WO2018212317A1 - Composition de revêtement clair, et procédé de formation de film de revêtement clair - Google Patents

Composition de revêtement clair, et procédé de formation de film de revêtement clair Download PDF

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Publication number
WO2018212317A1
WO2018212317A1 PCT/JP2018/019255 JP2018019255W WO2018212317A1 WO 2018212317 A1 WO2018212317 A1 WO 2018212317A1 JP 2018019255 W JP2018019255 W JP 2018019255W WO 2018212317 A1 WO2018212317 A1 WO 2018212317A1
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group
clear coating
coating film
acrylic resin
coating composition
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PCT/JP2018/019255
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English (en)
Japanese (ja)
Inventor
祐美子 林
侑紀 井上
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日本ペイント・オートモーティブコーティングス株式会社
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Publication of WO2018212317A1 publication Critical patent/WO2018212317A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to a clear coating composition and a method for forming a clear coating film.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2012-92232.
  • Patent Document 1 discloses an aqueous two-component clear coating material comprising (a) an acrylic resin having both a carboxyl group and a hydroxyl group having a solid content hydroxyl value of 80 to 200 mg KOH / g and a solid content acid value of 10 to 50 mg KOH / g.
  • a clear paint containing (b) an amine compound, (c) a polyisocyanate compound, and (d) a hindered phenol compound is disclosed (Claim 1).
  • Such a clear coating can be suitably used for coating many objects to be coated, and a coating film excellent in coating film performance is formed.
  • the clear coating composition according to Patent Document 1 is cured at a high temperature, for example, at a temperature of 160 ° C. as described in the paragraph “0061”. There is a need for clear coating compositions that can be cured.
  • a clear coating composition containing an alkyd resin can be cured at room temperature, but the resulting clear coating film is inferior in weather resistance, and the physical properties such as hardness of the cured coating film are not suitable for a clear coating film. It is enough.
  • the two-component clear paint as shown in Patent Document 1 has a technical problem that the workability of coating is inferior because the pot life is short. Therefore, there is a need for a paint that can ensure the workability of painting for a longer time.
  • the coating film can be cured under low-temperature heating conditions, and good film hardness can be obtained even when the coating film is cured under low-temperature heating conditions. Furthermore, chemical resistance and solvent resistance are obtained.
  • clear coating compositions that can form excellent coatings. Further, there is a need for a clear coating composition having excellent coating workability.
  • the present invention solves the above-mentioned conventional problems, and its object is a clear coating composition capable of curing a coating film under low-temperature heating conditions, and the obtained coating film hardness is good Providing a clear coating composition excellent in chemical resistance, solvent resistance and weather resistance of the coating film, and a method for forming a clear coating film having a coating film containing the clear coating composition ,It is in.
  • a clear coating composition comprising an acrylic resin (A) having an oxidative polymerizable functional group having 2 to 4 double bonds, an acrylic resin (B) having a reactive double bond group, and a metal dryer (C) .
  • the acrylic resin (B) having a reactive double bond group is a non-aqueous dispersion resin.
  • the reactive double bond group is at least one selected from an acryloyl group and a methacryloyl group.
  • the oxidative polymerizable functional group is represented by the following chemical formula (I) or (II): [Wherein R 1 represents a bond, an alkylene group having 1 to 10 carbon atoms which may have a substituent, or one or more unsaturated double bonds which may have a substituent. And a hydrocarbon group having 2 to 10 carbon atoms, and R 2 is hydrogen, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or 1 or This is a hydrocarbon group having 2 to 10 carbon atoms and containing an unsaturated double bond.
  • R 1 represents a bond, an alkylene group having 1 to 10 carbon atoms which may have a substituent, or one or more unsaturated double bonds which may have a substituent.
  • R 2 is hydrogen, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or 1 or This is a hydrocarbon group having 2 to 10 carbon atoms and containing an unsaturated double bond.
  • the amount of the acrylic resin (A) is 10 to 90 parts by mass with respect to 100 parts by mass of the total resin solids of the acrylic resin (A) and the acrylic resin (B) contained in the clear coating composition.
  • the temperature for performing the bake hardening is 60 ° C. or higher and 120 ° C. or lower.
  • the clear coating composition of the present invention even when the cured coating film is formed under low-temperature heating conditions, for example, at a temperature of 120 ° C. or less, it has good coating film hardness, and also has chemical resistance. There is an advantage that a clear coating film having excellent properties, solvent resistance and weather resistance can be formed.
  • the present inventors have studied to cure a coating composition containing a melamine resin, a urethane resin, an acrylic resin or the like under a low-temperature heating condition.
  • a coating composition containing such a resin simply under low-temperature heating conditions, for example, at 120 ° C. or lower, problems such as a problem that the curing time becomes long and physical properties of the coating film are inferior are caused. Therefore, the present inventors tried to cure under low-temperature heating conditions, for example, 120 ° C.
  • the present invention includes an acrylic resin (A) having an oxidative polymerizable functional group having 2 to 4 double bonds, an acrylic resin (B) having a reactive double bond group, and a metal dryer (C). It is a clear coating composition. Even if the cured coating film is formed at a temperature of 120 ° C. or less by the clear coating composition according to the present invention, it has a good coating film hardness, and in addition, it has chemical resistance, solvent resistance and weather resistance. An excellent clear coating film can be formed. Furthermore, a coating film excellent in chemical resistance, solvent resistance and weather resistance can be provided.
  • the clear coating composition according to the present invention is a one-pack type clear coating composition, has a long pot life, and is excellent in workability and storage stability. Moreover, a smooth coating film appearance can be formed.
  • oxidation-polymerizable functional group having 2 to 4 double bonds (A)
  • oxidation polymerization functional group is a functional group bonded directly or through other binding group in the main chain of the acrylic resin, the air at room temperature It is a functional group that undergoes oxidative polymerization with oxygen therein.
