Classifications

• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/24—Catalysts containing metal compounds of tin
  • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
  • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon 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
  • C08G18/28—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
  • C08G18/61—Polysiloxanes
• • 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
  • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
  • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
  • C08G18/6245—Polymers having terminal groups containing active hydrogen
• • 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
  • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
  • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
  • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
• • 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
  • C08G18/778—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur silicon
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/06—Polyurethanes from polyesters
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
• • 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
  • C09D175/06—Polyurethanes from polyesters
• • 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
  • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
• • 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
  • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • 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
  • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups

Definitions

• the present invention relates to a coating composition, a coated article, and a method for forming a cured film, and more specifically, a coating composition containing an organic resin and an organopolysiloxane, a coated article having a cured film comprising the coating composition, and The present invention relates to a method for forming a cured film comprising the coating composition.
• Paints containing organopolysiloxane resins as main components are widely used in the fields of architecture and civil engineering structures because of their excellent coating film hardness, chemical resistance, weather resistance, and the like. Although this organopolysiloxane coating has the above advantages, it also has the drawback that the curing speed is slow and the resulting coating film has poor crack resistance.
• Patent Document 1 proposes a coating composition containing a silyl group-containing vinyl polymer, a silanol group-containing organopolysiloxane, and an alkoxy group-containing organopolysiloxane.
• this composition improves curability and crack resistance, it reduces the hardness, chemical resistance, heat resistance, weather resistance, etc., which are the characteristics of organopolysiloxane resin coatings. There's a problem.
• Patent Documents 2 to 5 disclose a method of reacting an organic resin with an organosilane or an organopolysiloxane to form a composite. Since it is necessary, there is a problem in terms of versatility. Therefore, there is a demand for a simple technique for bringing out the properties of both the organopolysiloxane and the organic resin.
• the present invention has been made in view of the above circumstances, and is capable of being easily produced, and provides a cured film having excellent hardness, chemical resistance, antifouling properties, and weather resistance by combining an organic resin and an organopolysiloxane.
• the object is to provide a coating composition comprising:
• the present inventors have found that a coating composition obtained by mixing a polyol, a silane coupling agent having an isocyanurate skeleton, and a predetermined organopolysiloxane in a predetermined ratio can be cured by heating.
• the inventors have found that it is possible and that the coating film obtained from the composition satisfies the above properties such as hardness, and have completed the present invention.
• the present invention 1.
• each R 1 independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms
• R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• a coating composition comprising 2.
• the component (A) is an acrylic polyol, a polyester polyol, or both; 3.
• each R 3 independently represents an alkylene group having 1 to 20 carbon atoms, and each R 4 independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. group, R 5 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and f is each independently 0, 1 or 2.
• each R 1 is independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aryl group having 7 carbon atoms.
• each R 1 is independently a methyl group, an ethyl group or a phenyl group; 6.
• the coating composition of the present invention can be produced simply by mixing a polyol, a silane coupling agent having an isocyanurate skeleton, and a specific organopolysiloxane, and provides a cured film having excellent hardness, chemical resistance, antifouling properties, and weather resistance. , it is suitable for the manufacture of various coated articles.
• the coating composition of the present invention contains the following components (A) to (C).
• polyol The polyol of the component (A) has two or more reactive hydroxyl groups in one molecule and has a hydrolyzable silyl group in the presence or absence of a curing catalyst (B ) and component (C) to form a crosslinked structure.
• Polyols include acrylic polyols, which are (co)polymers of (meth)acrylic monomers having hydroxyl groups and other arbitrary (meth)acrylic monomers, polyesters, which are polycondensation products of polybasic acids and polyhydric alcohols.
• examples include polyols (including alkyd polyols, which are condensation polymers of polybasic acids and fatty acids and polyhydric alcohols), and polyether polyols, which are addition polymers of polyhydric alcohols and alkylene oxides.
