WO2015156073A1 - Antifouling coating material composition and coated article coated with same - Google Patents
Antifouling coating material composition and coated article coated with same Download PDFInfo
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- 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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- antifouling
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—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
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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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
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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
- 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
Description
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.
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.
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.
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.
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.
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. ]
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).
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.
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.
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.
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).
(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.
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.
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.
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.
(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.
(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.
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
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
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
Claims (6)
- 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). - 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.
- 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.
- 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.
- 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.
- 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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CN106164189A (en) | 2016-11-23 |
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