  • oxidative polymerization through such oxidative polymerizable functional groups proceeds, a three-dimensional network structure can be formed.
  • the oxidation-polymerizable functional group having 2 to 4 double bonds according to the present invention can increase the number of cross-linking reaction positions, and can perform cross-linking more effectively.
  • the reaction proceeds even at room temperature, it can contribute to reduction of carbon dioxide and energy saving.
  • the oxidatively polymerizable functional group in the present invention has 2 to 4 double bonds.
  • crosslinking between the acrylic resin (A) and the acrylic resin (B) having a reactive double bond group can be promoted.
  • the acrylic resin (A) and the acrylic resin (B) are baked under low temperature heating conditions, sufficient hardness, chemical resistance, solvent resistance, weather resistance, scratch resistance, and the like are provided. A coating film can be formed.
  • the oxidatively polymerizable functional group has 2 to 4 double bonds, preferably 2 to 3 double bonds, for example, 2 double bonds.
  • the number of carbon atoms of the oxidative polymerizable functional group is, for example, 3 or more and 30 or less, and in some embodiments, 4 or more and 30 or less, for example, 5 or more and 22 or less, and in some embodiments, 8 or more and 22 or less. is there.
  • the oxidative polymerizable functional group is linear.
  • the oxidative polymerizable functional group may be a non-conjugated dienyl group or a conjugated dienyl group.
  • Examples of the oxidatively polymerizable functional group having two double bonds include propadienyl group, 1,2-butadienyl group, 1,3-butadienyl group, 1,2-pentadienyl group, 1,3-pentadienyl group, 1,4- Pentadienyl group, 2,3-pentadienyl group, 2,4-pentadienyl group, 1,2-hexadienyl group, 1,3-hexadienyl group, 1,4-hexadienyl group, 1,5-hexadienyl group, 2,3-hexadienyl group Group, 2,4-hexadienyl group, 2,5-hexadienyl group, 3,4-hexadienyl group, 3,5-hexadienyl group, 4,5-hexadienyl group, 1,2-heptadienyl group, 1,3-heptadienyl group 1,4-heptadien
  • an oxidatively polymerizable functional group having 9 or more carbon atoms such as nonadienyl group and decadienyl group may be used.
  • the oxidation polymerizable functional group having two double bonds may appropriately have a functional group that R 1 and R 2 described later may have.
  • oxidatively polymerizable functional groups having 3 double bonds butatrienyl group, 1,2,3-pentatrienyl group, 1,2,4-pentatrienyl group, 1,2,3-hexatrienyl group 1,2,4-hexatrienyl group, 1,2,5-hexatrienyl group, 2,3,4-hexatrienyl group, 2,3,5-hexatrienyl group, 1,2,3 -Heptatrienyl group, 1,2,4-heptatrienyl group, 1,2,5-heptatrienyl group, 1,2,6-heptatrienyl group, 1,3,4-heptatrienyl group, 1,3,5-heptatrienyl group, , 3,6-heptatrienyl group, 2,3,4-heptatrienyl group, 2,3,5-heptatrienyl group, 2,3,6-heptatrienyl group, 2,4,5-heptatrienyl group, 2,4,6- Heptatrienyl group, 3,4,5-hept
  • a pentatetraenyl group, a hexatetraenyl group for example, 1,2,3,4-hexatetraenyl group, 1,2,3,5-hexatetra
  • the oxidatively polymerizable functional group may be a group introduced by an unsaturated fatty acid having 2 to 4 double bonds.
  • the oxidatively polymerizable functional group has the following chemical formula (I) or (II): [Wherein R 1 represents a bond, a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a substituent or 1 or A straight-chain or branched hydrocarbon group having 2 to 10 carbon atoms containing the above unsaturated double bond, and R 2 may be a hydrogen or a substituent, a straight-chain or branched group Linear or branched hydrocarbon having 1 to 10 carbon atoms, or having one or more unsaturated double bonds which may have a substituent It is a group. ] Indicated by
  • R 1 and R 2 may have include, for example, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, alkyl ester groups, nitrile groups, hydroxyl groups, cyano groups, sulfonyl groups, carboxyl groups, and aromatic hydrocarbons.
  • the group can be mentioned.
  • R 1 and R 2 may have the same or different substituents.
  • R 1 and R 2 are linear groups. More preferably, R 1 is a linear alkylene group having 1 to 10 carbon atoms, and R 2 is a linear alkyl group having 1 to 10 carbon atoms.
  • the coating film formed from the clear coating composition of the present invention has excellent coating hardness even under low-temperature heating conditions, and is excellent in chemical resistance, solvent resistance and weather resistance.
  • oxidatively polymerizable functional group represented by the formula (I) include a 1,4-heptadienyl group, a 2,5-heptadienyl group, depending on the case where R 1 is a bond or an alkylene group. 1,4-octadienyl group, 1,4-octadienyl group, 2,5-octadienyl group, 1,4-nonadienyl group, 2,5-nonadienyl group, 1,4-decadienyl group, 2,5-decadienyl group, etc. Can be mentioned.
  • oxidatively polymerizable functional group represented by the formula (II) include a 1,3-hexadienyl group, a 2,4-hexadienyl group, depending on the case where R 1 is a bond or an alkylene group. 1,3-heptadienyl group, 2,4-heptadienyl group, 1,3-octadienyl group, 2,4-octadienyl group, 1,3-nonadienyl group, 2,4-nonadienyl group, 1,3-decadienyl group, 2 , 4-decadienyl group and the like.
  • the oxidatively polymerizable functional group may be a group introduced by an unsaturated fatty acid having 2 to 4 double bonds.
  • the method for preparing the acrylic resin (A) having an oxidative polymerizable functional group having 2 to 4 double bonds is not particularly limited. For example, it is prepared by introducing an oxidative polymerizable functional group into the acrylic resin. be able to.