• acrylic polyols, polyester polyols, or both of them are preferable, and acrylic polyols are particularly preferable because the obtained coating film has excellent transparency and gloss.
• the (meth)acrylic monomer is meant to include both acrylic monomers and methacrylic monomers.
• (meth)acrylic monomers having a hydroxyl group which are raw material monomers for acrylic polyols, include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2- Hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, di-2-hydroxyethyl fumarate, mono-2 - various ⁇ , ⁇ such as hydroxyethyl monobutyl fumarate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, "PLAXEL FM or PLAXEL FA” [caprolactone addition monomer manufactured by Daicel Chemical Industries, Ltd.] -Hydroxyalkyl esters of ethylenically unsaturated carboxylic acids, or adducts of these
• (meth)acrylic monomers copolymerizable with the (meth)acrylic monomer having a hydroxyl group are not particularly limited, and known monomers can be used. Vinyl monomers can also be copolymerized. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2 - Alkyl (meth)acrylates having an alkyl group having 1 to 22 carbon atoms such as ethylhexyl (meth)acrylate and lauryl (meth)acrylate; aralkyl (such as benzyl (meth)acrylate and 2-phenylethyl (meth)acrylate) meth)acrylates; cycloalkyl (meth)acrylates such as cyclohexyl (
• the polymerization method, solvent, and polymerization initiator for copolymerizing these monomers are not particularly limited.
• hydrocarbons such as hexane, octane, toluene, and xylene; ketones such as methyl ethyl ketone; esters such as ethyl acetate; isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), tert-butylperoxypivalate, tert-butylperoxy Polymerization can be carried out using polymerization initiators such as benzoate, tert-butylperoxy-2-ethylhexanoate, di-tert-butylperoxide, cumene hydroperoxide, diisopropylperoxycarbonate and the like.
• the molecular weight of the polyol of component (A) is not particularly limited, but from the viewpoint of curability, weather resistance and paintability, the weight average molecular weight (Mw) in terms of polystyrene in gel permeation chromatography is preferably 1. ,000 to 100,000, more preferably 2,000 to 80,000.
• the amount of hydroxyl groups contained in component (A) is not particularly limited, the hydroxyl value is preferably 10 to 200 mgKOH/g, more preferably 20 to 180 mgKOH/g.
• a hydroxyl value is a value by JISK0070:1992.
• component (A) commercially available products can be used. Co., Ltd.) and the like.
• (A) component may be used individually by 1 type, or may be used in combination of 2 or more type.
• Silane coupling agent having an isocyanurate skeleton Component (B) is a silane cup having an isocyanurate skeleton and preferably having one or more hydrolyzable silyl groups or silanol groups per molecule. It is a ring agent.
• Hydrolyzable silyl groups include, for example, trialkoxysilyl groups such as trimethoxysilyl and triethoxysilyl groups; organodialkoxysilyl groups such as methyldimethoxysilyl and ethyldiethoxysilyl groups; diorganoalkoxysilyl groups such as silyl groups; halosilyl groups such as trichlorosilyl, dichloromethylsilyl and chlorodimethylsilyl groups; among these, trialkoxysilyl groups such as trimethoxysilyl and triethoxysilyl groups are preferred. , a trimethoxysilyl group is more preferred.
• silane coupling agents having an isocyanurate skeleton include compounds represented by the following formula (II).
• each R 3 independently represents an alkylene group having 1 to 20 carbon atoms
• each R 4 independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms
• R 5 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
• each f is independently 0, 1 or 2;
• the alkylene group for R 3 is preferably an alkylene group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms.
• the alkylene group for R3 may be either linear or branched, and specific examples include methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, Undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadecamethylene, eicosadecylene groups, and the like.
• R 3 is preferably a methylene, ethylene or trimethylene group, more preferably a trimethylene group.
