CN105658747A - Coating composition and coated article - Google Patents
Coating composition and coated article Download PDFInfo
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- CN105658747A CN105658747A CN201480049628.9A CN201480049628A CN105658747A CN 105658747 A CN105658747 A CN 105658747A CN 201480049628 A CN201480049628 A CN 201480049628A CN 105658747 A CN105658747 A CN 105658747A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
- C08G18/4638—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/4661—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
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- 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
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
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- 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
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- 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
- C08G2101/00—Manufacture of cellular products
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- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
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Abstract
The purpose of the present invention is to provide: a coating composition which can form, on plastic bases, a coating film excellent in terms of scratch resistance, hardness, appearance, adhesion, and chemical resistance; and a coated article. This coating composition comprises: a main ingredient comprising a specific hydroxylated acrylic resin (A) and a specific hydroxylated polyester resin (B); and a hardener comprising a specific polyisocyanate compound (C). The coating composition gives a coating film having a glass transition temperature of 20-60 DEG C.
Description
Technical field
The present invention relates to a kind of coating composition and coated article, it can form the film relative to plastic basis material with excellent scuff resistance, hardness, outward appearance, tack and chemical-resistant.
Background technology
In recent years, in the various mechanicalss such as signal equipment, family's electrical article, automobile part, the plastic basis materials such as ABS resin, polypropylene, urethane resin, polycarbonate resin are employed. This mechanicals is required scuff resistance, hardness, outward appearance, tack, chemical-resistant etc.
In various mechanicals, the multiple coating having the overlapping coating function of the mode of the coating of the excellent scratch resistance that the coating taking the first layer as the tack excellence to base material, the second layer are base material different and the mechanicals forming multilayer film, wherein, also have and require once to be coated with in the coating process once toasting (application is once sintered) at a kind of coating of utilization to meet tack and the mechanicals of various film performance, as problem, it is desired to be once coated with and once toast comparatively difficulty. In addition, as chemical-resistant, even if particularly requiring that the such composition for external application containing UV light absorber, sanitas and emulsifying agent of the makeup such as aqueous foundation cream, sun screen, Correct, sunscreen, beauty liquid, emulsion, hand lotion is placed when being attached to coated surface in recent years also can not occur that the attachment of film is bad, outward appearance reduces and hardness reduction etc. (following, to be sometimes slightly designated as " patience for the composition containing UV light absorber etc. ").
Such as in patent documentation 1, as the coating of traumatic resistance and acid resistance excellence, disclose a kind of automotive clear coating composition, it is the clear coating composition containing hydroxy acryl acid resin and polyfunctional isocyanate compound, it is characterized in that, described hydroxy acryl acid resin is the hydroxy acryl acid resin using (methyl) vinylformic acid hydroxyalkyl ester of the hydroxyalkyl with carbonatoms 4��9 to obtain as monomer at least partially, in described polyfunctional isocyanate compound is isocyanurate type isocyanate compound at least partially, there is the specific soft chain segment portion of 25��50 quality % relative to the solid substance total amount of described hydroxy acryl acid resin and polyfunctional isocyanate compound, so that the soft chain segment portion containing internal ester monomer that is derived from is below 4.5 quality % relative to the ratio of described hydroxy acryl acid resin and the solid substance total amount of polyfunctional isocyanate compound, and the dynamic second-order transition temperature of the cured coating film obtained is that the mode of scope of 30��60 DEG C is prepared.
But, this coating is mainly suitable for metal base, once toasts the tack in coating process and insufficient relative to the patience of the composition containing UV light absorber etc. relative to being once coated with of plastic basis material.
In patent documentation 2, car scratch resistant is washed as resistance to, acid resistance, the coating having excellent weather resistance, disclose a kind of coating composition, it is for taking hydroxyl value as 80��220mgKOH/g, second-order transition temperature is more than-50 DEG C and lower than 0 DEG C, and the hydroxy-containing resin (A) of the unit being derived from (methyl) vinylformic acid 4-hydroxybutyl containing 25��55 quality %, hydroxyl value is 80��220mgKOH/g, second-order transition temperature is the hydroxy-containing resin (B) of 0��50 DEG C, and the linking agent (C) being made up of polyisocyanate compound is the coating composition of required composition, it is characterized in that, the content ratio of hydroxy-containing resin (A) and hydroxy-containing resin (B) counts 95/5��50/50 with resin solid quality ratio, and as the isocyanate group of functional group of linking agent (C) relative to the content ratio of hydroxy-containing resin (A) and total hydroxyl of hydroxy-containing resin (B) taking the molar ratio computing of NCO/OH as 0.5��1.5.
But, this coating is mainly suitable for metal base, once toasts the tack in coating process, insufficient relative to the patience of the composition containing UV light absorber etc. relative to being once coated with of plastic basis material.
In patent documentation 3, disclose a kind of self-healing coating composition, it is characterised in that, containing lactone-modified acrylic resin and polycarbonate diol. Although this coating resin composition is in the excellent scratch resistance being once coated with once in baking coating process to ABS plate, but insufficient relative to the patience of the composition containing UV light absorber etc.
In patent documentation 4, disclose a kind of coating resin composition, it is characterized in that, the such ratio of scope taking both ratios [mole number of the isocyanate group in polyisocyanate compound]/[mole number of the hydroxyl in acrylic acid series multiple alcohol (B)] as 0.75��1.5 contains polyisocyanate compound (A) and acrylic acid series multiple alcohol (B), wherein the isocyanate group equivalent of polyisocyanate compound (A) is the scope of 100��280g/eq, the average glass transition temperature (Tg) of acrylic acid series multiple alcohol (B) is more than-55 DEG C and lower than-9 DEG C, the average functional group number of the hydroxyl of every 1 molecule is 4��20, and number-average molecular weight (Mn) is the scope of 3000��15000. although this coating resin composition is once being coated with once to the traumatic resistance of ABS plate and base material excellent adhesion in baking coating process, but insufficient relative to the patience of the composition containing UV light absorber etc.
In patent documentation 5, disclose a kind of coating resin composition, it is characterized in that, the such ratio of scope taking both ratios [mole number of the isocyanate group in polyisocyanate compound]/[mole number of the hydroxyl in polyester polyol (B)] as 0.75��1.5 contains the polyisocyanate compound (A) of scope that isocyanate group equivalent is 100��280g/eq and average Tg is-50��-10 DEG C, the average functional group number of the hydroxyl of every 1 molecule is 4��20, and number-average molecular weight (Mn) is the polyester polyol (B) of scope of 1000��3000. although this coating resin composition is once being coated with once to the traumatic resistance of ABS plate and base material excellent adhesion in baking coating process, but insufficient relative to the patience of the composition containing UV light absorber etc.
In patent documentation 6, as the coating composition of the film damaging the self-repairability in short period of time disappearance that can produce in the surface formation of various base material, disclose a kind of coating composition, it contains hydroxyl value is 40��80mgKOH/g, and second-order transition temperature is the polyester polyol (A) of-40��-10 DEG C, and hydroxyl value is 35��65mgKOH/g, and second-order transition temperature is the polyester polyol (B) of 50��70 DEG C, and the trimer of aliphatic diisocyanate (C), and the use weight ratio [(A)/(B)] of (A) composition and (B) composition is 45/55��85/15, and the ratio [NCO/OH] of the mole number (NCO) of the total mole number (OH) of hydroxyl of (A) composition and (B) composition and the isocyanate group of (C) composition is 0.8��2. but, although this coating composition is in the self-repairability being once coated with once in baking coating process and excellent adhesion, but insufficient relative to the patience of the composition containing UV light absorber etc.