  • the starting material used when the oxidative polymerizable functional group is introduced into the acrylic resin is not particularly limited as long as it is a compound that can form the above structure by introduction into the acrylic resin.
  • the structure of the acrylic resin used for the preparation of the acrylic resin (A) having an oxidative polymerizable functional group having 2 to 4 acrylic resin double bonds is not particularly limited as long as it can form a clear coating film.
  • the acrylic resin includes an alkyl ester group-containing monomer (1), a hydroxyl group-containing acrylic monomer (2), a carboxyl group-containing acrylic monomer (3), an epoxy group-containing acrylic monomer (4), and other acrylic monomers ( It can be prepared by introducing the oxidatively polymerizable functional group into a polymer obtained by polymerizing at least one monomer selected from 5).
  • the acrylic resin (A) according to the present invention is at least one selected from an acrylic monomer (2) having a hydroxyl group, an acrylic monomer (3) having a carboxyl group, and an acrylic monomer (4) having an epoxy group.
  • the above oxidatively polymerizable functional group is introduced into a copolymer obtained by polymerizing the monomer with at least one monomer selected from the monomer (1) having an alkyl ester group and the other acrylic monomer (5).
  • the total amount of the acrylic monomer (2) having a hydroxyl group, the acrylic monomer (3) having a carboxyl group, and the acrylic monomer (4) having an epoxy group is used when the acrylic resin (A) is synthesized. It is preferably used in the range of 5 to 70 parts by mass, more preferably in the range of 10 to 50 parts by mass, with respect to 100 parts by mass of the total amount of all monomers.
  • Acrylic monomer having alkyl ester group (1) may preferably contain an alkyl ester group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms.
  • Specific examples of the monomer include (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic.
  • Acrylic monomer having a hydroxyl group (2) examples include, for example, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and (meth) acrylic acid. 7-hydroxyheptyl, 8-hydroxyoctyl (meth) acrylate, 7-methyl-8-hydroxyoctyl (meth) acrylate, 2-methyl-8-hydroxyoctyl (meth) acrylate, and Examples include lactone-modified acrylic monomers obtained by reacting 1 to 5 moles of lactones such as ⁇ -caprolactone with hydroxyethyl (meth) acrylate.
  • examples include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the like.
  • acrylic monomers (2) having a hydroxyl group 4-hydroxybutyl (meth) acrylate, a reaction product of hydroxyethyl (meth) acrylate and ⁇ -caprolactone, Plaxel FM-1, FM-2, FA- A hydroxyl group-containing monomer consisting of 1 and FA-2 may be used.
  • Specific examples of commercially available products of acrylic monomers modified with caprolactone include, for example, trade names manufactured by Daicel Chemical Industries, Ltd., Plaxel FA-1, Plaxel FA-2, Plaxel FA-3 (hydroxyethyl acrylate with ⁇ -caprolactone 1 mol, 2 mol and 3 mol monomers), Plaxel FM-1, Plaxel FM-2, Plaxel FM-3 (1 mol of ⁇ -caprolactone in 1 mol of hydroxyethyl methacrylate, 2 mol, 3 mol, respectively) And a monomer manufactured by The Dow Chemical Company (USA), TONE m-100 (a monomer obtained by adding 2 moles of ⁇ -caprolactone to 1 mole of hydroxyethyl acrylate).
  • the monoester of polyether glycol and (meth) acrylic acid and the monoether of polyether glycol and hydroxyalkyl of (meth) acrylic acid are mentioned.
  • “Blemmer AP-150” manufactured by NOF Corporation may be used.
  • Monomer having a carboxyl group (3) examples include acrylic acid, methacrylic acid, acrylic acid dimer, crotonic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethylsuccinic acid, isocrotonic acid, maleic acid, fumaric acid And itaconic acid, 3-vinylsalicylic acid, 3-vinylacetylsalicylic acid, 2-acrylamido-2-methylpropanesulfonic acid, and the like.
  • acrylic acid and methacrylic acid are preferable.
  • Acrylic monomer having epoxy group (4) is not particularly limited as long as it has an epoxy group and a polymerizable unsaturated double bond in the molecule.
  • the acrylic monomer (4) having an epoxy group is not particularly limited as long as it has an epoxy group and a polymerizable unsaturated double bond in the molecule.
  • acrylic monomers (5) are other than acrylic monomers (1) having alkyl ester groups, acrylic monomers (2) having hydroxyl groups, acrylic monomers (3) having carboxyl groups, and monomers (4) having epoxy groups. And monomers copolymerizable with these acrylic monomers.
  • polymerizable amide compounds such as (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide N, N-dioctyl (meth) acrylamide, N-monobutyl (meth) acrylamide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, etc., polymerizable aromatic compounds such as styrene ⁇ -methyl styrene, vinyl ketone, t-butyl styrene, parachlorostyrene, vinyl naphthalene, etc., polymerizable nitriles such as acrylonitrile, methacrylonitrile, vinyl esters such as vinyl acetate, vinyl propionate, dienes such as , Tajien, is
  • the above monomers can be polymerized by, for example, solution polymerization using a radical polymerization catalyst by an ordinary method.
  • the acrylic resin (A) can be prepared by introducing an oxidatively polymerizable functional group having 2 to 4 double bonds into the copolymer of the monomer mixture.
  • a method for introducing an oxidatively polymerizable functional group having 2 to 4 double bonds for example, A monomer mixture containing a monomer having a carboxyl group is copolymerized, and then an epoxy group and a compound having an oxidative polymerizable functional group having 2 to 4 double bonds are reacted to have 2 to 4 double bonds.
  • Examples of the compound having an oxidatively polymerizable functional group having 2 to 4 epoxy groups and double bonds include cardanol-modified glycidyl ether.
  • a commercially available product may be used as the compound having an oxidatively polymerizable functional group having 2 to 4 epoxy groups and double bonds.
