TW201925367A - Curable composition - Google Patents

Curable composition Download PDF

Info

Publication number
TW201925367A
TW201925367A TW107132438A TW107132438A TW201925367A TW 201925367 A TW201925367 A TW 201925367A TW 107132438 A TW107132438 A TW 107132438A TW 107132438 A TW107132438 A TW 107132438A TW 201925367 A TW201925367 A TW 201925367A
Authority
TW
Taiwan
Prior art keywords
mass
meth
parts
curable composition
compound
Prior art date
Application number
TW107132438A
Other languages
Chinese (zh)
Other versions
TWI786185B (en
Inventor
安井未央
望月勝紀
花岡秀典
Original Assignee
日商住友化學股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商住友化學股份有限公司 filed Critical 日商住友化學股份有限公司
Publication of TW201925367A publication Critical patent/TW201925367A/en
Application granted granted Critical
Publication of TWI786185B publication Critical patent/TWI786185B/en

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • 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
    • C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Abstract

The present invention provides a curable composition which comprises: a multifunctional (meth) acrylate monomer (A) containing at least two kinds selected from the group consisting of trifunctional (meth) acrylate monomer, tetrafunctional (meth) acrylate monomer and octafunctional (meth) acrylate monomer, and a cationic polymerizable monomer (B), wherein the total mass of the trifunctional (meth) acrylate monomer, the tetrafunctional (meth) acrylate monomer and the octafunctional (meth) acrylate monomer is 50 parts by mass or more based on 100 parts by mass of the polyfunctional (meth) acrylate monomer (A).

Description

硬化性組成物    Hardening composition   

本專利申請案係根據日本國特許出願第2017-178243號(申請日：2017年9月15日)主張巴黎條約上的優先權，並在此藉由參考而將該全體內容納入於本說明書中。 This patent application is based on the Japanese Patent Application No. 2017-178243 (application date: September 15, 2017) to claim priority in the Paris Treaty, and hereby incorporated by reference the entire contents of this specification .

本發明係關於一種可形成作為影像顯示裝置等的前面板使用之積層體之硬化性組成物、使該硬化性組成物硬化而成之硬化膜、以及含有該硬化膜之積層體。 The present invention relates to a curable composition capable of forming a laminate used as a front panel of an image display device, a cured film obtained by curing the curable composition, and a laminate containing the cured film.

液晶顯示裝置或有機EL顯示裝置等影像顯示裝置係被廣泛地活用在行動電話或智慧型手機等各種用途。影像顯示裝置的前面板係使用積層體，該積層體含有使硬化性組成物硬化而成之硬化膜(例如專利文獻1)。 Image display devices such as liquid crystal display devices or organic EL display devices are widely used in various applications such as mobile phones and smart phones. The front panel of the image display device uses a laminate including a cured film obtained by curing the curable composition (for example, Patent Document 1).

[先前技術文獻]     [Prior Technical Literature]     [專利文獻]     [Patent Literature]    

[專利文獻1]日本特開2009-202456號公報 [Patent Document 1] Japanese Unexamined Patent Publication No. 2009-202456

如此之影像顯示裝置的前面板，由於使用者直接接觸或周圍的物體直接接觸，故要求高表面硬度。再者，使用為可撓性顯示器的前面板時，亦要求高彎曲性。然而，根據本發明者的探討，得知先前之影像顯示裝置的前面板無法同時且充分地滿足此等特性。 The front panel of such an image display device requires high surface hardness due to direct contact between the user and surrounding objects. Furthermore, when using the front panel as a flexible display, high flexibility is also required. However, according to the discussion of the inventor, it is known that the front panel of the previous image display device cannot satisfy these characteristics simultaneously and sufficiently.

因此，本發明之目的在於提供一種可形成表面硬度及彎曲性優異之積層體之硬化性組成物、使該硬化性組成物硬化而成之硬化膜、以及含有該硬化膜之積層體。 Therefore, an object of the present invention is to provide a curable composition capable of forming a laminate having excellent surface hardness and flexibility, a cured film obtained by curing the curable composition, and a laminate containing the cured film.

本發明者係為了解決上述課題而進行精心探討，結果發現若於含有包含選自由3官能(甲基)丙烯酸酯單體、4官能(甲基)丙烯酸酯單體及8官能(甲基)丙烯酸酯單體所組成之群組的至少2種之多官能(甲基)丙烯酸酯單體(A)、與陽離子聚合性單體(B)之硬化性組成物中，使3官能(甲基)丙烯酸酯單體、4官能(甲基)丙烯酸酯單體及8官能(甲基)丙烯酸酯單體的總質量為預定量以上時，可解決上述課題，進而完成本發明。亦即，本發明係包含下述者。 The present inventors have made intensive studies in order to solve the above-mentioned problems. As a result, it has been found that if it contains In the curable composition of at least two kinds of multifunctional (meth) acrylate monomers (A) and cationic polymerizable monomers (B) of the group consisting of ester monomers, trifunctional (meth) When the total mass of the acrylate monomer, the 4-functional (meth) acrylate monomer and the 8-functional (meth) acrylate monomer is more than a predetermined amount, the above-mentioned problems can be solved, and the present invention can be further completed. That is, the present invention includes the following.

[1]一種硬化性組成物，其係含有：包含選自由3官能(甲基)丙烯酸酯單體、4官能(甲基)丙烯酸酯單體及8官能(甲基)丙烯酸酯單體所組成之群組的至少2種之多官能(甲基)丙烯酸酯單體(A)，以及陽離子聚合性單體(B)之硬化性組成物，其中，相對於多官能(甲基)丙烯酸酯單體 (A)100質量份，3官能(甲基)丙烯酸酯單體、4官能(甲基)丙烯酸酯單體及8官能(甲基)丙烯酸酯單體的總質量，為50質量份以上。 [1] A curable composition comprising: selected from the group consisting of 3-functional (meth) acrylate monomers, 4-functional (meth) acrylate monomers and 8-functional (meth) acrylate monomers At least two kinds of polyfunctional (meth) acrylate monomers (A) and cationically polymerizable monomers (B) of the group, wherein the polyfunctional (meth) acrylate monomers 100 parts by mass of the body (A), the total mass of the trifunctional (meth) acrylate monomer, the 4-functional (meth) acrylate monomer and the 8-functional (meth) acrylate monomer is 50 parts by mass or more.

[2]如[1]所述之硬化性組成物，其中，陽離子聚合性單體(B)含有具有1個以上環氧基及/或1個以上氧雜環丁烷基之環狀醚化合物(B-1)。 [2] The curable composition according to [1], wherein the cationic polymerizable monomer (B) contains a cyclic ether compound having one or more epoxy groups and / or one or more oxetanyl groups (B-1).

[3]如[2]所述之硬化性組成物，其中，環狀醚化合物(B-1)含有具有2個以上環氧基及/或2個以上氧雜環丁烷基之雙環狀醚化合物(B-1-1)。 [3] The curable composition according to [2], wherein the cyclic ether compound (B-1) contains a bicyclic ring having two or more epoxy groups and / or two or more oxetanyl groups Ether compound (B-1-1).

[4]如[1]至[3]中任一項所述之硬化性組成物，其中，陽離子聚合性單體(B)更含有乙烯氧基化合物(B-2)。 [4] The curable composition according to any one of [1] to [3], wherein the cationic polymerizable monomer (B) further contains an ethyleneoxy compound (B-2).

[5]如[4]所述之硬化性組成物，其中，相對於硬化性組成物100質量份，多官能(甲基)丙烯酸酯單體(A)的含量為5至80質量份，環狀醚化合物(B-1)的含量為5至80質量份，乙烯氧基化合物(B-2)的含量為3至60質量份。 [5] The curable composition as described in [4], wherein the content of the polyfunctional (meth) acrylate monomer (A) is 5 to 80 parts by mass relative to 100 parts by mass of the curable composition, the ring The content of the ether compound (B-1) is 5 to 80 parts by mass, and the content of the vinyloxy compound (B-2) is 3 to 60 parts by mass.

[6]如[4]或[5]所述之硬化性組成物，其中，相對於多官能(甲基)丙烯酸酯單體(A)及陽離子聚合性單體(B)的總量100質量份，乙烯氧基化合物(B-2)的含量為3至50質量份。 [6] The hardenable composition according to [4] or [5], wherein the total amount of the polyfunctional (meth) acrylate monomer (A) and the cationic polymerizable monomer (B) is 100 mass Parts, the content of the vinyloxy compound (B-2) is 3 to 50 parts by mass.

[7]如[2]至[6]中任一項所述之硬化性組成物，其中，環狀醚化合物(B-1)含有具有1個以上自由基聚合性官能基之自由基聚合性環狀醚化合物(B-1-2)。 [7] The curable composition according to any one of [2] to [6], wherein the cyclic ether compound (B-1) contains radical polymerizable having one or more radical polymerizable functional groups Cyclic ether compound (B-1-2).

[8]如[7]所述之硬化性組成物，其中，相對於硬化性組成物100質量份，多官能(甲基)丙烯酸酯單體(A)的含量 為5至50質量份，雙環狀醚化合物(B-1-1)的含量為3至30質量份，自由基聚合性環狀醚化合物(B-1-2)的含量為5至40質量份。 [8] The curable composition as described in [7], wherein the content of the polyfunctional (meth) acrylate monomer (A) is 5 to 50 parts by mass relative to 100 parts by mass of the curable composition. The content of the cyclic ether compound (B-1-1) is 3 to 30 parts by mass, and the content of the radically polymerizable cyclic ether compound (B-1-2) is 5 to 40 parts by mass.

[9]如[7]或[8]所述之硬化性組成物，其中，相對於雙環狀醚化合物(B-1-1)1質量份，自由基聚合性環狀醚化合物(B-1-2)的含量為0.1至10質量份。 [9] The curable composition according to [7] or [8], wherein the radically polymerizable cyclic ether compound (B-) is 1 part by mass of the bicyclic ether compound (B-1-1) The content of 1-2) is 0.1 to 10 parts by mass.

[10]如[1]至[9]中任一項所述之硬化性組成物，其更含有自由基聚合起始劑(C)及陽離子聚合起始劑(D)。 [10] The hardenable composition according to any one of [1] to [9], further comprising a radical polymerization initiator (C) and a cationic polymerization initiator (D).

[11]如[10]所述之硬化性組成物，其中，相對於多官能(甲基)丙烯酸酯單體(A)100質量份，自由基聚合起始劑(C)的含量為1至15質量份；相對於陽離子聚合性單體(B)100質量份，陽離子聚合起始劑(D)的含量為1至15質量份。 [11] The curable composition according to [10], wherein the content of the radical polymerization initiator (C) is 1 to 100 parts by mass of the polyfunctional (meth) acrylate monomer (A) 15 parts by mass; the content of the cationic polymerization initiator (D) is 1 to 15 parts by mass relative to 100 parts by mass of the cationic polymerizable monomer (B).

[12]如[1]至[11]中任一項所述之硬化性組成物，其更含有無機粒子。 [12] The curable composition according to any one of [1] to [11], which further contains inorganic particles.

[13]如[12]所述之硬化性組成物，其中，無機粒子為反應性氧化矽粒子時，相對於硬化性組成物的質量，反應性氧化矽粒子的含量為1至70質量%。 [13] The curable composition according to [12], wherein when the inorganic particles are reactive silica particles, the content of the reactive silica particles is 1 to 70% by mass relative to the mass of the curable composition.

[14]一種硬化膜，其係使[1]至[13]中任一項所述之硬化性組成物硬化而成者。 [14] A cured film obtained by curing the curable composition according to any one of [1] to [13].

[15]一種積層體，其係於基材膜之至少一面積層有[14]所述之硬化膜。 [15] A laminate having a cured film as described in [14] on at least one area layer of a base film.

[16]如[15]所述之積層體，其中，基材膜係含有聚醯亞胺系高分子而成者。 [16] The laminate according to [15], wherein the base film contains a polyimide-based polymer.

[17]如[15]或[16]所述之積層體，其中，氧穿透度為800cc/(m2‧24h‧atm)以下。 [17] The laminate according to [15] or [16], wherein the oxygen permeability is 800 cc / (m 2 ‧24h‧atm) or less.

[18]一種可撓性顯示器，其係包含[15]至[17]中任一項所述之積層體。 [18] A flexible display comprising the laminate according to any one of [15] to [17].

本發明之硬化性組成物可形成表面硬度及彎曲性優異之積層體。 The curable composition of the present invention can form a laminate having excellent surface hardness and flexibility.

[1]硬化性組成物 [1] Hardening composition

本發明之硬化性組成物係含有多官能(甲基)丙烯酸酯單體(A)與陽離子聚合性單體(B)。 The curable composition of the present invention contains a polyfunctional (meth) acrylate monomer (A) and a cationic polymerizable monomer (B).

(1)多官能(甲基)丙烯酸酯單體(A) (1) Multifunctional (meth) acrylate monomer (A)

所謂多官能(甲基)丙烯酸酯單體(A)，意指於分子內具有2個以上(甲基)丙烯醯氧基之化合物，本發明之多官能(甲基)丙烯酸酯單體(A)包含選自由3官能(甲基)丙烯酸酯單體、4官能(甲基)丙烯酸酯單體及8官能(甲基)丙烯酸酯單體所組成之群組的至少2種。此外，本說明書中，用語「(甲基)丙烯酸酯」意指「丙烯酸酯」或「甲基丙烯酸酯」，用語「(甲基)丙烯醯基」亦同樣意指「丙烯醯基」或「甲基丙烯醯基」。 The so-called multifunctional (meth) acrylate monomer (A) means a compound having two or more (meth) acryloyloxy groups in the molecule. The multifunctional (meth) acrylate monomer (A) of the present invention ) Contains at least two kinds selected from the group consisting of 3-functional (meth) acrylate monomers, 4-functional (meth) acrylate monomers, and 8-functional (meth) acrylate monomers. In addition, in this specification, the term "(meth) acrylate" means "acrylate" or "methacrylate", and the term "(meth) acryloyl" also means "acryloyl" or "methacrylate" "Methacrylic acid".

3官能(甲基)丙烯酸酯單體為於分子內具有3個(甲基)丙烯醯氧基之單體，該例子可列舉：三(甲基) 丙烯酸甘油酯、三(甲基)丙烯酸三羥甲基丙烷酯、三(甲基)丙烯酸二(三羥甲基)丙烷酯、三(甲基)丙烯酸新戊四醇酯、三(甲基)丙烯酸新戊四醇酯與酸酐之反應物、經己內酯改質之三(甲基)丙烯酸三羥甲基丙烷酯、經己內酯改質之三(甲基)丙烯酸新戊四醇酯、異三聚氰酸三(甲基)丙烯酸酯、經己內酯改質之三(甲基)丙烯酸新戊四醇酯與酸酐之反應物等。此等當中，從具有使硬化性組成物硬化而成之硬化膜之積層體(有僅稱為積層體之情形)的表面硬度、彎曲性、氧阻隔性及耐翹曲性之觀點而言，較佳為三(甲基)丙烯酸三羥甲基丙烷酯。此等3官能(甲基)丙烯酸酯單體可單獨使用或組合兩種以上使用。 The trifunctional (meth) acrylate monomer is a monomer having three (meth) acryloyloxy groups in the molecule. Examples of this include triglyceride (meth) acrylate and tri (meth) acrylate. Reaction products of methylolpropane ester, di (trimethylol) propane tri (meth) acrylate, neopentyl tri (meth) acrylate, neopentyl tri (meth) acrylate and anhydride , Trimethylolpropane tri (meth) acrylate modified with caprolactone, Neopentaerythritol tri (meth) acrylate modified with caprolactone, Tri (methyl) isocyanurate Acrylic ester, reactant of caprolactone-modified tripentyl (meth) acrylate and acid anhydride, etc. Among these, from the viewpoint of the surface hardness, bendability, oxygen barrier properties, and warpage resistance of a laminate having a cured film obtained by curing a curable composition (sometimes referred to as a laminate only), Trimethylolpropane tri (meth) acrylate is preferred. These trifunctional (meth) acrylate monomers can be used alone or in combination of two or more.

本說明書中，所謂表面硬度，表示本發明之積層體中之硬化膜側的表面硬度。所謂彎曲性，意指彎曲本發明之積層體時可抑制龜裂等的產生之特性。所謂氧阻隔性，意指不容易使氧穿透之特性，氧阻隔性愈高表示氧穿透性或氧穿透度愈低。所謂耐翹曲性，意指不易引起翹曲之特性，耐翹曲性愈高表示愈不易引起翹曲。 In this specification, the surface hardness means the surface hardness on the cured film side in the laminate of the present invention. The bendability means a characteristic that can suppress the occurrence of cracks and the like when bending the laminate of the present invention. The so-called oxygen barrier refers to the characteristic that it is not easy for oxygen to penetrate. The higher the oxygen barrier, the lower the oxygen permeability or oxygen permeability. The term “warpage resistance” means a characteristic that warpage is hard to cause. The higher the warpage resistance, the less likely it is to cause warpage.

4官能(甲基)丙烯酸酯單體為於分子內具有4個(甲基)丙烯醯氧基之單體，該例子可列舉：四(甲基)丙烯酸二(三羥甲基)丙烷酯、四(甲基)丙烯酸新戊四醇酯、四(甲基)丙烯酸二新戊四醇酯、四(甲基)丙烯酸三新戊四醇酯、經己內酯改質之四(甲基)丙烯酸新戊四醇酯、經己內酯改質之四(甲基)丙烯酸三新戊四醇酯等。此等當中，從積層體的表面硬度、彎曲性、氧阻隔性及耐翹曲性之觀點 而言，較佳為四(甲基)丙烯酸新戊四醇酯。此等4官能(甲基)丙烯酸酯單體可單獨使用或組合兩種以上使用。 The 4-functional (meth) acrylate monomer is a monomer having four (meth) acryloyloxy groups in the molecule. Examples of this include di (trimethylol) propane tetra (meth) acrylate, Neopentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tetra (methyl) modified with caprolactone Neopentaerythritol acrylate, tripentaerythritol tetra (meth) acrylate modified with caprolactone, etc. Among these, from the viewpoint of the surface hardness, bendability, oxygen barrier properties, and warpage resistance of the laminate, neopentyl tetramethacrylate is preferred. These four functional (meth) acrylate monomers can be used alone or in combination of two or more.

8官能(甲基)丙烯酸酯單體為於分子內具有8個(甲基)丙烯醯氧基之單體，該例子可列舉：八(甲基)丙烯酸三新戊四醇酯、經己內酯改質之八(甲基)丙烯酸三新戊四醇酯等。此等當中，從積層體的表面硬度、彎曲性及氧阻隔性之觀點而言，較佳為(甲基)丙烯酸三新戊四醇酯。此等8官能(甲基)丙烯酸酯單體可單獨使用或組合兩種以上使用。 The 8-functional (meth) acrylate monomer is a monomer having 8 (meth) acryloyloxy groups in the molecule. This example may include: tripentaerythritol octa (meth) acrylate, via caprolactone Ester-modified octamethacrylate (tri-pentaerythritol), etc. Among these, from the viewpoint of the surface hardness, bendability, and oxygen barrier properties of the laminate, tripentaerythritol (meth) acrylate is preferred. These 8-functional (meth) acrylate monomers can be used alone or in combination of two or more.

