WO2013081022A1 - Composition de résine durcissable pour revêtement, et matière de revêtement transparent pour véhicule - Google Patents

Composition de résine durcissable pour revêtement, et matière de revêtement transparent pour véhicule Download PDF

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Publication number
WO2013081022A1
WO2013081022A1 PCT/JP2012/080780 JP2012080780W WO2013081022A1 WO 2013081022 A1 WO2013081022 A1 WO 2013081022A1 JP 2012080780 W JP2012080780 W JP 2012080780W WO 2013081022 A1 WO2013081022 A1 WO 2013081022A1
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resin composition
group
curable resin
coating
meth
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PCT/JP2012/080780
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English (en)
Japanese (ja)
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松尾　陽一
淳司 塚尾
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株式会社カネカ
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Priority to JP2013547194A priority Critical patent/JP6133785B2/ja
Publication of WO2013081022A1 publication Critical patent/WO2013081022A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6295—Polymers of silicium containing compounds having carbon-to-carbon double bonds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen

Definitions

  • the present invention is capable of forming a coating film under mild curing conditions, imparts excellent solvent resistance, acid resistance and chemical resistance, and has excellent scratch resistance and stain resistance, as well as coating curing.
  • the present invention relates to a conductive resin composition and an automobile clear coating agent containing the resin composition.
  • the demand for the durability of the formed coating film is increasing for the top coating used to form a coating film on automobiles, building materials, plastic parts, films and the like.
  • coating film performance excellent in weather resistance, solvent resistance, acid resistance, chemical resistance, scratch resistance, etc. is required.
  • a two-component curable coating material has been conventionally used.
  • paints used to protect automobiles, building materials, plastic parts, films, etc., and to provide design properties include acrylic lacquer paints, two-part curable urethane resin paints, and two-part curable acrylic silicon resin paints.
  • Acrylic lacquer paint is a one-pack paint that does not involve a crosslinking reaction of the resin and is easy to handle without the need for compounding a curing agent, but the resulting coating film is inferior in chemical resistance.
  • Patent Document 1 paints containing melamine resins such as alkyd melamine and acrylic melamine have been mainly used for painting automobiles, industrial machines, steel furniture, etc.
  • Patent Document 1 A harmful formalin is generated at the time of curing, and the cured coating film is inferior in acid resistance, so that it is affected by acid rain, and etching, whitening, spots and the like are generated on the coating film.
  • Patent Documents 2 and 3 are curable resin compositions comprising a combination of a hydroxyl group-containing resin and a polyfunctional isocyanate compound or a blocked isocyanate, although the acid resistance has been improved, the resulting coating film has insufficient scratch resistance and stain resistance. Absent.
  • Patent Document 4 The method of forming a coating film by applying a thermosetting two-component urethane paint (Patent Document 4) needs to increase the crosslinking density in order to obtain scratch resistance and chemical resistance, and has a high hydroxyl value. Will be. However, both scratch resistance and chemical resistance are not sufficient levels, and there is a problem that adhesion to a plastic substrate is further reduced.
  • Patent Literature 5 the use of polycarbonate diol in a urethane cross-linking paint using a hydroxyl group-containing resin such as an acrylic resin as a base resin and a polyisocyanate compound as a cross-linking agent has been studied (Patent Literature). 5).
  • the polycarbonate diol has insufficient compatibility with the acrylic polyol, and further, when a large amount of the polycarbonate diol is blended in order to ensure scratch resistance, the crosslinking density is lowered, so that the weather resistance and solvent resistance are insufficient. There is a problem.
  • Patent Document 6 a paint using a polymer having a hydrolyzable silyl group.
  • a vinyl polymer having a hydrolyzable silyl group and an alcoholic hydroxyl group By using a vinyl polymer having a hydrolyzable silyl group and an alcoholic hydroxyl group, a stable siloxane bond or siloxy bond is formed and cured by baking and drying, so that a coating film excellent in acid resistance and weather resistance can be obtained. Can be formed.
  • the obtained coating film has insufficient scratch resistance.