• the monovalent hydrocarbon group for R 4 may be linear, branched or cyclic, and examples thereof include alkyl groups having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms; is an alkenyl group having 2 to 8 carbon atoms; an aryl group having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms; an aralkyl group having 7 to 12 carbon atoms, preferably 7 to 10 carbon atoms; mentioned.
• alkyl groups having 1 to 12 carbon atoms are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl and n-hexyl. , n-heptyl and n-octyl groups.
• alkenyl groups having 2 to 12 carbon atoms include vinyl and allyl groups.
• aryl groups having 6 to 12 carbon atoms include phenyl and naphthyl groups.
• aralkyl groups having 7 to 12 carbon atoms include benzyl and phenylethyl groups.
• halogen atoms such as chlorine, fluorine, and bromine
• substituents such as cyano groups
• halogen-substituted hydrocarbon groups such as chloromethyl, bromoethyl, trifluoropropyl, chlorophenyl and bromophenyl groups
• cyano-substituted hydrocarbon groups such as cyanoethyl groups.
• R 4 is preferably a methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, phenyl, benzyl or vinyl group, more preferably a methyl, ethyl or phenyl group.
• the alkyl group for R 5 preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and may be either linear or branched .
• the same groups as those having 1 to 8 carbon atoms can be mentioned.
• those having 1 to 3 carbon atoms are preferred, and methyl and ethyl groups are more preferred.
• f 0, 1 or 2, with 0 being preferred.
• component (B) examples include 1,3,5-tris(3-trimethoxylylpropyl)isocyanurate, 1,3,5-tris(3-triethoxysilylpropyl)isocyanurate, 1, 3,5-tris(3-tripropoxysilylpropyl) isocyanurate, 1,3,5-tris(3-methyldimethoxysilylpropyl) isocyanurate, 1,3,5-tris(3-methyldiethoxysilylpropyl) isocyanurate, 1,3,5-tris(3-methyldipropoxysilylpropyl) isocyanurate, 1,3,5-tris(3-phenyldimethoxysilylpropyl) isocyanurate, 1,3,5-tris(3-phenyldiethoxysilylpropyl) isocyanurate, 1,3,5-tris(3-phenyldipropoxysilylpropyl) isocyanurate, 1,3,5-tris(
• 1,3,5-tris(3-trimethoxylylpropyl) isocyanurate 1,3,5-tris(3-triethoxysilylpropyl) isocyanurate are preferred, and 1,3,5-tris( 3-trimethoxylylpropyl)isocyanurate is more preferred.
• Component (B) may be a commercially available product such as KBM-9659 (manufactured by Shin-Etsu Chemical Co., Ltd.), but is not limited thereto.
• (B) component may be used individually by 1 type, and may use 2 or more types together.
• the blending amount of component (B) is 0.5 to 20 parts by mass per 100 parts by mass of the non-volatile content of component (A). If the component (B) is less than 0.5 parts by mass, the resulting cured film will have poor chemical resistance, antifouling properties, and weather resistance. Poor hardness.
• Organopolysiloxane Component (C) is an organopolysiloxane having a siloxane unit composition ratio represented by the following formula (I).
• R 1 each independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms
• R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
• e is a number that satisfies 0 ⁇ e ⁇ 4.
• the monovalent hydrocarbon group for R 1 may be linear, branched or cyclic, and examples thereof include alkyl groups having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms; and alkyl groups having 2 to 12 carbon atoms, preferably is an alkenyl group having 2 to 8 carbon atoms; an aryl group having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms; an aralkyl group having 7 to 12 carbon atoms, preferably 7 to 10 carbon atoms; mentioned.
• alkyl groups having 1 to 12 carbon atoms are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl and n-hexyl. , n-heptyl and n-octyl groups.
• alkenyl groups having 2 to 12 carbon atoms include vinyl and allyl groups.
• aryl groups having 6 to 12 carbon atoms include phenyl and naphthyl groups.
• aralkyl groups having 7 to 12 carbon atoms include benzyl and phenylethyl groups.
