WO2010119703A1 - Resin composition for coating material, and coated article which is coated with the resin composition for coating material - Google Patents

Resin composition for coating material, and coated article which is coated with the resin composition for coating material Download PDF

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Publication number
WO2010119703A1
WO2010119703A1 PCT/JP2010/002770 JP2010002770W WO2010119703A1 WO 2010119703 A1 WO2010119703 A1 WO 2010119703A1 JP 2010002770 W JP2010002770 W JP 2010002770W WO 2010119703 A1 WO2010119703 A1 WO 2010119703A1
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Prior art keywords
component
resin composition
group
carbon atoms
weight
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PCT/JP2010/002770
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French (fr)
Japanese (ja)
Inventor
松尾陽一
南部俊郎
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株式会社カネカ
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Priority to JP2011509226A priority Critical patent/JPWO2010119703A1/en
Publication of WO2010119703A1 publication Critical patent/WO2010119703A1/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
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • C09D5/165—Macromolecular compounds containing hydrolysable groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond

Definitions

  • the present invention relates to a one-component paint resin composition.
  • paints have been used for the purpose of protecting buildings or imparting design properties.
  • acrylic urethane resin paints, acrylic silicon resin paints, and fluororesin paints have been established as paints having excellent weather resistance.
  • low-contamination paints have been developed and marketed to protect the appearance from urban pollution such as exhaust gas.
  • a technique for making the coating surface hydrophilic using a specific silicon compound is known, and in order to fully demonstrate its performance, catalysts such as organometallic compounds are used.
  • the coating form is a two-pack type (Patent Document 1).
  • Patent Document 2 a coating material in which an unsaturated group is introduced into a resin and is oxidatively cured after coating has been proposed.
  • the present invention has been made in view of the circumstances as described above, and the object of the present invention is to develop sufficient low contamination with a compounding amount of a silicon compound that can maintain the coating film performance of the paint.
  • An object of the present invention is to provide a coating composition and a coated product, in which the blend has sufficient storage stability, and can obtain satisfactory low contamination even after storage, which is the same as the initial blend. In addition, the weather resistance can be improved. Furthermore, it is providing the coating compounding agent for it.
  • R 2 a -Si- (OR 1 ) 3-a (1)
  • R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms and an aralkyl having 7 to 12 carbon atoms.
  • a monovalent hydrocarbon group selected from the group, a represents an integer of 0 to 2) 100 parts by weight of the polymer (A) component having at least one silicon group bonded to the hydrolyzable group represented by (R 3 O) 4-b —Si—R 4 b (2)
  • R 3 is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms
  • R 4 is a carbon atom having 1 carbon atom
  • a monovalent hydrocarbon group selected from an alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, and b represents 0 or 1)
  • B partially hydrolyzed condensate
  • B component 50 to 1000 parts by weight
  • the sum of the weights of the component (A), the component (B), and the component (C) is 0.01 to 1.0 times the weight of the component (D).
  • Resin composition for liquid paint (III).
  • the resin composition for one-component paints according to any one of (I) to (IV), wherein the component (A) and the component (B) are premixed and then blended into the component (D), (VI).
  • the metal species of component (C) is a compound selected from Sn, Ti, Fe, Al, Mn, Co, Zr, Ni, Bi, Cu, Zn, Ba, according to any one of (I) to (V) One-pack type resin composition for paint, (VII).
  • the compound (E) having a dehydrating action is blended in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the component (D).
  • the curable resin composition of the present invention can be manufactured with low cost and simple operation.
  • a resin composition for coatings which is excellent in stain resistance, sufficiently exhibits its performance after storage, and has improved weather resistance. It can also be used as a one-component paint.
  • a low contamination imparting agent for producing the coating composition it is possible to provide a low contamination imparting agent for producing the coating composition.
  • the resin (A) component usable in the present invention may be contained in a form in which a hydrolyzable silyl group is bonded to a carbon atom.
  • the silyl group bonded to the hydrolyzable group may be bonded to the end of the main chain of the resin (A) component, may be bonded to the side chain, or bonded to the end of the main chain and the side chain. It may be.
  • a method for introducing a silyl group bonded to a hydrolyzable group a method of copolymerizing a monomer containing a silyl group bonded to a hydrolyzable group with another monomer, a method of reacting a silicate compound, or a hydroxyl group
  • a method of reacting a silicate compound with the containing copolymer There is a method of reacting a silicate compound with the containing copolymer.
  • a simple method is a method of copolymerizing a monomer containing a silyl group bonded to a hydrolyzable group and another monomer.
  • the hydrolyzable group in the silyl group bonded to the hydrolyzable group includes a halogen group and an alkoxy group.
  • an alkoxy group represented by the following general formula (1) is useful because of easy reaction control.
  • R 1 in the general formula (1) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- An alkyl group having 1 to 4 carbon atoms such as a butyl group. When the carbon number of the alkyl group exceeds 10, the reactivity of the hydrolyzable silyl group is lowered.
  • R 2 in the general formula (1) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably an aryl group such as a phenyl group or an alkyl group having 1 to 4 carbon atoms exemplified in the above R 1 .
  • an alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of excellent curability of the composition of the present invention.
  • (OR 1 ) 3-a is selected so that 3-a is 1 or more and 3 or less, that is, a is 0 to 2, but the composition of the present invention is cured.
  • A is preferably 0 or 1 from the viewpoint of improving the properties. Therefore, the number of bonds of R 2 is preferably 0 or 1.
  • the number of OR 1 or R 2 is plural, they may be the same or different.
  • Specific examples of the reactive silyl group bonded to the carbon atom represented by the general formula (1) include, for example, a hydrolyzable silyl group-containing vinyl monomer copolymerized with a resin (A) component described later. The group to be contained is mentioned.
  • Resin (A) component is, for example, a hydrolyzable silyl group-containing vinyl monomer (a) component and other copolymerizable monomer (b) component as a radical polymerization initiator such as azobisisobutyronitrile. Can be produced by copolymerization using a solution polymerization method or the like.
  • hydrolyzable silyl group-containing vinyl monomer (a) component examples include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, and vinyltris (2-methoxyethoxy) silane.
  • These hydrolyzable silyl group-containing vinyl monomers (a) may be used alone or in combination of two or more.
  • the hydrolyzable silyl group-containing monomer (a) component is preferably copolymerized using 0.1 to 50 parts by weight in 100 parts by weight of all monomers. If the amount is less than 0.1 parts by weight, sufficient low contamination may not be exhibited, and weather resistance may not be improved. On the other hand, when it exceeds 50 parts by weight, the storage stability tends to deteriorate.
  • the copolymerizable monomer (b) component examples include (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, glycidyl ( (Meth) acrylate, isobornyl (meth) acrylate, (meth) acrylamide, ⁇ -ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methyl (meth)
  • Unsaturated carboxylic acid esters vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate, and diallyl phthalate; amino group-containing vinyl compounds such as vinyl pyridine and aminoethyl vinyl ether; itaconic acid diamide, crotonic acid amide, maleic acid diamide
  • Amide group-containing vinyl compounds such as fumaric acid diamide and N-vinylpyrrolidone; (meth) acrylonitrile, 2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, Pyrene, butadiene, isoprene, fluoroolefin maleimide, N- vinylimidazole, like other vinyl compounds such as vinyl sulfonic acid.
  • These other monomer (b) components may be used alone or in combination of two or more.
  • hydroxyl group-containing vinyl monomer and / or its derivative (c) component it is also possible to copolymerize a hydroxyl group-containing vinyl monomer and / or its derivative (c) component.
  • the appearance of the resulting coating film may be improved in acrylic urethane resin paints.
  • hydroxyl group-containing vinyl monomer and / or derivative (c) component examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, 4-hydroxystyrene vinyl toluene, Allonics 5700, 4- manufactured by Toagosei Chemical Industry Co., Ltd. Hydroxystyrene, manufactured by Nippon Shokubai Chemical Industry Co., Ltd.
  • HE-10, HE-20, HP-1 and HP-2 (all of which are acrylic ester oligomers having a hydroxyl group at the terminal), manufactured by Nippon Oil & Fats Co., Ltd.
  • Examples thereof include polycarbonate-containing vinyl compounds such as Daicel Chemical Industries, Ltd., TONEM-201 (UCC), and HEAC-1 (Daicel Chemical Industries).
  • hydroxyl group-containing vinyl monomers and / or derivatives (c) thereof may be used alone or in combination of two or more.
  • the resin (A) component thus obtained has a number average molecular weight of 3000 to 3,000 because the coating film formed using the composition of the present invention is excellent in physical properties such as low contamination and durability. It is preferably 5000 to 20000, especially 25000. At this time, if necessary, the molecular weight may be adjusted using a chain transfer agent such as n-dodecyl mercaptan, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxysilane or the like.
  • a chain transfer agent such as n-dodecyl mercaptan, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxysilane or the like.
  • the main chain of the resin (A) component substantially consists of an acrylic copolymer chain means that 50% or more, more preferably 70% or more of the units constituting the main chain of the resin (A) component. It means that it is formed from a (meth) acrylic monomer unit.
  • (meth) acrylic is a general term for acrylic and methacrylic.
  • the general formula (2) is used for the purpose of improving the stain resistance of the coating film formed from the composition: (R 3 O) 4-b —Si—R 4 b (2) (Wherein R 3 is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, and R 4 is a carbon atom having 1 carbon atom) A monovalent hydrocarbon group selected from an alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, and b represents 0 or 1) And / or 50 to 1000 parts by weight of the partially hydrolyzed condensate (B) component (hereinafter referred to as the organosilicate compound (B) component).
  • organosilicate compound (B) component examples include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra Examples thereof include t-butoxysilane and partial hydrolysis / condensates thereof.
  • methyl silicate 51, ethyl silicate 45, ethyl silicate 40, ethyl silicate 48 (above, manufactured by Colcoat Co., Ltd.), silicate 45, silicate 40 (above, Tama Chemical Co., Ltd.) from the viewpoint that the obtained coating film has excellent contamination resistance.
  • Industrial Co., Ltd. is desirable.
  • the said compound may be single 1 type, and may use 2 or more types together.
  • organosilicates containing different alkoxysilyl groups in the same molecule can be used.
  • the ratio of these substituents can be arbitrarily changed between 0 and 100%.
  • the degree of condensation is preferably about 1 to 20. A more preferred range of the degree of condensation is 3-15.
  • the amount of the component (B) used is 50 to 1000 parts by weight, preferably 75 to 500 parts by weight, more preferably 100 to 400 parts by weight with respect to 100 parts by weight of the component (A). If the amount of the organosilicate compound (B) component exceeds 1000 parts, the coating film made of the coating composition becomes cloudy or the appearance is deteriorated such that sufficient gloss is not obtained, which is not preferable.
  • the organometallic compound (C) component is changed to (A), (B), (D) component. 1 part by weight or less is used in terms of metal with respect to the total amount.
  • the organometallic compound (C) component is not particularly limited, but Sn, Ti, Fe, Al, Mn, Co, Zr, and the like are excellent in terms of improving the stain resistance from the initial stage of coating and in terms of stability. It is preferable to use a metal selected from Ni, Bi, Cu, Zn, and Ba.
  • organic tin compound examples include dioctyltin bis (2-ethylhexyl maleate), dioctyltin oxide or a condensate of dibutyltin oxide and silicate, dibutyltin dioctate, dibutyltin dilaurate, dibutyl Tin distearate, dibutyltin diacetylacetonate, dibutyltin bis (ethylmaleate), dibutyltin bis (butylmaleate), dibutyltin bis (2-ethylhexylmaleate), dibutyltin bis (oleylmaleate) ), Stannous octoate, tin stearate, di-n-butyltin laurate oxide.
  • dibutyltin bisisononyl-3-mercaptopropionate dioctyltin bisisononyl-3-mercaptopropionate
  • octylbutyltin bisisononyl-3-mercaptopropionate dibutyl Examples thereof include tin bisisooctyl thiogluconate, dioctyl tin bisisooctyl thiogluconate, and octylbutyl tin bisisooctyl thiogluconate.
  • divalent tin such as tin dioctylate and tin distearate may be mentioned.
  • organic titanium compounds include titanium alkoxides such as titanium isopropoxide and titanium butoxide, and titanium chelates such as titanium acetylacetonate, titanium-2-ethylhexanate, and titanium diisopropoxybis (acetylacetonate). It is done.
  • organic iron compound examples include iron (II) or (III) acetate, acetylacetonate, 2-ethylhexanate, and the like.
  • organoaluminum compounds include aluminum alkoxides such as aluminum isopropoxide and aluminum butoxide, ethyl acetoacetonate aluminum diisopropoxide, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), and aluminum monoacetyl.
  • aluminum chelates such as acetonatobis (ethyl acetoacetate) and alkylacetylacetonate.
  • organic manganese compound examples include manganese (II) acetate, manganese (II) acetyl acetate, manganese (II) -2-ethylhexanate, and the like.
  • organic cobalt compound examples include cobalt (II) acetate, cobalt (II) acetyl acetate, cobalt (II) benzoylacetonate, cobalt (II) -2-ethylhexanate, and cobalt naphthanate.
  • organic zirconium compound examples include zirconium (IV) propoxide, zirconium (IV) acetate, zirconium (IV) acetyl acetate, zirconium (IV) -2-ethylhexanate and the like.
  • organic nickel compound examples include nickel (II) propoxide, nickel (II) stearate, nickel (II) acetate, nickel (II) acetyl acetate, nickel (II) -2-ethylhexanate and the like.
  • organic bismuth compound examples include bismuth (III) neodecanate, bismuth (III) acetate, bismuth (II) -2-ethylhexanate, and the like.
  • organic copper compound examples include copper (II) acetyl acetate and copper (II) butyl phthalate.
  • organic zinc compound examples include zinc (II) acetate, zinc (II) acetyl acetate, zinc (II) -2-ethylhexanate and the like.
  • organic barium compound examples include barium (II) acetate, barium (II) acetyl acetate, barium (II) -2-ethylhexanate and the like.
  • tin compounds and divalent tin compounds having an S atom in the molecule are preferred because they are not colored and are excellent in low contamination.
  • the amount of component (C) used is 1 part by weight or less, preferably 0.5 parts by weight or less, more preferably 0.3 parts by weight or less in terms of metal based on the total amount of components (A), (B), and (D). Less than parts by weight. As a minimum of the usage-amount, 0.01 weight part or more is preferable. When the amount of the component (C) exceeds 1 part by weight, the storage stability may be deteriorated or coloring may be remarkable, which is not preferable.
  • Organic resin (D) used in the present invention is not particularly limited as long as it is a solvent-type organic resin for paints, so that the stability and appearance of the composition can be obtained. Resins for use are preferred.
  • a paint by mixing the additives (A), (B) and (C) with a one-component paint resin and then adding various additives such as dehydrating agents and pigments. It is also possible to blend the components (A), (B), and (C) into a white enamel paint that has been made into a paint. When considering the point of improving storage stability and easier production, it is better to add the components (A), (B), and (C) to the white enamel paint already made into a paint. More preferred.
  • Examples of the resin for one-component paint at that time include oil-modified one-component paints, vinyl chloride and acrylic lacquer paints, moisture-curing one-component paints, and thermosetting one-component paints.
  • an oxidation-curing one-component paint, a moisture-curing one-component paint, and a thermosetting one-component paint that introduce an unsaturated group into the resin and are oxidatively cured after coating are preferred from the viewpoint of excellent weather resistance.
  • one-component paints Since there are many such one-component paints on the market, it is possible to mix the paint composition of the present invention using them.
  • Specific examples of the one-component paints that are commercially available include one-component fine urethane, fine silicon sera (both made by Nippon Paint Co., Ltd.), Ares autoimmunetan, Ares Eco Silicon (both made by Kansai Paint Co., Ltd.), One-part mild urethane, one-part mild silicon (both manufactured by SK Kaken) are listed.
  • the amount of the component (D) used is 150 to 10000 parts by weight, more preferably 300 to 7000 parts by weight, and even more preferably 500 to 5000 parts by weight with respect to 100 parts by weight of the component (A). If it is less than 150 parts by weight, the storage stability may be insufficient, which is not preferable. If it is 10000 parts by weight or more, the intended low-staining property is hardly exhibited, and improvement in weather resistance cannot be obtained. Therefore, it is not preferable.
  • the hydrolyzable silyl group-containing vinyl monomer (a) component and the silicon compound (B) component in the component (A) are reactive with moisture. Therefore, the storage stability of the composition can be improved by further adding a dehydrating agent (E) component.
  • Examples of the dehydrating agent include alkyl orthoformate such as methyl orthoformate, ethyl orthoformate or butyl orthoformate; alkyl orthoacetate such as methyl orthoacetate, ethyl orthoacetate or butyl orthoacetate; or methyl orthoborate, ethyl orthoborate, Examples thereof include orthocarboxylic acid esters such as alkyl orthoborate such as butyl orthoborate, and highly active silane compounds such as tetramethoxysilane, tetraethoxysilane, and methyltrimethoxysilane.
  • the amount of component (E) used is 0.1 to 10 parts by weight, preferably 0.3 to 8 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of component (D). .
  • the amount of the (E) component is less than 0.1 parts by weight, the moisture in the (D) component cannot be removed, and the stability may be impaired.
  • the amount is more than 10 parts by weight, the viscosity of the entire system is lowered, and there is a possibility that the diluting solvent at the time of coating cannot be brewed.
  • the amount of component (A), component (B), and component (C) used is the total weight, and is 0.01 to 1.0 times, preferably 0.02 to 0.7 times the weight of component (D). More preferably, it is 0.03 to 0.5 times. If it is less than 0.01 times, the intended stain resistance and weather resistance may not be obtained, and if it exceeds 1.0 times, the drying property, curability and water resistance may be insufficient.
  • the mixing order of the components (A) to (D) is not particularly limited and may be mixed in an arbitrary order. From the point that the effect is manifested due to a difference in compatibility even if the addition amount of the components (A) to (C) is small, the component (A) and the component (B) are mixed in advance. (D) It is preferable to mix
  • the blending order of the component (C) is not particularly limited, but in order to improve the storage stability, it is added to the component (D), or the component (A), (B) It is preferable to mix
  • the components (A) and (B) may be mixed and stirred at room temperature, but may be stirred at a temperature of about 100 ° C. or lower.
  • a condensation reaction proceeds with a part of the alkoxysilyl group of the component (A) and a part of the alkoxysilyl group of the component (B), and the weather resistance may be improved by combining them.
  • it is carried out at 100 ° C. or higher, it is difficult to control the reaction, and the stability is impaired.
  • curable resin composition of the present invention for example, diluents, ultraviolet absorbers, light stabilizers, anti-sagging agents, leveling agents and dispersants, color-separation preventing agents and the like that are usually used in paints; other than aminosilanes Silane coupling agent; Fibrin such as nitrocellulose and cellulose acetate butyrate; Add appropriate resin such as epoxy resin, melamine resin, vinyl chloride resin, fluororesin, chlorinated polypropylene, chlorinated rubber, polyvinyl butyral, polysiloxane May be.
  • the pigment-dispersing curable resin composition of the present invention is applied to an article to be coated by a usual method such as dipping, spraying, brushing, spraying, or the like, and is usually at room temperature or at 30 ° C. or higher. Bake in to cure.
  • Table 1 shows the solid content concentration of the obtained polymers (A-1 to 3) and the number average molecular weight measured by GPC.
  • the solid content concentration was adjusted to 50% using a polymerization solvent.
  • Solvesso 100 Organic solvent (manufactured by ExxonMobil Corp.)
  • Pegasol AN45 Organic solvent (Exxon Mobil Corporation)
  • the solid content in the component (A) and the component ratio of the component (B) are shown in Table 2.
  • the solid content in the component B was 71%.
  • Silicate 45 Ethyl silicate partial hydrolysis condensate (manufactured by Tama Chemical Industry Co., Ltd.)
  • ESi48 ethyl silicate partial hydrolysis condensate (manufactured by Colcoat Co., Ltd.)
  • the base material was an aluminum plate coated with esco (epoxy paint made by Kansai Paint) and one-component fine urethane every other day.
  • the one-component paint obtained in Table 3 was applied to the substrate to a thickness of about 40 ⁇ m by air spray to obtain a test plate.
  • a test plate was prepared in the same manner by applying the one-component paint in a sealed state at 50 ° C. for one month by air spraying.
  • the water contact angle test board was used for the outdoor rain-strip exposure stand, the dirt was lightly washed every week, and the water contact angle was measured.
  • a contact angle measuring machine (Kyowa Interface Science Co., Ltd .: CA-S150 type) was used to measure the water contact angle, which is an index of contamination resistance. It can be said that the lower the contact angle, the better the stain resistance.
  • the appearance of the test plate was evaluated according to the criteria shown below. Visual evaluation A: There are almost no rain stripes. ⁇ : Light rain streaks are seen, but disappears when washed lightly. ⁇ ⁇ : Rain streaks are observed, but it recovers to the extent that light rain streaks remain if washed with water. ⁇ : Rain streaks are observed, and it recovers slightly when washed with water. X: Dark rain streaks are observed, and it hardly disappears even when washed with water. -Weather resistance The accelerated weather resistance was evaluated for the test plate prepared by the above method using a sunshine weatherometer. Table 3 shows the 60 ° gloss retention (%) after a test time of 2000 hours. The higher the value, the better the weather resistance.
  • blend (C) component had favorable storage stability, since time was required for hydrophilic expression, it was a result in which contamination resistance is a little inferior.
  • Comparative Example 2 using a polymer having no hydrolyzable group-containing silicon group and Comparative Example 3 in which the component (A) was not added were all poor in stain resistance, storage stability and accelerated weather resistance. .
  • the resin composition for a one-component paint according to the present invention can be produced at a low cost with a simple operation.
  • a resin composition for coatings which is excellent in stain resistance, sufficiently exhibits its performance after storage, and has improved weather resistance. It can also be used as a one-component paint.
  • a low contamination imparting agent for producing the coating composition it is possible to provide a low contamination imparting agent for producing the coating composition.
  • the curable resin composition of the present invention can be suitably used for coating, for example, a building made of metal, ceramics, glass, cement, ceramic base material, plastic, wood, paper, fiber, etc., household appliances, and industrial equipment. .

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  • Paints Or Removers (AREA)

Abstract

Disclosed is a composition which exhibits excellent contamination resistance mainly in one-pack type coating materials. The use of the composition enables achievement of excellent storage stability and retention of excellent contamination resistance after storage. Specifically disclosed is a resin composition for one-pack type coating materials, which is obtained by blending (A) a polymer component in which the main chain is substantially composed of an acrylic copolymer chain and at least one silicon group bonded to a hydrolyzable group is contained at an end of the main chain and/or in a side chain, (B) a specific silicon compound component, and if necessary, (C) a specific organic metal compound component, into (D) another organic resin component. The resin composition for one-pack type coating materials has excellent storage stability, and can exhibit excellent contamination resistance after storage.