  • the two-component curable acrylic silicone resin paint can obtain excellent solvent resistance and chemical resistance, it is inferior in workability, recoatability, and coating film appearance as compared with the two-component curable urethane resin paint. There is a problem.
  • Patent Document 7 a method in which a polyfunctional monomer or oligomer is used as a main constituent and UV curing is performed using a photo radical generator has been reported. Since this method does not require heat drying for curing, there is an advantage that a substrate having a high hardness can be obtained in a short time without damaging a substrate such as plastic. However, there are problems such as poor flexibility and cracking or peeling of the coating film by impact.
  • Japanese Patent Laid-Open No. 5-202335 Japanese Patent Laid-Open No. 10-28931 JP-A-9-132753 JP 2008-296539 A International Publication No. 2007/119305 Pamphlet JP-A-7-82521 Japanese Patent Laid-Open No. 5-230397
  • the present inventors have found that a specific vinyl copolymer having a hydrolyzable silicon group and a hydroxyl group, a polyisocyanate compound, and a curing for coating containing a specific curing catalyst.
  • the curable resin composition can be cured under mild curing conditions, and has good weather resistance, solvent resistance, acid resistance, chemical resistance, scratch resistance, and excellent adhesion to various substrates.
  • the present inventors have found that a coating film having excellent stain resistance can be formed.
  • the main chain is a (meth) acrylic copolymer chain, and the general formula (I): R 2 a
  • a monovalent hydrocarbon group selected from the group a represents an integer of 0 to 2)
  • a vinyl-based copolymer having 10 or more hydrolyzable silicon groups represented by the formula, and having 10 or more hydroxyl groups in the main chain terminal and / or side chain (B) a compound containing two or more isocyanate groups, and (C)
  • the present invention relates to a multi-component curable resin composition for coating, comprising a hydrolyzable silicon group and an isocyanate curing catalyst.
  • the vinyl copolymer (A) is preferably a polymer having a hydroxyl value of 50 to 300 mgKOH / g.
  • the vinyl copolymer (A) preferably has a glass transition temperature of ⁇ 20 to 80 ° C.
  • the vinyl copolymer (A) is a monomer having a hydroxyl group bonded to a (meth) acryloyl group via an alkylene group having 3 or more carbon atoms and / or a polylactone type having a carbon-carbon double bond at the terminal. It is preferable to be obtained by copolymerizing monomers.
  • the curing catalyst (C) is at least one selected from the group consisting of a tin compound, an aluminum chelate compound, and a tertiary amine compound having no active hydrogen group.
  • the curing catalyst (C) is preferably a cyclic amine compound.
  • this invention relates to the motor vehicle clear coating agent containing the multi-component curable resin composition for coating of this invention.
  • the present invention relates to a coated product coated with the multi-component curable resin composition for coating of the present invention.
  • the multi-component curable resin composition for coating of the present invention can be cured under mild curing conditions to obtain a coating film having good weather resistance, solvent resistance, acid resistance, chemical resistance, and scratch resistance. be able to. Furthermore, it has a flaw-repairing property against scratches, and can form a coating film with excellent stain resistance.
  • the multi-component curable resin composition for coating of the present invention contains the components (A) to (C). First, each component will be described.
  • the main chain is a (meth) acrylic copolymer chain
  • the main chain terminal and / or side chain has the general formula (I): R 2 a
  • 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) As long as it is a vinyl copolymer having 10 or more hydrolyzable silicon groups represented by the formula and 10 or more hydroxyl groups at the main chain terminal and / or side chain, it can be used without any particular limitation. .
  • the hydrolyzable silicon group (hereinafter also referred to as a hydrolyzable silyl group) is a group containing a silicon atom to which a hydrolyzable group is bonded.
  • the hydrolyzable silyl group may be bonded to the main chain terminal of the component (A), may be bonded to the side chain, or may be bonded to the main chain terminal and the side chain.
  • the hydroxyl group may be bonded to the main chain end of the component (A), may be bonded to the side chain, or may be bonded to the main chain end and the side chain.