本發明之硬化性組成物，由於包含選自由3官能(甲基)丙烯酸酯單體、4官能(甲基)丙烯酸酯單體及8官能(甲基)丙烯酸酯單體所組成之群組的至少2種，且相對於多官能(甲基)丙烯酸酯單體(A)100質量份，3官能(甲基)丙烯酸酯單體、4官能(甲基)丙烯酸酯單體及8官能(甲基)丙烯酸酯單體的總質量為50質量份以上，所以可形成表面硬度及彎曲性優異之積層體。再者，本發明之硬化性組成物亦可更形成氧阻隔性及耐翹曲性優異之積層體。本發明之硬化性組成物100質量份中之3官能(甲基)丙烯酸酯單體、4官能(甲基)丙烯酸酯單體及8官能(甲基)丙烯酸酯單體的總質量，較佳為60質量份以上，尤佳為70質量份以上，更佳為80質量份以上，特佳為90質量份以上，最佳為100質量份。當3官能(甲基)丙烯酸酯單體、4官能(甲基)丙烯酸酯單體及8官能(甲基)丙烯酸酯單體的總質量為上述範圍時，可進一步提升積層體的表面硬度、彎曲 性、氧阻隔性及耐翹曲性。 The curable composition of the present invention includes a group selected from the group consisting of 3-functional (meth) acrylate monomers, 4-functional (meth) acrylate monomers, and 8-functional (meth) acrylate monomers. At least two kinds, and with respect to 100 parts by mass of the multifunctional (meth) acrylate monomer (A), a trifunctional (meth) acrylate monomer, a 4-functional (meth) acrylate monomer, and an 8-functional (meth) (Group) The total mass of the acrylate monomer is 50 parts by mass or more, so a laminate having excellent surface hardness and flexibility can be formed. Furthermore, the curable composition of the present invention can further form a laminate having excellent oxygen barrier properties and warpage resistance. The total mass of the 3-functional (meth) acrylate monomer, 4-functional (meth) acrylate monomer and 8-functional (meth) acrylate monomer in 100 parts by mass of the curable composition of the present invention is preferably It is 60 parts by mass or more, particularly preferably 70 parts by mass or more, more preferably 80 parts by mass or more, particularly preferably 90 parts by mass or more, and most preferably 100 parts by mass. When the total mass of the 3-functional (meth) acrylate monomer, 4-functional (meth) acrylate monomer and 8-functional (meth) acrylate monomer is within the above range, the surface hardness of the laminate can be further improved, Flexibility, oxygen barrier and warpage resistance.

本發明之較佳的一樣態中，本發明之硬化性組成物中的多官能(甲基)丙烯酸酯單體是由3官能(甲基)丙烯酸酯單體及4官能(甲基)丙烯酸酯單體所構成。當組合3官能(甲基)丙烯酸酯單體及4官能(甲基)丙烯酸酯單體時，從表面硬度、彎曲性、氧阻隔性及耐翹曲性之觀點而言較多情況為有利。此外，含有8官能(甲基)丙烯酸酯單體時，從彎曲性之觀點而言有有利之情形。 In a preferred state of the invention, the multifunctional (meth) acrylate monomer in the curable composition of the invention is composed of a trifunctional (meth) acrylate monomer and a 4-functional (meth) acrylate Consist of monomers. When a trifunctional (meth) acrylate monomer and a tetrafunctional (meth) acrylate monomer are combined, it is often advantageous from the viewpoint of surface hardness, flexibility, oxygen barrier properties, and warpage resistance. In addition, when an 8-functional (meth) acrylate monomer is contained, it is advantageous from the viewpoint of flexibility.

相對於3官能(甲基)丙烯酸酯單體1質量份，4官能(甲基)丙烯酸酯單體的含量較佳為0.5至5質量份，尤佳為1至3質量份。4官能(甲基)丙烯酸酯單體的含量為上述範圍時，容易提升積層體的表面硬度、彎曲性、氧阻隔性及耐翹曲性。 The content of the tetrafunctional (meth) acrylate monomer is preferably 0.5 to 5 parts by mass, and particularly preferably 1 to 3 parts by mass relative to 1 part by mass of the trifunctional (meth) acrylate monomer. When the content of the tetrafunctional (meth) acrylate monomer is within the above range, the surface hardness, bendability, oxygen barrier properties, and warpage resistance of the laminate are easily improved.

多官能(甲基)丙烯酸酯單體(A)可含有3官能(甲基)丙烯酸酯單體、4官能(甲基)丙烯酸酯單體及8官能(甲基)丙烯酸酯單體以外的其他(甲基)丙烯酸酯單體。其他(甲基)丙烯酸酯單體的種類並無特別限定，該例子可列舉：2官能(甲基)丙烯酸酯單體、5官能(甲基)丙烯酸酯單體、6官能(甲基)丙烯酸酯單體、7官能(甲基)丙烯酸酯單體等。 Multifunctional (meth) acrylate monomer (A) may contain other than trifunctional (meth) acrylate monomer, 4-functional (meth) acrylate monomer and 8-functional (meth) acrylate monomer (Meth) acrylate monomer. The type of other (meth) acrylate monomers is not particularly limited, and examples include bifunctional (meth) acrylate monomers, 5-functional (meth) acrylate monomers, and 6-functional (meth) acrylic acid. Ester monomers, 7-functional (meth) acrylate monomers, etc.

2官能(甲基)丙烯酸酯單體例如可列舉：二(甲基)丙烯酸乙二醇酯、二(甲基)丙烯酸1,3-丁二醇酯、二(甲基)丙烯酸1,4-丁二醇酯、二(甲基)丙烯酸1,6-己二醇酯、二(甲基)丙烯酸1,9-壬二醇酯及二(甲基)丙烯酸新戊二 醇酯等二(甲基)丙烯酸烷二醇酯；二(甲基)丙烯酸二乙二醇酯、二(甲基)丙烯酸三乙二醇酯、二(甲基)丙烯酸二丙二醇酯、二(甲基)丙烯酸三丙二醇酯、二(甲基)丙烯酸聚乙二醇酯、二(甲基)丙烯酸聚丙二醇酯及二(甲基)丙烯酸聚四亞甲基二醇酯等二(甲基)丙烯酸聚氧烷二醇酯；二(甲基)丙烯酸四氟乙二醇酯等二(甲基)丙烯酸經鹵素取代烷二醇酯；二(甲基)丙烯酸三羥甲基丙烷酯、二(甲基)丙烯酸二(三羥甲基)丙烷酯、二(甲基)丙烯酸新戊四醇酯等二(甲基)丙烯酸脂肪族多元醇酯；二(甲基)丙烯酸氫化二環戊二烯酯、二(甲基)丙烯酸三環癸烷二甲醇酯等氫化二環戊二烯或三環癸烷二烷醇的二(甲基)丙烯酸酯；二(甲基)丙烯酸1,3-二噁烷-2,5-二基酯[別名：二(甲基)丙烯酸二噁烷二醇酯]等二噁烷二醇或二噁烷二烷醇的二(甲基)丙烯酸酯；雙酚A環氧乙烷加成物二丙烯酸酯之物、雙酚F環氧乙烷加成物二丙烯酸酯之物等雙酚A或雙酚F的環氧烷加成物的二(甲基)丙烯酸酯；雙酚A二縮水甘油醚的丙烯酸加成物、雙酚F二縮水甘油醚的丙烯酸加成物等之雙酚A或雙酚F的二(甲基)丙烯酸環氧酯；二(甲基)丙烯酸聚矽氧酯；羥基三甲基乙酸新戊二醇酯的二(甲基)丙烯酸酯；2,2-雙[4-(甲基)丙烯醯氧基乙氧基乙氧基苯基]丙烷；2,2-雙[4-(甲基)丙烯醯氧基乙氧基乙氧基環己基]丙烷；2-(2-羥基-1,1-二甲基乙基)-5-乙基-5-羥基乙基-1,3-二噁烷]的二(甲基)丙烯酸酯；二(甲基)丙烯酸三(羥基乙基)異三聚氰酸酯等。此等2官能(甲基)丙烯酸酯單體可單獨使用或組合兩種以上使 用。 Examples of bifunctional (meth) acrylate monomers include ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, and 1,4-di (meth) acrylate. Butylene glycol ester, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate, etc. Group) alkyl glycol acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate Polyoxyalkylene glycols such as esters, polyethylene glycol di (meth) acrylates, polypropylene glycol di (meth) acrylates and polytetramethylene glycol di (meth) acrylates Ester; di (meth) acrylic acid tetrafluoroethylene glycol ester and other di (meth) acrylic acid halogen substituted alkyl glycol ester; di (meth) acrylic acid trimethylolpropane, di (meth) acrylic acid Dimethyl (meth) acrylate aliphatic polyol esters such as trimethylol) propane ester, neopentyl tetra (meth) acrylate; hydrogenated dicyclopentadienyl di (meth) acrylate, di (methyl) ) Hydrogenation of tricyclodecane dimethacrylate and the like Di (meth) acrylate of cyclopentadiene or tricyclodecanediokanol; 1,3-dioxane-2,5-diyl di (meth) acrylate [alias: di (methyl) Dioxanediol acrylate] di (meth) acrylates of dioxanediol or dioxanediokanol; bisphenol A ethylene oxide adduct diacrylate, bisphenol F ring Ethylene oxide adducts diacrylates and other di (meth) acrylates of alkylene oxide adducts of bisphenol A or bisphenol F; acrylic adducts of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether acrylic adducts such as bisphenol A or bisphenol F epoxy (meth) acrylate; di (meth) acrylate polysiloxane; hydroxy trimethyl acetate neopentyl glycol Di (meth) acrylates of esters; 2,2-bis [4- (meth) acryloyl ethoxyethoxyethoxyphenyl] propane; 2,2-bis [4- (meth) acrylic Acetyloxyethoxyethoxycyclohexyl] propane; 2- (2-hydroxy-1,1-dimethylethyl) -5-ethyl-5-hydroxyethyl-1,3-dioxane ] Di (meth) acrylate; di (meth) acrylate tri (hydroxyethyl) isocyanurate and so on. These bifunctional (meth) acrylate monomers can be used alone or in combination of two or more.

5官能(甲基)丙烯酸酯單體可列舉例如：五(甲基)丙烯酸二新戊四醇酯、五(甲基)丙烯酸三新戊四醇酯、五(甲基)丙烯酸二新戊四醇酯與酸酐之反應物、經己內酯改質之五(甲基)丙烯酸二新戊四醇酯、經己內酯改質之五(甲基)丙烯酸三新戊四醇酯、經己內酯改質之五(甲基)丙烯酸二新戊四醇酯與酸酐之反應物等。此等5官能(甲基)丙烯酸酯單體可單獨使用或組合兩種以上使用。 Examples of 5-functional (meth) acrylate monomers include dipentaerythritol penta (meth) acrylate, tripentaerythritol penta (meth) acrylate, and dipentaerythritol penta (meth) acrylate. The reactant of alcohol ester and anhydride, dipentaerythritol penta (meth) acrylate modified with caprolactone, tripentaerythritol penta (meth) acrylate modified with caprolactone, The reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride modified by lactone. These 5-functional (meth) acrylate monomers can be used alone or in combination of two or more.

6官能(甲基)丙烯酸酯單體例如可列舉：六(甲基)丙烯酸二新戊四醇酯、六(甲基)丙烯酸三新戊四醇酯、經己內酯改質六(甲基)丙烯酸二新戊四醇酯、經己內酯改質六(甲基)丙烯酸三新戊四醇酯等。此等6官能(甲基)丙烯酸酯單體可單獨使用或組合兩種以上使用。 Examples of 6-functional (meth) acrylate monomers include dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, and hexa (methyl) modified with caprolactone ) Dipentaerythritol acrylate, Tripentaerythritol hexa (meth) acrylate modified with caprolactone, etc. These 6-functional (meth) acrylate monomers can be used alone or in combination of two or more.

7官能(甲基)丙烯酸酯單體例如可列舉：七(甲基)丙烯酸三新戊四醇酯、七(甲基)丙烯酸三新戊四醇酯與酸酐之反應物、經己內酯改質之七(甲基)丙烯酸三新戊四醇酯、經己內酯改質之七(甲基)丙烯酸三新戊四醇酯與酸酐之反應物等。此等7官能(甲基)丙烯酸酯單體可單獨使用或組合兩種以上使用。 Examples of 7-functional (meth) acrylate monomers include: tripentaerythritol hepta (meth) acrylate, the reaction product of tripentaerythritol hepta (meth) acrylate with acid anhydride, modified by caprolactone It is the reaction product of tri-pentaerythritol (meth) acrylate and caprolactone-modified tri-pentaerythritol (meth) acrylate and acid anhydride. These 7-functional (meth) acrylate monomers can be used alone or in combination of two or more.

本發明之硬化性組成物含有陽離子聚合性單體(B)。所謂陽離子聚合性單體(B)，意指於分子內具有陽離子聚合性基之化合物。從積層體的表面硬度、彎曲性、氧阻隔性及耐翹曲性之觀點而言，陽離子聚合性單體(B)較佳係含有選自具有1個以上環氧基及/或1個以上氧雜環 丁烷基之環狀醚化合物(B-1)以及乙烯氧基化合物(B-2)的至少1種。 The curable composition of the present invention contains a cationic polymerizable monomer (B). The so-called cationic polymerizable monomer (B) means a compound having a cationic polymerizable group in the molecule. From the viewpoint of the surface hardness, flexibility, oxygen barrier properties, and warpage resistance of the laminate, the cationic polymerizable monomer (B) preferably contains at least one epoxy group and / or one or more At least one kind of oxetanyl cyclic ether compound (B-1) and ethyleneoxy compound (B-2).

(I)環狀醚化合物(B-1) (I) cyclic ether compound (B-1)

環狀醚化合物(B-1)可列舉例如：於分子內具有1個以上環氧基之環氧化合物[稱為環氧化合物(b)]，於分子內具有1個以上氧雜環丁烷基之氧雜環丁烷化合物[稱為氧雜環丁烷化合物(b)]，具有1個以上自由基聚合性官能基之自由基聚合性環狀醚化合物(B-1-2)等。環氧化合物(b)、氧雜環丁烷化合物(b)及自由基聚合性環狀醚化合物(B-1-2)可單獨使用或組合兩種以上使用。 Examples of the cyclic ether compound (B-1) include: an epoxy compound having one or more epoxy groups in the molecule [referred to as an epoxy compound (b)], and one or more oxetanes in the molecule An oxetane compound [referred to as an oxetane compound (b)], a radically polymerizable cyclic ether compound (B-1-2), etc. having one or more radically polymerizable functional groups. The epoxy compound (b), the oxetane compound (b), and the radical polymerizable cyclic ether compound (B-1-2) can be used alone or in combination of two or more.

環氧化合物(b)中的環氧基較佳為無取代或經碳數6以下，較佳為3以下的烴基修飾後之基，尤佳為無取代。環氧化合物(b)較佳係使用脂肪族環氧化合物(b1)、脂環式環氧化合物(b2)、芳香族環氧化合物(b3)。此等環氧化合物(b)可單獨使用或組合兩種以上使用。 The epoxy group in the epoxy compound (b) is preferably unsubstituted or modified with a hydrocarbon group having a carbon number of 6 or less, preferably 3 or less, and particularly preferably unsubstituted. The epoxy compound (b) preferably uses an aliphatic epoxy compound (b1), an alicyclic epoxy compound (b2), and an aromatic epoxy compound (b3). These epoxy compounds (b) can be used alone or in combination of two or more.

脂肪族環氧化合物(b1)為於分子內具有至少1個以上，較佳為至少2個以上之與脂肪族碳原子鍵結之環氧基之化合物。脂肪族環氧化合物(b1)可列舉例如：1,4-丁二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、環己烷二甲醇二縮水甘油醚、新戊二醇二縮水甘油醚等2官能環氧化合物；三羥甲基丙烷三縮水甘油醚、新戊四醇四縮水甘油醚等3官能以上的環氧化合物等。此等當中，較佳為1,4-丁二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、新戊二醇二縮水甘油醚等於分子內具有2個與脂肪族碳原 子鍵結之環氧基之2官能的環氧化合物(脂肪族二環氧化合物)。此等脂肪族環氧化合物(b1)可單獨使用或組合兩種以上使用。 The aliphatic epoxy compound (b1) is a compound having at least one, preferably at least two, epoxy groups bonded to an aliphatic carbon atom in the molecule. Examples of the aliphatic epoxy compound (b1) include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, and neopentyl glycol Difunctional glycidyl ether and other bifunctional epoxy compounds; trimethylolpropane triglycidyl ether, neopentyl alcohol tetraglycidyl ether and other trifunctional epoxy compounds. Among these, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl glycol diglycidyl ether are equivalent to having 2 aliphatic carbon atoms in the molecule. Bifunctional epoxy compound (aliphatic diepoxy compound) of bonded epoxy group. These aliphatic epoxy compounds (b1) can be used alone or in combination of two or more.

脂環式環氧化合物(b2)為於分子內具有至少1個以上與脂環式環鍵結之環氧基之化合物，較佳為於分子內具有2個以上環氧基之化合物，尤佳為於分子內具有2個環氧基之化合物(脂環式二環氧化合物(b2))。所謂「與脂環式環鍵結之環氧基」，意指於式(a)所表示之結構中交聯的氧原子-O-： 式(a)中，m為2至5的整數。 The alicyclic epoxy compound (b2) is a compound having at least one epoxy group bonded to the alicyclic ring in the molecule, preferably a compound having more than two epoxy groups in the molecule, particularly preferably It is a compound having two epoxy groups in its molecule (alicyclic diepoxy compound (b2)). The so-called "epoxy group bonded to an alicyclic ring" means an oxygen atom -O- crosslinked in the structure represented by formula (a): In formula (a), m is an integer of 2 to 5.

式(a)中，2個以上形態為扣除(CH2)m中的1個或複數個氫原子之基與其他化學結構鍵結而成之化合物，可成為脂環式環氧化合物(b2)。(CH2)m中的1個或複數個氫原子可藉由甲基或乙基等直鏈狀烷基適當地取代。 In formula (a), two or more forms are compounds obtained by deducting one or more hydrogen atoms in (CH 2 ) m and other chemical structures, which can become alicyclic epoxy compounds (b2) . One or a plurality of hydrogen atoms in (CH 2 ) m may be appropriately substituted by a linear alkyl group such as methyl or ethyl.

此等當中，較佳為具有環氧基環戊烷結構[式(a)中m=3者]或環氧基環己烷結構[式(a)中m=4者]之脂環式環氧化合物。 Among these, an alicyclic ring having an epoxycyclopentane structure [m = 3 in formula (a)] or an epoxycyclohexane structure [m = 4 in formula (a)] is preferred Oxygen compounds.

脂環式環氧化合物(b2)可列舉例如：3,4-環氧基環己烷羧酸3,4-環氧基環己基甲基酯、3,4-環氧基-6-甲基環己烷羧酸3,4-環氧基-6-甲基環己基甲酯、乙烯雙(3,4-環氧基環己烷羧酸酯)、雙(3,4-環氧基環己基甲基)己二酸酯、雙(3,4-環氧基-6-甲基環己基甲基)己二酸酯、二 乙二醇雙(3,4-環氧基環己基甲醚)、乙二醇雙(3,4-環氧基環己基甲醚)等。此等當中，從積層體的表面硬度、彎曲性、氧阻隔性及耐翹曲性之觀點而言，尤佳為3,4-環氧基環己烷羧酸3,4-環氧基環己基甲基酯。脂環式環氧化合物(b2)可單獨使用或組合兩種以上使用。 Examples of the alicyclic epoxy compound (b2) include 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl ester, 3,4-epoxy-6-methyl Cyclohexanecarboxylic acid 3,4-epoxy-6-methylcyclohexyl methyl ester, ethylene bis (3,4-epoxycyclohexane carboxylate), bis (3,4-epoxy ring Hexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, diethylene glycol bis (3,4-epoxycyclohexyl methyl ether ), Ethylene glycol bis (3,4-epoxycyclohexyl methyl ether), etc. Among these, 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxy ring is particularly preferred from the viewpoint of surface hardness, bendability, oxygen barrier properties and warpage resistance of the laminate Hexyl methyl ester. The alicyclic epoxy compound (b2) can be used alone or in combination of two or more.

