WO2021157555A1 - Method for manufacturing laminate structure, laminate structure, and inkjet composition set - Google Patents

Method for manufacturing laminate structure, laminate structure, and inkjet composition set Download PDF

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Publication number
WO2021157555A1
WO2021157555A1 PCT/JP2021/003672 JP2021003672W WO2021157555A1 WO 2021157555 A1 WO2021157555 A1 WO 2021157555A1 JP 2021003672 W JP2021003672 W JP 2021003672W WO 2021157555 A1 WO2021157555 A1 WO 2021157555A1
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WO
WIPO (PCT)
Prior art keywords
layer
composition
photocurable
light
thermosetting
Prior art date
Application number
PCT/JP2021/003672
Other languages
French (fr)
Japanese (ja)
Inventor
満 谷川
貴志 渡邉
佳史 杉沢
孝徳 井上
悠介 藤田
大地 濱田
Original Assignee
積水化学工業株式会社
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Publication date
Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to KR1020227020463A priority Critical patent/KR20220138370A/en
Priority to JP2021575795A priority patent/JPWO2021157555A1/ja
Priority to CN202180012951.9A priority patent/CN115052737A/en
Publication of WO2021157555A1 publication Critical patent/WO2021157555A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/02—Containers; Seals
    • H01L23/06—Containers; Seals characterised by the material of the container or its electrical properties
    • H01L23/08—Containers; Seals characterised by the material of the container or its electrical properties the material being an electrical insulator, e.g. glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/02—Containers; Seals
    • H01L23/10—Containers; Seals characterised by the material or arrangement of seals between parts, e.g. between cap and base of the container or between leads and walls of the container

Definitions

  • the present invention relates to a method for manufacturing a laminated structure using an inkjet device.
  • the present invention also relates to a laminated structure.
  • the present invention also relates to an inkjet composition set that is applied and used by using an inkjet device.
  • a method of applying a composition using an inkjet device is known.
  • a method is used in which an inkjet composition is applied onto the surface of a base material using an inkjet device, and the composition is cured by light, heat, or the like.
  • Patent Document 1 describes a curable composition for inkjet printing containing (A) a multi-branched oligomer or polymer having an ethylenically unsaturated group, (B) a photopolymerization initiator, and (C) a thermosetting compound. The thing is disclosed.
  • a cured product layer in which the ink jet composition is cured may be arranged.
  • the cured product layer is often used as an adhesive layer for adhering two parts or the like.
  • a region surrounded by a cured product layer can be formed to form a metal layer inside the region, or a partition wall can be formed with the cured product layer to prevent the underfill material from getting wet and spreading. This leads to miniaturization and cost reduction of electronic parts.
  • the material for example, the material for forming the metal layer and the underfill material
  • An object of the present invention is to provide a method for producing a laminated structure, a laminated structure, and a composition set for inkjet, which can enhance the leakage prevention property of a material. It is also an object of the present invention to provide an apparatus used for manufacturing the above-mentioned laminated structure.
  • a first light obtained by irradiating a first composition coated on the surface of a first base material by an inkjet method with light and photocuring the first composition is applied to the first photocuring step of forming the cured product layer and the second composition coated by the inkjet method on the surface side of the first photocured product layer opposite to the first base material side.
  • the second composition comprises a second photocuring step of forming a photocured second photocured layer by irradiating the first composition with a monofunctional (meth) acrylate.
  • the second composition contains a compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent, and the second composition comprises a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
  • a method for producing a laminated structure which comprises an agent and is a composition in which the first composition and the second composition are different.
  • the method for producing a laminated structure is on the surface side of the first photocured material layer opposite to the first base material side.
  • a second coating step of applying the composition of 2 by an inkjet method is provided, and in the second photocuring step, the second composition coated in the second coating step is irradiated with light.
  • a plurality of the second coating step and the second photocuring step are performed in the thickness direction of the first photocured product layer, respectively. It is done once.
  • the method for producing a laminated structure heats the first photocured material layer and the second photocured material layer to obtain the first photocured product layer.
  • the first and first photo-cured product layers are formed by the first photo-cured product layer in which the photo-cured product layer is heat-cured, and the second light and thermo-cured product layer in which the second photo-cured product layer is heat-cured. It is provided with the heating step for the photocurable material layer of 2.
  • the method for producing a laminated structure is such that the first photocurable layer and the second photocurable layer are heated to obtain the first photocurable layer.
  • the first and first photo-cured product layers are formed by the first photo- and heat-cured product layer in which the first photo-cured product layer is heat-cured, and the second photo- and heat-cured product layer in which the second photo-cured product layer is heat-cured.
  • the first and second heating steps for the photocurable material layer are provided with or without the heating step for the second photocurable material layer, the first of the second light and heat-curable material layer is provided.
  • a third composition coated by an inkjet method on the surface side opposite to the base material side of the above is irradiated with light to form a third photocurable material layer in which the third composition is photocured.
  • the photo-curing step of 3 is provided and the heating step for the first and second photo-cured product layers is not provided, the surface of the second photo-cured product layer opposite to that of the first substrate side.
  • a third photocuring step is provided in which a third composition coated on the side by an inkjet method is irradiated with light to form a third photocurable layer in which the third composition is photocured.
  • the third composition contains a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a heat-curing agent, and the second composition and the third composition are different from each other. It is a composition.
  • the first composition and the third composition are the same composition.
  • the method for producing a laminated structure is such that the first and second photocurable layer heating steps are provided. After the heating step for the second photocurable material layer, a flattening treatment step for flattening the surface of the second light and the heat-cured material layer opposite to the first base material side is provided. And when the heating step for the second photocurable material layer is not provided, after the second photocurable material layer, the surface of the second photocurable material layer opposite to the first base material side is flattened. A flattening treatment step for flattening treatment is provided, and the flattening treatment is a polishing treatment.
  • the method for producing a laminated structure is such that the method for producing a laminated structure is formed on a surface of the third photocured material layer opposite to the first base material side.
  • the arrangement step of arranging the second base material is provided.
  • the method for producing a laminated structure may be described in the case where the first and second heating steps for a photocurable material layer are provided.
  • the third photocurable material layer is heated to form a third light and a thermosetting material layer in which the third photocurable material layer is thermoset, and a third photocurable material layer heating step is provided.
  • the heating step for the second photocurable material layer is not provided, the first photocurable material layer, the second photocurable material layer and the third photocurable material layer are heated to obtain the first photocurable material layer.
  • the present invention includes a third light in which the material layer is thermoset and a heating step for the first, second and third photocurable material layers forming the thermosetting material layer.
  • a second light obtained by irradiating a second composition coated on the surface of a first base material by an inkjet method with light and photocuring the second composition.
  • the second photo-curing material layer is provided with a second photo-curing step of forming the cured product layer, and the second photo-cured product layer is heated to heat the second photo-cured product layer to heat-curing the second photo-cured product layer.
  • the heating step for the second photocurable material layer to be formed is provided or not provided, and the heating step for the second photocurable material layer is provided, the first of the second light and the heat-cured material layer is provided.
  • the first composition coated by an inkjet method on the surface side opposite to the base material side of the above is irradiated with light to form a first photocurable material layer in which the first composition is photocured.
  • inkjet is applied to the surface side of the second photo-curing material layer opposite to the first base material side.
  • the first composition comprises a first photocuring step of irradiating the first composition applied by the method with light to form a first photocurable layer in which the first composition is photocured.
  • the composition comprises a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a heat-curing agent
  • the second composition is a polyfunctional (meth) acrylate compound and an epoxy.
  • a method for producing a laminated structure which comprises a compound, a photopolymerization initiator, and a heat-curing agent, and the first composition and the second composition are different compositions.
  • the method for producing a laminated structure heats the second photocurable material layer, and the second photocurable material layer is thermoset.
  • the second photo-curing material layer for forming the second light and thermosetting material layer is provided, and in the first photo-curing step, the first light and thermosetting material layer is formed.
  • the first composition coated on the surface side opposite to the base material side by an inkjet method is irradiated with light to form a first photocurable product layer in which the first composition is photocured.
  • the second photocurable layer heating step when the second photocurable layer heating step is provided, the second photocurable layer heating step is followed by the second photocurable layer heating step.
  • a flattening treatment step for flattening the surface of the photo- and heat-cured product layer opposite to the first base material side is provided and the heating step for the second photo-cured product layer is not provided.
  • a flattening treatment step of flattening the surface of the second photocured material layer opposite to the first base material side is provided, and the flattening treatment is a polishing treatment. Is.
  • the method for producing a laminated structure is such that the first photocured product is provided with the heating step for the second photocured product layer.
  • the second photo-cured product is provided with a heating step for a first photo-cured product layer in which the layer is heated to form a first light and a thermosetting product layer in which the first photo-cured product layer is thermoset.
  • the layer heating step is not provided, the first photo-cured product layer and the second photo-cured product layer are heated so that the first photo-cured product layer is thermoset.
  • the present invention includes a heating step for a first and second photocurable material layer, which forms a thermosetting material layer and a second light and thermosetting material layer in which the second photocurable material layer is heat-cured.
  • the method for producing a laminated structure is such that the method for producing a laminated structure is formed on a surface of the first photocured material layer opposite to the first base material side.
  • the arrangement step of arranging the second base material is provided.
  • the surface roughness of the second base material is smaller than the surface roughness of the first base material.
  • the first base material, the first layer arranged on the surface of the first base material, and the first base material side of the first layer are A second layer arranged on the opposite surface is provided, and the combination of the first layer and the second layer is such that the first layer is a monofunctional (meth) acrylate compound.
  • the layer is a photocurable material layer or a light and thermosetting material layer of a second composition containing an acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent, or the first.
  • the layer is a photocurable material layer or a light and thermosetting material layer of a second composition containing a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent
  • the second layer is a photocurable layer or a light and thermosetting layer of the first composition containing a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
  • a laminated structure in which the first composition and the second composition are different compositions.
  • the first layer comprises a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
  • the composition is a photocurable layer or a light and thermosetting layer
  • the second layer contains a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
  • the photocured material layer or the light and thermosetting material layer of the second composition is a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
  • the second layer has a polished surface.
  • the laminated structure comprises a second substrate disposed on a surface of the second layer opposite to the first layer side. ..
  • the first layer is the light and thermosetting layer of the first composition
  • the second layer is the second composition. Light and thermosetting layer.
  • the thickness of the second layer is thicker than the thickness of the first layer.
  • the thickness of the first layer is 0.1 ⁇ m or more and 10 ⁇ m or less
  • the thickness of the second layer is 1 ⁇ m or more and 1000 ⁇ m or less.
  • the laminated structure comprises a third layer disposed on a surface of the second layer opposite to the first layer side.
  • the third layer is a photocurable layer or a light and thermosetting layer of a third composition containing a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
  • the second composition and the third composition are different compositions.
  • the first composition and the third composition are the same composition.
  • the laminated structure comprises a second substrate disposed on a surface of the third layer opposite to the second layer side. ..
  • the surface roughness of the first base material is smaller than the surface roughness of the second base material.
  • the third layer is a light and thermosetting layer of the third composition.
  • the thickness of the second layer is thicker than the thickness of the third layer.
  • the thickness of the third layer is 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the first layer contains a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
  • the composition is a photocurable layer or a light and thermosetting layer
  • the second layer contains a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
  • the photocured material layer or the light and thermosetting material layer of the first composition is a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
  • composition set for inkjet having a first composition and a second composition, wherein the first composition is a monofunctional (meth) acrylate compound and an epoxy.
  • the second composition comprises a compound, a photopolymerization initiator and a thermocuring agent, and the second composition comprises a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermocuring agent.
  • An epoxy composition set in which the first composition and the second composition are different compositions is provided.
  • the inkjet composition set has a first container and a second container, and the first container is filled with the first composition. Is contained, and the second composition is contained in the second container.
  • the method for producing a laminated structure, the laminated structure, and the composition set for inkjet according to the present invention have the above-mentioned configurations, it is possible to improve the material leakage prevention property.
  • FIG. 1A to 1C are cross-sectional views for explaining each step of the method for manufacturing a laminated structure according to the first embodiment of the present invention.
  • 2 (d) to 2 (f) are cross-sectional views for explaining each step of the method for manufacturing a laminated structure according to the first embodiment of the present invention.
  • 3 (g) and 3 (h) are cross-sectional views for explaining each step of the method for manufacturing a laminated structure according to the first embodiment of the present invention.
  • FIG. 4 is a flowchart for explaining each step of the method for manufacturing a laminated structure according to the first embodiment of the present invention.
  • FIG. 5 is a flowchart for explaining each step of the method for manufacturing a laminated structure according to a second embodiment of the present invention.
  • FIG. 6 is a flowchart for explaining each step of the method for manufacturing a laminated structure according to a second embodiment of the present invention.
  • FIG. 7 is a cross-sectional view of the laminated structure manufactured by the method for manufacturing the laminated structure according to the second embodiment.
  • FIG. 8 is a flowchart for explaining each step of the method for manufacturing a laminated structure according to a third embodiment of the present invention.
  • FIG. 9 is a flowchart for explaining each step of the method for manufacturing a laminated structure according to a third embodiment of the present invention.
  • FIG. 10 is a cross-sectional view of the laminated structure manufactured by the method for manufacturing the laminated structure according to the third embodiment.
  • FIG. 11 is a schematic configuration diagram showing an example of a part of the apparatus used in the method for manufacturing the laminated structure shown in FIGS. 1 to 3.
  • FIG. 12 is a schematic configuration diagram showing another example of the apparatus used in the method for manufacturing the laminated structure shown in FIGS. 1 to 3.
  • FIG. 13 is a cross-sectional view schematically showing an inkjet composition set according to the first embodiment of the present invention.
  • FIG. 14 is a cross-sectional view showing an electronic component obtained by using the laminated structure according to the first embodiment of the present invention.
  • the first composition coated on the surface of the first base material by an inkjet method is irradiated with light, and the first composition is irradiated with light.
  • the present invention includes a first photocuring step (a first photocuring step for a composition) for forming a cured first photocurable material layer.
  • the method (1) for producing a laminated structure according to the present invention is applied to a second composition coated on the surface side of the first photocured material layer opposite to the first base material side by an inkjet method.
  • the present invention comprises a second photocuring step (a photocuring step for a second composition) of irradiating light to form a second photocurable material layer in which the second composition is photocured.
  • the second composition coated on the surface of the first base material by an inkjet method is irradiated with light, and the second composition is irradiated with light.
  • the present invention includes a second photocuring step (a second photocuring step for a composition) for forming a cured second photocurable material layer.
  • the second photo-cured product layer is heated to heat the second photo-cured product layer and the second photo-cured product layer is heat-cured.
  • a heating step for the second photocurable layer to be formed is provided or not provided.
  • the method (2) for producing a laminated structure according to the present invention when the heating step for the second photocurable material layer is provided, the second light and the first base material side of the thermosetting material layer are provided.
  • a first photocuring layer is formed by irradiating a first composition coated on the opposite surface side by an inkjet method with light to form a photocured first photocured product layer in which the first composition is photocured.
  • a step (a first photocuring step for a composition) is provided.
  • the method (2) for producing a laminated structure according to the present invention when the heating step for the second photocurable material layer is not provided, the method (2) is different from that of the first base material side of the second photocurable material layer.
  • the first composition comprises a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
  • the second composition comprises a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
  • the first composition and the second composition are different compositions.
  • the method (1) for manufacturing the laminated structure includes a first coating step (coating step for the first composition) of applying the first composition on the surface of the first base material by an inkjet method. Is preferable.
  • a first coating step coating step for the first composition
  • the first base material side of the first photocurable layer is formed between the first photocuring step and the second photocuring step.
  • a second coating step coating step for the second composition
  • the second photocurable material layer is preferably in contact with the first photocurable material layer.
  • the method (2) for manufacturing the laminated structure includes a second coating step (coating step for the second composition) in which the second composition is coated on the surface of the first base material by an inkjet method. Is preferable.
  • the first base material side of the second photocurable layer is formed between the second photocuring step and the first photocuring step. It is preferable to provide a first coating step (coating step for the first composition) for coating the first composition on the opposite surface side by an inkjet method.
  • the first photocurable material layer is preferably in contact with the second photocurable material layer.
  • first coating step and the first photocuring step are collectively referred to as a first photocuring material layer forming step (first photocuring material layer forming step for composition). .. Further, in the present specification, the second coating step and the second photocuring step are collectively referred to as a second photocuring material layer forming step (second composition photocuring material layer forming step). It is called.
  • the first composition is coated on the surface of the first base material by an inkjet method, and the coated first composition is irradiated with light. Therefore, it is preferable to include a first photocurable material layer forming step in which the first composition forms a photocurable first photocurable material layer.
  • the second composition is coated and applied by an inkjet method on the surface side of the first photocurable material layer opposite to the first base material side. It is preferable to include a second photocurable product layer forming step of irradiating the second composition with light to form a second photocurable material layer in which the second composition is photocured.
  • the second composition is coated on the surface of the first base material by an inkjet method, and the coated second composition is irradiated with light. Therefore, it is preferable to include a second photocurable product layer forming step in which the second composition forms a photocurable second photocurable material layer.
  • the first composition is coated and applied by an inkjet method on the surface side of the second photocurable material layer opposite to the first base material side. It is preferable that the first composition is irradiated with light to form a first photocurable layer in which the first composition is photocured.
  • the laminated structure according to the present invention comprises a first base material, a first layer arranged on the surface of the first base material, and a side opposite to the base material side of the first layer. It comprises a second layer arranged on the surface.
  • the combination of the first layer and the second layer is the following first combination A or the following combination B.
  • Combination A The first layer is a photocurable layer or a light and thermosetting layer of the first composition containing a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent.
  • the second layer is a photocurable layer or a light and thermosetting layer of a second composition containing a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent.
  • the first layer is a photocurable layer or a light and thermosetting layer of a second composition containing a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent.
  • the second layer is a photocurable layer or a light and thermosetting product of the first composition containing a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent. It is a layer.
  • the first composition and the second composition are different compositions.
  • the laminated structure according to the present invention has the above configuration, it is possible to improve the material leakage prevention property.
  • the inkjet composition set according to the present invention is an inkjet composition set having a first composition and a second composition.
  • the first composition contains a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent, and the second composition.
  • the composition comprises a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
  • the first composition and the second composition are different compositions.
  • the inkjet composition set according to the present invention has the above-mentioned structure, it is possible to improve the material leakage prevention property.
  • the present inventors have found that the shape retention of the cured product layer may be low in the conventional inkjet composition, and the material leaks to the periphery of the cured product layer.
  • the composition for inkjet is a photocurable composition
  • the present inventors are likely to inhibit the photopolymerization reaction due to the influence of oxygen in the air on the surface of the composition applied by the inkjet device. I found the problem.
  • powder such as dust adheres to the surface of the inkjet composition light may not be sufficiently irradiated at the portion where the powder adheres, and the photopolymerization reaction may not proceed sufficiently.
  • the present inventors have found that in such a case, the composition for inkjet is not sufficiently cured, and the shape retention of the cured product layer tends to be deteriorated.
  • the surface of the base material is treated with a chemical solution or the surface of the base material is physically damaged to form irregularities on the surface of the base material.
  • Methods and methods for performing primer treatment are known. However, in these methods, the surface properties of the base material change even in the portion where the inkjet composition is not applied, so that problems such as a decrease in conductivity when parts are connected may occur. be.
  • the adhesive strength between the primer and the cured product layer may decrease.
  • the method for producing a laminated structure, the laminated structure, and the composition set for inkjet according to the present invention it is not necessary to perform surface treatment of the base material and to use an apparatus capable of nitrogen substitution.
  • the shape retention of the cured product layer obtained by curing the first composition and the second composition can be enhanced, and the adhesive strength with the substrate and the interlayer adhesive strength can be enhanced.
  • the first composition since a specific first composition and a specific second composition are used, the first composition. And the shape retention of the cured product layer in which the second composition is cured can be enhanced. Further, in the method for producing a laminated structure, the laminated structure, and the composition set for inkjet according to the present invention, since the specific first composition and the specific second composition are used, the base material and the base material are used. The adhesive strength of the first composition to the cured product layer can be enhanced, and the interlayer adhesive strength between the cured product layer of the first composition and the cured product layer of the second composition can be enhanced. ..
  • a material for example, a material for forming a metal layer and a material for forming a metal layer
  • a material may be formed from between a base material and a cured product layer.
  • Underfill material, etc. does not easily leak out.
  • the material is arranged inside the region surrounded by the cured product layer, the material is unlikely to leak from the inside to the outside of the region.
  • the material is arranged outside the region surrounded by the cured product layer, the material is unlikely to leak from the outside to the inside of the region.
  • the shapes of the photocurable material layer of the first composition and the second composition, and the light and thermosetting material layer are maintained. It can enhance the sex.
  • the strength of the cured product layer can be improved, so that damage to the cured product layer can be effectively suppressed.
  • FIGS. 1 (a) to (c), FIGS. 2 (d) to (f), and FIGS. 3 (g) and 3 (h) are steps of the method for manufacturing a laminated structure according to the first embodiment of the present invention. It is sectional drawing for demonstrating.
  • FIG. 4 is a flowchart for explaining each step of the method for manufacturing a laminated structure according to the first embodiment of the present invention.
  • the method for manufacturing the laminated structure according to the first embodiment in FIGS. 1 to 4 is the method for manufacturing the laminated structure (1).
  • the stage 11, the first discharge unit 12, the first light irradiation unit 13, the second discharge unit 14, and the second light irradiation unit are shown.
  • a device 10 including 15 is used.
  • the first ejection unit 12 is a member for ejecting the first composition and is an inkjet head.
  • the second ejection unit 14 is a member for ejecting the second composition and is an inkjet head. Therefore, the device 10 is an inkjet device.
  • a first light irradiation unit 13 is arranged between the first discharge unit 12 and the second discharge unit 14.
  • the second light irradiation unit 15 is arranged on the side of the second discharge unit 14 opposite to the first light irradiation unit 13 side.
  • the first light irradiation unit 13 and the second light irradiation unit 15 can irradiate ultraviolet rays.
  • First photocurable layer forming step (S1 and S2 in FIG. 4)> First, as shown in FIG. 1A, the first base material 3 is arranged on the surface of the stage 11. The first base material 3 is fixed on the surface of the stage 11. The first base material 3 is adsorbed on the stage 11. Next, the first composition 1 is applied onto the surface of the first base material 3 by an inkjet method (first coating step). The first composition 1 is applied from the first discharge portion 12. The first composition 1 is applied to a predetermined position of the first base material 3. The first composition 1 is partially coated on the surface of the first base material 3.
  • the stage 11 is moved until the applied first composition 1 is located below the first light irradiation unit 13.
  • the inkjet device may be moved instead of the stage 11.
  • the first composition 1 is irradiated with light (ultraviolet rays) from the first light irradiation unit 13 to form a first photocurable product layer 1A in which the first composition is photocured (first photocuring). Process).
  • the first photocuring step After the first photocuring step, it is determined whether or not to repeat the first photocuring layer forming step (S3 in FIG. 4). When the first photocurable layer forming step is repeated, the first composition is applied to the surface side of the formed first photocurable layer opposite to the first base material side. ..
  • the stage 11 is moved until the applied second composition 2 is located below the second light irradiation unit 15.
  • the inkjet device may be moved instead of the stage 11.
  • the second composition 2 is irradiated with light (ultraviolet rays) from the second light irradiation unit 15 to form a second photocurable product layer 2A in which the second composition is photocured (second photocuring). Process).
  • the second photocuring step After the second photocuring step, it is determined whether or not to repeat the second photocuring layer forming step (S6 in FIG. 4). When the second photocurable layer forming step is repeated, the second composition is applied to the surface side of the formed second photocurable layer opposite to the first base material side. ..
  • FIGS. 2 (e) and 2 (f) are diagrams showing the second second photocurable layer forming step.
  • the stage 11 is moved until the second photocurable material layer 2A is located below the second discharge portion 14.
  • the inkjet device may be moved instead of the stage 11.
  • the second composition 2 is applied on the surface of the second photocurable material layer 2A opposite to the first base material 3 side by an inkjet method. That is, the second composition 2 is applied to the surface side of the first photocurable material layer 1A opposite to the first base material 3 side (second coating step).
  • the second composition 2 is applied from the second discharge portion 14.
  • the stage 11 is moved until the applied second composition 2 is located below the second light irradiation unit 15.
  • the inkjet device may be moved instead of the stage 11.
  • the second composition 2 is irradiated with light (ultraviolet rays) from the second light irradiation unit 15 to form a second photocurable product layer 2A in which the second composition is photocured (second photocuring). Process).
  • FIGS. 1 (c) and 2 (d), and FIGS. 2 (e) and 2 (f). has been done twice.
  • the second photocurable layer forming step may be performed twice or more, or may be performed three or more times.
  • the first base material 3 and the first base material 3 By performing the second photocurable layer forming step a plurality of times in the thickness direction of the first photocurable layer, as shown in FIG. 3 (g), the first base material 3 and the first base material 3 A laminated structure including a first photo-cured product layer 1A and a second photo-cured product layer 2A, in which the thickness of the second photo-cured product layer 2A is larger than the thickness of the first photo-cured product layer 1A. 4A can be obtained.
  • a laminated structure 4B including the first base material 3, the first light and thermosetting layer 1B, and the second light and thermosetting layer 2B can be obtained.
  • FIG. 5 and 6 are flowcharts for explaining each step of the method for manufacturing a laminated structure according to the second embodiment of the present invention.
  • the method for manufacturing a laminated structure according to the second embodiment is the method for manufacturing a laminated structure (1).
  • FIG. 7 is a cross-sectional view of the laminated structure manufactured by the method for manufacturing the laminated structure according to the second embodiment.
  • the first photocuring step After the first photocuring step, it is determined whether or not to repeat the first photocuring layer forming step (S3 in FIG. 5). When the first photocurable layer forming step is repeated, the first composition is applied to the surface side of the formed first photocurable layer opposite to the first base material side. ..
  • the second photocuring step After the second photocuring step, it is determined whether or not to repeat the second photocuring layer forming step (S6 in FIG. 5). When the second photocurable layer forming step is repeated, the second composition is applied to the surface side of the formed second photocurable layer opposite to the first base material side. ..
  • a laminated structure including a first base material, a first light and thermosetting layer, and a second light and thermosetting layer by performing the heating steps for the first and second photocurable layers. You can get a body.
  • the first and second heating steps for the photocurable material layer are performed and the flattening treatment step is performed, the second light after the first and second heating steps for the photocurable material layer is performed. And the surface of the thermosetting layer opposite to the first base material side is flattened (flattening treatment step).
  • the heating step for the first and second photocurable material layers is not performed and the flattening treatment step is performed, the second photocurable material layer is opposite to the first base material side. The surface is flattened (flattening step).
  • a third photocurable layer forming step is performed using the third composition in the same manner as in the first photocurable layer forming step or the second photocured layer forming step.
  • the third composition is inkjetd on the surface of the second light and thermosetting material layer opposite to the first base material side. Apply by the method (third coating step (third coating step for composition)).
  • the third composition is inkjet-processed on the surface of the second photocurable material layer opposite to the first base material side. (Third coating step (third coating step for composition)).
  • the third composition is applied from a predetermined ejection portion provided in the inkjet device.
  • the first composition and the third composition are the same composition, in the third coating step, substantially, the second light and thermosetting layer or the second
  • the first composition is coated on the surface of the photocured material layer opposite to the first base material side by an inkjet method.
  • the third composition is irradiated with light (ultraviolet rays) from a predetermined light irradiation unit included in the inkjet device to form a third photocurable product layer in which the third composition is photocured (third).
  • light ultraviolet rays
  • the third photocuring step substantially light (ultraviolet rays) is emitted from a predetermined light irradiation portion included in the inkjet device. Will be irradiated to form a third photocurable layer in which the first composition is photocured.
  • the third photocuring step it is determined whether or not to repeat the third photocuring layer forming step (S13 in FIG. 6).
  • the third composition is applied to the surface side of the formed third photocurable layer opposite to the first base material side. ..
  • the third coating step and the third photocuring step are collectively referred to as a third photocuring material layer forming step (third composition photocuring material layer forming step).
  • ⁇ Third heating step for the photocurable material layer or the first, second and third heating steps for the photocurable material layer (S15 in FIG. 6)>
  • the third photocurable material layer is heated to form a third light and thermosetting material layer ().
  • Third heating step for the photocurable layer When the heating steps for the first and second photocurable material layers are not performed, the first photocurable material layer, the second photocurable material layer and the third photocurable product after the arrangement step are performed.
  • the layers are heated to form a first light and thermosetting layer, a second light and thermosetting layer, and a third light and thermosetting layer (first, second and third). Heating process for photocurable layer).
  • the first light and thermosetting layer is a layer obtained by thermosetting the first photocuring layer.
  • the second light and thermosetting layer is a layer obtained by thermosetting the second photocuring layer.
  • the third light and thermosetting layer is a layer obtained by thermosetting the third photocuring layer.
  • the first base material 3 the first light and thermosetting layer 1D, the second light and thermosetting layer 2D, and the third light and heat.
  • a laminated structure 4D including the cured product layer 6D and the second base material 7 in this order can be obtained.
  • FIG. 8 and 9 are flowcharts for explaining each step of the method for manufacturing a laminated structure according to a third embodiment of the present invention.
  • the method for manufacturing a laminated structure according to a third embodiment is the method for manufacturing a laminated structure (2).
  • FIG. 10 is a cross-sectional view of the laminated structure manufactured by the method for manufacturing the laminated structure according to the third embodiment.
  • the second composition is applied onto the surface of the first base material by an inkjet method (second coating step).
  • the second composition is applied in place on the first substrate.
  • the second composition is partially applied onto the surface of the first substrate.
  • the applied second composition is irradiated with light (ultraviolet rays) to form a second photocurable product layer in which the second composition is photocured (second photocuring step).
  • the second photocuring step After the second photocuring step, it is determined whether or not to repeat the second photocuring layer forming step (S3 in FIG. 8). When the second photocurable layer forming step is repeated, the second composition is applied to the surface side of the formed second photocurable layer opposite to the first base material side. ..
  • the second heating step for the photocurable material layer (S5 in FIG. 8)> After the second photocuring step, it is determined whether or not to perform the second heating step for the photocured material layer (S4 in FIG. 8).
  • the heating step for the second photocurable material layer is performed, the second photocurable material layer is heated to form a second light and thermosetting material layer in which the second photocurable material layer is heat-cured. (Second heating step for the photocurable material layer).
  • First photocurable layer forming step (S8 and S9 in FIG. 9)>
  • the heating step for the second photocurable material layer is performed, the first composition is applied to the surface side of the second light and the thermosetting material layer opposite to the first base material side by an inkjet method.
  • First coating step When the heating step for the second photocurable material layer is not performed, the first composition is applied to the surface side of the second photocurable material layer opposite to the first base material side by an inkjet method.
  • the heating step for the second photocurable material layer when the heating step for the second photocurable material layer was performed, the second light and the thermosetting material layer were coated on the surface side opposite to the first base material side by an inkjet method.
  • the first composition is irradiated with light to form a first photo-cured product layer in which the first composition is photo-cured (first photo-curing step).
  • the heating step for the second photocurable material layer is not performed, the first composition is applied by an inkjet method to the surface side of the second photocurable material layer opposite to the first base material side. By irradiating an object with light, the first composition forms a photo-cured first photo-cured product layer (first photo-curing step).
  • the first photocuring step After the first photocuring step, it is determined whether or not to repeat the first photocuring layer forming step (S10 in FIG. 9). When the first photocurable layer forming step is repeated, the first composition is applied to the surface side of the formed first photocurable layer opposite to the first base material side. ..
  • the first photocurable material layer is heated to form the first light and thermosetting material layer (first). Heating process for photocurable layer).
  • the heating step for the second photocurable material layer is not performed, the first photocurable material layer and the second photocurable material layer are heated after the arrangement step to obtain the first light and heat.
  • a cured product layer and a second light and thermosetting material layer are formed (heating steps for the first and second photocured product layers).
  • the first light and thermosetting layer is a layer obtained by thermosetting the first photocuring layer.
  • the second light and thermosetting layer is a layer obtained by thermosetting the second photocuring layer.
  • the first base material 3, the second light and thermosetting material layer 2E, the first light and thermosetting material layer 1E, and the second base material 7 It is possible to obtain a laminated structure 4E including the above in this order.
  • the method (1) for manufacturing the laminated structure may or may not include the first coating step.
  • the method (2) for manufacturing the laminated structure may or may not include the second coating step.
  • the laminated structure (1) preferably includes the first coating step, the first photocuring step, the second coating step, and the second photocuring step in this order. ..
  • the laminated structure (2) preferably includes the second coating step, the second photocuring step, the first coating step, and the first photocuring step in this order. ..
  • the method (1) for manufacturing the laminated structure may or may not include the third coating step.
  • the method (1) for manufacturing the laminated structure may or may not include the third photocuring step.
  • the method (1) for manufacturing the laminated structure may or may not include the third photocurable layer forming step.
  • the entire applied first composition is irradiated with light to obtain the first composition.
  • the photocurable material layer may be formed.
  • each time a plurality of drops of the first composition are applied the applied first composition is irradiated with light and the first photocuring is performed.
  • a material layer may be formed.
  • each time one drop of the first composition is applied the applied first composition is irradiated with light and the first photocuring is performed.
  • a material layer may be formed.
  • the first photocurable layer forming step is performed only once in the thickness direction of the first base material, as shown in FIG. You may be broken.
  • the first photocurable layer forming step may be performed a plurality of times in the thickness direction of the first base material. That is, in the methods (1) and (2) for manufacturing the laminated structure, the first coating step and the first photocuring step are performed only once in the thickness direction of the first base material, respectively. It may be performed, or it may be performed multiple times. By performing the first photocurable material layer forming step a plurality of times in the thickness direction of the first base material, the thickness of the first photocurable material layer can be increased.
  • the first photocurable layer forming step is performed before the second photocured layer forming step.
  • the second photocurable layer forming step is performed before the first photocured layer forming step.
  • the first photocurable material layer forming step and the second photocured material layer forming step are performed before the third photocured material layer forming step. It is said.
  • the entire applied second composition is irradiated with light to obtain a second composition.
  • the photocurable material layer may be formed.
  • every time a plurality of drops of the second composition are applied the applied second composition is irradiated with light and the second photocuring is performed.
  • a material layer may be formed.
  • each time one drop of the second composition is applied the applied second composition is irradiated with light to cure the second composition.
  • a material layer may be formed.
  • the second photocurable layer forming step may be performed only once in the thickness direction of the first photocurable layer.
  • the second photocurable layer forming step is performed a plurality of times in the thickness direction of the first photocurable layer, as shown in FIGS. 1 and 2. You may. That is, in the method (1) for manufacturing the laminated structure, the second coating step and the second photocuring step are performed only once in the thickness direction of the first photocured product layer, respectively. It may be performed a plurality of times.
  • the second photocurable layer forming step may be performed only once in the thickness direction of the first base material.
  • the second photocurable layer forming step may be performed a plurality of times in the thickness direction of the first base material.
  • the second coating step and the second photocuring step may be performed only once in the thickness direction of the first base material, respectively. It may be performed multiple times.
  • the thickness of the second photocurable material layer is formed by performing the second photocurable material layer forming step a plurality of times in the thickness direction of the first photocurable material layer or the thickness direction of the first base material. Can be increased.
  • the second photocurable material layer forming step is preferably performed a plurality of times in the thickness direction of the first photocurable material layer or the thickness direction of the first base material. The number of times the second photocurable layer forming step is repeated is appropriately changed according to the thickness of the target second photocurable layer.
  • the entire applied third composition is irradiated with light to form a third composition.
  • the photocurable material layer may be formed.
  • each time a plurality of drops of the third composition are applied the applied third composition is irradiated with light to be photocured.
  • a material layer may be formed.
  • each time one drop of the third composition is applied the applied third composition is irradiated with light to cure the third composition.
  • a material layer may be formed.
  • the third photo-cured product layer forming step may be performed only once in the thickness direction of the second photo-cured product layer.
  • the third photocurable layer forming step may be performed a plurality of times in the thickness direction of the second photocurable layer. That is, in the methods (1) and (2) for manufacturing the laminated structure, the third coating step and the third photocuring step are 1 in the thickness direction of the second photocured product layer, respectively. It may be performed only once, or it may be performed multiple times. By performing the third photocurable material layer forming step a plurality of times in the thickness direction of the second photocurable material layer, the thickness of the third photocurable material layer can be increased.
  • the light irradiation in the first photocuring step, the second photocuring step and the third photocuring step is preferably ultraviolet irradiation. ..
  • the illuminance and irradiation time of ultraviolet rays in the first photo-curing step, the second photo-curing step, and the third photo-curing step are the first composition, the second composition, and the third composition. It can be appropriately changed depending on the composition and the coating thickness of the composition.
  • the first light-curing process, the illuminance of ultraviolet rays in the second light-curing step and the third light-curing step may also be 1000 mW / cm 2 or more, even 5000 mW / cm 2 or more well, it may also be 10000 mW / cm 2 or less, may be 8000 MW / cm 2 or less.
  • the irradiation time of ultraviolet rays in the first photocuring step, the second photocuring step, and the third photocuring step may be, for example, 0.01 seconds or more, or 0.1 seconds or more. It may be 400 seconds or less, or 100 seconds or less.
  • the method (1) for manufacturing the laminated structure may or may not include the first and second heating steps for the photocurable material layer.
  • the method (1) for manufacturing the laminated structure may or may not include the third heating step for the photocurable material layer.
  • the method (1) for manufacturing the laminated structure may or may not include the first, second, and third heating steps for the photocurable material layer.
  • the method (2) for manufacturing the laminated structure may or may not include the second heating step for the photocurable material layer.
  • the method (2) for manufacturing the laminated structure may or may not include the first heating step for the photocurable material layer.
  • the method (2) for manufacturing the laminated structure may or may not include the first and second heating steps for the photocurable material layer.
  • the method (1) for producing the laminated structure may include the heating steps for the first and second photocured product layers. preferable. From the viewpoint of increasing the strength of the cured product layer of the third composition, it is preferable that the method (1) for producing the laminated structure includes the heating step for the third photocured product layer. From the viewpoint of increasing the strength of the cured product layers of the first, second and third compositions, the method (1) for producing the laminated structure is for the first, second and third photocured product layers. It is preferable to include a heating step. From the viewpoint of increasing the strength of the cured product layer of the second composition, it is preferable that the method (2) for producing the laminated structure includes the heating step for the second photocured product layer.
  • the method (2) for producing the laminated structure includes the heating step for the first photocured product layer. From the viewpoint of increasing the strength of the cured product layer of the first and second compositions, the method (2) for producing the laminated structure may include the heating steps for the first and second photocured product layers. preferable.
  • the first and second heating steps for the photocurable material layer are performed after the second photocurable material layer forming step.
  • the first and second heating steps for the photocurable material layer are preferably performed before the third photocurable material layer forming step, and the first and second photocurable material layer forming steps are preferably performed. It is preferable that the step is performed before the heating step for the photocurable material layer of 3.
  • the first and second heating steps for the photocurable material layer may be performed after the third photocurable material layer forming step.
  • the third heating step for the photocured material layer may be performed before the arrangement step or after the arrangement step.
  • the second heating step for the photocurable material layer is performed after the second photocurable material layer forming step.
  • the second heating step for the photocurable material layer is preferably performed before the first photocurable material layer forming step, and the first It is preferable that the step is performed before the heating step for the photocurable material layer of 1.
  • the first heating step for the photocurable product layer may be performed before the arrangement step or after the arrangement step.
  • the heating temperature and heating time in each of the heating steps can be appropriately changed depending on the composition of the first composition, the second composition and the third composition, and the coating thickness of the composition.
  • the heating temperature in the heating step may be, for example, 100 ° C. or higher, 120 ° C. or higher, 250 ° C. or lower, or 200 ° C. or lower.
  • the heating time in the heating step may be, for example, 5 minutes or more, 30 minutes or more, 600 minutes or less, or 300 minutes or less.
  • the method (1) for manufacturing the laminated structure may or may not include the flattening treatment step.
  • the method (2) for manufacturing the laminated structure may or may not include the flattening treatment step.
  • the methods (1) and (2) for manufacturing the laminated structure include the flattening treatment step. ..
  • the thickness of the cured product layer arranged between the second photocured material layer (or the second light and thermosetting material layer) and the second base material is reduced.
  • the adhesive force between the cured product layer and the second base material can be enhanced.
  • the flattening treatment step may be performed before or after the first and second heating steps for the photocurable product layer.
  • the method (1) for producing the laminated structure after the heating steps for the first and second photocurable material layers, the second light and the thermosetting material layer are opposite to those on the first base material side. It is preferable to flatten the surface.
  • the flattening treatment step may be performed before or after the second heating step for the photocurable product layer.
  • the method (2) for manufacturing the laminated structure after the heating step for the second photocurable material layer, the surface of the second light and the thermosetting material layer opposite to the first base material side is flattened. It is preferable to carry out the chemical treatment.
  • the adhesive strength between the base material and the cured product layer can be increased, and the strength of the cured product layer can be increased, so that the cured product layer can be removed from the first base material during the flattening treatment. It is possible to prevent peeling and destruction of the cured product layer.
  • Examples of the flattening treatment include polishing treatment and the like.
  • Examples of the polishing treatment include cutting polishing treatment by tool processing using diamond, chemical mechanical polishing treatment and the like.
  • the flattening treatment is preferably a polishing treatment. Since the flattening treatment is particularly easy, the polishing treatment is preferably a cutting polishing treatment by a cutting tool using diamond, and a cutting polishing treatment by a cutting tool using diamond and a chemical mechanical polishing treatment. It is more preferable that both treatments are performed.
  • Examples of the device that can be used for the flattening process include a "flattening device” manufactured by Keylink and a “DFS8910” manufactured by DISCO.
  • the absolute value of the difference between the maximum height and the minimum height of the surface of the second light and thermosetting layer (or the second photocured layer) after the flattening treatment is preferably 5 ⁇ m or less. It is more preferably 3 ⁇ m or less, and further preferably 1 ⁇ m or less.
  • the absolute value of the above difference may be 0.5 ⁇ m or more.
  • the methods (1) and (2) for manufacturing the laminated structure may or may not include the above-mentioned arrangement step.
  • the method (1) for manufacturing the laminated structure may include an arrangement step of arranging the second base material on the surface of the third photocurable material layer opposite to the first base material side. preferable.
  • the third heating step for the photocured material layer is performed before the placement step, the third light and the third light and the above-mentioned arrangement step are performed.
  • the second base material is placed on the surface of the thermosetting material layer opposite to the first base material side.
  • the method (2) for manufacturing the laminated structure may include an arrangement step of arranging the second base material on the surface of the first photocurable material layer opposite to the first base material side. preferable.
  • the first heating step for the photocured material layer is performed before the placement step, in the placement step, the first light and the above-mentioned first light and The second base material is placed on the surface of the thermosetting material layer opposite to the first base material side.
  • the method of arranging the second base material is not particularly limited.
  • the first base material and the second base material may be the same base material or different base materials.
  • the base material that comes into contact with the cured product layer of the second composition is preferably a base material having irregularities on the surface or a base material whose surface is primed.
  • the adhesiveness of the second composition to the cured product layer can be further enhanced, and the effects of the present invention can be further exerted.
  • long-term reliability can be improved.
  • the method of forming irregularities on the surface of the base material include a method using a brush and a method of blasting.
  • the surface roughness of the base material in contact with the cured product layer of the first composition is preferably smaller than the surface roughness of the base material in contact with the cured product layer of the second composition.
  • the base material that comes into contact with the cured product layer of the first composition is the second base material, and is in contact with the cured product layer of the second composition.
  • the base material to be used is the above-mentioned first base material. Therefore, in the method (2) for manufacturing the laminated structure, the surface roughness of the second base material is preferably smaller than the surface roughness of the first base material.
  • the surface roughness means the surface roughness in the region in contact with the cured product layer of the first composition, the second composition or the third composition.
  • the surface roughness means the arithmetic mean roughness Ra measured in accordance with JIS B0601: 1994.
  • the surface roughness of the base material in contact with the cured product layer of the second composition is preferably 100 nm or more, more preferably 200 nm or more, preferably 1000 nm or less, and more preferably 500 nm or less.
  • the absolute value of the difference between the surface roughness of the base material in contact with the cured product layer of the first composition and the surface roughness of the base material in contact with the cured product layer of the second composition is preferably 50 nm or more. , More preferably 100 nm or more, preferably 900 nm or less, and more preferably 800 nm or less.
  • the first base material is preferably a ceramic substrate or a silicon substrate, and more preferably a silicon substrate.
  • the second base material is preferably a glass substrate.
  • the first base material is preferably a ceramic substrate or a silicon substrate, and more preferably a ceramic substrate.
  • the second base material is preferably a glass substrate.
  • the present specification also discloses an apparatus used for manufacturing the laminated structure.
  • the apparatus includes a stage, a first discharge unit for discharging the first composition, a second discharge unit for discharging the second composition, and the first discharge unit. It includes a first light irradiation unit arranged between the second discharge unit and the second discharge unit.
  • the device includes a third discharge unit for discharging the third composition.
  • the first ejection unit is an inkjet head and the second ejection unit is an inkjet head.
  • the third ejection unit is preferably an inkjet head.
  • the device is preferably an inkjet device.
  • the third discharge unit can have the same configuration as the first discharge unit or the second discharge unit.
  • the device may include only one first discharge unit for discharging the first composition, or may include two or more of the first discharge portions.
  • the device may include only one second discharge portion for discharging the second composition, or may include two or more of the second discharge portions.
  • the apparatus is located on the opposite side of the first discharge portion from the first light irradiation portion, or the first light irradiation of the second discharge portion. It is preferable to provide a second light irradiation portion arranged on the side opposite to the portion.
  • the second light irradiation unit may be arranged on the side opposite to the first light irradiation unit of the first discharge unit, and the first light irradiation unit of the second discharge unit may be arranged. It may be arranged on the side opposite to the light irradiation part, the side opposite to the first light irradiation part of the first discharge part, and the first light irradiation part of the second discharge part. It may be arranged on both sides opposite to.
