferable that the acid component (a1) used for manufacture of a polyester resin (A) contains an aromatic polybasic acid from a viewpoint of antifouling property long-term maintenance, The content is acid. Based on the total number of moles of component (a1), it is at least 30 mol%, preferably at least 50 mol%, more preferably at least 70 mol%.
　アルコール成分（ａ２）
　本発明において、アルコール成分（ａ２）は、ポリエステル樹脂の製造に通常使用されるアルコール成分を使用することができる。そのようなアルコール成分としては、脂環族ジオール、脂肪族ジオール、芳香族ジオール等の２価アルコール及び／又は３価以上の多価アルコールを含むものが好ましく、例えば、エチレングリコ－ル、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ペンタエチレングリコール、１，２－プロピレングリコ－ル、ジ－１，２－プロピレングリコール、トリ－１，２－プロピレングリコール、１，２－ブチレングリコ－ル、２，３－ブチレングリコ－ル、１，２－ヘキサンジオール、１，２－ジヒドロキシシクロヘキサン、３－エトキシプロパン－１，２－ジオール、３－フェノキシプロパン－１，２－ジオール、ネオペンチルグリコール、２－メチル－１，３－プロパンジオール、２－メチル－２，４－ペンタンジオール、３－メチル－１，３－ブタンジオール、２－エチル－１，３－ヘキサンジオール、２，２－ジエチル－１，３－プロパンジオール、２，２，４－トリメチル－１，３－ペンタンジオール、２－ブチル－２－エチル－１，３－プロパンジオール、２－フェノキシプロパン－１，３－ジオール、２－メチル－２－フェニルプロパン－１，３－ジオール、１，３－プロピレングリコール、１，３－ブチレングリコール、２－エチル－１，３―オクタンジオール、１，３－ジヒドロキシシクロヘキサン、１，４－ブタンジオール、１，４－ジヒドロキシシクロヘキサン、１，５－ペンタンジオール、１，６－ヘキサンジオール、２，５－ヘキサンジオール、３－メチル－１，５－ペンタンジオール、１，４－ジメチロ－ルシクロヘキサン、トリシクロデカンジメタノール、２，２－ジメチル－３－ヒドロキシプロピル－２，２－ジメチル－３－ヒドロキシプロピオネート（ヒドロキシピバリン酸とネオペンチルグリコールとのエステル化物）、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＡのアルキレンオキサイド付加物、ビス（４－ヒドロキシヘキシル）－２，２－プロパン、ビス（４－ヒドロキシヘキシル）メタン、３，９－ビス（１，１－ジメチル－２－ヒドロキシエチル）－２，４，８，１０－テトラオキサスピロ［５，５］ウンデカン、ビス（ヒドロキシエチル）テレフタレート等のエステルジオール化合物、ジエチレングリコール、トリエチレングリコール、グリセリン、ジグリセリン、トリグリセリン、１，２，６－ヘキサントリオール、ペンタエリスリトール、ジペンタエリスリトール、ソルビトール、マンニット、トリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、トリス（２－ヒドロキシエチル）イソシアヌレート、これらの多価アルコールにε－カプロラクトン等のラクトン化合物を付加させたポリラクトンポリオール化合物などが挙げられ、これらは、それぞれ単独で又は２種以上を組み合わせて使用することができる。 Alcohol component (a2)
In this invention, the alcohol component (a2) can use the alcohol component normally used for manufacture of a polyester resin. As such an alcohol component, those containing dihydric alcohols such as alicyclic diols, aliphatic diols, aromatic diols and / or trihydric or higher polyhydric alcohols are preferable, for example, ethylene glycol, diethylene glycol, Triethylene glycol, tetraethylene glycol, pentaethylene glycol, 1,2-propylene glycol, di-1,2-propylene glycol, tri-1,2-propylene glycol, 1,2-butylene glycol, 2, 3-butylene glycol, 1,2-hexanediol, 1,2-dihydroxycyclohexane, 3-ethoxypropane-1,2-diol, 3-phenoxypropane-1,2-diol, neopentyl glycol, 2-methyl -1,3-propanediol, 2-methyl-2,4-pen Diol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentane Diol, 2-butyl-2-ethyl-1,3-propanediol, 2-phenoxypropane-1,3-diol, 2-methyl-2-phenylpropane-1,3-diol, 1,3-propylene glycol, 1,3-butylene glycol, 2-ethyl-1,3-octanediol, 1,3-dihydroxycyclohexane, 1,4-butanediol, 1,4-dihydroxycyclohexane, 1,5-pentanediol, 1,6- Hexanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, 1,4-dimethylolcyclohexa , Tricyclodecane dimethanol, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate (esterified product of hydroxypivalic acid and neopentyl glycol), bisphenol A, bisphenol F, Alkylene oxide adduct of bisphenol A, bis (4-hydroxyhexyl) -2,2-propane, bis (4-hydroxyhexyl) methane, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2 , 4,8,10-tetraoxaspiro [5,5] undecane, ester diol compounds such as bis (hydroxyethyl) terephthalate, diethylene glycol, triethylene glycol, glycerin, diglycerin, triglycerin, 1,2,6-hexane Triol, Pentaeri Thritol, dipentaerythritol, sorbitol, mannitol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tris (2-hydroxyethyl) isocyanurate, lactone compounds such as ε-caprolactone were added to these polyhydric alcohols A polylactone polyol compound etc. are mentioned, These can be used individually or in combination of 2 types or more, respectively.
　また、必要に応じて、メタノール、エタノール、プロピルアルコール、ｎ－ブタノール、イソブタノール、ｓｅｃ－ブタノール、ｎ－ヘキサノール、ｎ－オクタノール、ラウリルアルコール、２－エチルヘキサノール、デカノール、シクロヘキサノール、ベンジルアルコール、ステアリルアルコール、２－フェノキシエタノール、ドデシルアルコール等のモノアルコール；エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、合成高分岐飽和脂肪酸のグリシジルエステル（商品名「カージュラＥ１０」ＨＥＸＩＯＮ　Ｓｐｅｃｉａｌｔｙ　Ｃｈｅｍｉｃａｌｓ社製）等のモノエポキシ化合物とプロトン酸を有する化合物とを反応させて得られたアルコール化合物；乳酸亜鉛等の金属含有アルコール化合物なども、ポリエステル樹脂（Ａ）を製造する際の副原料として使用することができる。 If necessary, methanol, ethanol, propyl alcohol, n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, stearyl Mono-alcohol compounds such as alcohol, 2-phenoxyethanol and dodecyl alcohol; mono-epoxy compounds such as ethylene oxide, propylene oxide, butylene oxide, synthetic highly branched saturated fatty acid glycidyl ester (trade name “Cardura E10” manufactured by HEXION Specialty Chemicals) and protons Alcohol compounds obtained by reacting with acid-containing compounds; metal-containing alcohol compounds such as zinc lactate, etc. It can be used as a secondary raw material for producing the resin (A).
　本発明において、ポリエステル樹脂（Ａ）の製造方法は、特に限定されるものではなく、通常の方法を採用することができる。ポリエステル樹脂（Ａ）は、例えば、１種又は２種以上の酸成分（ａ１）と１種又は２種以上のアルコール成分（ａ２）とを、窒素気流中、１５０～２５０℃の温度で２～１０時間反応させてエステル化反応及び／又はエステル交換反応を行なうことにより、製造することができる。上記エステル化反応及び／又はエステル交換反応においては、酸成分（ａ１）及びアルコール成分（ａ２）を一度に添加してもよいし、数回に分けて添加してもよい。上記反応は、公知の有機溶剤の存在下で行ってもよい。 In the present invention, the production method of the polyester resin (A) is not particularly limited, and a normal method can be adopted. For example, the polyester resin (A) comprises one or more acid components (a1) and one or more alcohol components (a2) in a nitrogen stream at a temperature of 150 to 250 ° C. It can manufacture by making it react for 10 hours and performing esterification reaction and / or transesterification. In the esterification reaction and / or transesterification reaction, the acid component (a1) and the alcohol component (a2) may be added at once, or may be added in several portions. The above reaction may be performed in the presence of a known organic solvent.
　また、ポリエステル樹脂（Ａ）は、初めにカルボキシル基含有ポリエステル樹脂を合成した後、上記アルコール成分（ａ２）を用いて、前記カルボキシル基含有ポリエステル樹脂中のカルボキシル基の一部をエステル化しても得ることができる。さらに、ポリエステル樹脂（Ａ）は、初めに水酸基含有ポリエステル樹脂を合成した後、該水酸基含有ポリエステル樹脂と、前記酸無水物とを反応させても得ることができる。 The polyester resin (A) may be obtained by first synthesizing a carboxyl group-containing polyester resin and then esterifying a part of the carboxyl groups in the carboxyl group-containing polyester resin using the alcohol component (a2). be able to. Furthermore, the polyester resin (A) can be obtained by first synthesizing a hydroxyl group-containing polyester resin and then reacting the hydroxyl group-containing polyester resin with the acid anhydride.
　また、上記エステル化反応及び／又はエステル交換反応は、反応を促進させるために触媒を用いることができる。そのような触媒としては、例えば、ジブチル錫オキサイド、三酸化アンチモン、酢酸鉄、酢酸亜鉛、酢酸マンガン、酢酸コバルト、酢酸カルシウム、酢酸鉛、テトラブチルチタネート、テトライソプロピルチタネート、ホウ酸亜鉛、塩化亜鉛、硫酸亜鉛、ナフテン酸亜鉛、ホウ酸鉛、酢酸鉛、酢酸マンガン、酢酸アルミニウム、塩化アルミニウムなどの既知の触媒が挙げられる。 In the esterification reaction and / or transesterification reaction, a catalyst can be used to promote the reaction. Examples of such catalysts include dibutyltin oxide, antimony trioxide, iron acetate, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, tetraisopropyl titanate, zinc borate, zinc chloride, Known catalysts include zinc sulfate, zinc naphthenate, lead borate, lead acetate, manganese acetate, aluminum acetate, aluminum chloride and the like.
　本発明において、ポリエステル樹脂（Ａ）は、酸成分（ａ１）とアルコール成分（ａ２）とを主要原料として、これら各成分のエステル化反応及び／又はエステル交換によって製造されるが、必要に応じて、前記酸成分（ａ１）及び前記アルコール成分（ａ２）に由来する構成成分以外の、公知の有機及び／又は無機化合物を構成成分として含んでいてもよく、アミド化反応、ウレタン化反応、イミド化反応、カーボネート化反応、ウレア化反応等の公知の化学反応を伴って製造されてもよい。例えば、ポリエステル樹脂（Ａ）は、エステル化反応及び／又はエステル交換反応の反応中又は反応後に、反応中間体又は反応生成物を、有機酸亜鉛、有機酸銅、塩化亜鉛、塩化銅、水酸化亜鉛、水酸化銅、酸化亜鉛、酸化銅等の金属化合物、脂肪酸、油脂、モノ又はポリイソシアネート化合物、水素原子が結合した窒素を有するモノ又はポリアミン化合物、エポキシ化合物、アクリル樹脂、ビニルエステル樹脂などと反応させることによって得られる変性ポリエステル樹脂であってもよい。 In the present invention, the polyester resin (A) is produced by an esterification reaction and / or transesterification of each of these components using the acid component (a1) and the alcohol component (a2) as main raw materials. In addition to the components derived from the acid component (a1) and the alcohol component (a2), a known organic and / or inorganic compound may be included as a component, and amidation reaction, urethanization reaction, imidization It may be produced with a known chemical reaction such as a reaction, a carbonate reaction, a urea reaction. For example, in the polyester resin (A), during or after the esterification reaction and / or transesterification reaction, the reaction intermediate or reaction product is converted into an organic acid zinc, organic acid copper, zinc chloride, copper chloride, hydroxylation. Metal compounds such as zinc, copper hydroxide, zinc oxide, copper oxide, fatty acids, fats and oils, mono- or polyisocyanate compounds, mono- or polyamine compounds having nitrogen to which hydrogen atoms are bonded, epoxy compounds, acrylic resins, vinyl ester resins, etc. The modified polyester resin obtained by making it react may be sufficient.