Patent documentation 7 discloses a kind of curable resin composition towards thermoforming film, it is characterized in that, described thermoforming film has chemical-resistant, even if such as sun-proof emulsion, at high temperature expose to the open air for a long time under the state of hand lotion attachment, acrylic resin film surface also can not be coarse, in addition, when being configured as the molding of deep-draw shape, also crackle can not be produced on film surface, and there is surface hardness, described resin combination contains and has carboxyl and hydroxyl, solid substance acid number is 15��150mgKOH/g, second-order transition temperature is vinyl polymers (A) and the polyisocyanate compound (B) of 70��140 DEG C, the content of polyisocyanate compound (B) is the content that the solid substance hydroxyl value 2��80mgKOH/g with vinyl polymers (A) reacts. but, should be insufficient in tack and the scuff resistance being once coated with once in baking coating process to ABS plate towards the curable resin composition of thermoforming film.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-176634 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-46642 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2012-97127 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2012-97173 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2012-87183 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2012-140614 publication
Patent documentation 7: Japanese Unexamined Patent Publication 2012-97248 publication
Summary of the invention
Invent problem to be solved
The present invention considers these aspects and completes, its object is to, a kind of coating composition and coated article are provided, wherein, once being coated with once in baking coating process, described coating composition can be formed to be had excellent scuff resistance, hardness, outward appearance, tack relative to plastic basis material and has the film of the patience relative to the composition containing UV light absorber etc.
For solving the technical scheme of problem
The present inventor etc. have concentrated on studies to realize above-mentioned purpose, found that, above-mentioned problem can be solved with the use of following coating composition, so that completing the present invention, described coating composition comprises the host containing specific hydroxy acryl acid resin and hydroxyl group containing polyester resin and the solidifying agent containing specific polyisocyanate compound, and the second-order transition temperature of the film wherein obtained is 20��60 DEG C.
That is, the present invention provides following coating composition and this coating composition of application and the article that obtain.
The present invention relates to following (1)��(5).
(1) a kind of coating composition, it is for comprising host and the coating composition of the solidifying agent containing polyisocyanate compound (C), described host contains hydroxy acryl acid resin (A) and hydroxyl group containing polyester resin (B), wherein
The hydroxyl value of hydroxy acryl acid resin (A) is 100��200mgKOH/g, second-order transition temperature lower than-20 DEG C,
Described hydroxy acryl acid resin (A) is taking the total amount of polymerizability unsaturated monomer (a1)��(a3) as benchmark, make the hydroxy acryl acid resin that the polymerizability unsaturated monomer (a2) of the methyl methacrylate (a1) of 15��35 quality %, the hydroxyalkyl with carbonatoms 4��9 of 5��30 quality % and other polymerizability unsaturated monomer (a3) of 35��80 quality % react and obtain
The hydroxyl value of hydroxyl group containing polyester resin (B) is 50��200mgKOH/g, number-average molecular weight is 2,000��20,000, and the hydroxyl group containing polyester resin of described hydroxyl group containing polyester resin (B) for being obtained by the reaction of polyvalent alcohol and polyprotonic acid, described polyvalent alcohol comprises the cyclic polyols compound (b1) with urea acrylate structure (�� �� �� makes)
In the group that polyisocyanate compound (C) is made up of biuret-containing Quito isocyanate compound and special allophanates containing Quito isocyanate compound for being selected from least 1,
The second-order transition temperature of the film obtained is 20��60 DEG C.
(2) coating composition according to above-mentioned (1), wherein, taking the resin solid quality in host as benchmark, containing hydroxy acryl acid resin (A) 10��80 mass parts, hydroxyl group containing polyester resin (B) 20��90 mass parts.
(3) coating composition according to above-mentioned (1) or (2), wherein, the film obtained crosslinked between molecular weight be 300��1000.
(4) a kind of coating process, wherein coating composition according to any one of application above-mentioned (1)��(3) on plastic basis material.
(5) a kind of coated article, it is obtained by the coating composition according to any one of above-mentioned (1)��(3) of application on plastic basis material.
Invention effect
Coating composition according to the present invention, can once be coated with once in baking coating process to be formed have excellent scuff resistance, hardness, outward appearance, tack relative to plastic basis material and have the film of the patience relative to the composition containing UV light absorber etc.
Embodiment
Hereinafter, the coating composition of the present invention is described in further detail.
It should be noted that, in this manual, " quality " refers to " weight ".
The coating composition of the present invention comprises host and the solidifying agent containing polyisocyanate compound (C), and host contains hydroxy acryl acid resin (A) and hydroxyl group containing polyester resin (B).
(host)
<hydroxy acryl acid resin (A)>
In the present invention, hydroxy acryl acid resin (A) refers to the acrylic resin containing hydroxyl in molecule. Hydroxy acryl acid resin (A) by utilizing ordinary method to make the methyl methacrylate as polymerizability unsaturated monomer (a1), there is the polymerizability unsaturated monomer (a2) of the hydroxyalkyl of carbonatoms 4��9 and other polymerizability unsaturated monomer (a3) copolymerization and synthesize.
As the polymerizability unsaturated monomer (a2) of the hydroxyalkyl with carbonatoms 4��9, can enumerate: (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 5-hydroxyl pentyl ester, (methyl) vinylformic acid own ester of 6-hydroxyl, (methyl) vinylformic acid 7-hydroxyl ester in heptan, (methyl) vinylformic acid pungent ester of 8-hydroxyl, (methyl) vinylformic acid 7-methyl pungent ester of-8-hydroxyl, (methyl) vinylformic acid 2-methyl pungent ester of-8-hydroxyl, (methyl) vinylformic acid 9-hydroxyl ester in the ninth of the ten Heavenly Stems etc., these can individually use or combinationally use two or more.From the viewpoint of scuff resistance, outward appearance, tack and the patience excellence relative to the composition containing UV light absorber etc., as the polymerizability unsaturated monomer (a2) of the hydroxyalkyl with carbonatoms 4��9, wherein particularly preferably (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid own ester of 6-hydroxyl.