Description

塗料用樹脂組成物および該塗料用樹脂組成物を塗布してなる塗装物RESIN COMPOSITION FOR COATING AND COATED ARTICLE FORMED BY COATING THE COATING RESIN COMPOSITION
　本発明は、一液型塗料用樹脂組成物に関するものである。 The present invention relates to a one-component paint resin composition.
　従来、建築物を保護したり、意匠性を付与する目的で塗料は使用され、中でもアクリルウレタン樹脂塗料、アクリルシリコン樹脂塗料、フッ素樹脂塗料は耐候性に優れる塗料として定着している。また、排気ガス等の都市型汚染から外観を保護する為に、低汚染型塗料が開発・上市されている。外装用の低汚染型塗料としては、特定のシリコン化合物を用いて塗膜表面を親水性にする手法が知られており、その性能を充分に発揮する為に、有機金属化合物をはじめとする触媒が添加されるため、塗料形態は二液型となることが一般的である（特許文献１）。 Conventionally, paints have been used for the purpose of protecting buildings or imparting design properties. Among them, acrylic urethane resin paints, acrylic silicon resin paints, and fluororesin paints have been established as paints having excellent weather resistance. In addition, low-contamination paints have been developed and marketed to protect the appearance from urban pollution such as exhaust gas. As a low-contamination paint for exteriors, a technique for making the coating surface hydrophilic using a specific silicon compound is known, and in order to fully demonstrate its performance, catalysts such as organometallic compounds are used. In general, the coating form is a two-pack type (Patent Document 1).
　一方で、塗装作業性の利便さから使用されている塗料として一液型塗料があり、この場合にも、耐候性などの性能を向上させることを目的に、アクリルウレタン樹脂塗料やアクリルシリコン樹脂塗料といった高性能塗料が上市されている。中でも、樹脂中に不飽和基を導入し、塗装後に酸化硬化させる塗料が提案されている（特許文献２）。 On the other hand, there is a one-pack type paint as a paint used for the convenience of painting workability. In this case, acrylic urethane resin paint and acrylic silicon resin paint are used for the purpose of improving performance such as weather resistance. Such high-performance paints are on the market. Among them, a coating material in which an unsaturated group is introduced into a resin and is oxidatively cured after coating has been proposed (Patent Document 2).
　しかしながら現在、一液型塗料で低汚染性を充分に満足できるものは上市されていないのが実情である。これは、塗膜性能を維持できるシリコン化合物の配合量で低汚染性を発現するのが困難であったり、貯蔵安定性等の問題から、シリコン化合物の特性を発揮するのに必要な有機金属化合物を配合することが困難であることが原因である。 However, at present, no one-pack type paint that can sufficiently satisfy the low pollution property is marketed. This is an organometallic compound that is difficult to express low contamination with the compounding amount of the silicon compound that can maintain the coating film performance, and is necessary to exhibit the characteristics of the silicon compound due to problems such as storage stability. This is because it is difficult to blend.
特開平６－１４５４５３号公報JP-A-6-145453 特開２０００－１１９５９０号公報JP 2000-119590 A
　本発明は、前記のごとき実情に鑑みてなされたものであり、その目的とするところは、塗料の塗膜性能を維持できるほどのシリコン化合物の配合量で、充分な低汚染性を発現するとともに、配合物が充分な貯蔵安定性を有し、貯蔵後も配合初期と変わらず満足できる低汚染性を得ることができる塗料組成物および塗装物を提供することである。また、耐候性の向上も可能となる。さらには、そのための塗料配合剤を提供することである。 The present invention has been made in view of the circumstances as described above, and the object of the present invention is to develop sufficient low contamination with a compounding amount of a silicon compound that can maintain the coating film performance of the paint. An object of the present invention is to provide a coating composition and a coated product, in which the blend has sufficient storage stability, and can obtain satisfactory low contamination even after storage, which is the same as the initial blend. In addition, the weather resistance can be improved. Furthermore, it is providing the coating compounding agent for it.
　特定の加水分解性シリル基含有有機重合体に、特定のシリコン化合物および有機金属化合物を特定の割合で配合した組成物をその他の有機樹脂に配合することで、一液型塗料としても、充分な低汚染性が安定的に得られることを見出した。 Mixing a specific hydrolyzable silyl group-containing organic polymer with a specific silicon compound and organometallic compound at a specific ratio in another organic resin is sufficient as a one-component paint. It was found that low contamination can be stably obtained.
　すなわち本願は、
（Ｉ）．
　  Ｒ２ ａ
　　｜
　－Ｓｉ－（ＯＲ１）３－ａ　（１）
　（式中、Ｒ１は水素原子または炭素数１～１０のアルキル基、Ｒ２は水素原子または炭素数１～１０のアルキル基、炭素数６～２５のアリール基および炭素数７～１２のアラルキル基から選ばれた１価の炭化水素基、ａは０～２の整数を示す。）
で表される加水分解性基に結合したケイ素基を少なくとも1つ有する重合体（Ａ）成分１００重量部に対して、
（Ｒ３Ｏ）４－ｂ－Ｓｉ－Ｒ４ ｂ（２）
（式中、Ｒ３は炭素数１～１０のアルキル基、炭素数６～１０のアリール基および炭素数７～１０のアラルキル基から選ばれた１価の炭化水素基、Ｒ４は炭素数１～１０のアルキル基、炭素数が６～１０のアリール基および炭素数が７～１０のアラルキル基から選ばれた１価の炭化水素基、ｂは０または１を示す）で表されるシリコン化合物及び／またはその部分加水分解縮合物（Ｂ）成分５０～１０００重量部、その他の有機樹脂（Ｄ）成分１５０～１００００重量部、さらに有機金属化合物（Ｃ）成分を（Ａ）、（Ｂ）、（Ｄ）の総量に対して金属換算で１重量部以下を含有する一液型塗料用樹脂組成物、
（II）．
（Ａ）成分、（Ｂ）成分、（Ｃ）成分の重量の合計が、前記（Ｄ）成分の重量の０．０１～１．０倍であることを特徴とする（Ｉ）に記載の一液型塗料用樹脂組成物、
（III）．
（Ｄ）成分が、溶剤型有機樹脂である（Ｉ）～（II）のいずれかに記載の一液型塗料用樹脂組成物、
（IV）．
（Ｄ）成分が、既架橋型または酸化硬化型または熱硬化型の有機樹脂である（Ｉ）～（III）のいずれかに記載の一液型塗料用樹脂組成物、
（Ｖ）．
（Ａ）成分と（Ｂ）成分が予め混合された後に、（Ｄ）成分へ配合することを特徴とする（Ｉ）～（IV）のいずれかに記載の一液型塗料用樹脂組成物、
（VI）．
（Ｃ）成分の金属種がＳn、Ｔｉ、Ｆe、Ａｌ、Ｍｎ、Ｃｏ、Ｚｒ、Ｎｉ、Ｂｉ、Ｃｕ、Ｚｎ、Ｂａから選ばれる化合物である（Ｉ）～（Ｖ）のいずれかに記載の一液型塗料用樹脂組成物、
（VII）．
（Ｃ）成分の金属種がＳn、Ｔｉ、Ｆe、Ａｌ、Ｍｎ、Ｃｏ、Ｚｒ、Ｎｉ、Ｂｉから選ばれる化合物である（Ｉ）～（VI）のいずれかに記載の一液型塗料用樹脂組成物、
（VIII）．
　さらに、脱水作用のある化合物（Ｅ）成分が、前記（Ｄ）成分１００重量部に対して０．１～１０重量部配合されることを特徴とする（Ｉ）～（VII）のいずれかに記載の一液型塗料用樹脂組成物、
（IX）．
一液型塗料用樹脂組成物を密閉下で５０℃１ヶ月間保存した後に得た塗膜の４週間暴露後の水接触角の角度が、７０°以下である（Ｉ）～（VIII）のいずれかに記載の一液型塗料用樹脂組成物、
（Ｘ）．
（Ｉ）～（IX）のいずれかに記載の一液型塗料用樹脂組成物を塗布してなる塗装物、
に関する。 That is, this application
(I).
R 2 a
｜
-Si- (OR 1 ) 3-a (1)
Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms and an aralkyl having 7 to 12 carbon atoms. A monovalent hydrocarbon group selected from the group, a represents an integer of 0 to 2)
100 parts by weight of the polymer (A) component having at least one silicon group bonded to the hydrolyzable group represented by
(R 3 O) 4-b —Si—R 4 b (2)
(Wherein R 3 is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, and R 4 is a carbon atom having 1 carbon atom) A monovalent hydrocarbon group selected from an alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, and b represents 0 or 1) And / or its partially hydrolyzed condensate (B) component 50 to 1000 parts by weight, other organic resin (D) component 150 to 10000 parts by weight, and further, organometallic compound (C) component (A), (B), A resin composition for a one-component paint containing 1 part by weight or less in terms of metal with respect to the total amount of (D),
(II).
The sum of the weights of the component (A), the component (B), and the component (C) is 0.01 to 1.0 times the weight of the component (D). Resin composition for liquid paint,
(III).
(D) The one-component paint resin composition according to any one of (I) to (II), wherein the component is a solvent-type organic resin;
(IV).
(D) The one-component paint resin composition according to any one of (I) to (III), wherein the component is a cross-linked, oxidation-curable, or thermosetting organic resin;
(V).
The resin composition for one-component paints according to any one of (I) to (IV), wherein the component (A) and the component (B) are premixed and then blended into the component (D),
(VI).
The metal species of component (C) is a compound selected from Sn, Ti, Fe, Al, Mn, Co, Zr, Ni, Bi, Cu, Zn, Ba, according to any one of (I) to (V) One-pack type resin composition for paint,
(VII).
(C) One-component paint resin according to any one of (I) to (VI), wherein the metal species of the component is a compound selected from Sn, Ti, Fe, Al, Mn, Co, Zr, Ni, and Bi Composition,
(VIII).
Further, the compound (E) having a dehydrating action is blended in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the component (D). The one-component resin composition for coatings,
(IX).
(I) to (VIII) in which the water contact angle after exposure for 4 weeks of the coating film obtained after the resin composition for one-part paint is stored at 50 ° C. for 1 month in a sealed state is 70 ° or less Any one-part resin composition for paints,
(X).
(1) to (IX) a coated article obtained by applying the one-component paint resin composition according to any one of
About.
　本発明の硬化性樹脂組成物は、低コスト・簡易な操作で製造できる。特には、耐汚染性に優れ、貯蔵後もその性能を充分に発現するとともに、耐候性が向上した塗料用樹脂組成物を提供することが可能となる。また、一液型塗料としても用いることができる。さらに、該塗料組成物を製造するための、低汚染性付与剤を提供することが可能となる。 The curable resin composition of the present invention can be manufactured with low cost and simple operation. In particular, it is possible to provide a resin composition for coatings which is excellent in stain resistance, sufficiently exhibits its performance after storage, and has improved weather resistance. It can also be used as a one-component paint. Furthermore, it is possible to provide a low contamination imparting agent for producing the coating composition.
　以下に本発明をその実施の形態に基づき詳細に説明する。 Hereinafter, the present invention will be described in detail based on the embodiments.
　（有機樹脂成分Ａ）
　本発明で使用可能な樹脂（Ａ）成分は、加水分解性シリル基が炭素原子に結合した形式で含有されていればよい。 (Organic resin component A)
The resin (A) component usable in the present invention may be contained in a form in which a hydrolyzable silyl group is bonded to a carbon atom.
　前記加水分解性基と結合したシリル基は、樹脂（Ａ）成分の主鎖の末端に結合していてもよく、側鎖に結合していてもよく、主鎖の末端および側鎖に結合していてもよい。加水分解性基と結合したシリル基の導入方法としては、加水分解性基と結合したシリル基を含有する単量体をその他単量体と共重合する方法、シリケート化合物を反応させる方法、または水酸基含有共重合体にシリケート化合物を反応させる方法等がある。なかでも簡便な方法は、加水分解性基と結合したシリル基を含有する単量体とその他単量体を共重合する方法である。 The silyl group bonded to the hydrolyzable group may be bonded to the end of the main chain of the resin (A) component, may be bonded to the side chain, or bonded to the end of the main chain and the side chain. It may be. As a method for introducing a silyl group bonded to a hydrolyzable group, a method of copolymerizing a monomer containing a silyl group bonded to a hydrolyzable group with another monomer, a method of reacting a silicate compound, or a hydroxyl group There is a method of reacting a silicate compound with the containing copolymer. Among these, a simple method is a method of copolymerizing a monomer containing a silyl group bonded to a hydrolyzable group and another monomer.