　ポリエステル樹脂（Ａ）は、前記酸成分（ａ１）及び前記アルコール成分（ａ２）に由来する構成成分が、該樹脂の全構成成分の８０モル％以上であることが好ましく、９０モル％以上であることがより好ましい。 In the polyester resin (A), the constituent components derived from the acid component (a1) and the alcohol component (a2) are preferably 80 mol% or more of the total components of the resin, and 90 mol% or more. It is more preferable.
　また、ポリエステル樹脂（Ａ）の樹脂酸価は、得られる塗膜の防汚性を長期間に亘って維持する点から、０～１２０ｍｇＫＯＨ／ｇの範囲内であることが好ましく、０～９５ｍｇＫＯＨ／ｇの範囲内であることがより好ましく、０～４５ｍｇＫＯＨ／ｇの範囲内であることが特に好ましい。 Further, the resin acid value of the polyester resin (A) is preferably in the range of 0 to 120 mgKOH / g, from the viewpoint of maintaining the antifouling property of the obtained coating film over a long period, and is preferably 0 to 95 mgKOH / g. g is more preferable, and a range of 0 to 45 mgKOH / g is particularly preferable.
　さらに、ポリエステル樹脂（Ａ）の重量平均分子量は、得られる塗膜の防汚性の点及び該防汚性を長期間に亘って維持する点から、１５，０００以下であることが好ましく、１９０～７０００の範囲内であることがより好ましく、５００～４，０００の範囲内であることが特に好ましい。 Furthermore, the weight average molecular weight of the polyester resin (A) is preferably 15,000 or less from the viewpoint of the antifouling property of the obtained coating film and the antifouling property over a long period of time. It is more preferably within the range of ˜7000, and particularly preferably within the range of 500 to 4,000.
　本明細書において重量平均分子量は、ゲルパーミエーションクロマトグラフ（東ソー（株）製、「ＨＬＣ８１２０ＧＰＣ」）で測定した重量平均分子量をポリスチレンの重量平均分子量を基準にして換算した値である。重量平均分子量の測定は、４本のカラム（商品名「ＴＳＫｇｅｌ　Ｇ－４０００Ｈ×Ｌ」、「ＴＳＫｇｅｌ　Ｇ－３０００Ｈ×Ｌ」、「ＴＳＫｇｅｌ　Ｇ－２５００Ｈ×Ｌ」及び「ＴＳＫｇｅｌ　Ｇ－２０００Ｈ×Ｌ」（いずれも東ソー（株）製））を用い、移動相；テトラヒドロフラン、測定温度；４０℃、流速；１ｍｌ／分、検出器；ＲＩの条件で行うことができる。 In this specification, the weight average molecular weight is a value obtained by converting the weight average molecular weight measured by gel permeation chromatograph (“HLC8120GPC” manufactured by Tosoh Corporation) based on the weight average molecular weight of polystyrene. The weight average molecular weight was measured using four columns (trade names “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, and “TSKgel G-2000H × L” ( All of them are manufactured by Tosoh Corporation), and can be carried out under the conditions of mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: RI.
　［シリルエステル基含有樹脂（Ｂ）］
　本発明の防汚塗料組成物は、上記ポリエステル樹脂（Ａ）のほかに、更にシリルエステル基含有樹脂（Ｂ）を含む。シリルエステル基含有樹脂（Ｂ）は、下記の一般式（Ｉ）で表される、重合性不飽和基とトリオルガノシリルエステル基とを有する単量体（ｂ１）（以下、「単量体（ｂ１）」と称することがある。）の１種又は２種以上と、上記単量体（ｂ１）以外の重合性不飽和基を有する単量体（ｂ２）の１種又は２種以上との共重合体からなり、好ましくは重量平均分子量（Ｍｗ)が１，０００～１５０，０００の範囲内のものであり、更に好ましくは重量平均分子量（Ｍｗ)が３，０００～８０，０００の範囲内のものである。
　Ｒ5－ＣＨ＝Ｃ（Ｒ4）－ＣＯＯ－ＳｉＲ1Ｒ2Ｒ3・・・（Ｉ）
［式（Ｉ）中、Ｒ4は水素原子又はメチル基を示し、Ｒ1、Ｒ2及びＲ3はそれぞれ独立に炭化水素基を示し、Ｒ5は水素原子又はＲ6－Ｏ－ＣＯ－（ただし、Ｒ6は有機基又は－ＳｉＲ7Ｒ8Ｒ9で表されるシリル基を示し、Ｒ7、Ｒ8及びＲ9はそれぞれ独立に炭化水素基を示す。）を示す。］ [Silyl ester group-containing resin (B)]
The antifouling coating composition of the present invention further contains a silyl ester group-containing resin (B) in addition to the polyester resin (A). The silyl ester group-containing resin (B) is a monomer (b1) represented by the following general formula (I) and having a polymerizable unsaturated group and a triorganosilyl ester group (hereinafter referred to as “monomer ( b1) ”)) and one or more monomers (b2) having a polymerizable unsaturated group other than the monomer (b1). It is made of a copolymer, and preferably has a weight average molecular weight (Mw) in the range of 1,000 to 150,000, more preferably a weight average molecular weight (Mw) in the range of 3,000 to 80,000. belongs to.
R 5 —CH═C (R 4 ) —COO—SiR 1 R 2 R 3 (I)
[In the formula (I), R 4 represents a hydrogen atom or a methyl group, R 1 , R 2 and R 3 each independently represents a hydrocarbon group, and R 5 represents a hydrogen atom or R 6 —O—CO— ( R 6 represents an organic group or a silyl group represented by —SiR 7 R 8 R 9 , and R 7 , R 8 and R 9 each independently represents a hydrocarbon group. ]
　本発明の防汚塗料組成物に用いられるシリルエステル基含有樹脂（Ｂ）のＭｗが１，０００よりも小さいと、前記防汚塗料組成物から得られる塗膜の溶解速度は大きくなるものの、塗膜の物性が劣り、ブリスターやクラックが発生しやすくなることがある。また、前記シリルエステル基含有樹脂（Ｂ）のＭｗが１５０，０００を超えると、前記防汚塗料組成物から得られる塗膜の溶解速度が遅くなり、防汚性に劣ることがある。 When the Mw of the silyl ester group-containing resin (B) used in the antifouling paint composition of the present invention is less than 1,000, the dissolution rate of the coating film obtained from the antifouling paint composition increases, The physical properties of the film are inferior, and blisters and cracks are likely to occur. Moreover, when Mw of the said silyl ester group containing resin (B) exceeds 150,000, the melt | dissolution rate of the coating film obtained from the said antifouling coating composition will become slow, and it may be inferior to antifouling property.
　前記単量体（ｂ１）は、前記式（Ｉ）におけるＲ5が水素原子である場合、下記の一般式（Ｉ－１）で表される。
　ＣＨ2＝Ｃ（Ｒ4）－ＣＯＯ－ＳｉＲ1Ｒ2Ｒ3・・・・・（Ｉ－１）
　なお、式（Ｉ－１）中のＲ4、Ｒ1、Ｒ2及びＲ3は、それぞれ前記式（Ｉ）中のＲ4、Ｒ1、Ｒ2及びＲ3と同じである。 The monomer (b1) is represented by the following general formula (I-1) when R 5 in the formula (I) is a hydrogen atom.
CH 2 = C (R 4 ) —COO—SiR 1 R 2 R 3 (I-1)
Incidentally, R 4, R 1, R 2 and R 3 in the formula (I-1) is the same as R 4, R 1, R 2 and R 3 in each of the formula (I).
　前記式（Ｉ）又は前記式（Ｉ－１）中のＲ1、Ｒ2及びＲ3における炭化水素基は、炭素数が１～１０の直鎖状の若しくは分岐鎖を有するアルキル基、又は任意の置換基によって置換された若しくは無置換のフェニル基であることが好ましく、それぞれの炭化水素基は、同一であっても、異なっていてもよい。中でも、炭素数が１～５のアルキル基が好ましく、特に、メチル基、エチル基、プロピル基、ｎ－ブチル基、ｓ－ブチル基、ｔ－ブチル基、イソプロピル基などのアルキル基が好ましい。 The hydrocarbon group in R 1 , R 2 and R 3 in the formula (I) or the formula (I-1) is a linear or branched alkyl group having 1 to 10 carbon atoms, or any Are preferably substituted or unsubstituted phenyl groups, and each hydrocarbon group may be the same or different. Among them, an alkyl group having 1 to 5 carbon atoms is preferable, and an alkyl group such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an s-butyl group, a t-butyl group, and an isopropyl group is particularly preferable.
　前記式（Ｉ－１）で表される単量体（以下、「単量体（ｂ１－１）」という。）としては、例えば、（メタ）アクリル酸トリメチルシリル、（メタ）アクリル酸トリエチルシリル、（メタ）アクリル酸トリイソプロピルシリル等の（メタ）アクリル酸トリアルキルシリルが挙げられ、これらの中でも、得られる塗膜の溶解性、防汚性能の持続性、ブリスターやクラックの発生のしにくさなどの点から、（メタ）アクリル酸トリイソプロピルシリルが好ましい。 Examples of the monomer represented by the formula (I-1) (hereinafter referred to as “monomer (b1-1)”) include, for example, trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, Examples include (meth) acrylic acid trialkylsilyl such as (meth) acrylic acid triisopropylsilyl. Among these, solubility of the obtained coating film, durability of antifouling performance, resistance to occurrence of blisters and cracks. In view of the above, triisopropylsilyl (meth) acrylate is preferred.
　前記単量体（ｂ１）は、前記式（Ｉ）におけるＲ5が「Ｒ6－Ｏ－ＣＯ－」（ただし、Ｒ6は有機基又は－ＳｉＲ7Ｒ8Ｒ9で表されるシリル基を示し、Ｒ7、Ｒ8及びＲ9はそれぞれ独立に炭化水素基を示す。）である場合、下記の一般式（Ｉ－２）で表される。
　Ｒ6－Ｏ－ＣＯ－ＣＨ＝Ｃ（Ｒ4）－ＣＯＯ－ＳｉＲ1Ｒ2Ｒ3・・・・（Ｉ－２）
　なお、式（Ｉ－２）中のＲ4、Ｒ1、Ｒ2及びＲ3は、それぞれ前記式（Ｉ）又は前記式（Ｉ－１）中のＲ4、Ｒ1、Ｒ2及びＲ3と同じである。 In the monomer (b1), R 5 in the formula (I) is “R 6 —O—CO—” (where R 6 represents an organic group or a silyl group represented by —SiR 7 R 8 R 9). R 7 , R 8 and R 9 each independently represents a hydrocarbon group.), It is represented by the following general formula (I-2).
R 6 —O—CO—CH═C (R 4 ) —COO—SiR 1 R 2 R 3 ... (I-2)
Incidentally, R 4 in the formula (I-2), R 1, R 2 and R 3 are each the formula (I) or the formula (I-1) R 4 in, R 1, R 2 and R 3 Is the same.
　前記式（Ｉ）、前記式（Ｉ－１）又は前記式（Ｉ－２）中のＲ6における有機基としては、炭素数が１～１０の直鎖状の又は分枝鎖を有するアルキル基、シクロアルキル基、不飽和アルキル基、アラルキル基などが挙げられる。 In the formula (I), the formula (I-1) or the formula (I-2), the organic group represented by R 6 is a linear or branched alkyl group having 1 to 10 carbon atoms. Cycloalkyl group, unsaturated alkyl group, aralkyl group and the like.
　上記の炭素数が１～１０の直鎖状の又は分枝鎖を有するアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、イソブチル基、ｎ－ブチル基、ｓ－ブチル基、ｔ－ブチル基、２－メチルブチル基、２－エチルブチル基、ペンチル基、３－メチルペンチル基、ヘキシル基、ヘプチル基、オクチル基などが挙げられる。 Examples of the linear or branched alkyl group having 1 to 10 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, isobutyl group, n-butyl group, s- Examples include butyl group, t-butyl group, 2-methylbutyl group, 2-ethylbutyl group, pentyl group, 3-methylpentyl group, hexyl group, heptyl group, octyl group and the like.