芳香族環氧化合物(b3)可列舉例如：酚、甲酚、丁酚等具有至少1個芳香環之1元酚或是該環氧烷加成物的單/聚縮水甘油醚化物，例如雙酚A、雙酚F或進一步於此等加成有環氧烷之化合物的縮水甘油醚化物或環氧酚醛樹脂；間苯二酚(resorcinol)或對苯二酚(hydroquinone)、鄰苯二酚(catechol)等具有2個以上的酚性羥基之芳香族化合物的縮水甘油醚；苯二甲醇或苯二乙醇、苯二丁醇等具有2個以上醇性羥基之芳香族化合物的單/聚縮水甘油醚化物；鄰苯二甲酸、對苯二甲酸、偏苯三甲酸等具有2個以上羧酸之多質子酸芳香族化合物的縮水甘油酯；苯甲酸或甲苯酸、萘甲酸(naphthoic acid)等苯甲酸類的縮水甘油酯；氧化苯乙烯或二乙烯基苯的環氧化物等。此等芳香族環氧化合物(b3)可單獨使用或組合兩種以上使用。 Examples of the aromatic epoxy compound (b3) include monohydric phenols having at least one aromatic ring, such as phenol, cresol, and butylphenol, or mono / polyglycidyl etherate of the alkylene oxide adduct, for example, bis Phenol A, bisphenol F, or glycidyl etherate or epoxy novolak resin of compounds added with alkylene oxide; resorcinol or hydroquinone, catechol (Catechol) and other glycidyl ethers of aromatic compounds with two or more phenolic hydroxyl groups; mono / poly-shrinkage of aromatic compounds with two or more alcoholic hydroxyl groups such as benzenedimethanol, benzenediethanol, and benzenedibutanol Glycerol etherate; glycidyl esters of polyprotic acid aromatic compounds with two or more carboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid, etc .; benzoic acid or toluic acid, naphthoic acid, etc. Glycidyl benzoates; epoxides of styrene oxide or divinylbenzene. These aromatic epoxy compounds (b3) can be used alone or in combination of two or more.

環氧化合物(b)中，較佳為脂肪族環氧化合物(b1)，含有脂肪族環氧化合物(b1)時，從積層體的表面硬度、彎曲性、氧阻隔性及耐翹曲性之點而言為有利。 Among the epoxy compounds (b), the aliphatic epoxy compound (b1) is preferred. When the aliphatic epoxy compound (b1) is contained, from the surface hardness, flexibility, oxygen barrier properties and warpage resistance of the laminate Point of view is advantageous.

氧雜環丁烷化合物(b)中的氧雜環丁烷基較佳為無取代或經碳數6以下，較佳為1至3的烴基修飾後 之基，尤佳為經1至3的烴基修飾後之基。 The oxetane group in the oxetane compound (b) is preferably unsubstituted or modified with a hydrocarbon group having a carbon number of 6 or less, preferably 1 to 3, particularly preferably 1 to 3. Hydrocarbyl modified base.

氧雜環丁烷化合物(b)可列舉例如：3-乙基-3-羥基甲基氧雜環丁烷(有稱為氧雜環丁烷醇之情形)、2-乙基己基氧雜環丁烷、1,4-雙[{3-乙基氧雜環丁烷-3-基}甲氧基]甲基]苯(有稱為二甲苯雙氧雜環丁烷之情形)、3-乙基-3-(苯氧基甲基)氧雜環丁烷、3-(環己氧基)甲基-3-乙基氧雜環丁烷之單官能氧雜環丁烷化合物；3-乙基-3[{(3-乙基氧雜環丁烷-3-基)甲氧基}甲基]氧雜環丁烷、二甲苯雙氧雜環丁烷、二甲苯雙氧雜環丁烷的混合物(例如二甲苯骨架的重複單元數為1、2或3之二甲苯雙氧雜環丁烷的混合物)等之2官能氧雜環丁烷化合物等。此等氧雜環丁烷化合物(b)中，從表面硬度、彎曲性、氧阻隔性及耐翹曲性之觀點而言，較佳為2官能的氧雜環丁烷化合物，尤佳為3-乙基-3[{(3-乙基氧雜環丁烷-3-基)甲氧基}甲基]氧雜環丁烷、二甲苯雙氧雜環丁烷或二甲苯雙氧雜環丁烷的混合物等。此等氧雜環丁烷化合物(b)可單獨使用或組合兩種以上使用。 Examples of the oxetane compound (b) include 3-ethyl-3-hydroxymethyloxetane (in the case of oxetane alcohol), 2-ethylhexyloxane Butane, 1,4-bis [{3-ethyloxetane-3-yl} methoxy] methyl] benzene (sometimes called xylene dioxetane), 3- Monofunctional oxetane compounds of ethyl-3- (phenoxymethyl) oxetane, 3- (cyclohexyloxy) methyl-3-ethyloxetane; 3- Ethyl-3 [{(3-ethyloxetane-3-yl) methoxy} methyl] oxetane, xylene dioxetane, xylene dioxetane A bifunctional oxetane compound such as a mixture of alkane (for example, a mixture of xylene dioxetane having a repeating unit number of xylene skeleton of 1, 2, or 3). Among these oxetane compounds (b), from the viewpoint of surface hardness, flexibility, oxygen barrier properties, and warpage resistance, a bifunctional oxetane compound is preferred, and 3 is particularly preferred. -Ethyl-3 [{(3-ethyloxetane-3-yl) methoxy} methyl] oxetane, xylene dioxetane or xylene dioxetane Butane mixture etc. These oxetane compounds (b) may be used alone or in combination of two or more.

自由基聚合性環狀醚化合物(B-1-2)係於分子內具有1個以上自由基聚合性官能基。自由基聚合性官能基可列舉例如乙烯基、(甲基)丙烯醯基等，較佳為(甲基)丙烯醯基，尤佳為甲基丙烯醯基。自由基聚合性環狀醚化合物，可為具有自由基聚合性官能基之環氧化合物、具有自由基聚合性官能基之氧雜環丁烷化合物等，較佳為具有自由基聚合性官能基之環氧化合物。具有自由基聚合性官 能基之環氧化合物可為脂環式、脂肪族、芳香族中任一種，特佳為脂環式。由於自由基聚合性環狀醚化合物(B-1-2)具有自由基聚合性基與陽離子聚合性基(例如環氧基、氧雜環丁烷基等)，所以可產生自由基聚合與陽離子聚合兩者。 The radical polymerizable cyclic ether compound (B-1-2) has one or more radical polymerizable functional groups in the molecule. Examples of the radical polymerizable functional group include a vinyl group and a (meth) acryloyl group, preferably a (meth) acryloyl group, and particularly preferably a methacryloyl group. The radically polymerizable cyclic ether compound may be an epoxy compound having a radically polymerizable functional group, an oxetane compound having a radically polymerizable functional group, etc., preferably a radically polymerizable functional group Epoxy compounds. The epoxy compound having a radically polymerizable functional group may be any of alicyclic, aliphatic, and aromatic, particularly preferably alicyclic. Since the radically polymerizable cyclic ether compound (B-1-2) has a radically polymerizable group and a cationically polymerizable group (such as epoxy group, oxetanyl group, etc.), it can generate radical polymerization and cation Polymerize both.

自由基聚合性環狀醚化合物(B-1-2)的具體例可列舉：1,2-環氧基-4-乙烯基環己烷等具有乙烯基之環氧化合物；(甲基)丙烯酸3,4-環氧基環己基甲酯、(甲基)丙烯酸縮水甘油酯等具有(甲基)丙烯醯基之環氧化合物；(甲基)丙烯酸(3-乙基-3-氧雜環丁烷基)甲酯等具有(甲基)丙烯醯基之氧雜環丁烷化合物等。此等自由基聚合性環狀醚化合物可單獨使用或組合兩種以上使用。 Specific examples of the radical polymerizable cyclic ether compound (B-1-2) include: epoxy compounds having a vinyl group such as 1,2-epoxy-4-vinylcyclohexane; (meth) acrylic acid 3,4-epoxycyclohexyl methyl ester, glycidyl (meth) acrylate and other epoxy compounds having (meth) acryloyl group; (meth) acrylic acid (3-ethyl-3-oxo heterocycle Butane) methyl esters and the like, oxetane compounds having a (meth) acryloyl group and the like. These radically polymerizable cyclic ether compounds can be used alone or in combination of two or more.

從積層體的表面硬度、彎曲性、氧阻隔性及耐翹曲性之觀點而言，環狀醚化合物(B-1)較佳係含有具有2個以上環氧基及/或2個以上氧雜環丁烷基之雙環狀醚化合物(B-1-1)。雙環狀醚化合物(B-1-1)於上述環氧化合物(b)及氧雜環丁烷化合物(b)中，可列舉出具有2個以上環氧基之環氧化合物、具有2個以上氧雜環丁烷基之氧雜環丁烷化合物等。 The cyclic ether compound (B-1) preferably contains 2 or more epoxy groups and / or 2 or more oxygen from the viewpoint of surface hardness, flexibility, oxygen barrier properties, and warpage resistance of the laminate Heterocyclic alkyl bicyclic ether compound (B-1-1). Bicyclic ether compound (B-1-1) Among the above-mentioned epoxy compound (b) and oxetane compound (b), an epoxy compound having two or more epoxy groups and two The oxetane compounds of the above oxetane groups, etc.

再者，環狀醚化合物(B-1)較佳係含有自由基聚合性環狀醚化合物(B-1-2)。藉由含有自由基聚合性環狀醚化合物(B-1-2)，可進一步提升積層體的表面硬度、彎曲性、氧阻隔性及耐翹曲性。 Furthermore, the cyclic ether compound (B-1) preferably contains a radically polymerizable cyclic ether compound (B-1-2). By containing a radically polymerizable cyclic ether compound (B-1-2), the surface hardness, flexibility, oxygen barrier properties, and warpage resistance of the laminate can be further improved.

本發明之一實施樣態中，當本發明之硬化性組成物含有自由基聚合性環狀醚化合物(B-1-2)時，相對 於雙環狀醚化合物(B-1-1)1質量份，自由基聚合性環狀醚化合物(B-1-2)的含量較佳為0.1至10質量份，尤佳為0.15至7質量份，更佳為0.2至5質量份。其他樣態中，相對於雙環狀醚化合物(B-1-1)1質量份，自由基聚合性環狀醚化合物(B-1-2)的含量較佳為1至10質量份，尤佳為1.5至7質量份，更佳為2至5質量份。自由基聚合性環狀醚化合物(B-1-2)的含量為上述範圍時，可形成表面硬度、彎曲性、氧阻隔性及耐翹曲性更優異之積層體。 In one embodiment of the present invention, when the curable composition of the present invention contains a radically polymerizable cyclic ether compound (B-1-2), compared to the bicyclic ether compound (B-1-1) 1 The content of the radical polymerizable cyclic ether compound (B-1-2) is preferably 0.1 to 10 parts by mass, more preferably 0.15 to 7 parts by mass, and still more preferably 0.2 to 5 parts by mass. In other aspects, the content of the radically polymerizable cyclic ether compound (B-1-2) is preferably 1 to 10 parts by mass relative to 1 part by mass of the bicyclic ether compound (B-1-1), especially It is preferably 1.5 to 7 parts by mass, and more preferably 2 to 5 parts by mass. When the content of the radically polymerizable cyclic ether compound (B-1-2) is within the above range, a laminate having more excellent surface hardness, flexibility, oxygen barrier properties, and warpage resistance can be formed.

(II)乙烯氧基化合物(B-2) (II) Vinyloxy compound (B-2)

所謂乙烯氧基化合物(B-2)，意指於分子內具有1個以上乙烯氧基之化合物。特別是，乙烯氧基化合物(B-2)較佳為具有2個以上乙烯氧基之化合物。此等乙烯氧基化合物(B-2)可單獨使用或組合兩種以上使用。乙烯氧基化合物(B-2)可為單體或寡聚物，較佳為單體。 The vinyloxy compound (B-2) means a compound having one or more vinyloxy groups in the molecule. In particular, the vinyloxy compound (B-2) is preferably a compound having two or more vinyloxy groups. These vinyloxy compounds (B-2) can be used alone or in combination of two or more. The vinyloxy compound (B-2) may be a monomer or an oligomer, preferably a monomer.

乙烯氧基化合物(B-2)可列舉例如：2-乙基己基乙烯醚、十二基乙烯醚、4-羥基丁基乙烯醚、二乙二醇單乙烯醚、三乙二醇二乙烯醚、己二酸二乙烯酯等脂肪族乙烯醚化合物；環己基乙烯醚、環己烷二甲醇二乙烯醚等脂環式乙烯醚化合物；苯基乙烯醚、苯二甲醇二乙烯醚等芳香族乙烯醚化合物等。此等乙烯氧基化合物(B-2)可單獨使用或組合兩種以上使用。乙烯氧基化合物(B-2)中，從積層體的表面硬度、彎曲性、氧阻隔性及耐翹曲性之觀點而言，較佳為脂環式乙烯醚化合物。 Examples of the vinyloxy compound (B-2) include 2-ethylhexyl vinyl ether, dodecyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol divinyl ether , Aliphatic vinyl ether compounds such as divinyl adipate; alicyclic vinyl ether compounds such as cyclohexyl vinyl ether and cyclohexane dimethanol divinyl ether; aromatic vinyls such as phenyl vinyl ether and benzene dimethanol divinyl ether Ether compounds, etc. These vinyloxy compounds (B-2) can be used alone or in combination of two or more. Among the vinyloxy compounds (B-2), from the viewpoint of surface hardness, flexibility, oxygen barrier properties, and warpage resistance of the laminate, an alicyclic vinyl ether compound is preferred.

本發明之硬化性組成物中，從所得到之積 層體的表面硬度、彎曲性、氧阻隔性及耐翹曲性之觀點而言，有利的是陽離子聚合性單體(B)含有乙烯氧基化合物(B-2)。當本發明之硬化性組成物含有乙烯氧基化合物(B-2)時，相對於多官能(甲基)丙烯酸酯單體(A)及陽離子聚合性單體(B)的總量100質量份，乙烯氧基化合物(B-2)的含量較佳為3至50質量份，尤佳為10至40質量份，更佳為15至35質量份。乙烯氧基化合物(B-2)的含量為上述範圍時，可進一步提升積層體的表面硬度、彎曲性、氧阻隔性及耐翹曲性。 In the curable composition of the present invention, from the viewpoint of the surface hardness, flexibility, oxygen barrier properties, and warpage resistance of the obtained laminate, it is advantageous that the cationic polymerizable monomer (B) contains an vinyloxy group Compound (B-2). When the curable composition of the present invention contains an ethyleneoxy compound (B-2), it is 100 parts by mass relative to the total amount of the polyfunctional (meth) acrylate monomer (A) and the cationic polymerizable monomer (B) The content of the vinyloxy compound (B-2) is preferably 3 to 50 parts by mass, more preferably 10 to 40 parts by mass, and still more preferably 15 to 35 parts by mass. When the content of the vinyloxy compound (B-2) is within the above range, the surface hardness, bendability, oxygen barrier properties, and warpage resistance of the laminate can be further improved.

再者，本發明之硬化性組成物中，相對於環狀醚化合物(B-1)1質量份，乙烯氧基化合物(B-2)的含量較佳為0.1至3質量份，尤佳為0.5至2質量份，更佳為0.5至1.5質量份。乙烯氧基化合物(B-2)的含量為上述範圍時，可進一步提升積層體的表面硬度、彎曲性、氧阻隔性及耐翹曲性。 Furthermore, in the curable composition of the present invention, the content of the vinyloxy compound (B-2) is preferably 0.1 to 3 parts by mass relative to 1 part by mass of the cyclic ether compound (B-1), particularly preferably 0.5 to 2 parts by mass, more preferably 0.5 to 1.5 parts by mass. When the content of the vinyloxy compound (B-2) is within the above range, the surface hardness, bendability, oxygen barrier properties, and warpage resistance of the laminate can be further improved.

相對於多官能(甲基)丙烯酸酯單體(A)1質量份，陽離子聚合性單體(B)的含量較佳為0.1至5質量份，尤佳為0.5至3質量份，更佳為0.5至1.5質量份，特佳為0.8至1.2質量份。陽離子聚合性單體(B)的含量為上述範圍時，從積層體的表面硬度、彎曲性、氧阻隔性及耐翹曲性之觀點而言為有利。 The content of the cationic polymerizable monomer (B) is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, more preferably 1 part by mass of the multifunctional (meth) acrylate monomer (A). 0.5 to 1.5 parts by mass, particularly preferably 0.8 to 1.2 parts by mass. When the content of the cationic polymerizable monomer (B) is within the above range, it is advantageous from the viewpoint of the surface hardness, flexibility, oxygen barrier properties, and warpage resistance of the laminate.

本發明之較佳的一實施樣態中，相對於硬化性組成物100質量份，多官能(甲基)丙烯酸酯單體(A)的含量較佳為5至80質量份，尤佳為10至60質量份，更佳 為20至50質量份，特佳為25至40質量份，環狀醚化合物(B-1)的含量較佳為5至80質量份，尤佳為7至60質量份，更佳為10至50質量份，特佳為20至40質量份，乙烯氧基化合物(B-2)的含量較佳為3至60質量份，尤佳為5至40質量份，更佳為10至30質量份。多官能(甲基)丙烯酸酯單體(A)、環狀醚化合物(B-1)及乙烯氧基化合物(B-2)的含量為上述範圍時，容易形成表面硬度、彎曲性、氧阻隔性及耐翹曲性優異之積層體。 In a preferred embodiment of the present invention, the content of the polyfunctional (meth) acrylate monomer (A) is preferably from 5 to 80 parts by mass, and particularly preferably 10 parts relative to 100 parts by mass of the curable composition. To 60 parts by mass, more preferably 20 to 50 parts by mass, particularly preferably 25 to 40 parts by mass, the content of the cyclic ether compound (B-1) is preferably 5 to 80 parts by mass, particularly preferably 7 to 60 parts by mass Parts, more preferably 10 to 50 parts by mass, particularly preferably 20 to 40 parts by mass, and the content of the vinyloxy compound (B-2) is preferably 3 to 60 parts by mass, particularly preferably 5 to 40 parts by mass, more It is preferably 10 to 30 parts by mass. When the content of the multifunctional (meth) acrylate monomer (A), cyclic ether compound (B-1) and vinyloxy compound (B-2) is within the above range, surface hardness, flexibility, and oxygen barrier are easily formed A laminate with excellent resistance and warpage resistance.

本發明之較佳的一實施樣態中，相對於硬化性組成物100質量份，多官能(甲基)丙烯酸酯單體(A)的含量較佳為5至50質量份，尤佳為10至45質量份，更佳為20至40質量份，雙環狀醚化合物(B-1-1)的含量較佳為3至30質量份，尤佳為5至25質量份，自由基聚合性環狀醚化合物(B-1-2)的含量較佳為5至40質量份，尤佳為10至35質量份。本發明之較佳的其他實施樣態中，相對於硬化性組成物100質量份，多官能(甲基)丙烯酸酯單體(A)的含量較佳為5至50質量份，尤佳為10至45質量份，更佳為20至40質量份，雙環狀醚化合物(B-1-1)的含量較佳為3至20質量份，尤佳為5至15質量份，自由基聚合性環狀醚化合物(B-1-2)的含量較佳為15至40質量份，尤佳為20至35質量份。多官能(甲基)丙烯酸酯單體(A)、雙環狀醚化合物(B-1-1)及自由基聚合性環狀醚化合物(B-1-2)的含量為上述範圍時，容易形成表面硬度、彎曲性、氧阻隔性及耐翹曲性優異之積層體。 In a preferred embodiment of the present invention, the content of the polyfunctional (meth) acrylate monomer (A) is preferably 5 to 50 parts by mass relative to 100 parts by mass of the curable composition, particularly preferably 10 To 45 parts by mass, more preferably 20 to 40 parts by mass, and the content of the bicyclic ether compound (B-1-1) is preferably 3 to 30 parts by mass, particularly preferably 5 to 25 parts by mass, free radically polymerizable The content of the cyclic ether compound (B-1-2) is preferably 5 to 40 parts by mass, particularly preferably 10 to 35 parts by mass. In another preferred embodiment of the present invention, the content of the polyfunctional (meth) acrylate monomer (A) is preferably 5 to 50 parts by mass, and particularly preferably 10 parts relative to 100 parts by mass of the curable composition. To 45 parts by mass, more preferably 20 to 40 parts by mass, and the content of the bicyclic ether compound (B-1-1) is preferably 3 to 20 parts by mass, particularly preferably 5 to 15 parts by mass, free radically polymerizable The content of the cyclic ether compound (B-1-2) is preferably 15 to 40 parts by mass, and particularly preferably 20 to 35 parts by mass. When the content of the polyfunctional (meth) acrylate monomer (A), the bicyclic ether compound (B-1-1) and the radically polymerizable cyclic ether compound (B-1-2) is within the above range, it is easy A laminate with excellent surface hardness, bendability, oxygen barrier properties, and warpage resistance is formed.