  • Examples of the compound having an oxidatively polymerizable functional group having 2 to 4 carboxyl groups and double bonds include unsaturated fatty acids having 2 to 4 double bonds.
  • Specific examples of the compound having an oxidatively polymerizable functional group having 2 to 4 carboxyl groups and double bonds include, for example, ⁇ -linolenic acid, stearidonic acid, linoleic acid, ⁇ -linolenic acid, dihomo- ⁇ -linolenic acid, Examples include arachidonic acid.
  • the above reaction can be carried out under reaction conditions usually used by those skilled in the art.
  • the hydroxyl value of the produced acrylic resin (A) is preferably 0 to 200 mgKOH / g, more preferably 1 to 200 mgKOH / g, and further preferably 20 to 150 mgKOH / g. .
  • the acid value of the acrylic resin (A) is preferably 0 to 100 mgKOH / g, for example, preferably 1 to 100 mgKOH / g, and more preferably 2 to 70 mgKOH / g.
  • the number average molecular weight (M n ) of the acrylic resin (A) is preferably in the range of 300 to 50000, more preferably 500 to 30000, for example. If it is less than the lower limit, the coating film hardness may be insufficient, and if it exceeds the upper limit, the appearance of the coating film may be deteriorated.
  • the value of the number average molecular weight in the present specification is a value obtained by converting a measured value by gel permeation chromatogram (GPC) with a polystyrene standard.
  • the iodine value of the acrylic resin (A) is, for example, 30 to 130, and preferably 80 to 120. When the iodine value of the acrylic resin (A) is within such a range, sufficient curability can be obtained, and further excellent weather resistance can be provided.
  • the glass transition temperature (Tg) of the acrylic resin (A) is, for example, ⁇ 50 to 80 ° C., preferably ⁇ 30 to 50 ° C.
  • Tg glass transition temperature
  • the acrylic resin (A) may be used alone or in combination of two or more.
  • the amount of the acrylic resin (A) is 10 to 90 parts by mass with respect to 100 parts by mass of the total resin solids of the acrylic resin (A) and the acrylic resin (B) contained in the clear coating composition. It is preferably 25 to 75 parts by mass.
  • Acrylic resin having reactive double bond group (B) The acrylic resin (B) having a reactive double bond group in the present invention can be crosslinked with the acrylic resin (A), and is applied, for example, to a clear coating film formed from the clear coating composition of the present invention. Film strength can be provided.
  • the crosslinking density can be improved without impairing the weather resistance.
  • the reactive double bond group in the acrylic resin (B) according to the present invention includes, for example, alkenes such as vinyl group and allyl group, unsaturated carboxylic acids such as acryloyl group and methacryloyl group, and aromatic groups having vinyl group such as styrene. Group hydrocarbons and the like.
  • the reactive double bond group according to the present invention can be easily initiated and cross-linked by a radical or a cation, for example, an acrylic resin (B) having a reactive double bond group and an oxidative polymerizable functional group. Since the acrylic resin (A) can be cross-linked, the coating film can be cured under low-temperature heating conditions, the resulting coating film hardness is good, and the solvent resistance, chemical resistance, and weather resistance are excellent. An excellent clear coating composition can be obtained.
  • the number average molecular weight of the acrylic resin (B) is preferably in the range of 250 to 100,000,000.
  • the acrylic resin (B) is a non-aqueous dispersion resin
  • the number average molecular weight is more preferably in the range of 3,000 to 100,000,000.
  • the number average molecular weight of such an acrylic resin (B) can be calculated by a known method.
  • the acrylic resin (B) having a reactive double bond group may be a non-aqueous dispersion resin.
  • the “non-aqueous dispersion” means a non-aqueous dispersion type resin, which is obtained by dispersing and stabilizing the resin using an organic solvent as a medium.
  • the acrylic resin (B) having a reactive double bond group has a core-shell structure. By having the core-shell structure, for example, the core portion has a crosslinked structure, and a desired hardness can be imparted to the clear coating film formed from the clear coating composition of the present invention.
  • a clear coating composition which can perform crosslinking
  • the core means a layer including the central portion of the particle, and often includes a region generated during nucleation.
  • the shell is a layer that exists adjacent to the outside of the core and covers at least a part of the core.
  • the acrylic resin (B) having a reactive double bond group according to the present invention is a non-aqueous dispersion resin having a core-shell structure.
  • the reactive double bond group can be introduced into the acrylic resin (B) by modifying the functional group of the resin contained in the shell of the acrylic resin (B) with a known material and method.
  • the non-aqueous dispersion resin having a core-shell structure is obtained by polymerizing a polymerizable monomer in a specific organic solvent in the presence of a dispersion stable resin soluble in the organic solvent.
  • a specific organic solvent for example, an organic solvent that dissolves a polymerizable monomer and does not dissolve a polymer formed from the monomer can be used.
  • NAD non-aqueous dispersion
  • the dispersion stable resin is not particularly limited as long as it is a resin that can stably synthesize a non-aqueous dispersion resin in an organic solvent.
  • an acrylic resin can be used as the dispersion stable resin.
  • the acrylic resin that can be used as the dispersion stable resin preferably has a hydroxyl value (solid content) of 0 to 300 mgKOH / g, more preferably 10 to 250 mgKOH / g, for example 20 to 180 mgKOH / g. Is more preferable.
  • the acid value (solid content) is preferably 0 to 100 mgKOH / g, and more preferably 0 to 50 mgKOH / g.
  • the number average molecular weight is preferably from 800 to 100,000, more preferably from 1,000 to 20,000.
  • the method for synthesizing the dispersion stable resin is not particularly limited, and preferred examples include a method obtained by radical polymerization in the presence of a radical polymerization initiator, a method obtained by a condensation reaction or an addition reaction, and the like.
