TWI859411B - Method for manufacturing a laminated structure, laminated structure, and inkjet composition kit - Google Patents
Method for manufacturing a laminated structure, laminated structure, and inkjet composition kit Download PDFInfo
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- TWI859411B TWI859411B TW110104244A TW110104244A TWI859411B TW I859411 B TWI859411 B TW I859411B TW 110104244 A TW110104244 A TW 110104244A TW 110104244 A TW110104244 A TW 110104244A TW I859411 B TWI859411 B TW I859411B
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- Taiwan
- Prior art keywords
- layer
- light
- composition
- curing
- heat
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- 239000000203 mixture Substances 0.000 title claims abstract description 721
- 238000000034 method Methods 0.000 title claims description 217
- 238000004519 manufacturing process Methods 0.000 title claims description 149
- 239000000758 substrate Substances 0.000 claims abstract description 269
- 239000000463 material Substances 0.000 claims abstract description 214
- -1 acrylate compound Chemical class 0.000 claims abstract description 153
- 150000001875 compounds Chemical class 0.000 claims abstract description 110
- 239000004593 Epoxy Substances 0.000 claims abstract description 98
- 239000003999 initiator Substances 0.000 claims abstract description 81
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 68
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 64
- 238000001723 curing Methods 0.000 claims description 319
- 238000010438 heat treatment Methods 0.000 claims description 139
- 238000013007 heat curing Methods 0.000 claims description 78
- 239000011248 coating agent Substances 0.000 claims description 54
- 238000000576 coating method Methods 0.000 claims description 53
- 238000000016 photochemical curing Methods 0.000 claims description 46
- 230000003746 surface roughness Effects 0.000 claims description 35
- 230000001678 irradiating effect Effects 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 11
- 238000007641 inkjet printing Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 928
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 75
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- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 150000004901 trioxanes Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
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- Physics & Mathematics (AREA)
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- Spectroscopy & Molecular Physics (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Laminated Bodies (AREA)
Abstract
本發明提供一種積層構造體，其可提高材料之防漏出性。 本發明之積層構造體包含：第1基材；第1層，其配置於上述第1基材之表面上；及第2層，其配置於上述第1層之與上述第1基材側為相反側之表面上；上述第1層為含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第1組合物之光硬化物層，上述第2層為含有多官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第2組合物之光硬化物層，且上述第1組合物與上述第2組合物為不同之組合物。The present invention provides a laminated structure that can improve the anti-leakage property of the material. The laminated structure of the present invention comprises: a first substrate; a first layer, which is arranged on the surface of the first substrate; and a second layer, which is arranged on the surface of the first layer opposite to the first substrate 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, and the second layer is a photocurable layer of a second composition containing a multifunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent, and the first composition and the second composition are different compositions.
Description
本發明係關於一種使用噴墨裝置之積層構造體之製造方法。又，本發明係關於一種積層構造體。又，本發明係關於一種使用噴墨裝置進行塗佈使用之噴墨用組合物套組。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 kit for coating using an inkjet device.
已知有使用噴墨裝置來塗佈組合物之方法。例如，於電子零件之製造中，已知有使用噴墨裝置於基材之表面上塗佈噴墨用組合物，並利用光或熱等使該組合物硬化之方法。There is a known method of applying a composition using an inkjet device. For example, in the manufacture of electronic parts, there is a known method of applying an inkjet composition on the surface of a substrate using an inkjet device and curing the composition using light or heat.
下述專利文獻1中，揭示有含有(A)具有乙烯性不飽和基之多支鏈狀之低聚物或聚合物、(B)光聚合起始劑、及(C)熱硬化性化合物之噴墨印刷用硬化性組合物。 [先前技術文獻] [專利文獻]The following patent document 1 discloses 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. [Prior art document] [Patent document]
[專利文獻1]WO2019/189186A1[Patent Document 1] WO2019/189186A1
[發明所欲解決之問題][The problem the invention is trying to solve]
於半導體裝置及印刷配線板等電子零件中，有時配置噴墨用組合物硬化而成之硬化物層。上述硬化物層多用作用於將2個零件等進行接著之接著劑層。In electronic parts such as semiconductor devices and printed wiring boards, a hardened layer formed by hardening the inkjet composition is sometimes arranged. The hardened layer is often used as an adhesive layer for bonding two parts.
又，正在嘗試在與接著用途不同之用途中使用噴墨用組合物。In addition, attempts have been made to use the inkjet composition for applications different from the subsequent application.
例如，若能形成由硬化物層包圍之區域並於該區域之內側形成金屬層，或利用硬化物層形成間隔壁而使底部填充材不會潤濕擴散，則能夠實現電子零件之小型化、低成本化。For example, if a region surrounded by a hardened layer can be formed and a metal layer can be formed inside the region, or if a partition wall can be formed using the hardened layer so that the bottom filler does not wet and diffuse, the electronic components can be miniaturized and the cost can be reduced.
於上述用途中，需要使材料(例如，用於形成金屬層之材料及底部填充材等)不會漏出至計劃外之部位。In the above applications, it is necessary to prevent materials (for example, materials for forming a metal layer and bottom filling materials) from leaking out to unplanned locations.
本發明之目的在於提供一種可提高材料之防漏出性之積層構造體之製造方法、積層構造體及噴墨用組合物套組。又，本發明之目的亦在於提供一種用於製造上述積層構造體之裝置。 [解決問題之技術手段]The purpose of the present invention is to provide a method for manufacturing a laminated structure that can improve the anti-leakage property of the material, a laminated structure, and an inkjet composition kit. In addition, the purpose of the present invention is also to provide a device for manufacturing the above-mentioned laminated structure. [Technical means for solving the problem]
根據本發明之廣義態樣，提供一種積層構造體之製造方法，其包括：第1光硬化步驟，其係對以噴墨方式塗佈於第1基材之表面上之第1組合物照射光，而形成上述第1組合物光硬化而成之第1光硬化物層；及第2光硬化步驟，其係對以噴墨方式塗佈於上述第1光硬化物層之與上述第1基材側相反之表面側之第2組合物照射光，而形成上述第2組合物光硬化而成之第2光硬化物層；上述第1組合物含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑；上述第2組合物含有多官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑；且上述第1組合物與上述第2組合物為不同之組合物。According to a broad aspect of the present invention, a method for manufacturing a laminated structure is provided, which includes: a first photocuring step of irradiating a first composition coated on a surface of a first substrate by inkjet method with light to form a first photocurable material layer formed by photocuring the first composition; and a second photocuring step of irradiating a second composition coated on a surface side of the first photocurable material layer opposite to the first substrate side by inkjet method. The composition is irradiated with light to form a second photocurable material layer formed by photocuring the second composition; the first composition contains 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; and the first composition and the second composition are different compositions.
於本發明之積層構造體之製造方法之某特定態樣中，上述積層構造體之製造方法包括第2塗佈步驟，該第2塗佈步驟係將第2組合物以噴墨方式塗佈於上述第1光硬化物層之與上述第1基材側相反之表面側；且於上述第2光硬化步驟中，對上述第2塗佈步驟中所塗佈之上述第2組合物照射光。In a specific aspect of the method for manufacturing a laminated structure of the present invention, the method for manufacturing a laminated structure includes a second coating step, wherein the second coating step is to coat the second composition on the surface side of the first photocurable layer opposite to the first substrate side by inkjet method; and in the second photocuring step, the second composition coated in the second coating step is irradiated with light.
於本發明之積層構造體之製造方法之某特定態樣中，上述第2塗佈步驟與上述第2光硬化步驟分別於上述第1光硬化物層之厚度方向上進行複數次。In a specific aspect of the method for manufacturing a layered structure of the present invention, the second coating step and the second photocuring step are performed multiple times in the thickness direction of the first photocurable layer.
於本發明之積層構造體之製造方法之某特定態樣中，上述積層構造體之製造方法包括第1及第2光硬化物層用加熱步驟，該第1及第2光硬化物層用加熱步驟係對上述第1光硬化物層及上述第2光硬化物層進行加熱，而形成上述第1光硬化物層熱硬化而成之第1光及熱硬化物層、以及上述第2光硬化物層熱硬化而成之第2光及熱硬化物層。In a specific aspect of the method for manufacturing a laminated structure of the present invention, the method for manufacturing the laminated structure includes a heating step for the first and second light-curing layers, wherein the heating step for the first and second light-curing layers is to heat the first light-curing layer and the second light-curing layer to form a first light- and heat-curing layer formed by thermally curing the first light-curing layer and a second light- and heat-curing layer formed by thermally curing the second light-curing layer.
於本發明之積層構造體之製造方法之某特定態樣中，上述積層構造體之製造方法包括或不包括第1及第2光硬化物層用加熱步驟，該第1及第2光硬化物層用加熱步驟係對上述第1光硬化物層及上述第2光硬化物層進行加熱，而形成上述第1光硬化物層熱硬化而成之第1光及熱硬化物層、以及上述第2光硬化物層熱硬化而成之第2光及熱硬化物層；於包括上述第1及第2光硬化物層用加熱步驟之情形時包括如下第3光硬化步驟，其係對以噴墨方式塗佈於上述第2光及熱硬化物層之與上述第1基材側相反之表面側之第3組合物照射光，而形成上述第3組合物光硬化而成之第3光硬化物層；於不包括上述第1及第2光硬化物層用加熱步驟之情形時包括如下第3光硬化步驟，其係對以噴墨方式塗佈於上述第2光硬化物層之與上述第1基材側相反之表面側之第3組合物照射光，而形成上述第3組合物光硬化而成之第3光硬化物層；上述第3組合物含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑；且上述第2組合物與上述第3組合物為不同之組合物。In a specific aspect of the method for manufacturing a laminated structure of the present invention, the method for manufacturing a laminated structure includes or does not include a heating step for the first and second light-curing layers, wherein the first and second light-curing layers are heated to form a first light-curing layer and a second light-curing layer by heat-curing the first light-curing layer and a second light-curing layer by heat-curing the second light-curing layer; when the method includes the heating step for the first and second light-curing layers, the method includes a third light-curing step of heating the first and second light-curing layers and the second light-curing layers by heat-curing the first light-curing layer and the second light-curing layer. The method comprises: irradiating a third composition on a surface side opposite to the first substrate side with light to form a third photocurable material layer formed by photocuring the third composition; when the first and second photocurable material layers are not subjected to a heating step, the method comprises a third photocuring step of irradiating a third composition on a surface side opposite to the first substrate side of the second photocurable material layer with light to form a third photocurable material layer formed by photocuring the third composition; the third composition comprises a monofunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent; and the second composition and the third composition are different compositions.
於本發明之積層構造體之製造方法之某特定態樣中，上述第1組合物與上述第3組合物為相同之組合物。In a specific aspect of the method for producing a layered structure of the present invention, the first composition and the third composition are the same composition.
於本發明之積層構造體之製造方法之某特定態樣中，上述積層構造體之製造方法於包括上述第1及第2光硬化物層用加熱步驟之情形時包括如下平坦化處理步驟，其係在上述第1及第2光硬化物層用加熱步驟後，對上述第2光及熱硬化物層之與上述第1基材側相反之表面進行平坦化處理；於不包括上述第1及第2光硬化物層用加熱步驟之情形時包括如下平坦化處理步驟，其係在上述第2光硬化步驟後，對上述第2光硬化物層之與上述第1基材側相反之表面進行平坦化處理；且上述平坦化處理為研磨處理。In a specific aspect of the method for manufacturing a laminated structure of the present invention, the method for manufacturing a laminated structure includes the following planarization step when the heating step for the first and second photocurable layers is included, which is to planarize the surface of the second photocurable layer opposite to the first substrate side after the heating step for the first and second photocurable layers; when the heating step for the first and second photocurable layers is not included, the method includes the following planarization step, which is to planarize the surface of the second photocurable layer opposite to the first substrate side after the second photocurable layer is included; and the planarization treatment is a grinding treatment.
於本發明之積層構造體之製造方法之某特定態樣中，上述積層構造體之製造方法包括配置步驟，該配置步驟係於上述第3光硬化物層之與上述第1基材側相反之表面上配置第2基材。In a specific aspect of the method for manufacturing a laminated structure of the present invention, the method for manufacturing a laminated structure includes a disposing step of disposing a second substrate on the surface of the third photocurable material layer opposite to the first substrate side.
於本發明之積層構造體之製造方法之某特定態樣中，上述積層構造體之製造方法於包括上述第1及第2光硬化物層用加熱步驟之情形時包括如下第3光硬化物層用加熱步驟，其係對上述第3光硬化物層進行加熱，而形成上述第3光硬化物層熱硬化而成之第3光及熱硬化物層；於不包括上述第1及第2光硬化物層用加熱步驟之情形時包括如下第1、第2及第3光硬化物層用加熱步驟，其係對上述第1光硬化物層、上述第2光硬化物層及上述第3光硬化物層進行加熱，而形成上述第1光硬化物層熱硬化而成之第1光及熱硬化物層、上述第2光硬化物層熱硬化而成之第2光及熱硬化物層、以及上述第3光硬化物層熱硬化而成之第3光及熱硬化物層。In a specific aspect of the method for manufacturing a laminated structure of the present invention, the method for manufacturing a laminated structure includes the following heating step for a third light-curable layer when the first and second light-curable layers are included, wherein the third light-curable layer is heated to form a third light- and heat-curable layer formed by heat-curing the third light-curable layer; and when the method does not include the heating step for the first and second light-curable layers, the method In this case, the first, second and third light-curing layers are heated to form a first light-curing layer, a second light-curing layer, and a third light-curing layer by thermally curing the first light-curing layer, a second light-curing layer, and a third light-curing layer by thermally curing the second light-curing layer.
根據本發明之廣義態樣，提供一種積層構造體之製造方法，其包括第2光硬化步驟，該第2光硬化步驟係對以噴墨方式塗佈於第1基材之表面上之第2組合物照射光，而形成上述第2組合物光硬化而成之第2光硬化物層；包括或不包括第2光硬化物層用加熱步驟，該第2光硬化物層用加熱步驟係對上述第2光硬化物層進行加熱，而形成上述第2光硬化物層熱硬化而成之第2光及熱硬化物層；於包括上述第2光硬化物層用加熱步驟之情形時包括如下第1光硬化步驟，其係對以噴墨方式塗佈於上述第2光及熱硬化物層之與上述第1基材側相反之表面側之第1組合物照射光，而形成上述第1組合物光硬化而成之第1光硬化物層；於不包括上述第2光硬化物層用加熱步驟之情形時包括如下第1光硬化步驟，其係對以噴墨方式塗佈於上述第2光硬化物層之與上述第1基材側相反之表面側之第1組合物照射光，而形成上述第1組合物光硬化而成之第1光硬化物層；上述第1組合物含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑；上述第2組合物含有多官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑；且上述第1組合物與上述第2組合物為不同之組合物。According to a broad aspect of the present invention, a method for manufacturing a laminated structure is provided, which includes a second light curing step, wherein the second light curing step is to irradiate light on a second composition coated on a surface of a first substrate by inkjet method to form a second light curing material layer formed by light curing the second composition; and may or may not include a heating step for the second light curing material layer. The heating step for the material layer is to heat the second light-curing material layer to form a second light- and heat-curing material layer formed by heat-curing the second light-curing material layer; when the second light-curing material layer is included, the first light-curing step is included, which is to apply a second light-curing material layer coated on the surface side of the second light- and heat-curing material layer opposite to the first substrate side by inkjet method. The method comprises irradiating a first composition with light to form a first photocurable material layer formed by photocuring the first composition; when the second photocurable material layer is not subjected to a heating step, the method comprises the following first photocuring step, wherein the first composition coated on the surface side of the second photocurable material layer opposite to the first substrate side by inkjet method is irradiated with light to form the first photocurable material layer formed by photocuring the first composition; the first composition contains 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; and the first composition and the second composition are different compositions.
於本發明之積層構造體之製造方法之某特定態樣中，上述積層構造體之製造方法包括第2光硬化物層用加熱步驟，該第2光硬化物層用加熱步驟係對上述第2光硬化物層進行加熱，而形成上述第2光硬化物層熱硬化而成之第2光及熱硬化物層；且於上述第1光硬化步驟中，對以噴墨方式塗佈於上述第2光及熱硬化物層之與上述第1基材側相反之表面側之第1組合物照射光，而形成上述第1組合物光硬化而成之第1光硬化物層。In a specific aspect of the method for manufacturing a laminated structure of the present invention, the method for manufacturing a laminated structure includes a heating step for a second light-curable layer, wherein the second light-curable layer is heated to form a second light- and heat-curable layer formed by heat-curing the second light-curable layer; and in the first light-curing step, the first composition coated on the surface side of the second light- and heat-curable layer opposite to the first substrate side by inkjet is irradiated with light to form a first light-curable layer formed by light-curing the first composition.
於本發明之積層構造體之製造方法之某特定態樣中，於包括上述第2光硬化物層用加熱步驟之情形時包括如下平坦化處理步驟，其係在上述第2光硬化物層用加熱步驟後，對上述第2光及熱硬化物層之與上述第1基材側相反之表面進行平坦化處理；於不包括上述第2光硬化物層用加熱步驟之情形時包括如下平坦化處理步驟，其係在上述第2光硬化步驟後，對上述第2光硬化物層之與上述第1基材側相反之表面進行平坦化處理；且上述平坦化處理為研磨處理。In a specific embodiment of the method for manufacturing a multilayer structure of the present invention, when the heating step for the second light-curing layer is included, a planarization step is included, wherein after the heating step for the second light-curing layer, the surface of the second light- and heat-curing layer opposite to the first substrate side is planarized; when the heating step for the second light-curing layer is not included, a planarization step is included, wherein after the second light-curing step, the surface of the second light- and heat-curing layer opposite to the first substrate side is planarized; and the planarization treatment is a grinding treatment.
於本發明之積層構造體之製造方法之某特定態樣中，上述積層構造體之製造方法於包括上述第2光硬化物層用加熱步驟之情形時包括如下第1光硬化物層用加熱步驟，其係對上述第1光硬化物層進行加熱，而形成上述第1光硬化物層熱硬化而成之第1光及熱硬化物層；於不包括上述第2光硬化物層用加熱步驟之情形時包括如下第1及第2光硬化物層用加熱步驟，其係對上述第1光硬化物層及上述第2光硬化物層進行加熱，而形成上述第1光硬化物層熱硬化而成之第1光及熱硬化物層、以及上述第2光硬化物層熱硬化而成之第2光及熱硬化物層。In a specific aspect of the method for manufacturing a laminated structure of the present invention, the method for manufacturing a laminated structure includes a heating step for the first light-curable layer when the second light-curable layer heating step is included, wherein the first light-curable layer is heated to form a first light- and heat-curable layer formed by thermally curing the first light-curable layer; and does not include a heating step for the second light-curable layer, wherein the first and second light-curable layers are heated to form a first light- and heat-curable layer formed by thermally curing the first light-curable layer and a second light- and heat-curable layer formed by thermally curing the second light-curable layer.
於本發明之積層構造體之製造方法之某特定態樣中，上述積層構造體之製造方法包括配置步驟，該配置步驟係於上述第1光硬化物層之與上述第1基材側相反之表面上配置第2基材。In a specific aspect of the method for manufacturing a laminated structure of the present invention, the method for manufacturing a laminated structure includes a disposing step of disposing a second substrate on the surface of the first photocurable material layer opposite to the first substrate side.
於本發明之積層構造體之製造方法之某特定態樣中，上述第2基材之表面粗糙度小於上述第1基材之表面粗糙度。In a specific aspect of the method for manufacturing a layered structure of the present invention, the surface roughness of the second substrate is smaller than the surface roughness of the first substrate.
根據本發明之廣義態樣，提供一種積層構造體，其包含：第1基材；第1層，其配置於上述第1基材之表面上；及第2層，其配置於上述第1層之與上述第1基材側為相反側之表面上；上述第1層與上述第2層之組合係上述第1層為含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第1組合物之光硬化物層或光及熱硬化物層，且上述第2層為含有多官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第2組合物之光硬化物層或光及熱硬化物層的組合；或者上述第1層為含有多官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第2組合物之光硬化物層或光及熱硬化物層，且上述第2層為含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第1組合物之光硬化物層或光及熱硬化物層的組合；且上述第1組合物與上述第2組合物為不同之組合物。According to a broad aspect of the present invention, a laminate structure is provided, which comprises: a first substrate; a first layer, which is arranged on the surface of the first substrate; and a second layer, which is arranged on the surface of the first layer opposite to the first substrate side; the combination of the first layer and the second layer is that the first layer is a photocurable layer or a photo- and heat-curable layer of a first composition containing a monofunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent, and the second layer is a polyfunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent. A photocurable material layer of a second composition of a photopolymerization initiator and a thermosetting agent, or a combination of photocurable and thermosetting layers; or the first layer is a photocurable material layer or a combination of photocurable and thermosetting layers of a second composition containing a multifunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent, and the second layer is a photocurable material layer or a combination of photocurable and thermosetting layers of a first composition containing a monofunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent; and the first composition and the second composition are different compositions.
於本發明之積層構造體之某特定態樣中，上述第1層為含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第1組合物之光硬化物層或光及熱硬化物層，上述第2層為含有多官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第2組合物之光硬化物層或光及熱硬化物層。In a specific embodiment of the laminated structure of the present invention, the first layer is a photocurable layer or a photo- and heat-curable layer of a 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 photo- and heat-curable layer of a second composition containing a polyfunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent.
於本發明之積層構造體之某特定態樣中，上述第2層具有研磨過之表面。In a specific aspect of the layered structure of the present invention, the second layer has a polished surface.
於本發明之積層構造體之某特定態樣中，上述積層構造體包含第2基材，該第2基材配置於上述第2層之與上述第1層側為相反側之表面上。In a specific aspect of the laminated structure of the present invention, the laminated structure includes a second substrate, and the second substrate is disposed on a surface of the second layer opposite to the first layer.
於本發明之積層構造體之某特定態樣中，上述第1層為上述第1組合物之光及熱硬化物層，上述第2層為上述第2組合物之光及熱硬化物層。In a specific aspect of the layered structure of the present invention, the first layer is a photo- and heat-cured layer of the first composition, and the second layer is a photo- and heat-cured layer of the second composition.
於本發明之積層構造體之某特定態樣中，上述第2層之厚度厚於上述第1層之厚度。In a specific aspect of the layered structure of the present invention, the thickness of the second layer is thicker than the thickness of the first layer.
於本發明之積層構造體之某特定態樣中，上述第1層之厚度為0.1 μm以上10 μm以下，上述第2層之厚度為1 μm以上1000 μm以下。In a specific aspect of the layered structure of the present invention, the thickness of the first layer is greater than or equal to 0.1 μm and less than or equal to 10 μm, and the thickness of the second layer is greater than or equal to 1 μm and less than or equal to 1000 μm.
於本發明之積層構造體之某特定態樣中，上述積層構造體包含第3層，該第3層配置於上述第2層之與上述第1層側為相反側之表面上，上述第3層為含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第3組合物之光硬化物層或光及熱硬化物層，且上述第2組合物與上述第3組合物為不同之組合物。In a specific embodiment of the laminated structure of the present invention, the laminated structure includes a third layer, which is arranged on the surface of the second layer opposite to the first layer, and the third layer is a photocurable layer or a photo- and heat-curable layer of a third composition containing 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 compositions.
於本發明之積層構造體之某特定態樣中，上述第1組合物與上述第3組合物為相同之組合物。In a specific aspect of the layered structure of the present invention, the first composition and the third composition are the same composition.
於本發明之積層構造體之某特定態樣中，上述積層構造體包含第2基材，該第2基材配置於上述第3層之與上述第2層側為相反側之表面上。In a specific aspect of the laminated structure of the present invention, the laminated structure includes a second substrate, and the second substrate is disposed on a surface of the third layer opposite to a side of the second layer.
於本發明之積層構造體之某特定態樣中，上述第1基材之表面粗糙度小於上述第2基材之表面粗糙度。In a specific aspect of the layered structure of the present invention, the surface roughness of the first substrate is smaller than the surface roughness of the second substrate.
於本發明之積層構造體之某特定態樣中，上述第3層為上述第3組合物之光及熱硬化物層。In a specific aspect of the layered structure of the present invention, the third layer is a photo- and thermally cured layer of the third composition.
於本發明之積層構造體之某特定態樣中，上述第2層之厚度厚於上述第3層之厚度。In a specific aspect of the layered structure of the present invention, the thickness of the second layer is thicker than the thickness of the third layer.
於本發明之積層構造體之某特定態樣中，上述第3層之厚度為0.1 μm以上10 μm以下。In a specific aspect of the layered structure of the present invention, the thickness of the third layer is not less than 0.1 μm and not more than 10 μm.
於本發明之積層構造體之某特定態樣中，上述第1層為含有多官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第2組合物之光硬化物層或光及熱硬化物層，上述第2層為含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第1組合物之光硬化物層或光及熱硬化物層。In a specific embodiment of the laminated structure of the present invention, the first layer is a photocurable layer or a photo- and heat-curable layer of a second composition containing a multifunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent, and the second layer is a photocurable layer or a photo- and heat-curable layer of a first composition containing a monofunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent.
根據本發明之廣義態樣，提供一種噴墨用組合物套組，其係具有第1組合物與第2組合物之噴墨用組合物套組，上述第1組合物含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑，上述第2組合物含有多官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑，且上述第1組合物與上述第2組合物為不同之組合物。According to a broad aspect of the present invention, an inkjet composition kit is provided, which is an inkjet composition kit having a first composition and a second composition, wherein the first composition contains a monofunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent, and the second composition contains a multifunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent, and the first composition and the second composition are different compositions.
於本發明之噴墨用組合物套組之某特定態樣中，上述噴墨用組合物套組具有第1容器與第2容器，於上述第1容器中收容有上述第1組合物，於上述第2容器中收容有上述第2組合物。 [發明之效果]In a specific embodiment of the inkjet composition kit of the present invention, the inkjet composition kit has a first container and a second container, the first container contains the first composition, and the second container contains the second composition. [Effect of the invention]
本發明之積層構造體之製造方法、積層構造體及噴墨用組合物套組由於具備上述構成，故而可提高材料之防漏出性。The method for manufacturing the laminated structure, the laminated structure and the inkjet composition kit of the present invention have the above-mentioned structure, so the leakage prevention property of the material can be improved.
以下，對本發明進行詳細說明。Hereinafter, the present invention will be described in detail.
本發明之積層構造體之製造方法(1)包括第1光硬化步驟(第1組合物用光硬化步驟)，其係對以噴墨方式塗佈於第1基材之表面上之第1組合物照射光，而形成上述第1組合物光硬化而成之第1光硬化物層。本發明之積層構造體之製造方法(1)包括第2光硬化步驟(第2組合物用光硬化步驟)，其係對以噴墨方式塗佈於上述第1光硬化物層之與上述第1基材側相反之表面側之第2組合物照射光，而形成上述第2組合物光硬化而成之第2光硬化物層。The method (1) for producing a laminated structure of the present invention includes a first light curing step (a light curing step for the first composition), which is to irradiate light on the first composition applied on the surface of the first substrate by inkjet method, thereby forming a first light curing layer formed by light curing the first composition. The method (1) for producing a laminated structure of the present invention includes a second light curing step (a light curing step for the second composition), which is to irradiate light on the second composition applied on the surface side of the first light curing layer opposite to the first substrate side by inkjet method, thereby forming a second light curing layer formed by light curing the second composition.
本發明之積層構造體之製造方法(2)包括第2光硬化步驟(第2組合物用光硬化步驟)，其係對以噴墨方式塗佈於第1基材之表面上之第2組合物照射光，而形成上述第2組合物光硬化而成之第2光硬化物層。本發明之積層構造體之製造方法(2)包括或不包括第2光硬化物層用加熱步驟，其係對上述第2光硬化物層進行加熱，而形成上述第2光硬化物層熱硬化而成之第2光及熱硬化物層。本發明之積層構造體之製造方法(2)於包括上述第2光硬化物層用加熱步驟之情形時包括如下第1光硬化步驟(第1組合物用光硬化步驟)，其係對以噴墨方式塗佈於上述第2光及熱硬化物層之與上述第1基材側相反之表面側之第1組合物照射光，而形成上述第1組合物光硬化而成之第1光硬化物層。本發明之積層構造體之製造方法(2)於不包括上述第2光硬化物層用加熱步驟之情形時包括如下第1光硬化步驟(第1組合物用光硬化步驟)，其係對以噴墨方式塗佈於上述第2光硬化物層之與上述第1基材側相反之表面側之第1組合物照射光，而形成上述第1組合物光硬化而成之第1光硬化物層。The method (2) for producing a laminated structure of the present invention includes a second light curing step (a light curing step for the second composition), which is to irradiate the second composition coated on the surface of the first substrate by inkjet method with light to form a second light curing layer formed by light curing the second composition. The method (2) for producing a laminated structure of the present invention includes or does not include a heating step for the second light curing layer, which is to heat the second light curing layer to form a second light and heat curing layer formed by heat curing the second light curing layer. The method (2) for manufacturing a laminated structure of the present invention includes the following first photocuring step (first composition photocuring step) when including the heating step for the second photocurable layer, which is to irradiate light on the first composition coated on the surface side of the second photocurable layer opposite to the first substrate side by inkjet method, thereby forming the first photocurable layer formed by photocuring the first composition. The method (2) for manufacturing a laminated structure of the present invention, when not including the heating step for the second photocurable layer, includes the following first photocuring step (photocuring step for the first composition), which is to irradiate light on the first composition coated on the surface side of the second photocurable layer opposite to the first substrate side by inkjet method, thereby forming the first photocurable layer formed by photocuring the first composition.