  • a is 0 or 1 from the point that the sclerosis
  • OR 1 or R 2 there are a plurality of OR 1 or R 2 , they may be the same or different.
  • R 1 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms from the viewpoint of high curing speed and excellent solvent resistance, chemical resistance, and acid resistance of the resulting coating film. It is more preferably an atom or an alkyl group having 1 to 2 carbon atoms.
  • R 2 is preferably not sterically large, and a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group, and a phenyl group are preferable. More preferably, it is an alkyl group having 1 to 3 carbon atoms.
  • the vinyl copolymer (A) preferably has a glass transition temperature of ⁇ 20 to 80 ° C. from the viewpoint of excellent balance between chemical resistance and scratch resistance.
  • a glass transition temperature ⁇ 20 to 80 ° C.
  • tack remains in the coating film and solvent and chemical resistance tend to deteriorate.
  • the glass transition temperature exceeds 80 ° C., although the solvent resistance and chemical resistance are excellent, the coating film becomes brittle and the scratch resistance is not sufficient.
  • the hydroxyl value of the vinyl copolymer (A) is preferably 50 to 300 mgKOH / g.
  • the vinyl copolymer (A) is a monomer having a hydroxyl group bonded to a (meth) acryloyl group via an alkylene group having 3 or more carbon atoms and / or a polylactone unit having a carbon-carbon double bond at the terminal. It is preferably obtained by copolymerizing a monomer.
  • a manufacturing method of a vinyl type copolymer (A) For example, (a) Hydrolysis in the method in which the main chain is a (meth) acrylic-type copolymer chain is obtained. It is obtained by a method of polymerizing a polymerizable silyl group-containing vinyl monomer, (b) a hydroxyl group-containing vinyl monomer, and (c) another polymerizable vinyl monomer.
  • R 2 a -Si- (OR 1 ) 3-a (I)
  • 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)
  • hydrolyzable silyl group-containing vinyl monomer (a) examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (n-propoxy) silane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltris.
  • ( ⁇ -methoxyethoxy) silane allyltriethoxysilane, trimethoxysilylpropylallylamine, ⁇ - (meth) acryloxypropyltrimethoxysilane, ⁇ - (meth) acryloxypropyltriethoxysilane, ⁇ - (meth) acryloxy Propyltriisopropoxysilane, ⁇ - (meth) acryloxypropyltris ( ⁇ -methoxyethoxy) silane, ⁇ - (meth) acryloxypropylmethyldimethoxysilane, ⁇ - (meth) acryloxypropylmethyldiethoxysilane, ⁇ - (Meta) Acryloxypropyldimethylmethoxysilane, ⁇ - (meth) acryloxypropyldimethylethoxysilane, N-vinylbenzyl- ⁇ -aminopropyltrimethoxysilane, 2-styrylethyltrime
  • hydrolyzable silyl group-containing vinyl monomers (a) may be used alone or in combination of two or more.
  • (meth) acryl means acrylic and / or methacrylic.
  • (Meth) acryloxy means methacryloxy and / or acryloxy.
  • (Meth) acrylate means acrylate and / or methacrylate.
  • the hydrolyzable silyl group-containing vinyl monomer (a) contains 10 to 30, particularly preferably 10 to 20, hydrolyzable silyl groups per molecule of the vinyl copolymer (A). It is preferable to use it from the viewpoint of providing sufficient solvent resistance and chemical resistance and improving scratch resistance.
  • the number of hydrolyzable silyl groups in one molecule depends on the ratio (number of moles) of the hydrolyzable silyl group-containing vinyl monomer (a) in the monomer mixture and the vinyl monomer (a). It can be obtained by calculation from the number average molecular weight. *
  • the hydrolyzable silyl group-containing vinyl monomer (a) is preferably blended in an amount of 5 to 80 parts by weight in 100 parts by weight of the total monomers of the vinyl copolymer (A). It is particularly preferable to blend at least 60 parts by weight with no more than 60 parts by weight.
