WO2018116950A1 - Composite coating film, method for producing composite coating film, article and coating composition - Google Patents

Composite coating film, method for producing composite coating film, article and coating composition Download PDF

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Publication number
WO2018116950A1
WO2018116950A1 PCT/JP2017/044889 JP2017044889W WO2018116950A1 WO 2018116950 A1 WO2018116950 A1 WO 2018116950A1 JP 2017044889 W JP2017044889 W JP 2017044889W WO 2018116950 A1 WO2018116950 A1 WO 2018116950A1
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Prior art keywords
coating film
composite coating
coating composition
acid
skin layer
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PCT/JP2017/044889
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French (fr)
Japanese (ja)
Inventor
健吾 卜部
知哉 奥田
康学 湊
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日本ペイントホールディングス株式会社
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Publication of WO2018116950A1 publication Critical patent/WO2018116950A1/en

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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
    • 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
    • B05D3/12—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 mechanical means
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • 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
    • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
    • 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 composite coating film, a method for producing the composite coating film, an article, and a coating composition.
  • the coating film not only functions to color the object to be coated, but also has a function to impart functions such as solvent resistance, water resistance, weather resistance, chemical resistance or antifouling property to the object.
  • an object of the present invention is to provide a composite coating film that can be renewed at least once by peeling the surface layer of the composite coating film.
  • Another object of the present invention is to provide a method for producing a composite coating that can be renewed at least once by peeling the surface layer of the composite coating.
  • Another object of the present invention is to provide an article having the composite coating film on its surface.
  • Still another object of the present invention is to provide a coating composition capable of forming a composite coating film that can be renewed at least once by peeling the surface layer of the composite coating film.
  • the composite coating film according to the present invention is A composite coating consisting of an inner layer and a skin layer adjacent to the air interface side of the inner layer,
  • the composite coating film is formed from a single coating composition,
  • the coating composition is An active energy ray-curable compound (A); A light absorber (B); A photopolymerization initiator (C); Including
  • the inner layer is uncured,
  • the skin layer is a composite coating film that is cured and can be peeled off from the surface of the inner layer. Since the composite coating film is formed from such a coating composition, the inner layer is uncured, while the skin layer that is the surface layer of the composite coating film is cured, so that the skin layer can be peeled off. It is. And the surface layer of the inner layer which appeared by peeling hardens
  • the coating composition further includes an internal flow inhibitor (D), and the internal flow inhibitor (D) includes an organic gelling agent.
  • the rebound resilience of the composite coating film is 10 to 65%.
  • the thickness of the skin layer is 10 ⁇ m to 5 mm, and the thickness of the inner layer is equal to or greater than the thickness of the skin layer.
  • the method for producing the composite coating film according to the present invention comprises: On the substrate, An active energy ray-curable compound (A); A light absorber (B); A photopolymerization initiator (C); Applying a single coating composition comprising: forming a coating composition coating; Irradiating a film of the coating composition with active energy rays to form an uncured inner layer and a cured skin layer; Is a method for producing a composite coating film.
  • A active energy ray-curable compound
  • B A light absorber
  • C photopolymerization initiator
  • Applying a single coating composition comprising: forming a coating composition coating; Irradiating a film of the coating composition with active energy rays to form an uncured inner layer and a cured skin layer; Is a method for producing a composite coating film.
  • the article according to the present invention is an article having a composite coating film on the surface. Thereby, the coating film on the article surface can be updated at least once.
  • the coating composition according to the present invention comprises: An active energy ray-curable compound (A); A light absorber (B); A photopolymerization initiator (C); including, It is a coating composition.
  • A active energy ray-curable compound
  • B light absorber
  • C photopolymerization initiator
  • an internal flow inhibitor (D) is further included, and the internal flow inhibitor (D) includes an organic gelling agent.
  • the present invention it is possible to provide a composite coating film that can be renewed at least once by peeling the surface layer of the composite coating film.
  • the surface layer of a composite coating film can be peeled and the manufacturing method of the composite coating film which can be updated at least once can be provided.
  • item which has the said composite coating film on the surface can be provided.
  • the coating composition which can peel the surface layer of a composite coating film and can form the composite coating film which can be updated at least once can be provided.
  • FIG. 1 is a schematic diagram showing an example of the configuration and update of a composite coating film according to the present invention.
  • FIG. 2 is a schematic view showing an example of a method for producing a composite coating film according to the present invention.
  • FIG. 3 is a schematic view showing a method for measuring the rebound resilience of the composite coating film in the present invention.
  • FIG. 4 is a schematic view showing a method for measuring the peelability of the composite coating film in the present invention.
  • the paint and the paint composition can be used interchangeably.
  • active energy rays refer to visible rays, ultraviolet rays, electron beams, infrared rays, X rays, ⁇ rays and ⁇ rays.
  • (meth) acrylate means one or more selected from the group consisting of acrylate and methacrylate.
  • (meth) acrylic acid means one or more selected from the group consisting of acrylic acid and methacrylic acid.
  • (meth) allyl means one or more selected from the group consisting of allyl and methallyl.
  • the (un) saturated polyester means one or more selected from the group consisting of a saturated polyester and an unsaturated polyester.
  • the active energy ray-curable compound (A), the light absorber (B), the photopolymerization initiator (C) and the internal flow inhibitor (D) are respectively represented by the component (A) and the component (B). , (C) component and (D) component.
  • FIG. 1 is a schematic diagram showing an example of the composition and update of a composite coating film according to the present invention.
  • the uppermost drawing in FIG. 1 shows the composite coating film 1 on the workpiece 10.
  • the composite coating film 1 includes an inner layer 20 and a skin layer 30 adjacent to the air interface side of the inner layer 20.
  • the skin layer 30 is peelable from the surface of the inner layer 20.
  • the third figure from the top of FIG. 1 shows the composite coating film immediately after the skin layer 30 is peeled off.
  • the exposed surface layer of the inner layer 20 is cured by active energy rays, the lowermost part of FIG.
  • a new skin layer 31 is formed in the portion that was the surface layer of the inner layer 20, and the composite coating film 1 is updated.
  • the renewed inner layer 21 of the composite coating film 1 is uncured.
  • the coating composition according to the present invention comprises: An active energy ray-curable compound (A); A light absorber (B); A photopolymerization initiator (C); including, It is a coating composition.
  • A active energy ray-curable compound
  • B light absorber
  • C photopolymerization initiator
  • the skin layer (surface layer) of the composite coating film can be peeled to form a composite coating film that can be updated at least once.
  • the active energy ray-curable compound (A) is a component that has curability by active energy rays and functions as a binder.
  • the active energy ray-curable compound is not particularly limited as long as it is a known compound that can be cured with active energy rays.
  • Examples of such active energy ray curable compounds include radical polymerization type active energy ray curable compounds and cationic polymerization type active energy ray curable compounds described in JP-A-2004-337647, and combinations thereof. Examples thereof include a combined active energy ray-curable compound.
  • the component (A) may be a monomer, an oligomer, a polymer, or a combination of two or more of these.
  • a component may be used individually by 1 type and may be used in combination of 2 or more type.
  • radical polymerization type active energy ray-curable compound examples include compounds having one or more radical polymerizable reactive groups such as one or more ethylenically unsaturated groups in the molecule.
  • radical polymerization type active energy ray-curable compound examples include (un) saturated polyester resin, epoxy resin, urethane resin, acrylic resin, ethylenically unsaturated group-containing monomer such as (meth) acrylic acid, or glycidyl (meth). Resin modified with glycidyl group-containing monomers such as acrylate or (meth) allyl glycidyl ether; (un) saturated polyester resin, epoxy resin, urethane resin, acrylic resin, etc.
  • polyester resins modified with isocyanate monomers such as cyanate, modified epoxy resins, modified urethane resins, modified acrylic resins; ethylene glycol mono (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-hexanediol mono (meth) Acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate
  • a commercially available product may be used as the radical polymerization type active energy ray-curable compound.
  • examples of such commercially available products include Lipoxy (registered trademark) VR-77 (vinyl ester resin) from Showa Denko KK, M-211B (EO-modified bisphenol A diacrylate) from Toa Gosei Co., Ltd., M-350 ( Aronix (registered trademark) series such as EO modified product of trimethylolpropane EO triacrylate).
  • Examples of the cationic polymerization type active energy ray-curable compound include compounds having one or more epoxy polymerizable groups such as epoxy group, glycidyl group, oxetanyl group, tetrahydrofuryl group and vinyl group in the molecule. Can do. Examples of such a compound include an epoxy resin, an epoxidized polydiene resin, and a vinyl ether resin.
  • Examples of the combined active energy ray curable compound include a compound obtained by blending the radical polymerization type active energy ray curable compound and the cationic polymerization type active energy ray curable compound; one or more radical polymerizable reactions in the molecule And a compound having a group and one or more cationically polymerizable reactive groups.
  • the component (A) is a compound having an ethylenically unsaturated group. In another embodiment, the component (A) is a compound having two or more ethylenically unsaturated groups.
  • the content of the component (A) in the coating composition may be adjusted as appropriate. For example, it can be 40 to 98% by mass, 60 to 95% by mass with respect to the total mass of the component (A), the component (B) and the component (C).
  • the light absorber (B) prevents the penetration of active energy rays into the entire depth direction of the coating when the coating of the coating composition formed from the coating composition according to the present invention is irradiated with the active energy rays. , It has a function of suppressing the hardening of the entire film in the depth direction.
  • the component (B) is not used in the conventional normal active energy ray-curable coating composition because it inhibits the curing of the coating film in order to suppress the curing in the entire depth direction of the film.
  • (B) component contributes to formation of the skin layer hardened
  • a component may be used individually by 1 type and may be used in combination of 2 or more type.
  • the component (B) is not particularly limited as long as it is a component that can absorb, reflect or absorb and reflect active energy rays, and a known light absorbent can be used.
  • a known light absorbent can be used.
  • an inorganic light absorber and an organic light absorber can be used.
  • inorganic light absorbers include titanium oxide, zinc oxide, tin oxide, cerium oxide, carbon black, iron black, iron oxide, chromium oxide, ultramarine, alumina white, iron oxide yellow, viridian, zinc sulfide, cadmium.
  • inorganic coloring pigments such as yellow, cadmium red, yellow lead, molybdate orange, zinc chromate, strontium chromate, lead white, manganese violet, and bitumen.
  • the inorganic light absorber as component (B) is at least one selected from the group consisting of titanium oxide and zinc oxide.
  • organic light absorber examples include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine, 2- (2H-benzotriazole-2 -Yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2- (2H-benzotriazol-2-yl ) -P-cresol, 2- (5-chloro-2H-benzotriazol-2-yl) -6-tert-butyl-4-methylphenol, 2- (4,6-diphenyl-1,3,5-triazi 2-yl) -5-[2- (2-ethylhexanoyloxy) ethoxy]
  • organic light absorbers include, for example, acetaminosalol, benzal phthalide, benzophenone, benzophenone 1-12, 3-benzylidene camphor, benzylidene camphor hydrolyzed collagen sulfonamide, benzylidene camphor sulfonic acid, benzyl salicylate , Bornelon, Bumetriozole, Butylmethoxydibenzoylmethane, Butyl PABA, Shinoxate, Methoxycinnamic acid DEA, Dibenzoxazole naphthalene, Di-t-butylhydroxybenzylidene camphor, Digalloyl trioleate, Diisopropylcinnamic acid methyl, Dimethyl PABA, Tosylic acid Ethyl cetearyl dimonium, dioctyl butamido triazone, diphenylcarbomethoxyacetoxynaphthopyran, bisethylphen
  • organic light absorber Commercially available products may be used as the organic light absorber.
  • organic light absorbers include, for example, ADEKA UV absorbers, Adeka Stub (registered trademark) LA-24, LA-29, LA-31, LA-31RG, LA-31G, LA-32, LA- 36, LA-36RG, LA-46, 1413, Adeka Stub (registered trademark) LA series such as LA-F70, and the like.
  • the organic light absorber as the component is preferably a compound that absorbs light having an absorption wavelength of the photopolymerization initiator as the component (C).
  • the organic light absorber of component (B) is 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (LA- F70).
  • the absorption of light having the absorption wavelength of the photopolymerization initiator of component (C) means that the photopolymerization initiator absorbs light in an absorption peak that generates radicals and cations and in the nearby wavelength region.
  • the content of component (B) in the coating composition may be adjusted as appropriate.
  • a photoinitiator (C) has a function which accelerates
  • a component may be used individually by 1 type and may be used in combination of 2 or more type.
  • any known photopolymerization initiator can be used without particular limitation as long as it can accelerate the curing of the component (A).
  • component (C) examples include ⁇ -hydroxyacetophenone, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propane-1 -One, benzoin methyl ether, benzoin propyl ether, diphenyl diketone, benzyldimethyl ketal, benzoylcyclohexanol, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- (4-methylthiophenyl)- Photo-radical polymerization initiators such as 2-morpholinopropan-1-one; photocationic polymerization initiators such as triphenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluoroantimonate.
  • the photopolymerization initiator of component (C) is ⁇ -hydroxyacetophenone, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ - One or more selected from the group consisting of 2-methyl-propan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one.
  • (C) component in a coating composition For example, 1.0% by mass or more, 2.5% by mass or more, 3.0% by mass or more, 5% by mass with respect to the total mass of the components (A), (B) and (C) of the coating composition % Or more, 8 mass% or more, 40 mass% or less, 30 mass% or less, 20 mass% or less, or 15 mass% or less.
  • Component may be a commercially available product.
  • commercially available component (C) include Irgacure (registered trademark) series such as Irgacure (registered trademark) 1173, 127, and 907 manufactured by BASF.
  • an internal flow inhibitor (D) is further included. Thereby, in the use environment of the composite coating film which concerns on this invention, the flow of an unhardened internal layer is suppressed and it becomes easier to form a coating-film structure.
  • a component may be used individually by 1 type and may be used in combination of 2 or more type.
  • Examples of the internal flow inhibitor include organic gelling agents and layered minerals.
  • organic gelling agent examples include aliphatic ketone compounds, aliphatic ester compounds, petroleum waxes, plant waxes, animal waxes, mineral waxes, dibenzylidene sorbitols, and the like.
  • Examples of the aliphatic ketone compound include dilignoceryl ketone (C24-C24), dibehenyl ketone (C22-C22, melting point 88 ° C.), distearyl ketone (C18-C18, melting point 84 ° C.), dieicosyl ketone ( C20-C20), dipalmityl ketone (C16-C16, melting point 80 ° C.), dimyristyl ketone (C14-C14), dilauryl ketone (C12-C12, melting point 68 ° C.), lauryl myristyl ketone (C12-C14), Lauryl palmityl ketone (C12-C16), myristyl palmityl ketone (C14-C16), myristyl stearyl ketone (C14-C18), myristyl behenyl ketone (C14-C22), palmityl stearyl ketone (C16-
  • Examples of the aliphatic ester compound include behenyl behenate (C21-C22, melting point 70 ° C.), icosyl icosanoate (C19-C20), stearyl stearate (C17-C18, melting point 60 ° C.), palmitic acid stearate (C17- C16), lauryl stearate (C17-C12), cetyl palmitate (C15-C16, melting point 54 ° C.), stearyl palmitate (C15-C18), myristyl myristate (C13-C14, melting point 43 ° C.), cetyl myristate (C13-C16, melting point 50 ° C.), octyldodecyl myristate (C13-C20), stearyl oleate (C17-C18), stearyl erucate (C21-C18), stearyl linoleate (C17-C18), beheny
  • Examples of petroleum waxes include paraffin wax, microcrystalline wax, and petrolactam.
  • plant wax examples include candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil, jojoba solid wax, and jojoba ester.
  • animal waxes include beeswax, lanolin and whale wax.
  • mineral wax examples include montan wax and hydrogenated wax.
  • dibenzylidene sorbitols examples include sorbitol dibenzal (also known as 1,3: 2,4-bis-O-benzylidene-D-glucitol) and di-p-methylbenzylidene sorbitol (also known as 1,3: 2). , 4-bis-O- (4-methylbenzylidene) -D-sorbitol).
  • organic gelling agent examples include hardened castor oil or hardened castor oil derivative; modified wax such as montan wax derivative, paraffin wax derivative, microcrystalline wax derivative or polyethylene wax derivative; behenic acid, arachidic acid, stearin Higher fatty acids such as acid, palmitic acid, myristic acid, lauric acid, oleic acid and erucic acid; higher alcohols such as stearyl alcohol and behenyl alcohol; hydroxystearic acid such as 12-hydroxystearic acid; 12-hydroxystearic acid derivative; laurin Fatty acid amides such as acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, 12-hydroxystearic acid amide, etc .; N-substituted fatty acid amides such as allyl stearamide, N-oleyl palmitate, N, N′-ethylenebisstearylamide, N, N′-ethylenebis-12
  • the organic gelling agent as component (D) has a card house structure in which a compound containing a linear alkyl group having 12 or more carbon atoms or an aromatic ring, and organic crystals are physically combined. What is easy to form is desirable. In view of compatibility with monomers, oligomers and polymers, compounds having a partial polar functional group are more desirable.
