WO2023054486A1 - Surface modification layer, surface modification sheet, multilayer body, surface-modified member, coated article, method for producing surface-modified member, and method for producing coated article - Google Patents

Surface modification layer, surface modification sheet, multilayer body, surface-modified member, coated article, method for producing surface-modified member, and method for producing coated article Download PDF

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WO2023054486A1
WO2023054486A1 PCT/JP2022/036206 JP2022036206W WO2023054486A1 WO 2023054486 A1 WO2023054486 A1 WO 2023054486A1 JP 2022036206 W JP2022036206 W JP 2022036206W WO 2023054486 A1 WO2023054486 A1 WO 2023054486A1
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modified
polymer
modified layer
group
resin
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PCT/JP2022/036206
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French (fr)
Japanese (ja)
Inventor
絵里子 中尾
繁樹 石黒
智一 ▲高▼橋
涼平 大幡
明日香 遠藤
佳世 下川
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日東電工株式会社
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    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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

Definitions

  • the present invention relates to a surface-modified layer, a surface-modified sheet, a laminate, a surface-modified member, a coated article, a method for producing a surface-modified member, and a method for producing a coated article.
  • resins which are lightweight and have excellent impact resistance, are used for parts such as transportation equipment such as railway vehicles, aircraft, ships, and automobiles, electronic equipment, and housing equipment. is joined. Coating films having various functions are formed on the resin member.
  • a resin member having an unsaturated polyester resin which is a type of thermosetting resin, as a matrix resin is used for bathtubs and automobile exterior applications, and in particular when used for automobile exterior applications, a coating film made of paint is formed.
  • An unsaturated polyester resin member is used.
  • Rubber-epoxy-based curable resin compositions are conventionally known as such adhesives.
  • Patent Literature 1 describes a surface-modified sheet capable of imparting sufficient adhesive strength to a thermoplastic resin.
  • Patent Documents 2 and 3 describe surface-modified sheets capable of imparting sufficient adhesive strength to thermosetting resins such as thermosetting elastomers and silicone rubbers.
  • Japanese Patent Application Laid-Open No. 2017-128722 Japanese Patent Application Laid-Open No. 2019-194015 Japanese Patent Application Laid-Open No. 2021-020410 Japanese Patent Application Laid-Open No. 2017-114937 Japanese Patent Application Laid-Open No. 2017-110126
  • the surface treatment process of the resin member can be simplified by using the surface-modified sheet, and the adhesion to a specific coating film such as an adhesive is improved.
  • a new problem was found that the adhesive strength between the resin member and the coating film may be insufficient if the coating film provided on the substrate is a coating material.
  • the present invention provides a surface-modified layer having excellent adhesive strength, particularly adhesive strength to paint, and is capable of forming the surface-modified layer. It is an object of the present invention to provide a surface-modified sheet in which a surface-modified layer and a resin member can be integrally molded when forming a member. Another object of the present invention is to provide a laminate, a surface-modified member, a coated article, a method for producing a surface-modified member, and a method for producing a coated article using this surface-modified layer or surface-modified sheet.
  • Means for solving the above problems are as follows.
  • [1] A surface-modified layer containing at least one polar group-containing polymer and at least one unsaturated hydrocarbon group-containing polymer.
  • [2] The surface-modified layer according to [1], wherein the surface-modified layer has a polar group concentration of 10 mgKOH/g or more and a double bond equivalent of 12000 or less.
  • [3] A surface-modified sheet comprising the surface-modified layer according to [1] or [2] and a release sheet.
  • [4] A laminate comprising the surface-modified layer according to [1] or [2] and a resin material, wherein the surface-modified layer is laminated on at least part of the surface of the resin material.
  • [14] [1] or [2] A method for producing a coated article using the surface modified layer, a step of laminating the surface-modified layer on a resin member by thermoforming to produce a surface-modified member; and forming a coating film on the surface modification layer side of the surface modification member.
  • the coating film includes a coating material having a functional group that forms a chemical bond with or intermolecularly interacts with the polar group in the polar group-containing polymer.
  • [17] [3] A method for producing a coated object using the surface-modified sheet described in [3].
  • the surface-modified layer according to the embodiment of the present invention has excellent adhesive strength, and the surface-modified sheet according to the embodiment of the present invention can prevent the occurrence of unevenness and form the surface-modified layer. It is possible to integrally mold the surface modified layer and the resin member when forming the material member.
  • FIG. 1 is a schematic cross-sectional view showing an example of a surface modifying member.
  • FIG. 2 is a schematic cross-sectional view showing an example of a surface-modified sheet.
  • FIG. 3 is a schematic cross-sectional view showing a configuration in which the surface-modified layer side of a surface-modified sheet, which is a laminate of a release sheet and a surface-modified layer, is placed on at least part of the surface of a resin material.
  • FIG. 4 is a schematic cross-sectional view showing an example of a coated object.
  • the surface-modified layer according to the embodiment of the present invention contains at least one polar group-containing polymer and at least one unsaturated hydrocarbon group-containing polymer.
  • a surface-modified sheet according to an embodiment of the present invention includes a surface-modified layer and a release sheet.
  • the surface-modified sheet according to the embodiment of the present invention has a sheet-like surface-modified layer, it is not coated on the surface of the resin member, but is placed on the resin material and heat-treated, so that integral molding can be performed. can. Therefore, it is possible to prevent unevenness due to repelling or the like, and to form a surface modified layer with a uniform thickness on the surface of the resin member.
  • the surface modification layer is provided on a part of the surface of the resin member, it is possible to suppress a decrease in yield due to protrusion or the like.
  • the surface-modified sheet according to the embodiment of the present invention is a surface-modified member using a resin member containing a resin material, especially a resin member containing a thermosetting resin containing an unsaturated hydrocarbon group. It is suitable for use in manufacturing.
  • the surface-modified layer contains at least one polar group-containing polymer and at least one unsaturated hydrocarbon group-containing polymer, so that the unsaturated hydrocarbon groups in the unsaturated hydrocarbon group-containing polymer and the unsaturated hydrocarbon groups in the resin member It is speculated that the bonding strength between the surface-modified layer and the resin member is improved because covalent bonds are formed by chemical reaction with the unsaturated hydrocarbon groups of the thermosetting resin.
  • the coating film provided on the surface-modified layer contains a coating material having a functional group capable of reacting or interacting with a polar group, such as a urethane-based coating material, at the interface between the surface-modified layer and the coating film
  • a polar group such as a urethane-based coating material
  • the The polar groups in the polar group-containing polymer and the functional groups in the paint form chemical bonds or interact intermolecularly, thereby improving the adhesive strength between the surface-modified layer and the coating film.
  • Chemical bonds include covalent bonds, ionic bonds, and metallic bonds.
  • Intermolecular interactions include hydrogen bonding, electrostatic interactions, aromatic ring interactions, van der Waalska and the like.
  • the strength of the bonding force is covalent bond > ionic bond > metal bond > intermolecular interaction. Formation of covalent bonds is preferred.
  • the surface-modified layer (which may be the material of the surface-modified layer) according to the embodiment of the present invention contains at least one polar group-containing polymer and at least one unsaturated hydrocarbon group-containing polymer.
  • the polymer may be a compound obtained by reacting two or more monomers, and may be an oligomer or a polymer. That is, it means a compound excluding monomers.
  • a polymer shall represent the polymer whose weight average molecular weight is 10000 or more.
  • the polar group-containing polymer and the unsaturated hydrocarbon group-containing polymer are polymers having different structures, and the surface-modified layer according to the embodiment of the present invention contains at least two kinds of polymers. Includes amalgamation.
  • the polar group-containing polymer or unsaturated hydrocarbon group-containing polymer
  • a polymer having both a polar group and an unsaturated hydrocarbon group can be used as the polar group-containing polymer (or unsaturated hydrocarbon group-containing polymer). It includes unsaturated hydrocarbon group-containing polymers (or polar group-containing polymers) with different structures.
  • Polymers having polar groups may be oligomers or polymers as described above. At least one of the polar group-containing polymer and the below-described unsaturated hydrocarbon group-containing polymer is preferably a polymer from the viewpoint of film-forming properties of the surface-modified layer.
  • Polar groups in the polar group-containing polymer include, for example, hydroxyl groups, carboxyl groups, amino groups, urethane bonds and the like. Among them, a hydroxyl group or a carboxyl group is preferable.
  • the polar group-containing polymer may contain one type of the above polar group in one polymer, or may contain two or more types.
  • the rate of introduction of the polar groups into the polar group-containing polymer is not particularly limited, and may be designed so that the concentration of the polar groups in the surface-modified layer described later falls within a predetermined range.
  • the hydroxyl value of the polymer is preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more.
  • the hydroxyl value of a polymer is the number of mg of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group after acetylating 1 g of the sample polymer.
  • the acid value of the polymer is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more.
  • the amount is 50 mgKOH/g or more, sufficient covalent bonds are formed between the carboxyl groups in the polar group-containing copolymer and the functional groups in the coating film, thereby making it easier to obtain coating film adhesion.
  • the acid value is mg of potassium hydroxide required to neutralize 1 g of sample polymer. If the amount of the polar group introduced is within the above range, the covalent bond between the polar group in the polar group-containing copolymer and the functional group in the coating film is sufficiently formed, thereby easily obtaining coating film adhesion. Become.
  • the polar group-containing polymer is, for example, a polymer selected from acrylic polymers, polyester polymers, urethane polymers, polyether polymers, polyamide polymers, and epoxy acrylate polymers. and those having a polar group. From the viewpoint of improving adhesion, a polar group-containing acrylic polymer is preferable.
  • Polar group-containing polymers include hydroxyl group-containing polymers, carboxyl group-containing polymers, amino group-containing polymers, and urethane bond-containing polymers.
  • hydroxyl group-containing polymer any appropriate polymer can be employed as long as it is an oligomer or polymer containing a hydroxyl group (—OH) within a range that does not impair the effects of the present invention.
  • hydroxyl group-containing polymers include hydroxyl group-containing acrylic polymers and hydroxyl group-containing epoxy acrylate polymers.
  • a hydroxyl group-containing polymer is obtained, for example, by polymerizing a monomer component containing a hydroxyl group-containing monomer.
  • the hydroxyl group-containing polymer is a hydroxyl group-containing acrylic polymer, for example, it is obtained by polymerizing a monomer component containing a hydroxyl group-free acrylic monomer and a hydroxyl group-containing acrylic monomer as a hydroxyl group-containing monomer. It is preferably obtained by polymerizing a monomer component containing a (meth)acrylic acid alkyl ester and a hydroxyl group-containing (meth)acrylic acid alkyl ester.
  • (meth)acrylic acid refers to acrylic acid and/or methacrylic acid.
  • (Meth)acrylic acid alkyl esters include, for example, (meth)acrylic acid alkyl esters having a linear or branched alkyl group having 1 to 20 carbon atoms.
  • Examples of such (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, Isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, (meth) acrylic hexyl acid, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acryl
  • hydroxyl group-containing (meth)acrylic acid alkyl esters examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3 (meth)acrylic acid. -hydroxypropyl, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12 (meth)acrylic acid -hydroxylauryl, and (4-hydroxymethylcyclohexyl)methyl (meth)acrylate.
  • the hydroxyl group-containing (meth)acrylic acid alkyl esters may be used alone, or two or more of them may be used in combination.
  • the hydroxyl group-containing (meth)acrylic acid alkyl ester is preferably selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl acrylate, and 4-hydroxybutyl (meth)acrylate. at least one
  • the blending amount of the hydroxyl group-containing monomer such as the hydroxyl group-containing (meth)acrylic acid alkyl ester can be appropriately adjusted so that the hydroxyl group value of the resulting hydroxyl group-containing polymer is within the above range.
  • the component In 100 mol parts of the component, it is preferably 1 mol part or more, more preferably 5 mol parts or more, and preferably 50 mol parts or less, more preferably 40 mol parts or less. If the hydroxyl group-containing monomer is 1 mol part or more, the amount of hydroxyl groups suitable for interacting with the paint is obtained, and the adhesion with the paint is improved.
  • the hydroxyl group-containing monomer is 50 mol parts or less, it is possible to prevent gelation from occurring in the polymerization process of the hydroxyl group-containing polymer, which makes production difficult.
  • the monomer component may contain one or more other monomers copolymerizable therewith (copolymerizable monomers).
  • copolymerizable monomers include carboxyl group-containing monomers, nitrogen atom-containing ring-containing monomers, acid anhydride monomers such as maleic anhydride and itaconic anhydride, sulfonic acid group-containing monomers, epoxy group-containing monomers, and amide group-containing monomers.
  • Monomers, aromatic vinyl compounds, (meth)acrylic acid esters having an alicyclic hydrocarbon group, and (meth)acrylic acid esters having an aromatic hydrocarbon group can be mentioned.
  • the content of the copolymerizable monomer is the total amount of the hydroxyl group-containing (meth)acrylic acid alkyl ester with respect to 100 mol parts of the (meth)acrylic acid alkyl ester. , preferably 1 mol part or more, more preferably 5 mol parts or more, and preferably 50 mol parts or less, more preferably 40 mol parts or less.
  • Carboxyl group-containing monomers include, for example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
  • Examples of monomers having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine, and N- Vinyl isothiazole is mentioned.
  • sulfonic acid group-containing monomers examples include styrenesulfonic acid, allylsulfonic acid, sodium vinylsulfonate, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylates, and (meth)acryloyloxynaphthalenesulfonic acids.
  • Epoxy group-containing monomers include, for example, epoxy group-containing acrylates such as glycidyl (meth)acrylate and 2-ethyl glycidyl (meth)acrylate, allyl glycidyl ether, and glycidyl (meth)acrylate.
  • N,N-dialkyl(meth)acrylamides include, for example, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, and N,N-diisopropyl (Meth)acrylamide may be mentioned.
  • aromatic vinyl compounds examples include styrene, ⁇ -methylstyrene, and vinyltoluene.
  • (Meth)acrylic acid esters having an alicyclic hydrocarbon group include, for example, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate.
  • (Meth)acrylic acid esters having an aromatic hydrocarbon group include, for example, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate.
  • the hydroxyl group-containing acrylic polymer can be formed by polymerizing the above monomer components.
  • Polymerization techniques include, for example, solution polymerization, bulk polymerization, and emulsion polymerization, preferably solution polymerization.
  • solution polymerization for example, a monomer component and a polymerization initiator are blended in a solvent to prepare a reaction solution, and then the reaction solution is heated. Then, a polymer solution containing a polymer can be obtained through a polymerization reaction of the monomer components in the reaction solution.
  • the polymerization initiator a thermal polymerization initiator and a photopolymerization initiator can be used depending on the polymerization method.
  • the amount of the polymerization initiator used is, for example, 0.01 parts by mass or more and, for example, 5 parts by mass or less with respect to 100 parts by mass of the monomer component.
  • thermal polymerization initiators include azo polymerization initiators, peroxide polymerization initiators, and persulfates such as potassium persulfate.
  • azo polymerization initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis(2-methylpropionate)dimethyl , 4,4′-azobis-4-cyanovaleric acid, azobisisovaleronitrile, and 2,2′-azobis(2-amidinopropane) dihydrochloride.
  • Peroxide polymerization initiators include, for example, dibenzoyl peroxide, t-butyl permaleate, and lauroyl peroxide.
  • photopolymerization initiators include benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, ⁇ -ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, and photoactive oxime-based photopolymerization initiators.
  • hydroxyl group-containing polymer Commercially available products may be used as the hydroxyl group-containing polymer.
  • examples of such commercial products include, for example, "ARUFON (registered trademark) UH-2000 series” (manufactured by Toagosei Co., Ltd.), which is a hydroxyl group-containing acrylic polymer, and "IRR742", which is a hydroxyl group-containing urethane acrylate (Daicel). Allnex Co., Ltd.) and the like.
  • the number of hydroxyl group-containing polymers may be one, or two or more.
  • carboxyl group-containing polymer any appropriate polymer can be adopted as long as it is an oligomer or polymer containing a carboxyl group (--COOH) within a range that does not impair the effects of the present invention. obtain.
  • carboxyl group-containing polymers include carboxyl group-containing acrylic polymers.
  • Commercially available products may be employed as the carboxyl group-containing polymer. Examples of such commercial products include "ARUFON (registered trademark)", which is a carboxyl group-containing acrylic polymer.
  • the number of carboxyl group-containing polymers may be one, or two or more.
  • amino group-containing polymer any suitable polymer containing an amino group (—NH 2 ) can be employed as long as it does not impair the effects of the present invention.
  • amino group-containing polymers include amino group-containing acrylic polymers.
  • Commercially available products may be employed as the amino group-containing polymer. Examples of such commercial products include polyethyleneimine such as "EPOMIN (registered trademark)" (manufactured by Nippon Shokubai Co., Ltd.) and aminoethylated acrylic resins such as "Polyment (registered trademark)” (manufactured by Nippon Shokubai Co., Ltd.). polymers.
  • EPOMIN registered trademark
  • aminoethylated acrylic resins such as "Polyment (registered trademark)” (manufactured by Nippon Shokubai Co., Ltd.).
  • polymers One type of amino group-containing polymer may be used, or two or more types may be used.
  • any appropriate polymer can be used as long as it is a polymer containing a urethane bond (-O-CO-NH-) to the extent that the effects of the present invention are not impaired. can be adopted.
  • urethane bond-containing polymers include urethane bond-containing acrylic polymers.
  • Commercially available products may be used as the urethane bond-containing polymer. Examples of such commercially available products include urethane acrylates such as "EBECRYL” and "KRM" (Daicel-Ornex Co., Ltd.).
  • the urethane bond-containing polymer may be one kind, or two or more kinds.
  • the weight average molecular weight (Mw) of the polar group-containing polymer is not particularly limited, it is preferably 200 or more, more preferably 500 or more, from the viewpoint of film-forming properties and workability. It is preferably 5,000,000 or less, more preferably 3,000,000 or less, from the viewpoint of the coating properties of the surface-modifying composition containing the polymer and the adhesion to the coating film or the resin member.
  • the weight average molecular weight of the polymer is calculated by measuring with gel permeation chromatography (GPC) and converting to polystyrene.
  • Polymers having unsaturated hydrocarbon groups may be oligomeric or polymeric as described above. At least one of the polar group-containing polymer and the unsaturated hydrocarbon group-containing polymer is preferably a polymer from the viewpoint of the film-forming properties of the surface-modified layer.
  • unsaturated hydrocarbon group-containing polymers include polymers selected from acrylic polymers, polyester polymers, urethane polymers, polyether polymers, polyamide polymers, and epoxy acrylate polymers. Those which are coalesced and have unsaturated hydrocarbon groups are included. From the viewpoint of improving adhesion, an unsaturated hydrocarbon group-containing acrylic polymer is preferred.
  • the unsaturated hydrocarbon group-containing polymer is obtained, for example, by reacting a prepolymer having a functional group with an unsaturated hydrocarbon group-containing compound capable of reacting with and bonding to the functional group.
  • the term "prepolymer” used herein means a polymer obtained by partially polymerizing the monomers that constitute the polar group-containing polymer.
  • the unsaturated hydrocarbon group-containing polymer is an unsaturated hydrocarbon group-containing acrylic polymer
  • the hydroxyl group-containing acrylic polymer described above is used as a prepolymer, and this prepolymer and the unsaturated hydrocarbon group-containing compound It can be preferably obtained by an addition reaction with
  • the unsaturated hydrocarbon group-containing compound has a predetermined functional group capable of reacting and bonding with a hydroxyl group, and the hydroxyl group in the prepolymer reacts with the functional group in the unsaturated hydrocarbon group-containing compound. introduces a side chain containing an unsaturated hydrocarbon group derived from the unsaturated hydrocarbon group-containing compound into the prepolymer to obtain an unsaturated hydrocarbon group-containing polymer.
  • the prepolymer may have a hydroxyl group
  • the unsaturated hydrocarbon group-containing compound may be an unsaturated hydrocarbon group-containing isocyanate compound.
  • the above-mentioned hydroxyl group-containing acrylic polymer is used as the prepolymer.
  • Examples of monomers having a carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate and the like.
  • a monomer having a glycidyl group is preferable, and examples of the monomer having a glycidyl group include glycidyl (meth)acrylate and methylglycidyl (meth)acrylate.
  • unsaturated hydrocarbon group-containing isocyanate compounds examples include 2-methacryloyloxyethyl isocyanate (MOI) and 3-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate. From the viewpoint of ease of introduction of unsaturated hydrocarbon groups into polymer side chains, the unsaturated hydrocarbon group-containing isocyanate compound is preferably MOI.
  • the amount of the unsaturated hydrocarbon group-containing compound used in the above reaction can be appropriately adjusted so that the double bond equivalent of the resulting unsaturated hydrocarbon group-containing polymer falls within the above range.
  • the unsaturated hydrocarbon group-containing acrylic polymer obtained is It becomes a polymer having hydroxyl groups at the same time.
  • the reaction temperature is, for example, 40° C. to 60° C.
  • the reaction time is, for example, 4 to 10 hours.
  • an addition reaction catalyst may be used for the reaction.
  • the functional group in the unsaturated hydrocarbon group-containing compound is an isocyanate group
  • dibutyltin dilaurate for example, can be used as the addition reaction catalyst.
  • the amount of the addition reaction catalyst used is, for example, 0.3 to 0.6 parts by mass with respect to 100 parts by mass of the unsaturated hydrocarbon group-containing compound.
  • a reaction solution is prepared by adding an unsaturated hydrocarbon group-containing compound and an addition reaction catalyst to a prepolymer solution containing the above-described prepolymer, and the addition reaction is performed in the reaction solution. Through the reaction, an unsaturated hydrocarbon group-containing acrylic polymer solution containing an unsaturated hydrocarbon group-containing acrylic polymer can be obtained.
  • unsaturated hydrocarbon group-containing acrylic polymer Commercially available products may be used as the unsaturated hydrocarbon group-containing acrylic polymer.
  • One type of unsaturated hydrocarbon group-containing acrylic polymer may be used, or two or more types may be used.
  • the epoxy acrylate-based polymer may have a structure having an unsaturated hydrocarbon group at the end of a polyether-based polymer such as bisphenol-type epoxy acrylate or aliphatic-type epoxy acrylate. A structure having an unsaturated hydrocarbon group in the chain may also be used.
  • a commercially available product may be adopted as the epoxy acrylate polymer. Examples of such commercially available products include "EBECRYL3700” and “EBECRYL3701" (both manufactured by Daicel Allnex Co., Ltd.). One type of epoxy acrylate polymer may be used, or two or more types may be used.
  • urethane-based polymer any appropriate polymer can be employed as long as the effects of the present invention are not impaired.
  • urethane-based polymers include structures having unsaturated hydrocarbon groups in side chains, such as urethane acrylate.
  • a commercially available product may be used as the urethane-based polymer. Examples of such commercial products include "IRR742" (manufactured by Daicel-Ornex Co., Ltd.).
  • the number of urethane-based polymers may be one, or two or more.
  • the weight average molecular weight (Mw) of the unsaturated hydrocarbon group-containing polymer is not particularly limited, it is preferably 200 or more, more preferably 500 or more, from the viewpoint of film-forming properties and workability. Also, from the viewpoint of the coatability of the surface-modifying composition containing the unsaturated hydrocarbon group-containing polymer and the adhesion to a coating film or a resin member, it is preferably 5,000,000 or less, more preferably 3,000,000 or less. .
  • the weight average molecular weight of the polymer is calculated by measuring with gel permeation chromatography (GPC) and converting to polystyrene.
  • the content ratio of the polar group-containing polymer and the unsaturated hydrocarbon group-containing polymer in the surface modified layer depends on the introduction rate of the polar group and the unsaturated hydrocarbon group in each polymer, etc.
  • the mass ratio represented by polar group-containing polymer/unsaturated hydrocarbon group-containing polymer is preferably 0.01 to 100, more preferably 0.05 to 20, and 0.1 to 10. is more preferred.
  • the polar group concentration in the surface modified layer is preferably 10.0 mgKOH/g or more, more preferably 15.0 mgKOH/g or more, and even more preferably 20.0 mgKOH/g or more.
  • the polar group concentration X (mgKOH/g) in the surface modified layer is a value calculated using the following formula.
  • Polar group concentration (X) of the surface modified layer ⁇ (xi wi)
  • xi is the hydroxyl value (mgKOH/g) when the polymer i contained in the surface-modified layer is a hydroxyl-containing polymer, and when the polymer i is a carboxyl-containing polymer, each represents an acid value (mgKOH/g). wi represents the mass fraction of the polymer i in the surface-modified layer.
  • the hydroxyl value of a polymer is the number of mg of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group after acetylating 1 g of the sample polymer.
  • the acid value of a polymer is the mg of potassium hydroxide required to neutralize 1 g of sample polymer.
  • the mass (mg) of hydroxyl groups contained per 1 g of the polymer may be used instead of the hydroxyl value of the polymer described above. Further, the mass (mg) of carboxyl groups contained per 1 g of the polymer may be used instead of the acid value of the polymer.
  • the double bond equivalent Y of the surface modified layer can be calculated using the following formula.
  • the surface-modified layer in the embodiment of the present invention contains a polar group-containing polymer and an unsaturated hydrocarbon group-containing polymer. That is, it was found that the surface-modified layer in the embodiment of the present invention can obtain excellent adhesive strength by containing a blend polymer (or oligomer) of a polar group-containing polymer and an unsaturated hydrocarbon group-containing polymer. rice field. Although the reason for this is not clear, the present inventors found that by blending a polar group-containing polymer and an unsaturated hydrocarbon group-containing polymer, the polar group-containing polymer bleeds onto the surface of the surface modified layer. It is speculated that this is because the adhesiveness is improved by this.
  • the thickness of the surface modification layer is not particularly limited, and is preferably 0.01 ⁇ m to 2000 ⁇ m, more preferably 0.1 to 1000 ⁇ m, still more preferably 0.5 to 200 ⁇ m, particularly preferably 1 ⁇ m to 100 ⁇ m. be.
  • the thickness of the surface-modified layer is determined by measuring the thickness of the surface-modified sheet with a dial thickness gauge (eg, Peacock GC-9), measuring the thickness of the release sheet after removing the surface-modified layer at that point, and calculating the difference. can be measured as the thickness of the surface modification layer.
  • the average thickness of the surface modified layer is the average value obtained by measuring 10 points.
  • polyester-based resin sheet manufactured by Nitoflon
  • polymethylpentene-based resin sheet manufactured by Mitsui Chemicals Tohcello, Opulan (registered trademark)
  • polystyrene-based resin sheet manufactured by Kurabo Industries, Oidis (registered trademark)
  • polyamide-based A resin sheet a polyolefin-based resin sheet, and the like are included.
  • the release sheet that can be used for the surface-modified sheet includes, for example, unstretched polyamide 6, unstretched polyamide 66, biaxially stretched polyamide 6, biaxially stretched polyamide 66, biaxially stretched polypropylene, and biaxially stretched polyethylene.