　また、上記シクロアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基などが挙げられる。
　上記不飽和アルキル基としては、２－プロペニル基、２－ブテニル基、３－ブテニル基、２－ペンテニル基、３－ペンテニル基、４－ペンテニル基などが挙げられる。 Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
Examples of the unsaturated alkyl group include 2-propenyl group, 2-butenyl group, 3-butenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group and the like.
　上記アラルキル基としては、例えば、ベンジル基、フェネチル基、フェニルプロピル基などが挙げられる。 Examples of the aralkyl group include a benzyl group, a phenethyl group, and a phenylpropyl group.
　なお、上記のアルキル基、シクロアルキル基、不飽和アルキル基及びアラルキル基は、置換基を有していてもよい。そのような置換基としては、例えば、アルコキシ基、アシル基などが挙げられる。また、置換基の数、置換の位置等については、本発明の効果を妨げない範囲であれば、特に限定されるものではない。 In addition, said alkyl group, cycloalkyl group, unsaturated alkyl group, and aralkyl group may have a substituent. Examples of such a substituent include an alkoxy group and an acyl group. Further, the number of substituents, the position of substitution and the like are not particularly limited as long as the effects of the present invention are not hindered.
　前記式（Ｉ－２）で表される単量体（以下、「単量体（ｂ１－２）」という。）としては、例えば、マレイン酸ジエステル化合物、フマル酸ジエステル化合物（式（Ｉ－２）中のＲ4が水素原子のもの）などが挙げられる。 Examples of the monomer represented by the formula (I-2) (hereinafter referred to as “monomer (b1-2)”) include maleic acid diester compounds and fumaric acid diester compounds (formula (I-2)). In which R 4 is a hydrogen atom).
　前記式（Ｉ）、前記式（Ｉ－１）又は前記式（Ｉ－２）中のＲ7、Ｒ8及びＲ9における炭化水素基は、炭素数が１～１０の直鎖状の若しくは分岐鎖を有するアルキル基、又は任意の置換基によって置換された若しくは無置換のフェニル基であることが好ましく、それぞれの炭化水素基は、同一であっても、異なっていてもよい。中でも、炭素数が１～５のアルキル基が好ましく、特に、メチル基、エチル基、プロピル基、ｎ－ブチル基、ｓ－ブチル基、ｔ－ブチル基、イソプロピル基などのアルキル基が好ましい。 The hydrocarbon group in R 7 , R 8 and R 9 in the formula (I), the formula (I-1) or the formula (I-2) is linear or branched having 1 to 10 carbon atoms. It is preferably an alkyl group having a chain, or a phenyl group substituted or unsubstituted by an arbitrary substituent, and each hydrocarbon group may be the same or different. Among them, an alkyl group having 1 to 5 carbon atoms is preferable, and an alkyl group such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an s-butyl group, a t-butyl group, and an isopropyl group is particularly preferable.
　前記単量体（ｂ１）は、得られる塗膜の溶解性、防汚性能の持続性、ブリスターやクラックの発生のしにくさなどの点から、イソプロピルシリル基含有不飽和単量体が好ましい。そのようなイソプロピルシリル基含有不飽和単量体としては、例えば、（メタ）アクリル酸トリイソプロピルシリル、４－ペンテン酸トリイソプロピルシリル、マレイン酸ビス（トリイソプロピルシリル）、マレイン酸メチルトリイソプロピルシリル、マレイン酸エチルトリイソプロピルシリル、マレイン酸ｎ－ブチルトリイソプロピルシリル、マレイン酸イソブチルトリイソプロピルシリル、マレイン酸ｔ－ブチルトリイソプロピルシリル、マレイン酸ｎ－ペンチルトリイソプロピルシリル、マレイン酸イソペンチルトリイソプロピルシリル、マレイン酸２－エチルヘキシルトリイソプロピルシリル、マレイン酸シクロヘキシルトリイソプロピルシリル、フマル酸ビス（トリイソプロピルシリル）、フマル酸メチルトリイソプロピルシリル、フマル酸エチルトリイソプロピルシリル、フマル酸ｎ－ブチルトリイソプロピルシリル、フマル酸イソブチルトリイソプロピルシリル、フマル酸ｎ－ペンチルトリイソプロピルシリル、フマル酸イソペンチルトリイソプロピルシリル、フマル酸２－エチルヘキシルトリイソプロピルシリル、フマル酸シクロヘキシルトリイソプロピルシリルなどが挙げられ、特に、（メタ）アクリル酸トリイソプロピルシリルが好ましい。また、これらのトリイソプロピルシリル基含有単量体は、単独で又は２種以上を組み合わせて使用することができる。 The monomer (b1) is preferably an isopropylsilyl group-containing unsaturated monomer from the viewpoints of solubility of the resulting coating film, durability of the antifouling performance, difficulty in generating blisters and cracks, and the like. Examples of such isopropylsilyl group-containing unsaturated monomers include triisopropylsilyl (meth) acrylate, triisopropylsilyl 4-pentenoate, bis (triisopropylsilyl) maleate, methyltriisopropylsilyl maleate, Ethyl triisopropylsilyl maleate, n-butyltriisopropylsilyl maleate, isobutyltriisopropylsilyl maleate, t-butyltriisopropylsilyl maleate, n-pentyltriisopropylsilyl maleate, isopentyltriisopropylsilyl maleate, malein 2-ethylhexyl triisopropylsilyl acid, cyclohexyl triisopropylsilyl maleate, bis (triisopropylsilyl) fumarate, methyltriisopropylsilyl fumarate Ethyl triisopropylsilyl fumarate, n-butyltriisopropylsilyl fumarate, isobutyltriisopropylsilyl fumarate, n-pentyltriisopropylsilyl fumarate, isopentyltriisopropylsilyl fumarate, 2-ethylhexyltriisopropylsilyl fumarate, fumarate Examples include cyclohexyl triisopropylsilyl acid, and triisopropylsilyl (meth) acrylate is particularly preferable. These triisopropylsilyl group-containing monomers can be used alone or in combination of two or more.
　シリルエステル基含有樹脂（Ｂ）は、単量体（ｂ１）と単量体（ｂ２）とを２０／８０～７０／３０の範囲内の質量比（ｂ１）／（ｂ２）で共重合して得られたものが好ましく、単量体（ｂ１）と単量体（ｂ２）とを３０／７０～６０／４０の範囲内の質量比（ｂ１）／（ｂ２）で共重合して得られたものが更に好ましい。 The silyl ester group-containing resin (B) is obtained by copolymerizing the monomer (b1) and the monomer (b2) at a mass ratio (b1) / (b2) within the range of 20/80 to 70/30. What was obtained was preferable, and was obtained by copolymerizing the monomer (b1) and the monomer (b2) at a mass ratio (b1) / (b2) within the range of 30/70 to 60/40. More preferred.
　質量比（ｂ１）／（ｂ２）が２０／８０よりも小さい場合は、得られる塗膜の溶解速度が遅く、防汚性能が劣ることがあり、質量比（ｂ１）／（ｂ２）が７０／３０よりも大きい場合は、得られる塗膜の溶解性が大きくなるものの、防汚効果を長期間に亘って維持するのが困難になることがある。 When the mass ratio (b1) / (b2) is smaller than 20/80, the dissolution rate of the resulting coating film is slow and the antifouling performance may be inferior, and the mass ratio (b1) / (b2) is 70 / When it is larger than 30, the solubility of the resulting coating film is increased, but it may be difficult to maintain the antifouling effect over a long period of time.
　単量体（ｂ１）（あるいは単量体（ｂ１－１）及び／又は（ｂ１－２））と共重合し得る単量体（ｂ２）としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸ｉ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ラウリル等の（メタ）アクリル酸アルキル類；（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸２－メトキシプロピル、（メタ）アクリル酸４－メトキシブチル、（メタ）アクリル酸２－エトキシエチル等の（メタ）アクリル酸アルコキシアルキル類；（メタ）アクリル酸エチレングリコールモノメチル、片方の分子末端がアルコキシ基であるポリオキシエチレン鎖を有する（メタ）アクリレート、片方の分子末端がアルコキシ基であるポリオキシプロピレン鎖を有する（メタ）アクリレート、（メタ）アクリル酸プロピレングリコールモノメチル等の（メタ）アクリル酸アルキレングリコールモノメチル類；（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸と炭素数２～８の２価アルコールとのモノエステル化物のε－カプロラクトン変性体、アリルアルコ－ル、分子末端が水酸基であるポリオキシエチレン鎖を有する（メタ）アクリレート等の水酸基含有モノマーの（メタ）アクリル酸ヒドロキシアルキル類；（メタ）アクリロニトリル、（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、（メタ）アクリロイルモルホリン、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ－ヒドロキシメチル（メタ）アクリルアミド、Ｎ－アルコキシメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、グリシジル（メタ）アクリレートとアミン類との付加物等の窒素含有モノマー；（メタ）アクリル酸ベンジル、（メタ）アクリル酸フェニル等の（メタ）アクリル酸エステル類；塩化ビニル；塩化ビニリデン；（メタ）アクリロニトリル；酢酸ビニル；ブチルビニルエーテル；ラウリルビニルエーテル；Ｎ－ビニルピロリドン；スチレン；ビニルトルエン；α－メチルスチレンなどを挙げることができる。また、前記単量体（ｂ２）としては、例えば、プロピオン酸ビニル、酢酸ビニル等のビニルエステル化合物；（メタ）アクリル酸、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸、クロトン酸、（メタ）アクリル酸β－カルボキシエチル等のカルボキシル基含有モノマー；グリシジル（メタ）アクリレート、β－メチルグリシジル（メタ）アクリレート、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート、３，４－エポキシシクロヘキシルエチル（メタ）アクリレート、３，４－エポキシシクロヘキシルプロピル（メタ）アクリレート、アリルグリシジルエーテル等のエポキシ基含有モノマー；２－（メタ）アクリルアミド－２－メチルプロパンスルホン酸、アリルスルホン酸、スチレンスルホン酸、スルホエチル（メタ）アクリレート及びこれらのナトリウム塩又はアンモニウム塩等のスルホン酸基含有モノマー；２－（メタ）アクリロイルオキシエチルアシッドホスフェート等のリン酸基を有するモノマー；アクロレイン、ダイアセトン（メタ）アクリルアミド、アセトアセトキシエチル（メタ）アクリレート、４～７個の炭素原子を有するビニルアルキルケトン（例えば、ビニルメチルケトン、ビニルエチルケトン、ビニルブチルケトン）等のカルボニル基含有モノマーなども用いることができる。 Examples of the monomer (b2) copolymerizable with the monomer (b1) (or the monomer (b1-1) and / or (b1-2)) include, for example, methyl (meth) acrylate, (meta ) Ethyl acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, etc. (Meth) alkyl acrylates; (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 2-methoxypropyl, (meth) acrylic acid 4-methoxybutyl, (meth) acrylic acid 2-ethoxyethyl etc. ) Alkoxyalkyl acrylates; ethylene glycol monomethyl (meth) acrylate, having a polyoxyethylene chain in which one molecular end is an alkoxy group (meta Acrylates, (meth) acrylates having a polyoxypropylene chain with one molecular terminal being an alkoxy group, (meth) acrylic acid alkylene glycol monomethyls such as (meth) acrylic acid propylene glycol monomethyl; (meth) acrylic acid 2-hydroxy Ε-caprolactone modified product of ethyl, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monoester of (meth) acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms, allyl alcohol Hydroxyl group-containing monomers such as (meth) acrylates such as (meth) acrylates having a polyoxyethylene chain having a hydroxyl group at the molecular terminal; (meth) acrylonitriles, (meth) acrylonitriles, (meth) acrylamides, N, N-dimethyl ( (Meth) acrylamide, ( (Meth) acryloylmorpholine, N-isopropyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-alkoxymethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl ( Nitrogen-containing monomers such as adducts of (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, glycidyl (meth) acrylate and amines; (meth) acrylic acid benzyl, (meth) acrylic acid phenyl etc. (Meth) acrylic esters; vinyl chloride; vinylidene chloride; (meth) acrylonitrile; vinyl acetate; butyl vinyl ether; lauryl vinyl ether; N-vinyl pyrrolidone; styrene; vinyl toluene; It can be. Examples of the monomer (b2) include vinyl ester compounds such as vinyl propionate and vinyl acetate; (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, and croton. Acid, carboxyl group-containing monomers such as β-carboxyethyl (meth) acrylate; glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxy Epoxy group-containing monomers such as cyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether; 2- (meth) acrylamide-2-methylpropanesulfonic acid, allylsulfonic acid, styrenesulfonic acid , Sul Sulfonic acid group-containing monomers such as foethyl (meth) acrylate and sodium salts or ammonium salts thereof; monomers having a phosphoric acid group such as 2- (meth) acryloyloxyethyl acid phosphate; acrolein, diacetone (meth) acrylamide, aceto Carbonyl group-containing monomers such as acetoxyethyl (meth) acrylate and vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) can also be used.