  • the organic gelling agent is at least one selected from the group consisting of aliphatic ketone compounds, aliphatic ester compounds, higher fatty acids, higher alcohols, and fatty acid amides.
  • the organic gelling agent is at least one selected from the group consisting of sorbitol dibenzal, dilauryl ketone, oleic amide, cetyl myristate, and myristic acid.
  • sorbitol compounds include Gelall (registered trademark) series such as Gelol (registered trademark) D (sorbitol dibenzal), MD, MD-LM30G, E-200, etc., manufactured by Shin Nippon Chemical Co., Ltd. Can do.
  • an internal flow inhibitor (D) is further included, and the internal flow inhibitor (D) includes an organic gelling agent.
  • layered minerals include montmorillonite, zakonite, nontronite, saponite, hectorite, vermiculite, synthetic hectorite, and talc.
  • a commercially available product may be used as the layered mineral.
  • Commercially available layered minerals include, for example, KYTONE (registered trademark) 40 of BYK, CLAYTONE (registered trademark) series such as HT, APA, AF, HY, TIXOGEL VP, MP, MPI, VZ, MPZ, MP100, and MP250.
  • TIXOGEL series such as GARAMITE 7303, 1958, 7305, CLOISITE series, LAPONITE (registered trademark) RD, EP, RDS, JS, LAPONITE (registered trademark) series such as S482, OPTIGEL CK, CMO, W724, WA OPTIGEL series such as WM, WX, LX, BENTOLITE (registered trademark) series, OPTIBENT series such as OPTIBENT MF, 987, NT10, etc. It can gel.
  • the layered mineral is at least one selected from the group consisting of CLAYTONE (registered trademark) HY and talc.
  • the content of the component (D) in the coating composition may be adjusted as appropriate.
  • content of (D) component is 0.5 mass% or more, 1.0 mass% or more, 2.0 mass% or more, 5.0 mass with respect to 100 mass% of (A) component. % Or more, 10% or more, 20% or more, or 30% or more, 100% or less, 90% or less, 80% or less, 60% or less, or 50% or less.
  • content of an organic type gelatinizer is 0.5 mass% or more, 1.0 mass% or more, 2.0 mass% or more with respect to 100 mass% of (A) component.
  • the coating composition according to the present invention includes water, a solvent, an extender pigment, a photosensitizer, a dispersant, a film-forming aid, an antifreezing agent, a leveling agent, a surface conditioner, an antifoaming agent, It may contain paint additives such as antiseptics, fungicides, algae inhibitors and antioxidants. Each of these components may be used alone or in combination of two or more.
  • the solvent of a conventionally well-known coating composition can be selected suitably, and can be used.
  • alcohols such as methanol, ethanol, 2-propanol, 1-butanol; ethyl acetate, butyl acetate, isobutyl acetate, ethyl propionate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc.
  • ⁇ External pigment> When the extender pigment is used, a pigment of a conventionally known coating composition can be appropriately selected and used. Examples thereof include extender pigments such as calcium carbonate and precipitated barium.
  • the coating composition of the present invention may be a one-pack type or a two-pack type. In the case of the two-component type, they are mixed immediately before coating and used as a single coating composition.
  • the method for preparing the coating composition is not particularly limited, and the above-described components (A) to (C) can be mixed and prepared by a conventionally known method.
  • the composite coating film according to the present invention is A composite coating consisting of an inner layer and a skin layer adjacent to the air interface side of the inner layer,
  • the composite coating film is formed from a single coating composition,
  • the coating composition is An active energy ray-curable compound (A); A light absorber (B); A photopolymerization initiator (C); Including
  • the inner layer is uncured,
  • the skin layer is a composite coating film that is cured and can be peeled off from the surface of the inner layer.
  • the coating composition further includes an internal flow inhibitor (D), and the internal flow inhibitor (D) includes an organic gelling agent.
  • ⁇ Inner layer> The coating of the coating composition is not completely cured and the inner layer is uncured. When all the inner layers are completely cured, the skin layer cannot be peeled off and the coating film cannot be renewed.
  • the surface layer side is cured by active energy rays such as sunlight or ultraviolet rays, and a new skin layer can be formed at least once.
  • active energy rays such as sunlight or ultraviolet rays
  • the thickness of the inner layer is not particularly limited and may be adjusted as appropriate. Examples of a method for increasing the thickness of the inner layer include increasing the coating amount of the coating composition or decreasing the thickness of the skin layer. In one embodiment, the thickness of the inner layer is the same as or greater than the thickness of the skin layer.
  • the inner layer may be uncured, but preferably has no internal fluidity in the evaluation of internal fluidity described later in Examples. If there is no internal fluidity in the evaluation (no deformation of the coating film), there is an advantage that stringing is reduced when peeling the skin layer, and stickiness of the surface after peeling is reduced.
  • the inner layer is uncured when the rebound resilience of the composite coating is 10 to 65%. In another embodiment, the rebound resilience of the composite coating is 20% or more, 25% or more, or 30% or more. In another embodiment, the rebound resilience of the composite coating is 60% or less, 55 % Or less, or 50% or less.
  • the skin layer is a layer adjacent to the air interface side of the inner layer and is cured. As described above, since the inner layer is uncured and the skin layer is cured, the skin layer can be peeled from the surface of the inner layer.
  • the skin layer is hardened and “the skin layer is formed” means “coating” when measured in accordance with JIS K 5600-3-2: 1999 described later in Examples. A state in which it is determined that the film is dry on the surface.
  • the thickness of the skin layer is not particularly limited and may be adjusted as appropriate. In one embodiment, the thickness of the skin layer is 10 ⁇ m to 5 mm. In another embodiment, the thickness of the skin layer is 70-200 ⁇ m. In addition, the thickness of the skin layer in the initial stage (the state in which the skin layer has not been peeled once) and the thickness of the skin layer formed after peeling the skin layer once or more may be the same or different. Also good.
  • ⁇ Renewal method of composite coating film> As a method for renewing the composite coating film according to the present invention, for example, the skin layer is peeled off, and then the exposed inner surface layer is cured to form an uncured inner layer and a new cured skin layer. You can update it. Alternatively, the surface layer of the exposed inner layer may be simultaneously cured while peeling the skin layer.
  • the method for peeling the skin layer is not particularly limited and can be appropriately selected.
  • the skin layer may be peeled off by attaching an adhesive tape or a suction cup to the skin layer and pulling it.
  • only the cured skin layer may be peeled off with a spatula or the like.
  • the method for curing the exposed surface layer of the inner layer is not particularly limited and can be appropriately selected. Examples include irradiating active energy rays such as ultraviolet rays and exposing the inner layer to sunlight. In the case of irradiating ultraviolet rays as active energy rays, the irradiation conditions may be appropriately adjusted. For example, the output may be 30 to 200 W and the irradiation time may be 1 to 360 seconds.
  • the composite coating film according to the present invention may be used as a single layer coating film or as a lower layer.
  • the upper layer may be formed by applying a top coating material on the upper surface of the composite coating film or providing an interior material such as an exterior material or wallpaper.
  • an interior material such as an exterior material or wallpaper.
  • the method for peeling the skin layer of the composite coating film is not particularly limited.
  • an adhesive tape or the like is attached to the upper layer described above, and the upper layer and the composite according to the present invention
  • the skin layer of the coating film may be peeled together, or after removing the upper layer with a spatula or the like, the skin layer of the composite coating film according to the present invention may be peeled off.
  • the method for producing the composite coating film according to the present invention comprises: On the substrate, An active energy ray-curable compound (A); A light absorber (B); A photopolymerization initiator (C); Applying a single coating composition comprising: forming a coating composition coating; Irradiating a film of the coating composition with active energy rays to form an uncured inner layer and a cured skin layer; Is a method for producing a composite coating film.
  • a single coating using a single coating composition is used to produce a composite coating film that can be renewed at least once by peeling the skin layer of the composite coating film. Can do.
  • the coating composition used in the method for producing a composite coating film according to the present invention is the coating composition described above.
  • the coating composition further includes an internal flow inhibitor (D), and the internal flow inhibitor (D) comprises an organic gelling agent. Including.
  • FIG. 2 is a schematic view showing an example of a method for producing a composite coating film according to the present invention.
  • the coating composition is applied on the article 10 to form the coating composition film 40 (first and second views from the top in FIG. 2).
  • the active energy ray is irradiated to the film
  • the material to be coated is not particularly limited and can be appropriately selected.
  • a vehicle body such as an automobile or a railway vehicle, an aircraft body, a ship hull and an upper structure (fitting), interior and exterior; building interior and exterior; furniture, fittings; vehicle, Window glass for aircraft, ships, buildings, etc .; transparent bodies such as cases made of glass, acrylic, polycarbonate, containers, resin plates, films; housings and glass members for electrical appliances such as displays, monitors, refrigerators, etc. Can be mentioned.
  • the coating method is not particularly limited, and a known coating method can be appropriately selected and used.
  • Examples of the application method include brushes, trowels, rollers, air sprays, and airless sprays.
  • the thickness of the coating film of the coating composition is not particularly limited, and may be adjusted as appropriate.
  • the thickness of the film may be, for example, 20 ⁇ m to 50 mm, or 50 ⁇ m to 30 mm.
  • the coating composition film is the same as the method described in the method for renewing the composite coating film.
  • the film may be irradiated with active energy rays such as ultraviolet rays, or the coating composition film may be exposed to sunlight.
  • active energy rays such as ultraviolet rays
  • the irradiation conditions may be appropriately adjusted according to the desired thickness of the skin layer, etc.
  • the output may be 30 to 200 W and the irradiation time may be 1 to 360 seconds.
  • the active energy ray is applied under such a condition that the coating film of the conventional active energy ray-curable coating composition is completely cured. Even when the coating composition of the present invention is irradiated, a composite coating film can be produced by curing the skin layer and uncuring the inner layer. Examples of conditions for completely curing the coating film of such a conventional active energy ray-curable coating composition include an output of 80 to 120 W and an irradiation time of 0.5 to 10 seconds.
  • steps other than the steps described above may be included at any timing.
  • steps other than the steps described above may be included at any timing.
  • the coating composition film with active energy rays to form an uncured inner layer and a cured skin layer
  • either or both of the skin layer and the inner layer are naturally dried or heat dried. And the like.
  • the article according to the present invention is an article having the composite coating film on its surface. Thereby, the coating film on the article surface can be updated at least once.
  • Examples of the articles according to the present invention include vehicles such as automobiles and railroad cars, aircraft, ships, buildings, furniture, joinery, window glass, transparent bodies, electrical appliances, and the like.
  • Active energy ray-curable compound (A) trade name Lipoxy (registered trademark) VR-77 (vinyl ester resin) manufactured by Showa Denko KK
  • Active energy ray-curable compound (A) trade name Aronix (registered trademark) M-350 (trimethylolpropane EO-modified triacrylate) manufactured by Toa Gosei Co., Ltd.
  • Active energy ray-curable compound (A) trade name Aronix (registered trademark) M-211B (bisphenol A EO-modified diacrylate) manufactured by Toa Gosei Co., Ltd.
  • Light absorber (B) inorganic light absorber: titanium oxide, trade name CR-50 manufactured by Ishihara Sangyo Co., Ltd.
  • Light Absorber (B) Organic Light Absorber: Product name ADEKA STAB (registered trademark) LA-F70 (2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) manufactured by ADEKA ) -1,3,5-triazine)
  • Photopolymerization initiator (C) trade name Irgacure (registered trademark) 127 (2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2 from BASF -Methyl-propan-1-one)
  • Internal flow inhibitor (D) Organic gelling agent: Brand name Gelall D (sorbi)
  • Internal flow inhibitor (D) (layered mineral): trade name CLAYTONE (registered trademark) HY manufactured by BYK Internal flow inhibitor (D) (layered mineral): Talc, trade name Talc SP-42, manufactured by Maruo Calcium Extender pigment (light transmissive): heavy calcium carbonate, trade name N heavy charcoal manufactured by Maruo Calcium
  • Examples 1 to 18 and Comparative Examples 1 and 2 With the formulation (parts by mass) shown in Table 1, each component was mixed to prepare a coating composition.
  • the coating composition was applied to an aluminum container having a size of 10 cm ⁇ 5 cm and a height of 2.7 mm so that the coating film thickness was 2.5 mm to form a film.
  • the film was irradiated with ultraviolet rays with an output of 80 W and an irradiation time of 240 seconds.
  • the skin layer curability, the rebound resilience, the formability of the composite coating film, the internal flow are determined by the methods described below. , Peelability of the skin layer and peeled film thickness were measured or evaluated. The results are also shown in Table 1.
  • the impact resilience was measured only when it was determined to be cured in the evaluation of the skin layer curability.
  • peelability was evaluated only when it was determined to be acceptable in the evaluation of the composite coating film formability.
  • the skin layer curability was measured and evaluated by the methods and criteria described below. According to JIS K 5600-3-2: 1999, the prepared coating film was placed horizontally. About 0.5 g of Balotini (a fine glass sphere classified so as not to pass through a sieve with a nominal (dimension) size of 125 ⁇ m but through a 250 ⁇ m sieve) was dropped from the height of 100 mm onto the coating film. Ten seconds later, the test piece was tilted, and lightly brushed to remove the barotini. ⁇ Standard> Curing: Barotini can be removed without visually observing scratches on the coating film Uncured: Balotini cannot be removed because the coating film is scratched or buried
  • FIG. 3 is a schematic diagram showing a method of measuring the rebound resilience of the composite coating film in the present invention.
  • the rubber ball 50 was naturally dropped from the position of height H1 (70 cm) onto the coating film 70 formed on the marble base 60, and the bounce height H2 of the rubber ball 50 at that time was measured.
  • the impact resilience was calculated by the following formula. The rebound resilience was measured once for each coating, 3 times in total, and the average value was used.
  • the rubber ball used is a rubber ball having a hardness of 50 measured according to JIS K 6253-2012 “How to determine the hardness of a vulcanized rubber and a thermoplastic rubber”, a material silicone, a diameter of 2 cm, a spherical shape having a mass of 5 g.
  • Rebound resilience (%) (H2 / H1) ⁇ 100 ⁇ Criteria for forming composite coating film> Pass: Rebound resilience 10% to 65% (inner layer is uncured) Fail: Rebound resilience exceeding 65% (inner layer is too hard)
  • the coating film is composed of a viscous component and an elastic component.
  • the elastic component When the elastic component is large, the kinetic energy of the rubber ball is preserved, whereas when the viscous component is large, the falling energy is lost.
  • the composite coating film according to the present invention has an uncured inner layer.
  • An uncured inner layer is believed to have less elastic components and more viscous components than a fully cured layer of the same thickness. Therefore, when an uncured composite coating is formed on the inner layer, it is considered that the rebound resilience is lower than that of a fully cured coating. And the degree of curing thereof can be evaluated.
  • FIG. 4 is a schematic view showing a method for measuring the peelability of the composite coating film in the present invention.
  • the aluminum container around the coating film is not shown for simplification of explanation.
  • the cellophane tape 90 was attached to the surface (skin layer) 100 of 2 cm from one end to the other end of the central part of one short side of the coating film 80.
  • the cellophane tape part which was not affixed on the coating film was held up by hand, and the presence or absence of peelability of the skin layer was evaluated.
  • the thickness of the peeled skin layer was measured with an electronic caliper.
  • Composite coating film 10 Object to be coated 20: Inner layer 21: New inner layer 30 formed after peeling of skin layer 30: Skin layer 31: New skin layer 40 formed after peeling of skin layer: Paint composition Film 50: rubber ball 60: marble base 70: coating film 80: composite coating film 90 for peelability measurement: cellophane tape 100: skin layer 110: inner layer
  • the present invention it is possible to provide a composite coating film that can be renewed at least once by peeling the surface layer of the composite coating film.
  • the surface layer of a composite coating film can be peeled and the manufacturing method of the composite coating film which can be updated at least once can be provided.
  • item which has the said composite coating film on the surface can be provided.
  • the coating composition which can peel the surface layer of a composite coating film and can form the composite coating film which can be updated at least once can be provided.

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Abstract

The purpose of the present invention is to provide: a composite coating film capable of being renewed at least one time by peeling the surface layer of the composite coating film; a method for producing a composite coating film capable of being renewed at least one time by peeling the surface layer of the composite coating film; an article having said composite coating film on the surface; and a coating composition that can form a composite coating film capable of being renewed at least one time by peeling the surface layer of the composite coating film. The composite coating film is made of an internal layer and a cover layer adjacent to the air interface side of the internal layer, where the composite coating film is formed from a single coating composition, the coating composition comprises an actinic ray-curable compound (A), a photo-absorbing agent (B), and a photopolymerization initiator (C), the internal layer is uncured, and the cover layer is cured and can be peeled from the surface of the internal layer.

Description

複合塗膜、複合塗膜の製造方法、物品および塗料組成物Composite coating film, method for producing composite coating film, article and coating composition
　本発明は、複合塗膜、複合塗膜の製造方法、物品および塗料組成物に関する。 The present invention relates to a composite coating film, a method for producing the composite coating film, an article, and a coating composition.