(3)添加劑 (3) Additives

本發明之硬化性組成物可含有自由基聚合起始劑(C)及陽離子聚合起始劑(D)。從容易迅速地硬化之觀點而言，較佳係含有光自由基聚合起始劑(C)及光陽離子聚合起始劑(D)。於硬化性組成物中含有光自由基聚合起始劑時，可使屬於自由基聚合性化合物之多官能(甲基)丙烯酸酯單體(A)迅速地硬化。光自由基聚合起始劑，只要是可藉由如可見光、紫外線、X射線、電子束之活性能射線的照射而開始自由基聚合性化合物的硬化者，則無特別地限定，該具體例可列舉：苯乙酮、3-甲基苯乙酮、苄基二甲基縮酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、2-甲基-1-[4-(甲基硫)苯基]-2-嗎啉基丙烷-1-酮及2-羥基-2-甲基-1-苯基丙烷-1-酮等苯乙酮系起始劑；二苯基酮、4-氯二苯基酮及4,4'-二胺基二苯基酮等二苯基酮系起始劑；2,2-二甲氧基-1,2-二苯基乙烷-1-酮、1-羥基-環己基-苯基-酮等烷基苯酮系起始劑；安息香丙醚及安息香乙醚等安息香醚系起始劑；4-異丙基噻吨酮等之噻吨酮系起始劑；雙(2,4,6-三甲基苯甲醯)-苯基膦氧化物等醯基膦氧化物系起始劑；其他，氧雜蒽酮(xanthone)、茀酮(fluorenone)、樟腦醌、苯甲醛、蒽醌等。此等光自由基聚合起始劑中，較佳為烷基苯酮系起始劑、醯基膦氧化物系起始劑等。 The hardenable composition of the present invention may contain a radical polymerization initiator (C) and a cationic polymerization initiator (D). From the viewpoint of easy and rapid hardening, it preferably contains a photo radical polymerization initiator (C) and a photo cationic polymerization initiator (D). When the photo-radical polymerization initiator is included in the curable composition, the polyfunctional (meth) acrylate monomer (A) belonging to the radically polymerizable compound can be rapidly cured. The photo-radical polymerization initiator is not particularly limited as long as it can start curing of the radical-polymerizable compound by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams. List: Acetophenone, 3-methylacetophenone, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 2- Acetophenone such as methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropane-1-one and 2-hydroxy-2-methyl-1-phenylpropane-1-one Series initiator; diphenyl ketone series initiators such as diphenyl ketone, 4-chlorodiphenyl ketone and 4,4'-diaminodiphenyl ketone; 2,2-dimethoxy-1 , 2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone and other alkyl benzophenone series initiators; benzoin propyl ether and benzoin ether and other benzoin ether series initiators; 4- Thioxanthone-based initiators such as isopropylthioxanthone; acetylphosphine oxide-based initiators such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; others, Xanthone, fluorenone, camphorquinone, benzaldehyde, anthraquinone, etc. Among these photo-radical polymerization initiators, alkyl ketone-based initiators and acetylphosphine oxide-based initiators are preferred.

此外，於硬化性組成物中含有光陽離子聚合起始劑時，可使屬於陽離子聚合性化合物之陽離子聚合性單體(B)迅速地硬化。光陽離子聚合起始劑，只要是可藉 由活性能射線的照射產生陽離子物種或路易斯酸並開始陽離子聚合性單體的硬化者，則無特別地限定，該具體例可列舉：芳香族重氮鹽，例如，六氟銻酸苯重氮鹽、六氟磷酸苯重氮鹽、六氟硼酸苯重氮鹽；芳香族錪鹽，例如有四(五氟苯基)硼酸二苯基錪鹽、六氟磷酸(4-甲基苯基)[4-(2-甲基丙基)苯基]錪鹽、六氟磷酸二苯基錪鹽、六氟銻酸二苯基錪鹽、六氟磷酸雙(4-壬基苯基)錪鹽；芳香族鋶鹽，例如有六氟磷酸三苯基鋶鹽、六氟銻酸三苯基鋶鹽、四(五氟苯基)硼酸三苯基鋶鹽、雙(六氟)磷酸4,4’-雙(二苯基鋶基)二苯基硫化物、雙(六氟)銻酸4,4’-雙[二(β-羥基乙氧基)苯基鋶基]二苯基硫化物、雙(六氟)磷酸4,4’-雙[二(β-羥基乙氧基)苯基鋶基]二苯基硫化物、六氟銻酸7-[二(對甲苯基)鋶基]-2-異丙基噻吨酮、四(五氟苯基)硼酸7-[二(對甲苯基)鋶基]-2-異丙基噻吨酮(thioxanthone)、六氟磷酸4-苯基羰基-4'-二苯基鋶基二苯基硫化物、六氟銻酸4-(對第三丁基苯基羰基)-4’-二苯基鋶基二苯基硫化物、四(五氟苯基)硼酸4-(對第三丁基苯基羰基)-4’-二(對甲苯基)鋶基二苯基硫化物；鐵-芳烴基錯合物，例如有六氟銻酸二甲苯-環戊二烯鐵(II)、六氟磷酸異丙苯-環戊二烯鐵(II)、二甲苯-環戊二烯鐵(II)-三(三氟甲基磺醯基)甲烷化物等。此等光陽離子聚合起始劑可單獨使用或組合兩種以上使用。此等光陽離子聚合起始劑中，較佳為芳香族錪鹽、芳香族鋶鹽。由於自由基聚合性環狀醚化合物(B-1-2)具有自由基聚合性基與陽離子聚合性基(例如環氧基、氧雜環丁 烷基等)，所以可產生自由基聚合與陽離子聚合兩者。因此當併用光自由基聚合起始劑與光陽離子聚合起始劑時，可更容易迅速地硬化。 In addition, when the photocationic polymerization initiator is included in the curable composition, the cationic polymerizable monomer (B) belonging to the cationic polymerizable compound can be rapidly cured. The photo-cationic polymerization initiator is not particularly limited as long as it can generate a cationic species or a Lewis acid by the irradiation of active energy rays and start curing of the cationic polymerizable monomer, and specific examples thereof include aromatic diazo Salt, for example, benzene diazonium salt of hexafluoroantimonate, benzene diazonium salt of hexafluorophosphate, benzene diazonium salt of hexafluoroborate; Hexafluorophosphoric acid (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium salt, hexafluorophosphate diphenyl iodonium salt, hexafluoroantimonate diphenyl iodonium salt, hexafluorophosphoric acid Bis (4-nonylphenyl) ium salt; aromatic osmium salts such as triphenylammonium hexafluorophosphate, triphenylammonium hexafluoroantimonate, triphenylammonium tetrakis (pentafluorophenyl) borate Salt, bis (hexafluoro) phosphoric acid 4,4'-bis (diphenylamyl) diphenyl sulfide, bis (hexafluoro) antimonate 4,4'-bis [bis (β-hydroxyethoxy) Phenyl alkynyl] diphenyl sulfide, bis (hexafluoro) phosphoric acid 4,4'-bis [bis (β-hydroxyethoxy) phenyl alkynyl] diphenyl sulfide, hexafluoroantimonate 7- [Di (p-tolyl) alkyl] -2-isopropylthioxanthone, tetrakis (pentafluorophenyl) boronic acid 7- [ (P-tolyl) alkynyl) -2-isopropyl thioxanthone, hexafluorophosphate 4-phenylcarbonyl-4'-diphenyl alkynyl diphenyl sulfide, hexafluoroantimonate 4- (P-tert-butylphenylcarbonyl) -4'-diphenylalkyldiphenyl sulfide, tetrakis (pentafluorophenyl) boronic acid 4- (p-tert-butylphenylcarbonyl) -4'-di (P-tolyl) alkyl diphenyl sulfide; iron-aromatic hydrocarbon complex, such as hexafluoroantimonate xylene-cyclopentadiene iron (II), cumene hexafluorophosphate-cyclopentadiene Iron (II), xylene-cyclopentadiene iron (II) -tris (trifluoromethylsulfonyl) methanide, etc. These photo-cationic polymerization initiators can be used alone or in combination of two or more. Among these photo-cationic polymerization initiators, aromatic tungsten salts and aromatic monium salts are preferred. Since the radically polymerizable cyclic ether compound (B-1-2) has a radically polymerizable group and a cationically polymerizable group (such as epoxy group, oxetanyl group, etc.), it can generate radical polymerization and cation Polymerize both. Therefore, when the photo-radical polymerization initiator and the photo-cation polymerization initiator are used together, they can be hardened more quickly.

本發明之硬化性組成物，由於含有屬於自由基聚合性化合物之多官能(甲基)丙烯酸酯單體及屬於陽離子聚合性化合物之陽離子聚合性單體，故較佳為在硬化性組成物中含有光陽離子聚合起始劑與自由基聚合起始劑，藉由併用光陽離子聚合起始劑與光自由基聚合起始劑，可形成表面硬度、彎曲性、氧阻隔性及耐翹曲性更優異之積層體。 Since the curable composition of the present invention contains a polyfunctional (meth) acrylate monomer which is a radical polymerizable compound and a cationic polymerizable monomer which is a cationic polymerizable compound, it is preferably in the curable composition Contains photo-cationic polymerization initiator and radical polymerization initiator. By using photo-cationic polymerization initiator and photo radical polymerization initiator together, it can form surface hardness, flexibility, oxygen barrier and warpage resistance. Excellent laminate.

硬化性組成物含有自由基聚合起始劑時，相對於多官能(甲基)丙烯酸酯單體(A)100質量份，自由基聚合起始劑(C)的含量較佳為1至15質量份，尤佳為3至12質量份；相對於陽離子聚合性單體(B)100質量份，陽離子聚合起始劑(D)的含量較佳為1至15質量份，尤佳為3至10質量份。當自由基聚合起始劑或陽離子聚合起始劑的含量為上述範圍時，可更提高硬化性，而進一步提升表面硬度、彎曲性、氧阻隔性及耐翹曲性。 When the curable composition contains a radical polymerization initiator, the content of the radical polymerization initiator (C) is preferably 1 to 15 parts by mass relative to 100 parts by mass of the polyfunctional (meth) acrylate monomer (A). Parts, particularly preferably 3 to 12 parts by mass; relative to 100 parts by mass of the cationic polymerizable monomer (B), the content of the cationic polymerization initiator (D) is preferably 1 to 15 parts by mass, particularly preferably 3 to 10 Quality parts. When the content of the radical polymerization initiator or the cationic polymerization initiator is within the above range, the hardenability can be further improved, and the surface hardness, bendability, oxygen barrier property, and warpage resistance can be further improved.

本發明之硬化性組成物，從提高積層體的表面硬度之觀點而言，可含有無機粒子。無機粒子可列舉例如：氧化矽粒子、反應性氧化矽粒子、氧化鋁粒子、反應性氧化鋁粒子、滑石粒子、黏土粒子、碳酸鈣粒子、碳酸鎂粒子、硫酸鋇粒子、氫氧化鋁粒子、二氧化鈦粒子、氧化鋯粒子等。無機粒子可單獨使用或組合兩種以上使 用。較佳樣態中，本發明之硬化性組成物更含有反應性氧化矽粒子。於硬化性組成物含有反應性氧化矽粒子時，可與硬化性組成物所含有之具有反應性基或反應性部位之化合物等形成交聯結構，尤其可得到氧阻隔性優異之膜。反應性基可列舉例如：丙烯醯基、羥基、烷氧基(例如甲氧基、乙氧基等)、羧基、硫醇基、胺基、硝基、醯基、環氧基等。此等當中，從與多官能(甲基)丙烯酸酯單體(A)的丙烯醯基或自由基聚合性環狀醚化合物(B-1-2)的自由基聚合性基反應而形成交聯結構，尤其是提升積層體的氧穿透性之觀點而言，最佳為丙烯醯基。無機粒子可單獨使用或組合兩種以上使用。 The curable composition of the present invention may contain inorganic particles from the viewpoint of improving the surface hardness of the laminate. Examples of the inorganic particles include silica particles, reactive silica particles, alumina particles, reactive alumina particles, talc particles, clay particles, calcium carbonate particles, magnesium carbonate particles, barium sulfate particles, aluminum hydroxide particles, and titanium dioxide Particles, zirconia particles, etc. The inorganic particles can be used alone or in combination of two or more. In a preferred aspect, the curable composition of the present invention further contains reactive silicon oxide particles. When the curable composition contains reactive silicon oxide particles, a cross-linked structure can be formed with the compound having a reactive group or reactive site contained in the curable composition, and especially a film with excellent oxygen barrier properties can be obtained. Examples of the reactive group include acryloyl group, hydroxyl group, alkoxy group (for example, methoxy group and ethoxy group), carboxyl group, thiol group, amine group, nitro group, acetyl group and epoxy group. Among them, cross-links are formed by reacting with the radical polymerizable group of the acrylic functional group of the multifunctional (meth) acrylate monomer (A) or the radical polymerizable cyclic ether compound (B-1-2) The structure, especially from the viewpoint of improving the oxygen permeability of the laminate, is preferably acryl. The inorganic particles can be used alone or in combination of two or more.

反應性氧化矽粒子的粒徑，從積層體的氧阻隔性、透明性及粒子的凝聚抑制之觀點而言，較佳為1至100nm，尤佳為3至50nm，更佳為5至30nm。粒徑可使用慣用的方法，例如使用雷射繞射法等，作為平均一次粒徑而測定。 The particle size of the reactive silicon oxide particles is preferably from 1 to 100 nm, particularly preferably from 3 to 50 nm, and more preferably from 5 to 30 nm from the viewpoint of the oxygen barrier properties, transparency, and particle aggregation inhibition of the laminate. The particle diameter can be measured as an average primary particle diameter using a conventional method, for example, a laser diffraction method or the like.

於硬化性組成物含有反應性氧化矽粒子時，從氧阻隔性及彎曲性之觀點而言，相對於硬化性組成物100質量份，反應性氧化矽粒子的含量較佳為1至70質量份，尤佳為5至65質量份，更佳為5至60質量份，更佳為10至50質量份，特佳為15至45質量份。 When the curable composition contains reactive silicon oxide particles, the content of the reactive silicon oxide particles is preferably 1 to 70 parts by mass relative to 100 parts by mass of the curable composition from the viewpoint of oxygen barrier properties and flexibility. It is particularly preferably 5 to 65 parts by mass, more preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, and particularly preferably 15 to 45 parts by mass.

本發明之硬化性組成物可更含有紫外線吸收劑。可列舉出有機紫外線吸收劑及微粉末系紫外線阻隔劑。有機紫外線吸收劑可列舉例如：苯并三唑 (benzotriazole)系、三(triazine)系、丙烯腈系、二苯基酮系、胺基丁二烯系、柳酸酯系等。此等紫外線吸收劑中，從紫外線吸收性高，即使使用在影像顯示裝置時亦可顯現高紫外線截止能力之觀點而言，較佳為苯并三唑系或三系紫外線吸收劑。為了擴展紫外線吸收寬，可單獨或組合使用兩種以上之最大吸收波長相異的紫外線吸收劑。 The curable composition of the present invention may further contain an ultraviolet absorber. Examples include organic ultraviolet absorbers and micropowder ultraviolet blockers. Examples of organic ultraviolet absorbers include: benzotriazole (benzotriazole) based (triazine) system, acrylonitrile system, diphenyl ketone system, aminobutadiene system, salicylate system, etc. Among these ultraviolet absorbers, from the viewpoint of high ultraviolet absorbance and high ultraviolet cutoff capability even when used in an image display device, benzotriazole or triazole It is an ultraviolet absorber. In order to expand the ultraviolet absorption width, two or more ultraviolet absorption agents with different maximum absorption wavelengths may be used alone or in combination.

苯并三唑系可列舉例如：2,2-亞甲基雙[4-(1,1,3,3-四甲基丁基)-6[(2H-苯并三唑-2-基)酚]]、2-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)酚、2-[5-氯(2H)-苯并三唑-2-基]-4-甲基-6-(第三丁基)酚等。 Examples of the benzotriazole system include 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 [(2H-benzotriazol-2-yl) Phenol]], 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- [5-chloro (2H) -benzo Triazol-2-yl] -4-methyl-6- (third butyl) phenol and the like.

苯并三唑系有機紫外線吸收劑的代表性市售品，可列舉：Sumika Chemtex股份有限公司製之Sumisorb(註冊商標)200、Sumisorb 250、Sumisorb 300、Sumisorb 340、Sumisorb 350、Sumisorb 400、BASF公司製之TINUVIN(註冊商標)PS、TINUVIN 99-2、TINUVIN 384-2、TINUVIN 900、TINUVIN 928、TINUVIN 1130、ADEKA股份有限公司製之Adekastab(註冊商標)LA-24、Adekastab LA-29、Adekastab LA-31、Adekastab LA-32、Adekastab LA-36等。 Representative commercially available products of benzotriazole-based organic ultraviolet absorbers include Sumisorb (registered trademark) 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350, Sumisorb 400, and BASF Corporation manufactured by Sumika Chemtex Co., Ltd. TINUVIN (registered trademark) PS, TINUVIN 99-2, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, Adekastab (registered trademark) LA-24, Adekastab LA-29, Adekastab LA -31, Adekastab LA-32, Adekastab LA-36, etc.

三系可列舉例如：2-(4,6-二苯基-1,3,5-三-2-基)-5-[(己基)氧基]-酚等。 three For example, 2- (4,6-diphenyl-1,3,5-tri) -2-yl) -5-[(hexyl) oxy] -phenol and the like.

三系有機紫外線吸收劑的代表性市售品，可列舉出BASF公司製之TINUVIN 400、TINUVIN 405、TINUVIN 460、TINUVIN 477、TINUVIN 479、ADEKA股份有限公司製之Adekastab LA-46、Adekastab LA-F70 等。 three Typical commercially available products that are organic UV absorbers include TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, TINUVIN 479, Adekastab LA-46, Adekastab LA-F70 manufactured by BASF Corporation .

再者，亦可使用HALS劑，可列舉例如：雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、聚[[6-(1,1,3,3-四甲基丁基)胺基-1,3,5-三-2,4-二基][(2,2,6,6-四甲基-4-哌啶基)亞胺基]六亞甲基[(2,2,6,6-四甲基-4-哌啶基)亞胺]]、二丁基胺-1,3,5-三-N,N-雙(2,2,6,6-四甲基-4-哌啶基-1,6-六亞甲二胺N-(2,2,6,6-四甲基-4-哌啶基)丁基胺的聚縮合物等。 Furthermore, HALS agents can also be used, and examples include bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly [[6- (1,1,3, 3-tetramethylbutyl) amino-1,3,5-tri -2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] hexamethylene [(2,2,6,6-tetramethyl- 4-piperidinyl) imine]], dibutylamine-1,3,5-tri -N, N-bis (2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexamethylenediamine N- (2,2,6,6-tetramethyl-4 -Piperidinyl) butylamine polycondensate, etc.

HALS劑的代表性市售品，可列舉：BASF公司製之TINUVIN 111、TINUVIN 123、TINUVIN 144、TINUVIN 292、TINUVIN 5100；ADEKA股份有限公司製之Adekastab LA-52、Adekastab LA-57、Adekastab LA-63P、Adekastab LA-68、Adekastab LA-72、Adekastab LA-77、Adekastab LA-81、Adekastab LA-82、Adekastab LA-87、Adekastab LA-402、Adekastab LA-502等。 Representative commercial products of HALS agents include: TINUVIN 111, TINUVIN 123, TINUVIN 144, TINUVIN 292, TINUVIN 5100 manufactured by BASF; Adekastab LA-52, Adekastab LA-57, Adekastab LA- 63P, Adekastab LA-68, Adekastab LA-72, Adekastab LA-77, Adekastab LA-81, Adekastab LA-82, Adekastab LA-87, Adekastab LA-402, Adekastab LA-502, etc.