  • the monomer used for obtaining the dispersion-stable resin can be appropriately selected according to the characteristics of the resin, but it is preferable to use a monomer having a linear alkyl group having 8 to 12 carbon atoms.
  • the monomer having a linear alkyl group having 8 to 12 carbon atoms can be used in an amount of preferably 5 to 50 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the total amount of monomers.
  • a dispersion stable resin may be prepared from a monomer used for preparing the acrylic resin (A).
  • the non-aqueous dispersion resin can be obtained by polymerizing a polymerizable monomer in a mixed solution of a dispersion stable resin and an organic solvent.
  • a radical polymerizable monomer can be used as the polymerizable monomer.
  • the organic solvent used for polymerization dissolves the dispersion-stable resin but does not dissolve resin particles obtained by polymerizing the polymerizable monomer, and can be appropriately selected from various organic solvents.
  • the polymerizable monomer used for the synthesis of the non-aqueous dispersion resin it is preferable to use a monomer having a functional group.
  • Typical examples of the polymerizable monomer having a functional group are as follows.
  • Examples of the polymerizable monomer having a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxymethyl methacrylate, allyl alcohol, and hydroxyethyl (meth) methacrylate.
  • examples include adducts with ⁇ -caprolactone.
  • examples of the polymerizable monomer having an acidic group include polymerizable monomers having a carboxyl group, a sulfonic acid group, and the like.
  • examples of those having a carboxyl group include (meth) acrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, maleic anhydride, fumaric acid and the like.
  • examples of the polymerizable monomer having a sulfonic acid group include t-butylacrylamide sulfonic acid.
  • glycidyl group-containing unsaturated monomers such as glycidyl (meth) acrylate, isocyanate group-containing unsaturated monomers such as m-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, isocyanatoethyl acrylate, etc.
  • glycidyl group-containing unsaturated monomers such as glycidyl (meth) acrylate
  • isocyanate group-containing unsaturated monomers such as m-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, isocyanatoethyl acrylate, etc.
  • polymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, T-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, methacrylic acid (Meth) acrylic acid alkyl ester such as tridecyl, addition reaction product of oil fatty acid and acrylic acid or methacrylic acid ester monomer having oxirane structure (for example, addition reaction product of stearic acid and glycidyl methacrylate), having 3 or more carbon atoms
  • a monomer used for preparing the acrylic resin (A) may be selected as a polymerizable monomer according to the composition of the acrylic resin (A).
  • the composition ratio of the dispersion-stable resin and the polymerizable monomer can be arbitrarily selected according to the purpose.
  • the dispersion-stable resin is 3 to 80 masses based on the total mass of these two components. %, Particularly 5 to 60% by weight, and the polymerizable monomer is preferably 97 to 20% by weight, particularly 95 to 40% by weight.
  • the total concentration of the dispersion stabilizing resin and the polymerizable monomer in the organic solvent is preferably 30 to 80% by mass, particularly 40 to 60% by mass, based on the total mass.
  • the polymerization reaction for obtaining the non-aqueous dispersion resin is preferably performed in the presence of a radical polymerization initiator.
  • radical polymerization initiators include azo initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide, Examples thereof include t-butyl peroctoate. These initiators are used in an amount of 0.2 to 20 parts by weight, preferably 0.5 to 10 parts by weight per 100 parts by weight of the total polymerizable monomers.
  • the polymerization reaction for obtaining a non-aqueous dispersion in an organic solvent containing a dispersion-stable resin is generally preferably performed at a temperature range of about 60 to 160 ° C. for about 1 to 15 hours.
  • the non-aqueous dispersion resin thus obtained has a hydroxyl value (solid content) of preferably 0 to 300, for example 1 to 200, and in one embodiment, 20 to 150.
  • the acid value (solid content) is 0 to 200 mg KOH / g, preferably 0 to 50 mg KOH / g, and the average particle diameter (D50) is 0.05 to 10 ⁇ m, preferably 0.1 to 2 ⁇ m.
  • the average particle diameter (D50) can be measured by a dynamic light scattering method. Specifically, it can be measured using Nanotrac particle size distribution measuring instrument UPA (manufactured by Nikkiso Co., Ltd.).
  • non-aqueous dispersion resin is in the form of particles in the clear coating composition, by using the non-aqueous dispersion resin, it is possible to obtain a low-viscosity coating composition despite its high molecular weight. .
  • acrylic resin (B) having a reactive double bond group in addition to the non-aqueous dispersion resin, for example, a (meth) acrylate compound having one or more reactive double bond groups, one or more reactions (Meth) acrylate oligomers or polymers having an ionic double bond group can be used.
  • Commercial products may be used for these. Examples of commercially available products include Aronix series manufactured by Toagosei Co., Ltd. and Unidic series manufactured by DIC Corporation.
  • the acrylic resin (B) may be used alone or in combination of two or more.
  • the clear coating composition of the present invention comprises a metal dryer.
  • This metal dryer serves to crosslink unsaturated bonds.
  • any one can be used as long as it is usually used for paints.
  • cobalt, barium, vanadium, manganese, cerium, lead, iron, calcium, zinc are particularly representative.
  • Naphthenates and octylates such as zirconium, cerium, nickel or tin.
  • the metal dryer can be set to a metal amount in the range of 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the resin solid content of the clear coating composition.
  • the amount of metal in the metal dryer is less than 0.01% by mass, the reaction does not proceed sufficiently, and the adhesion to the object to be coated forming a clear coating film may be deteriorated.
  • the acrylic resin (A) and acrylic (B) according to the present invention are also insufficiently crosslinked, and the desired coating film hardness may not be obtained.
  • the amount of metal in the metal dryer is more than 3.0 parts by mass, the basic performance such as paint skin may be deteriorated.
  • the metal dryer is blended in an amount of preferably 0.01 to 2.9% by mass, more preferably 0.02 to 2.8% by mass with respect to 100 parts by mass of the resin solid content of the clear coating composition.