　前記加水分解性基と結合したシリル基における加水分解性基とは、ハロゲン基やアルコキシ基等がある。その中で、反応制御の簡便さから下記一般式（１）で表されるアルコキシ基が有用である。 The hydrolyzable group in the silyl group bonded to the hydrolyzable group includes a halogen group and an alkoxy group. Among them, an alkoxy group represented by the following general formula (1) is useful because of easy reaction control.
　　Ｒ２ ａ
　　｜
　－Ｓｉ－（ＯＲ１）３－ａ　（１）
一般式（１）中のＲ１としては、水素原子または炭素数１～１０のアルキル基、好ましくはたとえばメチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｉ－ブチル基などの炭素数１～４のアルキル基である。前記アルキル基の炭素数が１０を超える場合には、加水分解性シリル基の反応性が低下するようになる。また、一般式（１）中のＲ２としては、水素原子または炭素数１～１０のアルキル基、好ましくは例えば前記Ｒ１において例示された炭素数１～４のアルキル基、フェニル基などのアリール基、ベンジル基などのアラルキル基から選ばれた１価の炭化水素基である。これらの中では、本発明の組成物の硬化性が優れるという点から炭素数１～４のアルキル基が好ましい。 R 2 a
｜
-Si- (OR 1 ) 3-a (1)
R 1 in the general formula (1) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- An alkyl group having 1 to 4 carbon atoms such as a butyl group. When the carbon number of the alkyl group exceeds 10, the reactivity of the hydrolyzable silyl group is lowered. R 2 in the general formula (1) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably an aryl group such as a phenyl group or an alkyl group having 1 to 4 carbon atoms exemplified in the above R 1 . And a monovalent hydrocarbon group selected from an aralkyl group such as a benzyl group. Among these, an alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of excellent curability of the composition of the present invention.
　前記一般式（１）において、（ＯＲ１）３－ａ　は３－ａが１以上３以下になるように、即ちａが０～２になるように選ばれるが、本発明の組成物の硬化性が良好になるという点から、ａが０または１であることが好ましい。従って、Ｒ２の結合数は０または１であることが好ましい。ＯＲ１またはＲ２の数が複数個の場合は、それらは同一であっても異なっていてもよい。前記一般式（１）で表される炭素原子に結合した反応性シリル基の具体例としては、例えば後述の樹脂（Ａ）成分に共重合される加水分解性シリル基含有ビニル系単量体に含有される基が挙げられる。 In the general formula (1), (OR 1 ) 3-a is selected so that 3-a is 1 or more and 3 or less, that is, a is 0 to 2, but the composition of the present invention is cured. A is preferably 0 or 1 from the viewpoint of improving the properties. Therefore, the number of bonds of R 2 is preferably 0 or 1. When the number of OR 1 or R 2 is plural, they may be the same or different. Specific examples of the reactive silyl group bonded to the carbon atom represented by the general formula (1) include, for example, a hydrolyzable silyl group-containing vinyl monomer copolymerized with a resin (A) component described later. The group to be contained is mentioned.
　次に、樹脂（Ａ）成分の製法の一例について説明する。 Next, an example of a method for producing the resin (A) component will be described.
　樹脂（Ａ）成分は例えば、加水分解性シリル基含有ビニル系単量体（ａ）成分とその他の共重合可能な単量体（ｂ）成分をアゾビスイソブチロニトリルなどのラジカル重合開始剤を用いて溶液重合法などにより共重合することによって製造することができる。 Resin (A) component is, for example, a hydrolyzable silyl group-containing vinyl monomer (a) component and other copolymerizable monomer (b) component as a radical polymerization initiator such as azobisisobutyronitrile. Can be produced by copolymerization using a solution polymerization method or the like.
　加水分解性シリル基含有ビニル系単量体（ａ）成分の具体例としては、ビニルトリメトキシシラン、ビニルメチルジメトキシシラン、ビニルトリエトキシシラン、ビニルメチルジエトキシシラン、ビニルトリス（２－メトキシエトキシ）シラン、ビニルトリイソプロポキシシラン、γ－（メタ）アクリロキシプロピルトリメトキシシラン、γ－（メタ）アクリロキシプロピルメチルジメトキシシラン、γ－（メタ）アクリロキシプロピルトリエトキシシラン、γ－（メタ）アクリロキシプロピルメチルジエトキシシラン、γ－（メタ）アクリロキシプロピルトリ－ｎ－プロポキシシラン、γ－（メタ）アクリロキシプロピルトリイソプロポキシシラン、ビニルトリアセトキシシラン、β－（メタ）アクリロキシエチルトリメトキシシラン等が挙げられる。これらの加水分解性シリル基含有ビニル系単量体（ａ）成分は、単独で用いてもよいし、また２種以上を併用しても良い。 Specific examples of the hydrolyzable silyl group-containing vinyl monomer (a) component include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, and vinyltris (2-methoxyethoxy) silane. , Vinyltriisopropoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxy Propylmethyldiethoxysilane, γ- (meth) acryloxypropyltri-n-propoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, vinyltriacetoxysilane, β- (meth) acryloxyethyltrimethoxysilane Etc. It is. These hydrolyzable silyl group-containing vinyl monomers (a) may be used alone or in combination of two or more.
　取扱いの容易さ、価格および重合安定性、得られる組成物の硬化性が優れるという点から、γ－（メタ）アクリロキシプロピルトリメトキシシラン、γ－（メタ）アクリロキシプロピルメチルジメトキシシラン、γ－（メタ）アクリロキシプロピルトリエトキシシラン、γ－（メタ）アクリロキシプロピルメチルジエトキシシラン等が特に好ましい。 Γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- from the viewpoint of easy handling, cost and polymerization stability, and excellent curability of the resulting composition (Meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, and the like are particularly preferable.
　加水分解性シリル基含有単量体（ａ）成分は、全単量体１００重量部中に０．１～５０重量部用いて共重合されることが望ましい。０．１重量部未満では、充分な低汚染性が発現しなかったり、耐候性が向上しない場合がある。一方、５０重量部を越えると貯蔵安定性が悪化する傾向にある。 The hydrolyzable silyl group-containing monomer (a) component is preferably copolymerized using 0.1 to 50 parts by weight in 100 parts by weight of all monomers. If the amount is less than 0.1 parts by weight, sufficient low contamination may not be exhibited, and weather resistance may not be improved. On the other hand, when it exceeds 50 parts by weight, the storage stability tends to deteriorate.
　その他共重合可能な単量体（ｂ）成分の具体例としては、（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｉ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート、ベンジル（メタ）アクリレート、３，３，５－トリメチルシクロヘキシル（メタ）アクリレート、グリシジル（メタ）アクリレート、イソボルニル（メタ）アクリレート、（メタ）アクリルアミド、α－エチル（メタ）アクリルアミド、Ｎ－ブトキシメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ－メチル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド等のアクリルアミド、（メタ）アクリロイルモルホリン、２－ヒドロキシエチル（メタ）アクリレート、２ーヒドロキシプロピル（メタ）アクリレート、（メタ）アクリル酸のヒドロキシアルキルエステル類とリン酸またはリン酸エステル類との縮合生成物などのリン酸エステル基含有（メタ）アクリル系化合物、ウレタン結合やシロキサン結合を含む（メタ）アクリレートなどの（メタ）アクリル酸エステル系化合物；スチレン、αーメチルスチレン、クロロスチレン、スチレンスルホン酸、４ーヒドロキシスチレン、ビニルトルエンなどの芳香族炭化水素系ビニル化合物；マレイン酸、フマル酸、イタコン酸、（メタ）アクリル酸などの不飽和カルボン酸、これらのアルカリ金属塩、アンモニウム塩、アミン塩などの塩；無水マレイン酸などの不飽和カルボン酸の酸無水物、これら酸無水物と炭素数１～２０の直鎖状または分岐鎖を有するアルコールまたはアミンとのジエステルまたはハーフエステルなどの不飽和カルボン酸のエステル；酢酸ビニル、プロピオン酸ビニル、ジアリルフタレートなどのビニルエステルやアリル化合物；ビニルピリジン、アミノエチルビニルエーテルなどのアミノ基含有ビニル系化合物；イタコン酸ジアミド、クロトン酸アミド、マレイン酸ジアミド、フマル酸ジアミド、Ｎ－ビニルピロリドンなどのアミド基含有ビニル系化合物；（メタ）アクリロニトリル、２ーヒドロキシエチルビニルエーテル、メチルビニルエーテル、シクロヘキシルビニルエーテル、塩化ビニル、塩化ビニリデン、クロロプレン、プロピレン、ブタジエン、イソプレン、フルオロオレフィンマレイミド、Ｎ－ビニルイミダゾール、ビニルスルホン酸などのその他ビニル系化合物などが挙げられる。 Specific examples of the copolymerizable monomer (b) component include (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, glycidyl ( (Meth) acrylate, isobornyl (meth) acrylate, (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methyl (meth) acrylamide, Acrylamide such as methylol (meth) acrylamide, (meth) acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyalkyl esters of (meth) acrylic acid and phosphoric acid or phosphoric acid Phosphoric ester group-containing (meth) acrylic compounds such as condensation products with esters, (meth) acrylic ester compounds such as (meth) acrylates containing urethane bonds and siloxane bonds; styrene, α-methylstyrene, chlorostyrene , Aromatic hydrocarbon vinyl compounds such as styrenesulfonic acid, 4-hydroxystyrene and vinyltoluene; unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, (meth) acrylic acid, alkali metal salts thereof, ammonium salt Salts such as amine salts; acid anhydrides of unsaturated carboxylic acids such as maleic anhydride, diesters or half esters of these anhydrides with linear or branched alcohols or amines having 1 to 20 carbon atoms, etc. Unsaturated carboxylic acid esters; vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate, and diallyl phthalate; amino group-containing vinyl compounds such as vinyl pyridine and aminoethyl vinyl ether; itaconic acid diamide, crotonic acid amide, maleic acid diamide Amide group-containing vinyl compounds such as fumaric acid diamide and N-vinylpyrrolidone; (meth) acrylonitrile, 2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, Pyrene, butadiene, isoprene, fluoroolefin maleimide, N- vinylimidazole, like other vinyl compounds such as vinyl sulfonic acid.
　これらのその他単量体（ｂ）成分は、単独で用いてもよいし、また２種以上を併用しても良い。 These other monomer (b) components may be used alone or in combination of two or more.
　さらには、水酸基含有ビニル系単量体および／またはその誘導体（ｃ）成分を共重合することも可能である。水酸基含有ビニル系単量体および／またはその誘導体（ｃ）成分を共重合した場合には、アクリルウレタン樹脂塗料などでは、得られる塗膜の外観性が向上する場合がある。 Furthermore, it is also possible to copolymerize a hydroxyl group-containing vinyl monomer and / or its derivative (c) component. When the hydroxyl group-containing vinyl monomer and / or its derivative (c) component is copolymerized, the appearance of the resulting coating film may be improved in acrylic urethane resin paints.
　水酸基含有ビニル系単量体および／またはその誘導体（ｃ）成分の具体例としては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、グリセロールモノ（メタ）アクリレート、２－ヒドロキシエチルビニルエーテル、Ｎ－メチロール（メタ）アクリルアミド、４－ヒドロキシスチレンビニルトルエン、東亞合成化学工業（株）製のアロニクス５７００、４－ヒドロキシスチレン、日本触媒化学工業（株）製のＨＥ－１０、ＨＥ－２０、ＨＰ－１およびＨＰ－２（以上、何れも末端に水酸基を有するアクリル酸エステルオリゴマー）、日本油脂（株）製のブレンマーＰＰシリーズ、ブレンマーＰＥシリーズ、ブレンマーＰＥＰシリーズ等のポリアルキレングリコール（メタ）アクリレート誘導体、水酸基含有化合物とε―カプロラクトンとの反応により得られるε―カプロラクトン変性ヒドロキシアルキルビニル系共重合体化合物ＰｌａｃｃｅｌＦＭ－１、ＦＭ－４（以上ダイセル化学工業（株）製）、ＴＯＮＥＭ－２０１（ＵＣＣ社製）、ＨＥＡＣ－１（ダイセル化学工業（株）製）等のポリカーボネート含有ビニル系化合物などが挙げられる。 Specific examples of the hydroxyl group-containing vinyl monomer and / or derivative (c) component include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, 4-hydroxystyrene vinyl toluene, Allonics 5700, 4- manufactured by Toagosei Chemical Industry Co., Ltd. Hydroxystyrene, manufactured by Nippon Shokubai Chemical Industry Co., Ltd. HE-10, HE-20, HP-1 and HP-2 (all of which are acrylic ester oligomers having a hydroxyl group at the terminal), manufactured by Nippon Oil & Fats Co., Ltd. Blemmer PP series, Blemmer PE series , Blemmer PEP series polyalkylene glycol (meth) acrylate derivatives, ε-caprolactone modified hydroxyalkylvinyl copolymer compounds PlaccelFM-1, FM-4 (and above) obtained by reaction of a hydroxyl group-containing compound with ε-caprolactone Examples thereof include polycarbonate-containing vinyl compounds such as Daicel Chemical Industries, Ltd., TONEM-201 (UCC), and HEAC-1 (Daicel Chemical Industries).