　上記に例示した単量体（ｂ２）は、単独で又は２種以上を組み合わせて使用することができる。また、上記に例示した単量体（ｂ２）の中でも、特に、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸２－メトキシプロピルなどが好ましい。 The monomers (b2) exemplified above can be used alone or in combination of two or more. Among the monomers (b2) exemplified above, in particular, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( Preference is given to 2-methoxyethyl (meth) acrylate and 2-methoxypropyl (meth) acrylate.
　なお、本明細書において、「（メタ）アクリレート」は、アクリレート又はメタクリレートを意味し、「（メタ）アクリル酸」は、アクリル酸又はメタクリル酸を意味する。また、「（メタ）アクリロイル」は、アクリロイル又はメタクリロイルを意味し、「（メタ）アクリルアミド」は、アクリルアミド又はメタクリルアミドを意味する。 In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylic acid” means acrylic acid or methacrylic acid. “(Meth) acryloyl” means acryloyl or methacryloyl, and “(meth) acrylamide” means acrylamide or methacrylamide.
　本発明において、シリルエステル基含有樹脂（Ｂ）は、公知の重合方法により製造することができる。なお、シリルエステル基含有樹脂（Ｂ）は、ランダム共重合体、グラフト共重合体、傾斜構造型共重合体、ブロック共重合体等の公知の共重合体であれば、いずれのタイプの共重合体であってもよい。 In the present invention, the silyl ester group-containing resin (B) can be produced by a known polymerization method. The silyl ester group-containing resin (B) may be any type of copolymer as long as it is a known copolymer such as a random copolymer, a graft copolymer, a gradient structure copolymer, or a block copolymer. It may be a coalescence.
　シリルエステル基含有樹脂（Ｂ）は、例えば、ラジカル重合開始剤の存在下、前記単量体（ｂ１）と前記単量体（ｂ２）とを共重合させることにより得られる。 The silyl ester group-containing resin (B) can be obtained, for example, by copolymerizing the monomer (b1) and the monomer (b2) in the presence of a radical polymerization initiator.
　上記の共重合反応において使用されるラジカル重合開始剤としては、例えば、２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）、２，２’－アゾビス－２－メチルブチロニトリル、ジメチル－２，２’－アゾビスイソブチレート等のアゾ化合物類；ジベンゾイルパーオキサイド、ジ（３－メチルベンゾイル）パーオキサイド、ベンゾイル（３－メチルベンゾイル）パーオキサイド、ジラウリルパーオキサイド等のジアシルパーオキサイド化合物類；ジ－ｔ－ブチルパーオキサイド、ｔ－ブチルパーオキシベンゾエート、ｔ－ブチルパーオキシイソプロピルカーボネート、ｔ－ブチルパーオクトエート等のｔ－ブチルパーオキサイド化合物類；ｔ－アミルパーオキシ－２－エチルヘキサノエート、ｔ－アミルパーオキシアセテート、ｔ－アミルパーオキシイソノナノエート、ｔ－アミルパーオキシベンゾエート、ｔ－アミルパーオキシアセテート、ジ（ｔ－アミルパーオキサイド）、１，１－ジ（ｔ－アミルパーオキシ）シクロヘキサン等のｔ－アミルパーオキサイド化合物類；ｔ－ヘキシルパーオキシ－２－エチルヘキサノエート、ｔ－ヘキシルパーオキシベンゾエート、ｔ－ヘキシルパーオキシ－イソプロピルモノカーボネート、ｔ－ヘキシルパーオキシピバレート、ｔ－ヘキシルパーオキシネオデカノエート等のｔ－ヘキシルパーオキサイド化合物類などが挙げられる。これらの重合開始剤は、単独で又は２種以上を組み合わせて使用することができる。 Examples of the radical polymerization initiator used in the above copolymerization reaction include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis-2-methylbutyronitrile, and dimethyl-2. Azo compounds such as 2,2'-azobisisobutyrate; diacyl peroxide compounds such as dibenzoyl peroxide, di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dilauryl peroxide T-butyl peroxide compounds such as di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, t-butyl peroctoate; t-amylperoxy-2-ethyl Hexanoate, t-amyl peroxyacetate, t- T-amyl peroxides such as milperoxy isononanoate, t-amyl peroxybenzoate, t-amyl peroxyacetate, di (t-amyl peroxide), 1,1-di (t-amylperoxy) cyclohexane Compounds: t-hexylperoxy-2-ethylhexanoate, t-hexylperoxybenzoate, t-hexylperoxy-isopropyl monocarbonate, t-hexylperoxypivalate, t-hexylperoxyneodecanoate And t-hexyl peroxide compounds such as These polymerization initiators can be used alone or in combination of two or more.
　前記重合開始剤の使用量等を適宜設定することにより、前記シリルエステル基含有樹脂（Ｂ）の分子量を調整することができる。 The molecular weight of the silyl ester group-containing resin (B) can be adjusted by appropriately setting the amount of the polymerization initiator used.
　シリルエステル基含有樹脂（Ｂ）を得るための重合方法としては、例えば、溶液重合法、塊状重合法、乳化重合法、懸濁重合法などが挙げられる。これらの中でも、前記シリルエステル基含有樹脂（Ｂ）を簡便に、かつ、精度良く合成できるという点で、溶液重合法が特に好ましい。 Examples of the polymerization method for obtaining the silyl ester group-containing resin (B) include a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, and a suspension polymerization method. Among these, the solution polymerization method is particularly preferable in that the silyl ester group-containing resin (B) can be synthesized easily and accurately.
　上記の共重合反応においては、必要に応じて有機溶媒を用いてもよい。そのような有機溶剤としては、例えば、キシレン、トルエン等の芳香族炭化水素系溶剤；ヘキサン、ヘプタン等の脂肪族炭化水素系溶剤；酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸メトキシプロピル等のエステル系溶剤；イソプロピルアルコール、ブチルアルコール等のアルコール系溶剤；ジオキサン、ジエチルエーテル、ジブチルエーテル等のエーテル系溶剤；メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤などが挙げられる。これらの中でも、芳香族炭化水素系溶剤が好ましく、特にキシレンが好ましい。これらの溶剤は、単独で又は２種以上を組み合わせて使用することができる。 In the above copolymerization reaction, an organic solvent may be used as necessary. Examples of such organic solvents 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. Solvents; alcohol solvents such as isopropyl alcohol and butyl alcohol; ether solvents such as dioxane, diethyl ether and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Among these, aromatic hydrocarbon solvents are preferable, and xylene is particularly preferable. These solvents can be used alone or in combination of two or more.
　前記共重合反応における反応温度は、重合開始剤の種類等に応じて適宜設定すればよく、通常は７０～１６０℃の範囲内の温度、好ましくは８０～１４０℃の範囲内の温度である。前記共重合反応における反応時間は、反応温度や重合開始剤の種類等に応じて適宜設定すればよく、通常４～８時間程度である。また、前記共重合反応は、窒素ガス、アルゴンガス等の不活性ガスの雰囲気下で行われることが好ましい。 The reaction temperature in the copolymerization reaction may be appropriately set according to the type of the polymerization initiator and the like, and is usually a temperature in the range of 70 to 160 ° C., preferably a temperature in the range of 80 to 140 ° C. The reaction time in the copolymerization reaction may be appropriately set according to the reaction temperature, the type of polymerization initiator, and the like, and is usually about 4 to 8 hours. The copolymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen gas or argon gas.
　［防汚剤（Ｃ）］
　本発明の防汚塗料組成物は、上記ポリエステル樹脂（Ａ）及び上記シリルエステル基含有樹脂（Ｂ）のほかに、更に防汚剤（Ｃ）を含む。防汚剤（Ｃ）としては、従来より公知のものを用いることができる。上記防汚剤（Ｃ）としては、例えば、無機化合物、金属を含む有機化合物、金属を含まない有機化合物などが挙げられる。 [Anti-fouling agent (C)]
The antifouling coating composition of the present invention further contains an antifouling agent (C) in addition to the polyester resin (A) and the silyl ester group-containing resin (B). A conventionally well-known thing can be used as antifouling agent (C). Examples of the antifouling agent (C) include inorganic compounds, organic compounds containing metals, and organic compounds not containing metals.
　上記無機化合物としては、例えば、亜酸化銅、銅粉、チオシアン酸銅、炭酸銅、塩化銅、硫酸銅等の銅化合物、硫酸亜鉛、酸化亜鉛、硫酸ニッケル、銅－ニッケル合金などが挙げられる。 Examples of the inorganic compound include copper compounds such as cuprous oxide, copper powder, copper thiocyanate, copper carbonate, copper chloride, and copper sulfate, zinc sulfate, zinc oxide, nickel sulfate, and copper-nickel alloy.
　上記の金属を含む有機化合物としては、例えば、有機銅系化合物、有機ニッケル系化合物、有機亜鉛系化合物などが挙げられ、その他、マンネブ、マンセブ、プロピネブなども用いることができる。前記有機銅系化合物としては、例えば、オキシン銅、銅ピリチオン、ノニルフェノールスルホン酸銅、カッパービス（エチレンジアミン）－ビス（ドデシルベンゼンスルホネート）、酢酸銅、ナフテン酸銅、ビス（ペンタクロロフェノール酸）銅などが挙げられる。前記有機ニッケル系化合物としては、例えば、酢酸ニッケル、ジメチルジチオカルバミン酸ニッケルなどが挙げられる。前記有機亜鉛系化合物としては、例えば、酢酸亜鉛、カルバミン酸亜鉛、ジメチルジチオカルバミン酸亜鉛、ジンクピリチオン、エチレンビスジチオカルバミン酸亜鉛などが挙げられる。 Examples of the organic compound containing the above metal include organic copper compounds, organic nickel compounds, and organic zinc compounds. In addition, manneb, manceb, propineb, and the like can also be used. Examples of the organic copper compound include copper oxine, copper pyrithione, copper nonylphenol sulfonate, copper bis (ethylenediamine) -bis (dodecylbenzenesulfonate), copper acetate, copper naphthenate, bis (pentachlorophenolic acid) copper, and the like. Is mentioned. Examples of the organic nickel compound include nickel acetate and nickel dimethyldithiocarbamate. Examples of the organic zinc compound include zinc acetate, zinc carbamate, zinc dimethyldithiocarbamate, zinc pyrithione, and zinc ethylenebisdithiocarbamate.
　また、上記の金属を含まない有機化合物としては、例えば、Ｎ－トリハロメチルチオフタルイミド、ジチオカルバミン酸、Ｎ－アリールマレイミド、３－置換化アミノ－１，３－チアゾリジン－２，４－ジオン、ジチオシアノ系化合物、トリアジン系化合物などが挙げられる。 Examples of the organic compound containing no metal include N-trihalomethylthiophthalimide, dithiocarbamic acid, N-arylmaleimide, 3-substituted amino-1,3-thiazolidine-2,4-dione, and dithiocyano compounds. And triazine compounds.
　上記Ｎ－トリハロメチルチオフタルイミドとしては、例えば、Ｎ－トリクロロメチルチオフタルイミド、Ｎ－フルオロジクロロメチルチオフタルイミドなどが挙げられる。 Examples of the N-trihalomethylthiophthalimide include N-trichloromethylthiophthalimide and N-fluorodichloromethylthiophthalimide.