　塗膜は、被塗物を着色する働きだけでなく、被塗物に耐溶剤性、耐水性、耐候性、耐薬品性または防汚性などの機能を付与する働きも有する。 The coating film not only functions to color the object to be coated, but also has a function to impart functions such as solvent resistance, water resistance, weather resistance, chemical resistance or antifouling property to the object.
特開２００５－２９８７５９号公報JP 2005-298759 A
　しかし、塗膜の表面の損傷や汚染によって、塗膜の有する機能が低下または喪失すると、十分な機能を有する塗膜を形成するために再度、塗装を行う必要がある。常に清潔に保たなければならない病室や精密機器室、損傷や汚染されやすい道路の風よけ、湿度の高い場所、工場など再度の塗装が必要な箇所ほど、頻繁な塗装が困難である。 However, when the function of the coating film is reduced or lost due to damage or contamination of the surface of the coating film, it is necessary to perform coating again to form a coating film having a sufficient function. Frequent painting is difficult in hospital rooms and precision equipment rooms that must always be kept clean, windbreaks on roads that are easily damaged or polluted, humid places, and places that require repainting.
　例えば、特許文献１に記載の塗膜などの従来の塗膜は完全硬化する設計となっているために、塗膜の表面の損傷や汚染によって、塗膜の有する機能が低下または喪失した場合、その機能を回復するためには、再度の塗装が必要であった。しかし、上述したように、頻繁な塗装が困難な場合も多い。 For example, since the conventional coating film such as the coating film described in Patent Document 1 is designed to be completely cured, when the function of the coating film is reduced or lost due to damage or contamination of the surface of the coating film, To restore its function, it was necessary to paint again. However, as described above, frequent painting is often difficult.
　そこで、本発明は、複合塗膜の表層を剥離して少なくとも１回は更新可能な複合塗膜を提供することを目的とする。 Therefore, an object of the present invention is to provide a composite coating film that can be renewed at least once by peeling the surface layer of the composite coating film.
　本発明の別の目的は、複合塗膜の表層を剥離して少なくとも１回は更新可能な複合塗膜の製造方法を提供することである。 Another object of the present invention is to provide a method for producing a composite coating that can be renewed at least once by peeling the surface layer of the composite coating.
　本発明の別の目的は、上記複合塗膜を表面に有する物品を提供することである。 Another object of the present invention is to provide an article having the composite coating film on its surface.
　本発明のさらに別の目的は、複合塗膜の表層を剥離して少なくとも１回は更新可能な複合塗膜を形成可能な塗料組成物を提供することである。 Still another object of the present invention is to provide a coating composition capable of forming a composite coating film that can be renewed at least once by peeling the surface layer of the composite coating film.
　本発明に係る複合塗膜は、
　内部層と、前記内部層の空気界面側に隣接する表皮層とからなる複合塗膜であって、
　前記複合塗膜は、単一の塗料組成物から形成されており、
　前記塗料組成物は、
　　活性エネルギー線硬化性化合物（Ａ）と、
　　光吸収剤（Ｂ）と、
　　光重合開始剤（Ｃ）と、
　を含み、
　前記内部層は、未硬化であり、
　前記表皮層は、硬化しており、かつ、前記内部層の表面から剥離可能である、複合塗膜である。複合塗膜がこのような塗料組成物から形成されているため、内部層が未硬化である一方、複合塗膜の表層である表皮層は硬化しているため、表皮層を剥離することが可能である。そして、剥離によって現れた内部層の表層が硬化して新たな表皮層を形成して、複合塗膜を少なくとも１回更新することができる。 The composite coating film according to the present invention is
A composite coating consisting of an inner layer and a skin layer adjacent to the air interface side of the inner layer,
The composite coating film is formed from a single coating composition,
The coating composition is
An active energy ray-curable compound (A);
A light absorber (B);
A photopolymerization initiator (C);
Including
The inner layer is uncured,
The skin layer is a composite coating film that is cured and can be peeled off from the surface of the inner layer. Since the composite coating film is formed from such a coating composition, the inner layer is uncured, while the skin layer that is the surface layer of the composite coating film is cured, so that the skin layer can be peeled off. It is. And the surface layer of the inner layer which appeared by peeling hardens | cures, a new skin layer is formed, and a composite coating film can be updated at least once.
　本発明に係る複合塗膜の一実施形態では、さらに、前記塗料組成物が、内部流動抑制剤（Ｄ）を含み、前記内部流動抑制剤（Ｄ）が、有機系ゲル化剤を含む。 In one embodiment of the composite coating film according to the present invention, the coating composition further includes an internal flow inhibitor (D), and the internal flow inhibitor (D) includes an organic gelling agent.
　本発明に係る複合塗膜の一実施形態では、前記複合塗膜の反発弾性率が、１０～６５％である。 In one embodiment of the composite coating film according to the present invention, the rebound resilience of the composite coating film is 10 to 65%.
　本発明に係る複合塗膜の一実施形態では、前記表皮層の厚みが１０μｍ～５ｍｍであり、前記内部層の厚みが前記表皮層の厚みと同じまたはそれ以上である。 In one embodiment of the composite coating film according to the present invention, the thickness of the skin layer is 10 μm to 5 mm, and the thickness of the inner layer is equal to or greater than the thickness of the skin layer.
　本発明に係る前記複合塗膜の製造方法は、
　被塗物上に、
　　活性エネルギー線硬化性化合物（Ａ）と、
　　光吸収剤（Ｂ）と、
　　光重合開始剤（Ｃ）と、
　を含む単一の塗料組成物を塗布して、塗料組成物の皮膜を形成する工程、
　前記塗料組成物の皮膜に活性エネルギー線を照射して、未硬化の内部層と、硬化した表皮層を形成する工程、
　を含む、複合塗膜の製造方法である。このような塗料組成物を用いることによって、単一の塗料組成物を用いた一回の塗装で、複合塗膜の表層を剥離して少なくとも１回は更新可能な塗膜を製造することができる。 The method for producing the composite coating film according to the present invention comprises:
On the substrate,
An active energy ray-curable compound (A);
A light absorber (B);
A photopolymerization initiator (C);
Applying a single coating composition comprising: forming a coating composition coating;
Irradiating a film of the coating composition with active energy rays to form an uncured inner layer and a cured skin layer;
Is a method for producing a composite coating film. By using such a coating composition, it is possible to produce a coating film that can be renewed at least once by peeling the surface layer of the composite coating film by a single coating using a single coating composition. .
　本発明に係る物品は、複合塗膜を表面に有する物品である。これにより、物品表面の塗膜を少なくとも１回更新することができる。 The article according to the present invention is an article having a composite coating film on the surface. Thereby, the coating film on the article surface can be updated at least once.
　本発明に係る塗料組成物は、
　活性エネルギー線硬化性化合物（Ａ）と、
　光吸収剤（Ｂ）と、
　光重合開始剤（Ｃ）と、
　を含む、
　塗料組成物である。これによって、複合塗膜の表層を剥離して少なくとも１回は更新可能な複合塗膜を形成することができる。 The coating composition according to the present invention comprises:
An active energy ray-curable compound (A);
A light absorber (B);
A photopolymerization initiator (C);
including,
It is a coating composition. Thereby, the surface layer of the composite coating film can be peeled off to form a composite coating film that can be renewed at least once.
　本発明に係る塗料組成物の一実施形態では、さらに、内部流動抑制剤（Ｄ）を含み、前記内部流動抑制剤（Ｄ）が、有機系ゲル化剤を含む。 In one embodiment of the coating composition according to the present invention, an internal flow inhibitor (D) is further included, and the internal flow inhibitor (D) includes an organic gelling agent.
　本発明によれば、複合塗膜の表層を剥離して少なくとも１回は更新可能な複合塗膜を提供することができる。また、本発明によれば、複合塗膜の表層を剥離して少なくとも１回は更新可能な複合塗膜の製造方法を提供することができる。また、本発明によれば、上記複合塗膜を表面に有する物品を提供することができる。また、本発明によれば、複合塗膜の表層を剥離して少なくとも１回は更新可能な複合塗膜を形成可能な塗料組成物を提供することができる。 According to the present invention, it is possible to provide a composite coating film that can be renewed at least once by peeling the surface layer of the composite coating film. Moreover, according to this invention, the surface layer of a composite coating film can be peeled and the manufacturing method of the composite coating film which can be updated at least once can be provided. Moreover, according to this invention, the article | item which has the said composite coating film on the surface can be provided. Moreover, according to this invention, the coating composition which can peel the surface layer of a composite coating film and can form the composite coating film which can be updated at least once can be provided.
図１は、本発明に係る複合塗膜の構成と更新の一例を示した模式図である。FIG. 1 is a schematic diagram showing an example of the configuration and update of a composite coating film according to the present invention. 図２は、本発明に係る複合塗膜の製造方法の一例を示した模式図である。FIG. 2 is a schematic view showing an example of a method for producing a composite coating film according to the present invention. 図３は、本発明における複合塗膜の反発弾性率の測定方法を示した模式図である。FIG. 3 is a schematic view showing a method for measuring the rebound resilience of the composite coating film in the present invention. 図４は、本発明における複合塗膜の剥離性の測定方法を示した模式図である。FIG. 4 is a schematic view showing a method for measuring the peelability of the composite coating film in the present invention.
　以下、本発明の実施形態について説明する。これらの記載は、本発明の例示を目的とするものであり、本発明を何ら限定するものではない。 Hereinafter, embodiments of the present invention will be described. These descriptions are intended to exemplify the present invention and do not limit the present invention in any way.
　本発明において、２以上の実施形態を任意に組み合わせることができる。 In the present invention, two or more embodiments can be arbitrarily combined.
　本発明において、塗料と塗料組成物は相互互換的に用いることができる。 In the present invention, the paint and the paint composition can be used interchangeably.
　本発明において、活性エネルギー線とは、可視光線、紫外線、電子線、赤外線、Ｘ線、β線およびγ線をいう。 In the present invention, active energy rays refer to visible rays, ultraviolet rays, electron beams, infrared rays, X rays, β rays and γ rays.
　本発明において、（メタ）アクリレートは、アクリレートおよびメタアクリレートからなる群より選択される１種以上を意味する。本発明において、（メタ）アクリル酸は、アクリル酸およびメタクリル酸からなる群より選択される１種以上を意味する。本発明において、（メタ）アリルは、アリルおよびメタリルからなる群より選択される１種以上を意味する。本発明において、（不）飽和ポリエステルは、飽和ポリエステルおよび不飽和ポリエステルからなる群より選択される１種以上を意味する。 In the present invention, (meth) acrylate means one or more selected from the group consisting of acrylate and methacrylate. In the present invention, (meth) acrylic acid means one or more selected from the group consisting of acrylic acid and methacrylic acid. In the present invention, (meth) allyl means one or more selected from the group consisting of allyl and methallyl. In the present invention, the (un) saturated polyester means one or more selected from the group consisting of a saturated polyester and an unsaturated polyester.
　本明細書では、活性エネルギー線硬化性化合物（Ａ）、光吸収剤（Ｂ）、光重合開始剤（Ｃ）および内部流動抑制剤（Ｄ）、をそれぞれ、（Ａ）成分、（Ｂ）成分、（Ｃ）成分および（Ｄ）成分ということがある。 In the present specification, the active energy ray-curable compound (A), the light absorber (B), the photopolymerization initiator (C) and the internal flow inhibitor (D) are respectively represented by the component (A) and the component (B). , (C) component and (D) component.
　図１は、本発明に係る複合塗膜の構成と更新の一例を示した模式図である。図１の最も上の図は、被塗物１０上の、複合塗膜１を示している。複合塗膜１は、内部層２０と、その内部層２０の空気界面側に隣接する表皮層３０とからなる。図１の上から２つ目の図に示すように、表皮層３０は、内部層２０の表面から剥離可能である。図１の上から３つ目の図は、表皮層３０を剥離した直後の複合塗膜を示しており、この露出した内部層２０の表層が活性エネルギー線により硬化すると、図１の最も下の図に示すように、内部層２０の表層だった部分に新たな表皮層３１が形成され、複合塗膜１が更新される。このとき、更新された複合塗膜１の内部層２１は、未硬化である。 FIG. 1 is a schematic diagram showing an example of the composition and update of a composite coating film according to the present invention. The uppermost drawing in FIG. 1 shows the composite coating film 1 on the workpiece 10. The composite coating film 1 includes an inner layer 20 and a skin layer 30 adjacent to the air interface side of the inner layer 20. As shown in the second diagram from the top in FIG. 1, the skin layer 30 is peelable from the surface of the inner layer 20. The third figure from the top of FIG. 1 shows the composite coating film immediately after the skin layer 30 is peeled off. When the exposed surface layer of the inner layer 20 is cured by active energy rays, the lowermost part of FIG. As shown in the figure, a new skin layer 31 is formed in the portion that was the surface layer of the inner layer 20, and the composite coating film 1 is updated. At this time, the renewed inner layer 21 of the composite coating film 1 is uncured.
　本発明に係る複合塗膜の内部層と表皮層の説明の前に、本発明に係る複合塗膜を形成する塗料組成物を説明する。 Before describing the inner layer and the skin layer of the composite coating film according to the present invention, the coating composition for forming the composite coating film according to the present invention will be described.
　（塗料組成物）
　本発明に係る塗料組成物は、
　活性エネルギー線硬化性化合物（Ａ）と、
　光吸収剤（Ｂ）と、
　光重合開始剤（Ｃ）と、
　を含む、
　塗料組成物である。これによって、複合塗膜の表皮層（表層）を剥離して少なくとも１回は更新可能な複合塗膜を形成することができる。 (Coating composition)
The coating composition according to the present invention comprises:
An active energy ray-curable compound (A);
A light absorber (B);
A photopolymerization initiator (C);
including,
It is a coating composition. Thereby, the skin layer (surface layer) of the composite coating film can be peeled to form a composite coating film that can be updated at least once.
　＜活性エネルギー線硬化性化合物（Ａ）＞
　活性エネルギー線硬化性化合物（Ａ）は、活性エネルギー線による硬化性を有し、バインダーとして機能する成分である。活性エネルギー線硬化性化合物としては、活性エネルギー線で硬化し得る公知の化合物であれば特に限定されない。このような活性エネルギー線硬化性化合物としては、例えば、特開２００４－３３７６４７号公報に記載のラジカル重合型活性エネルギー線硬化性化合物、カチオン重合型活性エネルギー線硬化性化合物、および、これらを併用した併用型活性エネルギー線硬化性化合物などを挙げることができる。（Ａ）成分は、モノマー、オリゴマー、ポリマー、またはこれらのうちの２種以上の組み合わせであってもよい。（Ａ）成分は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 <Active energy ray-curable compound (A)>
The active energy ray-curable compound (A) is a component that has curability by active energy rays and functions as a binder. The active energy ray-curable compound is not particularly limited as long as it is a known compound that can be cured with active energy rays. Examples of such active energy ray curable compounds include radical polymerization type active energy ray curable compounds and cationic polymerization type active energy ray curable compounds described in JP-A-2004-337647, and combinations thereof. Examples thereof include a combined active energy ray-curable compound. The component (A) may be a monomer, an oligomer, a polymer, or a combination of two or more of these. (A) A component may be used individually by 1 type and may be used in combination of 2 or more type.
　ラジカル重合型活性エネルギー線硬化性化合物としては、例えば、分子内に１個以上のエチレン性不飽和基などのラジカル重合性反応基を有する化合物などを挙げることができる。 Examples of the radical polymerization type active energy ray-curable compound include compounds having one or more radical polymerizable reactive groups such as one or more ethylenically unsaturated groups in the molecule.
　ラジカル重合型活性エネルギー線硬化性化合物としては、例えば、（不）飽和ポリエステル樹脂、エポキシ樹脂、ウレタン樹脂、アクリル樹脂などを（メタ）アクリル酸などのエチレン性不飽和基含有モノマーまたはグリシジル（メタ）アクリレートもしくは（メタ）アリルグリシジルエーテルなどのグリシジル基含有モノマーで変性した樹脂；（不）飽和ポリエステル樹脂、エポキシ樹脂、ウレタン樹脂、アクリル樹脂などを２－ヒドロキシエチル（メタ）アクリレート、グリセリンジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートなどのヒドロキシル基含有アクリルモノマーとヘキサメチレンジイソシアネート、キシリレンジイソシアネート、トルエンジイソシアネートなどのイソシアネートモノマーで変性した変性ポリエステル樹脂、変性エポキシ樹脂、変性ウレタン樹脂、変性アクリル樹脂；エチレングリコールモノ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールモノ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ビスフェノールＡジ（メタ）アクリレート、ビスフェノールＦジ（メタ）アクリレートなどの（メタ）アクリレートおよびこれらの（メタ）アクリレートをエチレンオキサイド（ＥＯ）などのアルキレンオキサイドで変性した化合物などを挙げることができる。 Examples of the radical polymerization type active energy ray-curable compound include (un) saturated polyester resin, epoxy resin, urethane resin, acrylic resin, ethylenically unsaturated group-containing monomer such as (meth) acrylic acid, or glycidyl (meth). Resin modified with glycidyl group-containing monomers such as acrylate or (meth) allyl glycidyl ether; (un) saturated polyester resin, epoxy resin, urethane resin, acrylic resin, etc. with 2-hydroxyethyl (meth) acrylate, glycerin di (meth) Hydroxyl group-containing acrylic monomers such as acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, hexamethylene diisocyanate, xylylene diisocyanate, toluene dii Modified polyester resins modified with isocyanate monomers such as cyanate, modified epoxy resins, modified urethane resins, modified acrylic resins; ethylene glycol mono (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-hexanediol mono (meth) Acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol F di (meth) a Relate such as (meth) acrylates and of these (meth) acrylate and compounds modified with alkylene oxide such as ethylene oxide (EO).