  • EFE unstretched extruded tetrafluoroethylene-perfluoroalkoxyethylene copolymer
  • PFA polymer
  • FEP unstretched extruded tetrafluoroethylene-hexafluoropropylene joint
  • the thickness of the release sheet is preferably 1 ⁇ m to 1000 ⁇ m, more preferably 10 ⁇ m to 500 ⁇ m, still more preferably 20 ⁇ m to 300 ⁇ m, and particularly preferably 30 ⁇ m to 100 ⁇ m, from the viewpoint of conformability.
  • the surface of the release sheet on the surface modification layer side or both surfaces may be subjected to a release treatment with an appropriate release agent such as silicone.
  • a surface-modified sheet may be manufactured by any suitable method. For example, a method of dipping a release sheet in a solution (surface-modifying composition) containing a material for the surface-modifying layer and a solvent (surface-modifying composition) followed by drying as necessary, and a method of applying the material for the surface-modifying layer to the surface of the release sheet. A method of drying if necessary after applying a solution containing a solvent and a brush, and a method of drying if necessary after applying a solution containing the material of the surface modification layer and a solvent to the surface of the release sheet with various coaters. , a method of spray coating a solution containing the material for the surface-modifying layer and a solvent onto the surface of the release sheet, followed by drying as necessary.
  • the surface-modifying composition it is also preferable to use the polymer solution containing the polymer obtained in polymer synthesis as it is.
  • the solid content concentration in the surface-modifying composition can be appropriately set according to the purpose.
  • the mass ratio is preferably 1% to 60% by mass, more preferably 10% to 50% by mass, and still more preferably 15% to 40% by mass. is.
  • the surface-modifying composition may optionally contain other components that can be included in the surface-modifying layer together with the polymer described above.
  • a coloring agent for example, by adding a coloring agent, the surface modified layer can be visualized, making it easy to determine whether the surface of the resin member has already been modified, which is advantageous in terms of process control. It also functions as a base for improving the coloring of the paint.
  • Colorants include, for example, dyes and pigments. Further, the colorant may be a fluorescent material that can be visually recognized under black light.
  • the resin contained in the resin material is preferably a thermosetting resin, and from the viewpoint of improving adhesion between the resin member and the surface modification layer, it is preferably an unsaturated hydrocarbon group-containing thermosetting resin.
  • unsaturated hydrocarbon group-containing thermosetting resins include unsaturated polyester resins and vinyl ester resins, preferably unsaturated polyester resins.
  • the unsaturated hydrocarbon group-containing thermosetting resin contained in the resin material includes at least a part of the uncured unsaturated hydrocarbon group-containing thermosetting resin.
  • the resin material may contain a fiber-reinforced resin
  • the thermosetting resin may be a fiber-reinforced thermosetting resin.
  • fiber-reinforced thermosetting resins include carbon fiber-reinforced thermosetting resins and glass fiber-reinforced thermosetting resins.
  • the resin material preferably contains an unsaturated hydrocarbon group-containing thermosetting resin, as well as a reactive monomer, a curing agent, and glass fibers.
  • Unsaturated hydrocarbon group-containing thermosetting resins such as unsaturated polyester resins are polymerized (tertiary original cross-linking) to obtain a cured product.
  • the resin contained in the resin material is an unsaturated polyester resin
  • styrene is preferably used as the reactive monomer
  • benzoyl peroxide (BPO) is preferably used as the curing agent.
  • Examples of the shape of the resin material include a plate shape having a flat surface, a plate shape having a curved surface, a sheet shape, a film shape, and the like.
  • the thickness of the resin material is, for example, 0.001 mm to 10 mm.
  • At least part of the surface of the resin material means at least part of all the surfaces of the resin material.
  • the resin material is plate-shaped, sheet-shaped, or film-shaped, it means a part of at least one surface or the entirety of at least one surface.
  • the above description can be used as it is.
  • a surface modifying member according to an embodiment of the invention includes a laminate according to an embodiment of the invention.
  • a surface-modified member according to an embodiment of the present invention may be one in which the surface-modified layer according to the embodiment of the present invention is laminated on at least part of a surface of a resin member, and the resin member and the It is preferable that the surface modified layer is covalently bonded through a chemical reaction. In this case, since the resin member and the surface modification layer form a covalent bond, the adhesion strength between the resin member and the surface modification layer is excellent.
  • the resin member is obtained by molding a resin material, and the preferable shape and thickness of the resin member are the same as those of the resin material.
  • molding means processing a material into a predetermined shape regardless of whether a mold is used, and “molding” means processing a material into a predetermined shape using a mold.
  • At least part of the surface of the resin member means at least part of all the surfaces of the resin member.
  • the resin member is plate-shaped, sheet-shaped, or film-shaped, it means a part of at least one surface or the entirety of at least one surface.
  • the resin member preferably contains an unsaturated hydrocarbon group-containing thermosetting resin, and the unsaturated hydrocarbon group-containing thermosetting resin is an unsaturated polyester resin. is preferred. That is, in the surface modified member according to the embodiment of the present invention, the unsaturated hydrocarbon group-containing thermosetting resin in the resin member and the unsaturated hydrocarbon group-containing polymer in the surface modified layer are covalently bonded. preferably.
  • the unsaturated hydrocarbon group-containing thermosetting resin contained in the resin member includes a cured unsaturated hydrocarbon group-containing thermosetting resin, that is, a resin in which the unsaturated hydrocarbon groups have been consumed.
  • the thermoforming may be performed simultaneously with lamination of the resin material and the surface-modified sheet, or may be performed after lamination of the surface-modified sheet on the resin material.
  • surface-treating the resin member by such a method, it is possible to impart sufficient adhesive strength to the resin member, and to manufacture the surface-modified member with high productivity and low cost.
  • the method for manufacturing a surface-modified member can also be a method for treating the surface of a resin member (resin surface treatment method).
  • the method for producing the surface-modified member according to the embodiment of the present invention is not particularly limited.
  • the surface-modified member can be produced by placing the surface-modified layer side of the above and performing heat molding.
  • the interface between the surface modified layer and the resin material is melted and contacted by heat molding, and the unsaturated hydrocarbon group-containing polymer contained in the surface modified layer chemically reacts with the resin contained in the resin material, thereby forming a resin member.
  • and the surface-modified layer are covalently bonded to each other to form a surface-modified member.
  • Heat molding may be performed simultaneously with placing the surface-modified sheet, or may be performed after placing the surface-modified sheet.
  • the method for manufacturing a surface-modified member can also be a method for treating the surface of a resin member (method for surface treatment of a resin member).
  • the resin member preferably contains an unsaturated hydrocarbon group-containing thermosetting resin, and more preferably contains an unsaturated polyester resin.
  • the resin member the surface-modified sheet, the release sheet, and the surface-modified layer, the above descriptions can be used as they are.
  • a surface-modified layer is formed on at least part of the surface of the resin material containing the thermosetting resin, where the curing temperature of the thermosetting resin contained in the resin member is T 2 °C. It is preferable to perform the heat molding at a temperature of T 1 ° C. or higher.
  • the curing temperature is the temperature within the heat generation temperature range of the heat flow curve measured by DSC (differential scanning calorimetry) of the uncured thermosetting resin.
  • the thermoforming temperature is preferably T 1 ° C. to T 3 ° C., more preferably (T 1 +10) ° C. to (T 3 -10) ° C., still more preferably (T 1 +20) ° C. to (T 3 -20)°C.
  • T1 is the temperature (°C) at which heat generation begins when an uncured thermosetting resin is measured by DSC
  • T3 is the temperature (°C) at which heat generation ends.
  • the interface between the surface modified layer and the resin member melts and contacts to form a covalent bond through a chemical reaction, thereby forming a covalent bond on the resin member.
  • a surface-modified layer having excellent adhesion strength to the coating film. And such provision can be performed with high productivity and low cost.
  • thermosetting resin is a fiber-reinforced thermosetting resin
  • the molding method includes a hand lay-up method, a spray-up method, a filament winding method, a pultrusion method, a sheet mold compound method, a bulk mold compound method, and a resin transfer method. etc.
  • the surface-modified layer side of the surface-modified sheet is placed on at least a part of the surface of the resin member, and molding is performed with heating (for example, it is a mode in which integral molding by hot pressing is performed.
  • the molding pressure during compression molding is preferably 1 MPa or higher, more preferably 2 MPa or higher, and even more preferably 3 MPa or higher, from the viewpoint of deformation of the molded product by the mold.
  • the viscosity is preferably 30 MPa or less, more preferably 25 MPa or less, and even more preferably 20 MPa or less.
  • Injection molding may be used as the molding process for the resin member.
  • injection molding for example, an injection molding machine equipped with a movable mold and a fixed mold can be used.
  • the surface modified sheet is accommodated in the concave portion of the cavity of the movable side mold so that the release sheet faces the cavity, and the movable side mold and the fixed side mold are clamped. Then, the melted resin is injected into the cavity. After cooling and solidifying the resin in the mold, the movable side mold and the fixed side mold are separated from each other. Thus, a surface-modified member in which the surface-modified sheet and the resin member are integrated is obtained.
  • a surface-modified member having a surface-modified surface provided with the surface-modified layer can be obtained. Peeling of the release sheet is not particularly limited, and may be performed manually, using a dedicated peeling equipment, or the like. The release sheet can be left in place until just before painting. This can prevent contamination of the surface of the surface modified layer.
  • the release sheet After placing the surface-modified layer side of the surface-modified sheet, which is a laminate of the release sheet and the surface-modified layer, on at least a part of the surface of the resin member (which may be a resin material), and heat-molding. , preferably the release sheet is removed. By removing the release sheet in this way, the surface-modified layer is transferred to the surface of the resin member, and a surface-modified member (sometimes referred to as a laminated member of the resin member and the surface-modified layer) is obtained. . As described above, preferably, the resin in the resin member and the unsaturated hydrocarbon group-containing polymer in the surface-modified layer are covalently bonded between the resin member and the surface-modified layer.
  • the surface modified layer 10 is provided on the surface of the resin member 100 to obtain the surface modified member.
  • the surface-modified sheet which is a laminate of a release sheet and a surface-modified layer, is a surface-modified sheet 200, which is a laminate of a release sheet 20 and a surface-modified layer 10, as shown in FIG.
  • the surface-modified layer side of the surface-modified sheet which is a laminate of a release sheet and a surface-modified layer, is at least part of the surface of the resin member.
  • the surface-modified sheet 200 is placed on the surface of the resin material 400 so that the surface-modified layer 10 side of the surface-modified sheet 200 is on the surface side of the resin material 400. It is a form placed on the
  • a coated article according to an embodiment of the present invention includes a coating film on at least a portion of a surface modifying member. It is preferable to provide a coating film on at least part of the surface of the surface-modifying member on the surface-modifying layer side.
  • a coating film 30 is provided on the surface of the surface-modified member on the surface-modified layer side of the surface-modified member in which the surface-modified layer 10 is provided on the surface of the resin member 100 shown in FIG. 3 shows a painted object 300.
  • the coating film may be at least one selected from coating, printing layer, vapor deposition layer, and plating layer.
  • the coating film preferably contains paint, and forms a chemical bond with the polar group in the polar group-containing polymer, or forms an intermolecular interaction. It is more preferred to include a paint having functional groups that From the viewpoint of improving adhesion, the functional group is preferably a functional group that covalently bonds with the polar group in the polar group-containing polymer, and is preferably an isocyanate group or an amino group.
  • the paint contained in the coating film is preferably urethane paint such as urethane paint or acrylic/urethane paint, acrylic paint, epoxy paint, silicone paint, polyester resin, melamine resin paint or fluorine paint, more preferably urethane paint.
  • Urethane paint is a general term for paints that combine a resin (polyol) having multiple hydroxyl groups as a main agent and a polyisocyanate as a curing agent.
  • the polyisocyanate is not particularly limited as long as it is a compound having two or more isocyanate groups. Aliphatic ones such as hexamethylene diisocyanate, alicyclic ones such as isophorone diisocyanate, monomers thereof and multimers thereof such as burette type, nurate type and adduct type can be used.
  • the polar group in the polar group-containing polymer contained in the surface modification layer and the functional group in the paint contained in the coating film form a chemical bond or interact with each other to modify the surface.
  • the adhesive strength between the layer and the coating film is also increased, making it possible to form a coating film with extremely excellent adhesion.
  • a cleaning treatment process using an organic solvent to remove the mold release agent before forming the coating film and polishing are performed. It does not require a treatment process, is highly safe, and can reduce the environmental load and workload.
  • the thickness of the coating film is not particularly limited, and is preferably 0.01 to 2000 ⁇ m, more preferably 0.1 to 1000 ⁇ m, even more preferably 0.5 to 500 ⁇ m, particularly preferably 1 to 200 ⁇ m.
  • a method for producing a painted article according to an embodiment of the present invention is a method for producing a painted article using the above-described surface modification layer, a step of laminating the surface-modified layer on a resin member by thermoforming to produce a surface-modified member; and forming a coating film on the surface modification layer side of the surface modification member.
  • a method for manufacturing a coated object according to an embodiment of the present invention may be a method for manufacturing a coated object using the surface-modified sheet described above.
  • the resin member preferably contains an unsaturated hydrocarbon group-containing thermosetting resin, and more preferably contains an unsaturated polyester resin. It is preferable that the coating film contains a coating material having a functional group that forms a chemical bond with the polar group in the polar group-containing polymer described above, or that interacts intermolecularly.
  • the above descriptions can be used as they are.
  • the description in the above [Method for producing surface-modified member] can be used as it is.
  • the coating method of the coating film there are no particular restrictions on the coating method of the coating film, and general methods such as brush coating, roller coating, spray coating, and various coater coatings can be used, and the coating amount is not particularly limited.
  • the time and temperature for heating the coating film can be appropriately determined depending on the coating material to be used, the coating amount, and the like.
  • the surface-modifying composition or the surface-modifying layer may contain a dye, a pigment, or a crystalline substance. By containing such additives, the surface modified layer is visualized, making it easier to manage the manufacturing process.
  • the surface-modifying composition As for the surface-modifying composition, the surface-modifying sheet, the coated article, and the additive, the above descriptions can be used as they are.
  • a process control method for example, there is a method of visually confirming the surface-treated and colored part, or a method of recognizing and discriminating images taken with a camera.
  • a surface-modified layer containing at least one polar group-containing polymer and at least one unsaturated hydrocarbon group-containing polymer [2] The surface-modified layer according to [1], wherein the surface-modified layer has a polar group concentration of 10 mgKOH/g or more and a double bond equivalent of 12000 or less. [3] A surface-modified sheet comprising the surface-modified layer according to [1] or [2] and a release sheet. [4] A laminate comprising the surface-modified layer according to [1] or [2] and a resin material, wherein the surface-modified layer is laminated on at least part of the surface of the resin material.
  • [14] [1] or [2] A method for producing a coated article using the surface modified layer, a step of laminating the surface-modified layer on a resin member by thermoforming to produce a surface-modified member; and forming a coating film on the surface modification layer side of the surface modification member.
  • the coating film includes a coating material having a functional group that forms a chemical bond with or intermolecularly interacts with the polar group in the polar group-containing polymer.
  • [17] [3] A method for producing a coated object using the surface-modified sheet described in [3].
  • ⁇ Adhesion 2> The coated objects prepared in Examples and Comparative Examples were subjected to cross-cut evaluation (cross-cut peeling) by the cross-cut method described in JIS K5600-5-6, and the number of unpeeled coating films (number of adhesion) was counted. bottom. When the number of unpeeled coating films is 50 or more out of 100, the adhesion between the surface modification layer and the coating film is good ( ⁇ ), and when it is 49 or less, it is judged to be bad (x). bottom.
  • ⁇ Cut interval 2mm
  • Number of cross cuts 100 squares
  • Peeling tape (Nichiban) cellophane tape (registered trademark) 24 mm width
  • ⁇ Double bond equivalent of unsaturated hydrocarbon group-containing polymer The double bond equivalents of unsaturated hydrocarbon group-containing acrylic polymer 1, unsaturated hydrocarbon group-containing acrylic polymer 2, unsaturated hydrocarbon group-containing acrylic polymer 3, and hydroxyl group-containing acrylic polymer 2 synthesized below are Based on the molecular weight and blending mass ratio of the raw material monomers used in (1), the mass of the polymer per unsaturated hydrocarbon group was calculated and used as the double bond equivalent of the polymer. In calculating the double bond equivalent, all the isocyanate groups in 2-methacryloyloxyethyl isocyanate (MOI), which is a raw material monomer, reacted with hydroxyl groups in 2-hydroxyethyl acrylate.
  • MOI 2-methacryloyloxyethyl isocyanate
  • Double bond equivalent (Y) of the surface modified layer ⁇ (yi wi)
  • yi the double bond equivalent of polymer i contained in the surface-modified layer
  • wi the mass fraction of polymer i in the surface-modified layer.
  • ethyl acetate was appropriately added dropwise to control the temperature during the polymerization and to prevent a rapid increase in viscosity due to hydrogen bonding due to the polar groups in the side chains of the monomers.
  • V top H two-liquid curing urethane paint manufactured by Dainippon Toryo Co., Ltd.
  • a hydroxyl group-containing acrylic polymer solution having a solid concentration of 42.6% by mass was obtained.
  • ethyl acetate was appropriately added dropwise to control the temperature during the polymerization and to prevent a rapid increase in viscosity due to hydrogen bonding due to the polar groups in the side chains of the monomers.
  • a polymer solution containing the hydroxyl group-containing acrylic polymer, 2-methacryloyloxyethyl isocyanate (MOI) (trade name “Karenzu MOI”, manufactured by Showa Denko KK), and dibutyltin dilaurate (Wako Jun) as an addition reaction catalyst Yakukogyo Co., Ltd.) was stirred at 50° C. for 10 hours under an air atmosphere (addition reaction).
  • the amount of MOI compounded is 16 mol parts per 100 mol parts of 2-ethylhexyl acrylate (2EHA).
  • Example 6 A surface-modified composition (6) was prepared in the same manner as in Example 5 except that UC3510 (manufactured by Toagosei Co., Ltd., a carboxyl group-containing acrylic oligomer) was used as the polar group-containing polymer (A), A surface-modified sheet (6), a surface-modified member (6), and a coated article (6) were produced.
  • UC3510 manufactured by Toagosei Co., Ltd., a carboxyl group-containing acrylic oligomer
  • a polymer solution containing the hydroxyl group-containing acrylic polymer, 2-methacryloyloxyethyl isocyanate (MOI) (trade name “Karenzu MOI”, manufactured by Showa Denko KK), and dibutyltin dilaurate (Wako Jun) as an addition reaction catalyst Yakukogyo Co., Ltd.) was stirred at 50° C. for 10 hours under an air atmosphere (addition reaction).
  • the amount of MOI compounded is 1 mol part per 100 mol parts of the total amount of ethyl acrylate (EA) and butyl acrylate (BA).
  • a polymer solution containing the hydroxyl group-containing acrylic polymer, 2-methacryloyloxyethyl isocyanate (MOI) (trade name “Karenzu MOI”, manufactured by Showa Denko KK), and dibutyltin dilaurate (Wako Jun) as an addition reaction catalyst Yakukogyo Co., Ltd.) was stirred at 50° C. for 10 hours under an air atmosphere (addition reaction).
  • the amount of MOI compounded is 4 mol parts per 100 mol parts of the total amount of ethyl acrylate (EA) and butyl acrylate (BA).
  • the amount of dibutyltin dilaurate compounded is 0.5 parts by mass with respect to 100 parts by mass of MOI.
  • Example 1 A surface-modified composition (r1) was prepared in the same manner as in Example 1, except that EBECRYL3700 as the unsaturated hydrocarbon group-containing polymer (B) was not added, and the surface-modified sheet (r1), A surface-modified member (r1) and a coated article (r1) were produced.
  • Example 2 A surface-modified composition (r2) was prepared in the same manner as in Example 4, except that UH2041 as the polar group-containing polymer (A) was not added. A member (r2) and a coated article (r2) were produced.
  • a coated article using the surface-modified sheet of the present invention has good adhesion between the resin member and the surface-modified layer and good adhesion between the surface-modified layer and the coating film, and the adhesion strength of the coating film is good. A very high coating was obtained.
  • the surface-modified layer contains only one of the polar group-containing polymer (A) and the unsaturated hydrocarbon group-containing polymer (B), the surface Bonding between the modified layer and the coating film or between the surface modified layer and the resin member was not sufficiently formed, resulting in poor adhesion.
  • the surface-modified layer according to the embodiment of the present invention has excellent adhesive strength, and the surface-modified sheet according to the embodiment of the present invention can prevent the occurrence of unevenness and form the surface-modified layer. It is possible to integrally mold the surface modified layer and the resin member when forming the material member.

Abstract

The present invention provides: a surface modification layer which contains one or more polar group-containing polymers and one or more unsaturated hydrocarbon group-containing polymers; a surface modification sheet which comprises this surface modification layer and a mold release sheet; a multilayer body; a surface-modified member and a coated article, each of which uses this surface modification sheet; a method for producing a surface-modified member; and a method for producing a coated article.

Description

表面改質層、表面改質シート、積層体、表面改質部材、塗装物、表面改質部材の製造方法、及び塗装物の製造方法SURFACE-MODIFIED LAYER, SURFACE-MODIFIED SHEET, LAMINATE, SURFACE-MODIFIED MEMBER, COATED PRODUCT, METHOD FOR MANUFACTURING SURFACE-MODIFIED MEMBER, AND METHOD FOR MANUFACTURING COATED PRODUCT
　本発明は、表面改質層、表面改質シート、積層体、表面改質部材、塗装物、表面改質部材の製造方法、及び塗装物の製造方法に関する。 The present invention relates to a surface-modified layer, a surface-modified sheet, a laminate, a surface-modified member, a coated article, a method for producing a surface-modified member, and a method for producing a coated article.
　近年、鉄道車両、航空機、船舶、自動車等の輸送機器、電子機器、住宅設備等の部材には、軽量かつ対衝撃性に優れた樹脂が用いられ、その表面には種々の材質の被着体が接合されている。また、樹脂部材には種々の機能を有する塗膜が形成されている。 In recent years, resins, which are lightweight and have excellent impact resistance, are used for parts such as transportation equipment such as railway vehicles, aircraft, ships, and automobiles, electronic equipment, and housing equipment. is joined. Coating films having various functions are formed on the resin member.
　例えば、熱硬化性樹脂の一種である不飽和ポリエステル樹脂をマトリクス樹脂とした樹脂部材は、浴槽や自動車外装用途に使用され、特に自動車外装用途に使用される場合、塗料からなる塗膜が形成された不飽和ポリエステル樹脂部材が用いられている。
　樹脂部材を金属や他の樹脂と接合する際には、十分に接着させる必要がある。このような接着剤としては、従来、ゴムエポキシ系の硬化性樹脂組成物が知られている。 For example, a resin member having an unsaturated polyester resin, which is a type of thermosetting resin, as a matrix resin is used for bathtubs and automobile exterior applications, and in particular when used for automobile exterior applications, a coating film made of paint is formed. An unsaturated polyester resin member is used.
When joining a resin member to a metal or other resin, it is necessary to sufficiently bond them. Rubber-epoxy-based curable resin compositions are conventionally known as such adhesives.
　しかしながら、樹脂部材は、接着剤となじみにくく従来の接着剤や接着シートを用いても十分な接着強度が得られない。また、繊維複合材料等の強度に優れた樹脂部材は、高い水準の接着強度が求められる。
　このため、樹脂部材の接着にはプライマー溶液の塗布や、プライマー溶液の塗布に先立ち、下処理としてサンドブラスト処理、コロナ処理、プラズマ処理などの各種表面処理が必要となる。このような表面処理方法においては、工程が増え、生産性が低下するためコスト面にも問題がある。 However, the resin member is difficult to be compatible with the adhesive, and sufficient adhesive strength cannot be obtained even if the conventional adhesive or adhesive sheet is used. In addition, a high level of adhesive strength is required for a resin member having excellent strength such as a fiber composite material.
For this reason, adhesion of resin members requires application of a primer solution, and prior to application of the primer solution, various surface treatments such as sandblasting, corona treatment, and plasma treatment are required as pretreatments. In such a surface treatment method, the number of steps is increased and productivity is lowered, so there is a problem in terms of cost.
　また、樹脂部材に易接着処理をして十分な接着強度を付与するための手段の一つとして、表面改質シートを用いる技術がある。
　例えば、特許文献１には、熱可塑性樹脂に十分な接着強度を付与し得る表面改質シートが記載されている。 Further, as one of the means for imparting sufficient adhesive strength by subjecting a resin member to an easy-adhesion treatment, there is a technique using a surface-modified sheet.
For example, Patent Literature 1 describes a surface-modified sheet capable of imparting sufficient adhesive strength to a thermoplastic resin.
　さらに、熱硬化性エラストマーやシリコーンゴムといった熱硬化性樹脂に十分な接着強度を付与し得る表面改質シートが特許文献２、３に記載されている。 Furthermore, Patent Documents 2 and 3 describe surface-modified sheets capable of imparting sufficient adhesive strength to thermosetting resins such as thermosetting elastomers and silicone rubbers.
　他方、部材表面に塗布適用して用いられる表面改質組成物として、官能基を有する樹脂を含む組成物は種々知られており、例えば、水酸基含有（メタ）アクリル樹脂と不飽和二重結合を分子構造中に有するポリエステルポリオールとを含む接着性組成物が特許文献４、５に記載されている。 On the other hand, various compositions containing a resin having a functional group are known as a surface-modifying composition that is used by applying it to the surface of a member. Patent Documents 4 and 5 describe adhesive compositions containing polyester polyols in the molecular structure.
日本国特開２０１７－１２８７２２号公報Japanese Patent Application Laid-Open No. 2017-128722 日本国特開２０１９－１９４０１５号公報Japanese Patent Application Laid-Open No. 2019-194015 日本国特開２０２１－０２０４１０号公報Japanese Patent Application Laid-Open No. 2021-020410 日本国特開２０１７－１１４９３７号公報Japanese Patent Application Laid-Open No. 2017-114937 日本国特開２０１７－１１０１２６号公報Japanese Patent Application Laid-Open No. 2017-110126
　しかしながら、従来の技術においては、表面改質シートを用いることにより樹脂部材の表面処理工程を簡略化でき、粘着剤など特定の塗膜に対する接着性が向上するものの、例えば、熱硬化性樹脂部材上に設ける塗膜が塗料であると、樹脂部材と塗膜の接着強度が不十分となる場合があるという新たな課題が見いだされた。 However, in the conventional technology, the surface treatment process of the resin member can be simplified by using the surface-modified sheet, and the adhesion to a specific coating film such as an adhesive is improved. A new problem was found that the adhesive strength between the resin member and the coating film may be insufficient if the coating film provided on the substrate is a coating material.