於本發明之積層構造體之製造方法(1)、(2)中，上述第1組合物含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑，上述第2組合物含有多官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑。於本發明之積層構造體之製造方法(1)、(2)中，上述第1組合物與上述第2組合物為不同之組合物。In the methods (1) and (2) for producing a laminated structure of 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 contains 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 of the present invention, the first composition and the second composition are different compositions.
本發明之積層構造體之製造方法(1)、(2)由於具備上述構成，故而可提高材料之防漏出性。The manufacturing methods (1) and (2) of the layered structure of the present invention can improve the leakage prevention of the material because of the above-mentioned structure.
上述積層構造體之製造方法(1)較佳為包括第1塗佈步驟(第1組合物用塗佈步驟)，其係將第1組合物以噴墨方式塗佈於第1基材之表面上。上述積層構造體之製造方法(1)較佳為於上述第1光硬化步驟與上述第2光硬化步驟之間包括第2塗佈步驟(第2組合物用塗佈步驟)，其係將第2組合物以噴墨方式塗佈於上述第1光硬化物層之與上述第1基材側相反之表面側。於上述第2塗佈步驟中，較佳為將第2組合物以噴墨方式塗佈於上述第1光硬化物層之與上述第1基材側為相反側之表面上。上述第2光硬化物層較佳為與上述第1光硬化物層相接。The method (1) for producing a laminated structure preferably includes a first coating step (coating step for the first composition), which is to coat the first composition on the surface of the first substrate by inkjet. The method (1) for producing a laminated structure preferably includes a second coating step (coating step for the second composition) between the first photocuring step and the second photocuring step, which is to coat the second composition on the surface side of the first photocurable layer opposite to the first substrate side by inkjet. In the second coating step, the second composition is preferably coated on the surface of the first photocurable layer opposite to the first substrate side by inkjet. The second photocurable layer is preferably in contact with the first photocurable layer.
上述積層構造體之製造方法(2)較佳為包括第2塗佈步驟(第2組合物用塗佈步驟)，其係將第2組合物以噴墨方式塗佈於第1基材之表面上。上述積層構造體之製造方法(2)較佳為於上述第2光硬化步驟與上述第1光硬化步驟之間包括第1塗佈步驟(第1組合物用塗佈步驟)，其係將第1組合物以噴墨方式塗佈於上述第2光硬化物層之與上述第1基材側相反之表面側。於上述第1塗佈步驟中，較佳為將第1組合物以噴墨方式塗佈於上述第2光硬化物層之與上述第1基材側為相反側之表面上。上述第1光硬化物層較佳為與上述第2光硬化物層相接。The method (2) for producing a laminated structure preferably includes a second coating step (coating step for the second composition), which is coating the second composition on the surface of the first substrate by inkjet. The method (2) for producing a laminated structure preferably includes a first coating step (coating step for the first composition) between the second light curing step and the first light curing step, which is coating the first composition on the surface side of the second light curing layer opposite to the first substrate side by inkjet. In the first coating step, the first composition is preferably coated on the surface of the second photocurable layer opposite to the first substrate side by inkjet. The first photocurable layer is preferably in contact with the second photocurable layer.
於本說明書中，將上述第1塗佈步驟與上述第1光硬化步驟統稱為第1光硬化物層形成步驟(第1組合物用光硬化物層形成步驟)。又，於本說明書中，將上述第2塗佈步驟與上述第2光硬化步驟統稱為第2光硬化物層形成步驟(第2組合物用光硬化物層形成步驟)。In this specification, the first coating step and the first photocuring step are collectively referred to as the first photocurable layer forming step (first composition photocurable layer forming step). In addition, in this specification, the second coating step and the second photocuring step are collectively referred to as the second photocurable layer forming step (second composition photocurable layer forming step).
因此，上述積層構造體之製造方法(1)較佳為包括第1光硬化物層形成步驟，其係將第1組合物以噴墨方式塗佈於第1基材之表面上，且對所塗佈之上述第1組合物照射光，而形成上述第1組合物光硬化而成之第1光硬化物層。上述積層構造體之製造方法(1)較佳為包括第2光硬化物層形成步驟，其係將第2組合物以噴墨方式塗佈於上述第1光硬化物層之與上述第1基材側相反之表面側，且對所塗佈之上述第2組合物照射光，而形成上述第2組合物光硬化而成之第2光硬化物層。Therefore, the method (1) for producing a laminated structure preferably includes a first light-curable layer forming step, which comprises applying the first composition on the surface of the first substrate by inkjet method, and irradiating the applied first composition with light to form the first light-curable layer formed by light-curing the first composition. The method (1) for producing a laminated structure preferably includes a second light-curable layer forming step, which comprises applying the second composition on the surface side of the first light-curable layer opposite to the first substrate side by inkjet method, and irradiating the applied second composition with light to form the second light-curable layer formed by light-curing the second composition.
又，上述積層構造體之製造方法(2)較佳為包括第2光硬化物層形成步驟，其係將第2組合物以噴墨方式塗佈於第1基材之表面上，且對所塗佈之上述第2組合物照射光，而形成上述第2組合物光硬化而成之第2光硬化物層。上述積層構造體之製造方法(2)較佳為包括第1光硬化物層形成步驟，其係將第1組合物以噴墨方式塗佈於上述第2光硬化物層之與上述第1基材側相反之表面側，且對所塗佈之上述第1組合物照射光，而形成上述第1組合物光硬化而成之第1光硬化物層。Furthermore, the method (2) for producing a laminated structure preferably includes a second light-curable layer forming step, which comprises applying the second composition on the surface of the first substrate by inkjet method, and irradiating the applied second composition with light to form the second light-curable layer formed by light-curing the second composition. The method (2) for producing a laminated structure preferably includes a first light-curable layer forming step, which comprises applying the first composition on the surface side of the second light-curable layer opposite to the first substrate side by inkjet method, and irradiating the applied first composition with light to form the first light-curable layer formed by light-curing the first composition.
本發明之積層構造體包含：第1基材；第1層，其配置於上述第1基材之表面上；及第2層，其配置於上述第1層之與上述基材側為相反側之表面上。於本發明之積層構造體中，上述第1層與上述第2層之組合為以下之第1組合A或以下之組合B。組合A：上述第1層為含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第1組合物之光硬化物層或光及熱硬化物層，上述第2層為含有多官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第2組合物之光硬化物層或光及熱硬化物層。組合B：上述第1層為含有多官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第2組合物之光硬化物層或光及熱硬化物層，且上述第2層為含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第1組合物之光硬化物層或光及熱硬化物層。於本發明之積層構造體中，上述第1組合物與上述第2組合物為不同之組合物。The laminated structure of the present invention comprises: a first substrate; a first layer disposed on a surface of the first substrate; and a second layer disposed on a surface of the first layer opposite to the substrate side. In the laminated structure of 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 photo- and heat-curable layer of a 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 photo- and heat-curable layer of a second composition containing a polyfunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. Combination B: The first layer is a light-curable layer or a light-and-heat-curable layer of a second composition containing a multifunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent, and the second layer is a light-curable layer or a light-and-heat-curable layer of a first composition containing a monofunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. In the layered structure of the present invention, the first composition and the second composition are different compositions.
本發明之積層構造體由於具備上述構成，故而可提高材料之防漏出性。The multilayer structure of the present invention has the above-mentioned structure, so the leakage prevention property of the material can be improved.
本發明之噴墨用組合物套組係具有第1組合物與第2組合物之噴墨用組合物套組。於本發明之噴墨用組合物套組中，上述第1組合物含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑，上述第2組合物含有多官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑。於本發明之噴墨用組合物套組中，上述第1組合物與上述第2組合物為不同之組合物。The inkjet composition kit of the present invention is an inkjet composition kit having a first composition and a second composition. In the inkjet composition kit of 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 contains a multifunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator, and a thermosetting agent. In the inkjet composition kit of the present invention, the first composition and the second composition are different compositions.
本發明之噴墨用組合物套組由於具備上述構成，故而可提高材料之防漏出性。The inkjet composition kit of the present invention has the above-mentioned structure, so the leakage prevention property of the material can be improved.
本發明者等針對先前之噴墨用組合物發現如下課題：有硬化物層之形狀保持性較低之情形，材料會漏出至硬化物層之周邊。本發明者等發現如下課題：尤其於噴墨用組合物為光硬化性組合物之情形時，在利用噴墨裝置所塗佈之組合物之表面，因空氣中之氧之影響而易阻礙光聚合反應。又，有如下情形：若污物等粉體附著於噴墨用組合物之表面，則於粉體附著之部分未充分照射光，而不會充分進行光聚合反應。本發明者等發現如下課題：於此種情形時，噴墨用組合物未充分硬化，硬化物層之形狀保持性易下降。The inventors of the present invention have found the following problem with the previous inkjet composition: In some cases, the shape retention of the cured layer is low, and the material leaks out to the periphery of the cured layer. The inventors of the present invention have found the following problem: Especially when the inkjet composition is a photocurable composition, the surface of the composition applied by the inkjet device is easily hindered from photopolymerization due to the influence of oxygen in the air. In addition, there is the following situation: if powder such as dirt adheres to the surface of the inkjet composition, the part where the powder adheres is not fully irradiated with light, and the photopolymerization reaction will not fully proceed. The inventors of the present invention have found the following problem: In this case, the inkjet composition is not fully cured, and the shape retention of the cured layer is easily reduced.
進而，本發明者等發現如下課題：於僅使用含有光反應性較高之化合物之組合物之情形時，由於硬化收縮變大，故而基材與硬化物層之接著力易下降，材料易自基材與硬化物層之間漏出。Furthermore, the inventors of the present invention have discovered the following problem: when only a composition containing a compound with high photoreactivity is used, the adhesion between the substrate and the cured layer is easily reduced due to the large curing shrinkage, and the material is easily leaked from between the substrate and the cured layer.
進而，本發明者等針對先前之噴墨用組合物發現：於積層組成不同之硬化物層之情形時，難以充分提高層間接著力，材料易自層間接著力較低之部位漏出。Furthermore, the inventors of the present invention have found that, with respect to the previous inkjet composition, when different hardened layers are laminated, it is difficult to sufficiently increase the interlayer adhesion, and the material is likely to leak out from the portion with the lower interlayer adhesion.
先前，作為提高基材與硬化物層之接著力之方法，已知有利用藥液對基材之表面進行處理或物理上損傷基材之表面而於基材之表面形成凹凸之方法、進行底塗處理之方法。然而，該等方法中，於未塗佈噴墨用組合物之部分，基材之表面之性質亦發生變化，因此例如有於連接零件之情形時發生導電性下降等不良情況之情形。又，有底塗劑與硬化物層之接著強度下降之情形。Previously, as a method for improving the adhesion between the substrate and the cured layer, there are known methods of treating the surface of the substrate with a chemical solution or physically damaging the surface of the substrate to form unevenness on the surface of the substrate, and methods of performing primer treatment. However, in these methods, the properties of the surface of the substrate also change in the part where the inkjet composition is not applied, so there are cases where undesirable conditions such as reduced conductivity occur when connecting parts. In addition, there are cases where the adhesion strength between the primer and the cured layer is reduced.
又，為了減小空氣中之氧之影響，亦研究開發可一面利用氮氣等進行置換一面塗佈組合物之裝置。然而，裝置之尺寸變大，或裝置之費用變高。In order to reduce the influence of oxygen in the air, research and development have been conducted to develop a device that can replace the oxygen in the air with nitrogen or the like while applying the composition. However, the size of the device becomes larger or the cost of the device becomes higher.
針對本發明者發現之新課題，利用先前之方法難以提高材料之防漏出性。The inventors of the present invention have discovered a new problem in which it is difficult to improve the leakage resistance of materials using previous methods.
相對於此，本發明之積層構造體之製造方法、積層構造體及噴墨用組合物套組即便不進行基材之表面處理，且即便不使用可進行氮氣置換之裝置，亦可提高第1組合物及第2組合物硬化而成之硬化物層之形狀保持性，且可提高與基材之接著力及層間接著力。In contrast, the method for manufacturing a laminated structure, the laminated structure, and the inkjet composition kit of the present invention can improve the shape retention of the cured layer formed by curing the first composition and the second composition, and can improve the adhesion to the substrate and the inter-layer adhesion even without performing surface treatment on the substrate and even without using a device capable of nitrogen replacement.
本發明之積層構造體之製造方法、積層構造體及噴墨用組合物套組由於使用特定之第1組合物與特定之第2組合物，故而可提高第1組合物及第2組合物硬化而成之硬化物層之形狀保持性。又，本發明之積層構造體之製造方法、積層構造體及噴墨用組合物套組由於使用特定之第1組合物與特定之第2組合物，故而可提高基材與第1組合物之硬化物層之接著力，且可提高第1組合物之硬化物層與第2組合物之硬化物層之層間接著力。The method for manufacturing a laminated structure, the laminated structure, and the inkjet composition kit of the present invention use a specific first composition and a specific second composition, so that the shape retention of the cured layer formed by curing the first composition and the second composition can be improved. In addition, the method for manufacturing a laminated structure, the laminated structure, and the inkjet composition kit of the present invention use a specific first composition and a specific second composition, so that the adhesion between the substrate and the cured layer of the first composition can be improved, and the inter-layer adhesion between the cured layer of the first composition and the cured layer of the second composition can be improved.
因此，關於本發明之積層構造體之製造方法、積層構造體及噴墨用組合物套組，材料(例如，用於形成金屬層之材料及底部填充材等)難以自基材與硬化物層之間等漏出。例如，於在由硬化物層包圍之區域之內側配置材料之情形時，該材料難以自該區域之內側漏出至外側。又，例如，於在由硬化物層包圍之區域之外側配置材料之情形時，該材料難以自該區域之外側漏出至內側。Therefore, in the method for manufacturing a laminated structure, the laminated structure, and the inkjet composition kit of the present invention, materials (e.g., materials for forming a metal layer and bottom filler materials, etc.) are unlikely to leak out from between the substrate and the cured layer, etc. For example, when the material is disposed inside the region surrounded by the cured layer, the material is unlikely to leak out from the inside of the region to the outside. Also, when the material is disposed outside the region surrounded by the cured layer, the material is unlikely to leak out from the outside of the region to the inside.
本發明之積層構造體之製造方法、積層構造體及噴墨用組合物套組可提高第1組合物及第2組合物之光硬化物層以及光及熱硬化物層之形狀保持性。The method for manufacturing a laminated structure, the laminated structure and the inkjet composition kit of the present invention can improve the shape retention of the light-cured layer of the first composition and the second composition and the light- and heat-cured layer.
又，本發明之積層構造體之製造方法、積層構造體及噴墨用組合物套組由於可使硬化物層之強度變得良好，故而可有效抑制硬化物層之損傷，又，可有效抑制污物等粉體附著於硬化物層。Furthermore, the method for manufacturing a laminated structure, the laminated structure, and the inkjet composition kit of the present invention can improve the strength of the cured layer, thereby effectively suppressing damage to the cured layer and effectively suppressing the adhesion of powder such as dirt to the cured layer.
(積層構造體之製造方法) 以下，一面參照圖式，一面對本發明之具體實施方式進行說明。再者，於以下之圖式中，為便於圖示，有大小、厚度及形狀等與實際之大小、厚度及形狀等不同之情形。(Manufacturing method of laminated structure) The following describes the specific implementation method of the present invention with reference to the drawings. In addition, in the following drawings, for the convenience of illustration, there are cases where the size, thickness, shape, etc. are different from the actual size, thickness, shape, etc.
圖1(a)～(c)、圖2(d)～(f)及圖3(g)、(h)係用於對本發明之第1實施方式之積層構造體之製造方法的各步驟進行說明之剖視圖。圖4係用於對本發明之第1實施方式之積層構造體之製造方法的各步驟進行說明之流程圖。圖1～4中之第1實施方式之積層構造體之製造方法為上述積層構造體之製造方法(1)。Fig. 1 (a) to (c), Fig. 2 (d) to (f) and Fig. 3 (g) and (h) are cross-sectional views for explaining the steps of the method for manufacturing a laminated structure according to the first embodiment of the present invention. Fig. 4 is a flow chart for explaining the steps of the method for manufacturing a laminated structure according to the first embodiment of the present invention. The method for manufacturing a laminated structure according to the first embodiment in Figs. 1 to 4 is the above-mentioned method for manufacturing a laminated structure (1).
圖1～3中，為了製造積層構造體，而使用有具備載台11、第1噴出部12、第1光照射部13、第2噴出部14及第2光照射部15之裝置10。第1噴出部12係用於噴出第1組合物之構件且為噴墨頭。第2噴出部14係用於噴出第2組合物之構件且為噴墨頭。因此，裝置10為噴墨裝置。於第1噴出部12與第2噴出部14之間，配置有第1光照射部13。於第2噴出部14之與第1光照射部13側相反之側，配置有第2光照射部15。第1光照射部13及第2光照射部15可照射紫外線。In FIGS. 1 to 3, in order to manufacture a laminated structure, a device 10 having a carrier 11, a first ejection unit 12, a first light irradiation unit 13, a second ejection unit 14, and a second light irradiation unit 15 is used. The first ejection unit 12 is a component for ejecting a first composition and is an inkjet head. The second ejection unit 14 is a component for ejecting a second composition and is an inkjet head. Therefore, the device 10 is an inkjet device. The first light irradiation unit 13 is arranged between the first ejection unit 12 and the second ejection unit 14. The second light irradiation unit 15 is arranged on the side of the second ejection unit 14 opposite to the side of the first light irradiation unit 13. The first light irradiation unit 13 and the second light irradiation unit 15 can irradiate ultraviolet rays.
＜第1光硬化物層形成步驟(圖4之S1及S2)＞ 首先，如圖1(a)所示，於載台11之表面上配置第1基材3。第1基材3固定於載台11之表面上。第1基材3吸附於載台11。然後，以噴墨方式於第1基材3之表面上塗佈第1組合物1(第1塗佈步驟)。自第1噴出部12塗佈第1組合物1。第1組合物1塗佈於第1基材3之規定位置。第1組合物1局部地塗佈於第1基材3之表面上。<First light-curing layer formation step (S1 and S2 of FIG. 4)> First, as shown in FIG. 1(a), the first substrate 3 is arranged on the surface of the carrier 11. The first substrate 3 is fixed on the surface of the carrier 11. The first substrate 3 is adsorbed on the carrier 11. Then, the first composition 1 is applied on the surface of the first substrate 3 by inkjet method (first application step). The first composition 1 is applied from the first ejection part 12. The first composition 1 is applied to a predetermined position of the first substrate 3. The first composition 1 is partially applied on the surface of the first substrate 3.
其次，如圖1(b)所示，移動載台11直至所塗佈之第1組合物1位於第1光照射部13之下方為止。亦可移動噴墨裝置來代替載台11。自第1光照射部13對第1組合物1照射光(紫外線)，而形成第1組合物光硬化而成之第1光硬化物層1A(第1光硬化步驟)。Next, as shown in FIG. 1( b ), the stage 11 is moved until the coated first composition 1 is located below the first light irradiation section 13. Alternatively, an 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 section 13 to form a first light-cured material layer 1A formed by light-curing the first composition (first light-curing step).
於上述第1光硬化步驟後，判斷是否重複第1光硬化物層形成步驟(圖4之S3)。於重複上述第1光硬化物層形成步驟之情形時，在所形成之第1光硬化物層之與第1基材側相反之表面側塗佈第1組合物。After the first light curing step, it is determined whether to repeat the first light curing layer forming step (S3 of FIG. 4 ). When the first light curing layer forming step is repeated, the first composition is applied to the surface of the first light curing layer opposite to the first substrate.
＜第2光硬化物層形成步驟(圖4之S4及S5)＞ 其次，如圖1(c)所示，移動載台11直至第1光硬化物層1A位於第2噴出部14之下方為止。亦可移動噴墨裝置來代替載台11。以噴墨方式於第1光硬化物層1A之與第1基材3側相反之表面側塗佈第2組合物2(第2塗佈步驟)。自第2噴出部14塗佈第2組合物2。<Second light-curing layer formation step (S4 and S5 of FIG. 4 )> Next, as shown in FIG. 1(c), the stage 11 is moved until the first light-curing layer 1A is located below the second ejection unit 14. Instead of the stage 11, an inkjet device may be moved. The second composition 2 is applied to the surface of the first light-curing layer 1A opposite to the first substrate 3 by inkjet (second application step). The second composition 2 is applied from the second ejection unit 14.
其次，如圖2(d)所示，移動載台11直至所塗佈之第2組合物2位於第2光照射部15之下方為止。亦可移動噴墨裝置來代替載台11。自第2光照射部15對第2組合物2照射光(紫外線)，而形成第2組合物光硬化而成之第2光硬化物層2A(第2光硬化步驟)。Next, as shown in FIG. 2( d ), the stage 11 is moved until the coated second composition 2 is located below the second light irradiation section 15. Alternatively, an 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 section 15 to form a second light-cured material layer 2A formed by light-curing the second composition (second light-curing step).
於上述第2光硬化步驟後，判斷是否重複第2光硬化物層形成步驟(圖4之S6)。於重複上述第2光硬化物層形成步驟之情形時，在所形成之第2光硬化物層之與第1基材側相反之表面側塗佈第2組合物。After the second light curing step, it is determined whether to repeat the second light curing layer forming step (S6 of FIG. 4 ). When the second light curing layer forming step is repeated, the second composition is applied to the surface of the formed second light curing layer opposite to the first substrate side.
圖2(e)、(f)係表示第2次之第2光硬化物層形成步驟之圖。如圖2(e)所示，移動載台11直至第2光硬化物層2A位於第2噴出部14之下方為止。亦可移動噴墨裝置來代替載台11。以噴墨方式於第2光硬化物層2A之與第1基材3側相反之表面上塗佈第2組合物2。即，於第1光硬化物層1A之與第1基材3側相反之表面側塗佈第2組合物2(第2塗佈步驟)。自第2噴出部14塗佈第2組合物2。FIG. 2 (e) and (f) are diagrams showing the second step of forming the second light-curable layer. As shown in FIG. 2 (e), the stage 11 is moved until the second light-curable layer 2A is located below the second ejection unit 14. Instead of the stage 11, an inkjet device may be moved. The second composition 2 is applied to the surface of the second light-curable layer 2A opposite to the first substrate 3 by inkjet. That is, the second composition 2 is applied to the surface of the first light-curable layer 1A opposite to the first substrate 3 (second application step). The second composition 2 is applied from the second ejection unit 14.
其次，如圖2(f)所示，移動載台11直至所塗佈之第2組合物2位於第2光照射部15之下方為止。亦可移動噴墨裝置來代替載台11。自第2光照射部15對第2組合物2照射光(紫外線)，而形成第2組合物光硬化而成之第2光硬化物層2A(第2光硬化步驟)。Next, as shown in FIG. 2( f), the stage 11 is moved until the coated second composition 2 is located below the second light irradiation section 15. Alternatively, an 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 section 15 to form a second light-cured material layer 2A formed by light-curing the second composition (second light-curing step).
上述第2光硬化物層形成步驟係於第1光硬化物層之厚度方向上進行圖1(c)及圖2(d)、與圖2(e)及圖2(f)之2次。藉由在第1光硬化物層之厚度方向上進行複數次上述第2光硬化物層形成步驟，可增大第2光硬化物層之厚度。上述第2光硬化物層形成步驟可進行2次以上，亦可進行3次以上。The second light-curing layer forming step is performed twice in the thickness direction of the first light-curing layer, as shown in FIG. 1(c) and FIG. 2(d), and FIG. 2(e) and FIG. 2(f). By performing the second light-curing layer forming step a plurality of times in the thickness direction of the first light-curing layer, the thickness of the second light-curing layer can be increased. The second light-curing layer forming step can be performed more than twice, or more than three times.
藉由在第1光硬化物層之厚度方向上進而進行複數次上述第2光硬化物層形成步驟，可如圖3(g)所示獲得如下積層構造體4A，其具備第1基材3、第1光硬化物層1A及第2光硬化物層2A，且第2光硬化物層2A之厚度大於第1光硬化物層1A之厚度。By further performing the above-mentioned second photocurable layer forming step multiple times in the thickness direction of the first photocurable layer, the following layered structure 4A can be obtained as shown in Figure 3(g), which has a first substrate 3, a first photocurable layer 1A and a second photocurable layer 2A, and the thickness of the second photocurable layer 2A is greater than the thickness of the first photocurable layer 1A.
＜第1及第2光硬化物層用加熱步驟(圖4之S7)＞ 其次，對第1光硬化物層1A及第2光硬化物層2A進行加熱，而形成第1光硬化物層1A熱硬化而成之第1光及熱硬化物層1B、以及第2光硬化物層2A熱硬化而成之第2光及熱硬化物層2B(第1及第2光硬化物層用加熱步驟)。<Heating step for the first and second light-curing layers (S7 in FIG. 4 )> Next, the first light-curing layer 1A and the second light-curing layer 2A are heated to form the first light-curing layer 1B formed by thermally curing the first light-curing layer 1A, and the second light-curing layer 2B formed by thermally curing the second light-curing layer 2A (heating step for the first and second light-curing layers).
如此，可獲得具備第1基材3、第1光及熱硬化物層1B、以及第2光及熱硬化物層2B之積層構造體4B。In this way, a multilayer structure 4B including the first substrate 3, the first photo- and heat-cured material layer 1B, and the second photo- and heat-cured material layer 2B can be obtained.
圖5、6係用於對本發明之第2實施方式之積層構造體之製造方法的各步驟進行說明之流程圖。第2實施方式之積層構造體之製造方法為積層構造體之製造方法(1)。圖7係利用第2實施方式之積層構造體之製造方法所製造之積層構造體的剖視圖。Figures 5 and 6 are flow charts for explaining the steps 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). Figure 7 is a cross-sectional view of a laminated structure manufactured by the method for manufacturing a laminated structure according to the second embodiment.
＜第1光硬化物層形成步驟(圖5之S1及S2)＞ 於第2實施方式之積層構造體之製造方法中，以與上述第1實施方式之積層構造體之製造方法中之第1光硬化物層形成步驟(圖1(a)、(b))同樣之方式進行第1光硬化物層形成步驟。<First light-curing material layer formation step (S1 and S2 in FIG. 5)> In the method for manufacturing a laminated structure of the second embodiment, the first light-curing material layer formation step is performed in the same manner as the first light-curing material layer formation step (FIG. 1(a), (b)) in the method for manufacturing a laminated structure of the first embodiment described above.
於上述第1光硬化步驟後，判斷是否重複第1光硬化物層形成步驟(圖5之S3)。於重複上述第1光硬化物層形成步驟之情形時，在所形成之第1光硬化物層之與第1基材側相反之表面側塗佈第1組合物。After the first light curing step, it is determined whether to repeat the first light curing layer forming step (S3 of FIG. 5 ). When the first light curing layer forming step is repeated, the first composition is applied to the surface of the first light curing layer opposite to the first substrate.
＜第2光硬化物層形成步驟(圖5之S4及S5)＞ 於第2實施方式之積層構造體之製造方法中，以與上述第1實施方式之積層構造體之製造方法中之第2光硬化物層形成步驟(圖1(c)、(d))同樣之方式進行第2光硬化物層形成步驟。<Second light-curing material layer formation step (S4 and S5 of FIG. 5)> In the method for manufacturing a laminated structure of the second embodiment, the second light-curing material layer formation step is performed in the same manner as the second light-curing material layer formation step (FIG. 1(c), (d)) in the method for manufacturing a laminated structure of the first embodiment described above.
於上述第2光硬化步驟後，判斷是否重複第2光硬化物層形成步驟(圖5之S6)。於重複上述第2光硬化物層形成步驟之情形時，在所形成之第2光硬化物層之與第1基材側相反之表面側塗佈第2組合物。After the second light curing step, it is determined whether to repeat the second light curing layer forming step (S6 of FIG. 5 ). When the second light curing layer forming step is repeated, the second composition is applied to the surface of the formed second light curing layer opposite to the first substrate side.
＜第1及第2光硬化物層用加熱步驟(圖6之S8)＞ 於上述第2光硬化步驟後，判斷是否進行第1及第2光硬化物層用加熱步驟(圖6之S7)。於進行第1及第2光硬化物層用加熱步驟之情形時，對第1光硬化物層及第2光硬化物層進行加熱，而形成第1光硬化物層熱硬化而成之第1光及熱硬化物層、以及第2光硬化物層熱硬化而成之第2光及熱硬化物層(第1及第2光硬化物層用加熱步驟)。<Heating step for the first and second light-curing layers (S8 in FIG. 6)> After the second light-curing step, it is determined whether to perform the heating step for the first and second light-curing layers (S7 in FIG. 6). When the heating step for the first and second light-curing layers is performed, the first light-curing layer and the second light-curing layer are heated to form a first light- and heat-curing layer formed by thermally curing the first light-curing layer and a second light- and heat-curing layer formed by thermally curing the second light-curing layer (heating step for the first and second light-curing layers).
藉由進行第1及第2光硬化物層用加熱步驟，可獲得具備第1基材、第1光及熱硬化物層、以及第2光及熱硬化物層之積層構造體。By performing the heating step for the first and second light-curing layers, a layered structure having a first substrate, a first light- and heat-curing layer, and a second light- and heat-curing layer can be obtained.