  • the hydroxyl group-containing vinyl monomer (b) is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3- Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol Hydroxyl group-containing vinyl monomers such as (meth) acrylamide and 4-hydroxystyrene vinyltoluene; PlaceFA-1, PlaceFA-4, PlaceFM-1 and PlaceFM-4 (manufactured by Daicel Chemical Co., Ltd.) Modified lactone or polyester having a polymerizable carbon-carbon double bond at the end thereof; Blemmer PP series, Blemmer PE series, Blemmer PEP
  • 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are excellent in that they have excellent reactivity with isocyanate, and can provide coatings with excellent weather resistance, chemical resistance, and scratch resistance.
  • 2-hydroxybutyl (meth) acrylate is preferred.
  • an alkylene group having 3 or more carbon atoms, more preferably 3 to 10 carbon atoms such as 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and cyclohexanedimethanol mono (meth) acrylate.
  • a lactone-modified monomer (polylactone monomer) having a terminal carbon-carbon double bond such as Placcel, such as a monomer in which a hydroxyl group is bonded to a (meth) acryloyl group via an acid, is used for wound repair. Is preferable from the point that can be obtained.
  • hydroxyl group-containing vinyl monomers (b) may be used alone or in combination of two or more.
  • the amount used is designed to contain 10 to 50, particularly preferably 10 to 30 hydroxyl groups per molecule of the vinyl copolymer (A), and good scratch resistance can be obtained. It is preferable from the point.
  • the number of hydroxyl groups in one molecule is determined by calculation from the ratio (number of moles) of the hydroxyl group-containing vinyl monomer (b) in the monomer mixture and the number average molecular weight of the vinyl monomer (A). Can do.
  • the vinyl copolymer (A) it is preferable to design the vinyl copolymer (A) to have a hydroxyl value of 50 to 300 mgKOH / g from the viewpoint of improving chemical resistance and scratch resistance.
  • the hydroxyl group-containing vinyl monomer (b) is preferably blended in an amount of 10 to 80 parts by weight, based on 100 parts by weight of all monomers of the vinyl copolymer (A), and 15 to 60 parts by weight. It is particularly preferable to blend in an amount of no more than parts.
  • polymerizable vinyl monomers are not particularly limited as long as they have a carbon-carbon double bond.
  • methyl (meth) Alkyl (meth) acrylates having 1 to 20 carbon atoms such as acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.
  • Cycloalkyl (meth) acrylates having 4 to 20 carbon atoms such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate; allyl (meth) acrylate; dicyclopentenyl (meth) acrylate; Aralkyl having 3 to 20 carbon atoms such as benzyl (meth) acrylate ( ) Acrylate; epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate, oxycyclohexylinyl (meth) acrylate; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid , ⁇ , ⁇ -ethylenically unsaturated carboxylic acids such as fumaric acid and citraconic acid or salts thereof (alkali metal salts, ammonium salts, amine salt
  • the other polymerizable vinyl monomer (c) is preferably blended in an amount of 1 part by weight or more and 85 parts by weight or less, based on 100 parts by weight of the total monomers of the vinyl copolymer (A). It is particularly preferable to add 75 parts by weight or less.
  • the polymerization method is not particularly limited, and examples thereof include a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, and the like.
  • the solution polymerization method is preferable in terms of ease of synthesis.
  • Examples of the initiator used for the polymerization include known ones such as organic peroxides such as cumene hydroperoxide, azo compounds such as azobis-2-methylbutyronitrile, potassium persulfate, and the like. Examples include inorganic peroxide-based initiators, redox-based initiators combining peroxides and reducing agents.
  • the degree of polymerization of the resulting vinyl copolymer (A) is preferably 2000 to 50000 in terms of number average molecular weight, more preferably 3000 to 25000, and particularly preferably 3000 to 10,000.
  • the degree of polymerization can be adjusted by the type and amount of the radical generator, the polymerization temperature, and the use of a chain transfer agent.
  • the chain transfer agent n-dodecyl mercaptan, t-dodecyl mercaptan, ⁇ -mercaptopropyltrimethoxysilane and the like can be preferably used.