As other polymerizability unsaturated monomer (a3), such as can enumerate: (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, polyethyleneglycol (methyl) acrylate, the polyvalent alcohols such as polypropylene glycol (methyl) acrylate and (methyl) acrylic acid monoesters compound, the compound etc. acrylic acid to 6-caprolactone and this polyvalent alcohol and (methyl) monoesters compound ring-opening polymerization become has the hydroxyl polymerizability unsaturated monomer beyond the polymerizability unsaturated monomer of the hydroxyalkyl of carbonatoms 4��9,
Methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, 2-EHA, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid n-octyl, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid Lauryl Ester, (methyl) isobornyl acrylate, (methyl) acrylic acid alkyl esters such as (methyl) vinylformic acid stearyl,
(methyl) vinylformic acid, toxilic acid, maleic anhydride etc. are containing carboxyl polymerizability unsaturated monomer;
(methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N, N-diethylamino second ester, (methyl) vinylformic acid N, (methyl) the acrylic-amino alkyl esters such as N-dimethylamino propyl ester;
Acrylamide, Methacrylamide, N, N-dimethyl aminoethyl (methyl) acrylamide, N, (methyl) acrylamide or its derivatives such as N-diethylamino ethyl (methyl) acrylamide, N, N-dimethylaminopropyl (methyl) acrylamide, N hydroxymethyl acrylamide, N hydroxymethyl acrylamide methyl ether, N hydroxymethyl acrylamide butyl ether;
2-(methacryloxypropyl base) ethyl-trimethyl salmiac, 2-(methacryloxypropyl base) ethyMmethylammonium bromide etc. are containing the monomer of quaternary ammonium salt base;
(methyl) vinylformic acid sulfo group alkyl esters such as (methyl) acrylamide-alkansulfonic acids such as 2-acrylamide-2-methyl propane sulfonic acid, (methyl) vinylformic acid 2-sulfo group second ester;
Vinyl cyanide, methacrylonitrile, vinyl-acetic ester, vinylbenzene, Vinyl toluene, alpha-methyl styrene etc. are containing aromatic nucleus polymerizability unsaturated monomer;
Many vinyl compounds such as allyl methacrylate;
��-(methyl) acryloxy propyl trimethoxy silicane, ��-(methyl) acryloxy propyl-triethoxysilicane, ��-(methyl) acryloxy propyl group methyl dimethoxysilanes etc. are containing the polymerizability unsaturated monomer etc. of hydrolyzable silyl group, and these can individually use or combinationally use two or more.
Wherein, from the viewpoint of obtain the film of scuff resistance, hardness, outward appearance, tack and the patience excellence relative to the composition containing UV light absorber etc., as other polymerizability unsaturated monomer (a3), it is preferable that containing have carbonatoms 4��9 hydroxyalkyl polymerizability unsaturated monomer beyond hydroxyl polymerizability unsaturated monomer, (methyl) acrylic acid alkyl ester.
As have carbonatoms 4��9 hydroxyalkyl polymerizability unsaturated monomer beyond hydroxyl polymerizability unsaturated monomer, it is particularly preferred to (methyl) vinylformic acid 2-hydroxy methacrylate.
As (methyl) acrylic acid alkyl ester, particularly preferably the carbonatoms of moieties is the polymerizability unsaturated monomer of 4��8, wherein, from the scuff resistance of the film obtained, hardness, outward appearance, tack and consider relative to the viewpoint such as patience of the composition containing UV light absorber etc., it is particularly preferred to (methyl) n-butyl acrylate, (methyl) 2-EHA.
In addition, in this manual, " (methyl) acrylate " refers to acrylate or methacrylic ester, and " (methyl) vinylformic acid " refers to acrylic or methacrylic acid. In addition, " (methyl) acryl " refers to acryl or methacryloyl, and " (methyl) acrylamide " refers to acrylamide or Methacrylamide.
From the scuff resistance of the film obtained, hardness, outward appearance, tack and consider relative to the viewpoint such as patience of the composition containing UV light absorber etc., the methyl methacrylate (a1) in above-mentioned monomer component, the polymerizability unsaturated monomer (a2) of hydroxyalkyl with carbonatoms 4��9 and the use ratio of other polymerizability unsaturated monomer (a3) taking the total mass of monomer component (polymerizability unsaturated monomer (a1)��(a3)) as benchmark in following scope.
Methyl methacrylate (a1): 15��35 quality %, it is preferable to 20��30 quality %, more preferably 22��27 quality %;
There is the polymerizability unsaturated monomer (a2) of the hydroxyalkyl of carbonatoms 4��9: 5��30 quality %, it is preferable to 10��25 quality %, more preferably 12��20 quality %;
Other polymerizability unsaturated monomer (a3): 35��80 quality %, it is preferable to 45��70 quality %, more preferably 43��66 quality %.
The copolymerization of above-mentioned polymerizability unsaturated monomer (a1)��(a3) is preferably based on the copolymerization of solution polymerization process, such as can enumerate: make the mixture of polymerizability unsaturated monomer and radical polymerization initiator dissolve or be scattered in organic solvent, usually stir at the temperature of about 80 DEG C��about 200 DEG C and heat the method making it be polymerized in 1��10 hour.
In the present invention, hydroxy acryl acid resin (A) for hydroxyl value be 100��200mgKOH/g, be preferably 105��170mgKOH/g, more preferably 110��150mgKOH/g and second-order transition temperature lower than-20 DEG C, preferably lower than-23 DEG C, further preferably lower than the hydroxy acryl acid resin of-25 DEG C. If the hydroxyl value of hydroxy acryl acid resin (A) is more than 100mgKOH/g, then become good relative to the patience of the composition containing UV light absorber etc., if below 200mgKOH/g, then the scuff resistance of the film obtained becomes good, therefore preferably. In addition, if second-order transition temperature exceedes-20 DEG C, then the scuff resistance of film and hardness are deteriorated sometimes.
It should be noted that, in this manual, the glass transition temperature Tg of hydroxy acryl acid resin (A) is the value calculated by following formula.
1/Tg (K)=W1/T1+W2/T2+ Wn/Tn
Tg (DEG C)=Tg (K)-273
In formula, W1, W2, Wn are the mass fraction of each monomer, and T1, T2 Tn is the glass transition temperature Tg (K) of the homopolymer of each monomer.
It should be noted that, the second-order transition temperature of the homopolymer of each monomer is based on POLYMERHANDBOOKFourthEdition, J.Brandrup, E.h.Immergut, E.A.Grulke compiles the value that (1999) obtain, the second-order transition temperature of the monomer do not recorded in the document uses following value: the mode of the homopolymer of this monomer taking weight-average molecular weight as about 50,000 synthesized, value when measuring its second-order transition temperature by differential scanning type thermal analyses.
In the present invention, from the viewpoint of scuff resistance, hardness, outward appearance, tack and the patience etc. relative to the composition containing UV light absorber etc., the weight-average molecular weight of hydroxy acryl acid resin (A) is 5,000��33,000, it is preferable to 8, the scope of 000��30,000.
In addition, in this manual, weight-average molecular weight and number-average molecular weight are the value tried to achieve in the following manner: (maintenance capacity) between the maintenance using gel permeation chromatography (GPC) to record utilizes the hold-time (maintenance capacity) of the polystyrene standard that the molecular weight recorded in identical conditions is known be scaled the molecular weight of polystyrene. Pillar uses " TSKgelG-4000H �� L ", " TSKgelG-3000H �� L ", " TSKgelG-2500H �� L ", " TSKgelG-2000H �� L " (be east Cao's (strain) company manufactures, trade(brand)name) these 4, moving phase be tetrahydrofuran (THF), measure that temperature is 40 DEG C, flow velocity be 1ml/ minute, detector carries out when being RI.
In the present invention, the content of hydroxy acryl acid resin (A) is preferably 10��80 mass parts by benchmark of the total resin solid quality in host, it is more preferable to be 55��75 mass parts. If above-mentioned scope, then from the scuff resistance of the film obtained, hardness, outward appearance, tack and consider preferably relative to the viewpoint such as patience of the composition containing UV light absorber etc.
