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
  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/52—Two layers
• • 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
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/20—Heterocyclic amines; Salts thereof
  • C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
  • C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
• • 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
  • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
• • 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
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
  • C09D143/04—Homopolymers or copolymers of monomers containing silicon
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • 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
  • 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
  • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2502/00—Acrylic polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2507/00—Polyolefins

Definitions

• the present invention relates to a multi-component curable coating composition that has good adhesion, chemical resistance, non-adhesiveness, processability to a plastic substrate and the like, and that gives an excellent coating film appearance.
• the present invention relates to a method for forming a coating film using a liquid curable coating composition and a coated body coated with the multi-component curable coating composition.
• Acrylic lacquer paints are used for the purpose of protecting plastic molded products and imparting design properties.
• 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 trouble of blending a curing agent, but the obtained coating film is inferior in chemical resistance.
• the two-component curable urethane resin paint forms a dense coating film with a cross-linking reaction with the polyisocyanate compound, and can obtain better chemical resistance and non-tackiness than the acrylic lacquer paint.
• increasing the crosslink density improves chemical resistance and non-adhesiveness, but has other problems such as inferior physical properties of other coatings such as adhesion and workability.
• As a method of improving chemical resistance and non-adhesiveness while ensuring adhesion and workability there is a method of increasing the glass transition temperature of the resin, but when the glass transition temperature is increased, the appearance of the coating film becomes inferior. It is very difficult to design a liquid curable urethane resin paint with excellent chemical resistance, non-adhesiveness, adhesion, workability and appearance.
• the two-part curable acrylic silicone resin paint can provide excellent chemical resistance and non-adhesiveness, but is inferior in workability, recoatability, and coating film appearance as compared with the two-part curable urethane resin paint.
• a method has been proposed for solving the problems of conventional two-component curable acrylic silicone resin paints by blending an isocyanate compound with the two-component curable acrylic silicone resin paint (for example, Patent Documents). 1), an organometallic compound is used as a curing reaction catalyst.
• an object of the present invention is to provide a multi-component curable coating composition capable of forming a coating film having excellent chemical resistance, non-adhesiveness, adhesion, workability, and appearance at the same time.
• this invention provides the method of forming the coating film which has the outstanding chemical resistance, non-adhesiveness, adhesiveness, workability, and external appearance property simultaneously, and a coating body provided with such a coating film. Also aimed.
• the present inventor has substantially achieved urethane crosslinking and siloxane crosslinking by using a cyclic tertiary amine compound having no active hydrogen group as a curing reaction catalyst.
• the present inventors have found that it is possible to proceed at the same time, and have arrived at the present invention capable of forming a coating film having both excellent chemical resistance and non-adhesiveness, and good adhesion, workability and high appearance.
• the multi-component curable coating composition of the present invention is It consists of (1) acrylic resin paint and (2) curing agent, (1)
• the acrylic resin paint is a paint having a coating film forming component containing a vinyl copolymer (A) having a hydroxyl group, and the vinyl copolymer (A) having a hydroxyl group is further hydrolyzable. It is a paint having a silyl group, (2)
• the curing agent contains an isocyanate compound (B) and a cyclic tertiary amine compound (C) having no active hydrogen group.
• the vinyl copolymer (A) having a hydroxyl group comprises (a) 1 to 90% by weight of a hydrolyzable silyl group-containing vinyl monomer and (b) a hydroxyl group.
• a vinyl copolymer obtained by copolymerizing 1 to 50% by weight of a vinyl monomer and (c) another polymerizable vinyl monomer is preferable.
• the multi-component curable coating composition has the general formula (I): (R 1 O) 4-a -Si-R 2 a (I) (In the formula, R 1 represents a monovalent hydrocarbon group selected from the group consisting of an alkyl group, an aralkyl group of aryl and 7 to 10 carbon atoms of 6 to 10 carbon atoms having 1 to 10 carbon atoms, R 2 is A monovalent hydrocarbon group selected from the group consisting of 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, a represents 0 or 1) It is preferable to contain further the silicon compound represented by these, and / or its partial hydrolysis-condensation product.
• the cyclic tertiary amine compound (C) is preferably triethylenediamine.
• the curing agent (2) preferably further contains an acidic phosphorus compound (D).
• the acidic phosphorus compound is a group consisting of an acidic phosphate ester having at least one hydrocarbon group selected from an alkyl group having 12 or less carbon atoms, an alkylene group, and an aralkyl group, a phosphonic acid, and an acidic phosphonic acid ester. It is preferably at least one selected from
• the method for forming a coating film of the present invention is characterized by using the multi-component curable coating composition of the present invention as a coating agent.