　以上のような問題を鑑みて、本発明は接着強度、特に塗料との接着強度に優れた表面改質層を提供すること、及び、該表面改質層を形成することができ、表面改質部材の形成の際に表面改質層と樹脂部材との一体成形が可能な表面改質シートを提供することを目的とする。また、この表面改質層又は表面改質シートを用いた、積層体、表面改質部材、塗装物、表面改質部材の製造方法、及び塗装物の製造方法を提供することを目的とする。 In view of the above problems, the present invention provides a surface-modified layer having excellent adhesive strength, particularly adhesive strength to paint, and is capable of forming the surface-modified layer. It is an object of the present invention to provide a surface-modified sheet in which a surface-modified layer and a resin member can be integrally molded when forming a member. Another object of the present invention is to provide a laminate, a surface-modified member, a coated article, a method for producing a surface-modified member, and a method for producing a coated article using this surface-modified layer or surface-modified sheet.
　本発明者らは前記課題を解決するために鋭意検討を行った。その結果、表面改質層をシート状にし、表面改質層に極性基含有重合体と不飽和炭化水素基含有重合体をそれぞれ１種以上含有させることにより、接着強度に優れた表面改質層を形成することができ、積層体の成形や表面改質部材の形成の際に表面改質層と樹脂部材との一体成形が可能であることを見出し、本発明を完成するに至った。 The present inventors have made intensive studies to solve the above problems. As a result, the surface-modified layer is formed into a sheet, and the surface-modified layer contains at least one polar group-containing polymer and one or more unsaturated hydrocarbon group-containing polymers, thereby providing a surface-modified layer with excellent adhesive strength. The present inventors have found that the surface modified layer and the resin member can be integrally molded during the molding of the laminate and the formation of the surface modified member, thereby completing the present invention.
　前記課題を解決するための手段は、以下の通りである。
〔１〕
　極性基含有重合体と不飽和炭化水素基含有重合体をそれぞれ１種以上含む表面改質層。
〔２〕
　前記表面改質層の極性基濃度が１０ｍｇＫＯＨ／ｇ以上であり、前記表面改質層の二重結合当量が１２０００以下である、〔１〕に記載の表面改質層。
〔３〕
　〔１〕又は〔２〕に記載の表面改質層と離型シートとを備えた表面改質シート。
〔４〕
　〔１〕又は〔２〕に記載の表面改質層と樹脂材料との積層体であり、前記表面改質層が、樹脂材料の表面の少なくとも一部に積層された積層体。
〔５〕
　前記樹脂材料と前記表面改質層とが化学反応により共有結合した、〔４〕に記載の積層体。
〔６〕
　前記樹脂材料が不飽和炭化水素基含有熱硬化性樹脂を含む〔５〕に記載の積層体。
〔７〕
　前記不飽和炭化水素基含有熱硬化性樹脂が不飽和ポリエステル樹脂である〔６〕に記載の積層体。
〔８〕
　〔４〕に記載の積層体を含む表面改質部材。
〔９〕
　〔８〕に記載の表面改質部材の少なくとも一部に塗膜を備えた塗装物。
〔１０〕
　前記塗膜が前記極性基含有重合体における極性基と化学結合を形成、又は分子間相互作用する官能基を有する塗料を含む、〔９〕に記載の塗装物。
〔１１〕
　〔１〕又は〔２〕に記載の表面改質層を用いた表面改質部材の製造方法であって、
　前記表面改質層を加熱成形により樹脂部材に積層する積層工程を含む、表面改質部材の製造方法。
〔１２〕
　前記樹脂部材が不飽和ポリエステル樹脂を含む〔１１〕に記載の表面改質部材の製造方法。
〔１３〕
　〔３〕に記載の表面改質シートを用いた表面改質部材の製造方法。
〔１４〕
　〔１〕又は〔２〕に記載の表面改質層を用いた塗装物の製造方法であって、
　前記表面改質層を加熱成形により樹脂部材に積層して表面改質部材を製造する工程と、
　前記表面改質部材の前記表面改質層側に塗膜を形成する工程とを含む、塗装物の製造方法。
〔１５〕
　前記樹脂部材が不飽和ポリエステル樹脂を含む〔１４〕に記載の塗装物の製造方法。
〔１６〕
　前記塗膜が前記極性基含有重合体における極性基と化学結合を形成、又は分子間相互作用する官能基を有する塗料を含む、〔１４〕又は〔１５〕に記載の塗装物の製造方法。
〔１７〕
　〔３〕に記載の表面改質シートを用いた塗装物の製造方法。 Means for solving the above problems are as follows.
[1]
A surface-modified layer containing at least one polar group-containing polymer and at least one unsaturated hydrocarbon group-containing polymer.
[2]
The surface-modified layer according to [1], wherein the surface-modified layer has a polar group concentration of 10 mgKOH/g or more and a double bond equivalent of 12000 or less.
[3]
A surface-modified sheet comprising the surface-modified layer according to [1] or [2] and a release sheet.
[4]
A laminate comprising the surface-modified layer according to [1] or [2] and a resin material, wherein the surface-modified layer is laminated on at least part of the surface of the resin material.
[5]
The laminate according to [4], wherein the resin material and the surface-modified layer are covalently bonded through a chemical reaction.
[6]
The laminate according to [5], wherein the resin material contains an unsaturated hydrocarbon group-containing thermosetting resin.
[7]
The laminate according to [6], wherein the unsaturated hydrocarbon group-containing thermosetting resin is an unsaturated polyester resin.
[8]
A surface-modified member comprising the laminate according to [4].
[9]
A coated article comprising a coating film on at least a part of the surface-modified member according to [8].
[10]
The coated article according to [9], wherein the coating film includes a coating material having a functional group that forms a chemical bond with or intermolecularly interacts with the polar group in the polar group-containing polymer.
[11]
A method for producing a surface-modified member using the surface-modified layer according to [1] or [2],
A method for producing a surface-modified member, comprising a lamination step of laminating the surface-modified layer on a resin member by thermoforming.
[12]
The method for producing a surface-modified member according to [11], wherein the resin member contains an unsaturated polyester resin.
[13]
A method for producing a surface-modified member using the surface-modified sheet according to [3].
[14]
[1] or [2] A method for producing a coated article using the surface modified layer,
a step of laminating the surface-modified layer on a resin member by thermoforming to produce a surface-modified member;
and forming a coating film on the surface modification layer side of the surface modification member.
[15]
The method for producing a coated object according to [14], wherein the resin member contains an unsaturated polyester resin.
[16]
The method for producing a coated article according to [14] or [15], wherein the coating film includes a coating material having a functional group that forms a chemical bond with or intermolecularly interacts with the polar group in the polar group-containing polymer.
[17]
[3] A method for producing a coated object using the surface-modified sheet described in [3].
　本発明の実施形態に係る表面改質層は、接着強度に優れ、本発明の実施形態に係る表面改質シートは、むらの発生を防ぎ該表面改質層を形成することができ、表面改質部材の形成の際に表面改質層と樹脂部材との一体成形が可能である。 The surface-modified layer according to the embodiment of the present invention has excellent adhesive strength, and the surface-modified sheet according to the embodiment of the present invention can prevent the occurrence of unevenness and form the surface-modified layer. It is possible to integrally mold the surface modified layer and the resin member when forming the material member.
図１は、表面改質部材の一例を示す概略断面図である。FIG. 1 is a schematic cross-sectional view showing an example of a surface modifying member. 図２は、表面改質シートの一例を示す概略断面図である。FIG. 2 is a schematic cross-sectional view showing an example of a surface-modified sheet. 図３は、離型シートと表面改質層の積層体である表面改質シートの表面改質層側を樹脂材料の表面の少なくとも一部に載置する形態を示す概略断面図である。FIG. 3 is a schematic cross-sectional view showing a configuration in which the surface-modified layer side of a surface-modified sheet, which is a laminate of a release sheet and a surface-modified layer, is placed on at least part of the surface of a resin material. 図４は、塗装物の一例を示す概略断面図である。FIG. 4 is a schematic cross-sectional view showing an example of a coated object.
　以下、本発明の実施形態について、詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
〔表面改質層及び表面改質シート〕
　本発明の実施形態に係る表面改質層は、極性基含有重合体と不飽和炭化水素基含有重合体をそれぞれ１種以上含む。
　本発明の実施形態に係る表面改質シートは、表面改質層と、離型シートとを備える。 [Surface Modified Layer and Surface Modified Sheet]
The surface-modified layer according to the embodiment of the present invention contains at least one polar group-containing polymer and at least one unsaturated hydrocarbon group-containing polymer.
A surface-modified sheet according to an embodiment of the present invention includes a surface-modified layer and a release sheet.
　本発明の実施形態に係る表面改質シートは、表面改質層がシート状であるため樹脂部材の表面に塗設するのではなく、樹脂材料に載積して加熱処理することで一体成形ができる。そのため、ハジキ発生等によるむらの発生を防ぎ、樹脂部材の表面に均一な厚みで表面改質層を形成することができる。また、樹脂部材の表面の一部に表面改質層を設ける際には、はみだし等により歩留りが低下するのを抑制できる。 Since the surface-modified sheet according to the embodiment of the present invention has a sheet-like surface-modified layer, it is not coated on the surface of the resin member, but is placed on the resin material and heat-treated, so that integral molding can be performed. can. Therefore, it is possible to prevent unevenness due to repelling or the like, and to form a surface modified layer with a uniform thickness on the surface of the resin member. In addition, when the surface modification layer is provided on a part of the surface of the resin member, it is possible to suppress a decrease in yield due to protrusion or the like.
　また、後述するように、本発明の実施形態に係る表面改質シートは、樹脂材料を含む樹脂部材、中でも不飽和炭化水素基含有熱硬化性樹脂を含む樹脂部材を用いた表面改質部材の製造に好適に用いられるものである。表面改質層が極性基含有重合体と不飽和炭化水素基含有重合体とをそれぞれ１種以上含むことにより、該不飽和炭化水素基含有重合体中の不飽和炭化水素基と樹脂部材中の熱硬化性樹脂が有する不飽和炭化水素基とが化学反応により共有結合を形成することから、表面改質層と樹脂部材との接着強度が向上するものと推察している。
　さらに、表面改質層上に設けられる塗膜にウレタン系塗料など、極性基と反応又は相互作用し得る官能基を有する塗料を含む場合には、表面改質層と塗膜の界面において、該極性基含有重合体中の極性基と塗料中の官能基とが化学結合を形成、又は分子間相互作用することによって、表面改質層と塗膜との接着強度を向上し得る。
　化学結合としては、共有結合、イオン結合、金属結合が挙げられる。分子間相互作用としては、水素結合、静電的相互作用、芳香環相互作用、ファンデルワールスカ等が挙げられる。結合力の強さとしては、共有結合＞イオン結合＞金属結合＞分子間相互作用であり、表面改質層と塗膜との密着性向上の観点から、表面改質層と塗膜の界面で共有結合を形成することが好ましい。 Further, as will be described later, the surface-modified sheet according to the embodiment of the present invention is a surface-modified member using a resin member containing a resin material, especially a resin member containing a thermosetting resin containing an unsaturated hydrocarbon group. It is suitable for use in manufacturing. The surface-modified layer contains at least one polar group-containing polymer and at least one unsaturated hydrocarbon group-containing polymer, so that the unsaturated hydrocarbon groups in the unsaturated hydrocarbon group-containing polymer and the unsaturated hydrocarbon groups in the resin member It is speculated that the bonding strength between the surface-modified layer and the resin member is improved because covalent bonds are formed by chemical reaction with the unsaturated hydrocarbon groups of the thermosetting resin.
Furthermore, when the coating film provided on the surface-modified layer contains a coating material having a functional group capable of reacting or interacting with a polar group, such as a urethane-based coating material, at the interface between the surface-modified layer and the coating film, the The polar groups in the polar group-containing polymer and the functional groups in the paint form chemical bonds or interact intermolecularly, thereby improving the adhesive strength between the surface-modified layer and the coating film.
Chemical bonds include covalent bonds, ionic bonds, and metallic bonds. Intermolecular interactions include hydrogen bonding, electrostatic interactions, aromatic ring interactions, van der Waalska and the like. The strength of the bonding force is covalent bond > ionic bond > metal bond > intermolecular interaction. Formation of covalent bonds is preferred.
＜表面改質層＞
　本発明の実施形態に係る表面改質層（表面改質層の材料であってもよい）は、極性基含有重合体と不飽和炭化水素基含有重合体をそれぞれ１つ以上含む。
　本発明において重合体とは、２つ以上のモノマーが反応して得られる化合物であればよく、オリゴマーであってもポリマーであってもよい。すなわち、モノマーを除く化合物を意味する。
　なお、本明細書において、ポリマーとは、重量平均分子量が１００００以上の重合体を表すものとする。
　また、本発明において極性基含有重合体と不飽和炭化水素基含有重合体は、それぞれ異なる構造を有する重合体であり、本発明の実施形態に係る表面改質層には少なくとも２種以上の重合体が含まれる。例えば、極性基含有重合体（又は、不飽和炭化水素基含有重合体）として、極性基及び不飽和炭化水素基をいずれも有する重合体を用いることもできるが、この場合、該重合体とは異なる構造の不飽和炭化水素基含有重合体（又は、極性基含有重合体）を含むものである。 <Surface modification layer>
The surface-modified layer (which may be the material of the surface-modified layer) according to the embodiment of the present invention contains at least one polar group-containing polymer and at least one unsaturated hydrocarbon group-containing polymer.
In the present invention, the polymer may be a compound obtained by reacting two or more monomers, and may be an oligomer or a polymer. That is, it means a compound excluding monomers.
In addition, in this specification, a polymer shall represent the polymer whose weight average molecular weight is 10000 or more.
In the present invention, the polar group-containing polymer and the unsaturated hydrocarbon group-containing polymer are polymers having different structures, and the surface-modified layer according to the embodiment of the present invention contains at least two kinds of polymers. Includes amalgamation. For example, as the polar group-containing polymer (or unsaturated hydrocarbon group-containing polymer), a polymer having both a polar group and an unsaturated hydrocarbon group can be used. It includes unsaturated hydrocarbon group-containing polymers (or polar group-containing polymers) with different structures.
（極性基含有重合体）
　極性基を有する重合体は、上述のようにオリゴマーであってもポリマーであってもよい。表面改質層の成膜性の観点から、極性基含有重合体、及び後述の不飽和炭化水素基含有重合体の少なくとも一方がポリマーであることが好ましい。 (polar group-containing polymer)
Polymers having polar groups may be oligomers or polymers as described above. At least one of the polar group-containing polymer and the below-described unsaturated hydrocarbon group-containing polymer is preferably a polymer from the viewpoint of film-forming properties of the surface-modified layer.
　極性基含有重合体における極性基としては、例えば、水酸基、カルボキシル基、アミノ基、ウレタン結合などが挙げられる。なかでも、水酸基、又はカルボキシル基が好ましい。
　極性基含有重合体は、１つの重合体中に上記極性基を１種含んでいてもよく、２種以上を含んでいてもよい。 Polar groups in the polar group-containing polymer include, for example, hydroxyl groups, carboxyl groups, amino groups, urethane bonds and the like. Among them, a hydroxyl group or a carboxyl group is preferable.
The polar group-containing polymer may contain one type of the above polar group in one polymer, or may contain two or more types.
　極性基含有重合体中の極性基の導入率としては、特に限定されず、後述の表面改質層中の極性基濃度が所定の範囲となるように設計されればよいが極性基が水酸基である場合、重合体の水酸基価が１０ｍｇＫＯＨ／ｇ以上であることが好ましく、１５ｍｇＫＯＨ／ｇ以上がより好ましい。重合体の水酸基価とは、試料重合体１ｇをアセチル化した後、水酸基と結合した酢酸を中和するのに必要な水酸化カリウムのｍｇ数である。
　極性基がカルボキシル基である場合、重合体の酸価が５０ｍｇＫＯＨ／ｇ以上であることが好ましく、７０ｍｇＫＯＨ／ｇ以上がより好ましい。５０ｍｇＫＯＨ／ｇ以上とすることにより、極性基含有共重合体中のカルボキシル基と塗膜中の官能基との共有結合が十分に形成されることで塗膜密着性が得られやすくなる。酸価とは、試料重合体１ｇを中和するのに必要な水酸化カリウムのｍｇ数である。
　極性基の導入量が上記の範囲であれば、極性基含有共重合体中の極性基と塗膜中の官能基との共有結合が十分に形成されることで塗膜密着性が得られやすくなる。 The rate of introduction of the polar groups into the polar group-containing polymer is not particularly limited, and may be designed so that the concentration of the polar groups in the surface-modified layer described later falls within a predetermined range. In some cases, the hydroxyl value of the polymer is preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more. The hydroxyl value of a polymer is the number of mg of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group after acetylating 1 g of the sample polymer.
When the polar group is a carboxyl group, the acid value of the polymer is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more. When the amount is 50 mgKOH/g or more, sufficient covalent bonds are formed between the carboxyl groups in the polar group-containing copolymer and the functional groups in the coating film, thereby making it easier to obtain coating film adhesion. The acid value is mg of potassium hydroxide required to neutralize 1 g of sample polymer.
If the amount of the polar group introduced is within the above range, the covalent bond between the polar group in the polar group-containing copolymer and the functional group in the coating film is sufficiently formed, thereby easily obtaining coating film adhesion. Become.
　極性基含有重合体としては、例えば、アクリル系重合体、ポリエステル系重合体、ウレタン系重合体、ポリエーテル系重合体、ポリアミド系重合体、およびエポキシアクリレート系重合体から選択される重合体であって極性基を有するものが挙げられる。密着性向上の観点からは、好ましくは極性基含有アクリル系重合体である。 The polar group-containing polymer is, for example, a polymer selected from acrylic polymers, polyester polymers, urethane polymers, polyether polymers, polyamide polymers, and epoxy acrylate polymers. and those having a polar group. From the viewpoint of improving adhesion, a polar group-containing acrylic polymer is preferable.
　極性基含有重合体としては、水酸基含有重合体、カルボキシル基含有重合体、アミノ基含有重合体、ウレタン結合含有重合体などが挙げられる 　Polar group-containing polymers include hydroxyl group-containing polymers, carboxyl group-containing polymers, amino group-containing polymers, and urethane bond-containing polymers.
・水酸基含有重合体
　水酸基含有重合体としては、水酸基（－ＯＨ）を含有するオリゴマー、又はポリマーであれば、本発明の効果を損なわない範囲で、任意の適切な重合体を採用し得る。このような水酸基含有重合体としては、例えば、水酸基含有アクリル系重合体や、水酸基含有エポキシアクリレート系重合体などが挙げられる。 • Hydroxyl Group-Containing Polymer As the hydroxyl group-containing polymer, any appropriate polymer can be employed as long as it is an oligomer or polymer containing a hydroxyl group (—OH) within a range that does not impair the effects of the present invention. Examples of such hydroxyl group-containing polymers include hydroxyl group-containing acrylic polymers and hydroxyl group-containing epoxy acrylate polymers.
　水酸基含有重合体は、例えば、水酸基含有モノマーを含むモノマー成分を重合することによって得られる。 A hydroxyl group-containing polymer is obtained, for example, by polymerizing a monomer component containing a hydroxyl group-containing monomer.
　水酸基含有重合体が水酸基含有アクリル系重合体である場合、例えば、水酸基非含有アクリル系モノマーと、水酸基含有モノマーとしての水酸基含有アクリル系モノマーとを含むモノマー成分を重合することによって得られ、例えば、（メタ）アクリル酸アルキルエステルと、水酸基含有（メタ）アクリル酸アルキルエステルとを含むモノマー成分を重合することにより好ましく得られる。
　本明細書において、「（メタ）アクリル酸」とは、アクリル酸および／またはメタクリル酸をいうものとする。 When the hydroxyl group-containing polymer is a hydroxyl group-containing acrylic polymer, for example, it is obtained by polymerizing a monomer component containing a hydroxyl group-free acrylic monomer and a hydroxyl group-containing acrylic monomer as a hydroxyl group-containing monomer. It is preferably obtained by polymerizing a monomer component containing a (meth)acrylic acid alkyl ester and a hydroxyl group-containing (meth)acrylic acid alkyl ester.
As used herein, "(meth)acrylic acid" refers to acrylic acid and/or methacrylic acid.
　（メタ）アクリル酸アルキルエステルとしては、例えば、直鎖状または分岐状の炭素数１～２０のアルキル基を有する（メタ）アクリル酸アルキルエステルが挙げられる。そのような（メタ）アクリル酸アルキルエステルとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸ネオペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸イソトリドデシル、（メタ）アクリル酸テトラデシル、（メタ）アクリル酸イソテトラデシル、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸イソオクタデシル、（メタ）アクリル酸ノナデシル、および（メタ）アクリル酸エイコシルが挙げられる。
　（メタ）アクリル酸アルキルエステルは、単独で用いられてもよいし、二種類以上が併用されてもよい。 (Meth)acrylic acid alkyl esters include, for example, (meth)acrylic acid alkyl esters having a linear or branched alkyl group having 1 to 20 carbon atoms. Examples of such (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, Isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, (meth) acrylic hexyl acid, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, (meth)acrylate Decyl acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, isotridodecyl (meth)acrylate, tetradecyl (meth)acrylate, isotetradecyl (meth)acrylate, Pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, isooctadecyl (meth)acrylate, nonadecyl (meth)acrylate, and eicosyl (meth)acrylate is mentioned.
The (meth)acrylic acid alkyl esters may be used alone, or two or more of them may be used in combination.
　水酸基含有（メタ）アクリル酸アルキルエステルとしては、例えば、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸６－ヒドロキシヘキシル、（メタ）アクリル酸８－ヒドロキシオクチル、（メタ）アクリル酸１０－ヒドロキシデシル、（メタ）アクリル酸１２－ヒドロキシラウリル、および（４－ヒドロキシメチルシクロへキシル）メチル（メタ）アクリレートが挙げられる。
　水酸基含有（メタ）アクリル酸アルキルエステルは、単独で用いられてもよいし、二種類以上が併用されてもよい。
　水酸基含有（メタ）アクリル酸アルキルエステルは、好ましくはアクリル酸２－ヒドロキシエチル、メタクリル酸２－ヒドロキシエチル、アクリル酸２－ヒドロキシブチル、および（メタ）アクリル酸４－ヒドロキシブチルからなる群より選択される少なくとも一種である。 Examples of hydroxyl group-containing (meth)acrylic acid alkyl esters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3 (meth)acrylic acid. -hydroxypropyl, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12 (meth)acrylic acid -hydroxylauryl, and (4-hydroxymethylcyclohexyl)methyl (meth)acrylate.
The hydroxyl group-containing (meth)acrylic acid alkyl esters may be used alone, or two or more of them may be used in combination.
The hydroxyl group-containing (meth)acrylic acid alkyl ester is preferably selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl acrylate, and 4-hydroxybutyl (meth)acrylate. at least one
　モノマー成分中、水酸基含有（メタ）アクリル酸アルキルエステル等の水酸基含有モノマーの配合量は、得られる水酸基含有重合体の水酸基価が上述の範囲となるように適宜調整し得るが、例えば、全モノマー成分１００モル部中、好ましくは１モル部以上、より好ましくは５モル部以上であり、また、好ましくは５０モル部以下、より好ましくは４０モル部以下である。水酸基含有モノマーが１モル部以上であれば、塗料と相互作用するのに適した水酸基量が得られ、塗料との密着性が良好となる。また、水酸基含有モノマーが５０モル部以下であれば、水酸基含有重合体の重合プロセスでゲル化が起こり製造困難となるのを防ぐことができる。 Among the monomer components, the blending amount of the hydroxyl group-containing monomer such as the hydroxyl group-containing (meth)acrylic acid alkyl ester can be appropriately adjusted so that the hydroxyl group value of the resulting hydroxyl group-containing polymer is within the above range. In 100 mol parts of the component, it is preferably 1 mol part or more, more preferably 5 mol parts or more, and preferably 50 mol parts or less, more preferably 40 mol parts or less. If the hydroxyl group-containing monomer is 1 mol part or more, the amount of hydroxyl groups suitable for interacting with the paint is obtained, and the adhesion with the paint is improved. In addition, when the hydroxyl group-containing monomer is 50 mol parts or less, it is possible to prevent gelation from occurring in the polymerization process of the hydroxyl group-containing polymer, which makes production difficult.
　モノマー成分は、（メタ）アクリル酸アルキルエステル、水酸基含有（メタ）アクリル酸アルキルエステルの他に、これらと共重合可能な一種または二種以上の他のモノマー（共重合性モノマー）を含んでもよい。共重合性モノマーとしては、例えば、カルボキシル基含有モノマー、窒素原子含有環を有するモノマー、無水マレイン酸および無水イタコン酸などの酸無水物モノマー、スルホン酸基含有モノマー、エポキシ基含有モノマー、アミド基含有モノマー、芳香族ビニル化合物、脂環式炭化水素基を有する（メタ）アクリル酸エステル、および、芳香族炭化水素基を有する（メタ）アクリル酸エステルが挙げられる。
　モノマー成分中に上記共重合性モノマーを含む場合、共重合性モノマーの含有量は、（メタ）アクリル酸アルキルエステル１００モル部に対して、水酸基含有（メタ）アクリル酸アルキルエステルとの合計量として、好ましくは１モル部以上、より好ましくは５モル部以上であり、また、好ましくは５０モル部以下、より好ましくは４０モル部以下である。 In addition to the (meth)acrylic acid alkyl ester and the hydroxyl group-containing (meth)acrylic acid alkyl ester, the monomer component may contain one or more other monomers copolymerizable therewith (copolymerizable monomers). . Examples of copolymerizable monomers include carboxyl group-containing monomers, nitrogen atom-containing ring-containing monomers, acid anhydride monomers such as maleic anhydride and itaconic anhydride, sulfonic acid group-containing monomers, epoxy group-containing monomers, and amide group-containing monomers. Monomers, aromatic vinyl compounds, (meth)acrylic acid esters having an alicyclic hydrocarbon group, and (meth)acrylic acid esters having an aromatic hydrocarbon group can be mentioned.
When the above-mentioned copolymerizable monomer is contained in the monomer component, the content of the copolymerizable monomer is the total amount of the hydroxyl group-containing (meth)acrylic acid alkyl ester with respect to 100 mol parts of the (meth)acrylic acid alkyl ester. , preferably 1 mol part or more, more preferably 5 mol parts or more, and preferably 50 mol parts or less, more preferably 40 mol parts or less.