<hydroxyl group containing polyester resin (B)>
Hydroxyl group containing polyester resin (B) generally makes polyvalent alcohol and polyprotonic acid carry out esterification under hydroxyl is excessive and obtain by the method utilizing himself known. Polyvalent alcohol is the compound in 1 molecule with more than 2 hydroxyls, and polyprotonic acid is the compound in 1 molecule with more than 2 carboxyls.
In the coating composition of the present invention, hydroxyl group containing polyester resin (B) comprises the cyclic polyols compound (b1) with urea acrylate structure as polyvalent alcohol.
As the cyclic polyols compound (b1) with urea acrylate structure, such as can enumerate: three (hydroxyethyl) isocyanuric acid ester, three (hydroxyalkyl) isocyanuric acid esters such as three (hydroxypropyl) isocyanuric acid esters and three (hydroxybutyl) isocyanuric acid ester, the 6-caprolactone modifier of this three (hydroxyalkyl) isocyanuric acid ester, make three (hydroxyethyl) isocyanuric acid ester, reaction reaction diol compound and the dicarboxylic acid hydroxyl in three (hydroxyethyl) isocyanuric acid esters and diol compound is excessive relative to the carboxyl in dicarboxylic acid and the carboxylate of three (hydroxyethyl) isocyanuric acid ester that obtains and the hydroxyl making the polyisocyanate compound with urea acrylate structure and diol compound in diol compound are excessive relative to the isocyanate group in the polyisocyanate compound with urea acrylate structure and the resultant of reaction etc. that obtains. these can be used alone or combinationally use two or more.
Wherein, from the viewpoint of the film obtained is relative to the patience of the composition containing UV light absorber etc., the preferably 6-caprolactone modifier of three (2-hydroxyethyl) isocyanuric acid esters and three (2-hydroxyethyl) isocyanuric acid ester, further preferred three (2-hydroxyethyl) isocyanuric acid ester.
As the polyvalent alcohol beyond composition (b1), such as can enumerate: ethylene glycol, propylene glycol, Diethylene Glycol, trimethylene, four ethylene glycol, triethylene glycol, dipropylene glycol, 1, 4-butyleneglycol, 1, 3-butyleneglycol, 2, 3-butyleneglycol, 1, 2-butyleneglycol, 3-methyl isophthalic acid, 2-butyleneglycol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 4-pentanediol, 2, 4-pentanediol, 2, 3-dimethyl trimethylene, tetramethylene glycol, 3-methyl-4, 3-pentanediol, 3-methyl-4, 5-pentanediol, 2, 2, 4-trimethylammonium-1, 3-pentanediol, 1, 6-hexylene glycol, 1, 5-hexylene glycol, 1, 4-hexylene glycol, 2, 5-hexylene glycol, neopentyl glycol, the dibasic alcohol such as hydroxypivalic acid DOPCP,The lactone such as 6-caprolactone are added the polylactone glycol being formed in these 2 yuan of alcohol and become; The esterdiol classes such as two (hydroxyethyl) esters of terephthalic acid; The polyether glycol classes such as the alkylene oxide adducts of dihydroxyphenyl propane, polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol; The mono-epoxy compounds such as the alpha-olefin epoxide such as propylene oxide and butylene oxide ring, �� �� �� �� E10 [glycidyl ester of the manufacture of �� �� Le chemical company, trade(brand)name, synthesis highly-branched saturated fatty acid]; The alcohol of glycerine, TriMethylolPropane(TMP), trimethylolethane, two glycerine, three glycerine, 1,2,6-hexanetriol, tetramethylolmethane, Dipentaerythritol, sorbyl alcohol, N.F,USP MANNITOL etc. more than 3 yuan; The lactone such as 6-caprolactone are added the poly-lactone polyol class being formed in these alcohol of more than 3 yuan and become; The alicyclic polyols etc. such as 1,4 cyclohexane dimethanol, Tricyclodecane Dimethanol, Hydrogenated Bisphenol A, A Hydrogenated Bisphenol A F, Hydrogenated Bisphenol A and A Hydrogenated Bisphenol A F.
From the viewpoint of the film obtained is relative to the patience of composition containing UV light absorber etc., the content ratio of the cyclic polyols compound (b1) with urea acrylate structure in above-mentioned hydroxyl group containing polyester resin (B) is taking the total amount of alcohol composition as benchmark, preferably in the scope of 1��75mol%, it is more preferable in the scope of 10��60mol%. If the content ratio with the cyclic polyols compound (b1) of urea acrylate structure is above-mentioned scope, then become good relative to the patience of the composition containing UV light absorber etc.
Polyprotonic acid such as can be enumerated: terephthalic acid, m-phthalic acid, phthalic acid, naphthalene dicarboxylic acid, 4,4 '-diphenyl dicarboxylic acid, ditan-4,4 ' aromatic series polyprotonic acid and the acid anhydrides thereof such as-dicarboxylic acid; Alicyclic dicarboxylic acid and the acid anhydrides thereof such as six hydrogen m-phthalic acids, six hydrogen terephthalic acids, hexahydrophthalic acid, tetrahydrophthalic acid; Aliphatic polybasic acids and the acid anhydrides thereof such as hexanodioic acid, sebacic acid, suberic acid, succsinic acid, pentanedioic acid, toxilic acid, chloromaleic acid, fumaric acid, dodecanedioic acid, pimelic acid, nonane diacid, methylene-succinic acid, citraconic acid, dimeracid; The lower alkyl esters such as the methyl esters of these dicarboxylic acid, second ester; The polyprotonic acid etc. of more than 3 yuan, the own alkene polyprotonic acid of trimellitic acid, trimellitic acid 1,2-anhydride, pyromellitic acid, pyromellitic dianhydride, trimesic acid, tetrahydrotoluene tricarboxylic acid, tetrachloro and acid anhydrides etc. thereof.
The importing of hydroxyl is such as by also carrying out with the polyvalent alcohol in 1 molecule with more than 3 hydroxyls.
In addition, when the reaction of above-mentioned polyprotonic acid and polyvalent alcohol, it is also possible to use monoprotic acid, oil component (also comprising this lipid acid) etc. further as required. As monoprotic acid, such as can enumerate: phenylformic acid or t-butyl perbenzoate etc., as oil component, such as can enumerating: Viscotrol C, synourin oil, Thistle oil, soybean oil, Semen Lini oil, Yatall MA, Oleum Cocois and their lipid acid etc., these can use a kind or be mixed with two or more. And then, vibrin can also carry out modification with epoxy compoundss such as butyl glycidyl base ether, alkyl phenyl glycidyl ethers, glycidyl neodecanoate as required.
In the present invention, from the scuff resistance of the film obtained, hardness, outward appearance, tack and consider relative to the viewpoint such as patience of the composition containing UV light absorber etc., the hydroxyl value of hydroxyl group containing polyester resin (B) is 50��200mgKOH/g, is preferably 50��150gKOH/g, number-average molecular weight is 2,000��20,000, it is preferably 2,000��15,000.
From the scuff resistance of the film obtained, hardness, outward appearance, tack and consider relative to the viewpoint such as patience of the composition containing UV light absorber etc., the content of hydroxyl group containing polyester resin (B) is preferably 20��90 mass parts by benchmark of the total solid in host, it is more preferable to be the scope of 25��45 mass parts.