• the coated body of the present invention is characterized in that it is coated with the multi-component curable coating composition of the present invention.
• the multi-component curable coating composition of the present invention comprises an acrylic resin coating and a curing agent, and can proceed with siloxane crosslinking and urethane crosslinking almost simultaneously, so that it has excellent chemical resistance, non-adhesiveness and excellent A coating film having excellent adhesion, workability, and appearance is imparted to a plastic molded article or the like.
• the method for forming a coating film of the present invention uses the multi-component curable coating composition of the present invention as a coating agent, it has excellent chemical resistance, non-adhesiveness and excellent adhesion, workability, and appearance.
• the coating film which has can be formed.
• the coated body of the present invention is coated with the multi-component curable coating composition of the present invention, it has excellent chemical resistance, non-adhesiveness and excellent adhesion, workability, and appearance.
• a coating is provided.
• the multi-component curable coating composition of the present invention is characterized in that the main chain is a vinyl copolymer and the vinyl copolymer (A) having a hydroxyl group in the side chain, and the vinyl copolymer having the hydroxyl group is used.
• the acrylic resin paint in which the coalescence (A) further has a hydrolyzable silyl group is used using a curing agent containing the isocyanate compound (B) and a cyclic tertiary amine compound (C) having no active hydrogen group. It can be cured.
• vinyl copolymer (A) examples include (a) a hydrolyzable silyl group-containing vinyl monomer and (b) a hydroxyl group-containing vinyl system. It can be obtained by polymerizing monomers and (c) other polymerizable vinyl monomers.
• hydrolyzable silyl group-containing vinyl monomer (a) for example, an organosilicon compound represented by the following general formula (II), which has an alkoxy group and a reactive double bond Is mentioned.
• R 1 R 2 (3-a) Si (OR 3 ) a (II) (Wherein R 1 is a monovalent organic group having a reactive double bond, R 2 is an alkyl group having 1 to 6 carbon atoms, R 3 is an alkyl group having 1 to 4 carbon atoms, and a is an integer of 1 to 3) )
• hydrolyzable silyl group-containing vinyl monomer examples include, for example, 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, ⁇ - ( T) Acryloxypropyldimethylmethoxysilane, ⁇ - (meth) acryloxypropyldimethylethoxysilane, N-vinylbenzyl- ⁇ -aminopropyltrimethoxysilane, 2-styrylethyltrimeth
• an alkoxysilyl group-containing vinyl monomer, ⁇ - (meth) acryloxypropyltrimethoxysilane, and ⁇ - (meth) acryloxypropyltriethoxysilane are preferred from the viewpoint of stability.
• the (meth) acryloxy refers to methacryloxy and / or acryloxy.
• hydrolyzable silyl group-containing vinyl monomers may be used alone or in combination of two or more.
• the ratio of the hydrolyzable silyl group-containing vinyl monomer is 1 to 90% by weight, more preferably 3 to 70% by weight, particularly 3 to 50% by weight based on the total monomers used for copolymerization. %, More particularly 3 to 20% by weight is preferable from the viewpoint of providing sufficient curability and relaxing internal stress.
• the hydroxyl group-containing vinyl monomer (b) is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, and 2-hydroxyethyl.
• Hydroxyl group-containing vinyl monomers such as vinyl ether, N-methylol (meth) acrylamide, hydroxystyrene, etc .; Polymerization such as PlaccelFA-1, PlaccelFA-4, PlaccelFM-1, and PlaccelFM-4 (manufactured by Daicel Chemical Co., Ltd.) is possible.
• At least one of these hydroxyl group-containing vinyl monomers is used.
• the proportion of the hydroxyl group-containing vinyl monomer used is 1 to 50% by weight of the total monomers used for copolymerization. Further, it is preferably 5 to 30% by weight from the viewpoint of chemical resistance and processability, and more preferably 10 to 25% by weight from the viewpoint of adhesion to a plastic material.
• the other polymerizable vinyl monomer (c) is not particularly limited as long as it has a carbon-carbon double bond.
• methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl C1-C20 alkyl (meth) acrylates such as (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) C4-C20 cycloalkyl (meth) acrylate such as acrylate, dicyclopentanyl (meth) acrylate, etc .; C3-carbon such as allyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, etc.