  • the device does not have to include the second light irradiation unit.
  • the apparatus does not include the second light irradiation unit, the first photocuring step and the second photocuring step are performed using the first light irradiation unit.
  • the first light irradiation unit and the second light irradiation unit can irradiate ultraviolet rays.
  • the first light irradiation unit is preferably a first ultraviolet irradiation unit
  • the second light irradiation unit is preferably a second ultraviolet irradiation unit.
  • Examples of the first ultraviolet irradiation unit and the second ultraviolet irradiation unit include a light emitting diode (UV-LED) that generates ultraviolet rays.
  • UV-LED light emitting diode
  • the apparatus may include a first ink tank 16 in which the first composition is stored and a first circulation flow path portion 17.
  • a second ink tank 18 in which the second composition is stored and a second circulation flow path portion 19 may be provided.
  • the first circulation flow path portion 17 connects the first ink tank 16 and the first ejection portion 12.
  • the first composition flows inside the first circulation flow path portion 17.
  • the second circulation flow path portion 19 connects the second ink tank 18 and the second ejection portion 14.
  • the second composition flows inside the second circulation flow path portion 19.
  • the first circulation flow path portion 17 has a buffer tank 17A and a pump 17B in the first circulation flow path portion 17. However, as shown in FIG. 12A, the first circulation flow path portion 17X does not have to have the buffer tank and the pump in the first circulation flow path portion 17X.
  • the first circulation flow path portion preferably has the buffer tank in the first circulation flow path portion, and preferably has the pump. Further, the first circulation flow path portion may have a current meter, a thermometer, a filter, a liquid level sensor, and the like in addition to the buffer tank and the pump in the first circulation flow path portion.
  • the second circulation flow path portion 19 has a buffer tank 19A and a pump 19B in the second circulation flow path portion 19. However, as shown in FIG. 12B, the second circulation flow path portion 19X does not have to have the buffer tank and the pump in the second circulation flow path portion 19X.
  • the second circulation flow path portion preferably has the buffer tank in the second circulation flow path portion, and preferably has the pump. Further, the second circulation flow path portion may have a current meter, a thermometer, a filter, a liquid level sensor, and the like in addition to the buffer tank and the pump in the second circulation flow path portion.
  • the buffer tanks 17A, 19A or the pumps 17B, 19B may be arranged between the ejection portions 12, 14 and the ink tanks 16, 18, respectively. preferable.
  • the buffer tanks 17A and 19A are arranged on the discharge portions 12 and 14 side of the pumps 17B and 19B.
  • the pumps 17B and 19B are arranged on the ink tanks 16 and 18 side of the buffer tanks 17A and 19A.
  • the first composition is temporarily stored in the buffer tank 17A.
  • the second composition is temporarily stored in the buffer tank 19A.
  • the circulation method of the first composition and the second composition it is possible to circulate the composition by using its own weight or by applying pressure, depressurization, etc. using a pump or the like. It is possible. A plurality of these may be used in combination.
  • the pump include a cylinder type pulsation-free pump, a propeller pump, a gear pump, a diaphragm pump and the like. From the viewpoint of increasing the circulation efficiency and further improving the formation accuracy of the cured product layer, the first and second circulation flow paths are placed in the first and second circulation flow paths in the first and second circulation flow paths. It is preferable to include a pump for transferring the composition of 2.
  • the first and second circulation flow paths are provided with the first and second circulation channels in the first and second circulation flow paths. It is preferable to include a buffer tank for temporary storage.
  • a heating heater may be introduced into the first and second ink tanks, or the first and second circulation flow paths may be heated. By using a heater or the like, it is possible to adjust the temperature of the first and second compositions.
  • the first circulation flow path portion is preferably a circulation flow path portion for circulating the first composition at 30 ° C. or higher, and is a circulation flow path portion for circulating at 40 ° C. or higher. Is more preferable, and it is preferable that it is a circulation flow path portion for circulating at 100 ° C. or lower, and it is preferable that it is a circulation flow path portion for circulating at 90 ° C. or lower. In this case, the viscosity of the first composition can be optimized, and the discharge property of the first composition can be improved.
  • the second circulation flow path portion is preferably a circulation flow path portion for circulating the second composition at 30 ° C. or higher, and is a circulation flow path portion for circulating at 40 ° C. or higher. Is more preferable, and it is preferable that it is a circulation flow path portion for circulating at 100 ° C. or lower, and it is preferable that it is a circulation flow path portion for circulating at 90 ° C. or lower. In this case, the viscosity of the second composition can be optimized, and the discharge property of the second composition can be improved.
  • the discharge nozzle of the discharge portion keeps an appropriate pressure and the pressure fluctuation (pulsation) is small within that range.
  • an attenuator between the pump and the discharge portion in order to suppress the pulsation of the pump.
  • Examples of such an attenuator include a buffer tank in which the first and second compositions are temporarily stored, a membrane type damper, and the like.
  • the first and second compositions are first.
  • the first and second compositions that have not been ejected from the first and second ejection portions are flowed into the first and second circulation flow path portions and moved to the first and second ink tanks.
  • the first and second compositions can be coated while being circulated.
  • the laminated structure according to the present invention comprises a first base material, a first layer (layer X) arranged on the surface of the first base material, and the first group of the first layer. It includes a second layer (layer Y) arranged on the surface opposite to the material side.
  • the combination of the first layer and the second layer is the following combination A or the following combination B.
  • Combination A The first layer is a photocurable layer or a light and thermosetting layer of the first composition containing a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent.
  • the second layer is a photocurable layer or a light and thermosetting layer of a second composition containing a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent.
  • the first layer is a photocurable layer or a light and thermosetting layer of a second composition containing a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent.
  • the second layer is a photocurable layer or a light and thermosetting product of the first composition containing a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent. It is a layer.
  • the first composition and the second composition are different compositions.
  • the laminated structure according to the present invention may satisfy the combination A or the combination B.
  • a first layer which is a cured product layer of the first composition
  • a second layer which is a cured product layer of the second composition
  • a first layer which is a photo-cured product layer of the first composition
  • a second layer which is a photo-cured product layer of the second composition
  • the first layer is preferably a light and thermosetting layer of the first composition
  • the second layer is the above. It is preferably a light and thermosetting layer of the second composition.
  • the first layer is preferably a light and thermosetting layer of the second composition
  • the second layer is the above-mentioned second layer. It is preferably a light and thermosetting layer of the first composition.
  • the second layer preferably has a polished surface.
  • the laminated structure may include a third layer (layer Z) arranged on the surface of the second layer opposite to the first layer side.
  • the third layer is a photocurable layer of a third composition containing a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
  • the second composition and the third composition are different compositions.
  • the laminated structure according to the present invention preferably includes the third layer.
  • the laminated structure preferably includes a second base material arranged on the surface of the second layer opposite to the first layer side.
  • the laminated structure has a second base material arranged on the surface of the third layer opposite to the second layer side. It is preferable to prepare.
  • the surface roughness of the base material in contact with the cured product layer of the first composition is smaller than the surface roughness of the base material in contact with the cured product layer of the second composition. Is preferable.
  • the surface roughness of the base material in contact with the cured product layer of the third composition is smaller than the surface roughness of the base material in contact with the cured product layer of the second composition. Is preferable. Therefore, in the case of the combination A, it is preferable that the surface roughness of the first base material is smaller than the surface roughness of the second base material in the laminated structure. In the case of the combination B, in the laminated structure, it is preferable that the surface roughness of the second base material is smaller than the surface roughness of the first base material.
  • the surface roughness means the surface roughness in the region in contact with the cured product layer of the first composition, the second composition or the third composition.
  • the surface roughness means the arithmetic mean roughness Ra measured in accordance with JIS B0601: 1994.
  • the surface roughness of the base material in contact with the cured product layer of the second composition is preferably 100 nm or more, more preferably 200 nm or more, preferably 1000 nm or less, and more preferably 500 nm or less. ..
  • Absolute value of the difference between the surface roughness of the base material in contact with the cured product layer of the first composition and the surface roughness of the base material in contact with the cured product layer of the second composition in the laminated structure is preferably 50 nm or more, more preferably 100 nm or more, preferably 900 nm or less, and more preferably 800 nm or less.
  • the thickness of the second layer is preferably thicker than the thickness of the first layer, and is 40 ⁇ m or more than the thickness of the first layer. It is more preferably thick, and further preferably 50 ⁇ m or more thicker than the thickness of the first layer.
  • the thickness of the second layer is preferably thicker than the thickness of the third layer, and is 40 ⁇ m or more than the thickness of the third layer. It is more preferably thick, and even more preferably 50 ⁇ m or more thicker than the thickness of the third layer.
  • the thickness of the first layer is preferably 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 5 m or less. Is.
  • the thickness of the second layer is preferably 40 ⁇ m or more, more preferably 50 ⁇ m or more, preferably 1000 ⁇ m or less, and more preferably 800 m or less.
  • the thickness of the third layer is preferably 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 5 m or less. Is.
  • the ratio (thickness / width) to the width of the thickness is preferably 0.01 or more, more preferably 0.1 or more, preferably 200 or less, and more. It is preferably 150 or less.
  • the ratio (thickness / width) is equal to or greater than the above lower limit and equal to or less than the above upper limit, the effect of the present invention can be exhibited even more effectively.
  • the ratio (thickness / width) to the width of the thickness is preferably 0.01 or more, more preferably 0.1 or more. It is preferably 200 or less, more preferably 150 or less.
  • the ratio (thickness / width) is equal to or greater than the above lower limit and equal to or less than the above upper limit, the effect of the present invention can be exhibited even more effectively.
  • the ratio (thickness / width) to the width of the thickness is preferably 0.01 or more, more preferably 0.1 or more, preferably 200 or less, and more preferably 150 or less.
  • the ratio (thickness / width) is equal to or greater than the above lower limit and equal to or less than the above upper limit, the effect of the present invention can be exhibited even more effectively.
  • the inkjet composition set includes the first composition and the second composition. In the inkjet composition set, the first composition and the second composition are not mixed. The first composition is preferably contained in a first container, and the second composition is preferably contained in a second container.
  • the inkjet composition set is a set of the first composition and the second composition. In the inkjet composition set, it is preferable that the first composition is applied and then the second composition is applied and used. In the inkjet composition set, it is preferable that the first composition is applied and photocured, and then the second composition is applied and photocured before use.
  • the inkjet composition set is preferably used for producing the above-mentioned laminated structure.
  • the inkjet composition set may have a third composition.
  • the first composition, the second composition, and the third composition are not mixed.
  • the third composition is preferably contained in a third container.
  • the inkjet composition set having the third composition is a set of the first composition, the second composition, and the third composition.
  • the first photocurable material layer (or the first light and thermosetting material layer) and the third photocurable material layer (or the third light and thermosetting material layer) are formed by the same composition.
  • the first composition in the set product of the first composition and the second composition is used as the third photocurable layer (or the third light and thermosetting layer). ) Can be used to form.
  • FIG. 13 is a cross-sectional view schematically showing an inkjet composition set according to the first embodiment of the present invention.
  • the inkjet composition set 5 has a first container 101, a first composition 1, a second container 102, and a second composition 2.
  • the first composition 1 is contained in the first container 101.
  • the second composition 2 is contained in the second container 102.
  • the second composition is consumed more than the first composition. Therefore, in the above inkjet composition set, the amount (volume) of the first composition contained in the first container is the first composition of the second composition contained in the second container. It is preferably larger than the amount (volume) of the object.
  • (meth) acrylate means one or both of "acrylate” and “methacrylate”.
  • the first composition and the second composition are different compositions, and the third composition and the second composition are different compositions. That is, the composition of the first composition and the composition of the second composition are different, and the composition of the third composition and the composition of the second composition are different.
  • the first composition and the third composition may be different compositions or the same composition. From the viewpoint of increasing the production efficiency of the laminated structure, it is preferable that the first composition and the third composition are the same composition. That is, it is preferable that the first composition and the third composition have the same composition.
  • the first composition and the third composition include a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
  • the second composition contains a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
  • the first composition and the third composition may or may not contain a polyfunctional (meth) acrylate compound, respectively.
  • the second composition may or may not contain a monofunctional (meth) acrylate compound.
  • the polyfunctional (meth) acrylate compound contained in the first composition and the above It may be the same as or different from the polyfunctional (meth) acrylate compound contained in the second composition.
  • the third composition and the second composition contain a polyfunctional (meth) acrylate compound
  • the polyfunctional (meth) acrylate compound contained in the third composition and the above It may be the same as or different from the polyfunctional (meth) acrylate compound contained in the second composition.
  • both the first composition and the second composition contain a monofunctional (meth) acrylate compound
  • the monofunctional (meth) acrylate compound contained in the first composition and the above It may be the same as or different from the monofunctional (meth) acrylate compound contained in the second composition.
  • the third composition and the second composition contain a monofunctional (meth) acrylate compound
  • the monofunctional (meth) acrylate compound contained in the third composition and the above It may be the same as or different from the monofunctional (meth) acrylate compound contained in the second composition.
  • the first composition comprises a monofunctional (meth) acrylate compound.
  • the second composition comprises a polyfunctional (meth) acrylate compound.
  • the third composition comprises a monofunctional (meth) acrylate compound.
  • a (meth) acrylate compound having an epoxy group is regarded as a (meth) acrylate compound, not an epoxy compound. Only one kind of the monofunctional (meth) acrylate compound and the polyfunctional (meth) acrylate compound may be used, or two or more kinds thereof may be used in combination.
  • Examples of the monofunctional (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, and i-.
  • the polyfunctional (meth) acrylate compound may be a bifunctional (meth) acrylate compound, a trifunctional (meth) acrylate compound, or a tetrafunctional or higher functional (meth) acrylate compound. You may.
  • bifunctional (meth) acrylate compound examples include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonandi (meth) acrylate, and 1, 10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,4-dimethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol (meth) acrylate, ethoxylated cyclohexanemethanol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2-ethyl-2-butylbutanediol di (meth) acrylate, 2-ethyl- Examples thereof include 2-butyl
  • trifunctional (meth) acrylate compound examples include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, alkylene oxide-modified tri (meth) acrylate of trimethylolpropane, and pentaerythritol tri (meth).
  • tetrafunctional (meth) acrylate compound examples include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol tetra (meth) acrylate propionate. Can be mentioned.
  • pentafunctional (meth) acrylate compound examples include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.
  • hexafunctional (meth) acrylate compound examples include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, and phosphazene alkylene oxide-modified hexa (meth) acrylate.
  • Examples of the (meth) acrylate compound having an epoxy group include glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether.
  • the glass transition temperatures of the homopolymers of the monofunctional (meth) acrylate compounds contained in the first composition and the third composition are respectively. It is preferably ⁇ 100 ° C. or higher, more preferably ⁇ 90 ° C. or higher, preferably less than 0 ° C., and more preferably ⁇ 10 ° C. or lower.
  • the glass transition temperature of the homopolymer of the polyfunctional (meth) acrylate compound contained in the second composition is preferably 50 ° C. or higher. It is more preferably 80 ° C. or higher, preferably 200 ° C. or lower, and more preferably 180 ° C. or lower.
  • the polymerization method is not particularly limited.
  • the homopolymer can be obtained by homopolymerizing the monofunctional (meth) acrylate compound or the polyfunctional (meth) acrylate compound by a known method.
  • all the above monofunctional (meth) acrylate compounds or all the above polyfunctional (meth) acrylate compounds may be polymerized at one time, and the above monofunctional (meth) acrylate compound or the above polyfunctionality may be polymerized at once.
  • the (meth) acrylate compound of the above may be sequentially added and polymerized.
  • the glass transition temperature can be measured in accordance with JIS-K7121 under the condition of a heating rate of 10 ° C./min using a differential scanning calorimeter.
  • Examples of the differential scanning calorimeter include "DSC7020" manufactured by Hitachi High-Tech Science Corporation.
  • the monofunctional (meth) acrylate compounds contained in the first composition and the third composition each have an ester structure of an acrylic acid structure portion. It is preferable that the compound has a group having 4 or more carbon atoms bonded to the oxygen atom constituting the above.
  • the group having 4 or more carbon atoms may be a group having a branched structure or a group having no branched structure (a group having a linear structure).
  • the monofunctional (meth) acrylate compound contained in the first composition and the third composition may be isodecyl acrylate, isononyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, or dodecyl acrylate, respectively. preferable.
  • These monofunctional (meth) acrylate compounds are compounds in which a group having 4 or more carbon atoms is bonded to an oxygen atom constituting the ester structure of the acrylic acid structure portion.
  • the polyfunctional (meth) acrylate compound contained in the second composition is a bifunctional or trifunctional (meth) acrylate compound. Is preferable.
  • the polyfunctional (meth) acrylate compound contained in the second composition is trimethylolpropane triacrylate, 1,6-hexanediol di. It is preferably acrylate or dicyclopentenyl dimethanol diacrylate.
  • the content of the monofunctional (meth) acrylate compound in 100% by weight of the first composition or 100% by weight of the third composition is preferably 5% by weight or more, more preferably 10% by weight. % Or more, preferably 95% by weight or less, more preferably 90% by weight or less.
  • the content of the monofunctional (meth) acrylate compound is not less than the above lower limit and not more than the above upper limit, the effect of the present invention can be exhibited even more effectively.
  • the content of the polyfunctional (meth) acrylate compound in 100% by weight of the first composition is preferably 0. It is 1% by weight or more, more preferably 0.5% by weight or more, preferably 50% by weight or less, and more preferably 30% by weight or less.
  • the third composition contains the polyfunctional (meth) acrylate compound
  • the content of the polyfunctional (meth) acrylate compound in 100% by weight of the third composition is preferably 0. It is 1% by weight or more, more preferably 0.5% by weight or more, preferably 50% by weight or less, and more preferably 30% by weight or less.
  • the content of the polyfunctional (meth) acrylate compound in 100% by weight of the second composition is preferably 10% by weight or more, more preferably 20% by weight or more, preferably 99% by weight or less, more preferably 99% by weight or less. It is 90% by weight or less.
  • the content of the polyfunctional (meth) acrylate compound is not less than the above lower limit and not more than the above upper limit, the effect of the present invention can be exhibited even more effectively.
  • the content of the monofunctional (meth) acrylate compound in 100% by weight of the second composition is preferably 0. It is 1% by weight or more, more preferably 0.5% by weight or more, preferably 50% by weight or less, and more preferably 30% by weight or less.
  • the content of the monofunctional (meth) acrylate compound is not less than the above lower limit and not more than the above upper limit, the effect of the present invention can be exhibited even more effectively.
  • the content of the polyfunctional (meth) acrylate compound in 100% by weight of the first composition is the second composition. It is preferably less than the content of the polyfunctional (meth) acrylate compound in 100% by weight of the composition.
  • the third composition contains the polyfunctional (meth) acrylate compound
  • the content of the polyfunctional (meth) acrylate compound in 100% by weight of the third composition is the second composition. It is preferably less than the content of the polyfunctional (meth) acrylate compound in 100% by weight of the composition. In this case, the effect of the present invention can be exhibited even more effectively.
  • the content of the monofunctional (meth) acrylate compound in 100% by weight of the second composition is the above-mentioned first. It is preferably less than the content of the monofunctional (meth) acrylate compound in 100% by weight of the composition.
  • the content of the monofunctional (meth) acrylate compound in 100% by weight of the second composition is the third It is preferably less than the content of the monofunctional (meth) acrylate compound in 100% by weight of the composition. In this case, the effect of the present invention can be exhibited even more effectively.
  • the first composition contains an epoxy compound.
  • the second composition contains an epoxy compound.
  • the third composition contains an epoxy compound.
  • the epoxy compound contained in the first composition, the epoxy compound contained in the second composition, and the epoxy compound contained in the third composition may be the same or different from each other. May be good. Only one type of each of the above epoxy compounds may be used, or two or more types may be used in combination.
  • Examples of the epoxy compound include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, phenol novolac type epoxy compound, biphenyl type epoxy compound, biphenyl novolac type epoxy compound, biphenol type epoxy compound, and naphthalene type epoxy compound.
  • Examples thereof include epoxy compounds and epoxy compounds having a triazine nucleus as a skeleton.
  • the epoxy compounds contained in the first composition and the third composition are bisphenol A type epoxy compounds or dicyclopentadiene type epoxy compounds, respectively. Is preferable.
  • the epoxy compound contained in the second composition is preferably a bisphenol A type epoxy compound or a dicyclopentadiene type epoxy compound.
  • the content of the epoxy compound in 100% by weight of the first composition or 100% by weight of the third composition is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 1% by weight or more. Is 90% by weight or less, more preferably 70% by weight or less.
  • the content of the epoxy compound is not less than the above lower limit and not more than the above upper limit, the effect of the present invention can be exhibited even more effectively.
  • the content of the epoxy compound in 100% by weight of the second composition is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 90% by weight or less, and more preferably 70% by weight or less. Is. When the content of the epoxy compound is not less than the above lower limit and not more than the above upper limit, the effect of the present invention can be exhibited even more effectively.
  • the first composition contains a photopolymerization initiator.
  • the second composition contains a photopolymerization initiator.
  • the third composition contains a photopolymerization initiator.
  • the photopolymerization initiator contained in the first composition, the photopolymerization initiator contained in the second composition, and the photopolymerization initiator contained in the third composition are the same. May be different. Only one kind of the photopolymerization initiator may be used, or two or more kinds thereof may be used in combination.
  • the photopolymerization initiator examples include a photoradical polymerization initiator and a photocationic polymerization initiator.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator. Only one kind of the photopolymerization initiator may be used, or two or more kinds thereof may be used in combination.
  • the photoradical polymerization initiator is a compound for initiating a radical polymerization reaction by generating radicals by irradiation with light.
  • the photoradical polymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; and alkylphenone compounds such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one; Acetphenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl]- 2-Molholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinopheny
  • Aminoacetophenone compounds such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butyl anthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropyl Thioxanthone compounds such as thioxanthone; Ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; acylphos such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
  • a photopolymerization initiator may be used together with the photoradical polymerization initiator.
  • the photopolymerization initiator include N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like.
  • Other photopolymerization initiators may be used.
  • the photopolymerization initiator only one kind may be used, or two or more kinds may be used in combination.
  • a titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals), which absorbs in the visible light region, may be used to promote the photoreaction.
  • photocationic polymerization initiator examples include sulfonium salts, iodonium salts, metallocene compounds, benzointosilates and the like. Only one kind of the photocationic polymerization initiator may be used, or two or more kinds thereof may be used in combination.
  • the content of the photopolymerization initiator in 100% by weight of the first composition is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, preferably 30% by weight or less, more preferably. It is 20% by weight or less.
  • the content of the photopolymerization initiator in 100% by weight of the second composition is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, preferably 30% by weight or less, more preferably. It is 20% by weight or less.
  • the content of the photopolymerization initiator in 100% by weight of the third composition is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, preferably 30% by weight or less, more preferably. It is 20% by weight or less.
  • the first composition contains a thermosetting agent.
  • the second composition contains a thermosetting agent.
  • the third composition contains a thermosetting agent.
  • the thermosetting agent contained in the first composition, the thermosetting agent contained in the second composition, and the thermosetting agent contained in the third composition may be the same. It may be different. Only one type of the thermosetting agent may be used, or two or more types may be used in combination.
  • heat-curing agent examples include organic acids, amine compounds, amide compounds, hydrazide compounds, imidazole compounds, imidazoline compounds, phenol compounds, urea compounds, polysulfid compounds, acid anhydrides and the like.
  • thermosetting agent a modified polyamine compound such as amine-epoxy adduct may be used. Thermosetting agents other than these may be used.
  • the amine compound means a compound having one or more primary to tertiary amino groups.
  • the amine compound include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, hydrazides, and guanidine derivatives.
  • an epoxy compound-added polyamine a reaction product of an epoxy compound and a polyamine
  • a Michael-added polyamine a reaction product of an ⁇ , ⁇ -unsaturated ketone and a polyamine
  • a Mannig-added polyamine a condensation of a polyamine and a formalin and a phenol.
  • thiourea-added polyamines reactants of thiourea and polyamines
  • ketone-blocking polyamines reactions of ketone compounds and polyamines [ketimine]
  • other adducts may be used.
  • aliphatic polyamine examples include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine and the like.
  • alicyclic polyamine examples include mensendiamine, isophoronediamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane.
  • Adduct, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane and the like can be mentioned.
  • aromatic polyamine examples include m-phenylenediamine, p-phenylenediamine, o-xylene diamine, m-xylene diamine, p-xylene diamine, 4,4-diaminodiphenylmethane, 4,4-diaminodiphenylpropane, and 4,4.
  • hydrazide examples include carbodihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecane diacid dihydrazide, and isophthalic acid dihydrazide.
  • guanidine derivative examples include dicyandiamide, 1-o-tolyldiguanide, ⁇ -2,5-dimethylguanide, ⁇ , ⁇ -diphenyldiguanide, ⁇ , ⁇ -bisguanylguanidinodiphenyl ether, p-chlorophenyldiguanide, ⁇ , ⁇ . -Hexamethylenebis [ ⁇ - (p-chlorophenol)] diguanide, phenyldiguanidooxalate, acetylguanidine, diethylcyanoacetylguanidine and the like can be mentioned.
  • Examples of the phenol compound include a multivalent phenol compound and the like.
  • Examples of the polyhydric phenol compound include phenol, cresol, ethylphenol, butylphenol, octylphenol, bisphenol A, tetrabrom bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenylphenol, naphthalene skeleton-containing phenol novolac resin, and the like.
  • examples thereof include a xylylene skeleton-containing phenol novolac resin, a dicyclopentadiene skeleton-containing phenol novolac resin, and a fluorene skeleton-containing phenol novolac resin.
  • Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, dodecyl anhydride, chlorendic anhydride, and pyromellitic anhydride.
  • Examples thereof include benzophenone tetracarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, trimellitic anhydride, polyazelineic acid anhydride and the like.
  • the content of the thermosetting agent in 100% by weight of the first composition is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 50% by weight or less, and more preferably 40% by weight. It is as follows.
  • the content of the thermosetting agent in 100% by weight of the second composition is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 50% by weight or less, and more preferably 40% by weight. It is as follows.
  • the content of the thermosetting agent in 100% by weight of the third composition is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 50% by weight or less, and more preferably 40% by weight. It is as follows.
  • the first composition may or may not contain a curing accelerator.
  • the second composition may or may not contain a curing accelerator.
  • the third composition may or may not contain a curing accelerator.
  • the curing accelerator contained in the first composition, the curing accelerator contained in the second composition, and the curing accelerator contained in the third composition may be the same. It may be different. Only one type of the curing accelerator may be used, or two or more types may be used in combination.
  • curing accelerator examples include tertiary amines, imidazoles, quaternary ammonium salts, quaternary phosphonium salts, organic metal salts, phosphorus compounds, urea compounds and the like.
  • the content of the curing accelerator in 100% by weight of the first composition is preferably 0.01% by weight or more, more preferably 0. It is 1% by weight or more, preferably 10% by weight or less, and more preferably 8% by weight or less.
  • the content of the curing accelerator in 100% by weight of the second composition is preferably 0.01% by weight or more, more preferably 0. It is 1% by weight or more, preferably 10% by weight or less, and more preferably 8% by weight or less.
  • the content of the curing accelerator in 100% by weight of the third composition is preferably 0.01% by weight or more, more preferably 0. It is 1% by weight or more, preferably 10% by weight or less, and more preferably 8% by weight or less.
  • the first composition may or may not contain a solvent.
  • the second composition may or may not contain a solvent.
  • the third composition may or may not contain a solvent.
  • the solvent contained in the first composition, the solvent contained in the second composition, and the solvent contained in the third composition may be the same or different from each other. Only one type of the solvent may be used, or two or more types may be used in combination.
  • Examples of the solvent include water and organic solvents.
  • the solvent is preferably an organic solvent.
  • organic solvent examples include alcohols such as ethanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol and methylcarbitol.
  • alcohols such as ethanol
  • ketones such as acetone, methyl ethyl ketone and cyclohexanone
  • aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene
  • cellosolve methyl cellosolve
  • butyl cellosolve carbitol and methylcarbitol.
  • Butyl carbitol propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether and other glycol ethers, ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol.
  • the content of the solvent in 100% by weight of the first composition is preferably 5% by weight or less, more preferably 1% by weight or less, still more preferably. It is 0.5% by weight or less. Most preferably, the first composition does not contain the solvent.
  • the content of the solvent in 100% by weight of the second composition is preferably 5% by weight or less, more preferably 1% by weight or less, still more preferably. It is 0.5% by weight or less. Most preferably, the second composition does not contain the solvent.
  • the content of the solvent in 100% by weight of the third composition is preferably 5% by weight or less, more preferably 1% by weight or less, still more preferably. It is 0.5% by weight or less. Most preferably, the third composition does not contain the solvent.
  • the first composition may or may not contain a filler.
  • the second composition may or may not contain a filler.
  • the third composition may or may not contain a filler.
  • the filler contained in the first composition, the filler contained in the second composition, and the filler contained in the third composition may be the same or different from each other. Only one type of the filler may be used, or two or more types may be used in combination.
  • the cured product layer (photo-cured product layer or light and thermosetting material layer) of the first composition From the viewpoint of further improving the thickness accuracy of the cured product layer (photo-cured product layer or light and thermosetting material layer) of the first composition, and further making it more difficult for voids to occur in the cured product layer of the first composition.
  • the smaller the content of the filler in the first composition the better. Further, the smaller the content of the filler in the first composition, the more the occurrence of ejection defects by the inkjet device can be suppressed.
  • the cured product layer (photo-cured product layer or light and thermosetting material layer) of the second composition From the viewpoint of further improving the thickness accuracy of the cured product layer (photo-cured product layer or light and thermosetting material layer) of the second composition, and further making it more difficult for voids to occur in the cured product layer of the second composition.
  • the smaller the content of the filler in the second composition the better. Further, the smaller the content of the filler in the second composition, the more the occurrence of ejection defects by the inkjet device can be suppressed.
  • the cured product layer (photo-cured product layer or light and thermosetting material layer) of the third composition From the viewpoint of further improving the thickness accuracy of the cured product layer (photo-cured product layer or light and thermosetting material layer) of the third composition, and further making it more difficult for voids to occur in the cured product layer of the third composition.
  • the smaller the content of the filler in the third composition the better. Further, the smaller the content of the filler in the third composition, the more the occurrence of ejection defects by the inkjet device can be suppressed.
  • filler examples include silica, talcite, clay, mica, hydrotalcite, alumina, magnesium oxide, aluminum hydroxide, aluminum nitride, and boron nitride.
  • the content of the filler in 100% by weight of the first composition is preferably 30% by weight or less, more preferably 10% by weight or less, still more preferably. It is 1% by weight or less. Most preferably, the first composition does not contain the filler.
  • the content of the filler in 100% by weight of the second composition is preferably 30% by weight or less, more preferably 10% by weight or less, still more preferably. It is 1% by weight or less. Most preferably, the second composition does not contain the filler.
  • the content of the filler in 100% by weight of the third composition is preferably 30% by weight or less, more preferably 10% by weight or less, still more preferably. It is 1% by weight or less. Most preferably, the third composition does not contain the filler.
  • the first composition, the second composition, and the third composition may each contain other components.
  • the other components are not particularly limited, and examples thereof include adhesive aids such as coupling agents, pigments, dyes, leveling agents, antifoaming agents, and polymerization inhibitors.
  • the method for producing a laminated structure, the laminated structure, and the composition set for inkjet according to the present invention can enhance the leakage prevention property of the material, and are therefore suitable for forming a partition wall material and a dam material in electronic parts. Can be used for.
  • the method for producing a laminated structure, the laminated structure, and the composition set for inkjet according to the present invention can be used for other purposes.
  • the first layer and the second layer may be used to form a coating agent.
  • FIG. 14 is a cross-sectional view showing an electronic component obtained by using the laminated structure according to the first embodiment of the present invention.
  • 14 (a) is a plan view of the electronic component
  • FIG. 14 (b) is a cross-sectional view taken along the line II in FIG. 14 (a).
  • the electronic component 80 includes a laminated structure 4C.
  • the laminated structure 4C includes a first base material 3, a first light and thermosetting layer (first layer) 1B, a second light and thermosetting layer (second layer) 2B, and the like. It includes an underfill material 60, a solder ball 65, and a semiconductor chip 70.
  • the first light and thermosetting layer 1B is formed by photocuring and thermosetting the first composition.
  • the second light and thermosetting layer 2B is formed by photocuring and thermosetting the second composition.
  • the first light and thermosetting material layer 1B and the second light and thermosetting material layer 2B are arranged in a frame shape.
  • the underfill material 60, the solder balls 65, and the semiconductor chip 70 are arranged inside the frame-shaped region.
  • the electronic component 80 can be obtained by pouring the underfill material 60 into the inside of the frame-shaped region.
  • the underfill material 60 is poured into and after the underfill material 60 is poured into the frame-shaped region. 60 does not easily leak to the outside of the frame-shaped area.
  • TMPTA Trimethylolpropane triacrylate
  • HDDA 1,6-Hexanediol diacrylate
  • Aromatic amine compound (“EH-105L” manufactured by ADEKA Corporation)
  • Inkjet device A stage having a vacuum suction function, a first discharge unit, a second discharge unit, and a first ultraviolet irradiation unit (LED) arranged between the first discharge unit and the second discharge unit.
  • An inkjet device having the above was prepared.
  • Examples 1 to 8 and Comparative Examples 1 to 3 Preparation of the first composition: The components shown in Tables 1 to 3 were blended in the blending amounts shown in Tables 1 to 3 to obtain the first composition.
  • Preparation of the second composition The components shown in Tables 1 to 3 were blended in the blending amounts shown in Tables 1 to 3 to obtain a second composition.
  • the silicon wafer was adsorbed on the stage and fixed.
  • the first composition was discharged from the first discharge section.
  • the first composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2.
  • a first layer (photocured product layer) having a linear shape having a width of 150 ⁇ m, a length of 10 mm, and a thickness of 3 ⁇ m was formed.
  • the second composition was discharged from the second discharge portion on the surface of the first layer (photo-cured product layer).
  • the second composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2.
  • a second layer (photo-cured product layer) having a linear shape having a width of 150 ⁇ m, a length of 10 mm, and a thickness of 100 ⁇ m is placed on the surface of the first layer (photo-cured product layer).
  • a second layer (photo-cured product layer) having a linear shape having a width of 150 ⁇ m, a length of 10 mm, and a thickness of 100 ⁇ m is placed on the surface of the first layer (photo-cured product layer).
  • a laminated structure (X) including a base material (silicon wafer), a first layer (photo-cured product layer), and a second layer (photo-cured product layer) in this order was obtained.
  • Example 5 a first layer (photocured product layer) having a linear shape having a width of 300 ⁇ m, a length of 10 mm, and a thickness of 3 ⁇ m is formed, and a linear shape having a width of 300 ⁇ m, a length of 10 mm, and a thickness of 100 ⁇ m is formed. Two layers (photo-cured product layer) were formed.
  • Example 6 a first layer (photocured material layer) having a linear shape having a width of 150 ⁇ m, a length of 10 mm, and a thickness of 3 ⁇ m is formed, and a linear shape having a width of 150 ⁇ m, a length of 10 mm, and a thickness of 200 ⁇ m is formed. Two layers (photo-cured product layer) were formed.
  • Example 7 a first layer (photocured product layer) having a linear shape having a width of 150 ⁇ m, a length of 10 mm, and a thickness of 5 ⁇ m is formed, and a linear shape having a width of 150 ⁇ m, a length of 10 mm, and a thickness of 100 ⁇ m is formed. Two layers (photo-cured product layer) were formed.
  • Example 8 a first layer (photocured product layer) having a linear shape having a width of 150 ⁇ m, a length of 10 mm, and a thickness of 5 ⁇ m is formed, and a linear shape having a width of 150 ⁇ m, a length of 10 mm, and a thickness of 200 ⁇ m is formed. Two layers (photo-cured product layer) were formed.
  • the silicon wafer was adsorbed on the stage and fixed.
  • the first composition was discharged from the first discharge section.
  • the first composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2.
  • a first layer (photocured product layer) having a linear shape having a width of 150 ⁇ m, a length of 10 mm, and a thickness of 103 ⁇ m was formed. This was designated as a laminated structure (X) provided with a photocurable material layer.
  • the silicon wafer was adsorbed on the stage and fixed.
  • the second composition was discharged from the second discharge section. After 0.1 seconds from the discharge, the second composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2.
  • a second layer photocured product layer having a linear shape having a width of 150 ⁇ m, a length of 10 mm, and a thickness of 103 ⁇ m was formed. This was designated as a laminated structure (X) provided with a photocurable material layer.
  • the width and thickness of the first layer (photo-cured product layer) and the second layer (photo-cured product layer) in the laminated structure (X) are determined by a laser microscope (“OLS4100” manufactured by Olympus Corporation”. ) was used for measurement. In Examples 1 to 8, the shape of the photocurable product layer was retained.
  • laminated structure (X) including light and thermosetting material layer Fabrication of laminated structure (X) including light and thermosetting material layer: The first and second layers (photo-cured product layer) in the obtained laminated structure (X) including the photo-cured product layer are heat-cured by heating at 170 ° C. for 1 hour, and the light and thermosetting product layer are heat-cured. The first and second layers were obtained. In this way, a laminated structure (X) including a base material (silicon wafer), a first layer (light and thermosetting layer), and a second layer (light and thermosetting layer) is obtained. rice field.
  • the first layer (light and thermosetting layer) and the second layer (light and thermosetting layer) in the obtained laminated structure (X) are subjected to a cross-section polishing device (“Teglamin 25” manufactured by Struas). I cut it.
  • An optical microscope Keyence “Digital Microscope VH-Z100" shows the cross sections of the first layer (light and thermocured product layer) and the second layer (light and thermocured product layer) obtained by cutting. The thickness of the first layer and the thickness of the second layer were measured by observing with.
  • the second composition was discharged from the second discharge unit (in Comparative Example 4, the first composition was discharged from the first discharge unit). After 0.1 seconds from the discharge, the second composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2. By repeating the coating and the irradiation with ultraviolet rays, a second layer (photocurable material layer) having a shape having a width of 10 mm, a length of 10 mm, and a thickness of 20 ⁇ m was formed.
  • silica powder (“Sea Horster KE-P250” manufactured by Nippon Shokubai Co., Ltd.) was placed on the surface of the photocurable material layer, and nitrogen was sprayed on the surface of the photocurable material layer at 400 L / min for 10 seconds. The amount of silica powder remaining on the surface of the photocured material layer was measured.
  • a silicon wafer was adsorbed and fixed on the stage.
  • the first composition was discharged from the first discharge section. After 0.1 seconds from the discharge, the first composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2.
  • a first layer photocurable material layer having a square frame shape having a width of 150 ⁇ m, a side length of 10 mm, and a thickness of 3 ⁇ m was formed.
  • the second composition was discharged from the second discharge portion on the surface of the first layer (photo-cured product layer).
  • the second composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2.
  • a second layer having a square frame shape having a width of 150 ⁇ m, a side length of 10 mm, and a thickness of 100 ⁇ m is formed on the surface of the first layer (photocured product layer).
  • a photocured product layer) was formed.
  • first and second layers were heat-cured by heating at 170 ° C. for 1 hour to obtain first and second layers which are light and thermosetting product layers.
  • first and second layers which are light and thermosetting product layers.
  • a laminated structure including a base material (silicon wafer), a first layer (light and thermosetting layer), and a second layer (light and thermosetting layer) was obtained.
  • Preparation of material X The following components were mixed with a planetary stirrer, and the obtained mixture was dispersed and treated with three rolls to obtain Material X.
  • Bisphenol F type epoxy resin (“EPICLON830” manufactured by DIC) 70 parts by weight Reactive diluent (“ED-529” manufactured by ADEKA) 30 parts by weight Thermosetting agent (“EH105L” manufactured by ADEKA) 30 parts by weight Molten silica ( Admatex “SO-C5") 300 parts by weight Coupling agent (JNC “S510”) 3 parts by weight Carbon black (Mitsubishi Chemical "MA-600”) 0.5 parts by weight
  • the obtained material X is filled inside a light and thermosetting layer (a laminate of a first layer and a second layer) having a square frame shape so as to have a thickness of 50 ⁇ m, and 150 Material X was thermoset by heating at ° C. for 1 hour.
  • Comparative Example 4 after forming a first layer (photocured material layer) having a square frame shape having a width of 150 ⁇ m, a side length of 10 mm, and a thickness of 103 ⁇ m on a silicon wafer, the first layer was formed.
  • the evaluation was carried out in the same manner as above, except that the layer (photocurable material layer) was heat-cured by heating at 170 ° C. for 1 hour to obtain a first layer which is a light and thermosetting material layer. rice field.
  • Comparative Example 5 after forming a second layer (photocured product layer) having a square frame shape having a width of 150 ⁇ m, a side length of 10 mm, and a thickness of 103 ⁇ m on the silicon wafer, the second layer was formed.
  • the evaluation was carried out in the same manner as above, except that the layer (photo-cured product layer) was heat-cured by heating at 170 ° C. for 1 hour to obtain a second layer which is a light and thermosetting product layer. rice field.
  • Comparative Example 4 the shape of the light and the thermosetting layer (the laminate of the first layer and the second layer) changed during the thermosetting, and the thickness of the light and the thermosetting layer decreased to about 30 ⁇ m. Material X leaked to the outside of the light and thermosetting layer. Further, in Comparative Examples 1 to 3 and 5, since the adhesive force between the base material (silicon wafer) and the first layer or the adhesive force between the first layer and the second layer is low, the heat of the material X is low. Unable to withstand expansion, material X leaked to the outside of the light and thermosetting layer.
  • Example 9 to 14 Preparation of the first composition and the third composition: The components shown in Tables 4 and 5 were blended in the blending amounts shown in Tables 4 and 5 to obtain a first composition and a third composition.
  • Preparation of the second composition The components shown in Tables 4 and 5 were blended in the blending amounts shown in Tables 4 and 5 to obtain a second composition.
  • the silicon wafer was adsorbed on the stage and fixed.
  • the first composition was discharged from the first discharge section.
  • the first composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2.
  • a first layer photocurable material layer having a square frame shape having a width of 200 ⁇ m, a side length of 10 mm, and a thickness of 5 ⁇ m was formed.
  • the second composition was discharged from the second discharge portion on the surface of the first layer (photo-cured product layer).
  • the second composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2.
  • a second layer having a square frame shape having a width of 200 ⁇ m, a side length of 10 mm, and a thickness of 1000 ⁇ m is formed on the surface of the first layer (photocured product layer).
  • a photocured product layer) was formed.
  • the third composition (first composition) was discharged from the first discharge portion on the surface of the second layer (photocurable product layer). After 0.1 seconds from the discharge, the third composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2. By repeating the coating and irradiation with ultraviolet rays, a third layer (photocurable material layer) having a square frame shape having a width of 200 ⁇ m, a side length of 10 mm, and a thickness of 10 ⁇ m was formed.
  • a glass substrate was attached onto the surface of the third layer using a bonder (“FTD-7000P” manufactured by Shibaura Mechatronics Co., Ltd.), and heated at 170 ° C. for 1 hour to obtain the first layer (photocured product).
  • Layer), the second layer (photo-cured product layer) and the third layer (photo-cured product layer) were heat-cured.
  • the first base material silicon wafer
  • the first layer light and thermosetting layer
  • the second layer light and thermosetting layer
  • the third layer light
  • a thermosetting layer and a second base material (glass substrate) in this order to obtain a laminated structure (X).
  • Example 10 In Examples 10 and 11, the following operations were additionally performed, and a third layer (photocured product) having a square frame shape having a width of 200 ⁇ m, a side length of 10 mm, and a thickness of 5 ⁇ m was performed.
  • a laminated structure (X) was produced in the same manner as in Example 9 except that the layer) was formed.
  • the base material silicon wafer
  • the first layer photo-cured product layer
  • the second layer photo-cured product layer
  • the first layer (photo-cured product layer) and the second layer (photo-cured product layer) were thermally cured by heating the laminate with the layer) at 170 ° C. for 1 hour.
  • a flattening treatment was performed by cutting and polishing the surface of the second layer (light and thermosetting layer) by 100 ⁇ m using a flattening device (manufactured by Keylink).
  • the absolute value of the difference between the maximum height and the minimum height of the surface of the second layer after the flattening treatment was 3 ⁇ m or less.
  • the substrate silicon wafer
  • the first layer light and thermosetting layer
  • the second layer light and thermosetting layer
  • the third layer light and thermosetting.
  • Example 12 a laminated structure (X) was produced as follows.
  • the ceramic substrate was adsorbed on the stage and fixed.
  • the second composition was discharged from the second discharge section. After 0.1 seconds from the discharge, the second composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2.
  • a second layer photocurable layer having a square frame shape having a width of 200 ⁇ m, a side length of 10 mm, and a thickness of 1000 ⁇ m was formed on the surface of the base material.
  • the first composition was discharged from the first discharge portion on the surface of the second layer (photocurable product layer). After 0.1 seconds from the discharge, the first composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2. By repeating coating and irradiation with ultraviolet rays, a first layer having a square frame shape having a width of 200 ⁇ m, a side length of 10 mm, and a thickness of 10 ⁇ m on the surface of the second layer (photocured product layer) ( A photocured product layer) was formed.
  • a glass substrate was attached onto the surface of the first layer using a bonder (“FTD-7000P” manufactured by Shibaura Mechatronics Co., Ltd.), and heated at 170 ° C. for 1 hour to obtain the first layer (photocured product).
  • the layer) and the second layer (photocurable layer) were heat-cured.
  • Example 13 and 14 the following operations were additionally performed, and the first layer (photocured product) having a square frame shape having a width of 200 ⁇ m, a side length of 10 mm, and a thickness of 5 ⁇ m was performed.
  • a laminated structure (X) was produced in the same manner as in Example 12 except that the layer) was formed.
