WO2011027640A1 - Composition de revêtement transparente - Google Patents

Composition de revêtement transparente Download PDF

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Publication number
WO2011027640A1
WO2011027640A1 PCT/JP2010/063078 JP2010063078W WO2011027640A1 WO 2011027640 A1 WO2011027640 A1 WO 2011027640A1 JP 2010063078 W JP2010063078 W JP 2010063078W WO 2011027640 A1 WO2011027640 A1 WO 2011027640A1
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Prior art keywords
hydroxyl group
coating composition
clear coating
coating
coating film
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PCT/JP2010/063078
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English (en)
Japanese (ja)
Inventor
薮内尚哉
山下博文
三輪安紀
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日本ビー・ケミカル株式会社
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Application filed by 日本ビー・ケミカル株式会社 filed Critical 日本ビー・ケミカル株式会社
Priority to JP2010546159A priority Critical patent/JP4673938B1/ja
Publication of WO2011027640A1 publication Critical patent/WO2011027640A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • 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
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a clear coating composition.
  • a urethane crosslinking system using a hydroxyl group-containing resin such as an acrylic resin as a base resin and a polyisocyanate compound as a crosslinking agent is widely used.
  • a hydroxyl group-containing resin such as an acrylic resin as a base resin
  • a polyisocyanate compound as a crosslinking agent
  • Patent Document 1 describes a coating composition in which a polycarbonate diol is used in combination with a polyol compound and a polyisocyanate compound as a clear coating composition for improving scratch resistance.
  • the polycarbonate diol has a problem that the physical properties of the coating film are liable to deteriorate because the compatibility with other resin components, particularly acrylic polyol, is not good. Further, when a large amount of polycarbonate diol is blended, the crosslink density is lowered, and physical properties such as weather resistance and solvent resistance become insufficient.
  • Patent Document 2 describes a polyurethane resin coating agent using acrylate polyol and acrylic polyol in combination.
  • the coating agent described in the cited document 2 is a coating agent containing a urethanized resin. For this reason, sufficient crosslinking density cannot be obtained, and it cannot be used as a paint for automobiles.
  • Patent Document 3 a coating composition using a polycarbonate diol and a polyisocyanate compound in combination is described.
  • a coating composition is a soft-feel coating and cannot obtain performances such as acid resistance, solvent resistance, and weather resistance that are used in automobile coating.
  • Patent Document 4 discloses a coating composition containing a polycarbonate diol-modified polymer and a polyisocyanate compound.
  • a coating composition containing a polycarbonate diol-modified polymer and a polyisocyanate compound.
  • such a coating composition has a complicated composition and therefore requires a large amount of labor in synthesis, which causes an increase in cost.
  • the present invention has better scratch recovery than conventional coating compositions, and also has the same performance as conventional coating compositions in terms of finished appearance, weather resistance, and water resistance. It aims at providing the coating composition which has.
  • the present invention comprises a polycarbonate diol compound (A), a hydroxyl group-containing acrylic resin (B), a polycaprolactone polyol (C) having 3 to 5 branches and a hydroxyl group equivalent of 170 to 1600, and a curing agent (D).
  • the clear coating composition comprises a polycarbonate diol compound (A), a hydroxyl group-containing acrylic resin (B), a polycaprolactone polyol (C) having 3 to 5 branches and a hydroxyl group equivalent of 170 to 1600, and a curing agent (D).
  • the polycarbonate diol compound (A) preferably has a hydroxyl group equivalent of 320 to 2000.
  • the hydroxyl group-containing acrylic resin (B) preferably has a hydroxyl group equivalent of 200 to 600 and the number of hydroxyl groups in one molecule of 4.0 to 30.
  • the hydroxyl group-containing acrylic resin (B) preferably has a glass transition temperature of ⁇ 20 to 60 ° C.
  • the blending ratio ((A) / (B) + (C)) of the polycarbonate diol compound (A), the hydroxyl group-containing acrylic resin (B) and the polycaprolactone polyol (C) is 90/10 to 10/90. Is preferred.
  • the clear coating composition of the present invention can provide a coating film having excellent scratch recovery properties and having a finished appearance, water resistance, weather resistance and the like that can be sufficiently used as an automotive coating.
  • the present invention uses a polycarbonate-based diol compound (A), a hydroxyl group-containing acrylic resin (B), and a polycaprolactone polyol (C) in combination to provide a coating film having excellent finished appearance, water resistance, weather resistance, stain resistance, and the like. It has both physical properties and scratch resistance recovery. That is, the problem of deterioration in compatibility that occurs when the polycarbonate diol compound (A) and the hydroxyl group-containing acrylic resin (B) are used in combination is solved by using the polycaprolactone polyol (C) having specific properties in combination. .
  • the polycaprolactone polyol (C) used in the present invention is a resin having affinity for both the polycarbonate diol compound (A) and the hydroxyl group-containing acrylic resin (B), the compatibility thereof is increased. Has an effect.