＜平坦化處理步驟(圖6之S10)＞ 於進行上述第1及第2光硬化物層用加熱步驟之情形時，在上述第1及第2光硬化物層用加熱步驟後，判斷是否進行平坦化處理步驟(圖6之S9)。於不進行上述第1及第2光硬化物層用加熱步驟之情形時，在上述第2光硬化步驟後，判斷是否進行平坦化處理步驟(圖6之S9)。於本實施方式中，作為平坦化處理，判斷是否進行研磨處理。<Flattening treatment step (S10 in FIG. 6)> When the heating step for the first and second photocurable layers is performed, after the heating step for the first and second photocurable layers, it is determined whether the flattening treatment step is performed (S9 in FIG. 6). When the heating step for the first and second photocurable layers is not performed, after the second photocurable layer is performed, it is determined whether the flattening treatment step is performed (S9 in FIG. 6). In this embodiment, it is determined whether the polishing treatment is performed as the flattening treatment.
於進行上述第1及第2光硬化物層用加熱步驟，且進行上述平坦化處理步驟之情形時，在上述第1及第2光硬化物層用加熱步驟後，對上述第2光及熱硬化物層之與上述第1基材側相反之表面進行平坦化處理(平坦化處理步驟)。於不進行上述第1及第2光硬化物層用加熱步驟，且進行上述平坦化處理步驟之情形時，對上述第2光硬化物層之與上述第1基材側相反之表面進行平坦化處理(平坦化處理步驟)。When the heating step for the first and second light-curable layers is performed and the planarization step is performed, after the heating step for the first and second light-curable layers, the surface of the second light- and heat-curable layer opposite to the first substrate side is planarized (planarization step). When the heating step for the first and second light-curable layers is not performed and the planarization step is performed, the surface of the second light-curable layer opposite to the first substrate side is planarized (planarization step).
＜第3光硬化物層形成步驟(圖6之S11及S12)＞ 利用與上述第1光硬化物層形成步驟或上述第2光硬化物層形成步驟同樣之方法，使用上述第3組合物進行第3光硬化物層形成步驟。<Third light-curing layer forming step (S11 and S12 in FIG. 6 )> The third light-curing layer forming step is performed using the third composition in the same manner as the first light-curing layer forming step or the second light-curing layer forming step.
於進行上述第1及第2光硬化物層用加熱步驟之情形時，將第3組合物以噴墨方式塗佈於第2光及熱硬化物層之與上述第1基材側相反之表面上(第3塗佈步驟(第3組合物用塗佈步驟))。於不進行上述第1及第2光硬化物層用加熱步驟之情形時，將第3組合物以噴墨方式塗佈於第2光硬化物層之與上述第1基材側相反之表面上(第3塗佈步驟(第3組合物用塗佈步驟))。自噴墨裝置所具備之規定噴出部塗佈第3組合物。再者，於第1組合物與第3組合物為相同之組合物之情形時，在第3塗佈步驟中，實質上將第1組合物以噴墨方式塗佈於第2光及熱硬化物層或第2光硬化物層之與上述第1基材側相反之表面上。When the heating step for the first and second light-curable layers is performed, the third composition is applied by inkjet on the surface of the second light-curable layer opposite to the first substrate side (third application step (application step for the third composition)). When the heating step for the first and second light-curable layers is not performed, the third composition is applied by inkjet on the surface of the second light-curable layer opposite to the first substrate side (third application step (application step for the third composition)). The third composition is applied from a predetermined ejection portion of the inkjet device. Furthermore, when the first composition and the third composition are the same composition, in the third coating step, the first composition is substantially coated on the second light and heat curable layer or on the surface of the second light curable layer opposite to the first substrate side by inkjet.
其次，自噴墨裝置所具備之規定光照射部對第3組合物照射光(紫外線)，而形成第3組合物光硬化而成之第3光硬化物層(第3光硬化步驟(第3組合物用光硬化步驟))。於第1組合物與第3組合物為相同之組合物之情形時，在第3光硬化步驟中，實質上自噴墨裝置所具備之規定光照射部照射光(紫外線)，而形成第1組合物光硬化而成之第3光硬化物層。Next, the third composition is irradiated with light (ultraviolet rays) from a predetermined light irradiation portion of the inkjet device, thereby forming a third light-cured material layer formed by light-curing the third composition (third light-curing step (light-curing step for the third composition)). When the first composition and the third composition are the same composition, in the third light-curing step, light (ultraviolet rays) is irradiated from a predetermined light irradiation portion of the inkjet device, thereby forming a third light-cured material layer formed by light-curing the first composition.
於上述第3光硬化步驟後，判斷是否重複第3光硬化物層形成步驟(圖6之S13)。於重複上述第3光硬化物層形成步驟之情形時，在所形成之第3光硬化物層之與第1基材側相反之表面側塗佈第3組合物。After the third light curing step, it is determined whether to repeat the third light curing layer forming step (S13 in FIG. 6 ). When the third light curing layer forming step is repeated, the third composition is applied to the surface of the third light curing layer opposite to the first substrate side.
再者，於說明書中，將上述第3塗佈步驟與上述第3光硬化步驟統稱為第3光硬化物層形成步驟(第3組合物用光硬化物層形成步驟)。Furthermore, in the specification, the third coating step and the third photocuring step are collectively referred to as a third photocurable material layer forming step (third composition photocurable material layer forming step).
＜配置步驟(圖6之S14)＞ 於上述第3光硬化物層形成步驟後，在上述第3光硬化物層之與上述第1基材側相反之表面上配置第2基材(配置步驟)。<Configuration step (S14 in FIG. 6 )> After the third light-curing material layer is formed, a second substrate is configured on the surface of the third light-curing material layer opposite to the first substrate side (configuration step).
＜第3光硬化物層用加熱步驟、或第1、第2及第3光硬化物層用加熱步驟(圖6之S15)＞ 於進行上述第1及第2光硬化物層用加熱步驟之情形時，在上述配置步驟後，對上述第3光硬化物層進行加熱，而形成第3光及熱硬化物層(第3光硬化物層用加熱步驟)。於不進行上述第1及第2光硬化物層用加熱步驟之情形時，在上述配置步驟後，對上述第1光硬化物層、上述第2光硬化物層及上述第3光硬化物層進行加熱，而形成第1光及熱硬化物層、第2光及熱硬化物層、以及第3光及熱硬化物層(第1、第2及第3光硬化物層用加熱步驟)。上述第1光及熱硬化物層為上述第1光硬化物層熱硬化而成之層。上述第2光及熱硬化物層為上述第2光硬化物層熱硬化而成之層。上述第3光及熱硬化物層為上述第3光硬化物層熱硬化而成之層。<Heating step for the third light-curing material layer, or heating step for the first, second and third light-curing material layers (S15 in FIG. 6 )> When the heating step for the first and second light-curing material layers is performed, after the configuration step, the third light-curing material layer is heated to form a third light- and heat-curing material layer (heating step for the third light-curing material layer). In the case where the heating step for the first and second light-curable layers is not performed, the first light-curable layer, the second light-curable layer, and the third light-curable layer are heated after the arrangement step to form the first light- and heat-curable layer, the second light- and heat-curable layer, and the third light- and heat-curable layer (the heating step for the first, second, and third light-curable layers). The first light- and heat-curable layer is a layer formed by heat-curing the first light-curable layer. The second light- and heat-curable layer is a layer formed by heat-curing the second light-curable layer. The third light- and heat-curable layer is a layer formed by heat-curing the third light-curable layer.
如此，可如圖7所示獲得如下積層構造體4D，其依序具備第1基材3、第1光及熱硬化物層1D、第2光及熱硬化物層2D、第3光及熱硬化物層6D以及第2基材7。In this way, as shown in FIG. 7 , a layered structure 4D can be obtained, which sequentially includes a first substrate 3, a first light and heat-cured material layer 1D, a second light and heat-cured material layer 2D, a third light and heat-cured material layer 6D, and a second substrate 7.
圖8、9係用於對本發明之第3實施方式之積層構造體之製造方法的各步驟進行說明之流程圖。第3實施方式之積層構造體之製造方法為積層構造體之製造方法(2)。圖10係利用第3實施方式之積層構造體之製造方法所製造之積層構造體的剖視圖。Fig. 8 and Fig. 9 are flow charts for explaining the steps of the method for manufacturing a laminated structure according to the third embodiment of the present invention. The method for manufacturing a laminated structure according to the third embodiment is the method for manufacturing a laminated structure (2). Fig. 10 is a cross-sectional view of a laminated structure manufactured by the method for manufacturing a laminated structure according to the third embodiment.
＜第2光硬化物層形成步驟(圖8之S1及S2)＞ 於第3實施方式之積層構造體之製造方法中，除將第2組合物塗佈於第1基材之表面上以外，以與上述第1實施方式之積層構造體之製造方法中之第2光硬化物層形成步驟(圖1(c)、(d))同樣之方式進行第2光硬化物層形成步驟。<Second light-curing material layer formation step (S1 and S2 of FIG. 8 )> In the method for manufacturing a laminated structure of the third embodiment, the second light-curing material layer formation step is performed in the same manner as the second light-curing material layer formation step (FIG. 1 (c), (d)) in the method for manufacturing a laminated structure of the first embodiment described above, except that the second composition is applied to the surface of the first substrate.
具體而言，以噴墨方式於第1基材之表面上塗佈第2組合物(第2塗佈步驟)。第2組合物塗佈於第1基材之規定位置。第2組合物局部地塗佈於第1基材之表面上。Specifically, the second composition is applied on the surface of the first substrate by inkjet method (second application step). The second composition is applied on a predetermined position of the first substrate. The second composition is partially applied on the surface of the first substrate.
其次，對所塗佈之第2組合物照射光(紫外線)，而形成第2組合物光硬化而成之第2光硬化物層(第2光硬化步驟)。Next, the applied second composition is irradiated with light (ultraviolet rays) to form a second photocurable material layer by photocuring the second composition (second photocuring step).
於上述第2光硬化步驟後，判斷是否重複第2光硬化物層形成步驟(圖8之S3)。於重複上述第2光硬化物層形成步驟之情形時，在所形成之第2光硬化物層之與第1基材側相反之表面側塗佈第2組合物。After the second light curing step, it is determined whether to repeat the second light curing layer forming step (S3 of FIG. 8 ). When the second light curing layer forming step is repeated, the second composition is applied to the surface of the formed second light curing layer opposite to the first substrate side.
＜第2光硬化物層用加熱步驟(圖8之S5)＞ 於上述第2光硬化步驟後，判斷是否進行第2光硬化物層用加熱步驟(圖8之S4)。於進行第2光硬化物層用加熱步驟之情形時，對第2光硬化物層進行加熱，而形成第2光硬化物層熱硬化而成之第2光及熱硬化物層(第2光硬化物層用加熱步驟)。<Heating step for the second light-curing layer (S5 of FIG. 8 )> After the second light-curing step, it is determined whether to perform the heating step for the second light-curing layer (S4 of FIG. 8 ). When the heating step for the second light-curing layer is performed, the second light-curing layer is heated to form a second light- and heat-cured layer (heating step for the second light-curing layer) by thermally curing the second light-curing layer.
＜平坦化處理步驟(圖9之S7)＞ 於進行上述第2光硬化物層用加熱步驟之情形時，在上述第2光硬化物層用加熱步驟後，判斷是否進行平坦化處理步驟(圖9之S6)。於不進行上述第2光硬化物層用加熱步驟之情形時，在上述第2光硬化步驟後，判斷是否進行平坦化處理步驟(圖9之S6)。<Flattening treatment step (S7 of FIG. 9)> When the heating step for the second light-curing material layer is performed, after the heating step for the second light-curing material layer, it is determined whether the flattening treatment step is performed (S6 of FIG. 9). When the heating step for the second light-curing material layer is not performed, after the second light-curing step, it is determined whether the flattening treatment step is performed (S6 of FIG. 9).
於進行上述第2光硬化物層用加熱步驟，且進行上述平坦化處理步驟之情形時，在上述第2光硬化物層用加熱步驟後，對上述第2光及熱硬化物層之與上述第1基材側相反之表面進行平坦化處理(平坦化處理步驟(第2光及熱硬化物層用平坦化處理步驟))。於不進行上述第2光硬化物層用加熱步驟，且進行上述平坦化處理步驟之情形時，對上述第2光硬化物層之與上述第1基材側相反之表面進行平坦化處理(平坦化處理步驟(第2光硬化物層用平坦化處理步驟))。In the case where the heating step for the second light-curable layer is performed and the planarization step is performed, after the heating step for the second light-curable layer, the surface of the second light- and heat-curable layer opposite to the first substrate side is planarized (planarization step (planarization step for the second light- and heat-curable layer)). In the case where the heating step for the second light-curable layer is not performed and the planarization step is performed, the surface of the second light-curable layer opposite to the first substrate side is planarized (planarization step (planarization step for the second light-curable layer)).
＜第1光硬化物層形成步驟(圖9之S8及S9)＞ 於進行上述第2光硬化物層用加熱步驟之情形時，以噴墨方式於第2光及熱硬化物層之與第1基材側相反之表面側塗佈第1組合物(第1塗佈步驟)。於不進行上述第2光硬化物層用加熱步驟之情形時，以噴墨方式於第2光硬化物層之與第1基材側相反之表面側塗佈第1組合物(第1塗佈步驟)。<First light-curable layer formation step (S8 and S9 in FIG. 9 )> When the heating step for the second light-curable layer is performed, the first composition is applied to the surface of the second light-curable layer opposite to the first substrate side by inkjet (first coating step). When the heating step for the second light-curable layer is not performed, the first composition is applied to the surface of the second light-curable layer opposite to the first substrate side by inkjet (first coating step).
其次，於進行上述第2光硬化物層用加熱步驟之情形時，對以噴墨方式塗佈於上述第2光及熱硬化物層之與上述第1基材側相反之表面側之第1組合物照射光，而形成上述第1組合物光硬化而成之第1光硬化物層(第1光硬化步驟)。於不進行上述第2光硬化物層用加熱步驟之情形時，對以噴墨方式塗佈於上述第2光硬化物層之與上述第1基材側相反之表面側之第1組合物照射光，而形成上述第1組合物光硬化而成之第1光硬化物層(第1光硬化步驟)。Next, when the heating step for the second light-curable layer is performed, the first composition applied by inkjet on the surface side of the second light- and heat-curable layer opposite to the first substrate side is irradiated with light to form the first light-curable layer formed by light-curing the first composition (first light-curing step). When the heating step for the second light-curable layer is not performed, the first composition applied by inkjet on the surface side of the second light-curable layer opposite to the first substrate side is irradiated with light to form the first light-curable layer formed by light-curing the first composition (first light-curing step).
於上述第1光硬化步驟後，判斷是否重複第1光硬化物層形成步驟(圖9之S10)。於重複上述第1光硬化物層形成步驟之情形時，在所形成之第1光硬化物層之與第1基材側相反之表面側塗佈第1組合物。After the first light curing step, it is determined whether to repeat the first light curing layer forming step (S10 in FIG. 9 ). When the first light curing layer forming step is repeated, the first composition is applied to the surface of the first light curing layer opposite to the first substrate.
＜配置步驟(圖9之S11)＞ 於上述第1光硬化物層形成步驟後，在上述第1光硬化物層之與上述第1基材側相反之表面上配置第2基材(配置步驟)。<Configuration step (S11 in FIG. 9 )> After the step of forming the first light-curing material layer, a second substrate is configured on the surface of the first light-curing material layer opposite to the first substrate side (configuration step).
＜第1光硬化物層用加熱步驟、或第1及第2光硬化物層用加熱步驟(圖9之S12)＞ 於進行上述第2光硬化物層用加熱步驟之情形時，在上述配置步驟後，對上述第1光硬化物層進行加熱，而形成第1光及熱硬化物層(第1光硬化物層用加熱步驟)。於不進行上述第2光硬化物層用加熱步驟之情形時，在上述配置步驟後，對上述第1光硬化物層及上述第2光硬化物層進行加熱，而形成第1光及熱硬化物層、以及第2光及熱硬化物層(第1及第2光硬化物層用加熱步驟)。上述第1光及熱硬化物層為上述第1光硬化物層熱硬化而成之層。上述第2光及熱硬化物層為上述第2光硬化物層熱硬化而成之層。<Heating step for the first light-curable layer, or heating step for the first and second light-curable layers (S12 in FIG. 9 )> When the heating step for the second light-curable layer is performed, the first light-curable layer is heated after the configuration step to form the first light- and heat-curable layer (heating step for the first light-curable layer). When the heating step for the second light-curable layer is not performed, the first light-curable layer and the second light-curable layer are heated after the configuration step to form the first light- and heat-curable layer and the second light- and heat-curable layer (heating step for the first and second light-curable layers). The first light-curable and heat-curable layer is a layer formed by heat-curing the first light-curable layer. The second light-curable and heat-curable layer is a layer formed by heat-curing the second light-curable layer.
如此，可如圖10所示獲得如下積層構造體4E，其依序具備第1基材3、第2光及熱硬化物層2E、第1光及熱硬化物層1E以及第2基材7。In this way, as shown in FIG. 10 , a layered structure 4E can be obtained, which includes the first substrate 3, the second light and heat cured material layer 2E, the first light and heat cured material layer 1E, and the second substrate 7 in this order.
＜積層構造體之製造方法之其他詳情＞ 第1、第2及第3光硬化物層形成步驟之其他詳情： 上述積層構造體之製造方法(1)可包括亦可不包括上述第1塗佈步驟。上述積層構造體之製造方法(2)可包括亦可不包括上述第2塗佈步驟。上述積層構造體(1)較佳為依序包括上述第1塗佈步驟、上述第1光硬化步驟、上述第2塗佈步驟及上述第2光硬化步驟。上述積層構造體(2)較佳為依序包括上述第2塗佈步驟、上述第2光硬化步驟、上述第1塗佈步驟及上述第1光硬化步驟。上述積層構造體之製造方法(1)可包括亦可不包括上述第3塗佈步驟。上述積層構造體之製造方法(1)可包括亦可不包括上述第3光硬化步驟。上述積層構造體之製造方法(1)可包括亦可不包括上述第3光硬化物層形成步驟。<Other details of the method for manufacturing a laminated structure> Other details of the first, second and third light-curing layer formation steps: The method for manufacturing a laminated structure (1) may or may not include the first coating step. The method for manufacturing a laminated structure (2) may or may not include the second coating step. The laminated structure (1) preferably includes the first coating step, the first light-curing step, the second coating step and the second light-curing step in sequence. The laminated structure (2) preferably includes the second coating step, the second light curing step, the first coating step, and the first light curing step in sequence. The manufacturing method (1) of the laminated structure may or may not include the third coating step. The manufacturing method (1) of the laminated structure may or may not include the third light curing step. The manufacturing method (1) of the laminated structure may or may not include the third light curing step.
於上述積層構造體之製造方法(1)、(2)中，可在特定區域塗佈第1組合物之後，對所塗佈之第1組合物之整體照射光而形成第1光硬化物層。於上述積層構造體之製造方法(1)、(2)中，亦可每塗佈複數滴第1組合物時，對所塗佈之第1組合物照射光而形成第1光硬化物層。於上述積層構造體之製造方法(1)、(2)中，亦可每塗佈1滴第1組合物時，對所塗佈之第1組合物照射光而形成第1光硬化物層。In the above-mentioned methods (1) and (2) for producing a laminated structure, after applying the first composition to a specific area, the entire applied first composition may be irradiated with light to form a first light-curable material layer. In the above-mentioned methods (1) and (2) for producing a laminated structure, each time a plurality of drops of the first composition are applied, the applied first composition may be irradiated with light to form a first light-curable material layer. In the above-mentioned methods (1) and (2) for producing a laminated structure, each time a single drop of the first composition is applied, the applied first composition may be irradiated with light to form a first light-curable material layer.
於上述積層構造體之製造方法(1)、(2)中，上述第1光硬化物層形成步驟如圖1所示可於第1基材之厚度方向上僅進行1次。於上述積層構造體之製造方法(1)、(2)中，上述第1光硬化物層形成步驟亦可於第1基材之厚度方向上進行複數次。即，於上述積層構造體之製造方法(1)、(2)中，上述第1塗佈步驟與上述第1光硬化步驟可分別於第1基材之厚度方向上僅進行1次，亦可進行複數次。藉由在第1基材之厚度方向上進行複數次上述第1光硬化物層形成步驟，可增大第1光硬化物層之厚度。In the above-mentioned methods (1) and (2) for manufacturing a laminated structure, the above-mentioned first light-curable material layer forming step may be performed only once in the thickness direction of the first substrate as shown in FIG. 1. In the above-mentioned methods (1) and (2) for manufacturing a laminated structure, the above-mentioned first light-curable material layer forming step may be performed multiple times in the thickness direction of the first substrate. That is, in the above-mentioned methods (1) and (2) for manufacturing a laminated structure, the above-mentioned first coating step and the above-mentioned first light-curing step may be performed only once or multiple times in the thickness direction of the first substrate, respectively. By performing the above-mentioned first light-curable material layer forming step multiple times in the thickness direction of the first substrate, the thickness of the first light-curable material layer can be increased.
於上述積層構造體之製造方法(1)中，上述第1光硬化物層形成步驟較上述第2光硬化物層形成步驟更先進行。於上述積層構造體之製造方法(2)中，上述第2光硬化物層形成步驟較上述第1光硬化物層形成步驟更先進行。於上述積層構造體之製造方法(1)中，上述第1光硬化物層形成步驟及上述第2光硬化物層形成步驟較上述第3光硬化物層形成步驟更先進行。In the method (1) for manufacturing a laminated structure, the first light-curing material layer forming step is performed before the second light-curing material layer forming step. In the method (2) for manufacturing a laminated structure, the second light-curing material layer forming step is performed before the first light-curing material layer forming step. In the method (1) for manufacturing a laminated structure, the first light-curing material layer forming step and the second light-curing material layer forming step are performed before the third light-curing material layer forming step.
於上述積層構造體之製造方法(1)、(2)中，可在特定區域塗佈第2組合物之後，對所塗佈之第2組合物之整體照射光而形成第2光硬化物層。於上述積層構造體之製造方法(1)、(2)中，亦可每塗佈複數滴第2組合物時，對所塗佈之第2組合物照射光而形成第2光硬化物層。於上述積層構造體之製造方法(1)、(2)中，亦可每塗佈1滴第2組合物時，對所塗佈之第2組合物照射光而形成第2光硬化物層。In the above-mentioned methods (1) and (2) for producing a laminated structure, after applying the second composition to a specific area, the entire applied second composition may be irradiated with light to form a second light-curable material layer. In the above-mentioned methods (1) and (2) for producing a laminated structure, each time a plurality of drops of the second composition are applied, the applied second composition may be irradiated with light to form a second light-curable material layer. In the above-mentioned methods (1) and (2) for producing a laminated structure, each time a single drop of the second composition is applied, the applied second composition may be irradiated with light to form a second light-curable material layer.
於上述積層構造體之製造方法(1)中，上述第2光硬化物層形成步驟可於第1光硬化物層之厚度方向上僅進行1次。於上述積層構造體之製造方法(1)中，上述第2光硬化物層形成步驟亦可如圖1、2所示於第1光硬化物層之厚度方向上進行複數次。即，於上述積層構造體之製造方法(1)中，上述第2塗佈步驟與上述第2光硬化步驟可分別於第1光硬化物層之厚度方向上僅進行1次，亦可進行複數次。於上述積層構造體之製造方法(2)中，上述第2光硬化物層形成步驟可於第1基材之厚度方向上僅進行1次。於上述積層構造體之製造方法(2)中，上述第2光硬化物層形成步驟亦可於第1基材之厚度方向上進行複數次。於上述積層構造體之製造方法(2)中，上述第2塗佈步驟與上述第2光硬化步驟可分別於第1基材之厚度方向上僅進行1次，亦可進行複數次。藉由在第1光硬化物層之厚度方向或第1基材之厚度方向上進行複數次上述第2光硬化物層形成步驟，可增大第2光硬化物層之厚度。上述第2光硬化物層形成步驟較佳為於第1光硬化物層之厚度方向或第1基材之厚度方向上進行複數次。再者，根據目標之第2光硬化物層之厚度，而適當變更重複上述第2光硬化物層形成步驟之次數。In the above-mentioned method (1) for manufacturing a laminated structure, the above-mentioned second light-curing material layer forming step may be performed only once in the thickness direction of the first light-curing material layer. In the above-mentioned method (1) for manufacturing a laminated structure, the above-mentioned second light-curing material layer forming step may be performed multiple times in the thickness direction of the first light-curing material layer as shown in Figures 1 and 2. That is, in the above-mentioned method (1) for manufacturing a laminated structure, the above-mentioned second coating step and the above-mentioned second light-curing step may be performed only once in the thickness direction of the first light-curing material layer, or may be performed multiple times. In the above-mentioned method (2) for manufacturing a laminated structure, the above-mentioned second light-curing material layer forming step may be performed only once in the thickness direction of the first substrate. In the above-mentioned method (2) for manufacturing a laminated structure, the above-mentioned second light-curing layer forming step may be performed multiple times in the thickness direction of the first substrate. In the above-mentioned method (2) for manufacturing a laminated structure, the above-mentioned second coating step and the above-mentioned second light-curing step may be performed only once or multiple times in the thickness direction of the first substrate, respectively. By performing the above-mentioned second light-curing layer forming step multiple times in the thickness direction of the first light-curing layer or in the thickness direction of the first substrate, the thickness of the second light-curing layer can be increased. The above-mentioned second light-curing layer forming step is preferably performed multiple times in the thickness direction of the first light-curing layer or in the thickness direction of the first substrate. Furthermore, the number of times of repeating the second light-curing layer forming step is appropriately changed according to the target thickness of the second light-curing layer.
於上述積層構造體之製造方法(1)、(2)中，可在特定區域塗佈第3組合物之後，對所塗佈之第3組合物之整體照射光而形成第3光硬化物層。於上述積層構造體之製造方法(1)、(2)中，每塗佈複數滴第3組合物時，對所塗佈之第3組合物照射光而形成第3光硬化物層。於上述積層構造體之製造方法(1)、(2)中，每塗佈1滴第3組合物時，對所塗佈之第3組合物照射光而形成第3光硬化物層。In the above-mentioned methods (1) and (2) for producing a laminated structure, after applying the third composition to a specific area, the entire applied third composition may be irradiated with light to form a third light-curable material layer. In the above-mentioned methods (1) and (2) for producing a laminated structure, each time a plurality of drops of the third composition are applied, the applied third composition is irradiated with light to form a third light-curable material layer. In the above-mentioned methods (1) and (2) for producing a laminated structure, each time a single drop of the third composition is applied, the applied third composition is irradiated with light to form a third light-curable material layer.
於上述積層構造體之製造方法(1)、(2)中，上述第3光硬化物層形成步驟可於第2光硬化物層之厚度方向上僅進行1次。於上述積層構造體之製造方法(1)、(2)中，上述第3光硬化物層形成步驟亦可於第2光硬化物層之厚度方向上進行複數次。即，於上述積層構造體之製造方法(1)、(2)中，上述第3塗佈步驟與上述第3光硬化步驟可分別於第2光硬化物層之厚度方向上僅進行1次，亦可進行複數次。藉由在第2光硬化物層之厚度方向上進行複數次上述第3光硬化物層形成步驟，可增大第3光硬化物層之厚度。In the above-mentioned methods (1) and (2) for manufacturing a laminated structure, the above-mentioned third light-curable layer forming step may be performed only once in the thickness direction of the second light-curable layer. In the above-mentioned methods (1) and (2) for manufacturing a laminated structure, the above-mentioned third light-curable layer forming step may be performed multiple times in the thickness direction of the second light-curable layer. That is, in the above-mentioned methods (1) and (2) for manufacturing a laminated structure, the above-mentioned third coating step and the above-mentioned third light-curing step may be performed only once or multiple times in the thickness direction of the second light-curable layer, respectively. By performing the above-mentioned third light-curable layer forming step multiple times in the thickness direction of the second light-curable layer, the thickness of the third light-curable layer can be increased.
於上述積層構造體之製造方法(1)、(2)中，上述第1光硬化步驟、上述第2光硬化步驟及第3光硬化步驟中之光照射較佳為紫外線照射。In the above-mentioned methods (1) and (2) for manufacturing a laminated structure, the light irradiation in the above-mentioned first light curing step, the above-mentioned second light curing step and the third light curing step is preferably ultraviolet irradiation.
上述第1光硬化步驟、上述第2光硬化步驟及第3光硬化步驟中之紫外線之照度及照射時間可根據第1組合物、上述第2組合物及第3組合物之組成、以及組合物之塗佈厚度而適當變更。上述第1光硬化步驟、上述第2光硬化步驟及第3光硬化步驟中之紫外線之照度例如可為1000 mW/cm2 以上，亦可為5000 mW/cm2 以上，且可為10000 mW/cm2 以下，亦可為8000 mW/cm2 以下。上述第1光硬化步驟、上述第2光硬化步驟及第3光硬化步驟中之紫外線之照射時間例如可為0.01秒以上，亦可為0.1秒以上，且可為400秒以下，亦可為100秒以下。The irradiance and irradiation time of the ultraviolet light in the first photocuring step, the second photocuring step, and the third photocuring step can be appropriately changed according to the composition of the first composition, the second composition, and the third composition, and the coating thickness of the composition. The irradiance of the ultraviolet light in the first photocuring step, the second photocuring step, and the third photocuring step can be, for example, 1000 mW/cm2 or more , or 5000 mW/cm2 or more , or 10000 mW/ cm2 or less, or 8000 mW/ cm2 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, and may be 400 seconds or less, or 100 seconds or less.