• aralkyl (meth) acrylates glycidyl ( A) Epoxy group-containing vinyl monomers such as acrylate and oxycyclohexylinyl (meth) acrylate; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid, citraconic acid ⁇ , ⁇ -ethylenically unsaturated carboxylic acids such as, or salts thereof (alkali metal salts, ammonium salts, amine salts, etc.); acid anhydrides such as maleic anhydride, and straight chain having 1 to 20 carbon atoms Or a half ester with a branched alcohol or a salt thereof (alkali metal salt, ammonium salt, amine salt, etc.); styrene sulfonic acid, vinyl sulfonic acid, 2- (meth) acryloxyethyl sulfonic acid, 2- (met
• Amino group-containing vinyl monomers or salts thereof (hydrochloride, acetate, etc.); vinyl monomers having a quaternary amino group such as trimethylaminoethyl (meth) acrylate hydrochloride; (meth) acrylamide, ⁇ -(Meth) acrylamide such as ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methyl (meth) acrylamide, acryloylmorpholine, or salts thereof (hydrochloric acid) Salts, acetates, etc.); N-vinylpyrrolidone, N-vinylpyridine Nitrogen-containing vinyl monomers such as N-vinylimidazole; Phosphoric esters of hydroxyalkyl esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids; Vinyl compounds such as (meth) acrylates containing urethane
• Esters and allyl compounds Nitrile group-containing vinyl monomers such as (meth) acrylonitrile; Aromatic hydrocarbon vinyl monomers such as styrene, ⁇ -methylstyrene, chlorostyrene, 4-hydroxystyrene, vinyltoluene; Vinyl Methyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene , And the like other vinyl monomers such as butadiene. These may be used alone or in combination of two or more.
• the vinyl copolymer (A) having a hydroxyl group can be obtained as a liquid composition containing a solvent by copolymerizing the monomers (a) to (c).
• the solvent to be used is not particularly limited, and for example, a known aromatic solvent, aliphatic hydrocarbon solvent, ether solvent, ketone solvent, ester solvent, alcohol solvent, water, or the like can be used. Of these, use of toluene, xylene, butyl acetate, and aliphatic hydrocarbon-containing solvents is preferred from the viewpoint of the solubility of the vinyl copolymer.
• the method for producing the hydroxyl group-containing vinyl copolymer (A) is not particularly limited as long as it is a method for obtaining a liquid composition containing the vinyl copolymer from the monomers (a) to (c).
• examples of the polymerization method include a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, and the like, and the solution polymerization method is preferable from the viewpoint of ease of synthesis.
• the initiator used in the copolymerization examples include known ones such as an organic peroxide type such as cumene hydroperoxide; an azo compound type such as azobis-2-methylbutyronitrile; Inorganic peroxide type compounds such as potassium sulfate; redox type initiators combining peroxides and reducing agents can be mentioned.
• an organic peroxide type such as cumene hydroperoxide
• an azo compound type such as azobis-2-methylbutyronitrile
• Inorganic peroxide type compounds such as potassium sulfate
• redox type initiators combining peroxides and reducing agents can be mentioned.
• the polymerization degree of the hydroxyl group-containing vinyl copolymer (A) is preferably 5,000 to 150,000 in terms of weight average molecular weight.
• the degree of polymerization can be adjusted by the type and amount of the radical generator, the polymerization temperature, the use of a chain transfer agent, and the like.
• the chain transfer agent for example, n-dodecyl mercaptan, t-dodecyl mercaptan, ⁇ -mercaptopropyltrimethoxysilane and the like can be preferably used.
• the weight average molecular weight is less than 5,000, an unpolymerized monomer tends to remain, which is not preferable.
• the weight average molecular weight exceeds 150,000, the resulting vinyl-based copolymer (A) having a hydroxyl group has defects such as stringing during the coating of the multi-component curable coating composition. Often occurs.
• the acrylic resin paint may further contain a silicon compound and / or a partial hydrolysis condensate thereof.
• the silicon compound and / or its partial hydrolysis condensate is not particularly limited as long as it is a compound having a hydrolyzable silyl group.
• the hardness of the coating film can be increased and the tackiness of the coating film is improved. Will be.
• organosilicate compound component examples include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra Examples thereof include t-butoxysilane and partial hydrolysis / condensation products thereof.
• methyl silicate 51, methyl silicate 56 (manufactured by Mitsubishi Chemical Corporation), and ethyl silicate 40 are particularly preferred because of the excellent appearance of the resulting coating film.
• the said organosilicate compound component may be used individually by 1 type, and may use 2 or more types together.
• organosilicate compound component organosilicates containing different alkoxysilyl groups in the same molecule can also be used.