微粉末系紫外線阻隔劑較佳為微粒子金屬氧化物，尤佳為該平均一次粒徑於1至100nm的範圍且具有紫外線防禦效果之微粒子金屬氧化物。金屬氧化物可列舉例如：氧化鈦、氧化鋅、氧化鈰、氧化鐵、氧化鎂等。可組合此等微粒子金屬氧化物的1種以上，較佳為2種以上。再者，微粒子金屬氧化物的形狀可為球狀、針狀、棒狀、紡錘狀、不定形狀、板狀等，並無特別限定，再者，關於結晶形，有非晶質、金紅石(rutile)型、銳鈦礦(anatase)型等，並無特別限定。 The fine powder-based ultraviolet blocking agent is preferably a fine particle metal oxide, and particularly preferably the fine particle metal oxide has an average primary particle size in the range of 1 to 100 nm and has an ultraviolet protection effect. Examples of metal oxides include titanium oxide, zinc oxide, cerium oxide, iron oxide, and magnesium oxide. One or more types of these fine particle metal oxides may be combined, preferably two or more types. In addition, the shape of the fine particle metal oxide may be spherical, needle-shaped, rod-shaped, spindle-shaped, indefinite shape, plate-like, etc., and is not particularly limited. Furthermore, the crystalline form includes amorphous and rutile ( Rutile type, anatase type, etc. are not particularly limited.

微粒子金屬氧化物較佳係藉由先前所知的表面處理，例如氟化合物處理、聚矽氧處理、聚矽氧樹脂處理、懸垂處理、矽烷偶合劑處理、鈦偶合劑處理、油劑處理、N-醯化離胺酸處理、聚丙烯酸處理、金屬皂處理、胺基酸處理、無機化合物處理、電漿處理、機械化學處理等預先進行表面處理，特佳藉由選自聚矽氧、矽烷、氟化合物、胺基酸系化合物、金屬皂之一種以上的表面處理劑進行撥水化處理。 The fine particle metal oxide is preferably treated by a previously known surface treatment, such as fluorine compound treatment, polysiloxane treatment, polysiloxane resin treatment, drape treatment, silane coupling agent treatment, titanium coupling agent treatment, oil treatment, N -Acylidene amine acid treatment, polyacrylic acid treatment, metal soap treatment, amino acid treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment and other surface treatments are carried out in advance. One or more surface treatment agents of fluorine compound, amino acid compound, and metal soap are subjected to water repellent treatment.

微粒子金屬氧化物的代表性市售品，可列舉Sumitomo Osaka Cement股份有限公司製之HMZD-50等。 Representative commercial products of fine particle metal oxides include HMZD-50 manufactured by Sumitomo Osaka Cement Co., Ltd. and the like.

於硬化性組成物含有紫外線吸收劑時，紫外線吸收劑的含量可因應紫外線穿透率或紫外線吸收劑的吸光度而適當地選擇，例如相對於多官能(甲基)丙烯酸酯單體(A)及陽離子聚合性單體(B)的總量100質量份，較佳為1至10質量份，尤佳為2至8質量份。當紫外線吸收劑的含量為上述下限值以上時，可有效地顯現所得到之積層體的紫外線吸收性，為上述上限值以下時，可抑制硬化性組成物之硬化性的降低。 When the curable composition contains an ultraviolet absorber, the content of the ultraviolet absorber can be appropriately selected according to the ultraviolet transmittance or the absorbance of the ultraviolet absorber, for example, relative to the multifunctional (meth) acrylate monomer (A) and The total amount of the cationic polymerizable monomer (B) is 100 parts by mass, preferably 1 to 10 parts by mass, and particularly preferably 2 to 8 parts by mass. When the content of the ultraviolet absorber is at least the above lower limit value, the ultraviolet absorbency of the obtained laminate can be effectively expressed, and when it is at most the above upper limit value, the decrease in curability of the curable composition can be suppressed.

本發明之硬化性組成物可更含有勻染劑。勻染劑具有調整硬化性組成物的流動性以使塗佈硬化性組成物所得到之硬化膜成為更平坦之功能，該例子可列舉：聚二甲基矽氧烷等聚矽氧系、聚丙烯酸系及全氟烷基系的界面活性劑等。相對於硬化性組成物100質量份，勻染劑 的含量較佳為0.01至5質量份，尤佳為0.05至3質量份。 The curable composition of the present invention may further contain a leveling agent. The leveling agent has the function of adjusting the fluidity of the curable composition so that the cured film obtained by applying the curable composition becomes flatter. Examples of this include polysiloxane systems such as polydimethylsiloxane and poly Acrylic and perfluoroalkyl surfactants, etc. The content of the levelling agent is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the curable composition, particularly preferably 0.05 to 3 parts by mass.

從對積層體賦予抗靜電能力之觀點而言，可於硬化性組成物中含有抗靜電劑。抗靜電劑較佳為金屬氧化物及金屬鹽。該金屬氧化物可列舉例如：ITO(銦-錫複合氧化物)、ATO(銻-錫複合氧化物)、氧化錫、五氧化銻、氧化鋅、氧化鋯、氧化鈦、氧化鋁等。金屬鹽可列舉銻酸鋅等。於硬化性組成物中含有抗靜電劑時，抗靜電劑的含量雖因所要求之抗靜電性能而不同，但相對於多官能(甲基)丙烯酸酯單體(A)及陽離子聚合性單體(B)的總量100質量份，較佳為0.1至20質量份，尤佳為1至10質量份。 From the viewpoint of imparting antistatic ability to the laminate, an antistatic agent may be contained in the curable composition. The antistatic agent is preferably a metal oxide and a metal salt. Examples of the metal oxide include ITO (indium-tin composite oxide), ATO (antimony-tin composite oxide), tin oxide, antimony pentoxide, zinc oxide, zirconium oxide, titanium oxide, and aluminum oxide. Examples of metal salts include zinc antimonate. When an antistatic agent is included in the hardenable composition, although the content of the antistatic agent varies depending on the required antistatic properties, it is relative to the multifunctional (meth) acrylate monomer (A) and cationic polymerizable monomer The total amount of (B) is 100 parts by mass, preferably 0.1 to 20 parts by mass, particularly preferably 1 to 10 parts by mass.

本發明之硬化性組成物，在不損及表面硬度及彎曲性之範圍內，可更含有其他添加劑。其他添加劑可列舉例如：抗氧化劑、脫模劑、穩定劑、上藍劑、阻燃劑、pH調整劑、潤滑劑、增黏劑。此等其他添加劑可單獨使用或組合兩種以上使用。於硬化性組成物中含有其他添加劑時，對於硬化性組成物100質量份，其他添加劑的含量較佳為0.01至20質量份，尤佳為0.1至10質量份。 The curable composition of the present invention may further contain other additives within a range that does not impair surface hardness and flexibility. Other additives include, for example, antioxidants, mold release agents, stabilizers, blueing agents, flame retardants, pH adjusters, lubricants, and tackifiers. These other additives may be used alone or in combination of two or more. When other additives are contained in the curable composition, the content of the other additives is preferably 0.01 to 20 parts by mass, and particularly preferably 0.1 to 10 parts by mass for 100 parts by mass of the curable composition.

本發明之硬化性組成物較佳為影像顯示裝置之前面板的硬塗層用硬化性組成物。 The curable composition of the present invention is preferably a curable composition for a hard coat layer of a front panel of an image display device.

本發明之硬化性組成物，係可將組成物所含有之成分、多官能(甲基)丙烯酸酯單體(A)、陽離子聚合性單體(B)、以及視需要之自由基聚合起始劑、陽離子聚合起始劑、無機粒子、紫外線吸收劑及其他添加劑等藉由慣用的方法，例如進行混合而得到，混合順序等並無特別限 定。 The curable composition of the present invention can start the components contained in the composition, the multifunctional (meth) acrylate monomer (A), the cationically polymerizable monomer (B), and if necessary, free radical polymerization Agents, cationic polymerization initiators, inorganic particles, ultraviolet absorbers, and other additives are obtained by conventional methods such as mixing, and the order of mixing is not particularly limited.

[2]硬化膜、積層體及其製造方法 [2] Hardened film, laminate and manufacturing method thereof

(1)硬化膜、積層體 (1) Hardened film and laminate

本發明係包含使前述硬化性組成物硬化而成之硬化膜。該硬化膜為前述硬化性組成物的硬化物。本發明之硬化膜係由本發明之硬化性組成物所構成，所以表面硬度及彎曲性優異。再者，本發明之硬化膜亦具有優異的氧阻隔性及耐翹曲性。 The present invention includes a cured film obtained by curing the curable composition. The cured film is a cured product of the curable composition. Since the cured film of the present invention is composed of the curable composition of the present invention, it has excellent surface hardness and flexibility. Furthermore, the cured film of the present invention also has excellent oxygen barrier properties and warpage resistance.

本發明亦包含於基材膜之至少一面積層有本發明之硬化膜之積層體。本發明之積層體中，基材膜所含有之高分子較佳係具有透明性，其例可列舉：聚對苯二甲酸乙二酯等聚酯系高分子、聚碳酸酯系高分子、聚芳酯系高分子、聚醚碸系高分子、聚醯亞胺系高分子、聚醯胺系高分子等。此等當中，聚醯亞胺系高分子由於耐熱性、可撓特性及剛性優異，故為較佳。具有含有聚醯亞胺系高分子而成之基材膜之積層體，係有用於作為影像顯示裝置的前面板，尤其是可撓性顯示器的前面板(觸控膜)。基材膜可為單層或複數層。當基材膜為複數層時，各層可由相同或相異之組成物所構成。 The present invention also includes a laminate having a cured film of the present invention on at least one area of the base film. In the laminate of the present invention, the polymer contained in the base film preferably has transparency. Examples thereof include polyester-based polymers such as polyethylene terephthalate, polycarbonate-based polymers, and polymers. Aryl ester-based polymers, polyether-based polymers, polyimide-based polymers, polyamide-based polymers, etc. Among these, polyimide-based polymers are preferred because they are excellent in heat resistance, flexibility, and rigidity. The laminate having a base film containing a polyimide-based polymer is used as a front panel of an image display device, especially a front panel (touch film) of a flexible display. The base film may be a single layer or multiple layers. When the base film is a plurality of layers, each layer may be composed of the same or different compositions.

所謂聚醯亞胺系高分子，意指含有聚醯亞胺以及包含醯亞胺基及醯胺基兩者之重複結構單元之聚合物。所謂聚醯亞胺意指含有包含醯亞胺基之重複結構單元之聚合物。 The polyimide-based polymer means a polymer containing a polyimide and a repeating structural unit containing both an imide group and an amido group. The so-called polyimide means a polymer containing repeating structural units containing an imide group.

聚醯亞胺系高分子例如可將四羧酸化合物 與二胺化合物作為主要原料進行製造。本發明之一實施樣態中，聚醯亞胺系高分子具有式(10)所表示之重複結構單元。在此，G為4價的有機基，A為2價的有機基。聚醯亞胺系高分子中，可含有G及/或A相異之2種以上式(10)所表示之結構。 The polyimide-based polymer can be produced using, for example, a tetracarboxylic acid compound and a diamine compound as main raw materials. In one embodiment of the present invention, the polyimide-based polymer has a repeating structural unit represented by formula (10). Here, G is a tetravalent organic group, and A is a divalent organic group. The polyimide-based polymer may contain two or more types of structures represented by formula (10) different in G and / or A.

再者，在不損及基材膜的各種物性之範圍內，聚醯亞胺系高分子可含有選自由式(11)、式(12)及式(13)所表示之結構所組成之群組的1種以上。當聚醯亞胺系高分子含有式(13)所表示之結構時，具有顯現良好的表面硬度之傾向，故而較佳。此外，將含有式(10)所表示之重複結構單元及式(13)所表示之重複結構單元之聚醯亞胺系高分子稱為聚醯胺醯亞胺。 Furthermore, the polyimide-based polymer may contain a group selected from the structures represented by formula (11), formula (12), and formula (13) within a range that does not impair various physical properties of the base film More than one kind of group. When the polyimide-based polymer contains the structure represented by the formula (13), it has a tendency to exhibit good surface hardness, which is preferable. In addition, the polyimide-based polymer containing the repeating structural unit represented by the formula (10) and the repeating structural unit represented by the formula (13) is referred to as polyamide imide.

G及G1分別獨立地為4價的有機基，較佳為可藉由烴基或經氟取代之烴基所取代之有機基。G及G1 可例示式(20)至式(29)所示之基，以及4價之碳數6以下的鏈式烴基。 G and G 1 are each independently a tetravalent organic group, preferably an organic group that can be substituted by a hydrocarbon group or a fluorine-substituted hydrocarbon group. G and G 1 can be exemplified by groups represented by formula (20) to formula (29), and a chain hydrocarbon group having a carbon number of 4 or less and a carbon number of 6 or less.

式(20)至式(29)中，＊表示鍵結處，Z表示單鍵、-O-、-CH2-、-CH2-CH2-、-CH(CH3)-、-C(CH3)2-、-Ar-、-SO2-、-CO-、-O-Ar-O-、-Ar-CH2-Ar-、-Ar-C(CH3)2-Ar-或Ar-SO2-Ar-。Ar表示可經氟原子取代之碳數6至20的伸芳基，具體例可列舉出伸苯基。 In formula (20) to formula (29), * represents a bond, Z represents a single bond, -O-, -CH 2- , -CH 2 -CH 2- , -CH (CH 3 )-, -C ( CH 3) 2 -, - Ar -, - SO 2 -, - CO -, - O-Ar-O -, - Ar-CH 2 -Ar -, - Ar-C (CH 3) 2 -Ar- or Ar -SO 2 -Ar-. Ar represents a C6-C20 arylene group which may be substituted with a fluorine atom, and specific examples include phenylene group.

G2為3價的有機基，較佳為可藉由烴基或經氟取代之烴基所取代之有機基。G2可例示式(20)至式(29)所示之基的鍵結處中任一個經取代成氫原子之基，以及3價之碳數6以下的鏈式烴基。 G 2 is a trivalent organic group, preferably an organic group that can be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. G 2 can be exemplified by a group in which any one of the bonding sites of the groups represented by formula (20) to formula (29) is substituted with a hydrogen atom, and a trivalent chain hydrocarbon group having a carbon number of 6 or less.

G3為2價的有機基，較佳為可藉由烴基或經氟取代之烴基所取代之有機基。G3可例示式(20)至式(29) 所示之基的鍵結處中，未相鄰接的2個經取代成氫原子之基，以及碳數6以下的鏈式烴基。具體例可列舉出伸苯基。 G 3 is a divalent organic group, preferably an organic group that can be substituted by a hydrocarbon group or a fluorine-substituted hydrocarbon group. G 3 can be exemplified by the bonding groups of the groups represented by formula (20) to formula (29), two groups not substituted to be replaced by hydrogen atoms, and a chain hydrocarbon group having a carbon number of 6 or less. Specific examples include phenylene.

A、A1、A2及A3分別獨立地為2價的有機基，較佳為可藉由烴基或經氟取代之烴基所取代之有機基。A、A1、A2及A3可例示式(30)至式(38)所示之基；此等經甲基、氟基、氯基或三氟甲基取代之基；以及碳數6以下的鏈式烴基。 A, A 1 , A 2 and A 3 are each independently a divalent organic group, preferably an organic group that can be substituted by a hydrocarbon group or a fluorine-substituted hydrocarbon group. A, A 1 , A 2 and A 3 can exemplify the groups represented by formula (30) to formula (38); these groups substituted with methyl, fluoro, chloro or trifluoromethyl; and carbon number 6 The following chain hydrocarbon group.

式(30)至式(38)中，＊表示鍵結處，Z1、Z2及Z3分別獨立地表示單鍵、-O-、-CH2-、-CH2-CH2-、-CH(CH3)-、-C(CH3)2-、-C(CF3)2-、-SO2-或-CO-。 In formula (30) to formula (38), * represents a bond, Z 1 , Z 2 and Z 3 independently represent a single bond, -O-, -CH 2- , -CH 2 -CH 2 -,- CH (CH 3 )-, -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2 -or -CO-.

一例為Z1及Z3為-O-且Z2為-CH2-、-C(CH3)2-、-C(CF3)2-或-SO2-。Z1與Z2之相對於各環之鍵結位置以及Z2與Z3之相對於各環之鍵結位置，較佳係分別相對於各 環為間位或對位。 As an example, Z 1 and Z 3 are -O- and Z 2 is -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , or -SO 2- . The bonding positions of Z 1 and Z 2 relative to each ring and the bonding positions of Z 2 and Z 3 relative to each ring are preferably meta or para with respect to each ring, respectively.

基材膜可併用前述聚醯亞胺系高分子及聚醯胺系高分子。所謂聚醯胺系高分子為含有包含醯胺基之重複結構單元之聚合物。本實施形態中的聚醯胺系高分子，是以式(13)所示之重複結構單元為主之聚合物。較佳例及具體例係與聚醯亞胺系高分子中的G3及A3相同。可含有G3及/或A3相異之2種以上之式(13)所示之結構。 The base film may use the aforementioned polyimide-based polymer and polyamide-based polymer in combination. The so-called polyamide polymer is a polymer containing repeating structural units containing an amide group. The polyamide-based polymer in this embodiment is a polymer mainly composed of repeating structural units represented by formula (13). Preferred examples and specific examples are the same as G 3 and A 3 in the polyimide-based polymer. Two or more types of structures represented by formula (13) different in G 3 and / or A 3 may be included.

本發明之一實施樣態中，基材膜所含有之聚醯亞胺系高分子可含有複數種G3，複數種G3可互為相同或相異。尤其是，從作為基材膜之含有聚醯亞胺系高分子的積層體的表面硬度及彎曲性提升之觀點而言，較佳為G3的至少一部分係式(3)所示之結構單元： [式(3)中，R1至R8分別獨立地表示氫原子、碳數1至6的烷基或碳數6至12的芳基，R1至R8所含有之氫原子可分別獨立地經鹵素原子取代，B表示單鍵、-O-、-CH2-、-CH2-CH2-、-CH(CH3)-、-C(CH3)2-、-C(CF3)2-、-SO2-、-S-、-CO-或-NR9-，R9表示氫原子、可經鹵素原子取代之碳數1至12的烴基，n為0至4的整數，＊表示鍵結處]。 In one embodiment of the present invention, the polyimide-based polymer contained in the base film may contain a plurality of types of G 3 , and the plurality of types of G 3 may be the same or different from each other. In particular, from the viewpoint of improving the surface hardness and flexibility of the laminate containing a polyimide-based polymer as a base film, at least a part of G 3 is preferably a structural unit represented by formula (3) : [In formula (3), R 1 to R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and the hydrogen atoms contained in R 1 to R 8 may be independently The ground is substituted with a halogen atom, B represents a single bond, -O-, -CH 2- , -CH 2 -CH 2- , -CH (CH 3 )-, -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2- , -S-, -CO- or -NR 9- , R 9 represents a hydrogen atom, a hydrocarbon group of 1 to 12 carbon atoms which may be substituted by a halogen atom, n is an integer of 0 to 4, ＊ Indicates the junction].

式(3)中，B分別獨立地表示單鍵、-O-、-CH2-、-CH2-CH2-、-CH(CH3)-、-C(CH3)2-、-C(CF3)2-、-SO2-、-S-、-CO-或-NR9-，從積層體的彎曲性提升之觀點而言，較佳係表示-O-或-S-，尤佳表示-O-。R1、R2、R3、R4、R5、R6、R7、R8分別獨立地表示氫原子、碳數1至6的烷基或碳數6至12的芳基。碳數1至6的烷基可列舉例如：甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、2-甲基丁基、3-甲基丁基、2-乙基丙基、正己基等。再者，碳數6至12的芳基可列舉例如：苯基、甲苯基、二甲苯基、萘基、聯苯基等。從積層體的表面硬度及柔軟性之觀點而言，R1至R8較佳是分別獨立地表示氫原子或碳數1至6的烷基，尤佳表示氫原子或碳數1至3的烷基，更佳表示氫原子。在此，R1至R8所含有之氫原子可分別獨立地經鹵素原子取代。R9表示氫原子、可經鹵素原子取代之碳數1至12的烴基。 In formula (3), B independently represents a single bond, -O-, -CH 2- , -CH 2 -CH 2- , -CH (CH 3 )-, -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2- , -S-, -CO- or -NR 9- , from the viewpoint of improving the flexibility of the laminate, preferably represents -O- or -S-, especially Good means -O-. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, n-pentyl and 2-methylbutyl , 3-methylbutyl, 2-ethylpropyl, n-hexyl, etc. In addition, examples of the aryl group having 6 to 12 carbon atoms include phenyl, tolyl, xylyl, naphthyl, and biphenyl. From the viewpoint of the surface hardness and flexibility of the laminate, R 1 to R 8 preferably independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably represent a hydrogen atom or a carbon number of 1 to 3 Alkyl, more preferably represents a hydrogen atom. Here, the hydrogen atoms contained in R 1 to R 8 may be independently substituted by halogen atoms, respectively. R 9 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom.