  • the clear coating composition of the present invention may contain additives usually used by those skilled in the art, such as ultraviolet absorbers, hindered amine light stabilizers, antioxidants, rheology control agents, and surface conditioners.
  • the clear coating composition of the present invention can be of a one-part type. For example, since the pot life can be made longer than that of the two-pack type clear coating composition, the workability is excellent. Furthermore, since it is a one-pack type coating composition, the baking process can be performed under low-temperature heating conditions, and energy consumption and CO 2 emission can be reduced. Moreover, it is excellent also in storage stability and drying property.
  • organic solvent used in the clear coating composition of the present invention examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, and isopentane.
  • Alkyl alcohol solvents such as tanol; methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, etc.
  • Glycol ether solvents aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene Exxon Aromatic Naphtha No.
  • Alicyclic hydrocarbon solvents such as tetrahydrofuran, dioxane, diisopropyl ether, di-n-butyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; methyl acetate, ethyl acetate, n-propyl acetate , Isopropyl acetate, n acetate Butyl, isobutyl acetate, n- amyl, isoamyl acetate, hexyl acetate, ethyl propionate, and ester solvents such as butyl propionate.
  • a small amount of water may be used in combination with these organic solvents.
  • the clear coating composition of the present invention has an advantage that the temperature for baking and curing can be set to 60 ° C. or higher and 120 ° C. or lower. That is, the clear coating composition according to the present invention can be cured under a lower temperature heating condition than before. Moreover, the clear coating composition of the present invention has a good coating film hardness even when the coating film is cured under low-temperature heating conditions, and additionally has chemical resistance, solvent resistance and weather resistance. There is an advantage that an excellent clear coating film can be formed.
  • the temperature for performing the baking and curing is 60 ° C. or higher and 110 ° C. or lower.
  • the temperature for performing the baking and curing is 70 ° C. or higher and 90 ° C. or lower.
  • the solvent resistance and weather resistance may be inferior.
  • the clear coating composition of the present invention is characterized in that a clear coating film having good coating film hardness can be formed even when cured under low temperature heating conditions.
  • the clear coating composition of the present invention can be heat-cured under general baking curing conditions such as 120 to 180 ° C., if necessary.
  • the present invention further provides a method for forming a clear coating film.
  • the method for forming a clear coating film according to the present invention comprises a step of coating the clear coating composition according to the present invention on an object to be formed to form an uncured clear coating film; and an uncured clear coating film Baking and curing to form a clear coating; Including
  • the temperature for performing the bake hardening is 60 ° C. or higher and 120 ° C. or lower.
  • a method for forming a multi-layer coating film on a coating material which comprises sequentially applying a base coating composition and a clear coating composition on the coating material by wet-on-wet.
  • the method for forming a multilayer coating film comprises: Applying a base coating composition on an object to form an uncured base coating; Applying the clear coating composition according to the present invention on an uncured base coating to form an uncured clear coating; and simultaneously baking and curing the uncured base coating and the clear coating.
  • a step of forming a multilayer coating film The temperature for performing the bake hardening is 60 ° C. or higher and 120 ° C. or lower.
  • the temperature for baking and curing can be set to 60 ° C. or higher and 120 ° C. or lower.
  • the temperature for performing the bake curing is 60 ° C. or higher and 110 ° C. or lower, for example, the temperature for performing the bake curing is 60 ° C. or higher and 90 ° C. or lower, and in one embodiment, 70 ° C. or higher and 90 ° C. or lower.
  • the clear coating composition of the present invention can be baked and cured under conditions of, for example, 120 ° C. or higher as necessary.
  • a base coating composition and a clear coating composition can be sequentially applied by wet-on-wet on various objects to be coated.
  • the article to be coated may be an automobile body on which an electrodeposition coating film is formed.
  • the electrodeposition coating film is formed by applying an electrodeposition coating composition to an automobile body and baking and curing it.
  • the automobile body to be coated is not particularly limited as long as it is a metal product capable of cationic electrodeposition coating. For example, iron, copper, aluminum, tin, zinc, an alloy containing these metals, and the like can be given.
  • the article to be coated is a resin product used in the vehicle field.
  • the clear coating composition according to the present invention can be cured under low-temperature heating conditions, a clear coating film excellent in coating film hardness and various physical properties described above can be formed on resin products. Further, the article to be coated may have both a metal product and a resin product.
  • the electrodeposition coating composition is not particularly limited, and known cationic electrodeposition coating compositions and anionic electrodeposition coating compositions can be used. Electrodeposition coating and baking may be performed by a method and conditions usually used for electrodeposition coating of automobile bodies.
  • the method includes a step of applying an intermediate coating composition on an article on which an electrodeposition coating has been formed to form an uncured intermediate coating, and then applying the base coating composition.
  • an intermediate coating composition known ones can be used, and for example, an aqueous intermediate coating composition can be used.
  • the intermediate coating composition can be applied by spraying using, for example, an air electrostatic spray, a rotary atomizing electrostatic coater or the like.
  • the coating amount is adjusted so that the film thickness of the cured coating film is 10 to 40 ⁇ m, preferably 15 to 30 ⁇ m. If the film thickness is less than 10 ⁇ m, the appearance and chipping resistance of the resulting coating film may be reduced, and if it exceeds 40 ⁇ m, problems such as sagging during coating and pinholes during baking hardening may occur.
  • the applied intermediate coating composition is preheated (pre-dried) by heating or blowing air before applying the base coating composition.
  • preheating means that the applied coating composition is dried by heating under conditions such as temperature and time at which curing does not occur.
  • the coated intermediate coating composition is preheated at 60 to 90 ° C., preferably 70 to 90 ° C. for 3 to 10 minutes.
  • the base coating composition is applied wet-on-wet on an uncoated intermediate coating film on an object on which an electrodeposition coating film has been formed.
  • a known base coating composition can be used.