加熱步驟之其他詳情： 上述積層構造體之製造方法(1)可包括亦可不包括上述第1及第2光硬化物層用加熱步驟。上述積層構造體之製造方法(1)可包括亦可不包括上述第3光硬化物層用加熱步驟。上述積層構造體之製造方法(1)可包括亦可不包括上述第1、第2及第3光硬化物層用加熱步驟。上述積層構造體之製造方法(2)可包括亦可不包括上述第2光硬化物層用加熱步驟。上述積層構造體之製造方法(2)可包括亦可不包括上述第1光硬化物層用加熱步驟。上述積層構造體之製造方法(2)可包括亦可不包括上述第1及第2光硬化物層用加熱步驟。就提高第1及第2組合物之硬化物層之強度之觀點而言，上述積層構造體之製造方法(1)較佳為包括上述第1及第2光硬化物層用加熱步驟。就提高第3組合物之硬化物層之強度之觀點而言，上述積層構造體之製造方法(1)較佳為包括上述第3光硬化物層用加熱步驟。就提高第1、第2及第3組合物之硬化物層之強度之觀點而言，上述積層構造體之製造方法(1)較佳為包括上述第1、第2及第3光硬化物層用加熱步驟。就提高第2組合物之硬化物層之強度之觀點而言，上述積層構造體之製造方法(2)較佳為包括上述第2光硬化物層用加熱步驟。就提高第1組合物之硬化物層之強度之觀點而言，上述積層構造體之製造方法(2)較佳為包括上述第1光硬化物層用加熱步驟。就提高第1及第2組合物之硬化物層之強度之觀點而言，上述積層構造體之製造方法(2)較佳為包括上述第1及第2光硬化物層用加熱步驟。Other details of the heating step: The manufacturing method (1) of the above-mentioned laminated structure may include or exclude the heating step for the above-mentioned first and second light-curing material layers. The manufacturing method (1) of the above-mentioned laminated structure may include or exclude the heating step for the above-mentioned third light-curing material layer. The manufacturing method (1) of the above-mentioned laminated structure may include or exclude the heating step for the above-mentioned first, second and third light-curing material layers. The manufacturing method (2) of the above-mentioned laminated structure may include or exclude the heating step for the above-mentioned second light-curing material layer. The manufacturing method (2) of the above-mentioned laminated structure may include or exclude the heating step for the above-mentioned first light-curing material layer. The method (2) for producing a laminated structure may or may not include the heating step for the first and second light-curing layers. From the viewpoint of increasing the strength of the hardened layers of the first and second compositions, the method (1) for producing a laminated structure preferably includes the heating step for the first and second light-curing layers. From the viewpoint of increasing the strength of the hardened layers of the third composition, the method (1) for producing a laminated structure preferably includes the heating step for the third light-curing layer. From the viewpoint of increasing the strength of the hardened layers of the first, second, and third compositions, the method (1) for producing a laminated structure preferably includes the heating step for the first, second, and third light-curing layers. From the viewpoint of increasing the strength of the cured layer of the second composition, the method (2) for producing a laminated structure preferably includes a heating step for the second light-curable layer. From the viewpoint of increasing the strength of the cured layer of the first composition, the method (2) for producing a laminated structure preferably includes a heating step for the first light-curable layer. From the viewpoint of increasing the strength of the cured layers of the first and second compositions, the method (2) for producing a laminated structure preferably includes a heating step for the first and second light-curable layers.
於上述積層構造體之製造方法(1)中，上述第1及第2光硬化物層用加熱步驟較上述第2光硬化物層形成步驟更後進行。於上述積層構造體之製造方法(1)中，上述第1及第2光硬化物層用加熱步驟較佳為較上述第3光硬化物層形成步驟更先進行，且較佳為較上述第3光硬化物層用加熱步驟更先進行。於上述積層構造體之製造方法(1)中，上述第1及第2光硬化物層用加熱步驟亦可較上述第3光硬化物層形成步驟更後進行。於上述積層構造體之製造方法(1)中，上述第3光硬化物層用加熱步驟可較上述配置步驟更先進行，亦可較上述配置步驟更後進行。於上述積層構造體之製造方法(2)中，上述第2光硬化物層用加熱步驟較上述第2光硬化物層形成步驟更後進行。於上述第2積層構造體之製造方法(2)中，上述第2光硬化物層用加熱步驟較佳為較上述第1光硬化物層形成步驟更先進行，且較佳為較上述第1光硬化物層用加熱步驟更先進行。於上述積層構造體之製造方法(2)中，上述第1光硬化物層用加熱步驟可較上述配置步驟更先進行，亦可較上述配置步驟更後進行。In the method (1) for manufacturing a laminated structure, the first and second light-curing layer heating steps are performed after the second light-curing layer forming step. In the method (1) for manufacturing a laminated structure, the first and second light-curing layer heating steps are preferably performed before the third light-curing layer forming step, and are preferably performed before the third light-curing layer heating step. In the method (1) for manufacturing a laminated structure, the first and second light-curing layer heating steps may be performed after the third light-curing layer forming step. In the method (1) for manufacturing a laminated structure, the third light-curable layer heating step may be performed before or after the arrangement step. In the method (2) for manufacturing a laminated structure, the second light-curable layer heating step may be performed after the second light-curable layer forming step. In the method (2) for manufacturing a second laminated structure, the second light-curable layer heating step may be performed before the first light-curable layer forming step, and may be performed before the first light-curable layer heating step. In the above-mentioned method (2) for manufacturing a laminated structure, the above-mentioned heating step for the first light-curable material layer may be performed before the above-mentioned arrangement step, or may be performed after the above-mentioned arrangement step.
於上述加熱步驟中，較佳為同時對所配置之各光硬化物層進行加熱。In the above-mentioned heating step, it is preferred to heat the configured photocurable material layers simultaneously.
上述加熱步驟各自之加熱溫度及加熱時間可根據第1組合物、上述第2組合物及第3組合物之組成、以及組合物之塗佈厚度而適當變更。上述加熱步驟中之加熱溫度例如可為100℃以上，亦可為120℃以上，且可為250℃以下，亦可為200℃以下。上述加熱步驟中之加熱時間例如可為5分鐘以上，亦可為30分鐘以上，且可為600分鐘以下，亦可為300分鐘以下。The heating temperature and heating time of each of the above-mentioned heating steps can be appropriately changed according to 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 above-mentioned heating step can be, for example, 100° C. or more, or 120° C. or more, and can be 250° C. or less, or 200° C. or less. The heating time in the above-mentioned heating step can be, for example, 5 minutes or more, or 30 minutes or more, and can be 600 minutes or less, or 300 minutes or less.
平坦化處理步驟之其他詳情： 上述積層構造體之製造方法(1)可包括亦可不包括上述平坦化處理步驟。上述積層構造體之製造方法(2)可包括亦可不包括上述平坦化處理步驟。於製造具備第1基材與第2基材之積層構造體之情形時，上述積層構造體之製造方法(1)、(2)較佳為包括上述平坦化處理步驟。藉由進行上述平坦化處理，即便配置於上述第2光硬化物層(或上述第2光及熱硬化物層)與第2基材之間之硬化物層之厚度較小，亦可提高該硬化物層與第2基材之接著力。Other details of the planarization step: The manufacturing method (1) of the above-mentioned laminated structure may or may not include the above-mentioned planarization step. The manufacturing method (2) of the above-mentioned laminated structure may or may not include the above-mentioned planarization step. In the case of manufacturing a laminated structure having a first substrate and a second substrate, the manufacturing methods (1) and (2) of the above-mentioned laminated structure preferably include the above-mentioned planarization step. By performing the above-mentioned planarization treatment, even if the thickness of the hardened layer disposed between the above-mentioned second light-curing layer (or the above-mentioned second light- and heat-curing layer) and the second substrate is small, the bonding strength between the hardened layer and the second substrate can be improved.
於上述積層構造體之製造方法(1)中，上述平坦化處理步驟可較上述第1及第2光硬化物層用加熱步驟更先進行，亦可較其更後進行。於上述積層構造體之製造方法(1)中，較佳為在上述第1及第2光硬化物層用加熱步驟後，對上述第2光及熱硬化物層之與上述第1基材側相反之表面進行平坦化處理。於上述積層構造體之製造方法(2)中，上述平坦化處理步驟可較上述第2光硬化物層用加熱步驟更先進行，亦可較其更後進行。於上述積層構造體之製造方法(2)中，較佳為在上述第2光硬化物層用加熱步驟後，對上述第2光及熱硬化物層之與上述第1基材側相反之表面進行平坦化處理。於該等情形時，可提高基材與硬化物層之接著力，又，可提高硬化物層之強度，因此可抑制平坦化處理時硬化物層自第1基材剝離或硬化物層損壞。In the method (1) for manufacturing a laminated structure, the planarization step may be performed before or after the heating step for the first and second light-curing layers. In the method (1) for manufacturing a laminated structure, it is preferred that after the heating step for the first and second light-curing layers, the surface of the second light- and heat-curing layer opposite to the first substrate side is planarized. In the method (2) for manufacturing a laminated structure, the planarization step may be performed before or after the heating step for the second light-curing layer. In the method (2) for manufacturing a laminated structure, it is preferred that after the second light-cured layer is heated, a planarization treatment is performed on the surface of the second light-cured layer opposite to the first substrate. In such a case, the adhesion between the substrate and the cured layer can be improved, and the strength of the cured layer can be improved, thereby preventing the cured layer from peeling off from the first substrate or damaging the cured layer during the planarization treatment.
作為上述平坦化處理，可例舉研磨處理等。作為上述研磨處理，可例舉利用使用金剛石之車刀加工之切削研磨處理及化學機械研磨處理等。Examples of the planarization process include polishing, etc. Examples of the polishing process include cutting polishing using a diamond turning tool and chemical mechanical polishing.
就容易進行上述平坦化處理之方面而言，上述平坦化處理較佳為研磨處理。就尤其容易進行上述平坦化處理之方面而言，上述研磨處理較佳為利用使用金剛石之車刀加工之切削研磨處理，更佳為利用使用金剛石之車刀加工之切削研磨處理與化學機械研磨處理之兩種處理。In terms of ease of performing the planarization process, the planarization process is preferably a grinding process. In terms of ease of performing the planarization process, the grinding process is preferably a cutting grinding process using a diamond turning tool, and more preferably a combination of a cutting grinding process using a diamond turning tool and a chemical mechanical grinding process.
作為可用於上述平坦化處理(研磨處理)之裝置，可例舉KeyLink公司製造之「平坦化裝置」、DISCO公司製造之「DFS8910」等。Examples of devices that can be used for the above-mentioned planarization process (polishing process) include "planarization device" manufactured by KeyLink Corporation and "DFS8910" manufactured by DISCO Corporation.
上述平坦化處理後之上述第2光及熱硬化物層(或上述第2光硬化物層)之表面之最大高度與最小高度的差之絕對值較佳為5 μm以下，更佳為3 μm以下，進而較佳為1 μm以下。若上述差之絕對值為上述上限以下，則可更有效地抑制接著不良，或更有效地抑制貼合於平坦化處理後之表面之零件之傾斜。再者，上述差之絕對值可為0.5 μm以上。The absolute value of the difference between the maximum height and the minimum height of the surface of the second light and heat cured layer (or the second light cured layer) after the planarization treatment is preferably 5 μm or less, more preferably 3 μm or less, and further preferably 1 μm or less. If the absolute value of the difference is below the upper limit, it is more effective to suppress poor adhesion or to suppress the tilt of the parts attached to the surface after the planarization treatment. Furthermore, the absolute value of the difference may be 0.5 μm or more.
配置步驟之其他詳情： 上述積層構造體之製造方法(1)、(2)可包括上述配置步驟亦可不包括上述配置步驟。上述積層構造體之製造方法(1)較佳為包括在上述第3光硬化物層之與上述第1基材側相反之表面上配置第2基材之配置步驟。再者，於上述積層構造體之製造方法(1)中，上述第3光硬化物層用加熱步驟較上述配置步驟更先進行之情形時，在上述配置步驟中，將第2基材配置於上述第3光及熱硬化物層之與上述第1基材側相反之表面上。上述積層構造體之製造方法(2)較佳為包括在上述第1光硬化物層之與上述第1基材側相反之表面上配置第2基材的配置步驟。再者，於上述積層構造體之製造方法(2)中，上述第1光硬化物層用加熱步驟較上述配置步驟更先進行之情形時，在上述配置步驟中，將第2基材配置於上述第1光及熱硬化物層之與上述第1基材側相反之表面上。Other details of the configuration step: The above-mentioned manufacturing methods (1) and (2) of the laminated structure may include the above-mentioned configuration step or may not include the above-mentioned configuration step. The above-mentioned manufacturing method (1) of the laminated structure preferably includes a configuration step of configuring the second substrate on the surface of the above-mentioned third light-curing material layer opposite to the above-mentioned first substrate side. Furthermore, in the above-mentioned manufacturing method (1) of the laminated structure, when the heating step of the above-mentioned third light-curing material layer is performed before the above-mentioned configuration step, in the above-mentioned configuration step, the second substrate is configured on the surface of the above-mentioned third light- and heat-curing material layer opposite to the above-mentioned first substrate side. The method (2) for manufacturing a laminated structure preferably includes a disposition step of disposing a second substrate on the surface of the first light-curable material layer opposite to the first substrate side. Furthermore, in the method (2) for manufacturing a laminated structure, when the heating step for the first light-curable material layer is performed before the disposition step, in the disposition step, the second substrate is disposed on the surface of the first light- and heat-curable material layer opposite to the first substrate side.
配置上述第2基材之方法並無特別限定。The method of disposing the second substrate is not particularly limited.
上述第1基材與上述第2基材可為相同之基材，亦可為不同之基材。The first substrate and the second substrate may be the same substrate or different substrates.
與上述第2組合物之硬化物層接觸之基材較佳為表面具有凹凸之基材，或表面經過底塗處理之基材。於此情形時，可進一步提高與上述第2組合物之硬化物層之接著性，而可更有效地發揮本發明之效果。又，可提高長期可靠性。作為於基材之表面形成凹凸之方法，可例舉使用毛刷之方法及進行噴砂加工之方法等。The substrate in contact with the hardened layer of the second composition is preferably a substrate having a surface with unevenness, or a substrate having a surface treated with a primer. In this case, the adhesion with the hardened layer of the second composition can be further improved, and the effect of the present invention can be more effectively exerted. In addition, long-term reliability can be improved. As a method for forming unevenness on the surface of the substrate, a method using a brush and a method of performing sandblasting can be cited.
與上述第1組合物之硬化物層接觸之基材之表面粗糙度較佳為小於與上述第2組合物之硬化物層接觸之基材之表面粗糙度。於上述積層構造體之製造方法(2)中，與上述第1組合物之硬化物層接觸之基材為上述第2基材，與上述第2組合物之硬化物層接觸之基材為上述第1基材。因此，於上述積層構造體之製造方法(2)中，上述第2基材之表面粗糙度較佳為小於上述第1基材之表面粗糙度。The surface roughness of the substrate in contact with the cured layer of the first composition is preferably smaller than the surface roughness of the substrate in contact with the cured layer of the second composition. In the method (2) for manufacturing a laminated structure, the substrate in contact with the cured layer of the first composition is the second substrate, and the substrate in contact with the cured layer of the second composition is the first substrate. Therefore, in the method (2) for manufacturing a laminated structure, the surface roughness of the second substrate is preferably smaller than the surface roughness of the first substrate.
上述表面粗糙度係指與第1組合物、第2組合物或第3組合物之硬化物層接觸之區域之表面粗糙度。又，上述表面粗糙度係指依照JIS(Japanese Industrial Standards，日本工業標準) B0601：1994而測定之算術平均粗糙度Ra。The surface roughness is the surface roughness of the area in contact with the hardened layer of the first composition, the second composition or the third composition. The surface roughness is the arithmetic mean roughness Ra measured in accordance with JIS (Japanese Industrial Standards) B0601:1994.
與上述第2組合物之硬化物層接觸之基材之表面粗糙度較佳為100 nm以上，更佳為200 nm以上，且較佳為1000 nm以下，更佳為500 nm以下。The surface roughness of the substrate in contact with the cured layer of the second composition is preferably 100 nm or more, more preferably 200 nm or more, and preferably 1000 nm or less, more preferably 500 nm or less.
接觸於上述第1組合物之硬化物層之基材之表面粗糙度與接觸於上述第2組合物之硬化物層之基材之表面粗糙度的差之絕對值較佳為50 nm以上，更佳為100 nm以上，且較佳為900 nm以下，更佳為800 nm以下。The absolute value of the difference between the surface roughness of the substrate contacting the cured layer of the first composition and the surface roughness of the substrate contacting the cured layer of the second composition is preferably 50 nm or more, more preferably 100 nm or more, and preferably 900 nm or less, more preferably 800 nm or less.
於上述積層構造體之製造方法(1)中，上述第1基材較佳為陶瓷基板或矽基板，更佳為矽基板。於上述積層構造體之製造方法(1)中，上述第2基材較佳為玻璃基板。In the above-mentioned method (1) for manufacturing a multilayer structure, the above-mentioned first substrate is preferably a ceramic substrate or a silicon substrate, and more preferably a silicon substrate. In the above-mentioned method (1) for manufacturing a multilayer structure, the above-mentioned second substrate is preferably a glass substrate.
於上述積層構造體之製造方法(2)中，上述第1基材較佳為陶瓷基板或矽基板，更佳為陶瓷基板。於上述積層構造體之製造方法(2)中，上述第2基材較佳為玻璃基板。In the above-mentioned method (2) for manufacturing a multilayer structure, the above-mentioned first substrate is preferably a ceramic substrate or a silicon substrate, and more preferably a ceramic substrate. In the above-mentioned method (2) for manufacturing a multilayer structure, the above-mentioned second substrate is preferably a glass substrate.
(裝置) 於本說明書中，亦揭示用於製造上述積層構造體之裝置。上述裝置具備：載台；第1噴出部，其用於噴出上述第1組合物；第2噴出部，其用於噴出上述第2組合物；及第1光照射部，其配置於上述第1噴出部與上述第2噴出部之間。於上述第1組合物與上述第3組合物為不同之組合物之情形時，上述裝置較佳為具備用於噴出上述第3組合物之第3噴出部。(Device) This specification also discloses a device for manufacturing the above-mentioned laminated structure. The above-mentioned device comprises: a carrier; a first ejection part for ejecting the above-mentioned first composition; a second ejection part for ejecting the above-mentioned second composition; and a first light irradiation part arranged between the above-mentioned first ejection part and the above-mentioned second ejection part. When the above-mentioned first composition and the above-mentioned third composition are different compositions, the above-mentioned device preferably comprises a third ejection part for ejecting the above-mentioned third composition.
較佳為上述第1噴出部為噴墨頭，上述第2噴出部為噴墨頭。上述第3噴出部較佳為噴墨頭。上述裝置較佳為噴墨裝置。Preferably, the first ejection unit is an inkjet head, the second ejection unit is an inkjet head, the third ejection unit is an inkjet head, and the device is an inkjet device.
以下，對不具備第3噴出部之裝置進行詳細敍述，第3噴出部可設為與第1噴出部或第2噴出部同樣之構成。The following describes in detail a device that does not include a third ejection unit. The third ejection unit may have the same configuration as the first ejection unit or the second ejection unit.
上述裝置可僅具備1個用於噴出上述第1組合物之上述第1噴出部，亦可具備2個以上。上述裝置可僅具備1個用於噴出上述第2組合物之上述第2噴出部，亦可具備2個以上。於上述裝置具備複數個上述第1噴出部及上述第2噴出部之情形時，可提高積層構造體之製造效率。The device may have only one first ejection unit for ejecting the first composition, or may have two or more. The device may have only one second ejection unit for ejecting the second composition, or may have two or more. When the device has a plurality of first ejection units and second ejection units, the manufacturing efficiency of the laminated structure can be improved.
就提高積層構造體之製造效率之觀點而言，上述裝置較佳為具備第2光照射部，該第2光照射部配置於上述第1噴出部之與上述第1光照射部相反之側或上述第2噴出部之與上述第1光照射部相反之側。於此情形時，上述第2光照射部可配置於上述第1噴出部之與上述第1光照射部相反之側，亦可配置於上述第2噴出部之與上述第1光照射部相反之側，亦可配置於上述第1噴出部之與上述第1光照射部相反之側、及上述第2噴出部之與上述第1光照射部相反之側之雙方。From the viewpoint of improving the manufacturing efficiency of the laminated structure, the device is preferably provided with a second light irradiation section, and the second light irradiation section is arranged on the side of the first ejection section opposite to the first light irradiation section or on the side of the second ejection section opposite to the first light irradiation section. In this case, the second light irradiation section may be arranged on the side of the first ejection section opposite to the first light irradiation section, or on the side of the second ejection section opposite to the first light irradiation section, or on both the side of the first ejection section opposite to the first light irradiation section and the side of the second ejection section opposite to the first light irradiation section.
但，上述裝置亦可不具備上述第2光照射部。於上述裝置不具備上述第2光照射部之情形時，使用上述第1光照射部進行上述第1光硬化步驟及上述第2光硬化步驟。However, the device may not include the second light irradiation unit. When the device does not include the second light irradiation unit, the first light irradiation unit is used to perform the first light curing step and the second light curing step.
上述第1光照射部及上述第2光照射部較佳為可照射紫外線。上述第1光照射部較佳為第1紫外線照射部，上述第2光照射部較佳為第2紫外線照射部。The first light irradiation section and the second light irradiation section are preferably capable of irradiating ultraviolet rays. The first light irradiation section is preferably a first ultraviolet irradiation section, and the second light irradiation section is preferably a second ultraviolet irradiation section.
作為第1紫外線照射部及上述第2紫外線照射部，可例舉會產生紫外線之發光二極體(UV-LED)等。As the first ultraviolet irradiation unit and the second ultraviolet irradiation unit, a light emitting diode (UV-LED) that generates ultraviolet rays can be cited.
又，上述裝置可如圖11(a)所示具備貯存第1組合物之第1墨水匣16與第1循環流路部17，且可如圖11(b)所示具備貯存第2組合物之第2墨水匣18與第2循環流路部19。第1循環流路部17將第1墨水匣16與第1噴出部12連接。於第1循環流路部17之內部流通第1組合物。又，第2循環流路部19將第2墨水匣18與第2噴出部14連接。於第2循環流路部19之內部流通第2組合物。Furthermore, the above device may include a first ink cartridge 16 and a first circulation flow path portion 17 for storing the first composition as shown in FIG11(a), and may include a second ink cartridge 18 and a second circulation flow path portion 19 for storing the second composition as shown in FIG11(b). The first circulation flow path portion 17 connects the first ink cartridge 16 with the first ejection portion 12. The first composition flows inside the first circulation flow path portion 17. Furthermore, the second circulation flow path portion 19 connects the second ink cartridge 18 with the second ejection portion 14. The second composition flows inside the second circulation flow path portion 19.
第1循環流路部17於第1循環流路部17內具有緩衝槽17A與泵17B。但，如圖12(a)所示，第1循環流路部17X亦可於第1循環流路部17X內不具有緩衝槽與泵。上述第1循環流路部較佳為於上述第1循環流路部內具有上述緩衝槽，且較佳為具有上述泵。又，上述第1循環流路部於上述第1循環流路部內，除緩衝槽及泵以外亦可具有流速計、溫度計、過濾器、液面感測器等。The first circulation flow path section 17 has a buffer groove 17A and a pump 17B in the first circulation flow path section 17. However, as shown in FIG12(a), the first circulation flow path section 17X may not have a buffer groove and a pump in the first circulation flow path section 17X. The first circulation flow path section preferably has the buffer groove in the first circulation flow path section, and preferably has the pump. Furthermore, the first circulation flow path section may also have a flow meter, a thermometer, a filter, a liquid level sensor, etc. in the first circulation flow path section in addition to the buffer groove and the pump.
第2循環流路部19於第2循環流路部19內具有緩衝槽19A與泵19B。但，如圖12(b)所示，第2循環流路部19X亦可於第2循環流路部19X內不具有緩衝槽與泵。上述第2循環流路部較佳為於上述第2循環流路部內具有上述緩衝槽，且較佳為具有上述泵。又，上述第2循環流路部於上述第2循環流路部內，除緩衝槽及泵以外亦可具有流速計、溫度計、過濾器、液面感測器等。The second circulation flow path section 19 has a buffer groove 19A and a pump 19B in the second circulation flow path section 19. However, as shown in FIG12(b), the second circulation flow path section 19X may not have a buffer groove and a pump in the second circulation flow path section 19X. The second circulation flow path section preferably has the buffer groove in the second circulation flow path section, and preferably has the pump. Furthermore, the second circulation flow path section may also have a flow meter, a thermometer, a filter, a liquid level sensor, etc. in the second circulation flow path section in addition to the buffer groove and the pump.
於具備緩衝槽17A、19A或泵17B、19B之情形時，緩衝槽17A、19A及泵17B、19B較佳為分別配置於噴出部12、14與墨水匣16、18之間。緩衝槽17A、19A配置於較泵17B、19B更靠噴出部12、14側。泵17B、19B配置於較緩衝槽17A、19A更靠墨水匣16、18側。於緩衝槽17A暫時貯存上述第1組合物。於緩衝槽19A暫時貯存上述第2組合物。In the case where the buffer tank 17A, 19A or the pump 17B, 19B is provided, the buffer tank 17A, 19A and the pump 17B, 19B are preferably disposed between the ejection portion 12, 14 and the ink cartridge 16, 18, respectively. The buffer tank 17A, 19A is disposed closer to the ejection portion 12, 14 than the pump 17B, 19B. The pump 17B, 19B is disposed closer to the ink cartridge 16, 18 than the buffer tank 17A, 19A. The first composition is temporarily stored in the buffer tank 17A. The second composition is temporarily stored in the buffer tank 19A.
關於上述第1組合物及上述第2組合物之循環方法，可利用該組合物之自重或利用泵等進行加壓、減壓等而使之循環。該等亦可組合複數種而使用。作為泵，可例舉缸方式之無脈動泵、螺旋槳泵、齒輪泵及隔膜泵等。就提高循環效率，且進一步提高硬化物層之形成精度之觀點而言，上述第1、第2循環流路部較佳為於上述第1、第2循環流路部內包含移送上述第1、第2組合物之泵。Regarding the circulation method of the above-mentioned first composition and the above-mentioned second composition, the composition can be circulated by using its own weight or by using a pump or the like to pressurize or depressurize the composition. These can also be used in combination. As a pump, a non-pulsating pump of a cylinder type, a propeller pump, a gear pump, and a diaphragm pump can be used. From the perspective of improving the circulation efficiency and further improving the formation accuracy of the hardened material layer, the above-mentioned first and second circulation flow paths are preferably included in the above-mentioned first and second circulation flow paths. The pump for transferring the above-mentioned first and second compositions.
就進一步提高硬化物層之形成精度之觀點而言，上述第1、第2循環流路部較佳為於上述第1、第2循環流路部包含暫時貯存上述第1、第2組合物之緩衝槽。From the viewpoint of further improving the formation accuracy of the hardened layer, the first and second circulation flow paths preferably include buffer grooves for temporarily storing the first and second compositions.
於將上述第1、第2組合物一面加熱一面循環之情形時，可藉由在上述第1、第2墨水匣內導入加熱器，或於上述第1、第2循環流路部使用加熱器，而調節上述第1、第2組合物之溫度。When the first and second compositions are circulated while being heated, the temperature of the first and second compositions can be adjusted by introducing a heater into the first and second ink cartridges or using a heater in the first and second circulation flow paths.
上述第1循環流路部較佳為用於使上述第1組合物以30℃以上循環之循環流路部，更佳為用於使其以40℃以上循環之循環流路部，且較佳為用於使其以100℃以下循環之循環流路部，更佳為用於使其以90℃以下循環之循環流路部。於此情形時，可使第1組合物之黏度最佳，而可提高第1組合物之噴出性。The first circulation flow path is preferably a circulation flow path for circulating the first composition at 30° C. or higher, more preferably a circulation flow path for circulating the first composition at 40° C. or higher, and preferably a circulation flow path for circulating the first composition at 100° C. or lower, more preferably a circulation flow path for circulating the first composition at 90° C. or lower. In this case, the viscosity of the first composition can be optimized, and the sprayability of the first composition can be improved.
上述第2循環流路部較佳為用於使上述第2組合物以30℃以上循環之循環流路部，更佳為用於使其以40℃以上循環之循環流路部，且較佳為用於使其以100℃以下循環之循環流路部，更佳為用於使其以90℃以下循環之循環流路部。於此情形時，可使第2組合物之黏度最佳，而可提高第2組合物之噴出性。The second circulation flow path is preferably a circulation flow path for circulating the second composition at 30° C. or higher, more preferably a circulation flow path for circulating the second composition at 40° C. or higher, and preferably a circulation flow path for circulating the second composition at 100° C. or lower, more preferably a circulation flow path for circulating the second composition at 90° C. or lower. In this case, the viscosity of the second composition can be optimized, and the sprayability of the second composition can be improved.
於上述噴出部之噴出嘴，較佳為保持適當之壓力，且於該範圍內壓力變動(脈動)較少。於使用泵等之情形時，為了抑制泵之脈動，較佳為於泵與上述噴出部之間設置衰減器。作為此種衰減器，可例舉暫時貯存上述第1、第2組合物之緩衝槽、膜式之阻尼器等。It is preferred that the nozzle of the ejection part maintains an appropriate pressure, and the pressure variation (pulsation) is small within the range. When a pump is used, in order to suppress the pulsation of the pump, it is preferred to provide an attenuator between the pump and the ejection part. Examples of such an attenuator include a buffer tank temporarily storing the first and second compositions, a membrane-type damper, and the like.