  • (B) Compound having two or more isocyanate groups
  • a compound (B) having two or more isocyanate groups (hereinafter referred to as polyisocyanate compound (B)) is used as a crosslinking agent.
  • the number of isocyanate groups is preferably less than 7. Naturally, when the number of isocyanate groups is less than 2, it does not work as a crosslinking agent. However, when the number of isocyanate groups is 7 or more, the crosslinking points may be concentrated so as to inhibit adhesion.
  • Examples of the polyisocyanate compound (B) include aliphatic or aromatic compounds.
  • aliphatic polyisocyanate examples include hexamethylene diisocyanate, dicyclohexylmethane 4,4′-isocyanate, 2,2,4-trimethyl-1,6-diisocyanate, and isophorone diisocyanate.
  • Aromatic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylene diisocyanate, polymethylene-polyphenylel-polyisocyanate, etc. There is. From the viewpoint of no yellowing and good weather resistance, aliphatic polyisocyanate is more preferable.
  • the structure of the polyisocyanate compound (B) includes a monomer, a burette type, an adduct type, and an isocyanurate type. These compounds can be used for normal temperature curing, and further, those obtained by masking these isocyanate groups with a blocking agent can also be used.
  • the blocking agents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, benzyl alcohol, furfuryl alcohol, cyclohexyl alcohol.
  • polyisocyanate compounds (B) include Coronate HL (manufactured by Nippon Polyurethane Industry Co., Ltd.), Duranate P-301, Duranate E-402, Duranate E-405 (above, manufactured by Asahi Kasei Chemicals Corporation).
  • Adduct types such as Duranate 18H, Duranate 21S, Duranate 22A (above, manufactured by Asahi Kasei Chemicals), Coronate HX, Coronate HK, Coronate 2760, Coronate 2349 (above, Nippon Polyurethane Industry Co., Ltd.) , Duranate MFA, Duranate TPA100, Duranate THA100, Duranate TSA100 (above, manufactured by Asahi Kasei Chemicals), Coronate AP-M, Coronate BI301, Coronate 2507 (above, Nippon Polyurethane Industry) Ltd.)), Duranate 17B, Duranate MF (manufactured by Asahi Kasei Chemicals), and the block type and the like.
  • the proportion of the vinyl copolymer (A) and the polyisocyanate compound (B) used is preferably 0.3 to 2 equivalents, more preferably an isocyanate group with respect to the hydroxyl group in the vinyl copolymer (A). Is 0.5 to 1.5 equivalents. If the polyisocyanate compound is too little, the resulting cured product tends to have poor chemical resistance, and if it is too much, the processability such as impact resistance is poor, and it is difficult to rub at the time of coating. May occur.
  • the curing catalyst is not particularly limited, and a tin compound, an aluminum chelate compound, and a tertiary amine compound having no active hydrogen group are preferable from the viewpoint of excellent curability of the coating film and overall physical properties of the resulting coating film. .
  • tin compound examples include dioctyltin bis (2-ethylhexyl malate), dioctyltin oxide or a condensate of dibutyltin oxide and silicate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin distearate, dibutyltin diacetylacetate Nert, dibutyltin bis (ethyl malate), dibutyltin bis (butylmalate), dibutyltin bis (2-ethylhexylmalate), dibutyltin bis (oleylmalate), stannous octoate, tin stearate, di-n-butyl There is tin laurate oxide.
  • tin compounds compounds having an S atom in the molecule are preferred because they have good storage stability and usable time when an isocyanate is blended, and in particular, dibutyltin bisisononyl-3-mercaptopropio Nate and dibutyltin bisisooctylthioglucolate are more preferable, and dioctyltin bisisooctylthioglucolate is particularly preferable from the viewpoint of balance between curability, storage stability, and pot life.
  • Aluminum chelate compounds include ethyl acetoacetate aluminum diisopropylate, aluminum tris (acetylacetate), aluminum tris (ethylacetoacetate), aluminum monoacetylacetonate bis (ethylacetoacetate), alkylacetylacetate aluminum diisopropylate Etc.