  • the laminate of the base material (ceramic substrate) and the second layer (photocurable material layer) is placed at 170 ° C.
  • the second layer (photocurable material layer) was thermoset by heating for 1 hour.
  • a flattening device manufactured by Keylink
  • the absolute value of the difference between the maximum height and the minimum height of the second layer after the flattening treatment was 3 ⁇ m or less.

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Abstract

Provided is a laminate structure which can improve material leakage prevention.　The laminate structure according to the present invention comprises a first base material, a first layer disposed on the surface of the first base material, and a second layer disposed on the surface of the side opposite the first layer on the first base material side. The first layer is a photocurable layer of a first composition containing a monofunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. The second layer is a photocurable layer of a second composition containing a polyfunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. The first composition and second composition are different compositions.

Description

積層構造体の製造方法、積層構造体、及びインクジェット用組成物セットLaminated structure manufacturing method, laminated structure, and inkjet composition set
　本発明は、インクジェット装置を用いた積層構造体の製造方法に関する。また、本発明は、積層構造体に関する。また、本発明は、インクジェット装置を用いて塗布されて用いられるインクジェット用組成物セットに関する。 The present invention relates to a method for manufacturing a laminated structure using an inkjet device. The present invention also relates to a laminated structure. The present invention also relates to an inkjet composition set that is applied and used by using an inkjet device.
　インクジェット装置を用いて組成物を塗布する方法が知られている。例えば、電子部品の製造では、インクジェット装置を用いて、基材の表面上に、インクジェット用組成物を塗布し、該組成物を光又は熱等により硬化させる方法が用いられている。 A method of applying a composition using an inkjet device is known. For example, in the manufacture of electronic components, a method is used in which an inkjet composition is applied onto the surface of a base material using an inkjet device, and the composition is cured by light, heat, or the like.
　下記の特許文献１には、（Ａ）エチレン性不飽和基を有する多分岐状のオリゴマー又はポリマー、（Ｂ）光重合開始剤、及び（Ｃ）熱硬化性化合物を含むインクジェット印刷用硬化性組成物が開示されている。 The following Patent Document 1 describes a curable composition for inkjet printing containing (A) a multi-branched oligomer or polymer having an ethylenically unsaturated group, (B) a photopolymerization initiator, and (C) a thermosetting compound. The thing is disclosed.
ＷＯ２０１９／１８９１８６Ａ１WO2019 / 189186A1
　半導体装置及びプリント配線板等の電子部品においては、インクジェット用組成物が硬化した硬化物層が配置されることがある。上記硬化物層は、２つの部品等を接着するための接着剤層として用いられることが多い。 In electronic components such as semiconductor devices and printed wiring boards, a cured product layer in which the ink jet composition is cured may be arranged. The cured product layer is often used as an adhesive layer for adhering two parts or the like.
　また、接着用途とは異なる用途でインクジェット用組成物を用いる試みが行われている。 In addition, attempts are being made to use inkjet compositions for purposes other than adhesive applications.
　例えば、硬化物層で囲まれた領域を形成して該領域の内側に金属層を形成したり、硬化物層で隔壁を形成してアンダーフィル材が濡れ拡がらないようにしたりすることができれば、電子部品の小型化、低コスト化につながる。 For example, if a region surrounded by a cured product layer can be formed to form a metal layer inside the region, or a partition wall can be formed with the cured product layer to prevent the underfill material from getting wet and spreading. This leads to miniaturization and cost reduction of electronic parts.
　上記の用途では、材料（例えば、金属層を形成するための材料及びアンダーフィル材等）が意図しない箇所に漏れ出さないことが必要である。 In the above applications, it is necessary that the material (for example, the material for forming the metal layer and the underfill material) does not leak to an unintended place.
　本発明の目的は、材料の漏れ出し防止性を高めることができる積層構造体の製造方法、積層構造体及びインクジェット用組成物セットを提供することである。また、本発明は、上記積層構造体を製造するために用いられる装置を提供することも目的とする。 An object of the present invention is to provide a method for producing a laminated structure, a laminated structure, and a composition set for inkjet, which can enhance the leakage prevention property of a material. It is also an object of the present invention to provide an apparatus used for manufacturing the above-mentioned laminated structure.
　本発明の広い局面によれば、第１の基材の表面上にインクジェット方式で塗布された第１の組成物に光を照射して、前記第１の組成物が光硬化した第１の光硬化物層を形成する第１の光硬化工程と、前記第１の光硬化物層の前記第１の基材側とは反対の表面側にインクジェット方式で塗布された第２の組成物に光を照射して、前記第２の組成物が光硬化した第２の光硬化物層を形成する第２の光硬化工程とを備え、前記第１の組成物が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含み、前記第２の組成物が、多官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含み、前記第１の組成物と前記第２の組成物とが異なる組成物である、積層構造体の製造方法が提供される。 According to a broad aspect of the present invention, a first light obtained by irradiating a first composition coated on the surface of a first base material by an inkjet method with light and photocuring the first composition. Light is applied to the first photocuring step of forming the cured product layer and the second composition coated by the inkjet method on the surface side of the first photocured product layer opposite to the first base material side. The second composition comprises a second photocuring step of forming a photocured second photocured layer by irradiating the first composition with a monofunctional (meth) acrylate. The second composition contains a compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent, and the second composition comprises a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. Provided is a method for producing a laminated structure, which comprises an agent and is a composition in which the first composition and the second composition are different.
　本発明に係る積層構造体の製造方法のある特定の局面では、前記積層構造体の製造方法は、前記第１の光硬化物層の前記第１の基材側とは反対の表面側に第２の組成物をインクジェット方式で塗布する第２の塗布工程を備え、前記第２の光硬化工程において、前記第２の塗布工程で塗布された前記第２の組成物に光を照射する。 In a specific aspect of the method for producing a laminated structure according to the present invention, the method for producing a laminated structure is on the surface side of the first photocured material layer opposite to the first base material side. A second coating step of applying the composition of 2 by an inkjet method is provided, and in the second photocuring step, the second composition coated in the second coating step is irradiated with light.
　本発明に係る積層構造体の製造方法のある特定の局面では、前記第２の塗布工程と前記第２の光硬化工程とがそれぞれ、前記第１の光硬化物層の厚み方向にて、複数回行われる。 In a specific aspect of the method for producing a laminated structure according to the present invention, a plurality of the second coating step and the second photocuring step are performed in the thickness direction of the first photocured product layer, respectively. It is done once.
　本発明に係る積層構造体の製造方法のある特定の局面では、前記積層構造体の製造方法は、前記第１の光硬化物層及び前記第２の光硬化物層を加熱して、前記第１の光硬化物層が熱硬化した第１の光及び熱硬化物層、並びに、前記第２の光硬化物層が熱硬化した第２の光及び熱硬化物層を形成する第１及び第２の光硬化物層用加熱工程を備える。 In a specific aspect of the method for producing a laminated structure according to the present invention, the method for producing a laminated structure heats the first photocured material layer and the second photocured material layer to obtain the first photocured product layer. The first and first photo-cured product layers are formed by the first photo-cured product layer in which the photo-cured product layer is heat-cured, and the second light and thermo-cured product layer in which the second photo-cured product layer is heat-cured. It is provided with the heating step for the photocurable material layer of 2.
　本発明に係る積層構造体の製造方法のある特定の局面では、前記積層構造体の製造方法は、前記第１の光硬化物層及び前記第２の光硬化物層を加熱して、前記第１の光硬化物層が熱硬化した第１の光及び熱硬化物層、並びに、前記第２の光硬化物層が熱硬化した第２の光及び熱硬化物層を形成する第１及び第２の光硬化物層用加熱工程を備えるか又は備えず、前記第１及び第２の光硬化物層用加熱工程が備えられる場合に、前記第２の光及び熱硬化物層の前記第１の基材側とは反対の表面側にインクジェット方式で塗布された第３の組成物に光を照射して、前記第３の組成物が光硬化した第３の光硬化物層を形成する第３の光硬化工程を備え、前記第１及び第２の光硬化物層用加熱工程が備えられない場合に、前記第２の光硬化物層の前記第１の基材側とは反対の表面側にインクジェット方式で塗布された第３の組成物に光を照射して、前記第３の組成物が光硬化した第３の光硬化物層を形成する第３の光硬化工程を備え、前記第３の組成物が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含み、前記第２の組成物と前記第３の組成物とが異なる組成物である。 In a specific aspect of the method for producing a laminated structure according to the present invention, the method for producing a laminated structure is such that the first photocurable layer and the second photocurable layer are heated to obtain the first photocurable layer. The first and first photo-cured product layers are formed by the first photo- and heat-cured product layer in which the first photo-cured product layer is heat-cured, and the second photo- and heat-cured product layer in which the second photo-cured product layer is heat-cured. When the first and second heating steps for the photocurable material layer are provided with or without the heating step for the second photocurable material layer, the first of the second light and heat-curable material layer is provided. A third composition coated by an inkjet method on the surface side opposite to the base material side of the above is irradiated with light to form a third photocurable material layer in which the third composition is photocured. When the photo-curing step of 3 is provided and the heating step for the first and second photo-cured product layers is not provided, the surface of the second photo-cured product layer opposite to that of the first substrate side. A third photocuring step is provided in which a third composition coated on the side by an inkjet method is irradiated with light to form a third photocurable layer in which the third composition is photocured. The third composition contains a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a heat-curing agent, and the second composition and the third composition are different from each other. It is a composition.
　本発明に係る積層構造体の製造方法のある特定の局面では、前記第１の組成物と前記第３の組成物とが同一の組成物である。 In a specific aspect of the method for producing a laminated structure according to the present invention, the first composition and the third composition are the same composition.
　本発明に係る積層構造体の製造方法のある特定の局面では、前記積層構造体の製造方法は、前記第１及び第２の光硬化物層用加熱工程が備えられる場合に、前記第１及び第２の光硬化物層用加熱工程後に、前記第２の光及び熱硬化物層の前記第１の基材側とは反対の表面を平坦化処理する平坦化処理工程を備え、前記第１及び第２の光硬化物層用加熱工程が備えられない場合に、前記第２の光硬化工程後に、前記第２の光硬化物層の前記第１の基材側とは反対の表面を平坦化処理する平坦化処理工程を備え、前記平坦化処理が、研磨処理である。 In a specific aspect of the method for producing a laminated structure according to the present invention, the method for producing a laminated structure is such that the first and second photocurable layer heating steps are provided. After the heating step for the second photocurable material layer, a flattening treatment step for flattening the surface of the second light and the heat-cured material layer opposite to the first base material side is provided. And when the heating step for the second photocurable material layer is not provided, after the second photocurable material layer, the surface of the second photocurable material layer opposite to the first base material side is flattened. A flattening treatment step for flattening treatment is provided, and the flattening treatment is a polishing treatment.
　本発明に係る積層構造体の製造方法のある特定の局面では、前記積層構造体の製造方法は、前記第３の光硬化物層の前記第１の基材側とは反対の表面上に、第２の基材を配置する配置工程を備える。 In a specific aspect of the method for producing a laminated structure according to the present invention, the method for producing a laminated structure is such that the method for producing a laminated structure is formed on a surface of the third photocured material layer opposite to the first base material side. The arrangement step of arranging the second base material is provided.
　本発明に係る積層構造体の製造方法のある特定の局面では、前記積層構造体の製造方法は、前記第１及び第２の光硬化物層用加熱工程が備えられる場合に、前記第３の光硬化物層を加熱して、前記第３の光硬化物層が熱硬化した第３の光及び熱硬化物層を形成する第３の光硬化物層用加熱工程を備え、前記第１及び第２の光硬化物層用加熱工程が備えられない場合に、前記第１の光硬化物層、前記第２の光硬化物層及び前記第３の光硬化物層を加熱して、前記第１の光硬化物層が熱硬化した第１の光及び熱硬化物層、前記第２の光硬化物層が熱硬化した第２の光及び熱硬化物層、並びに、前記第３の光硬化物層が熱硬化した第３の光及び熱硬化物層を形成する第１、第２及び第３の光硬化物層用加熱工程を備える。 In a specific aspect of the method for producing a laminated structure according to the present invention, the method for producing a laminated structure may be described in the case where the first and second heating steps for a photocurable material layer are provided. The third photocurable material layer is heated to form a third light and a thermosetting material layer in which the third photocurable material layer is thermoset, and a third photocurable material layer heating step is provided. When the heating step for the second photocurable material layer is not provided, the first photocurable material layer, the second photocurable material layer and the third photocurable material layer are heated to obtain the first photocurable material layer. The first light and thermosetting material layer in which the photocurable material layer 1 is heat-cured, the second light and thermosetting material layer in which the second photocurable material layer is heat-cured, and the third photocurable material layer. The present invention includes a third light in which the material layer is thermoset and a heating step for the first, second and third photocurable material layers forming the thermosetting material layer.
　本発明の広い局面によれば、第１の基材の表面上にインクジェット方式で塗布された第２の組成物に光を照射して、前記第２の組成物が光硬化した第２の光硬化物層を形成する第２の光硬化工程を備え、前記第２の光硬化物層を加熱して、前記第２の光硬化物層が熱硬化した第２の光及び熱硬化物層を形成する第２の光硬化物層用加熱工程を備えるか又は備えず、前記第２の光硬化物層用加熱工程が備えられる場合に、前記第２の光及び熱硬化物層の前記第１の基材側とは反対の表面側にインクジェット方式で塗布された第１の組成物に光を照射して、前記第１の組成物が光硬化した第１の光硬化物層を形成する第１の光硬化工程を備え、前記第２の光硬化物層用加熱工程が備えられない場合に、前記第２の光硬化物層の前記第１の基材側とは反対の表面側にインクジェット方式で塗布された第１の組成物に光を照射して、前記第１の組成物が光硬化した第１の光硬化物層を形成する第１の光硬化工程を備え、前記第１の組成物が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含み、前記第２の組成物が、多官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含み、前記第１の組成物と前記第２の組成物とが異なる組成物である、積層構造体の製造方法が提供される。 According to a broad aspect of the present invention, a second light obtained by irradiating a second composition coated on the surface of a first base material by an inkjet method with light and photocuring the second composition. The second photo-curing material layer is provided with a second photo-curing step of forming the cured product layer, and the second photo-cured product layer is heated to heat the second photo-cured product layer to heat-curing the second photo-cured product layer. When the heating step for the second photocurable material layer to be formed is provided or not provided, and the heating step for the second photocurable material layer is provided, the first of the second light and the heat-cured material layer is provided. The first composition coated by an inkjet method on the surface side opposite to the base material side of the above is irradiated with light to form a first photocurable material layer in which the first composition is photocured. When the photo-curing step of 1 is provided and the heating step for the second photo-curing material layer is not provided, inkjet is applied to the surface side of the second photo-curing material layer opposite to the first base material side. The first composition comprises a first photocuring step of irradiating the first composition applied by the method with light to form a first photocurable layer in which the first composition is photocured. The composition comprises a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a heat-curing agent, and the second composition is a polyfunctional (meth) acrylate compound and an epoxy. Provided is a method for producing a laminated structure, which comprises a compound, a photopolymerization initiator, and a heat-curing agent, and the first composition and the second composition are different compositions.
　本発明に係る積層構造体の製造方法のある特定の局面では、前記積層構造体の製造方法は、前記第２の光硬化物層を加熱して、前記第２の光硬化物層が熱硬化した第２の光及び熱硬化物層を形成する第２の光硬化物層用加熱工程を備え、前記第１の光硬化工程において、前記第２の光及び熱硬化物層の前記第１の基材側とは反対の表面側にインクジェット方式で塗布された第１の組成物に光を照射して、前記第１の組成物が光硬化した第１の光硬化物層を形成する。 In a specific aspect of the method for producing a laminated structure according to the present invention, the method for producing a laminated structure heats the second photocurable material layer, and the second photocurable material layer is thermoset. The second photo-curing material layer for forming the second light and thermosetting material layer is provided, and in the first photo-curing step, the first light and thermosetting material layer is formed. The first composition coated on the surface side opposite to the base material side by an inkjet method is irradiated with light to form a first photocurable product layer in which the first composition is photocured.
　本発明に係る積層構造体の製造方法のある特定の局面では、前記第２の光硬化物層用加熱工程が備えられる場合に、前記第２の光硬化物層用加熱工程後に、前記第２の光及び熱硬化物層の前記第１の基材側とは反対の表面を平坦化処理する平坦化処理工程を備え、前記第２の光硬化物層用加熱工程が備えられない場合に、前記第２の光硬化工程後に、前記第２の光硬化物層の前記第１の基材側とは反対の表面を平坦化処理する平坦化処理工程を備え、前記平坦化処理が、研磨処理である。 In a specific aspect of the method for producing a laminated structure according to the present invention, when the second photocurable layer heating step is provided, the second photocurable layer heating step is followed by the second photocurable layer heating step. When a flattening treatment step for flattening the surface of the photo- and heat-cured product layer opposite to the first base material side is provided and the heating step for the second photo-cured product layer is not provided. After the second photocuring step, a flattening treatment step of flattening the surface of the second photocured material layer opposite to the first base material side is provided, and the flattening treatment is a polishing treatment. Is.
　本発明に係る積層構造体の製造方法のある特定の局面では、前記積層構造体の製造方法は、前記第２の光硬化物層用加熱工程が備えられる場合に、前記第１の光硬化物層を加熱して、前記第１の光硬化物層が熱硬化した第１の光及び熱硬化物層を形成する第１の光硬化物層用加熱工程を備え、前記第２の光硬化物層用加熱工程が備えられない場合に、前記第１の光硬化物層及び前記第２の光硬化物層を加熱して、前記第１の光硬化物層が熱硬化した第１の光及び熱硬化物層、並びに、前記第２の光硬化物層が熱硬化した第２の光及び熱硬化物層を形成する第１及び第２の光硬化物層用加熱工程を備える。 In a specific aspect of the method for producing a laminated structure according to the present invention, the method for producing a laminated structure is such that the first photocured product is provided with the heating step for the second photocured product layer. The second photo-cured product is provided with a heating step for a first photo-cured product layer in which the layer is heated to form a first light and a thermosetting product layer in which the first photo-cured product layer is thermoset. When the layer heating step is not provided, the first photo-cured product layer and the second photo-cured product layer are heated so that the first photo-cured product layer is thermoset. The present invention includes a heating step for a first and second photocurable material layer, which forms a thermosetting material layer and a second light and thermosetting material layer in which the second photocurable material layer is heat-cured.
　本発明に係る積層構造体の製造方法のある特定の局面では、前記積層構造体の製造方法は、前記第１の光硬化物層の前記第１の基材側とは反対の表面上に、第２の基材を配置する配置工程を備える。 In a specific aspect of the method for producing a laminated structure according to the present invention, the method for producing a laminated structure is such that the method for producing a laminated structure is formed on a surface of the first photocured material layer opposite to the first base material side. The arrangement step of arranging the second base material is provided.
　本発明に係る積層構造体の製造方法のある特定の局面では、前記第２の基材の表面粗さが、前記第１の基材の表面粗さよりも小さい。 In a specific aspect of the method for producing a laminated structure according to the present invention, the surface roughness of the second base material is smaller than the surface roughness of the first base material.
　本発明の広い局面によれば、第１の基材と、前記第１の基材の表面上に配置された第１の層と、前記第１の層の前記第１の基材側とは反対側の表面上に配置された第２の層とを備え、前記第１の層と前記第２の層との組合せが、前記第１の層が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第１の組成物の光硬化物層又は光及び熱硬化物層であり、かつ前記第２の層が、多官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第２の組成物の光硬化物層又は光及び熱硬化物層である組合せであるか、又は、前記第１の層が、多官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第２の組成物の光硬化物層又は光及び熱硬化物層であり、かつ前記第２の層が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第１の組成物の光硬化物層又は光及び熱硬化物層である組合せであり、前記第１の組成物と前記第２の組成物とが異なる組成物である、積層構造体が提供される。 According to a broad aspect of the present invention, the first base material, the first layer arranged on the surface of the first base material, and the first base material side of the first layer are A second layer arranged on the opposite surface is provided, and the combination of the first layer and the second layer is such that the first layer is a monofunctional (meth) acrylate compound. A photocurable layer or a light and thermosetting layer of the first composition containing an epoxy compound, a photopolymerization initiator, and a thermosetting agent, and the second layer is a polyfunctional (meth). It is a combination of a photocurable material layer or a light and thermosetting material layer of a second composition containing an acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent, or the first. The layer is a photocurable material layer or a light and thermosetting material layer of a second composition containing a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent, and The second layer is a photocurable layer or a light and thermosetting layer of the first composition containing a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. Provided is a laminated structure in which the first composition and the second composition are different compositions.
　本発明に係る積層構造体のある特定の局面では、前記第１の層が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第１の組成物の光硬化物層又は光及び熱硬化物層であり、前記第２の層が、多官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第２の組成物の光硬化物層又は光及び熱硬化物層である。 In certain aspects of the laminated structure according to the present invention, the first layer comprises a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. The composition is a photocurable layer or a light and thermosetting layer, and the second layer contains a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. The photocured material layer or the light and thermosetting material layer of the second composition.
　本発明に係る積層構造体のある特定の局面では、前記第２の層が、研磨された表面を有する。 In certain aspects of the laminated structure according to the present invention, the second layer has a polished surface.
　本発明に係る積層構造体のある特定の局面では、前記積層構造体は、前記第２の層の前記第１の層側とは反対側の表面上に配置された第２の基材を備える。 In certain aspects of the laminated structure according to the present invention, the laminated structure comprises a second substrate disposed on a surface of the second layer opposite to the first layer side. ..
　本発明に係る積層構造体のある特定の局面では、前記第１の層が、前記第１の組成物の光及び熱硬化物層であり、前記第２の層が、前記第２の組成物の光及び熱硬化物層である。 In certain aspects of the laminated structure according to the present invention, the first layer is the light and thermosetting layer of the first composition, and the second layer is the second composition. Light and thermosetting layer.
　本発明に係る積層構造体のある特定の局面では、前記第２の層の厚みが、前記第１の層の厚みよりも厚い。 In a specific aspect of the laminated structure according to the present invention, the thickness of the second layer is thicker than the thickness of the first layer.
　本発明に係る積層構造体のある特定の局面では、前記第１の層の厚みが、０．１μｍ以上１０μｍ以下であり、前記第２の層の厚みが、１μｍ以上１０００μｍ以下である。 In a specific aspect of the laminated structure according to the present invention, the thickness of the first layer is 0.1 μm or more and 10 μm or less, and the thickness of the second layer is 1 μm or more and 1000 μm or less.
　本発明に係る積層構造体のある特定の局面では、前記積層構造体は、前記第２の層の前記第１の層側とは反対側の表面上に配置された第３の層を備え、前記第３の層が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第３の組成物の光硬化物層又は光及び熱硬化物層であり、前記第２の組成物と前記第３の組成物とが異なる組成物である。 In certain aspects of the laminated structure according to the present invention, the laminated structure comprises a third layer disposed on a surface of the second layer opposite to the first layer side. The third layer is a photocurable layer or a light and thermosetting layer of a third composition containing a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. The second composition and the third composition are different compositions.
　本発明に係る積層構造体のある特定の局面では、前記第１の組成物と前記第３の組成物とが同一の組成物である。 In a specific aspect of the laminated structure according to the present invention, the first composition and the third composition are the same composition.
　本発明に係る積層構造体のある特定の局面では、前記積層構造体は、前記第３の層の前記第２の層側とは反対側の表面上に配置された第２の基材を備える。 In certain aspects of the laminated structure according to the present invention, the laminated structure comprises a second substrate disposed on a surface of the third layer opposite to the second layer side. ..
　本発明に係る積層構造体のある特定の局面では、前記第１の基材の表面粗さが、前記第２の基材の表面粗さよりも小さい。 In a specific aspect of the laminated structure according to the present invention, the surface roughness of the first base material is smaller than the surface roughness of the second base material.
　本発明に係る積層構造体のある特定の局面では、前記第３の層が、前記第３の組成物の光及び熱硬化物層である。 In a specific aspect of the laminated structure according to the present invention, the third layer is a light and thermosetting layer of the third composition.
　本発明に係る積層構造体のある特定の局面では、前記第２の層の厚みが、前記第３の層の厚みよりも厚い。 In a specific aspect of the laminated structure according to the present invention, the thickness of the second layer is thicker than the thickness of the third layer.
　本発明に係る積層構造体のある特定の局面では、前記第３の層の厚みが、０．１μｍ以上１０μｍ以下である。 In a specific aspect of the laminated structure according to the present invention, the thickness of the third layer is 0.1 μm or more and 10 μm or less.
　本発明に係る積層構造体のある特定の局面では、前記第１の層が、多官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第２の組成物の光硬化物層又は光及び熱硬化物層であり、前記第２の層が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第１の組成物の光硬化物層又は光及び熱硬化物層である。 In certain aspects of the laminated structure according to the present invention, the first layer contains a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. The composition is a photocurable layer or a light and thermosetting layer, and the second layer contains a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. The photocured material layer or the light and thermosetting material layer of the first composition.
　本発明の広い局面によれば、第１の組成物と第２の組成物とを有するインクジェット用組成物セットであり、前記第１の組成物が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含み、前記第２の組成物が、多官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含み、前記第１の組成物と前記第２の組成物とが異なる組成物である、インクジェット用組成物セットが提供される。 According to a broad aspect of the present invention, it is a composition set for inkjet having a first composition and a second composition, wherein the first composition is a monofunctional (meth) acrylate compound and an epoxy. The second composition comprises a compound, a photopolymerization initiator and a thermocuring agent, and the second composition comprises a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermocuring agent. , An epoxy composition set in which the first composition and the second composition are different compositions is provided.
　本発明に係るインクジェット用組成物セットのある特定の局面では、前記インクジェット用組成物セット第１の容器と、第２の容器とを有し、前記第１の容器に、前記第１の組成物が収容されており、前記第２の容器に、前記第２の組成物が収容されている。 In a specific aspect of the inkjet composition set according to the present invention, the inkjet composition set has a first container and a second container, and the first container is filled with the first composition. Is contained, and the second composition is contained in the second container.
　本発明に係る積層構造体の製造方法、積層構造体及びインクジェット用組成物セットでは、上記の構成が備えられているので、材料の漏れ出し防止性を高めることができる。 Since the method for producing a laminated structure, the laminated structure, and the composition set for inkjet according to the present invention have the above-mentioned configurations, it is possible to improve the material leakage prevention property.
図１（ａ）～（ｃ）は、本発明の第１の実施形態に係る積層構造体の製造方法の各工程を説明するための断面図である。1A to 1C are cross-sectional views for explaining each step of the method for manufacturing a laminated structure according to the first embodiment of the present invention. 図２（ｄ）～（ｆ）は、本発明の第１の実施形態に係る積層構造体の製造方法の各工程を説明するための断面図である。2 (d) to 2 (f) are cross-sectional views for explaining each step of the method for manufacturing a laminated structure according to the first embodiment of the present invention. 図３（ｇ），（ｈ）は、本発明の第１の実施形態に係る積層構造体の製造方法の各工程を説明するための断面図である。3 (g) and 3 (h) are cross-sectional views for explaining each step of the method for manufacturing a laminated structure according to the first embodiment of the present invention. 図４は、本発明の第１の実施形態に係る積層構造体の製造方法の各工程を説明するためのフローチャートである。FIG. 4 is a flowchart for explaining each step of the method for manufacturing a laminated structure according to the first embodiment of the present invention. 図５は、本発明の第２の実施形態に係る積層構造体の製造方法の各工程を説明するためのフローチャートである。FIG. 5 is a flowchart for explaining each step of the method for manufacturing a laminated structure according to a second embodiment of the present invention. 図６は、本発明の第２の実施形態に係る積層構造体の製造方法の各工程を説明するためのフローチャートである。FIG. 6 is a flowchart for explaining each step of the method for manufacturing a laminated structure according to a second embodiment of the present invention. 図７は、第２の実施形態に係る積層構造体の製造方法で製造された積層構造体の断面図である。FIG. 7 is a cross-sectional view of the laminated structure manufactured by the method for manufacturing the laminated structure according to the second embodiment. 図８は、本発明の第３の実施形態に係る積層構造体の製造方法の各工程を説明するためのフローチャートである。FIG. 8 is a flowchart for explaining each step of the method for manufacturing a laminated structure according to a third embodiment of the present invention. 図９は、本発明の第３の実施形態に係る積層構造体の製造方法の各工程を説明するためのフローチャートである。FIG. 9 is a flowchart for explaining each step of the method for manufacturing a laminated structure according to a third embodiment of the present invention. 図１０は、第３の実施形態に係る積層構造体の製造方法で製造された積層構造体の断面図である。FIG. 10 is a cross-sectional view of the laminated structure manufactured by the method for manufacturing the laminated structure according to the third embodiment. 図１１は、図１～３に示す積層構造体の製造方法において用いられる装置の一部の例を示す概略構成図である。FIG. 11 is a schematic configuration diagram showing an example of a part of the apparatus used in the method for manufacturing the laminated structure shown in FIGS. 1 to 3. 図１２は、図１～３に示す積層構造体の製造方法において用いられる装置の他の例を示す概略構成図である。FIG. 12 is a schematic configuration diagram showing another example of the apparatus used in the method for manufacturing the laminated structure shown in FIGS. 1 to 3. 図１３は、本発明の第１の実施形態に係るインクジェット用組成物セットを模式的に示す断面図である。FIG. 13 is a cross-sectional view schematically showing an inkjet composition set according to the first embodiment of the present invention. 図１４は、本発明の第１の実施形態に係る積層構造体を用いて得られる電子部品を示す断面図である。FIG. 14 is a cross-sectional view showing an electronic component obtained by using the laminated structure according to the first embodiment of the present invention.
　以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
　本発明に係る積層構造体の製造方法（１）は、第１の基材の表面上にインクジェット方式で塗布された第１の組成物に光を照射して、上記第１の組成物が光硬化した第１の光硬化物層を形成する第１の光硬化工程（第１の組成物用光硬化工程）を備える。本発明に係る積層構造体の製造方法（１）は、上記第１の光硬化物層の上記第１の基材側とは反対の表面側にインクジェット方式で塗布された第２の組成物に光を照射して、上記第２の組成物が光硬化した第２の光硬化物層を形成する第２の光硬化工程（第２の組成物用光硬化工程）を備える。 In the method (1) for producing a laminated structure according to the present invention, the first composition coated on the surface of the first base material by an inkjet method is irradiated with light, and the first composition is irradiated with light. The present invention includes a first photocuring step (a first photocuring step for a composition) for forming a cured first photocurable material layer. The method (1) for producing a laminated structure according to the present invention is applied to a second composition coated on the surface side of the first photocured material layer opposite to the first base material side by an inkjet method. The present invention comprises a second photocuring step (a photocuring step for a second composition) of irradiating light to form a second photocurable material layer in which the second composition is photocured.
　本発明に係る積層構造体の製造方法（２）は、第１の基材の表面上にインクジェット方式で塗布された第２の組成物に光を照射して、上記第２の組成物が光硬化した第２の光硬化物層を形成する第２の光硬化工程（第２の組成物用光硬化工程）を備える。本発明に係る積層構造体の製造方法（２）は、上記第２の光硬化物層を加熱して、上記第２の光硬化物層が熱硬化した第２の光及び熱硬化物層を形成する第２の光硬化物層用加熱工程を備えるか又は備えない。本発明に係る積層構造体の製造方法（２）は、上記第２の光硬化物層用加熱工程が備えられる場合に、上記第２の光及び熱硬化物層の上記第１の基材側とは反対の表面側にインクジェット方式で塗布された第１の組成物に光を照射して、上記第１の組成物が光硬化した第１の光硬化物層を形成する第１の光硬化工程（第１の組成物用光硬化工程）を備える。本発明に係る積層構造体の製造方法（２）は、上記第２の光硬化物層用加熱工程が備えられない場合に、上記第２の光硬化物層の上記第１の基材側とは反対の表面側にインクジェット方式で塗布された第１の組成物に光を照射して、上記第１の組成物が光硬化した第１の光硬化物層を形成する第１の光硬化工程（第１の組成物用光硬化工程）を備える。 In the method (2) for producing a laminated structure according to the present invention, the second composition coated on the surface of the first base material by an inkjet method is irradiated with light, and the second composition is irradiated with light. The present invention includes a second photocuring step (a second photocuring step for a composition) for forming a cured second photocurable material layer. In the method (2) for producing a laminated structure according to the present invention, the second photo-cured product layer is heated to heat the second photo-cured product layer and the second photo-cured product layer is heat-cured. A heating step for the second photocurable layer to be formed is provided or not provided. In the method (2) for producing a laminated structure according to the present invention, when the heating step for the second photocurable material layer is provided, the second light and the first base material side of the thermosetting material layer are provided. A first photocuring layer is formed by irradiating a first composition coated on the opposite surface side by an inkjet method with light to form a photocured first photocured product layer in which the first composition is photocured. A step (a first photocuring step for a composition) is provided. In the method (2) for producing a laminated structure according to the present invention, when the heating step for the second photocurable material layer is not provided, the method (2) is different from that of the first base material side of the second photocurable material layer. Is a first photocuring step of irradiating a first composition coated on the opposite surface side by an inkjet method with light to form a first photocurable layer in which the first composition is photocured. (The first photocuring step for the composition) is provided.
　本発明に係る積層構造体の製造方法（１），（２）では、上記第１の組成物が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含み、上記第２の組成物が、多官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む。本発明に係る積層構造体の製造方法（１），（２）では、上記第１の組成物と上記第２の組成物とが異なる組成物である。 In the methods (1) and (2) for producing a laminated structure according to the present invention, the first composition comprises a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. The second composition comprises a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. In the methods (1) and (2) for producing a laminated structure according to the present invention, the first composition and the second composition are different compositions.
　本発明に係る積層構造体の製造方法（１），（２）では、上記の構成が備えられているので、材料の漏れ出し防止性を高めることができる。 Since the above-mentioned configurations are provided in the methods (1) and (2) for manufacturing the laminated structure according to the present invention, it is possible to improve the material leakage prevention property.
　上記積層構造体の製造方法（１）は、第１の基材の表面上に第１の組成物をインクジェット方式で塗布する第１の塗布工程（第１の組成物用塗布工程）を備えることが好ましい。上記積層構造体の製造方法（１）は、上記第１の光硬化工程と上記第２の光硬化工程との間に、上記第１の光硬化物層の上記第１の基材側とは反対の表面側に第２の組成物をインクジェット方式で塗布する第２の塗布工程（第２の組成物用塗布工程）を備えることが好ましい。上記第２の塗布工程において、上記第１の光硬化物層の上記第１の基材側とは反対側の表面上に第２の組成物をインクジェット方式で塗布することが好ましい。上記第２の光硬化物層は、上記第１の光硬化物層と接することが好ましい。 The method (1) for manufacturing the laminated structure includes a first coating step (coating step for the first composition) of applying the first composition on the surface of the first base material by an inkjet method. Is preferable. In the method (1) for manufacturing the laminated structure, between the first photocuring step and the second photocuring step, the first base material side of the first photocurable layer is formed. It is preferable to provide a second coating step (coating step for the second composition) of coating the second composition on the opposite surface side by an inkjet method. In the second coating step, it is preferable to apply the second composition on the surface of the first photocurable material layer on the side opposite to the first base material side by an inkjet method. The second photocurable material layer is preferably in contact with the first photocurable material layer.
　上記積層構造体の製造方法（２）は、第１の基材の表面上に第２の組成物をインクジェット方式で塗布する第２の塗布工程（第２の組成物用塗布工程）を備えることが好ましい。上記積層構造体の製造方法（２）は、上記第２の光硬化工程と上記第１の光硬化工程との間に、上記第２の光硬化物層の上記第１の基材側とは反対の表面側に第１の組成物をインクジェット方式で塗布する第１の塗布工程（第１の組成物用塗布工程）を備えることが好ましい。上記第1の塗布工程において、上記第２の光硬化物層の上記第１の基材側とは反対側の表面上に第１の組成物をインクジェット方式で塗布することが好ましい。上記第１の光硬化物層は、上記第２の光硬化物層と接することが好ましい。 The method (2) for manufacturing the laminated structure includes a second coating step (coating step for the second composition) in which the second composition is coated on the surface of the first base material by an inkjet method. Is preferable. In the method (2) for manufacturing the laminated structure, between the second photocuring step and the first photocuring step, the first base material side of the second photocurable layer is formed. It is preferable to provide a first coating step (coating step for the first composition) for coating the first composition on the opposite surface side by an inkjet method. In the first coating step, it is preferable to apply the first composition on the surface of the second photocurable material layer on the side opposite to the first base material side by an inkjet method. The first photocurable material layer is preferably in contact with the second photocurable material layer.
　本明細書においては、上記第１の塗布工程と上記第１の光硬化工程とをまとめて、第１の光硬化物層形成工程（第１の組成物用光硬化物層形成工程）と称する。また、本明細書においては、上記第２の塗布工程と上記第２の光硬化工程とをまとめて、第２の光硬化物層形成工程（第２の組成物用光硬化物層形成工程）と称する。 In the present specification, the first coating step and the first photocuring step are collectively referred to as a first photocuring material layer forming step (first photocuring material layer forming step for composition). .. Further, in the present specification, the second coating step and the second photocuring step are collectively referred to as a second photocuring material layer forming step (second composition photocuring material layer forming step). It is called.
　したがって、上記積層構造体の製造方法（１）は、第１の基材の表面上に第１の組成物をインクジェット方式で塗布し、かつ、塗布された上記第１の組成物に光を照射して、上記第１の組成物が光硬化した第１の光硬化物層を形成する第１の光硬化物層形成工程を備えることが好ましい。上記積層構造体の製造方法（１）は、上記第１の光硬化物層の上記第１の基材側とは反対の表面側に第２の組成物をインクジェット方式で塗布し、かつ、塗布された上記第２の組成物に光を照射して、上記第２の組成物が光硬化した第２の光硬化物層を形成する第２の光硬化物層形成工程を備えることが好ましい。 Therefore, in the method (1) for producing the laminated structure, the first composition is coated on the surface of the first base material by an inkjet method, and the coated first composition is irradiated with light. Therefore, it is preferable to include a first photocurable material layer forming step in which the first composition forms a photocurable first photocurable material layer. In the method (1) for producing the laminated structure, the second composition is coated and applied by an inkjet method on the surface side of the first photocurable material layer opposite to the first base material side. It is preferable to include a second photocurable product layer forming step of irradiating the second composition with light to form a second photocurable material layer in which the second composition is photocured.
　また、上記積層構造体の製造方法（２）は、第１の基材の表面上に第２の組成物をインクジェット方式で塗布し、かつ、塗布された上記第２の組成物に光を照射して、上記第２の組成物が光硬化した第２の光硬化物層を形成する第２の光硬化物層形成工程を備えることが好ましい。上記積層構造体の製造方法（２）は、上記第２の光硬化物層の上記第１の基材側とは反対の表面側に第１の組成物をインクジェット方式で塗布し、かつ、塗布された上記第１の組成物に光を照射して、上記第１の組成物が光硬化した第１の光硬化物層を形成する第１の光硬化物層形成工程を備えることが好ましい。 Further, in the method (2) for manufacturing the laminated structure, the second composition is coated on the surface of the first base material by an inkjet method, and the coated second composition is irradiated with light. Therefore, it is preferable to include a second photocurable product layer forming step in which the second composition forms a photocurable second photocurable material layer. In the method (2) for producing the laminated structure, the first composition is coated and applied by an inkjet method on the surface side of the second photocurable material layer opposite to the first base material side. It is preferable that the first composition is irradiated with light to form a first photocurable layer in which the first composition is photocured.
　本発明に係る積層構造体は、第１の基材と、上記第１の基材の表面上に配置された第１の層と、上記第１の層の上記基材側とは反対側の表面上に配置された第２の層とを備える。本発明に係る積層構造体では、上記第１の層と上記第２の層との組合せが、以下の第１の組合せＡ、又は以下の組合せＢである。組合せＡ：上記第１の層が、単官能の（メタ）アクリレート化合物とエポキシ化合物と光重合開始剤と熱硬化剤とを含む第１の組成物の光硬化物層又は光及び熱硬化物層であり、上記第２の層が、多官能の（メタ）アクリレート化合物とエポキシ化合物と光重合開始剤と熱硬化剤とを含む第２の組成物の光硬化物層又は光及び熱硬化物層である。組合せＢ：上記第１の層が、多官能の（メタ）アクリレート化合物とエポキシ化合物と光重合開始剤と熱硬化剤とを含む第２の組成物の光硬化物層又は光及び熱硬化物層であり、かつ上記第２の層が、単官能の（メタ）アクリレート化合物とエポキシ化合物と光重合開始剤と熱硬化剤とを含む第１の組成物の光硬化物層又は光及び熱硬化物層である。本発明に係る積層構造体では、上記第１の組成物と上記第２の組成物とが異なる組成物である。 The laminated structure according to the present invention comprises a first base material, a first layer arranged on the surface of the first base material, and a side opposite to the base material side of the first layer. It comprises a second layer arranged on the surface. In the laminated structure according to the present invention, the combination of the first layer and the second layer is the following first combination A or the following combination B. Combination A: The first layer is a photocurable layer or a light and thermosetting layer of the first composition containing a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent. The second layer is a photocurable layer or a light and thermosetting layer of a second composition containing a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent. Is. Combination B: The first layer is a photocurable layer or a light and thermosetting layer of a second composition containing a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent. The second layer is a photocurable layer or a light and thermosetting product of the first composition containing a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent. It is a layer. In the laminated structure according to the present invention, the first composition and the second composition are different compositions.
　本発明に係る積層構造体では、上記の構成が備えられているので、材料の漏れ出し防止性を高めることができる。 Since the laminated structure according to the present invention has the above configuration, it is possible to improve the material leakage prevention property.
　本発明に係るインクジェット用組成物セットは、第１の組成物と第２の組成物とを有するインクジェット用組成物セットである。本発明に係るインクジェット用組成物セットでは、上記第１の組成物が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含み、上記第２の組成物が、多官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む。本発明に係るインクジェット用組成物セットでは、上記第１の組成物と上記第２の組成物とが異なる組成物である。 The inkjet composition set according to the present invention is an inkjet composition set having a first composition and a second composition. In the composition set for inkjet according to the present invention, the first composition contains a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent, and the second composition. The composition comprises a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. In the inkjet composition set according to the present invention, the first composition and the second composition are different compositions.
　本発明に係るインクジェット用組成物セットでは、上記の構成が備えられているので、材料の漏れ出し防止性を高めることができる。 Since the inkjet composition set according to the present invention has the above-mentioned structure, it is possible to improve the material leakage prevention property.
　本発明者らは、従来のインクジェット用組成物では、硬化物層の形状保持性が低いことがあり、材料が硬化物層の周辺に漏れ出すという課題を見出した。本発明者らは、特に、インクジェット用組成物が光硬化性組成物である場合に、インクジェット装置により塗布された組成物の表面において、空気中の酸素の影響により、光重合反応が阻害されやすいという課題を見出した。また、インクジェット用組成物の表面にゴミ等の粉体が付着すると、粉体が付着した部分において、光が十分に照射されず、光重合反応が十分に進行しないことがある。本発明者らは、このような場合、インクジェット用組成物が十分に硬化せず、硬化物層の形状保持性が低下しやすいという課題を見出した。 The present inventors have found that the shape retention of the cured product layer may be low in the conventional inkjet composition, and the material leaks to the periphery of the cured product layer. In particular, when the composition for inkjet is a photocurable composition, the present inventors are likely to inhibit the photopolymerization reaction due to the influence of oxygen in the air on the surface of the composition applied by the inkjet device. I found the problem. Further, when powder such as dust adheres to the surface of the inkjet composition, light may not be sufficiently irradiated at the portion where the powder adheres, and the photopolymerization reaction may not proceed sufficiently. The present inventors have found that in such a case, the composition for inkjet is not sufficiently cured, and the shape retention of the cured product layer tends to be deteriorated.
　さらに、本発明者らは、光反応性の高い化合物を含む組成物を単に用いた場合には、硬化収縮が大きくなるため、基材と硬化物層との接着力が低下しやすく、基材と硬化物層との間から、材料が漏れ出しやすいという課題を見出した。 Furthermore, when a composition containing a highly photoreactive compound is simply used, the present inventors have a large curing shrinkage, so that the adhesive force between the base material and the cured product layer tends to decrease, and the base material tends to decrease. We have found a problem that the material easily leaks from between the cured product layer and the cured product layer.
　またさらに、本発明者らは、従来のインクジェット用組成物では、組成の異なる硬化物層が積層された場合に、層間接着力を十分に高めることは困難であり、層間接着力の低い箇所から、材料が漏れ出しやすいことを見出した。 Furthermore, in the conventional inkjet composition, it is difficult for the present inventors to sufficiently increase the interlayer adhesive strength when cured product layers having different compositions are laminated, and the interlayer adhesive strength is low. , Found that the material is easy to leak.
　従来、基材と硬化物層との接着力を高める方法として、基材の表面を薬液により処理したり、基材の表面を物理的に傷つけたりして、基材の表面に凹凸を形成する方法、プライマー処理を行う方法が知られている。しかしながら、これらの方法では、インクジェット用組成物が塗布されない部分においても、基材の表面の性質が変化するため、例えば、部品を接続した場合に導電性が低下するなどの不具合が発生することがある。また、プライマーと硬化物層との接着強度が低下することがある。 Conventionally, as a method of increasing the adhesive force between the base material and the cured product layer, the surface of the base material is treated with a chemical solution or the surface of the base material is physically damaged to form irregularities on the surface of the base material. Methods and methods for performing primer treatment are known. However, in these methods, the surface properties of the base material change even in the portion where the inkjet composition is not applied, so that problems such as a decrease in conductivity when parts are connected may occur. be. In addition, the adhesive strength between the primer and the cured product layer may decrease.