  • By improving the compatibility of each component in the paint by such a method it is possible to sufficiently exhibit performance such as scratch recovery, finished appearance, water resistance, and weather resistance, and a coating film with excellent performance can be obtained. Obtainable.
  • the polycaprolactone polyol (C) has 3 to 5 branches, the crosslinking density can be increased. Thus, even when the polycarbonate diol compound (A) which is a diol component is used, the crosslinking density does not decrease. For this reason, performance, such as water resistance and a weather resistance, can be improved. Furthermore, by using a polycaprolactone polyol (C) having a hydroxyl group equivalent in the range of 170 to 1600, the balance between the hydrophilization and the hydrophobization degree is achieved, whereby the polycarbonate diol compound (A) and the hydroxyl group-containing acrylic resin (B )) And a particularly uniform effect can be obtained by forming a more uniform coating film.
  • the polycarbonate diol compound (A) is a component for imparting scratch recovery properties. Furthermore, by using together with the hydroxyl group-containing acrylic resin (B), both a network structure having a high crosslink density and a low molecular weight between crosslinks and a large network structure can be formed in the cured coating film. At the same time, excellent physical properties as a coating film can be obtained. Furthermore, since the polycarbonate diol compound (A) is a polycarbonate diol compound (A) having excellent hydrolysis resistance, it has excellent performance in water resistance and weather resistance.
  • the polycarbonate diol compound (A) is represented by the following general formula (1);
  • the structure of R is determined by the diol component used in the production of the polycarbonate diol.
  • the diol component include divalent alcohols having 2 to 10 carbon atoms, preferably 4 to 8 carbon atoms.
  • Aliphatic systems such as 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like; aromatic systems such as p-xylenediol and p-tetrachloroxylenediol; Examples thereof include diols such as diethylene glycol and dipropylene glycol. These diols can be used alone or in combination of two or more.
  • the polycarbonate diol can be obtained by reacting the diol with a carbonylating agent such as phosgene.
  • R in the general formula (1) is preferably a linear alkyl group.
  • the polycarbonate diol compound (A) in which R is a linear alkyl group has the following general formula (2):
  • 1,6-hexanediol as an essential diol component in combination of two or more diol components, a combination of 1,6-hexanediol and 1,5-pentanediol, -A polycarbonate diol obtained by polycondensation of a diol component and a carbonylating agent such as a combination of hexanediol and 1,4-butanediol or a combination of 1,6-hexanediol and 1,4-dimethylolcyclohexane. Can do.
  • 1,6-hexanediol / 1,5-pentanediol 80/20 to 20/80 (molar ratio)
  • 1 type, or 2 or more types such as a normally used alkylene carbonate, dialkyl carbonate, diallyl carbonate, and phosgene, can be used, for example.
  • a normally used alkylene carbonate dialkyl carbonate, diallyl carbonate, and phosgene
  • preferred are ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and diphenyl carbonate.
  • the polycarbonate diol compound (A) preferably has a hydroxyl group equivalent of 320 to 2000. If the hydroxyl equivalent is less than 320, the crosslink density becomes too high, and there is a possibility that the scratch recovery property is deteriorated. When the hydroxyl equivalent exceeds 2000, the stain resistance and water resistance may be deteriorated.
  • the hydroxyl equivalent is more preferably 350 to 1000.
  • a commercial item can be used as said polycarbonate diol.
  • Commercially available products include, for example, T-5650J, T-5651, T-5651 (diol components: 1,6-hexanediol and 1,5-pentanediol) and T-4671 (diol component: 1) manufactured by Asahi Kasei Chemicals Corporation. , 6-hexanediol and 1,4-butanediol); ETERNACOLL UM-90 (1/1, 1/3) manufactured by Ube Industries, Ltd. (diol components: 1,6-hexanediol and 1,4-dimethylolcyclohexane) And the like.
  • the hydroxyl group-containing acrylic resin (B) used in the present invention is a component that imparts water resistance, weather resistance and the like.
  • the hydroxyl group-containing acrylic resin (B) is not particularly limited as long as it is a polymer in which a structural unit derived from the acrylic monomer (a) having a hydroxyl group is essential. (B), single monomers such as acrylic monomers (c) having ester groups copolymerizable with the acrylic monomers (a) and (b), and other vinyl monomers (d)
  • the copolymer may further include a structural unit derived from the body, and the type of the structural unit constituting the polymer is not particularly limited.
  • acrylic monomer (a) having a hydroxyl group examples include 1-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic.
  • examples include 4-hydroxybutyl acid, 2-hydroxyethyl (meth) acrylate, and ⁇ -caprolactone adducts thereof. Only one kind may be used, or two or more kinds may be used in combination as required. . Among them, it is preferable to use 1-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, or 3-hydroxypropyl (meth) acrylate that does not contain alkyl having 4 or more carbon atoms in the molecule. .
  • a site having a small network structure is formed. This is preferable from the viewpoint of forming a portion having a large network structure and a portion having a small network structure, and forming a coating film having a plurality of performances as described above.
  • acrylic monomer (b) having a carboxyl group examples include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and anhydrides thereof. You may use 2 or more types together only with a seed
  • acrylic monomer (c) having an ester group examples include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and t-butyl (meth) acrylate.