　上記ジチオカルバミン酸としては、ビス（ジメチルチオカルバモイル）ジスルフィド、Ｎ－メチルジチオカルバミン酸アンモニウム、エチレンビス（ジチオカルバミン酸）アンモニウム、ミルネブなどが挙げられる。 Examples of the dithiocarbamic acid include bis (dimethylthiocarbamoyl) disulfide, ammonium N-methyldithiocarbamate, ethylenebis (dithiocarbamic acid) ammonium, and milneb.
　上記Ｎ－アリールマレイミドとしては、例えば、Ｎ－（２，４，６－トリクロロフェニル）マレイミド、Ｎ－４－トリルマレイミド、Ｎ－３－クロロフェニルマレイミド、Ｎ－（４－ｎ－ブチルフェニル）マレイミド、Ｎ－（アニリノフェニル）マレイミド、Ｎ－（２，３－キシリル）マレイミド、２，３－ジクロロ－Ｎ－（２’，６’－ジエチルフェニル）マレイミド、２，３－ジクロロ－Ｎ－（２’－エチル－６’－メチルフェニル）マレイミドなどが挙げられる。 Examples of the N-arylmaleimide include N- (2,4,6-trichlorophenyl) maleimide, N-4-tolylmaleimide, N-3-chlorophenylmaleimide, N- (4-n-butylphenyl) maleimide, N- (anilinophenyl) maleimide, N- (2,3-xylyl) maleimide, 2,3-dichloro-N- (2 ', 6'-diethylphenyl) maleimide, 2,3-dichloro-N- (2 And '-ethyl-6'-methylphenyl) maleimide.
　上記３－置換化アミノ－１，３－チアゾリジン－２，４－ジオンとしては、例えば、３－ベンジリデンアミノ－１，３－チアゾリジン－２，４－ジオン、３－（４－メチルベンジリデンアミノ）－１，３－チアゾリジン－２，４－ジオン、３－（２－ヒドロキシベンジリデンアミノ）－１，３－チアゾリジン－２，４－ジオン、３－（４－ジメチルアミノベンジリデンアミノ）－１，３－チアゾリン－２，４－ジオン、３－（２，４－ジクロロベンジリデンアミノ）－１，３－チアゾリジン－２，４－ジオンなどが挙げられる。 Examples of the 3-substituted amino-1,3-thiazolidine-2,4-dione include 3-benzylideneamino-1,3-thiazolidine-2,4-dione, 3- (4-methylbenzylideneamino)- 1,3-thiazolidine-2,4-dione, 3- (2-hydroxybenzylideneamino) -1,3-thiazolidine-2,4-dione, 3- (4-dimethylaminobenzylideneamino) -1,3-thiazoline -2,4-dione, 3- (2,4-dichlorobenzylideneamino) -1,3-thiazolidine-2,4-dione, and the like.
　上記ジチオシアノ系化合物としては、例えば、ジチオシアノメタン、ジチオシアノエタン、２，５－ジチオシアノチオフエンなどが挙げられる。 Examples of the dithiocyano compound include dithiocyanomethane, dithiocyanoethane, and 2,5-dithiocyanothiophene.
　上記トリアジン系化合物としては、例えば、２－メチルチオ－４－ｔ－ブチルアミノ－６－シクロプロピルアミノ－ｓ－トリアジンなどが挙げられる。 Examples of the triazine compound include 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine.
　また、上記の金属を含まない有機化合物は、上記に例示した有機化合物のほか、例えば、２，４，５，６－テトラクロロイソフタロニトリル、Ｎ，Ｎ－ジメチルジクロロフェニル尿素、４，５－ジクロロ－２－Ｎ－オクチル－３－（２Ｈ）イソチアゾロン、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、テトラメチルチウラムジスルフィド、３－ヨード－２－プロピニルブチルカルバメート、２－（メトキシカルボニルアミノ）ベンズイミダゾール、２，３，５，６－テトラクロロ－４－（メチルスルホニル）ピリジン、ジヨードメチルパラトリルスルホン、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、フェニル（ビスピリジン）ビスマスジクロライド、２－（４－チアゾリル）ベンズイミダゾール、トリフェニルボロンピリジン・アミン錯体、メデトミジン（体系名：（±）４－［１－（２，３－ジメチルフェニル）エチル］－１Ｈ－イミダゾール）、ジクロロ－Ｎ－（（ジメチルアミノ）スルフォニル）フルオロ－Ｎ－（ｐ－トリル）メタンスルフェンアミド、２－（ｐ－クロロフェニル）－３－シアノ－４－ブロモ－５－トリフルオロメチルピロール、クロロメチル－ｎ－オクチルジスルフィドなども用いることができる。 In addition to the organic compounds exemplified above, for example, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, 4,5-dichloro -2-N-octyl-3- (2H) isothiazolone, N, N-dimethyl-N′-phenyl- (N-fluorodichloromethylthio) sulfamide, tetramethylthiuram disulfide, 3-iodo-2-propynylbutylcarbamate, 2 -(Methoxycarbonylamino) benzimidazole, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, diiodomethylparatolylsulfone, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, phenyl (bispyridine) bismuth Dichloride, 2- (4 Thiazolyl) benzimidazole, triphenylboronpyridine-amine complex, medetomidine (system name: (±) 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole), dichloro-N-((dimethylamino ) Sulfonyl) fluoro-N- (p-tolyl) methanesulfenamide, 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole, chloromethyl-n-octyl disulfide, etc. be able to.
　前記防汚剤（Ｃ）は、上記に例示した各化合物を単独で又は２種以上を組み合わせて用いることができる。また、前記防汚剤（Ｃ）は、上記に例示した各化合物の中でも、安定した防汚性能を発揮するという観点から、亜酸化銅を用いることが好ましく、特に亜酸化銅と銅ピリチオンを併用することが好ましい。 The antifouling agent (C) can be used alone or in combination of two or more of the compounds exemplified above. The antifouling agent (C) is preferably cuprous oxide from the viewpoint of exhibiting stable antifouling performance among the compounds exemplified above, and in particular, cuprous oxide and copper pyrithione are used in combination. It is preferable to do.
　［防汚塗料組成物及び塗装物品］
　本発明の防汚塗料組成物は、前記ポリエステル樹脂（Ａ）、前記シリルエステル基含有樹脂（Ｂ）及び前記防汚剤（Ｃ）を含む防汚塗料組成物であって、前記ポリエステル樹脂（Ａ）と前記シリルエステル基含有樹脂（Ｂ）との質量比が３／９７～８０／２０の範囲内であり、かつ、前記防汚剤（Ｃ）の含有量が前記ポリエステル樹脂（Ａ）と前記シリルエステル基含有樹脂（Ｂ）との合計質量を基準として５０～５００質量％の範囲内であることを特徴とする。 [Anti-fouling paint composition and coated article]
The antifouling paint composition of the present invention is an antifouling paint composition comprising the polyester resin (A), the silyl ester group-containing resin (B) and the antifouling agent (C), wherein the polyester resin (A ) And the silyl ester group-containing resin (B) in a range of 3/97 to 80/20, and the antifouling agent (C) is contained in the polyester resin (A) and the resin. It is characterized by being in the range of 50 to 500% by mass based on the total mass with the silyl ester group-containing resin (B).
　前記ポリエステル樹脂（Ａ）と前記シリルエステル基含有樹脂（Ｂ）との質量比は、３／９７～８０／２０の範囲内であるが、好ましくは７／９３～６０／４０の範囲内であり、より好ましくは１０／９０～４０／６０の範囲内である。前記ポリエステル樹脂（Ａ）と前記シリルエステル基含有樹脂（Ｂ）との質量比が３／９７～８０／２０の範囲内であると、本発明の防汚塗料組成物によって得られる防汚塗膜の優れた防汚性能を長期間に亘って維持することができ、また、前記防汚塗膜に塗膜剥離、ブリスター、クラックなどの塗膜欠陥が発生し難くなる。前記ポリエステル樹脂（Ａ）と前記シリルエステル基含有樹脂（Ｂ）との質量比が３／９７よりも小さい場合又は８０／２０よりも大きい場合は、得られる塗膜の防汚性能を長期に維持することが困難になることがある。 The mass ratio of the polyester resin (A) to the silyl ester group-containing resin (B) is in the range of 3/97 to 80/20, preferably in the range of 7/93 to 60/40. More preferably, it is within the range of 10/90 to 40/60. When the mass ratio of the polyester resin (A) to the silyl ester group-containing resin (B) is in the range of 3/97 to 80/20, the antifouling coating film obtained by the antifouling coating composition of the present invention Excellent antifouling performance can be maintained over a long period of time, and coating film defects such as coating film peeling, blistering and cracking are less likely to occur in the antifouling coating film. When the mass ratio of the polyester resin (A) and the silyl ester group-containing resin (B) is smaller than 3/97 or larger than 80/20, the antifouling performance of the obtained coating film is maintained for a long time. May be difficult to do.
　前記防汚剤（Ｃ）の含有量は、前記ポリエステル樹脂（Ａ）と前記シリルエステル基含有樹脂（Ｂ）との合計質量を基準として５０～５００質量％の範囲内であるが、好ましくは２５０～４００質量％の範囲内である。前記防汚剤（Ｃ）の含有量が５０質量％よりも少ないと、得られる塗膜の防汚性能を長期に維持することが困難になることがあり、また、前記防汚剤（Ｃ）の含有量が５００質量％よりも多いと、得られる塗膜の物性が低下して、剥離やフクレ等の不具合を発生することがある。 The content of the antifouling agent (C) is in the range of 50 to 500% by mass based on the total mass of the polyester resin (A) and the silyl ester group-containing resin (B), preferably 250 Within the range of ˜400 mass%. If the content of the antifouling agent (C) is less than 50% by mass, it may be difficult to maintain the antifouling performance of the resulting coating film for a long period of time, and the antifouling agent (C) When there is more content than 500 mass%, the physical property of the coating film obtained may fall and malfunctions, such as peeling and a swelling, may generate | occur | produce.
　本発明の防汚塗料組成物は、上記のポリエステル樹脂（Ａ）、シリルエステル基含有樹脂（Ｂ）及び防汚剤（Ｃ）のほかに、顔料、染料、脱水剤、可塑剤、搖変剤（タレ止剤）、消泡剤、酸化防止剤、前記ポリエステル樹脂（Ａ）又は前記シリルエステル基含有樹脂（Ｂ）以外の樹脂、有機酸、溶剤などの一般的な塗料組成物に用いられている各種成分を、必要に応じて配合することができる。これらの成分は、単独で又は２種以上を組み合わせて用いることができる。 The antifouling coating composition of the present invention comprises, in addition to the above-mentioned polyester resin (A), silyl ester group-containing resin (B) and antifouling agent (C), pigments, dyes, dehydrating agents, plasticizers, and alteration agents. (Sagging agent), antifoaming agent, antioxidant, used in general coating compositions such as resins other than the polyester resin (A) or the silyl ester group-containing resin (B), organic acids, solvents, etc. Various components can be blended as necessary. These components can be used alone or in combination of two or more.
　上記顔料としては、例えば、ベンガラ、タルク、酸化チタン、黄色酸化鉄、シリカ、炭酸カルシウム、硫酸バリウム、酸化カルシウム、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着色顔料、タルク、シリカ、マイカ、クレー、炭酸カルシウム、カオリン、アルミナホワイト、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、硫化亜鉛等の体質顔料が挙げられる。 Examples of the pigment include color pigments such as bengara, talc, titanium oxide, yellow iron oxide, silica, calcium carbonate, barium sulfate, calcium oxide, carbon black, naphthol red, phthalocyanine blue, talc, silica, mica, clay, Examples of extender pigments include calcium carbonate, kaolin, alumina white, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, and zinc sulfide.
　防汚塗料組成物中の前記顔料の含有量は、ポリエステル樹脂（Ａ）とシリルエステル基含有樹脂（Ｂ）との合計質量を基準として０．０５～１０００質量％の範囲内であることが好ましく、１～５００質量％の範囲内であることがより好ましい。 The content of the pigment in the antifouling coating composition is preferably in the range of 0.05 to 1000% by mass based on the total mass of the polyester resin (A) and the silyl ester group-containing resin (B). More preferably, it is in the range of 1 to 500% by mass.