　また、空気中の酸素の影響を少なくするために、窒素等で置換しながら組成物を塗布可能な装置の開発も検討されている。しかしながら、装置のサイズが大きくなったり、装置の費用が高くなったりする。 In addition, in order to reduce the influence of oxygen in the air, the development of a device capable of applying the composition while substituting with nitrogen or the like is also being considered. However, the size of the device becomes large and the cost of the device becomes high.
　本発明者が見出した新たな課題に対して、従来の方法では、材料の漏れ出し防止性を高めることは困難である。 For the new problem found by the present inventor, it is difficult to improve the material leakage prevention property by the conventional method.
　これに対して、本発明に係る積層構造体の製造方法、積層構造体及びインクジェット用組成物セットでは、基材の表面処理を行わなくても、また、窒素置換が可能な装置を用いなくても、第１の組成物及び第２の組成物が硬化した硬化物層の形状保持性を高めることができ、かつ、基材との接着力及び層間接着力を高めることができる。 On the other hand, in the method for producing a laminated structure, the laminated structure, and the composition set for inkjet according to the present invention, it is not necessary to perform surface treatment of the base material and to use an apparatus capable of nitrogen substitution. In addition, the shape retention of the cured product layer obtained by curing the first composition and the second composition can be enhanced, and the adhesive strength with the substrate and the interlayer adhesive strength can be enhanced.
　本発明に係る積層構造体の製造方法、積層構造体及びインクジェット用組成物セットでは、特定の第１の組成物と特定の第２の組成物とが用いられているので、第１の組成物及び第２の組成物が硬化した硬化物層の形状保持性を高めることができる。また、本発明に係る積層構造体の製造方法、積層構造体及びインクジェット用組成物セットでは、特定の第１の組成物と特定の第２の組成物とが用いられているので、基材と第１の組成物の硬化物層との接着力を高めることができ、かつ、第１の組成物の硬化物層と第２の組成物の硬化物層との層間接着力を高めることができる。 In the method for producing a laminated structure, the laminated structure, and the composition set for inkjet according to the present invention, since a specific first composition and a specific second composition are used, the first composition. And the shape retention of the cured product layer in which the second composition is cured can be enhanced. Further, in the method for producing a laminated structure, the laminated structure, and the composition set for inkjet according to the present invention, since the specific first composition and the specific second composition are used, the base material and the base material are used. The adhesive strength of the first composition to the cured product layer can be enhanced, and the interlayer adhesive strength between the cured product layer of the first composition and the cured product layer of the second composition can be enhanced. ..
　このため、本発明に係る積層構造体の製造方法、積層構造体及びインクジェット用組成物セットでは、基材と硬化物層との間などから、材料（例えば、金属層を形成するための材料及びアンダーフィル材等）が漏れ出しにくい。例えば、硬化物層で囲まれた領域の内側に材料を配置した場合に、該材料が該領域の内側から外側に漏れ出しにくい。また、例えば、硬化物層で囲まれた領域の外側に材料を配置した場合に、該材料が該領域の外側から内側に漏れ出しにくい。 Therefore, in the method for producing a laminated structure, the laminated structure, and the composition set for inkjet according to the present invention, a material (for example, a material for forming a metal layer and a material for forming a metal layer) may be formed from between a base material and a cured product layer. Underfill material, etc.) does not easily leak out. For example, when the material is arranged inside the region surrounded by the cured product layer, the material is unlikely to leak from the inside to the outside of the region. Further, for example, when the material is arranged outside the region surrounded by the cured product layer, the material is unlikely to leak from the outside to the inside of the region.
　本発明に係る積層構造体の製造方法、積層構造体及びインクジェット用組成物セットでは、第１の組成物及び第２の組成物の光硬化物層、並びに、光及び熱硬化物層の形状保持性を高めることができる。 In the method for producing a laminated structure, the laminated structure, and the composition set for inkjet according to the present invention, the shapes of the photocurable material layer of the first composition and the second composition, and the light and thermosetting material layer are maintained. It can enhance the sex.
　また、本発明に係る積層構造体の製造方法、積層構造体及びインクジェット用組成物セットでは、硬化物層の強度を良好にすることができるため、硬化物層の傷つきを効果的に抑えることができ、また、硬化物層にゴミ等の粉体が付着することを効果的に抑えることができる。 Further, in the method for producing a laminated structure, the laminated structure and the composition set for inkjet according to the present invention, the strength of the cured product layer can be improved, so that damage to the cured product layer can be effectively suppressed. In addition, it is possible to effectively prevent powder such as dust from adhering to the cured product layer.
　（積層構造体の製造方法）
　以下、図面を参照しつつ、本発明の具体的な実施形態を説明する。なお、以下の図面において、大きさ、厚み、及び形状等は、図示の便宜上、実際の大きさ、厚み、及び形状等と異なる場合がある。 (Manufacturing method of laminated structure)
Hereinafter, specific embodiments of the present invention will be described with reference to the drawings. In the drawings below, the size, thickness, shape, etc. may differ from the actual size, thickness, shape, etc. for convenience of illustration.
　図１（ａ）～（ｃ）、図２（ｄ）～（ｆ）及び図３（ｇ），（ｈ）は、本発明の第１の実施形態に係る積層構造体の製造方法の各工程を説明するための断面図である。図４は、本発明の第１の実施形態に係る積層構造体の製造方法の各工程を説明するためのフローチャートである。図１～４における第１の実施形態に係る積層構造体の製造方法は、上記積層構造体の製造方法（１）である。 1 (a) to (c), FIGS. 2 (d) to (f), and FIGS. 3 (g) and 3 (h) are steps of the method for manufacturing a laminated structure according to the first embodiment of the present invention. It is sectional drawing for demonstrating. FIG. 4 is a flowchart for explaining each step of the method for manufacturing a laminated structure according to the first embodiment of the present invention. The method for manufacturing the laminated structure according to the first embodiment in FIGS. 1 to 4 is the method for manufacturing the laminated structure (1).
　図１～３では、積層構造体を製造するために、ステージ１１と、第１の吐出部１２と、第１の光照射部１３と、第２の吐出部１４と、第２の光照射部１５とを備える装置１０が用いられている。第１の吐出部１２は、第１の組成物を吐出するための部材であり、インクジェットヘッドである。第２の吐出部１４は、第２の組成物を吐出するための部材であり、インクジェットヘッドである。したがって、装置１０は、インクジェット装置である。第１の吐出部１２と、第２の吐出部１４との間に、第１の光照射部１３が配置されている。第２の吐出部１４の第１の光照射部１３側とは反対側に、第２の光照射部１５が配置されている。第１の光照射部１３及び第２の光照射部１５は、紫外線を照射可能である。 In FIGS. 1 to 3, in order to manufacture the laminated structure, the stage 11, the first discharge unit 12, the first light irradiation unit 13, the second discharge unit 14, and the second light irradiation unit are shown. A device 10 including 15 is used. The first ejection unit 12 is a member for ejecting the first composition and is an inkjet head. The second ejection unit 14 is a member for ejecting the second composition and is an inkjet head. Therefore, the device 10 is an inkjet device. A first light irradiation unit 13 is arranged between the first discharge unit 12 and the second discharge unit 14. The second light irradiation unit 15 is arranged on the side of the second discharge unit 14 opposite to the first light irradiation unit 13 side. The first light irradiation unit 13 and the second light irradiation unit 15 can irradiate ultraviolet rays.
　＜第１の光硬化物層形成工程（図４のＳ１及びＳ２）＞
　まず、図１（ａ）に示すように、ステージ１１の表面上に第１の基材３を配置する。第１の基材３は、ステージ１１の表面上に固定されている。第１の基材３は、ステージ１１に吸着している。次いで、インクジェット方式で、第１の基材３の表面上に、第１の組成物１を塗布する（第１の塗布工程）。第１の吐出部１２から、第１の組成物１を塗布する。第１の組成物１は、第１の基材３の所定の位置に塗布されている。第１の組成物１は、第１の基材３の表面上に、部分的に塗布されている。 <First photocurable layer forming step (S1 and S2 in FIG. 4)>
First, as shown in FIG. 1A, the first base material 3 is arranged on the surface of the stage 11. The first base material 3 is fixed on the surface of the stage 11. The first base material 3 is adsorbed on the stage 11. Next, the first composition 1 is applied onto the surface of the first base material 3 by an inkjet method (first coating step). The first composition 1 is applied from the first discharge portion 12. The first composition 1 is applied to a predetermined position of the first base material 3. The first composition 1 is partially coated on the surface of the first base material 3.
　次に、図１（ｂ）に示すように、塗布された第１の組成物１が、第１の光照射部１３の下方に位置するまで、ステージ１１を移動する。ステージ１１に代えて、インクジェット装置を移動してもよい。第１の組成物１に、第１の光照射部１３から光（紫外線）を照射し、第１の組成物が光硬化した第１の光硬化物層１Ａを形成する（第１の光硬化工程）。 Next, as shown in FIG. 1 (b), the stage 11 is moved until the applied first composition 1 is located below the first light irradiation unit 13. The inkjet device may be moved instead of the stage 11. The first composition 1 is irradiated with light (ultraviolet rays) from the first light irradiation unit 13 to form a first photocurable product layer 1A in which the first composition is photocured (first photocuring). Process).
　上記第１の光硬化工程後、第１の光硬化物層形成工程を繰り返すか否か判断する（図４のＳ３）。上記第１の光硬化物層形成工程が繰り返される場合には、形成された第１の光硬化物層の第１の基材側とは反対の表面側に第１の組成物が塗布される。 After the first photocuring step, it is determined whether or not to repeat the first photocuring layer forming step (S3 in FIG. 4). When the first photocurable layer forming step is repeated, the first composition is applied to the surface side of the formed first photocurable layer opposite to the first base material side. ..
　＜第２の光硬化物層形成工程（図４のＳ４及びＳ５）＞
　次に、図１（ｃ）に示すように、第１の光硬化物層１Ａが、第２の吐出部１４の下方に位置するまで、ステージ１１を移動する。ステージ１１に代えて、インクジェット装置を移動してもよい。インクジェット方式で、第１の光硬化物層１Ａの第１の基材３側とは反対の表面側に第２の組成物２を塗布する（第２の塗布工程）。第２の吐出部１４から、第２の組成物２を塗布する。 <Second photocurable layer forming step (S4 and S5 in FIG. 4)>
Next, as shown in FIG. 1 (c), the stage 11 is moved until the first photocurable product layer 1A is located below the second discharge portion 14. The inkjet device may be moved instead of the stage 11. The second composition 2 is applied to the surface side of the first photocured material layer 1A opposite to the first base material 3 side by an inkjet method (second coating step). The second composition 2 is applied from the second discharge portion 14.
　次に、図２（ｄ）に示すように、塗布された第２の組成物２が、第２の光照射部１５の下方に位置するまで、ステージ１１を移動する。ステージ１１に代えて、インクジェット装置を移動してもよい。第２の組成物２に、第２の光照射部１５から光（紫外線）を照射し、第２の組成物が光硬化した第２の光硬化物層２Ａを形成する（第２の光硬化工程）。 Next, as shown in FIG. 2D, the stage 11 is moved until the applied second composition 2 is located below the second light irradiation unit 15. The inkjet device may be moved instead of the stage 11. The second composition 2 is irradiated with light (ultraviolet rays) from the second light irradiation unit 15 to form a second photocurable product layer 2A in which the second composition is photocured (second photocuring). Process).
　上記第２の光硬化工程後、第２の光硬化物層形成工程を繰り返すか否か判断する（図４のＳ６）。上記第２の光硬化物層形成工程が繰り返される場合には、形成された第２の光硬化物層の第１の基材側とは反対の表面側に第２の組成物が塗布される。 After the second photocuring step, it is determined whether or not to repeat the second photocuring layer forming step (S6 in FIG. 4). When the second photocurable layer forming step is repeated, the second composition is applied to the surface side of the formed second photocurable layer opposite to the first base material side. ..
　図２（ｅ），（ｆ）は、２回目の第２の光硬化物層形成工程を示す図である。図２（ｅ）に示すように、第２の光硬化物層２Ａが、第２の吐出部１４の下方に位置するまで、ステージ１１を移動する。ステージ１１に代えて、インクジェット装置を移動してもよい。インクジェット方式で、第２の光硬化物層２Ａの第１の基材３側とは反対の表面上に第２の組成物２を塗布する。すなわち、第１の光硬化物層１Ａの第１の基材３側とは反対の表面側に第２の組成物２を塗布する（第２の塗布工程）。第２の吐出部１４から、第２の組成物２を塗布する。 FIGS. 2 (e) and 2 (f) are diagrams showing the second second photocurable layer forming step. As shown in FIG. 2E, the stage 11 is moved until the second photocurable material layer 2A is located below the second discharge portion 14. The inkjet device may be moved instead of the stage 11. The second composition 2 is applied on the surface of the second photocurable material layer 2A opposite to the first base material 3 side by an inkjet method. That is, the second composition 2 is applied to the surface side of the first photocurable material layer 1A opposite to the first base material 3 side (second coating step). The second composition 2 is applied from the second discharge portion 14.
　次に、図２（ｆ）に示すように、塗布された第２の組成物２が、第２の光照射部１５の下方に位置するまで、ステージ１１を移動する。ステージ１１に代えて、インクジェット装置を移動してもよい。第２の組成物２に、第２の光照射部１５から光（紫外線）を照射し、第２の組成物が光硬化した第２の光硬化物層２Ａを形成する（第２の光硬化工程）。 Next, as shown in FIG. 2 (f), the stage 11 is moved until the applied second composition 2 is located below the second light irradiation unit 15. The inkjet device may be moved instead of the stage 11. The second composition 2 is irradiated with light (ultraviolet rays) from the second light irradiation unit 15 to form a second photocurable product layer 2A in which the second composition is photocured (second photocuring). Process).
　上記第２の光硬化物層形成工程は、第１の光硬化物層の厚み方向にて、図１（ｃ）及び図２（ｄ）と、図２（ｅ）と図２（ｆ）との２回行われている。上記第２の光硬化物層形成工程を、第１の光硬化物層の厚み方向にて複数回行うことにより、第２の光硬化物層の厚みを大きくすることができる。上記第２の光硬化物層形成工程は、２回以上行われてもよく、３回以上行われてもよい。 In the second photocurable layer forming step, in the thickness direction of the first photocurable layer, FIGS. 1 (c) and 2 (d), and FIGS. 2 (e) and 2 (f). It has been done twice. By performing the second photocurable material layer forming step a plurality of times in the thickness direction of the first photocurable material layer, the thickness of the second photocurable material layer can be increased. The second photocurable layer forming step may be performed twice or more, or may be performed three or more times.
　上記第２の光硬化物層形成工程を、第１の光硬化物層の厚み方向にて、さらに複数回行うことにより、図３（ｇ）に示すように、第１の基材３と、第１の光硬化物層１Ａと、第２の光硬化物層２Ａとを備え、第２の光硬化物層２Ａの厚みが、第１の光硬化物層１Ａの厚みよりも大きい積層構造体４Ａを得ることができる。 By performing the second photocurable layer forming step a plurality of times in the thickness direction of the first photocurable layer, as shown in FIG. 3 (g), the first base material 3 and the first base material 3 A laminated structure including a first photo-cured product layer 1A and a second photo-cured product layer 2A, in which the thickness of the second photo-cured product layer 2A is larger than the thickness of the first photo-cured product layer 1A. 4A can be obtained.
　＜第１及び第２の光硬化物層用加熱工程（図４のＳ７）＞
　次に、第１の光硬化物層１Ａ及び第２の光硬化物層２Ａを加熱して、第１の光硬化物層１Ａが熱硬化した第１の光及び熱硬化物層１Ｂ、並びに、第２の光硬化物層２Ａが熱硬化した第２の光及び熱硬化物層２Ｂを形成する（第１及び第２の光硬化物層用加熱工程）。 <Heating steps for the first and second photocurable layer (S7 in FIG. 4)>
Next, the first photo-cured product layer 1A and the second photo-cured product layer 2A are heated, and the first photo-cured product layer 1A is heat-cured, and the first light and thermosetting product layer 1B, and The second photo-cured product layer 2A forms a second photo-cured product layer 2B that has been heat-cured (heating steps for the first and second photo-cured product layers).
　このようにして、第１の基材３と、第１の光及び熱硬化物層１Ｂと、第２の光及び熱硬化物層２Ｂとを備える積層構造体４Ｂを得ることができる。 In this way, a laminated structure 4B including the first base material 3, the first light and thermosetting layer 1B, and the second light and thermosetting layer 2B can be obtained.
　図５，６は、本発明の第２の実施形態に係る積層構造体の製造方法の各工程を説明するためのフローチャートである。第２の実施形態に係る積層構造体の製造方法は、積層構造体の製造方法（１）である。図７は、第２の実施形態に係る積層構造体の製造方法で製造された積層構造体の断面図である。 5 and 6 are flowcharts for explaining each step of the method for manufacturing a laminated structure according to the second embodiment of the present invention. The method for manufacturing a laminated structure according to the second embodiment is the method for manufacturing a laminated structure (1). FIG. 7 is a cross-sectional view of the laminated structure manufactured by the method for manufacturing the laminated structure according to the second embodiment.
　＜第１の光硬化物層形成工程（図５のＳ１及びＳ２）＞
　第２の実施形態に係る積層構造体の製造方法では、上記第１の実施形態に係る積層構造体の製造方法における第１の光硬化物層形成工程（図１（ａ），（ｂ））と同様にして、第１の光硬化物層形成工程が行われている。 <First photocurable layer forming step (S1 and S2 in FIG. 5)>
In the method for producing a laminated structure according to the second embodiment, the first photocurable layer forming step in the method for producing a laminated structure according to the first embodiment (FIGS. 1A and 1B). In the same manner as above, the first photocurable material layer forming step is performed.
　上記第１の光硬化工程後、第１の光硬化物層形成工程を繰り返すか否か判断する（図５のＳ３）。上記第１の光硬化物層形成工程が繰り返される場合には、形成された第１の光硬化物層の第１の基材側とは反対の表面側に第１の組成物が塗布される。 After the first photocuring step, it is determined whether or not to repeat the first photocuring layer forming step (S3 in FIG. 5). When the first photocurable layer forming step is repeated, the first composition is applied to the surface side of the formed first photocurable layer opposite to the first base material side. ..
　＜第２の光硬化物層形成工程（図５のＳ４及びＳ５）＞
　第２の実施形態に係る積層構造体の製造方法では、上記第１の実施形態に係る積層構造体の製造方法における第２の光硬化物層形成工程（図１（ｃ），（ｄ））と同様にして、第２の光硬化物層形成工程が行われている。 <Second photocurable layer forming step (S4 and S5 in FIG. 5)>
In the method for producing a laminated structure according to the second embodiment, the second photocurable layer forming step in the method for producing a laminated structure according to the first embodiment (FIGS. 1 (c) and 1 (d)). In the same manner as above, the second photocurable material layer forming step is performed.
　上記第２の光硬化工程後、第２の光硬化物層形成工程を繰り返すか否か判断する（図５のＳ６）。上記第２の光硬化物層形成工程が繰り返される場合には、形成された第２の光硬化物層の第１の基材側とは反対の表面側に第２の組成物が塗布される。 After the second photocuring step, it is determined whether or not to repeat the second photocuring layer forming step (S6 in FIG. 5). When the second photocurable layer forming step is repeated, the second composition is applied to the surface side of the formed second photocurable layer opposite to the first base material side. ..
　＜第１及び第２の光硬化物層用加熱工程（図６のＳ８）＞
　上記第２の光硬化工程後、第１及び第２の光硬化物層用加熱工程を行うか否か判断する（図６のＳ７）。第１及び第２の光硬化物層用加熱工程を行う場合には、第１の光硬化物層及び第２の光硬化物層を加熱して、第１の光硬化物層が熱硬化した第１の光及び熱硬化物層、並びに、第２の光硬化物層が熱硬化した第２の光及び熱硬化物層を形成する（第１及び第２の光硬化物層用加熱工程）。 <Heating steps for the first and second photocurable layer (S8 in FIG. 6)>
After the second photocuring step, it is determined whether or not to perform the first and second heating steps for the photocured material layer (S7 in FIG. 6). When the heating steps for the first and second photocurable material layers are performed, the first photocurable material layer and the second photocurable material layer are heated, and the first photocurable material layer is thermoset. The first light and thermosetting layer and the second photocurable layer form a second light and thermosetting layer that has been heat-cured (heating steps for the first and second photocurable layers). ..
　第１及び第２の光硬化物層用加熱工程を行うことにより、第１の基材と、第１の光及び熱硬化物層と、第２の光及び熱硬化物層とを備える積層構造体を得ることができる。 A laminated structure including a first base material, a first light and thermosetting layer, and a second light and thermosetting layer by performing the heating steps for the first and second photocurable layers. You can get a body.
　＜平坦化処理工程（図６のＳ１０）＞
　上記第１及び第２の光硬化物層用加熱工程を行う場合に、上記第１及び第２の光硬化物層用加熱工程後に、平坦化処理工程を行うか否か判断する（図６のＳ９）。上記第１及び第２の光硬化物層用加熱工程を行わない場合に、上記第２の光硬化工程後に、平坦化処理工程を行うか否か判断する（図６のＳ９）。本実施形態では、平坦化処理として、研磨処理を行うか否かを判断する。 <Flatification process (S10 in FIG. 6)>
When the first and second photocurable layer heating steps are performed, it is determined whether or not the flattening treatment step is performed after the first and second photocurable layer heating steps (FIG. 6). S9). When the first and second photocurable layer heating steps are not performed, it is determined whether or not the flattening treatment step is performed after the second photocuring step (S9 in FIG. 6). In the present embodiment, it is determined whether or not the polishing process is performed as the flattening process.
　上記第１及び第２の光硬化物層用加熱工程を行い、かつ上記平坦化処理工程を行う場合には、上記第１及び第２の光硬化物層用加熱工程後に、上記第２の光及び熱硬化物層の上記第１の基材側とは反対の表面を平坦化処理する（平坦化処理工程）。上記第１及び第２の光硬化物層用加熱工程を行わず、かつ上記平坦化処理工程を行う場合には、上記第２の光硬化物層の上記第１の基材側とは反対の表面を平坦化処理する（平坦化処理工程）。 When the first and second heating steps for the photocurable material layer are performed and the flattening treatment step is performed, the second light after the first and second heating steps for the photocurable material layer is performed. And the surface of the thermosetting layer opposite to the first base material side is flattened (flattening treatment step). When the heating step for the first and second photocurable material layers is not performed and the flattening treatment step is performed, the second photocurable material layer is opposite to the first base material side. The surface is flattened (flattening step).
　＜第３の光硬化物層形成工程（図６のＳ１１及びＳ１２）＞
　上記第１の光硬化物層形成工程又は上記第２の光硬化物層形成工程と同様の方法にて、上記第３の組成物を用いて第３の光硬化物層形成工程を行う。 <Third photocurable layer forming step (S11 and S12 in FIG. 6)>
A third photocurable layer forming step is performed using the third composition in the same manner as in the first photocurable layer forming step or the second photocured layer forming step.
　上記第１及び第２の光硬化物層用加熱工程を行う場合に、第２の光及び熱硬化物層の上記第１の基材側とは反対の表面上に第３の組成物をインクジェット方式で塗布する（第３の塗布工程（第３の組成物用塗布工程））。上記第１及び第２の光硬化物層用加熱工程を行わない場合に、第２の光硬化物層の上記第１の基材側とは反対の表面上に第３の組成物をインクジェット方式で塗布する（第３の塗布工程（第３の組成物用塗布工程））。インクジェット装置が備える所定の吐出部から、第３の組成物を塗布する。なお、第１の組成物と第３の組成物とが同一の組成物である場合には、第３の塗布工程においては、実質的に、第２の光及び熱硬化物層又は第２の光硬化物層の上記第１の基材側とは反対の表面上に第１の組成物をインクジェット方式で塗布することになる。 When the heating steps for the first and second photocurable material layers are performed, the third composition is inkjetd on the surface of the second light and thermosetting material layer opposite to the first base material side. Apply by the method (third coating step (third coating step for composition)). When the heating steps for the first and second photocurable material layers are not performed, the third composition is inkjet-processed on the surface of the second photocurable material layer opposite to the first base material side. (Third coating step (third coating step for composition)). The third composition is applied from a predetermined ejection portion provided in the inkjet device. When the first composition and the third composition are the same composition, in the third coating step, substantially, the second light and thermosetting layer or the second The first composition is coated on the surface of the photocured material layer opposite to the first base material side by an inkjet method.
　次に、第３の組成物に、インクジェット装置が備える所定の光照射部から光（紫外線）を照射し、第３の組成物が光硬化した第３の光硬化物層を形成する（第３の光硬化工程（第３の組成物用光硬化工程））。第１の組成物と第３の組成物とが同一の組成物である場合には、第３の光硬化工程においては、実質的に、インクジェット装置が備える所定の光照射部から光（紫外線）を照射し、第１の組成物が光硬化した第３の光硬化物層を形成することになる。 Next, the third composition is irradiated with light (ultraviolet rays) from a predetermined light irradiation unit included in the inkjet device to form a third photocurable product layer in which the third composition is photocured (third). (Photo-curing step for the third composition). When the first composition and the third composition are the same composition, in the third photocuring step, substantially light (ultraviolet rays) is emitted from a predetermined light irradiation portion included in the inkjet device. Will be irradiated to form a third photocurable layer in which the first composition is photocured.
　上記第３の光硬化工程後、第３の光硬化物層形成工程を繰り返すか否か判断する（図６のＳ１３）。上記第３の光硬化物層形成工程が繰り返される場合には、形成された第３の光硬化物層の第１の基材側とは反対の表面側に第３の組成物が塗布される。 After the third photocuring step, it is determined whether or not to repeat the third photocuring layer forming step (S13 in FIG. 6). When the third photocurable layer forming step is repeated, the third composition is applied to the surface side of the formed third photocurable layer opposite to the first base material side. ..
　なお、明細書においては、上記第３の塗布工程と上記第３の光硬化工程とをまとめて、第３の光硬化物層形成工程（第３の組成物用光硬化物層形成工程）と称する。 In the specification, the third coating step and the third photocuring step are collectively referred to as a third photocuring material layer forming step (third composition photocuring material layer forming step). Refer to.
　＜配置工程（図６のＳ１４）＞
　上記第３の光硬化物層形成工程後に、上記第３の光硬化物層の上記第１の基材側とは反対の表面上に、第２の基材を配置する（配置工程）。 <Arrangement process (S14 in FIG. 6)>
After the third photocurable material layer forming step, the second base material is placed on the surface of the third photocurable material layer opposite to the first base material side (placement step).
　＜第３の光硬化物層用加熱工程、又は、第１、第２及び第３の光硬化物層用加熱工程（図６のＳ１５）＞
　上記第１及び第２の光硬化物層用加熱工程を行う場合に、上記配置工程後に、上記第３の光硬化物層を加熱して、第３の光及び熱硬化物層を形成する（第３の光硬化物層用加熱工程）。上記第１及び第２の光硬化物層用加熱工程を行わない場合に、上記配置工程後に、上記第１の光硬化物層、上記第２の光硬化物層及び上記第３の光硬化物層を加熱して、第１の光及び熱硬化物層、第２の光及び熱硬化物層、並びに、第３の光及び熱硬化物層を形成する（第１、第２及び第３の光硬化物層用加熱工程）。上記第１の光及び熱硬化物層は、上記第１の光硬化物層が熱硬化した層である。上記第２の光及び熱硬化物層は、上記第２の光硬化物層が熱硬化した層である。上記第３の光及び熱硬化物層は、上記第３の光硬化物層が熱硬化した層である。 <Third heating step for the photocurable material layer or the first, second and third heating steps for the photocurable material layer (S15 in FIG. 6)>
When the first and second photocurable material layer heating steps are performed, after the arrangement step, the third photocurable material layer is heated to form a third light and thermosetting material layer (). Third heating step for the photocurable layer). When the heating steps for the first and second photocurable material layers are not performed, the first photocurable material layer, the second photocurable material layer and the third photocurable product after the arrangement step are performed. The layers are heated to form a first light and thermosetting layer, a second light and thermosetting layer, and a third light and thermosetting layer (first, second and third). Heating process for photocurable layer). The first light and thermosetting layer is a layer obtained by thermosetting the first photocuring layer. The second light and thermosetting layer is a layer obtained by thermosetting the second photocuring layer. The third light and thermosetting layer is a layer obtained by thermosetting the third photocuring layer.
　このようにして、図７に示すように、第１の基材３と、第１の光及び熱硬化物層１Ｄと、第２の光及び熱硬化物層２Ｄと、第３の光及び熱硬化物層６Ｄと、第２の基材７とをこの順で備える積層構造体４Ｄを得ることができる。 In this way, as shown in FIG. 7, the first base material 3, the first light and thermosetting layer 1D, the second light and thermosetting layer 2D, and the third light and heat. A laminated structure 4D including the cured product layer 6D and the second base material 7 in this order can be obtained.
　図８，９は、本発明の第３の実施形態に係る積層構造体の製造方法の各工程を説明するためのフローチャートである。第３の実施形態に係る積層構造体の製造方法は、積層構造体の製造方法（２）である。図１０は、第３の実施形態に係る積層構造体の製造方法で製造された積層構造体の断面図である。 8 and 9 are flowcharts for explaining each step of the method for manufacturing a laminated structure according to a third embodiment of the present invention. The method for manufacturing a laminated structure according to a third embodiment is the method for manufacturing a laminated structure (2). FIG. 10 is a cross-sectional view of the laminated structure manufactured by the method for manufacturing the laminated structure according to the third embodiment.
　＜第２の光硬化物層形成工程（図８のＳ１及びＳ２）＞
　第３の実施形態に係る積層構造体の製造方法では、第１の基材の表面上に第２の組成物を塗布すること以外は、上記第１の実施形態に係る積層構造体の製造方法における第２の光硬化物層形成工程（図１（ｃ），（ｄ））と同様にして、第２の光硬化物層形成工程が行われている。 <Second photocurable layer forming step (S1 and S2 in FIG. 8)>
In the method for producing a laminated structure according to a third embodiment, the method for producing a laminated structure according to the first embodiment is described except that the second composition is applied on the surface of the first base material. In the same manner as the second photocurable material layer forming step (FIGS. 1 (c) and 1 (d)) in the above, the second photocured material layer forming step is performed.
　具体的には、インクジェット方式で、第１の基材の表面上に、第２の組成物を塗布する（第２の塗布工程）。第２の組成物は、第１の基材の所定の位置に塗布される。第２の組成物は、第１の基材の表面上に、部分的に塗布される。 Specifically, the second composition is applied onto the surface of the first base material by an inkjet method (second coating step). The second composition is applied in place on the first substrate. The second composition is partially applied onto the surface of the first substrate.
　次に、塗布された第２の組成物に、光（紫外線）を照射し、第２の組成物が光硬化した第２の光硬化物層を形成する（第２の光硬化工程）。 Next, the applied second composition is irradiated with light (ultraviolet rays) to form a second photocurable product layer in which the second composition is photocured (second photocuring step).
　上記第２の光硬化工程後、第２の光硬化物層形成工程を繰り返すか否か判断する（図８のＳ３）。上記第２の光硬化物層形成工程が繰り返される場合には、形成された第２の光硬化物層の第１の基材側とは反対の表面側に第２の組成物が塗布される。 After the second photocuring step, it is determined whether or not to repeat the second photocuring layer forming step (S3 in FIG. 8). When the second photocurable layer forming step is repeated, the second composition is applied to the surface side of the formed second photocurable layer opposite to the first base material side. ..
　＜第２の光硬化物層用加熱工程（図８のＳ５）＞
　上記第２の光硬化工程後、第２の光硬化物層用加熱工程を行うか否か判断する（図８のＳ４）。第２の光硬化物層用加熱工程を行う場合には、第２の光硬化物層を加熱して、第２の光硬化物層が熱硬化した第２の光及び熱硬化物層を形成する（第２の光硬化物層用加熱工程）。 <The second heating step for the photocurable material layer (S5 in FIG. 8)>
After the second photocuring step, it is determined whether or not to perform the second heating step for the photocured material layer (S4 in FIG. 8). When the heating step for the second photocurable material layer is performed, the second photocurable material layer is heated to form a second light and thermosetting material layer in which the second photocurable material layer is heat-cured. (Second heating step for the photocurable material layer).
　＜平坦化処理工程（図９のＳ７）＞
　上記第２の光硬化物層用加熱工程を行う場合に、上記第２の光硬化物層用加熱工程後に、平坦化処理工程を行うか否か判断する（図９のＳ６）。上記第２の光硬化物層用加熱工程を行わない場合に、上記第２の光硬化工程後に、平坦化処理工程を行うか否か判断する（図９のＳ６）。 <Flatification process (S7 in FIG. 9)>
When the second heating step for the photocurable material layer is performed, it is determined whether or not the flattening treatment step is performed after the second heating step for the photocured material layer (S6 in FIG. 9). When the second photocuring layer heating step is not performed, it is determined whether or not the flattening treatment step is performed after the second photocuring step (S6 in FIG. 9).
　上記第２の光硬化物層用加熱工程を行い、かつ上記平坦化処理工程を行う場合には、上記第２の光硬化物層用加熱工程後に、上記第２の光及び熱硬化物層の上記第１の基材側とは反対の表面を平坦化処理する（平坦化処理工程（第２の光及び熱硬化物層用平坦化処理工程））。上記第２の光硬化物層用加熱工程を行わず、かつ上記平坦化処理工程を行う場合には、上記第２の光硬化物層の上記第１の基材側とは反対の表面を平坦化処理する（平坦化処理工程（第２の光硬化物層用平坦化処理工程））。 When the heating step for the second photocurable material layer is performed and the flattening treatment step is performed, after the heating step for the second photocurable material layer, the second light and the thermosetting material layer The surface opposite to the first base material side is flattened (flattening treatment step (second light and thermosetting layer flattening treatment step)). When the heating step for the second photo-cured product layer is not performed and the flattening treatment step is performed, the surface of the second photo-cured product layer opposite to the first base material side is flattened. The flattening treatment (flattening treatment step (second flattening treatment step for the photocurable material layer)).
　＜第１の光硬化物層形成工程（図９のＳ８及びＳ９）＞
　上記第２の光硬化物層用加熱工程を行う場合に、インクジェット方式で、第２の光及び熱硬化物層の第１の基材側とは反対の表面側に第１の組成物を塗布する（第１の塗布工程）。上記第２の光硬化物層用加熱工程を行わない場合に、インクジェット方式で、第２の光硬化物層の第１の基材側とは反対の表面側に第１の組成物を塗布する（第１の塗布工程）。 <First photocurable layer forming step (S8 and S9 in FIG. 9)>
When the heating step for the second photocurable material layer is performed, the first composition is applied to the surface side of the second light and the thermosetting material layer opposite to the first base material side by an inkjet method. (First coating step). When the heating step for the second photocurable material layer is not performed, the first composition is applied to the surface side of the second photocurable material layer opposite to the first base material side by an inkjet method. (First coating step).
　次に、上記第２の光硬化物層用加熱工程を行う場合に、上記第２の光及び熱硬化物層の上記第１の基材側とは反対の表面側にインクジェット方式で塗布された第１の組成物に光を照射して、前記第１の組成物が光硬化した第１の光硬化物層を形成する（第１の光硬化工程）。上記第２の光硬化物層用加熱工程を行わない場合に、上記第２の光硬化物層の上記第１の基材側とは反対の表面側にインクジェット方式で塗布された第１の組成物に光を照射して、前記第１の組成物が光硬化した第１の光硬化物層を形成する（第１の光硬化工程）。 Next, when the heating step for the second photocurable material layer was performed, the second light and the thermosetting material layer were coated on the surface side opposite to the first base material side by an inkjet method. The first composition is irradiated with light to form a first photo-cured product layer in which the first composition is photo-cured (first photo-curing step). When the heating step for the second photocurable material layer is not performed, the first composition is applied by an inkjet method to the surface side of the second photocurable material layer opposite to the first base material side. By irradiating an object with light, the first composition forms a photo-cured first photo-cured product layer (first photo-curing step).
　上記第１の光硬化工程後、第１の光硬化物層形成工程を繰り返すか否か判断する（図９のＳ１０）。上記第１の光硬化物層形成工程が繰り返される場合には、形成された第１の光硬化物層の第１の基材側とは反対の表面側に第１の組成物が塗布される。 After the first photocuring step, it is determined whether or not to repeat the first photocuring layer forming step (S10 in FIG. 9). When the first photocurable layer forming step is repeated, the first composition is applied to the surface side of the formed first photocurable layer opposite to the first base material side. ..
　＜配置工程（図９のＳ１１）＞
　上記第１の光硬化物層形成工程後に、上記第１の光硬化物層の上記第１の基材側とは反対の表面上に、第２の基材を配置する（配置工程）。 <Arrangement process (S11 in FIG. 9)>
After the first photo-cured product layer forming step, the second base material is placed on the surface of the first photo-cured product layer opposite to the first base material side (placement step).
　＜第１の光硬化物層用加熱工程、又は、第１及び第２の光硬化物層用加熱工程（図９のＳ１２）＞
　上記第２の光硬化物層用加熱工程を行う場合に、上記配置工程後に、上記第１の光硬化物層を加熱して、第１の光及び熱硬化物層を形成する（第１の光硬化物層用加熱工程）。上記第２の光硬化物層用加熱工程を行わない場合に、上記配置工程後に、上記第１の光硬化物層及び上記第２の光硬化物層を加熱して、第１の光及び熱硬化物層、並びに、第２の光及び熱硬化物層を形成する（第１及び第２の光硬化物層用加熱工程）。上記第１の光及び熱硬化物層は、上記第１の光硬化物層が熱硬化した層である。上記第２の光及び熱硬化物層は、上記第２の光硬化物層が熱硬化した層である。 <The first heating step for the photocurable material layer or the first and second heating steps for the photocurable material layer (S12 in FIG. 9)>
When the second photocurable material layer heating step is performed, after the arrangement step, the first photocurable material layer is heated to form the first light and thermosetting material layer (first). Heating process for photocurable layer). When the heating step for the second photocurable material layer is not performed, the first photocurable material layer and the second photocurable material layer are heated after the arrangement step to obtain the first light and heat. A cured product layer and a second light and thermosetting material layer are formed (heating steps for the first and second photocured product layers). The first light and thermosetting layer is a layer obtained by thermosetting the first photocuring layer. The second light and thermosetting layer is a layer obtained by thermosetting the second photocuring layer.
　このようにして、図１０に示すように、第１の基材３と、第２の光及び熱硬化物層２Ｅと、第１の光及び熱硬化物層１Ｅと、第２の基材７とをこの順で備える積層構造体４Ｅを得ることができる。 In this way, as shown in FIG. 10, the first base material 3, the second light and thermosetting material layer 2E, the first light and thermosetting material layer 1E, and the second base material 7 It is possible to obtain a laminated structure 4E including the above in this order.
　＜積層構造体の製造方法の他の詳細＞
　第１、第２及び第３の光硬化物層形成工程の他の詳細：
　上記積層構造体の製造方法（１）は、上記第１の塗布工程を備えていてもよく、備えていなくてもよい。上記積層構造体の製造方法（２）は、上記第２の塗布工程を備えていてもよく、備えていなくてもよい。上記積層構造体（１）は、上記第１の塗布工程と、上記第１の光硬化工程と、上記第２の塗布工程と、上記第２の光硬化工程とをこの順で備えることが好ましい。上記積層構造体（２）は、上記第２の塗布工程と、上記第２の光硬化工程と、上記第１の塗布工程と、上記第１の光硬化工程とをこの順で備えることが好ましい。上記積層構造体の製造方法（１）は、上記第３の塗布工程を備えていてもよく、備えていなくてもよい。上記積層構造体の製造方法（１）は、上記第３の光硬化工程を備えていてもよく、備えていなくてもよい。上記積層構造体の製造方法（１）は、上記第３の光硬化物層形成工程を備えていてもよく、備えていなくてもよい。 <Other details of manufacturing method of laminated structure>
Other details of the first, second and third photocurable layer forming steps:
The method (1) for manufacturing the laminated structure may or may not include the first coating step. The method (2) for manufacturing the laminated structure may or may not include the second coating step. The laminated structure (1) preferably includes the first coating step, the first photocuring step, the second coating step, and the second photocuring step in this order. .. The laminated structure (2) preferably includes the second coating step, the second photocuring step, the first coating step, and the first photocuring step in this order. .. The method (1) for manufacturing the laminated structure may or may not include the third coating step. The method (1) for manufacturing the laminated structure may or may not include the third photocuring step. The method (1) for manufacturing the laminated structure may or may not include the third photocurable layer forming step.
　上記積層構造体の製造方法（１），（２）では、特定の領域に第１の組成物を塗布した後、塗布された第１の組成物の全体に対して光を照射して第１の光硬化物層を形成してもよい。上記積層構造体の製造方法（１），（２）では、第１の組成物を複数滴塗布するごとに、塗布された第１の組成物に対して光を照射して第１の光硬化物層を形成してもよい。上記積層構造体の製造方法（１），（２）では、第１の組成物を１滴塗布するごとに、塗布された第１の組成物に対して光を照射して第１の光硬化物層を形成してもよい。 In the methods (1) and (2) for producing the laminated structure, after the first composition is applied to a specific region, the entire applied first composition is irradiated with light to obtain the first composition. The photocurable material layer may be formed. In the above-mentioned methods for producing a laminated structure (1) and (2), each time a plurality of drops of the first composition are applied, the applied first composition is irradiated with light and the first photocuring is performed. A material layer may be formed. In the methods (1) and (2) for producing the laminated structure, each time one drop of the first composition is applied, the applied first composition is irradiated with light and the first photocuring is performed. A material layer may be formed.
　上記積層構造体の製造方法（１），（２）では、上記第１の光硬化物層形成工程は、図１に示すように、第１の基材の厚み方向にて、１回のみ行われてもよい。上記積層構造体の製造方法（１），（２）では、上記第１の光硬化物層形成工程は、第１の基材の厚み方向にて、複数回行われてもよい。すなわち、上記積層構造体の製造方法（１），（２）では、上記第１の塗布工程と上記第１の光硬化工程とがそれぞれ、第１の基材の厚み方向にて、１回のみ行われてもよく、複数回行われてもよい。上記第１の光硬化物層形成工程が、第１の基材の厚み方向にて、複数回行われることにより、第１の光硬化物層の厚みを大きくすることができる。 In the methods (1) and (2) for manufacturing the laminated structure, the first photocurable layer forming step is performed only once in the thickness direction of the first base material, as shown in FIG. You may be broken. In the methods (1) and (2) for producing the laminated structure, the first photocurable layer forming step may be performed a plurality of times in the thickness direction of the first base material. That is, in the methods (1) and (2) for manufacturing the laminated structure, the first coating step and the first photocuring step are performed only once in the thickness direction of the first base material, respectively. It may be performed, or it may be performed multiple times. By performing the first photocurable material layer forming step a plurality of times in the thickness direction of the first base material, the thickness of the first photocurable material layer can be increased.
　上記積層構造体の製造方法（１）では、上記第１の光硬化物層形成工程は、上記第２の光硬化物層形成工程よりも前に行われる。上記積層構造体の製造方法（２）では、上記第２の光硬化物層形成工程は、上記第１の光硬化物層形成工程よりも前に行われる。上記積層構造体の製造方法（１）では、上記第１の光硬化物層形成工程及び上記第２の光硬化物層形成工程は、上記第３の光硬化物層形成工程よりも前に行われる。 In the method (1) for manufacturing a laminated structure, the first photocurable layer forming step is performed before the second photocured layer forming step. In the method (2) for producing a laminated structure, the second photocurable layer forming step is performed before the first photocured layer forming step. In the method for producing a laminated structure (1), the first photocurable material layer forming step and the second photocured material layer forming step are performed before the third photocured material layer forming step. It is said.
　上記積層構造体の製造方法（１），（２）では、特定の領域に第２の組成物を塗布した後、塗布された第２の組成物の全体に対して光を照射して第２の光硬化物層を形成してもよい。上記積層構造体の製造方法（１），（２）では、第２の組成物を複数滴塗布するごとに、塗布された第２の組成物に対して光を照射して第２の光硬化物層を形成してもよい。上記積層構造体の製造方法（１），（２）では、第２の組成物を１滴塗布するごとに、塗布された第２の組成物に対して光を照射して第２の光硬化物層を形成してもよい。 In the methods (1) and (2) for producing the laminated structure, after the second composition is applied to a specific region, the entire applied second composition is irradiated with light to obtain a second composition. The photocurable material layer may be formed. In the above-mentioned methods for producing a laminated structure (1) and (2), every time a plurality of drops of the second composition are applied, the applied second composition is irradiated with light and the second photocuring is performed. A material layer may be formed. In the methods (1) and (2) for producing the laminated structure, each time one drop of the second composition is applied, the applied second composition is irradiated with light to cure the second composition. A material layer may be formed.