　ラジカル重合型活性エネルギー線硬化性化合物は、市販品を用いてもよい。このような市販品としては、例えば、昭和電工社のリポキシ（登録商標）ＶＲ－７７（ビニルエステル樹脂）、東亜合成社のＭ－２１１Ｂ（ビスフェノールＡジアクリレートのＥＯ変性体）、Ｍ－３５０（トリメチロールプロパンＥＯトリアクリレートのＥＯ変性体）などのアロニックス（登録商標）シリーズなどを挙げることができる。 A commercially available product may be used as the radical polymerization type active energy ray-curable compound. Examples of such commercially available products include Lipoxy (registered trademark) VR-77 (vinyl ester resin) from Showa Denko KK, M-211B (EO-modified bisphenol A diacrylate) from Toa Gosei Co., Ltd., M-350 ( Aronix (registered trademark) series such as EO modified product of trimethylolpropane EO triacrylate).
　カチオン重合型活性エネルギー線硬化性化合物としては、例えば、分子内に１個以上のエポキシ基、グリシジル基、オキセタニル基、テトラヒドロフリル基、ビニル基などのカチオン重合性反応基を有する化合物などを挙げることができる。このような化合物としては、例えば、エポキシ樹脂、エポキシ化ポリジエン樹脂、ビニルエーテル樹脂などを挙げることができる。 Examples of the cationic polymerization type active energy ray-curable compound include compounds having one or more epoxy polymerizable groups such as epoxy group, glycidyl group, oxetanyl group, tetrahydrofuryl group and vinyl group in the molecule. Can do. Examples of such a compound include an epoxy resin, an epoxidized polydiene resin, and a vinyl ether resin.
　併用型活性エネルギー線硬化性化合物としては、例えば、上記ラジカル重合型活性エネルギー線硬化性化合物と上記カチオン重合型活性エネルギー線硬化性化合物をブレンドした化合物；分子内に１個以上のラジカル重合性反応基と１個以上のカチオン重合性反応基とを有する化合物などを挙げることができる。 Examples of the combined active energy ray curable compound include a compound obtained by blending the radical polymerization type active energy ray curable compound and the cationic polymerization type active energy ray curable compound; one or more radical polymerizable reactions in the molecule And a compound having a group and one or more cationically polymerizable reactive groups.
　一実施形態では、（Ａ）成分は、エチレン性不飽和基を有する化合物である。別の実施形態では、（Ａ）成分は、エチレン性不飽和基を２以上有する化合物である。 In one embodiment, the component (A) is a compound having an ethylenically unsaturated group. In another embodiment, the component (A) is a compound having two or more ethylenically unsaturated groups.
　塗料組成物における（Ａ）成分の含有量は、適宜調節すればよい。例えば、（Ａ）成分、（Ｂ）成分および（Ｃ）成分の合計質量に対して、４０～９８質量％、６０～９５質量％とすることができる。 The content of the component (A) in the coating composition may be adjusted as appropriate. For example, it can be 40 to 98% by mass, 60 to 95% by mass with respect to the total mass of the component (A), the component (B) and the component (C).
　＜光吸収剤（Ｂ）＞
　光吸収剤（Ｂ）は、本発明に係る塗料組成物から形成された塗料組成物の皮膜に活性エネルギー線が照射された際に、皮膜の深さ方向全体への活性エネルギー線の侵入を防ぎ、皮膜の深さ方向全体の硬化を抑制する働きを有する。このように、（Ｂ）成分は、皮膜の深さ方向全体の硬化を抑制するため、従来の通常の活性エネルギー線硬化性塗料組成物では、塗膜の硬化を阻害するため、使用されない。これに対して、本発明に係る塗料組成物では、（Ｂ）成分が、上記働きを有することで、複合塗膜において硬化した表皮層と未硬化の内部層の形成に寄与する。（Ｂ）成分は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 <Light absorber (B)>
The light absorber (B) prevents the penetration of active energy rays into the entire depth direction of the coating when the coating of the coating composition formed from the coating composition according to the present invention is irradiated with the active energy rays. , It has a function of suppressing the hardening of the entire film in the depth direction. Thus, the component (B) is not used in the conventional normal active energy ray-curable coating composition because it inhibits the curing of the coating film in order to suppress the curing in the entire depth direction of the film. On the other hand, in the coating composition which concerns on this invention, (B) component contributes to formation of the skin layer hardened | cured in the composite coating film, and an unhardened internal layer because it has the said function. (B) A component may be used individually by 1 type and may be used in combination of 2 or more type.
　（Ｂ）成分としては、活性エネルギー線を吸収、反射または吸収および反射し得る成分であれば特に制限なく、公知の光吸収剤を使用することができる。例えば、無機系光吸収剤および有機系光吸収剤などが挙げられる。 The component (B) is not particularly limited as long as it is a component that can absorb, reflect or absorb and reflect active energy rays, and a known light absorbent can be used. For example, an inorganic light absorber and an organic light absorber can be used.
　無機系光吸収剤としては、例えば、酸化チタン、酸化亜鉛、酸化錫、酸化セリウム、カーボンブラック、鉄黒、酸化鉄、酸化クロム、ウルトラマリン、アルミナ白、酸化鉄黄、ビリジアン、硫化亜鉛、カドミウムイエロー、カドミウムレッド、黄鉛、モリブデートオレンジ、ジンククロメート、ストロンチウムクロメート、鉛白、マンガンバイオレット、紺青などの無機の着色顔料などが挙げられる。 Examples of inorganic light absorbers include titanium oxide, zinc oxide, tin oxide, cerium oxide, carbon black, iron black, iron oxide, chromium oxide, ultramarine, alumina white, iron oxide yellow, viridian, zinc sulfide, cadmium. Examples thereof include inorganic coloring pigments such as yellow, cadmium red, yellow lead, molybdate orange, zinc chromate, strontium chromate, lead white, manganese violet, and bitumen.
　一実施形態では、（Ｂ）成分の無機系光吸収剤は、酸化チタンおよび酸化亜鉛からなる群より選択される１種以上である。 In one embodiment, the inorganic light absorber as component (B) is at least one selected from the group consisting of titanium oxide and zinc oxide.
　有機系光吸収剤としては、例えば、２，４，６－トリス（２－ヒドロキシ－４－ヘキシルオキシ－３－メチルフェニル）－１，３，５－トリアジン、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ビス（１－メチル－１－フェニルエチル）フェノール、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４－（１，１，３，３－テトラメチルブチル）フェノール、２，２’－メチレンビス［６－（２Ｈ－ベンゾトリアゾール－２－イル）－４－（１，１，３，３－テトラメチルブチル）フェノール］、２－（２Ｈ－ベンゾトリアゾール－２－イル）－ｐ－クレゾール、２－（５－クロロ－２Ｈ－ベンゾトリアゾール－２－イル）－６－ｔｅｒｔ－ブチル－４－メチルフェノール、２－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－５－［２－（２－エチルヘキサノイルオキシ）エトキシ］フェノールなどが挙げられる。 Examples of the organic light absorber include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine, 2- (2H-benzotriazole-2 -Yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2- (2H-benzotriazol-2-yl ) -P-cresol, 2- (5-chloro-2H-benzotriazol-2-yl) -6-tert-butyl-4-methylphenol, 2- (4,6-diphenyl-1,3,5-triazi 2-yl) -5-[2- (2-ethylhexanoyloxy) ethoxy] phenol.
　有機系光吸収剤としては、この他、例えば、アセトアミノサロール、ベンザールフタリド、ベンゾフェノン、ベンゾフェノン１－１２、３－ベンジリデンカンファー、ベンジリデンカンファー加水分解コラーゲンスルホンアミド、ベンジリデンカンファースルホン酸、サリチル酸ベンジル、ボルネロン、ブメトリオゾール、ブチルメトキシジベンゾイルメタン、ブチルＰＡＢＡ、シノキセート、メトキシ桂皮酸ＤＥＡ、ジベンゾキサゾールナフタレン、ジ－ｔ－ブチルヒドロキシベンジリデンカンファー、三オレイン酸ジガロイル、ジイソプロピル桂皮酸メチル、ジメチルＰＡＢＡ、トシル酸エチルセテアリールジモニウム、ジオクチルブタミドトリアゾン、ジフェニルカルボメトキシアセトキシナフトピラン、ビスエチルフェニルトリアミノトリアジンスチルベン二スルホン酸二ナトリウム、ジスチリルビフェニルトリアミノトリアジンスチルベン二スルホン酸二ナトリウム、ジスチリルビフェニル二スルホン酸二ナトリウム、ドロメトリゾール、ドロメトリゾールトリシロキサン、エチルジヒドロキシプロピルＰＡＢＡ、ジイソプロピル桂皮酸エチル、メトキシ桂皮酸エチル、エチルＰＡＢＡ、ウロカニン酸エチル、エトロクリレン、フェルラ酸、オクタン酸ジメトキシ桂皮酸グリセリル、グリセリルＰＡＢＡ、サリチル酸グリコール、ホモサレート、メトキシ桂皮酸カリウム、ｐ－メトキシ桂皮酸イソアミル、メトキシ桂皮酸イソプロピル、メトキシ桂皮酸オクチル、サリチル酸イソプロピルベンジル、イソプロピルジベンゾイルメタン、アントラニル酸メンチル、サリチル酸メンチル、４－メチルベンジリデンカンファー、オクトクリレン、オクトリゾール、オクチルジメチルＰＡＢＡ、サリチル酸オクチル、オクチルトリアゾン、４－アミノ安息香酸（ＰＡＢＡ）、アラトインＰＡＢＡ、ＰＥＧ－２５ＰＡＢＡ、ペンチルジメチルＰＡＢＡ、赤ワセリン、ポリアクリルアミドメチルベンジリデンカンファー、フェニルベンズイミダゾールスルホン酸、フェニルベンズイミダゾールスルホン酸カリウム、フェニルベンズイミダゾールスルホン酸ナトリウム、ウロカニン酸ナトリウム、フェニルベンズイミダゾールスルホン酸トリエタノールアミン（ＴＥＡ）、サリチル酸ＴＥＡ、テレフタリリデン二カンファースルホン酸、トリＰＡＢＡパンテノール、ウロカニン酸、および酢酸ビニル（ＶＡ）／クロトン酸／メタクリロキシベンゾフェノン－１コポリマー、捺染系顔料（レーキ顔料）、アゾ系顔料、フタロシアニン顔料、縮合多環顔料、ニトロ系顔料などが挙げられる。 Other organic light absorbers include, for example, acetaminosalol, benzal phthalide, benzophenone, benzophenone 1-12, 3-benzylidene camphor, benzylidene camphor hydrolyzed collagen sulfonamide, benzylidene camphor sulfonic acid, benzyl salicylate , Bornelon, Bumetriozole, Butylmethoxydibenzoylmethane, Butyl PABA, Shinoxate, Methoxycinnamic acid DEA, Dibenzoxazole naphthalene, Di-t-butylhydroxybenzylidene camphor, Digalloyl trioleate, Diisopropylcinnamic acid methyl, Dimethyl PABA, Tosylic acid Ethyl cetearyl dimonium, dioctyl butamido triazone, diphenylcarbomethoxyacetoxynaphthopyran, bisethylphenyltria Notriazine stilbene disulphonate disodium, distyryl biphenyl triaminotriazine disodium stilbene disulfonate, disodium distyryl biphenyl disulphonate, drometrizole, drometrizol trisiloxane, ethyl dihydroxypropyl PABA, ethyl diisopropylcinnamate , Ethyl methoxycinnamate, ethyl PABA, ethyl urocanate, etorocrilene, ferulic acid, dimethoxycinnamate octylate, glyceryl PABA, glycol salicylate, homosalate, potassium methoxycinnamate, isoamyl p-methoxycinnamate, isopropyl methoxycinnamate, Octyl methoxycinnamate, isopropylbenzyl salicylate, isopropyldibenzoylmethane, menthyl anthranilate, salicy Menthyl acid, 4-methylbenzylidene camphor, octocrylene, octtrizole, octyldimethyl PABA, octyl salicylate, octyltriazone, 4-aminobenzoic acid (PABA), allatoin PABA, PEG-25PABA, pentyldimethyl PABA, red petrolatum, polyacrylamide Methyl benzylidene camphor, phenyl benzimidazole sulfonic acid, potassium phenyl benzimidazole sulfonate, sodium phenyl benzimidazole sulfonate, sodium urocanate, phenyl benzimidazole sulfonate triethanolamine (TEA), salicylic acid TEA, terephthalylidene dicamphor sulfonic acid, tri PABA panthenol, urocanic acid, and vinyl acetate (VA) / crotonic acid / medium Examples include a tacryloxybenzophenone-1 copolymer, a printing pigment (lake pigment), an azo pigment, a phthalocyanine pigment, a condensed polycyclic pigment, and a nitro pigment.
　有機系光吸収剤は、市販品を用いてもよい。有機系光吸収剤の市販品としては、例えば、ＡＤＥＫＡ社の紫外線吸収剤　アデカスタブ（登録商標）ＬＡ－２４、ＬＡ－２９、ＬＡ－３１、ＬＡ－３１ＲＧ、ＬＡ－３１Ｇ、ＬＡ－３２、ＬＡ－３６、ＬＡ－３６ＲＧ、ＬＡ－４６、１４１３、ＬＡ－Ｆ７０などのアデカスタブ（登録商標）ＬＡシリーズなどを挙げることができる。 Commercially available products may be used as the organic light absorber. Commercially available organic light absorbers include, for example, ADEKA UV absorbers, Adeka Stub (registered trademark) LA-24, LA-29, LA-31, LA-31RG, LA-31G, LA-32, LA- 36, LA-36RG, LA-46, 1413, Adeka Stub (registered trademark) LA series such as LA-F70, and the like.
　（Ｂ）成分の有機系光吸収剤は、（Ｃ）成分の光重合開始剤の吸収波長の光を吸収する化合物がよい。一実施形態では、（Ｂ）成分の有機系光吸収剤は、２，４，６－トリス（２－ヒドロキシ－４－ヘキシルオキシ－３－メチルフェニル）－１，３，５－トリアジン（ＬＡ－Ｆ７０）である。ここで（Ｃ）成分の光重合開始剤の吸収波長の光を吸収するとは、光重合開始剤がラジカルやカチオンを発生させる吸収ピークおよび近傍の波長域の光を吸収することを意味する。 (B) The organic light absorber as the component is preferably a compound that absorbs light having an absorption wavelength of the photopolymerization initiator as the component (C). In one embodiment, the organic light absorber of component (B) is 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (LA- F70). Here, the absorption of light having the absorption wavelength of the photopolymerization initiator of component (C) means that the photopolymerization initiator absorbs light in an absorption peak that generates radicals and cations and in the nearby wavelength region.
　塗料組成物における（Ｂ）成分の含有量は、適宜調節すればよい。例えば、塗料組成物の（Ａ）成分、（Ｂ）成分および（Ｃ）成分の合計質量に対して、０．５質量％以上、１質量％以上、または５質量％以上、２５質量％以下、２０質量％以下、１５質量％以下、または１０質量％以下とすることができる。 The content of component (B) in the coating composition may be adjusted as appropriate. For example, with respect to the total mass of the components (A), (B) and (C) of the coating composition, 0.5% by mass or more, 1% by mass or more, or 5% by mass or more, 25% by mass or less, It can be 20 mass% or less, 15 mass% or less, or 10 mass% or less.
　＜光重合開始剤（Ｃ）＞
　光重合開始剤（Ｃ）は、上記（Ａ）成分の硬化を促進する働きを有する。（Ｃ）成分は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 <Photopolymerization initiator (C)>
A photoinitiator (C) has a function which accelerates | stimulates hardening of the said (A) component. (C) A component may be used individually by 1 type and may be used in combination of 2 or more type.
　（Ｃ）成分としては、（Ａ）成分の硬化を促進し得る成分であれば特に制限なく、公知の光重合開始剤を使用することができる。 As the component (C), any known photopolymerization initiator can be used without particular limitation as long as it can accelerate the curing of the component (A).