The host of the present invention is using hydroxy acryl acid resin (A) and hydroxyl group containing polyester resin (B) as required composition, it is possible to further as required containing resinous principles such as hydroxyl urethane resin, resol, polycarbonate resin and epoxy resin.
(solidifying agent)
The solidifying agent used in the present invention contains polyisocyanate compound (C).
<polyisocyanate compound (C)>
Polyisocyanate compound (C) is containing the required composition of at least 1 conduct being selected from the group being made up of special allophanates containing Quito isocyanate compound and biuret-containing Quito isocyanate compound.
Above-mentioned special allophanates containing Quito isocyanate compound is the compound making the polyisocyanates being selected from aliphatic polyisocyante, alicyclic polyisocyanates and aromatic polyisocyanate etc. carry out allophanatization reaction and obtain by known method.
Above-mentioned biuret-containing Quito isocyanate compound is the compound making the polyisocyanates being selected from aliphatic polyisocyante, alicyclic polyisocyanates and aromatic polyisocyanate etc. carry out biuretized reaction and obtain by known method.
As above-mentioned aliphatic polyisocyante, can enumerate: vulcabond (such as trimethylene diisocyanate, 1, 2-trimethylene diisocyanate, tetramethylene diisocyanate, 1, 2-tetramethylene diisocyanate, 2, 3-tetramethylene diisocyanate, 1, 3-tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 2, 4, 4-or 2, 2, the C2-16 alkane diisocyanates such as 4-trimethyl hexamethylene diisocyanate, 2, 6-bis-isocyanatomethyl capronate etc.), polyisocyanates (such as Methionin ester triisocyanate, 1, 4, 8-tri-isocyanato-octane, 1, 6, 11-tri-isocyanato-undecane, 1, 8-bis-isocyanato--4-isocyanatomethyl octane, 1, 3, 6-tri-isocyanato-hexane, 2, 5, 7-trimethylammonium-1, the C6-20 alkane triisocyanates etc. such as 8-bis-isocyanato--5-isocyanatomethyl octane) etc.
As above-mentioned alicyclic polyisocyanates, can enumerate: vulcabond is (such as, 1, 3-pentamethylene vulcabond, 1, 4-cyclohexyl diisocyanate, 1, 3-cyclohexyl diisocyanate, 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexylisocyanate (trivial name: isophorone diisocyanate), 4, 4 '-methylene-bis (cyclohexyl isocyanate), methyl-2, 4-cyclohexyl diisocyanate, methyl-2, 6-cyclohexyl diisocyanate, 1, 3-or 1, two (isocyanatomethyl) hexanaphthenes (trivial name: hydrogenated xylylene vulcabond) of 4-or its mixture, norbornene alkyl diisocyanate etc.), polyisocyanates is (such as, 1, 3, 5-tri-isocyanatocyclohexane, 1, 3, 5-trimethylammonium isocyanatocyclohexane, 2-(3-isocyanatopropyl)-2, 5-bis-(isocyanatomethyl)-bis-ring [2.2.1] heptane, 2-(3-isocyanatopropyl)-2, 6-bis-(isocyanatomethyl)-bis-ring [2.2.1] heptane, 3-(3-isocyanatopropyl)-2, 5-bis-(isocyanatomethyl)-bis-ring [2.2.1] heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bis-ring [2.2.1] heptane, 6-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bis-ring [2.2.1] heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bis-ring [2.2.1]-heptane, the triisocyanates etc. such as 6-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bis-ring [2.2.1] heptane).
Such as, as above-mentioned aromatic polyisocyanate, it is possible to enumerate: vulcabond (1,3-or 1,4-xylylene vulcabond or its mixture, ��, �� '-two isocyanato--1,4-diethylbenzene, two (1-isocyanato--1-methylethyl) benzene (trivial name: tetramethyl-benzene dimethyl vulcabond) of 1,3-or 1,4-or its mixture, metaphenylene vulcabond, to phenylene vulcabond, 4,4 '-diphenylmethanediisocyanate, 1,5-naphthalene diisocyanate, 2,4 '-or 4,4 '-diphenylmethanediisocyanate or its mixture, 2,4-or 2,6-tolylene diisocyanate or its mixture, 4,4 '-Tolylamine vulcabond, 4,4 '-diphenyl ether vulcabond etc.), such as, the polyisocyanates (triisocyanate such as 1,3,5-tri-isocyanatomethylbenzene, triphenyl methane-4,4 ', 4 "-triisocyanate, 1,3,5-tri-isocyanato-benzene, the triisocyanates such as 2,4,6-tri-isocyanato-toluene, such as 4,4 '-ditan-2,2 ', the tetraisocyanates etc. such as 5,5 '-tetraisocyanate).
Wherein, from the viewpoint of the scuff resistance of the film obtained, hardness, outward appearance, tack and the patience etc. relative to the composition containing UV light absorber etc., can particularly preferably use biuret-containing Quito isocyanate compound or special allophanates containing Quito isocyanate compound of aliphatic polyisocyante.
In above-mentioned aliphatic polyisocyante, from the viewpoint of the scuff resistance of the film obtained, hardness, outward appearance, tack and the patience etc. relative to the composition containing UV light absorber etc., can particularly preferably use hexamethylene diisocyanate.
Polyisocyanate compound (C) can as required containing the polyisocyanate compound beyond above-mentioned special allophanates containing Quito isocyanate compound and/or biuret-containing Quito isocyanate compound.
Such as can enumerate: the aliphatic polyisocyante classes such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, lysinediisocyanate; The isocyanurate ring affixture of these aliphatic polyisocyantes, urea diketone type affixture; The alicyclic diisocyanate classes such as isophorone diisocyanate, 4,4 '-methylene-bis (cyclohexyl isocyanate), methylcyclohexane-2,4-or-2,6-vulcabond; The isocyanurate ring affixture of these alicyclic diisocyanates; Xylylene vulcabond, tetramethyl-benzene dimethyl vulcabond, tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate (MDI), 1, the aromatic diisocyanate compounds such as 5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate; The isocyanurate ring affixture of these aromatic diisocyanates; The derivative of hydrogenation MDI and hydrogenation MDI; Make the polyurethane-reinforcement affixture that the hydroxyl of the polyvalent alcohols such as ethylene glycol, propylene glycol, 1,4-butyleneglycol, dimethylol propionic acid, polyalkylene glycol, TriMethylolPropane(TMP), hexanetriol reacts with polyisocyanate compound and become with the ratio that isocyanate group is excessive; The isocyanurate ring affixture etc. of these polyurethane-reinforcement affixtures.
About the usage quantity of above-mentioned polyisocyanate compound (C), it is comparatively suitable that the mode be generally 0.5��2.0 in wherein contained isocyanate group (NCO) relative to the equivalence ratio of the NCO/OH of the hydroxyl (OH) in above-mentioned host, being preferably in the scope of 0.8��1.5 carries out selecting.
In the coating composition of the present invention, it is possible to the additive for coatings that uses in the field of the usual coating such as proper combination organic solvent, curing catalysts, pigment, pigment dispersing agent, flow agent, UV light absorber, photostabilizer, softening agent as required is also matched with in host and/or solidifying agent.
It is not particularly limited as above-mentioned organic solvent, such as, can use the common paint solvent such as hydrocarbon system, ester system, ether system, alcohol system, ketone system.