　カルボキシル基含有モノマーとしては、例えば、アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、およびイソクロトン酸が挙げられる。 Carboxyl group-containing monomers include, for example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
　窒素原子含有環を有するモノマーとしては、例えば、Ｎ－ビニル－２－ピロリドン、Ｎ－メチルビニルピロリドン、Ｎ－ビニルピリジン、Ｎ－ビニルピペリドン、Ｎ－ビニルピリミジン、Ｎ－ビニルピペラジン、Ｎ－ビニルピラジン、Ｎ－ビニルピロール、Ｎ－ビニルイミダゾール、Ｎ－ビニルオキサゾール、Ｎ－（メタ）アクリロイル－２－ピロリドン、Ｎ－（メタ）アクリロイルピペリジン、Ｎ－（メタ）アクリロイルピロリジン、Ｎ－ビニルモルホリン、およびＮ－ビニルイソチアゾールが挙げられる。 Examples of monomers having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine, and N- Vinyl isothiazole is mentioned.
　スルホン酸基含有モノマーとしては、例えば、スチレンスルホン酸、アリルスルホン酸、ビニルスルホン酸ナトリウム、２－（メタ）アクリルアミド－２－メチルプロパンスルホン酸、（メタ）アクリルアミドプロパンスルホン酸、スルホプロピル（メタ）アクリレート、および（メタ）アクリロイルオキシナフタレンスルホン酸が挙げられる。 Examples of sulfonic acid group-containing monomers include styrenesulfonic acid, allylsulfonic acid, sodium vinylsulfonate, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylates, and (meth)acryloyloxynaphthalenesulfonic acids.
　エポキシ基含有モノマーとしては、例えば、（メタ）アクリル酸グリシジルおよび（メタ）アクリル酸－２－エチルグリシジルエーテルなどのエポキシ基含有アクリレート、アリルグリシジルエーテル、および（メタ）アクリル酸グリシジルエーテルが挙げられる。 Epoxy group-containing monomers include, for example, epoxy group-containing acrylates such as glycidyl (meth)acrylate and 2-ethyl glycidyl (meth)acrylate, allyl glycidyl ether, and glycidyl (meth)acrylate.
　アミド基含有モノマーとしては、例えば、（メタ）アクリルアミド、Ｎ－アルキル（メタ）アクリルアミド、Ｎ，Ｎ－ジアルキル（メタ）アクリルアミド、およびＮ－（メタ）アクリロイルモルホリンが挙げられる。Ｎ－アルキル（メタ）アクリルアミドとしては、例えば、Ｎ－エチル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、およびＮ－ブチル（メタ）アクリルアミドが挙げられる。Ｎ，Ｎ－ジアルキル（メタ）アクリルアミドとしては、例えば、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジプロピル（メタ）アクリルアミド、およびＮ，Ｎ－ジイソプロピル（メタ）アクリルアミドが挙げられる。 Amide group-containing monomers include, for example, (meth)acrylamide, N-alkyl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, and N-(meth)acryloylmorpholine. N-alkyl(meth)acrylamides include, for example, N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, and N-butyl(meth)acrylamide. N,N-dialkyl(meth)acrylamides include, for example, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, and N,N-diisopropyl (Meth)acrylamide may be mentioned.
　芳香族ビニル化合物としては、例えば、スチレン、α－メチルスチレン、およびビニルトルエンが挙げられる。 Examples of aromatic vinyl compounds include styrene, α-methylstyrene, and vinyltoluene.
　脂環式炭化水素基を有する（メタ）アクリル酸エステルとしては、例えば、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、およびジシクロペンタニル（メタ）アクリレートが挙げられる。 (Meth)acrylic acid esters having an alicyclic hydrocarbon group include, for example, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate.
　芳香族炭化水素基を有する（メタ）アクリル酸エステルとしては、例えば、フェニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、およびベンジル（メタ）アクリレートが挙げられる。 (Meth)acrylic acid esters having an aromatic hydrocarbon group include, for example, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate.
　水酸基含有アクリル系重合体は、上述のモノマー成分を重合させることによって形成することができる。重合手法としては、例えば溶液重合、塊状重合、および乳化重合が挙げられ、好ましくは溶液重合が挙げられる。溶液重合では、例えば、モノマー成分と重合開始剤とを溶媒に配合して反応溶液を調製した後、その反応溶液を加熱する。そして、反応溶液中でのモノマー成分の重合反応を経ることによって、重合体を含む重合体溶液を得ることができる。重合開始剤としては、重合方法に応じて、熱重合開始剤および光重合開始剤を用いることができる。重合開始剤の使用量は、モノマー成分１００質量部に対して、例えば０．０１質量部以上であり、また、例えば５質量部以下である。 The hydroxyl group-containing acrylic polymer can be formed by polymerizing the above monomer components. Polymerization techniques include, for example, solution polymerization, bulk polymerization, and emulsion polymerization, preferably solution polymerization. In solution polymerization, for example, a monomer component and a polymerization initiator are blended in a solvent to prepare a reaction solution, and then the reaction solution is heated. Then, a polymer solution containing a polymer can be obtained through a polymerization reaction of the monomer components in the reaction solution. As the polymerization initiator, a thermal polymerization initiator and a photopolymerization initiator can be used depending on the polymerization method. The amount of the polymerization initiator used is, for example, 0.01 parts by mass or more and, for example, 5 parts by mass or less with respect to 100 parts by mass of the monomer component.
　熱重合開始剤としては、例えば、アゾ系重合開始剤、過酸化物系重合開始剤、および、過硫酸カリウムなどの過硫酸塩が、挙げられる。アゾ系重合開始剤としては、例えば、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス－２－メチルブチロニトリル、２，２’－アゾビス（２－メチルプロピオン酸）ジメチル、４，４’－アゾビス－４－シアノバレリアン酸、アゾビスイソバレロニトリル、および２，２’－アゾビス（２－アミジノプロパン）ジヒドロクロライドが挙げられる。過酸化物系重合開始剤としては、例えば、ジベンゾイルペルオキシド、ｔ－ブチルペルマレエート、および過酸化ラウロイルが挙げられる。 Examples of thermal polymerization initiators include azo polymerization initiators, peroxide polymerization initiators, and persulfates such as potassium persulfate. Examples of azo polymerization initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis(2-methylpropionate)dimethyl , 4,4′-azobis-4-cyanovaleric acid, azobisisovaleronitrile, and 2,2′-azobis(2-amidinopropane) dihydrochloride. Peroxide polymerization initiators include, for example, dibenzoyl peroxide, t-butyl permaleate, and lauroyl peroxide.
　光重合開始剤としては、例えば、ベンゾインエーテル系光重合開始剤、アセトフェノン系光重合開始剤、α－ケトール系光重合開始剤、芳香族スルホニルクロリド系光重合開始剤、光活性オキシム系光重合開始剤、ベンゾイン系光重合開始剤、ベンジル系光重合開始剤、ベンゾフェノン系光重合開始剤、ケタール系光重合開始剤、チオキサントン系光重合開始剤、および、アシルフォスフィンオキサイド系光重合開始剤が挙げられる。 Examples of photopolymerization initiators include benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, α-ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, and photoactive oxime-based photopolymerization initiators. benzoin-based photopolymerization initiator, benzyl-based photopolymerization initiator, benzophenone-based photopolymerization initiator, ketal-based photopolymerization initiator, thioxanthone-based photopolymerization initiator, and acylphosphine oxide-based photopolymerization initiator. be done.
　水酸基含有重合体としては、市販品を採用してもよい。このような市販品としては、例えば、水酸基含有アクリル系重合体である「ＡＲＵＦＯＮ（登録商標）　ＵＨ－２０００シリーズ」（東亞合成株式会社製）や、水酸基含有ウレタンアクリレートである「ＩＲＲ７４２」（ダイセル・オルネクス株式会社製）などが挙げられる。
　水酸基含有重合体は、１種であってもよいし、２種以上であってもよい。 Commercially available products may be used as the hydroxyl group-containing polymer. Examples of such commercial products include, for example, "ARUFON (registered trademark) UH-2000 series" (manufactured by Toagosei Co., Ltd.), which is a hydroxyl group-containing acrylic polymer, and "IRR742", which is a hydroxyl group-containing urethane acrylate (Daicel). Allnex Co., Ltd.) and the like.
The number of hydroxyl group-containing polymers may be one, or two or more.
・カルボキシル基含有重合体
　カルボキシル基含有重合体としては、カルボキシル基（－ＣＯＯＨ）を含有するオリゴマー、又はポリマーであれば、本発明の効果を損なわない範囲で、任意の適切な重合体を採用し得る。このようなカルボキシル基含有重合体としては、例えば、カルボキシル基含有アクリル系重合体などが挙げられる。
　カルボキシル基含有重合体としては、市販品を採用してもよい。このような市販品としては、例えば、カルボキシル基含有アクリル系重合体である「ＡＲＵＦＯＮ（登録商標）
　ＵＣ－３０００シリーズ」（東亞合成株式会社製）やロジンエステル（荒川化学工業株式会社製）等が挙げられる。
　カルボキシル基含有重合体は、１種であってもよいし、２種以上であってもよい。 Carboxyl Group-Containing Polymer As the carboxyl group-containing polymer, any appropriate polymer can be adopted as long as it is an oligomer or polymer containing a carboxyl group (--COOH) within a range that does not impair the effects of the present invention. obtain. Examples of such carboxyl group-containing polymers include carboxyl group-containing acrylic polymers.
Commercially available products may be employed as the carboxyl group-containing polymer. Examples of such commercial products include "ARUFON (registered trademark)", which is a carboxyl group-containing acrylic polymer.
UC-3000 series” (manufactured by Toagosei Co., Ltd.) and rosin ester (manufactured by Arakawa Chemical Industries, Ltd.).
The number of carboxyl group-containing polymers may be one, or two or more.
・アミノ基含有重合体
　アミノ基含有重合体としては、アミノ基（－ＮＨ２）を含有するポリマーであれば、本発明の効果を損なわない範囲で、任意の適切なポリマーを採用し得る。このようなアミノ基含有重合体としては、例えばアミノ基含有アクリル系重合体などが挙げられる。
　アミノ基含有ポリマーとしては、市販品を採用してもよい。このような市販品としては、例えば、「ＥＰＯＭＩＮ（登録商標）」（株式会社日本触媒製）等のポリエチレンイミンや、「ポリメント（登録商標）」（株式会社日本触媒製）等のアミノエチル化アクリルポリマーが挙げられる。
　アミノ基含有ポリマーは、１種であってもよいし、２種以上であってもよい。 Amino Group-Containing Polymer As the amino group-containing polymer, any suitable polymer containing an amino group (—NH 2 ) can be employed as long as it does not impair the effects of the present invention. Examples of such amino group-containing polymers include amino group-containing acrylic polymers.
Commercially available products may be employed as the amino group-containing polymer. Examples of such commercial products include polyethyleneimine such as "EPOMIN (registered trademark)" (manufactured by Nippon Shokubai Co., Ltd.) and aminoethylated acrylic resins such as "Polyment (registered trademark)" (manufactured by Nippon Shokubai Co., Ltd.). polymers.
One type of amino group-containing polymer may be used, or two or more types may be used.
・ウレタン結合含有重合体
　ウレタン結合含有重合体としては、ウレタン結合（－Ｏ－ＣＯ－ＮＨ－）を含有する重合体であれば、本発明の効果を損なわない範囲で、任意の適切なポリマーを採用し得る。このようなウレタン結合含有重合体としては、例えばウレタン結合含有アクリル系重合体などが挙げられる。
　ウレタン結合含有重合体としては、市販品を採用してもよい。このような市販品としては、例えば、「ＥＢＥＣＲＹＬ」、「ＫＲＭ」（ダイセル・オルネクス株式会社）製などのウレタンアクリレートが挙げられる。
　ウレタン結合含有重合体は、１種であってもよいし、２種以上であってもよい。 - Urethane bond-containing polymer As the urethane bond-containing polymer, any appropriate polymer can be used as long as it is a polymer containing a urethane bond (-O-CO-NH-) to the extent that the effects of the present invention are not impaired. can be adopted. Examples of such urethane bond-containing polymers include urethane bond-containing acrylic polymers.
Commercially available products may be used as the urethane bond-containing polymer. Examples of such commercially available products include urethane acrylates such as "EBECRYL" and "KRM" (Daicel-Ornex Co., Ltd.).
The urethane bond-containing polymer may be one kind, or two or more kinds.
　極性基含有重合体の重量平均分子量（Ｍｗ）は特に制限されるものではないが、成膜性・加工性、の観点からは、好ましくは２００以上、より好ましくは５００以上であり、また、上記重合体を含む表面改質組成物の塗工性、塗膜や樹脂部材との密着性の観点からは、好ましくは５００００００以下、より好ましくは３００００００以下である。
　重合体の重量平均分子量は、ゲル・パーミエーション・クロマトグラフ（ＧＰＣ）によって測定してポリスチレン換算により算出される。 Although the weight average molecular weight (Mw) of the polar group-containing polymer is not particularly limited, it is preferably 200 or more, more preferably 500 or more, from the viewpoint of film-forming properties and workability. It is preferably 5,000,000 or less, more preferably 3,000,000 or less, from the viewpoint of the coating properties of the surface-modifying composition containing the polymer and the adhesion to the coating film or the resin member.
The weight average molecular weight of the polymer is calculated by measuring with gel permeation chromatography (GPC) and converting to polystyrene.
（不飽和炭化水素基含有重合体）
　不飽和炭化水素基を有する重合体は、上述のようにオリゴマーであってもポリマーであってもよい。表面改質層の成膜性の観点から、上述の極性基含有重合体、及び不飽和炭化水素基含有重合体の少なくともいずれか一方がポリマーであることが好ましい。 (Unsaturated hydrocarbon group-containing polymer)
Polymers having unsaturated hydrocarbon groups may be oligomeric or polymeric as described above. At least one of the polar group-containing polymer and the unsaturated hydrocarbon group-containing polymer is preferably a polymer from the viewpoint of the film-forming properties of the surface-modified layer.
　不飽和炭化水素基含有重合体としては、不飽和炭化水素基を含有するオリゴマー、又はポリマーであれば、本発明の効果を損なわない範囲で、任意の適切な重合体を採用し得る。 As the unsaturated hydrocarbon group-containing polymer, any appropriate polymer can be adopted as long as it is an oligomer or polymer containing an unsaturated hydrocarbon group, as long as it does not impair the effects of the present invention.
　不飽和炭化水素基含有重合体中の不飽和炭化水素基の導入率としては、特に限定されず、後述の表面改質層の二重結合当量が所定の範囲となるように設計されればよいが、例えば、不飽和炭化水素基含有重合体の二重結合当量が、４０００以下であることが好ましく、３０００以下であることがより好ましい。
　不飽和炭化水素基含有重合体の二重結合当量は、重合体の分子量を、重合体１分子あたりの不飽和炭化水素基の数で除して得られる値であり、値が小さいほど、重合体の単位質量あたりに含まれる不飽和炭化水素基の量が多いことを表す。
　不飽和炭化水素基含有重合体の二重結合当量を、４０００以下とすることにより、不飽和炭化水素基含有重合体中の不飽和炭化水素基と樹脂部材中の不飽和炭化水素基含有樹脂との共有結合が十分に形成されることで樹脂部材との密着性が得られやすくなる。 The introduction rate of the unsaturated hydrocarbon group in the unsaturated hydrocarbon group-containing polymer is not particularly limited, and may be designed so that the double bond equivalent of the surface-modified layer described later is within a predetermined range. However, for example, the double bond equivalent of the unsaturated hydrocarbon group-containing polymer is preferably 4000 or less, more preferably 3000 or less.
The double bond equivalent of the unsaturated hydrocarbon group-containing polymer is a value obtained by dividing the molecular weight of the polymer by the number of unsaturated hydrocarbon groups per molecule of the polymer. It means that the amount of unsaturated hydrocarbon groups contained per unit mass of coalescence is large.
By setting the double bond equivalent of the unsaturated hydrocarbon group-containing polymer to 4000 or less, the unsaturated hydrocarbon group in the unsaturated hydrocarbon group-containing polymer and the unsaturated hydrocarbon group-containing resin in the resin member is sufficiently formed, it becomes easier to obtain adhesion with the resin member.
　不飽和炭化水素基含有重合体としては、例えば、アクリル系重合体、ポリエステル系重合体、ウレタン系重合体、ポリエーテル系重合体、ポリアミド系重合体、およびエポキシアクリレート系重合体から選択される重合体であって不飽和炭化水素基を有するものが挙げられる。密着性向上の観点からは、好ましくは不飽和炭化水素基含有アクリル系重合体である。 Examples of unsaturated hydrocarbon group-containing polymers include polymers selected from acrylic polymers, polyester polymers, urethane polymers, polyether polymers, polyamide polymers, and epoxy acrylate polymers. Those which are coalesced and have unsaturated hydrocarbon groups are included. From the viewpoint of improving adhesion, an unsaturated hydrocarbon group-containing acrylic polymer is preferred.
　不飽和炭化水素基含有重合体は、例えば、官能基を有するプレポリマーと該官能基と反応を生じて結合し得る不飽和炭化水素基含有化合物とを反応させることによって得られる。
　本明細書で用いる「プレポリマー」の用語は、極性基含有重合体を構成するモノマーを一部重合させた重合体を意味する。 The unsaturated hydrocarbon group-containing polymer is obtained, for example, by reacting a prepolymer having a functional group with an unsaturated hydrocarbon group-containing compound capable of reacting with and bonding to the functional group.
The term "prepolymer" used herein means a polymer obtained by partially polymerizing the monomers that constitute the polar group-containing polymer.
・不飽和炭化水素基含有アクリル系重合体
　プレポリマーに不飽和炭化水素基を導入する方法は特に制限されず、種々の方法を採用することができる。不飽和炭化水素基をプレポリマーの側鎖に導入することは、分子設計の点からも有利である。
　このような方法としては、例えば、予めプレポリマーに官能基を有するモノマーを共重合させ、その後、この官能基と反応し得る官能基と不飽和炭化水素基とを有する化合物を不飽和炭化水素基の熱硬化性を維持したまま縮合又は付加反応させる方法が挙げられる。
　例えば、不飽和炭化水素基含有重合体が不飽和炭化水素基含有アクリル系重合体である場合、上述の水酸基含有アクリル系重合体をプレポリマーとして用い、このプレポリマーと不飽和炭化水素基含有化合物との付加反応により好ましく得ることができる。不飽和炭化水素基含有化合物は、水酸基と反応を生じて結合しうる所定の官能基を有し、プレポリマー中の水酸基と、不飽和炭化水素基含有化合物中の該官能基とが反応することにより、不飽和炭化水素基含有化合物に由来する不飽和炭化水素基を含む側鎖がプレポリマーに導入され、不飽和炭化水素基含有重合体が得られる。 • Unsaturated Hydrocarbon Group-Containing Acrylic Polymer The method for introducing unsaturated hydrocarbon groups into the prepolymer is not particularly limited, and various methods can be employed. Introducing an unsaturated hydrocarbon group to the side chain of the prepolymer is also advantageous in terms of molecular design.
As such a method, for example, a prepolymer is previously copolymerized with a monomer having a functional group, and then a compound having a functional group capable of reacting with the functional group and an unsaturated hydrocarbon group is added to the unsaturated hydrocarbon group. A method of condensation or addition reaction while maintaining the thermosetting property of is mentioned.
For example, when the unsaturated hydrocarbon group-containing polymer is an unsaturated hydrocarbon group-containing acrylic polymer, the hydroxyl group-containing acrylic polymer described above is used as a prepolymer, and this prepolymer and the unsaturated hydrocarbon group-containing compound It can be preferably obtained by an addition reaction with The unsaturated hydrocarbon group-containing compound has a predetermined functional group capable of reacting and bonding with a hydroxyl group, and the hydroxyl group in the prepolymer reacts with the functional group in the unsaturated hydrocarbon group-containing compound. introduces a side chain containing an unsaturated hydrocarbon group derived from the unsaturated hydrocarbon group-containing compound into the prepolymer to obtain an unsaturated hydrocarbon group-containing polymer.
　これら官能基の組合せの例としては、カルボキシル基とエポキシ基（特に、グリシジル基）、カルボキシル基とアジリジル基、水酸基とイソシアネート基等が挙げられる。これら官能基の組合せのなかでも反応追跡の容易さから、水酸基とイソシアネート基との組合せが好適である。また、これら官能基の組合せにより、前記不飽和炭化水素基含有重合体を生成するような組合せであれば、官能基はプレポリマーと不飽和炭化水素基含有化合物のいずれの側にあってもよい。 Examples of combinations of these functional groups include a carboxyl group and an epoxy group (especially a glycidyl group), a carboxyl group and an aziridyl group, a hydroxyl group and an isocyanate group, and the like. Among these combinations of functional groups, a combination of a hydroxyl group and an isocyanate group is preferable because of the ease of tracking the reaction. In addition, the functional group may be on either side of the prepolymer or the unsaturated hydrocarbon group-containing compound as long as the combination of these functional groups produces the unsaturated hydrocarbon group-containing polymer. .
　例えば、プレポリマーが水酸基を有し、不飽和炭化水素基含有化合物が不飽和炭化水素基含有イソシアネート化合物であってもよい。その場合、プレポリマーとしては、上述の水酸基含有アクリル系重合体が用いられる。 For example, the prepolymer may have a hydroxyl group, and the unsaturated hydrocarbon group-containing compound may be an unsaturated hydrocarbon group-containing isocyanate compound. In that case, the above-mentioned hydroxyl group-containing acrylic polymer is used as the prepolymer.
　カルボシキル基を有するモノマーとしては、例えば、（メタ）アクリル酸、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレート等が挙げられる。
　エポキシ基を有するモノマーとしてはグリシジル基を有するモノマーが好ましく、グリシジル基を有するモノマーとしては、例えば、（メタ）アクリル酸グリシジル、（メタ）アクリル酸メチルグリシジル等が挙げられる。 Examples of monomers having a carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate and the like.
As the monomer having an epoxy group, a monomer having a glycidyl group is preferable, and examples of the monomer having a glycidyl group include glycidyl (meth)acrylate and methylglycidyl (meth)acrylate.
　不飽和炭化水素基含有イソシアネート化合物としては、例えば、２－メタクリロイルオキシエチルイソシアネート（ＭＯＩ）、及びイソシアン酸３－イソプロペニル－α，α－ジメチルベンジル等が挙げられる。ポリマー側鎖への不飽和炭化水素基の導入のしやすさの観点からは、不飽和炭化水素基含有イソシアネート化合物は、好ましくはＭＯＩである。 Examples of unsaturated hydrocarbon group-containing isocyanate compounds include 2-methacryloyloxyethyl isocyanate (MOI) and 3-isopropenyl-α,α-dimethylbenzyl isocyanate. From the viewpoint of ease of introduction of unsaturated hydrocarbon groups into polymer side chains, the unsaturated hydrocarbon group-containing isocyanate compound is preferably MOI.
　上記反応に用いる不飽和炭化水素基含有化合物の配合量としては、得られる不飽和炭化水素基含有重合体の二重結合当量が上述の範囲となるように適宜調整し得る。
　ここで、水酸基含有アクリル系重合体の原料となる水酸基含有モノマーに対する不飽和炭化水素基含有化合物の配合モル比率が１未満である場合には、得られる不飽和炭化水素基含有アクリル系重合体は水酸基も同時に有する重合体となる。 The amount of the unsaturated hydrocarbon group-containing compound used in the above reaction can be appropriately adjusted so that the double bond equivalent of the resulting unsaturated hydrocarbon group-containing polymer falls within the above range.
Here, when the blending molar ratio of the unsaturated hydrocarbon group-containing compound to the hydroxyl group-containing monomer that is the raw material of the hydroxyl group-containing acrylic polymer is less than 1, the unsaturated hydrocarbon group-containing acrylic polymer obtained is It becomes a polymer having hydroxyl groups at the same time.
　上記付加反応において、反応温度は例えば４０℃～６０℃であり、反応時間は例えば４～１０時間である。また、当該反応には、付加反応触媒を用いてもよい。不飽和炭化水素基含有化合物中の官能基がイソシアネート基である場合、付加反応触媒としては、例えばジラウリン酸ジブチルスズを用いることができる。付加反応触媒の使用量は、不飽和炭化水素基含有化合物１００質量部に対して例えば０．３～０．６質量部である。
　不飽和炭化水素基含有アクリル系重合体は、例えば上述のプレポリマーを含むプレポリマー溶液に不飽和炭化水素基含有化合物と付加反応触媒とを添加した反応溶液を調製し、反応溶液中で上記付加反応を経ることによって、不飽和炭化水素基含有アクリル系重合体を含む不飽和炭化水素基含有アクリル系重合体溶液として得ることができる。 In the above addition reaction, the reaction temperature is, for example, 40° C. to 60° C., and the reaction time is, for example, 4 to 10 hours. Moreover, an addition reaction catalyst may be used for the reaction. When the functional group in the unsaturated hydrocarbon group-containing compound is an isocyanate group, dibutyltin dilaurate, for example, can be used as the addition reaction catalyst. The amount of the addition reaction catalyst used is, for example, 0.3 to 0.6 parts by mass with respect to 100 parts by mass of the unsaturated hydrocarbon group-containing compound.
For the unsaturated hydrocarbon group-containing acrylic polymer, for example, a reaction solution is prepared by adding an unsaturated hydrocarbon group-containing compound and an addition reaction catalyst to a prepolymer solution containing the above-described prepolymer, and the addition reaction is performed in the reaction solution. Through the reaction, an unsaturated hydrocarbon group-containing acrylic polymer solution containing an unsaturated hydrocarbon group-containing acrylic polymer can be obtained.
　不飽和炭化水素基含有アクリル系重合体としては、市販品を採用してもよい。
　不飽和炭化水素基含有アクリル系重合体は、１種であってもよいし、２種以上であってもよい。 Commercially available products may be used as the unsaturated hydrocarbon group-containing acrylic polymer.
One type of unsaturated hydrocarbon group-containing acrylic polymer may be used, or two or more types may be used.
・エポキシアクリレート系重合体
　エポキシアクリレート系重合体としては、本発明の効果を損なわない範囲で、任意の適切な重合体を採用し得る。エポキシアクリレート系重合体は、ビスフェノール型エポキシアクリレートや脂肪族型エポキシアクリレートなど、ポリエーテル系重合体の末端に不飽和炭化水素基を有する構造であってもよく、ノボラック型エポキシアクリレートのように、側鎖に不飽和炭化水素基を有する構造であってもよい。
　エポキシアクリレート系重合体としては、市販品を採用してもよい。このような市販品としては、例えば、「ＥＢＥＣＲＹＬ３７００」、「ＥＢＥＣＲＹＬ３７０１」（いずれもダイセル・オルネクス株式会社製）などが挙げられる。
　エポキシアクリレート系重合体は、１種であってもよいし、２種以上であってもよい。 - Epoxy acrylate-based polymer As the epoxy acrylate-based polymer, any suitable polymer can be adopted as long as the effects of the present invention are not impaired. The epoxy acrylate-based polymer may have a structure having an unsaturated hydrocarbon group at the end of a polyether-based polymer such as bisphenol-type epoxy acrylate or aliphatic-type epoxy acrylate. A structure having an unsaturated hydrocarbon group in the chain may also be used.