於上述第1、第2塗佈步驟中，在上述裝置內使上述第1、第2組合物自第1、第2墨水匣移動至第1、第2噴出部之後，使未自第1、第2噴出部噴出之上述第1、第2組合物於第1、第2循環流路部內流動，並向第1、第2墨水匣移動。藉此，於上述第1、第2塗佈步驟中，可將上述第1、第2組合物一面循環一面塗佈。In the first and second coating steps, after the first and second compositions are moved from the first and second ink cartridges to the first and second ejection parts in the apparatus, the first and second compositions that have not been ejected from the first and second ejection parts are made to flow in the first and second circulation flow paths and move to the first and second ink cartridges. Thus, in the first and second coating steps, the first and second compositions can be coated while being circulated.
(積層構造體) 本發明之積層構造體具備第1基材、配置於上述第1基材之表面上之第1層(層X)、及配置於上述第1層之與上述第1基材側為相反側之表面上之第2層(層Y)。於本發明之積層構造體中，上述第1層與上述第2層之組合為以下之組合A或以下之組合B。組合A：上述第1層為含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第1組合物之光硬化物層或光及熱硬化物層，上述第2層為含有多官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第2組合物之光硬化物層或光及熱硬化物層。組合B：上述第1層為含有多官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第2組合物之光硬化物層或光及熱硬化物層，且上述第2層為含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第1組合物之光硬化物層或光及熱硬化物層。於本發明之積層構造體中，上述第1組合物與上述第2組合物為不同之組合物。本發明之積層構造體可滿足上述組合A，亦可滿足上述組合B。(Layered structure) The layered structure of the present invention comprises a first substrate, a first layer (layer X) disposed on the surface of the first substrate, and a second layer (layer Y) disposed on the surface of the first layer opposite to the first substrate. In the layered structure of 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 photo- and heat-curable layer of a 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 photo- and heat-curable layer of a second composition containing a polyfunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator and a thermosetting agent. Combination B: The first layer is a photocurable layer or a photo- and heat-curable layer of a second composition containing a multifunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator, and a heat curing agent, and the second layer is a photocurable layer or a photo- and heat-curable layer of a first composition containing a monofunctional (meth)acrylate compound, an epoxy compound, a photopolymerization initiator, and a heat curing agent. In the laminate structure of the present invention, the first composition and the second composition are different compositions. The laminate structure of the present invention may satisfy the above combination A or the above combination B.
藉由使上述第1組合物硬化，而形成作為第1組合物之硬化物層之第1層。藉由使上述第2組合物硬化，而形成作為第2組合物之硬化物層之第2層。更具體而言，藉由對上述第1組合物照射紫外線等光使其光硬化，而形成作為第1組合物之光硬化物層之第1層。藉由對上述第2組合物照射紫外線等光使其光硬化，而形成作為第2組合物之光硬化物層之第2層。The first layer is formed as a cured material layer of the first composition by curing the first composition. The second layer is formed as a cured material layer of the second composition by curing the second composition. More specifically, the first layer is formed as a photocurable material layer of the first composition by irradiating the first composition with light such as ultraviolet rays to cure the composition. The second layer is formed as a photocurable material layer of the second composition by irradiating the second composition with light such as ultraviolet rays to cure the composition.
於本發明之積層構造體滿足上述組合A之情形時，本發明之積層構造體較佳為進而滿足以下之構成。就更有效地發揮本發明之效果之觀點而言，上述第1層較佳為上述第1組合物之光及熱硬化物層，上述第2層較佳為上述第2組合物之光及熱硬化物層。藉由對上述第1組合物之光硬化物層(第1光硬化物層)進行加熱，而形成作為光及熱硬化物層之第1層(第1光及熱硬化物層)。藉由對上述第2組合物之光硬化物層(第2光硬化物層)進行加熱，而形成作為光及熱硬化物層之第2層(第2光及熱硬化物層)。When the laminated structure of the present invention satisfies the above-mentioned combination A, the laminated structure of the present invention preferably further satisfies the following configuration. From the viewpoint of more effectively exerting the effect of the present invention, the first layer is preferably a light and heat curable layer of the first composition, and the second layer is preferably a light and heat curable layer of the second composition. The first layer (first light and heat curable layer) as a light and heat curable layer is formed by heating the light curable layer (first light curable layer) of the first composition. The second layer (second light- and heat-curable layer) which is a light- and heat-curable layer is formed by heating the light-curable layer (second light- and heat-curable layer) of the second composition.
於本發明之積層構造體滿足上述組合B之情形時，本發明之積層構造體較佳為進而滿足以下之構成。就更有效地發揮本發明之效果之觀點而言，上述第1層較佳為上述第2組合物之光及熱硬化物層，上述第2層較佳為上述第1組合物之光及熱硬化物層。藉由對上述第2組合物之光硬化物層(第2光硬化物層)進行加熱，而形成作為光及熱硬化物層之第1層(第2光及熱硬化物層)。藉由對上述第1組合物之光硬化物層(第1光硬化物層)進行加熱，而形成作為光及熱硬化物層之第2層(第1光及熱硬化物層)。When the laminated structure of the present invention satisfies the above-mentioned combination B, the laminated structure of the present invention preferably further satisfies the following configuration. From the viewpoint of more effectively exerting the effect of the present invention, the above-mentioned first layer is preferably a light and heat curing layer of the above-mentioned second composition, and the above-mentioned second layer is preferably a light and heat curing layer of the above-mentioned first composition. The first layer (second light and heat curing layer) as a light and heat curing layer is formed by heating the light curing layer (second light curing layer) of the above-mentioned second composition. The second layer (first light- and heat-curable layer) as a light- and heat-curable layer is formed by heating the light-curable layer (first light- and heat-curable layer) of the first composition.
上述第2層較佳為具有研磨過之表面。The second layer preferably has a polished surface.
上述積層構造體亦可具備配置於上述第2層之與上述第1層側為相反側之表面上之第3層(層Z)。上述第3層為含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑之第3組合物之光硬化物層。於上述積層構造體中，上述第2組合物與上述第3組合物為不同之組合物。於本發明之積層構造體滿足上述組合A之情形時，本發明之積層構造體較佳為具備上述第3層。The laminated structure may also include a third layer (layer Z) disposed on the surface of the second layer opposite to the first layer. 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 of the present invention satisfies the combination A, the laminated structure of the present invention preferably includes the third layer.
上述積層構造體較佳為具備配置於上述第2層之與上述第1層側為相反側之表面上之第2基材。於上述積層構造體具備上述第3層之情形時，上述積層構造體較佳為具備配置於上述第3層之與上述第2層側為相反側之表面上之第2基材。The laminated structure preferably has a second substrate disposed on a surface of the second layer opposite to the first layer. When the laminated structure has a third layer, the laminated structure preferably has a second substrate disposed on a surface of the third layer opposite to the second layer.
於上述積層構造體中，較佳為與上述第1組合物之硬化物層接觸之基材之表面粗糙度小於與上述第2組合物之硬化物層接觸之基材之表面粗糙度。於上述積層構造體中，較佳為與上述第3組合物之硬化物層接觸之基材之表面粗糙度小於與上述第2組合物之硬化物層接觸之基材之表面粗糙度。因此，於上述組合A之情形時，於上述積層構造體中，較佳為上述第1基材之表面粗糙度小於上述第2基材之表面粗糙度。於上述組合B之情形時，於上述積層構造體中，較佳為上述第2基材之表面粗糙度小於上述第1基材之表面粗糙度。In the above-mentioned laminated structure, it is preferred that the surface roughness of the substrate in contact with the cured layer of the first composition is smaller than the surface roughness of the substrate in contact with the cured layer of the second composition. In the above-mentioned laminated structure, it is preferred that the surface roughness of the substrate in contact with the cured layer of the third composition is smaller than the surface roughness of the substrate in contact with the cured layer of the second composition. Therefore, in the case of the above-mentioned combination A, in the above-mentioned laminated structure, it is preferred that the surface roughness of the first substrate is smaller than the surface roughness of the second substrate. In the case of the above-mentioned combination B, in the above-mentioned laminated structure, it is preferred that the surface roughness of the second substrate is smaller than the surface roughness of the first substrate.
上述表面粗糙度係指與第1組合物、第2組合物或第3組合物之硬化物層接觸之區域之表面粗糙度。又，上述表面粗糙度係依照JIS B0601：1994而測定之算術平均粗糙度Ra。The surface roughness is the surface roughness of the area in contact with the hardened layer of the first composition, the second composition or the third composition. The surface roughness is the arithmetic mean roughness Ra measured in accordance with JIS B0601:1994.
於上述積層構造體中，與上述第2組合物之硬化物層接觸之基材之表面粗糙度較佳為100 nm以上，更佳為200 nm以上，且較佳為1000 nm以下，更佳為500 nm以下。In the above-mentioned laminated structure, the surface roughness of the substrate in contact with the cured layer of the second composition is preferably 100 nm or more, more preferably 200 nm or more, and preferably 1000 nm or less, more preferably 500 nm or less.
於上述積層構造體中，接觸於上述第1組合物之硬化物層之基材之表面粗糙度與接觸於上述第2組合物之硬化物層之基材之表面粗糙度的差之絕對值較佳為50 nm以上，更佳為100 nm以上，且較佳為900 nm以下，更佳為800 nm以下。In the above-mentioned laminated structure, the absolute value of the difference between the surface roughness of the substrate in contact with the cured layer of the first composition and the surface roughness of the substrate in contact with the cured layer of the second composition is preferably 50 nm or more, more preferably 100 nm or more, and preferably 900 nm or less, more preferably 800 nm or less.
就更有效地發揮本發明之效果之觀點而言，上述第2層之厚度較佳為厚於上述第1層之厚度，更佳為較上述第1層之厚度厚40 μm以上，進而較佳為較上述第1層之厚度厚50 μm以上。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, more preferably 40 μm or more thicker than the thickness of the first layer, and further preferably 50 μm or more thicker than the thickness of the first layer.
就更有效地發揮本發明之效果之觀點而言，上述第2層之厚度較佳為厚於上述第3層之厚度，更佳為較上述第3層之厚度厚40 μm以上，進而較佳為較上述第3層之厚度厚50 μm以上。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, more preferably 40 μm or more thicker than the thickness of the third layer, and further preferably 50 μm or more thicker than the thickness of the third layer.
就更有效地發揮本發明之效果之觀點而言，上述第1層之厚度較佳為0.1 μm以上，更佳為0.3 μm以上，且較佳為10 μm以下，更佳為5 m以下。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, and is preferably 10 μm or less, more preferably 5 μm or less.
就更有效地發揮本發明之效果之觀點而言，上述第2層之厚度較佳為40 μm以上，更佳為50 μm以上，且較佳為1000 μm以下，更佳為800 m以下。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, and is preferably 1000 μm or less, more preferably 800 μm or less.
就更有效地發揮本發明之效果之觀點而言，上述第3層之厚度較佳為0.1 μm以上，更佳為0.3 μm以上，且較佳為10 μm以下，更佳為5 m以下。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, and is preferably 10 μm or less, more preferably 5 μm or less.
於上述第1層與上述第2層之積層物中，厚度相對於寬度之比(厚度/寬度)較佳為0.01以上，更佳為0.1以上，且較佳為200以下，更佳為150以下。若上述比(厚度/寬度)為上述下限以上及上述上限以下，則可更有效地發揮本發明之效果。In the laminate of the first layer and the second layer, the ratio of thickness to width (thickness/width) is preferably 0.01 or more, more preferably 0.1 or more, and preferably 200 or less, more preferably 150 or less. If the ratio (thickness/width) is above the lower limit and below the upper limit, the effect of the present invention can be more effectively exerted.
於上述第1層、上述第2層及上述第3層之積層物中，厚度相對於寬度之比(厚度/寬度)較佳為0.01以上，更佳為0.1以上，且較佳為200以下，更佳為150以下。若上述比(厚度/寬度)為上述下限以上及上述上限以下，則可更有效地發揮本發明之效果。In the laminate of the first layer, the second layer, and the third layer, the ratio of thickness to width (thickness/width) is preferably 0.01 or more, more preferably 0.1 or more, and preferably 200 or less, more preferably 150 or less. If the ratio (thickness/width) is above the lower limit and below the upper limit, the effect of the present invention can be more effectively exerted.
於上述第2層中，厚度相對於寬度之比(厚度/寬度)較佳為0.01以上，更佳為0.1以上，且較佳為200以下，更佳為150以下。若上述比(厚度/寬度)為上述下限以上及上述上限以下，則可更有效地發揮本發明之效果。In the second layer, the ratio of thickness to width (thickness/width) is preferably 0.01 or more, more preferably 0.1 or more, and preferably 200 or less, more preferably 150 or less. If the ratio (thickness/width) is above the lower limit and below the upper limit, the effect of the present invention can be more effectively exerted.
(噴墨用組合物套組) 上述噴墨用組合物套組具有上述第1組合物與上述第2組合物。於上述噴墨用組合物套組中，上述第1組合物與上述第2組合物並未混合。上述第1組合物較佳為收容於第1容器，上述第2組合物較佳為收容於第2容器。上述噴墨用組合物套組為上述第1組合物與上述第2組合物之套組品。於上述噴墨用組合物套組中，較佳為於塗佈上述第1組合物之後塗佈上述第2組合物而使用。於上述噴墨用組合物套組中，較佳為於塗佈上述第1組合物及使其光硬化之後塗佈上述第2組合物及使其光硬化而使用。上述噴墨用組合物套組較佳為用於製造上述積層構造體。(Inkjet composition kit) The inkjet composition kit comprises the first composition and the second composition. In the inkjet composition kit, 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 kit is a set of the first composition and the second composition. In the inkjet composition kit, it is preferably used after applying the first composition. In the inkjet composition kit, it is preferably used after applying the first composition and photocuring it, and then applying and photocuring it. The inkjet composition kit is preferably used to manufacture the above-mentioned laminated structure.
上述噴墨用組合物套組亦可具有第3組合物。於此情形時，上述第1組合物、上述第2組合物及上述第3組合物並未混合。上述第3組合物較佳為收容於第3容器。具有上述第3組合物之上述噴墨用組合物套組為上述第1組合物、上述第2組合物及上述第3組合物之套組品。又，於由相同之組合物形成第1光硬化物層(或第1光及熱硬化物層)與第3光硬化物層(或第3光及熱硬化物層)之情形時，可將上述第1組合物與上述第2組合物之套組品中之上述第1組合物用於形成上述第3光硬化物層(或第3光及熱硬化物層)。The inkjet composition kit may also 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 kit having the third composition is a set of the first composition, the second composition and the third composition. Furthermore, in the case where the first light-curable layer (or the first light- and heat-curable layer) and the third light-curable layer (or the third light- and heat-curable layer) are formed from the same composition, the first composition in the set of the first composition and the second composition may be used to form the third light-curable layer (or the third light- and heat-curable layer).
圖13係模式性表示本發明之第1實施方式之噴墨用組合物套組之剖視圖。FIG. 13 is a cross-sectional view schematically showing an inkjet composition kit according to the first embodiment of the present invention.
噴墨用組合物套組5具有第1容器101、第1組合物1、第2容器102及第2組合物2。於第1容器101中收容有第1組合物1。於第2容器102中收容有第2組合物2。The inkjet composition set 5 includes a first container 101, a first composition 1, a second container 102, and a second composition 2. The first container 101 contains the first composition 1. The second container 102 contains the second composition 2.
於上述積層構造體之製造方法中，第2組合物較第1組合物消耗更多。因此，於上述噴墨用組合物套組中，較佳為收容於第1容器之第1組合物之量(體積)多於收容於第2容器之第2組合物之第1組合物之量(體積)。In the above-mentioned method for manufacturing the laminated structure, the second composition is consumed more than the first composition. Therefore, in the above-mentioned inkjet composition kit, it is preferred that the amount (volume) of the first composition contained in the first container is greater than the amount (volume) of the first composition contained in the second container.
(第1組合物、第2組合物及第3組合物) 以下，對上述第1組合物、上述第2組合物及第3組合物中所含有之各成分之詳情進行說明。再者，於本說明書中，「(甲基)丙烯酸酯」係指「丙烯酸酯」與「甲基丙烯酸酯」之一者或兩者。(First Composition, Second Composition, and Third Composition) The following describes the details of each component contained in the first composition, the second composition, and the third composition. In this specification, "(meth)acrylate" refers to one or both of "acrylate" and "methacrylate".
上述第1組合物與上述第2組合物為不同之組合物，上述第3組合物與上述第2組合物為不同之組合物。即，上述第1組合物與上述第2組合物之組成不同，上述第3組合物與上述第2組合物之組成不同。上述第1組合物與上述第3組合物可為不同之組合物，亦可為相同之組合物。就提高積層構造體之製造效率之觀點而言，上述第1組合物與上述第3組合物較佳為相同之組合物。即，上述第1組合物與上述第3組合物較佳為組成相同。The first composition and the second composition are different compositions, and the third composition and the second composition are different compositions. That is, the first composition and the second composition have different compositions, and the third composition and the second composition have different compositions. The first composition and the third composition may be different compositions or the same composition. From the viewpoint of improving the manufacturing efficiency of the layered structure, the first composition and the third composition are preferably the same composition. That is, the first composition and the third composition are preferably the same composition.
上述第1組合物及第3組合物含有單官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑。上述第2組合物含有多官能之(甲基)丙烯酸酯化合物、環氧化合物、光聚合起始劑及熱硬化劑。The first composition and the third composition contain 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.
再者，上述第1組合物及第3組合物分別可含有亦可不含有多官能之(甲基)丙烯酸酯化合物。又，上述第2組合物可含有亦可不含有單官能之(甲基)丙烯酸酯化合物。於上述第1組合物與上述第2組合物均含有多官能之(甲基)丙烯酸酯化合物之情形時，上述第1組合物中所含有之多官能之(甲基)丙烯酸酯化合物與上述第2組合物中所含有之多官能之(甲基)丙烯酸酯化合物可相同亦可不同。於上述第3組合物與上述第2組合物均含有多官能之(甲基)丙烯酸酯化合物之情形時，上述第3組合物中所含有之多官能之(甲基)丙烯酸酯化合物與上述第2組合物中所含有之多官能之(甲基)丙烯酸酯化合物可相同亦可不同。於上述第1組合物與上述第2組合物均含有單官能之(甲基)丙烯酸酯化合物之情形時，上述第1組合物中所含有之單官能之(甲基)丙烯酸酯化合物與上述第2組合物中所含有之單官能之(甲基)丙烯酸酯化合物可相同亦可不同。於上述第3組合物與上述第2組合物均含有單官能之(甲基)丙烯酸酯化合物之情形時，上述第3組合物中所含有之單官能之(甲基)丙烯酸酯化合物與上述第2組合物中所含有之單官能之(甲基)丙烯酸酯化合物可相同亦可不同。Furthermore, the first composition and the third composition may or may not contain a polyfunctional (meth)acrylate compound, respectively. Moreover, the second composition may or may not contain a monofunctional (meth)acrylate compound. In the case where both the first composition and the second composition contain a polyfunctional (meth)acrylate compound, the polyfunctional (meth)acrylate compound contained in the first composition may be the same as or different from the polyfunctional (meth)acrylate compound contained in the second composition. In the case where both the third composition and the second composition contain a polyfunctional (meth)acrylate compound, the polyfunctional (meth)acrylate compound contained in the third composition 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 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 may be the same as or different from the monofunctional (meth)acrylate compound contained in the second composition.
＜(甲基)丙烯酸酯化合物＞ 上述第1組合物含有單官能之(甲基)丙烯酸酯化合物。上述第2組合物含有多官能之(甲基)丙烯酸酯化合物。上述第3組合物含有單官能之(甲基)丙烯酸酯化合物。再者，於本說明書中，具有環氧基之(甲基)丙烯酸酯化合物並非環氧化合物，而視為(甲基)丙烯酸酯化合物。上述單官能之(甲基)丙烯酸酯化合物及上述多官能之(甲基)丙烯酸酯化合物分別可僅使用1種，亦可併用2種以上。<(Meth)acrylate compound> The first composition contains a monofunctional (meth)acrylate compound. The second composition contains a polyfunctional (meth)acrylate compound. The third composition contains a monofunctional (meth)acrylate compound. In this specification, a (meth)acrylate compound having an epoxy group is not an epoxy compound but is regarded as a (meth)acrylate compound. The monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound may be used alone or in combination of two or more.
作為上述單官能之(甲基)丙烯酸酯化合物，可例舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸3-羥丁酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-苯氧基乙酯、甲氧基二乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、甲氧基丙二醇(甲基)丙烯酸酯、甲氧基二丙二醇(甲基)丙烯酸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異𦯉酯、(甲基)丙烯酸二環戊二烯酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、單(甲基)丙烯酸甘油酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸二羥基環戊二烯酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十二烷基酯、及(甲基)丙烯酸硬脂酯等。Examples of the monofunctional (meth)acrylate compound include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-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, and 2-phenoxyethyl (meth)acrylate. , methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, isodecyl (meth)acrylate, isononyl (meth)acrylate, isothiocyanate (meth)acrylate, dicyclopentadienyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glyceryl mono(meth)acrylate, 2-ethylhexyl (meth)acrylate, dihydroxycyclopentadienyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, naphthyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate, etc.
上述多官能之(甲基)丙烯酸酯化合物可為二官能之(甲基)丙烯酸酯化合物，亦可為三官能之(甲基)丙烯酸酯化合物，亦可為四官能以上之(甲基)丙烯酸酯化合物。The multifunctional (meth)acrylate compound may be a difunctional (meth)acrylate compound, a trifunctional (meth)acrylate compound, or a tetrafunctional or higher functional (meth)acrylate compound.
作為上述二官能之(甲基)丙烯酸酯化合物，例如可例舉：1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬烷二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、2,4-二甲基-1,5-戊二醇二(甲基)丙烯酸酯、丁基乙基丙二醇(甲基)丙烯酸酯、乙氧化環己烷甲醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、低聚乙二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、2-乙基-2-丁基丁二醇二(甲基)丙烯酸酯、2-乙基-2-丁基丙二醇二(甲基)丙烯酸酯、三環癸烷二(甲基)丙烯酸酯、及二丙二醇二(甲基)丙烯酸酯等。Examples of the bifunctional (meth)acrylate compound include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonane di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2,4-dimethyl-1,5-pentanediol di(meth)acrylate, butylethylpropylene glycol (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-2-butylpropylene glycol di(meth)acrylate, tricyclodecane di(meth)acrylate, and dipropylene glycol di(meth)acrylate.
作為上述三官能之(甲基)丙烯酸酯化合物，例如可例舉：三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、三羥甲基丙烷之環氧烷改性三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷三((甲基)丙烯醯氧基丙基)醚、異三聚氰酸環氧烷改性三(甲基)丙烯酸酯、丙酸二季戊四醇三(甲基)丙烯酸酯、異氰尿酸三((甲基)丙烯醯氧基乙基)酯、及山梨糖醇三(甲基)丙烯酸酯等。Examples of the trifunctional (meth)acrylate compound include trihydroxymethylpropane tri(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, epoxide-modified tri(meth)acrylate of trihydroxymethylpropane, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trihydroxymethylpropane tri((meth)acryloxypropyl) ether, isocyanuric acid epoxide-modified tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, isocyanuric acid tri((meth)acryloxyethyl) ester, and sorbitol tri(meth)acrylate.
作為上述四官能之(甲基)丙烯酸酯化合物，例如可例舉：季戊四醇四(甲基)丙烯酸酯、山梨糖醇四(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、及丙酸二季戊四醇四(甲基)丙烯酸酯等。Examples of the tetrafunctional (meth)acrylate compound include pentaerythritol tetra(meth)acrylate, sorbitol tetra(meth)acrylate, di-trihydroxymethylpropane tetra(meth)acrylate, and dipentaerythritol propionate tetra(meth)acrylate.
作為上述五官能之(甲基)丙烯酸酯化合物，例如可例舉：山梨糖醇五(甲基)丙烯酸酯及二季戊四醇五(甲基)丙烯酸酯。Examples of the pentafunctional (meth)acrylate compound include sorbitol penta(meth)acrylate and dipentaerythritol penta(meth)acrylate.
作為上述六官能之(甲基)丙烯酸酯化合物，例如可例舉：二季戊四醇六(甲基)丙烯酸酯、山梨糖醇六(甲基)丙烯酸酯、及膦腈之環氧烷改性六(甲基)丙烯酸酯等。Examples of the hexafunctional (meth)acrylate compound include dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, and phosphazene epoxide-modified hexa(meth)acrylate.
又，作為上述具有環氧基之(甲基)丙烯酸酯化合物，可例舉：(甲基)丙烯酸縮水甘油酯及(甲基)丙烯酸4-羥丁酯縮水甘油醚等。Examples of the (meth)acrylate compound having an epoxy group include glycidyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether.
就更有效地發揮本發明之效果之觀點而言，上述第1組合物及第3組合物中所含有之上述單官能之(甲基)丙烯酸酯化合物之均聚物的玻璃轉移溫度分別較佳為-100℃以上，更佳為-90℃以上，且較佳為未達0℃，更佳為-10℃以下。From the viewpoint of more effectively exerting the effects of the present invention, the glass transition temperature of the homopolymer of the monofunctional (meth)acrylate compound contained in the first composition and the third composition is preferably above -100°C, more preferably above -90°C, and preferably below 0°C, more preferably below -10°C.
就更有效地發揮本發明之效果之觀點而言，上述第2組合物中所含有之上述多官能之(甲基)丙烯酸酯化合物之均聚物的玻璃轉移溫度較佳為50℃以上，更佳為80℃以上，且較佳為200℃以下，更佳為180℃以下。From the viewpoint of more effectively exerting the effects of the present invention, the glass transition temperature of the homopolymer of the above-mentioned multifunctional (meth)acrylate compound contained in the above-mentioned second composition is preferably 50°C or more, more preferably 80°C or more, and preferably 200°C or less, more preferably 180°C or less.
於獲得上述均聚物之聚合時，聚合方法並無特別限定。可藉由利用公知之方法使上述單官能之(甲基)丙烯酸酯化合物或上述多官能之(甲基)丙烯酸酯化合物均聚，而獲得上述均聚物。於上述聚合方法中，可使所有上述單官能之(甲基)丙烯酸酯化合物或所有上述多官能之(甲基)丙烯酸酯化合物一次性聚合，亦可逐次添加上述單官能之(甲基)丙烯酸酯化合物或上述多官能之(甲基)丙烯酸酯化合物而進行聚合。When the polymerization is performed to obtain the 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 using a known method. In the polymerization method, all the monofunctional (meth)acrylate compounds or all the polyfunctional (meth)acrylate compounds can be polymerized at once, or the monofunctional (meth)acrylate compounds or the polyfunctional (meth)acrylate compounds can be added one by one to perform the polymerization.
上述玻璃轉移溫度可依照JIS-K7121，使用示差掃描熱量計於升溫速度10℃/分鐘之條件下進行測定。作為上述示差掃描熱量計，可例舉Hitachi High-Tech Science公司製造之「DSC7020」等。The glass transition temperature can be measured using a differential scanning calorimeter at a temperature increase rate of 10°C/min in accordance with JIS-K7121. Examples of the differential scanning calorimeter include "DSC7020" manufactured by Hitachi High-Tech Science Co., Ltd.
就更有效地發揮本發明之效果之觀點而言，上述第1組合物及第3組合物中所含有之上述單官能之(甲基)丙烯酸酯化合物分別較佳為於丙烯酸結構部分之構成酯結構之氧原子上鍵結有碳數4以上之基的化合物。上述碳數4以上之基可為具有支鏈結構之基，亦可為不具有支鏈結構之基(具有直鏈結構之基)。上述第1組合物及第3組合物中所含有之上述單官能之(甲基)丙烯酸酯化合物分別較佳為丙烯酸異癸酯、丙烯酸異壬酯、丙烯酸2-乙基己酯、丙烯酸月桂酯、或丙烯酸十二烷基酯。該等單官能之(甲基)丙烯酸酯化合物係於丙烯酸結構部分之構成酯結構之氧原子上鍵結有碳數4以上之基的化合物。From the viewpoint of more effectively exerting the effect of the present invention, the monofunctional (meth)acrylate compounds contained in the first composition and the third composition are preferably compounds in which a group having 4 or more carbon atoms is bonded to an oxygen atom constituting an ester structure of an acrylic acid structure portion. 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 straight chain structure). The monofunctional (meth)acrylate compounds contained in the first composition and the third composition are preferably isodecyl acrylate, isononyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, or dodecyl acrylate. The monofunctional (meth)acrylate compounds are compounds in which a group having 4 or more carbon atoms is bonded to an oxygen atom constituting an ester structure of an acrylic acid structure portion.
就更有效地發揮本發明之效果之觀點而言，上述第2組合物中所含有之上述多官能之(甲基)丙烯酸酯化合物較佳為2官能或3官能之(甲基)丙烯酸酯化合物。From the viewpoint of more effectively exerting the effects of the present invention, the polyfunctional (meth)acrylate compound contained in the second composition is preferably a bifunctional or trifunctional (meth)acrylate compound.