　（Ｃ）成分としては、例えば、α－ヒドロキシアセトフェノン、２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン、ベンゾインメチルエーテル、ベンゾインプロピルエーテル、ジフェニルジケトン、ベンジルジメチルケタール、ベンゾイルシクロヘキサノール、ジフェニル－（２，４，６－トリメチルベンゾイル）ホスフィンオキサイド、２－メチル－１－（４－メチルチオフェニル）－２－モルホリノプロパン－１－オンなどの光ラジカル重合開始剤；トリフェニルスルホニウムヘキサフルオロフォスフェート、トリフェニルスルホニウムヘキサフルオロアンチモネートなどの光カチオン重合開始剤などが挙げられる。 Examples of the component (C) include α-hydroxyacetophenone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1 -One, benzoin methyl ether, benzoin propyl ether, diphenyl diketone, benzyldimethyl ketal, benzoylcyclohexanol, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- (4-methylthiophenyl)- Photo-radical polymerization initiators such as 2-morpholinopropan-1-one; photocationic polymerization initiators such as triphenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluoroantimonate.
　一実施形態では、（Ｃ）成分の光重合開始剤は、α－ヒドロキシアセトフェノン、２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オンおよび２－メチル－１－（４－メチルチオフェニル）－２－モルホリノプロパン－１－オンからなる群より選択される１種以上である。 In one embodiment, the photopolymerization initiator of component (C) is α-hydroxyacetophenone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl}- One or more selected from the group consisting of 2-methyl-propan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one.
　塗料組成物における（Ｃ）成分の含有量は、適宜調節すればよい。例えば、塗料組成物の（Ａ）成分、（Ｂ）成分および（Ｃ）成分の合計質量に対して、１．０質量％以上、２．５質量％以上、３．０質量％以上、５質量％以上、または８質量％以上、４０質量％以下、３０質量％以下、２０質量％以下、または１５質量％以下とすることができる。 What is necessary is just to adjust suitably content of (C) component in a coating composition. For example, 1.0% by mass or more, 2.5% by mass or more, 3.0% by mass or more, 5% by mass with respect to the total mass of the components (A), (B) and (C) of the coating composition % Or more, 8 mass% or more, 40 mass% or less, 30 mass% or less, 20 mass% or less, or 15 mass% or less.
　（Ｃ）成分は、市販品を用いてもよい。（Ｃ）成分の市販品としては、例えば、ＢＡＳＦ社のイルガキュア（登録商標）１１７３、１２７、９０７などのイルガキュア（登録商標）シリーズなどを挙げることができる。 (C) Component may be a commercially available product. Examples of the commercially available component (C) include Irgacure (registered trademark) series such as Irgacure (registered trademark) 1173, 127, and 907 manufactured by BASF.
　＜内部流動抑制剤（Ｄ）＞
　本発明に係る塗料組成物の一実施形態では、さらに、内部流動抑制剤（Ｄ）を含む。これにより、本発明に係る複合塗膜の使用環境において、未硬化の内部層の流動を抑制して、塗膜構造をより形成し易くなる。（Ｄ）成分は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 <Internal flow inhibitor (D)>
In one embodiment of the coating composition according to the present invention, an internal flow inhibitor (D) is further included. Thereby, in the use environment of the composite coating film which concerns on this invention, the flow of an unhardened internal layer is suppressed and it becomes easier to form a coating-film structure. (D) A component may be used individually by 1 type and may be used in combination of 2 or more type.
　内部流動抑制剤としては、例えば、有機系ゲル化剤、層状鉱物などが挙げられる。 Examples of the internal flow inhibitor include organic gelling agents and layered minerals.
　有機系ゲル化剤としては、例えば、脂肪族ケトン化合物、脂肪族エステル化合物、石油系ワックス、植物系ワックス、動物系ワックス、鉱物系ワックス、ジベンジリデンソルビトール類などなどが挙げられる。 Examples of the organic gelling agent include aliphatic ketone compounds, aliphatic ester compounds, petroleum waxes, plant waxes, animal waxes, mineral waxes, dibenzylidene sorbitols, and the like.
　脂肪族ケトン化合物としては、例えば、ジリグノセリルケトン（Ｃ２４－Ｃ２４）、ジベヘニルケトン（Ｃ２２－Ｃ２２、融点８８℃）、ジステアリルケトン（Ｃ１８－Ｃ１８、融点８４℃）、ジエイコシルケトン（Ｃ２０－Ｃ２０）、ジパルミチルケトン（Ｃ１６－Ｃ１６、融点８０℃）、ジミリスチルケトン（Ｃ１４－Ｃ１４）、ジラウリルケトン（Ｃ１２－Ｃ１２、融点６８℃）、ラウリルミリスチルケトン（Ｃ１２－Ｃ１４）、ラウリルパルミチルケトン（Ｃ１２－Ｃ１６）、ミリスチルパルミチルケトン（Ｃ１４－Ｃ１６）、ミリスチルステアリルケトン（Ｃ１４－Ｃ１８）、ミリスチルベヘニルケトン（Ｃ１４－Ｃ２２）、パルミチルステアリルケトン（Ｃ１６－Ｃ１８）、パルミチルベヘニルケトン（Ｃ１６－Ｃ２２）、ステアリルベヘニルケトン（Ｃ１８－Ｃ２２）などが挙げられる。 Examples of the aliphatic ketone compound include dilignoceryl ketone (C24-C24), dibehenyl ketone (C22-C22, melting point 88 ° C.), distearyl ketone (C18-C18, melting point 84 ° C.), dieicosyl ketone ( C20-C20), dipalmityl ketone (C16-C16, melting point 80 ° C.), dimyristyl ketone (C14-C14), dilauryl ketone (C12-C12, melting point 68 ° C.), lauryl myristyl ketone (C12-C14), Lauryl palmityl ketone (C12-C16), myristyl palmityl ketone (C14-C16), myristyl stearyl ketone (C14-C18), myristyl behenyl ketone (C14-C22), palmityl stearyl ketone (C16-C18), palmityl Behenyl ketone (C16-C22), Such as allyl behenyl ketone (C18-C22), and the like.
　脂肪族エステル化合物としては、例えば、ベヘニン酸ベヘニル（Ｃ２１－Ｃ２２、融点７０℃）、イコサン酸イコシル（Ｃ１９－Ｃ２０）、ステアリン酸ステアリル（Ｃ１７－Ｃ１８、融点６０℃）、ステアリン酸パルミチル（Ｃ１７－Ｃ１６）、ステアリン酸ラウリル（Ｃ１７－Ｃ１２）、パルミチン酸セチル（Ｃ１５－Ｃ１６、融点５４℃）、パルミチン酸ステアリル（Ｃ１５－Ｃ１８）、ミリスチン酸ミリスチル（Ｃ１３－Ｃ１４、融点４３℃）、ミリスチン酸セチル（Ｃ１３－Ｃ１６、融点５０℃）、ミリスチン酸オクチルドデシル（Ｃ１３－Ｃ２０）、オレイン酸ステアリル（Ｃ１７－Ｃ１８）、エルカ酸ステアリル（Ｃ２１－Ｃ１８）、リノール酸ステアリル（Ｃ１７－Ｃ１８）、オレイン酸ベヘニル（Ｃ１８－Ｃ２２）、セロチン酸ミリシル（Ｃ２５－Ｃ１６）、リノール酸アラキジル（Ｃ１７－Ｃ２０）などが挙げられる。 Examples of the aliphatic ester compound include behenyl behenate (C21-C22, melting point 70 ° C.), icosyl icosanoate (C19-C20), stearyl stearate (C17-C18, melting point 60 ° C.), palmitic acid stearate (C17- C16), lauryl stearate (C17-C12), cetyl palmitate (C15-C16, melting point 54 ° C.), stearyl palmitate (C15-C18), myristyl myristate (C13-C14, melting point 43 ° C.), cetyl myristate (C13-C16, melting point 50 ° C.), octyldodecyl myristate (C13-C20), stearyl oleate (C17-C18), stearyl erucate (C21-C18), stearyl linoleate (C17-C18), behenyl oleate (C18-C22), C Chin acid myricyl (C25-C16), arachidyl linoleic acid (C17-C20), and the like.
　石油系ワックスとしては、例えば、パラフィンワックス、マイクロクリスタリンワックス、ペトロラクタムなどが挙げられる。 Examples of petroleum waxes include paraffin wax, microcrystalline wax, and petrolactam.
　植物系ワックスとしては、例えば、キャンデリラワックス、カルナウバワックス、ライスワックス、木ロウ、ホホバ油、ホホバ固体ロウ、およびホホバエステルなどが挙げられる。 Examples of the plant wax include candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil, jojoba solid wax, and jojoba ester.
　動物系ワックスとしては、例えば、ミツロウ、ラノリンおよび鯨ロウなどが挙げられる。 Examples of animal waxes include beeswax, lanolin and whale wax.
　鉱物系ワックスとしては、例えば、モンタンワックス、および水素化ワックスなどが挙げられる。 Examples of the mineral wax include montan wax and hydrogenated wax.
　ジベンジリデンソルビトール類としては、例えば、ソルビトールジベンザール（別名：１，３：２，４－ビス－Ｏ－ベンジリデン－Ｄ－グルシトール）、ジ－ｐ－メチルベンジリデンソルビトール（別名：１，３：２，４－ビス－Ｏ－（４－メチルベンジリデン）－Ｄ－ソルビトール）などが挙げられる。 Examples of dibenzylidene sorbitols include sorbitol dibenzal (also known as 1,3: 2,4-bis-O-benzylidene-D-glucitol) and di-p-methylbenzylidene sorbitol (also known as 1,3: 2). , 4-bis-O- (4-methylbenzylidene) -D-sorbitol).
　この他、有機系ゲル化剤としては、例えば、硬化ヒマシ油または硬化ヒマシ油誘導体；モンタンワックス誘導体、パラフィンワックス誘導体、マイクロクリスタリンワックス誘導体またはポリエチレンワックス誘導体などの変性ワックス；ベヘン酸、アラキジン酸、ステアリン酸、パルミチン酸、ミリスチン酸、ラウリン酸、オレイン酸、およびエルカ酸などの高級脂肪酸；ステアリルアルコール、ベヘニルアルコールなどの高級アルコール；１２－ヒドロキシステアリン酸などのヒドロキシステアリン酸；１２－ヒドロキシステアリン酸誘導体；ラウリン酸アミド、ステアリン酸アミド、ベヘン酸アミド、オレイン酸アミド、エルカ酸アミド、リシノール酸アミド、１２－ヒドロキシステアリン酸アミドなどの脂肪酸アミドなど；Ｎ－ステアリルステアリン酸アミド、Ｎ－オレイルパルミチン酸アミドなどのＮ－置換脂肪酸アミド；Ｎ，Ｎ’－エチレンビスステアリルアミド、Ｎ，Ｎ’－エチレンビス－１２－ヒドロキシステアリルアミド、およびＮ，Ｎ’－キシリレンビスステアリルアミドなどの特殊脂肪酸アミド；ドデシルアミン、テトラデシルアミンまたはオクタデシルアミンなどの高級アミン；ショ糖ステアリン酸、ショ糖パルミチン酸などのショ糖脂肪酸のエステル；ポリエチレンワックス、α－オレフィン無水マレイン酸共重合体ワックスなどの合成ワックスなど；ダイマー酸；ダイマージオールなど；ステアリン酸イヌリンなどの脂肪酸イヌリン；パルミチン酸デキストリン、ミリスチン酸デキストリンなどの脂肪酸デキストリンなど；ベヘン酸エイコサン二酸グリセリル；ベヘン酸エイコサンポリグリセリルなど；Ｎ－ラウロイル－Ｌ－グルタミン酸ジブチルアミド、Ｎ－（２－エチルヘキサノイル）－Ｌ－グルタミン酸ジブチルアミド、Ｎ－ヘキサノイルグルタミン酸ジイソプロピルアミド、Ｎ－ヘキサノイルグルタミン酸ジブチルアミド、Ｎ－ヘキサノイルグルタミン酸ジ－ｓｅｃ－ブチルアミド、Ｎ－ヘキサノイルグルタミン酸ジイソブチルアミド、Ｎ－オクタノイルグルタミン酸ジイソプロピルアミド、Ｎ－オクタノイルグルタミン酸ジブチルアミド、Ｎ－オクタノイルグルタミン酸ジ－ｓｅｃ－ブチルアミド、Ｎ－オクタノイルグルタミン酸ジイソブチルアミド、Ｎ－２－エチルヘキサノイルグルタミン酸ジメチルアミド、Ｎ－２－エチルヘキサノイルグルタミン酸ジエチルアミド、Ｎ－２－エチルヘキサノイルグルタミン酸ジプロピルアミド、Ｎ－２－エチルヘキサノイルグルタミン酸ジイソプロピルアミド、Ｎ－２－エチルヘキサノイルグルタミン酸ジブチルアミド、Ｎ－２－エチルヘキサノイルグルタミン酸ジ－ｓｅｃ－ブチルアミド、Ｎ－２－エチルヘキサノイルグルタミン酸ジイソブチルアミド、Ｎ－２－エチルヘキサノイルグルタミン酸ジペンチルアミド、Ｎ－２－エチルヘキサノイルグルタミン酸ジヘキシルアミド、Ｎ－デカノイルグルタミン酸ジイソプロピルアミド、Ｎ－デカノイルグルタミン酸ジブチルアミド、Ｎ－デカノイルグルタミン酸ジ－ｓｅｃ－ブチルアミド、Ｎ－デカノイルグルタミン酸ジイソブチルアミド、Ｎ－ラウロイルグルタミン酸ジメチルアミド、Ｎ－ラウロイルグルタミン酸ジエチルアミド、Ｎ－ラウロイルグルタミン酸ジプロピルアミド、Ｎ－ラウロイルグルタミン酸ジイソプロピルアミド、Ｎ－ラウロイルグルタミン酸ジブチルアミド、Ｎ－ラウロイルグルタミン酸ジ－ｓｅｃ－ブチルアミド、Ｎ－ラウロイルグルタミン酸ジイソブチルアミド、Ｎ－ラウロイルグルタミン酸ジペンチルアミド、Ｎ－ラウロイルグルタミン酸ジヘキシルアミド、Ｎ－パルミトイルグルタミン酸ジイソプロピルアミド、Ｎ－パルミトイルグルタミン酸ジブチルアミド、Ｎ－パルミトイルグルタミン酸ジ－ｓｅｃ－ブチルアミド、Ｎ－パルミトイルグルタミン酸ジイソブチルアミド、Ｎ－ミリストイルグルタミン酸ジイソプロピルアミド、Ｎ－ミリストイルグルタミン酸ジブチルアミド、Ｎ－ミリストイルグルタミン酸ジ－ｓｅｃ－ブチルアミド、Ｎ－ミリストイルグルタミン酸ジイソブチルアミド、Ｎ－２－エチルヘキサノイルアスパラギン酸ジイソプロピルアミド、Ｎ－２－エチルヘキサノイルアスパラギン酸ジブチルアミド、Ｎ－２－エチルヘキサノイルアスパラギン酸ジ－ｓｅｃ－ブチルアミド、Ｎ－２－エチルヘキサノイルアスパラギン酸ジイソブチルアミド、Ｎ－ラウロイルアスパラギン酸ジイソプロピルアミド、Ｎ－ラウロイルアスパラギン酸ジブチルアミド、Ｎ－ラウロイルアスパラギン酸ジ－ｓｅｃ－ブチルアミド、Ｎ－ラウロイルアスパラギン酸ジイソブチルアミドなどのアミド化合物；特開２００５－１２６５０７号公報、特開２００５－２５５８２１号公報および特開２０１０－１１１７９０号公報に記載の低分子オイルゲル化剤などが挙げられる。 Other examples of the organic gelling agent include hardened castor oil or hardened castor oil derivative; modified wax such as montan wax derivative, paraffin wax derivative, microcrystalline wax derivative or polyethylene wax derivative; behenic acid, arachidic acid, stearin Higher fatty acids such as acid, palmitic acid, myristic acid, lauric acid, oleic acid and erucic acid; higher alcohols such as stearyl alcohol and behenyl alcohol; hydroxystearic acid such as 12-hydroxystearic acid; 12-hydroxystearic acid derivative; laurin Fatty acid amides such as acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, 12-hydroxystearic acid amide, etc .; N-substituted fatty acid amides such as allyl stearamide, N-oleyl palmitate, N, N′-ethylenebisstearylamide, N, N′-ethylenebis-12-hydroxystearylamide, and N, N′-xylyl Special fatty acid amides such as lenbisstearylamide; higher amines such as dodecylamine, tetradecylamine or octadecylamine; esters of sucrose fatty acids such as sucrose stearic acid and sucrose palmitic acid; polyethylene wax, α-olefin maleic anhydride Synthetic waxes such as copolymer waxes; dimer acids; dimer diols; fatty acid inulins such as inulin stearate; fatty acid dextrins such as dextrin palmitate and dextrin myristate; eicosane diacid behenate Lyceryl; behenic acid eicosane polyglyceryl, etc .; N-lauroyl-L-glutamic acid dibutylamide, N- (2-ethylhexanoyl) -L-glutamic acid dibutylamide, N-hexanoylglutamic acid diisopropylamide, N-hexanoylglutamic acid dibutylamide N-hexanoylglutamic acid di-sec-butyramide, N-hexanoylglutamic acid diisobutyramide, N-octanoylglutamic acid diisopropylamide, N-octanoylglutamic acid dibutylamide, N-octanoylglutamic acid di-sec-butyramide, N-octa Noyl glutamic acid diisobutyramide, N-2-ethylhexanoyl glutamic acid dimethylamide, N-2-ethylhexanoyl glutamic acid diethylamide, N-2 Ethylhexanoylglutamic acid dipropylamide, N-2-ethylhexanoylglutamic acid diisopropylamide, N-2-ethylhexanoylglutamic acid dibutylamide, N-2-ethylhexanoylglutamic acid di-sec-butylamide, N-2-ethylhexa Noylglutamic acid diisobutyramide, N-2-ethylhexanoylglutamic acid dipentylamide, N-2-ethylhexanoylglutamic acid dihexylamide, N-decanoylglutamic acid diisopropylamide, N-decanoylglutamic acid dibutylamide, N-decanoylglutamic acid di- sec-Butylamide, N-decanoyl glutamic acid diisobutyramide, N-lauroyl glutamic acid dimethylamide, N-lauroyl glutamic acid diethylamino N-lauroylglutamic acid dipropylamide, N-lauroylglutamic acid diisopropylamide, N-lauroylglutamic acid dibutylamide, N-lauroylglutamic acid di-sec-butylamide, N-lauroylglutamic acid diisobutyramide, N-lauroylglutamic acid dipentylamide, N-lauroyl Glutamic acid dihexylamide, N-palmitoylglutamic acid diisopropylamide, N-palmitoylglutamic acid dibutylamide, N-palmitoylglutamic acid di-sec-butylamide, N-palmitoylglutamic acid diisobutylamide, N-myristoylglutamic acid diisopropylamide, N-myristoylglutamic acid dibutyramide -Myristoyl glutamic acid di-sec-butyramide, N-myristoylglutamic acid diisobutyramide, N-2-ethylhexanoylaspartic acid diisopropylamide, N-2-ethylhexanoylaspartic acid dibutylamide, N-2-ethylhexanoylaspartic acid di-sec-butylamide, N-2- Amide compounds such as ethylhexanoylaspartic acid diisobutyramide, N-lauroylaspartic acid diisopropylamide, N-lauroylaspartic acid dibutylamide, N-lauroylaspartic acid di-sec-butylamide, N-lauroylaspartic acid diisobutyramide; -126507, JP-A-2005-255821 and JP-A-2010-111790 include low-molecular oil gelling agents.