  • N-amyl (meth) acrylate N-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (Meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meta Acrylate, dicyclopentenyl can be mentioned oxyethyl (meth) acrylate, alone, or may be used in combination of two or more as necessary.
  • Examples of other vinyl monomers (d) include acrylamide monomers such as acrylamide, methacrylamide, N-methylol acrylamide, N, N-dimethylacrylamide, diacetone acrylamide, and the like. You may use 2 or more types together only with a seed
  • the hydroxyl group-containing acrylic resin can be obtained by appropriately selecting a monomer from the acrylic monomers (a) to (c) and the vinyl monomer (d) and polymerizing them.
  • the hydroxyl equivalent of the hydroxyl group-containing acrylic resin (B) is not particularly limited, but is preferably 200 to 600, and more preferably 300 to 500. If the hydroxyl equivalent is less than 200, the crosslink density becomes too high, and there is a possibility that the scratch recovery property is deteriorated. Moreover, when 600 is exceeded, stain resistance and water resistance may deteriorate.
  • the hydroxyl group-containing acrylic resin (B) preferably has 4.0 to 30 hydroxyl groups in one molecule. If the number of hydroxyl groups is less than 4.0, there is a possibility that the coating film strength is lowered, and if it exceeds 30, there is a possibility that the scratch recovery property is lowered.
  • the glass transition temperature of the hydroxyl group-containing acrylic resin (B) is not particularly limited, but is preferably ⁇ 20 to 60 ° C., more preferably 0 ° C. to 40 ° C. If it is lower than ⁇ 20 ° C., the stain resistance may be deteriorated, and if it exceeds 60 ° C., scratch recovery may be deteriorated.
  • the number average molecular weight of the hydroxyl group-containing acrylic resin (B) is not particularly limited, but is preferably 1000 to 20000, and more preferably 1500 to 10,000. If it is less than 1000, the resulting clear coating composition may have a large variation in hue. If it exceeds 20000, the finished appearance may be poor and the film thickness may be reduced.
  • the SP value (solubility parameter) of the hydroxyl group-containing acrylic resin (B) is not particularly limited, but is preferably 10.0 to 11.5, and more preferably 10.3 to 11.0. . If it is less than 10.0, peeling may occur at the interface with the base coating film. If it exceeds 11.5, familiarity may occur at the interface with the base coating film, and the coating film appearance may deteriorate.
  • the polycaprolactone polyol (C) used in the present invention has the following general formula (3):
  • R in the general formula (3) represents a branched alkyl group.
  • the polycaprolactone polyol (C) has 3 to 5 branches.
  • the number of branches refers to the number of terminal groups present in the molecule, and is indicated as p in the general formula (3).
  • the number of branches of the polycaprolactone polyol (C) is less than 3, the weather resistance tends to decrease and the stain resistance tends to deteriorate.
  • the number of branches of the polycaprolactone polyol (C) exceeds 5
  • the force becomes insufficient, the dent produced by the impact cannot be returned to the original coating film surface state, and the scratch resistance may be lowered.
  • the polycaprolactone polyol (C) is preferably obtained by reacting caprolactone with a compound having 3 to 5 hydroxyl groups in one molecule.
  • examples of the compound having 3 to 5 hydroxyl groups in one molecule include trimethylolpropane, pentaerythritol, ditrimethylolpropane, trimethylolethane, and glycerin.
  • the polycaprolactone polyol (C) preferably has a hydroxyl equivalent weight of 170 to 1600.
  • the hydroxyl group equivalent is outside the range of 170 to 1600, the compatibility of the polycarbonate diol compound (A) and the hydroxyl group-containing acrylic resin (B) is insufficient and the coating film performance is deteriorated.
  • the hydroxyl group equivalent is 200 to 1500. It is more preferable that
  • polycaprolactone polyols can also be used.
  • examples of commercially available polycaprolactone polyol include Plaxel 305 (3 branches, hydroxyl group equivalent 183), Plaxel 308 (3 branches, hydroxyl group equivalent 283), Plaxel 312 (3 branches, hydroxyl group equivalent 417) manufactured by Daicel Chemical Industries, Ltd. be able to.
  • the mixing ratio of the polycarbonate-based diol compound (A), the hydroxyl group-containing acrylic resin (B) and the polycaprolactone polyol (C) ((A) / ((B) + (C))) Is preferably 90/10 to 10/90, more preferably 80/20 to 20/80 in terms of solid content mass ratio. If it exceeds 90/10, the water resistance and stain resistance may deteriorate. If it is less than 10/90, the scratch recovery property may not be sufficient.
  • the clear coating composition of the present invention further contains a curing agent (D).
  • the clear coating composition may be a two-pack type or a one-pack type, and in the case of a two-pack type, the polycarbonate diol compound (A), the hydroxyl group-containing acrylic resin (B), and the polycaprolactone polyol. It can be set as the coating composition which consists of a main ingredient containing (C) and a hardening
  • the curing agent (D) acts on the hydroxyl group contained in the polycarbonate diol compound (A), the hydroxyl group-containing acrylic resin (B) and the polycaprolactone polyol (C).