　これらの水酸基含有ビニル系単量体および／またはその誘導体（ｃ）成分は、単独で用いてもよいし、また２種以上を併用しても良い。 These hydroxyl group-containing vinyl monomers and / or derivatives (c) thereof may be used alone or in combination of two or more.
　このようにして得られた樹脂（Ａ）成分は、本発明の組成物を用いて形成される塗膜の低汚染性や耐久性などの物性が優れるという点から、数平均分子量が、３０００～２５０００なかんずく５０００～２００００であることが好ましい。この際、必要に応じて、例えば、ｎ－ドデシルメルカプタンやγ―メルカプトプロピルトリメトキシシラン、γ―メルカプトプロピルトリエトキシシラン等の連鎖移動剤を使って、分子量を調整してもよい。 The resin (A) component thus obtained has a number average molecular weight of 3000 to 3,000 because the coating film formed using the composition of the present invention is excellent in physical properties such as low contamination and durability. It is preferably 5000 to 20000, especially 25000. At this time, if necessary, the molecular weight may be adjusted using a chain transfer agent such as n-dodecyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane or the like.
　尚、前記樹脂（Ａ）成分の主鎖が実質的にアクリル共重合体鎖からなるとは、樹脂（Ａ）成分の主鎖を構成する単位のうちの５０％以上、さらに好ましくは７０％以上が（メタ）アクリル系単量体単位（メタ）アクリル系単量体単位から形成されていることを意味する。なお本発明において（メタ）アクリル系とはアクリル系およびメタクリル系の総称である。 The main chain of the resin (A) component substantially consists of an acrylic copolymer chain means that 50% or more, more preferably 70% or more of the units constituting the main chain of the resin (A) component. It means that it is formed from a (meth) acrylic monomer unit. In the present invention, (meth) acrylic is a general term for acrylic and methacrylic.
　（シリコン化合物）
　本発明においては、前述の樹脂（Ａ）成分とともに、組成物から形成される塗膜の耐汚染性を向上させる目的で一般式（２）：
（Ｒ３Ｏ）４－ｂ－Ｓｉ－Ｒ４ ｂ （２）
（式中、Ｒ３は炭素数１～１０のアルキル基、炭素数６～１０のアリール基および炭素数７～１０のアラルキル基から選ばれた１価の炭化水素基、Ｒ４は炭素数１～１０のアルキル基、炭素数が６～１０のアリール基および炭素数が７～１０のアラルキル基から選ばれた１価の炭化水素基、ｂは０または１を示す）で表されるシリコン化合物及び／またはその部分加水分解縮合物（Ｂ）成分（以下、オルガノシリケート化合物（Ｂ）成分という）５０～１０００重量部を使用することができる。 (Silicon compound)
In the present invention, together with the resin (A) component, the general formula (2) is used for the purpose of improving the stain resistance of the coating film formed from the composition:
(R 3 O) 4-b —Si—R 4 b (2)
(Wherein R 3 is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, and R 4 is a carbon atom having 1 carbon atom) A monovalent hydrocarbon group selected from an alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, and b represents 0 or 1) And / or 50 to 1000 parts by weight of the partially hydrolyzed condensate (B) component (hereinafter referred to as the organosilicate compound (B) component).
　オルガノシリケート化合物（Ｂ）成分の具体例としては、テトラメトキシシラン、テトラエトキシシラン、テトラ－ｎ－プロポキシシラン、テトラ－ｉ－プロポキシシラン、テトラ－ｎ－ブトキシシラン、テトラ－ｉ－ブトキシシラン、テトラ－ｔ－ブトキシシラン及びそれらの部分加水分解・縮合物が例示できる。中でも得られる塗膜の耐汚染性が優れるという点から、メチルシリケート５１、エチルシリケート４５、エチルシリケート４０、エチルシリケート４８（以上、コルコート（株）製）、シリケート４５、シリケート４０（以上、多摩化学工業（株）製）が望ましい。上記化合物は１種単独でもよく、２種以上を併用しても良い。 Specific examples of the organosilicate compound (B) component include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra Examples thereof include t-butoxysilane and partial hydrolysis / condensates thereof. Among them, methyl silicate 51, ethyl silicate 45, ethyl silicate 40, ethyl silicate 48 (above, manufactured by Colcoat Co., Ltd.), silicate 45, silicate 40 (above, Tama Chemical Co., Ltd.) from the viewpoint that the obtained coating film has excellent contamination resistance. Industrial Co., Ltd.) is desirable. The said compound may be single 1 type, and may use 2 or more types together.
　また、同一分子中に異なったアルコキシシリル基を含有するオルガノシリケートも使用可能である。例えば、メチルエチルシリケート、メチルプロピルシリケート、メチルブチルシリケート、エチルプロピルシリケート、プロピルブチルシリケートなどである。これら置換基の比率が０～１００％の間で任意に変更可能である。また、これらのシリケートの部分加水分解・縮合物も使用可能であると記述したが、縮合度は１～２０程度が好ましい。更に好ましい縮合度の範囲は、３～１５である。 Also, organosilicates containing different alkoxysilyl groups in the same molecule can be used. For example, methyl ethyl silicate, methyl propyl silicate, methyl butyl silicate, ethyl propyl silicate, propyl butyl silicate and the like. The ratio of these substituents can be arbitrarily changed between 0 and 100%. In addition, although it has been described that a partially hydrolyzed / condensed product of these silicates can be used, the degree of condensation is preferably about 1 to 20. A more preferred range of the degree of condensation is 3-15.
　前記（Ｂ）成分の使用量は、（Ａ）成分１００重量部に対して５０～１０００重量部、好ましくは、７５～５００重量部、より好ましくは１００～４００重量部である。オルガノシリケート化合物（Ｂ）成分の量が１０００部を超えると、該塗料組成物からなる塗膜が濁ったり、充分な光沢が得られないなど外観性が低下するので好ましくない。 The amount of the component (B) used is 50 to 1000 parts by weight, preferably 75 to 500 parts by weight, more preferably 100 to 400 parts by weight with respect to 100 parts by weight of the component (A). If the amount of the organosilicate compound (B) component exceeds 1000 parts, the coating film made of the coating composition becomes cloudy or the appearance is deteriorated such that sufficient gloss is not obtained, which is not preferable.
　（有機金属化合物）
　本発明において、得られる一液型塗料用硬化性組成物の塗装初期からの耐汚染性をさらに向上させる目的で、有機金属化合物（Ｃ）成分を（Ａ）、（Ｂ）、（Ｄ）成分の総量に対して金属換算で１重量部以下を使用する。 (Organic metal compound)
In the present invention, for the purpose of further improving the stain resistance from the initial coating of the resulting curable composition for a one-component coating material, the organometallic compound (C) component is changed to (A), (B), (D) component. 1 part by weight or less is used in terms of metal with respect to the total amount.
　有機金属化合物（Ｃ）成分にはとくに限定はないが、塗装初期からの耐汚染性の向上に優れるという点および安定性に優れるという点からＳn、Ｔｉ、Ｆe、Ａｌ、Ｍｎ、Ｃｏ、Ｚｒ、Ｎｉ、Ｂｉ、Ｃｕ、Ｚｎ、Ｂａから選ばれる金属を用いることが好ましい。 The organometallic compound (C) component is not particularly limited, but Sn, Ti, Fe, Al, Mn, Co, Zr, and the like are excellent in terms of improving the stain resistance from the initial stage of coating and in terms of stability. It is preferable to use a metal selected from Ni, Bi, Cu, Zn, and Ba.
　有機錫化合物の具体例としては、ジオクチル錫ビス（２－エチルヘキシルマレ－ト）、ジオクチル錫オキサイドまたはジブチル錫オキサイドとシリケ－トとの縮合物、ジブチル錫ジオクトエ－ト、ジブチル錫ジラウレ－ト、ジブチル錫ジステアレ－ト、ジブチル錫ジアセチルアセトナ－ト、ジブチル錫ビス（エチルマレ－ト）、ジブチル錫ビス（ブチルマレ－ト）、ジブチル錫ビス（２－エチルヘキシルマレ－ト）、ジブチル錫ビス（オレイルマレ－ト）、スタナスオクトエ－ト、ステアリン酸錫、ジ－ｎ－ブチル錫ラウレ－トオキサイドがある。また、分子内にＳ原子有する錫化合物として、ジブチル錫ビスイソノニル－３－メルカプトプロピオネ－ト、ジオクチル錫ビスイソノニル－３－メルカプトプロピオネ－ト、オクチルブチル錫ビスイソノニル－３－メルカプトプロピオネ－ト、ジブチル錫ビスイソオクチルチオグルコレ－ト、ジオクチル錫ビスイソオクチルチオグルコレ－ト、オクチルブチル錫ビスイソオクチルチオグルコレ－トなどが挙げられる。さらに、ジオクチル酸錫やジステアリン酸錫などの2価錫なども挙げられる。 Specific examples of the organic tin compound include dioctyltin bis (2-ethylhexyl maleate), dioctyltin oxide or a condensate of dibutyltin oxide and silicate, dibutyltin dioctate, dibutyltin dilaurate, dibutyl Tin distearate, dibutyltin diacetylacetonate, dibutyltin bis (ethylmaleate), dibutyltin bis (butylmaleate), dibutyltin bis (2-ethylhexylmaleate), dibutyltin bis (oleylmaleate) ), Stannous octoate, tin stearate, di-n-butyltin laurate oxide. Further, as tin compounds having S atoms in the molecule, dibutyltin bisisononyl-3-mercaptopropionate, dioctyltin bisisononyl-3-mercaptopropionate, octylbutyltin bisisononyl-3-mercaptopropionate, dibutyl Examples thereof include tin bisisooctyl thiogluconate, dioctyl tin bisisooctyl thiogluconate, and octylbutyl tin bisisooctyl thiogluconate. In addition, divalent tin such as tin dioctylate and tin distearate may be mentioned.
　有機チタン化合物の具体例としては、チタンイソプロポキシド、チタンブトキシドなどのチタンアルコキシドやチタンアセチルアセトネート、チタン－２－エチルヘキサネート、チタンジイソプロポキシビス（アセチルアセトネート）などのチタンキレートが挙げられる。 Specific examples of organic titanium compounds include titanium alkoxides such as titanium isopropoxide and titanium butoxide, and titanium chelates such as titanium acetylacetonate, titanium-2-ethylhexanate, and titanium diisopropoxybis (acetylacetonate). It is done.
　有機鉄化合物の具体例としては、鉄（II）または（III）のアセテート、アセチルアセトネート、２－エチルヘキサネートなどが挙げられる。 Specific examples of the organic iron compound include iron (II) or (III) acetate, acetylacetonate, 2-ethylhexanate, and the like.
　有機アルミニウム化合物の具体例としては、アルミニウムイソプロポキシド、アルミニウムブトキシドなどのアルミニウムアルコキシドやエチルアセトアセトネートアルミニウムジイソプロポキシド、アルミニウムトリス（アセチルアセトネート）、アルミニウムトリス（エチルアセトアセテート）、アルミニウムモノアセチルアセトネ－トビス（エチルアセトアセテート）、アルキルアセチルアセトネ－トなどのアルミニウムキレートが挙げられる。 Specific examples of organoaluminum compounds include aluminum alkoxides such as aluminum isopropoxide and aluminum butoxide, ethyl acetoacetonate aluminum diisopropoxide, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), and aluminum monoacetyl. Examples thereof include aluminum chelates such as acetonatobis (ethyl acetoacetate) and alkylacetylacetonate.
　有機マンガン化合物の具体例としては、マンガン（II）アセテート、マンガン（II）アセチルアセテート、マンガン（II）－２－エチルヘキサネートなどが挙げられる。 Specific examples of the organic manganese compound include manganese (II) acetate, manganese (II) acetyl acetate, manganese (II) -2-ethylhexanate, and the like.
　有機コバルト化合物の具体例としては、コバルト（II）アセテート、コバルト（II）アセチルアセテート、コバルト（II）ベンゾイルアセトナート、コバルト（II）－２－エチルヘキサネート、コバルトナフタネートなどが挙げられる。 Specific examples of the organic cobalt compound include cobalt (II) acetate, cobalt (II) acetyl acetate, cobalt (II) benzoylacetonate, cobalt (II) -2-ethylhexanate, and cobalt naphthanate.
　有機ジルコニウム化合物の具体例としては、ジルコニウム（IV）プロポキシド、ジルコニウム（IV）アセテート、ジルコニウム（IV）アセチルアセテート、ジルコニウム（IV）－２－エチルヘキサネートなどが挙げられる。 Specific examples of the organic zirconium compound include zirconium (IV) propoxide, zirconium (IV) acetate, zirconium (IV) acetyl acetate, zirconium (IV) -2-ethylhexanate and the like.