就更有效地發揮本發明之效果之觀點而言，上述第2組合物中所含有之上述多官能之(甲基)丙烯酸酯化合物較佳為三羥甲基丙烷三丙烯酸酯、1,6-己二醇二丙烯酸酯、或二環戊烯基二甲醇二丙烯酸酯。From the viewpoint of more effectively exerting the effect of the present invention, the polyfunctional (meth)acrylate compound contained in the second composition is preferably trihydroxymethylpropane triacrylate, 1,6-hexanediol diacrylate, or dicyclopentenyl dimethanol diacrylate.
於上述第1組合物100重量%中或上述第3組合物100重量%中，上述單官能之(甲基)丙烯酸酯化合物之含量較佳為5重量%以上，更佳為10重量%以上，且較佳為95重量%以下，更佳為90重量%以下。若上述單官能之(甲基)丙烯酸酯化合物之含量為上述下限以上及上述上限以下，則可更有效地發揮本發明之效果。In 100 wt % of the first composition or 100 wt % of the third composition, the content of the monofunctional (meth)acrylate compound is preferably 5 wt % or more, more preferably 10 wt % or more, and preferably 95 wt % or less, more preferably 90 wt % or less. If the content of the monofunctional (meth)acrylate compound is above the lower limit and below the upper limit, the effect of the present invention can be more effectively exerted.
於上述第1組合物含有上述多官能之(甲基)丙烯酸酯化合物之情形時，於上述第1組合物100重量%中，上述多官能之(甲基)丙烯酸酯化合物之含量較佳為0.1重量%以上，更佳為0.5重量%以上，且較佳為50重量%以下，更佳為30重量%以下。於上述第3組合物含有上述多官能之(甲基)丙烯酸酯化合物之情形時，於上述第3組合物100重量%中，上述多官能之(甲基)丙烯酸酯化合物之含量較佳為0.1重量%以上，更佳為0.5重量%以上，且較佳為50重量%以下，更佳為30重量%以下。若上述多官能之(甲基)丙烯酸酯化合物之含量為上述下限以上及上述上限以下，則可更有效地發揮本發明之效果。When the first composition contains the multifunctional (meth)acrylate compound, the content of the multifunctional (meth)acrylate compound in 100% by weight of the first composition is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and preferably 50% by weight or less, and more preferably 30% by weight or less. When the third composition contains the multifunctional (meth)acrylate compound, the content of the multifunctional (meth)acrylate compound in 100% by weight of the third composition is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and preferably 50% by weight or less, and more preferably 30% by weight or less. If the content of the multifunctional (meth)acrylate compound is above the lower limit and below the upper limit, the effect of the present invention can be more effectively exerted.
於上述第2組合物100重量%中，上述多官能之(甲基)丙烯酸酯化合物之含量較佳為10重量%以上，更佳為20重量%以上，且較佳為99重量%以下，更佳為90重量%以下。若上述多官能之(甲基)丙烯酸酯化合物之含量為上述下限以上及上述上限以下，則可更有效地發揮本發明之效果。In 100 wt % of the second composition, the content of the multifunctional (meth)acrylate compound is preferably 10 wt % or more, more preferably 20 wt % or more, and preferably 99 wt % or less, more preferably 90 wt % or less. If the content of the multifunctional (meth)acrylate compound is above the lower limit and below the upper limit, the effect of the present invention can be more effectively exerted.
於上述第2組合物含有上述單官能之(甲基)丙烯酸酯化合物之情形時，於上述第2組合物100重量%中，上述單官能之(甲基)丙烯酸酯化合物之含量較佳為0.1重量%以上，更佳為0.5重量%以上，且較佳為50重量%以下，更佳為30重量%以下。若上述單官能之(甲基)丙烯酸酯化合物之含量為上述下限以上及上述上限以下，則可更有效地發揮本發明之效果。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 0.1% by weight or more, more preferably 0.5% by weight or more, and preferably 50% by weight or less, more preferably 30% by weight or less. If the content of the monofunctional (meth)acrylate compound is above the lower limit and below the upper limit, the effect of the present invention can be more effectively exerted.
於上述第1組合物含有上述多官能之(甲基)丙烯酸酯化合物之情形時，上述第1組合物100重量%中之上述多官能之(甲基)丙烯酸酯化合物之含量較佳為少於上述第2組合物100重量%中之上述多官能之(甲基)丙烯酸酯化合物之含量。於上述第3組合物含有上述多官能之(甲基)丙烯酸酯化合物之情形時，上述第3組合物100重量%中之上述多官能之(甲基)丙烯酸酯化合物之含量較佳為少於上述第2組合物100重量%中之上述多官能之(甲基)丙烯酸酯化合物之含量。於此情形時，可更有效地發揮本發明之效果。When the first composition contains the multifunctional (meth)acrylate compound, the content of the multifunctional (meth)acrylate compound in 100% by weight of the first composition is preferably less than the content of the multifunctional (meth)acrylate compound in 100% by weight of the second composition. When the third composition contains the multifunctional (meth)acrylate compound, the content of the multifunctional (meth)acrylate compound in 100% by weight of the third composition is preferably less than the content of the multifunctional (meth)acrylate compound in 100% by weight of the second composition. In this case, the effect of the present invention can be more effectively exerted.
於上述第2組合物含有上述單官能之(甲基)丙烯酸酯化合物之情形時，上述第2組合物100重量%中之上述單官能之(甲基)丙烯酸酯化合物之含量較佳為少於上述第1組合物100重量%中之上述單官能之(甲基)丙烯酸酯化合物之含量。於上述第2組合物含有上述單官能之(甲基)丙烯酸酯化合物之情形時，上述第2組合物100重量%中之上述單官能之(甲基)丙烯酸酯化合物之含量較佳為少於上述第3組合物100重量%中之上述單官能之(甲基)丙烯酸酯化合物之含量。於此情形時，可更有效地發揮本發明之效果。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 less than the content of the monofunctional (meth)acrylate compound in 100% by weight of the first 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 preferably less than the content of the monofunctional (meth)acrylate compound in 100% by weight of the third composition. In this case, the effect of the present invention can be more effectively exerted.
＜環氧化合物＞ 上述第1組合物含有環氧化合物。上述第2組合物含有環氧化合物。上述第3組合物含有環氧化合物。上述第1組合物中所含有之環氧化合物、上述第2組合物中所含有之環氧化合物及上述第3組合物中所含有之環氧化合物分別可相同，亦可不同。上述環氧化合物分別可僅使用1種，亦可併用2種以上。<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. The epoxy compounds may be used alone or in combination of two or more.
作為上述環氧化合物，可例舉：雙酚A型環氧化合物、雙酚F型環氧化合物、雙酚S型環氧化合物、酚系酚醛清漆型環氧化合物、聯苯型環氧化合物、聯苯酚醛清漆型環氧化合物、聯苯酚型環氧化合物、萘型環氧化合物、茀型環氧化合物、苯酚芳烷基型環氧化合物、萘酚芳烷基型環氧化合物、二環戊二烯型環氧化合物、蒽型環氧化合物、具有金剛烷骨架之環氧化合物、具有三環癸烷骨架之環氧化合物、伸萘基醚型環氧化合物、及骨架具有三𠯤核之環氧化合物等。Examples of the epoxy compound include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolac type epoxy compounds, biphenyl type epoxy compounds, biphenyl novolac type epoxy compounds, biphenol type epoxy compounds, naphthalene type epoxy compounds, fluorene type epoxy compounds, phenol aralkyl type epoxy compounds, naphthol aralkyl type epoxy compounds, dicyclopentadiene type epoxy compounds, anthracene type epoxy compounds, epoxy compounds having an adamantane skeleton, epoxy compounds having a tricyclodecane skeleton, naphthyl ether type epoxy compounds, and epoxy compounds having a trioxane nucleus as the skeleton.
就更有效地發揮本發明之效果之觀點而言，上述第1組合物及第3組合物中所含有之上述環氧化合物分別較佳為雙酚A型環氧化合物或二環戊二烯型環氧化合物。From the viewpoint of more effectively exerting the effects of the present invention, the epoxy compound contained in the first composition and the third composition is preferably a bisphenol A type epoxy compound or a dicyclopentadiene type epoxy compound.
就更有效地發揮本發明之效果之觀點而言，上述第2組合物中所含有之上述環氧化合物較佳為雙酚A型環氧化合物或二環戊二烯型環氧化合物。From the viewpoint of more effectively exerting the effects of the present invention, the epoxy compound contained in the second composition is preferably a bisphenol A type epoxy compound or a dicyclopentadiene type epoxy compound.
於上述第1組合物100重量%中或上述第3組合物100重量%中，上述環氧化合物之含量較佳為0.1重量%以上，更佳為1重量%以上，且較佳為90重量%以下，更佳為70重量%以下。若上述環氧化合物之含量為上述下限以上及上述上限以下，則可更有效地發揮本發明之效果。In 100 wt % of the first composition or 100 wt % of the third composition, the content of the epoxy compound is preferably 0.1 wt % or more, more preferably 1 wt % or more, and preferably 90 wt % or less, more preferably 70 wt % or less. If the content of the epoxy compound is above the lower limit and below the upper limit, the effect of the present invention can be more effectively exerted.
於上述第2組合物100重量%中，上述環氧化合物之含量較佳為0.1重量%以上，更佳為1重量%以上，且較佳為90重量%以下，更佳為70重量%以下。若上述環氧化合物之含量為上述下限以上及上述上限以下，則可更有效地發揮本發明之效果。In 100 wt % of the second composition, the content of the epoxy compound is preferably 0.1 wt % or more, more preferably 1 wt % or more, and preferably 90 wt % or less, more preferably 70 wt % or less. If the content of the epoxy compound is above the lower limit and below the upper limit, the effect of the present invention can be more effectively exerted.
＜光聚合起始劑＞ 上述第1組合物含有光聚合起始劑。上述第2組合物含有光聚合起始劑。上述第3組合物含有光聚合起始劑。上述第1組合物中所含有之光聚合起始劑、上述第2組合物中所含有之光聚合起始劑及上述第3組合物中所含有之光聚合起始劑分別可相同，亦可不同。上述光聚合起始劑可僅使用1種，亦可併用2種以上。<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 may be the same or different. Only one type of the photopolymerization initiator may be used, or two or more types may be used in combination.
作為上述光聚合起始劑，可例舉光自由基聚合起始劑及光陽離子聚合起始劑等。上述光聚合起始劑較佳為光自由基聚合起始劑。上述光聚合起始劑可僅使用1種，亦可併用2種以上。Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more.
上述光自由基聚合起始劑係用於藉由照射光而產生自由基，使自由基聚合反應開始之化合物。作為上述光自由基聚合起始劑，可例舉：安息香、安息香甲醚、安息香乙醚、安息香異丙醚等安息香化合物；2-羥基-2-甲基-1-苯基丙烷-1-酮等苯烷酮化合物；苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、1,1-二氯苯乙酮等苯乙酮化合物；2-甲基-1-[4-(甲硫基)苯基]-2-𠰌啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-𠰌啉基苯基)丁烷-1-酮、2-苄基-2-二甲基胺基-1-(4-𠰌啉基苯基)丁酮-1、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-𠰌啉基)苯基]-1-丁酮、N,N-二甲基胺基苯乙酮等胺基苯乙酮化合物；2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌等蒽醌化合物；2,4-二甲基9-氧硫𠮿、2,4-二乙基9-氧硫𠮿、2-氯9-氧硫𠮿、2,4-二異丙基9-氧硫𠮿等9-氧硫𠮿化合物；苯乙酮二甲基縮酮、苄基二甲基縮酮等縮酮化合物；2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦等醯基氧化膦化合物；1,2-辛二酮、1-[4-(苯硫基)-2-(鄰苯甲醯基肟)]、乙酮、1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-1-(鄰乙醯基肟)等肟酯化合物；雙(環戊二烯基)二苯基鈦、雙(環戊二烯基)二氯化鈦、雙(環戊二烯基)雙(2,3,4,5,6-五氟苯基)鈦、雙(環戊二烯基)雙(2,6-二氟-3-(吡咯-1-基)苯基)鈦等二茂鈦化合物等。上述光自由基聚合起始劑可僅使用1種，亦可併用2種以上。The above-mentioned photoradical polymerization initiator is a compound used to generate free radicals by irradiating light to start a free radical polymerization reaction. Examples of the above-mentioned photoradical polymerization initiator include: benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; phenanone compounds such as 2-hydroxy-2-methyl-1-phenylpropane-1-one; acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-oxo-1-ol-1-one, 2-benzyl-1-one, and 1-[4-(methylthio)phenyl]-2-oxo-1-ol-1-one. aminoacetophenone compounds such as 2-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(4-(2-dimethylamino-2-dimethylamino-1-(4-((4-dimethylamino-2-dimethylamino-1-(4 ...(4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-((4-(( , 2,4-diethyl 9-oxysulfide , 2-chloro-9-oxysulfuron 、2,4-Diisopropyl 9-oxysulfide 9-Oxysulfuron compounds; acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketal compounds; 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzyl) phenylphosphine oxide and other acyl phosphine oxide compounds; 1,2-octanedione, 1-[4-(phenylthio)-2-(o-benzoyloxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylphenyl)- Oxime ester compounds such as bis(cyclopentadienyl)diphenyltitanium, bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl)titanium, and bis(cyclopentadienyl)bis(2,6-difluoro-3-(pyrrol-1-yl)phenyl)titanium. The above-mentioned photoradical polymerization initiator may be used alone or in combination of two or more.
亦可與上述光自由基聚合起始劑一起使用光聚合起始助劑。作為該光聚合起始助劑，可例舉：N,N-二甲基胺基苯甲酸乙酯、N,N-二甲基胺基苯甲酸異戊酯、4-二甲基胺基苯甲酸戊酯、三乙基胺及三乙醇胺等。亦可使用該等以外之光聚合起始助劑。上述光聚合起始助劑可僅使用1種，亦可併用2種以上。A photopolymerization initiator aid may be used together with the above-mentioned photo-free radical polymerization initiator. Examples of the photopolymerization initiator aid include ethyl N,N-dimethylaminobenzoate, isopentyl N,N-dimethylaminobenzoate, pentyl 4-dimethylaminobenzoate, triethylamine, and triethanolamine. Photopolymerization initiators other than these may also be used. The above-mentioned photopolymerization initiators may be used alone or in combination of two or more.
又，亦可將於可見光區域具有吸收之CGI-784等(Ciba Specialty Chemicals公司製造)之二茂鈦化合物等用於促進光反應。Furthermore, a titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals) that absorbs in the visible light region may be used to promote the photoreaction.
作為上述光陽離子聚合起始劑，可例舉：鋶鹽、錪鹽、茂金屬化合物及安息香甲苯磺酸酯等。上述光陽離子聚合起始劑可僅使用1種，亦可併用2種以上。Examples of the photocatalytic polymerization initiator include cobalt salts, iodonium salts, metallocene compounds, and benzoin toluenesulfonate. The photocatalytic polymerization initiator may be used alone or in combination of two or more.
於上述第1組合物100重量%中，上述光聚合起始劑之含量較佳為0.1重量%以上，更佳為0.5重量%以上，且較佳為30重量%以下，更佳為20重量%以下。In 100 wt % of the first composition, the content of the photopolymerization initiator is preferably 0.1 wt % or more, more preferably 0.5 wt % or more, and is preferably 30 wt % or less, more preferably 20 wt % or less.
於上述第2組合物100重量%中，上述光聚合起始劑之含量較佳為0.1重量%以上，更佳為0.5重量%以上，且較佳為30重量%以下，更佳為20重量%以下。In 100 wt % of the second composition, the content of the photopolymerization initiator is preferably 0.1 wt % or more, more preferably 0.5 wt % or more, and is preferably 30 wt % or less, more preferably 20 wt % or less.
於上述第3組合物100重量%中，上述光聚合起始劑之含量較佳為0.1重量%以上，更佳為0.5重量%以上，且較佳為30重量%以下，更佳為20重量%以下。In 100 wt % of the third composition, the content of the photopolymerization initiator is preferably 0.1 wt % or more, more preferably 0.5 wt % or more, and is preferably 30 wt % or less, more preferably 20 wt % or less.
＜熱硬化劑＞ 上述第1組合物含有熱硬化劑。上述第2組合物含有熱硬化劑。上述第3組合物含有熱硬化劑。上述第1組合物中所含有之熱硬化劑、上述第2組合物中所含有之熱硬化劑及上述第3組合物中所含有之熱硬化劑分別可相同，亦可不同。上述熱硬化劑可僅使用1種，亦可併用2種以上。<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 or different. Only one type of the thermosetting agent may be used, or two or more types may be used in combination.
作為上述熱硬化劑，可例舉：有機酸、胺化合物、醯胺化合物、醯肼化合物、咪唑化合物、咪唑啉化合物、酚系化合物、尿素化合物、多硫化合物及酸酐等。作為上述熱硬化劑，亦可使用胺-環氧加成物等改性聚胺化合物。亦可使用該等以外之熱硬化劑。Examples of the above-mentioned heat curing agent include organic acids, amine compounds, amide compounds, hydrazide compounds, imidazole compounds, imidazoline compounds, phenolic compounds, urea compounds, polysulfide compounds, and acid anhydrides. As the above-mentioned heat curing agent, modified polyamine compounds such as amine-epoxy adducts can also be used. Heat curing agents other than these can also be used.
所謂上述胺化物係指具有1個以上之一級～三級胺基之化合物。作為上述胺化合物，可例舉：脂肪族聚胺、脂環族聚胺、芳香族聚胺、醯肼、及胍衍生物等。又，作為上述胺化合物，亦可使用環氧化合物加成聚胺(環氧化合物與聚胺之反應物)、麥可加成聚胺(α,β-不飽和酮與聚胺之反應物)、曼尼希加成聚胺(聚胺與福馬林及苯酚之縮合物)、硫脲加成聚胺(硫脲與聚胺之反應物)、酮封阻聚胺(酮化合物與聚胺之反應物[酮亞胺])等加成產物。The above-mentioned amine compound refers to a compound having one or more primary to tertiary amine groups. Examples of the above-mentioned amine compound include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, hydrazides, and guanidine derivatives. In addition, as the above-mentioned amine compound, addition products such as epoxy compound addition polyamines (reaction products of epoxy compounds and polyamines), Michel addition polyamines (reaction products of α, β-unsaturated ketones and polyamines), Mannich addition polyamines (condensation products of polyamines, formalin and phenol), thiourea addition polyamines (reaction products of thiourea and polyamines), and ketone blocked polyamines (reaction products of ketone compounds and polyamines [ketimines]) can also be used.
作為上述脂肪族聚胺，可例舉：二伸乙基三胺、三伸乙基四胺、四伸乙基五胺、及二乙基胺基丙基胺等。Examples of the aliphatic polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and diethylaminopropylamine.
作為上述脂環族聚胺，可例舉：薄荷烷二胺、異佛爾酮二胺、N-胺基乙基哌𠯤、3,9-雙(3-胺基丙基)-2,4,8,10-四氧雜螺(5,5)十一烷加成物、雙(4-胺基-3-甲基環己基)甲烷、及雙(4-胺基環己基)甲烷等。Examples of the alicyclic polyamine include menthanediamine, isophoronediamine, N-aminoethylpiperidinium, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane adduct, bis(4-amino-3-methylcyclohexyl)methane, and bis(4-aminocyclohexyl)methane.
作為上述芳香族聚胺，可例舉：間苯二胺、對苯二胺、鄰苯二甲胺、間苯二甲胺、對苯二甲胺、4,4-二胺基二苯基甲烷、4,4-二胺基二苯基丙烷、4,4-二胺基二苯基碸、4,4-二胺基二環己烷、雙(4-胺基苯基)苯基甲烷、1,5-二胺基萘、1,1-雙(4-胺基苯基)環己烷、2,2-雙[(4-胺基苯氧基)苯基]丙烷、雙[4-(4-胺基苯氧基)苯基]碸、1,3-雙(4-胺基苯氧基)苯、4,4-亞甲基雙(2-氯苯胺)、及4,4-二胺基二苯基碸等。Examples of the aromatic polyamine include meta-phenylenediamine, para-phenylenediamine, o-phenylenediamine, meta-phenylenediamine, p-phenylenediamine, 4,4-diaminodiphenylmethane, 4,4-diaminodiphenylpropane, 4,4-diaminodiphenylsulfone, 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-methylenebis(2-chloroaniline), and 4,4-diaminodiphenylsulfone.
作為上述醯肼，可例舉：碳二醯肼、己二酸二醯肼、癸二酸二醯肼、十二烷二酸二醯肼、及間苯二甲酸二醯肼等。Examples of the hydrazide include carbohydrazide, adipic acid dihydrazide, sebacate acid dihydrazide, dodecanedioic acid dihydrazide, and isophthalic acid dihydrazide.
作為上述胍衍生物，可例舉：雙氰胺、1-鄰甲苯基雙胍、α-2,5-二甲基胍、α,ω-二苯基二胍、α,α-雙甲脒基胍基二苯基醚、對氯苯基二胍、α,α-六亞甲基雙[ω-(對氯苯酚)]二胍、苯基二胍草酸酯、乙醯基胍、及二乙基氰基乙醯基胍等。Examples of the guanidine derivatives include dicyandiamide, 1-o-tolylbiguanidine, α-2,5-dimethylguanidine, α,ω-diphenylbiguanidine, α,α-biscarbamimidoguanidine diphenyl ether, p-chlorophenylbiguanidine, α,α-hexamethylenebis[ω-(p-chlorophenol)]biguanide, phenylbiguanide oxalate, acetylguanidine, and diethylcyanoacetylguanidine.
作為上述酚系化合物，可例舉多酚化合物等。作為上述多酚化合物，例如可例舉：苯酚、甲酚、乙基苯酚、丁基苯酚、辛基苯酚、雙酚A、四溴雙酚A、雙酚F、雙酚S、4,4'-聯苯酚、含萘骨架之酚系酚醛清漆樹脂、含二甲苯骨架之酚系酚醛清漆樹脂、含二環戊二烯骨架之酚系酚醛清漆樹脂、及含茀骨架之酚系酚醛清漆樹脂等。Examples of the phenolic compound include polyphenolic compounds, etc. Examples of the polyphenolic compound include phenol, cresol, ethylphenol, butylphenol, octylphenol, bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, 4,4'-biphenol, phenolic novolac resins containing a naphthalene skeleton, phenolic novolac resins containing a xylene skeleton, phenolic novolac resins containing a dicyclopentadiene skeleton, and phenolic novolac resins containing a fluorene skeleton.
作為上述酸酐，例如可例舉：鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基耐地酸酐、十二烷基琥珀酸酐、氯茵酸酐、均苯四甲酸二酐、二苯甲酮四羧酸酐、甲基環己烯四羧酸酐、偏苯三甲酸酐、及聚壬二酸酐等。Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnalidic anhydride, dodecylsuccinic anhydride, chlorendic anhydride, pyromellitic dianhydride, benzophenonetetracarboxylic anhydride, methylcyclohexenetetracarboxylic anhydride, trimellitic anhydride, and polyazelaic anhydride.
於上述第1組合物100重量%中，上述熱硬化劑之含量較佳為0.1重量%以上，更佳為1重量%以上，且較佳為50重量%以下，更佳為40重量%以下。In 100 wt % of the first composition, the content of the thermosetting agent is preferably 0.1 wt % or more, more preferably 1 wt % or more, and is preferably 50 wt % or less, more preferably 40 wt % or less.
於上述第2組合物100重量%中，上述熱硬化劑之含量較佳為0.1重量%以上，更佳為1重量%以上，且較佳為50重量%以下，更佳為40重量%以下。In 100 wt % of the second composition, the content of the thermosetting agent is preferably 0.1 wt % or more, more preferably 1 wt % or more, and is preferably 50 wt % or less, more preferably 40 wt % or less.
於上述第3組合物100重量%中，上述熱硬化劑之含量較佳為0.1重量%以上，更佳為1重量%以上，且較佳為50重量%以下，更佳為40重量%以下。In 100 wt % of the third composition, the content of the thermosetting agent is preferably 0.1 wt % or more, more preferably 1 wt % or more, and is preferably 50 wt % or less, more preferably 40 wt % or less.
＜硬化促進劑＞ 上述第1組合物可含有亦可不含有硬化促進劑。上述第2組合物可含有亦可不含有硬化促進劑。上述第3組合物可含有亦可不含有硬化促進劑。上述第1組合物中所含有之硬化促進劑、上述第2組合物中所含有之硬化促進劑及上述第3組合物中所含有之硬化促進劑分別可相同，亦可不同。上述硬化促進劑可僅使用1種，亦可併用2種以上。<Hardening accelerator> The first composition may or may not contain a hardening accelerator. The second composition may or may not contain a hardening accelerator. The third composition may or may not contain a hardening accelerator. The hardening accelerator contained in the first composition, the hardening accelerator contained in the second composition, and the hardening accelerator contained in the third composition may be the same or different. The hardening accelerator may be used alone or in combination of two or more.
作為上述硬化促進劑，可例舉：三級胺、咪唑、四級銨鹽、四級鏻鹽、有機金屬鹽、磷化合物及脲系化合物等。Examples of the hardening accelerator include tertiary amines, imidazoles, quaternary ammonium salts, quaternary phosphonium salts, organic metal salts, phosphorus compounds, and urea compounds.
於上述第1組合物含有上述硬化促進劑之情形時，於上述第1組合物100重量%中，上述硬化促進劑之含量較佳為0.01重量%以上，更佳為0.1重量%以上，且較佳為10重量%以下，更佳為8重量%以下。When the first composition contains the hardening accelerator, the content of the hardening accelerator in 100 wt % of the first composition is preferably 0.01 wt % or more, more preferably 0.1 wt % or more, and preferably 10 wt % or less, more preferably 8 wt % or less.
於上述第2組合物含有上述硬化促進劑之情形時，於上述第2組合物100重量%中，上述硬化促進劑之含量較佳為0.01重量%以上，更佳為0.1重量%以上，且較佳為10重量%以下，更佳為8重量%以下。When the second composition contains the hardening accelerator, the content of the hardening accelerator in 100 wt % of the second composition is preferably 0.01 wt % or more, more preferably 0.1 wt % or more, and preferably 10 wt % or less, more preferably 8 wt % or less.
於上述第3組合物含有上述硬化促進劑之情形時，於上述第3組合物100重量%中，上述硬化促進劑之含量較佳為0.01重量%以上，更佳為0.1重量%以上，且較佳為10重量%以下，更佳為8重量%以下。When the third composition contains the curing accelerator, the content of the curing accelerator is preferably 0.01 wt % or more, more preferably 0.1 wt % or more, and preferably 10 wt % or less, more preferably 8 wt % or less, based on 100 wt % of the third composition.
(溶劑) 上述第1組合物可含有亦可不含有溶劑。上述第2組合物可含有亦可不含有溶劑。上述第3組合物可含有亦可不含有溶劑。上述第1組合物中所含有之溶劑、上述第2組合物中所含有之溶劑及上述第3組合物中所含有之溶劑分別可相同，亦可不同。上述溶劑可僅使用1種，亦可併用2種以上。(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. Only one of the above solvents may be used, or two or more of them may be used in combination.
就進一步提高第1組合物之硬化物層(光硬化物層或光及熱硬化物層)之厚度精度，進而於第1組合物之硬化物層更難產生孔隙之觀點而言，上述第1組合物中之溶劑之含量越少越佳。From the viewpoint of further improving the thickness accuracy of the cured layer (light-cured layer or light and heat-cured layer) of the first composition and making it more difficult for voids to form in the cured layer of the first composition, the content of the solvent in the first composition is preferably as small as possible.
就進一步提高第2組合物之硬化物層(光硬化物層或光及熱硬化物層)之厚度精度，進而於第2組合物之硬化物層更難產生孔隙之觀點而言，上述第2組合物中之溶劑之含量越少越佳。From the viewpoint of further improving the thickness accuracy of the hardened layer (light-hardened layer or light and heat-hardened layer) of the second composition and making it more difficult for voids to form in the hardened layer of the second composition, the content of the solvent in the second composition is preferably as small as possible.
就進一步提高第3組合物之硬化物層(光硬化物層或光及熱硬化物層)之厚度精度，進而於第3組合物之硬化物層更難產生孔隙之觀點而言，上述第3組合物中之溶劑之含量越少越佳。From the viewpoint of further improving the thickness accuracy of the cured layer (light-cured layer or light and heat-cured layer) of the third composition and making it more difficult for voids to form in the cured layer of the third composition, the content of the solvent in the third composition is preferably as small as possible.
作為上述溶劑，可例舉：水及有機溶劑等。Examples of the solvent include water and organic solvents.
就進一步提高殘留物之去除性之觀點而言，上述溶劑較佳為有機溶劑。From the viewpoint of further improving the removal performance of residues, the above-mentioned solvent is preferably an organic solvent.
作為上述有機溶劑，可例舉：乙醇等醇類；丙酮、甲基乙基酮、環己酮等酮類；甲苯、二甲苯、四甲基苯等芳香族烴類；溶纖劑、甲基溶纖劑、丁基溶纖劑、卡必醇、甲基卡必醇、丁基卡必醇、丙二醇單甲醚、二丙二醇單甲醚、二丙二醇二乙醚、三丙二醇單甲醚等二醇醚類；乙酸乙酯、乙酸丁酯、乳酸丁酯、溶纖劑乙酸酯、丁基溶纖劑乙酸酯、卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇單甲醚乙酸酯、二丙二醇單甲醚乙酸酯、碳酸丙二酯等酯類；辛烷、癸烷等脂肪族烴類；及石油醚、石腦油等石油系溶劑等。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; glycol ethers such as solvent, methyl solvent, butyl solvent, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl acetate, butyl lactate, solvent acetate, butyl solvent acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether and naphtha.