　上記積層構造体の製造方法（１）では、上記第２の光硬化物層形成工程は、第１の光硬化物層の厚み方向にて、１回のみ行われてもよい。上記積層構造体の製造方法（１）では、上記第２の光硬化物層形成工程は、図１，２に示すように、第１の光硬化物層の厚み方向にて、複数回行われてもよい。すなわち、上記積層構造体の製造方法（１）では、上記第２の塗布工程と上記第２の光硬化工程とがそれぞれ、第１の光硬化物層の厚み方向にて、１回のみ行われてもよく、複数回行われてもよい。上記積層構造体の製造方法（２）では、上記第２の光硬化物層形成工程は、第１の基材の厚み方向にて、１回のみ行われてもよい。上記積層構造体の製造方法（２）では、上記第２の光硬化物層形成工程は、第１の基材の厚み方向にて、複数回行われてもよい。上記積層構造体の製造方法（２）では、上記第２の塗布工程と上記第２の光硬化工程とがそれぞれ、第１の基材の厚み方向にて、１回のみ行われてもよく、複数回行われてもよい。上記第２の光硬化物層形成工程が、第１の光硬化物層の厚み方向又は第１の基材の厚み方向にて、複数回行われることにより、第２の光硬化物層の厚みを大きくすることができる。上記第２の光硬化物層形成工程は、第１の光硬化物層の厚み方向又は第１の基材の厚み方向にて、複数回行われることが好ましい。なお、目的とする第２の光硬化物層の厚みに応じて、上記第２の光硬化物層形成工程が繰り返される回数は適宜変更される。 In the method (1) for manufacturing the laminated structure, the second photocurable layer forming step may be performed only once in the thickness direction of the first photocurable layer. In the method (1) for manufacturing the laminated structure, the second photocurable layer forming step is performed a plurality of times in the thickness direction of the first photocurable layer, as shown in FIGS. 1 and 2. You may. That is, in the method (1) for manufacturing the laminated structure, the second coating step and the second photocuring step are performed only once in the thickness direction of the first photocured product layer, respectively. It may be performed a plurality of times. In the method (2) for manufacturing the laminated structure, the second photocurable layer forming step may be performed only once in the thickness direction of the first base material. In the method (2) for manufacturing the laminated structure, the second photocurable layer forming step may be performed a plurality of times in the thickness direction of the first base material. In the method (2) for manufacturing the laminated structure, the second coating step and the second photocuring step may be performed only once in the thickness direction of the first base material, respectively. It may be performed multiple times. The thickness of the second photocurable material layer is formed by performing the second photocurable material layer forming step a plurality of times in the thickness direction of the first photocurable material layer or the thickness direction of the first base material. Can be increased. The second photocurable material layer forming step is preferably performed a plurality of times in the thickness direction of the first photocurable material layer or the thickness direction of the first base material. The number of times the second photocurable layer forming step is repeated is appropriately changed according to the thickness of the target second photocurable layer.
　上記積層構造体の製造方法（１），（２）では、特定の領域に第３の組成物を塗布した後、塗布された第３の組成物の全体に対して光を照射して第３の光硬化物層を形成してもよい。上記積層構造体の製造方法（１），（２）では、第３の組成物を複数滴塗布するごとに、塗布された第３の組成物に対して光を照射して第３の光硬化物層を形成してもよい。上記積層構造体の製造方法（１），（２）では、第３の組成物を１滴塗布するごとに、塗布された第３の組成物に対して光を照射して第３の光硬化物層を形成してもよい。 In the methods (1) and (2) for producing the laminated structure, after the third composition is applied to a specific region, the entire applied third composition is irradiated with light to form a third composition. The photocurable material layer may be formed. In the methods (1) and (2) for producing the laminated structure, each time a plurality of drops of the third composition are applied, the applied third composition is irradiated with light to be photocured. A material layer may be formed. In the methods (1) and (2) for producing the laminated structure, each time one drop of the third composition is applied, the applied third composition is irradiated with light to cure the third composition. A material layer may be formed.
　上記積層構造体の製造方法（１），（２）では、上記第３の光硬化物層形成工程は、第２の光硬化物層の厚み方向にて、１回のみ行われてもよい。上記積層構造体の製造方法（１），（２）では、上記第３の光硬化物層形成工程は、第２の光硬化物層の厚み方向にて、複数回行われてもよい。すなわち、上記積層構造体の製造方法（１），（２）では、上記第３の塗布工程と上記第３の光硬化工程とがそれぞれ、第２の光硬化物層の厚み方向にて、１回のみ行われてもよく、複数回行われてもよい。上記第３の光硬化物層形成工程が、第２の光硬化物層の厚み方向にて、複数回行われることにより、第３の光硬化物層の厚みを大きくすることができる。 In the above-mentioned manufacturing methods (1) and (2) of the laminated structure, the third photo-cured product layer forming step may be performed only once in the thickness direction of the second photo-cured product layer. In the methods (1) and (2) for producing the laminated structure, the third photocurable layer forming step may be performed a plurality of times in the thickness direction of the second photocurable layer. That is, in the methods (1) and (2) for manufacturing the laminated structure, the third coating step and the third photocuring step are 1 in the thickness direction of the second photocured product layer, respectively. It may be performed only once, or it may be performed multiple times. By performing the third photocurable material layer forming step a plurality of times in the thickness direction of the second photocurable material layer, the thickness of the third photocurable material layer can be increased.
　上記積層構造体の製造方法（１），（２）では、上記第１の光硬化工程、上記第２の光硬化工程及び第３の光硬化工程における光照射は、紫外線照射であることが好ましい。 In the methods (1) and (2) for producing the laminated structure, the light irradiation in the first photocuring step, the second photocuring step and the third photocuring step is preferably ultraviolet irradiation. ..
　上記第１の光硬化工程、上記第２の光硬化工程及び第３の光硬化工程における紫外線の照度及び照射時間は、第１の組成物、上記第２の組成物及び第３の組成物の組成、並びに、組成物の塗布厚みにより適宜変更可能である。上記第１の光硬化工程、上記第２の光硬化工程及び第３の光硬化工程における紫外線の照度は、例えば、１０００ｍＷ／ｃｍ２以上であってもよく、５０００ｍＷ／ｃｍ２以上であってもよく、１００００ｍＷ／ｃｍ２以下であってもよく、８０００ｍＷ／ｃｍ２以下であってもよい。上記第１の光硬化工程、上記第２の光硬化工程及び第３の光硬化工程における紫外線の照射時間は、例えば、０．０１秒以上であってもよく、０．１秒以上であってもよく、４００秒以下であってもよく、１００秒以下であってもよい。 The illuminance and irradiation time of ultraviolet rays in the first photo-curing step, the second photo-curing step, and the third photo-curing step are the first composition, the second composition, and the third composition. It can be appropriately changed depending on the composition and the coating thickness of the composition. The first light-curing process, the illuminance of ultraviolet rays in the second light-curing step and the third light-curing step, for example, may also be 1000 mW / cm 2 or more, even 5000 mW / cm 2 or more well, it may also be 10000 mW / cm 2 or less, may be 8000 MW / cm 2 or less. The irradiation time of ultraviolet rays in the first photocuring step, the second photocuring step, and the third photocuring step may be, for example, 0.01 seconds or more, or 0.1 seconds or more. It may be 400 seconds or less, or 100 seconds or less.
　加熱工程の他の詳細：
　上記積層構造体の製造方法（１）は、上記第１及び第２の光硬化物層用加熱工程を備えていてもよく、備えていなくてもよい。上記積層構造体の製造方法（１）は、上記第３の光硬化物層用加熱工程を備えていてもよく、備えていなくてもよい。上記積層構造体の製造方法（１）は、上記第１、第２及び第３の光硬化物層用加熱工程を備えていてもよく、備えていなくてもよい。上記積層構造体の製造方法（２）は、上記第２の光硬化物層用加熱工程を備えていてもよく、備えていなくてもよい。上記積層構造体の製造方法（２）は、上記第１の光硬化物層用加熱工程を備えていてもよく、備えていなくてもよい。上記積層構造体の製造方法（２）は、上記第１及び第２の光硬化物層用加熱工程を備えていてもよく、備えていなくてもよい。第１及び第２の組成物の硬化物層の強度を高める観点からは、上記積層構造体の製造方法（１）は、上記第１及び第２の光硬化物層用加熱工程を備えることが好ましい。第３の組成物の硬化物層の強度を高める観点からは、上記積層構造体の製造方法（１）は、上記第３の光硬化物層用加熱工程を備えることが好ましい。第１、第２及び第３の組成物の硬化物層の強度を高める観点からは、上記積層構造体の製造方法（１）は、上記第１、第２及び第３の光硬化物層用加熱工程を備えることが好ましい。第２の組成物の硬化物層の強度を高める観点からは、上記積層構造体の製造方法（２）は、上記第２の光硬化物層用加熱工程を備えることが好ましい。第１の組成物の硬化物層の強度を高める観点からは、上記積層構造体の製造方法（２）は、上記第１の光硬化物層用加熱工程を備えることが好ましい。第１及び第２の組成物の硬化物層の強度を高める観点からは、上記積層構造体の製造方法（２）は、上記第１及び第２の光硬化物層用加熱工程を備えることが好ましい。 Other details of the heating process:
The method (1) for manufacturing the laminated structure may or may not include the first and second heating steps for the photocurable material layer. The method (1) for manufacturing the laminated structure may or may not include the third heating step for the photocurable material layer. The method (1) for manufacturing the laminated structure may or may not include the first, second, and third heating steps for the photocurable material layer. The method (2) for manufacturing the laminated structure may or may not include the second heating step for the photocurable material layer. The method (2) for manufacturing the laminated structure may or may not include the first heating step for the photocurable material layer. The method (2) for manufacturing the laminated structure may or may not include the first and second heating steps for the photocurable material layer. From the viewpoint of increasing the strength of the cured product layer of the first and second compositions, the method (1) for producing the laminated structure may include the heating steps for the first and second photocured product layers. preferable. From the viewpoint of increasing the strength of the cured product layer of the third composition, it is preferable that the method (1) for producing the laminated structure includes the heating step for the third photocured product layer. From the viewpoint of increasing the strength of the cured product layers of the first, second and third compositions, the method (1) for producing the laminated structure is for the first, second and third photocured product layers. It is preferable to include a heating step. From the viewpoint of increasing the strength of the cured product layer of the second composition, it is preferable that the method (2) for producing the laminated structure includes the heating step for the second photocured product layer. From the viewpoint of increasing the strength of the cured product layer of the first composition, it is preferable that the method (2) for producing the laminated structure includes the heating step for the first photocured product layer. From the viewpoint of increasing the strength of the cured product layer of the first and second compositions, the method (2) for producing the laminated structure may include the heating steps for the first and second photocured product layers. preferable.
　上記積層構造体の製造方法（１）では、上記第１及び第２の光硬化物層用加熱工程は、上記第２の光硬化物層形成工程よりも後に行われる。上記積層構造体の製造方法（１）では、上記第１及び第２の光硬化物層用加熱工程は、上記第３の光硬化物層形成工程よりも前に行われることが好ましく、上記第３の光硬化物層用加熱工程よりも前に行われることが好ましい。上記積層構造体の製造方法（１）では、上記第１及び第２の光硬化物層用加熱工程は、上記第３の光硬化物層形成工程よりも後に行われてもよい。上記積層構造体の製造方法（１）では、上記第３の光硬化物層用加熱工程は、上記配置工程よりも前に行われてもよく、上記配置工程よりも後に行われてもよい。上記積層構造体の製造方法（２）では、上記第２の光硬化物層用加熱工程は、上記第２の光硬化物層形成工程よりも後に行われる。上記第２の積層構造体の製造方法（２）では、上記第２の光硬化物層用加熱工程は、上記第１の光硬化物層形成工程よりも前に行われることが好ましく、上記第１の光硬化物層用加熱工程よりも前に行われることが好ましい。上記積層構造体の製造方法（２）では、上記第１の光硬化物層用加熱工程は、上記配置工程よりも前に行われてもよく、上記配置工程よりも後に行われてもよい。 In the method for producing a laminated structure (1), the first and second heating steps for the photocurable material layer are performed after the second photocurable material layer forming step. In the method for producing a laminated structure (1), the first and second heating steps for the photocurable material layer are preferably performed before the third photocurable material layer forming step, and the first and second photocurable material layer forming steps are preferably performed. It is preferable that the step is performed before the heating step for the photocurable material layer of 3. In the method for producing a laminated structure (1), the first and second heating steps for the photocurable material layer may be performed after the third photocurable material layer forming step. In the method (1) for manufacturing the laminated structure, the third heating step for the photocured material layer may be performed before the arrangement step or after the arrangement step. In the method (2) for manufacturing the laminated structure, the second heating step for the photocurable material layer is performed after the second photocurable material layer forming step. In the method (2) for producing the second laminated structure, the second heating step for the photocurable material layer is preferably performed before the first photocurable material layer forming step, and the first It is preferable that the step is performed before the heating step for the photocurable material layer of 1. In the method (2) for manufacturing the laminated structure, the first heating step for the photocurable product layer may be performed before the arrangement step or after the arrangement step.
　上記加熱工程では、配置されている各光硬化物層を同時に加熱することが好ましい。 In the above heating step, it is preferable to heat each of the arranged photocurable material layers at the same time.
　上記加熱工程のそれぞれにおける加熱温度及び加熱時間は、第１の組成物、上記第２の組成物及び第３の組成物の組成、並びに、組成物の塗布厚みにより適宜変更可能である。上記加熱工程における加熱温度は、例えば、１００℃以上であってもよく、１２０℃以上であってもよく、２５０℃以下であってもよく、２００℃以下であってもよい。上記加熱工程における加熱時間は、例えば、５分以上であってもよく、３０分以上であってもよく、６００分以下であってもよく、３００分以下であってもよい。 The heating temperature and heating time in each of the heating steps can be appropriately changed depending on the composition of the first composition, the second composition and the third composition, and the coating thickness of the composition. The heating temperature in the heating step may be, for example, 100 ° C. or higher, 120 ° C. or higher, 250 ° C. or lower, or 200 ° C. or lower. The heating time in the heating step may be, for example, 5 minutes or more, 30 minutes or more, 600 minutes or less, or 300 minutes or less.
　平坦化処理工程の他の詳細：
　上記積層構造体の製造方法（１）は、上記平坦化処理工程を備えていてもよく、備えていなくてもよい。上記積層構造体の製造方法（２）は、上記平坦化処理工程を備えていてもよく、備えていなくてもよい。第１の基材と第２の基材とを備える積層構造体を製造する場合には、上記積層構造体の製造方法（１），（２）は、上記平坦化処理工程を備えることが好ましい。上記平坦化処理を行うことにより、上記第２の光硬化物層（又は上記第２の光及び熱硬化物層）と第２の基材との間に配置される硬化物層の厚みが小さくても、該硬化物層と第２の基材との接着力を高めることができる。 Other details of the flattening process:
The method (1) for manufacturing the laminated structure may or may not include the flattening treatment step. The method (2) for manufacturing the laminated structure may or may not include the flattening treatment step. When manufacturing a laminated structure including a first base material and a second base material, it is preferable that the methods (1) and (2) for manufacturing the laminated structure include the flattening treatment step. .. By performing the flattening treatment, the thickness of the cured product layer arranged between the second photocured material layer (or the second light and thermosetting material layer) and the second base material is reduced. However, the adhesive force between the cured product layer and the second base material can be enhanced.
　上記積層構造体の製造方法（１）では、上記平坦化処理工程は、上記第１及び第２の光硬化物層用加熱工程よりも前に行われてもよく、後に行われてもよい。上記積層構造体の製造方法（１）では、上記第１及び第２の光硬化物層用加熱工程後に、上記第２の光及び熱硬化物層の上記第１の基材側とは反対の表面を平坦化処理することが好ましい。上記積層構造体の製造方法（２）では、上記平坦化処理工程は、上記第２の光硬化物層用加熱工程よりも前に行われてもよく、後に行われてもよい。上記積層構造体の製造方法（２）では、上記第２の光硬化物層用加熱工程後に、上記第２の光及び熱硬化物層の上記第１の基材側とは反対の表面を平坦化処理することが好ましい。これらの場合には、基材と硬化物層との接着力を高めることができ、また、硬化物層の強度を高めることができるので、平坦化処理時に第１の基材から硬化物層が剥離したり、硬化物層が破壊したりすることを抑えることができる。 In the method for producing a laminated structure (1), the flattening treatment step may be performed before or after the first and second heating steps for the photocurable product layer. In the method (1) for producing the laminated structure, after the heating steps for the first and second photocurable material layers, the second light and the thermosetting material layer are opposite to those on the first base material side. It is preferable to flatten the surface. In the method for producing a laminated structure (2), the flattening treatment step may be performed before or after the second heating step for the photocurable product layer. In the method (2) for manufacturing the laminated structure, after the heating step for the second photocurable material layer, the surface of the second light and the thermosetting material layer opposite to the first base material side is flattened. It is preferable to carry out the chemical treatment. In these cases, the adhesive strength between the base material and the cured product layer can be increased, and the strength of the cured product layer can be increased, so that the cured product layer can be removed from the first base material during the flattening treatment. It is possible to prevent peeling and destruction of the cured product layer.
　上記平坦化処理としては、研磨処理等が挙げられる。上記研磨処理としては、ダイヤモンドを用いたバイト加工による切削研磨処理、及び化学機械研磨処理等が挙げられる。 Examples of the flattening treatment include polishing treatment and the like. Examples of the polishing treatment include cutting polishing treatment by tool processing using diamond, chemical mechanical polishing treatment and the like.
　上記平坦化処理が容易であることから、上記平坦化処理は、研磨処理であることが好ましい。上記平坦化処理が特に容易であることから、上記研磨処理は、ダイヤモンドを用いたバイト加工による切削研磨処理であることが好ましく、ダイヤモンドを用いたバイト加工による切削研磨処理と化学機械研磨処理との双方の処理であることがより好ましい。 Since the flattening treatment is easy, the flattening treatment is preferably a polishing treatment. Since the flattening treatment is particularly easy, the polishing treatment is preferably a cutting polishing treatment by a cutting tool using diamond, and a cutting polishing treatment by a cutting tool using diamond and a chemical mechanical polishing treatment. It is more preferable that both treatments are performed.
　上記平坦化処理（研磨処理）に用いることが可能な装置としては、キーリンク社製「平坦化装置」、ＤＩＳＣＯ社製「ＤＦＳ８９１０」等が挙げられる。 Examples of the device that can be used for the flattening process (polishing process) include a "flattening device" manufactured by Keylink and a "DFS8910" manufactured by DISCO.
　上記平坦化処理後の上記第２の光及び熱硬化物層（又は上記第２の光硬化物層）の表面の最大高さと最小高さとの差の絶対値は、５μｍ以下であることが好ましく、３μｍ以下であることがより好ましく、１μｍ以下であることが更に好ましい。上記差の絶対値が上記上限以下であると、接着不良をより一層効果的に抑制したり、平坦化処理後の表面に貼り合わせる部品の傾きをより一層効果的に抑制したりすることができる。なお、上記差の絶対値は０．５μｍ以上であってもよい。 The absolute value of the difference between the maximum height and the minimum height of the surface of the second light and thermosetting layer (or the second photocured layer) after the flattening treatment is preferably 5 μm or less. It is more preferably 3 μm or less, and further preferably 1 μm or less. When the absolute value of the above difference is not more than the above upper limit, it is possible to more effectively suppress the poor adhesion and further effectively suppress the inclination of the component to be bonded to the surface after the flattening treatment. .. The absolute value of the above difference may be 0.5 μm or more.
　配置工程の他の詳細：
　上記積層構造体の製造方法（１），（２）は、上記配置工程を備えていてもよく、備えていなくてもよい。上記積層構造体の製造方法（１）は、上記第３の光硬化物層の上記第１の基材側とは反対の表面上に、第２の基材を配置する配置工程を備えることが好ましい。なお、上記積層構造体の製造方法（１）において、上記第３の光硬化物層用加熱工程が上記配置工程よりも前に行われる場合には、上記配置工程では、上記第３の光及び熱硬化物層の上記第１の基材側とは反対の表面上に、第２の基材を配置する。上記積層構造体の製造方法（２）は、上記第１の光硬化物層の上記第１の基材側とは反対の表面上に、第２の基材を配置する配置工程を備えることが好ましい。なお、上記積層構造体の製造方法（２）において、上記第１の光硬化物層用加熱工程が上記配置工程よりも前に行われる場合には、上記配置工程では、上記第１の光及び熱硬化物層の上記第１の基材側とは反対の表面上に、第２の基材を配置する。 Other details of the placement process:
The methods (1) and (2) for manufacturing the laminated structure may or may not include the above-mentioned arrangement step. The method (1) for manufacturing the laminated structure may include an arrangement step of arranging the second base material on the surface of the third photocurable material layer opposite to the first base material side. preferable. In the method (1) for manufacturing the laminated structure, when the third heating step for the photocured material layer is performed before the placement step, the third light and the third light and the above-mentioned arrangement step are performed. The second base material is placed on the surface of the thermosetting material layer opposite to the first base material side. The method (2) for manufacturing the laminated structure may include an arrangement step of arranging the second base material on the surface of the first photocurable material layer opposite to the first base material side. preferable. In the method (2) for manufacturing the laminated structure, when the first heating step for the photocured material layer is performed before the placement step, in the placement step, the first light and the above-mentioned first light and The second base material is placed on the surface of the thermosetting material layer opposite to the first base material side.
　上記第２の基材を配置する方法は、特に限定されない。 The method of arranging the second base material is not particularly limited.
　上記第１の基材と上記第２の基材とは同一の基材であってもよく、異なる基材であってもよい。 The first base material and the second base material may be the same base material or different base materials.
　上記第２の組成物の硬化物層と接触する基材は、表面に凹凸を有する基材であるか、又は表面がプライマー処理された基材であることが好ましい。この場合には、上記第２の組成物の硬化物層との接着性をより一層高めることができ、本発明の効果をより一層効果的に発揮することができる。また、長期信頼性を高めることができる。基材の表面に凹凸を形成する方法としては、ブラシを用いる方法及びブラスト加工する方法等が挙げられる。 The base material that comes into contact with the cured product layer of the second composition is preferably a base material having irregularities on the surface or a base material whose surface is primed. In this case, the adhesiveness of the second composition to the cured product layer can be further enhanced, and the effects of the present invention can be further exerted. In addition, long-term reliability can be improved. Examples of the method of forming irregularities on the surface of the base material include a method using a brush and a method of blasting.
　上記第１の組成物の硬化物層と接触する基材の表面粗さは、上記第２の組成物の硬化物層と接触する基材の表面粗さよりも、小さいことが好ましい。上記積層構造体の製造方法（２）において、上記第１の組成物の硬化物層と接触する基材は、上記第２の基材であり、上記第２の組成物の硬化物層と接触する基材は、上記第１の基材である。したがって、上記積層構造体の製造方法（２）では、上記第２の基材の表面粗さは、上記第１の基材の表面粗さよりも小さいことが好ましい。 The surface roughness of the base material in contact with the cured product layer of the first composition is preferably smaller than the surface roughness of the base material in contact with the cured product layer of the second composition. In the method (2) for producing the laminated structure, the base material that comes into contact with the cured product layer of the first composition is the second base material, and is in contact with the cured product layer of the second composition. The base material to be used is the above-mentioned first base material. Therefore, in the method (2) for manufacturing the laminated structure, the surface roughness of the second base material is preferably smaller than the surface roughness of the first base material.
　上記表面粗さは、第１の組成物、第２の組成物又は第３の組成物の硬化物層と接触する領域における表面粗さを意味する。また、上記表面粗さは、ＪＩＳ　Ｂ０６０１：１９９４に準拠して測定される算術平均粗さＲａを意味する。 The surface roughness means the surface roughness in the region in contact with the cured product layer of the first composition, the second composition or the third composition. The surface roughness means the arithmetic mean roughness Ra measured in accordance with JIS B0601: 1994.
　上記第２の組成物の硬化物層と接触する基材の表面粗さは、好ましくは１００ｎｍ以上、より好ましくは２００ｎｍ以上、好ましくは１０００ｎｍ以下、より好ましくは５００ｎｍ以下である。 The surface roughness of the base material in contact with the cured product layer of the second composition is preferably 100 nm or more, more preferably 200 nm or more, preferably 1000 nm or less, and more preferably 500 nm or less.
　上記第１の組成物の硬化物層と接触する基材の表面粗さと、上記第２の組成物の硬化物層と接触する基材の表面粗さとの差の絶対値は、好ましくは５０ｎｍ以上、より好ましくは１００ｎｍ以上、好ましくは９００ｎｍ以下、より好ましくは８００ｎｍ以下である。 The absolute value of the difference between the surface roughness of the base material in contact with the cured product layer of the first composition and the surface roughness of the base material in contact with the cured product layer of the second composition is preferably 50 nm or more. , More preferably 100 nm or more, preferably 900 nm or less, and more preferably 800 nm or less.
　上記積層構造体の製造方法（１）において、上記第１の基材は、セラミック基板又はシリコン基板であることが好ましく、シリコン基板であることがより好ましい。上記積層構造体の製造方法（１）において、上記第２の基材は、ガラス基板であることが好ましい。 In the method (1) for manufacturing a laminated structure, the first base material is preferably a ceramic substrate or a silicon substrate, and more preferably a silicon substrate. In the method (1) for manufacturing the laminated structure, the second base material is preferably a glass substrate.
　上記積層構造体の製造方法（２）において、上記第１の基材は、セラミック基板又はシリコン基板であることが好ましく、セラミック基板であることがより好ましい。上記積層構造体の製造方法（２）において、上記第２の基材は、ガラス基板であることが好ましい。 In the method (2) for manufacturing a laminated structure, the first base material is preferably a ceramic substrate or a silicon substrate, and more preferably a ceramic substrate. In the method (2) for manufacturing the laminated structure, the second base material is preferably a glass substrate.
　（装置）
　本明細書では、上記積層構造体を製造するために用いられる装置も開示する。上記装置は、ステージと、上記第１の組成物を吐出するための第１の吐出部と、上記第２の組成物を吐出するための第２の吐出部と、上記第１の吐出部と上記第２の吐出部との間に配置された第１の光照射部とを備える。上記第１の組成物と上記第３の組成物とが異なる組成物である場合、上記装置は、上記第３の組成物を吐出するための第３の吐出部を備えることが好ましい。 (Device)
The present specification also discloses an apparatus used for manufacturing the laminated structure. The apparatus includes a stage, a first discharge unit for discharging the first composition, a second discharge unit for discharging the second composition, and the first discharge unit. It includes a first light irradiation unit arranged between the second discharge unit and the second discharge unit. When the first composition and the third composition are different compositions, it is preferable that the device includes a third discharge unit for discharging the third composition.
　上記第１の吐出部はインクジェットヘッドであり、上記第２の吐出部が、インクジェットヘッドであることが好ましい。上記第３の吐出部はインクジェットヘッドであることが好ましい。上記装置は、インクジェット装置であることが好ましい。 It is preferable that the first ejection unit is an inkjet head and the second ejection unit is an inkjet head. The third ejection unit is preferably an inkjet head. The device is preferably an inkjet device.
　以下、第３の吐出部を備えない装置について詳述するが、第３の吐出部は、第１の吐出部又は第２の吐出部と同様の構成とすることができる。 Hereinafter, the device not provided with the third discharge unit will be described in detail, but the third discharge unit can have the same configuration as the first discharge unit or the second discharge unit.
　上記装置は、上記第１の組成物を吐出するための上記第１の吐出部を１個のみ備えていてもよく、２個以上備えていてもよい。上記装置は、上記第２の組成物を吐出するための上記第２の吐出部を１個のみ備えていてもよく、２個以上備えていてもよい。上記装置が上記第１の吐出部及び上記第２の吐出部を複数備える場合には、積層構造体の製造効率を高めることができる。 The device may include only one first discharge unit for discharging the first composition, or may include two or more of the first discharge portions. The device may include only one second discharge portion for discharging the second composition, or may include two or more of the second discharge portions. When the apparatus includes a plurality of the first discharge portion and the second discharge portion, the manufacturing efficiency of the laminated structure can be improved.
　積層構造体の製造効率を高める観点からは、上記装置は、上記第１の吐出部の上記第１の光照射部とは反対側、又は、上記第２の吐出部の上記第１の光照射部とは反対側に配置された第２の光照射部を備えることが好ましい。この場合に、上記第２の光照射部は、上記第１の吐出部の上記第１の光照射部とは反対側に配置されていてもよく、上記第２の吐出部の上記第１の光照射部とは反対側に配置されていてもよく、上記第１の吐出部の上記第１の光照射部とは反対側、及び、上記第２の吐出部の上記第１の光照射部とは反対側の双方に配置されていてもよい。 From the viewpoint of increasing the manufacturing efficiency of the laminated structure, the apparatus is located on the opposite side of the first discharge portion from the first light irradiation portion, or the first light irradiation of the second discharge portion. It is preferable to provide a second light irradiation portion arranged on the side opposite to the portion. In this case, the second light irradiation unit may be arranged on the side opposite to the first light irradiation unit of the first discharge unit, and the first light irradiation unit of the second discharge unit may be arranged. It may be arranged on the side opposite to the light irradiation part, the side opposite to the first light irradiation part of the first discharge part, and the first light irradiation part of the second discharge part. It may be arranged on both sides opposite to.
　ただし、上記装置は、上記第２の光照射部を備えなくてもよい。上記装置が上記第２の光照射部を備えない場合、上記第１の光照射部を用いて、上記第１の光硬化工程及び上記第２の光硬化工程が行われる。 However, the device does not have to include the second light irradiation unit. When the apparatus does not include the second light irradiation unit, the first photocuring step and the second photocuring step are performed using the first light irradiation unit.
　上記第１の光照射部及び上記第２の光照射部は、紫外線を照射可能であることが好ましい。上記第１の光照射部は、第１の紫外線照射部であることが好ましく、上記第２の光照射部は、第２の紫外線照射部であることが好ましい。 It is preferable that the first light irradiation unit and the second light irradiation unit can irradiate ultraviolet rays. The first light irradiation unit is preferably a first ultraviolet irradiation unit, and the second light irradiation unit is preferably a second ultraviolet irradiation unit.
　第１の紫外線照射部及び上記第２の紫外線照射部としては、紫外線を発生する発光ダイオード（ＵＶ－ＬＥＤ）等が挙げられる。 Examples of the first ultraviolet irradiation unit and the second ultraviolet irradiation unit include a light emitting diode (UV-LED) that generates ultraviolet rays.
　また、上記装置は、図１１（ａ）に示すように、第１の組成物が貯留される第１のインクタンク１６と、第１の循環流路部１７とを備えていてもよく、図１１（ｂ）に示すように、第２の組成物が貯留される第２のインクタンク１８と、第２の循環流路部１９とを備えていてもよい。第１の循環流路部１７は、第１のインクタンク１６と、第１の吐出部１２とを接続している。第１の循環流路部１７の内部には、第１の組成物が流れる。また、第２の循環流路部１９は、第２のインクタンク１８と、第２の吐出部１４とを接続している。第２の循環流路部１９の内部には、第２の組成物が流れる。 Further, as shown in FIG. 11A, the apparatus may include a first ink tank 16 in which the first composition is stored and a first circulation flow path portion 17. As shown in 11 (b), a second ink tank 18 in which the second composition is stored and a second circulation flow path portion 19 may be provided. The first circulation flow path portion 17 connects the first ink tank 16 and the first ejection portion 12. The first composition flows inside the first circulation flow path portion 17. Further, the second circulation flow path portion 19 connects the second ink tank 18 and the second ejection portion 14. The second composition flows inside the second circulation flow path portion 19.
　第１の循環流路部１７は、第１の循環流路部１７内に、バッファタンク１７Ａとポンプ１７Ｂとを有する。但し、図１２（ａ）に示すように、第１の循環流路部１７Ｘは、第１の循環流路部１７Ｘ内に、バッファタンクとポンプとを有していなくてもよい。上記第１の循環流路部は、上記第１の循環流路部内に、上記バッファタンクを有することが好ましく、上記ポンプを有することが好ましい。また、上記第１の循環流路部は、上記第１の循環流路部内に、バッファタンク及びポンプの他に、流速計、温度計、フィルター、液面センサー等を有していてもよい。 The first circulation flow path portion 17 has a buffer tank 17A and a pump 17B in the first circulation flow path portion 17. However, as shown in FIG. 12A, the first circulation flow path portion 17X does not have to have the buffer tank and the pump in the first circulation flow path portion 17X. The first circulation flow path portion preferably has the buffer tank in the first circulation flow path portion, and preferably has the pump. Further, the first circulation flow path portion may have a current meter, a thermometer, a filter, a liquid level sensor, and the like in addition to the buffer tank and the pump in the first circulation flow path portion.
　第２の循環流路部１９は、第２の循環流路部１９内に、バッファタンク１９Ａとポンプ１９Ｂとを有する。但し、図１２（ｂ）に示すように、第２の循環流路部１９Ｘは、第２の循環流路部１９Ｘ内に、バッファタンクとポンプとを有していなくてもよい。上記第２の循環流路部は、上記第２の循環流路部内に、上記バッファタンクを有することが好ましく、上記ポンプを有することが好ましい。また、上記第２の循環流路部は、上記第２の循環流路部内に、バッファタンク及びポンプの他に、流速計、温度計、フィルター、液面センサー等を有していてもよい。 The second circulation flow path portion 19 has a buffer tank 19A and a pump 19B in the second circulation flow path portion 19. However, as shown in FIG. 12B, the second circulation flow path portion 19X does not have to have the buffer tank and the pump in the second circulation flow path portion 19X. The second circulation flow path portion preferably has the buffer tank in the second circulation flow path portion, and preferably has the pump. Further, the second circulation flow path portion may have a current meter, a thermometer, a filter, a liquid level sensor, and the like in addition to the buffer tank and the pump in the second circulation flow path portion.
　バッファタンク１７Ａ，１９Ａ又はポンプ１７Ｂ，１９Ｂが備えられる場合には、バッファタンク１７Ａ，１９Ａ及びポンプ１７Ｂ，１９Ｂはそれぞれ、吐出部１２，１４とインクタンク１６，１８との間に配置されることが好ましい。バッファタンク１７Ａ，１９Ａはポンプ１７Ｂ，１９Ｂよりも吐出部１２，１４側に配置されている。ポンプ１７Ｂ，１９Ｂは、バッファタンク１７Ａ，１９Ａよりもインクタンク１６，１８側に配置されている。バッファタンク１７Ａには、上記第１の組成物が仮貯留される。バッファタンク１９Ａには、上記第２の組成物が仮貯留される。 When the buffer tanks 17A, 19A or the pumps 17B, 19B are provided, the buffer tanks 17A, 19A and the pumps 17B, 19B may be arranged between the ejection portions 12, 14 and the ink tanks 16, 18, respectively. preferable. The buffer tanks 17A and 19A are arranged on the discharge portions 12 and 14 side of the pumps 17B and 19B. The pumps 17B and 19B are arranged on the ink tanks 16 and 18 side of the buffer tanks 17A and 19A. The first composition is temporarily stored in the buffer tank 17A. The second composition is temporarily stored in the buffer tank 19A.
　上記第１の組成物及び上記第２の組成物の循環方法に関しては、該組成物の自重を利用したり、ポンプ等を利用して加圧、減圧等を行ったりして、循環させることが可能である。これらは複数組み合わせて用いてもよい。ポンプとしてはシリンダ方式の無脈動ポンプ、プロペラポンプ、ギヤポンプ及びダイヤフラムポンプ等が挙げられる。循環効率を高めて、硬化物層の形成精度をより一層高める観点からは、上記第１，第２の循環流路部は、上記第１，第２の循環流路部内に上記第１，第２の組成物を移送させるポンプを含むことが好ましい。 Regarding the circulation method of the first composition and the second composition, it is possible to circulate the composition by using its own weight or by applying pressure, depressurization, etc. using a pump or the like. It is possible. A plurality of these may be used in combination. Examples of the pump include a cylinder type pulsation-free pump, a propeller pump, a gear pump, a diaphragm pump and the like. From the viewpoint of increasing the circulation efficiency and further improving the formation accuracy of the cured product layer, the first and second circulation flow paths are placed in the first and second circulation flow paths in the first and second circulation flow paths. It is preferable to include a pump for transferring the composition of 2.
　硬化物層の形成精度をより一層高める観点からは、上記第１，第２の循環流路部は、上記第１，第２の循環流路部に、上記第１，第２の組成物が仮貯留されるバッファタンクを含むことが好ましい。 From the viewpoint of further improving the formation accuracy of the cured product layer, the first and second circulation flow paths are provided with the first and second circulation channels in the first and second circulation flow paths. It is preferable to include a buffer tank for temporary storage.
　上記第１，第２の組成物を加熱しながら循環させる場合には、上記第１，第２のインクタンク内に加熱ヒーターを導入したり、上記第１，第２の循環流路部に加熱ヒーターを用いたりすることで、上記第１，第２の組成物の温度を調節することが可能である。 When the first and second compositions are circulated while being heated, a heating heater may be introduced into the first and second ink tanks, or the first and second circulation flow paths may be heated. By using a heater or the like, it is possible to adjust the temperature of the first and second compositions.
　上記第１の循環流路部は、上記第１の組成物を３０℃以上で循環させるための循環流路部であることが好ましく、４０℃以上で循環させるための循環流路部であることがより好ましく、１００℃以下で循環させるための循環流路部であることが好ましく、９０℃以下で循環させるための循環流路部であることが好ましい。この場合には、第１の組成物の粘度を最適にすることができ、第１の組成物の吐出性を高めることができる。 The first circulation flow path portion is preferably a circulation flow path portion for circulating the first composition at 30 ° C. or higher, and is a circulation flow path portion for circulating at 40 ° C. or higher. Is more preferable, and it is preferable that it is a circulation flow path portion for circulating at 100 ° C. or lower, and it is preferable that it is a circulation flow path portion for circulating at 90 ° C. or lower. In this case, the viscosity of the first composition can be optimized, and the discharge property of the first composition can be improved.
　上記第２の循環流路部は、上記第２の組成物を３０℃以上で循環させるための循環流路部であることが好ましく、４０℃以上で循環させるための循環流路部であることがより好ましく、１００℃以下で循環させるための循環流路部であることが好ましく、９０℃以下で循環させるための循環流路部であることが好ましい。この場合には、第２の組成物の粘度を最適にすることができ、第２の組成物の吐出性を高めることができる。 The second circulation flow path portion is preferably a circulation flow path portion for circulating the second composition at 30 ° C. or higher, and is a circulation flow path portion for circulating at 40 ° C. or higher. Is more preferable, and it is preferable that it is a circulation flow path portion for circulating at 100 ° C. or lower, and it is preferable that it is a circulation flow path portion for circulating at 90 ° C. or lower. In this case, the viscosity of the second composition can be optimized, and the discharge property of the second composition can be improved.
　上記吐出部の吐出ノズルにおいては、適切な圧力に保ちかつ、その範囲内で圧力変動（脈動）が少ないことが好ましい。ポンプ等を使用する場合にはポンプの脈動を抑えるために、ポンプと上記吐出部との間に減衰器を設けることが好ましい。このような減衰器としては、上記第１，第２の組成物が仮貯留されるバッファタンクや膜式のダンパ等が挙げられる。 It is preferable that the discharge nozzle of the discharge portion keeps an appropriate pressure and the pressure fluctuation (pulsation) is small within that range. When a pump or the like is used, it is preferable to provide an attenuator between the pump and the discharge portion in order to suppress the pulsation of the pump. Examples of such an attenuator include a buffer tank in which the first and second compositions are temporarily stored, a membrane type damper, and the like.
　上記第１，第２の塗布工程において、上記装置内で、上記第１，第２の組成物を第１，第２のインクタンクから第１，第２の吐出部に移動させた後に、第１，第２の吐出部から吐出されなかった上記第１，第２の組成物を、第１，第２の循環流路部内に流して、第１，第２のインクタンクへ移動させる。それによって、上記第１，第２の塗布工程において、上記第１，第２の組成物を循環させながら、塗布することができる。 In the first and second coating steps, after the first and second compositions are moved from the first and second ink tanks to the first and second ejection portions in the apparatus, the first and second compositions are first. The first and second compositions that have not been ejected from the first and second ejection portions are flowed into the first and second circulation flow path portions and moved to the first and second ink tanks. Thereby, in the first and second coating steps, the first and second compositions can be coated while being circulated.
　（積層構造体）
　本発明に係る積層構造体は、第１の基材と、上記第１の基材の表面上に配置された第１の層（層Ｘ）と、上記第１の層の上記第１の基材側とは反対側の表面上に配置された第２の層（層Ｙ）とを備える。本発明に係る積層構造体では、上記第１の層と上記第２の層との組合せが、以下の組合せＡ、又は以下の組合せＢである。組合せＡ：上記第１の層が、単官能の（メタ）アクリレート化合物とエポキシ化合物と光重合開始剤と熱硬化剤とを含む第１の組成物の光硬化物層又は光及び熱硬化物層であり、上記第２の層が、多官能の（メタ）アクリレート化合物とエポキシ化合物と光重合開始剤と熱硬化剤とを含む第２の組成物の光硬化物層又は光及び熱硬化物層である。組合せＢ：上記第１の層が、多官能の（メタ）アクリレート化合物とエポキシ化合物と光重合開始剤と熱硬化剤とを含む第２の組成物の光硬化物層又は光及び熱硬化物層であり、かつ上記第２の層が、単官能の（メタ）アクリレート化合物とエポキシ化合物と光重合開始剤と熱硬化剤とを含む第１の組成物の光硬化物層又は光及び熱硬化物層である。本発明に係る積層構造体では、上記第１の組成物と上記第２の組成物とが異なる組成物である。本発明に係る積層構造体は、上記組合せＡを満たしてもよく、上記組合せＢを満たしてもよい。 (Laminated structure)
The laminated structure according to the present invention comprises a first base material, a first layer (layer X) arranged on the surface of the first base material, and the first group of the first layer. It includes a second layer (layer Y) arranged on the surface opposite to the material side. In the laminated structure according to the present invention, the combination of the first layer and the second layer is the following combination A or the following combination B. Combination A: The first layer is a photocurable layer or a light and thermosetting layer of the first composition containing a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent. The second layer is a photocurable layer or a light and thermosetting layer of a second composition containing a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent. Is. Combination B: The first layer is a photocurable layer or a light and thermosetting layer of a second composition containing a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent. The second layer is a photocurable layer or a light and thermosetting product of the first composition containing a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent. It is a layer. In the laminated structure according to the present invention, the first composition and the second composition are different compositions. The laminated structure according to the present invention may satisfy the combination A or the combination B.
　上記第１の組成物を硬化させることにより、第１の組成物の硬化物層である第１の層が形成される。上記第２の組成物を硬化させることにより、第２の組成物の硬化物層である第２の層が形成される。より具体的には、上記第１の組成物に紫外線等の光を照射して光硬化させることにより、第１の組成物の光硬化物層である第１の層が形成される。上記第２の組成物に紫外線等の光を照射して光硬化させることにより、第２の組成物の光硬化物層である第２の層が形成される。 By curing the first composition, a first layer, which is a cured product layer of the first composition, is formed. By curing the second composition, a second layer, which is a cured product layer of the second composition, is formed. More specifically, by irradiating the first composition with light such as ultraviolet rays and photo-curing it, a first layer which is a photo-cured product layer of the first composition is formed. By irradiating the second composition with light such as ultraviolet rays and photo-curing it, a second layer, which is a photo-cured product layer of the second composition, is formed.
　本発明に係る積層構造体が上記組合せＡを満たす場合に、本発明に係る積層構造体は、以下の構成をさらに満たすことが好ましい。本発明の効果をより一層効果的に発揮する観点からは、上記第１の層は、上記第１の組成物の光及び熱硬化物層であることが好ましく、上記第２の層は、上記第２の組成物の光及び熱硬化物層であることが好ましい。上記第１の組成物の光硬化物層（第１の光硬化物層）を加熱することにより、光及び熱硬化物層である第１の層（第１の光及び熱硬化物層）が形成される。上記第２の組成物の光硬化物層（第２の光硬化物層）を加熱することにより、光及び熱硬化物層である第２の層（第２の光及び熱硬化物層）が形成される。 When the laminated structure according to the present invention satisfies the above combination A, it is preferable that the laminated structure according to the present invention further satisfies the following configurations. From the viewpoint of more effectively exerting the effects of the present invention, the first layer is preferably a light and thermosetting layer of the first composition, and the second layer is the above. It is preferably a light and thermosetting layer of the second composition. By heating the photo-cured product layer (first photo-cured product layer) of the first composition, the first layer (first light and thermosetting product layer) which is a light and thermosetting product layer is formed. It is formed. By heating the photo-cured product layer (second photo-cured product layer) of the second composition, the second layer (second light and thermosetting product layer) which is a light and thermosetting product layer is formed. It is formed.
　本発明に係る積層構造体が上記組合せＢを満たす場合に、本発明に係る積層構造体は、以下の構成をさらに満たすことが好ましい。本発明の効果をより一層効果的に発揮する観点からは、上記第１の層は、上記第２の組成物の光及び熱硬化物層であることが好ましく、上記第２の層は、上記第１の組成物の光及び熱硬化物層であることが好ましい。上記第２の組成物の光硬化物層（第２の光硬化物層）を加熱することにより、光及び熱硬化物層である第１の層（第２の光及び熱硬化物層）が形成される。上記第１の組成物の光硬化物層（第１の光硬化物層）を加熱することにより、光及び熱硬化物層である第２の層（第１の光及び熱硬化物層）が形成される。 When the laminated structure according to the present invention satisfies the above combination B, it is preferable that the laminated structure according to the present invention further satisfies the following configurations. From the viewpoint of more effectively exerting the effects of the present invention, the first layer is preferably a light and thermosetting layer of the second composition, and the second layer is the above-mentioned second layer. It is preferably a light and thermosetting layer of the first composition. By heating the photo-cured product layer (second photo-cured product layer) of the second composition, the first layer (second light and thermosetting product layer) which is a light and thermosetting product layer is formed. It is formed. By heating the photo-cured product layer (first photo-cured product layer) of the first composition, the second layer (first light and thermosetting product layer) which is a light and thermosetting product layer is formed. It is formed.
　上記第２の層は、研磨された表面を有することが好ましい。 The second layer preferably has a polished surface.
　上記積層構造体は、上記第２の層の上記第１の層側とは反対側の表面上に配置された第３の層（層Ｚ）を備えていてもよい。上記第３の層は、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第３の組成物の光硬化物層である。上記積層構造体では、上記第２の組成物と上記第３の組成物とが異なる組成物である。本発明に係る積層構造体が上記組合せＡを満たす場合に、本発明に係る積層構造体は、上記第３の層を備えることが好ましい。 The laminated structure may include a third layer (layer Z) arranged on the surface of the second layer opposite to the first layer side. The third layer is a photocurable layer of a third composition containing a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. In the laminated structure, the second composition and the third composition are different compositions. When the laminated structure according to the present invention satisfies the combination A, the laminated structure according to the present invention preferably includes the third layer.