　（Ｄ）成分の有機系ゲル化剤は、特に炭素数が１２以上の直鎖アルキル基を含む化合物、もしくは芳香族環を有し、有機結晶が物理的に組み合わさってできたカードハウス構造を形成しやすいものが望ましい。また、モノマー、オリゴマー、ポリマーとの相溶性を考えると、一部極性官能基を有する化合物がより望ましい。 The organic gelling agent as component (D) has a card house structure in which a compound containing a linear alkyl group having 12 or more carbon atoms or an aromatic ring, and organic crystals are physically combined. What is easy to form is desirable. In view of compatibility with monomers, oligomers and polymers, compounds having a partial polar functional group are more desirable.
　一実施形態では、有機系ゲル化剤は、脂肪族ケトン化合物、脂肪族エステル化合物、高級脂肪酸、高級アルコールおよび脂肪酸アミドからなる群より選択される１種以上である。 In one embodiment, the organic gelling agent is at least one selected from the group consisting of aliphatic ketone compounds, aliphatic ester compounds, higher fatty acids, higher alcohols, and fatty acid amides.
　一実施形態では、有機系ゲル化剤は、ソルビトールジベンザール、ジラウリルケトン、オレイン酸アミド、ミリスチン酸セチルおよびミリスチン酸からなる群より選択される１種以上である。 In one embodiment, the organic gelling agent is at least one selected from the group consisting of sorbitol dibenzal, dilauryl ketone, oleic amide, cetyl myristate, and myristic acid.
　有機系ゲル化剤は、市販品を用いてもよい。ソルビトール系化合物の市販品としては、例えば、新日本理化社のゲルオール（登録商標）Ｄ（ソルビトールジベンザール）、ＭＤ、ＭＤ－ＬＭ３０Ｇ、Ｅ－２００などのゲルオール（登録商標）シリーズなどを挙げることができる。 Commercially available products may be used as the organic gelling agent. Examples of commercially available sorbitol compounds include Gelall (registered trademark) series such as Gelol (registered trademark) D (sorbitol dibenzal), MD, MD-LM30G, E-200, etc., manufactured by Shin Nippon Chemical Co., Ltd. Can do.
　本発明に係る塗料組成物の一実施形態では、さらに、内部流動抑制剤（Ｄ）を含み、前記内部流動抑制剤（Ｄ）が、有機系ゲル化剤を含む。 In one embodiment of the coating composition according to the present invention, an internal flow inhibitor (D) is further included, and the internal flow inhibitor (D) includes an organic gelling agent.
　層状鉱物としては、例えば、モンモリロナイト、ザコウナイト、ノントロナイト、サポナイト、ヘクトライト、バーミキュライト、合成ヘクトライト、タルクなどが挙げられる。 Examples of layered minerals include montmorillonite, zakonite, nontronite, saponite, hectorite, vermiculite, synthetic hectorite, and talc.
　層状鉱物は、市販品を用いてもよい。層状鉱物の市販品としては、例えば、ＢＹＫ社のＣＬＡＹＴＯＮＥ（登録商標）４０、ＨＴ、ＡＰＡ、ＡＦ、ＨＹなどのＣＬＡＹＴＯＮＥ（登録商標）シリーズ、ＴＩＸＯＧＥＬ　ＶＰ、ＭＰ、ＭＰＩ、ＶＺ、ＭＰＺ、ＭＰ１００、ＭＰ２５０などのＴＩＸＯＧＥＬシリーズ、ＧＡＲＡＭＩＴＥ　７３０３、１９５８、７３０５などのＧＡＲＡＭＩＴＥシリーズ、ＣＬＯＩＳＩＴＥシリーズ、ＬＡＰＯＮＩＴＥ（登録商標）ＲＤ、ＥＰ、ＲＤＳ、ＪＳ、Ｓ４８２などのＬＡＰＯＮＩＴＥ（登録商標）シリーズ、ＯＰＴＩＧＥＬ　ＣＫ、ＣＭＯ、Ｗ７２４、ＷＡ、ＷＭ、ＷＸ、ＬＸなどのＯＰＴＩＧＥＬシリーズ、ＢＥＮＴＯＬＩＴＥ（登録商標）シリーズ、ＯＰＴＩＢＥＮＴ　ＭＦ、９８７、ＮＴ１０などのＯＰＴＩＢＥＮＴシリーズなどを挙げることができる。 A commercially available product may be used as the layered mineral. Commercially available layered minerals include, for example, KYTONE (registered trademark) 40 of BYK, CLAYTONE (registered trademark) series such as HT, APA, AF, HY, TIXOGEL VP, MP, MPI, VZ, MPZ, MP100, and MP250. Such as TIXOGEL series, GARAMITE series such as GARAMITE 7303, 1958, 7305, CLOISITE series, LAPONITE (registered trademark) RD, EP, RDS, JS, LAPONITE (registered trademark) series such as S482, OPTIGEL CK, CMO, W724, WA OPTIGEL series such as WM, WX, LX, BENTOLITE (registered trademark) series, OPTIBENT series such as OPTIBENT MF, 987, NT10, etc. It can gel.
　一実施形態では、層状鉱物は、ＣＬＡＹＴＯＮＥ（登録商標）ＨＹおよびタルクからなる群より選択される１種以上である。 In one embodiment, the layered mineral is at least one selected from the group consisting of CLAYTONE (registered trademark) HY and talc.
　塗料組成物における（Ｄ）成分の含有量は、適宜調節すればよい。一実施形態では、（Ｄ）成分の含有量は（Ａ）成分の１００質量％に対して、０．５質量％以上、１．０質量％以上、２．０質量％以上、５．０質量％以上、１０質量％以上、２０質量％以上、または３０質量％以上、１００質量％以下、９０質量％以下、８０質量％以下、６０質量％以下、または５０質量％以下とすることができる。別の実施形態では、有機系ゲル化剤の含有量は（Ａ）成分の１００質量％に対して、０．５質量％以上、１．０質量％以上、２．０質量％以上、５．０質量％以上、１０質量％以上、２０質量％以上、または３０質量％以上、１００質量％以下、９０質量％以下、８０質量％以下、６０質量％以下、５０質量％以下、３０質量％以下、２０質量％以下、または１５質量％以下とすることができる。 The content of the component (D) in the coating composition may be adjusted as appropriate. In one Embodiment, content of (D) component is 0.5 mass% or more, 1.0 mass% or more, 2.0 mass% or more, 5.0 mass with respect to 100 mass% of (A) component. % Or more, 10% or more, 20% or more, or 30% or more, 100% or less, 90% or less, 80% or less, 60% or less, or 50% or less. In another embodiment, content of an organic type gelatinizer is 0.5 mass% or more, 1.0 mass% or more, 2.0 mass% or more with respect to 100 mass% of (A) component. 0% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass or more, 100% by mass or less, 90% by mass or less, 80% by mass or less, 60% by mass or less, 50% by mass or less, 30% by mass or less , 20% by mass or less, or 15% by mass or less.
　＜その他の成分＞
　本発明に係る塗料組成物は、上述した成分以外に、水、溶剤、体質顔料、光増感剤、分散剤、造膜助剤、凍結防止剤、レベリング剤、表面調整剤、消泡剤、防腐剤、防カビ剤、防藻剤、酸化防止剤などの塗料用添加剤を含んでいてもよい。これらの成分はそれぞれ、１種単独でまたは２種以上を組み合わせて用いてもよい。 <Other ingredients>
In addition to the components described above, the coating composition according to the present invention includes water, a solvent, an extender pigment, a photosensitizer, a dispersant, a film-forming aid, an antifreezing agent, a leveling agent, a surface conditioner, an antifoaming agent, It may contain paint additives such as antiseptics, fungicides, algae inhibitors and antioxidants. Each of these components may be used alone or in combination of two or more.
　＜溶剤＞
　溶剤を用いる場合、従来公知の塗料組成物の溶剤を適宜選択して用いることができる。例えば、メタノール、エタノール、２－プロパノール、１－ブタノールなどのアルコール類；酢酸エチル、酢酸ブチル、酢酸イソブチル、プロピオン酸エチル、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテートなどのエステル類；ジエチルエーテル、プロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジオキサン、テトラヒドロフラン（ＴＨＦ）などのエーテル類；エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、１、３－ブチレングリコール、ペンタメチレングリコール、１、３－オクチレングリコールなどのグリコール類；ホルムアミド、Ｎ－メチルホルムアミド、ジメチルホルムアミド（ＤＭＦ）、ジメチルアセトアミド、ジメチルスルフォキシド（ＤＭＳＯ）、Ｎ－メチルピロリドン（ＮＭＰ）などのアミド類；アセトン、メチルエチルケトン（ＭＥＫ）、メチルプロピルケトン、メチルイソブチルケトン、アセチルアセトン、シクロヘキサノンなどのケトン類；ミネラルスピリット、灯油などの脂肪族炭化水素；トルエン、キシレン、メシチレン、ドデシルベンゼンなどの芳香族炭化水素；クロロホルム、ジクロロメチレンなどのハロゲン系溶媒などが挙げられる。 <Solvent>
When using a solvent, the solvent of a conventionally well-known coating composition can be selected suitably, and can be used. For example, alcohols such as methanol, ethanol, 2-propanol, 1-butanol; ethyl acetate, butyl acetate, isobutyl acetate, ethyl propionate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. Esters of diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dioxane, tetrahydrofuran (THF), etc .; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3- Butylene glycol, pentamethylene glycol, 1,3-octylene glycol Glycols such as formaldehyde; amides such as formamide, N-methylformamide, dimethylformamide (DMF), dimethylacetamide, dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP); acetone, methyl ethyl ketone (MEK), methyl Ketones such as propyl ketone, methyl isobutyl ketone, acetylacetone, and cyclohexanone; aliphatic hydrocarbons such as mineral spirits and kerosene; aromatic hydrocarbons such as toluene, xylene, mesitylene, and dodecylbenzene; halogen solvents such as chloroform and dichloromethylene Etc.
　＜体質顔料＞
　体質顔料を用いる場合、従来公知の塗料組成物の顔料を適宜選択して用いることができる。例えば、炭酸カルシウム、沈降性バリウムなどの体質顔料などが挙げられる。 <External pigment>
When the extender pigment is used, a pigment of a conventionally known coating composition can be appropriately selected and used. Examples thereof include extender pigments such as calcium carbonate and precipitated barium.
　本発明の塗料組成物は、１液型でもよいし、２液型でもよい。２液型の場合は、塗装直前に混合して単一の塗料組成物として使用する。 The coating composition of the present invention may be a one-pack type or a two-pack type. In the case of the two-component type, they are mixed immediately before coating and used as a single coating composition.
　＜塗料組成物の調製方法＞
　塗料組成物の調製方法は、特に限定されず、上述した（Ａ）～（Ｃ）成分などを従来公知の方法により、混合して調製することができる。 <Method for preparing coating composition>
The method for preparing the coating composition is not particularly limited, and the above-described components (A) to (C) can be mixed and prepared by a conventionally known method.
　（複合塗膜）
　本発明に係る複合塗膜は、
　内部層と、前記内部層の空気界面側に隣接する表皮層とからなる複合塗膜であって、
　前記複合塗膜は、単一の塗料組成物から形成されており、
　前記塗料組成物は、
　　活性エネルギー線硬化性化合物（Ａ）と、
　　光吸収剤（Ｂ）と、
　　光重合開始剤（Ｃ）と、
　を含み、
　前記内部層は、未硬化であり、
　前記表皮層は、硬化しており、かつ、前記内部層の表面から剥離可能である、複合塗膜である。 (Composite coating)
The composite coating film according to the present invention is
A composite coating consisting of an inner layer and a skin layer adjacent to the air interface side of the inner layer,
The composite coating film is formed from a single coating composition,
The coating composition is
An active energy ray-curable compound (A);
A light absorber (B);
A photopolymerization initiator (C);
Including
The inner layer is uncured,
The skin layer is a composite coating film that is cured and can be peeled off from the surface of the inner layer.
　本発明に係る複合塗膜の一実施形態では、さらに、前記塗料組成物が、内部流動抑制剤（Ｄ）を含み、前記内部流動抑制剤（Ｄ）が、有機系ゲル化剤を含む。 In one embodiment of the composite coating film according to the present invention, the coating composition further includes an internal flow inhibitor (D), and the internal flow inhibitor (D) includes an organic gelling agent.
　＜内部層＞
　内部層は、塗料組成物の皮膜が完全には硬化しておらず、未硬化である。内部層全てが完全に硬化すると、表皮層を剥離することができず、塗膜を更新することができない。 <Inner layer>
The coating of the coating composition is not completely cured and the inner layer is uncured. When all the inner layers are completely cured, the skin layer cannot be peeled off and the coating film cannot be renewed.
　図１に示したように、内部層は、表皮層が剥離後に、太陽光または紫外線などの活性エネルギー線により表層側が硬化し、新たな表皮層を少なくとも１回形成し得る。内部層の厚みが厚いほど、新たな表皮層を形成する余地が多くなり、複合塗膜の更新可能な回数が増える。 As shown in FIG. 1, after the skin layer is peeled off, the surface layer side is cured by active energy rays such as sunlight or ultraviolet rays, and a new skin layer can be formed at least once. The thicker the inner layer, the more room for forming a new skin layer, and the greater the number of times the composite coating can be updated.
　内部層の厚みは、特に限定されず、適宜調節すればよい。内部層の厚みを厚くする方法としては、例えば、塗料組成物の塗布量を多くする、あるいは、表皮層の厚みを薄くするなどが挙げられる。一実施形態では、内部層の厚みは、表皮層の厚みと同じまたはそれ以上である。 The thickness of the inner layer is not particularly limited and may be adjusted as appropriate. Examples of a method for increasing the thickness of the inner layer include increasing the coating amount of the coating composition or decreasing the thickness of the skin layer. In one embodiment, the thickness of the inner layer is the same as or greater than the thickness of the skin layer.
　内部層は、未硬化であればよいが、実施例で後述する内部流動性の評価において、内部流動性がないことが好ましい。当該評価で内部流動性がない（塗膜の変形がない）と、表皮層を剥離する際に糸曳きが低減される、および剥離後の表面のべたつきが低減されるという利点がある。 The inner layer may be uncured, but preferably has no internal fluidity in the evaluation of internal fluidity described later in Examples. If there is no internal fluidity in the evaluation (no deformation of the coating film), there is an advantage that stringing is reduced when peeling the skin layer, and stickiness of the surface after peeling is reduced.