A commercially available product may be adopted as the epoxy acrylate polymer. Examples of such commercially available products include "EBECRYL3700" and "EBECRYL3701" (both manufactured by Daicel Allnex Co., Ltd.).
One type of epoxy acrylate polymer may be used, or two or more types may be used.
・ウレタン系重合体
　ウレタン系重合体としては、本発明の効果を損なわない範囲で、任意の適切な重合体を採用し得る。ウレタン系重合体としては、ウレタンアクリレートのように側鎖に不飽和炭化水素基を有する構造が挙げられる。
　ウレタン系重合体としては、市販品を採用してもよい。このような市販品としては、例えば、「ＩＲＲ７４２」（ダイセル・オルネクス株式会社製）などが挙げられる。
　ウレタン系重合体は、１種であってもよいし、２種以上であってもよい。 - Urethane-based polymer As the urethane-based polymer, any appropriate polymer can be employed as long as the effects of the present invention are not impaired. Examples of urethane-based polymers include structures having unsaturated hydrocarbon groups in side chains, such as urethane acrylate.
A commercially available product may be used as the urethane-based polymer. Examples of such commercial products include "IRR742" (manufactured by Daicel-Ornex Co., Ltd.).
The number of urethane-based polymers may be one, or two or more.
　上記不飽和炭化水素基含有重合体の重量平均分子量（Ｍｗ）は特に制限されるものではないが、成膜性・加工性、の観点からは、好ましくは２００以上、より好ましくは５００以上であり、また、上記不飽和炭化水素基含有重合体を含む表面改質組成物の塗工性、塗膜や樹脂部材との密着性の観点からは、好ましくは５００００００以下、より好ましくは３００００００以下である。
　重合体の重量平均分子量は、ゲル・パーミエーション・クロマトグラフ（ＧＰＣ）によって測定してポリスチレン換算により算出される。 Although the weight average molecular weight (Mw) of the unsaturated hydrocarbon group-containing polymer is not particularly limited, it is preferably 200 or more, more preferably 500 or more, from the viewpoint of film-forming properties and workability. Also, from the viewpoint of the coatability of the surface-modifying composition containing the unsaturated hydrocarbon group-containing polymer and the adhesion to a coating film or a resin member, it is preferably 5,000,000 or less, more preferably 3,000,000 or less. .
The weight average molecular weight of the polymer is calculated by measuring with gel permeation chromatography (GPC) and converting to polystyrene.
　表面改質層中の上記極性基含有重合体と不飽和炭化水素基含有重合体との含有比率としては、各重合体における極性基や不飽和炭化水素基の導入率等にも拠るが、（極性基含有重合体／不飽和炭化水素基含有重合体）で表される質量比率が、０．０１～１００であることが好ましく、０．０５～２０がより好ましく、０．１～１０であることがさらに好ましい。 The content ratio of the polar group-containing polymer and the unsaturated hydrocarbon group-containing polymer in the surface modified layer depends on the introduction rate of the polar group and the unsaturated hydrocarbon group in each polymer, etc. ( The mass ratio represented by polar group-containing polymer/unsaturated hydrocarbon group-containing polymer) is preferably 0.01 to 100, more preferably 0.05 to 20, and 0.1 to 10. is more preferred.
　表面改質層中の極性基濃度は、１０．０ｍｇＫＯＨ／ｇ以上であることが好ましく、１５．０ｍｇＫＯＨ／ｇ以上がより好ましく、２０．０ｍｇＫＯＨ／ｇ以上であることがさらに好ましい。 The polar group concentration in the surface modified layer is preferably 10.0 mgKOH/g or more, more preferably 15.0 mgKOH/g or more, and even more preferably 20.0 mgKOH/g or more.
　本明細書において、表面改質層中の極性基濃度Ｘ（ｍｇＫＯＨ／ｇ）は、下記式を用いて算出される値である。
　　表面改質層の極性基濃度（Ｘ）＝Σ（ｘｉ・ｗｉ）
　上記式において、ｘｉは、表面改質層中に含まれる重合体ｉが水酸基含有重合体である場合には水酸基価（ｍｇＫＯＨ／ｇ）を、重合体ｉがカルボキシル基含有重合体である場合には酸価（ｍｇＫＯＨ／ｇ）をそれぞれ表す。ｗｉは、重合体ｉの表面改質層における質量分率を表す。
　重合体の水酸基価とは、試料重合体１ｇをアセチル化した後、水酸基と結合した酢酸を中和するのに必要な水酸化カリウムのｍｇ数である。
　重合体の酸価とは、試料重合体１ｇを中和するのに必要な水酸化カリウムのｍｇ数である。 In this specification, the polar group concentration X (mgKOH/g) in the surface modified layer is a value calculated using the following formula.
Polar group concentration (X) of the surface modified layer = Σ (xi wi)
In the above formula, xi is the hydroxyl value (mgKOH/g) when the polymer i contained in the surface-modified layer is a hydroxyl-containing polymer, and when the polymer i is a carboxyl-containing polymer, each represents an acid value (mgKOH/g). wi represents the mass fraction of the polymer i in the surface-modified layer.
The hydroxyl value of a polymer is the number of mg of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group after acetylating 1 g of the sample polymer.
The acid value of a polymer is the mg of potassium hydroxide required to neutralize 1 g of sample polymer.
　表面改質層の極性基濃度の算出にあたっては、上記の重合体の水酸基価に替えて、重合体１ｇあたりに含まれる水酸基の質量（ｍｇ）を用いてもよい。また、上記の重合体の酸価に替えて、重合体１ｇあたりに含まれるカルボキシル基の質量（ｍｇ）を用いてもよい。 In calculating the polar group concentration of the surface-modified layer, the mass (mg) of hydroxyl groups contained per 1 g of the polymer may be used instead of the hydroxyl value of the polymer described above. Further, the mass (mg) of carboxyl groups contained per 1 g of the polymer may be used instead of the acid value of the polymer.
　表面改質層中の不飽和炭化水素基の含有量としては、僅かに含有していればよい。具体的には、表面改質層の二重結合当量が、１２０００以下であればよい。本明細書において、表面改質層の二重結合当量とは、不飽和炭化水素基１つあたりの表面改質層の質量で表される量であり、値が小さいほど、表面改質層の単位質量あたりに含まれる不飽和炭化水素基の量が多いことを表す。表面改質層の二重結合当量のより好ましい範囲としては、１００００以下であることが好ましく、５０００以下がより好ましい。 The content of unsaturated hydrocarbon groups in the surface-modified layer may be small. Specifically, the double bond equivalent of the surface modified layer should be 12000 or less. As used herein, the double bond equivalent of the surface modified layer is the amount represented by the mass of the surface modified layer per unsaturated hydrocarbon group, and the smaller the value, the more the surface modified layer. It means that the amount of unsaturated hydrocarbon groups contained per unit mass is large. A more preferable range for the double bond equivalent of the surface modified layer is preferably 10,000 or less, more preferably 5,000 or less.
　表面改質層の二重結合当量Ｙは、下記式を用いて算出することができる。 The double bond equivalent Y of the surface modified layer can be calculated using the following formula.
　　表面改質層の二重結合当量（Ｙ）＝Σ（ｙｉ・ｗｉ）
　上記式において、ｙｉは、表面改質層中に含まれる重合体ｉの二重結合当量、ｗｉは、重合体ｉの表面改質層における質量分率を表す。
　重合体の二重結合当量は、不飽和炭化水素基１つあたりの重合体の質量で表される量であり、重合体の分子量を重合体１分子あたりの不飽和炭化水素基の数で除した値である。 Double bond equivalent (Y) of the surface modified layer = Σ (yi wi)
In the above formula, yi represents the double bond equivalent of polymer i contained in the surface-modified layer, and wi represents the mass fraction of polymer i in the surface-modified layer.
The double bond equivalent weight of a polymer is the amount expressed in mass of the polymer per unsaturated hydrocarbon group, the molecular weight of the polymer divided by the number of unsaturated hydrocarbon groups per molecule of the polymer. is the value
　本発明の実施形態において、表面改質層の極性基濃度が１０ｍｇＫＯＨ／ｇ以上であり、表面改質層の二重結合当量が１２０００以下であることが好ましい。
　本発明の実施形態に係る表面改質層は、表面改質層の極性基濃度を１０．０ｍｇＫＯＨ／ｇ以上に設計し、表面改質層の二重結合当量を１２０００以下に設計することで、塗膜密着性と樹脂部材との密着性とを両立しやすくなる。すなわち、表面改質層の極性基濃度が１０．０ｍｇＫＯＨ／ｇ以上であることで、良好な塗膜密着性を得ることができる。また、表面改質層の二重結合当量が１２０００以下であることで、樹脂部材との密着性を得ることができる。 In an embodiment of the present invention, it is preferable that the surface modified layer has a polar group concentration of 10 mgKOH/g or more and a double bond equivalent of 12000 or less.
In the surface modified layer according to the embodiment of the present invention, the polar group concentration of the surface modified layer is designed to be 10.0 mgKOH / g or more, and the double bond equivalent of the surface modified layer is designed to be 12000 or less. It becomes easier to achieve both coating film adhesion and adhesion to the resin member. That is, when the polar group concentration of the surface modified layer is 10.0 mgKOH/g or more, good coating film adhesion can be obtained. Further, when the double bond equivalent of the surface modified layer is 12000 or less, it is possible to obtain adhesion to the resin member.
　このように、本発明の実施形態における表面改質層は、極性基含有重合体と不飽和炭化水素基含有重合体とをそれぞれ含有している。すなわち本発明の実施形態における表面改質層は極性基含有重合体と不飽和炭化水素基含有重合体とのブレンドポリマー（もしくはオリゴマー）を含有することにより、優れた接着強度を得られることが判った。この理由は定かではないが、本発明者らは、極性基含有重合体と不飽和炭化水素基含有重合体とをブレンドすることで、極性基含有重合体が表面改質層の表面にブリートすることにより密着性が向上するためと推察している。また、極性基と不飽和炭化水素基とを同一の重合体中に含む場合に比して、重合体材料の選択肢が広い上、複雑なポリマー設計を要さず、両者の含有比率の調整によって表面改質層と樹脂部材との接着強度や表面改質層と塗膜との接着強度の向上といった機能発現が可能となる。 Thus, the surface-modified layer in the embodiment of the present invention contains a polar group-containing polymer and an unsaturated hydrocarbon group-containing polymer. That is, it was found that the surface-modified layer in the embodiment of the present invention can obtain excellent adhesive strength by containing a blend polymer (or oligomer) of a polar group-containing polymer and an unsaturated hydrocarbon group-containing polymer. rice field. Although the reason for this is not clear, the present inventors found that by blending a polar group-containing polymer and an unsaturated hydrocarbon group-containing polymer, the polar group-containing polymer bleeds onto the surface of the surface modified layer. It is speculated that this is because the adhesiveness is improved by this. In addition, compared to the case where the same polymer contains a polar group and an unsaturated hydrocarbon group, there is a wider range of choices for polymer materials, and complicated polymer design is not required. It is possible to exhibit functions such as an improvement in the adhesive strength between the surface modified layer and the resin member and the adhesive strength between the surface modified layer and the coating film.
　表面改質層中の上記極性基含有重合体と不飽和炭化水素基含有重合体重合体との合計の含有割合は、好ましくは５０質量％～１００質量％であり、より好ましくは７０質量％～１００質量％であり、さらに好ましくは９０質量％～１００質量％であり、特に好ましくは９２質量％～１００質量％であり、最も好ましくは９５質量％～１００質量％である。 The total content of the polar group-containing polymer and the unsaturated hydrocarbon group-containing polymer in the surface modified layer is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass. % by mass, more preferably 90% by mass to 100% by mass, particularly preferably 92% by mass to 100% by mass, most preferably 95% by mass to 100% by mass.
　表面改質層（表面改質層の材料であってもよい）は、上記の重合体成分とともに、必要に応じて他の成分を含有してもよい。他の成分としては、例えば、ｐＨ調整剤、架橋剤、粘度調整剤（増粘剤等）、レベリング剤、剥離調整剤、可塑剤、軟化剤、充填剤、着色剤（顔料および染料等）、界面活性剤、帯電防止剤、防腐剤、老化防止剤、紫外線吸収剤、酸化防止剤、および光安定剤が挙げられる。 The surface-modified layer (which may be the material of the surface-modified layer) may contain other components as necessary along with the polymer components described above. Other components include, for example, pH adjusters, cross-linking agents, viscosity modifiers (thickeners, etc.), leveling agents, release modifiers, plasticizers, softeners, fillers, colorants (pigments, dyes, etc.), Surfactants, antistatic agents, preservatives, anti-aging agents, UV absorbers, antioxidants, and light stabilizers are included.
　表面改質層の厚みは、特に制限は無く、０．０１μｍ～２０００μｍであり、より好ましくは０．１～１０００μｍであり、さらに好ましくは０．５～２００μｍであり、特に好ましくは１μｍ～１００μｍである。
　表面改質層の厚みはダイヤルシックネスゲージ（例えば、ピーコックＧＣ－９）により表面改質シートの厚みを測定し、その箇所の表面改質層を除去した離型シートの厚みを測定し、その差を表面改質層の厚みとして測定できる。
　表面改質層の平均厚みとは１０点を測定した平均値である。 The thickness of the surface modification layer is not particularly limited, and is preferably 0.01 μm to 2000 μm, more preferably 0.1 to 1000 μm, still more preferably 0.5 to 200 μm, particularly preferably 1 μm to 100 μm. be.
The thickness of the surface-modified layer is determined by measuring the thickness of the surface-modified sheet with a dial thickness gauge (eg, Peacock GC-9), measuring the thickness of the release sheet after removing the surface-modified layer at that point, and calculating the difference. can be measured as the thickness of the surface modification layer.
The average thickness of the surface modified layer is the average value obtained by measuring 10 points.
＜離型シート＞
　離型シートとしては、特に限定されないが、耐熱性が１００℃以上であることが好ましく、１００℃における引張弾性率が１ＧＰａ以下であることが好ましい。また、非シリコーン系の樹脂シートであっても、シリコーン系の樹脂シートであってもよいが、非シリコーン系の樹脂シートであることが好ましく、例えば、フッ素系の樹脂シートフィルム（日東電工株式会社製、ニトフロン）、ポリエステル系の樹脂シート、ポリメチルペンテン系の樹脂シート（三井化学東セロ製、オピュラン（登録商標））、ポリスチレン系の樹脂シート（クラボウ製、オイディス（登録商標））、ポリアミド系の樹脂シート、ポリオレフィン系の樹脂シートなどが挙げられる。 <Release sheet>
The release sheet is not particularly limited, but preferably has a heat resistance of 100° C. or higher and a tensile elastic modulus at 100° C. of 1 GPa or lower. In addition, it may be a non-silicone resin sheet or a silicone resin sheet, but it is preferably a non-silicone resin sheet. manufactured by Nitoflon), polyester-based resin sheet, polymethylpentene-based resin sheet (manufactured by Mitsui Chemicals Tohcello, Opulan (registered trademark)), polystyrene-based resin sheet (manufactured by Kurabo Industries, Oidis (registered trademark)), polyamide-based A resin sheet, a polyolefin-based resin sheet, and the like are included.
　表面改質シートに使用できる離型シートとしてより具体的には、例えば、未延伸ポリアミド６、未延伸ポリアミド６６、二軸延伸ポリアミド６、二軸延伸ポリアミド６６、二軸延伸ポリプロピレン、二軸延伸ポリエチレンテレフタレート、二軸延伸ポリブチレンテレフタレート、易成形ポリエチレンテレフタレート、キャスト成形ポリテトラフルオロエチレン、未延伸押出成形テトラフルオロエチレン－エチレン共重合体（ＥＴＦＥ）、未延伸押出成形テトラフルオロエチレン－パーフルオロアルコキシエチレン共重合体（ＰＦＡ）、未延伸押出成形テトラフルオロエチレン－ヘキサフルオロプロピレン共同合体（ＦＥＰ）、これらを主層とした積層品などが挙げられる。 More specifically, the release sheet that can be used for the surface-modified sheet includes, for example, unstretched polyamide 6, unstretched polyamide 66, biaxially stretched polyamide 6, biaxially stretched polyamide 66, biaxially stretched polypropylene, and biaxially stretched polyethylene. Terephthalate, biaxially oriented polybutylene terephthalate, easily moldable polyethylene terephthalate, cast polytetrafluoroethylene, unstretched extruded tetrafluoroethylene-ethylene copolymer (ETFE), unstretched extruded tetrafluoroethylene-perfluoroalkoxyethylene copolymer Examples include polymer (PFA), unstretched extruded tetrafluoroethylene-hexafluoropropylene joint (FEP), laminates having these as main layers, and the like.
　離型シートの厚みは、形状追従性の観点から、好ましくは１μｍ～１０００μｍであり、より好ましくは１０μｍ～５００μｍであり、さらに好ましくは２０μｍ～３００μｍであり、特に好ましくは３０μｍ～１００μｍである。
　また、必要に応じて、離型シートの表面改質層側の面あるいは両面にシリコーンなど適宜な離型処理剤による離型処理を施してもよい。 The thickness of the release sheet is preferably 1 μm to 1000 μm, more preferably 10 μm to 500 μm, still more preferably 20 μm to 300 μm, and particularly preferably 30 μm to 100 μm, from the viewpoint of conformability.
In addition, if necessary, the surface of the release sheet on the surface modification layer side or both surfaces may be subjected to a release treatment with an appropriate release agent such as silicone.
〔表面改質シートの製造〕
　表面改質シートは、任意の適切な方法によって製造し得る。例えば、表面改質層の材料と溶剤を含む溶液（表面改質組成物）への離型シートのディッピングの後に必要に応じて乾燥する方法、離型シートの表面への表面改質層の材料と溶剤を含む溶液の刷毛塗りの後に必要に応じて乾燥する方法、離型シートの表面への表面改質層の材料と溶剤を含む溶液の各種コーターによる塗布の後に必要に応じて乾燥する方法、離型シートの表面への表面改質層の材料と溶剤を含む溶液のスプレー塗布の後に必要に応じて乾燥する方法などが挙げられる。 [Production of surface-modified sheet]
A surface-modified sheet may be manufactured by any suitable method. For example, a method of dipping a release sheet in a solution (surface-modifying composition) containing a material for the surface-modifying layer and a solvent (surface-modifying composition) followed by drying as necessary, and a method of applying the material for the surface-modifying layer to the surface of the release sheet. A method of drying if necessary after applying a solution containing a solvent and a brush, and a method of drying if necessary after applying a solution containing the material of the surface modification layer and a solvent to the surface of the release sheet with various coaters. , a method of spray coating a solution containing the material for the surface-modifying layer and a solvent onto the surface of the release sheet, followed by drying as necessary.
　表面改質組成物としては、表面改質層の材料を、溶剤に溶解した溶液が挙げられる。
　溶剤としては、例えば、水；メタノール、エタノール、イソプロピルアルコール（ＩＰＡ）などのアルコール類；メチルエチルケトンなどのケトン類；酢酸エチルなどのエステル類；脂肪族、脂環族、並びに芳香族炭化水素；ハロゲン化炭化水素；ジメチルホルムアミドなどのアミド類；ジメチルスルホキシドなどのスルホキシド類；ジメチルエーテル、テトラヒドロフランなどのエーテル類；などが挙げられる。溶剤は、１種のみであってもよいし、２種以上であってもよい。 Examples of the surface-modifying composition include a solution obtained by dissolving the material of the surface-modifying layer in a solvent.
Examples of solvents include water; alcohols such as methanol, ethanol, and isopropyl alcohol (IPA); ketones such as methyl ethyl ketone; esters such as ethyl acetate; amides such as dimethylformamide; sulfoxides such as dimethylsulfoxide; ethers such as dimethyl ether and tetrahydrofuran; Only one kind of solvent may be used, or two or more kinds thereof may be used.
　表面改質組成物としては、重合体の合成において得られる重合体を含むポリマー溶液をそのまま用いることも好ましい。 As the surface-modifying composition, it is also preferable to use the polymer solution containing the polymer obtained in polymer synthesis as it is.
　表面改質組成物における固形分濃度は、目的に応じて適宜設定し得る。表面改質層の厚み精度の観点から、質量割合として、好ましくは１質量％～６０質量％であり、より好ましくは１０質量％～５０質量％であり、さらに好ましくは１５質量％～４０質量％である。 The solid content concentration in the surface-modifying composition can be appropriately set according to the purpose. From the viewpoint of thickness accuracy of the surface modified layer, the mass ratio is preferably 1% to 60% by mass, more preferably 10% to 50% by mass, and still more preferably 15% to 40% by mass. is.
　表面改質組成物には、必要に応じて、上述の重合体とともに表面改質層に含みうる他の成分を含有してもよい。
　例えば、着色剤を添加することにより表面改質層が可視化し、樹脂部材の表面を既に改質したかどうかが判別し易くなり工程管理の面でメリットがある。また、塗装の発色を改善するための下地としての機能も果たす。
　着色剤としては、例えば、染料、又は顔料が挙げられる。また、着色剤としては、ブラックライトで視認できる蛍光材料であってもよい。 The surface-modifying composition may optionally contain other components that can be included in the surface-modifying layer together with the polymer described above.
For example, by adding a coloring agent, the surface modified layer can be visualized, making it easy to determine whether the surface of the resin member has already been modified, which is advantageous in terms of process control. It also functions as a base for improving the coloring of the paint.
Colorants include, for example, dyes and pigments. Further, the colorant may be a fluorescent material that can be visually recognized under black light.
〔積層体〕
　本発明の実施形態に係る積層体は、本発明の実施形態に係る表面改質層と樹脂材料との積層体であり、前記表面改質層が、樹脂材料の表面の少なくとも一部に積層された積層体である。
　本発明の実施形態における表面改質層付き樹脂材料である積層体は、成形前の樹脂材料の表面の少なくとも一部に表面改質シートの表面改質層側を積層することにより製造することができる。
　また、本発明の実施形態に係る積層体は、前記樹脂材料と前記表面改質層とが化学反応により共有結合した積層体であってもよい。
　樹脂材料と表面改質層とが化学反応により共有結合した積層体は、後述の表面改質部材の製造方法と同様の方法により製造することができる。 [Laminate]
A laminate according to an embodiment of the present invention is a laminate of the surface-modified layer according to the embodiment of the present invention and a resin material, and the surface-modified layer is laminated on at least part of the surface of the resin material. It is a laminated body.
The laminate, which is the resin material with a surface modified layer according to the embodiment of the present invention, can be produced by laminating the surface modified layer side of the surface modified sheet on at least part of the surface of the resin material before molding. can.
Moreover, the laminated body which concerns on embodiment of this invention may be the laminated body which the said resin material and the said surface modification layer covalently bonded by chemical reaction.
A laminate in which a resin material and a surface-modifying layer are covalently bonded by a chemical reaction can be manufactured by a method similar to the method for manufacturing a surface-modifying member described later.
　樹脂材料に含まれる樹脂は、熱硬化性樹脂であることが好ましく、樹脂部材と表面改質層との密着性向上の観点から、不飽和炭化水素基含有熱硬化性樹脂であることが好ましい。
　不飽和炭化水素基含有熱硬化性樹脂としては、例えば、不飽和ポリエステル樹脂、ビニルエステル樹脂等を挙げることができ、好ましくは不飽和ポリエステル樹脂である。
　なお、樹脂材料に含まれる不飽和炭化水素基含有熱硬化性樹脂は、少なくとも一部の未硬化状態の不飽和炭化水素基含有熱硬化性樹脂を含むものとする。 The resin contained in the resin material is preferably a thermosetting resin, and from the viewpoint of improving adhesion between the resin member and the surface modification layer, it is preferably an unsaturated hydrocarbon group-containing thermosetting resin.
Examples of unsaturated hydrocarbon group-containing thermosetting resins include unsaturated polyester resins and vinyl ester resins, preferably unsaturated polyester resins.
The unsaturated hydrocarbon group-containing thermosetting resin contained in the resin material includes at least a part of the uncured unsaturated hydrocarbon group-containing thermosetting resin.
　樹脂材料は繊維強化樹脂を含んでいてもよく、熱硬化性樹脂が、繊維強化熱硬化性樹脂であってもよい。
　繊維強化熱硬化性樹脂としては、例えば、炭素繊維強化熱硬化性樹脂、ガラス繊維強化熱硬化性樹脂などが挙げられる。 The resin material may contain a fiber-reinforced resin, and the thermosetting resin may be a fiber-reinforced thermosetting resin.
Examples of fiber-reinforced thermosetting resins include carbon fiber-reinforced thermosetting resins and glass fiber-reinforced thermosetting resins.
　樹脂材料は不飽和炭化水素基含有熱硬化性樹脂の他、さらに反応性モノマー及び硬化剤、ガラス繊維を含むことが好ましい。不飽和ポリエステル樹脂等の不飽和炭化水素基含有熱硬化性樹脂は、硬化剤の存在下で、熱硬化性樹脂中の不飽和炭化水素基と反応性モノマーとのラジカル重合により高分子化（三次元架橋）し、硬化物が得られる。
　樹脂材料に含まれる樹脂が不飽和ポリエステル樹脂である場合、反応性モノマーとしては例えばスチレンが好ましく用いられ、硬化剤としては例えば過酸化ベンゾイル（ＢＰＯ）が好ましく用いられる。 The resin material preferably contains an unsaturated hydrocarbon group-containing thermosetting resin, as well as a reactive monomer, a curing agent, and glass fibers. Unsaturated hydrocarbon group-containing thermosetting resins such as unsaturated polyester resins are polymerized (tertiary original cross-linking) to obtain a cured product.
When the resin contained in the resin material is an unsaturated polyester resin, styrene is preferably used as the reactive monomer, and benzoyl peroxide (BPO) is preferably used as the curing agent.
　樹脂材料の形状としては、例えば、平面を有する板状、曲面を有する板状、シート状、フィルム状などが挙げられる。
　樹脂材料の厚みは、例えば、０．００１ｍｍ～１０ｍｍである。 Examples of the shape of the resin material include a plate shape having a flat surface, a plate shape having a curved surface, a sheet shape, a film shape, and the like.
The thickness of the resin material is, for example, 0.001 mm to 10 mm.
　「樹脂材料の表面の少なくとも一部」とは、樹脂材料が有する全ての表面の中の少なくとも一部を意味する。例えば、樹脂材料が板状やシート状やフィルム状の場合は、その少なくとも一方の表面の一部や、その少なくとも一方の表面の全部などを意味する。 "At least part of the surface of the resin material" means at least part of all the surfaces of the resin material. For example, when the resin material is plate-shaped, sheet-shaped, or film-shaped, it means a part of at least one surface or the entirety of at least one surface.
　表面改質シート、表面改質層としては、上述の説明をそのまま援用し得る。 As for the surface-modified sheet and the surface-modified layer, the above description can be used as it is.