• halogen atoms such as chlorine, fluorine, and bromine
• substituents such as cyano groups
• halogen-substituted hydrocarbon groups such as chloromethyl, bromoethyl, trifluoropropyl, chlorophenyl and bromophenyl groups
• cyano-substituted hydrocarbon groups such as cyanoethyl groups.
• R 1 is preferably a methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, phenyl, benzyl or vinyl group, more preferably a methyl, ethyl or phenyl group.
• preferably 20% or more of the total number of R 1 is a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, more preferably a carbon atom optionally substituted with a halogen atom It is an aryl group of numbers 6 to 12.
• alkyl groups having 1 to 6 carbon atoms for R 2 include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n- A hexyl group and the like can be mentioned, and among these, those having 1 to 3 carbon atoms are preferred, and methyl and ethyl groups are more preferred.
• the proportion of alkyl groups having 1 to 6 carbon atoms in the total number of R 2 is preferably 80% or more, more preferably 90% or more, and even more preferably 100%.
• a is a number that satisfies 0 ⁇ a ⁇ 1, it is preferably 0 ⁇ a ⁇ 1, more preferably 0.5 ⁇ a ⁇ 1, from the viewpoint of the hardness of the resulting cured film.
• b is a number that satisfies 0 ⁇ b ⁇ 1, but from the viewpoint of the scratch resistance of the resulting cured film, 0.1 ⁇ b ⁇ 0.8 is preferable, and 0.2 ⁇ b ⁇ 0.6 is more preferable. preferable.
• c is a number that satisfies 0 ⁇ c ⁇ 0.5, but from the viewpoint of the curability of the composition and the hardness of the resulting cured film, 0 ⁇ c ⁇ 0.4 is preferable, and 0.1 ⁇ c ⁇ 0 .3 is more preferred.
• d is a number that satisfies 0 ⁇ d ⁇ 1, but from the viewpoint of the curability of the composition and the hardness of the resulting cured film, 0 ⁇ d ⁇ 0.4 is preferred, and 0 is more preferred.
• e is a number that satisfies 0 ⁇ e ⁇ 4, but from the viewpoint of being effective in suppressing the condensation reaction by the condensable functional group and the crack resistance, water resistance and weather resistance of the resulting cured film, 0 ⁇ e ⁇ 3 is preferable, and a number that satisfies 0 ⁇ e ⁇ 1 is more preferable.
• a+b+c+d 1
• a+b is a number that satisfies 0.5 ⁇ (a+b) ⁇ 1, preferably 0.7 ⁇ (a+b) ⁇ 1.
• Component (C) can be produced according to a general method for producing organopolysiloxane, and can be obtained, for example, by hydrolytically condensing a silane compound having a hydrolyzable group.
• the silane compound having a hydrolyzable group is particularly limited as long as it is a silane compound containing 1 to 4 chloro or alkoxy groups, which are hydrolyzable groups, on the silicon atom and having an organic substituent that satisfies the above conditions.
• tetrachlorosilane tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and methyltributoxysilane.
• methoxysilane and ethoxysilane are preferred in terms of operability, ease of distilling off by-products, and availability of raw materials.
• the said silane compound may be used individually by 1 type, or may be used in combination of 2 or more type.
• a hydrolysis catalyst may be used in carrying out the hydrolysis.
• a conventionally known catalyst can be used, and the aqueous solution thereof preferably exhibits an acidity of pH 1 to 7, particularly acidic hydrogen halide, sulfonic acid, carboxylic acid, acidic or weakly acidic inorganic Solid acids such as salts and ion exchange resins are preferred.
• acidic catalysts include hydrogen fluoride, hydrochloric acid, nitric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, formic acid, acetic acid, maleic acid, benzoic acid, lactic acid, phosphoric acid, sulfonic acid or carboxylic acid groups on the surface.