　一実施形態では、複合塗膜の反発弾性率が、１０～６５％であることによって、内部層が未硬化であると判断する。別の実施形態では、複合塗膜の反発弾性率は、２０％以上、２５％以上、または３０％以上であり、別の実施形態では、複合塗膜の反発弾性率は、６０％以下、５５％以下、または５０％以下である。 In one embodiment, it is determined that the inner layer is uncured when the rebound resilience of the composite coating is 10 to 65%. In another embodiment, the rebound resilience of the composite coating is 20% or more, 25% or more, or 30% or more. In another embodiment, the rebound resilience of the composite coating is 60% or less, 55 % Or less, or 50% or less.
　＜表皮層＞
　表皮層は、前記内部層の空気界面側に隣接する層であり、硬化している。上述したように、内部層が未硬化であり、かつ表皮層が、硬化していることにより、表皮層が内部層の表面から剥離可能となる。 <Skin layer>
The skin layer is a layer adjacent to the air interface side of the inner layer and is cured. As described above, since the inner layer is uncured and the skin layer is cured, the skin layer can be peeled from the surface of the inner layer.
　本発明において、「表皮層が硬化している」および「表皮層が形成されている」とは、実施例で後述するＪＩＳ　Ｋ　５６００－３－２：１９９９に準拠して測定した際に「塗膜が表面乾燥である」と判定される状態をいう。 In the present invention, “the skin layer is hardened” and “the skin layer is formed” means “coating” when measured in accordance with JIS K 5600-3-2: 1999 described later in Examples. A state in which it is determined that the film is dry on the surface.
　表皮層の厚みは、特に限定されず、適宜調節すればよい。一実施形態では、表皮層の厚みは、１０μｍ～５ｍｍである。別の実施形態では、表皮層の厚みは、７０～２００μｍである。また、初期（一度も表皮層を剥離していない状態）の表皮層の厚みと、表皮層を１回以上剥離後に形成される表皮層の厚みは、同じであってもよいし、異なっていてもよい。 The thickness of the skin layer is not particularly limited and may be adjusted as appropriate. In one embodiment, the thickness of the skin layer is 10 μm to 5 mm. In another embodiment, the thickness of the skin layer is 70-200 μm. In addition, the thickness of the skin layer in the initial stage (the state in which the skin layer has not been peeled once) and the thickness of the skin layer formed after peeling the skin layer once or more may be the same or different. Also good.
　＜複合塗膜の更新方法＞
　本発明に係る複合塗膜を更新する方法としては、例えば、表皮層を剥離し、次いで露出した内部層の表層を硬化させて、未硬化の内部層と、新たな硬化した表皮層とを形成することで更新することができる。あるいは、上記の表皮層を剥離しながら、露出した内部層の表層の硬化を同時に行ってもよい。 <Renewal method of composite coating film>
As a method for renewing the composite coating film according to the present invention, for example, the skin layer is peeled off, and then the exposed inner surface layer is cured to form an uncured inner layer and a new cured skin layer. You can update it. Alternatively, the surface layer of the exposed inner layer may be simultaneously cured while peeling the skin layer.
　表皮層の剥離方法は、特に限定されず、適宜選択することができる。例えば、表皮層に粘着テープまたは吸盤などを貼り付けて引っ張ることで表皮層を剥離させてもよい。または、硬化した表皮層のみをヘラなどで剥離してもよい。 The method for peeling the skin layer is not particularly limited and can be appropriately selected. For example, the skin layer may be peeled off by attaching an adhesive tape or a suction cup to the skin layer and pulling it. Alternatively, only the cured skin layer may be peeled off with a spatula or the like.
　露出した内部層の表層を硬化させる方法は、特に限定されず、適宜選択することができる。例えば、紫外線などの活性エネルギー線を照射する、太陽光に内部層を暴露するなどが挙げられる。活性エネルギー線として紫外線を照射する場合、照射条件は、適宜調節すればよいが、例えば、出力３０～２００Ｗ、照射時間１～３６０秒とすればよい。 The method for curing the exposed surface layer of the inner layer is not particularly limited and can be appropriately selected. Examples include irradiating active energy rays such as ultraviolet rays and exposing the inner layer to sunlight. In the case of irradiating ultraviolet rays as active energy rays, the irradiation conditions may be appropriately adjusted. For example, the output may be 30 to 200 W and the irradiation time may be 1 to 360 seconds.
　本発明に係る複合塗膜は、単層の塗膜として用いてもよいし、下層として用いてもよい。本発明に係る複合塗膜を下層として用いる場合、複合塗膜の上面に、上塗り塗料を塗装する、または外装材もしくは壁紙などの内装材を設けて上層を形成してもよい。上塗り塗料や外装材、壁紙などの内装材は、特に限定されず、公知の材料を使用することができる。本発明に係る複合塗膜を下層として用いる場合、複合塗膜の表皮層を剥離する方法は特に限定されず、例えば、上述した上層に粘着テープなどを貼り付け、当該上層と本発明に係る複合塗膜の表皮層を一緒に剥離してもよいし、または上層をヘラなどで除去後に、本発明に係る複合塗膜の表皮層を剥離してもよい。 The composite coating film according to the present invention may be used as a single layer coating film or as a lower layer. When the composite coating film according to the present invention is used as the lower layer, the upper layer may be formed by applying a top coating material on the upper surface of the composite coating film or providing an interior material such as an exterior material or wallpaper. There are no particular limitations on the interior materials such as the top coat, exterior material, and wallpaper, and any known material can be used. When the composite coating film according to the present invention is used as the lower layer, the method for peeling the skin layer of the composite coating film is not particularly limited. For example, an adhesive tape or the like is attached to the upper layer described above, and the upper layer and the composite according to the present invention The skin layer of the coating film may be peeled together, or after removing the upper layer with a spatula or the like, the skin layer of the composite coating film according to the present invention may be peeled off.
　（複合塗膜の製造方法）
　本発明に係る前記複合塗膜の製造方法は、
　被塗物上に、
　　活性エネルギー線硬化性化合物（Ａ）と、
　　光吸収剤（Ｂ）と、
　　光重合開始剤（Ｃ）と、
　を含む単一の塗料組成物を塗布して、塗料組成物の皮膜を形成する工程、
　前記塗料組成物の皮膜に活性エネルギー線を照射して、未硬化の内部層と、硬化した表皮層を形成する工程、
　を含む、複合塗膜の製造方法である。このような塗料組成物を用いることによって、単一の塗料組成物を用いた一回の塗装で、複合塗膜の表皮層を剥離して少なくとも１回は更新可能な複合塗膜を製造することができる。 (Production method of composite coating film)
The method for producing the composite coating film according to the present invention comprises:
On the substrate,
An active energy ray-curable compound (A);
A light absorber (B);
A photopolymerization initiator (C);
Applying a single coating composition comprising: forming a coating composition coating;
Irradiating a film of the coating composition with active energy rays to form an uncured inner layer and a cured skin layer;
Is a method for producing a composite coating film. By using such a coating composition, a single coating using a single coating composition is used to produce a composite coating film that can be renewed at least once by peeling the skin layer of the composite coating film. Can do.
　本発明に係る前記複合塗膜の製造方法で用いる塗料組成物は、上述した塗料組成物である。 The coating composition used in the method for producing a composite coating film according to the present invention is the coating composition described above.
　本発明に係る複合塗膜の製造方法の一実施形態では、さらに、前記塗料組成物が、内部流動抑制剤（Ｄ）を含み、前記内部流動抑制剤（Ｄ）が、有機系ゲル化剤を含む。 In one embodiment of the method for producing a composite coating film according to the present invention, the coating composition further includes an internal flow inhibitor (D), and the internal flow inhibitor (D) comprises an organic gelling agent. Including.
　図２は、本発明に係る複合塗膜の製造方法の一例を示した模式図である。この一例では、被塗物１０上に、塗料組成物を塗布して、塗料組成物の皮膜４０を形成する（図２の上から１つ目および２つ目の図）。そして、その塗料組成物の皮膜４０に活性エネルギー線を照射して、未硬化の内部層２０と、硬化した表皮層３０を形成して、複合塗膜１を得る（図２の最も下の図）。 FIG. 2 is a schematic view showing an example of a method for producing a composite coating film according to the present invention. In this example, the coating composition is applied on the article 10 to form the coating composition film 40 (first and second views from the top in FIG. 2). And the active energy ray is irradiated to the film | membrane 40 of the coating composition, the uncured inner layer 20 and the hardened skin layer 30 are formed, and the composite coating film 1 is obtained (the bottom figure of FIG. 2). ).
　被塗布物としては、特に限定されず、適宜選択することができる。被塗布物として、例えば、自動車、鉄道車両などの車両の車体、航空機の機体、船舶の船体および上部構造物（艤装）、の内装および外装；建築物の内装および外装；家具、建具；車両、航空機、船舶、建築物などの窓ガラス；ガラス製、アクリル製、ポリカーボネート製などのケース、容器、樹脂板、フィルムなどの透明体；ディスプレイ、モニター、冷蔵庫などの電化製品の筺体およびガラス部材などが挙げられる。 The material to be coated is not particularly limited and can be appropriately selected. As an object to be coated, for example, a vehicle body such as an automobile or a railway vehicle, an aircraft body, a ship hull and an upper structure (fitting), interior and exterior; building interior and exterior; furniture, fittings; vehicle, Window glass for aircraft, ships, buildings, etc .; transparent bodies such as cases made of glass, acrylic, polycarbonate, containers, resin plates, films; housings and glass members for electrical appliances such as displays, monitors, refrigerators, etc. Can be mentioned.
　被塗物上に塗料組成物を塗布して、塗料組成物の皮膜を形成する工程では、塗布方法は特に限定されず、公知の塗布方法を適宜選択して用いることができる。塗布方法としては、例えば、刷毛、コテ、ローラー、エアスプレー、エアレススプレーなどが挙げられる。 In the step of applying the coating composition on the object to be coated to form the coating composition film, the coating method is not particularly limited, and a known coating method can be appropriately selected and used. Examples of the application method include brushes, trowels, rollers, air sprays, and airless sprays.
　塗料組成物の皮膜の厚みは、特に限定されず、適宜調節すればよい。皮膜の厚みは、例えば、２０μｍ～５０ｍｍ、または５０μｍ～３０ｍｍとすればよい。 The thickness of the coating film of the coating composition is not particularly limited, and may be adjusted as appropriate. The thickness of the film may be, for example, 20 μm to 50 mm, or 50 μm to 30 mm.
　塗料組成物の皮膜に活性エネルギー線を照射して、未硬化の内部層と、硬化した表皮層を形成する工程では、複合塗膜の更新方法で述べた方法と同様に、塗料組成物の皮膜に紫外線などの活性エネルギー線を照射してもよいし、太陽光に塗料組成物の皮膜を暴露してもよい。活性エネルギー線として紫外線を照射する場合、照射条件は、所望の表皮層の厚みなどに応じて適宜調節すればよいが、例えば、出力３０～２００Ｗ、照射時間１～３６０秒とすればよい。本発明に係る複合塗膜の製造方法では、上述した本発明の塗料組成物を用いることにより、従来の活性エネルギー線硬化性塗料組成物の塗膜が完全硬化するような条件で活性エネルギー線を本発明の塗料組成物に照射した場合であっても、表皮層を硬化させ、内部層を未硬化として複合塗膜を製造することができる。このような従来の活性エネルギー線硬化性塗料組成物の塗膜が完全硬化するような条件としては、例えば、出力８０～１２０Ｗ、照射時間０．５～１０秒が挙げられる。 In the step of irradiating the coating composition film with active energy rays to form an uncured inner layer and a cured skin layer, the coating composition film is the same as the method described in the method for renewing the composite coating film. The film may be irradiated with active energy rays such as ultraviolet rays, or the coating composition film may be exposed to sunlight. In the case of irradiating ultraviolet rays as active energy rays, the irradiation conditions may be appropriately adjusted according to the desired thickness of the skin layer, etc. For example, the output may be 30 to 200 W and the irradiation time may be 1 to 360 seconds. In the method for producing a composite coating film according to the present invention, by using the above-described coating composition of the present invention, the active energy ray is applied under such a condition that the coating film of the conventional active energy ray-curable coating composition is completely cured. Even when the coating composition of the present invention is irradiated, a composite coating film can be produced by curing the skin layer and uncuring the inner layer. Examples of conditions for completely curing the coating film of such a conventional active energy ray-curable coating composition include an output of 80 to 120 W and an irradiation time of 0.5 to 10 seconds.
　本発明に係る前記複合塗膜の製造方法では、上述した工程以外の工程を任意のタイミングで含んでいてもよい。例えば、塗料組成物の皮膜に活性エネルギー線を照射して、未硬化の内部層と、硬化した表皮層を形成する工程の後に、表皮層と内部層のいずれかまたは両方を自然乾燥または加熱乾燥させる工程などを含んでいてもよい。 In the method for producing a composite coating film according to the present invention, steps other than the steps described above may be included at any timing. For example, after irradiating the coating composition film with active energy rays to form an uncured inner layer and a cured skin layer, either or both of the skin layer and the inner layer are naturally dried or heat dried. And the like.
　（物品）
　本発明に係る物品は、上記複合塗膜を表面に有する物品である。これにより、物品表面の塗膜を少なくとも１回更新することができる。 (Goods)
The article according to the present invention is an article having the composite coating film on its surface. Thereby, the coating film on the article surface can be updated at least once.
　本発明に係る物品としては、例えば、自動車、鉄道車両などの車両、航空機、船舶、建築物、家具、建具、窓ガラス、透明体、電化製品などが挙げられる。 Examples of the articles according to the present invention include vehicles such as automobiles and railroad cars, aircraft, ships, buildings, furniture, joinery, window glass, transparent bodies, electrical appliances, and the like.
　以下、実施例を挙げて本発明をさらに詳しく説明するが、これらの実施例は、本発明の例示を目的とするものであり、本発明を何ら限定するものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are intended to illustrate the present invention and do not limit the present invention in any way.
　実施例で用いた塗料組成物の各成分の詳細は以下のとおりである。
活性エネルギー線硬化性化合物（Ａ）：昭和電工社製の商品名リポキシ（登録商標）ＶＲ－７７（ビニルエステル樹脂）
活性エネルギー線硬化性化合物（Ａ）：東亜合成社の商品名アロニックス（登録商標）Ｍ－３５０（トリメチロールプロパンＥＯ変性トリアクリレート）
活性エネルギー線硬化性化合物（Ａ）：東亜合成社の商品名アロニックス（登録商標）Ｍ－２１１Ｂ（ビスフェノールＡ　ＥＯ変性ジアクリレート）
光吸収剤（Ｂ）（無機系光吸収剤）：酸化チタン、石原産業社製の商品名ＣＲ－５０
光吸収剤（Ｂ）（有機系光吸収剤）：ＡＤＥＫＡ社製の商品名アデカスタブ（登録商標）ＬＡ－Ｆ７０（２，４，６－トリス（２－ヒドロキシ－４－ヘキシルオキシ－３－メチルフェニル）－１，３，５－トリアジン）
光重合開始剤（Ｃ）：ＢＡＳＦ社の商品名イルガキュア（登録商標）１１７３（α－ヒドロキシアセトフェノン）
光重合開始剤（Ｃ）：ＢＡＳＦ社の商品名イルガキュア（登録商標）１２７（２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン）
内部流動抑制剤（Ｄ）（有機系ゲル化剤）：新日本理化社製の商品名ゲルオールＤ（ソルビトールジベンザール）
内部流動抑制剤（Ｄ）（層状鉱物）：ＢＹＫ社製の商品名ＣＬＡＹＴＯＮＥ（登録商標）ＨＹ
内部流動抑制剤（Ｄ）（層状鉱物）：タルク、丸尾カルシウム社製の商品名タルクＳＰ－４２
体質顔料（光透過性）：重質炭酸カルシウム、丸尾カルシウム社製の商品名Ｎ重炭 The detail of each component of the coating composition used in the Example is as follows.
Active energy ray-curable compound (A): trade name Lipoxy (registered trademark) VR-77 (vinyl ester resin) manufactured by Showa Denko KK
Active energy ray-curable compound (A): trade name Aronix (registered trademark) M-350 (trimethylolpropane EO-modified triacrylate) manufactured by Toa Gosei Co., Ltd.
Active energy ray-curable compound (A): trade name Aronix (registered trademark) M-211B (bisphenol A EO-modified diacrylate) manufactured by Toa Gosei Co., Ltd.
Light absorber (B) (inorganic light absorber): titanium oxide, trade name CR-50 manufactured by Ishihara Sangyo Co., Ltd.
Light Absorber (B) (Organic Light Absorber): Product name ADEKA STAB (registered trademark) LA-F70 (2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) manufactured by ADEKA ) -1,3,5-triazine)
Photopolymerization initiator (C): trade name Irgacure (registered trademark) 1173 (α-hydroxyacetophenone) of BASF
Photopolymerization initiator (C): trade name Irgacure (registered trademark) 127 (2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2 from BASF -Methyl-propan-1-one)
Internal flow inhibitor (D) (Organic gelling agent): Brand name Gelall D (sorbitol dibenzal) manufactured by Shin Nippon Chemical Co., Ltd.