　有機ニッケル化合物の具体例としては、ニッケル（II）プロポキシド、ニッケル（II）ステアレート、ニッケル（II）アセテート、ニッケル（II）アセチルアセテート、ニッケル（II）－２－エチルヘキサネートなどが挙げられる。 Specific examples of the organic nickel compound include nickel (II) propoxide, nickel (II) stearate, nickel (II) acetate, nickel (II) acetyl acetate, nickel (II) -2-ethylhexanate and the like. .
　有機ビスマス化合物の具体例としては、ビスマス（III）ネオデカネート、ビスマス（III）アセテート、ビスマス（II）－２－エチルヘキサネートなどが挙げられる。 Specific examples of the organic bismuth compound include bismuth (III) neodecanate, bismuth (III) acetate, bismuth (II) -2-ethylhexanate, and the like.
　有機銅化合物の具体例としては、銅（II）アセチルアセテート、銅（II）ブチルフタレートなどが挙げられる。 Specific examples of the organic copper compound include copper (II) acetyl acetate and copper (II) butyl phthalate.
　有機亜鉛化合物の具体例としては、亜鉛（II）アセテート、亜鉛（II）アセチルアセテート、亜鉛（II）－２－エチルヘキサネートなどが挙げられる。 Specific examples of the organic zinc compound include zinc (II) acetate, zinc (II) acetyl acetate, zinc (II) -2-ethylhexanate and the like.
　有機バリウム化合物の具体例としては、バリウム（II）アセテート、バリウム（II）アセチルアセテート、バリウム（II）－２－エチルヘキサネートなどが挙げられる。
　中でも、着色がないことや低汚染性に優れることから、分子内にＳ原子を有する錫化合物や２価錫化合物が好ましい。 Specific examples of the organic barium compound include barium (II) acetate, barium (II) acetyl acetate, barium (II) -2-ethylhexanate and the like.
Of these, tin compounds and divalent tin compounds having an S atom in the molecule are preferred because they are not colored and are excellent in low contamination.
　前記（Ｃ）成分の使用量は、（Ａ）、（Ｂ）、（Ｄ）成分の総量に対して金属換算で１重量部以下、好ましくは０．５重量部以下、より好ましくは０．３重量部以下である。使用量の下限としては、０．０１重量部以上が好ましい。（Ｃ）成分の量が１重量部を超えると、貯蔵安定性が悪化したり、着色が著しくなる場合があるので好ましくない。 The amount of component (C) used is 1 part by weight or less, preferably 0.5 parts by weight or less, more preferably 0.3 parts by weight or less in terms of metal based on the total amount of components (A), (B), and (D). Less than parts by weight. As a minimum of the usage-amount, 0.01 weight part or more is preferable. When the amount of the component (C) exceeds 1 part by weight, the storage stability may be deteriorated or coloring may be remarkable, which is not preferable.
　（有機樹脂）
　本発明で使用する有機樹脂（Ｄ）としては、塗料用の溶剤型有機樹脂であれば、組成物の安定性や外観性が得られるのでとくに限定はないが、使い勝手の良さから一液型塗料用樹脂が好ましい。 (Organic resin)
The organic resin (D) used in the present invention is not particularly limited as long as it is a solvent-type organic resin for paints, so that the stability and appearance of the composition can be obtained. Resins for use are preferred.
　一液型塗料用樹脂に前記（Ａ）、（Ｂ）、（Ｃ）成分を混合した後、脱水剤や顔料など各種添加剤を配合して塗料を製造することも勿論可能であるが、すでに塗料化された白エナメル塗料などに、前記（Ａ）、（Ｂ）、（Ｃ）成分を配合することも可能である。貯蔵安定性を向上させることや、より簡便に製造する点を考慮した場合には、すでに塗料化された白エナメル塗料などに、（Ａ）、（Ｂ）、（Ｃ）成分を配合する方がより好ましい。 Of course, it is possible to produce a paint by mixing the additives (A), (B) and (C) with a one-component paint resin and then adding various additives such as dehydrating agents and pigments. It is also possible to blend the components (A), (B), and (C) into a white enamel paint that has been made into a paint. When considering the point of improving storage stability and easier production, it is better to add the components (A), (B), and (C) to the white enamel paint already made into a paint. More preferred.
　その際の一液型塗料用樹脂としては、油変性一液型塗料や塩化ビニル系やアクリル系のラッカー塗料、湿気硬化型一液塗料、熱硬化性一液塗料などが挙げられる。なかでも、樹脂中に不飽和基を導入し、塗装後に酸化硬化させる酸化硬化型一液塗料や湿気硬化型一液塗料、熱硬化性一液塗料が耐候性に優れる点から好ましい。 Examples of the resin for one-component paint at that time include oil-modified one-component paints, vinyl chloride and acrylic lacquer paints, moisture-curing one-component paints, and thermosetting one-component paints. Of these, an oxidation-curing one-component paint, a moisture-curing one-component paint, and a thermosetting one-component paint that introduce an unsaturated group into the resin and are oxidatively cured after coating are preferred from the viewpoint of excellent weather resistance.
　このような一液型塗料は、数多く上市されているため、これらを使用して本発明の塗料用組成物を配合することも可能である。市販されている上記一液型塗料の具体例としては、一液ファインウレタン、ファインシリコンセラ（ともに日本ペイント（株）製）やアレスエコレタン、アレスエコシリコン（ともに関西ペイント（株）製）や一液マイルドウレタン、一液マイルドシリコン（ともにエスケー化研（株）製）などが挙げられる。 Since there are many such one-component paints on the market, it is possible to mix the paint composition of the present invention using them. Specific examples of the one-component paints that are commercially available include one-component fine urethane, fine silicon sera (both made by Nippon Paint Co., Ltd.), Ares Ecoletan, Ares Eco Silicon (both made by Kansai Paint Co., Ltd.), One-part mild urethane, one-part mild silicon (both manufactured by SK Kaken) are listed.
　前記（Ｄ）成分の使用量は、（Ａ）成分１００重量部に対して１５０～１００００重量部、より好ましくは３００～７０００重量部、さらにより好ましくは５００～５０００重量部である。１５０重量部未満であると貯蔵安定性が不充分となる場合があるため好ましくなく、１００００重量部以上であると目的とする低汚染性が発現し難くなったり、耐侯性の向上が得られなくなるため好ましくない。 The amount of the component (D) used is 150 to 10000 parts by weight, more preferably 300 to 7000 parts by weight, and even more preferably 500 to 5000 parts by weight with respect to 100 parts by weight of the component (A). If it is less than 150 parts by weight, the storage stability may be insufficient, which is not preferable. If it is 10000 parts by weight or more, the intended low-staining property is hardly exhibited, and improvement in weather resistance cannot be obtained. Therefore, it is not preferable.
　（脱水剤）
　本発明の一液型塗料用樹脂組成物では、（Ａ）成分中の加水分解性シリル基含有ビニル系単量体（ａ）成分や、シリコン化合物（Ｂ）成分が、湿分との反応性を有するため、さらに脱水剤（Ｅ）成分を配合することによって、組成物の保存安定性を向上させることができる。 (Dehydrating agent)
In the one-component paint resin composition of the present invention, the hydrolyzable silyl group-containing vinyl monomer (a) component and the silicon compound (B) component in the component (A) are reactive with moisture. Therefore, the storage stability of the composition can be improved by further adding a dehydrating agent (E) component.
　脱水剤としては、例えば、オルソ蟻酸メチル、オルソ蟻酸エチルもしくはオルソ蟻酸ブチル等のオルソ蟻酸アルキル；オルソ酢酸メチル、オルソ酢酸エチルもしくはオルソ酢酸ブチル等のオルソ酢酸アルキル；またはオルソほう酸メチル、オルソほう酸エチル、オルソほう酸ブチル等のオルソほう酸アルキル等のオルソカルボン酸エステルや、テトラメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン等の高活性シラン化合物などが挙げられる。 Examples of the dehydrating agent include alkyl orthoformate such as methyl orthoformate, ethyl orthoformate or butyl orthoformate; alkyl orthoacetate such as methyl orthoacetate, ethyl orthoacetate or butyl orthoacetate; or methyl orthoborate, ethyl orthoborate, Examples thereof include orthocarboxylic acid esters such as alkyl orthoborate such as butyl orthoborate, and highly active silane compounds such as tetramethoxysilane, tetraethoxysilane, and methyltrimethoxysilane.
　前記（Ｅ）成分の使用量は、（Ｄ）成分１００重量部に対して０．１から１０重量部、好ましくは０．３から８重量部、より好ましくは０．５から５重量部である。 The amount of component (E) used is 0.1 to 10 parts by weight, preferably 0.3 to 8 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of component (D). .
　（Ｅ）成分の量が０．１重量部より少ないと（Ｄ）成分中の水分を除去しきれず、安定性を損なう可能性がある。また１０重量部より多い場合には、系全体の粘度が低下し、塗装時の希釈溶剤を捻出できない可能性がある。 If the amount of the (E) component is less than 0.1 parts by weight, the moisture in the (D) component cannot be removed, and the stability may be impaired. On the other hand, when the amount is more than 10 parts by weight, the viscosity of the entire system is lowered, and there is a possibility that the diluting solvent at the time of coating cannot be brewed.
　（配合方法）
　前記（Ａ）成分、（Ｂ）成分、（Ｃ）成分の使用量は重量の合計で、（Ｄ）成分の重量の０．０１～１．０倍、好ましくは０．０２～０．７倍、より好ましくは０．０３～０．５倍であることが好ましい。０．０１倍未満では、目的とする耐汚染性や耐候性が得られない場合があり、１．０倍をこえると、乾燥性や硬化性、耐水性が不充分になる場合がある。 (Formulation method)
The amount of component (A), component (B), and component (C) used is the total weight, and is 0.01 to 1.0 times, preferably 0.02 to 0.7 times the weight of component (D). More preferably, it is 0.03 to 0.5 times. If it is less than 0.01 times, the intended stain resistance and weather resistance may not be obtained, and if it exceeds 1.0 times, the drying property, curability and water resistance may be insufficient.
　（Ａ）～（Ｄ）成分の混合順序はとくに制限されず任意の順序で混合すればよい。（Ｄ）成分に対する（Ａ）～（Ｃ）成分の添加量が少量でも相溶性の差などから効果が発現すると言う点からは、前記（Ａ）成分と（Ｂ）成分が予め混合された後に、（Ｄ）成分へ配合することが好ましい。また、その場合の（Ｃ）成分の配合順序としては、とくに制限はないが、貯蔵安定性をより良くするためには、（Ｄ）成分に添加するか若しくは、（Ａ）成分、（Ｂ）成分、（Ｄ）成分が混合された後に配合することが好ましい。 The mixing order of the components (A) to (D) is not particularly limited and may be mixed in an arbitrary order. From the point that the effect is manifested due to a difference in compatibility even if the addition amount of the components (A) to (C) is small, the component (A) and the component (B) are mixed in advance. (D) It is preferable to mix | blend with a component. In this case, the blending order of the component (C) is not particularly limited, but in order to improve the storage stability, it is added to the component (D), or the component (A), (B) It is preferable to mix | blend after a component and (D) component are mixed.
　また、（Ａ）成分と（Ｂ）成分は、常温下混合攪拌するだけでもよいが、１００℃以下程度の温度で攪拌してもよい。（Ａ）成分のアルコキシシリル基の一部と（Ｂ）成分のアルコキシシリル基の一部で縮合反応が進行し、複合化することで耐候性が向上する場合がある。１００℃以上で実施した場合には、反応の制御が難しく、安定性を損ねるので好ましくない。 The components (A) and (B) may be mixed and stirred at room temperature, but may be stirred at a temperature of about 100 ° C. or lower. In some cases, a condensation reaction proceeds with a part of the alkoxysilyl group of the component (A) and a part of the alkoxysilyl group of the component (B), and the weather resistance may be improved by combining them. When it is carried out at 100 ° C. or higher, it is difficult to control the reaction, and the stability is impaired.