  • examples of the curing agent (D) include polyisocyanate.
  • the polyisocyanate is not particularly limited as long as it is a compound having two or more isocyanate groups in one molecule. For example, aliphatic, alicyclic, aromatic and aromatic-aliphatic Any of these may be used.
  • polyisocyanates include aromatic diisocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), p-phenylene diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate (HDI), 2,2,4- C3-C12 aliphatic diisocyanates such as trimethylhexane diisocyanate and lysine diisocyanate; 1,4-cyclohexane diisocyanate (CDI), isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI) Methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, and 1,3-diisocyanatomethyl cyclohexyl Carbon such as xane (hydrogenated
  • Aliphatic diisocyanates having a number of 5 to 18 aliphatic diisocyanates having aromatic rings such as xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI); modified products of these diisocyanates (urethanized products, carbodiimides, Uretdione, uretoimine, burette and / or isocyanurate modified product); and the like. These may be used alone or in combination of two or more.
  • XDI xylylene diisocyanate
  • TXDI tetramethylxylylene diisocyanate
  • modified products of these diisocyanates urethanized products, carbodiimides, Uretdione, uretoimine, burette and / or isocyanurate modified product
  • examples of the curing agent (D) include a blocked isocyanate compound and a melamine resin.
  • said blocked isocyanate compound the block polyisocyanate which blocked the isocyanate group of polyisocyanate can be mentioned.
  • the polyisocyanate those described above can be used.
  • the blocking agent is added to a polyisocyanate group and is stable at ordinary temperature, but can regenerate a free isocyanate group when heated to a temperature higher than the dissociation temperature.
  • the blocking agent those usually used such as ⁇ -caprolactam and butyl cellosolve can be used. However, among these, many volatile blocking agents are regulated as targets of HAPs, and it is preferable that the amount used is minimized.
  • Adducts or prepolymers obtained by reacting polyisocyanates with polyhydric alcohols such as ethylene glycol, propylene glycol, trimethylolpropane and hexanetriol at an NCO / OH ratio of 2 or more may also be used as the block isocyanate curing agent.
  • the curing agent (D) When polyisocyanate or a block isocyanate compound is used as the curing agent (D), the total number of hydroxyl groups contained in the polycarbonate diol compound (A), the hydroxyl group-containing acrylic resin (B) and the polycaprolactone polyol (C) is 1
  • the curing agent is preferably blended so that the isocyanate group is in the range of 0.6 to 1.8. If the blending ratio is less than the lower limit, sufficient curing tends not to be obtained. If the blending ratio exceeds the upper limit, unreacted isocyanate groups react with moisture in the air, and the scratch resistance of the coating film tends to deteriorate.
  • the melamine resin examples include alkyl etherified melamines such as methyl etherified melamine, ethyl etherified melamine, and butyl etherified melamine, and only one kind or two or more kinds may be used in combination. Also good.
  • the content of the melamine resin is preferably 10 to 40% by mass with respect to the resin solid content of the clear coating composition. If the upper limit is exceeded, the coating film may be hard and brittle, and if it is less than the lower limit, the curability of the coating film may be reduced.
  • the content of the melamine resin is more preferably 20 to 30% by mass.
  • the clear coating composition may have an organotin compound curing catalyst.
  • the organotin compound curing catalyst is not particularly limited, and examples thereof include dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin dioctate.
  • the blending amount of the curing catalyst is preferably a lower limit of 0.005% by mass and an upper limit of 0.05% by mass with respect to the resin solid content in the clear coating composition.
  • an ultraviolet absorber In the clear coating composition of the present invention, an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant, a crosslinked resin particle, a surface conditioner, an antifoaming agent, a film-forming aid and the like may be blended.
  • the crosslinked resin particles it is preferable that the lower limit is 0.01% by mass and the upper limit is 10% by mass with respect to the resin solid content of the clear coating composition of the present invention.
  • the lower limit is more preferably 0.1% by mass, and the upper limit is more preferably 5% by mass.
  • the added amount of the crosslinked resin particles exceeds 10% by mass, the appearance of the obtained coating film tends to deteriorate, and when it is less than 0.01% by mass, the rheology control effect tends to be not obtained.
  • the surface conditioner to be blended is not particularly limited, but it is preferable to use a silicon-based surface conditioner, and in particular, use a polyester-modified silicon-based surface conditioner. Is more preferable.
  • An acrylic copolymer surface conditioner can also be suitably used. These surface conditioners can be used alone or in combination of two or more. Such a surface conditioner is particularly preferable in terms of both the finished appearance (leveling property and repellency prevention property) and stain resistance.
  • the blending amount of the surface conditioner is preferably blended at a lower limit of 0.01% by mass and an upper limit of 10% by mass with respect to the total solid content in the paint, and further, a lower limit of 0.1% by mass and an upper limit of 5%.