於上述第1組合物含有上述溶劑之情形時，於上述第1組合物100重量%中，上述溶劑之含量較佳為5重量%以下，更佳為1重量%以下，進而較佳為0.5重量%以下。上述第1組合物最佳為不含上述溶劑。When the first composition contains the solvent, the content of the solvent is preferably 5 wt % or less, more preferably 1 wt % or less, and further preferably 0.5 wt % or less in 100 wt % of the first composition. It is most preferred that the first composition does not contain the solvent.
於上述第2組合物含有上述溶劑之情形時，於上述第2組合物100重量%中，上述溶劑之含量較佳為5重量%以下，更佳為1重量%以下，進而較佳為0.5重量%以下。上述第2組合物最佳為不含上述溶劑。When the second composition contains the solvent, the content of the solvent is preferably 5 wt % or less, more preferably 1 wt % or less, and further preferably 0.5 wt % or less in 100 wt % of the second composition. It is most preferred that the second composition does not contain the solvent.
於上述第3組合物含有上述溶劑之情形時，於上述第3組合物100重量%中，上述溶劑之含量較佳為5重量%以下，更佳為1重量%以下，進而較佳為0.5重量%以下。上述第3組合物最佳為不含上述溶劑。When the third composition contains the solvent, the content of the solvent is preferably 5 wt % or less, more preferably 1 wt % or less, and further preferably 0.5 wt % or less in 100 wt % of the third composition. It is most preferred that the third composition does not contain the solvent.
(填料) 上述第1組合物可含有亦可不含有填料。上述第2組合物可含有亦可不含有填料。上述第3組合物可含有亦可不含有填料。上述第1組合物中所含有之填料、上述第2組合物中所含有之填料及上述第3組合物中所含有之填料分別可相同，亦可不同。上述填料可僅使用1種，亦可併用2種以上。(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. Only one type of the filler may be used, or two or more types may be used in combination.
就進一步提高第1組合物之硬化物層(光硬化物層或光及熱硬化物層)之厚度精度，進而於第1組合物之硬化物層更難產生孔隙之觀點而言，上述第1組合物中之填料之含量越少越佳。又，上述第1組合物中之填料之含量越少，越抑制噴墨裝置發生噴出不良。From the viewpoint of further improving the thickness accuracy of the cured layer (light-cured layer or light and heat-cured layer) of the first composition and making it more difficult for voids to form in the cured layer of the first composition, the smaller the content of the filler in the first composition, the better. In addition, the smaller the content of the filler in the first composition, the more the occurrence of ejection defects in the inkjet device can be suppressed.
就進一步提高第2組合物之硬化物層(光硬化物層或光及熱硬化物層)之厚度精度，進而於第2組合物之硬化物層更難產生孔隙之觀點而言，上述第2組合物中之填料之含量越少越佳。又，上述第2組合物中之填料之含量越少，越抑制噴墨裝置發生噴出不良。From the viewpoint of further improving the thickness accuracy of the cured layer (light-cured layer or light and heat-cured layer) of the second composition and making it more difficult for voids to form in the cured layer of the second composition, the smaller the content of the filler in the second composition, the better. In addition, the smaller the content of the filler in the second composition, the more the occurrence of ejection defects in the inkjet device can be suppressed.
就進一步提高第3組合物之硬化物層(光硬化物層或光及熱硬化物層)之厚度精度，進而於第3組合物之硬化物層更難產生孔隙之觀點而言，上述第3組合物中之填料之含量越少越佳。又，上述第3組合物中之填料之含量越少，越抑制噴墨裝置發生噴出不良。From the viewpoint of further improving the thickness accuracy of the cured layer (light-cured layer or light and heat-cured layer) of the third composition and making it more difficult for voids to form in the cured layer of the third composition, the smaller the content of the filler in the third composition, the better. In addition, the smaller the content of the filler in the third composition, the more the occurrence of ejection defects in the inkjet device can be suppressed.
作為上述填料，可例舉：二氧化矽、滑石、黏土、雲母、水滑石、氧化鋁、氧化鎂、氫氧化鋁、氮化鋁及氮化硼等。Examples of the filler include silicon dioxide, talc, clay, mica, hydrotalcite, aluminum oxide, magnesium oxide, aluminum hydroxide, aluminum nitride, and boron nitride.
於上述第1組合物含有上述填料之情形時，於上述第1組合物100重量%中，上述填料之含量較佳為30重量%以下，更佳為10重量%以下，進而較佳為1重量%以下。上述第1組合物最佳為不含上述填料。When the first composition contains the filler, the content of the filler is preferably 30 wt % or less, more preferably 10 wt % or less, and further preferably 1 wt % or less in 100 wt % of the first composition. It is most preferred that the first composition does not contain the filler.
於上述第2組合物含有上述填料之情形時，於上述第2組合物100重量%中，上述填料之含量較佳為30重量%以下，更佳為10重量%以下，進而較佳為1重量%以下。上述第2組合物最佳為不含上述填料。When the second composition contains the filler, the content of the filler is preferably 30 wt % or less, more preferably 10 wt % or less, and further preferably 1 wt % or less in 100 wt % of the second composition. It is most preferred that the second composition does not contain the filler.
於上述第3組合物含有上述填料之情形時，於上述第3組合物100重量%中，上述填料之含量較佳為30重量%以下，更佳為10重量%以下，進而較佳為1重量%以下。上述第3組合物最佳為不含上述填料。When the third composition contains the filler, the content of the filler is preferably 30 wt % or less, more preferably 10 wt % or less, and further preferably 1 wt % or less in 100 wt % of the third composition. It is most preferred that the third composition does not contain the filler.
(其他成分) 上述第1組合物、上述第2組合物及上述第3組合物分別亦可含有其他成分。作為上述其他成分，並無特別限定，可例舉：偶合劑等接著助劑、顏料、染料、調平劑、消泡劑、及聚合抑制劑等。(Other components) 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: bonding aids such as coupling agents, pigments, dyes, leveling agents, defoaming agents, and polymerization inhibitors.
(其他詳情及電子零件) 本發明之積層構造體之製造方法、積層構造體及噴墨用組合物套組可提高材料之防漏出性，因此於電子零件中，可較佳地用於形成間隔壁材及障壁材。但，本發明之積層構造體之製造方法、積層構造體及噴墨用組合物套組亦可用於該用途以外。例如，於本發明之積層構造體之製造方法、積層構造體及噴墨用組合物套組中，上述第1層及上述第2層亦可用於形成塗佈劑。(Other details and electronic components) The method for manufacturing a laminated structure, the laminated structure, and the inkjet composition kit of the present invention can improve the anti-leakage property of the material, and therefore can be preferably used to form partition materials and barrier materials in electronic components. However, the method for manufacturing a laminated structure, the laminated structure, and the inkjet composition kit of the present invention can also be used for purposes other than these. For example, in the method for manufacturing a laminated structure, the laminated structure, and the inkjet composition kit of the present invention, the first layer and the second layer can also be used to form a coating agent.
圖14係表示使用本發明之第1實施方式之積層構造體而獲得之電子零件的剖視圖。圖14(a)為電子零件之俯視圖，圖14(b)為沿圖14(a)中之I-I線之剖視圖。Fig. 14 is a cross-sectional view showing an electronic component obtained by using the laminated structure of the first embodiment of the present invention. Fig. 14(a) is a top view of the electronic component, and Fig. 14(b) is a cross-sectional view along the line I-I in Fig. 14(a).
電子零件80具備積層構造體4C。積層構造體4C具備第1基材3、第1光及熱硬化物層(第1層)1B、第2光及熱硬化物層(第2層)2B、底部填充材60、焊料球65、及半導體晶片70。第1光及熱硬化物層1B係藉由使上述第1組合物進行光硬化及熱硬化而形成。第2光及熱硬化物層2B係藉由使上述第2組合物進行光硬化及熱硬化而形成。The electronic component 80 has a laminated structure 4C. The laminated structure 4C has a first substrate 3, a first light and heat curing material layer (first layer) 1B, a second light and heat curing material layer (second layer) 2B, an underfill material 60, solder balls 65, and a semiconductor chip 70. The first light and heat curing material layer 1B is formed by photocuring and heat curing the first composition. The second light and heat curing material layer 2B is formed by photocuring and heat curing the second composition.
於基材3之表面上，第1光及熱硬化物層1B、第2光及熱硬化物層2B配置成框狀。於上述框狀區域之內側，配置有底部填充材60、焊料球65及半導體晶片70。The first photo- and heat-curable material layer 1B and the second photo- and heat-curable material layer 2B are arranged in a frame shape on the surface of the substrate 3. Inside the frame-shaped area, an underfill material 60, solder balls 65 and a semiconductor chip 70 are arranged.
藉由將底部填充材60流入至上述框狀區域之內側，可獲得電子零件80。於本發明中，由於使用特定之第1組合物及特定之第2組合物，故而於將底部填充材60流入至上述框狀區域之內側時及流入後，底部填充材60難以漏出至框狀區域之外側。By flowing the bottom filling material 60 into the inner side of the frame-shaped region, the electronic component 80 can be obtained. In the present invention, since a specific first composition and a specific second composition are used, when and after flowing the bottom filling material 60 into the inner side of the frame-shaped region, the bottom filling material 60 is unlikely to leak out of the frame-shaped region.
以下，藉由舉出實施例及比較例，對本發明進行具體說明。本發明並不限定於以下之實施例。The present invention is described in detail below by giving examples and comparative examples. The present invention is not limited to the following examples.
準備以下之材料。Prepare the following materials.
(單官能之(甲基)丙烯酸酯化合物) 丙烯酸異癸酯(大阪有機化學工業公司製造之「IDAA」，均聚物之玻璃轉移溫度-68℃) 丙烯酸異壬酯(大阪有機化學工業公司製造之「INAA」，均聚物之玻璃轉移溫度-60℃)(Monofunctional (meth)acrylate compound) Isodecyl acrylate ("IDAA" manufactured by Osaka Organic Chemical Industry Co., Ltd., the glass transition temperature of the homopolymer is -68°C) Isononyl acrylate ("INAA" manufactured by Osaka Organic Chemical Industry Co., Ltd., the glass transition temperature of the homopolymer is -60°C)
(多官能之(甲基)丙烯酸酯化合物) 三羥甲基丙烷三丙烯酸酯(DAICEL-ALLNEX公司製造之「TMPTA」，均聚物之玻璃轉移溫度58℃) 1,6-己二醇二丙烯酸酯(DAICEL-ALLNEX公司製造之「HDDA」，均聚物之玻璃轉移溫度98℃)(Multifunctional (meth)acrylate compound) Trihydroxymethylpropane triacrylate ("TMPTA" manufactured by DAICEL-ALLNEX, glass transition temperature of homopolymer is 58℃) 1,6-Hexanediol diacrylate ("HDDA" manufactured by DAICEL-ALLNEX, glass transition temperature of homopolymer is 98℃)
(環氧化合物) 二環戊二烯型環氧化合物(DIC公司製造之「HP7200L」) 雙酚A型環氧化合物(DIC公司製造之「EXA-850CRP」)(Epoxy compounds) Dicyclopentadiene epoxy compounds ("HP7200L" manufactured by DIC Corporation) Bisphenol A epoxy compounds ("EXA-850CRP" manufactured by DIC Corporation)
(光聚合起始劑) 2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-𠰌啉基)苯基]-1-丁酮(IGM Resins公司製造之「Omnirad 379EG」)(Photopolymerization initiator) 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-oxo-1-phenyl)phenyl]-1-butanone ("Omnirad 379EG" manufactured by IGM Resins)
(熱硬化劑) 芳香族胺化合物(ADEKA公司製造之「EH-105L」)(Thermosetting agent) Aromatic amine compound ("EH-105L" manufactured by ADEKA)
(基材) 矽晶圓(與組合物接觸之區域之表面粗糙度Ra：0.5 nm) 玻璃基板(與組合物接觸之區域之表面粗糙度Ra：1 nm) 陶瓷基板(與組合物接觸之區域之表面粗糙度Ra：380 nm)(Substrate) Silicon wafer (surface roughness Ra of the area in contact with the composition: 0.5 nm) Glass substrate (surface roughness Ra of the area in contact with the composition: 1 nm) Ceramic substrate (surface roughness Ra of the area in contact with the composition: 380 nm)
噴墨裝置： 準備如下噴墨裝置，其包含具有真空吸附功能之載台、第1噴出部、第2噴出部、及配置於第1噴出部與第2噴出部之間之第1紫外線照射部(LED)。Inkjet device: Prepare the following inkjet device, which includes a carrier with a vacuum adsorption function, a first ejection unit, a second ejection unit, and a first ultraviolet irradiation unit (LED) arranged between the first ejection unit and the second ejection unit.
(實施例1～8及比較例1～3) 第1組合物之製作： 以表1～3所示之調配量調配表1～3所示之成分，而獲得第1組合物。(Examples 1 to 8 and Comparative Examples 1 to 3) Preparation of the first composition: The ingredients shown in Tables 1 to 3 are mixed in the amounts shown in Tables 1 to 3 to obtain the first composition.
第2組合物之製作： 以表1～3所示之調配量調配表1～3所示之成分，而獲得第2組合物。Preparation of the second composition: The ingredients shown in Tables 1 to 3 are mixed in the amounts shown in Tables 1 to 3 to obtain the second composition.
(比較例4) 第1組合物之製作： 以表3所示之調配量調配表3所示之成分，而獲得第1組合物。再者，不使用第2組合物。(Comparative Example 4) Preparation of the first composition: The components shown in Table 3 were mixed in the amounts shown in Table 3 to obtain the first composition. In addition, the second composition was not used.
(比較例5) 第2組合物之製作： 以表3所示之調配量調配表3所示之成分，而獲得第2組合物。再者，不使用第1組合物。(Comparative Example 5) Preparation of the second composition: The components shown in Table 3 are mixed in the amounts shown in Table 3 to obtain the second composition. In addition, the first composition is not used.
(評估) (1)光硬化物層之形狀保持性 (1-1)於實施例1～4及比較例1～3中，以如下方式製作具備光硬化物層之積層構造體(X)。(Evaluation) (1) Shape retention of photocured material layer (1-1) In Examples 1 to 4 and Comparative Examples 1 to 3, a layered structure (X) having a photocured material layer was prepared as follows.
具備光硬化物層之積層構造體(X)之製作： 使矽晶圓吸附固定於載台。自第1噴出部噴出第1組合物。於距噴出0.1秒之後，自第1紫外線照射部以照度2000 mW/cm2 照射波長365 nm之紫外線0.2秒，而使第1組合物進行光硬化。藉由重複塗佈及紫外線之照射，而形成具有寬度150 μm、長度10 mm、厚度3 μm之直線形狀之第1層(光硬化物層)。Preparation of a multilayer structure (X) having a photocurable layer: A silicon wafer is fixed to a carrier by adsorption. A first composition is ejected from a first ejection portion. 0.1 seconds after ejection, ultraviolet light with a wavelength of 365 nm is irradiated from a first ultraviolet irradiation portion at an illumination of 2000 mW/ cm2 for 0.2 seconds to photocure the first composition. By repeating coating and ultraviolet irradiation, a first layer (photocurable layer) having a linear shape of 150 μm in width, 10 mm in length, and 3 μm in thickness is formed.
然後，自第2噴出部將第2組合物噴出於第1層(光硬化物層)之表面上。於距噴出0.1秒之後，自第1紫外線照射部以照度2000 mW/cm2 照射波長365 nm之紫外線0.2秒，而使第2組合物進行光硬化。藉由重複塗佈及紫外線之照射，而於第1層(光硬化物層)之表面上形成具有寬度150 μm、長度10 mm、厚度100 μm之直線形狀之第2層(光硬化物層)。Then, the second composition is sprayed from the second spraying part onto the surface of the first layer (photocurable layer). 0.1 second after spraying, ultraviolet rays with a wavelength of 365 nm are irradiated from the first ultraviolet irradiation part at an illuminance of 2000 mW/ cm2 for 0.2 seconds to photocure the second composition. By repeating the coating and ultraviolet irradiation, a second layer (photocurable layer) having a straight line shape of 150 μm in width, 10 mm in length, and 100 μm in thickness is formed on the surface of the first layer (photocurable layer).
以此方式獲得依序具備基材(矽晶圓)、第1層(光硬化物層)及第2層(光硬化物層)之積層構造體(X)。In this way, a layered structure (X) is obtained which sequentially comprises a substrate (silicon wafer), a first layer (photocurable layer), and a second layer (photocurable layer).
(1-2)於實施例5～8中，以如下方式進行變更，除此以外，以與實施例1同樣之方式製作具備光硬化物層之積層構造體(X)。(1-2) In Examples 5 to 8, except that the following changes were made, a multilayer structure (X) having a photocurable material layer was produced in the same manner as in Example 1.
於實施例5中，形成具有寬度300 μm、長度10 mm、厚度3 μm之直線形狀之第1層(光硬化物層)，且形成具有寬度300 μm、長度10 mm、厚度100 μm之直線形狀之第2層(光硬化物層)。In Example 5, a first layer (photocurable layer) having a linear shape of 300 μm in width, 10 mm in length, and 3 μm in thickness was formed, and a second layer (photocurable layer) having a linear shape of 300 μm in width, 10 mm in length, and 100 μm in thickness was formed.
於實施例6中，形成具有寬度150 μm、長度10 mm、厚度3 μm之直線形狀之第1層(光硬化物層)，且形成具有寬度150 μm、長度10 mm、厚度200 μm之直線形狀之第2層(光硬化物層)。In Example 6, a first layer (photocurable layer) having a linear shape of 150 μm in width, 10 mm in length, and 3 μm in thickness was formed, and a second layer (photocurable layer) having a linear shape of 150 μm in width, 10 mm in length, and 200 μm in thickness was formed.
於實施例7中，形成具有寬度150 μm、長度10 mm、厚度5 μm之直線形狀之第1層(光硬化物層)，且形成具有寬度150 μm、長度10 mm、厚度100 μm之直線形狀之第2層(光硬化物層)。In Example 7, a first layer (photocurable layer) having a linear shape of 150 μm in width, 10 mm in length, and 5 μm in thickness was formed, and a second layer (photocurable layer) having a linear shape of 150 μm in width, 10 mm in length, and 100 μm in thickness was formed.
於實施例8中，形成具有寬度150 μm、長度10 mm、厚度5 μm之直線形狀之第1層(光硬化物層)，且形成具有寬度150 μm、長度10 mm、厚度200 μm之直線形狀之第2層(光硬化物層)。In Example 8, a first layer (photocurable layer) having a linear shape of 150 μm in width, 10 mm in length, and 5 μm in thickness was formed, and a second layer (photocurable layer) having a linear shape of 150 μm in width, 10 mm in length, and 200 μm in thickness was formed.
(1-3)於比較例4中，以如下方式製作具備光硬化物層之積層構造體(X)。(1-3) In Comparative Example 4, a multilayer structure (X) having a photocurable layer was prepared in the following manner.
具備光硬化物層之積層構造體(X)之製作： 使矽晶圓吸附固定於載台。自第1噴出部噴出第1組合物。於距噴出0.1秒之後，自第1紫外線照射部以照度2000 mW/cm2 照射波長365 nm之紫外線0.2秒，而使第1組合物進行光硬化。藉由重複塗佈及紫外線之照射，而形成具有寬度150 μm、長度10 mm、厚度103 μm之直線形狀之第1層(光硬化物層)。將其作為具備光硬化物層之積層構造體(X)。Preparation of a laminated structure (X) having a photocurable layer: A silicon wafer is fixed to a carrier by adsorption. The first composition is ejected from the first ejection section. 0.1 seconds after ejection, ultraviolet rays with a wavelength of 365 nm are irradiated from the first ultraviolet irradiation section at an illumination of 2000 mW/ cm2 for 0.2 seconds to photocure the first composition. By repeating coating and ultraviolet irradiation, a first layer (photocurable layer) having a straight line shape of 150 μm in width, 10 mm in length, and 103 μm in thickness is formed. This is used as a laminated structure (X) having a photocurable layer.
(1-4)於比較例5中，以如下方式製作具備光硬化物層之積層構造體(X)。(1-4) In Comparative Example 5, a multilayer structure (X) having a photocurable layer was prepared in the following manner.
具備光硬化物層之積層構造體(X)之製作： 使矽晶圓吸附固定於載台。自第2噴出部噴出第2組合物。於距噴出0.1秒之後，自第1紫外線照射部以照度2000 mW/cm2 照射波長365 nm之紫外線0.2秒，而使第2組合物進行光硬化。藉由重複塗佈及紫外線之照射，而形成具有寬度150 μm、長度10 mm、厚度103 μm之直線形狀之第2層(光硬化物層)。將其作為具備光硬化物層之積層構造體(X)。Preparation of a multilayer structure (X) having a photocurable layer: A silicon wafer is fixed to a carrier by adsorption. A second composition is ejected from a second ejection section. 0.1 seconds after ejection, ultraviolet rays with a wavelength of 365 nm are irradiated from a first ultraviolet irradiation section at an illumination of 2000 mW/ cm2 for 0.2 seconds to photocure the second composition. By repeating coating and ultraviolet irradiation, a second layer (photocurable layer) having a straight line shape of 150 μm in width, 10 mm in length, and 103 μm in thickness is formed. This is used as a multilayer structure (X) having a photocurable layer.
(1-5)再者，積層構造體(X)中之第1層(光硬化物層)及第2層(光硬化物層)之寬度及厚度係使用雷射顯微鏡(Olympus公司製造之「OLS4100」)而測定。於實施例1～8中，光硬化物層之形狀得以保持。(1-5) Furthermore, the width and thickness of the first layer (photocurable layer) and the second layer (photocurable layer) in the laminated structure (X) were measured using a laser microscope ("OLS4100" manufactured by Olympus Corporation). In Examples 1 to 8, the shape of the photocurable layer was maintained.
(2)光及熱硬化物層之形狀保持性 具備光及熱硬化物層之積層構造體(X)之製作： 將所得之具備光硬化物層之積層構造體(X)中之第1、第2層(光硬化物層)藉由以170℃加熱1小時而熱硬化，獲得作為光及熱硬化物層之第1、第2層。以此方式獲得具備基材(矽晶圓)、第1層(光及熱硬化物層)及第2層(光及熱硬化物層)之積層構造體(X)。(2) Shape retention of light- and heat-cured layers Production of a laminated structure (X) having light- and heat-cured layers: The first and second layers (light-cured layers) in the obtained laminated structure (X) having light-cured layers are heat-cured by heating at 170°C for 1 hour to obtain the first and second layers as light- and heat-cured layers. In this way, a laminated structure (X) having a substrate (silicon wafer), a first layer (light- and heat-cured layer), and a second layer (light- and heat-cured layer) is obtained.
利用截面研磨裝置(Struers公司製造之「Tegramin 25」)對所得之積層構造體(X)中之第1層(光及熱硬化物層)及第2層(光及熱硬化物層)進行切削。使用光學顯微鏡(KEYENCE公司製造之「數位顯微鏡VH-Z100」)觀察藉由切削而獲得之第1層(光及熱硬化物層)及第2層(光及熱硬化物層)之截面，藉此分別測定該第1層及該第2層之厚度。The first layer (light- and heat-cured layer) and the second layer (light- and heat-cured layer) of the obtained layered structure (X) were cut using a cross-section grinding device ("Tegramin 25" manufactured by Struers). The cross-sections of the first layer (light- and heat-cured layer) and the second layer (light- and heat-cured layer) obtained by cutting were observed using an optical microscope ("Digital Microscope VH-Z100" manufactured by KEYENCE) to measure the thickness of the first layer and the second layer, respectively.
[光及熱硬化物層之形狀保持性之判定基準] ○：於加熱前後，各硬化物層無厚度變化(變化率未達5%) △：於加熱前後，各硬化物層稍微存在厚度變化(變化率為5%以上且未達10%) ×：於加熱前後，各硬化物層存在厚度變化(變化率為10%以上)[Criteria for determining shape retention of light- and heat-cured layers] ○: There is no thickness change in each cured layer before and after heating (change rate less than 5%) △: There is a slight thickness change in each cured layer before and after heating (change rate of 5% or more and less than 10%) ×: There is a thickness change in each cured layer before and after heating (change rate of 10% or more)
(3)粉體之附著性 使矽晶圓吸附固定於載台。自第2噴出部噴出第2組合物(比較例4中自第1噴出部噴出第1組合物)。於距噴出0.1秒之後，自第1紫外線照射部以照度2000 mW/cm2 照射波長365 nm之紫外線0.2秒，而使第2組合物進行光硬化。藉由重複塗佈及紫外線之照射，而形成具有寬度10 mm、長度10 mm、厚度20 μm之形狀之第2層(光硬化物層)。(3) The adhesion of the powder allows the silicon wafer to be adsorbed and fixed to the carrier. The second composition is ejected from the second ejection portion (compared with the first ejection portion in Example 4, where the first composition is ejected from the first ejection portion). 0.1 seconds after ejection, the second composition is photocured by irradiating ultraviolet light with a wavelength of 365 nm at an illumination of 2000 mW/ cm2 for 0.2 seconds from the first ultraviolet irradiation portion. By repeating coating and ultraviolet irradiation, a second layer (photocuring layer) having a shape of 10 mm in width, 10 mm in length, and 20 μm in thickness is formed.
然後，將100 mg之二氧化矽粉末(日本觸媒公司製造之「SEAHOSTAR KE-P250」)配置於光硬化物層之表面，以400 L/min對光硬化物層之表面吹送氮氣10秒。測定殘存於光硬化物層之表面之二氧化矽粉末之量。Then, 100 mg of silicon dioxide powder ("SEAHOSTAR KE-P250" manufactured by Japan Catalyst Co., Ltd.) was placed on the surface of the photocurable layer, and nitrogen gas was blown onto the surface of the photocurable layer at 400 L/min for 10 seconds. The amount of silicon dioxide powder remaining on the surface of the photocurable layer was measured.
＜粉體之附著性之判定基準＞ ○：殘存之二氧化矽粉末之量未達10% ×：殘存之二氧化矽粉末之量為10%以上<Criteria for determining the adhesion of powder> ○: The amount of residual silicon dioxide powder is less than 10% ×: The amount of residual silicon dioxide powder is more than 10%
(4)與基材之接著性及層間接著性(冷熱循環試驗) 將「(2)光及熱硬化物層之形狀保持性」中所得之具備光及熱硬化物層之積層構造體(X)放入至溫度循環試驗機(楠本化成公司製造之「TA530A」)，將「-40℃下30分鐘，125℃下30分鐘」設為1個循環，進行合計100個循環之冷熱循環試驗。以400 L/min對冷熱循環試驗後之積層構造體(X)吹送氮氣10秒。確認基材與第1層之間(比較例4中為基材與第2層之間)或第1層與第2層之間是否產生剝離。(4) Adhesion to substrate and interlayer adhesion (hot and cold cycle test) The laminated structure (X) with light- and heat-cured layers obtained in "(2) Shape retention of light- and heat-cured layers" was placed in a temperature cycle tester ("TA530A" manufactured by Kusumoto Chemicals Co., Ltd.) and subjected to a total of 100 hot and cold cycle tests, with "-40°C for 30 minutes, 125°C for 30 minutes" as one cycle. After the hot and cold cycle test, nitrogen gas was blown through the laminated structure (X) at 400 L/min for 10 seconds. It was confirmed whether peeling occurred between the substrate and the first layer (between the substrate and the second layer in Comparative Example 4) or between the first layer and the second layer.
＜與基材之接著性及層間接著性(冷熱循環試驗)之評估基準＞ ○：與基材之間未產生剝離 ×：與基材之間產生剝離 ○：層間未產生剝離 ×：層間產生剝離<Evaluation criteria for adhesion to substrate and inter-layer adhesion (hot and cold cycle test)> ○: No peeling from substrate ×: Peeling from substrate ○: No peeling between layers ×: Peeling between layers
(5)材料之防漏出性 使矽晶圓吸附固定於載台。自第1噴出部噴出第1組合物。於距噴出0.1秒之後，自第1紫外線照射部以照度2000 mW/cm2 照射波長365 nm之紫外線0.2秒，而使第1組合物進行光硬化。藉由重複塗佈及紫外線之照射，而形成具有寬度150 μm、一邊之長度10 mm、厚度3 μm之正方形之框狀形狀的第1層(光硬化物層)。(5) The anti-leakage property of the material allows the silicon wafer to be adsorbed and fixed on the carrier. The first composition is ejected from the first ejection part. 0.1 seconds after the ejection, ultraviolet rays with a wavelength of 365 nm are irradiated from the first ultraviolet irradiation part at an illumination of 2000 mW/ cm2 for 0.2 seconds to photocure the first composition. By repeating the coating and ultraviolet irradiation, the first layer (photocurable material layer) having a square frame shape with a width of 150 μm, a length of 10 mm on one side, and a thickness of 3 μm is formed.