　上記脱水剤は、塗料の貯蔵安定性の向上に寄与する成分である。そのような脱水剤としては、例えば、無機系では、無水石膏、半水石膏（焼石膏）、合成ゼオライト系吸着剤（商品名「モレキュラーシーブ」等）などが挙げられ、その他、オルソエステル類（オルソギ酸メチル、オルソ酢酸メチル、オルソホウ酸エステル等）、シリケート類、イソシアネート類なども用いることができる。これらの中でも、無機系の脱水剤である無水石膏、半水石膏（焼石膏）が好ましい。また、これらの脱水剤は、単独で用いてもよく、２種以上を併用してもよい。なお、防汚塗料組成物中の前記脱水剤の含有量は、適宜調整することができるが、ポリエステル樹脂（Ａ）とシリルエステル基含有樹脂（Ｂ）との合計質量を基準として０～１００質量％の範囲内であることが好ましく、０．５～２５質量％の範囲内であることがより好ましい。 The above dehydrating agent is a component that contributes to improving the storage stability of the paint. Examples of such dehydrating agents include inorganic gypsum, hemihydrate gypsum (calcined gypsum), synthetic zeolite-based adsorbents (trade name “Molecular Sieve”, etc.), and other orthoesters ( (Methyl orthoformate, methyl orthoacetate, orthoborate, etc.), silicates, isocyanates, and the like can also be used. Among these, anhydrous gypsum and hemihydrate gypsum (calcined gypsum) which are inorganic dehydrating agents are preferable. These dehydrating agents may be used alone or in combination of two or more. The content of the dehydrating agent in the antifouling coating composition can be adjusted as appropriate, but is 0 to 100 mass based on the total mass of the polyester resin (A) and the silyl ester group-containing resin (B). %, Preferably in the range of 0.5 to 25% by mass.
　前記可塑剤としては、得られる防汚塗膜の耐クラック性や耐水性の向上などに寄与する成分である。そのような可塑剤としては、例えば、トリクレジルフォスフェート、ジオクチルフタレート、塩素化パラフィン、流動パラフィン、ｎ－パラフィン、塩素化パラフィン、ポリブテン、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などが挙げられる。これらの可塑剤は、単独で用いてもよく、２種以上を併用してもよい。防汚塗料組成物中の前記可塑剤の含有量は、適宜調整することができるが、ポリエステル樹脂（Ａ）とシリルエステル基含有樹脂（Ｂ）との合計質量を基準として０．５～１０質量％の範囲内であることが好ましく、１～５質量％の範囲内であることがより好ましい。 The plasticizer is a component that contributes to improving the crack resistance and water resistance of the resulting antifouling coating film. Examples of such plasticizers include tricresyl phosphate, dioctyl phthalate, chlorinated paraffin, liquid paraffin, n-paraffin, chlorinated paraffin, polybutene, terpene phenol, tricresyl phosphate (TCP), polyvinylethyl. Examples include ether. These plasticizers may be used alone or in combination of two or more. The content of the plasticizer in the antifouling coating composition can be appropriately adjusted, but is 0.5 to 10 mass based on the total mass of the polyester resin (A) and the silyl ester group-containing resin (B). %, Preferably 1 to 5% by mass.
　上記酸化防止剤としては、例えば、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノールなどを挙げることができる。 Examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol.
　前記搖変剤としては、例えば、有機系ワックス（ポリエチレンワックス、酸化ポリエチレンワックス、ポリアマイドワックス、アマイドワックス、水添ヒマシ油ワックス等）、有機粘土系化合物（Ａｌ、Ｃａ、Ｚｎのアミン塩、ステアレート塩、レシチン塩、アルキルスルホン酸塩等）、ベントナイト、合成微粉シリカなどが挙げられる。これらの搖変剤は、単独で用いてもよく、２種以上を併用してもよい。防汚塗料組成物中の前記搖変剤の含有量は、適宜調整することができるが、例えば、ポリエステル樹脂（Ａ）とシリルエステル基含有樹脂（Ｂ）との合計質量を基準として０．２５～５０質量％の範囲内である。 Examples of the alteration agent include organic waxes (polyethylene wax, oxidized polyethylene wax, polyamide wax, amide wax, hydrogenated castor oil wax, etc.), organic clay compounds (Al, Ca, Zn amine salts, stears). Rate salts, lecithin salts, alkyl sulfonates, etc.), bentonite, synthetic fine silica and the like. These alteration agents may be used alone or in combination of two or more. The content of the discoloring agent in the antifouling coating composition can be appropriately adjusted. For example, the content is 0.25 based on the total mass of the polyester resin (A) and the silyl ester group-containing resin (B). Within the range of ˜50 mass%.
　本発明の防汚塗料組成物は、前述のようなポリエステル樹脂（Ａ）及びシリルエステル基含有樹脂（Ｂ）以外にも、必要に応じて１種又は２種以上のその他の樹脂類を含有していてもよく、そのような樹脂類としては、例えば、シリルエステル基を有さないアクリル樹脂、アクリルシリコーン樹脂、エポキシ樹脂、フッ素樹脂、ポリブテン樹脂、シリコーンゴム、ウレタン樹脂、ポリアミド樹脂、塩化ビニル系共重合樹脂、塩化ゴム、塩素化オレフィン樹脂、スチレン・ブタジエン共重合樹脂、ケトン樹脂、エチレン－酢酸ビニル共重合樹脂、塩化ビニル樹脂、アルキッド樹脂、クマロン樹脂、テルペンフェノール樹脂、石油樹脂などが挙げられる。 The antifouling coating composition of the present invention contains one or more other resins as necessary in addition to the polyester resin (A) and the silyl ester group-containing resin (B) as described above. Examples of such resins include acrylic resins having no silyl ester group, acrylic silicone resins, epoxy resins, fluororesins, polybutene resins, silicone rubbers, urethane resins, polyamide resins, and vinyl chloride-based resins. Examples include copolymer resins, chlorinated rubber, chlorinated olefin resins, styrene / butadiene copolymer resins, ketone resins, ethylene-vinyl acetate copolymer resins, vinyl chloride resins, alkyd resins, coumarone resins, terpene phenol resins, petroleum resins, etc. .
　また、本発明の防汚塗料組成物は、公知のロジン系化合物を含んでいてもよい。そのようなロジン系化合物としては、例えば、ロジン、ロジン誘導体、ロジン金属塩などが挙げられる。前記ロジンとしては、例えば、トールロジン、ガムロジン、ウッドロジンなどが挙げられる。前記ロジン誘導体としては、例えば、水添ロジン、ロジンと無水マレイン酸を反応させたマレイン化ロジン、ホルミル化ロジン、重合ロジンなどが挙げられる。前記ロジン金属塩としては、ジンクロジネート、カルシウムロジネート、カッパーロジネート、マグネシウムロジネート、その他、金属化合物とロジンとの反応物などが挙げられる。これらロジン系化合物は、単独で又は２種以上を組み合わせて用いることができる。 Further, the antifouling coating composition of the present invention may contain a known rosin compound. Examples of such rosin compounds include rosin, rosin derivatives, rosin metal salts, and the like. Examples of the rosin include tall rosin, gum rosin, and wood rosin. Examples of the rosin derivative include hydrogenated rosin, maleated rosin obtained by reacting rosin and maleic anhydride, formylated rosin, and polymerized rosin. Examples of the rosin metal salt include zinc chloride, calcium rosinate, copper rosinate, magnesium rosinate, and other reactants of metal compounds and rosin. These rosin compounds can be used alone or in combination of two or more.
　前記ロジン系化合物の使用量は、特に限定されるものではないが、ポリエステル樹脂（Ａ）とシリルエステル基含有樹脂（Ｂ）との合計質量を基準として５０質量％以下が好ましく、３０質量％以下がさらに好ましい。 Although the usage-amount of the said rosin type compound is not specifically limited, 50 mass% or less is preferable on the basis of the total mass of polyester resin (A) and silyl ester group containing resin (B), and 30 mass% or less. Is more preferable.
　本発明の防汚塗料組成物は、脂肪族溶剤、芳香族溶剤（キシレン、トルエン等）、ケトン溶剤（メチルイソブチルケトン、シクロヘキサノン等）、エステル溶剤、エーテル溶剤（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）、アルコール溶剤（イソプロピルアルコール等）などの防汚塗料用の溶剤として一般的に用いられている有機溶剤を配合することができる。なお、有機溶剤の配合量は、適宜調整することができるが、例えば、防汚塗料組成物の全固形分率が２０～９０質量％の範囲内となるような配合量であり、塗装時に作業性等に応じて更に添加してもよい。 The antifouling coating composition of the present invention comprises an aliphatic solvent, an aromatic solvent (xylene, toluene, etc.), a ketone solvent (methyl isobutyl ketone, cyclohexanone, etc.), an ester solvent, an ether solvent (propylene glycol monomethyl ether, propylene glycol monomethyl ether). An organic solvent generally used as a solvent for an antifouling paint such as an acetate solvent or the like, or an alcohol solvent (such as isopropyl alcohol) can be blended. The blending amount of the organic solvent can be adjusted as appropriate. For example, the blending amount is such that the total solid content of the antifouling coating composition is in the range of 20 to 90% by mass. You may add further according to property etc.
　本発明の防汚塗料組成物は、公知の防汚塗料組成物と同様の方法により調製することができる。例えば、ポリエステル樹脂（Ａ）と、シリルエステル基含有樹脂（Ｂ）と、防汚剤（Ｃ）と、必要に応じて前記有機溶剤や添加剤等とを、攪拌槽に一度に又は順次添加し、撹拌、混合することにより製造することができる。 The antifouling paint composition of the present invention can be prepared by the same method as known antifouling paint compositions. For example, the polyester resin (A), the silyl ester group-containing resin (B), the antifouling agent (C), and, if necessary, the organic solvent and additives are added to the stirring tank at once or sequentially. , Stirring and mixing.
　本発明の塗装物品は、基材の表面が本発明の防汚塗料組成物によって被覆されてなる物品である。上記塗装物品は、少なくとも、基材の表面に上記防汚塗料組成物を１回～複数回塗布あるいは含浸させる工程と、前記基材の表面を被覆する防汚塗料組成物を乾燥させる工程とを含む製造方法によって得ることができる。 The coated article of the present invention is an article in which the surface of a base material is coated with the antifouling paint composition of the present invention. The coated article includes at least a step of applying or impregnating the antifouling coating composition to the surface of the substrate one or more times, and a step of drying the antifouling coating composition covering the surface of the substrate. It can obtain by the manufacturing method containing.
　上記基材としては、例えば、海水又は真水と（例えば、常時又は断続的に）接触する基材、具体的には、水中構造物；船舶外板又は船底；発電所の導水管や冷却管；養殖用又は定置用の漁網、漁具又はこれらに用いられる浮き子；ロープ等の漁網付属具などが挙げられる。なお、本発明の防汚塗料組成物から得られる塗膜の膜厚は、塗膜の消耗速度（溶解速度）等を考慮して適宜調整することができるが、例えば、塗装１回当たりの膜厚（μｍ）として３０～２５０μｍ／回、好ましくは７５～１５０μｍ／回程度とすればよく、必要に応じて２回以上塗り重ねてもよい。 Examples of the base material include a base material that is in contact with seawater or fresh water (for example, constantly or intermittently), specifically, an underwater structure; a ship outer plate or a ship bottom; a water conduit or a cooling pipe of a power plant; Examples include aquaculture or stationary fishing nets, fishing gear, or floats used in them; fishing net accessories such as ropes. In addition, although the film thickness of the coating film obtained from the antifouling coating composition of the present invention can be appropriately adjusted in consideration of the consumption rate (dissolution rate) of the coating film, for example, the film per coating time The thickness (μm) may be 30 to 250 μm / time, preferably about 75 to 150 μm / time, and may be applied twice or more as necessary.