• organosilicate include, for example, methyl ethyl silicate, methyl propyl silicate, methyl butyl silicate, ethyl propyl silicate, propyl butyl silicate and the like.
• the ratio of the substituents in the same molecule can be arbitrarily changed between 0% and less than 100%.
• partial hydrolysis / condensation products of these silicates can be used.
• the degree of condensation of the partial hydrolysis / condensation product is preferably about 1 to 20. A more preferable range of the degree of condensation is 3-15.
• the amount of the organosilicate compound component used is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight, with respect to 100 parts by weight of the vinyl copolymer (A) having the hydroxyl group. Is more preferable.
• the amount of the organosilicate compound component used is less than 5 parts by weight, the expected tack-free property is often not obtained.
• the amount exceeds 100 parts by weight the coating film becomes too hard and cracks are formed, or the appearance is sufficient. This is because there is a case that cannot be obtained.
• the acrylic resin paint may further contain a dehydrating agent. Since the hydrolyzable silyl group and the vinyl copolymer (A) having a hydroxyl group and the above-mentioned organosilicate compound component have reactivity with moisture, the storage stability of the composition can be further improved by adding a dehydrating agent. Can be improved.
• Examples of the dehydrating agent include alkyl orthoformate such as methyl orthoformate, ethyl orthoformate and butyl orthoformate; alkyl orthoacetate such as methyl orthoacetate, ethyl orthoacetate and butyl orthoacetate; methyl orthoborate, ethyl orthoborate, Examples thereof include orthocarboxylic acid esters such as alkyl orthoborate such as butyl orthoborate; 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) having a hydroxyl group.
• isocyanate compound (B) As said isocyanate compound (B), the compound which has 2 or more isocyanate groups in 1 molecule can be mentioned, for example, As a specific example of the isocyanate compound which has 2 or more isocyanate groups in 1 molecule, for example, tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), lysine diisocyanate, 4,4'-methylenebis (cyclohexyl) Isocyanate), aliphatic, aromatic or alicyclic diisocyanate compounds such as methylcyclohexane-2,4-diisocyanate and trimethylhexane diisocyanate; isocyanurate-modified HDI Examples of the diisocyanate compound isocyanurate bond or
• the amount of the isocyanate compound (B) used relative to the hydroxyl group-containing vinyl copolymer (A) is 0.3 to 2 equivalents of the isocyanate group relative to the hydroxyl group in the hydroxyl group-containing vinyl copolymer (A). An amount of 0.5 to 1.5 equivalents is more preferable. If the isocyanate compound (B) is too small, the resulting coating film will be poor in chemical resistance and non-tackiness, while if too large, workability such as impact resistance will be inferior, In addition, itching may occur at the time of painting.
• Cyclic tertiary amine compound having no active hydrogen group (C) contains a cyclic tertiary amine compound (C) having no active hydrogen group, and the cyclic tertiary amine compound (C ), Urethane crosslinking and siloxane crosslinking can proceed almost simultaneously.
• the cyclic tertiary amine compound (C) having no active hydrogen group is not particularly limited as long as it is a compound having a small steric hindrance around an unshared electron pair on a nitrogen atom and a high nucleophilicity.
• triethylenediamine 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1-n-propyl-2-methyl-1,4,5,6-tetrahydropyrimidine, DBU, DBA-DBU DBN, 1,3,4,6,7,8-hexahydro-1-methyl-2H-pyrimidopyrimidine and the like.
• triethylenediamine is particularly preferable.
• the curing agent (2) may further contain an acidic phosphorus compound (D).
• the acidic phosphorus compound (D) is an acidic compound containing phosphorus. Examples of such an acidic phosphorus compound include phosphoric acid, acidic phosphate ester, phosphonic acid or acidic phosphone represented by the following formula (III). Examples thereof include acid esters, acidic phosphate group-containing polymers, and condensates thereof.
• an acidic phosphorus compound (D) is used, the curing activity of siloxane crosslinking can be increased, and the non-tackiness of the formed coating film is improved.
• R 1 and R 2 represent a monovalent organic group, and Q represents an oxygen or sulfur atom.
• m and n are integers of 0 to 2, and m + n is 2 or less.
• R 1 or R 2 may be the same or different when m or n is 2.
• R 1 and R 2 are each independently selected from an alkyl group having 12 or less carbon atoms, an alkylene group, or an aralkyl group.