　上記積層構造体は、上記第２の層の上記第１の層側とは反対側の表面上に配置された第２の基材を備えることが好ましい。上記積層構造体が上記第３の層を備える場合に、上記積層構造体は、上記第３の層の上記第２の層側とは反対側の表面上に配置された第２の基材を備えることが好ましい。 The laminated structure preferably includes a second base material arranged on the surface of the second layer opposite to the first layer side. When the laminated structure includes the third layer, the laminated structure has a second base material arranged on the surface of the third layer opposite to the second layer side. It is preferable to prepare.
　上記積層構造体では、上記第１の組成物の硬化物層と接触する基材の表面粗さが、上記第２の組成物の硬化物層と接触する基材の表面粗さよりも、小さいことが好ましい。上記積層構造体では、上記第３の組成物の硬化物層と接触する基材の表面粗さが、上記第２の組成物の硬化物層と接触する基材の表面粗さよりも、小さいことが好ましい。したがって、上記組合せＡの場合に、上記積層構造体では、上記第１の基材の表面粗さが、上記第２の基材の表面粗さよりも小さいこと好ましい。上記組合せＢの場合に、上記積層構造体では、上記第２の基材の表面粗さが、上記第１の基材の表面粗さよりも小さいこと好ましい。 In the laminated structure, the surface roughness of the base material in contact with the cured product layer of the first composition is smaller than the surface roughness of the base material in contact with the cured product layer of the second composition. Is preferable. In the laminated structure, the surface roughness of the base material in contact with the cured product layer of the third composition is smaller than the surface roughness of the base material in contact with the cured product layer of the second composition. Is preferable. Therefore, in the case of the combination A, it is preferable that the surface roughness of the first base material is smaller than the surface roughness of the second base material in the laminated structure. In the case of the combination B, in the laminated structure, it is preferable that the surface roughness of the second base material is smaller than the surface roughness of the first base material.
　上記表面粗さは、第１の組成物、第２の組成物又は第３の組成物の硬化物層と接触する領域における表面粗さを意味する。また、上記表面粗さは、ＪＩＳ　Ｂ０６０１：１９９４に準拠して測定される算術平均粗さＲａを意味する。 The surface roughness means the surface roughness in the region in contact with the cured product layer of the first composition, the second composition or the third composition. The surface roughness means the arithmetic mean roughness Ra measured in accordance with JIS B0601: 1994.
　上記積層構造体において、上記第２の組成物の硬化物層と接触する基材の表面粗さは、好ましくは１００ｎｍ以上、より好ましくは２００ｎｍ以上、好ましくは１０００ｎｍ以下、より好ましくは５００ｎｍ以下である。 In the laminated structure, the surface roughness of the base material in contact with the cured product layer of the second composition is preferably 100 nm or more, more preferably 200 nm or more, preferably 1000 nm or less, and more preferably 500 nm or less. ..
　上記積層構造体において、上記第１の組成物の硬化物層と接触する基材の表面粗さと、上記第２の組成物の硬化物層と接触する基材の表面粗さとの差の絶対値は、好ましくは５０ｎｍ以上、より好ましくは１００ｎｍ以上、好ましくは９００ｎｍ以下、より好ましくは８００ｎｍ以下である。 Absolute value of the difference between the surface roughness of the base material in contact with the cured product layer of the first composition and the surface roughness of the base material in contact with the cured product layer of the second composition in the laminated structure. Is preferably 50 nm or more, more preferably 100 nm or more, preferably 900 nm or less, and more preferably 800 nm or less.
　本発明の効果をより一層効果的に発揮する観点からは、上記第２の層の厚みは、上記第１の層の厚みよりも厚いことが好ましく、上記第１の層の厚みよりも４０μｍ以上厚いことがより好ましく、上記第１の層の厚みよりも５０μｍ以上厚いことが更に好ましい。 From the viewpoint of more effectively exerting the effect of the present invention, the thickness of the second layer is preferably thicker than the thickness of the first layer, and is 40 μm or more than the thickness of the first layer. It is more preferably thick, and further preferably 50 μm or more thicker than the thickness of the first layer.
　本発明の効果をより一層効果的に発揮する観点からは、上記第２の層の厚みは、上記第３の層の厚みよりも厚いことが好ましく、上記第３の層の厚みよりも４０μｍ以上厚いことがより好ましく、上記第３の層の厚みよりも５０μｍ以上厚いことが更に好ましい。 From the viewpoint of more effectively exerting the effect of the present invention, the thickness of the second layer is preferably thicker than the thickness of the third layer, and is 40 μm or more than the thickness of the third layer. It is more preferably thick, and even more preferably 50 μm or more thicker than the thickness of the third layer.
　本発明の効果をより一層効果的に発揮する観点からは、上記第１の層の厚みは、好ましくは０．１μｍ以上、より好ましくは０．３μｍ以上、好ましくは１０μｍ以下、より好ましくは５ｍ以下である。 From the viewpoint of more effectively exerting the effect of the present invention, the thickness of the first layer is preferably 0.1 μm or more, more preferably 0.3 μm or more, preferably 10 μm or less, more preferably 5 m or less. Is.
　本発明の効果をより一層効果的に発揮する観点からは、上記第２の層の厚みは、好ましくは４０μｍ以上、より好ましくは５０μｍ以上、好ましくは１０００μｍ以下、より好ましくは８００ｍ以下である。 From the viewpoint of more effectively exerting the effect of the present invention, the thickness of the second layer is preferably 40 μm or more, more preferably 50 μm or more, preferably 1000 μm or less, and more preferably 800 m or less.
　本発明の効果をより一層効果的に発揮する観点からは、上記第３の層の厚みは、好ましくは０．１μｍ以上、より好ましくは０．３μｍ以上、好ましくは１０μｍ以下、より好ましくは５ｍ以下である。 From the viewpoint of more effectively exerting the effect of the present invention, the thickness of the third layer is preferably 0.1 μm or more, more preferably 0.3 μm or more, preferably 10 μm or less, more preferably 5 m or less. Is.
　上記第１の層と上記第２の層との積層物において、厚みの幅に対する比（厚み／幅）は、好ましくは０．０１以上、より好ましくは０．１以上、好ましくは２００以下、より好ましくは１５０以下である。上記比（厚み／幅）が上記下限以上及び上記上限以下であると、本発明の効果をより一層効果的に発揮することができる。 In the laminate of the first layer and the second layer, the ratio (thickness / width) to the width of the thickness is preferably 0.01 or more, more preferably 0.1 or more, preferably 200 or less, and more. It is preferably 150 or less. When the ratio (thickness / width) is equal to or greater than the above lower limit and equal to or less than the above upper limit, the effect of the present invention can be exhibited even more effectively.
　上記第１の層と上記第２の層と上記第３の層との積層物において、厚みの幅に対する比（厚み／幅）は、好ましくは０．０１以上、より好ましくは０．１以上、好ましくは２００以下、より好ましくは１５０以下である。上記比（厚み／幅）が上記下限以上及び上記上限以下であると、本発明の効果をより一層効果的に発揮することができる。 In the laminate of the first layer, the second layer, and the third layer, the ratio (thickness / width) to the width of the thickness is preferably 0.01 or more, more preferably 0.1 or more. It is preferably 200 or less, more preferably 150 or less. When the ratio (thickness / width) is equal to or greater than the above lower limit and equal to or less than the above upper limit, the effect of the present invention can be exhibited even more effectively.
　上記第２の層において、厚みの幅に対する比（厚み／幅）は、好ましくは０．０１以上、より好ましくは０．１以上、好ましくは２００以下、より好ましくは１５０以下である。上記比（厚み／幅）が上記下限以上及び上記上限以下であると、本発明の効果をより一層効果的に発揮することができる。 In the second layer, the ratio (thickness / width) to the width of the thickness is preferably 0.01 or more, more preferably 0.1 or more, preferably 200 or less, and more preferably 150 or less. When the ratio (thickness / width) is equal to or greater than the above lower limit and equal to or less than the above upper limit, the effect of the present invention can be exhibited even more effectively.
　（インクジェット用組成物セット）
　上記インクジェット用組成物セットは、上記第１の組成物と上記第２の組成物とを有する。上記インクジェット用組成物セットでは、上記第１の組成物と上記第２の組成物とは混合されていない。上記第１の組成物は、第１の容器に収容されていることが好ましく、上記第２の組成物は、第２の容器に収容されていることが好ましい。上記インクジェット用組成物セットは、上記第１の組成物と上記第２の組成物とのセット品である。上記インクジェット用組成物セットでは、上記第１の組成物を塗布した後に上記第２の組成物を塗布して用いられることが好ましい。上記インクジェット用組成物セットでは、上記第１の組成物を塗布及び光硬化した後に上記第２の組成物を塗布及び光硬化して用いられることが好ましい。上記インクジェット用組成物セットは、上述した積層構造体を製造するために用いられることが好ましい。 (Inkjet composition set)
The inkjet composition set includes the first composition and the second composition. In the inkjet composition set, the first composition and the second composition are not mixed. The first composition is preferably contained in a first container, and the second composition is preferably contained in a second container. The inkjet composition set is a set of the first composition and the second composition. In the inkjet composition set, it is preferable that the first composition is applied and then the second composition is applied and used. In the inkjet composition set, it is preferable that the first composition is applied and photocured, and then the second composition is applied and photocured before use. The inkjet composition set is preferably used for producing the above-mentioned laminated structure.
　上記インクジェット用組成物セットは、第３の組成物を有していてもよい。この場合に、上記第１の組成物と上記第２の組成物と上記第３の組成物とは混合されていない。上記第３の組成物は、第３の容器に収容されていることが好ましい。上記第３の組成物を有する上記インクジェット用組成物セットは、上記第１の組成物と上記第２の組成物と上記第３の組成物とのセット品である。また、第１の光硬化物層（又は第１の光及び熱硬化物層）と、第３の光硬化物層（又は第３の光及び熱硬化物層）とを同一の組成物により形成する場合には、上記第１の組成物と上記第２の組成物とのセット品における上記第１の組成物を、上記第３の光硬化物層（又は第３の光及び熱硬化物層）を形成するために用いることができる。 The inkjet composition set may have a third composition. In this case, the first composition, the second composition, and the third composition are not mixed. The third composition is preferably contained in a third container. The inkjet composition set having the third composition is a set of the first composition, the second composition, and the third composition. Further, the first photocurable material layer (or the first light and thermosetting material layer) and the third photocurable material layer (or the third light and thermosetting material layer) are formed by the same composition. In this case, the first composition in the set product of the first composition and the second composition is used as the third photocurable layer (or the third light and thermosetting layer). ) Can be used to form.
　図１３は、本発明の第１の実施形態に係るインクジェット用組成物セットを模式的に示す断面図である。 FIG. 13 is a cross-sectional view schematically showing an inkjet composition set according to the first embodiment of the present invention.
　インクジェット用組成物セット５は、第１の容器１０１と、第１の組成物１と、第２の容器１０２と、第２の組成物２とを有する。第１の容器１０１に、第１の組成物１が収容されている。第２の容器１０２に、第２の組成物２が収容されている。 The inkjet composition set 5 has a first container 101, a first composition 1, a second container 102, and a second composition 2. The first composition 1 is contained in the first container 101. The second composition 2 is contained in the second container 102.
　上記積層構造体の製造方法においては、第１の組成物よりも第２の組成物の方がより多く消費される。そのため、上記インクジェット用組成物セットでは、第１の容器に収容されている第１の組成物の量（体積）が、第２の容器に収容されている第２の組成物の第１の組成物の量（体積）よりも多いことが好ましい。 In the method for producing the laminated structure, the second composition is consumed more than the first composition. Therefore, in the above inkjet composition set, the amount (volume) of the first composition contained in the first container is the first composition of the second composition contained in the second container. It is preferably larger than the amount (volume) of the object.
　（第１の組成物、第２の組成物及び第３の組成物）
　以下、上記第１の組成物、上記第２の組成物及び第３の組成物に含まれる各成分の詳細を説明する。なお、本明細書において、「（メタ）アクリレート」は「アクリレート」と「メタクリレート」との一方又は双方を意味する。 (1st composition, 2nd composition and 3rd composition)
Hereinafter, details of each component contained in the first composition, the second composition and the third composition will be described. In addition, in this specification, "(meth) acrylate" means one or both of "acrylate" and "methacrylate".
　上記第１の組成物と上記第２の組成物とは異なる組成物であり、上記第３の組成物と上記第２の組成物とは異なる組成物である。すなわち、上記第１の組成物と上記第２の組成物とは、組成が異なり、上記第３の組成物と上記第２の組成物とは、組成が異なる。上記第１の組成物と上記第３の組成物とは異なる組成物であってもよく、同一の組成物であってもよい。積層構造体の製造効率を高める観点からは、上記第１の組成物と上記第３の組成物とは同一の組成物であることが好ましい。すなわち、上記第１の組成物と上記第３の組成物とは、組成が同一であることが好ましい。 The first composition and the second composition are different compositions, and the third composition and the second composition are different compositions. That is, the composition of the first composition and the composition of the second composition are different, and the composition of the third composition and the composition of the second composition are different. The first composition and the third composition may be different compositions or the same composition. From the viewpoint of increasing the production efficiency of the laminated structure, it is preferable that the first composition and the third composition are the same composition. That is, it is preferable that the first composition and the third composition have the same composition.
　上記第１の組成物及び第３の組成物は、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む。上記第２の組成物は、多官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む。 The first composition and the third composition include a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. The second composition contains a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
　なお、上記第１の組成物及び第３の組成物はそれぞれ、多官能の（メタ）アクリレート化合物を含んでいてもよく、含んでいなくてもよい。また、上記第２の組成物は、単官能の（メタ）アクリレート化合物を含んでいてもよく、含んでいなくてもよい。上記第１の組成物と上記第２の組成物との双方が多官能の（メタ）アクリレート化合物を含む場合に、上記第１の組成物に含まれる多官能の（メタ）アクリレート化合物と、上記第２の組成物に含まれる多官能の（メタ）アクリレート化合物とは同一であってもよく、異なっていてもよい。上記第３の組成物と上記第２の組成物との双方が多官能の（メタ）アクリレート化合物を含む場合に、上記第３の組成物に含まれる多官能の（メタ）アクリレート化合物と、上記第２の組成物に含まれる多官能の（メタ）アクリレート化合物とは同一であってもよく、異なっていてもよい。上記第１の組成物と上記第２の組成物との双方が単官能の（メタ）アクリレート化合物を含む場合に、上記第１の組成物に含まれる単官能の（メタ）アクリレート化合物と、上記第２の組成物に含まれる単官能の（メタ）アクリレート化合物とは同一であってもよく、異なっていてもよい。上記第３の組成物と上記第２の組成物との双方が単官能の（メタ）アクリレート化合物を含む場合に、上記第３の組成物に含まれる単官能の（メタ）アクリレート化合物と、上記第２の組成物に含まれる単官能の（メタ）アクリレート化合物とは同一であってもよく、異なっていてもよい。 The first composition and the third composition may or may not contain a polyfunctional (meth) acrylate compound, respectively. In addition, the second composition may or may not contain a monofunctional (meth) acrylate compound. When both the first composition and the second composition contain a polyfunctional (meth) acrylate compound, the polyfunctional (meth) acrylate compound contained in the first composition and the above It may be the same as or different from the polyfunctional (meth) acrylate compound contained in the second composition. When both the third composition and the second composition contain a polyfunctional (meth) acrylate compound, the polyfunctional (meth) acrylate compound contained in the third composition and the above It may be the same as or different from the polyfunctional (meth) acrylate compound contained in the second composition. When both the first composition and the second composition contain a monofunctional (meth) acrylate compound, the monofunctional (meth) acrylate compound contained in the first composition and the above It may be the same as or different from the monofunctional (meth) acrylate compound contained in the second composition. When both the third composition and the second composition contain a monofunctional (meth) acrylate compound, the monofunctional (meth) acrylate compound contained in the third composition and the above It may be the same as or different from the monofunctional (meth) acrylate compound contained in the second composition.
　＜（メタ）アクリレート化合物＞
　上記第１の組成物は、単官能の（メタ）アクリレート化合物を含む。上記第２の組成物は、多官能の（メタ）アクリレート化合物を含む。上記第３の組成物は、単官能の（メタ）アクリレート化合物を含む。なお、本明細書において、エポキシ基を有する（メタ）アクリレート化合物は、エポキシ化合物ではなく、（メタ）アクリレート化合物とみなす。上記単官能の（メタ）アクリレート化合物及び上記多官能の（メタ）アクリレート化合物はそれぞれ、１種のみが用いられてもよく、２種以上が併用されてもよい。 <(Meta) acrylate compound>
The first composition comprises a monofunctional (meth) acrylate compound. The second composition comprises a polyfunctional (meth) acrylate compound. The third composition comprises a monofunctional (meth) acrylate compound. In addition, in this specification, a (meth) acrylate compound having an epoxy group is regarded as a (meth) acrylate compound, not an epoxy compound. Only one kind of the monofunctional (meth) acrylate compound and the polyfunctional (meth) acrylate compound may be used, or two or more kinds thereof may be used in combination.
　上記単官能の（メタ）アクリレート化合物としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｉ－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｉ－ブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、アリル（メタ）アクリレート、ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、フェニル（メタ）アクリレート、２－メトキシエチル（メタ）アクリレート、２－フェノキシエチル（メタ）アクリレート、メトキシジエチレングルコール（メタ）アクリレート、メトキシトリエチレングルコール（メタ）アクリレート、メトキシプロピレングリコール（メタ）アクリレート、メトキシジプロピレングリコール（メタ）アクリレート、イソデシル（メタ）アクリレート、イソノニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタジエニル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、グリセロールモノ（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ジヒドロキシシクロペンタジエニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ナフチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ドデシル（メタ）アクリレート、及びステアリル（メタ）アクリレート等が挙げられる。 Examples of the monofunctional (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, and i-. Butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2 -Hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glucol (meth) acrylate, methoxytriethylene glucol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol ( Meta) acrylate, isodecyl (meth) acrylate, isononyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) Acrylate, 2-ethylhexyl (meth) acrylate, dihydroxycyclopentadienyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, naphthyl (meth) ) Acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate and the like.
　上記多官能の（メタ）アクリレート化合物は、二官能の（メタ）アクリレート化合物であってもよく、三官能の（メタ）アクリレート化合物であってもよく、四官能以上の（メタ）アクリレート化合物であってもよい。 The polyfunctional (meth) acrylate compound may be a bifunctional (meth) acrylate compound, a trifunctional (meth) acrylate compound, or a tetrafunctional or higher functional (meth) acrylate compound. You may.
　上記二官能の（メタ）アクリレート化合物としては、例えば、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、２，４－ジメチル－１，５－ペンタンジオールジ（メタ）アクリレート、ブチルエチルプロパンジオール（メタ）アクリレート、エトキシ化シクロヘキサンメタノールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、オリゴエチレングリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、２－エチル－２－ブチルブタンジオールジ（メタ）アクリレート、２－エチル－２－ブチルプロパンジオールジ（メタ）アクリレート、トリシクロデカンジ（メタ）アクリレート、及びジプロピレングリコールジ（メタ）アクリレート等が挙げられる。 Examples of the bifunctional (meth) acrylate compound include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonandi (meth) acrylate, and 1, 10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,4-dimethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol (meth) acrylate, ethoxylated cyclohexanemethanol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2-ethyl-2-butylbutanediol di (meth) acrylate, 2-ethyl- Examples thereof include 2-butylpropanediol di (meth) acrylate, tricyclodecandi (meth) acrylate, and dipropylene glycol di (meth) acrylate.
　上記三官能の（メタ）アクリレート化合物としては、例えば、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、トリメチロールプロパンのアルキレンオキシド変性トリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパントリ（（メタ）アクリロイルオキシプロピル）エーテル、イソシアヌル酸アルキレンオキシド変性トリ（メタ）アクリレート、プロピオン酸ジペンタエリスリトールトリ（メタ）アクリレート、トリ（（メタ）アクリロイルオキシエチル）イソシアヌレート、及びソルビトールトリ（メタ）アクリレート等が挙げられる。 Examples of the trifunctional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, alkylene oxide-modified tri (meth) acrylate of trimethylolpropane, and pentaerythritol tri (meth). ) Acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide-modified tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, tri ( Examples thereof include (meth) acryloyloxyethyl) isocyanurate and sorbitol tri (meth) acrylate.
　上記四官能の（メタ）アクリレート化合物としては、例えば、ペンタエリスリトールテトラ（メタ）アクリレート、ソルビトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、及びプロピオン酸ジペンタエリスリトールテトラ（メタ）アクリレート等が挙げられる。 Examples of the tetrafunctional (meth) acrylate compound include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol tetra (meth) acrylate propionate. Can be mentioned.
　上記五官能の（メタ）アクリレート化合物としては、例えば、ソルビトールペンタ（メタ）アクリレート、及びジペンタエリスリトールペンタ（メタ）アクリレートが挙げられる。 Examples of the pentafunctional (meth) acrylate compound include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.
　上記六官能の（メタ）アクリレート化合物としては、例えば、ジペンタエリスリトールヘキサ（メタ）アクリレート、ソルビトールヘキサ（メタ）アクリレート、及びフォスファゼンのアルキレンオキシド変性ヘキサ（メタ）アクリレート等が挙げられる。 Examples of the hexafunctional (meth) acrylate compound include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, and phosphazene alkylene oxide-modified hexa (meth) acrylate.
　また、上記エポキシ基を有する（メタ）アクリレート化合物としては、グリシジル（メタ）アクリレート、及び４－ヒドロキシブチル（メタ）アクリレートグリシジルエーテル等が挙げられる。 Examples of the (meth) acrylate compound having an epoxy group include glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether.
　本発明の効果をより一層効果的に発揮する観点からは、上記第１の組成物及び第３の組成物に含まれる上記単官能の（メタ）アクリレート化合物の単独重合体のガラス転移温度はそれぞれ、好ましくは－１００℃以上、より好ましくは－９０℃以上、好ましくは０℃未満、より好ましくは－１０℃以下である。 From the viewpoint of exerting the effects of the present invention even more effectively, the glass transition temperatures of the homopolymers of the monofunctional (meth) acrylate compounds contained in the first composition and the third composition are respectively. It is preferably −100 ° C. or higher, more preferably −90 ° C. or higher, preferably less than 0 ° C., and more preferably −10 ° C. or lower.
　本発明の効果をより一層効果的に発揮する観点からは、上記第２の組成物に含まれる上記多官能の（メタ）アクリレート化合物の単独重合体のガラス転移温度は、好ましくは５０℃以上、より好ましくは８０℃以上、好ましくは２００℃以下、より好ましくは１８０℃以下である。 From the viewpoint of more effectively exerting the effects of the present invention, the glass transition temperature of the homopolymer of the polyfunctional (meth) acrylate compound contained in the second composition is preferably 50 ° C. or higher. It is more preferably 80 ° C. or higher, preferably 200 ° C. or lower, and more preferably 180 ° C. or lower.
　上記単独重合体を得る重合において、重合方法は特に限定されない。上記単官能の（メタ）アクリレート化合物又は上記多官能の（メタ）アクリレート化合物を、公知の方法により単独重合させることで、上記単独重合体を得ることができる。上記重合方法において、全ての上記単官能の（メタ）アクリレート化合物又は全ての上記多官能の（メタ）アクリレート化合物を一度に重合させてもよく、上記単官能の（メタ）アクリレート化合物又は上記多官能の（メタ）アクリレート化合物を逐次的に加えて重合させてもよい。 In the polymerization for obtaining the above homopolymer, the polymerization method is not particularly limited. The homopolymer can be obtained by homopolymerizing the monofunctional (meth) acrylate compound or the polyfunctional (meth) acrylate compound by a known method. In the above polymerization method, all the above monofunctional (meth) acrylate compounds or all the above polyfunctional (meth) acrylate compounds may be polymerized at one time, and the above monofunctional (meth) acrylate compound or the above polyfunctionality may be polymerized at once. The (meth) acrylate compound of the above may be sequentially added and polymerized.
　上記ガラス転移温度は、ＪＩＳ－Ｋ７１２１に準拠して、示差走査熱量計を用いて、昇温速度１０℃／分の条件で測定することができる。上記示差走査熱量計としては、日立ハイテクサイエンス社製「ＤＳＣ７０２０」等が挙げられる。 The glass transition temperature can be measured in accordance with JIS-K7121 under the condition of a heating rate of 10 ° C./min using a differential scanning calorimeter. Examples of the differential scanning calorimeter include "DSC7020" manufactured by Hitachi High-Tech Science Corporation.
　本発明の効果をより一層効果的に発揮する観点からは、上記第１の組成物及び第３の組成物に含まれる上記単官能の（メタ）アクリレート化合物はそれぞれ、アクリル酸構造部分のエステル構造を構成する酸素原子に炭素数４以上の基が結合した化合物であることが好ましい。上記炭素数４以上の基は、分岐構造を有する基であってもよく、分岐構造を有さない基（直鎖構造を有する基）であってもよい。上記第１の組成物及び第３の組成物に含まれる上記単官能の（メタ）アクリレート化合物はそれぞれ、イソデシルアクリレート、イソノニルアクリレート、２－エチルヘキシルアクリレート、ラウリルアクリレート、又はドデシルアクリレートであることが好ましい。これらの単官能の（メタ）アクリレート化合物は、アクリル酸構造部分のエステル構造を構成する酸素原子に炭素数４以上の基が結合した化合物である。 From the viewpoint of exerting the effects of the present invention even more effectively, the monofunctional (meth) acrylate compounds contained in the first composition and the third composition each have an ester structure of an acrylic acid structure portion. It is preferable that the compound has a group having 4 or more carbon atoms bonded to the oxygen atom constituting the above. The group having 4 or more carbon atoms may be a group having a branched structure or a group having no branched structure (a group having a linear structure). The monofunctional (meth) acrylate compound contained in the first composition and the third composition may be isodecyl acrylate, isononyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, or dodecyl acrylate, respectively. preferable. These monofunctional (meth) acrylate compounds are compounds in which a group having 4 or more carbon atoms is bonded to an oxygen atom constituting the ester structure of the acrylic acid structure portion.
　本発明の効果をより一層効果的に発揮する観点からは、上記第２の組成物に含まれる上記多官能の（メタ）アクリレート化合物は、２官能又は３官能の（メタ）アクリレート化合物であることが好ましい。 From the viewpoint of exerting the effects of the present invention even more effectively, the polyfunctional (meth) acrylate compound contained in the second composition is a bifunctional or trifunctional (meth) acrylate compound. Is preferable.
　本発明の効果を更により一層効果的に発揮する観点からは、上記第２の組成物に含まれる上記多官能の（メタ）アクリレート化合物は、トリメチロールプロパントリアクリレート、１，６－ヘキサンジオールジアクリレート、又はジシクロペンテニルジメタノールジアクリレートであることが好ましい。 From the viewpoint of exerting the effects of the present invention even more effectively, the polyfunctional (meth) acrylate compound contained in the second composition is trimethylolpropane triacrylate, 1,6-hexanediol di. It is preferably acrylate or dicyclopentenyl dimethanol diacrylate.
　上記第１の組成物１００重量％中、又は、上記第３の組成物１００重量％中、上記単官能の（メタ）アクリレート化合物の含有量は、好ましくは５重量％以上、より好ましくは１０重量％以上、好ましくは９５重量％以下、より好ましくは９０重量％以下である。上記単官能の（メタ）アクリレート化合物の含有量が上記下限以上及び上記上限以下であると、本発明の効果をより一層効果的に発揮することができる。 The content of the monofunctional (meth) acrylate compound in 100% by weight of the first composition or 100% by weight of the third composition is preferably 5% by weight or more, more preferably 10% by weight. % Or more, preferably 95% by weight or less, more preferably 90% by weight or less. When the content of the monofunctional (meth) acrylate compound is not less than the above lower limit and not more than the above upper limit, the effect of the present invention can be exhibited even more effectively.
　上記第１の組成物が上記多官能の（メタ）アクリレート化合物を含む場合に、上記第１の組成物１００重量％中、上記多官能の（メタ）アクリレート化合物の含有量は、好ましくは０．１重量％以上、より好ましくは０．５重量％以上、好ましくは５０重量％以下、より好ましくは３０重量％以下である。上記第３の組成物が上記多官能の（メタ）アクリレート化合物を含む場合に、上記第３の組成物１００重量％中、上記多官能の（メタ）アクリレート化合物の含有量は、好ましくは０．１重量％以上、より好ましくは０．５重量％以上、好ましくは５０重量％以下、より好ましくは３０重量％以下である。上記多官能の（メタ）アクリレート化合物の含有量が上記下限以上及び上記上限以下であると、本発明の効果をより一層効果的に発揮することができる。 When the first composition contains the polyfunctional (meth) acrylate compound, the content of the polyfunctional (meth) acrylate compound in 100% by weight of the first composition is preferably 0. It is 1% by weight or more, more preferably 0.5% by weight or more, preferably 50% by weight or less, and more preferably 30% by weight or less. When the third composition contains the polyfunctional (meth) acrylate compound, the content of the polyfunctional (meth) acrylate compound in 100% by weight of the third composition is preferably 0. It is 1% by weight or more, more preferably 0.5% by weight or more, preferably 50% by weight or less, and more preferably 30% by weight or less. When the content of the polyfunctional (meth) acrylate compound is not less than the above lower limit and not more than the above upper limit, the effect of the present invention can be exhibited even more effectively.
　上記第２の組成物１００重量％中、上記多官能の（メタ）アクリレート化合物の含有量は、好ましくは１０重量％以上、より好ましくは２０重量％以上、好ましくは９９重量％以下、より好ましくは９０重量％以下である。上記多官能の（メタ）アクリレート化合物の含有量が上記下限以上及び上記上限以下であると、本発明の効果をより一層効果的に発揮することができる。 The content of the polyfunctional (meth) acrylate compound in 100% by weight of the second composition is preferably 10% by weight or more, more preferably 20% by weight or more, preferably 99% by weight or less, more preferably 99% by weight or less. It is 90% by weight or less. When the content of the polyfunctional (meth) acrylate compound is not less than the above lower limit and not more than the above upper limit, the effect of the present invention can be exhibited even more effectively.
　上記第２の組成物が上記単官能の（メタ）アクリレート化合物を含む場合に、上記第２の組成物１００重量％中、上記単官能の（メタ）アクリレート化合物の含有量は、好ましくは０．１重量％以上、より好ましくは０．５重量％以上、好ましくは５０重量％以下、より好ましくは３０重量％以下である。上記単官能の（メタ）アクリレート化合物の含有量が上記下限以上及び上記上限以下であると、本発明の効果をより一層効果的に発揮することができる。 When the second composition contains the monofunctional (meth) acrylate compound, the content of the monofunctional (meth) acrylate compound in 100% by weight of the second composition is preferably 0. It is 1% by weight or more, more preferably 0.5% by weight or more, preferably 50% by weight or less, and more preferably 30% by weight or less. When the content of the monofunctional (meth) acrylate compound is not less than the above lower limit and not more than the above upper limit, the effect of the present invention can be exhibited even more effectively.
　上記第１の組成物が上記多官能の（メタ）アクリレート化合物を含む場合に、上記第１の組成物１００重量％中の上記多官能の（メタ）アクリレート化合物の含有量は、上記第２の組成物１００重量％中の上記多官能の（メタ）アクリレート化合物の含有量よりも少ないことが好ましい。上記第３の組成物が上記多官能の（メタ）アクリレート化合物を含む場合に、上記第３の組成物１００重量％中の上記多官能の（メタ）アクリレート化合物の含有量は、上記第２の組成物１００重量％中の上記多官能の（メタ）アクリレート化合物の含有量よりも少ないことが好ましい。この場合には、本発明の効果をより一層効果的に発揮することができる。 When the first composition contains the polyfunctional (meth) acrylate compound, the content of the polyfunctional (meth) acrylate compound in 100% by weight of the first composition is the second composition. It is preferably less than the content of the polyfunctional (meth) acrylate compound in 100% by weight of the composition. When the third composition contains the polyfunctional (meth) acrylate compound, the content of the polyfunctional (meth) acrylate compound in 100% by weight of the third composition is the second composition. It is preferably less than the content of the polyfunctional (meth) acrylate compound in 100% by weight of the composition. In this case, the effect of the present invention can be exhibited even more effectively.
　上記第２の組成物が上記単官能の（メタ）アクリレート化合物を含む場合に、上記第２の組成物１００重量％中の上記単官能の（メタ）アクリレート化合物の含有量は、上記第１の組成物１００重量％中の上記単官能の（メタ）アクリレート化合物の含有量よりも少ないことが好ましい。上記第２の組成物が上記単官能の（メタ）アクリレート化合物を含む場合に、上記第２の組成物１００重量％中の上記単官能の（メタ）アクリレート化合物の含有量は、上記第３の組成物１００重量％中の上記単官能の（メタ）アクリレート化合物の含有量よりも少ないことが好ましい。この場合には、本発明の効果をより一層効果的に発揮することができる。 When the second composition contains the monofunctional (meth) acrylate compound, the content of the monofunctional (meth) acrylate compound in 100% by weight of the second composition is the above-mentioned first. It is preferably less than the content of the monofunctional (meth) acrylate compound in 100% by weight of the composition. When the second composition contains the monofunctional (meth) acrylate compound, the content of the monofunctional (meth) acrylate compound in 100% by weight of the second composition is the third It is preferably less than the content of the monofunctional (meth) acrylate compound in 100% by weight of the composition. In this case, the effect of the present invention can be exhibited even more effectively.
　＜エポキシ化合物＞
　上記第１の組成物は、エポキシ化合物を含む。上記第２の組成物は、エポキシ化合物を含む。上記第３の組成物は、エポキシ化合物を含む。上記第１の組成物に含まれるエポキシ化合物と、上記第２の組成物に含まれるエポキシ化合物と、上記第３の組成物に含まれるエポキシ化合物とはそれぞれ同一であってもよく、異なっていてもよい。上記エポキシ化合物はそれぞれ、１種のみが用いられてもよく、２種以上が併用されてもよい。 <Epoxy compound>
The first composition contains an epoxy compound. The second composition contains an epoxy compound. The third composition contains an epoxy compound. The epoxy compound contained in the first composition, the epoxy compound contained in the second composition, and the epoxy compound contained in the third composition may be the same or different from each other. May be good. Only one type of each of the above epoxy compounds may be used, or two or more types may be used in combination.
　上記エポキシ化合物としては、ビスフェノールＡ型エポキシ化合物、ビスフェノールＦ型エポキシ化合物、ビスフェノールＳ型エポキシ化合物、フェノールノボラック型エポキシ化合物、ビフェニル型エポキシ化合物、ビフェニルノボラック型エポキシ化合物、ビフェノール型エポキシ化合物、ナフタレン型エポキシ化合物、フルオレン型エポキシ化合物、フェノールアラルキル型エポキシ化合物、ナフトールアラルキル型エポキシ化合物、ジシクロペンタジエン型エポキシ化合物、アントラセン型エポキシ化合物、アダマンタン骨格を有するエポキシ化合物、トリシクロデカン骨格を有するエポキシ化合物、ナフチレンエーテル型エポキシ化合物、及びトリアジン核を骨格に有するエポキシ化合物等が挙げられる。 Examples of the epoxy compound include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, phenol novolac type epoxy compound, biphenyl type epoxy compound, biphenyl novolac type epoxy compound, biphenol type epoxy compound, and naphthalene type epoxy compound. , Fluorene type epoxy compound, phenol aralkyl type epoxy compound, naphthol aralkyl type epoxy compound, dicyclopentadiene type epoxy compound, anthracene type epoxy compound, adamantan skeleton epoxy compound, tricyclodecane skeleton epoxy compound, naphthylene ether type Examples thereof include epoxy compounds and epoxy compounds having a triazine nucleus as a skeleton.
　本発明の効果をより一層効果的に発揮する観点からは、上記第１の組成物及び第３の組成物に含まれる上記エポキシ化合物はそれぞれ、ビスフェノールＡ型エポキシ化合物、又はジシクロペンタジエン型エポキシ化合物であることが好ましい。 From the viewpoint of more effectively exerting the effects of the present invention, the epoxy compounds contained in the first composition and the third composition are bisphenol A type epoxy compounds or dicyclopentadiene type epoxy compounds, respectively. Is preferable.
　本発明の効果をより一層効果的に発揮する観点からは、上記第２の組成物に含まれる上記エポキシ化合物は、ビスフェノールＡ型エポキシ化合物、又はジシクロペンタジエン型エポキシ化合物であることが好ましい。 From the viewpoint of exerting the effects of the present invention even more effectively, the epoxy compound contained in the second composition is preferably a bisphenol A type epoxy compound or a dicyclopentadiene type epoxy compound.
　上記第１の組成物１００重量％中、又は、上記第３の組成物１００重量％中、上記エポキシ化合物の含有量は、好ましくは０．１重量％以上、より好ましくは１重量％以上、好ましくは９０重量％以下、より好ましくは７０重量％以下である。上記エポキシ化合物の含有量が上記下限以上及び上記上限以下であると、本発明の効果をより一層効果的に発揮することができる。 The content of the epoxy compound in 100% by weight of the first composition or 100% by weight of the third composition is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 1% by weight or more. Is 90% by weight or less, more preferably 70% by weight or less. When the content of the epoxy compound is not less than the above lower limit and not more than the above upper limit, the effect of the present invention can be exhibited even more effectively.
　上記第２の組成物１００重量％中、上記エポキシ化合物の含有量は、好ましくは０．１重量％以上、より好ましくは１重量％以上、好ましくは９０重量％以下、より好ましくは７０重量％以下である。上記エポキシ化合物の含有量が上記下限以上及び上記上限以下であると、本発明の効果をより一層効果的に発揮することができる。 The content of the epoxy compound in 100% by weight of the second composition is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 90% by weight or less, and more preferably 70% by weight or less. Is. When the content of the epoxy compound is not less than the above lower limit and not more than the above upper limit, the effect of the present invention can be exhibited even more effectively.
　＜光重合開始剤＞
　上記第１の組成物は、光重合開始剤を含む。上記第２の組成物は、光重合開始剤を含む。上記第３の組成物は、光重合開始剤を含む。上記第１の組成物に含まれる光重合開始剤と、上記第２の組成物に含まれる光重合開始剤と、上記第３の組成物に含まれる光重合開始剤とはそれぞれ同一であってもよく、異なっていてもよい。上記光重合開始剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 <Photopolymerization initiator>
The first composition contains a photopolymerization initiator. The second composition contains a photopolymerization initiator. The third composition contains a photopolymerization initiator. The photopolymerization initiator contained in the first composition, the photopolymerization initiator contained in the second composition, and the photopolymerization initiator contained in the third composition are the same. May be different. Only one kind of the photopolymerization initiator may be used, or two or more kinds thereof may be used in combination.
　上記光重合開始剤としては、光ラジカル重合開始剤及び光カチオン重合開始剤等が挙げられる。上記光重合開始剤は、光ラジカル重合開始剤であることが好ましい。上記光重合開始剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. Only one kind of the photopolymerization initiator may be used, or two or more kinds thereof may be used in combination.
　上記光ラジカル重合開始剤は、光の照射によりラジカルを発生し、ラジカル重合反応を開始するための化合物である。上記光ラジカル重合開始剤としては、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のベンゾイン化合物；２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン等のアルキルフェノン化合物；アセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、１，１－ジクロロアセトフェノン等のアセトフェノン化合物；２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン、Ｎ，Ｎ－ジメチルアミノアセトフェノン等のアミノアセトフェノン化合物；２－メチルアントラキノン、２－エチルアントラキノン、２－ｔ－ブチルアントラキノン等のアントラキノン化合物；２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２－クロロチオキサントン、２，４－ジイソプロピルチオキサントン等のチオキサントン化合物；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール化合物；２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド等のアシルフォスフィンオキサイド化合物；１，２－オクタンジオン、１－［４－（フェニルチオ）－２－（ｏ－ベンゾイルオキシム）］、エタノン、１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－１－（ｏ－アセチルオキシム）等のオキシムエステル化合物；ビス（シクロペンタジエニル）－ジ－フェニル－チタニウム、ビス（シクロペンタジエニル）－ジ－クロロ－チタニウム、ビス（シクロペンタジエニル）－ビス（２，３，４，５，６－ペンタフルオロフェニル）チタニウム、ビス（シクロペンタジエニル）－ビス（２，６－ジフルオロ－３－（ピロール－１－イル）フェニル）チタニウムなどのチタノセン化合物等が挙げられる。上記光ラジカル重合開始剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 The photoradical polymerization initiator is a compound for initiating a radical polymerization reaction by generating radicals by irradiation with light. Examples of the photoradical polymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; and alkylphenone compounds such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one; Acetphenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl]- 2-Molholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone, etc. Aminoacetophenone compounds; anthraquinone compounds such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butyl anthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropyl Thioxanthone compounds such as thioxanthone; Ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; acylphos such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Finoxide compounds; 1,2-octanedione, 1- [4- (phenylthio) -2- (o-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazole-3-yl] -1- (o-acetyloxime) and other oxime ester compounds; bis (cyclopentadienyl) -di-phenyl-titanium, bis (cyclopentadienyl) -di-chloro-titanium, bis (Cyclopentadienyl) -bis (2,3,4,5,6-pentafluorophenyl) titanium, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrrole-1-yl)) Examples thereof include titanosen compounds such as phenyl) titanium. Only one kind of the photoradical polymerization initiator may be used, or two or more kinds thereof may be used in combination.
　上記光ラジカル重合開始剤とともに、光重合開始助剤を用いてもよい。該光重合開始助剤としては、Ｎ，Ｎ－ジメチルアミノ安息香酸エチルエステル、Ｎ，Ｎ－ジメチルアミノ安息香酸イソアミルエステル、ペンチル－４－ジメチルアミノベンゾエート、トリエチルアミン及びトリエタノールアミン等が挙げられる。これら以外の光重合開始助剤を用いてもよい。上記光重合開始助剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 A photopolymerization initiator may be used together with the photoradical polymerization initiator. Examples of the photopolymerization initiator include N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like. Other photopolymerization initiators may be used. As the photopolymerization initiator, only one kind may be used, or two or more kinds may be used in combination.
　また、可視光領域に吸収があるＣＧＩ－７８４等（チバ・スペシャルティ・ケミカルズ社製）のチタノセン化合物などを、光反応を促進するために用いてもよい。 Further, a titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals), which absorbs in the visible light region, may be used to promote the photoreaction.
　上記光カチオン重合開始剤としては、スルホニウム塩、ヨードニウム塩、メタロセン化合物及びベンゾイントシレート等が挙げられる。上記光カチオン重合開始剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 Examples of the photocationic polymerization initiator include sulfonium salts, iodonium salts, metallocene compounds, benzointosilates and the like. Only one kind of the photocationic polymerization initiator may be used, or two or more kinds thereof may be used in combination.
　上記第１の組成物１００重量％中、上記光重合開始剤の含有量は、好ましくは０．１重量％以上、より好ましくは０．５重量％以上、好ましくは３０重量％以下、より好ましくは２０重量％以下である。 The content of the photopolymerization initiator in 100% by weight of the first composition is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, preferably 30% by weight or less, more preferably. It is 20% by weight or less.
　上記第２の組成物１００重量％中、上記光重合開始剤の含有量は、好ましくは０．１重量％以上、より好ましくは０．５重量％以上、好ましくは３０重量％以下、より好ましくは２０重量％以下である。 The content of the photopolymerization initiator in 100% by weight of the second composition is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, preferably 30% by weight or less, more preferably. It is 20% by weight or less.
　上記第３の組成物１００重量％中、上記光重合開始剤の含有量は、好ましくは０．１重量％以上、より好ましくは０．５重量％以上、好ましくは３０重量％以下、より好ましくは２０重量％以下である。 The content of the photopolymerization initiator in 100% by weight of the third composition is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, preferably 30% by weight or less, more preferably. It is 20% by weight or less.
　＜熱硬化剤＞
　上記第１の組成物は、熱硬化剤を含む。上記第２の組成物は、熱硬化剤を含む。上記第３の組成物は、熱硬化剤を含む。上記第１の組成物に含まれる熱硬化剤と、上記第２の組成物に含まれる熱硬化剤と、上記第３の組成物に含まれる熱硬化剤とはそれぞれ同一であってもよく、異なっていてもよい。上記熱硬化剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 <Thermosetting agent>
The first composition contains a thermosetting agent. The second composition contains a thermosetting agent. The third composition contains a thermosetting agent. The thermosetting agent contained in the first composition, the thermosetting agent contained in the second composition, and the thermosetting agent contained in the third composition may be the same. It may be different. Only one type of the thermosetting agent may be used, or two or more types may be used in combination.
　上記熱硬化剤としては、有機酸、アミン化合物、アミド化合物、ヒドラジド化合物、イミダゾール化合物、イミダゾリン化合物、フェノール化合物、ユリア化合物、ポリスルフィッド化合物及び酸無水物等が挙げられる。上記熱硬化剤として、アミン－エポキシアダクトなどの変性ポリアミン化合物を用いてもよい。これら以外の熱硬化剤を用いてもよい。 Examples of the heat-curing agent include organic acids, amine compounds, amide compounds, hydrazide compounds, imidazole compounds, imidazoline compounds, phenol compounds, urea compounds, polysulfid compounds, acid anhydrides and the like. As the thermosetting agent, a modified polyamine compound such as amine-epoxy adduct may be used. Thermosetting agents other than these may be used.
　上記アミン化合物とは、１級～３級のアミノ基を１個以上有する化合物を意味する。上記アミン化合物としては、脂肪族ポリアミン、脂環族ポリアミン、芳香族ポリアミン、ヒドラジド、及びグアニジン誘導体等が挙げられる。また、上記アミン化合物として、エポキシ化合物付加ポリアミン（エポキシ化合物とポリアミンの反応物）、マイケル付加ポリアミン（α，β－不飽和ケトンとポリアミンの反応物）、マンニッヒ付加ポリアミン（ポリアミンとホルマリン及びフェノールの縮合体）、チオ尿素付加ポリアミン（チオ尿素とポリアミンの反応物）、ケトン封鎖ポリアミン（ケトン化合物とポリアミンの反応物［ケチミン］）などのアダクト体を用いてもよい。 The amine compound means a compound having one or more primary to tertiary amino groups. Examples of the amine compound include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, hydrazides, and guanidine derivatives. In addition, as the above-mentioned amine compounds, an epoxy compound-added polyamine (a reaction product of an epoxy compound and a polyamine), a Michael-added polyamine (a reaction product of an α, β-unsaturated ketone and a polyamine), and a Mannig-added polyamine (a condensation of a polyamine and a formalin and a phenol). Body), thiourea-added polyamines (reactants of thiourea and polyamines), ketone-blocking polyamines (reactions of ketone compounds and polyamines [ketimine]) and other adducts may be used.