然後，自第2噴出部將第2組合物噴出於第1層(光硬化物層)之表面上。於距噴出0.1秒之後，自第1紫外線照射部以照度2000 mW/cm2 照射波長365 nm之紫外線0.2秒，而使第2組合物進行光硬化。藉由重複塗佈及紫外線之照射，而於第1層(光硬化物層)之表面上形成具有寬度150 μm、一邊之長度10 mm、厚度100 μm之正方形之框狀形狀的第2層(光硬化物層)。Then, the second composition is sprayed from the second spraying part onto the surface of the first layer (photocurable layer). 0.1 second after spraying, ultraviolet rays with a wavelength of 365 nm are irradiated from the first ultraviolet irradiation part at an illuminance of 2000 mW/ cm2 for 0.2 seconds to photocure the second composition. By repeating the coating and ultraviolet irradiation, a second layer (photocurable layer) having a square frame shape with a width of 150 μm, a length of 10 mm on one side, and a thickness of 100 μm is formed on the surface of the first layer (photocurable layer).
然後，將第1、第2層(光硬化物層)藉由以170℃加熱1小時而熱硬化，獲得作為光及熱硬化物層之第1、第2層。以此方式獲得具備基材(矽晶圓)、第1層(光及熱硬化物層)及第2層(光及熱硬化物層)之積層構造體。Then, the first and second layers (light-curing layers) are thermally cured by heating at 170°C for 1 hour to obtain the first and second layers as light- and heat-curing layers. In this way, a layered structure having a substrate (silicon wafer), a first layer (light- and heat-curing layer), and a second layer (light- and heat-curing layer) is obtained.
材料X之製作： 利用行星式攪拌機將以下之成分混合，利用三輥研磨機對所得之混合物進行分散處理，而獲得材料X。Preparation of Material X: The following ingredients are mixed using a planetary mixer, and the resulting mixture is dispersed using a three-roll mill to obtain Material X.
雙酚F型環氧樹脂(DIC公司製造之「EPICLON830」)70重量份 反應性稀釋劑(ADEKA公司製造之「ED-529」)30重量份 熱硬化劑(ADEKA公司製造之「EH105L」)30重量份 熔融二氧化矽(Admatechs公司製造之「SO-C5」)300重量份 偶合劑(JNC公司製造之「S510」)3重量份 碳黑(三菱化學公司製造之「MA-600」)0.5重量份Bisphenol F 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 Fused silica ("SO-C5" manufactured by Admatechs) 300 parts by weight Coupling agent ("S510" manufactured by JNC) 3 parts by weight Carbon black ("MA-600" manufactured by Mitsubishi Chemical) 0.5 parts by weight
於具有正方形之框狀形狀之光及熱硬化物層(第1層與第2層之積層物)之內側，以厚度成為50 μm之方式填充所得之材料X，藉由以150℃加熱1小時而使材料X進行熱硬化。The obtained material X was filled into the inner side of the photo- and heat-curable material layer (the laminate of the first layer and the second layer) having a square frame shape so as to have a thickness of 50 μm, and the material X was heat-cured by heating at 150° C. for 1 hour.
使用光學顯微鏡(KEYENCE公司製造之「數位顯微鏡VH-Z100」)確認材料X是否漏出至光及熱硬化物層之外側。Use an optical microscope ("Digital Microscope VH-Z100" manufactured by KEYENCE) to check whether material X has leaked out of the light and heat cured layer.
再者，於比較例4中，在矽晶圓上形成具有寬度150 μm、一邊之長度10 mm、厚度103 μm之正方形之框狀形狀的第1層(光硬化物層)之後，將第1層(光硬化物層)藉由以170℃加熱1小時而熱硬化，獲得作為光及熱硬化物層之第1層，除此以外，以與上述同樣之方式進行評估。Furthermore, in Comparative Example 4, after forming the first layer (photocurable layer) in 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 (photocurable layer) was thermally cured by heating at 170°C for 1 hour to obtain the first layer as a photo- and thermal-curable layer. Except for this, evaluation was performed in the same manner as above.
又，於比較例5中，在矽晶圓上形成具有寬度150 μm、一邊之長度10 mm、厚度103 μm之正方形之框狀形狀的第2層(光硬化物層)之後，將第2層(光硬化物層)藉由以170℃加熱1小時而熱硬化，獲得作為光及熱硬化物層之第2層，除此以外，以與上述同樣之方式進行評估。In Comparative Example 5, after forming the second layer (photocurable layer) in 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 second layer (photocurable layer) was thermally cured by heating at 170°C for 1 hour to obtain the second layer as a photo- and thermal-curable layer. Except for this, evaluation was performed in the same manner as above.
＜材料之防漏出性之判定基準＞ ○：未能確認到漏出 ×：確認到漏出<Criteria for judging the leakage resistance of materials> ○: No leakage was confirmed ×: Leakage was confirmed
於比較例4中，在熱硬化時光及熱硬化物層(第1層與第2層之積層物)之形狀發生變化，上述光及熱硬化物層之厚度下降至約30 μm，因此材料X漏出至光及熱硬化物層之外側。又，於比較例1～3、5中，基材(矽晶圓)與第1層之接著力或第1層與第2層之接著力較低，因此無法抵抗材料X之熱膨脹，材料X漏出至光及熱硬化物層之外側。In Comparative Example 4, the shape of the light and heat curing layer (the laminate of the first layer and the second layer) changes during thermal curing, and the thickness of the light and heat curing layer decreases to about 30 μm, so the material X leaks out of the light and heat curing layer. In Comparative Examples 1 to 3 and 5, the adhesion between the substrate (silicon wafer) and the first layer or the adhesion between the first layer and the second layer is low, so the thermal expansion of the material X cannot be resisted, and the material X leaks out of the light and heat curing layer.
(實施例9～14) 第1組合物及第3組合物之製作： 以表4、5所示之調配量調配表4、5所示之成分，而獲得第1組合物及第3組合物。(Examples 9 to 14) Preparation of the first and third compositions: The components shown in Tables 4 and 5 are mixed in the amounts shown in Tables 4 and 5 to obtain the first and third compositions.
第2組合物之製作： 以表4、5所示之調配量調配表4、5所示之成分，而獲得第2組合物。Preparation of the second composition: The ingredients shown in Tables 4 and 5 are mixed in the amounts shown in Tables 4 and 5 to obtain the second composition.
(評估) (1)光硬化物層之形狀保持性 (1-1)於實施例9中，以如下方式製作積層構造體(X)。(Evaluation) (1) Shape retention of photocured material layer (1-1) In Example 9, a layered structure (X) was prepared as follows.
積層構造體(X)之製作： 使矽晶圓吸附固定於載台。自第1噴出部噴出第1組合物。於距噴出0.1秒之後，自第1紫外線照射部以照度2000 mW/cm2 照射波長365 nm之紫外線0.2秒，而使第1組合物進行光硬化。藉由重複塗佈及紫外線之照射，而形成具有寬度200 μm、一邊之長度10 mm、厚度5 μm之正方形之框狀形狀的第1層(光硬化物層)。Preparation of the laminated structure (X): A silicon wafer is fixed to a carrier by adsorption. The first composition is ejected from the first ejection unit. 0.1 seconds after ejection, ultraviolet light with a wavelength of 365 nm is irradiated from the first ultraviolet irradiation unit at an illumination of 2000 mW/ cm2 for 0.2 seconds to photocure the first composition. By repeating coating and ultraviolet irradiation, a first layer (photocurable material layer) having a square frame shape with a width of 200 μm, a length of 10 mm on one side, and a thickness of 5 μm is formed.
然後，自第2噴出部將第2組合物噴出於第1層(光硬化物層)之表面上。於距噴出0.1秒之後，自第1紫外線照射部以照度2000 mW/cm2 照射波長365 nm之紫外線0.2秒，而使第2組合物進行光硬化。藉由重複塗佈及紫外線之照射，而於第1層(光硬化物層)之表面上形成具有寬度200 μm、一邊之長度10 mm、厚度1000 μm之正方形之框狀形狀的第2層(光硬化物層)。Then, the second composition is sprayed from the second spraying part onto the surface of the first layer (photocurable layer). 0.1 second after spraying, ultraviolet rays with a wavelength of 365 nm are irradiated from the first ultraviolet irradiation part at an illuminance of 2000 mW/ cm2 for 0.2 seconds to photocure the second composition. By repeating the coating and ultraviolet irradiation, a second layer (photocurable layer) having a square frame shape with a width of 200 μm, a length of 10 mm on one side, and a thickness of 1000 μm is formed on the surface of the first layer (photocurable layer).
然後，自第1噴出部將第3組合物(第1組合物)噴出於第2層(光硬化物層)之表面上。於距噴出0.1秒之後，自第1紫外線照射部以照度2000 mW/cm2 照射波長365 nm之紫外線0.2秒，而使第3組合物進行光硬化。藉由重複塗佈及紫外線之照射，而形成具有寬度200 μm、一邊之長度10 mm、厚度10 μm之正方形之框狀形狀的第3層(光硬化物層)。Then, the third composition (first composition) is sprayed from the first spraying part onto the surface of the second layer (photocurable layer). 0.1 seconds after spraying, ultraviolet rays with a wavelength of 365 nm are irradiated from the first ultraviolet irradiation part at an illuminance of 2000 mW/ cm2 for 0.2 seconds to photocure the third composition. By repeating the coating and ultraviolet irradiation, the third layer (photocurable layer) having a square frame shape with a width of 200 μm, a length of 10 mm on one side, and a thickness of 10 μm is formed.
然後，使用貼合機(SHIBAURA MECHATRONICS公司製造之「FTD-7000P」)，於第3層之表面上貼合玻璃基板，藉由以170℃加熱1小時，而使第1層(光硬化物層)、第2層(光硬化物層)及第3層(光硬化物層)進行熱硬化。Then, a glass substrate was bonded to the surface of the third layer using a bonding machine ("FTD-7000P" manufactured by SHIBAURA MECHATRONICS), and the first layer (photocurable layer), the second layer (photocurable layer), and the third layer (photocurable layer) were thermally cured by heating at 170°C for 1 hour.
以此方式獲得依序具備第1基材(矽晶圓)、第1層(光及熱硬化物層)、第2層(光及熱硬化物層)、第3層(光及熱硬化物層)、及第2基材(玻璃基板)之積層構造體(X)。In this way, a multilayer structure (X) is obtained which sequentially comprises a first substrate (silicon wafer), a first layer (light and heat curing layer), a second layer (light and heat curing layer), a third layer (light and heat curing layer), and a second substrate (glass substrate).
(1-2)於實施例10、11中，追加進行以下之操作，且形成具有寬度200 μm、一邊之長度10 mm、厚度5 μm之正方形之框狀形狀的第3層(光硬化物層)，除此以外，以與實施例9同樣之方式製作積層構造體(X)。(1-2) In Examples 10 and 11, the following operation was additionally performed to form a third layer (photocurable material layer) having a square frame shape with a width of 200 μm, a side length of 10 mm, and a thickness of 5 μm. A layered structure (X) was produced in the same manner as in Example 9.
於第2層(光硬化物層)之形成後且第3組合物之噴出前，以170℃將基材(矽晶圓)、第1層(光硬化物層)及第2層(光硬化物層)之積層體加熱1小時，藉此使第1層(光硬化物層)及第2層(光硬化物層)進行熱硬化。然後，藉由使用平坦化裝置(KeyLink公司製造)對第2層(光及熱硬化物層)之表面切削研磨100 μm而進行平坦化處理。再者，於實施例10、11中，平坦化處理後之第2層之表面之最大高度與最小高度的差之絕對值為3 μm以下。After the formation of the second layer (photocurable layer) and before the ejection of the third composition, the laminate of the substrate (silicon wafer), the first layer (photocurable layer) and the second layer (photocurable layer) was heated at 170°C for 1 hour to thermally cure the first layer (photocurable layer) and the second layer (photocurable layer). Then, the surface of the second layer (photo- and thermal-curable layer) was planarized by cutting and polishing by 100 μm using a planarization 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 planarization treatment was less than 3 μm.
以此方式獲得依序具備基材(矽晶圓)、第1層(光及熱硬化物層)、第2層(光及熱硬化物層)、第3層(光及熱硬化物層)、及第2基材(玻璃基板)之積層構造體(X)。In this way, a multilayer structure (X) is obtained which sequentially comprises a base material (silicon wafer), a first layer (light and heat curing layer), a second layer (light and heat curing layer), a third layer (light and heat curing layer), and a second base material (glass substrate).
(1-3)於實施例12中，以如下方式製作積層構造體(X)。(1-3) In Example 12, a layered structure (X) is produced in the following manner.
積層構造體(X)之製作： 使陶瓷基板吸附固定於載台。自第2噴出部噴出第2組合物。於距噴出0.1秒之後，自第1紫外線照射部以照度2000 mW/cm2 照射波長365 nm之紫外線0.2秒，而使第2組合物進行光硬化。藉由重複塗佈及紫外線之照射，而於基材之表面上形成具有寬度200 μm、一邊之長度10 mm、厚度1000 μm之正方形之框狀形狀的第2層(光硬化物層)。Preparation of the laminated structure (X): The ceramic substrate is fixed to the carrier by adsorption. The second composition is ejected from the second ejection part. 0.1 seconds after the ejection, the second composition is photocured by irradiating ultraviolet rays with a wavelength of 365 nm at an illumination of 2000 mW/ cm2 from the first ultraviolet irradiation part for 0.2 seconds. By repeating the coating and ultraviolet irradiation, a second layer (photocurable material layer) having a square frame shape with a width of 200 μm, a length of 10 mm on one side, and a thickness of 1000 μm is formed on the surface of the substrate.
然後，自第1噴出部將第1組合物噴出於第2層(光硬化物層)之表面上。於距噴出0.1秒之後，自第1紫外線照射部以照度2000 mW/cm2 照射波長365 nm之紫外線0.2秒，而使第1組合物進行光硬化。藉由重複塗佈及紫外線之照射，而於第2層(光硬化物層)之表面上形成具有寬度200 μm、一邊之長度10 mm、厚度10 μm之正方形之框狀形狀的第1層(光硬化物層)。Then, the first composition is sprayed from the first spraying part onto the surface of the second layer (photocurable layer). 0.1 second after spraying, ultraviolet rays with a wavelength of 365 nm are irradiated from the first ultraviolet irradiation part at an illuminance of 2000 mW/ cm2 for 0.2 seconds to photocure the first composition. By repeating the coating and ultraviolet irradiation, a first layer (photocurable layer) having a square frame shape with a width of 200 μm, a length of 10 mm on one side, and a thickness of 10 μm is formed on the surface of the second layer (photocurable layer).
然後，使用貼合機(SHIBAURA MECHATRONICS公司製造之「FTD-7000P」)於第1層之表面上貼合玻璃基板，藉由以170℃加熱1小時，而使第1層(光硬化物層)及第2層(光硬化物層)進行熱硬化。Then, a glass substrate was bonded to the surface of the first layer using a bonding machine ("FTD-7000P" manufactured by SHIBAURA MECHATRONICS), and the first layer (photocurable layer) and the second layer (photocurable layer) were thermally cured by heating at 170°C for 1 hour.
以此方式獲得依序具備基材(陶瓷基板)、第2層(光硬化物層)、第1層(光硬化物層)、及基材(玻璃基板)之積層構造體(X)。In this way, a layered structure (X) is obtained which sequentially comprises a base material (ceramic substrate), a second layer (photocurable layer), a first layer (photocurable layer), and a base material (glass substrate).
(1-4)於實施例13、14中，追加進行以下之操作，且形成具有寬度200 μm、一邊之長度10 mm、厚度5 μm之正方形之框狀形狀的第1層(光硬化物層)，除此以外，以與實施例12同樣之方式製作積層構造體(X)。(1-4) In Examples 13 and 14, the following operation was additionally performed to form a first layer (photocurable layer) having a square frame shape with a width of 200 μm, a side length of 10 mm, and a thickness of 5 μm. A layered structure (X) was produced in the same manner as in Example 12, except that the following operation was additionally performed to form a first layer (photocurable layer) having a square frame shape with a width of 200 μm, a side length of 10 mm, and a thickness of 5 μm.
於第2層(光硬化物層)之形成後且第1組合物之噴出前，藉由以170℃將基材(陶瓷基板)與第2層(光硬化物層)之積層體加熱1小時，而使第2層(光硬化物層)進行熱硬化。然後，藉由使用平坦化裝置(KeyLink公司製造)對第2層(光及熱硬化物層)之表面切削研磨100 μm而進行平坦處理。再者，於實施例13、14中，平坦化處理後之第2層之最大高度與最小高度之差的絕對值為3 μm以下。After the second layer (photocurable layer) was formed and before the first composition was ejected, the laminate of the substrate (ceramic substrate) and the second layer (photocurable layer) was heated at 170°C for 1 hour to thermally cure the second layer (photocurable layer). Then, the surface of the second layer (photocurable layer) was flattened by grinding and polishing 100 μm using a flattening device (manufactured by KeyLink). 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.
以此方式獲得依序具備基材(陶瓷基板)、第2層(光硬化物層)、第1層(光硬化物層)、及基材(玻璃基板)之積層構造體(X)。In this way, a layered structure (X) is obtained which sequentially comprises a base material (ceramic substrate), a second layer (photocurable layer), a first layer (photocurable layer), and a base material (glass substrate).
(1-5)再者，積層構造體(X)中之第1層(光硬化物層)、第2層(光硬化物層)及第3層(光硬化物層)之寬度及厚度係使用雷射顯微鏡(Olympus公司製造之「OLS4100」)而測定。於實施例9～14中，光硬化物層之形狀得以保持。(1-5) Furthermore, the width and thickness of the first layer (photocurable layer), the second layer (photocurable layer), and the third layer (photocurable layer) in the laminated structure (X) were measured using a laser microscope ("OLS4100" manufactured by Olympus Corporation). In Examples 9 to 14, the shape of the photocurable layer was maintained.
(2)光及熱硬化物層之形狀保持性 以與實施例1～8及比較例1～6中評估過之「(2)光及熱硬化物層之形狀保持性」同樣之方式對光及熱硬化物層之形狀保持性進行評估。再者，於進行過平坦化處理之實施例10、11、13、14中不進行本評估。(2) Shape retention of light- and heat-cured layers The shape retention of light- and heat-cured layers was evaluated in the same manner as in "(2) Shape retention of light- and heat-cured layers" evaluated in Examples 1 to 8 and Comparative Examples 1 to 6. This evaluation was not performed in Examples 10, 11, 13, and 14 that had undergone a planarization treatment.
[光及熱硬化物層之形狀保持性之判定基準] ○：於加熱前後，各硬化物層無厚度變化(變化率未達5%) △：於加熱前後，各硬化物層稍微存在厚度變化(變化率為5%以上且未達10%) ×：於加熱前後，各硬化物層存在厚度變化(變化率為10%以上)[Criteria for determining shape retention of light- and heat-cured layers] ○: There is no thickness change in each cured layer before and after heating (change rate less than 5%) △: There is a slight thickness change in each cured layer before and after heating (change rate of 5% or more and less than 10%) ×: There is a thickness change in each cured layer before and after heating (change rate of 10% or more)
(3)粉體之附著性 以與實施例1～8及比較例1～6中評估過之「(3)粉體之附著性」同樣之方式對粉體對於第2層(光硬化物層)之附著性進行評估。(3) Adhesion of powders The adhesion of powders to the second layer (photocuring layer) was evaluated in the same manner as in "(3) Adhesion of powders" evaluated in Examples 1 to 8 and Comparative Examples 1 to 6.
＜粉體之附著性之判定基準＞ ○：殘存之二氧化矽粉末之量未達10% ×：殘存之二氧化矽粉末之量為10%以上<Criteria for determining the adhesion of powder> ○: The amount of residual silicon dioxide powder is less than 10% ×: The amount of residual silicon dioxide powder is more than 10%
(4)與基材之接著性及層間接著性(冷熱循環試驗) 使用所得之積層構造體(X)，除此以外，以與實施例1～8及比較例1～6中評估過之「(4)與基材之接著性及層間接著性(冷熱循環試驗)」同樣之方式對與基材之接著性及層間接著性進行評估。再者，確認基材與第1層之間、第1層與第2層之間、第2層與第3層之間、或第3層與基材之間是否產生剝離。(4) Adhesion to substrate and interlayer adhesion (hot and cold cycle test) The obtained multilayer structure (X) was used to evaluate the adhesion to substrate and interlayer adhesion in the same manner as in "(4) Adhesion to substrate and interlayer adhesion (hot and cold cycle test)" evaluated in Examples 1 to 8 and Comparative Examples 1 to 6. Furthermore, it was confirmed whether peeling occurred between the substrate 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 substrate.
＜與基材之接著性及層間接著性(冷熱循環試驗)之評估基準＞ ○：與基材之間未產生剝離 ×：與基材之間產生剝離 ○：層間未產生剝離 ×：層間產生剝離<Evaluation criteria for adhesion to substrate and inter-layer adhesion (hot and cold cycle test)> ○: No peeling from substrate ×: Peeling from substrate ○: No peeling between layers ×: Peeling between layers
(5)材料之防漏出性(與第2基材之界面) 利用雷射對所得之積層構造體(X)中之基材(玻璃基板)之中央部進行切割，而設置材料X之注入口。然後，自注入口向具有正方形之框狀形狀之光及熱硬化物層之內側填充材料X，以150℃加熱1小時，藉此使材料X熱硬化。使用光學顯微鏡(KEYENCE公司製造之「數位顯微鏡VH-Z100」)，於實施例9～11中確認材料X是否自第2基材(玻璃基板)與第3層之間漏出，於實施例12～14中確認材料X是否自第2基材(玻璃基板)與第1層之間漏出。(5) Material leakage prevention (interface with the second substrate) The center of the substrate (glass substrate) in the obtained multilayer structure (X) was cut by laser to set an injection port for material X. Then, material X was filled into the inner side of the photo- and heat-curable material layer having a square frame shape from the injection port, and heated at 150°C for 1 hour to thermally cure material X. An optical microscope ("Digital Microscope VH-Z100" manufactured by KEYENCE) was used to confirm whether material X leaked from between the second substrate (glass substrate) and the third layer in Examples 9 to 11, and whether material X leaked from between the second substrate (glass substrate) and the first layer in Examples 12 to 14.
＜材料之防漏出性之判定基準＞ ○：未能確認到漏出 ×：確認到漏出<Criteria for judging the leakage resistance of materials> ○: No leakage was confirmed ×: Leakage was confirmed
將構成及結果示於下述表1～5。The compositions and results are shown in Tables 1 to 5 below.
[表1]
[表2]
[表3]
[表4]
[表5]
1:第1組合物 1A:第1光硬化物層 1B,1D,1E:第1光及熱硬化物層 2:第2組合物 2A:第2光硬化物層 2B,2D,2E:第2光及熱硬化物層 3:第1基材 4A,4B,4C,4D,4E:積層構造體 5:噴墨用組合物套組 6D:第3光及熱硬化物層 7:第2基材 10:裝置 11:載台 12:第1噴出部 13:第1光照射部 14:第2噴出部 15:第2光照射部 16:第1墨水匣 17,17X:第1循環流路部 17A,19A:緩衝槽 17B,19B:泵 18:第2墨水匣 19,19X:第2循環流路部 60:底部填充材 65:焊料球 70:半導體晶片 80:電子零件 101:第1容器 102:第2容器1: 1st composition 1A: 1st light-curing layer 1B, 1D, 1E: 1st light-curing and heat-curing layer 2: 2nd composition 2A: 2nd light-curing layer 2B, 2D, 2E: 2nd light-curing and heat-curing layer 3: 1st substrate 4A, 4B, 4C, 4D, 4E: laminated structure 5: inkjet composition set 6D: 3rd light-curing and heat-curing layer 7: 2nd substrate 10: device 11: carrier 12: 1st Spraying section 13: 1st light irradiation section 14: 2nd spraying section 15: 2nd light irradiation section 16: 1st ink cartridge 17,17X: 1st circulation flow path section 17A,19A: Buffer tank 17B,19B: Pump 18: 2nd ink cartridge 19,19X: 2nd circulation flow path section 60: Bottom filling material 65: Solder ball 70: Semiconductor chip 80: Electronic component 101: 1st container 102: 2nd container
圖1(a)～(c)係用於對本發明之第1實施方式之積層構造體之製造方法的各步驟進行說明之剖視圖。 圖2(d)～(f)係用於對本發明之第1實施方式之積層構造體之製造方法的各步驟進行說明之剖視圖。 圖3(g)、(h)係用於對本發明之第1實施方式之積層構造體之製造方法的各步驟進行說明之剖視圖。 圖4係用於對本發明之第1實施方式之積層構造體之製造方法的各步驟進行說明之流程圖。 圖5係用於對本發明之第2實施方式之積層構造體之製造方法的各步驟進行說明之流程圖。 圖6係用於對本發明之第2實施方式之積層構造體之製造方法的各步驟進行說明之流程圖。 圖7係利用第2實施方式之積層構造體之製造方法所製造之積層構造體的剖視圖。 圖8係用於對本發明之第3實施方式之積層構造體之製造方法的各步驟進行說明之流程圖。 圖9係用於對本發明之第3實施方式之積層構造體之製造方法的各步驟進行說明之流程圖。 圖10係利用第3實施方式之積層構造體之製造方法所製造之積層構造體的剖視圖。 圖11(a)、(b)係表示圖1～3所示之積層構造體之製造方法中所使用之裝置的一部分之例之概略構成圖。 圖12(a)、(b)係表示圖1～3所示之積層構造體之製造方法中所使用之裝置的其他例之概略構成圖。 圖13係模式性表示本發明之第1實施方式之噴墨用組合物套組之剖視圖。 圖14(a)、(b)係表示使用本發明之第1實施方式之積層構造體而獲得之電子零件的剖視圖。Figures 1(a) to (c) are cross-sectional views for illustrating each step of the method for manufacturing a laminated structure of the first embodiment of the present invention. Figures 2(d) to (f) are cross-sectional views for illustrating each step of the method for manufacturing a laminated structure of the first embodiment of the present invention. Figures 3(g) and (h) are cross-sectional views for illustrating each step of the method for manufacturing a laminated structure of the first embodiment of the present invention. Figure 4 is a flow chart for illustrating each step of the method for manufacturing a laminated structure of the first embodiment of the present invention. FIG. 5 is a flow chart for explaining each step of the method for manufacturing a laminated structure of the second embodiment of the present invention. FIG. 6 is a flow chart for explaining each step of the method for manufacturing a laminated structure of the second embodiment of the present invention. FIG. 7 is a cross-sectional view of a laminated structure manufactured by the method for manufacturing a laminated structure of the second embodiment. FIG. 8 is a flow chart for explaining each step of the method for manufacturing a laminated structure of the third embodiment of the present invention. FIG. 9 is a flow chart for explaining each step of the method for manufacturing a laminated structure of the third embodiment of the present invention. FIG. 10 is a cross-sectional view of a laminated structure manufactured by the method for manufacturing a laminated structure of the third embodiment. FIG. 11 (a) and (b) are schematic structural views showing a part of an example of the device used in the method for manufacturing a laminated structure shown in FIG. 1 to 3. FIG. 12 (a) and (b) are schematic structural views showing other examples of the device used in the method for manufacturing a laminated structure shown in FIG. 1 to 3. FIG. 13 is a schematic cross-sectional view of an inkjet composition kit of the first embodiment of the present invention. FIG. 14 (a) and (b) are cross-sectional views showing an electronic component obtained by using the laminated structure of the first embodiment of the present invention.
Claims (32)
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| TW201623497A (en) * | 2014-11-17 | 2016-07-01 | 積水化學工業股份有限公司 | Inkjet light and thermosetting adhesive, method of manufacturing semiconductor device, and electronic component |
| CN107109139A (en) * | 2015-01-22 | 2017-08-29 | 积水化学工业株式会社 | Adhesive for inkjet, method for manufacturing semiconductor device, and electronic component |
| WO2018143303A1 (en) * | 2017-01-31 | 2018-08-09 | マクセルホールディングス株式会社 | Ink set for stereolithography, stereolithographic article, and method for producing stereolithographic article |
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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 |
| JP6152325B2 (en) * | 2013-09-11 | 2017-06-21 | 株式会社やまびこ | Tightening nut retaining structure and tightening nut anchoring member in portable power work machine |
| JP2015110206A (en) * | 2013-11-06 | 2015-06-18 | 積水化学工業株式会社 | Manufacturing method of curable film |
| WO2015115539A1 (en) | 2014-01-31 | 2015-08-06 | 富士フイルム株式会社 | Green coloring composition for use in color filter, colored film, color filter, and solid-state imaging element |
| JP6122454B2 (en) | 2014-01-31 | 2017-04-26 | 富士フイルム株式会社 | Red coloring composition for color filter, colored film, color filter, solid-state imaging device |
| JP6329102B2 (en) * | 2015-04-17 | 2018-05-23 | 積水化学工業株式会社 | Inkjet composition, method for manufacturing semiconductor device, electronic component, and method for manufacturing electronic component |
| WO2017056663A1 (en) * | 2015-09-30 | 2017-04-06 | 太陽インキ製造株式会社 | Curable composition for inkjet, cured coating film using same and printed wiring board |
| TW201942144A (en) | 2018-03-30 | 2019-11-01 | 日商太陽油墨製造股份有限公司 | Curable composition for inkjet printing, cured product of same, and electronic component having said cured product |
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| TW201623497A (en) * | 2014-11-17 | 2016-07-01 | 積水化學工業股份有限公司 | Inkjet light and thermosetting adhesive, method of manufacturing semiconductor device, and electronic component |
| CN107109139A (en) * | 2015-01-22 | 2017-08-29 | 积水化学工业株式会社 | Adhesive for inkjet, method for manufacturing semiconductor device, and electronic component |
| WO2018143303A1 (en) * | 2017-01-31 | 2018-08-09 | マクセルホールディングス株式会社 | Ink set for stereolithography, stereolithographic article, and method for producing stereolithographic article |
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