• a cation exchange resin having The amount of the hydrolysis catalyst to be used is not particularly limited, but considering the rapid progress of the reaction and the ease of removal of the catalyst after the reaction, it is 0.0002 per 1 mol of the hydrolyzable silane. A range of ⁇ 0.5 molar is preferred.
• the mass ratio of the hydrolyzable silane to the water required for the hydrolytic condensation reaction is not particularly limited. Considering easiness, it is preferable to use 0.1 to 10 mol of water with respect to 1 mol of hydrolyzable silane.
• the reaction temperature during hydrolytic condensation is not particularly limited, but in consideration of improving the reaction rate and preventing decomposition of the organic functional group of the hydrolyzable silane, -10 to 150°C is preferred. preferable.
• organic solvent may be used during the hydrolytic condensation.
• usable organic solvents include methanol, ethanol, propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, toluene, and xylene.
• the component (C) preferably has a non-volatile content of 85% by mass or more, more preferably 90% by mass or more, excluding solvents and the like. If the volatile matter content increases, there is a risk that voids will be generated when the composition is cured, resulting in deterioration in appearance and deterioration in mechanical properties.
• the molecular weight of component (C) is not particularly limited, it preferably has a polystyrene equivalent weight average molecular weight (Mw) of 500 to 10,000 in gel permeation chromatography.
• the kinematic viscosity of component (C) is not particularly limited, but is preferably 1 to 200 mm 2 /s, more preferably 1 to 150 mm 2 /s, and even more preferably 3 to 120 mm 2 /s.
• the kinematic viscosity is a value measured at 25° C. with a Canon Fenske viscometer according to JIS-Z-8803.
• the amount of component (C) is 5 to 100 parts by mass, preferably 8 to 60 parts by mass, based on 100 parts by mass of nonvolatile content of component (A). If the amount of component (C) is less than the above range, the obtained cured film will have insufficient weather resistance and antifouling properties. .
• the (C) component may be a single composition or a mixture of a plurality of compounds having different compositions.
• the composition of the present invention can be suitably produced by mixing a plurality of compounds having different average compositions.
• the coating composition of the present invention may contain a curing catalyst.
• the curing catalyst is not particularly limited as long as it is commonly used in organosiloxane coatings, but organometallic compounds are preferred, for example, metal alkoxide compounds such as Ti, Al, Zr, Sn, etc. Examples include metal chelate compounds and metal ester compounds, and those containing organic tin compounds are preferred.
• metal alkoxide compounds include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-s- aluminum alkoxides such as butoxide and aluminum tri-t-butoxide; -titanium alkoxides such as n-hexyl titanate, tetraisooctyl titanate, tetra-n-lauryl titanate; tetraethyl zirconate, tetra-n-propyl zirconate, tetraisopropyl zirconate, tetra-n-butyl zirconate, tetra-s -butyl zirconate, tetra-t-butyl zirconate, tetra-n-pentyl zirconate, tetra-t-pentyl zirconate, te
• metal chelate compounds include tris(ethylacetoacetate)aluminum, tris(n-propylacetoacetate)aluminum, tris(isopropylacetoacetate)aluminum, tris(n-butylacetoacetate)aluminum, isopropoxybis(ethyl acetoacetate)aluminum, tris(acetylacetonato)aluminum, tris(propionylacetonato)aluminum, diisopropoxypropionylacetonatoaluminum, acetylacetonato bis(propionylacetonato)aluminum, monoethylacetoacetate bis(acetylacetonate) Nath) aluminum, acetylacetonato aluminum di-s-butylate, methyl acetoacetate aluminum di-s-butyrate, di(methyl acetoacetate) aluminum mono-tert-butylate, diisopropoxy
• component (D) When component (D) is blended, its blending amount may be an amount sufficient to cure the composition, but it is usually 0.01 to 20 parts per 100 parts by mass of the nonvolatile content of component (A). Parts by mass are preferable, and 0.1 to 10 parts by mass are more preferable.
• the curing catalyst of component (D) may be used alone or in combination of two or more.