〔表面改質部材〕
　本発明の実施形態に係る表面改質部材は、本発明の実施形態に係る積層体を含む。
　本発明の実施形態に係る表面改質部材は、本発明の実施形態に係る表面改質層が、樹脂部材の表面の少なくとも一部に積層されたものであってもよく、前記樹脂部材と前記表面改質層とが化学反応により共有結合していることが好ましい。この場合、樹脂部材と表面改質層とが共有結合を形成しているため、樹脂部材と表面改質層との接着強度に優れる。 [Surface modification member]
A surface modifying member according to an embodiment of the invention includes a laminate according to an embodiment of the invention.
A surface-modified member according to an embodiment of the present invention may be one in which the surface-modified layer according to the embodiment of the present invention is laminated on at least part of a surface of a resin member, and the resin member and the It is preferable that the surface modified layer is covalently bonded through a chemical reaction. In this case, since the resin member and the surface modification layer form a covalent bond, the adhesion strength between the resin member and the surface modification layer is excellent.
　表面改質シート、表面改質層、及び樹脂材料としては、上述の説明をそのまま援用し得る。樹脂部材は、樹脂材料を成形することにより得られ、樹脂部材の好ましい形状及び厚みについては樹脂材料と同様である。
　ここで、「成形」とは、型を使用するか否かにかかわらず素材を所定の形に加工することを意味し、「成型」とは、型を使って素材を所定の形に加工することを意味する。 As for the surface-modified sheet, the surface-modified layer, and the resin material, the above descriptions can be used as they are. The resin member is obtained by molding a resin material, and the preferable shape and thickness of the resin member are the same as those of the resin material.
Here, "molding" means processing a material into a predetermined shape regardless of whether a mold is used, and "molding" means processing a material into a predetermined shape using a mold. means that
　「樹脂部材の表面の少なくとも一部」とは、樹脂部材が有する全ての表面の中の少なくとも一部を意味する。例えば、樹脂部材が板状やシート状やフィルム状の場合は、その少なくとも一方の表面の一部や、その少なくとも一方の表面の全部などを意味する。 "At least part of the surface of the resin member" means at least part of all the surfaces of the resin member. For example, when the resin member is plate-shaped, sheet-shaped, or film-shaped, it means a part of at least one surface or the entirety of at least one surface.
　本発明の実施形態に係る表面改質部材は、樹脂部材が不飽和炭化水素基含有熱硬化性樹脂を含むことが好ましく、不飽和炭化水素基含有熱硬化性樹脂は不飽和ポリエステル樹脂であることが好ましい。
　すなわち、本発明の実施形態に係る表面改質部材は、樹脂部材中の不飽和炭化水素基含有熱硬化性樹脂と表面改質層中の不飽和炭化水素基含有重合体とが共有結合していることが好ましい。
　なお、樹脂部材中に含まれる不飽和炭化水素基含有熱硬化性樹脂は、硬化状態の不飽和炭化水素基含有熱硬化性樹脂、すなわち不飽和炭化水素基が消費された樹脂を含むものとする。 In the surface-modified member according to the embodiment of the present invention, the resin member preferably contains an unsaturated hydrocarbon group-containing thermosetting resin, and the unsaturated hydrocarbon group-containing thermosetting resin is an unsaturated polyester resin. is preferred.
That is, in the surface modified member according to the embodiment of the present invention, the unsaturated hydrocarbon group-containing thermosetting resin in the resin member and the unsaturated hydrocarbon group-containing polymer in the surface modified layer are covalently bonded. preferably.
The unsaturated hydrocarbon group-containing thermosetting resin contained in the resin member includes a cured unsaturated hydrocarbon group-containing thermosetting resin, that is, a resin in which the unsaturated hydrocarbon groups have been consumed.
　加熱成形は、樹脂材料と表面改質シートとの積層と同時に行ってもよいし、表面改質シートを樹脂材料に積層した後に行ってもよい。
　このような方法で樹脂部材の表面処理を行うことにより、樹脂部材に十分な接着強度を付与することができ、表面改質部材を高い生産性と低コストで製造することができる。表面改質部材の製造方法は、樹脂部材の表面を処理する方法（樹脂の表面処理方法）でもあり得る。 The thermoforming may be performed simultaneously with lamination of the resin material and the surface-modified sheet, or may be performed after lamination of the surface-modified sheet on the resin material.
By surface-treating the resin member by such a method, it is possible to impart sufficient adhesive strength to the resin member, and to manufacture the surface-modified member with high productivity and low cost. The method for manufacturing a surface-modified member can also be a method for treating the surface of a resin member (resin surface treatment method).
〔表面改質部材の製造方法〕
　本発明の実施形態に係る表面改質部材の製造方法に特に制限はないが、例えば、樹脂材料の表面の少なくとも一部に、離型シートと表面改質層の積層体である表面改質シートの該表面改質層側を載置し、加熱成形を行うことにより表面改質部材を製造することができる。
　加熱成形により表面改質層と樹脂材料の界面が溶融接触し、表面改質層中に含まれる不飽和炭化水素基含有重合体が、樹脂材料が含有する樹脂と化学反応することで、樹脂部材と表面改質層とが共有結合した表面改質部材を形成することができる。
　加熱成形は、表面改質シートの載置と同時に行ってもよいし、表面改質シートを載置した後に行ってもよい。
　このような方法で樹脂部材の表面処理を行うことにより、樹脂部材に十分な接着強度を付与することができ、表面改質部材を高い生産性と低コストで製造することができる。表面改質部材の製造方法は、樹脂部材の表面を処理する方法（樹脂部材の表面処理方法）でもあり得る。 [Method for producing surface-modified member]
The method for producing the surface-modified member according to the embodiment of the present invention is not particularly limited. The surface-modified member can be produced by placing the surface-modified layer side of the above and performing heat molding.
The interface between the surface modified layer and the resin material is melted and contacted by heat molding, and the unsaturated hydrocarbon group-containing polymer contained in the surface modified layer chemically reacts with the resin contained in the resin material, thereby forming a resin member. and the surface-modified layer are covalently bonded to each other to form a surface-modified member.
Heat molding may be performed simultaneously with placing the surface-modified sheet, or may be performed after placing the surface-modified sheet.
By surface-treating the resin member by such a method, it is possible to impart sufficient adhesive strength to the resin member, and to manufacture the surface-modified member with high productivity and low cost. The method for manufacturing a surface-modified member can also be a method for treating the surface of a resin member (method for surface treatment of a resin member).
　樹脂部材は不飽和炭化水素基含有熱硬化性樹脂を含むことが好ましく、不飽和ポリエステル樹脂を含むことがより好ましい。
　樹脂部材、表面改質シート、離型シート、及び表面改質層としては、上述の説明をそのまま援用し得る。 The resin member preferably contains an unsaturated hydrocarbon group-containing thermosetting resin, and more preferably contains an unsaturated polyester resin.
As for the resin member, the surface-modified sheet, the release sheet, and the surface-modified layer, the above descriptions can be used as they are.
　表面改質部材の製造においては、樹脂部材が含有する熱硬化性樹脂の硬化温度をＴ２℃としたとき、該熱硬化性樹脂を含む樹脂材料の表面の少なくとも一部に表面改質層を設け、Ｔ１℃以上の温度で加熱成形を行うことが好ましい。なお、硬化温度は未硬化の熱硬化性樹脂をＤＳＣ（示差走査熱量測定）にて測定したヒートフロー曲線の発熱温度域内の温度とする。
　加熱成形温度は、好ましくはＴ１℃～Ｔ３℃であり、より好ましくは（Ｔ１＋１０）℃～（Ｔ３－１０）℃であり、さらに好ましくは（Ｔ１＋２０）℃～（Ｔ３－２０）℃である。
　ここで、Ｔ１は未硬化の熱硬化性樹脂をＤＳＣにて測定した際の発熱が始まる温度（℃）であり、Ｔ３は発熱が終わる温度（℃）である。 In the production of the surface-modified member, a surface-modified layer is formed on at least part of the surface of the resin material containing the thermosetting resin, where the curing temperature of the thermosetting resin contained in the resin member is T 2 °C. It is preferable to perform the heat molding at a temperature of T 1 ° C. or higher. The curing temperature is the temperature within the heat generation temperature range of the heat flow curve measured by DSC (differential scanning calorimetry) of the uncured thermosetting resin.
The thermoforming temperature is preferably T 1 ° C. to T 3 ° C., more preferably (T 1 +10) ° C. to (T 3 -10) ° C., still more preferably (T 1 +20) ° C. to (T 3 -20)°C.
Here, T1 is the temperature (°C) at which heat generation begins when an uncured thermosetting resin is measured by DSC, and T3 is the temperature (°C) at which heat generation ends.
　加熱成形温度を上記範囲内として、上記のような方法で樹脂部材の表面処理を行うことにより、表面改質層と樹脂部材の界面が溶融接触して化学反応によって共有結合を形成し、樹脂部材に塗膜との接着強度に優れた表面改質層を付与することができる。そして、このような付与を高い生産性と低コストで行うことができる。 By carrying out the surface treatment of the resin member by the method described above with the heat molding temperature within the above range, the interface between the surface modified layer and the resin member melts and contacts to form a covalent bond through a chemical reaction, thereby forming a covalent bond on the resin member. can be provided with a surface-modified layer having excellent adhesion strength to the coating film. And such provision can be performed with high productivity and low cost.
　本発明の実施形態に係る表面改質部材の製造方法は、上述の表面改質層を用いた表面改質部材の製造方法であって、前記表面改質層を加熱成形により樹脂部材に積層する積層工程を含んでいてもよい。
　本発明の実施形態に係る表面改質部材の製造方法は、上述の表面改質シートを用いた表面改質部材の製造方法であってもよい。 A method for producing a surface-modified member according to an embodiment of the present invention is a method for producing a surface-modified member using the above-described surface-modified layer, wherein the surface-modified layer is laminated on a resin member by heat molding. A lamination step may be included.
A method for manufacturing a surface-modified member according to an embodiment of the present invention may be a method for manufacturing a surface-modified member using the surface-modified sheet described above.
　加熱成形の方法としては、例えば、圧縮成形、トランスファー成形、射出成形などが挙げられ、樹脂成形によって行われることが好ましく、より好ましくは圧縮成形である。熱硬化性樹脂が、繊維強化熱硬化性樹脂の場合、成形方法として、ハンドレイアップ法、スプレイアップ法、フィラメントワインディング法、引抜き成形法、シートモールドコンパウンド法、バルクモールドンパウンド法、レジントランスファ法などが挙げられる。 Examples of heat molding methods include compression molding, transfer molding, and injection molding. Resin molding is preferable, and compression molding is more preferable. When the thermosetting resin is a fiber-reinforced thermosetting resin, the molding method includes a hand lay-up method, a spray-up method, a filament winding method, a pultrusion method, a sheet mold compound method, a bulk mold compound method, and a resin transfer method. etc.
　圧縮成形としては、例えば、成形加工機（例えば、プレス機など）内で、樹脂部材の表面の少なくとも一部に表面改質シートの表面改質層側を載置し、加熱を伴う成形加工（例えば、加熱プレスによる一体成形）を行う態様である。このような態様によれば、樹脂部材の表面処理とともに、樹脂部材の成形加工も同時に行うことができるため、高い生産性と低コストを提供できる。圧縮成形の際の成形圧は、好ましくは金型により成形品を変形させる観点から１ＭＰａ以上であることが好ましく、２ＭＰａ以上であることがより好ましく、３ＭＰａ以上であることがさらに好ましい。また、成形品の樹脂量保持の観点から３０ＭＰａ以下であることが好ましく、２５ＭＰａ以下であることがより好ましく、２０ＭＰａ以下であることがさらに好ましい。 As compression molding, for example, in a molding machine (for example, a press machine), the surface-modified layer side of the surface-modified sheet is placed on at least a part of the surface of the resin member, and molding is performed with heating ( For example, it is a mode in which integral molding by hot pressing is performed. According to this aspect, since the surface treatment of the resin member and the molding of the resin member can be performed at the same time, high productivity and low cost can be provided. The molding pressure during compression molding is preferably 1 MPa or higher, more preferably 2 MPa or higher, and even more preferably 3 MPa or higher, from the viewpoint of deformation of the molded product by the mold. In addition, from the viewpoint of maintaining the amount of resin in the molded product, the viscosity is preferably 30 MPa or less, more preferably 25 MPa or less, and even more preferably 20 MPa or less.
　樹脂部材の成形加工としては、射出成形であってもよい。
　射出成形は、例えば、可動側金型及び固定側金型を備えた射出成形機を用いることができる。例えば、表面改質シートを可動側金型のキャビティの凹部に離型シートが対向するように収容し、可動側金型及び固定側金型を型締めする。そして、キャビティに溶融された樹脂を射出する。
　そして、樹脂を金型内で冷却固化させた後、可動側金型と固定側金型とを離間させる。このようにして、表面改質シートと樹脂部材とが一体化された表面改質部材が得られる。 Injection molding may be used as the molding process for the resin member.
For injection molding, for example, an injection molding machine equipped with a movable mold and a fixed mold can be used. For example, the surface modified sheet is accommodated in the concave portion of the cavity of the movable side mold so that the release sheet faces the cavity, and the movable side mold and the fixed side mold are clamped. Then, the melted resin is injected into the cavity.
After cooling and solidifying the resin in the mold, the movable side mold and the fixed side mold are separated from each other. Thus, a surface-modified member in which the surface-modified sheet and the resin member are integrated is obtained.
　また、表面改質部材から離型シートを剥離することにより、表面改質層を表面に備えた表面改質部材が得られる。離型シートの剥離は、手で剥離する、専用の剥離設備を用いて剥離する等、特に限定されない。離型シートは塗装の直前まで設置しておくことができる。このことによって、表面改質層の表面の汚染を防止することができる。 Further, by peeling off the release sheet from the surface-modified member, a surface-modified member having a surface-modified surface provided with the surface-modified layer can be obtained. Peeling of the release sheet is not particularly limited, and may be performed manually, using a dedicated peeling equipment, or the like. The release sheet can be left in place until just before painting. This can prevent contamination of the surface of the surface modified layer.
　離型シートと表面改質層の積層体である表面改質シートの表面改質層側を樹脂部材（樹脂材料であってもよい）の表面の少なくとも一部に載置し、加熱成形した後、好ましくは、離型シートが除去される。このように離型シートが除去されることにより、樹脂部材の表面に表面改質層が転写され、表面改質部材（樹脂部材と表面改質層の積層部材と称することもある）が得られる。
　なお、前述したように、好ましくは、樹脂部材と表面改質層との層間において、該樹脂部材中の樹脂と該表面改質層中の不飽和炭化水素基含有重合体とが共有結合している。 After placing the surface-modified layer side of the surface-modified sheet, which is a laminate of the release sheet and the surface-modified layer, on at least a part of the surface of the resin member (which may be a resin material), and heat-molding. , preferably the release sheet is removed. By removing the release sheet in this way, the surface-modified layer is transferred to the surface of the resin member, and a surface-modified member (sometimes referred to as a laminated member of the resin member and the surface-modified layer) is obtained. .
As described above, preferably, the resin in the resin member and the unsaturated hydrocarbon group-containing polymer in the surface-modified layer are covalently bonded between the resin member and the surface-modified layer. there is
　上記の製造方法により、図１に示すように、樹脂部材１００の表面に表面改質層１０が設けられ、表面改質部材が得られる。 By the above manufacturing method, as shown in FIG. 1, the surface modified layer 10 is provided on the surface of the resin member 100 to obtain the surface modified member.
　離型シートと表面改質層の積層体である表面改質シートは、図２に示すように、離型シート２０と表面改質層１０の積層体である表面改質シート２００である。 The surface-modified sheet, which is a laminate of a release sheet and a surface-modified layer, is a surface-modified sheet 200, which is a laminate of a release sheet 20 and a surface-modified layer 10, as shown in FIG.
　本発明の実施形態に係る表面改質部材の製造方法において、離型シートと表面改質層の積層体である表面改質シートの該表面改質層側を該樹脂部材の表面の少なくとも一部に載置する形態は、図３に示すように、該表面改質シート２００の表面改質層１０側が樹脂材料４００の表面側になるように該表面改質シート２００を該樹脂材料４００の表面に載置させた形態である。 In the method for producing a surface-modified member according to the embodiment of the present invention, the surface-modified layer side of the surface-modified sheet, which is a laminate of a release sheet and a surface-modified layer, is at least part of the surface of the resin member. 3, the surface-modified sheet 200 is placed on the surface of the resin material 400 so that the surface-modified layer 10 side of the surface-modified sheet 200 is on the surface side of the resin material 400. It is a form placed on the
〔塗装物及び塗装物の製造方法〕
　本発明の実施形態に係る塗装物は、表面改質部材の少なくとも一部に塗膜を備える。表面改質部材の表面改質層側の表面の少なくとも一部に塗膜を備えることが好ましい。
　本発明の実施形態に係る塗装物の一例として、図４に樹脂部材１００の表面に表面改質層１０が設けられた表面改質部材の、表面改質層側の表面に塗膜３０を備えた塗装物３００を示す。 [Painted article and method for producing the painted article]
A coated article according to an embodiment of the present invention includes a coating film on at least a portion of a surface modifying member. It is preferable to provide a coating film on at least part of the surface of the surface-modifying member on the surface-modifying layer side.
As an example of a coated object according to an embodiment of the present invention, a coating film 30 is provided on the surface of the surface-modified member on the surface-modified layer side of the surface-modified member in which the surface-modified layer 10 is provided on the surface of the resin member 100 shown in FIG. 3 shows a painted object 300. FIG.
　塗膜は、塗装、印刷層、蒸着層、及びめっき層より選択される少なくとも１種であってもよい。 The coating film may be at least one selected from coating, printing layer, vapor deposition layer, and plating layer.
　本発明の表面改質シートを適用することによる密着性向上効果の観点からは、塗膜は塗料を含むことが好ましく、極性基含有重合体における極性基と化学結合を形成、又は分子間相互作用する官能基を有する塗料を含むことがより好ましい。
　密着性向上の観点から、該官能基は極性基含有重合体中の極性基と共有結合する官能基であることが好ましく、イソシアネート基、アミノ基であることが好ましい。 From the viewpoint of the effect of improving adhesion by applying the surface-modified sheet of the present invention, the coating film preferably contains paint, and forms a chemical bond with the polar group in the polar group-containing polymer, or forms an intermolecular interaction. It is more preferred to include a paint having functional groups that
From the viewpoint of improving adhesion, the functional group is preferably a functional group that covalently bonds with the polar group in the polar group-containing polymer, and is preferably an isocyanate group or an amino group.
　塗膜に含まれる塗料はウレタン系塗料やアクリル・ウレタン塗料等のウレタン系塗料、アクリル塗料、エポキシ塗料、シリコーン塗料、ポリエステル樹脂、メラミン樹脂系塗料又はフッ素塗料が好ましく、ウレタン系塗料がより好ましい。
　ウレタン系塗料は、主剤として複数の水酸基を持つ樹脂（ポリオール）と硬化剤としてのポリイソシアネートを組み合わせた塗料の総称である。ポリイソシアネートとしては、イソシアネート基を２個以上有する化合物であれば特に限定されず、例えば、トリレンジイソシアネート、４，４′－ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、メタキシリレンジイソシアネート等の芳香族のもの、ヘキサメチレンジイソシアネート等の脂肪族のもの、イソホロンジイソシアネート等の脂環族のもの、その単量体及びそのビュレットタイプ、ヌレートタイプ、アダクトタイプ等の多量体等を挙げることができる。 The paint contained in the coating film is preferably urethane paint such as urethane paint or acrylic/urethane paint, acrylic paint, epoxy paint, silicone paint, polyester resin, melamine resin paint or fluorine paint, more preferably urethane paint.
Urethane paint is a general term for paints that combine a resin (polyol) having multiple hydroxyl groups as a main agent and a polyisocyanate as a curing agent. The polyisocyanate is not particularly limited as long as it is a compound having two or more isocyanate groups. Aliphatic ones such as hexamethylene diisocyanate, alicyclic ones such as isophorone diisocyanate, monomers thereof and multimers thereof such as burette type, nurate type and adduct type can be used.
　表面改質層は部材の表面に塗設するのではなくシート状の表面改質シートを用いて形成されるため、ハジキ発生等によるむらの発生を防ぐことができる。そのため、表面改質層を樹脂部材の表面に均一な厚みで形成することができ、塗膜を均一な膜厚で塗設することができる。
　また、溶融状態又は軟化状態の樹脂部材の表面に表面改質層を設けることにより、樹脂部材の表面の熱によって表面改質層と樹脂部材が化学結合し、表面改質層と樹脂部材との接着強度が高くなるため、密着性に優れた塗膜が形成できる。加えて、表面改質層に含まれる極性基含有重合体中の極性基と、塗膜に含まれる塗料中の上記官能基が化学結合を形成、又は分子間相互作用することにより、表面改質層と塗膜との接着強度も高くなり、密着性に非常に優れた塗膜が形成可能となる。
　さらに、塗装物の形成に際して、表面改質層と樹脂部材との一体成形が可能であるため、塗膜を形成する前に離型剤を除去するための有機溶剤を用いた洗浄処理工程や研磨処理工程が必要なく安全性に優れ環境負荷や作業負荷が軽減できる。 Since the surface-modifying layer is formed using a sheet-like surface-modifying sheet rather than coating the surface of the member, it is possible to prevent the occurrence of unevenness due to repelling or the like. Therefore, the surface modified layer can be formed with a uniform thickness on the surface of the resin member, and the coating film can be applied with a uniform thickness.
Further, by providing the surface modified layer on the surface of the resin member in a molten state or a softened state, the surface modified layer and the resin member are chemically bonded by the heat of the surface of the resin member, and the surface modified layer and the resin member are bonded together. Since the adhesive strength increases, a coating film with excellent adhesion can be formed. In addition, the polar group in the polar group-containing polymer contained in the surface modification layer and the functional group in the paint contained in the coating film form a chemical bond or interact with each other to modify the surface. The adhesive strength between the layer and the coating film is also increased, making it possible to form a coating film with extremely excellent adhesion.
Furthermore, since it is possible to integrally mold the surface modified layer and the resin member when forming the coated object, a cleaning treatment process using an organic solvent to remove the mold release agent before forming the coating film and polishing are performed. It does not require a treatment process, is highly safe, and can reduce the environmental load and workload.
　塗膜の厚みは、特に制限は無く、０．０１～２０００μｍであり、より好ましくは０．１～１０００μｍであり、さらに好ましくは０．５～５００μｍであり、特に好ましくは１～２００μｍである。 The thickness of the coating film is not particularly limited, and is preferably 0.01 to 2000 μm, more preferably 0.1 to 1000 μm, even more preferably 0.5 to 500 μm, particularly preferably 1 to 200 μm.
　本発明の実施形態に係る塗装物の製造方法は、上述の表面改質層を用いた塗装物の製造方法であって、
　前記表面改質層を加熱成形により樹脂部材に積層して表面改質部材を製造する工程と、
　前記表面改質部材の前記表面改質層側に塗膜を形成する工程とを含む。
　本発明の実施形態に係る塗装物の製造方法は、上述の表面改質シートを用いた塗装物の製造方法であってもよい。 A method for producing a painted article according to an embodiment of the present invention is a method for producing a painted article using the above-described surface modification layer,
a step of laminating the surface-modified layer on a resin member by thermoforming to produce a surface-modified member;
and forming a coating film on the surface modification layer side of the surface modification member.
A method for manufacturing a coated object according to an embodiment of the present invention may be a method for manufacturing a coated object using the surface-modified sheet described above.
　前記樹脂部材は不飽和炭化水素基含有熱硬化性樹脂を含むことが好ましく、不飽和ポリエステル樹脂を含むことがより好ましい。
　前記塗膜は上述の極性基含有重合体中の極性基と化学結合を形成、又は分子間相互作用する官能基を有する塗料を含むことが好ましい。 The resin member preferably contains an unsaturated hydrocarbon group-containing thermosetting resin, and more preferably contains an unsaturated polyester resin.
It is preferable that the coating film contains a coating material having a functional group that forms a chemical bond with the polar group in the polar group-containing polymer described above, or that interacts intermolecularly.
　樹脂部材、表面改質シート、表面改質層、及び表面改質部材としては、上述の説明をそのまま援用し得る。また、表面改質部材を形成する工程については、上述の〔表面改質部材の製造方法〕における説明をそのまま援用し得る。 As for the resin member, the surface-modified sheet, the surface-modified layer, and the surface-modified member, the above descriptions can be used as they are. In addition, for the step of forming the surface-modified member, the description in the above [Method for producing surface-modified member] can be used as it is.
　塗膜の塗装方法に特に制限は無く、刷毛塗り、ローラー塗装、スプレー塗装、各種コーター塗装などの一般的な方法を用いることができ、その塗布量は特に限定されるものではない。また、塗膜を加熱する時間や温度等も、用いる塗料、塗布量等によって適宜決定することができる。 There are no particular restrictions on the coating method of the coating film, and general methods such as brush coating, roller coating, spray coating, and various coater coatings can be used, and the coating amount is not particularly limited. In addition, the time and temperature for heating the coating film can be appropriately determined depending on the coating material to be used, the coating amount, and the like.
〔工程管理方法〕
　本発明の実施形態に係る表面改質シートの製造、表面改質部材の製造、及び塗装物の製造に際し、例えば、表面改質組成物、又は表面改質層に染料、顔料、又は結晶性物質等の添加剤を含有させることで、表面改質層が可視化し製造工程を管理しやすくなる。 [Process control method]
In the production of the surface-modified sheet, the surface-modified member, and the coated article according to the embodiment of the present invention, for example, the surface-modifying composition or the surface-modifying layer may contain a dye, a pigment, or a crystalline substance. By containing such additives, the surface modified layer is visualized, making it easier to manage the manufacturing process.
　表面改質組成物、表面改質シート、塗装物、及び添加剤としては、上述の説明をそのまま援用し得る。 As for the surface-modifying composition, the surface-modifying sheet, the coated article, and the additive, the above descriptions can be used as they are.
　工程管理方法としては、例えば、表面処理して着色した部分を目視で確認する、または、カメラで撮影した画像を認識して判別する方法が挙げられる。 As a process control method, for example, there is a method of visually confirming the surface-treated and colored part, or a method of recognizing and discriminating images taken with a camera.