Internal flow inhibitor (D) (layered mineral): trade name CLAYTONE (registered trademark) HY manufactured by BYK
Internal flow inhibitor (D) (layered mineral): Talc, trade name Talc SP-42, manufactured by Maruo Calcium
Extender pigment (light transmissive): heavy calcium carbonate, trade name N heavy charcoal manufactured by Maruo Calcium
（実施例１～１８および比較例１～２）
　表１に示す配合（質量部）で、各成分を混合して塗料組成物を調製した。その塗料組成物を用いて、１０ｃｍ×５ｃｍ、高さが２．７ｍｍのアルミニウム容器に塗装膜厚が２．５ｍｍとなるように塗布して皮膜を形成した。その皮膜に紫外線を出力８０Ｗ、２４０秒の照射時間で照射した。得られた塗膜（実施例の複合塗膜を含む。以下、実施例において同じ。）について、以下に説明する方法により、表皮層硬化性、反発弾性率、複合塗膜の形成性、内部流動性、表皮層の剥離性および剥離膜厚を測定ないし評価した。その結果を表１に合わせて示す。ただし、表皮層硬化性の評価で硬化と判断した場合のみ、反発弾性率の測定を行った。また、複合塗膜形成性の評価で合格と判断した場合のみ、剥離性の評価を行った。 (Examples 1 to 18 and Comparative Examples 1 and 2)
With the formulation (parts by mass) shown in Table 1, each component was mixed to prepare a coating composition. The coating composition was applied to an aluminum container having a size of 10 cm × 5 cm and a height of 2.7 mm so that the coating film thickness was 2.5 mm to form a film. The film was irradiated with ultraviolet rays with an output of 80 W and an irradiation time of 240 seconds. With respect to the obtained coating film (including the composite coating film of the example, hereinafter the same in the examples), the skin layer curability, the rebound resilience, the formability of the composite coating film, the internal flow are determined by the methods described below. , Peelability of the skin layer and peeled film thickness were measured or evaluated. The results are also shown in Table 1. However, the impact resilience was measured only when it was determined to be cured in the evaluation of the skin layer curability. Moreover, peelability was evaluated only when it was determined to be acceptable in the evaluation of the composite coating film formability.
（表皮層硬化性）
　以下に述べる方法および基準で表皮層硬化性を測定および評価した。
ＪＩＳ　Ｋ　５６００－３－２：１９９９に準拠して、上記調製した塗膜を水平に置いた。その塗膜に、約０．５ｇのバロチニ（呼び（寸法）目開き１２５μｍのふるいを通過せず，２５０μｍのふるいを全通するように級分けされた細かいガラス球）を１００ｍｍの高さから落とし、１０秒後に試験片を傾け、軽くはけではいてバロチニを除去した。
＜基準＞
硬化：塗膜に目視で確認できる傷をつけずにバロチニを除去できる
未硬化：塗膜に傷がついたまたはバロチニが埋まってバロチニを除去できない (Skin layer curability)
The skin layer curability was measured and evaluated by the methods and criteria described below.
According to JIS K 5600-3-2: 1999, the prepared coating film was placed horizontally. About 0.5 g of Balotini (a fine glass sphere classified so as not to pass through a sieve with a nominal (dimension) size of 125 μm but through a 250 μm sieve) was dropped from the height of 100 mm onto the coating film. Ten seconds later, the test piece was tilted, and lightly brushed to remove the barotini.
<Standard>
Curing: Barotini can be removed without visually observing scratches on the coating film Uncured: Balotini cannot be removed because the coating film is scratched or buried
（複合塗膜形成性）
　大理石の台上に、上述した方法により、各実施例および比較例の塗料組成物を用いて乾燥膜厚２．５ｍｍの塗膜を３枚形成した。ここで、図３は、本発明における複合塗膜の反発弾性率の測定方法を示した模式図である。２３℃雰囲気下、高さＨ１（７０ｃｍ）の位置からゴムボール５０を、大理石の台６０上に形成した塗膜７０上に自然落下させ、その際のゴムボール５０の跳ね返り高さＨ２を計測した。そして、以下の式で反発弾性率を算出した。反発弾性率の測定を各塗膜について１回ずつ、計３回行い、その平均値を用いた。用いたゴムボールは、材質シリコーン、直径２ｃｍ、質量５ｇの球状、ＪＩＳ　Ｋ　６２５３－２０１２「加硫ゴム及び熱可塑性ゴム硬さの求め方」にて測定した硬さが５０のゴムボールである。
反発弾性率（％）＝（Ｈ２／Ｈ１）×１００
＜複合塗膜の形成性評価基準＞
合格：反発弾性率１０％～６５％（内部層が未硬化である）
不合格：反発弾性率６５％超え（内部層が硬化しすぎている） (Composite coating formability)
Three coating films having a dry film thickness of 2.5 mm were formed on the marble table by the above-described method using the coating compositions of the examples and comparative examples. Here, FIG. 3 is a schematic diagram showing a method of measuring the rebound resilience of the composite coating film in the present invention. In a 23 ° C. atmosphere, the rubber ball 50 was naturally dropped from the position of height H1 (70 cm) onto the coating film 70 formed on the marble base 60, and the bounce height H2 of the rubber ball 50 at that time was measured. . And the impact resilience was calculated by the following formula. The rebound resilience was measured once for each coating, 3 times in total, and the average value was used. The rubber ball used is a rubber ball having a hardness of 50 measured according to JIS K 6253-2012 “How to determine the hardness of a vulcanized rubber and a thermoplastic rubber”, a material silicone, a diameter of 2 cm, a spherical shape having a mass of 5 g.
Rebound resilience (%) = (H2 / H1) × 100
<Criteria for forming composite coating film>
Pass: Rebound resilience 10% to 65% (inner layer is uncured)
Fail: Rebound resilience exceeding 65% (inner layer is too hard)
　反発弾性率測定の考え方は以下のとおりである。すなわち、塗膜は粘性成分と弾性成分で構成されている。弾性成分が多いと、ゴムボールの運動エネルギーが保存されるのに対し、粘性成分が多いと、落下エネルギーが失われる。通常の完全硬化した塗膜と、本発明に係る複合塗膜を比べると、本発明に係る複合塗膜は未硬化の内部層が存在する。未硬化の内部層では、完全硬化した同じ厚みの層よりも、弾性成分がより少なく、粘性成分がより多いと考えられる。したがって、内部層が未硬化の複合塗膜が形成されている場合、完全硬化した塗膜に比べて反発弾性率が低くなると考えられるため、反発弾性率の値によって、未硬化の内部層の形成およびその硬化の程度を評価することができる。 The concept of rebound resilience measurement is as follows. That is, the coating film is composed of a viscous component and an elastic component. When the elastic component is large, the kinetic energy of the rubber ball is preserved, whereas when the viscous component is large, the falling energy is lost. When a normal fully cured coating film is compared with the composite coating film according to the present invention, the composite coating film according to the present invention has an uncured inner layer. An uncured inner layer is believed to have less elastic components and more viscous components than a fully cured layer of the same thickness. Therefore, when an uncured composite coating is formed on the inner layer, it is considered that the rebound resilience is lower than that of a fully cured coating. And the degree of curing thereof can be evaluated.
（内部流動性）
　２３℃雰囲気下、形成した塗膜を水平に対して９０°に傾けて静置した。そして、１時間後の塗膜の流動（変形）の有無を目視で評価した。
＜基準＞
内部流動性あり：塗膜の変形あり
内部流動性なし：塗膜の変形なし (Internal fluidity)
In a 23 ° C. atmosphere, the formed coating film was allowed to stand at 90 ° with respect to the horizontal. And the presence or absence of the flow (deformation) of the coating film after 1 hour was visually evaluated.
<Standard>
With internal fluidity: With coating film deformation Without internal fluidity: Without coating film deformation
（表皮層の剥離性と剥離膜厚）
　アルミニウム容器の内壁に接している塗膜部分をカッターナイフで内壁から切り離した。長さ５ｃｍに切ったセロハンテープ（ニチバン社製の商品名セロテープ（登録商標）ＣＴ－２４）を準備した。ここで、図４は、本発明における複合塗膜の剥離性の測定方法を示した模式図である。図４では、説明の簡略化のため、塗膜周囲のアルミニウム容器は図示していない。図４に示すように、塗膜８０の１つの短辺の中央部分の一方の端から他方の端に向かって２ｃｍまでの表面（表皮層）１００に上記セロハンテープ９０を貼り付けた。そして、塗膜に貼り付けていないセロハンテープ部分を手で持って引き上げて、表皮層の剥離性の有無を評価した。また、表皮層を剥離できた場合はその剥離された表皮層の膜厚を電子ノギスで測定した。 (Removability of skin layer and peeled film thickness)
The coating film part in contact with the inner wall of the aluminum container was cut off from the inner wall with a cutter knife. A cellophane tape (trade name Cellotape (registered trademark) CT-24 manufactured by Nichiban Co., Ltd.) cut to a length of 5 cm was prepared. Here, FIG. 4 is a schematic view showing a method for measuring the peelability of the composite coating film in the present invention. In FIG. 4, the aluminum container around the coating film is not shown for simplification of explanation. As shown in FIG. 4, the cellophane tape 90 was attached to the surface (skin layer) 100 of 2 cm from one end to the other end of the central part of one short side of the coating film 80. And the cellophane tape part which was not affixed on the coating film was held up by hand, and the presence or absence of peelability of the skin layer was evaluated. When the skin layer could be peeled off, the thickness of the peeled skin layer was measured with an electronic caliper.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から、（Ｂ）成分である光吸収剤を含まない比較例１，２では、反発弾性率が高く、内部層が硬化しすぎで複合塗膜が形成できなかった。これに対して、光吸収剤を含む実施例では、複合塗膜を形成でき、表皮層を剥離することができた。（Ｄ）成分のうち、有機系ゲル化剤を含む実施例６などでは、有機系ゲル化剤を含まない実施例１，３，４と比べて、内部流動性がなく、より良好な結果となった。実施例６，８，９の対比および実施例１０，１１の対比から、光吸収剤の含有量を多くすると、反発弾性率が低下し、内部層をより未硬化とすることができることがわかる。また、実施例１３～１６の対比から、（Ｃ）成分である光重合開始剤の含有量を少なくすると、反発弾性率が低下し、内部層をより未硬化とすることができることがわかる。また、実施例５～７の対比から、有機系ゲル化剤の含有量の調節によって、反発弾性率が変化し、内部層の硬化の程度を調節することができることがわかる。 From Table 1, in Comparative Examples 1 and 2 that do not contain the light absorber as the component (B), the impact resilience was high and the inner layer was too hard to form a composite coating film. On the other hand, in the Example containing a light absorber, the composite coating film could be formed and the skin layer could be peeled off. Among the components (D), in Example 6 and the like containing an organic gelling agent, compared with Examples 1, 3, and 4 not containing an organic gelling agent, there is no internal fluidity, and better results. became. From the comparison between Examples 6, 8, and 9 and the comparison between Examples 10 and 11, it can be seen that when the content of the light absorber is increased, the rebound resilience decreases and the inner layer can be further uncured. Further, from the comparison of Examples 13 to 16, it can be seen that when the content of the photopolymerization initiator as the component (C) is decreased, the rebound resilience is lowered and the inner layer can be further uncured. Further, it can be seen from the comparison of Examples 5 to 7 that the rebound resilience changes by adjusting the content of the organic gelling agent, and the degree of curing of the inner layer can be adjusted.
１：複合塗膜
１０：被塗物
２０：内部層
２１：表皮層の剥離後に形成された新たな内部層
３０：表皮層
３１：表皮層の剥離後に形成された新たな表皮層
４０：塗料組成物の皮膜
５０：ゴムボール
６０：大理石の台
７０：塗膜
８０：剥離性測定の複合塗膜
９０：セロハンテープ
１００：表皮層
１１０：内部層 1: Composite coating film 10: Object to be coated 20: Inner layer 21: New inner layer 30 formed after peeling of skin layer 30: Skin layer 31: New skin layer 40 formed after peeling of skin layer: Paint composition Film 50: rubber ball 60: marble base 70: coating film 80: composite coating film 90 for peelability measurement: cellophane tape 100: skin layer 110: inner layer
　本発明によれば、複合塗膜の表層を剥離して少なくとも１回は更新可能な複合塗膜を提供することができる。また、本発明によれば、複合塗膜の表層を剥離して少なくとも１回は更新可能な複合塗膜の製造方法を提供することができる。また、本発明によれば、上記複合塗膜を表面に有する物品を提供することができる。また、本発明によれば、複合塗膜の表層を剥離して少なくとも１回は更新可能な複合塗膜を形成可能な塗料組成物を提供することができる。 According to the present invention, it is possible to provide a composite coating film that can be renewed at least once by peeling the surface layer of the composite coating film. Moreover, according to this invention, the surface layer of a composite coating film can be peeled and the manufacturing method of the composite coating film which can be updated at least once can be provided. Moreover, according to this invention, the article | item which has the said composite coating film on the surface can be provided. Moreover, according to this invention, the coating composition which can peel the surface layer of a composite coating film and can form the composite coating film which can be updated at least once can be provided.

Claims (8)

  1. 　内部層と、前記内部層の空気界面側に隣接する表皮層とからなる複合塗膜であって、
    　前記複合塗膜は、単一の塗料組成物から形成されており、
    　前記塗料組成物は、
    　　活性エネルギー線硬化性化合物（Ａ）と、
    　　光吸収剤（Ｂ）と、
    　　光重合開始剤（Ｃ）と、
    　を含み、
    　前記内部層は、未硬化であり、
    　前記表皮層は、硬化しており、かつ、前記内部層の表面から剥離可能である、複合塗膜。     A composite coating consisting of an inner layer and a skin layer adjacent to the air interface side of the inner layer,
    The composite coating film is formed from a single coating composition,
    The coating composition is
    An active energy ray-curable compound (A);
    A light absorber (B);
    A photopolymerization initiator (C);
    Including
    The inner layer is uncured,
    The composite coating film, wherein the skin layer is cured and can be peeled off from the surface of the inner layer.
  2. 　さらに、前記塗料組成物が、内部流動抑制剤（Ｄ）を含み、前記内部流動抑制剤（Ｄ）が、有機系ゲル化剤を含む、請求項１に記載の複合塗膜。 Furthermore, the composite coating film according to claim 1, wherein the coating composition contains an internal flow inhibitor (D), and the internal flow inhibitor (D) contains an organic gelling agent.
  3. 　前記複合塗膜の反発弾性率が、１０～６５％である、請求項１または２に記載の複合塗膜。 The composite coating film according to claim 1 or 2, wherein the rebound resilience of the composite coating film is 10 to 65%.
  4. 　前記表皮層の厚みが１０μｍ～５ｍｍであり、前記内部層の厚みが前記表皮層の厚みと同じまたはそれ以上である、請求項１～３のいずれか一項に記載の複合塗膜。 4. The composite coating film according to claim 1, wherein the thickness of the skin layer is 10 μm to 5 mm, and the thickness of the inner layer is equal to or greater than the thickness of the skin layer.
  5. 　請求項１に記載の複合塗膜の製造方法であって、
    　被塗物上に、
    　　活性エネルギー線硬化性化合物（Ａ）と、
    　　光吸収剤（Ｂ）と、
    　　光重合開始剤（Ｃ）と、
    　を含む単一の塗料組成物を塗布して、塗料組成物の皮膜を形成する工程、
    　前記塗料組成物の皮膜に活性エネルギー線を照射して、未硬化の内部層と、硬化した表皮層を形成する工程、
    　を含む、複合塗膜の製造方法。     A method for producing the composite coating film according to claim 1,
    On the substrate,
    An active energy ray-curable compound (A);
    A light absorber (B);
    A photopolymerization initiator (C);
    Applying a single coating composition comprising: forming a coating composition coating;
    Irradiating a film of the coating composition with active energy rays to form an uncured inner layer and a cured skin layer;
    The manufacturing method of the composite coating film containing this.
  6. 　請求項１～４のいずれか一項に記載の複合塗膜を表面に有する物品。 An article having on its surface the composite coating film according to any one of claims 1 to 4.
  7. 　活性エネルギー線硬化性化合物（Ａ）と、
    　光吸収剤（Ｂ）と、
    　光重合開始剤（Ｃ）と、
    　を含む、
    　塗料組成物。     An active energy ray-curable compound (A);
    A light absorber (B);
    A photopolymerization initiator (C);
    including,
    Paint composition.
  8. 　さらに、内部流動抑制剤（Ｄ）を含み、前記内部流動抑制剤（Ｄ）が、有機系ゲル化剤を含む、請求項７に記載の塗料組成物。 The coating composition according to claim 7, further comprising an internal flow inhibitor (D), wherein the internal flow inhibitor (D) comprises an organic gelling agent.
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