As above-mentioned curing catalysts, such as can enumerating: the organometallic compounds such as stannous octoate, two (2 ethyl hexanoic acid) dibutyl tin, two (2 ethyl hexanoic acid) dioctyl tin, oxalic acid dioctyl tin, dibutyl tin laurate, Dibutyltin oxide, dioctyl tin oxide, dibutyl tin soap, 2 ethyl hexanoic acid lead, zinc octoate, zinc naphthenate, fatty acid zinc class, cobalt naphthenate, calcium octoate, copper naphthenate, metatitanic acid four (2-ethylhexyl) ester, these can use a kind or be mixed with two or more. These can also further as required and with the known urethane cures catalyzer such as tertiary amine, phosphate cpd. When the coating composition of the present invention contains curing catalysts, the usage quantity of curing catalysts is 0.001��2 mass parts relative to resin solid substance 100 mass parts in coating composition usually, it is preferable that be suitable in the scope of 0.01��1 mass parts.
As above-mentioned pigment, such as, can enumerate: the tinting pigment such as titanium oxide, zinc white, carbon black, cadmium red, molybdenum are red, chrome yellow, chromic oxide, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, intellectual circle's series pigments, perylene pigment; The pigment extenders such as talcum, clay, kaolin, barium oxide, barium sulfate, barium carbonate, calcium carbonate, aluminum oxide are white; Aluminium powder form, mica powder, with metallic pigment etc. such as the coating mica powder of titanium oxide. These pigment can be used alone or combinationally use two or more.
When the coating composition of the present invention uses as Clear paint, when containing pigment, the use level of pigment preferably can not hinder the amount of the degree of the transparency of the film obtained, such as taking solid substance 100 mass parts in coating composition as benchmark is usually preferably in the scope of 0.1��20 mass parts, more preferably in the scope of 0.3��10 mass parts, further preferably in the scope of 0.5��5 mass parts.
In addition, when the coating composition of the present invention uses as pigmented coating, when containing pigment, the use level of pigment is taking solid substance 100 mass parts in coating composition as benchmark is usually preferably in the scope of 1��200 mass parts, more preferably in the scope of 2��100 mass parts, further preferably in the scope of 5��50 mass parts.
As above-mentioned UV light absorber, existing known UV light absorber can be used, such as, can enumerate: the UV light absorber such as benzotriazole system absorption agent, triazine system absorption agent, salicyclic acid derivatives system absorption agent, benzophenone series absorption agent. These UV light absorber can be used alone or combinationally use two or more.
When the coating composition of the present invention contains UV light absorber, the use level of UV light absorber is taking solid substance 100 mass parts in coating composition as benchmark is preferably in the scope of 0.1��10 mass parts, more preferably in the scope of 0.2��5 mass parts, further preferably in the scope of 0.3��2 mass parts.
As photostabilizer, existing known photostabilizer can be used, such as, can enumerate: hindered amine system photostabilizer.
When the coating composition of the present invention contains photostabilizer, the use level of photostabilizer is taking solid substance 100 mass parts in flatting coating composition as benchmark is preferably in the scope of 0.1��10 mass parts, more preferably in the scope of 0.2��5 mass parts, further preferably in the scope of 0.3��2 mass parts.
In the present invention, aforementioned coating composition can be coated on plastic basis material face and obtain coated article. As plastic basis material, it does not have be particularly limited to, such as, can enumerate: the polyolefin-based resins that polyethylene, polypropylene etc. are representative; The thermoplastic polyesters such as pet resin, polybutylene terephthalate (PBT) resin, polycarbonate (PC) resin, polycarbonate-polybutylene terephthalate (PC/PBT) resin; The phenylethylene resin series such as acrylonitrile styrene resin (AS), acrylonitrile-butadiene-styrene (ABS) (ABS) resin, acrylonitrile-styrene-acrylic ester (ASA) resin; The starting material face of other plexiglass, acrylic resin, vinylidene chloride, polyamide resin, polyphenylene oxide resin, polyformaldehyde resin, urethane resin, epoxy resin etc. or their hybrid resin and fibre reinforced plastics (Fiber-ReinforcedPlastics) etc. These starting material faces can be suitable for carrying out skimming treatment or surface treatment as required. And then, it is also possible to the coating composition of application the present invention after plastic basis material face forms primary coat film.
The method of the coating composition of application the present invention is not particularly limited. Such as can by air-atomizing, carry out application without gas blowout mist, rotary-atomizing coating machine, dipping coating, bristle etc.
The film utilizing the coating composition of the present invention to be formed usually usually can as 3��100 ��m to solidify film thickness gauge, it is preferable that can in the scope of 3��50 ��m.
Heating condition in the film forming method of the coating composition of the present invention is not particularly limited, by 50��100 DEG C, preferably keep carrying out for 10��90 minutes at 50��90 DEG C. About causing plastic material with heating condition during distortion because of thermal conductance, such as, preferably keep 10 minutes��90 minutes at 50 DEG C��80 DEG C when use ABS resin etc.
From the viewpoint of scuff resistance, hardness, outward appearance, tack and the patience etc. relative to the composition containing UV light absorber etc., the second-order transition temperature of the cured coating film of the film obtained by the coating composition of the present invention is 20��60 DEG C, it is preferably 30��55 DEG C, more preferably 35��50 DEG C. About above-mentioned second-order transition temperature, for using Measurement of Dynamic Viscoelasticity device, the sample using the free film (0.5cm �� 2cm) that the film of the thickness 25 ��m having carried out being heating and curing for 30 minutes at 80 DEG C is prepared into strip and obtain is as mensuration sample, when measuring tan �� value when heat-up rate 3 DEG C/min, temperature range-25��100 DEG C, frequency 11Hz, the value of tan �� shows temperature during maximum value. As Measurement of Dynamic Viscoelasticity device, it is possible to use FT �� �� �� �� Network �� �� DVE-V4 (trade(brand)name, �� �� �� �� company manufactures).
From the viewpoint of scuff resistance, hardness, outward appearance, tack and the patience etc. relative to the composition containing UV light absorber etc., between crosslinked after the solidification of the film obtained by the coating composition of the present invention, molecular weight is preferably 300��1000, it is more preferably 350��900, more preferably 400��800.Above-mentioned crosslinked between molecular weight be the calculated value that the value of the second-order transition temperature by the film recorded by above-mentioned method is substituted into the following rubber Theory of Viscoelasticity formula of Flory etc. and tries to achieve.
Molecular weight (Mc)=3 �� RT/E between crosslinkedmin
[in formula, EminRepresenting the storage elastic modulus (dyne/cm) in rubber areas, �� represents the proportion (g/cm of coated film of sample3), R is gas law constant, R=8.31 �� 107(erg/deg mol), T represents that storage elastic modulus is EminTime absolute temperature. ]
Embodiment
Hereinafter, embodiment is enumerated and the present invention is described by comparative example further specifically. But, the present invention is not limited to these embodiments. It should be noted that, " part " and " % " represents " mass parts " and " quality % " respectively. In addition, the thickness of film is based on cured coating film.