• the coating composition of the present invention may contain any additives as appropriate within a range that does not impair the effects of the present invention.
• additives include solvents, non-reactive silicone oils, reactive silicone oils, adhesion promoters such as silane coupling agents other than component (B), non-reactive polymer resins, fillers, leveling agents, Rheology modifier, reactive diluent, non-reactive diluent, surfactant, dispersant, antifoaming agent, dehydrating agent, anti-aging agent, antioxidant, antistatic agent, infrared absorber, ultraviolet absorber, light Stabilizers, fluorescent agents, dyes, pigments, perfumes, abrasives, rust preventives, thixotropic imparting agents and the like. These may be used individually by 1 type, respectively, or may be used in combination of 2 or more type.
• solvents examples include esters such as ethyl acetate, butyl acetate and cellosolve acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aliphatic hydrocarbons such as hexane and octane; aromatics such as benzene, toluene and xylene. group hydrocarbons, etc., and these may be used singly or in combination of two or more.
• the blending amount is preferably 1 to 50 parts by mass, more preferably 2 to 30 parts by mass, per 100 parts by mass of the total nonvolatile matter of components (A) to (C).
• pigments include coloring pigments such as titanium oxide, red iron oxide, cyanine coloring pigments, carbon black, and zircon powder; silica, barita powder, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, white carbon, and diatomaceous earth.
• coloring pigments such as titanium oxide, red iron oxide, cyanine coloring pigments, carbon black, and zircon powder
• silica barita powder, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, white carbon, and diatomaceous earth.
• Extender pigments such as talc, magnesium carbonate, alumina white, gloss white, tancal; zinc phosphate, zinc phosphorus silicate, zinc aluminum phosphate, zinc calcium phosphate, calcium phosphate, aluminum pyrophosphate, calcium pyrophosphate, aluminum dihydrogen tripolyphosphate , aluminum metaphosphate, calcium metaphosphate, zinc oxide, zinc phosphomolybdate, aluminum phosphomolybdate, zinc, zinc oxide, zinc molybdate, calcium molybdate, borate, barium metaborate, zinc calcium cyanamide, calcium silicate , calcium metasilicate; modified silica in which cations such as calcium, zinc, cobalt, lead, strontium, and barium are bound to porous silica particles; ion-exchanged silica obtained by binding cations by ion exchange; aluminum pyrophosphate; Antirust pigments such as vanadium compounds such as vanadium pentoxide, calcium vanadate, and ammonium metavanadate
• the blending amount is, from the viewpoint of the weather resistance of the coating film formed, to 100 parts by mass of the total nonvolatile content of components (A) to (C). It is preferably 5 to 100 parts by mass, more preferably 30 to 90 parts by mass.
• the coating composition of the present invention is prepared by mixing the components (A), (B), (C), and optionally (D) and optional components in any order, followed by stirring.
• Mixing conditions are not particularly limited, but mixing at 10 to 40° C. is preferable in consideration of workability and stability of the coating composition.
• the viscosity of the coating composition of the present invention is not particularly limited. is preferably 100,000 mPa ⁇ s or less, more preferably 20,000 mPa ⁇ s or less. Although the lower limit of the viscosity is not particularly limited, it is preferably 10 mPa ⁇ s or more.
• the coating composition of the present invention is applied to an object to be coated and cured to obtain a cured film and coated article.
• the method of application is not limited, and known methods such as spray coating, roller coating, brush coating, and flow coating can be employed.
• the coating composition of the present invention can be cured by heating, and the heating temperature is preferably 80 to 200° C., whereby the cured coating film formed has excellent hardness, chemical resistance, antifouling properties, and weather resistance. can demonstrate.
• Materials to be coated include glass and optionally pretreated metal materials such as steel sheets, galvanized steel sheets, stainless steel, aluminum, etc., alkaline substrates such as concrete, mortar, slate, slate roof tiles, etc., and ceramics. building materials, plastics, etc., and those on which an old coating film is formed.