　本発明の硬化性樹脂組成物には、通常塗料に用いられる例えば、希釈剤、紫外線吸収剤、光安定剤、タレ防止剤、レベリング剤や分散剤、色別れ防止剤などの添加剤；アミノシラン以外のシランカップリング剤；ニトロセルロース、セルロースアセテートブチレートなどの繊維素；エポキシ樹脂、メラミン樹脂、塩化ビニル樹脂、フッ素樹脂、塩素化ポリプロピレン、塩化ゴム、ポリビニルブチラール、ポリシロキサンなどの樹脂などを適宜加えてもよい。 In the curable resin composition of the present invention, for example, diluents, ultraviolet absorbers, light stabilizers, anti-sagging agents, leveling agents and dispersants, color-separation preventing agents and the like that are usually used in paints; other than aminosilanes Silane coupling agent; Fibrin such as nitrocellulose and cellulose acetate butyrate; Add appropriate resin such as epoxy resin, melamine resin, vinyl chloride resin, fluororesin, chlorinated polypropylene, chlorinated rubber, polyvinyl butyral, polysiloxane May be.
　本発明の顔料分散用硬化性樹脂組成物は、たとえば浸漬、吹き付け、刷毛、スプレ－などを用いた塗布などの通常の方法によって被塗物に塗布され、通常、常温でそのまま、または３０℃以上で焼き付けて硬化せしめる。 The pigment-dispersing curable resin composition of the present invention is applied to an article to be coated by a usual method such as dipping, spraying, brushing, spraying, or the like, and is usually at room temperature or at 30 ° C. or higher. Bake in to cure.
　次に、本発明の一液型塗料用樹脂組成物を実施例に基づいてさらに詳細に説明するが、本発明はかかる実施例のみに限定されるものではない。 Next, the one-component paint resin composition of the present invention will be described in more detail based on examples, but the present invention is not limited to such examples.
　（重合体（Ａ）成分の製造方法：製造例Ａ－１～３）
攪拌機、温度計、還流冷却器、窒素ガス導入管および滴下ロ－トを備えた反応器に表１の（イ）成分を仕込み、窒素ガスを導入しつつ１１０℃に昇温した後、表１の（ア）成分の混合物を滴下ロ－トから５時間かけて等速滴下した。次に、（ウ）成分の混合溶液を１時間かけて等速滴下した。その後、引き続き、１１０℃で２時間攪拌した後に、室温まで冷却した。最後に表１の（エ）成分を加えて攪拌し、重合体（Ａ）を合成した。 (Production Method of Polymer (A) Component: Production Examples A-1 to A-3)
A reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction pipe and a dropping funnel was charged with the component (a) in Table 1, and the temperature was raised to 110 ° C. while introducing nitrogen gas. The mixture of component (a) was added dropwise at a constant rate over 5 hours from the dropping funnel. Next, the mixed solution of the component (c) was dropped at a constant rate over 1 hour. Then, after stirring at 110 degreeC for 2 hours continuously, it cooled to room temperature. Finally, component (D) in Table 1 was added and stirred to synthesize polymer (A).
　得られた重合体（Ａ－１～３）の固形分濃度、ＧＰＣで測定した数平均分子量を表１に示した。 Table 1 shows the solid content concentration of the obtained polymers (A-1 to 3) and the number average molecular weight measured by GPC.
　さらに、重合溶剤を用いて固形分濃度を５０％へ調整した。 Furthermore, the solid content concentration was adjusted to 50% using a polymerization solvent.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（表中、（ア）～（エ）成分の量は重量部）
ソルベッソ１００：有機溶剤（エクソン・モービル(株)製）
ペガソールＡＮ４５：有機溶剤（エクソン・モービル(株)製） (In the table, the amount of components (A) to (D) is by weight)
Solvesso 100: Organic solvent (manufactured by ExxonMobil Corp.)
Pegasol AN45: Organic solvent (Exxon Mobil Corporation)
　（重合体（Ａ）成分およびシリコン化合物（Ｂ）成分からなる組成物の製造方法：製造例ＡＢ－１～７）
　さらに、得られた重合体（Ａ）成分の固形分１００重量部に対して、表２の（Ｂ）成分を加えて各温度で1時間攪拌し、固形分濃度が５０％になるように重合溶剤で希釈して樹脂組成物（ＡＢ－１～７）を得た。 (Production Method of Composition Comprising Polymer (A) Component and Silicon Compound (B) Component: Production Examples AB-1 to 7)
Furthermore, with respect to 100 parts by weight of the solid content of the obtained polymer (A) component, the component (B) in Table 2 is added and stirred at each temperature for 1 hour to polymerize so that the solid content concentration becomes 50%. Dilution with a solvent gave resin compositions (AB-1 to 7).
　得られた樹脂組成物（ＡＢ－１～７）について、構成された（Ａ）成分中の固形分および（Ｂ）成分の構成比を表２中に示した。尚、Ｂ成分中の固形分は７１％とした。 For the obtained resin compositions (AB-1 to 7), the solid content in the component (A) and the component ratio of the component (B) are shown in Table 2. The solid content in the component B was 71%.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
（表中、（Ｂ）成分の量は重量部）
シリケート４５：　エチルシリケート部分加水分解縮合物（多摩化学工業（株）製）
ＥＳｉ４８：エチルシリケート部分加水分解縮合物（コルコート（株）製） (In the table, the amount of component (B) is by weight)
Silicate 45: Ethyl silicate partial hydrolysis condensate (manufactured by Tama Chemical Industry Co., Ltd.)
ESi48: ethyl silicate partial hydrolysis condensate (manufactured by Colcoat Co., Ltd.)
　（一液型塗料組成物の作成方法）
　（Ｄ）成分に対して、（Ｅ）成分を加え混合した後、密閉し５０℃で３時間静置した。次に室温にて（ＡＢ）成分を加え攪拌機を用いて１０００ｒｐｍで３分間混合した。最後に（Ｃ）成分を同様にして加え、１０００ｒｐｍで３分間混合し、一液型塗料を得た。 (Method for making a one-component paint composition)
The component (E) was added to and mixed with the component (D), and then sealed and allowed to stand at 50 ° C. for 3 hours. Next, (AB) component was added at room temperature, and it mixed for 3 minutes at 1000 rpm using the stirrer. Finally, component (C) was added in the same manner and mixed at 1000 rpm for 3 minutes to obtain a one-component paint.
　（物性評価）
　アルミ板に、エスコ（関西ペイント製エポキシ塗料）および一液ファインウレタンを１日置きに順次塗布したものを基材とした。
基材に対して、表３で得られた一液型塗料をエアスプレーにて約４０μｍの厚みに塗布し、試験板を得た。
また、該一液型塗料を密閉下で５０℃にて１ヶ月保存した塗料についても、同様にエアスプレーで塗布し、試験板を作成した。
・水接触角
試験板を屋外雨筋曝露台に供し、１週間毎に汚れを軽く水洗し、水接触角を測定した。尚、耐汚染性の指標となる水接触角の測定には、接触角測定機（協和界面科学（株）製：ＣＡ－Ｓ１５０型）を用いた。接触角が低いほど耐汚染性が優れていると言える。
・目視
以下に示す基準で、試験板の外観を評価した。
目視評価
◎：ほとんど雨筋がみられない。
○：うすい雨筋がみられるが、軽く水洗すれば消える。
○△：雨筋がみられるが、水洗すればうすく雨筋が残る程度に回復する。
△：雨筋がみられ、水洗すれば少し回復する。
×：濃い雨筋がみられ、水洗してもほとんど消えない。
・耐候性
前記の方法にて作成した試験板をサンシャインウエザオメーターを用いて、促進耐候性を評価した。
試験時間２０００時間後の６０°光沢保持率（％）を表３に示した。数値が高いほど良好な耐候性を示す。 (Evaluation of the physical properties)
The base material was an aluminum plate coated with esco (epoxy paint made by Kansai Paint) and one-component fine urethane every other day.
The one-component paint obtained in Table 3 was applied to the substrate to a thickness of about 40 μm by air spray to obtain a test plate.
In addition, a test plate was prepared in the same manner by applying the one-component paint in a sealed state at 50 ° C. for one month by air spraying.
-The water contact angle test board was used for the outdoor rain-strip exposure stand, the dirt was lightly washed every week, and the water contact angle was measured. In addition, a contact angle measuring machine (Kyowa Interface Science Co., Ltd .: CA-S150 type) was used to measure the water contact angle, which is an index of contamination resistance. It can be said that the lower the contact angle, the better the stain resistance.
-The appearance of the test plate was evaluated according to the criteria shown below.
Visual evaluation A: There are almost no rain stripes.
○: Light rain streaks are seen, but disappears when washed lightly.
○ △: Rain streaks are observed, but it recovers to the extent that light rain streaks remain if washed with water.
Δ: Rain streaks are observed, and it recovers slightly when washed with water.
X: Dark rain streaks are observed, and it hardly disappears even when washed with water.
-Weather resistance The accelerated weather resistance was evaluated for the test plate prepared by the above method using a sunshine weatherometer.
Table 3 shows the 60 ° gloss retention (%) after a test time of 2000 hours. The higher the value, the better the weather resistance.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
（表中、各成分の量は重量部）
　一液ファインウレタン：日本ペイント株式会社製（一液型ウレタン塗料　白）
　ファインシリコンセラ：日本ペイント株式会社製（一液型シリコン塗料　白）
　尚、ともに有機樹脂（Ｄ）成分の含有量を３０％とした。 (In the table, the amount of each component is by weight)
One-pack fine urethane: Made by Nippon Paint Co., Ltd. (One-pack urethane paint white)
Fine silicon sera: Nippon Paint Co., Ltd. (one-part silicone paint white)
In both cases, the content of the organic resin (D) component was 30%.
　本発明の一液型塗料用樹脂組成物である実施例１～７は、いずれも良好な耐汚染性と貯蔵安定性を示した。（Ｃ）成分を配合しなかった比較例１は、貯蔵安定性は良好なものの、親水性の発現に時間を要するため、耐汚染性がやや劣る結果であった。加水分解性基含有ケイ素基を有しない重合体を用いた比較例２、（Ａ）成分を添加しなかった比較例３は、いずれも耐汚染性と貯蔵安定性および促進耐候性が劣っていた。（Ｃ）成分を１重量部以上配合した比較例４は、初期の低汚染は優れているものの、貯蔵安定性が劣る結果であった。 Examples 1 to 7, which are resin compositions for a one-part coating material of the present invention, all showed good stain resistance and storage stability. Although the comparative example 1 which did not mix | blend (C) component had favorable storage stability, since time was required for hydrophilic expression, it was a result in which contamination resistance is a little inferior. Comparative Example 2 using a polymer having no hydrolyzable group-containing silicon group and Comparative Example 3 in which the component (A) was not added were all poor in stain resistance, storage stability and accelerated weather resistance. . The comparative example 4 which mix | blended 1 weight part or more of (C) component was the result in which storage stability is inferior although the initial low pollution is excellent.
　上記に示した通り、本発明の一液型塗料用樹脂組成物は、低コスト・簡易な操作で製造できる。特には、耐汚染性に優れ、貯蔵後もその性能を充分に発現するとともに、耐候性が向上した塗料用樹脂組成物を提供することが可能となる。また、一液型塗料としても用いることができる。さらに、該塗料組成物を製造するための、低汚染性付与剤を提供することが可能となる。 As described above, the resin composition for a one-component paint according to the present invention can be produced at a low cost with a simple operation. In particular, it is possible to provide a resin composition for coatings which is excellent in stain resistance, sufficiently exhibits its performance after storage, and has improved weather resistance. It can also be used as a one-component paint. Furthermore, it is possible to provide a low contamination imparting agent for producing the coating composition.
　本発明の硬化性樹脂組成物は、例えば金属、セラミックス、ガラス、セメント、窯業系基材、プラスチック、木材、紙、繊維などからなる建築物、家電用品、産業機器などの塗装に好適に使用できる。
  The curable resin composition of the present invention can be suitably used for coating, for example, a building made of metal, ceramics, glass, cement, ceramic base material, plastic, wood, paper, fiber, etc., household appliances, and industrial equipment. .