式(3)中，n為0至4的範圍之整數，n為此範圍內時，積層體的彎曲性或彈性率良好。再者，式(3)中，n較佳為0至3的範圍之整數，尤佳為0至2的範圍之整數，更佳為0或1，n為此範圍內時，積層體的彎曲性或彈性率良好，同時原料的取得性相對良好。再者，G3可含有1種或2種以上之式(3)所示之構成單元，從積層體的彈性率及彎曲性的提升以及黃色度(YI值)降低之觀點而言，尤其是可含有n值相異之2種以上的構成單元，較佳是含有n值相異之2種構成單元。此時從積層體容易顯現 高彈性率、彎曲性，以及低黃色度(YI值)之觀點而言，較佳係n含有0與1的構成單元兩者。 In formula (3), n is an integer in the range of 0 to 4. When n is in this range, the laminate has good bendability or elastic modulus. Furthermore, in formula (3), n is preferably an integer in the range of 0 to 3, particularly preferably an integer in the range of 0 to 2, more preferably 0 or 1, and when n is within this range, the laminate is bent The property or elasticity is good, and the availability of raw materials is relatively good. In addition, G 3 may contain one or more than two types of structural units represented by formula (3). In particular, from the viewpoint of improvement in the elastic modulus and flexibility of the laminate and reduction in yellowness (YI value), especially It may contain two or more types of structural units with different values of n, and preferably contains two types of structural units with different values of n. At this time, from the viewpoint of the layered body easily exhibiting high elastic modulus, flexibility, and low yellowness (YI value), it is preferable that n contains both 0 and 1 constituent units.

本發明之較佳實施樣態中，式(3)為式(3’)所表示之構成單元： 亦即複數個G3的至少一部分是式(3’)所示之構成單元。此時，積層體可發揮高表面硬度，同時具有高彎曲性，並可降低黃色度。 In a preferred embodiment of the present invention, formula (3) is a structural unit represented by formula (3 '): That is, at least a part of the plurality of G 3 is a structural unit represented by formula (3 ′). At this time, the laminate can exhibit high surface hardness, have high flexibility, and can reduce yellowness.

本發明之較佳實施樣態中，相對於聚醯亞胺系高分子之式(10)所示之構成單元及式(13)所示之構成單元的合計，式(3)所示之構成單元較佳為20莫耳%以上，尤佳為30莫耳%以上，更佳為40莫耳%以上，特佳為50莫耳%以上，最佳為60莫耳%以上，較佳為90莫耳%以下，尤佳為85莫耳%以下，更佳為80莫耳%以下。相對於聚醯亞胺系高分子之式(10)所示之構成單元及式(13)所示之構成單元的合計，式(3)所表示之構成單元為上述下限以上時，積層體可顯現高表面硬度，並且彎曲性及彈性率優異。相對於聚醯亞胺系高分子之式(10)所示之構成單元及式(13)所示之構成單元的合計，式(3)所示之構成單元為上述上限以下時，藉由抑制來自式(3)之醯胺鍵間的氫鍵所造成之增黏，可抑制樹脂清漆的黏度，而容易進行基材膜的加工。再者，本發明之較佳實施樣態中，相對於聚醯亞胺系高分子之式(10)所示之構成單元及式(13)所示之構成單元 的合計，式(3)的n為1至4者所示之構成單元較佳為3莫耳%以上，尤佳為5莫耳%以上，更佳為7莫耳%以上，特佳為9莫耳%以上，較佳為90莫耳%以下，尤佳為70莫耳%以下，更佳為50莫耳%以下，特佳為30莫耳%以下。相對於聚醯亞胺系高分子之式(10)所示之構成單元及式(13)所示之構成單元的合計，式(3)的n為1至4者所示之構成單元為上述下限以上時，積層體可顯現高表面硬度，並且可進一步提升彎曲性。相對於聚醯亞胺系高分子之式(10)所示之構成單元及式(13)所示之構成單元的合計，式(3)的n為1至4者所示之構成單元為上述上限以下時，藉由抑制來自式(3)之醯胺鍵間的氫鍵所造成之增黏，可抑制樹脂清漆的黏度，而容易進行基材膜的加工。式(3)所示之構成單元的含量，例如可使用1H-NMR來測定或是從原料的投入比來算出。 In a preferred embodiment of the present invention, with respect to the total of the structural unit represented by formula (10) and the structural unit represented by formula (13) of the polyimide-based polymer, the configuration represented by formula (3) The unit is preferably 20 mol% or more, particularly preferably 30 mol% or more, more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 60 mol% or more, preferably 90 Mole% or less, particularly preferably 85 mole% or less, more preferably 80 mole% or less. With respect to the total of the structural unit represented by the formula (10) and the structural unit represented by the formula (13) of the polyimide-based polymer, when the structural unit represented by the formula (3) is at least the above lower limit, the laminate can It exhibits high surface hardness and is excellent in bendability and elastic modulus. With respect to the total of the structural unit represented by the formula (10) and the structural unit represented by the formula (13) of the polyimide-based polymer, when the structural unit represented by the formula (3) is equal to or lower than the above upper limit, the The thickening caused by the hydrogen bond between the amide bond of formula (3) can suppress the viscosity of the resin varnish and facilitate the processing of the base film. Furthermore, in a preferred embodiment of the present invention, with respect to the total of the structural unit represented by formula (10) and the structural unit represented by formula (13) of the polyimide-based polymer, the formula (3) The constituent unit shown by n being 1 to 4 is preferably 3 mol% or more, particularly preferably 5 mol% or more, more preferably 7 mol% or more, and particularly preferably 9 mol% or more, preferably 90 mol% or less, particularly preferably 70 mol% or less, more preferably 50 mol% or less, and particularly preferably 30 mol% or less. With respect to the total of the structural unit represented by formula (10) and the structural unit represented by formula (13) of the polyimide-based polymer, the structural units represented by n in formula (3) of 1 to 4 are the above Above the lower limit, the laminate can exhibit high surface hardness and can further improve the flexibility. With respect to the total of the structural unit represented by formula (10) and the structural unit represented by formula (13) of the polyimide-based polymer, the structural units represented by n in formula (3) of 1 to 4 are the above When it is below the upper limit, the viscosity of the resin varnish can be suppressed by suppressing the thickening caused by the hydrogen bond between the amide bond of formula (3), and the substrate film can be easily processed. The content of the structural unit represented by formula (3) can be measured using 1 H-NMR or calculated from the input ratio of raw materials, for example.

本發明之較佳實施樣態中，上述聚醯亞胺系高分子中的G3之較佳為5莫耳%以上，尤佳為8莫耳%以上，更佳為10莫耳%以上，特佳為12莫耳%以上，是以n為1至4時之式(3)表示。當聚醯亞胺系高分子之G3的上述下限以上為以n為1至4時的式(3)表示時，積層體可顯現高表面硬度，同時具有高彎曲性。再者，聚醯亞胺系高分子中的G3之較佳為90莫耳%以下，尤佳為70莫耳%以下，更佳為50莫耳%以下，特佳為30莫耳%以下，較佳是以n為1至4時之式(3)所表示。當聚醯亞胺系高分子之G3的上述上限以下為以n為1至4時的式(3)所表示時， 藉由抑制來自n為1至4時的式(3)之醯胺鍵間的氫鍵所造成之增黏，可抑制樹脂清漆的黏度，而容易進行積層體的加工。聚醯亞胺系高分子中之n為1至4時的式(3)所表示之構成單元的比率，例如可使用1H-NMR來測定或是從原料的投入比來算出。 In a preferred embodiment of the present invention, the G 3 in the polyimide-based polymer is preferably 5 mol% or more, particularly preferably 8 mol% or more, and more preferably 10 mol% or more. Particularly good is 12 mol% or more, which is expressed by formula (3) when n is 1 to 4. When the above lower limit of the G 3 of the polyimide-based polymer is expressed by the formula (3) when n is 1 to 4, the laminate can exhibit high surface hardness while having high flexibility. Furthermore, the G 3 in the polyimide-based polymer is preferably 90 mol% or less, particularly preferably 70 mol% or less, more preferably 50 mol% or less, and particularly preferably 30 mol% or less , Preferably expressed by equation (3) when n is 1 to 4. When the above upper limit of G 3 of the polyimide-based polymer is represented by formula (3) when n is 1 to 4, by suppressing the amide from formula (3) when n is 1 to 4, The thickening caused by the hydrogen bonding between the bonds can suppress the viscosity of the resin varnish and facilitate the processing of the laminate. The ratio of the structural unit represented by the formula (3) when n in the polyimide-based polymer is 1 to 4 can be measured using 1 H-NMR or calculated from the input ratio of raw materials, for example.

本發明之較佳實施樣態中，式(10)及式(13)中之複數個A及A3的至少一部分為以式(4)所表示之構成單元： [式(4)中，R10至R17分別獨立地表示氫原子、碳數1至6的烷基或碳數6至12的芳基，R10至R17所含有之氫原子可分別獨立地經鹵素原子取代，＊表示鍵結處]。當式(10)及式(13)中之複數個A及A3的至少一部分為式(4)所示之基時，積層體可顯現高表面硬度，同時可具有高透明性。 In a preferred embodiment of the present invention, at least a part of the plural A and A 3 in formula (10) and formula (13) are the structural units represented by formula (4): [In formula (4), R 10 to R 17 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and the hydrogen atoms contained in R 10 to R 17 may each independently The ground is replaced by a halogen atom, * indicates the bond]. When at least a part of the plurality of A and A 3 in the formula (10) and the formula (13) is the base shown in the formula (4), the laminate can exhibit high surface hardness and high transparency.

式(4)中，R10、R11、R12、R13、R14、R15、R16、R17分別獨立地表示氫原子、碳數1至6的烷基或碳數6至12的芳基。碳數1至6的烷基或碳數6至12的芳基可列舉出式(3)中作為碳數1至6的烷基或碳數6至12的芳基所例示者。R10至R17較佳分別獨立地表示氫原子或碳數1至6的烷基，尤佳表示氫原子或碳數1至3的烷基， 在此，R10至R17所含有之氫原子可分別獨立地經鹵素原子取代。鹵素原子可列舉：氟原子、氯原子、溴原子、碘原子。從積層體的表面硬度、透明性及彎曲性之觀點而言，R10至R17更佳是分別獨立地為氫原子、甲基、氟基、氯基或三氟甲基，特佳係R10、R12、R13、R14、R15及R16為氫原子，R11及R17為氫原子、甲基、氟基、氯基或三氟甲基，特佳係R11及R17為甲基或三氟甲基。 In formula (4), R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or 6 to 12 carbon atoms Aryl. Examples of the alkyl group having 1 to 6 carbon atoms or the aryl group having 6 to 12 carbon atoms include those exemplified as the alkyl group having 1 to 6 carbon atoms or the aryl group having 6 to 12 carbon atoms in formula (3). R 10 to R 17 preferably independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and here, the hydrogen contained in R 10 to R 17 The atoms can be independently substituted by halogen atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. From the viewpoint of the surface hardness, transparency, and flexibility of the laminate, R 10 to R 17 are more preferably independently hydrogen atoms, methyl groups, fluorine groups, chlorine groups, or trifluoromethyl groups, particularly R 10, R 12, R 13, R 14, R 15 and R 16 is a hydrogen atom, R 11 and R 17 is a hydrogen atom, methyl, fluoro, chloro or trifluoromethyl group, particularly preferably R 11 and R-based 17 is methyl or trifluoromethyl.

本發明之較佳實施樣態中，式(4)所示之構成單元為式(4’)所表示之構成單元： 亦即複數個A及A3的至少一部分是式(4’)所示之構成單元。此時積層體可顯現高透明性，同時可藉由含氟元素骨架來提升該聚醯亞胺系高分子對溶劑之溶解性，可將樹脂清漆的黏度抑制地較低，而容易進行基材膜的加工。 In a preferred embodiment of the present invention, the structural unit represented by formula (4) is the structural unit represented by formula (4 '): That is, at least a part of the plurality of A and A 3 is a structural unit represented by formula (4 ′). At this time, the laminate can exhibit high transparency, and at the same time, the solubility of the polyimide-based polymer to the solvent can be improved by the fluorine-containing skeleton, and the viscosity of the resin varnish can be suppressed to be low, and the substrate can be easily processed Film processing.

本發明之較佳實施樣態中，上述聚醯亞胺系高分子中的A及A3之較佳為30莫耳%以上，尤佳為50莫耳%以上，更佳為70莫耳%以上，是式(4)，尤其是式(4’)所表示。當聚醯亞胺系高分子中之上述範圍內的A及A3為式(4)，尤其是式(4’)所表示時，積層體可顯現高透明性，同時可藉由含氟元素骨架來提升該聚醯亞胺系高分子對溶劑之溶解性，可將樹脂清漆的黏度抑制地較低，而容易進 行基材膜的加工。較佳者，上述聚醯亞胺系高分子中的A及A3之100莫耳%以下是式(4)，尤其是式(4’)所表示。上述聚醯亞胺系高分子中的A及A3可為式(4)，尤其是式(4’)。上述聚醯亞胺系高分子中的A及A3之式(4)所表示之構成單元的比率，例如可使用1H-NMR來測定或是從原料的投入比來算出。 In a preferred embodiment of the present invention, the A and A 3 in the polyimide-based polymer are preferably 30 mol% or more, particularly preferably 50 mol% or more, and more preferably 70 mol% The above is represented by formula (4), especially formula (4 '). When A and A 3 in the above range in the polyimide-based polymer are represented by formula (4), especially formula (4 '), the laminate can exhibit high transparency and can also contain fluorine-containing elements The framework improves the solubility of the polyimide-based polymer in the solvent, and can suppress the viscosity of the resin varnish to be low, making it easy to process the base film. Preferably, 100 mol% or less of A and A 3 in the polyimide-based polymer is represented by formula (4), especially formula (4 ′). A and A 3 in the polyimide-based polymer may be formula (4), especially formula (4 '). The ratio of the structural unit represented by the formula (4) of A and A 3 in the polyimide-based polymer can be measured using 1 H-NMR or calculated from the input ratio of raw materials, for example.

本發明之較佳實施樣態中，式(10)中之複數個G的至少一部分為式(5)所表示之構成單元： [式(5)中，R18至R25分別獨立地表示氫原子、碳數1至6的烷基或碳數6至12的芳基，R18至R25所含有之氫原子可分別獨立地經鹵素原子取代，＊表示鍵結處]。當式(10)中之複數個G的至少一部分為式(5)所示之基時，積層體可顯現高透明性，同時可提升聚醯亞胺系高分子對溶劑之溶解性，可將樹脂清漆的黏度抑制地較低，並且容易進行基材膜的加工。 In a preferred embodiment of the present invention, at least a part of the plurality of Gs in formula (10) is a structural unit represented by formula (5): [In formula (5), R 18 to R 25 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and the hydrogen atoms contained in R 18 to R 25 may be independently The ground is replaced by a halogen atom, * indicates the bond]. When at least a part of the plurality of Gs in the formula (10) is the base shown in the formula (5), the laminate can exhibit high transparency, and at the same time, the solubility of the polyimide-based polymer in the solvent can be improved, and the The viscosity of the resin varnish is suppressed low, and it is easy to process the base film.

式(5)中，R18、R19、R20、R21、R22、R23、R24、R25分別獨立地表示氫原子、碳數1至6的烷基或碳數6至12的芳基。碳數1至6的烷基或碳數6至12的芳基可列舉式(3)中作為碳數1至6的烷基或碳數6至12的芳基所例示者。R18至R25較佳分別獨立地表示氫原子或碳 數1至6的烷基，尤佳表示氫原子或碳數1至3的烷基，在此，R18至R25所含有之氫原子可分別獨立地經鹵素原子取代。鹵素原子可列舉：氟原子、氯原子、溴原子、碘原子。從容易提升積層體的表面硬度、彎曲性及透明性之觀點而言，R18至R25更佳是分別獨立地為氫原子、甲基、氟基、氯基或三氟甲基，更佳係R18、R19、R20、R23、R24及R25為氫原子，R21及R22為氫原子、甲基、氟基、氯基或三氟甲基，特佳係R21及R22為甲基或三氟甲基。 In formula (5), R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or 6 to 12 carbon atoms Aryl. Examples of the alkyl group having 1 to 6 carbon atoms or the aryl group having 6 to 12 carbon atoms include those exemplified as the alkyl group having 1 to 6 carbon atoms or the aryl group having 6 to 12 carbon atoms in formula (3). R 18 to R 25 preferably independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and here, the hydrogen contained in R 18 to R 25 The atoms can be independently substituted by halogen atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. From the viewpoint of easily improving the surface hardness, flexibility, and transparency of the laminate, R 18 to R 25 are more preferably independently hydrogen atoms, methyl groups, fluorine groups, chlorine groups, or trifluoromethyl groups, and more preferably R 18 , R 19 , R 20 , R 23 , R 24 and R 25 are hydrogen atoms, R 21 and R 22 are hydrogen atoms, methyl, fluoro, chloro or trifluoromethyl, especially R 21 And R 22 is methyl or trifluoromethyl.

本發明之較佳實施樣態中，式(5)所表示之構成單元為式(5’)所表示之構成單元： 亦即複數個G的至少一部分是式(5’)所表示之構成單元。此時積層體可具有高透明性。 In a preferred embodiment of the present invention, the structural unit represented by formula (5) is the structural unit represented by formula (5 '): That is, at least a part of the plurality of Gs is a structural unit represented by formula (5 '). In this case, the laminate can have high transparency.

本發明之較佳實施樣態中，上述聚醯亞胺系高分子中的G之較佳為50莫耳%以上，尤佳為60莫耳%以上，更佳為70莫耳%以上，是式(5)，尤其是式(5’)所示者。當上述聚醯亞胺系高分子中之上述範圍內的G為式(5)，尤其是式(5’)所示時，積層體可具有高透明性，更可藉由含氟元素骨架來提升該聚醯亞胺系高分子對溶劑之溶解性，可將樹脂清漆的黏度抑制地較低，而容易進行積層體的製造。較佳者，上述聚醯亞胺系高分子中的G之100莫耳%以下是式(5)，尤其是式(5’)所示者。上述聚醯亞胺 系高分子中的G可為式(5)，尤其是式(5’)。上述聚醯亞胺系高分子中的G之式(5)所示之構成單元的比率，例如可使用1H-NMR來測定或是從原料的投入比來算出。 In a preferred embodiment of the present invention, the G in the polyimide-based polymer is preferably 50 mol% or more, particularly preferably 60 mol% or more, and more preferably 70 mol% or more. Formula (5), especially those shown in Formula (5 '). When G in the above range of the polyimide-based polymer is represented by formula (5), especially represented by formula (5 '), the laminate may have high transparency, and may be derived from a fluorine-containing skeleton Increasing the solubility of the polyimide-based polymer in the solvent can suppress the viscosity of the resin varnish to be low, making it easy to manufacture the laminate. Preferably, 100 mol% or less of G in the above-mentioned polyimide-based polymer is represented by formula (5), especially formula (5 ′). G in the polyimide-based polymer may be formula (5), especially formula (5 '). The ratio of the structural unit represented by the formula (5) of G in the polyimide-based polymer can be measured using 1 H-NMR or calculated from the input ratio of raw materials, for example.