• metal materials such as steel sheets, galvanized steel sheets, stainless steel, aluminum, etc.
• alkaline substrates such as concrete, mortar, slate, slate roof tiles, etc., and ceramics. building materials, plastics, etc., and those on which an old coating film is formed.
• Uses of the coating composition of the present invention are not particularly limited, but include heavy-duty anti-corrosion coatings for steel structures such as bridges, power transmission towers, plants, and tanks.
• the coating composition of the present invention is excellent in long-term weather resistance, and the composition alone protects the coated object from harsh environments and gives a cured film that maintains aesthetic appearance, but if necessary, a known undercoat and / or A layer of intermediate coating may be provided.
• undercoat paint examples include epoxy resin paint, modified epoxy resin paint, epoxy resin-based glass flake paint, epoxy resin coating material, ultra-thick film type epoxy resin paint, epoxy resin zinc-rich paint, inorganic zinc-rich paint, and chlorinated rubber.
• examples include resin-based paints, phthalic acid resin-based paints, and epoxy ester resin-based paints.
• intermediate paints include epoxy resin-based paints, polyurethane-based paints, epoxy resin MIO paints, phenolic resin-based MIO paints, and chlorinated rubber resin-based paints. paints, phthalate resin-based paints, and the like.
• the hydroxyl value is a value measured by a neutralization titration method in accordance with JIS K 0070: 1992, and the weight average molecular weight is measured using GPC (gel permeation chromatography, HLC-8220 manufactured by Tosoh Corporation). Measured by using tetrahydrofuran (THF) as a developing solvent, and the non-volatile content is measured by the residual heat method after heating and drying on an aluminum petri dish at 105 ° C. for 3 hours according to JIS K 5601-1-2: 2008.
• the kinematic viscosity is a value measured at 25° C. using a Canon Fenske viscometer.
• the compositional ratio of each siloxane unit in component (C) below was calculated from the results of 1 H-NMR and 29 Si-NMR measurements.
• A-1) Acrydic A-801P (acrylic polyol, non-volatile content 50% by mass, hydroxyl value 50 mg KOH/g, manufactured by DIC Corporation)
• A-2) Barnock D-220 (polyester polyol, non-volatile content 100% by mass, hydroxyl value 147 mg KOH/g, manufactured by DIC Corporation)
• B) KBM-9659 (tris-(trimethoxylylpropyl) isocyanurate, manufactured by Shin-Etsu Chemical Co., Ltd.)
• x Remarkably much ink remains compared to the current test piece.
• (5) Accelerated weather resistance The accelerated weather resistance test was performed using a super-accelerated weather resistance tester (eye super UV tester, manufactured by Iwasaki Electric Co., Ltd.). A polyester coated steel plate (0.8 mm ⁇ 70 mm ⁇ 60 mm) was used as a test piece. The test conditions were irradiation for 3 hours (ultraviolet irradiance 90 mW, black panel temperature 63°C, 70% RH), darkness for 4 hours (black panel temperature 63°C, 70% RH), condensation for 3 hours (black panel temperature 30°C, 90% RH) for 10 hours was defined as one cycle, and 30 cycles were tested.
• the cured films obtained in Examples 2-1 to 2-7 were found to be excellent in chemical resistance, hardness, antifouling property and weather resistance.
• the cured film of Comparative Example 2-1 using the composition in which the amount of component (B) was insufficient the chemical resistance, antifouling property and weather resistance were insufficient.
• the coating film of Comparative Example 2-3 using the excessively blended composition resulted in inferior hardness.
• the coating film of Comparative Example 2-2 using the composition in which the amount of the component (C) was insufficient the chemical resistance, hardness, antifouling property and weather resistance were insufficient, and the component (C) was insufficient.
• the coating films of Comparative Examples 2-4 using compositions containing an excessive amount of the coating film surface was uneven, resulting in poor chemical resistance and weather resistance.

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