[manufacture of hydroxy acryl acid resin (A)]
Production Example 1
Load butylacetate 60 parts possessing whipping appts, thermometer, reflux exchanger, thermostatted and drip in the reaction vessel adding with pump, it is blown into nitrogen while stirring at 125 DEG C �� 3 DEG C, dripped wherein with certain speed with 3 hours and add methyl methacrylate 26 parts, vinylformic acid 4-hydroxybutyl 14 parts, n-butyl acrylate 24 parts, 2-EHA 24 parts, vinylformic acid 2-hydroxy methacrylate 12 parts and 2, the mixture that 2 '-azobis isobutyronitrile is 2.0 parts, then at same temperature slaking 1 hour. Then, then dripped in reaction vessel with 1 hour add 2,2 ' mixture of-azobis isobutyronitrile 0.5 part and butylacetate 21 parts, drip after adding end, slaking 1 hour, terminate reaction.
Hydroxy acryl acid resin (A-1) solution obtained to be solid substance be 55% uniform clear solution. In addition, the weight-average molecular weight of acrylic resin is about 21,000, hydroxyl value is 113mgKOH/g, glass transition point temperature is-29 DEG C.
Production Example 2��19
Except, in above-mentioned Production Example 1, being set to the mixture of monomer carry out the operation same with Production Example 1, obtain hydroxy acryl acid resin (A-2)��(A-19) solution that solid substance is 55% beyond the composition of the cooperation shown in table 1. The weight-average molecular weight of each hydroxy acryl acid resin obtained, hydroxyl value, second-order transition temperature are shown in table 1 in the lump.
[table 1]
[table 2]
[manufacture of hydroxyl group containing polyester resin (B)]
Production Example 20
The reaction vessel being equipped with stirrer, thermometer, rectifying tower and water separator loads hexahydrophthalic anhydride 136 parts, 1,6-HD 83 parts and three (2-hydroxyethyl) isocyanuric acid ester 78 parts, is warming up to 160 DEG C under nitrogen atmosphere.
Then, it was warming up to 220 DEG C with 3 hours, adds dimethylbenzene, distill and react under reflux except anhydrating. When becoming the acid number of expectation after cooling, then dilute with butylacetate, obtain vibrin (B-1) solution that solid substance is 50%. The number-average molecular weight of this vibrin (B-1) is 2,200, and hydroxyl value is 106mgKOH/g.
Production Example 21��28
Except in above-mentioned Production Example 20, the mixture of monomer and polymerization starter is set to beyond the composition of the cooperation shown in table 2, carry out the operation same with Production Example 20, obtain hydroxyl group containing polyester resin (B-2)��(B-9) solution that solid substance is 50%. The number-average molecular weight of each hydroxyl group containing polyester resin obtained, hydroxyl value are shown in table 2 in the lump.
[table 3]
[table 4]
[manufacture of coating composition]
Embodiment and comparative example
In the way of becoming the composition of the cooperation shown in table 3, mix and blend composition (A), composition (B) and black pigment, make each host that solid substance is about 40%.In the way of becoming the composition of the cooperation shown in table 3, in this host, add the solidifying agent of composition (C) and evenly mix. Then, adding diluting solvent in the mixture obtained, the viscosity utilizing Ford cup No.4 to measure obtained at 20 DEG C is the coating composition of 25 seconds.
In addition, table 3 represents for solid substance, (C-1) in table 3��(C-3) as follows described in.
: �� �� �� �� �� 24A-90E, (C-1) trade(brand)name, chemistry company of Asahi Chemical Industry manufactures, and take hexamethylene diisocyanate as biuret-containing Quito isocyanate compound of raw material, solid substance 90%, isocyanate group containing ratio 21.2%
(C-2) XP2580: trade(brand)name, Bayer company manufactures, and take hexamethylene diisocyanate as special allophanates containing Quito isocyanate compound of raw material, solid substance 100%, isocyanate group containing ratio 19.5%
(C-3) �� �� �� �� Le N3300: trade(brand)name, Sumitomo BayerUrethane company manufactures, the urea acid esters body of hexamethylene diisocyanate, solid substance 100%, isocyanate group containing ratio 21.8%
In addition, the black pigment recorded in table 3 coordinates after being pre-mixed with dispersion agent (" �� Le �� �� �� 37500 ", trade(brand)name, Le �֥�� company manufacture) 1 part.
[making of test coated plate]
To solidify each coating composition that thickness as above manufactures as the mode air-atomizing application of about 25 ��m on ABS plate (black, through skimming treatment), at 80 DEG C, heating makes it solidify in 30 minutes, obtains each test coated plate.
By each test coated plate of obtaining for following performance test. Table 3 will be the results are shown in.
[film performance test]
Scuff resistance: the test coated plate that setting as above obtains in the vibration shape rubs strong trier " RT-200 " (the machine-processed Zuo Suo company of trade(brand)name, great Rong chemistry essence manufactures). Attaching the sand paper of No.2000 on frictionshoe with double sticky tape, load the weight of 200g on frictionshoe, back and forth grinding 2 times, cause damage to film. Leave standstill after 24 hours at 25 DEG C, measure L15 �� of value of film, by with cause damage before the difference (�� L15 ��) of L15 �� of value of film evaluated by following benchmark.
About the mensuration of L15 �� of value, multi-angle color difference meter " MA68II " (trade(brand)name, X-rite company manufacture) is used to read the direction vertically incident (relative to damaging as vertical direction) relative to light, light angle is the L value (being referred to as L15 �� of value) in 15 degree of directions, calculates difference �� L15 �� before and after test. The situation of �� L15 �� more than 30 is defective.
Pencil hardness: implement according to JISK5600-5-4 (1999). To be contacted with coated surface by pencil-lead relative to the angle of the coated surface of each test coated plate as about 45 ��, under the degree that core can not fracture, press on coated surface energetically, while pencil is moved about 10mm to front with uniform speed. This operation change position is repeated 5 times, the vestige not applying pencil-lead is set to pencil hardness in the hardness mark of the hardest pencil of film.
Tack: utilize cutting machine to the coated surface incision line of cut of each test coated plate according to the mode arriving bed material, make the grid of 100 size 2mm �� 2mm. Then, fit at this coated surface cellulose film adhesive tape and cloth adhesive tape, after it sharply being peeled off at 20 DEG C, the number of the grid that investigation film remains, is evaluated by following benchmark.
��: when cellulose film adhesive tape is peeled off the number of the grid that film remains be 100 and when cloth adhesive tape is peeled off the number of the grid that film remains be 100
Zero: when cellulose film adhesive tape is peeled off the number of the grid that film remains be 100 and when cloth adhesive tape is peeled off the number of the grid that film remains be less than 99
��: when cellulose film adhesive tape is peeled off the number of the grid that film remains be less than 99 and when cloth adhesive tape is peeled off the number of the grid that film remains be less than 99
Relative to the patience of the composition containing UV light absorber etc.: it is 0.5g/100cm that the coated surface at each test coated plate is coated with relative to unit coating area2Makeup (GivenchyDWUVShield, trade(brand)name, ParfumsGivenchy company manufacture, SPF50PA+++), after placing 4 hours at 55 DEG C, it is cooled to room temperature, wipes the makeup on surface, evaluate appearance of film, pencil hardness and tack.
The mensuration of pencil hardness is undertaken by the method same with aforesaid method, by pencil hardness mark be the hardness mark obtained from the item of above-mentioned " pencil hardness: " decline the situation within 2 grades be set to qualified.