  • the addition amount of the surface conditioner exceeds 10% by mass, the stain resistance of the resulting coating film tends to deteriorate, and if it is less than 0.01% by mass, rheology controllability may not be obtained.
  • the coating form of the clear coating composition of the present invention may be either an organic solvent type or an aqueous type (water-soluble, water-dispersible, emulsion).
  • organic solvents include ester organic solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and ethylene glycol monoethyl ether acetate; ether organic solvents such as methoxypropanol and ethoxypropanol; alcohol organics such as butanol, ethanol, and propyl alcohol Solvents; ketone organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic organic solvents such as toluene and xylene. These may be used alone or in combination of two or more.
  • the method for obtaining the clear coating composition is not particularly limited, and all methods well known to those skilled in the art such as kneading various formulations using a kneader, roll, etc., and dispersing using a sand grind mill, disper, etc. Can be used.
  • the clear coating composition of the present invention can be used for any substrate, for example, wood, iron, copper, aluminum, tin, zinc, alloys containing these metals, glass, cloth, plastics, foams, and molded articles.
  • it can be advantageously used for plastic and metal surfaces. That is, the clear coating composition of the present application can be suitably used for automobile parts such as automobile bodies and bumpers.
  • it is possible to simultaneously coat a plurality of objects made of different materials such as a bumper and an automobile body.
  • the base material is a steel plate
  • an undercoat coating film, an intermediate coating film and a base coating film are formed before applying the clear coating composition of the present invention.
  • a base material is a metal, what was chemically converted in advance with phosphate, chromate, etc. is especially preferable.
  • Examples of the method for forming the undercoat coating film include a method using an electrodeposition paint.
  • As the electrodeposition paint a cation type and an anion type can be used, but a cationic type electrodeposition paint composition is preferable in terms of anticorrosion.
  • the intermediate coating film is for concealing underlying defects, ensuring surface smoothness after coating with a clear coating (appearance improvement), and imparting coating film properties (impact resistance, chipping resistance, etc.).
  • an intermediate coating is used, and the intermediate coating usually contains various organic and inorganic color pigments, extender pigments, a film-forming resin, a curing agent, and the like. It is a waste.
  • Examples of the film-forming resin and curing agent used in the intermediate coating composition include film-forming resins such as acrylic resins, polyester resins, alkyd resins, and fluorine resins, and amino resins and / or block polyisocyanate compounds.
  • a curing agent such as is used. From the viewpoint of pigment dispersibility and workability, a combination of an alkyd resin and / or a polyester resin and an amino resin is preferable.
  • a gray intermediate coating material mainly containing carbon black and titanium dioxide is used. Furthermore, a so-called color intermediate coating composition in which set gray or various colored pigments are combined can also be used.
  • the curing temperature has a lower limit of 100. It is preferable that it is 0 degreeC and an upper limit is 180 degreeC. If it is less than 100 ° C, curing may not be sufficient, and if it exceeds 180 ° C, the coating film may be hard and brittle.
  • the lower limit is more preferably 120 ° C.
  • the upper limit is more preferably 160 ° C. Thereby, a cured coating film having a high degree of crosslinking can be obtained.
  • the curing time varies depending on the curing temperature, but 10 to 30 minutes at 120 to 160 ° C. is appropriate.
  • the base coating film is usually obtained from a base paint containing a color pigment, a coating film-forming resin and a curing agent, and additives as required.
  • the color pigments contained in the base paint include conventionally known color pigments such as organic azo lake pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, indigo pigments, perinone pigments, and perylene-based pigments. Examples thereof include pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments, inorganic yellow lead, yellow iron oxide, bengara, carbon black, titanium dioxide, and the like. Further, flat pigments such as aluminum powder and graphite powder may be added. Further, extender pigments such as calcium carbonate, barium sulfate, clay and talc may be contained. Furthermore, you may contain bright materials, such as an interference mica pigment and an aluminum pigment, as needed.
  • Examples of the film-forming resin and curing agent for the base coating include curing of a film-forming resin such as an acrylic resin, a polyester resin, an alkyd resin, and a fluorine resin, and an amino resin and / or a block polyisocyanate compound An agent is used.
  • a film-forming resin such as an acrylic resin, a polyester resin, an alkyd resin, and a fluorine resin
  • an amino resin and / or a block polyisocyanate compound An agent is used.
  • the total pigment concentration (PWC) in the base paint is preferably a lower limit of 3% by mass and an upper limit of 70% by mass. When it exceeds 70% by mass, the appearance of the coating film is deteriorated.
  • the lower limit is more preferably 4% by mass, and still more preferably 5% by mass.
  • the upper limit is more preferably 65% by mass, and still more preferably 60% by mass.
  • the base paint is preferably a solution type, and may be any of an organic solvent type, an aqueous type (water-soluble, water-dispersible, and emulsion) or a non-aqueous dispersion type as long as it is a solution type.
  • the base paint film is formed by applying in the same manner as the method of applying the clear paint composition described later. be able to.