Claims (10)

  1. 　　Ｒ２ ａ
    　　｜
    　－Ｓｉ－（ＯＲ１）３－ａ　（１）
    　（式中、Ｒ１は水素原子または炭素数１～１０のアルキル基、Ｒ２は水素原子または炭素数１～１０のアルキル基、炭素数６～２５のアリール基および炭素数７～１２のアラルキル基から選ばれた１価の炭化水素基、ａは０～２の整数を示す。）
    で表される加水分解性基に結合したケイ素基を少なくとも1つ有する重合体（Ａ）成分１００重量部に対して、
    （Ｒ３Ｏ）４－ｂ－Ｓｉ－Ｒ４ ｂ（２）
    （式中、Ｒ３は炭素数１～１０のアルキル基、炭素数６～１０のアリール基および炭素数７～１０のアラルキル基から選ばれた１価の炭化水素基、Ｒ４は炭素数１～１０のアルキル基、炭素数が６～１０のアリール基および炭素数が７～１０のアラルキル基から選ばれた１価の炭化水素基、ｂは０または１を示す）で表されるシリコン化合物及び／またはその部分加水分解縮合物（Ｂ）成分５０～１０００重量部、その他の有機樹脂（Ｄ）成分１５０～１００００重量部、さらに有機金属化合物（Ｃ）成分を（Ａ）、（Ｂ）、（Ｄ）の総量に対して金属換算で１重量部以下を含有する一液型塗料用樹脂組成物。     R 2 a
    ｜
    -Si- (OR 1 ) 3-a (1)
    Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms and an aralkyl having 7 to 12 carbon atoms. A monovalent hydrocarbon group selected from the group, a represents an integer of 0 to 2)
    100 parts by weight of the polymer (A) component having at least one silicon group bonded to the hydrolyzable group represented by
    (R 3 O) 4-b —Si—R 4 b (2)
    (Wherein R 3 is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, and R 4 is a carbon atom having 1 carbon atom) A monovalent hydrocarbon group selected from an alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, and b represents 0 or 1) And / or its partially hydrolyzed condensate (B) component 50 to 1000 parts by weight, other organic resin (D) component 150 to 10000 parts by weight, and further, organometallic compound (C) component (A), (B), A resin composition for a one-component paint containing 1 part by weight or less in terms of metal with respect to the total amount of (D).
  2. 　（Ａ）成分、（Ｂ）成分、（Ｃ）成分の重量の合計が、前記（Ｄ）成分の重量の０．０１～１．０倍であることを特徴とする請求項１に記載の一液型塗料用樹脂組成物。 2. The weight of the component (A), the component (B), and the component (C) is 0.01 to 1.0 times the weight of the component (D). Resin composition for liquid paints.
  3. 　（Ｄ）成分が、溶剤型有機樹脂である請求項１から２のいずれかに記載の一液型塗料用樹脂組成物。 The component (D) is a solvent-type organic resin. The resin composition for a one-component paint according to any one of claims 1 to 2.
  4. 　（Ｄ）成分が、既架橋型または酸化硬化型または熱硬化型の有機樹脂である請求項１から３のいずれかに記載の一液型塗料用樹脂組成物。 4. The resin composition for a one-component coating material according to any one of claims 1 to 3, wherein the component (D) is a cross-linked, oxidation-cured or thermosetting organic resin.
  5. 　（Ａ）成分と（Ｂ）成分が予め混合された後に、（Ｄ）成分へ配合することを特徴とする請求項１から４のいずれかに記載の一液型塗料用樹脂組成物。 The resin composition for a one-component paint according to any one of claims 1 to 4, wherein the component (A) and the component (B) are mixed in advance and then blended into the component (D).
  6. 　（Ｃ）成分の金属種がＳn、Ｔｉ、Ｆe、Ａｌ、Ｍｎ、Ｃｏ、Ｚｒ、Ｎｉ、Ｂｉ、Ｃｕ、Ｚｎ、Ｂａから選ばれる化合物である請求項１から５のいずれかに記載の一液型塗料用樹脂組成物。 The component (C) is a compound selected from the group consisting of Sn, Ti, Fe, Al, Mn, Co, Zr, Ni, Bi, Cu, Zn, and Ba. Resin composition for mold paint.
  7. 　（Ｃ）成分の金属種がＳn、Ｔｉ、Ｆe、Ａｌ、Ｍｎ、Ｃｏ、Ｚｒ、Ｎｉ、Ｂｉから選ばれる化合物である請求項１から６のいずれかに記載の一液型塗料用樹脂組成物。 7. The resin composition for a one-component paint according to claim 1, wherein the metal species of component (C) is a compound selected from Sn, Ti, Fe, Al, Mn, Co, Zr, Ni, and Bi. .
  8. 　さらに、脱水作用のある化合物（Ｅ）成分が、前記（Ｄ）成分１００重量部に対して０．１～１０重量部配合されることを特徴とする請求項１から７のいずれかに記載の一液型塗料用樹脂組成物。 8. The dehydrating compound (E) component is further blended in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the component (D). One-pack type resin composition for paints.
  9. 　一液型塗料用樹脂組成物を密閉下で５０℃１ヶ月間保存した後に得た塗膜の４週間暴露後の水接触角の角度が、７０°以下である請求項１から８のいずれかに記載の一液型塗料用樹脂組成物。 9. The water contact angle after exposure for 4 weeks of a coating film obtained after storing the resin composition for a one-part paint in a sealed state at 50 ° C. for 1 month is 70 ° or less. 9. The resin composition for one-component paints described in 1.
  10. 　請求項１から９のいずれかに記載の一液型塗料用樹脂組成物を塗布してなる塗装物。
          A coated product obtained by applying the one-component resin composition for paints according to any one of claims 1 to 9.
PCT/JP2010/002770 2009-04-16 2010-04-16 Resin composition for coating material, and coated article which is coated with the resin composition for coating material WO2010119703A1 (en)