　上記脂肪族ポリアミンとしては、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、及びジエチルアミノプロピルアミン等が挙げられる。 Examples of the aliphatic polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine and the like.
　上記脂環族ポリアミンとしては、メンセンジアミン、イソホロンジアミン、Ｎ－アミノエチルピペラジン、３，９－ビス（３－アミノプロピル）－２，４，８，１０－テトラオキサスピロ（５，５）ウンデカンアダクト、ビス（４－アミノ－３－メチルシクロヘキシル）メタン、及びビス（４－アミノシクロヘキシル）メタン等が挙げられる。 Examples of the alicyclic polyamine include mensendiamine, isophoronediamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane. Adduct, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane and the like can be mentioned.
　上記芳香族ポリアミンとしては、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、ｏ－キシレンジアミン、ｍ－キシレンジアミン、ｐ－キシレンジアミン、４，４－ジアミノジフェニルメタン、４，４－ジアミノジフェニルプロパン、４，４－ジアミノジフェニルスルフォン、４，４－ジアミノジシクロヘキサン、ビス（４－アミノフェニル）フェニルメタン、１，５－ジアミノナフタレン、１，１－ビス（４－アミノフェニル）シクロヘキサン、２，２－ビス［（４－アミノフェノキシ）フェニル］プロパン、ビス［４－（４－アミノフェノキシ）フェニル］スルフォン、１，３－ビス（４－アミノフェノキシ）ベンゼン、４，４－メチレン－ビス（２－クロロアニリン）、及び４，４－ジアミノジフェニルスルフォン等が挙げられる。 Examples of the aromatic polyamine include m-phenylenediamine, p-phenylenediamine, o-xylene diamine, m-xylene diamine, p-xylene diamine, 4,4-diaminodiphenylmethane, 4,4-diaminodiphenylpropane, and 4,4. -Diaminodiphenyl sulfone, 4,4-diaminodicyclohexane, bis (4-aminophenyl) phenylmethane, 1,5-diaminonaphthalene, 1,1-bis (4-aminophenyl) cyclohexane, 2,2-bis [( 4-Aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,3-bis (4-aminophenoxy) benzene, 4,4-methylene-bis (2-chloroaniline), And 4,4-diaminodiphenyl sulphon and the like.
　上記ヒドラジドとしては、カルボジヒドラジド、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド、ドデカン二酸ジヒドラジド、及びイソフタル酸ジヒドラジド等が挙げられる。 Examples of the hydrazide include carbodihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecane diacid dihydrazide, and isophthalic acid dihydrazide.
　上記グアニジン誘導体としては、ジシアンジアミド、１－ｏ－トリルジグアニド、α－２，５－ジメチルグアニド、α，ω－ジフェニルジグアニジド、α，α－ビスグアニルグアニジノジフェニルエーテル、ｐ－クロロフェニルジグアニド、α，α－ヘキサメチレンビス［ω－（ｐ－クロロフェノール）］ジグアニド、フェニルジグアニドオキサレート、アセチルグアニジン、及びジエチルシアノアセチルグアニジン等が挙げられる。 Examples of the guanidine derivative include dicyandiamide, 1-o-tolyldiguanide, α-2,5-dimethylguanide, α, ω-diphenyldiguanide, α, α-bisguanylguanidinodiphenyl ether, p-chlorophenyldiguanide, α, α. -Hexamethylenebis [ω- (p-chlorophenol)] diguanide, phenyldiguanidooxalate, acetylguanidine, diethylcyanoacetylguanidine and the like can be mentioned.
　上記フェノール化合物としては、多価フェノール化合物等が挙げられる。上記多価フェノール化合物としては、例えば、フェノール、クレゾール、エチルフェノール、ブチルフェノール、オクチルフェノール、ビスフェノールＡ、テトラブロムビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、４，４’－ビフェニルフェノール、ナフタレン骨格含有フェノールノボラック樹脂、キシリレン骨格含有フェノールノボラック樹脂、ジシクロペンタジエン骨格含有フェノールノボラック樹脂、及びフルオレン骨格含有フェノールノボラック樹脂等が挙げられる。 Examples of the phenol compound include a multivalent phenol compound and the like. Examples of the polyhydric phenol compound include phenol, cresol, ethylphenol, butylphenol, octylphenol, bisphenol A, tetrabrom bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenylphenol, naphthalene skeleton-containing phenol novolac resin, and the like. Examples thereof include a xylylene skeleton-containing phenol novolac resin, a dicyclopentadiene skeleton-containing phenol novolac resin, and a fluorene skeleton-containing phenol novolac resin.
　上記酸無水物としては、例えば、無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ドデシル無水コハク酸、無水クロレンディック酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸無水物、メチルシクロヘキセンテトラカルボン酸無水物、無水トリメリット酸、及びポリアゼライン酸無水物等が挙げられる。 Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, dodecyl anhydride, chlorendic anhydride, and pyromellitic anhydride. Examples thereof include benzophenone tetracarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, trimellitic anhydride, polyazelineic acid anhydride and the like.
　上記第１の組成物１００重量％中、上記熱硬化剤の含有量は、好ましくは０．１重量％以上、より好ましくは１重量％以上、好ましくは５０重量％以下、より好ましくは４０重量％以下である。 The content of the thermosetting agent in 100% by weight of the first composition is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 50% by weight or less, and more preferably 40% by weight. It is as follows.
　上記第２の組成物１００重量％中、上記熱硬化剤の含有量は、好ましくは０．１重量％以上、より好ましくは１重量％以上、好ましくは５０重量％以下、より好ましくは４０重量％以下である。 The content of the thermosetting agent in 100% by weight of the second composition is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 50% by weight or less, and more preferably 40% by weight. It is as follows.
　上記第３の組成物１００重量％中、上記熱硬化剤の含有量は、好ましくは０．１重量％以上、より好ましくは１重量％以上、好ましくは５０重量％以下、より好ましくは４０重量％以下である。 The content of the thermosetting agent in 100% by weight of the third composition is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 50% by weight or less, and more preferably 40% by weight. It is as follows.
　＜硬化促進剤＞
　上記第１の組成物は、硬化促進剤を含んでいてもよく、含んでいなくてもよい。上記第２の組成物は、硬化促進剤を含んでいてもよく、含んでいなくてもよい。上記第３の組成物は、硬化促進剤を含んでいてもよく、含んでいなくてもよい。上記第１の組成物に含まれる硬化促進剤と、上記第２の組成物に含まれる硬化促進剤と、上記第３の組成物に含まれる硬化促進剤とはそれぞれ同一であってもよく、異なっていてもよい。上記硬化促進剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 <Curing accelerator>
The first composition may or may not contain a curing accelerator. The second composition may or may not contain a curing accelerator. The third composition may or may not contain a curing accelerator. The curing accelerator contained in the first composition, the curing accelerator contained in the second composition, and the curing accelerator contained in the third composition may be the same. It may be different. Only one type of the curing accelerator may be used, or two or more types may be used in combination.
　上記硬化促進剤としては、第三級アミン、イミダゾール、第四級アンモニウム塩、第四級ホスホニウム塩、有機金属塩、リン化合物及び尿素系化合物等が挙げられる。 Examples of the curing accelerator include tertiary amines, imidazoles, quaternary ammonium salts, quaternary phosphonium salts, organic metal salts, phosphorus compounds, urea compounds and the like.
　上記第１の組成物が上記硬化促進剤を含む場合に、上記第１の組成物１００重量％中、上記硬化促進剤の含有量は、好ましくは０．０１重量％以上、より好ましくは０．１重量％以上、好ましくは１０重量％以下、より好ましくは８重量％以下である。 When the first composition contains the curing accelerator, the content of the curing accelerator in 100% by weight of the first composition is preferably 0.01% by weight or more, more preferably 0. It is 1% by weight or more, preferably 10% by weight or less, and more preferably 8% by weight or less.
　上記第２の組成物が上記硬化促進剤を含む場合に、上記第２の組成物１００重量％中、上記硬化促進剤の含有量は、好ましくは０．０１重量％以上、より好ましくは０．１重量％以上、好ましくは１０重量％以下、より好ましくは８重量％以下である。 When the second composition contains the curing accelerator, the content of the curing accelerator in 100% by weight of the second composition is preferably 0.01% by weight or more, more preferably 0. It is 1% by weight or more, preferably 10% by weight or less, and more preferably 8% by weight or less.
　上記第３の組成物が上記硬化促進剤を含む場合に、上記第３の組成物１００重量％中、上記硬化促進剤の含有量は、好ましくは０．０１重量％以上、より好ましくは０．１重量％以上、好ましくは１０重量％以下、より好ましくは８重量％以下である。 When the third composition contains the curing accelerator, the content of the curing accelerator in 100% by weight of the third composition is preferably 0.01% by weight or more, more preferably 0. It is 1% by weight or more, preferably 10% by weight or less, and more preferably 8% by weight or less.
　（溶剤）
　上記第１の組成物は、溶剤を含んでいてもよく、含んでいなくてもよい。上記第２の組成物は、溶剤を含んでいてもよく、含んでいなくてもよい。上記第３の組成物は、溶剤を含んでいてもよく、含んでいなくてもよい。上記第１の組成物に含まれる溶剤と、上記第２の組成物に含まれる溶剤と、上記第３の組成物に含まれる溶剤とはそれぞれ同一であってもよく、異なっていてもよい。上記溶剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 (solvent)
The first composition may or may not contain a solvent. The second composition may or may not contain a solvent. The third composition may or may not contain a solvent. The solvent contained in the first composition, the solvent contained in the second composition, and the solvent contained in the third composition may be the same or different from each other. Only one type of the solvent may be used, or two or more types may be used in combination.
　第１の組成物の硬化物層（光硬化物層又は光及び熱硬化物層）の厚み精度をより一層高め、更に第１の組成物の硬化物層にボイドをより一層生じ難くする観点からは、上記第１の組成物における溶剤の含有量は少ないほどよい。 From the viewpoint of further improving the thickness accuracy of the cured product layer (photo-cured product layer or light and thermosetting material layer) of the first composition, and further making it more difficult for voids to occur in the cured product layer of the first composition. The smaller the solvent content in the first composition, the better.
　第２の組成物の硬化物層（光硬化物層又は光及び熱硬化物層）の厚み精度をより一層高め、更に第２の組成物の硬化物層にボイドをより一層生じ難くする観点からは、上記第２の組成物における溶剤の含有量は少ないほどよい。 From the viewpoint of further improving the thickness accuracy of the cured product layer (photo-cured product layer or light and thermosetting material layer) of the second composition, and further making it more difficult for voids to occur in the cured product layer of the second composition. The smaller the solvent content in the second composition, the better.
　第３の組成物の硬化物層（光硬化物層又は光及び熱硬化物層）の厚み精度をより一層高め、更に第３の組成物の硬化物層にボイドをより一層生じ難くする観点からは、上記第３の組成物における溶剤の含有量は少ないほどよい。 From the viewpoint of further improving the thickness accuracy of the cured product layer (photo-cured product layer or light and thermosetting material layer) of the third composition, and further making it more difficult for voids to occur in the cured product layer of the third composition. The smaller the solvent content in the third composition, the better.
　上記溶剤としては、水及び有機溶剤等が挙げられる。 Examples of the solvent include water and organic solvents.
　残留物の除去性をより一層高める観点からは、上記溶剤は、有機溶剤であることが好ましい。 From the viewpoint of further improving the removability of the residue, the solvent is preferably an organic solvent.
　上記有機溶剤としては、エタノール等のアルコール類、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン類、トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類、セロソルブ、メチルセロソルブ、ブチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジエチルエーテル、トリプロピレングリコールモノメチルエーテル等のグリコールエーテル類、酢酸エチル、酢酸ブチル、乳酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、炭酸プロピレン等のエステル類、オクタン、デカン等の脂肪族炭化水素類、並びに石油エーテル、ナフサ等の石油系溶剤等が挙げられる。 Examples of the organic solvent include alcohols such as ethanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol and methylcarbitol. , Butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether and other glycol ethers, ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol. Acetates, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, esters such as propylene carbonate, aliphatic hydrocarbons such as octane and decane, and petroleum solvents such as petroleum ether and naphtha. Can be mentioned.
　上記第１の組成物が上記溶剤を含む場合に、上記第１の組成物１００重量％中、上記溶剤の含有量は、好ましくは５重量％以下、より好ましくは１重量％以下、更に好ましくは０．５重量％以下である。上記第１の組成物は、上記溶剤を含まないことが最も好ましい。 When the first composition contains the solvent, the content of the solvent in 100% by weight of the first composition is preferably 5% by weight or less, more preferably 1% by weight or less, still more preferably. It is 0.5% by weight or less. Most preferably, the first composition does not contain the solvent.
　上記第２の組成物が上記溶剤を含む場合に、上記第２の組成物１００重量％中、上記溶剤の含有量は、好ましくは５重量％以下、より好ましくは１重量％以下、更に好ましくは０．５重量％以下である。上記第２の組成物は、上記溶剤を含まないことが最も好ましい。 When the second composition contains the solvent, the content of the solvent in 100% by weight of the second composition is preferably 5% by weight or less, more preferably 1% by weight or less, still more preferably. It is 0.5% by weight or less. Most preferably, the second composition does not contain the solvent.
　上記第３の組成物が上記溶剤を含む場合に、上記第３の組成物１００重量％中、上記溶剤の含有量は、好ましくは５重量％以下、より好ましくは１重量％以下、更に好ましくは０．５重量％以下である。上記第３の組成物は、上記溶剤を含まないことが最も好ましい。 When the third composition contains the solvent, the content of the solvent in 100% by weight of the third composition is preferably 5% by weight or less, more preferably 1% by weight or less, still more preferably. It is 0.5% by weight or less. Most preferably, the third composition does not contain the solvent.
　（フィラー）
　上記第１の組成物は、フィラーを含んでいてもよく、含んでいなくてもよい。上記第２の組成物は、フィラーを含んでいてもよく、含んでいなくてもよい。上記第３の組成物は、フィラーを含んでいてもよく、含んでいなくてもよい。上記第１の組成物に含まれるフィラーと、上記第２の組成物に含まれるフィラーと、上記第３の組成物に含まれるフィラーとはそれぞれ同一であってもよく、異なっていてもよい。上記フィラーは、１種のみが用いられてもよく、２種以上が併用されてもよい。 (Filler)
The first composition may or may not contain a filler. The second composition may or may not contain a filler. The third composition may or may not contain a filler. The filler contained in the first composition, the filler contained in the second composition, and the filler contained in the third composition may be the same or different from each other. Only one type of the filler may be used, or two or more types may be used in combination.
　第１の組成物の硬化物層（光硬化物層又は光及び熱硬化物層）の厚み精度をより一層高め、更に第１の組成物の硬化物層にボイドをより一層生じ難くする観点からは、上記第１の組成物におけるフィラーの含有量は少ないほどよい。また、上記第１の組成物におけるフィラーの含有量が少ないほど、インクジェット装置による吐出不良の発生が抑えられる。 From the viewpoint of further improving the thickness accuracy of the cured product layer (photo-cured product layer or light and thermosetting material layer) of the first composition, and further making it more difficult for voids to occur in the cured product layer of the first composition. The smaller the content of the filler in the first composition, the better. Further, the smaller the content of the filler in the first composition, the more the occurrence of ejection defects by the inkjet device can be suppressed.
　第２の組成物の硬化物層（光硬化物層又は光及び熱硬化物層）の厚み精度をより一層高め、更に第２の組成物の硬化物層にボイドをより一層生じ難くする観点からは、上記第２の組成物におけるフィラーの含有量は少ないほどよい。また、上記第２の組成物におけるフィラーの含有量が少ないほど、インクジェット装置による吐出不良の発生が抑えられる。 From the viewpoint of further improving the thickness accuracy of the cured product layer (photo-cured product layer or light and thermosetting material layer) of the second composition, and further making it more difficult for voids to occur in the cured product layer of the second composition. The smaller the content of the filler in the second composition, the better. Further, the smaller the content of the filler in the second composition, the more the occurrence of ejection defects by the inkjet device can be suppressed.
　第３の組成物の硬化物層（光硬化物層又は光及び熱硬化物層）の厚み精度をより一層高め、更に第３の組成物の硬化物層にボイドをより一層生じ難くする観点からは、上記第３の組成物におけるフィラーの含有量は少ないほどよい。また、上記第３の組成物におけるフィラーの含有量が少ないほど、インクジェット装置による吐出不良の発生が抑えられる。 From the viewpoint of further improving the thickness accuracy of the cured product layer (photo-cured product layer or light and thermosetting material layer) of the third composition, and further making it more difficult for voids to occur in the cured product layer of the third composition. The smaller the content of the filler in the third composition, the better. Further, the smaller the content of the filler in the third composition, the more the occurrence of ejection defects by the inkjet device can be suppressed.
　上記フィラーとしては、シリカ、タルク、クレイ、マイカ、ハイドロタルサイト、アルミナ、酸化マグネシウム、水酸化アルミニウム、窒化アルミニウム及び窒化ホウ素等が挙げられる。 Examples of the filler include silica, talcite, clay, mica, hydrotalcite, alumina, magnesium oxide, aluminum hydroxide, aluminum nitride, and boron nitride.
　上記第１の組成物が上記フィラーを含む場合に、上記第１の組成物１００重量％中、上記フィラーの含有量は、好ましくは３０重量％以下、より好ましくは１０重量％以下、更に好ましくは１重量％以下である。上記第１の組成物は、上記フィラーを含まないことが最も好ましい。 When the first composition contains the filler, the content of the filler in 100% by weight of the first composition is preferably 30% by weight or less, more preferably 10% by weight or less, still more preferably. It is 1% by weight or less. Most preferably, the first composition does not contain the filler.
　上記第２の組成物が上記フィラーを含む場合に、上記第２の組成物１００重量％中、上記フィラーの含有量は、好ましくは３０重量％以下、より好ましくは１０重量％以下、更に好ましくは１重量％以下である。上記第２の組成物は、上記フィラーを含まないことが最も好ましい。 When the second composition contains the filler, the content of the filler in 100% by weight of the second composition is preferably 30% by weight or less, more preferably 10% by weight or less, still more preferably. It is 1% by weight or less. Most preferably, the second composition does not contain the filler.
　上記第３の組成物が上記フィラーを含む場合に、上記第３の組成物１００重量％中、上記フィラーの含有量は、好ましくは３０重量％以下、より好ましくは１０重量％以下、更に好ましくは１重量％以下である。上記第３の組成物は、上記フィラーを含まないことが最も好ましい。 When the third composition contains the filler, the content of the filler in 100% by weight of the third composition is preferably 30% by weight or less, more preferably 10% by weight or less, still more preferably. It is 1% by weight or less. Most preferably, the third composition does not contain the filler.
　（他の成分）
　上記第１の組成物、上記第２の組成物及び上記第３の組成物はそれぞれ、他の成分を含んでいてもよい。上記他の成分としては特に限定されないが、カップリング剤等の接着助剤、顔料、染料、レベリング剤、消泡剤、及び重合禁止剤等が挙げられる。 (Other ingredients)
The first composition, the second composition, and the third composition may each contain other components. The other components are not particularly limited, and examples thereof include adhesive aids such as coupling agents, pigments, dyes, leveling agents, antifoaming agents, and polymerization inhibitors.
　（その他の詳細及び電子部品）
　本発明に係る積層構造体の製造方法、積層構造体及びインクジェット用組成物セットでは、材料の漏れ出し防止性を高めることができるので、電子部品において、隔壁材及びダム材を形成するために好適に用いることができる。ただし、本発明に係る積層構造体の製造方法、積層構造体及びインクジェット用組成物セットは、この用途以外に用いることもできる。例えば、本発明に係る積層構造体の製造方法、積層構造体及びインクジェット用組成物セットにおいて、上記第１の層及び上記第２の層は、コーティング剤を形成するために用いられてもよい。 (Other details and electronic components)
The method for producing a laminated structure, the laminated structure, and the composition set for inkjet according to the present invention can enhance the leakage prevention property of the material, and are therefore suitable for forming a partition wall material and a dam material in electronic parts. Can be used for. However, the method for producing a laminated structure, the laminated structure, and the composition set for inkjet according to the present invention can be used for other purposes. For example, in the method for producing a laminated structure, the laminated structure, and the composition set for inkjet according to the present invention, the first layer and the second layer may be used to form a coating agent.
　図１４は、本発明の第１の実施形態に係る積層構造体を用いて得られる電子部品を示す断面図である。図１４（ａ）は、電子部品の平面図であり、図１４（ｂ）は、図１４（ａ）中のＩ－Ｉ線に沿う断面図である。 FIG. 14 is a cross-sectional view showing an electronic component obtained by using the laminated structure according to the first embodiment of the present invention. 14 (a) is a plan view of the electronic component, and FIG. 14 (b) is a cross-sectional view taken along the line II in FIG. 14 (a).
　電子部品８０は、積層構造体４Ｃを備える。積層構造体４Ｃは、第１の基材３と、第１の光及び熱硬化物層（第１の層）１Ｂと、第２の光及び熱硬化物層（第２の層）２Ｂと、アンダーフィル材６０と、半田ボール６５と、半導体チップ７０とを備える。第１の光及び熱硬化物層１Ｂは、上記第１の組成物を光硬化及び熱硬化させることにより形成されている。第２の光及び熱硬化物層２Ｂは、上記第２の組成物を光硬化及び熱硬化させることにより形成されている。 The electronic component 80 includes a laminated structure 4C. The laminated structure 4C includes a first base material 3, a first light and thermosetting layer (first layer) 1B, a second light and thermosetting layer (second layer) 2B, and the like. It includes an underfill material 60, a solder ball 65, and a semiconductor chip 70. The first light and thermosetting layer 1B is formed by photocuring and thermosetting the first composition. The second light and thermosetting layer 2B is formed by photocuring and thermosetting the second composition.
　基材３の表面上にて、第１の光及び熱硬化物層１Ｂ、第２の光及び熱硬化物層２Ｂは、枠状に配置されている。上記枠状の領域の内側にて、アンダーフィル材６０と、半田ボール６５と、半導体チップ７０とが配置されている。 On the surface of the base material 3, the first light and thermosetting material layer 1B and the second light and thermosetting material layer 2B are arranged in a frame shape. The underfill material 60, the solder balls 65, and the semiconductor chip 70 are arranged inside the frame-shaped region.
　上記枠状の領域の内側に、アンダーフィル材６０を流し込むことにより、電子部品８０を得ることができる。本発明では、特定の第１の組成物及び特定の第２の組成物が用いられているので、上記枠状の領域の内側にアンダーフィル材６０を流し込む際及び流し込んだ後において、アンダーフィル材６０が、枠状の領域の外側に漏れ出しにくい。 The electronic component 80 can be obtained by pouring the underfill material 60 into the inside of the frame-shaped region. In the present invention, since the specific first composition and the specific second composition are used, the underfill material 60 is poured into and after the underfill material 60 is poured into the frame-shaped region. 60 does not easily leak to the outside of the frame-shaped area.
　以下、実施例及び比較例を挙げることにより、本発明を具体的に説明する。本発明は、以下の実施例に限定されない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.
　以下の材料を用意した。 The following materials were prepared.
　（単官能の（メタ）アクリレート化合物）
　イソデシルアクリレート（大阪有機化学工業社製「ＩＤＡＡ」、単独重合体のガラス転移温度－６８℃）
　イソノニルアクリレート（大阪有機化学工業社製「ＩＮＡＡ」、単独重合体のガラス転移温度－６０℃） (Monofunctional (meth) acrylate compound)
Isodecyl acrylate (“IDAA” manufactured by Osaka Organic Chemical Industry Co., Ltd., glass transition temperature of homopolymer-68 ° C)
Isononyl acrylate (“INAA” manufactured by Osaka Organic Chemical Industry Co., Ltd., glass transition temperature of homopolymer -60 ° C)
　（多官能の（メタ）アクリレート化合物）
　トリメチロールプロパントリアクリレート（ダイセル・オルネクス社製「ＴＭＰＴＡ」、単独重合体のガラス転移温度５８℃）
　１，６－ヘキサンジオールジアクリレート（ダイセル・オルネクス社製「ＨＤＤＡ」、単独重合体のガラス転移温度９８℃） (Polyfunctional (meth) acrylate compound)
Trimethylolpropane triacrylate (“TMPTA” manufactured by Daicel Ornex, glass transition temperature of homopolymer 58 ° C)
1,6-Hexanediol diacrylate (“HDDA” manufactured by Daicel Ornex, glass transition temperature of homopolymer 98 ° C)
　（エポキシ化合物）
　ジシクロペンタジエン型エポキシ化合物（ＤＩＣ社製「ＨＰ７２００Ｌ」）
　ビスフェノールＡ型エポキシ化合物（ＤＩＣ社製「ＥＸＡ－８５０ＣＲＰ」） (Epoxy compound)
Dicyclopentadiene type epoxy compound ("HP7200L" manufactured by DIC Corporation)
Bisphenol A type epoxy compound ("EXA-850CRP" manufactured by DIC Corporation)
　（光重合開始剤）
　２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン（ＩＧＭ　Ｒｅｓｉｎｓ社製「Ｏｍｎｉｒａｄ３７９ＥＧ」） (Photopolymerization initiator)
2- (Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone ("Omnirad 379EG" manufactured by IGM Resins)
　（熱硬化剤）
　芳香族アミン化合物（ＡＤＥＫＡ社製「ＥＨ－１０５Ｌ」） (Thermosetting agent)
Aromatic amine compound ("EH-105L" manufactured by ADEKA Corporation)
　（基材）
　シリコンウエハ（組成物と接触する領域における表面粗さＲａ：０．５ｎｍ）
　ガラス基板（組成物と接触する領域における表面粗さＲａ：１ｎｍ）
　セラミック基板（組成物と接触する領域における表面粗さＲａ：３８０ｎｍ） (Base material)
Silicon wafer (surface roughness Ra in the region in contact with the composition: 0.5 nm)
Glass substrate (surface roughness Ra: 1 nm in the region in contact with the composition)
Ceramic substrate (surface roughness Ra in the region in contact with the composition: 380 nm)
　インクジェット装置：
　真空吸着機能を有するステージと、第１の吐出部と、第２の吐出部と、第１の吐出部と第２の吐出部との間に配置された第１の紫外線照射部（ＬＥＤ）とを有するインクジェット装置を用意した。 Inkjet device:
A stage having a vacuum suction function, a first discharge unit, a second discharge unit, and a first ultraviolet irradiation unit (LED) arranged between the first discharge unit and the second discharge unit. An inkjet device having the above was prepared.
　（実施例１～８及び比較例１～３）
　第１の組成物の作製：
　表１～３に示す成分を表１～３に示す配合量で配合し、第１の組成物を得た。 (Examples 1 to 8 and Comparative Examples 1 to 3)
Preparation of the first composition:
The components shown in Tables 1 to 3 were blended in the blending amounts shown in Tables 1 to 3 to obtain the first composition.
　第２の組成物の作製：
　表１～３に示す成分を表１～３に示す配合量で配合し、第２の組成物を得た。 Preparation of the second composition:
The components shown in Tables 1 to 3 were blended in the blending amounts shown in Tables 1 to 3 to obtain a second composition.
　（比較例４）
　第１の組成物の作製：
　表３に示す成分を表３に示す配合量で配合し、第１の組成物を得た。なお、第２の組成物は用いなかった。 (Comparative Example 4)
Preparation of the first composition:
The components shown in Table 3 were blended in the blending amounts shown in Table 3 to obtain the first composition. The second composition was not used.
　（比較例５）
　第２の組成物の作製：
　表３に示す成分を表３に示す配合量で配合し、第２の組成物を得た。なお、第１の組成物は用いなかった。 (Comparative Example 5)
Preparation of the second composition:
The components shown in Table 3 were blended in the blending amounts shown in Table 3 to obtain a second composition. The first composition was not used.
　（評価）
　（１）光硬化物層の形状保持性
　（１－１）実施例１～４及び比較例１～３では、以下のようにして、光硬化物層を備える積層構造体（Ｘ）を作製した。 (evaluation)
(1) Shape Retention of Photocurable Material Layer (1-1) In Examples 1 to 4 and Comparative Examples 1 to 3, a laminated structure (X) having a photocurable material layer was prepared as follows. ..
　光硬化物層を備える積層構造体（Ｘ）の作製：
　ステージにシリコンウエハを吸着させて固定した。第１の組成物を第１の吐出部から吐出した。吐出から０．１秒後に、第１の紫外線照射部から、波長３６５ｎｍの紫外線を照度２０００ｍＷ／ｃｍ２で０．２秒間照射して、第１の組成物を光硬化させた。塗布及び紫外線の照射を繰り返すことにより、幅１５０μｍ、長さ１０ｍｍ、厚さ３μｍの直線形状を有する第１の層（光硬化物層）を形成した。 Fabrication of Laminated Structure (X) with Photocurable Layer:
The silicon wafer was adsorbed on the stage and fixed. The first composition was discharged from the first discharge section. After 0.1 seconds from the discharge, the first composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2. By repeating the coating and irradiation with ultraviolet rays, a first layer (photocured product layer) having a linear shape having a width of 150 μm, a length of 10 mm, and a thickness of 3 μm was formed.
　次いで、第１の層（光硬化物層）の表面上に、第２の組成物を第２の吐出部から吐出した。吐出から０．１秒後に、第１の紫外線照射部から、波長３６５ｎｍの紫外線を照度２０００ｍＷ／ｃｍ２で０．２秒間照射して、第２の組成物を光硬化させた。塗布及び紫外線の照射を繰り返すことにより、第１の層（光硬化物層）の表面上に、幅１５０μｍ、長さ１０ｍｍ、厚さ１００μｍの直線形状を有する第２の層（光硬化物層）を形成した。 Next, the second composition was discharged from the second discharge portion on the surface of the first layer (photo-cured product layer). After 0.1 seconds from the discharge, the second composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2. By repeating coating and irradiation with ultraviolet rays, a second layer (photo-cured product layer) having a linear shape having a width of 150 μm, a length of 10 mm, and a thickness of 100 μm is placed on the surface of the first layer (photo-cured product layer). Was formed.
　このようにして、基材（シリコンウエハ）と、第１の層（光硬化物層）と、第２の層（光硬化物層）とをこの順に備える積層構造体（Ｘ）を得た。 In this way, a laminated structure (X) including a base material (silicon wafer), a first layer (photo-cured product layer), and a second layer (photo-cured product layer) in this order was obtained.
　（１－２）実施例５～８では、以下のように変更したこと以外は、実施例１と同様にして、光硬化物層を備える積層構造体（Ｘ）を作製した。 (1-2) In Examples 5 to 8, a laminated structure (X) provided with a photocurable material layer was produced in the same manner as in Example 1 except that the following changes were made.
　実施例５では、幅３００μｍ、長さ１０ｍｍ、厚さ３μｍの直線形状を有する第１の層（光硬化物層）を形成し、幅３００μｍ、長さ１０ｍｍ、厚さ１００μｍの直線形状を有する第２の層（光硬化物層）を形成した。 In Example 5, a first layer (photocured product layer) having a linear shape having a width of 300 μm, a length of 10 mm, and a thickness of 3 μm is formed, and a linear shape having a width of 300 μm, a length of 10 mm, and a thickness of 100 μm is formed. Two layers (photo-cured product layer) were formed.
　実施例６では、幅１５０μｍ、長さ１０ｍｍ、厚さ３μｍの直線形状を有する第１の層（光硬化物層）を形成し、幅１５０μｍ、長さ１０ｍｍ、厚さ２００μｍの直線形状を有する第２の層（光硬化物層）を形成した。 In Example 6, a first layer (photocured material layer) having a linear shape having a width of 150 μm, a length of 10 mm, and a thickness of 3 μm is formed, and a linear shape having a width of 150 μm, a length of 10 mm, and a thickness of 200 μm is formed. Two layers (photo-cured product layer) were formed.
　実施例７では、幅１５０μｍ、長さ１０ｍｍ、厚さ５μｍの直線形状を有する第１の層（光硬化物層）を形成し、幅１５０μｍ、長さ１０ｍｍ、厚さ１００μｍの直線形状を有する第２の層（光硬化物層）を形成した。 In Example 7, a first layer (photocured product layer) having a linear shape having a width of 150 μm, a length of 10 mm, and a thickness of 5 μm is formed, and a linear shape having a width of 150 μm, a length of 10 mm, and a thickness of 100 μm is formed. Two layers (photo-cured product layer) were formed.
　実施例８では、幅１５０μｍ、長さ１０ｍｍ、厚さ５μｍの直線形状を有する第１の層（光硬化物層）を形成し、幅１５０μｍ、長さ１０ｍｍ、厚さ２００μｍの直線形状を有する第２の層（光硬化物層）を形成した。 In Example 8, a first layer (photocured product layer) having a linear shape having a width of 150 μm, a length of 10 mm, and a thickness of 5 μm is formed, and a linear shape having a width of 150 μm, a length of 10 mm, and a thickness of 200 μm is formed. Two layers (photo-cured product layer) were formed.
　（１－３）比較例４では、以下のようにして、光硬化物層を備える積層構造体（Ｘ）を作製した。 (1-3) In Comparative Example 4, a laminated structure (X) provided with a photocurable material layer was produced as follows.
　光硬化物層を備える積層構造体（Ｘ）の作製：
　ステージにシリコンウエハを吸着させて固定した。第１の組成物を第１の吐出部から吐出した。吐出から０．１秒後に、第１の紫外線照射部から、波長３６５ｎｍの紫外線を照度２０００ｍＷ／ｃｍ２で０．２秒間照射して、第１の組成物を光硬化させた。塗布及び紫外線の照射を繰り返すことにより、幅１５０μｍ、長さ１０ｍｍ、厚さ１０３μｍの直線形状を有する第１の層（光硬化物層）を形成した。これを、光硬化物層を備える積層構造体（Ｘ）とした。 Fabrication of Laminated Structure (X) with Photocurable Layer:
The silicon wafer was adsorbed on the stage and fixed. The first composition was discharged from the first discharge section. After 0.1 seconds from the discharge, the first composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2. By repeating the coating and irradiation with ultraviolet rays, a first layer (photocured product layer) having a linear shape having a width of 150 μm, a length of 10 mm, and a thickness of 103 μm was formed. This was designated as a laminated structure (X) provided with a photocurable material layer.
　（１－４）比較例５では、以下のようにして、光硬化物層を備える積層構造体（Ｘ）を作製した。 (1-4) In Comparative Example 5, a laminated structure (X) provided with a photocurable material layer was produced as follows.
　光硬化物層を備える積層構造体（Ｘ）の作製：
　ステージにシリコンウエハを吸着させて固定した。第２の組成物を第２の吐出部から吐出した。吐出から０．１秒後に、第１の紫外線照射部から、波長３６５ｎｍの紫外線を照度２０００ｍＷ／ｃｍ２で０．２秒間照射して、第２の組成物を光硬化させた。塗布及び紫外線の照射を繰り返すことにより、幅１５０μｍ、長さ１０ｍｍ、厚さ１０３μｍの直線形状を有する第２の層（光硬化物層）を形成した。これを、光硬化物層を備える積層構造体（Ｘ）とした。 Fabrication of Laminated Structure (X) with Photocurable Layer:
The silicon wafer was adsorbed on the stage and fixed. The second composition was discharged from the second discharge section. After 0.1 seconds from the discharge, the second composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2. By repeating the coating and irradiation with ultraviolet rays, a second layer (photocured product layer) having a linear shape having a width of 150 μm, a length of 10 mm, and a thickness of 103 μm was formed. This was designated as a laminated structure (X) provided with a photocurable material layer.
　（１－５）なお、積層構造体（Ｘ）における第１の層（光硬化物層）及び第２の層（光硬化物層）の幅及び厚みは、レーザー顕微鏡（オリンパス社製「ＯＬＳ４１００」）を用いて測定した。実施例１～８では、光硬化物層の形状は保持されていた。 (1-5) The width and thickness of the first layer (photo-cured product layer) and the second layer (photo-cured product layer) in the laminated structure (X) are determined by a laser microscope (“OLS4100” manufactured by Olympus Corporation”. ) Was used for measurement. In Examples 1 to 8, the shape of the photocurable product layer was retained.
　（２）光及び熱硬化物層の形状保持性
　光及び熱硬化物層を備える積層構造体（Ｘ）の作製：
　得られた光硬化物層を備える積層構造体（Ｘ）における第１，第２の層（光硬化物層）を、１７０℃で１時間加熱することで熱硬化し、光及び熱硬化物層である第１，第２の層を得た。このようして、基材（シリコンウエハ）と、第１の層（光及び熱硬化物層）と、第２の層（光及び熱硬化物層）とを備える積層構造体（Ｘ）を得た。 (2) Shape retention of light and thermosetting material layer Fabrication of laminated structure (X) including light and thermosetting material layer:
The first and second layers (photo-cured product layer) in the obtained laminated structure (X) including the photo-cured product layer are heat-cured by heating at 170 ° C. for 1 hour, and the light and thermosetting product layer are heat-cured. The first and second layers were obtained. In this way, a laminated structure (X) including a base material (silicon wafer), a first layer (light and thermosetting layer), and a second layer (light and thermosetting layer) is obtained. rice field.
　得られた積層構造体（Ｘ）における第１の層（光及び熱硬化物層）及び第２の層（光及び熱硬化物層）を、断面研磨装置（ストルアス社製「テグラミン２５」）で切削した。切削することにより得られた第１の層（光及び熱硬化物層）及び第２の層（光及び熱硬化物層）の断面を光学顕微鏡（キーエンス社製「デジタルマイクロスコープＶＨ－Ｚ１００」）を用いて観察することにより、該第１の層及び該第２の層の厚みをそれぞれ測定した。 The first layer (light and thermosetting layer) and the second layer (light and thermosetting layer) in the obtained laminated structure (X) are subjected to a cross-section polishing device (“Teglamin 25” manufactured by Struas). I cut it. An optical microscope (Keyence "Digital Microscope VH-Z100") shows the cross sections of the first layer (light and thermocured product layer) and the second layer (light and thermocured product layer) obtained by cutting. The thickness of the first layer and the thickness of the second layer were measured by observing with.
　［光及び熱硬化物層の形状保持性の判定基準］
　○：加熱前後において、各硬化物層の厚み変化がない（変化率５％未満）
　△：加熱前後において、各硬化物層の厚み変化がわずかにある（変化率５％以上１０％未満）
　×：加熱前後において、各硬化物層の厚み変化がある（変化率１０％以上） [Criteria for determining shape retention of light and thermosetting layer]
◯: There is no change in the thickness of each cured product layer before and after heating (change rate less than 5%).
Δ: There is a slight change in the thickness of each cured product layer before and after heating (change rate 5% or more and less than 10%).
X: There is a change in the thickness of each cured product layer before and after heating (change rate of 10% or more).
　（３）粉体の付着性
　ステージにシリコンウエハを吸着させて固定した。第２の組成物を第２の吐出部（比較例４では第１の組成物を第１の吐出部）から吐出した。吐出から０．１秒後に、第１の紫外線照射部から、波長３６５ｎｍの紫外線を照度２０００ｍＷ／ｃｍ２で０．２秒間照射して、第２の組成物を光硬化させた。塗布及び紫外線の照射を繰り返すことにより、幅１０ｍｍ、長さ１０ｍｍ、厚さ２０μｍの形状を有する第２の層（光硬化物層）を形成した。 (3) Adsorption of powder A silicon wafer was adsorbed and fixed on the stage. The second composition was discharged from the second discharge unit (in Comparative Example 4, the first composition was discharged from the first discharge unit). After 0.1 seconds from the discharge, the second composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2. By repeating the coating and the irradiation with ultraviolet rays, a second layer (photocurable material layer) having a shape having a width of 10 mm, a length of 10 mm, and a thickness of 20 μm was formed.
　次いで、１００ｍｇのシリカ粉末（日本触媒社製「シーホースターＫＥ－Ｐ２５０」）を光硬化物層の表面に配置し、光硬化物層の表面に、窒素を４００Ｌ／分で１０秒間吹き付けた。光硬化物層の表面に残存しているシリカ粉末の量を測定した。 Next, 100 mg of silica powder (“Sea Horster KE-P250” manufactured by Nippon Shokubai Co., Ltd.) was placed on the surface of the photocurable material layer, and nitrogen was sprayed on the surface of the photocurable material layer at 400 L / min for 10 seconds. The amount of silica powder remaining on the surface of the photocured material layer was measured.
　＜粉体の付着性の判定基準＞
　○：残存しているシリカ粉末の量が１０％未満
　×：残存しているシリカ粉末の量が１０％以上 <Criteria for powder adhesion>
◯: The amount of residual silica powder is less than 10% ×: The amount of residual silica powder is 10% or more
　（４）基材との接着性及び層間接着性（冷熱サイクル試験）
　「（２）光及び熱硬化物層の形状保持性」で得られた、光及び熱硬化物層を備える積層構造体（Ｘ）を、温度サイクル試験機（楠本化成社製「ＴＡ５３０Ａ」）に入れ、「－４０℃で３０分、１２５℃で３０分」を１サイクルとして、合計１００サイクルの冷熱サイクル試験を行った。冷熱サイクル試験後の積層構造体（Ｘ）に、窒素を４００Ｌ／分で１０秒間吹き付けた。基材と第１の層との間（比較例４では、基材と第２の層との間）、又は、第１の層と第２の層との間に剥離が生じているかを確認した。 (4) Adhesion to the substrate and interlayer adhesion (cold heat cycle test)
The laminated structure (X) provided with the light and thermosetting layer obtained in "(2) Shape retention of the light and thermosetting layer" was applied to a temperature cycle tester ("TA530A" manufactured by Kusumoto Kasei Co., Ltd.). The thermosetting cycle test was carried out for a total of 100 cycles, with "-40 minutes at -40 ° C. and 30 minutes at 125 ° C." as one cycle. Nitrogen was sprayed on the laminated structure (X) after the thermal cycle test at 400 L / min for 10 seconds. Check if peeling has occurred between the base material and the first layer (in Comparative Example 4, between the base material and the second layer) or between the first layer and the second layer. did.
　＜基材との接着性及び層間接着性（冷熱サイクル試験）の評価基準＞
　○：基材との間に剥離が生じていない
　×：基材との間に剥離が生じている
　○：層間に剥離が生じていない
　×：層間に剥離が生じている <Evaluation criteria for adhesion to base material and interlayer adhesion (cold heat cycle test)>
◯: No peeling with the base material ×: Peeling with the base material ○: No peeling between layers ×: Peeling between layers
　（５）材料の漏れ出し防止性
　ステージにシリコンウエハを吸着させて固定した。第１の組成物を第１の吐出部から吐出した。吐出から０．１秒後に、第１の紫外線照射部から、波長３６５ｎｍの紫外線を照度２０００ｍＷ／ｃｍ２で０．２秒間照射して、第１の組成物を光硬化させた。塗布及び紫外線の照射を繰り返すことにより、幅１５０μｍ、一辺の長さ１０ｍｍ、厚さ３μｍの正方形の枠状形状を有する第１の層（光硬化物層）を形成した。 (5) Material leakage prevention property A silicon wafer was adsorbed and fixed on the stage. The first composition was discharged from the first discharge section. After 0.1 seconds from the discharge, the first composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2. By repeating the coating and irradiation with ultraviolet rays, a first layer (photocurable material layer) having a square frame shape having a width of 150 μm, a side length of 10 mm, and a thickness of 3 μm was formed.
　次いで、第１の層（光硬化物層）の表面上に、第２の組成物を第２の吐出部から吐出した。吐出から０．１秒後に、第１の紫外線照射部から、波長３６５ｎｍの紫外線を照度２０００ｍＷ／ｃｍ２で０．２秒間照射して、第２の組成物を光硬化させた。塗布及び紫外線の照射を繰り返すことにより、第１の層（光硬化物層）の表面上に、幅１５０μｍ、一辺の長さ１０ｍｍ、厚さ１００μｍの正方形の枠状形状を有する第２の層（光硬化物層）を形成した。 Next, the second composition was discharged from the second discharge portion on the surface of the first layer (photo-cured product layer). After 0.1 seconds from the discharge, the second composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2. By repeating coating and irradiation with ultraviolet rays, a second layer having a square frame shape having a width of 150 μm, a side length of 10 mm, and a thickness of 100 μm is formed on the surface of the first layer (photocured product layer). A photocured product layer) was formed.
　次いで、第１，第２の層（光硬化物層）を、１７０℃で１時間加熱することで熱硬化して、光及び熱硬化物層である第１，第２の層を得た。このようして、基材（シリコンウエハ）と、第１の層（光及び熱硬化物層）と、第２の層（光及び熱硬化物層）とを備える積層構造体を得た。 Next, the first and second layers (photo-cured product layers) were heat-cured by heating at 170 ° C. for 1 hour to obtain first and second layers which are light and thermosetting product layers. In this way, a laminated structure including a base material (silicon wafer), a first layer (light and thermosetting layer), and a second layer (light and thermosetting layer) was obtained.
　材料Ｘの作製：
　以下の成分を、遊星式撹拌機で混合し、得られた混合物を３本ロールで分散処理し、材料Ｘを得た。 Preparation of material X:
The following components were mixed with a planetary stirrer, and the obtained mixture was dispersed and treated with three rolls to obtain Material X.