  • a tertiary amine compound having no active hydrogen group is preferable because it is non-tin and excellent film properties can be obtained.
  • tertiary amine compound having no active hydrogen group examples include trialkylamines such as triethylamine, triethylenediamine, and trimethylamine, tetramethylenediamine, N, N, N ′, N′-tetramethyl-1,3- Tetraalkyldiamines such as butanediamine, esteramines such as bis (diethylethanolamine) adipate, cyclohexylamine derivatives such as N, N-dimethylcyclohexylamine, morpholine derivatives such as N-methylmorpholine, N, N ′ -Piperazine derivatives such as -diethyl-2-methylpiperazine are preferable, but from the viewpoint of curing activity, a cyclic amine compound is preferable, and triethylenediamine is particularly preferable.
  • trialkylamines such as triethylamine, triethylenediamine, and trimethylamine, tetramethylenediamine, N, N, N ′,
  • curing catalysts (C) may be used alone or in combination of two or more.
  • the amount of the curing catalyst (C) used may be appropriately adjusted depending on the curing temperature and time, but is 0.01 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer (A). It is preferable that the amount is 0.1 to 5 parts by weight. When the amount is less than 0.01 part by weight, the reactivity of the hydrolyzable silyl group tends to be insufficient and the balance of the coating film performance tends to be inferior. There is a tendency.
  • the curable resin composition of the present invention may contain, for example, the following components in addition to the components (A) to (C) as necessary.
  • solvent there is no particular limitation on the solvent used in the multi-component curable resin composition containing the vinyl copolymer (A), and known aromatic, aliphatic hydrocarbon, ether, ketone, ester, Alcohol-based solvents such as water can be used. From the viewpoint of the solubility of the vinyl copolymer (A), it is preferable to use an ester type such as toluene, xylene or butyl acetate, a ketone type such as methyl isobutyl ketone, or an aliphatic hydrocarbon-containing solvent. In consideration of the appearance of the coating film during curing, it is desirable to adjust the volatilization rate by mixing other solvents.
  • 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; methyl orthoborate, ethyl orthoborate, ortho Examples thereof include orthocarboxylic acid esters such as alkyl orthoborate such as butyl borate, and highly active silane compounds such as tetramethoxysilane, tetraethoxysilane, and methyltrimethoxysilane.
  • the amount of the dehydrating agent used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl copolymer (A).
  • An additive can be mix
  • the additive include a plasticizer, a dispersant, a dehydrating agent, a wetting agent, a thickening agent, an antifoaming agent, a preservative, an anti-settling agent, a leveling agent, an ultraviolet absorber, and a light stabilizer.
  • a pigment may be added as necessary.
  • the pigment include white pigments such as titanium dioxide, calcium carbonate, barium carbonate, and kaolin, and colored pigments such as carbon black, bengara, and cyanine blue.
  • the method for preparing the curable resin composition of the present invention is not particularly limited as long as the curable resin composition is multi-component.
  • the compounding components are mixed in multiple liquids and mixed at the time of use. That is, in the case of the two-pack type, the blending component is divided into two liquids, liquid A and liquid B, and the liquids are mixed at the time of use.
  • the method of dividing the liquid A and the liquid B can be variously combined depending on the storage stability and the like. Moreover, it is also possible to divide into three liquid type or more if necessary.
  • the multi-component curable resin composition for coating according to the present invention is obtained.
  • a roll coater method, a blade coater method, a gravure coater method, a beat coater method, a curtain flow coater method, a dip coating method, and a spray coating method is possible.
  • the curable resin composition can be cured at an arbitrary temperature from room temperature to 300 ° C.
  • the heating time can be shortened as the heating temperature increases. In that case, it is preferable to heat cure at a temperature of 65 to 250 ° C. for 5 seconds to 60 minutes.