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CN106661373A (en) * 2014-06-06 2017-05-10 信越化学工业株式会社 Primer composition
JP2020011232A (en) * 2018-07-10 2020-01-23 東京応化工業株式会社 Hydrophilic treatment method, and surface treatment liquid
WO2021161968A1 (en) * 2020-02-12 2021-08-19 日本製鉄株式会社 Metal plate coating material and coated metal plate production method using same

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JPH10212446A (en) * 1997-01-31 1998-08-11 Mitsubishi Chem Corp Composition for coating
JPH11181347A (en) * 1997-12-22 1999-07-06 Kanegafuchi Chem Ind Co Ltd Curable resin composition for coating material
JP2009040874A (en) * 2007-08-08 2009-02-26 Kaneka Corp Coating method using curing composition, and coated object

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Publication number Priority date Publication date Assignee Title
JPH0931401A (en) * 1995-05-16 1997-02-04 Sk Kaken Co Ltd Nonstaining coating composition
JPH10212446A (en) * 1997-01-31 1998-08-11 Mitsubishi Chem Corp Composition for coating
JPH11181347A (en) * 1997-12-22 1999-07-06 Kanegafuchi Chem Ind Co Ltd Curable resin composition for coating material
JP2009040874A (en) * 2007-08-08 2009-02-26 Kaneka Corp Coating method using curing composition, and coated object

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106661373A (en) * 2014-06-06 2017-05-10 信越化学工业株式会社 Primer composition
CN106661373B (en) * 2014-06-06 2019-01-18 信越化学工业株式会社 Primer composition
JP2020011232A (en) * 2018-07-10 2020-01-23 東京応化工業株式会社 Hydrophilic treatment method, and surface treatment liquid
JP7319850B2 (en) 2018-07-10 2023-08-02 東京応化工業株式会社 Hydrophilization treatment method and surface treatment liquid
WO2021161968A1 (en) * 2020-02-12 2021-08-19 日本製鉄株式会社 Metal plate coating material and coated metal plate production method using same

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