　ビスフェノールＦ型エポキシ樹脂（ＤＩＣ社製「ＥＰＩＣＬＯＮ８３０」）７０重量部
　反応性希釈剤（ＡＤＥＫＡ社製「ＥＤ－５２９」）３０重量部
　熱硬化剤（ＡＤＥＫＡ社製「ＥＨ１０５Ｌ」）３０重量部
　溶融シリカ（アドマテックス社製「ＳＯ－Ｃ５」）３００重量部
　カップリング剤（ＪＮＣ社製「Ｓ５１０」）３重量部
　カーボンブラック（三菱化学社製「ＭＡ－６００」）０．５重量部 Bisphenol F type epoxy resin ("EPICLON830" manufactured by DIC) 70 parts by weight Reactive diluent ("ED-529" manufactured by ADEKA) 30 parts by weight Thermosetting agent ("EH105L" manufactured by ADEKA) 30 parts by weight Molten silica ( Admatex "SO-C5") 300 parts by weight Coupling agent (JNC "S510") 3 parts by weight Carbon black (Mitsubishi Chemical "MA-600") 0.5 parts by weight
　正方形の枠状形状を有する光及び熱硬化物層（第１の層と第２の層との積層物）の内側に、得られた材料Ｘを、５０μｍの厚みとなるように充填し、１５０℃で１時間加熱することで、材料Ｘを熱硬化させた。 The obtained material X is filled inside a light and thermosetting layer (a laminate of a first layer and a second layer) having a square frame shape so as to have a thickness of 50 μm, and 150 Material X was thermoset by heating at ° C. for 1 hour.
　光及び熱硬化物層の外側に、材料Ｘが漏れ出しているか否かを、光学顕微鏡（キーエンス社製「デジタルマイクロスコープＶＨ－Ｚ１００」）を用いて確認をした。 Whether or not material X leaked to the outside of the light and thermosetting layer was confirmed using an optical microscope (“Digital Microscope VH-Z100” manufactured by KEYENCE CORPORATION).
　なお、比較例４においては、シリコンウエハ上に幅１５０μｍ、一辺の長さ１０ｍｍ、厚さ１０３μｍの正方形の枠状形状を有する第１の層（光硬化物層）を形成した後、第１の層（光硬化物層）を、１７０℃で１時間加熱することで熱硬化して、光及び熱硬化物層である第１の層を得たこと以外は、上記と同様にして評価を行った。 In Comparative Example 4, after forming a first layer (photocured material layer) having a square frame shape having a width of 150 μm, a side length of 10 mm, and a thickness of 103 μm on a silicon wafer, the first layer was formed. The evaluation was carried out in the same manner as above, except that the layer (photocurable material layer) was heat-cured by heating at 170 ° C. for 1 hour to obtain a first layer which is a light and thermosetting material layer. rice field.
　また、比較例５においては、シリコンウエハ上に幅１５０μｍ、一辺の長さ１０ｍｍ、厚さ１０３μｍの正方形の枠状形状を有する第２の層（光硬化物層）を形成した後、第２の層（光硬化物層）を、１７０℃で１時間加熱することで熱硬化して、光及び熱硬化物層である第２の層を得たこと以外は、上記と同様にして評価を行った。 Further, in Comparative Example 5, after forming a second layer (photocured product layer) having a square frame shape having a width of 150 μm, a side length of 10 mm, and a thickness of 103 μm on the silicon wafer, the second layer was formed. The evaluation was carried out in the same manner as above, except that the layer (photo-cured product layer) was heat-cured by heating at 170 ° C. for 1 hour to obtain a second layer which is a light and thermosetting product layer. rice field.
　＜材料の漏れ出し防止性の判定基準＞
　○：漏れ出しが確認できない
　×：漏れ出しが確認される <Criteria for preventing material leakage>
○: Leakage cannot be confirmed ×: Leakage is confirmed
　比較例４では、熱硬化時に光及び熱硬化物層（第１の層と第２の層との積層物）の形状が変化し、上記光及び熱硬化物層の厚みが約３０μｍまで低下したため、光及び熱硬化物層の外側に、材料Ｘが漏れ出していた。また、比較例１～３，５では、基材（シリコンウエハ）と第１の層との接着力、又は、第１の層と第２の層との接着力が低いため、材料Ｘの熱膨張に耐えることができず、光及び熱硬化物層の外側に、材料Ｘが漏れ出していた。 In Comparative Example 4, the shape of the light and the thermosetting layer (the laminate of the first layer and the second layer) changed during the thermosetting, and the thickness of the light and the thermosetting layer decreased to about 30 μm. Material X leaked to the outside of the light and thermosetting layer. Further, in Comparative Examples 1 to 3 and 5, since the adhesive force between the base material (silicon wafer) and the first layer or the adhesive force between the first layer and the second layer is low, the heat of the material X is low. Unable to withstand expansion, material X leaked to the outside of the light and thermosetting layer.
　（実施例９～１４）
　第１の組成物及び第３の組成物の作製：
　表４，５に示す成分を表４，５に示す配合量で配合し、第１の組成物及び第３の組成物を得た。 (Examples 9 to 14)
Preparation of the first composition and the third composition:
The components shown in Tables 4 and 5 were blended in the blending amounts shown in Tables 4 and 5 to obtain a first composition and a third composition.
　第２の組成物の作製：
　表４，５に示す成分を表４，５に示す配合量で配合し、第２の組成物を得た。 Preparation of the second composition:
The components shown in Tables 4 and 5 were blended in the blending amounts shown in Tables 4 and 5 to obtain a second composition.
　（評価）
　（１）光硬化物層の形状保持性
　（１－１）実施例９では、以下のようにして、積層構造体（Ｘ）を作製した。 (evaluation)
(1) Shape Retention of Photocured Material Layer (1-1) In Example 9, a laminated structure (X) was produced as follows.
　積層構造体（Ｘ）の作製：
　ステージにシリコンウエハを吸着させて固定した。第１の組成物を第１の吐出部から吐出した。吐出から０．１秒後に、第１の紫外線照射部から、波長３６５ｎｍの紫外線を照度２０００ｍＷ／ｃｍ２で０．２秒間照射して、第１の組成物を光硬化させた。塗布及び紫外線の照射を繰り返すことにより、幅２００μｍ、一辺の長さ１０ｍｍ、厚さ５μｍの正方形の枠状形状を有する第１の層（光硬化物層）を形成した。 Fabrication of laminated structure (X):
The silicon wafer was adsorbed on the stage and fixed. The first composition was discharged from the first discharge section. After 0.1 seconds from the discharge, the first composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2. By repeating the coating and irradiation with ultraviolet rays, a first layer (photocurable material layer) having a square frame shape having a width of 200 μm, a side length of 10 mm, and a thickness of 5 μm was formed.
　次いで、第１の層（光硬化物層）の表面上に、第２の組成物を第２の吐出部から吐出した。吐出から０．１秒後に、第１の紫外線照射部から、波長３６５ｎｍの紫外線を照度２０００ｍＷ／ｃｍ２で０．２秒間照射して、第２の組成物を光硬化させた。塗布及び紫外線の照射を繰り返すことにより、第１の層（光硬化物層）の表面上に、幅２００μｍ、一辺の長さ１０ｍｍ、厚さ１０００μｍの正方形の枠状形状を有する第２の層（光硬化物層）を形成した。 Next, the second composition was discharged from the second discharge portion on the surface of the first layer (photo-cured product layer). After 0.1 seconds from the discharge, the second composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2. By repeating coating and irradiation with ultraviolet rays, a second layer having a square frame shape having a width of 200 μm, a side length of 10 mm, and a thickness of 1000 μm is formed on the surface of the first layer (photocured product layer). A photocured product layer) was formed.
　次いで、第２の層（光硬化物層）の表面上に第３の組成物（第１の組成物）を第１の吐出部から吐出した。吐出から０．１秒後に、第１の紫外線照射部から、波長３６５ｎｍの紫外線を照度２０００ｍＷ／ｃｍ２で０．２秒間照射して、第３の組成物を光硬化させた。塗布及び紫外線の照射を繰り返すことにより、幅２００μｍ、一辺の長さ１０ｍｍ、厚さ１０μｍの正方形の枠状形状を有する第３の層（光硬化物層）を形成した。 Next, the third composition (first composition) was discharged from the first discharge portion on the surface of the second layer (photocurable product layer). After 0.1 seconds from the discharge, the third composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2. By repeating the coating and irradiation with ultraviolet rays, a third layer (photocurable material layer) having a square frame shape having a width of 200 μm, a side length of 10 mm, and a thickness of 10 μm was formed.
　次いで、第３の層の表面上に、ボンダー（芝浦メカトロニクス社製「ＦＴＤ－７０００Ｐ」）を用いてガラス基板を貼り合わせ、１７０℃で１時間加熱することにより、第１の層（光硬化物層）、第２の層（光硬化物層）及び第３の層（光硬化物層）を熱硬化させた。 Next, a glass substrate was attached onto the surface of the third layer using a bonder (“FTD-7000P” manufactured by Shibaura Mechatronics Co., Ltd.), and heated at 170 ° C. for 1 hour to obtain the first layer (photocured product). Layer), the second layer (photo-cured product layer) and the third layer (photo-cured product layer) were heat-cured.
　このようにして、第１の基材（シリコンウエハ）と、第１の層（光及び熱硬化物層）と、第２の層（光及び熱硬化物層）と、第３の層（光及び熱硬化物層）と、第２の基材（ガラス基板）とをこの順に備える積層構造体（Ｘ）を得た。 In this way, the first base material (silicon wafer), the first layer (light and thermosetting layer), the second layer (light and thermosetting layer), and the third layer (light). And a thermosetting layer) and a second base material (glass substrate) in this order to obtain a laminated structure (X).
　（１－２）実施例１０，１１では、以下の操作を追加で行ったこと、幅２００μｍ、一辺の長さ１０ｍｍ、厚さ５μｍの正方形の枠状形状を有する第３の層（光硬化物層）を形成したこと以外は実施例９と同様にして、積層構造体（Ｘ）を作製した。 (1-2) In Examples 10 and 11, the following operations were additionally performed, and a third layer (photocured product) having a square frame shape having a width of 200 μm, a side length of 10 mm, and a thickness of 5 μm was performed. A laminated structure (X) was produced in the same manner as in Example 9 except that the layer) was formed.
　第２の層（光硬化物層）の形成後かつ第３の組成物の吐出前に、基材（シリコンウエハ）と第１の層（光硬化物層）と第２の層（光硬化物層）との積層体を、１７０℃で１時間加熱することにより、第１の層（光硬化物層）及び第２の層（光硬化物層）を熱硬化させた。次いで、平坦化装置（キーリンク社製）を用いて、第２の層（光及び熱硬化物層）の表面を１００μｍ切削研磨することにより平坦化処理を行った。なお、実施例１０，１１では、平坦化処理後の第２の層の表面の最大高さと最小高さとの差の絶対値は３μｍ以下であった。 After the formation of the second layer (photo-cured product layer) and before the ejection of the third composition, the base material (silicon wafer), the first layer (photo-cured product layer), and the second layer (photo-cured product) The first layer (photo-cured product layer) and the second layer (photo-cured product layer) were thermally cured by heating the laminate with the layer) at 170 ° C. for 1 hour. Next, a flattening treatment was performed by cutting and polishing the surface of the second layer (light and thermosetting layer) by 100 μm using a flattening device (manufactured by Keylink). In Examples 10 and 11, the absolute value of the difference between the maximum height and the minimum height of the surface of the second layer after the flattening treatment was 3 μm or less.
　このようにして、基材（シリコンウエハ）と、第１の層（光及び熱硬化物層）と、第２の層（光及び熱硬化物層）と、第３の層（光及び熱硬化物層）と、第２の基材（ガラス基板）とをこの順に備える積層構造体（Ｘ）を得た。 In this way, the substrate (silicon wafer), the first layer (light and thermosetting layer), the second layer (light and thermosetting layer), and the third layer (light and thermosetting). A laminated structure (X) including a material layer) and a second base material (glass substrate) in this order was obtained.
　（１－３）実施例１２では、以下のようにして、積層構造体（Ｘ）を作製した。 (1-3) In Example 12, a laminated structure (X) was produced as follows.
　積層構造体（Ｘ）の作製：
　ステージにセラミック基板を吸着させて固定した。第２の組成物を第２の吐出部から吐出した。吐出から０．１秒後に、第１の紫外線照射部から、波長３６５ｎｍの紫外線を照度２０００ｍＷ／ｃｍ２で０．２秒間照射して、第２の組成物を光硬化させた。塗布及び紫外線の照射を繰り返すことにより、基材の表面上に幅２００μｍ、一辺の長さ１０ｍｍ、厚さ１０００μｍの正方形の枠状形状を有する第２の層（光硬化物層）を形成した。 Fabrication of laminated structure (X):
The ceramic substrate was adsorbed on the stage and fixed. The second composition was discharged from the second discharge section. After 0.1 seconds from the discharge, the second composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2. By repeating coating and irradiation with ultraviolet rays, a second layer (photocurable layer) having a square frame shape having a width of 200 μm, a side length of 10 mm, and a thickness of 1000 μm was formed on the surface of the base material.
　次いで、第２の層（光硬化物層）の表面上に、第１の組成物を第１の吐出部から吐出した。吐出から０．１秒後に、第１の紫外線照射部から、波長３６５ｎｍの紫外線を照度２０００ｍＷ／ｃｍ２で０．２秒間照射して、第１の組成物を光硬化させた。塗布及び紫外線の照射を繰り返すことにより、第２の層（光硬化物層）の表面上に、幅２００μｍ、一辺の長さ１０ｍｍ、厚さ１０μｍの正方形の枠状形状を有する第１の層（光硬化物層）を形成した。 Next, the first composition was discharged from the first discharge portion on the surface of the second layer (photocurable product layer). After 0.1 seconds from the discharge, the first composition was photocured by irradiating the first ultraviolet irradiation unit with ultraviolet rays having a wavelength of 365 nm for 0.2 seconds at an illuminance of 2000 mW / cm 2. By repeating coating and irradiation with ultraviolet rays, a first layer having a square frame shape having a width of 200 μm, a side length of 10 mm, and a thickness of 10 μm on the surface of the second layer (photocured product layer) ( A photocured product layer) was formed.
　次いで、第１の層の表面上に、ボンダー（芝浦メカトロニクス社製「ＦＴＤ－７０００Ｐ」）を用いてガラス基板を貼り合わせ、１７０℃で１時間加熱することにより、第１の層（光硬化物層）及び第２の層（光硬化物層）を熱硬化させた。 Next, a glass substrate was attached onto the surface of the first layer using a bonder (“FTD-7000P” manufactured by Shibaura Mechatronics Co., Ltd.), and heated at 170 ° C. for 1 hour to obtain the first layer (photocured product). The layer) and the second layer (photocurable layer) were heat-cured.
　このようにして、基材（セラミック基板）と、第２の層（光硬化物層）と、第１の層（光硬化物層）と、基材（ガラス基板）とをこの順に備える積層構造体（Ｘ）を得た。 In this way, a laminated structure including a base material (ceramic substrate), a second layer (photo-cured product layer), a first layer (photo-cured product layer), and a base material (glass substrate) in this order. Body (X) was obtained.
　（１－４）実施例１３，１４では、以下の操作を追加で行ったこと、幅２００μｍ、一辺の長さ１０ｍｍ、厚さ５μｍの正方形の枠状形状を有する第１の層（光硬化物層）を形成したこと以外は実施例１２と同様にして、積層構造体（Ｘ）を作製した。 (1-4) In Examples 13 and 14, the following operations were additionally performed, and the first layer (photocured product) having a square frame shape having a width of 200 μm, a side length of 10 mm, and a thickness of 5 μm was performed. A laminated structure (X) was produced in the same manner as in Example 12 except that the layer) was formed.
　第２の層（光硬化物層）の形成後かつ第１の組成物の吐出前に、基材（セラミック基板）と第２の層（光硬化物層）との積層体を、１７０℃で１時間加熱することにより、第２の層（光硬化物層）を熱硬化させた。次いで、平坦化装置（キーリンク社製）を用いて、第２の層（光及び熱硬化物層）の表面を１００μｍ切削研磨することにより平坦処理を行った。なお、実施例１３，１４では、平坦化処理後の第２の層の最大高さと最小高さとの差の絶対値は３μｍ以下であった。 After the formation of the second layer (photocurable material layer) and before the discharge of the first composition, the laminate of the base material (ceramic substrate) and the second layer (photocurable material layer) is placed at 170 ° C. The second layer (photocurable material layer) was thermoset by heating for 1 hour. Next, a flattening device (manufactured by Keylink) was used to perform flattening by cutting and polishing the surface of the second layer (light and thermosetting layer) by 100 μm. In Examples 13 and 14, the absolute value of the difference between the maximum height and the minimum height of the second layer after the flattening treatment was 3 μm or less.
　このようにして、基材（セラミック基板）と、第２の層（光硬化物層）と、第１の層（光硬化物層）と、基材（ガラス基板）とをこの順に備える積層構造体（Ｘ）を得た。 In this way, a laminated structure including a base material (ceramic substrate), a second layer (photo-cured product layer), a first layer (photo-cured product layer), and a base material (glass substrate) in this order. Body (X) was obtained.
　（１－５）なお、積層構造体（Ｘ）における第１の層（光硬化物層）、第２の層（光硬化物層）及び第３の層（光硬化物層）の幅及び厚みは、レーザー顕微鏡（オリンパス社製「ＯＬＳ４１００」）を用いて測定した。実施例９～１４では、光硬化物層の形状は保持されていた。 (1-5) The width and thickness of the first layer (photo-cured product layer), the second layer (photo-cured product layer), and the third layer (photo-cured product layer) in the laminated structure (X). Was measured using a laser microscope (“OLS4100” manufactured by Olympus Corporation). In Examples 9 to 14, the shape of the photocurable product layer was retained.
　（２）光及び熱硬化物層の形状保持性
　実施例１～８及び比較例１～６の評価で行った「（２）光及び熱硬化物層の形状保持性」と同様にして、光及び熱硬化物層の形状保持性を評価した。なお、平坦化処理を行った実施例１０，１１，１３，１４では、本評価を行わなかった。 (2) Shape retention of light and thermosetting layer Light in the same manner as "(2) Shape retention of light and thermosetting layer" performed in the evaluations of Examples 1 to 8 and Comparative Examples 1 to 6. And the shape retention of the thermosetting layer was evaluated. In Examples 10, 11, 13, and 14 in which the flattening treatment was performed, this evaluation was not performed.
　［光及び熱硬化物層の形状保持性の判定基準］
　○：加熱前後において、各硬化物層の厚み変化がない（変化率５％未満）
　△：加熱前後において、各硬化物層の厚み変化がわずかにある（変化率５％以上１０％未満）
　×：加熱前後において、各硬化物層の厚み変化がある（変化率１０％以上） [Criteria for determining shape retention of light and thermosetting layer]
◯: There is no change in the thickness of each cured product layer before and after heating (change rate less than 5%).
Δ: There is a slight change in the thickness of each cured product layer before and after heating (change rate 5% or more and less than 10%).
X: There is a change in the thickness of each cured product layer before and after heating (change rate of 10% or more).
　（３）粉体の付着性
　実施例１～８及び比較例１～６の評価で行った「（３）粉体の付着性」と同様にして、第２の層（光硬化物層）に対する粉体の付着性を評価した。 (3) Adhesiveness of powder Similar to "(3) Adhesiveness of powder" performed in the evaluations of Examples 1 to 8 and Comparative Examples 1 to 6, the adhesiveness to the second layer (photocurable material layer). The adhesiveness of the powder was evaluated.
　＜粉体の付着性の判定基準＞
　○：残存しているシリカ粉末の量が１０％未満
　×：残存しているシリカ粉末の量が１０％以上 <Criteria for powder adhesion>
◯: The amount of residual silica powder is less than 10% ×: The amount of residual silica powder is 10% or more
　（４）基材との接着性及び層間接着性（冷熱サイクル試験）
　得られた積層構造体（Ｘ）を用いたこと以外は、実施例１～８及び比較例１～６の評価で行った「（４）基材との接着性及び層間接着性（冷熱サイクル試験）」と同様にして、基材との接着性及び層間接着性を評価した。なお、基材と第１の層との間、第１の層と第２の層との間、第２の層と第３の層との間、又は、第３の層と基材との間に剥離が生じているかを確認した。 (4) Adhesion to the substrate and interlayer adhesion (cold heat cycle test)
Except for using the obtained laminated structure (X), the evaluations of Examples 1 to 8 and Comparative Examples 1 to 6 were carried out in "(4) Adhesion to the substrate and interlayer adhesion (cold heat cycle test). ) ”, And the adhesiveness to the substrate and the interlayer adhesiveness were evaluated. Between the base material and the first layer, between the first layer and the second layer, between the second layer and the third layer, or between the third layer and the base material. It was confirmed whether peeling occurred between them.
　＜基材との接着性及び層間接着性（冷熱サイクル試験）の評価基準＞
　○：基材との間に剥離が生じていない
　×：基材との間に剥離が生じている
　○：層間に剥離が生じていない
　×：層間との間に剥離が生じている <Evaluation criteria for adhesion to base material and interlayer adhesion (cold heat cycle test)>
◯: No peeling between the base material ×: Peeling between the base material ○: No peeling between the layers ×: Peeling between the layers
　（５）材料の漏れ出し防止性（第２の基材との界面）
　得られた積層構造体（Ｘ）における基材（ガラス基板）の中央部をレーザーでカットして、材料Ｘの注入口を設けた。次いで、注入口から、正方形の枠状形状を有する光及び熱硬化物層の内側に、材料Ｘを充填し、１５０℃で１時間加熱することで、材料Ｘを熱硬化させた。実施例９～１１では、第２の基材（ガラス基板）と第３の層との間から、実施例１２～１４では、第２の基材（ガラス基板）と第１の層との間から、材料Ｘが漏れ出しているか否かを、光学顕微鏡（キーエンス社製「デジタルマイクロスコープＶＨ－Ｚ１００」）を用いて確認をした。 (5) Material leakage prevention (interface with the second base material)
The central portion of the base material (glass substrate) in the obtained laminated structure (X) was cut with a laser to provide an injection port for the material X. Next, the material X was heat-cured by filling the inside of the light and thermosetting material layer having a square frame shape from the injection port and heating at 150 ° C. for 1 hour. In Examples 9 to 11, between the second base material (glass substrate) and the third layer, and in Examples 12 to 14, between the second base material (glass substrate) and the first layer. Therefore, it was confirmed by using an optical microscope (“Digital Microscope VH-Z100” manufactured by KEYENCE CORPORATION) whether or not the material X was leaking.
　＜材料の漏れ出し防止性の判定基準＞
　○：漏れ出しが確認できない
　×：漏れ出しが確認される <Criteria for preventing material leakage>
○: Leakage cannot be confirmed ×: Leakage is confirmed
　構成及び結果を下記の表１～５に示す。 The configuration and results are shown in Tables 1 to 5 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　１…第１の組成物
　１Ａ…第１の光硬化物層
　１Ｂ，１Ｄ，１Ｅ…第１の光及び熱硬化物層
　２…第２の組成物
　２Ａ…第２の光硬化物層
　２Ｂ，２Ｄ，２Ｅ…第２の光及び熱硬化物層
　３…第１の基材
　４Ａ，４Ｂ，４Ｃ，４Ｄ，４Ｅ…積層構造体
　５…インクジェット用組成物セット
　６Ｄ…第３の光及び熱硬化物層
　７…第２の基材
　１０…装置
　１１…ステージ
　１２…第１の吐出部
　１３…第１の光照射部
　１４…第２の吐出部
　１５…第２の光照射部
　１６…第１のインクタンク
　１７，１７Ｘ…第１の循環流路部
　１７Ａ，１９Ａ…バッファタンク
　１７Ｂ，１９Ｂ…ポンプ
　１８…第２のインクタンク
　１９，１９Ｘ…第２の循環流路部
　６０…アンダーフィル材
　６５…半田ボール
　７０…半導体チップ
　８０…電子部品
　１０１…第１の容器
　１０２…第２の容器 1 ... 1st composition 1A ... 1st photocurable layer 1B, 1D, 1E ... 1st light and thermosetting layer 2 ... 2nd composition 2A ... 2nd photocurable layer 2B, 2D , 2E ... Second light and thermosetting layer 3 ... First base material 4A, 4B, 4C, 4D, 4E ... Laminated structure 5 ... Inkjet composition set 6D ... Third light and thermosetting layer 7 ... Second base material 10 ... Device 11 ... Stage 12 ... First ejection unit 13 ... First light irradiation unit 14 ... Second ejection unit 15 ... Second light irradiation unit 16 ... First ink tank 17, 17X ... First circulation flow path 17A, 19A ... Buffer tank 17B, 19B ... Pump 18 ... Second ink tank 19, 19X ... Second circulation flow path 60 ... Underfill material 65 ... Solder ball 70 ... Semiconductor chip 80 ... Electronic parts 101 ... First container 102 ... Second container

Claims (32)

  1. 　第１の基材の表面上にインクジェット方式で塗布された第１の組成物に光を照射して、前記第１の組成物が光硬化した第１の光硬化物層を形成する第１の光硬化工程と、
    　前記第１の光硬化物層の前記第１の基材側とは反対の表面側にインクジェット方式で塗布された第２の組成物に光を照射して、前記第２の組成物が光硬化した第２の光硬化物層を形成する第２の光硬化工程とを備え、
    　前記第１の組成物が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含み、
    　前記第２の組成物が、多官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含み、
    　前記第１の組成物と前記第２の組成物とが異なる組成物である、積層構造体の製造方法。     A first composition obtained by irradiating a first composition coated on the surface of a first base material by an inkjet method with light to form a first photocurable product layer in which the first composition is photocured. Photo-curing process and
    The second composition coated by an inkjet method on the surface side of the first photocurable material layer opposite to the first base material side is irradiated with light, and the second composition is photocured. A second photo-curing step of forming a second photo-curing material layer is provided.
    The first composition comprises a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
    The second composition comprises a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
    A method for producing a laminated structure, wherein the first composition and the second composition are different compositions.
  2. 　前記第１の光硬化物層の前記第１の基材側とは反対の表面側に第２の組成物をインクジェット方式で塗布する第２の塗布工程を備え、
    　前記第２の光硬化工程において、前記第２の塗布工程で塗布された前記第２の組成物に光を照射する、請求項１に記載の積層構造体の製造方法。     A second coating step of applying the second composition to the surface side of the first photocurable material layer opposite to the first base material side by an inkjet method is provided.
    The method for producing a laminated structure according to claim 1, wherein in the second photocuring step, the second composition coated in the second coating step is irradiated with light.
  3. 　前記第２の塗布工程と前記第２の光硬化工程とがそれぞれ、前記第１の光硬化物層の厚み方向にて、複数回行われる、請求項２に記載の積層構造体の製造方法。 The method for producing a laminated structure according to claim 2, wherein the second coating step and the second photocuring step are performed a plurality of times in the thickness direction of the first photocured product layer, respectively.
  4. 　前記第１の光硬化物層及び前記第２の光硬化物層を加熱して、前記第１の光硬化物層が熱硬化した第１の光及び熱硬化物層、並びに、前記第２の光硬化物層が熱硬化した第２の光及び熱硬化物層を形成する第１及び第２の光硬化物層用加熱工程を備える、請求項１～３のいずれか１項に記載の積層構造体の製造方法。 The first light and thermosetting layer in which the first photocurable layer and the second photocurable layer are heated and the first photocurable layer is heat-cured, and the second photocurable layer. The lamination according to any one of claims 1 to 3, further comprising a heating step for the first and second photocurable material layers in which the photocurable material layer is heat-cured to form a second light and a thermosetting material layer. Method of manufacturing the structure.
  5. 　前記第１の光硬化物層及び前記第２の光硬化物層を加熱して、前記第１の光硬化物層が熱硬化した第１の光及び熱硬化物層、並びに、前記第２の光硬化物層が熱硬化した第２の光及び熱硬化物層を形成する第１及び第２の光硬化物層用加熱工程を備えるか又は備えず、
    　前記第１及び第２の光硬化物層用加熱工程が備えられる場合に、前記第２の光及び熱硬化物層の前記第１の基材側とは反対の表面側にインクジェット方式で塗布された第３の組成物に光を照射して、前記第３の組成物が光硬化した第３の光硬化物層を形成する第３の光硬化工程を備え、
    　前記第１及び第２の光硬化物層用加熱工程が備えられない場合に、前記第２の光硬化物層の前記第１の基材側とは反対の表面側にインクジェット方式で塗布された第３の組成物に光を照射して、前記第３の組成物が光硬化した第３の光硬化物層を形成する第３の光硬化工程を備え、
    　前記第３の組成物が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含み、
    　前記第２の組成物と前記第３の組成物とが異なる組成物である、請求項１～３のいずれか１項に記載の積層構造体の製造方法。     The first light and thermosetting layer in which the first photocurable layer and the second photocurable layer are heated and the first photocurable layer is heat-cured, and the second photocurable layer. With or without a second light and a heating step for the first and second photocurable layers in which the photocurable layer is thermoset to form a thermosetting layer.
    When the heating steps for the first and second photocurable material layers are provided, the second light and the thermosetting material layer is coated on the surface side of the second light and thermosetting material layer opposite to the first base material side by an inkjet method. A third photocuring step is provided in which the third composition is irradiated with light to form a third photocurable layer in which the third composition is photocured.
    When the heating steps for the first and second photocurable material layers were not provided, the second photocurable material layer was coated on the surface side of the second photocurable material layer opposite to the first base material side by an inkjet method. The third composition is provided with a third photocuring step of irradiating the third composition with light to form a third photocurable layer in which the third composition is photocured.
    The third composition comprises a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
    The method for producing a laminated structure according to any one of claims 1 to 3, wherein the second composition and the third composition are different compositions.
  6. 　前記第１の組成物と前記第３の組成物とが同一の組成物である、請求項５に記載の積層構造体の製造方法。 The method for producing a laminated structure according to claim 5, wherein the first composition and the third composition are the same composition.
  7. 　前記第１及び第２の光硬化物層用加熱工程が備えられる場合に、前記第１及び第２の光硬化物層用加熱工程後に、前記第２の光及び熱硬化物層の前記第１の基材側とは反対の表面を平坦化処理する平坦化処理工程を備え、
    　前記第１及び第２の光硬化物層用加熱工程が備えられない場合に、前記第２の光硬化工程後に、前記第２の光硬化物層の前記第１の基材側とは反対の表面を平坦化処理する平坦化処理工程を備え、
    　前記平坦化処理が、研磨処理である、請求項５又は６に記載の積層構造体の製造方法。     When the heating steps for the first and second photocurable material layers are provided, after the heating steps for the first and second photocurable material layers, the first of the second light and thermosetting material layers. It is provided with a flattening treatment step for flattening the surface opposite to the base material side of the above.
    When the heating steps for the first and second photocurable material layers are not provided, after the second photocuring step, the second photocurable material layer is opposite to the first base material side. Equipped with a flattening process that flattens the surface
    The method for producing a laminated structure according to claim 5 or 6, wherein the flattening treatment is a polishing treatment.
  8. 　前記第３の光硬化物層の前記第１の基材側とは反対の表面上に、第２の基材を配置する配置工程を備える、請求項５～７のいずれか１項に記載の積層構造体の製造方法。 The invention according to any one of claims 5 to 7, further comprising an arrangement step of arranging the second base material on the surface of the third photocurable material layer opposite to the first base material side. A method for manufacturing a laminated structure.
  9. 　前記第１及び第２の光硬化物層用加熱工程が備えられる場合に、前記第３の光硬化物層を加熱して、前記第３の光硬化物層が熱硬化した第３の光及び熱硬化物層を形成する第３の光硬化物層用加熱工程を備え、
    　前記第１及び第２の光硬化物層用加熱工程が備えられない場合に、前記第１の光硬化物層、前記第２の光硬化物層及び前記第３の光硬化物層を加熱して、前記第１の光硬化物層が熱硬化した第１の光及び熱硬化物層、前記第２の光硬化物層が熱硬化した第２の光及び熱硬化物層、並びに、前記第３の光硬化物層が熱硬化した第３の光及び熱硬化物層を形成する第１、第２及び第３の光硬化物層用加熱工程を備える、請求項５～８のいずれか１項に記載の積層構造体の製造方法。     When the heating steps for the first and second photocurable material layers are provided, the third photocurable material layer is heated to heat the third photocurable material layer, and the third light and the third photocurable material layer are thermally cured. A third photocurable layer heating step for forming a thermosetting layer is provided.
    When the heating steps for the first and second photocurable material layers are not provided, the first photocurable material layer, the second photocurable material layer and the third photocurable material layer are heated. The first light and thermosetting layer in which the first photocurable layer is thermoset, the second light and thermosetting layer in which the second photocurable layer is thermoset, and the first. Any one of claims 5 to 8, further comprising a heating step for the first, second and third photocurable material layers, wherein the photocurable material layer of 3 forms a thermosetting third light and a thermosetting material layer. The method for manufacturing a laminated structure according to the section.
  10. 　第１の基材の表面上にインクジェット方式で塗布された第２の組成物に光を照射して、前記第２の組成物が光硬化した第２の光硬化物層を形成する第２の光硬化工程を備え、
    　前記第２の光硬化物層を加熱して、前記第２の光硬化物層が熱硬化した第２の光及び熱硬化物層を形成する第２の光硬化物層用加熱工程を備えるか又は備えず、
    　前記第２の光硬化物層用加熱工程が備えられる場合に、前記第２の光及び熱硬化物層の前記第１の基材側とは反対の表面側にインクジェット方式で塗布された第１の組成物に光を照射して、前記第１の組成物が光硬化した第１の光硬化物層を形成する第１の光硬化工程を備え、
    　前記第２の光硬化物層用加熱工程が備えられない場合に、前記第２の光硬化物層の前記第１の基材側とは反対の表面側にインクジェット方式で塗布された第１の組成物に光を照射して、前記第１の組成物が光硬化した第１の光硬化物層を形成する第１の光硬化工程を備え、
    　前記第１の組成物が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含み、
    　前記第２の組成物が、多官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含み、
    　前記第１の組成物と前記第２の組成物とが異なる組成物である、積層構造体の製造方法。     A second composition obtained by irradiating a second composition coated on the surface of the first substrate by an inkjet method with light to form a second photocurable layer in which the second composition is photocured. Equipped with a photo-curing process
    Does the second photocurable material layer have a heating step for a second photocurable material layer that heats the second photocurable material layer to form a second light and a thermosetting material layer in which the second photocurable material layer is heat-cured? Or not prepared
    When the heating step for the second photocurable material layer is provided, the first light and the first surface side of the thermosetting material layer opposite to the first base material side is coated by an inkjet method. The composition comprises a first photocuring step of irradiating the composition with light to form a first photocurable layer in which the first composition is photocured.
    When the heating step for the second photocurable material layer is not provided, the first coating is applied to the surface side of the second photocurable material layer opposite to the first base material side by an inkjet method. The composition comprises a first photocuring step of irradiating the composition with light to form a first photocurable layer in which the first composition is photocured.
    The first composition comprises a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
    The second composition comprises a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
    A method for producing a laminated structure, wherein the first composition and the second composition are different compositions.
  11. 　前記第２の光硬化物層を加熱して、前記第２の光硬化物層が熱硬化した第２の光及び熱硬化物層を形成する第２の光硬化物層用加熱工程を備え、
    　前記第１の光硬化工程において、前記第２の光及び熱硬化物層の前記第１の基材側とは反対の表面側にインクジェット方式で塗布された第１の組成物に光を照射して、前記第１の組成物が光硬化した第１の光硬化物層を形成する、請求項１０に記載の積層構造体の製造方法。     The second photocurable material layer is heated to form a second light and a thermosetting material layer in which the second photocurable material layer is heat-cured, and a second photocurable material layer heating step is provided.
    In the first photocuring step, the first composition coated by the inkjet method on the surface side of the second light and the thermosetting material layer opposite to the first base material side is irradiated with light. The method for producing a laminated structure according to claim 10, wherein the first composition forms a photocured first photocured product layer.
  12. 　前記第２の光硬化物層用加熱工程が備えられる場合に、前記第２の光硬化物層用加熱工程後に、前記第２の光及び熱硬化物層の前記第１の基材側とは反対の表面を平坦化処理する平坦化処理工程を備え、
    　前記第２の光硬化物層用加熱工程が備えられない場合に、前記第２の光硬化工程後に、前記第２の光硬化物層の前記第１の基材側とは反対の表面を平坦化処理する平坦化処理工程を備え、
    　前記平坦化処理が、研磨処理である、請求項１０に記載の積層構造体の製造方法。     When the heating step for the second photocurable material layer is provided, after the heating step for the second photocurable material layer, the second light and the first base material side of the thermosetting material layer are It has a flattening process that flattens the opposite surface.
    When the heating step for the second photocurable material layer is not provided, after the second photocuring step, the surface of the second photocurable material layer opposite to the first base material side is flattened. Equipped with a flattening process
    The method for manufacturing a laminated structure according to claim 10, wherein the flattening treatment is a polishing treatment.
  13. 　前記第２の光硬化物層用加熱工程が備えられる場合に、前記第１の光硬化物層を加熱して、前記第１の光硬化物層が熱硬化した第１の光及び熱硬化物層を形成する第１の光硬化物層用加熱工程を備え、
    　前記第２の光硬化物層用加熱工程が備えられない場合に、前記第１の光硬化物層及び前記第２の光硬化物層を加熱して、前記第１の光硬化物層が熱硬化した第１の光及び熱硬化物層、並びに、前記第２の光硬化物層が熱硬化した第２の光及び熱硬化物層を形成する第１及び第２の光硬化物層用加熱工程を備える、請求項１２に記載の積層構造体の製造方法。     When the heating step for the second photocurable material layer is provided, the first light and thermosetting material in which the first photocurable material layer is heated and the first photocurable material layer is thermally cured. A heating step for a first photocurable layer to form a layer is provided.
    When the heating step for the second photocurable material layer is not provided, the first photocurable material layer and the second photocurable material layer are heated to heat the first photocurable material layer. Heating for the first and second photo-cured material layers in which the cured first light and thermosetting material layer and the second photo-cured material layer form a heat-cured second light and thermosetting material layer. The method for manufacturing a laminated structure according to claim 12, further comprising a step.
  14. 　前記第１の光硬化物層の前記第１の基材側とは反対の表面上に、第２の基材を配置する配置工程を備える、請求項１０～１３のいずれか１項に記載の積層構造体の製造方法。 15. A method for manufacturing a laminated structure.
  15. 　前記第２の基材の表面粗さが、前記第１の基材の表面粗さよりも小さい、請求項１４に記載の積層構造体の製造方法。 The method for manufacturing a laminated structure according to claim 14, wherein the surface roughness of the second base material is smaller than the surface roughness of the first base material.
  16. 　第１の基材と、
    　前記第１の基材の表面上に配置された第１の層と、
    　前記第１の層の前記第１の基材側とは反対側の表面上に配置された第２の層とを備え、
    　前記第１の層と前記第２の層との組合せが、前記第１の層が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第１の組成物の光硬化物層又は光及び熱硬化物層であり、かつ前記第２の層が、多官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第２の組成物の光硬化物層又は光及び熱硬化物層である組合せであるか、又は、前記第１の層が、多官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第２の組成物の光硬化物層又は光及び熱硬化物層であり、かつ前記第２の層が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第１の組成物の光硬化物層又は光及び熱硬化物層である組合せであり、
    　前記第１の組成物と前記第２の組成物とが異なる組成物である、積層構造体。     The first base material and
    With the first layer arranged on the surface of the first base material,
    A second layer arranged on a surface of the first layer opposite to the first base material side is provided.
    The combination of the first layer and the second layer is such that the first layer contains a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. The composition is a photocurable material layer or a light and thermosetting material layer, and the second layer is a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. A combination of a photocurable layer or a light and thermosetting layer of the second composition containing the above, or the first layer is a polyfunctional (meth) acrylate compound, an epoxy compound, and the like. A photocurable material layer or a light and thermosetting material layer of a second composition containing a photopolymerization initiator and a thermosetting agent, and the second layer is a monofunctional (meth) acrylate compound. A combination of a photocurable material layer or a light and thermosetting material layer of the first composition containing an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
    A laminated structure in which the first composition and the second composition are different compositions.
  17. 　前記第１の層が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第１の組成物の光硬化物層又は光及び熱硬化物層であり、
    　前記第２の層が、多官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第２の組成物の光硬化物層又は光及び熱硬化物層である、請求項１６に記載の積層構造体。     The first layer is a photocurable layer or a light and thermosetting layer of the first composition containing a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. And
    The second layer is a photocurable layer or a light and thermosetting layer of a second composition containing a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. The laminated structure according to claim 16.
  18. 　前記第２の層が、研磨された表面を有する、請求項１７に記載の積層構造体。 The laminated structure according to claim 17, wherein the second layer has a polished surface.
  19. 　前記第２の層の前記第１の層側とは反対側の表面上に配置された第２の基材を備える、請求項１７又は１８に記載の積層構造体。 The laminated structure according to claim 17 or 18, further comprising a second base material arranged on a surface of the second layer opposite to the first layer side.
  20. 　前記第１の層が、前記第１の組成物の光及び熱硬化物層であり、
    　前記第２の層が、前記第２の組成物の光及び熱硬化物層である、請求項１７～１９のいずれか１項に記載の積層構造体。     The first layer is a light and thermosetting layer of the first composition.
    The laminated structure according to any one of claims 17 to 19, wherein the second layer is a light and thermosetting layer of the second composition.
  21. 　前記第２の層の厚みが、前記第１の層の厚みよりも厚い、請求項１７～２０のいずれか１項に記載の積層構造体。 The laminated structure according to any one of claims 17 to 20, wherein the thickness of the second layer is thicker than the thickness of the first layer.
  22. 　前記第１の層の厚みが、０．１μｍ以上１０μｍ以下であり、
    　前記第２の層の厚みが、１μｍ以上１０００μｍ以下である、請求項１７～２１のいずれか１項に記載の積層構造体。     The thickness of the first layer is 0.1 μm or more and 10 μm or less.
    The laminated structure according to any one of claims 17 to 21, wherein the thickness of the second layer is 1 μm or more and 1000 μm or less.
  23. 　前記第２の層の前記第１の層側とは反対側の表面上に配置された第３の層を備え、
    　前記第３の層が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第３の組成物の光硬化物層又は光及び熱硬化物層であり、
    　前記第２の組成物と前記第３の組成物とが異なる組成物である、請求項１７～２２のいずれか１項に記載の積層構造体。     It comprises a third layer arranged on the surface of the second layer opposite to the first layer side.
    The third layer is a photocurable layer or a light and thermosetting layer of a third composition containing a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. And
    The laminated structure according to any one of claims 17 to 22, wherein the second composition and the third composition are different compositions.
  24. 　前記第１の組成物と前記第３の組成物とが同一の組成物である、請求項２３に記載の積層構造体。 The laminated structure according to claim 23, wherein the first composition and the third composition are the same composition.
  25. 　前記第３の層の前記第２の層側とは反対側の表面上に配置された第２の基材を備える、請求項２３又は２４に記載の積層構造体。 The laminated structure according to claim 23 or 24, comprising a second base material arranged on a surface of the third layer opposite to the second layer side.
  26. 　前記第１の基材の表面粗さが、前記第２の基材の表面粗さよりも小さい、請求項２５に記載の積層構造体。 The laminated structure according to claim 25, wherein the surface roughness of the first base material is smaller than the surface roughness of the second base material.
  27. 　前記第３の層が、前記第３の組成物の光及び熱硬化物層である、請求項２３～２６のいずれか１項に記載の積層構造体。 The laminated structure according to any one of claims 23 to 26, wherein the third layer is a light and thermosetting layer of the third composition.
  28. 　前記第２の層の厚みが、前記第３の層の厚みよりも厚い、請求項２３～２７のいずれか１項に記載の積層構造体。 The laminated structure according to any one of claims 23 to 27, wherein the thickness of the second layer is thicker than the thickness of the third layer.
  29. 　前記第３の層の厚みが、０．１μｍ以上１０μｍ以下である、請求項２３～２８のいずれか１項に記載の積層構造体。 The laminated structure according to any one of claims 23 to 28, wherein the thickness of the third layer is 0.1 μm or more and 10 μm or less.
  30. 　前記第１の層が、多官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第２の組成物の光硬化物層又は光及び熱硬化物層であり、
    　前記第２の層が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含む第１の組成物の光硬化物層又は光及び熱硬化物層である、請求項１６に記載の積層構造体。     The first layer is a photocurable layer or a light and thermosetting layer of a second composition containing a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. And
    The second layer is a photocurable layer or a light and thermosetting layer of the first composition containing a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. The laminated structure according to claim 16.
  31. 　第１の組成物と第２の組成物とを有するインクジェット用組成物セットであり、
    　前記第１の組成物が、単官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含み、
    　前記第２の組成物が、多官能の（メタ）アクリレート化合物と、エポキシ化合物と、光重合開始剤と、熱硬化剤とを含み、
    　前記第１の組成物と前記第２の組成物とが異なる組成物である、インクジェット用組成物セット。     An inkjet composition set comprising a first composition and a second composition.
    The first composition comprises a monofunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
    The second composition comprises a polyfunctional (meth) acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent.
    An inkjet composition set in which the first composition and the second composition are different compositions.
  32. 　第１の容器と、第２の容器とを有し、
    　前記第１の容器に、前記第１の組成物が収容されており、
    　前記第２の容器に、前記第２の組成物が収容されている、請求項３１に記載のインクジェット用組成物セット。     It has a first container and a second container,
    The first composition is contained in the first container.
    The inkjet composition set according to claim 31, wherein the second composition is contained in the second container.
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JP2014055288A (en) * 2012-08-13 2014-03-27 Sekisui Chem Co Ltd Curable composition for ink-jet and method for producing electronic component
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JP2014055288A (en) * 2012-08-13 2014-03-27 Sekisui Chem Co Ltd Curable composition for ink-jet and method for producing electronic component
JP2015110206A (en) * 2013-11-06 2015-06-18 積水化学工業株式会社 Manufacturing method of curable film
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