  • the thickness of the coating film of the multi-component coating curable resin composition of the present invention is preferably 0.5 to 70 ⁇ m, more preferably 5 to 50 ⁇ m. If it is too thin, the coating film is likely to be damaged due to physical wear, which is not preferable in terms of durability, and if it is too thick, the coating film may be cracked and peeled off when the coating material is processed. It becomes easy and is not preferable.
  • Examples of the coated object of the multi-component curable resin composition for coating according to the present invention include metals, inorganic substances, organic substances, and composite materials.
  • Examples of the metal include stainless steel, aluminum, tinplate, tin, mild steel plate, copper, brass, various plated steel plates, and titanium.
  • a substrate subjected to a surface treatment such as a chemical conversion treatment or an alumite treatment can also be suitably used.
  • Examples of the inorganic material include glass, mortar, slate, concrete and roof tile.
  • organic substances include plastic molded products such as polypropylene, polyethylene, acrylic, polycarbonate, ABS, polystyrene, PET, nylon, polyester, rubber, and elastomer, and products obtained by processing these into films (note that these are From the viewpoint of adhesion, it may be subjected to surface treatment if necessary). Furthermore, since the present invention has a sufficient function when applied as a top coat, it can also be used for various organic undercoats such as epoxy paints, urethane paints and melamine paints. Examples of the composite material include FRP, FRTP, a laminate, and a sandwich material in which a metal and an organic material are pressure-bonded.
  • curable resin composition examples include cell phones, (personal) computer casings, plastic molded products such as home appliances, flat panel displays, touch panel films, wood products such as tables, desks, and furniture. Examples include painting on various metal products.
  • plastic molded products such as home appliances, flat panel displays, touch panel films, wood products such as tables, desks, and furniture. Examples include painting on various metal products.
  • an automotive clear coating agent used as a top coat for automobiles is also cited as a preferred application.
  • the automotive clear coating agent according to the present invention comprises the multi-component curable resin composition for coating according to the present invention.
  • the coated object which concerns on this invention is what coated the multi-component curable resin composition for coating of this invention.
  • Table 1 shows the solid content concentration of the obtained copolymer, the number average molecular weight measured by GPC, and the like.
  • the copolymers (A-1 to A-8) were once diluted with a polymerization solvent so that the solid content concentration became 50%, and proceeded to the next blending.
  • Curing agents H-1 to H-7 were prepared according to the formulation shown in Table 2.
  • FM-4 Lactone modified hydroxyethyl methacrylate coronate manufactured by Daicel Chemical Industries, Ltd.
  • a coating solution was prepared according to the formulation shown in Table 3, applied to a polycarbonate resin molded plate by an air spray coating method so that the dry film thickness was 20 to 30 ⁇ m, dried at 80 ° C. for 30 minutes, solvent resistance, and The chemical resistance was evaluated.
  • Aqueous base coat white (AXUZ-DRY: made by Isamu Paint Co., Ltd.) is applied to the cation electrodeposition coated zinc phosphate treated steel plate (Nippon Test Panel Co., Ltd. Valbond treated plate) and preheated at 80 ° C for 5 minutes. Went.
  • a coating solution prepared according to the formulation shown in Table 3 was applied by an air spray coating method so that the dry film thickness was 30 to 40 ⁇ m, and baked at 140 ° C. for 30 minutes to form a coating film for evaluation. It was.
  • the stain-resistant prepared coated plate was placed at an angle of 30 ° outdoors in Settsu City, Osaka, and exposed. After exposure for 2 months, the degree of contamination on the coating film surface was visually observed and evaluated. ⁇ : Not very dirty and excellent in stain resistance ⁇ : Thin stain can be confirmed ⁇ : Clearly noticeable stain can be confirmed
  • Example 1 a well-balanced coating film having high solvent resistance, acid resistance and chemical resistance as well as excellent scratch resistance was obtained immediately after curing. Furthermore, it was difficult to get dirty when used outdoors, and was excellent in stain resistance.
  • Example 7 using FM-4 which is a system monomer, in addition to solvent resistance, acid resistance, chemical resistance and scratch resistance, scratch repairability was also observed.