　上記基材の表面にプライマー、防食塗料、及び必要に応じてバインダー塗料を塗装した後の表面に、刷毛塗り、吹付け塗り、ローラー塗り、浸漬等の手段で本発明の防汚塗料組成物を塗装してもよい。また、本発明の防汚塗料組成物は、既存の防汚塗膜表面に重ね塗りしてもよい。塗膜の乾燥は室温で行なうことができるが、必要に応じて約１００℃までの温度で加熱乾燥を行なってもよい。 The antifouling paint composition of the present invention is applied to the surface of the base material after applying a primer, an anticorrosive paint, and, if necessary, a binder paint to the surface by brushing, spraying, roller coating, dipping or the like. It may be painted. Further, the antifouling coating composition of the present invention may be overcoated on the surface of an existing antifouling coating film. Although the coating film can be dried at room temperature, it may be dried by heating at a temperature up to about 100 ° C. if necessary.
　以下、実施例及び比較例を挙げて、本発明をさらに具体的に説明するが、本発明は実施例のみに限定されるものではない。なお、下記実施例中の「部」及び「％」は、それぞれ「質量部」及び「質量％」を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to only the examples. In the following examples, “part” and “%” mean “part by mass” and “% by mass”, respectively.
　ポリエステル樹脂（Ａ）の製造
　（製造例１）　ポリエステル樹脂（Ａ１）の製造
　温度計、攪拌機及び精留塔を具備した２Ｌの反応装置に、ＰＡを５２７．２部、ＮＰＧを２６７．２部、ＤＥＧを２６９．７部仕込み、反応装置の内容物温度を１６０℃まで昇温した。次いで１６０℃から２３０℃までを３時間で昇温し、２３０℃で２時間、内容物温度を保持した後、精留塔を水分離器と置換し、反応装置にキシレン約５０．０部を仕込み、水とキシレンとを共沸させて縮合水を除去しながら重縮合を進めた。生成したポリエステル樹脂の酸価が１．０ｍｇＫＯＨ／ｇ以下であることを確認した後、加熱を停止して冷却を開始し、キシレンを添加して希釈することにより、固形分７０％のポリエステル樹脂（Ａ１）溶液を得た。なお、樹脂酸価は、トルエンとイソプロパノールとの混合液（質量比１／１）を溶媒として測定試料を溶解し、１／１０規定の水酸化カリウムのアルコール系溶液の滴定によって測定した。 Production of polyester resin (A) (Production Example 1) Production of polyester resin (A1) In a 2 L reactor equipped with a thermometer, a stirrer and a rectifying tower, 527.2 parts of PA, 267.2 parts of NPG, 269.7 parts of DEG were charged, and the temperature of the reactor contents was raised to 160 ° C. Next, the temperature was raised from 160 ° C. to 230 ° C. in 3 hours, and the content temperature was maintained at 230 ° C. for 2 hours. Then, the rectification column was replaced with a water separator, and about 50.0 parts of xylene was added to the reactor. The polycondensation was carried out while removing the condensed water by azeotropically distilling water and xylene. After confirming that the acid value of the produced polyester resin was 1.0 mgKOH / g or less, heating was stopped and cooling was started, and xylene was added to dilute to obtain a polyester resin having a solid content of 70% ( A1) A solution was obtained. The resin acid value was measured by dissolving a measurement sample using a mixed solution of toluene and isopropanol (mass ratio 1/1) as a solvent and titrating an alcoholic solution of 1/10 normal potassium hydroxide.
　ここで、本明細書におけるポリエステル原料の略号と相当する化合物の関係を以下に示す。
ＰＡ；無水フタル酸、ｉＰＡ；イソフタル酸、ＡＤ；アジピン酸、ＨＨＰＡ；ヘキサヒドロ無水フタル酸、ＥＧ；エチレングリコール、ＰＧ；プロピレングリコール、ＮＰＧ；ネオペンチルグリコール、１，６－ＨＤ；１，６－ヘキサンジオール、ＢＥＰＧ；２－ブチル－２－エチル－１，３－プロパンジオール、ＣＨＤＭ；１，４－シクロヘキサンジメタノール、ＤＥＧ；ジエチレングリコール、ＴＥＧ；トリエチレングリコール、テトラＥＧ；テトラエチレングリコール、ＤＰＧ；ジプロピレングリコール、ＴＭＰ；トリメチロールプロパン、Ｇ；グリセリン、ＰＥ；ペンタエリスリトール Here, the relationship between the abbreviations of the polyester raw materials in the present specification and the corresponding compounds is shown below.
PA; phthalic anhydride, iPA; isophthalic acid, AD; adipic acid, HHPA; hexahydrophthalic anhydride, EG; ethylene glycol, PG; propylene glycol, NPG; neopentyl glycol, 1,6-HD; 1,6-hexane Diol, BEPG; 2-butyl-2-ethyl-1,3-propanediol, CHDM; 1,4-cyclohexanedimethanol, DEG; diethylene glycol, TEG; triethylene glycol, tetraEG; tetraethylene glycol, DPG; dipropylene Glycol, TMP; Trimethylolpropane, G; Glycerin, PE; Pentaerythritol
　（製造例２～１２、１６，１７）　ポリエステル樹脂（Ａ２）～（Ａ１２）、（Ａ１６）、（Ａ１７）の製造
　製造例１における酸成分とアルコール成分とを、表１に示す配合としたこと以外は、製造例１と同様にして固形分７０％の各ポリエステル樹脂（Ａ２）～（Ａ１２）、（Ａ１６）、（Ａ１７）の樹脂溶液を得た。なお、製造例１７においては、生成するポリエステル樹脂の酸価を１．０ｍｇＫＯＨ／ｇ以下にすることが困難であったため、やや高めの酸価で反応を終了した。 (Production Examples 2 to 12, 16, 17) Production of polyester resins (A2) to (A12), (A16), (A17) The acid components and alcohol components in Production Example 1 were formulated as shown in Table 1. Except for the above, resin solutions of polyester resins (A2) to (A12), (A16) and (A17) having a solid content of 70% were obtained in the same manner as in Production Example 1. In Production Example 17, it was difficult to set the acid value of the produced polyester resin to 1.0 mgKOH / g or less, so the reaction was terminated at a slightly higher acid value.
　（製造例１３）　ポリエステル樹脂（Ａ１３）の製造
　温度計、攪拌機及び精留塔を具備した２Ｌの反応装置に、ｉＰＡを３７７．８部、ＢＥＰＧを３６４．２部、ＴＥＧを２２７．６部仕込み、反応装置の内容物温度を１６０℃まで昇温した。次いで１６０℃から２３０℃までを３時間で昇温し、２３０℃で２時間、内容物温度を保持した後、精留塔を水分離器と置換し、反応装置にキシレン約５０．０部を仕込み、水とキシレンとを共沸させて縮合水を除去しながら重縮合を進めた。生成したポリエステル樹脂の酸価が１．０ｍｇＫＯＨ／ｇ以下であることを確認した後、内容物温度を１６０℃まで冷却した。さらに、ＰＡを１１２．３部添加し、１６０℃で１時間保持して付加反応（ハーフエステル化）した後、冷却を開始した。１３０℃まで冷却した後、キシレンを添加して希釈することにより、固形分７０％のポリエステル樹脂（Ａ１３）の樹脂溶液を得た。 Production Example 13 Production of Polyester Resin (A13) A 2 L reactor equipped with a thermometer, a stirrer, and a rectifying tower was charged with 377.8 parts iPA, 364.2 parts BEPG, and 227.6 parts TEG. The temperature of the reactor contents was raised to 160 ° C. Next, the temperature was raised from 160 ° C. to 230 ° C. in 3 hours, and the content temperature was maintained at 230 ° C. for 2 hours. Then, the rectification column was replaced with a water separator, and about 50.0 parts of xylene was added to the reactor. The polycondensation was carried out while removing the condensed water by azeotropically distilling water and xylene. After confirming that the acid value of the produced polyester resin was 1.0 mgKOH / g or less, the content temperature was cooled to 160 ° C. Further, 112.3 parts of PA was added and maintained at 160 ° C. for 1 hour for addition reaction (half esterification), and then cooling was started. After cooling to 130 ° C., xylene was added and diluted to obtain a resin solution of a polyester resin (A13) having a solid content of 70%.
　（製造例１４）　ポリエステル樹脂（Ａ１４）の製造
　製造例１３における酸成分とアルコール成分とを、表１に示す配合としたこと以外は、製造例１３と同様にして固形分７０％のポリエステル樹脂（Ａ１４）の樹脂溶液を得た。 (Manufacture example 14) Manufacture of polyester resin (A14) Except having made the mixing | blending which shows the acid component and alcohol component in manufacture example 13 into Table 1, it is the polyester resin (70% of solid content) like manufacture example 13 ( A resin solution of A14) was obtained.
　（製造例１５）　ポリエステル樹脂（Ａ１５）の製造
　温度計、攪拌機及び水分離機を具備した２Ｌの反応装置に、ＰＡを２３７．５部、ＥＧを２９．３部、ＰＥを１９８．２部、大豆油脂肪酸を６０２．６部、キシレンを５０．０部仕込み、反応装置の内容物温度を１６０℃まで昇温し、１時間保持した。次いで１６０℃から２４０℃までを４時間で昇温し、２４０℃のまま、生成した縮合水を除去しながら重縮合を進めた。樹脂酸価が約３．０ｍｇＫＯＨ／ｇであることを確認した後、加熱を停止して冷却を開始し、キシレンを添加して希釈することにより、固形分７０％のポリエステル樹脂（Ａ１５）の樹脂溶液を得た。 (Production Example 15) Production of polyester resin (A15) In a 2 L reactor equipped with a thermometer, a stirrer and a water separator, 237.5 parts of PA, 29.3 parts of EG, 198.2 parts of PE, 602.6 parts of soybean oil fatty acid and 50.0 parts of xylene were charged, and the temperature of the reactor was raised to 160 ° C. and held for 1 hour. Next, the temperature was raised from 160 ° C. to 240 ° C. over 4 hours, and the polycondensation proceeded while removing the generated condensed water at 240 ° C. After confirming that the resin acid value is about 3.0 mgKOH / g, heating is stopped, cooling is started, and xylene is added to dilute to obtain a polyester resin (A15) resin having a solid content of 70%. A solution was obtained.
　上記の各製造例にて得られたポリエステル樹脂（Ａ１）～（Ａ１７）の樹脂酸価及び重量平均分子量を、各製造例の配合量と併せて表１に示す。 The resin acid values and weight average molecular weights of the polyester resins (A1) to (A17) obtained in each of the above production examples are shown in Table 1 together with the blending amounts of the respective production examples.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　シリルエステル基含有樹脂（Ｂ）の製造
　（製造例１８）　シリルエステル基含有樹脂（Ｂ１）の製造
　攪拌機付きのフラスコに、キシレン４０部を仕込んだ後、液相温度を１４０℃に維持し、表２に記した各不飽和単量体の各単量と、過酸化物系重合開始剤「パーブチルＩ」（商品名、日油（株）製）１部との混合物を、フラスコの中へ３時間で滴下した。滴下終了後、同温度で３０分間保持した。次いでキシレン１０部と「パーブチルＩ」１部との混合物を２０分間で滴下し、同温度で２時間攪拌を続けてから、液相の冷却を開始した。生成した樹脂の固形分濃度が５０質量％となるように、フラスコの中にキシレンを加えて樹脂溶液を調製し、シリルエステル基含有樹脂（Ｂ１）の樹脂溶液を得た。 Production of silyl ester group-containing resin (B) (Production Example 18) Production of silyl ester group-containing resin (B1) After charging 40 parts of xylene into a flask equipped with a stirrer, the liquidus temperature was maintained at 140 ° C. A mixture of each unit amount of each unsaturated monomer described in 2 and 1 part of a peroxide-based polymerization initiator “Perbutyl I” (trade name, manufactured by NOF Corporation) was placed into a flask. Dropped over time. After completion of the dropping, the temperature was maintained for 30 minutes. Next, a mixture of 10 parts of xylene and 1 part of “Perbutyl I” was added dropwise over 20 minutes. Stirring was continued for 2 hours at the same temperature, and then cooling of the liquid phase was started. A resin solution was prepared by adding xylene to the flask so that the solid content concentration of the produced resin was 50% by mass, and a resin solution of the silyl ester group-containing resin (B1) was obtained.