• Examples of such acidic phosphorus compound (D) include inorganic phosphate compounds such as phosphoric acid, metaphosphoric acid, pyrophosphoric acid; monopropyl phosphate, mono-isopropyl phosphate, monobutyl phosphate, mono- (2-ethylhexyl) phosphate , Monooctyl phosphate, monodecyl phosphate, monoisodecyl phosphate, monolauryl phosphate, mono- (methacryloxyethyl) phosphate, mono- (acryloxyethyl) phosphate, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, di-isopropyl phosphate Dibutyl phosphate, di- (2-ethylhexyl) phosphate, di- (2-ethylhexyl) dithiophosphate, dioctyl phosphate, didecyl phosphate, Acid phosphate esters such
• Phosphonic acid or acidic phosphonic acid ester reaction product of phosphoric acid or acidic phosphoric acid ester and polyvalent epoxide such as bisphenol A type epoxy resin, copolymer of mono- (methacryloxyethyl) phosphate and other vinyl monomers, etc. And an acidic phosphoric acid group-containing polymer.
• a dialkyl monophosphate compound is preferable, and di- (2-ethylhexyl) phosphate is particularly preferable.
• These acidic phosphorus compounds (D) may be used alone or in combination of two or more.
• An additive can be mix
• the additive include a plasticizer, a solvent, a dispersant, a dehydrating agent, a wetting agent, a thickening agent, an antifoaming agent, an antiseptic, an anti-settling agent, a leveling agent, an ultraviolet absorber, and a light stabilizer. It is done.
• a pigment may be added to the acrylic resin paint (1) as necessary in the multi-component curable coating composition.
• the pigment include titanium dioxide, calcium carbonate, barium carbonate, kaolin and the like.
• the multi-component curable composition of the present invention is composed of the acrylic resin paint (1) and the curing agent (2), and is usually a two-component curable composition.
• the liquid curable composition is not limited to the two-component curable composition.
• the liquid containing the isocyanate compound (B) in addition to the curing agent (2) and a cyclic structure having no active hydrogen group may be used.
• the multi-component curable coating composition of the present invention can be obtained. And a coating film can be formed by using the said multi-component curable coating composition as a coating agent. Such a method for forming a coating film is also one aspect of the present invention.
• the multi-component curable coating composition of the present invention when applying the multi-component curable coating composition of the present invention as a coating agent, for example, roll coater method, blade coater method, gravure coater method, beat coater method, curtain flow coater method, dip coating method, spray coating Any method such as a method can be used.
• coated multi-component curable coating composition is hardened.
• the curing may be performed at an arbitrary temperature from room temperature to 300 ° C., but it is preferable to perform heat curing at a temperature of 65 to 250 ° C. for 5 seconds to 60 minutes. In the case of heat curing, the heating time can be shortened as the heating temperature increases.
• the thickness of the coating film is preferably 0.5 to 50 ⁇ m. If it is too thin, the coating tends to be damaged due to physical wear, which is not preferable in terms of durability, and if it is too thick, the coating may be cracked and peeled off when the coated body is processed. It becomes easy and is not preferable.
• Examples of the object to be coated with the multi-component curable coating composition of 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, roof tile and the like.
• Examples of the organic material include plastic molded products made of organic materials such as polypropylene, polyethylene, acrylic, polycarbonate, ABS, polystyrene, PET, nylon, polyester, rubber, and elastomer, and products obtained by processing these organic materials into a film. (In addition, these may be surface-treated as necessary from the viewpoint of adhesion).
• 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.
• a coated body obtained by coating the multi-component curable coating composition of the present invention on such an object is also one aspect of the present invention.
• Examples 1 to 4 Comparative Examples 1 to 10.
• a coating solution is prepared according to the formulation shown in Tables 3 and 4, and is applied to an ABS resin molded plate and a polycarbonate molded plate so that the dry film thickness is 10 to 15 ⁇ m by an air spray coating method.
• the coating film was formed by drying for 30 minutes, and the coating film was evaluated by the following method.
• the multi-component curable coating composition of the present invention is excellent in chemical resistance and non-adhesiveness, as well as in adhesion, workability and appearance.
• Examples 1 to 4 When a tertiary amine compound having no active hydrogen group and an organometallic catalyst are used as a curing catalyst, sufficient chemical resistance and non-adhesiveness cannot be obtained (Comparative Examples 1 to 10). Further, a tertiary amine compound having an active hydrogen group reacted when mixed with an isocyanate compound, and the stability of the curing agent could not be maintained (Formulation Example 3).

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• 2012
  • 2012-03-26 WO PCT/JP2012/057789 patent/WO2012133337A1/ja active Application Filing
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  • 2012-03-26 CN CN201280015630.5A patent/CN103459528B/zh not_active Expired - Fee Related
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