聚醯亞胺系高分子例如可藉由二胺化合物與四羧酸化合物(四羧酸二酐等)之聚縮合而得到，例如可依循日本特開2006-199945號公報或日本特開2008-163107號公報所記載之方法來合成。聚醯亞胺地市售品可列舉：三菱瓦斯化學股份有限公司製之Neopulim(註冊商標)、河村產業股份有限公司製之KPI-MX300F等。含有式(13)所示之結構之聚醯亞胺系高分子，例如可依循日本特表2014-528490號公報所記載之方法來合成。 The polyimide-based polymer can be obtained, for example, by polycondensation of a diamine compound and a tetracarboxylic acid compound (tetracarboxylic dianhydride, etc.), for example, according to Japanese Patent Application Publication No. 2006-199945 or Japanese Patent Application Publication No. 2008- It is synthesized by the method described in 163107. Examples of commercially available polyimide products include Neopulim (registered trademark) manufactured by Mitsubishi Gas Chemical Co., Ltd., and KPI-MX300F manufactured by Kawamura Industries Co., Ltd. The polyimide-based polymer containing the structure represented by formula (13) can be synthesized, for example, according to the method described in Japanese Patent Publication No. 2014-528490.

本發明之較佳樣態中，具有式(10)所示之重複結構單元之聚醯亞胺系高分子(聚醯亞胺)，可藉由使二胺化合物與四羧酸化合物反應而得到，具有式(10)所示之重複結構單元及式(13)所示之重複結構單元之聚醯亞胺系高分子(聚醯胺醯亞胺)，可藉由在使二胺化合物與四羧酸化合物反應後，進一步使二羧酸化合物反應而得到，具有式(13)所示之重複結構單元之聚醯胺系高分子，可藉由使二胺化合物與二羧酸化合物反應而得到。 In a preferred aspect of the present invention, a polyimide-based polymer (polyimide) having a repeating structural unit represented by formula (10) can be obtained by reacting a diamine compound and a tetracarboxylic acid compound , A polyimide-based polymer having a repeating structural unit represented by formula (10) and a repeating structural unit represented by formula (13) (polyamide imide) can be obtained by After the carboxylic acid compound is reacted, a dicarboxylic acid compound is further reacted. The polyamide polymer having a repeating structural unit represented by formula (13) can be obtained by reacting the diamine compound and the dicarboxylic acid compound .

四羧酸化合物可列舉出芳香族四羧酸二酐等芳香族四羧酸化合物；以及脂肪族四羧酸二酐等脂肪族四羧酸化合物等。四羧酸化合物可單獨使用或組合兩種以上使用。四羧酸化合物除了二酐之外，亦可為醯氯化合物等四羧酸化合物類似物。 Examples of the tetracarboxylic acid compound include aromatic tetracarboxylic acid compounds such as aromatic tetracarboxylic dianhydride; and aliphatic tetracarboxylic acid compounds such as aliphatic tetracarboxylic dianhydride. The tetracarboxylic acid compound can be used alone or in combination of two or more. In addition to the dianhydride, the tetracarboxylic acid compound may be an analog of a tetracarboxylic acid compound such as an acetyl chloride compound.

芳香族四羧酸二酐的具體例，可列舉：非縮合多環式的芳香族四羧酸二酐、單環式的芳香族四羧酸二酐及縮合多環式的芳香族四羧酸二酐。非縮合多環式的芳香族四羧酸二酐可列舉例如：4,4’-氧基二鄰苯二甲酸二酐、3,3’,4,4’-二苯基酮四羧酸二酐、2,2’,3,3’-二苯基酮四羧酸二酐、3,3’,4,4’-聯苯四羧酸二酐、2,2’,3,3’-聯苯四羧酸二酐、3,3’,4,4’-二苯基碸四羧酸二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐、2,2-雙(2,3-二羧基苯基)丙烷二酐、4,4’-(六氟異亞丙基)二鄰苯二甲酸二酐(有記載為6FDA之情形)、1,2-雙(2,3-二羧基苯基)乙烷二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、1,2-雙(3,4-二羧基苯基)乙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、雙(3,4-二羧基苯基)甲烷二酐、雙(2,3-二羧基苯基)甲烷二酐、4,4’-(對苯二氧基)二鄰苯二甲酸二酐、4,4’-(間苯二氧基)二鄰苯二甲酸二酐等。再者，單環式的芳香族四羧酸二酐可列舉例如1,2,4,5-苯四羧酸二酐，縮合多環式的芳香族四羧酸二酐可列舉例如2,3,6,7-萘四羧酸二酐。 Specific examples of the aromatic tetracarboxylic dianhydride include non-condensed polycyclic aromatic tetracarboxylic dianhydride, monocyclic aromatic tetracarboxylic dianhydride and condensed polycyclic aromatic tetracarboxylic acid Dianhydride. Examples of non-condensed polycyclic aromatic tetracarboxylic dianhydrides include: 4,4'-oxydiphthalic dianhydride, 3,3 ', 4,4'-diphenyl ketone tetracarboxylic dianhydride Anhydride, 2,2 ', 3,3'-diphenyl ketone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'- Biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl ash tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2 -Bis (2,3-dicarboxyphenyl) propane dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (in the case of 6FDA), 1,2-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,2-bis (3,4-dicarboxyphenyl) Ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl ) Methane dianhydride, 4,4 '-(p-phenylenedioxy) diphthalic dianhydride, 4,4'-(m-phenylenedioxy) diphthalic dianhydride, etc. Furthermore, examples of monocyclic aromatic tetracarboxylic dianhydride include 1,2,4,5-benzenetetracarboxylic dianhydride, and examples of condensed polycyclic aromatic tetracarboxylic dianhydride include 2,3 , 6,7-Naphthalenetetracarboxylic dianhydride.

此等當中，較佳可列舉：4,4’-氧基二鄰苯二甲酸二酐、3,3’,4,4’-二苯基酮四羧酸二酐、2,2’,3,3’-二苯基酮四羧酸二酐、3,3’,4,4’-聯苯四羧酸二酐、2,2’,3,3’-聯苯四羧酸二酐、3,3’,4,4’-二苯基碸四羧酸二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐、2,2-雙(2,3-二羧基苯基)丙烷二酐、4,4’-(六氟異亞丙基)二鄰苯二甲酸二酐(6FDA)、1,2-雙(2,3-二羧基苯基)乙烷二酐、1,1-雙(2,3-二羧基苯基)乙烷 二酐、1,2-雙(3,4-二羧基苯基)乙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、雙(3,4-二羧基苯基)甲烷二酐、雙(2,3-二羧基苯基)甲烷二酐、4,4'-(對苯二氧基)二鄰苯二甲酸二酐及4,4’-(間苯二氧基)二鄰苯二甲酸二酐，尤佳可列舉：4,4’-氧基二鄰苯二甲酸二酐、3,3’,4,4’-聯苯四羧酸二酐、2,2’,3,3’-聯苯四羧酸二酐、4,4’-(六氟異亞丙基)二鄰苯二甲酸二酐(6FDA)、雙(3,4-二羧基苯基)甲烷二酐及4,4’-(對苯二氧基)二鄰苯二甲酸二酐。此等可單獨使用或組合兩種以上使用。 Among these, preferred examples include: 4,4'-oxydiphthalic dianhydride, 3,3 ', 4,4'-diphenyl ketone tetracarboxylic dianhydride, 2,2', 3 , 3'-Diphenyl ketone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylbenzene tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-di Carboxyphenyl) propane dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA), 1,2-bis (2,3-dicarboxyphenyl) ethane di Anhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 4,4 '-(p-benzene Dioxy) diphthalic dianhydride and 4,4 '-(m-phenylenedioxy) diphthalic dianhydride, particularly preferred are: 4,4'-oxydiphthalic dianhydride Anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 4,4 '-(hexafluoroisopropylidene ) Diphthalic dianhydride (6FDA), bis (3,4-dicarboxyphenyl) methyl Dianhydride and 4,4 '- (p-phenylene) di-phthalic dianhydride. These can be used alone or in combination of two or more.

脂肪族四羧酸二酐可列舉：環式或非環式的脂肪族四羧酸二酐。所謂環式脂肪族四羧酸二酐，為具有脂環式烴結構之四羧酸二酐，該具體例可列舉：1,2,4,5-環己烷四羧酸二酐、1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐等環烷四羧酸二酐；雙環[2.2.2]-辛-7-烯-2,3,5,6-四羧酸二酐、二環己基3,3'-4,4'-四羧酸二酐及此等之位置異構物。此等可單獨使用或組合兩種以上使用。非環式脂肪族四羧酸二酐的具體例，可列舉：1,2,3,4-丁烷四羧酸二酐及1,2,3,4-戊烷四羧酸二酐等，此等可單獨使用或組合兩種以上使用。再者，可組合使用環式脂肪族四羧酸二酐及非環式脂肪族四羧酸二酐。 Examples of the aliphatic tetracarboxylic dianhydride include cyclic or acyclic aliphatic tetracarboxylic dianhydride. The so-called cycloaliphatic tetracarboxylic dianhydride is tetracarboxylic dianhydride having an alicyclic hydrocarbon structure. Specific examples include: 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1, 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride and other naphthenic tetracarboxylic dianhydride; bicyclo [2.2.2] -oct-7 -Ene-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyl 3,3'-4,4'-tetracarboxylic dianhydride and these positional isomers. These can be used alone or in combination of two or more. Specific examples of the non-cyclic aliphatic tetracarboxylic dianhydride include 1,2,3,4-butane tetracarboxylic dianhydride, 1,2,3,4-pentane tetracarboxylic dianhydride, etc., These can be used alone or in combination of two or more. Furthermore, cyclic aliphatic tetracarboxylic dianhydride and acyclic aliphatic tetracarboxylic dianhydride can be used in combination.

上述四羧酸二酐中，從積層體的高表面硬度、高透明性、高柔軟性、高彎曲性及低著色性之觀點而言，較佳為4,4’-氧基二鄰苯二甲酸二酐、3,3’,4,4’-二苯基酮四羧酸二酐、3,3’,4,4’-聯苯四羧酸二酐、2,2’,3,3’-聯苯 四羧酸二酐、3,3’,4,4’-二苯基碸四羧酸二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐、4,4’-(六氟異亞丙基)二鄰苯二甲酸二酐以及此等之混合物，尤佳為3,3’,4,4’-聯苯四羧酸二酐及4,4’-(六氟異亞丙基)二鄰苯二甲酸二酐以及此等之混合物，更佳為4,4’-(六氟異亞丙基)二鄰苯二甲酸二酐(6FDA)。 Among the above-mentioned tetracarboxylic dianhydrides, from the viewpoint of high surface hardness, high transparency, high flexibility, high flexibility, and low colorability of the laminate, 4,4′-oxydiphthalic acid is preferred Formic dianhydride, 3,3 ', 4,4'-diphenyl ketone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3 '-Biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 4 , 4 '-(Hexafluoroisopropylidene) diphthalic dianhydride and mixtures thereof, particularly preferably 3,3', 4,4'-biphenyltetracarboxylic dianhydride and 4,4 ' -(Hexafluoroisopropylidene) diphthalic dianhydride and mixtures thereof, more preferably 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA).

二羧酸化合物可較佳地使用4,4’-氧基雙苯甲酸及/或該酸的醯氯化合物。除了4,4’-氧基雙苯甲酸或該酸的醯氯化合物之外，亦可使用其他二羧酸化合物。其他二羧酸化合物可列舉：芳香族二羧酸、脂肪族二羧酸及此等之類似的醯氯化合物、酸酐等，可組合兩種以上使用。具體例可列舉：對苯二甲酸；間苯二甲酸；萘二羧酸；4,4’-聯苯二羧酸；3,3’-聯苯二羧酸；碳數8以下之鏈式烴的二羧酸化合物以及2個苯甲酸藉由單鍵、-CH2-、-C(CH3)2-、-C(CF3)2-、-SO2-或伸苯基所連結而成之化合物，以及此等之醯氯化合物。此等其他二羧酸化合物中，較佳為對苯二甲酸。具體例較佳為4,4’-氧基雙(氯化苯甲醯)、對苯二甲醯氯，更佳係組合使用4,4’-氧基雙(氯化苯甲醯)與對苯二甲醯氯。 As the dicarboxylic acid compound, 4,4′-oxybisbenzoic acid and / or the acetyl chloride compound of the acid can be preferably used. In addition to 4,4'-oxybisbenzoic acid or the acetyl chloride compound of the acid, other dicarboxylic acid compounds can also be used. Other dicarboxylic acid compounds may include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and similar acetyl chloride compounds, acid anhydrides, and the like, and may be used in combination of two or more kinds. Specific examples include: terephthalic acid; isophthalic acid; naphthalene dicarboxylic acid; 4,4'-biphenyl dicarboxylic acid; 3,3'-biphenyl dicarboxylic acid; chain hydrocarbons with a carbon number of 8 or less The dicarboxylic acid compound and two benzoic acids are connected by a single bond, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2 -or phenylene Compounds, and these acetyl chloride compounds. Among these other dicarboxylic acid compounds, terephthalic acid is preferred. Specific examples are preferably 4,4'-oxybis (chlorobenzoyl chloride) and terephthaloyl chloride, and it is more preferable to use 4,4'-oxybis (chlorobenzoyl chloride) in combination with Xylylenedichloride.

上述聚醯亞胺系高分子，在不損及積層體的各種物性之範圍內，除了上述聚醯亞胺系高分子的合成所使用之四羧酸化合物之外，更可為使四羧酸及三羧酸以及此等之酸酐及衍生物經反應者。 The polyimide-based polymer may be a tetracarboxylic acid compound in addition to the tetracarboxylic acid compound used in the synthesis of the polyimide-based polymer within a range that does not impair various physical properties of the laminate. And tricarboxylic acids and these anhydrides and derivatives reacted.

四羧酸可舉出上述四羧酸化合物之酸酐的 水加成物。 Examples of the tetracarboxylic acid include water adducts of anhydrides of the aforementioned tetracarboxylic acid compounds.

三羧酸化合物可列舉：芳香族三羧酸、脂肪族三羧酸及此等之類似的醯氯化合物、酸酐等，可組合兩種以上使用。具體例可列舉：1,2,4-苯三羧酸的酐；2,3,6-萘三羧酸-2,3-酐；鄰苯二甲酸酐與苯甲酸藉由單鍵、-O-、-CH2-、-C(CH3)2-、-C(CF3)2-、-SO2-或伸苯基所連結之化合物。 Examples of the tricarboxylic acid compound include aromatic tricarboxylic acid, aliphatic tricarboxylic acid, and similar acetyl chloride compounds, acid anhydrides, and the like, which can be used in combination of two or more kinds. Specific examples include: 1,2,4-benzenetricarboxylic acid anhydride; 2,3,6-naphthalenetricarboxylic acid-2,3-anhydride; phthalic anhydride and benzoic acid through a single bond, -O -, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2 -or a compound linked by phenylene.

二胺化合物可列舉例如：脂肪族二胺、芳香族二胺及此等之混合物。本實施形態中所謂「芳香族二胺」，表示胺基與芳香環直接鍵結之二胺，於該結構的一部分可含有脂肪族基或其他取代基。此芳香環可為單環或縮合環，可例示苯環、萘環、蒽環、茀環等，但並不限定於此等。此等當中，較佳為苯環。此外，所謂「脂肪族二胺」，表示胺基與脂肪族基直接鍵結之二胺，於該結構的一部分可含有芳香環或其他取代基。 Examples of the diamine compound include aliphatic diamines, aromatic diamines, and mixtures thereof. The "aromatic diamine" in this embodiment means a diamine in which an amine group is directly bonded to an aromatic ring, and an aliphatic group or other substituents may be contained in a part of the structure. The aromatic ring may be a single ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a fused ring, but it is not limited thereto. Among these, a benzene ring is preferred. In addition, the "aliphatic diamine" means a diamine in which an amine group and an aliphatic group are directly bonded, and an aromatic ring or other substituents may be contained in a part of the structure.

脂肪族二胺可列舉例如：六亞甲基二胺等非環式脂肪族二胺；以及1,3-雙(胺基甲基)環己烷、1,4-雙(胺基甲基)環己烷、降莰烷二胺及4,4’-二胺基二環己基甲烷等環式脂肪族二胺等。此等可單獨使用或組合兩種以上使用。 Examples of the aliphatic diamine include non-cyclic aliphatic diamines such as hexamethylenediamine; and 1,3-bis (aminomethyl) cyclohexane and 1,4-bis (aminomethyl) Cycloaliphatic diamines such as cyclohexane, norbornane diamine and 4,4'-diaminodicyclohexylmethane. These can be used alone or in combination of two or more.

芳香族二胺可列舉例如：對苯二胺、間苯二胺、2,4-甲苯二胺、間二甲苯二胺、對二甲苯二胺、1,5-二胺基萘、2,6-二胺基萘等具有1個芳香環之芳香族二胺；4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基丙烷、4,4’-二 胺基二苯基醚、3,4’-二胺基二苯基醚、3,3’-二胺基二苯基醚、4,4’-二胺基二苯基碸、3,4’-二胺基二苯基碸、3,3’-二胺基二苯基碸、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(3-胺基苯氧基)苯基]丙烷、2,2’-二甲基聯苯胺、2,2’-雙(三氟甲基)-4,4’-二胺基二苯基(有記載為TFMB之情形)、4,4’-雙(4-胺基苯氧基)聯苯、9,9-雙(4-胺基苯基)茀9,9-雙(4-胺基-3-甲基苯基)茀、9,9-雙(4-胺基-3-氯苯基)茀、9,9-雙(4-胺基-3-氟苯基)茀等具有2個以上芳香環之芳香族二胺。此等可單獨使用或組合兩種以上使用。 Examples of aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylenediamine, p-xylenediamine, 1,5-diaminonaphthalene, 2,6 -Aromatic diamines with one aromatic ring such as diaminonaphthalene; 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diamine Diphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'- Diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) ) Benzene, bis [4- (4-aminophenoxy) phenyl] phenanthrene, bis [4- (3-aminophenoxy) phenyl] phenanthrene, 2,2-bis [4- (4- Aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2'-dimethylbenzidine, 2,2'-bis (Trifluoromethyl) -4,4'-diaminodiphenyl (in the case described as TFMB), 4,4'-bis (4-aminophenoxy) biphenyl, 9,9-bis (4-aminophenyl) stilbene 9,9-bis (4-amino-3-methylphenyl) stilbene, 9,9-bis (4-amino-3-chlorophenyl) stilbene, 9, 9-bis (4-amino-3-fluorophenyl) fusi etc. aromatics with more than 2 aromatic rings Aromatic diamine. These can be used alone or in combination of two or more.

芳香族二胺較佳為4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基丙烷、4,4’-二胺基二苯基醚、3,3’-二胺基二苯基醚、4,4’-二胺基二苯基碸、3,3’-二胺基二苯基碸、1,4-雙(4-胺基苯氧基)苯、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(3-胺基苯氧基)苯基]丙烷、2,2’-二甲基聯苯胺、2,2’-雙(三氟甲基)-4,4’-二胺基二苯基(TFMB)、4,4’-雙(4-胺基苯氧基)聯苯，尤佳為4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基丙烷、4,4’-二胺基二苯基醚、4,4’-二胺基二苯基碸、1,4-雙(4-胺基苯氧基)苯、雙[4-(4-胺基苯氧基)苯基]碸、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2’-二甲基聯苯胺、2,2’-雙(三氟甲基)-4,4’-二胺基二苯基(TFMB)、4,4’-雙(4-胺基苯氧基)聯苯。此等可單獨 使用或組合兩種以上使用。 The aromatic diamine is preferably 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,3 ' -Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 1,4-bis (4-aminophenoxy) benzene 、 Bis [4- (4-aminophenoxy) phenyl] 碸, bis [4- (3-aminophenoxy) phenyl] 碸, 2,2-bis [4- (4-amino Phenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2'-dimethylbenzidine, 2,2'-bis (tris Fluoromethyl) -4,4'-diaminodiphenyl (TFMB), 4,4'-bis (4-aminophenoxy) biphenyl, especially 4,4'-diaminodiphenyl Phenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 1,4-bis (4 -Aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2 , 2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl (TFMB), 4,4'-bis (4-aminobenzene Oxy) biphenyl. These can be used alone or in combination of two or more.