  • the film thickness of the coating film when applied with the base paint varies depending on the desired application, but in many cases, 10 to 30 ⁇ m is useful. If the thickness is less than 10 ⁇ m, the substrate may not be concealed and the film may be cut. If the thickness exceeds 30 ⁇ m, the sharpness may be deteriorated, or defects such as unevenness and flow may occur during painting.
  • the dry film thickness of the base coating film is usually 10-30 ⁇ m. When the thickness is less than 10 ⁇ m, the concealability is inferior, and when it exceeds 30 ⁇ m, the economical efficiency is insufficient.
  • the coating film formed from the above base paint may be directly coated with the next clear paint composition without being dried by heat, but may be dried at a temperature of 60 ° C. to 120 ° C.
  • a temperature of 60 ° C. to 120 ° C. in particular, in the case of a water-based paint, when the drying temperature is 60 ° C. or lower, the familiarity with the clear paint may occur and the appearance of the coating film may be deteriorated. If the temperature is too high, peeling may occur between the base coating and the clear coating.
  • the drying time varies depending on the drying temperature, more preferable drying conditions are 80 ° C. to 100 ° C. and 1 minute to 5 minutes.
  • the method for applying the clear coating composition of the present invention to the substrate is not particularly limited, and examples thereof include a spray coating method and an electrostatic coating method.
  • a spray coating method and an electrostatic coating method for example, an air electrostatic spray coating machine called “react gun” or a rotary atomizing electrostatic coating machine called “micro micro bell”, “micro bell”, “metallic bell” or the like is used.
  • an air electrostatic spray coating machine called “react gun” or a rotary atomizing electrostatic coating machine called “micro micro bell”, “micro bell”, “metallic bell” or the like is used.
  • the dry film thickness of the clear coating film formed with the said clear coating composition generally a minimum of 10 micrometers and an upper limit of 70 micrometers are preferable. If the thickness is less than 10 ⁇ m, the unevenness of the base may not be concealed, and if it exceeds 70 ⁇ m, problems such as cracking and sagging may occur during coating.
  • the lower limit is more preferably 20 ⁇ m, and the upper limit is more preferably 50 ⁇ m.
  • the curing temperature for curing the coating film is preferably a lower limit of 60 ° C. and an upper limit of 180 ° C. If it is less than 60 ° C, curing may not be sufficient, and if it exceeds 180 ° C, the coating film may become brittle.
  • the lower limit is more preferably 80 ° C.
  • the curing time varies depending on the curing temperature, but it is suitably 20 to 30 minutes at 80 to 160 ° C.
  • the clear coating When the clear coating is applied on a plastic substrate, it may be applied on a substrate having a known coating such as primer coating or base coating, if necessary.
  • Synthesis Example 2 Synthesis of Compound B-2 A 1 L separable flask equipped with a temperature controller, stirring blade, reflux tube and nitrogen inlet was charged with 200 g of xylene and 150 g of butyl acetate, and the temperature was raised to 90 ° C. Kept. On the other hand, a mixed liquid of 100 g of styrene, 136 g of 2-ethylhexyl methacrylate, 160 g of hydroxyethyl methacrylate, 4 g of methacrylic acid and 16 g of azobisisobutyronitrile was added dropwise to the dropping funnel over 3 hours. After the reaction was continued for another hour, a mixed solution of 50 g of butyl acetate and 1.6 g of azobisisobutyronitrile was added dropwise over 30 minutes, and the reaction was further continued for 1 hour.
  • Synthesis Example 3 Synthesis of Compound B-3 A 1 L separable flask equipped with a temperature controller, a stirring blade, a reflux tube, and a nitrogen inlet was charged with 200 g of xylene and 150 g of propylene glycol monomethyl ether acetate, and the temperature was raised to 130 ° C. , Kept constant. On the other hand, a mixed solution of 100 g of styrene, 116 g of 2-ethylhexyl acrylate, 180 g of hydroxyethyl methacrylate, 4 g of methacrylic acid, and 30 g of azobisisobutyronitrile was put into a dropping funnel and dropped over 3 hours. After continuing the reaction for another hour, a mixed solution of 50 g of propylene glycol monomethyl ether acetate and 3.2 g of azobisisobutyronitrile was added dropwise over 30 minutes, and the reaction was continued for another hour.
  • Synthesis Example 4 Synthesis of Compound B-4 A 1 L separable flask equipped with a temperature controller, a stirring blade, a reflux tube, and a nitrogen inlet was charged with 200 g of xylene and 150 g of butyl acetate, and the temperature was raised to 110 ° C. Kept. On the other hand, a mixed solution of 240 g of cyclohexyl methacrylate, 60 g of 2-ethylhexyl methacrylate, 100 g of hydroxyethyl acrylate, and 16 g of t-butylperoxy-2-ethylhexanoate was put in a dropping funnel and dropped over 3 hours.
  • reaction was further continued for 1 hour, and then a mixed solution of 50 g of butyl acetate and 1.6 g of t-butylperoxy-2-ethylhexanoate was added dropwise over 30 minutes, and the reaction was further continued for 1 hour.