　（製造例１９、２０）　シリルエステル基含有樹脂（Ｂ２）、（Ｂ３）の製造
　製造例１８における不飽和単量体を、表２に示す配合としたこと以外は、製造例１８と同様にしてシリルエステル基含有樹脂（Ｂ２）及び（Ｂ３）の樹脂溶液（固形分濃度５０質量％）を得た。 (Production Examples 19 and 20) Production of silyl ester group-containing resins (B2) and (B3) As in Production Example 18, except that the unsaturated monomer in Production Example 18 was formulated as shown in Table 2. Resin solutions (solid content concentration 50 mass%) of silyl ester group-containing resins (B2) and (B3) were obtained.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　防汚塗料組成物の調製と各種試験
　（実施例１～２３）及び（比較例１～５）
　評価
　ポリエステル樹脂（Ａ１）～（Ａ１７）の樹脂溶液及びシリルエステル基含有樹脂（Ｂ１）～（Ｂ３）の樹脂溶液、防汚剤、顔料等を、表３－１及び３－２に示す配合組成にて混合し、ホモミキサーを用いて約２，０００ｒｐｍの攪拌速度により混合分散した。分散後、ディスパロンＡ６３０－２０ＸＮ（楠本化成社製、タレ止剤）及び溶剤を添加し、ディスパー撹拌して塗料組成物（Ｅ１）～（Ｅ２８）を調製した。調製した塗料組成物を、下記の防汚性能試験、密着性試験及び耐クラック性試験に供した。これら各試験の結果は、表４～表６に示す。 Preparation of antifouling paint composition and various tests (Examples 1 to 23) and (Comparative Examples 1 to 5)
Resin solution evaluation polyester resin (A1) ~ (A17) of the resin solution and the silyl ester group-containing resin (B1) ~ (B3), an antifouling agent, a pigment, etc., blended composition shown in Tables 3-1 and 3-2 And mixed and dispersed using a homomixer at a stirring speed of about 2,000 rpm. After dispersion, Disparon A630-20XN (manufactured by Enomoto Kasei Co., Ltd., sagging agent) and a solvent were added, and the mixture was stirred with a disper to prepare coating compositions (E1) to (E28). The prepared coating composition was subjected to the following antifouling performance test, adhesion test and crack resistance test. The results of these tests are shown in Tables 4-6.
　＜防汚性能試験＞
　サンドブラスト処理鋼板（１００ｍｍ×３００ｍｍ×２ｍｍ）の両面に、エポキシ系防錆塗料を２００μｍの乾燥膜厚となるようにスプレー塗装し、さらに、エポキシ系バインダーコートを、乾燥膜厚が１００μｍとなるように塗装した。この塗装板の両面に、上記の各塗料組成物を、乾燥膜厚が片面４８０μｍとなるようにスプレー塗装により４回塗装し、温度２０℃、湿度７５％の恒温恒湿室にて１週間乾燥させて、試験片を作製した。この試験片を用いて、三重県尾鷲湾にて４８ケ月の海水浸漬を行い、試験塗膜上の付着生物の占有面積の割合（付着面積）を経時的に測定した。
　◎：（合格）付着生物が観察されなかった
　○：（合格）付着生物の占有面積が５％未満
　△：（不合格）付着生物の占有面積が５％以上、３０％未満
　×：（不合格）付着生物の占有面積が３０％以上 <Anti-fouling performance test>
On both sides of a sandblasted steel plate (100 mm x 300 mm x 2 mm), an epoxy-based anticorrosive paint is spray-coated so as to have a dry film thickness of 200 μm, and further an epoxy-based binder coat is applied so that the dry film thickness becomes 100 μm. Painted. Each of the above coating compositions is applied to both surfaces of this coated plate by spray coating so that the dry film thickness is 480 μm on one side, and dried in a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 75% for one week. A test piece was prepared. Using this test piece, 48 months of seawater immersion was carried out in Owase Bay, Mie Prefecture, and the ratio of the area occupied by attached organisms (attachment area) on the test coating was measured over time.
◎: (Accepted) No attached organisms were observed ○: (Accepted) The occupied area of attached organisms was less than 5% △: (Failed) The occupied area of attached organisms was 5% or more and less than 30% ×: (Failure ) The area occupied by attached organisms is 30% or more
　＜密着性試験＞
　円筒形のドラム（直径５００ｍｍ×高さ２４０ｍｍ）に装着可能な湾曲性を有するサンドブラスト処理鋼板（１２０ｍｍ×１２０ｍｍ×１ｍｍ）に、エポキシ系防錆塗料を２００μｍの乾燥膜厚となるようにスプレー塗装し、さらに、エポキシ系バインダーコートを乾燥膜厚が１００μｍとなるように塗装した。この塗装後の鋼板の片面に、上記の各塗料組成物を、乾燥膜厚が片面４８０μｍとなるようにスプレー塗装により４回塗装し、温度２０℃、湿度７５％の恒温恒湿室にて１週間乾燥させて、試験片を作製した。この試験片を上記の円筒形ドラムに装着し、該円筒形ドラムを兵庫県由良湾の海面下５００ｍｍにて１６ノットで２４ヶ月間回転させた。海中から試験片を経時的に回収し、５ｍｍ間隔のゴバン目試験を実施した。評価はＩＳＯ　２４０９：１９９２に準拠するものとした。
　◎：（合格）Ｔａｂｌｅ１　Ｃｌａｓｓｉｆｉｃａｔｉｏｎ　０・１
　○：（合格）Ｔａｂｌｅ１　Ｃｌａｓｓｉｆｉｃａｔｉｏｎ　２
　△：（不合格）Ｔａｂｌｅ１　Ｃｌａｓｓｉｆｉｃａｔｉｏｎ　３
　×：（不合格）Ｔａｂｌｅ１　Ｃｌａｓｓｉｆｉｃａｔｉｏｎ　４・５ <Adhesion test>
A sandblasted steel plate (120 mm x 120 mm x 1 mm) with a curvature that can be mounted on a cylindrical drum (diameter 500 mm x height 240 mm) is spray-coated with an epoxy-based anticorrosive paint to a dry film thickness of 200 µm. Furthermore, an epoxy binder coat was applied so that the dry film thickness was 100 μm. On each side of the steel sheet after coating, each of the coating compositions described above was applied four times by spray coating so that the dry film thickness was 480 μm on one side, and 1 in a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 75%. Test pieces were prepared by drying for a week. This test piece was mounted on the above cylindrical drum, and the cylindrical drum was rotated for 24 months at 16 knots at 500 mm below the sea surface in Yura Bay, Hyogo Prefecture. Test specimens were collected over time from the sea, and a Gobang eye test was conducted at intervals of 5 mm. Evaluation was based on ISO 2409: 1992.
A: (Pass) Table1 Classification 0 · 1
○: (Pass) Table1 Classification 2
Δ: (Fail) Table 1 Classification 3
X: (failed) Table1 Classification 4.5
　＜耐クラック性試験＞
　上記密着性試験に供した試験片の塗膜を目視観察し、クラックの発生の有無を調べた。
　◎：（合格）クラックが観察されなかった
　○：（合格）微細なクラックが塗膜表面の一部の範囲で観察された
　△：（不合格）微細又は明確なクラックが塗膜表面の広い範囲で観察された
　×：（不合格）下地に至るクラックが観察された <Crack resistance test>
The coating film of the test piece subjected to the adhesion test was visually observed to check for the occurrence of cracks.
A: (Pass) No crack was observed. ○: (Pass) A fine crack was observed in a part of the surface of the coating film. Δ: (Fail) A fine or clear crack was in a wide range of the coating surface. X: (Fail) Cracks leading to the ground were observed
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007

Claims (6)

  1. 　ポリエステル樹脂（Ａ）、シリルエステル基含有樹脂（Ｂ）及び防汚剤（Ｃ）を含む防汚塗料組成物であって、
    　前記シリルエステル基含有樹脂（Ｂ）が、一般式（Ｉ）：
    Ｒ5－ＣＨ＝Ｃ（Ｒ4）－ＣＯＯ－ＳｉＲ1Ｒ2Ｒ3・・・（Ｉ）
    ［式（Ｉ）中、Ｒ4は水素原子又はメチル基を示し、Ｒ1、Ｒ2及びＲ3はそれぞれ独立に炭化水素基を示し、Ｒ5は水素原子又はＲ6－Ｏ－ＣＯ－（ただし、Ｒ6は有機基又は－ＳｉＲ7Ｒ8Ｒ9で表されるシリル基を示し、Ｒ7、Ｒ8及びＲ9はそれぞれ独立に炭化水素基を示す。）を示す。］で表される単量体（ｂ１）の１種又は２種以上と、前記単量体（ｂ１）以外の単量体（ｂ２）の１種又は２種以上との共重合体からなり、
    　前記ポリエステル樹脂（Ａ）と前記シリルエステル基含有樹脂（Ｂ）との質量比が３／９７～８０／２０の範囲内であり、かつ、前記防汚剤（Ｃ）の含有量が前記ポリエステル樹脂（Ａ）と前記シリルエステル基含有樹脂（Ｂ）との合計質量を基準として５０～５００質量％の範囲内であることを特徴とする、前記防汚塗料組成物。     An antifouling paint composition comprising a polyester resin (A), a silyl ester group-containing resin (B) and an antifouling agent (C),
    The silyl ester group-containing resin (B) is represented by the general formula (I):
    R 5 —CH═C (R 4 ) —COO—SiR 1 R 2 R 3 (I)
    [In the formula (I), R 4 represents a hydrogen atom or a methyl group, R 1 , R 2 and R 3 each independently represents a hydrocarbon group, and R 5 represents a hydrogen atom or R 6 —O—CO— ( R 6 represents an organic group or a silyl group represented by —SiR 7 R 8 R 9 , and R 7 , R 8 and R 9 each independently represents a hydrocarbon group. And a copolymer of one or more monomers (b1) and one or more monomers (b2) other than the monomer (b1),
    The mass ratio of the polyester resin (A) to the silyl ester group-containing resin (B) is in the range of 3/97 to 80/20, and the content of the antifouling agent (C) is the polyester resin. The antifouling coating composition, wherein the antifouling coating composition is in the range of 50 to 500% by mass based on the total mass of (A) and the silyl ester group-containing resin (B).
  2. 　前記ポリエステル樹脂（Ａ）の酸価が０～１２０ＫＯＨｍｇ／ｇの範囲内である、請求項１に記載の防汚塗料組成物。 The antifouling paint composition according to claim 1, wherein the acid value of the polyester resin (A) is in the range of 0 to 120 KOHmg / g.
  3. 　前記ポリエステル樹脂（Ａ）の重量平均分子量が１５０００以下である、請求項１又は２に記載の防汚塗料組成物。 The antifouling paint composition according to claim 1 or 2, wherein the polyester resin (A) has a weight average molecular weight of 15000 or less.
  4. 　前記ポリエステル樹脂（Ａ）と前記シリルエステル基含有樹脂（Ｂ）との質量比が７／９３～６０／４０の範囲内である、請求項１～３のいずれか一項に記載の防汚塗料組成物。 The antifouling paint according to any one of claims 1 to 3, wherein a mass ratio of the polyester resin (A) to the silyl ester group-containing resin (B) is in the range of 7/93 to 60/40. Composition.
  5. 　前記シリルエステル基含有樹脂（Ｂ）は、前記単量体（ｂ１）と前記単量体（ｂ２）との質量比（ｂ１）／（ｂ２）が２０／８０～７０／３０の範囲内である、請求項１～４のいずれか一項に記載の防汚塗料組成物。 In the silyl ester group-containing resin (B), the mass ratio (b1) / (b2) between the monomer (b1) and the monomer (b2) is in the range of 20/80 to 70/30. The antifouling paint composition according to any one of claims 1 to 4.
  6. 　請求項１～５のいずれか一項に記載の防汚塗料組成物を被塗物に塗装してなる塗装物品。 6. A coated article obtained by coating an object to be coated with the antifouling paint composition according to any one of claims 1 to 5.
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JP6755176B2 (en) 2020-09-16
CN106164189B (en) 2018-09-25
KR20160143662A (en) 2016-12-14
CN106164189A (en) 2016-11-23

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