  • an aqueous base coating composition can be used.
  • the coating amount of the base coating composition is usually adjusted so that the film thickness after curing of the coating film is 10 to 20 ⁇ m. If the film thickness after curing is less than 10 ⁇ m, the masking of the underlayer may be insufficient or color unevenness may occur. If the film thickness exceeds 20 ⁇ m, sagging may occur during painting and pinholes may occur during heat curing. There is a risk of doing so.
  • the base coating composition is preheated to form an uncured base coating.
  • the preheating temperature is 60 to 90 ° C., preferably 70 to 90 ° C., and preheating is performed for 3 to 10 minutes.
  • the clear coating composition of the present invention may be applied to form an uncured clear coating film.
  • the coating amount of the clear coating composition is usually adjusted so that the film thickness after drying and curing of the coating film is 15 to 60 ⁇ m.
  • the film thickness after curing is less than 15 ⁇ m, the appearance such as glossiness of the multilayer coating film is deteriorated, and when it exceeds 60 ⁇ m, the sharpness is deteriorated or defects such as unevenness and flow occur at the time of coating.
  • the uncured intermediate coating film, base coating film and clear coating film formed as desired are baked and cured simultaneously.
  • Baking is usually performed by heating to a temperature of 60 ° C. or higher and 120 ° C. or lower, preferably 60 to 110 ° C., for example, 70 to 90 ° C. Thereby, a cured coating film having a high degree of crosslinking can be obtained. If the heating temperature is less than 60 ° C, curing tends to be insufficient, and if it exceeds 120 ° C, the resulting coating film may be hard and brittle.
  • the heating time can be appropriately set according to the above temperature. For example, when the temperature is 60 to 120 ° C., the heating time is 10 to 60 minutes.
  • parts means “parts by mass” unless otherwise specified.
  • Shell synthesis A solvent is charged into a 0.5 liter Kolben equipped with a stirring blade, a temperature controller, a reflux tube, a nitrogen inlet, and a dropping funnel, and blended as shown in Table 2 under a nitrogen atmosphere at 110 ° C. and 150 rpm. The monomer and the initiator were dropped for 3 hours and then aged for 0.5 hour, followed by a subsequent shot for 0.5 hour, and further aged for 1 hour to prepare an acrylic resin.
  • the temperature was lowered to 100 ° C., a polymerization inhibitor (hydroquinone monomethyl ether; MEHQ) and a catalyst (dibutyltin dilaurate; DBTDL) were added, and then 0.25 mol Karenz AOI with respect to 1.0 mol of the main chain synthesized in an air atmosphere. (Showa Denko Co., Ltd., 2-isocyanatoethyl acrylate) was added dropwise over 0.5 hours. Thereafter, aging was performed over 2 hours, and a double bond for core-shell graft was introduced into the shell.
  • a polymerization inhibitor hydroquinone monomethyl ether
  • DBTDL dibutyltin dilaurate
  • NAD synthesis in another Kolben equipped with a 1 liter stirring blade, temperature controller, reflux tube, nitrogen inlet, and dropping funnel, the above prepared shell resin with a double bond and butyl acetate / A mixture of Isopar E was charged, and the temperature and the temperature were increased to 110 rpm and 110 ° C. in a nitrogen atmosphere, and then the monomers and initiators shown in Table 3 were added dropwise for 3 hours. After aging for 0.5 hour, a post shot was dropped for 0.5 hour and then further aged for 1 hour to obtain NAD.
  • Example 1 Preparation of Clear Coating Composition
  • an oxidation-polymerizable acrylic resin was prepared with the formulation shown in Table 1, the same as in Production Example (A-1), An acrylic resin (A-2) having an oxidatively polymerizable functional group was prepared.
  • the acrylic resin (B-1) having a reactive double bond group, the solvent, and the acrylic resin (A-2) having an oxidative polymerizable functional group were added in the order shown in Table 5; After stirring well, a catalyst (metal dryer) was added and stirred to prepare a clear coating composition. Since the amount of the catalyst added was small, it was diluted with the solvent shown in Table 5 and added.
  • the clear coating composition prepared above was applied onto a glass plate using a 4 mil film applicator to form an uncured clear coating film.
  • the uncured clear coating film was baked at a temperature of 80 ° C. for 30 minutes to form a clear coating film.
  • the laminated coating-film board was produced for weather resistance evaluation.
  • SPCC-SD steel plate dull steel plate
  • “Power Top U-80” a cationic electrodeposition paint made by Nippon Paint Automotive Coatings Co., Ltd.
  • the coating was coated with “Orga P-2”, an intermediate coating material manufactured by Nippon Paint Automotive Coatings Co., Ltd., and baked and dried.
  • a base plate “AQUAREX AR-2000 Blue Mica” manufactured by Nippon Paint Automotive Coatings Co., Ltd. was applied to the test plate after the intermediate coating was applied, and then preheated at 80 ° C. for 3 minutes. Thereafter, the clear coating composition prepared above was spray-coated to a dry film thickness of 35 ⁇ m and baked at 80 ° C. for 30 minutes to form a laminated coating film.
  • Examples 2 to 9, Comparative Examples 1 to 8) Except that the acrylic resin (A) having an oxidative polymerizable functional group was used in the composition shown in Table 1, and the solvent was added depending on the catalyst amount and conditions used in the preparation of the clear coating composition. In the same manner as in Example 1, a clear coating composition was prepared. Further, a clear coating film was formed in the same manner as in Example 1 except that the baking temperature at the time of forming the coating film was described in Table 5.
  • Evaluation was performed according to the following procedures using the coating compositions, coating films and evaluation coating plates prepared in the above Examples, Comparative Examples and Reference Examples. The evaluation results are shown in the following table.