　以上説明したように、本明細書には次の事項が開示されている。
〔１〕
　極性基含有重合体と不飽和炭化水素基含有重合体をそれぞれ１種以上含む表面改質層。
〔２〕
　前記表面改質層の極性基濃度が１０ｍｇＫＯＨ／ｇ以上であり、前記表面改質層の二重結合当量が１２０００以下である、〔１〕に記載の表面改質層。
〔３〕
　〔１〕又は〔２〕に記載の表面改質層と離型シートとを備えた表面改質シート。
〔４〕
　〔１〕又は〔２〕に記載の表面改質層と樹脂材料との積層体であり、前記表面改質層が、樹脂材料の表面の少なくとも一部に積層された積層体。
〔５〕
　前記樹脂材料と前記表面改質層とが化学反応により共有結合した、〔４〕に記載の積層体。
〔６〕
　前記樹脂材料が不飽和炭化水素基含有熱硬化性樹脂を含む〔４〕又は〔５〕に記載の積層体。
〔７〕
　前記不飽和炭化水素基含有熱硬化性樹脂が不飽和ポリエステル樹脂である〔６〕に記載の積層体。
〔８〕
　〔４〕～〔７〕のいずれか１項に記載の積層体を含む表面改質部材。
〔９〕
　〔８〕に記載の表面改質部材の少なくとも一部に塗膜を備えた塗装物。
〔１０〕
　前記塗膜が前記極性基含有重合体における極性基と化学結合を形成、又は分子間相互作用する官能基を有する塗料を含む、〔９〕に記載の塗装物。
〔１１〕
　〔１〕又は〔２〕に記載の表面改質層を用いた表面改質部材の製造方法であって、
　前記表面改質層を加熱成形により樹脂部材に積層する積層工程を含む、表面改質部材の製造方法。
〔１２〕
　前記樹脂部材が不飽和ポリエステル樹脂を含む〔１１〕に記載の表面改質部材の製造方法。
〔１３〕
　〔３〕に記載の表面改質シートを用いた表面改質部材の製造方法。
〔１４〕
　〔１〕又は〔２〕に記載の表面改質層を用いた塗装物の製造方法であって、
　前記表面改質層を加熱成形により樹脂部材に積層して表面改質部材を製造する工程と、
　前記表面改質部材の前記表面改質層側に塗膜を形成する工程とを含む、塗装物の製造方法。
〔１５〕
　前記樹脂部材が不飽和ポリエステル樹脂を含む〔１４〕に記載の塗装物の製造方法。
〔１６〕
　前記塗膜が前記極性基含有重合体における極性基と化学結合を形成、又は分子間相互作用する官能基を有する塗料を含む、〔１４〕又は〔１５〕に記載の塗装物の製造方法。
〔１７〕
　〔３〕に記載の表面改質シートを用いた塗装物の製造方法。 As described above, this specification discloses the following matters.
[1]
A surface-modified layer containing at least one polar group-containing polymer and at least one unsaturated hydrocarbon group-containing polymer.
[2]
The surface-modified layer according to [1], wherein the surface-modified layer has a polar group concentration of 10 mgKOH/g or more and a double bond equivalent of 12000 or less.
[3]
A surface-modified sheet comprising the surface-modified layer according to [1] or [2] and a release sheet.
[4]
A laminate comprising the surface-modified layer according to [1] or [2] and a resin material, wherein the surface-modified layer is laminated on at least part of the surface of the resin material.
[5]
The laminate according to [4], wherein the resin material and the surface-modified layer are covalently bonded through a chemical reaction.
[6]
The laminate according to [4] or [5], wherein the resin material contains an unsaturated hydrocarbon group-containing thermosetting resin.
[7]
The laminate according to [6], wherein the unsaturated hydrocarbon group-containing thermosetting resin is an unsaturated polyester resin.
[8]
[4] A surface-modified member comprising the laminate according to any one of [7].
[9]
A coated article comprising a coating film on at least a part of the surface-modified member according to [8].
[10]
The coated article according to [9], wherein the coating film includes a coating material having a functional group that forms a chemical bond with or intermolecularly interacts with the polar group in the polar group-containing polymer.
[11]
A method for producing a surface-modified member using the surface-modified layer according to [1] or [2],
A method for producing a surface-modified member, comprising a lamination step of laminating the surface-modified layer on a resin member by thermoforming.
[12]
The method for producing a surface-modified member according to [11], wherein the resin member contains an unsaturated polyester resin.
[13]
A method for producing a surface-modified member using the surface-modified sheet according to [3].
[14]
[1] or [2] A method for producing a coated article using the surface modified layer,
a step of laminating the surface-modified layer on a resin member by thermoforming to produce a surface-modified member;
and forming a coating film on the surface modification layer side of the surface modification member.
[15]
The method for producing a coated object according to [14], wherein the resin member contains an unsaturated polyester resin.
[16]
The method for producing a coated article according to [14] or [15], wherein the coating film includes a coating material having a functional group that forms a chemical bond with or intermolecularly interacts with the polar group in the polar group-containing polymer.
[17]
[3] A method for producing a coated object using the surface-modified sheet described in [3].
　以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例になんら限定されるものではない。 The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
〔評価〕
＜密着性１＞
　実施例及び比較例で作製した表面改質部材の離型シートを剥離し、ＪＩＳ　Ｋ５６００－５－６記載のクロスカット法にてクロスカット評価（碁盤目剥離）を実施し、剥がれていない表面改質層の枚数（密着数）をカウントした。剥がれていない表面改質層の枚数が１００枚中５０枚以上の時、樹脂部材と表面改質層との密着性が良好（○）であり、４９枚以下の時、不良（×）であると判断した。
　　・カットの間隔：２ｍｍ
　　・クロスカット個数：１００マス
　　・剥離テープ：（ニチバン）セロハンテープ（登録商標）２４ｍｍ幅 〔evaluation〕
<Adhesion 1>
The release sheets of the surface-modified members produced in Examples and Comparative Examples were peeled off, and cross-cut evaluation (cross-cut peeling) was performed according to the cross-cut method described in JIS K5600-5-6. The number of layers (number of adhesion) was counted. The adhesion between the resin member and the surface modified layer is good (○) when the number of unpeeled surface modified layers is 50 or more out of 100, and poor (x) when the number is 49 or less. I decided.
・Cut interval: 2mm
・ Number of cross cuts: 100 squares ・ Peeling tape: (Nichiban) cellophane tape (registered trademark) 24 mm width
＜密着性２＞
　実施例及び比較例で作製した塗装物を、ＪＩＳ　Ｋ５６００－５－６記載のクロスカット法にてクロスカット評価（碁盤目剥離）を実施し、剥がれていない塗膜の枚数（密着数）をカウントした。剥がれていない塗膜の枚数が１００枚中５０枚以上の時、表面改質層と塗膜との密着性が良好（○）であり、４９枚以下の時、不良（×）であると判断した。
　　・カットの間隔：２ｍｍ
　　・クロスカット個数：１００マス
　　・剥離テープ：（ニチバン）セロハンテープ（登録商標）２４ｍｍ幅 <Adhesion 2>
The coated objects prepared in Examples and Comparative Examples were subjected to cross-cut evaluation (cross-cut peeling) by the cross-cut method described in JIS K5600-5-6, and the number of unpeeled coating films (number of adhesion) was counted. bottom. When the number of unpeeled coating films is 50 or more out of 100, the adhesion between the surface modification layer and the coating film is good (○), and when it is 49 or less, it is judged to be bad (x). bottom.
・Cut interval: 2mm
・ Number of cross cuts: 100 squares ・ Peeling tape: (Nichiban) cellophane tape (registered trademark) 24 mm width
＜塗膜厚み＞
　塗膜厚みはダイヤルゲージ（ピーコック製ＧＣ－９）により測定した。塗装物と塗膜形成前の表面改質樹脂部材の厚みを測定し、その差を塗膜厚み（μｍ）（平均厚み（μｍ））とした。平均厚み（μｍ）は１０点を測定した平均値である。 <Paint thickness>
The coating thickness was measured with a dial gauge (GC-9 manufactured by Peacock). The thicknesses of the coated article and the surface-modified resin member before coating film formation were measured, and the difference was defined as the coating film thickness (μm) (average thickness (μm)). The average thickness (μm) is the average value obtained by measuring 10 points.
＜表面改質層の膜厚＞
　表面改質層の膜厚はダイヤルゲージ（ピーコック製ＧＣ－９）により測定した。表面改質シートの厚みを測定し、その箇所の表面改質層を除去した離型シートの厚み（μｍ）を測定し、その差を表面改質層の厚み（μｍ）（平均厚み（μｍ））とした。平均厚み（μｍ）は１０点を測定した平均値である。 <Thickness of Surface Modified Layer>
The film thickness of the surface modified layer was measured with a dial gauge (GC-9 manufactured by Peacock). The thickness of the surface-modified sheet is measured, the thickness (μm) of the release sheet after removing the surface-modified layer at that location is measured, and the difference is the thickness (μm) of the surface-modified layer (average thickness (μm) ). The average thickness (μm) is the average value obtained by measuring 10 points.
＜重合体の極性基濃度＞
　水酸基含有重合体においては水酸基価（ｍｇＫＯＨ／ｇ）を、カルボキシル基含有重合体においては酸価（ｍｇＫＯＨ／ｇ）を、重合体の極性基濃度（ｍｇＫＯＨ／ｇ）とした。 <Polar Group Concentration of Polymer>
The hydroxyl value (mgKOH/g) for the hydroxyl group-containing polymer, the acid value (mgKOH/g) for the carboxyl group-containing polymer, and the polar group concentration (mgKOH/g) of the polymer were used.
　市販の水酸基含有重合体であるＵＨ２０４１（東亞合成株式会社製、水酸基含有アクリルオリゴマー）、ＥＢＥＣＲＹＬ３７００（ダイセル・オルネクス株式会社製、エポキシアクリレート）、ＥＢＥＣＲＹＬ３７０１（ダイセル・オルネクス株式会社製、エポキシアクリレート）、及びＩＲＲ７４２（ダイセル・オルネクス株式会社製、ウレタンアクリレート）については、カタログに掲載の水酸基価（ｍｇＫＯＨ／ｇ）を用いた。 Commercially available hydroxyl group-containing polymers UH2041 (manufactured by Toagosei Co., Ltd., hydroxyl group-containing acrylic oligomer), EBECRYL3700 (manufactured by Daicel-Ornex Co., Ltd., epoxy acrylate), EBECRYL3701 (manufactured by Daicel-Ornex Co., Ltd., epoxy acrylate), and IRR742 (Urethane acrylate manufactured by Daicel Allnex Co., Ltd.), the hydroxyl value (mgKOH/g) listed in the catalog was used.
　下記で合成した水酸基含有アクリルポリマー１、水酸基含有アクリルポリマー２、不飽和炭化水素基含有アクリルポリマー１、不飽和炭化水素基含有アクリルポリマー２、不飽和炭化水素基含有アクリルポリマー３については、重合体の合成に使用した原料モノマーの分子量及び配合質量比に基づいて、重合体１ｇあたりに含まれる水酸基の質量（ｍｇ）を算出し、これを重合体の水酸基価とした。
　なお、水酸基含有アクリルポリマー２、不飽和炭化水素基含有アクリルポリマー１、不飽和炭化水素基含有アクリルポリマー２、及び不飽和炭化水素基含有アクリルポリマー３においては、２－メタクリロイルオキシエチルイソシアネート（ＭＯＩ）におけるイソシアネート基が全て、アクリル酸２－ヒドロキシエチルにおける水酸基と反応したものとして算出した。 For the hydroxyl group-containing acrylic polymer 1, hydroxyl group-containing acrylic polymer 2, unsaturated hydrocarbon group-containing acrylic polymer 1, unsaturated hydrocarbon group-containing acrylic polymer 2, and unsaturated hydrocarbon group-containing acrylic polymer 3 synthesized below, the polymer The mass (mg) of hydroxyl groups contained per 1 g of the polymer was calculated based on the molecular weight and blending mass ratio of the raw material monomers used in the synthesis of , and this was taken as the hydroxyl value of the polymer.
In the hydroxyl group-containing acrylic polymer 2, the unsaturated hydrocarbon group-containing acrylic polymer 1, the unsaturated hydrocarbon group-containing acrylic polymer 2, and the unsaturated hydrocarbon group-containing acrylic polymer 3, 2-methacryloyloxyethyl isocyanate (MOI) It was calculated that all the isocyanate groups in were reacted with hydroxyl groups in 2-hydroxyethyl acrylate.
　市販のカルボキシル基含有重合体であるＵＣ３５１０（東亞合成株式会社製、カルボキシル基含有アクリルオリゴマー）については、カタログに掲載の酸価（ｍｇＫＯＨ／ｇ）を用いた。 For UC3510 (a carboxyl group-containing acrylic oligomer manufactured by Toagosei Co., Ltd.), which is a commercially available carboxyl group-containing polymer, the acid value (mgKOH/g) listed in the catalog was used.
＜表面改質層中の極性基濃度＞
　下記式を用いて表面改質層中の極性基濃度Ｘ（ｍｇＫＯＨ／ｇ）を算出した。
　　表面改質層の極性基濃度（Ｘ）＝Σ（ｘｉ・ｗｉ）
　上記式において、ｘｉは、表面改質層中に含まれる重合体ｉが水酸基含有重合体である場合には水酸基価（ｍｇＫＯＨ／ｇ）を、重合体ｉがカルボキシル基含有重合体である場合には酸価（ｍｇＫＯＨ／ｇ）をそれぞれ表す。ｗｉは、重合体ｉの表面改質層における質量分率を表す。 <Polar Group Concentration in Surface Modified Layer>
The polar group concentration X (mgKOH/g) in the surface modified layer was calculated using the following formula.
Polar group concentration (X) of the surface modified layer = Σ (xi wi)
In the above formula, xi is the hydroxyl value (mgKOH/g) when the polymer i contained in the surface-modified layer is a hydroxyl-containing polymer, and when the polymer i is a carboxyl-containing polymer, each represents an acid value (mgKOH/g). wi represents the mass fraction of the polymer i in the surface-modified layer.
＜不飽和炭化水素基含有重合体の二重結合当量＞
　下記で合成した不飽和炭化水素基含有アクリルポリマー１、不飽和炭化水素基含有アクリルポリマー２、不飽和炭化水素基含有アクリルポリマー３、水酸基含有アクリルポリマー２の二重結合当量は、重合体の合成に使用した原料モノマーの分子量及び配合質量比に基づいて、不飽和炭化水素基１つあたりの重合体の質量を算出し、重合体の二重結合当量とした。なお、二重結合当量の算出に当たっては、原料モノマーである２－メタクリロイルオキシエチルイソシアネート（ＭＯＩ）におけるイソシアネート基が全て、アクリル酸２－ヒドロキシエチルにおける水酸基と反応したものとした。
　市販の不飽和炭化水素基含有重合体であるＥＢＥＣＲＹＬ３７００（ダイセル・オルネクス株式会社製、エポキシアクリレート）、ＥＢＥＣＲＹＬ３７０１（ダイセル・オルネクス株式会社製、エポキシアクリレート）、及びＩＲＲ７４２（ダイセル・オルネクス株式会社製、ウレタンアクリレート）については、重量平均分子量（カタログ値）を１分子当たりの不飽和炭化水素基の数（カタログ値）で除することで算出した。 <Double bond equivalent of unsaturated hydrocarbon group-containing polymer>
The double bond equivalents of unsaturated hydrocarbon group-containing acrylic polymer 1, unsaturated hydrocarbon group-containing acrylic polymer 2, unsaturated hydrocarbon group-containing acrylic polymer 3, and hydroxyl group-containing acrylic polymer 2 synthesized below are Based on the molecular weight and blending mass ratio of the raw material monomers used in (1), the mass of the polymer per unsaturated hydrocarbon group was calculated and used as the double bond equivalent of the polymer. In calculating the double bond equivalent, all the isocyanate groups in 2-methacryloyloxyethyl isocyanate (MOI), which is a raw material monomer, reacted with hydroxyl groups in 2-hydroxyethyl acrylate.
EBECRYL3700 (manufactured by Daicel-Ornex Co., Ltd., epoxy acrylate), EBECRYL3701 (manufactured by Daicel-Ornex Co., Ltd., epoxy acrylate), and IRR742 (manufactured by Daicel-Ornex Co., Ltd., urethane acrylate), which are commercially available unsaturated hydrocarbon group-containing polymers ) was calculated by dividing the weight average molecular weight (catalog value) by the number of unsaturated hydrocarbon groups per molecule (catalog value).
＜表面改質層の二重結合当量＞
　下記式を用いて表面改質層の二重結合当量Ｙを算出した。
　　表面改質層の二重結合当量（Ｙ）＝Σ（ｙｉ・ｗｉ）
　上記式において、ｙｉは、表面改質層中に含まれる重合体ｉの二重結合当量、ｗｉは、重合体ｉの表面改質層における質量分率を表す。 <Double bond equivalent of surface modified layer>
The double bond equivalent Y of the surface modified layer was calculated using the following formula.
Double bond equivalent (Y) of the surface modified layer = Σ (yi wi)
In the above formula, yi represents the double bond equivalent of polymer i contained in the surface-modified layer, and wi represents the mass fraction of polymer i in the surface-modified layer.
〔実施例１〕
＜水酸基含有アクリルポリマー１の合成＞
　セパラブルカバーと、分液ロートと、温度計と、窒素導入管と、リービッヒ冷却器と、バキュームシールと、撹拌装置とを備える反応容器内で、アクリル酸２－エチルヘキシル（２ＥＨＡ）１００モル部と、アクリル酸２－ヒドロキシエチル（ＨＥＡ）２０モル部と、これらモノマー成分１００質量部に対して０．５質量部の重合開始剤としての２，２’－アゾビスイソブチロニトリルと、モノマー成分１００質量部に対して１５０質量部の重合溶媒としての酢酸エチルとを含む混合物を、窒素雰囲気下で、６２℃で３時間撹拌し、その後７５℃で２時間撹拌した（重合反応）。これにより、固形分濃度４２．６質量％の水酸基含有アクリルポリマー１溶液（２ＥＨＡ：ＨＥＡ＝１００：２０［ｍｏｌ］）を得た。なお、重合途中に、重合中の温度制御のため、モノマー側鎖の極性基等による水素結合に起因する急激な粘度上昇を防止するために、酢酸エチルを適宜滴下した。 [Example 1]
<Synthesis of hydroxyl group-containing acrylic polymer 1>
100 mole parts of 2-ethylhexyl acrylate (2EHA) and , 20 mol parts of 2-hydroxyethyl acrylate (HEA), 2,2'-azobisisobutyronitrile as a polymerization initiator of 0.5 parts by mass per 100 parts by mass of these monomer components, and monomer components A mixture containing 150 parts by mass of ethyl acetate as a polymerization solvent with respect to 100 parts by mass was stirred under a nitrogen atmosphere at 62° C. for 3 hours and then at 75° C. for 2 hours (polymerization reaction). As a result, a hydroxyl group-containing acrylic polymer 1 solution (2EHA:HEA=100:20 [mol]) having a solid concentration of 42.6% by mass was obtained. During the polymerization, ethyl acetate was appropriately added dropwise to control the temperature during the polymerization and to prevent a rapid increase in viscosity due to hydrogen bonding due to the polar groups in the side chains of the monomers.
（表面改質組成物（１）の調製）
　極性基含有重合体（Ａ）としての上記水酸基含有アクリルポリマー１溶液１００質量部（固形分率）と、不飽和炭化水素基含有重合体（Ｂ）としてのＥＢＥＣＲＹＬ３７００（ダイセル・オルネクス株式会社製、エポキシアクリレート（Ｃ＝Ｃ基含有オリゴマー））２０質量部を混合し、酢酸エチルを添加して固形分濃度２５質量％に調整し、極性基含有重合体（Ａ）と不飽和炭化水素基含有重合体（Ｂ）を配合した表面改質組成物（１）を得た。 (Preparation of surface-modified composition (1))
100 parts by mass (solid content) of the hydroxyl group-containing acrylic polymer 1 solution as the polar group-containing polymer (A), and EBECRYL3700 as the unsaturated hydrocarbon group-containing polymer (B) (manufactured by Daicel Allnex Co., Ltd., epoxy 20 parts by mass of acrylate (C=C group-containing oligomer) was mixed, ethyl acetate was added to adjust the solid content concentration to 25% by mass, and the polar group-containing polymer (A) and the unsaturated hydrocarbon group-containing polymer were obtained. A surface-modified composition (1) containing (B) was obtained.
（表面改質シート（１））
　作製した表面改質組成物（１）を目開き１８８μｍのナイロンメッシュでろ過した後、離型シート（ニフトロン９００ＵＬ：日東電工株式会社製　フッ素樹脂シートフィルム（ポリテトラフルオロエチレン（ＰＴＦＥ）（厚み０．０５ｍｍ、寸法：幅２５０ｍｍ×長さ４５０ｍｍ））にアプリケーターにて塗工し、恒温乾燥器にて１００℃×２分間乾燥させ、表面改質層を備えた離型シートである表面改質シート（１）を作製した。 (Surface modified sheet (1))
After filtering the prepared surface-modified composition (1) through a nylon mesh with an opening of 188 μm, a release sheet (Niftron 900UL: manufactured by Nitto Denko Co., Ltd. fluororesin sheet film (polytetrafluoroethylene (PTFE) (thickness: 0.05 mm)). 05 mm, dimensions: width 250 mm × length 450 mm))), dried at 100 ° C. for 2 minutes in a constant temperature dryer, and a surface-modified sheet that is a release sheet having a surface-modified layer ( 1) was produced.
（表面改質部材（１））
　上記で作製した表面改質シート（１）の表面改質層側の面を不飽和ポリエステル樹脂含有樹脂シート（京セラ株式会社製、京セラプリミックスＡＰ２１２ＳＫ２）（寸法：幅１５０ｍｍ×長さ１２０ｍｍ×厚み１ｍｍ）の上に重ね、プレス機による圧縮成形（成形圧３ＭＰａ、上型１４５℃、下型１３５℃、４分間）にて積層体を作製し、これを表面改質部材（１）とした。 (Surface modification member (1))
A resin sheet containing an unsaturated polyester resin (Kyocera Primix AP212SK2, manufactured by Kyocera Corporation) (dimensions: width 150 mm x length 120 mm x thickness 1 mm) was applied to the surface of the surface-modified sheet (1) prepared above on the surface-modified layer side. ), and compression molding was performed using a press (3 MPa, upper mold 145° C., lower mold 135° C., 4 minutes) to prepare a laminate, which was used as a surface-modified member (1).
（塗装物（１））
　上記で作製した表面改質部材（１）の離型シートを剥離後、表面改質層に大日本塗料株式会社製ＶトップＨ（２液硬化型ウレタン塗料）をアプリケーターで塗布し、常温（２５℃）で３日塗膜を硬化させ、塗装物（１）を作製した。 (Painted object (1))
After peeling off the release sheet of the surface-modified member (1) prepared above, apply V top H (two-liquid curing urethane paint) manufactured by Dainippon Toryo Co., Ltd. to the surface-modified layer with an applicator, ° C.) for 3 days to prepare a coated article (1).
〔実施例２～３〕
　不飽和炭化水素基含有重合体（Ｂ）として、表１に記載したエポキシアクリレート（Ｃ＝Ｃ基含有オリゴマー）を使用した以外は実施例１と同様にして、表面改質組成物（２）～（３）を調製し、表面改質シート（２）～（３）、表面改質部材（２）～（３）、及び塗装物（２）～（３）を作製した。 [Examples 2 and 3]
As the unsaturated hydrocarbon group-containing polymer (B), the surface-modified composition (2)- (3) was prepared, and surface-modified sheets (2)-(3), surface-modified members (2)-(3), and coated objects (2)-(3) were produced.
〔実施例４〕
＜不飽和炭化水素基含有アクリルポリマー１の合成＞
　セパラブルカバーと、分液ロートと、温度計と、窒素導入管と、リービッヒ冷却器と、バキュームシールと、撹拌装置とを備える反応容器内で、アクリル酸２－エチルヘキシル（２ＥＨＡ）１００モル部と、アクリル酸２－ヒドロキシエチル（ＨＥＡ）２０モル部と、これらモノマー成分１００質量部に対して０．５質量部の重合開始剤としての２，２’－アゾビスイソブチロニトリルと、モノマー成分１００質量部に対して１５０質量部の重合溶媒としての酢酸エチルとを含む混合物を、窒素雰囲気下で、６２℃で３時間撹拌し、その後７５℃で２時間撹拌した（重合反応）。これにより、固形分濃度４２．６質量％の水酸基含有アクリルポリマー溶液を得た。なお、重合途中に、重合中の温度制御のため、モノマー側鎖の極性基等による水素結合に起因する急激な粘度上昇を防止するために、酢酸エチルを適宜滴下した。
　次に、上記水酸基含有アクリルポリマーを含有するポリマー溶液と、２－メタクリロイルオキシエチルイソシアネート（ＭＯＩ）（商品名「カレンズＭＯＩ」，昭和電工社製）と、付加反応触媒としてのジラウリン酸ジブチルスズ（和光純薬工業製）とを含む反応溶液を、５０℃で１０時間、空気雰囲気下で撹拌した（付加反応）。当該反応溶液において、ＭＯＩの配合量は、上記のアクリル酸２－エチルヘキシル（２ＥＨＡ）１００モル部に対して１６モル部である。また、当該反応溶液において、ジブチル錫ジラウリレートの配合量は、ＭＯＩ１００質量部に対して０．５質量部である。この付加反応により固形分濃度４５．８質量％の不飽和炭化水素基含有アクリルポリマー１溶液（２ＥＨＡ：ＨＥＡ：ＭＯＩ＝１００：２０：１６［ｍｏｌ］）を得た。 [Example 4]
<Synthesis of unsaturated hydrocarbon group-containing acrylic polymer 1>
100 mole parts of 2-ethylhexyl acrylate (2EHA) and , 20 mol parts of 2-hydroxyethyl acrylate (HEA), 2,2'-azobisisobutyronitrile as a polymerization initiator of 0.5 parts by mass per 100 parts by mass of these monomer components, and monomer components A mixture containing 150 parts by mass of ethyl acetate as a polymerization solvent with respect to 100 parts by mass was stirred under a nitrogen atmosphere at 62° C. for 3 hours and then at 75° C. for 2 hours (polymerization reaction). As a result, a hydroxyl group-containing acrylic polymer solution having a solid concentration of 42.6% by mass was obtained. During the polymerization, ethyl acetate was appropriately added dropwise to control the temperature during the polymerization and to prevent a rapid increase in viscosity due to hydrogen bonding due to the polar groups in the side chains of the monomers.
Next, a polymer solution containing the hydroxyl group-containing acrylic polymer, 2-methacryloyloxyethyl isocyanate (MOI) (trade name “Karenzu MOI”, manufactured by Showa Denko KK), and dibutyltin dilaurate (Wako Jun) as an addition reaction catalyst Yakukogyo Co., Ltd.) was stirred at 50° C. for 10 hours under an air atmosphere (addition reaction). In the reaction solution, the amount of MOI compounded is 16 mol parts per 100 mol parts of 2-ethylhexyl acrylate (2EHA). Further, in the reaction solution, the amount of dibutyltin dilaurate compounded is 0.5 parts by mass with respect to 100 parts by mass of MOI. This addition reaction gave a solution of unsaturated hydrocarbon group-containing acrylic polymer 1 (2EHA:HEA:MOI=100:20:16 [mol]) with a solid content concentration of 45.8% by mass.