  • V H is the volume fraction of n-hexane
  • V D is the volume fraction of deionized water
  • ⁇ H is the SP value of n-hexane
  • ⁇ D is the SP value of deionized water
  • 0.5 g of the dried resin composition (solid content) was dissolved in 10 ml of acetone, n-hexane was gradually added, and the titration amount H (ml) at the cloud point was read.
  • the titration amount D (ml) at the turbidity point with deionized water added thereto is read and applied to the following formula to calculate V H , V D , ⁇ H , and ⁇ D.
  • V H H / (10 + H)
  • ⁇ D 9.75 ⁇ 10 / (10 + D) + 23.43 ⁇ D / (10 + D)
  • polycarbonate diol T-5650 (hydroxyl equivalent 400) manufactured by Asahi Kasei Chemicals Corporation was used.
  • compound A-2 polycarbonate diol T-5651 manufactured by Asahi Kasei Chemicals Corporation was used. The hydroxyl equivalent of compound A-2 is 500.
  • compound A-3 polycarbonate boat diol T4672 manufactured by Asahi Kasei Chemicals Corporation was used. The hydroxyl equivalent of compound A-3 is 1000.
  • Synthesis Example 5 Synthesis of Compound C-1 A 1 L separable flask equipped with a temperature controller, a stirring blade, a reflux tube, and a nitrogen inlet was charged with 36.8 g of trimethylolpropane, 563.2 g of ⁇ -caprolactone, and 0.2% of dibutyltin laurate. 3 g was charged and the reaction was continued at 160 ° C. for 6 hours. The number of branches of the obtained resin was 3, and the hydroxyl equivalent was 730.
  • Synthesis Examples 6 to 11 Synthesis of Compounds C-2 to 7 Reactions were carried out in the same manner as in Synthesis Example 5 using the raw materials shown in Table 2.
  • Table 2 shows the number of branches and the OH equivalent of the obtained compound.
  • Example 1 In the proportions shown in Table 3, A-1, B-1, C-1, BYK310 0.6 g manufactured by Big Chemie Japan, Tinuvin 292 1.0 g manufactured by Ciba Specialty Chemicals, and Tinuvin 384 manufactured by Ciba Specialty Chemicals 2 2.1 g and 0.01 g of dibutyltin dilaurate were mixed, and butyl acetate was added to adjust the solid content rate to 30%.
  • a clear coating composition was prepared by adding Sumidur N3300 manufactured by Sumika Bayer Urethane Co., Ltd. such that the molar ratio of hydroxyl group / isocyanate group was 1.0 / 1.2.
  • Compound A-1, Compound B-1, and Compound C-1 each show the solid content ratio.
  • Spray gun (“W-101-134G” manufactured by Anest Iwata Co., Ltd.) as a primer on polypropylene material (70 mm ⁇ 150 mm ⁇ 3 mm: JNB-117 manufactured by Topra Sangyo Co., Ltd.) as a primer )
  • a dry film thickness of 7 ⁇ m left in the coating environment for 1 minute, and then “R-303N Black” manufactured by Nippon Bee Chemical Co., Ltd. is used as the base paint using the above spray gun.
  • ⁇ Adhesion evaluation method> A single-blade cutting tool specified in JIS K5600-5-6 was vertically applied to the coating surface of the test piece, and 11 cutting lines reaching the substrate were drawn in parallel. Draw 11 parallel lines perpendicularly intersecting the parallel lines and make 100 square squares surrounded by 4 straight lines. The interval between the parallel lines was 2 mm.
  • the transparent pressure-sensitive adhesive tape specified in JIS K5600-5-6 is closely attached to the grid area so as not to contain bubbles between the coated surfaces, and the tape is applied at once in 0.5 to 1.0 seconds. It peeled off and the residual film peeling state of the grid part was evaluated visually. ⁇ : No peeling at all ⁇ : Slight peeling can be observed along the grid-like cuts ⁇ : The area of the peeling part exceeds 15% of the grid part
  • ⁇ Scratch recovery evaluation method> On the coated surface of the test piece, a 4-line brass brush made by Industry Kowa was scratched in parallel with the handle at a load of 500 g, a stroke speed of 30 cm / second, and a stroke width of 15 cm. . After the scratch, the test piece was immersed in hot water at 80 ° C. for 2 seconds, and the degree of recovery of the scratch on the coated surface was visually evaluated. ⁇ : All scratches recovered ⁇ : Unrecovered scratches were observed. Also, leave the test piece with scratches under the same conditions as above in the test environment, and visually check the degree of recovery of the scratches. Evaluated. ⁇ : All wounds recovered within 5 minutes ⁇ : All wounds recovered within 1 hour ⁇ : All wounds recovered within 24 hours ⁇ : Unrecovered scratches observed after 24 hours thing
  • ⁇ Compatibility evaluation method 50 g of a resin solution in which (A) to (C) are mixed with a predetermined composition is put into a 100 ml glass bottle and stored at 40 ° C. for 30 days. After that, the resin solution that was transparent and matched was marked with ⁇ , and that with separation or turbidity confirmed was marked with ⁇ .