  • Viscosity ⁇ Change before and after test ⁇ 2 seconds or less ⁇ : Change before and after test exceeds ⁇ 2 seconds Hue 3: No yellowing is observed 2: Yellowing is observed 1: Remarkably yellowed Particle size ⁇ : Particle size of less than 5 ⁇ m ⁇ : Particle size of 5 ⁇ m or more
  • the prepared coating film was subjected to an accelerated weather resistance test using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.), and the discoloration before and after the test was evaluated visually.
  • the operating conditions were based on JIS K5400, and the operating time was 1000 hours.
  • the evaluation criteria are as follows. Table 5 shows the evaluation results of Examples and Comparative Examples, and Table 6 shows the evaluation results of Reference Examples. 4: Discoloration is not recognized in the coating film 3: Discoloration of the coating film is slightly observed 2: The coating film is discolored 1: The coating film is remarkably discolored
  • the coating films obtained in the examples were evaluated for chemical resistance (JIS K5600). As a result, they were not inferior to the clear coating films obtained in the reference examples using conventional clear coating compositions. It was confirmed that there was no problem.
  • the clear coating composition of the present invention has a good coating film hardness even when the coating film is cured under low temperature heating conditions (eg, 60 to 120 ° C.).
  • a clear coating film excellent in chemical resistance, solvent resistance and weather resistance can be formed.
  • the coating film excellent also in the coating-film haze can be obtained.
  • the clear coating composition had a solvent resistance and a weather resistance because the acrylic resin (A) did not have the oxidation polymerizable functional group according to the present invention. It was a bad coating film.
  • the acrylic resin (B) according to the present invention since the acrylic resin (B) according to the present invention was not included, the obtained coating film had a place where traces such as whitening and scratching occurred, and the weather resistance was poor. It was a coating film.
  • Comparative Example 4 is a clear coating composition using an alkyd resin instead of the acrylic resin (A) according to the present invention, and the obtained coating films are all paint stability, solvent resistance, coating film haze. The film was insufficient in both weather resistance and weather resistance.
  • Comparative Example 5 is a clear coating composition using a general-purpose acrylic resin instead of the acrylic resin (A) according to the present invention, and the obtained coating film was dissolved in the coating film in the solvent resistance test. In addition, the coating film had poor weather resistance.
  • Comparative Example 6 is a clear coating composition that does not contain the metal dryer (C) according to the present invention, and the obtained coating film was dissolved in the solvent resistance test, and in addition, the weather resistance was poor. It was a coating film.
  • Reference Examples 1 to 3 are commercially available clear coating compositions that are designed to have a baking temperature of about 140 ° C. As is clear from the evaluation results of Reference Examples 1 to 3 and the evaluation results of Examples 1 to 9, the clear coating composition of the present invention has a baking temperature of 60 to 120 ° C. even under low temperature heat curing conditions. It can be seen that solvent resistance and weather resistance comparable to conventional clear coating films are obtained.
  • the clear coating composition of the present invention has the advantage that the coating film can be cured under low temperature heat curing conditions. Further, even when heat curing is performed under low temperature heating conditions, a coating film having good coating film hardness can be obtained, and further, there is an advantage of excellent chemical resistance, solvent resistance and weather resistance. .
  • the present invention can also provide a method for forming a multilayer coating film using the clear coating composition.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

L'invention fournit une composition de revêtement clair permettant d'effectuer un durcissement de film de revêtement dans des conditions de chauffage à basse température, qui présente une dureté satisfaisante d'un film de revêtement obtenu, et qui se révèle excellente en termes de résistance aux produits chimiques du film de revêtement, de résistance aux solvants et de résistance aux intempéries. Plus précisément, l'invention concerne une composition de revêtement clair qui contient une résine acrylique (A) possédant un groupe fonctionnel polymérisable par oxydation de 2 à 4 liaisons doubles, une résine acrylique (B) possédant un groupe à liaison double réactif, et un siccatif métallique (C). En outre, l'invention fournit un procédé de formation d'un film de revêtement clair présentant un fil de revêtement contenant la composition de revêtement clair de l'invention.
PCT/JP2018/019255 2017-05-19 2018-05-18 Composition de revêtement clair, et procédé de formation de film de revêtement clair WO2018212317A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60110725A (ja) * 1983-11-22 1985-06-17 Showa Highpolymer Co Ltd 常温で硬化可能な組成物
JPS6254716A (ja) * 1985-09-04 1987-03-10 Nippon Synthetic Chem Ind Co Ltd:The 空乾性樹脂組成物
JPH07228815A (ja) * 1994-02-18 1995-08-29 Asahi Glass Co Ltd 塗料用樹脂組成物
JPH11323242A (ja) * 1998-05-12 1999-11-26 Nof Corp 自動車外板上塗り塗料組成物及び塗装方法
JP2011084663A (ja) * 2009-10-16 2011-04-28 Kansai Paint Co Ltd 水性塗料組成物及び塗装方法
WO2013005471A1 (fr) * 2011-07-07 2013-01-10 ナミックス株式会社 Composition de résine

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012092232A (ja) * 2010-10-27 2012-05-17 Nippon Paint Co Ltd クリヤー塗膜を形成する方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60110725A (ja) * 1983-11-22 1985-06-17 Showa Highpolymer Co Ltd 常温で硬化可能な組成物
JPS6254716A (ja) * 1985-09-04 1987-03-10 Nippon Synthetic Chem Ind Co Ltd:The 空乾性樹脂組成物
JPH07228815A (ja) * 1994-02-18 1995-08-29 Asahi Glass Co Ltd 塗料用樹脂組成物
JPH11323242A (ja) * 1998-05-12 1999-11-26 Nof Corp 自動車外板上塗り塗料組成物及び塗装方法
JP2011084663A (ja) * 2009-10-16 2011-04-28 Kansai Paint Co Ltd 水性塗料組成物及び塗装方法
WO2013005471A1 (fr) * 2011-07-07 2013-01-10 ナミックス株式会社 Composition de résine

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