（表面改質組成物（４）の調製）
　極性基含有重合体（Ａ）としてのＵＨ２０４１（東亞合成（株）製、水酸基含有アクリルオリゴマー）４０質量部と、不飽和炭化水素基含有重合体（Ｂ）としての上記不飽和炭化水素基含有アクリルポリマー１溶液１００質量部（固形分率）を混合し、酢酸エチルを添加して固形分濃度２５質量％に調整し、極性基含有重合体（Ａ）と不飽和炭化水素基含有重合体（Ｂ）を配合した表面改質組成物（４）を得た。 (Preparation of surface-modified composition (4))
UH2041 (manufactured by Toagosei Co., Ltd., hydroxyl group-containing acrylic oligomer) as the polar group-containing polymer (A) 40 parts by mass, and the unsaturated hydrocarbon group-containing acrylic as the unsaturated hydrocarbon group-containing polymer (B) 100 parts by mass of the polymer 1 solution (solid content rate) was mixed, ethyl acetate was added to adjust the solid content concentration to 25 mass%, and the polar group-containing polymer (A) and the unsaturated hydrocarbon group-containing polymer (B ) to obtain a surface-modified composition (4).
　表面改質組成物（４）を使用した以外は実施例１と同様にして、表面改質シート（４）、表面改質部材（４）、及び塗装物（４）を作製した。 A surface-modified sheet (4), a surface-modified member (4), and a coated article (4) were produced in the same manner as in Example 1, except that the surface-modified composition (4) was used.
〔実施例５〕
＜不飽和炭化水素基含有アクリルポリマー２の合成＞
　アクリル酸２－エチルヘキシル（２ＥＨＡ）１００モル部に代えて、アクリル酸ブチル（ＢＡ）５０モル部及びアクリル酸エチル（ＥＡ）５０モル部を使用した以外は不飽和炭化水素基含有アクリルポリマー１の合成と同様にして、不飽和炭化水素基含有アクリルポリマー２溶液（ＢＡ：ＥＡ：ＨＥＡ：ＭＯＩ＝５０：５０：２０：１６［ｍｏｌ］）を得た。 [Example 5]
<Synthesis of unsaturated hydrocarbon group-containing acrylic polymer 2>
Synthesis of unsaturated hydrocarbon group-containing acrylic polymer 1 except that 50 mol parts of butyl acrylate (BA) and 50 mol parts of ethyl acrylate (EA) were used instead of 100 mol parts of 2-ethylhexyl acrylate (2EHA) In the same manner as above, an unsaturated hydrocarbon group-containing acrylic polymer 2 solution (BA: EA: HEA: MOI = 50: 50: 20: 16 [mol]) was obtained.
（表面改質組成物（５）の調製）
　極性基含有重合体（Ａ）としてのＵＨ２０４１（東亞合成（株）製、水酸基含有アクリルオリゴマー）４０質量部と、不飽和炭化水素基含有重合体（Ｂ）としての上記不飽和炭化水素基含有アクリルポリマー２溶液１００質量部（固形分率）を混合し、酢酸エチルを添加して固形分濃度２５質量％に調整し、極性基含有重合体（Ａ）と不飽和炭化水素基含有重合体（Ｂ）を配合した表面改質組成物（５）を得た。 (Preparation of surface-modified composition (5))
UH2041 (manufactured by Toagosei Co., Ltd., hydroxyl group-containing acrylic oligomer) as the polar group-containing polymer (A) 40 parts by mass, and the unsaturated hydrocarbon group-containing acrylic as the unsaturated hydrocarbon group-containing polymer (B) 100 parts by mass of the polymer 2 solution (solid content rate) was mixed, ethyl acetate was added to adjust the solid content concentration to 25 mass%, and the polar group-containing polymer (A) and the unsaturated hydrocarbon group-containing polymer (B ) to obtain a surface-modified composition (5).
　表面改質組成物（５）を使用した以外は実施例１と同様にして、表面改質シート（５）、表面改質部材（５）、及び塗装物（５）を作製した。 A surface-modified sheet (5), a surface-modified member (5), and a coated article (5) were produced in the same manner as in Example 1, except that the surface-modified composition (5) was used.
〔実施例６〕
　極性基含有重合体（Ａ）として、ＵＣ３５１０（東亞合成（株）製、カルボキシル基含有アクリルオリゴマー）を使用した以外は実施例５と同様にして、表面改質組成物（６）を調製し、表面改質シート（６）、表面改質部材（６）、及び塗装物（６）を作製した。 [Example 6]
A surface-modified composition (6) was prepared in the same manner as in Example 5 except that UC3510 (manufactured by Toagosei Co., Ltd., a carboxyl group-containing acrylic oligomer) was used as the polar group-containing polymer (A), A surface-modified sheet (6), a surface-modified member (6), and a coated article (6) were produced.
〔実施例７〕
＜水酸基含有アクリルポリマー２の合成＞
　セパラブルカバーと、分液ロートと、温度計と、窒素導入管と、リービッヒ冷却器と、バキュームシールと、撹拌装置とを備える反応容器内で、アクリル酸エチル（ＥＡ）５０モル部、アクリル酸ブチル（ＢＡ）５０モル部、アクリル酸２－ヒドロキシエチル（ＨＥＡ）２０モル部と、これらモノマー成分１００質量部に対して０．５質量部の重合開始剤としての２，２’－アゾビスイソブチロニトリルと、モノマー成分１００質量部に対して１５０質量部の重合溶媒としての酢酸エチルとを含む混合物を、窒素雰囲気下で、６２℃で３時間撹拌し、その後７５℃で２時間撹拌した（重合反応）。これにより、固形分濃度４２．６質量％の水酸基含有アクリルポリマー溶液を得た。なお、重合途中に、重合中の温度制御のため、モノマー側鎖の極性基等による水素結合に起因する急激な粘度上昇を防止するために、酢酸エチルを適宜滴下した。
　次に、上記水酸基含有アクリルポリマーを含有するポリマー溶液と、２－メタクリロイルオキシエチルイソシアネート（ＭＯＩ）（商品名「カレンズＭＯＩ」，昭和電工社製）と、付加反応触媒としてのジラウリン酸ジブチルスズ（和光純薬工業製）とを含む反応溶液を、５０℃で１０時間、空気雰囲気下で撹拌した（付加反応）。当該反応溶液において、ＭＯＩの配合量は、上記のアクリル酸エチル（ＥＡ）とアクリル酸ブチル（ＢＡ）の合計量１００モル部に対して１モル部である。また、当該反応溶液において、ジブチル錫ジラウリレートの配合量は、ＭＯＩ１００質量部に対して０．５質量部である。この付加反応により固形分濃度４５．８質量％の水酸基含有アクリルポリマー２溶液（ＥＡ：ＢＡ：ＨＥＡ：ＭＯＩ＝５０：５０：２０：１［ｍｏｌ］）を得た。 [Example 7]
<Synthesis of hydroxyl group-containing acrylic polymer 2>
In a reaction vessel equipped with a separable cover, a separating funnel, a thermometer, a nitrogen inlet tube, a Liebig condenser, a vacuum seal, and a stirrer, 50 mol parts of ethyl acrylate (EA), acrylic acid 50 mol parts of butyl (BA), 20 mol parts of 2-hydroxyethyl acrylate (HEA), and 0.5 parts by mass of 2,2'-azobisiso as a polymerization initiator per 100 parts by mass of these monomer components. A mixture containing butyronitrile and 150 parts by mass of ethyl acetate as a polymerization solvent per 100 parts by mass of the monomer component was stirred under a nitrogen atmosphere at 62°C for 3 hours and then at 75°C for 2 hours. (polymerization reaction). As a result, a hydroxyl group-containing acrylic polymer solution having a solid concentration of 42.6% by mass was obtained. During the polymerization, ethyl acetate was appropriately added dropwise to control the temperature during the polymerization and to prevent a rapid increase in viscosity due to hydrogen bonding due to the polar groups in the side chains of the monomers.
Next, a polymer solution containing the hydroxyl group-containing acrylic polymer, 2-methacryloyloxyethyl isocyanate (MOI) (trade name “Karenzu MOI”, manufactured by Showa Denko KK), and dibutyltin dilaurate (Wako Jun) as an addition reaction catalyst Yakukogyo Co., Ltd.) was stirred at 50° C. for 10 hours under an air atmosphere (addition reaction). In the reaction solution, the amount of MOI compounded is 1 mol part per 100 mol parts of the total amount of ethyl acrylate (EA) and butyl acrylate (BA). Further, in the reaction solution, the amount of dibutyltin dilaurate compounded is 0.5 parts by mass with respect to 100 parts by mass of MOI. This addition reaction yielded a solution of hydroxyl group-containing acrylic polymer 2 (EA:BA:HEA:MOI=50:50:20:1 [mol]) with a solid concentration of 45.8% by mass.
（表面改質組成物（７）の調製）
　極性基含有重合体（Ａ）としての上記水酸基含有アクリルポリマー２溶液１００質量部（固形分率）と、不飽和炭化水素基含有重合体（Ｂ）としてのＥＢＥＣＲＹＬ３７００（ダイセル・オルネクス株式会社製、エポキシアクリレート（Ｃ＝Ｃ基含有オリゴマー））２０質量部を混合し、酢酸エチルを添加して固形分濃度２５質量％に調整し、極性基含有重合体（Ａ）と不飽和炭化水素基含有重合体（Ｂ）を配合した表面改質組成物（７）を得た。 (Preparation of surface-modified composition (7))
100 parts by mass (solid content) of the hydroxyl group-containing acrylic polymer 2 solution as the polar group-containing polymer (A), and EBECRYL3700 as the unsaturated hydrocarbon group-containing polymer (B) (manufactured by Daicel Allnex Co., Ltd., epoxy 20 parts by mass of acrylate (C=C group-containing oligomer) was mixed, ethyl acetate was added to adjust the solid content concentration to 25% by mass, and the polar group-containing polymer (A) and the unsaturated hydrocarbon group-containing polymer were obtained. A surface-modified composition (7) containing (B) was obtained.
〔実施例８〕
＜不飽和炭化水素基含有アクリルポリマー３の合成＞
　セパラブルカバーと、分液ロートと、温度計と、窒素導入管と、リービッヒ冷却器と、バキュームシールと、撹拌装置とを備える反応容器内で、アクリル酸エチル（ＥＡ）５０モル部、アクリル酸ブチル（ＢＡ）５０モル部、アクリル酸２－ヒドロキシエチル（ＨＥＡ）４モル部と、これらモノマー成分１００質量部に対して０．５質量部の重合開始剤としての２，２’－アゾビスイソブチロニトリルと、モノマー成分１００質量部に対して１５０質量部の重合溶媒としての酢酸エチルとを含む混合物を、窒素雰囲気下で、６２℃で３時間撹拌し、その後７５℃で２時間撹拌した（重合反応）。これにより、固形分濃度４２．６質量％の水酸基含有アクリルポリマー溶液を得た。なお、重合途中に、重合中の温度制御のため、モノマー側鎖の極性基等による水素結合に起因する急激な粘度上昇を防止するために、酢酸エチルを適宜滴下した。
　次に、上記水酸基含有アクリルポリマーを含有するポリマー溶液と、２－メタクリロイルオキシエチルイソシアネート（ＭＯＩ）（商品名「カレンズＭＯＩ」，昭和電工社製）と、付加反応触媒としてのジラウリン酸ジブチルスズ（和光純薬工業製）とを含む反応溶液を、５０℃で１０時間、空気雰囲気下で撹拌した（付加反応）。当該反応溶液において、ＭＯＩの配合量は、上記のアクリル酸エチル（ＥＡ）とアクリル酸ブチル（ＢＡ）の合計量１００モル部に対して４モル部である。また、当該反応溶液において、ジブチル錫ジラウリレートの配合量は、ＭＯＩ１００質量部に対して０．５質量部である。この付加反応により固形分濃度４５．８質量％の不飽和炭化水素基含有アクリルポリマー３溶液（ＥＡ：ＢＡ：ＨＥＡ：ＭＯＩ＝５０：５０：４：４［ｍｏｌ］）を得た。 [Example 8]
<Synthesis of unsaturated hydrocarbon group-containing acrylic polymer 3>
In a reaction vessel equipped with a separable cover, a separating funnel, a thermometer, a nitrogen inlet tube, a Liebig condenser, a vacuum seal, and a stirrer, 50 mol parts of ethyl acrylate (EA), acrylic acid 50 mol parts of butyl (BA), 4 mol parts of 2-hydroxyethyl acrylate (HEA), and 0.5 parts by mass of 2,2'-azobisiso as a polymerization initiator per 100 parts by mass of these monomer components. A mixture containing butyronitrile and 150 parts by mass of ethyl acetate as a polymerization solvent per 100 parts by mass of the monomer component was stirred under a nitrogen atmosphere at 62°C for 3 hours and then at 75°C for 2 hours. (polymerization reaction). As a result, a hydroxyl group-containing acrylic polymer solution having a solid concentration of 42.6% by mass was obtained. During the polymerization, ethyl acetate was appropriately added dropwise to control the temperature during the polymerization and to prevent a rapid increase in viscosity due to hydrogen bonding due to the polar groups in the side chains of the monomers.
Next, a polymer solution containing the hydroxyl group-containing acrylic polymer, 2-methacryloyloxyethyl isocyanate (MOI) (trade name “Karenzu MOI”, manufactured by Showa Denko KK), and dibutyltin dilaurate (Wako Jun) as an addition reaction catalyst Yakukogyo Co., Ltd.) was stirred at 50° C. for 10 hours under an air atmosphere (addition reaction). In the reaction solution, the amount of MOI compounded is 4 mol parts per 100 mol parts of the total amount of ethyl acrylate (EA) and butyl acrylate (BA). Further, in the reaction solution, the amount of dibutyltin dilaurate compounded is 0.5 parts by mass with respect to 100 parts by mass of MOI. This addition reaction gave a solution of unsaturated hydrocarbon group-containing acrylic polymer 3 (EA:BA:HEA:MOI=50:50:4:4 [mol]) with a solid content concentration of 45.8% by mass.
（表面改質組成物（８）の調製）
　極性基含有重合体（Ａ）としてのＵＨ２０４１（東亞合成（株）製、水酸基含有アクリルオリゴマー）４０質量部と、不飽和炭化水素基含有重合体（Ｂ）としての上記不飽和炭化水素基含有アクリルポリマー３溶液１００質量部（固形分率）を混合し、酢酸エチルを添加して固形分濃度２５質量％に調整し、極性基含有重合体（Ａ）と不飽和炭化水素基含有重合体（Ｂ）を配合した表面改質組成物（８）を得た。 (Preparation of surface-modified composition (8))
UH2041 (manufactured by Toagosei Co., Ltd., hydroxyl group-containing acrylic oligomer) as the polar group-containing polymer (A) 40 parts by mass, and the unsaturated hydrocarbon group-containing acrylic as the unsaturated hydrocarbon group-containing polymer (B) 100 parts by mass of the polymer 3 solution (solid content rate) was mixed, ethyl acetate was added to adjust the solid content concentration to 25 mass%, and the polar group-containing polymer (A) and the unsaturated hydrocarbon group-containing polymer (B ) to obtain a surface-modified composition (8).
〔比較例１〕
　不飽和炭化水素基含有重合体（Ｂ）としてのＥＢＥＣＲＹＬ３７００を添加しなかったこと以外は実施例１と同様にして、表面改質組成物（ｒ１）を調製し、表面改質シート（ｒ１）、表面改質部材（ｒ１）、及び塗装物（ｒ１）を作製した。 [Comparative Example 1]
A surface-modified composition (r1) was prepared in the same manner as in Example 1, except that EBECRYL3700 as the unsaturated hydrocarbon group-containing polymer (B) was not added, and the surface-modified sheet (r1), A surface-modified member (r1) and a coated article (r1) were produced.
〔比較例２〕
　極性基含有重合体（Ａ）としてのＵＨ２０４１を添加しなかったこと以外は実施例４と同様にして、表面改質組成物（ｒ２）を調製し、表面改質シート（ｒ２）、表面改質部材（ｒ２）、及び塗装物（ｒ２）を作製した。 [Comparative Example 2]
A surface-modified composition (r2) was prepared in the same manner as in Example 4, except that UH2041 as the polar group-containing polymer (A) was not added. A member (r2) and a coated article (r2) were produced.
〔比較例３〕
　極性基含有重合体（Ａ）としてのＵＨ２０４１を添加しなかったこと以外は実施例５と同様にして、表面改質組成物（ｒ３）を調製し、表面改質シート（ｒ３）、表面改質部材（ｒ３）、及び塗装物（ｒ３）を作製した。 [Comparative Example 3]
A surface-modified composition (r3) was prepared in the same manner as in Example 5, except that UH2041 as the polar group-containing polymer (A) was not added. A member (r3) and a coated article (r3) were produced.
　実施例及び比較例について、以下の表１及び２に示す。 Examples and comparative examples are shown in Tables 1 and 2 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１及び２中に記載の材料は下記のとおりである。
　ＵＨ２０４１：東亞合成株式会社製（水酸基含有アクリルオリゴマー）
　ＵＣ３５１０：東亞合成株式会社製（カルボキシル基含有アクリルオリゴマー）
　ＥＢＥＣＲＹＬ３７００：ダイセル・オルネクス株式会社製（エポキシアクリレート（Ｃ＝Ｃ基含有オリゴマー））
　ＥＢＥＣＲＹＬ３７０１：ダイセル・オルネクス株式会社製（エポキシアクリレート（Ｃ＝Ｃ基含有オリゴマー））
　ＩＲＲ７４２：ダイセル・オルネクス株式会社製（ウレタンアクリレート）
　ＰＴＦＥ：ポリテトラフルオロエチレン
　ＶトップＨ：大日本塗料株式会社製ＶトップＨ（２液硬化型ウレタン塗料） The materials listed in Tables 1 and 2 are as follows.
UH2041: manufactured by Toagosei Co., Ltd. (hydroxyl group-containing acrylic oligomer)
UC3510: manufactured by Toagosei Co., Ltd. (carboxyl group-containing acrylic oligomer)
EBECRYL3700: manufactured by Daicel Allnex Co., Ltd. (epoxy acrylate (C=C group-containing oligomer))
EBECRYL3701: manufactured by Daicel Allnex Co., Ltd. (epoxy acrylate (C=C group-containing oligomer))
IRR742: Daicel Allnex Co., Ltd. (urethane acrylate)
PTFE: Polytetrafluoroethylene V top H: Dainippon Toryo Co., Ltd. V top H (two-liquid curing urethane paint)
　本発明の表面改質シートを用いた塗装物は、樹脂部材と表面改質層との密着性、表面改質層と塗膜との密着性のいずれもが良好であり、塗膜の接着強度が非常に高い塗装物が得られた。一方、比較例１～３の塗装物は、表面改質層に極性基含有重合体（Ａ）、及び不飽和炭化水素基含有重合体（Ｂ）のうちのいずれかしか含んでいないため、表面改質層と塗膜との間、又は表面改質層と樹脂部材との間の結合が十分に形成されず、密着性が不良となった。 A coated article using the surface-modified sheet of the present invention has good adhesion between the resin member and the surface-modified layer and good adhesion between the surface-modified layer and the coating film, and the adhesion strength of the coating film is good. A very high coating was obtained. On the other hand, in the coated objects of Comparative Examples 1 to 3, since the surface-modified layer contains only one of the polar group-containing polymer (A) and the unsaturated hydrocarbon group-containing polymer (B), the surface Bonding between the modified layer and the coating film or between the surface modified layer and the resin member was not sufficiently formed, resulting in poor adhesion.
　本発明は前述した各実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、異なる実施形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。 The present invention is not limited to the above-described embodiments, but can be modified in various ways within the scope of the claims, and can be obtained by appropriately combining technical means disclosed in different embodiments. is also included in the technical scope of the present invention.
　本発明の実施形態に係る表面改質層は、接着強度に優れ、本発明の実施形態に係る表面改質シートは、むらの発生を防ぎ該表面改質層を形成することができ、表面改質部材の形成の際に表面改質層と樹脂部材との一体成形が可能である。 The surface-modified layer according to the embodiment of the present invention has excellent adhesive strength, and the surface-modified sheet according to the embodiment of the present invention can prevent the occurrence of unevenness and form the surface-modified layer. It is possible to integrally mold the surface modified layer and the resin member when forming the material member.
　本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
　本出願は、２０２１年９月２９日出願の日本特許出願（特願２０２１－１６００５４）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2021-160054) filed on September 29, 2021, the content of which is incorporated herein by reference.
１０　　　表面改質層
２０　　　離型シート
３０　　　塗膜
１００　　樹脂部材
２００　　表面改質シート
３００　　塗装物
４００　　樹脂材料 10 Surface Modified Layer 20 Release Sheet 30 Coating Film 100 Resin Member 200 Surface Modified Sheet 300 Painted Object 400 Resin Material

Claims (17)

  1. 　極性基含有重合体と不飽和炭化水素基含有重合体をそれぞれ１種以上含む表面改質層。 A surface-modified layer containing one or more of each of a polar group-containing polymer and an unsaturated hydrocarbon group-containing polymer.
  2. 　前記表面改質層の極性基濃度が１０ｍｇＫＯＨ／ｇ以上であり、前記表面改質層の二重結合当量が１２０００以下である、請求項１に記載の表面改質層。 The surface-modified layer according to claim 1, wherein the surface-modified layer has a polar group concentration of 10 mgKOH/g or more and a double bond equivalent of 12000 or less.
  3. 　請求項１又は２に記載の表面改質層と離型シートとを備えた表面改質シート。 A surface-modified sheet comprising the surface-modified layer according to claim 1 or 2 and a release sheet.
  4. 　請求項１又は２に記載の表面改質層と樹脂材料との積層体であり、
    　前記表面改質層が、前記樹脂材料の表面の少なくとも一部に積層された積層体。     A laminate of the surface-modified layer according to claim 1 or 2 and a resin material,
    A laminate in which the surface-modified layer is laminated on at least part of the surface of the resin material.
  5. 　前記樹脂材料と前記表面改質層とが化学反応により共有結合した請求項４に記載の積層体。 The laminate according to claim 4, wherein the resin material and the surface-modified layer are covalently bonded through a chemical reaction.
  6. 　前記樹脂材料が不飽和炭化水素基含有熱硬化性樹脂を含む請求項５に記載の積層体。 The laminate according to claim 5, wherein the resin material contains an unsaturated hydrocarbon group-containing thermosetting resin.
  7. 　前記不飽和炭化水素基含有熱硬化性樹脂が不飽和ポリエステル樹脂である請求項６に記載の積層体。 The laminate according to claim 6, wherein the unsaturated hydrocarbon group-containing thermosetting resin is an unsaturated polyester resin.
  8. 　請求項４に記載の積層体を含む表面改質部材。 A surface-modified member including the laminate according to claim 4.
  9. 　請求項８に記載の表面改質部材の少なくとも一部に塗膜を備えた塗装物。 A coated article comprising a coating film on at least a part of the surface modifying member according to claim 8.
  10. 　前記塗膜が前記極性基含有重合体における極性基と化学結合を形成、又は分子間相互作用する官能基を有する塗料を含む、請求項９に記載の塗装物。 The coated article according to claim 9, wherein the coating film includes a coating material having a functional group that forms a chemical bond with the polar group in the polar group-containing polymer or that interacts intermolecularly.
  11. 　請求項１又は２に記載の表面改質層を用いた表面改質部材の製造方法であって、
    　前記表面改質層を加熱成形により樹脂部材に積層する積層工程を含む、表面改質部材の製造方法。     A method for producing a surface-modified member using the surface-modified layer according to claim 1 or 2,
    A method for producing a surface-modified member, comprising a lamination step of laminating the surface-modified layer on a resin member by thermoforming.
  12. 　前記樹脂部材が不飽和ポリエステル樹脂を含む請求項１１に記載の表面改質部材の製造方法。 The method for manufacturing a surface-modified member according to claim 11, wherein the resin member contains an unsaturated polyester resin.
  13. 　請求項３に記載の表面改質シートを用いた表面改質部材の製造方法。 A method for manufacturing a surface-modified member using the surface-modified sheet according to claim 3.
  14. 　請求項１に記載の表面改質層を用いた塗装物の製造方法であって、
    　前記表面改質層を加熱成形により樹脂部材に積層して表面改質部材を製造する工程と、
    　前記表面改質部材の前記表面改質層側に塗膜を形成する工程とを含む、塗装物の製造方法。     A method for producing a coated object using the surface modified layer according to claim 1,
    a step of laminating the surface-modified layer on a resin member by thermoforming to produce a surface-modified member;
    and forming a coating film on the surface modification layer side of the surface modification member.
  15. 　前記樹脂部材が不飽和ポリエステル樹脂を含む請求項１４に記載の塗装物の製造方法。 The method for manufacturing a coated object according to claim 14, wherein the resin member contains an unsaturated polyester resin.
  16. 　前記塗膜が前記極性基含有重合体における極性基と化学結合を形成、又は分子間相互作用する官能基を有する塗料を含む、請求項１４又は１５に記載の塗装物の製造方法。 The method for producing a painted object according to claim 14 or 15, wherein the coating film includes a coating material having a functional group that forms a chemical bond with the polar group in the polar group-containing polymer or has an intermolecular interaction.
  17. 　請求項３に記載の表面改質シートを用いた塗装物の製造方法。 A method for manufacturing a coated object using the surface-modified sheet according to claim 3.
PCT/JP2022/036206 2021-09-29 2022-09-28 Surface modification layer, surface modification sheet, multilayer body, surface-modified member, coated article, method for producing surface-modified member, and method for producing coated article WO2023054486A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010077293A (en) * 2008-09-26 2010-04-08 Toyo Ink Mfg Co Ltd Photosensitive resin composition and resin sheet
JP2011143719A (en) * 2009-12-17 2011-07-28 Dic Corp Active energy ray curable transfer sheet and method for producing the same
JP2012183519A (en) * 2011-03-08 2012-09-27 Kansai Paint Co Ltd Multi-layered coated film formation method, and coated article
JP2019194016A (en) * 2018-04-26 2019-11-07 日東電工株式会社 Surface modification sheet, surface modification member, coated article and method for producing coated article

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010077293A (en) * 2008-09-26 2010-04-08 Toyo Ink Mfg Co Ltd Photosensitive resin composition and resin sheet
JP2011143719A (en) * 2009-12-17 2011-07-28 Dic Corp Active energy ray curable transfer sheet and method for producing the same
JP2012183519A (en) * 2011-03-08 2012-09-27 Kansai Paint Co Ltd Multi-layered coated film formation method, and coated article
JP2019194016A (en) * 2018-04-26 2019-11-07 日東電工株式会社 Surface modification sheet, surface modification member, coated article and method for producing coated article

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