  • a resin solution in which only the components (A) to (C) were mixed at the ratios shown in Tables 3 and 4 was prepared, and the compatibility of the solution was evaluated. The results are shown in Tables 3 and 4.
  • the coating film obtained by the clear coating composition of the present invention has sufficient water resistance and weather resistance and is excellent in scratch recovery.
  • the coating film obtained with the clear coating composition of the comparative example was inferior in any of these performances.
  • the clear coating composition of the present invention does not cause deterioration of substances originally required in clear coatings such as sufficient water resistance and weather resistance, and has excellent scratch recovery, so that it can be used as a top coating for automobiles. It can be used suitably.

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

Abstract

La présente invention concerne une composition de revêtement qui présente non seulement une recouvrance en rayure meilleure que celle des compositions de revêtement classiques, mais également un aspect fini, une résistance aux intempéries et une imperméabilité à l'eau qui sont équivalents à ceux des compositions de revêtement classiques. Une composition de revêtement transparente, comprenant (A) un composé de polycarbonate diol, (B) une résine acrylique contenant un ou plusieurs groupes hydroxyle, (C) un polycaprolactone polyol qui possède un nombre de branches compris entre 3 et 5 et un équivalent hydroxyle de 170 à 1600, et (D) un agent de durcissement.
PCT/JP2010/063078 2009-09-02 2010-08-03 Composition de revêtement transparente WO2011027640A1 (fr)

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Cited By (7)

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JP2014516375A (ja) * 2011-04-15 2014-07-10 エルジー・ハウシス・リミテッド ハードコーティング用組成物及びこれを用いた低温成形性及びスリップ性に優れたハードコーティング形成用シート
JP2014169434A (ja) * 2013-02-06 2014-09-18 Kansai Paint Co Ltd 塗料組成物及び複層塗膜形成方法
WO2016042143A1 (fr) * 2014-09-19 2016-03-24 Jotun A/S Composition
JP2018059072A (ja) * 2016-09-28 2018-04-12 旭化成株式会社 塗料組成物
JP6364604B1 (ja) * 2017-08-30 2018-08-01 ナトコ株式会社 塗料組成物、塗膜、塗膜を備えた物品
JP2019198822A (ja) * 2018-05-16 2019-11-21 関西ペイント株式会社 複層塗膜の形成方法
WO2021095443A1 (fr) * 2019-11-15 2021-05-20 旭化成株式会社 Composition de polycarbonate diol et composition de revêtement dans laquelle celle-ci est utilisée

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JPH09194560A (ja) * 1996-01-11 1997-07-29 Toray Ind Inc 湿気硬化性組成物
JP2004346321A (ja) * 2003-05-20 2004-12-09 Bayer Materialscience Ag バインダー組成物
JP2007031690A (ja) * 2005-06-23 2007-02-08 Nissan Motor Co Ltd 塗料組成物とこれを用いた複層塗膜形成方法および塗装物品

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JPH09194560A (ja) * 1996-01-11 1997-07-29 Toray Ind Inc 湿気硬化性組成物
JP2004346321A (ja) * 2003-05-20 2004-12-09 Bayer Materialscience Ag バインダー組成物
JP2007031690A (ja) * 2005-06-23 2007-02-08 Nissan Motor Co Ltd 塗料組成物とこれを用いた複層塗膜形成方法および塗装物品

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014516375A (ja) * 2011-04-15 2014-07-10 エルジー・ハウシス・リミテッド ハードコーティング用組成物及びこれを用いた低温成形性及びスリップ性に優れたハードコーティング形成用シート
JP2014169434A (ja) * 2013-02-06 2014-09-18 Kansai Paint Co Ltd 塗料組成物及び複層塗膜形成方法
WO2016042143A1 (fr) * 2014-09-19 2016-03-24 Jotun A/S Composition
CN107075299A (zh) * 2014-09-19 2017-08-18 佐敦集团 一种组合物
AU2015316771B2 (en) * 2014-09-19 2018-07-05 Jotun A/S Composition
JP2018059072A (ja) * 2016-09-28 2018-04-12 旭化成株式会社 塗料組成物
JP7073064B2 (ja) 2016-09-28 2022-05-23 旭化成株式会社 塗料組成物
JP6364604B1 (ja) * 2017-08-30 2018-08-01 ナトコ株式会社 塗料組成物、塗膜、塗膜を備えた物品
JP2019043990A (ja) * 2017-08-30 2019-03-22 ナトコ株式会社 塗料組成物、塗膜、塗膜を備えた物品
JP2019198822A (ja) * 2018-05-16 2019-11-21 関西ペイント株式会社 複層塗膜の形成方法
WO2021095443A1 (fr) * 2019-11-15 2021-05-20 旭化成株式会社 Composition de polycarbonate diol et composition de revêtement dans laquelle celle-ci est utilisée
CN114729178A (zh) * 2019-11-15 2022-07-08 旭化成株式会社 聚碳酸酯二醇组合物和使用其的涂料组合物

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