The evaluation of tack is undertaken by same with aforesaid method. By following benchmark, appearance of film is evaluated.
Zero: not abnormal
��: produce reduce, variable color, vestige, stripping
[table 5]
[table 6]
[table 7]
[table 8]
Explain the present invention with reference to specific enforcement mode, but it should be apparent to those skilled in the art that and can make various changes and modifications without departing from the spirit and scope of the present invention. The Japanese patent application (Japanese Patent Application 2013-186025) that the application applied for based on September 9th, 2013, its content is incorporated to the present invention as a reference.
Claims (5)
1. a coating composition, it is for comprising host and the coating composition of the solidifying agent containing polyisocyanate compound (C), and described host contains hydroxy acryl acid resin (A) and hydroxyl group containing polyester resin (B), wherein,
The hydroxyl value of hydroxy acryl acid resin (A) is 100 to 200mgKOH/g, second-order transition temperature lower than-20 DEG C,
Described hydroxy acryl acid resin (A) is taking the total amount of polymerizability unsaturated monomer (a1)��(a3) as benchmark, make the hydroxy acryl acid resin that the polymerizability unsaturated monomer (a2) of the methyl methacrylate (a1) of 15 to 35 quality %, the hydroxyalkyl with carbonatoms 4��9 of 5 to 30 quality % and other polymerizability unsaturated monomer (a3) of 35 to 80 quality % react and obtain
The hydroxyl value of hydroxyl group containing polyester resin (B) is 50 to 200mgKOH/g, number-average molecular weight is 2,000 to 20,000, and the hydroxyl group containing polyester resin of described hydroxyl group containing polyester resin (B) for being obtained by the reaction of polyvalent alcohol and polyprotonic acid, described polyvalent alcohol comprises the cyclic polyols compound (b1) with urea acrylate structure
In the group that polyisocyanate compound (C) is made up of biuret-containing Quito isocyanate compound and special allophanates containing Quito isocyanate compound for being selected from least 1,
The second-order transition temperature of the film obtained is 20 to 60 DEG C.
2. coating composition according to claim 1, wherein, taking the resin solid quality in host as benchmark, containing hydroxy acryl acid resin (A) 10 to 80 mass parts, hydroxyl group containing polyester resin (B) 20 to 90 mass parts.
3. coating composition according to claim 1 and 2, wherein, the film obtained crosslinked between molecular weight be 300 to 1000.
4. a coating process, wherein application coating composition according to any one of claim 1 to 3 on plastic basis material.
5. a coated article, it is obtained by the coating composition according to any one of claim 1 to 3 of application on plastic basis material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-186025 | 2013-09-09 | ||
| JP2013186025 | 2013-09-09 | ||
| PCT/JP2014/063893 WO2015033624A1 (en) | 2013-09-09 | 2014-05-26 | Coating composition and coated article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105658747A true CN105658747A (en) | 2016-06-08 |
| CN105658747B CN105658747B (en) | 2017-09-29 |
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| CN201480049628.9A Active CN105658747B (en) | 2013-09-09 | 2014-05-26 | Coating composition and coated article |
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| Country | Link |
|---|---|
| JP (1) | JP5692481B1 (en) |
| CN (1) | CN105658747B (en) |
| WO (1) | WO2015033624A1 (en) |
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| CN107177289A (en) * | 2017-06-13 | 2017-09-19 | Ppg涂料(天津)有限公司 | One-component coating compositions and the substrate coated with it |
| CN108727955A (en) * | 2017-04-20 | 2018-11-02 | 关西涂料株式会社 | The water-borne primer coating composition and coating process of multicomponent type |
| CN109836989A (en) * | 2017-11-29 | 2019-06-04 | 关西涂料株式会社 | Aqueous double-formulation is once coated with coating composition |
| CN109971292A (en) * | 2019-04-11 | 2019-07-05 | 益帆涂料(无锡)有限公司 | A kind of scratch-resistant can laser carving automobile interior decoration coating and its spraying method |
| CN110872467A (en) * | 2018-09-03 | 2020-03-10 | 富士施乐株式会社 | Surface-protective resin member, laminated resin member, and liquid set |
| CN112424301A (en) * | 2018-07-02 | 2021-02-26 | 阿克佐诺贝尔国际涂料股份有限公司 | Two-component solvent-borne coating composition, method of coating a substrate, coated substrate and use of the coating composition for improving erosion resistance |
| CN112500808A (en) * | 2020-12-02 | 2021-03-16 | 合肥乐凯科技产业有限公司 | Antibacterial paint surface protective film |
| CN114787226A (en) * | 2019-09-17 | 2022-07-22 | 株式会社大赛璐 | Composition and cured product thereof |
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| JP6917694B2 (en) * | 2016-11-04 | 2021-08-11 | サカタインクス株式会社 | Matte coating agent, matte coating layer, and laminated film |
| JP2019172811A (en) * | 2018-03-28 | 2019-10-10 | 東洋紡株式会社 | Copolymerized polyester resin and adhesive composition containing the same |
| JP7052774B2 (en) * | 2018-06-27 | 2022-04-12 | 荒川化学工業株式会社 | Thermosetting coatings, cured products and films |
| EP3950862A4 (en) | 2019-03-28 | 2023-01-04 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Coating composition and coating film |
| JP7461754B2 (en) * | 2020-02-20 | 2024-04-04 | 株式会社ダイセル | Polyisocyanate compound, polyurethane resin-forming composition using the same, and cured product thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108727955A (en) * | 2017-04-20 | 2018-11-02 | 关西涂料株式会社 | The water-borne primer coating composition and coating process of multicomponent type |
| CN107177289A (en) * | 2017-06-13 | 2017-09-19 | Ppg涂料(天津)有限公司 | One-component coating compositions and the substrate coated with it |
| CN109836989A (en) * | 2017-11-29 | 2019-06-04 | 关西涂料株式会社 | Aqueous double-formulation is once coated with coating composition |
| CN112424301A (en) * | 2018-07-02 | 2021-02-26 | 阿克佐诺贝尔国际涂料股份有限公司 | Two-component solvent-borne coating composition, method of coating a substrate, coated substrate and use of the coating composition for improving erosion resistance |
| CN110872467A (en) * | 2018-09-03 | 2020-03-10 | 富士施乐株式会社 | Surface-protective resin member, laminated resin member, and liquid set |
| CN109971292A (en) * | 2019-04-11 | 2019-07-05 | 益帆涂料(无锡)有限公司 | A kind of scratch-resistant can laser carving automobile interior decoration coating and its spraying method |
| CN114787226A (en) * | 2019-09-17 | 2022-07-22 | 株式会社大赛璐 | Composition and cured product thereof |
| CN112500808A (en) * | 2020-12-02 | 2021-03-16 | 合肥乐凯科技产业有限公司 | Antibacterial paint surface protective film |
| CN112500808B (en) * | 2020-12-02 | 2022-04-15 | 合肥乐凯科技产业有限公司 | Antibacterial paint surface protective film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2015033624A1 (en) | 2017-03-02 |
| CN105658747B (en) | 2017-09-29 |
| WO2015033624A1 (en) | 2015-03-12 |
| JP5692481B1 (en) | 2015-04-01 |
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