  • Comparative Example 1 using a copolymer (A-6) having less than 10 hydrolyzable silicon groups and hydroxyl groups in one molecule, sufficient chemical resistance and scratch resistance were not obtained. . Further, although there are 10 or more hydrolyzable silicon groups in one molecule, in Comparative Example 2 which does not contain a hydroxyl group, the stain resistance is excellent, but the scratch resistance is, on the contrary, there are 10 or more hydroxyl groups in one molecule. However, Comparative Example 3 containing no hydrolyzable silicon group resulted in extremely poor chemical resistance and stain resistance.
  • the curable resin composition for coating of the present invention exhibits high solvent resistance, acid resistance and chemical resistance, and is excellent in scratch resistance and stain resistance. It was confirmed that it was a curable resin composition for coating that could be solved in a well-balanced manner. Furthermore, it was confirmed that the use of a specific monomer as the copolymer component can also be expected to provide wound repairability.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne une composition de résine durcissable pour revêtement, cette composition permettant de former un film de revêtement dans des conditions de durcissement modérées, et conférant une résistance aux solvants, aux acides, aux produits chimiques, aux éraflures, aux taches ainsi qu'une facilité de réparation des défauts. L'invention concerne une composition de résine durcissable multicomposants pour revêtement, qui est caractérisée en ce qu'elle contient : (A) un copolymère à base de vinyle, dans lequel la chaîne principale est une chaîne de copolymère (méth)acrylique, les terminaisons de chaîne principale et/ou les chaînes latérales contiennent un nombre supérieur ou égal à 10 groupes silicium hydrolysables, et les terminaisons de chaîne principale et/ou les chaînes latérales contiennent un nombre supérieur ou égal à 10 groupes hydroxyle, (B) un composé comportant deux ou davantage de groupes isocyanate, et (C) un catalyseur de durcissement destiné aux groupes silicum hydrolysables et aux groupes isocyanate.
PCT/JP2012/080780 2011-11-29 2012-11-28 Composition de résine durcissable pour revêtement, et matière de revêtement transparent pour véhicule WO2013081022A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016013761A1 (fr) * 2014-07-25 2016-01-28 양철호 Composition d'agent de revêtement inorganique écologique et procédé de préparation associé

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JPH115943A (ja) * 1997-04-24 1999-01-12 Kansai Paint Co Ltd 塗料組成物
JPH11100566A (ja) * 1997-09-26 1999-04-13 Nippon Nsc Ltd 初期タックの改良されたアクリルウレタン系シーリング材組成物
JPH11285670A (ja) * 1998-04-01 1999-10-19 Kansai Paint Co Ltd 複層塗膜形成方法
JPH11286648A (ja) * 1997-04-11 1999-10-19 Kanegafuchi Chem Ind Co Ltd 上塗り塗料用硬化性組成物およびそれを塗布してなる塗装物
JP2007186690A (ja) * 2005-12-16 2007-07-26 Sanyo Chem Ind Ltd 粉体塗料用樹脂組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11286648A (ja) * 1997-04-11 1999-10-19 Kanegafuchi Chem Ind Co Ltd 上塗り塗料用硬化性組成物およびそれを塗布してなる塗装物
JPH115943A (ja) * 1997-04-24 1999-01-12 Kansai Paint Co Ltd 塗料組成物
JPH11100566A (ja) * 1997-09-26 1999-04-13 Nippon Nsc Ltd 初期タックの改良されたアクリルウレタン系シーリング材組成物
JPH11285670A (ja) * 1998-04-01 1999-10-19 Kansai Paint Co Ltd 複層塗膜形成方法
JP2007186690A (ja) * 2005-12-16 2007-07-26 Sanyo Chem Ind Ltd 粉体塗料用樹脂組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016013761A1 (fr) * 2014-07-25 2016-01-28 양철호 Composition d'agent de revêtement inorganique écologique et procédé de préparation associé
KR101615713B1 (ko) 2014-07-25 2016-04-26 양철호 친환경 무기질계 코팅제 조성물 및 이의 제조방법

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