上述二胺化合物中，從積層體的高表面硬度、高透明性、高柔軟性、高彎曲性及低著色性之觀點而言，較佳係使用選自由具有聯苯結構之芳香族二胺所組成之群組的1種以上。尤佳使用選自由2,2’-二甲基聯苯胺、2,2’-雙(三氟甲基)聯苯胺、4,4’-雙(4-胺基苯氧基)聯苯及4,4’-二胺基二苯基醚所組成之群組的1種以上，更佳為使用2,2’-雙(三氟甲基)-4,4’-二胺基二苯基(TFMB)。 Among the above diamine compounds, from the viewpoint of high surface hardness, high transparency, high flexibility, high flexibility, and low colorability of the laminate, it is preferably selected from aromatic diamines having a biphenyl structure. More than one kind of group. It is especially preferred to use a group selected from 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) benzidine, 4,4'-bis (4-aminophenoxy) biphenyl and 4 , 4'-diaminodiphenyl ether, more than one group, more preferably 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ( TFMB).

本發明之一實施樣態中，於聚醯亞胺系高分子的合成反應中，可存在醯亞胺化觸媒。醯亞胺化觸媒可列舉例如：三丙基胺、二丁基丙基胺、乙基二丁基胺等脂肪族胺；N-乙基哌啶、N-丙基哌啶、N-丁基吡咯啶、N-丁基哌啶及N-丙基六氫吖呯(N-propylhexahydro azepine)等脂環式胺(單環式)；氮雜雙環[2.2.1]庚烷、氮雜雙環[3.2.1]辛烷、氮雜雙環[2.2.2]辛烷及氮雜雙環[3.2.2]壬烷等脂環式胺(多環式)；以及吡啶、2-甲基吡啶(2-甲吡啶(2-picoline))、3-甲基吡啶(3-甲吡啶)、4-甲基吡啶(4-甲吡啶)、2-乙基吡啶、3-乙基吡啶、4-乙基吡啶、2,4-二甲基吡啶、2,4,6-三甲基吡啶、3,4-環戊烯基吡啶、5,6,7,8-四氫異喹啉以及異喹啉等芳香族胺。再者，從容易促進醯亞胺化之觀點而言，較佳係與醯亞胺化觸媒一同使用酸酐。酸酐可列舉醯亞胺化反應所使用之慣用的酸酐等，該具體例可列舉：乙酸酐、丙酸酐、丁酸酐等脂肪族酸酐；鄰苯二甲酸等芳香族酸酐等。 In one embodiment of the present invention, in the synthesis reaction of the polyimide-based polymer, an amide imidization catalyst may be present. Examples of the amide imidization catalyst include aliphatic amines such as tripropylamine, dibutylpropylamine, and ethyldibutylamine; N-ethylpiperidine, N-propylpiperidine, and N-butyl Cyclopyridine, N-butylpiperidine and N-propylhexahydroazepine (N-propylhexahydro azepine) and other alicyclic amines (monocyclic); azabicyclo [2.2.1] heptane, azabicyclo [3.2.1] Octane, azabicyclo [2.2.2] octane and azabicyclo [3.2.2] nonane and other alicyclic amines (polycyclic); and pyridine, 2-methylpyridine (2 -Picoline (2-picoline)), 3-picoline (3-picoline), 4-picoline (4-picoline), 2-ethylpyridine, 3-ethylpyridine, 4-ethyl Pyridine, 2,4-lutidine, 2,4,6-trimethylpyridine, 3,4-cyclopentenylpyridine, 5,6,7,8-tetrahydroisoquinoline and isoquinoline etc. Aromatic amine. In addition, from the viewpoint of easily promoting the imidization, the acid anhydride is preferably used together with the imidization catalyst. Examples of the acid anhydride include conventional acid anhydrides used in the amide imidization reaction, and specific examples include aliphatic acid anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride; aromatic acid anhydrides such as phthalic acid.

二胺化合物、四羧酸化合物及二羧酸化合物的反應溫度並無特別限定，例如為50至350℃。反應時間亦無特別限定，例如約30分鐘至10小時左右。可因應所需於惰性環境或減壓的條件下進行反應。再者，反應可在溶劑中進行，溶劑可列舉樹脂清漆的調製中所使用之後述溶劑。 The reaction temperature of the diamine compound, the tetracarboxylic acid compound, and the dicarboxylic acid compound is not particularly limited, and is, for example, 50 to 350 ° C. The reaction time is not particularly limited, for example, about 30 minutes to 10 hours. The reaction can be carried out in an inert environment or under reduced pressure as required. In addition, the reaction can be carried out in a solvent. Examples of the solvent include the solvents described below used in the preparation of the resin varnish.

本發明之一實施樣態中，聚醯亞胺系高分子或聚醯胺系高分子的重量平均分子量較佳為200,000以上，尤佳為250,000以上，更佳為300,000以上，特佳為400,000以上，較佳為600,000以下，尤佳為500,000以下。本發明之其他實施樣態中，聚醯亞胺系高分子或聚醯胺系高分子的重量平均分子量較佳為10,000至500,000，尤佳為50,000至480,000，更佳為70,000至450,000，特佳為100,000至400,000。當重量平均分子量於前述範圍內時，聚醯亞胺系高分子可得到高彎曲性，且可將樹脂清漆的黏度抑制地較低，更容易進行聚醯亞胺系高分子的延伸，所以加工性良好。重量平均分子量可進行GPC測定並藉由標準聚苯乙烯換算而求取。 In one embodiment of the present invention, the weight average molecular weight of the polyimide-based polymer or the polyamidoamine-based polymer is preferably 200,000 or more, particularly preferably 250,000 or more, more preferably 300,000 or more, and particularly preferably 400,000 or more. , Preferably 600,000 or less, particularly preferably 500,000 or less. In other embodiments of the present invention, the weight average molecular weight of the polyimide-based polymer or the polyamide-based polymer is preferably from 10,000 to 500,000, particularly preferably from 50,000 to 480,000, more preferably from 70,000 to 450,000, and particularly preferably From 100,000 to 400,000. When the weight average molecular weight is within the aforementioned range, the polyimide-based polymer can obtain high flexibility, and the viscosity of the resin varnish can be suppressed to be low, and the polyimide-based polymer can be more easily extended, so processing Sexuality is good. The weight average molecular weight can be determined by GPC measurement and converted from standard polystyrene.

本發明之較佳實施樣態中，基材膜所含有之聚醯亞胺系高分子及聚醯胺系高分子，可含有藉由上述氟系取代基等而可導入之氟原子等鹵素原子。含氟取代基的具體例可列舉氟基及三氟甲基。藉由使聚醯亞胺系高分子及聚醯胺系高分子含有鹵素原子，可提升基材膜的彈性率，同時可降低黃色度(YI值)，所以較佳為聚醯亞胺系高 分子及聚醯胺系高分子於分子內含有鹵素原子。再者，從黃色度的降低(透明性的提升)、吸水率的降低及基材膜的變形抑制之觀點而言，鹵素原子較佳為氟原子。再者，鹵素原子為氟原子時，該積層體可特別有用地使用於將積層體彎折時不易殘存彎折線，於可撓性顯示器引起彎折等變形之情形。 In a preferred embodiment of the present invention, the polyimide-based polymer and the polyamide-based polymer contained in the base film may contain halogen atoms such as fluorine atoms that can be introduced through the above-mentioned fluorine-based substituents, etc. . Specific examples of the fluorine-containing substituent include fluorine group and trifluoromethyl group. By containing a halogen atom in the polyimide-based polymer and the polyamide-based polymer, the elasticity of the base film can be improved and the yellowness (YI value) can be reduced, so the polyimide-based polymer is preferably high Molecules and polyamide-based polymers contain halogen atoms in the molecule. In addition, from the viewpoint of reduction in yellowness (improvement in transparency), reduction in water absorption, and suppression of deformation of the base film, the halogen atom is preferably a fluorine atom. In addition, when the halogen atom is a fluorine atom, the laminate can be particularly useful for bending lines that do not easily remain when the laminate is folded, and can cause deformations such as bending in flexible displays.

從硬度的提升、彈性率的提升、黃色度的降低(透明性的提升)、吸水率的降低及基材膜的變形抑制之觀點而言，相對於聚醯亞胺系高分子100質量份，聚醯亞胺系高分子及聚醯胺系高分子中之鹵素原子的含量，較佳為1至40質量份，尤佳為3至35質量份，更佳為5至32質量份。 From the viewpoints of improvement in hardness, improvement in elasticity, reduction in yellowness (increase in transparency), reduction in water absorption, and deformation suppression of the base film, it is 100 parts by mass of the polyimide-based polymer, The content of halogen atoms in the polyimide-based polymer and the polyamide-based polymer is preferably 1 to 40 parts by mass, particularly preferably 3 to 35 parts by mass, and more preferably 5 to 32 parts by mass.

本發明之較佳實施樣態中，基材膜含有前述聚醯亞胺系高分子而成。相對於基材膜100質量份，基材膜中之聚醯亞胺系高分子的含量較佳為40質量份以上，尤佳為50質量份以上，更佳為70質量份以上，更佳為90質量份以上，特佳為100質量份。當聚醯亞胺系高分子的含量為40質量份以上時，基材膜的彎曲性良好。 In a preferred embodiment of the present invention, the base film contains the aforementioned polyimide-based polymer. The content of the polyimide-based polymer in the base film is preferably 40 parts by mass or more, particularly preferably 50 parts by mass or more, more preferably 70 parts by mass or more, more preferably 100 parts by mass of the base film More than 90 parts by mass, especially 100 parts by mass. When the content of the polyimide-based polymer is 40 parts by mass or more, the flexibility of the base film is good.

基材膜可含有添加劑。添加劑可列舉例如：無機材料、前述紫外線吸收劑、前述其他添加劑等。此等添加劑可單獨使用或組合兩種以上使用。無機材料除了前述無機粒子之外，可列舉出四乙氧基矽烷(TEOS)等4級烷氧基矽烷等矽化合物等。用以製造基材膜之樹脂清漆，從聚醯亞胺系樹脂清漆的穩定性之觀點而言，無機材料較佳 為無機粒子，特佳為氧化矽粒子。無機粒子彼此可藉由具有矽氧烷鍵之分子而鍵結。 The base film may contain additives. Examples of additives include inorganic materials, the aforementioned ultraviolet absorbers, and the aforementioned other additives. These additives can be used alone or in combination of two or more. In addition to the aforementioned inorganic particles, inorganic materials include silicon compounds such as quaternary alkoxysilane such as tetraethoxysilane (TEOS). From the viewpoint of the stability of the polyimide-based resin varnish for the resin varnish used to produce the base film, the inorganic material is preferably inorganic particles, and particularly preferably silicon oxide particles. The inorganic particles can be bonded to each other by molecules having siloxane bonds.

氧化矽粒子的平均粒徑較佳為10nm以上，尤佳為15nm以上，更佳為20nm以上，較佳為100nm以下，尤佳為90nm以下，更佳為80nm以下，更佳為70nm以下，特佳為60nm以下，特佳為50nm以下，最佳為40nm以下。氧化矽粒子的平均粒徑為上述範圍時，容易提升積層體的彎曲性及透明性。積層體的平均粒徑可藉由BET法來測定。亦可藉由穿透型電子顯微鏡(TEM)或掃描型電子顯微鏡(SEM)的影像解析來測定平均粒徑。 The average particle diameter of the silicon oxide particles is preferably 10 nm or more, particularly preferably 15 nm or more, more preferably 20 nm or more, preferably 100 nm or less, particularly preferably 90 nm or less, more preferably 80 nm or less, more preferably 70 nm or less, and particularly It is preferably 60 nm or less, particularly preferably 50 nm or less, and most preferably 40 nm or less. When the average particle diameter of the silicon oxide particles is within the above range, the flexibility and transparency of the laminate are easily improved. The average particle diameter of the laminate can be measured by the BET method. The average particle size can also be determined by image analysis of a transmission electron microscope (TEM) or a scanning electron microscope (SEM).

當基材膜含有氧化矽粒子時，相對於基材膜100質量份，氧化矽粒子的含量較佳為1質量份以上，尤佳為5質量份以上，更佳為10質量份以上，特佳為20質量份以上，較佳為60質量份以下，尤佳為50質量份以下。氧化矽粒子的含量為上述範圍時，容易提升基材膜的彈性率及彎曲性。 When the base film contains silicon oxide particles, the content of the silicon oxide particles is preferably 1 part by mass or more, particularly preferably 5 parts by mass or more, more preferably 10 parts by mass or more, particularly preferably 100 parts by mass of the base film. It is 20 parts by mass or more, preferably 60 parts by mass or less, and particularly preferably 50 parts by mass or less. When the content of the silicon oxide particles is within the above range, it is easy to increase the elastic modulus and flexibility of the base film.

當基材膜含有添加劑時，添加劑的含量可因應添加劑的種類來適當地選擇，相對於基材膜100質量份，例如為0.01至60質量份，較佳為0.1至60質量份，尤佳為1至50質量份。 When the base film contains an additive, the content of the additive can be appropriately selected according to the type of the additive, and is, for example, 0.01 to 60 parts by mass, preferably 0.1 to 60 parts by mass, and particularly preferably 100 parts by mass of the base film. 1 to 50 parts by mass.

基材膜的厚度可因應用途而適當地調整，通常為10至1,000μm，較佳為15至500μm，尤佳為20至400μm，更佳為25至300μm，更佳為25至100μm，特佳為25至75μm。基材膜的厚度為上述範圍時，彎曲性良好， 同時有益於影像顯示裝置的薄型化，除此之外，有容易確保作為基材之機械強度、積層體製作時的表面硬度之傾向。 The thickness of the base film can be appropriately adjusted according to the application, and it is usually 10 to 1,000 μm, preferably 15 to 500 μm, particularly preferably 20 to 400 μm, more preferably 25 to 300 μm, more preferably 25 to 100 μm, and particularly preferably 25 to 75 μm. When the thickness of the base film is within the above range, the flexibility is good, which is beneficial to the thinning of the image display device. In addition to this, there is a tendency to easily ensure the mechanical strength of the base material and the surface hardness when the laminate is produced.

本發明中，基材膜的製造方法並無特別限定，例如可藉由包含以下步驟之方法來製造：(a)調製含有前述樹脂之液(有稱為樹脂清漆之情形)之步驟(清漆調製步驟)、(b)將樹脂清漆塗佈於支撐材而形成塗膜之步驟(塗佈步驟)、以及(c)使塗佈後之液(塗膜)乾燥而形成基材膜之步驟(基材膜形成步驟)。 In the present invention, the production method of the base film is not particularly limited, and for example, it can be produced by a method including the following steps: (a) the step of preparing a liquid containing the aforementioned resin (in the case of a resin varnish) (varnish preparation) Step), (b) The step of applying a resin varnish to the support material to form a coating film (coating step), and (c) The step of drying the liquid (coating film) after coating to form a base film (based Material film forming step).

於清漆調製步驟中，使前述樹脂溶解於溶劑，且因應所需將前述氧化矽粒子等前述添加劑攪拌混合而調製樹脂清漆。此外，使用氧化矽粒子作為添加劑時，可藉由可溶解前述樹脂之溶劑，例如下述清漆的調製所使用之溶劑，對含有氧化矽粒子之氧化矽溶膠的分散液進行置換而得到氧化矽溶膠，並將此氧化矽溶膠添加於樹脂。 In the varnish preparation step, the resin is dissolved in a solvent, and the additives such as the silica particles are stirred and mixed as necessary to prepare a resin varnish. In addition, when silica particles are used as additives, the silica silica sol can be obtained by replacing the dispersion of silica sol containing silica particles with a solvent that can dissolve the resin, such as the solvent used in the preparation of the following varnish And add this silica sol to the resin.

樹脂清漆的調製所使用之溶劑，只要是可溶解前述高分子即可，並無特別限定。該溶劑可列舉例如：N,N-二甲基乙醯胺、N,N-二甲基甲醯胺等醯胺系溶劑；γ-丁內酯(GBL)、γ-戊內酯等內酯系溶劑；二甲基碸、二甲基亞碸、環丁碸等含硫系溶劑；碳酸乙烯酯、碳酸丙烯酯等碳酸酯系溶劑；及此等之組合(混合溶劑)。此等當中，較佳為醯胺系溶劑或內酯系溶劑。此等溶劑可單獨使用或組 合兩種以上使用。再者，清漆亦可含有水、醇系溶劑、酮系溶劑、非環狀酯系溶劑、醚系溶劑等。清漆的固形份濃度較佳為1至25質量%，尤佳為5至15質量%。 The solvent used for preparing the resin varnish is not particularly limited as long as it can dissolve the aforementioned polymer. Examples of the solvent include: acrylamide-based solvents such as N, N-dimethylacetamide and N, N-dimethylformamide; lactones such as γ-butyrolactone (GBL) and γ-valerolactone Solvents; sulfur-containing solvents such as dimethyl ash, dimethyl sulfoxide, cis-pyridine; carbonate-based solvents such as ethylene carbonate and propylene carbonate; and combinations of these (mixed solvents). Among these, an amide-based solvent or a lactone-based solvent is preferred. These solvents can be used alone or in combination of two or more. Furthermore, the varnish may contain water, alcohol-based solvents, ketone-based solvents, acyclic ester-based solvents, ether-based solvents, and the like. The solid content concentration of the varnish is preferably 1 to 25% by mass, particularly preferably 5 to 15% by mass.

於塗佈步驟中，可藉由一般所知的塗佈法將清漆塗佈於基材上而形成塗膜。一般所知的塗佈方法可列舉例如：繞線棒塗佈法、反轉塗佈法、凹版塗佈法等輥塗佈法、壓模塗佈法、刮刀塗佈法、唇板塗佈法、旋轉塗佈法、網版塗佈法、淋幕塗佈法、浸泡法、噴霧法、流體澆注成形法等。 In the coating step, the varnish can be coated on the substrate by a generally known coating method to form a coating film. Commonly known coating methods include, for example, roll coating methods such as wire bar coating method, reverse coating method, and gravure coating method, die coating method, blade coating method, and lip coating method , Spin coating method, screen coating method, curtain coating method, dipping method, spray method, fluid casting method, etc.

於基材膜形成步驟中，藉由使塗膜乾燥並從基材中剝離，可形成基材膜。剝離後可更進行使基材膜乾燥之乾燥步驟。塗膜的乾燥通常可在50至350℃的溫度進行。可因應所需在惰性環境或減壓的條件下進行塗膜的乾燥。 In the base film forming step, the base film can be formed by drying and peeling the coating film from the base. After peeling, a drying step of drying the base film may be further performed. The drying of the coating film can usually be performed at a temperature of 50 to 350 ° C. The coating film can be dried in an inert environment or under reduced pressure as required.

支撐材的例子可列舉出PET膜、PEN膜、其他聚醯亞胺系高分子或聚醯胺系高分子膜等。其中，從耐熱性優異之觀點而言，較佳為PET膜、PEN膜等，再者，從與基材之成膜時的密著性、易剝離性及成本之觀點而言，尤佳為PET膜。其他亦可使用不鏽鋼等金屬製之帶或玻璃板。 Examples of the supporting material include PET films, PEN films, other polyimide-based polymers or polyamide-based polymer films, and the like. Among them, from the viewpoint of excellent heat resistance, PET films, PEN films, etc. are preferred, and from the viewpoint of adhesion, easy peelability, and cost during film formation with a substrate, particularly preferred are PET film. Others can also use stainless steel and other metal belts or glass plates.

本發明之積層體中，硬化膜可為單層構造或複數層構造。硬化膜的厚度可因應積層體所適用之影像顯示裝置等的用途來適當地選擇，例如為1至50μm，較佳為2至30μm。從表面硬度及彎曲性優異者而言，硬化膜的 厚度尤佳為3至20μm，更佳為6至18μm，特佳為8至16μm。硬化膜的厚度可使用接觸式的數位式量錶來測定。 In the laminated body of the present invention, the cured film may have a single-layer structure or a multiple-layer structure. The thickness of the cured film can be appropriately selected according to the application of the image display device to which the laminate is applied, for example, 1 to 50 μm, preferably 2 to 30 μm. From the viewpoint of those having excellent surface hardness and flexibility, the thickness of the cured film is particularly preferably 3 to 20 µm, more preferably 6 to 18 µm, and particularly preferably 8 to 16 µm. The thickness of the cured film can be measured using a contact-type digital scale.

本發明之一實施樣態中，本發明之積層體可於基材膜與硬化膜之間配置底漆層(primer layer)。當於基材膜兩表面配置有硬化膜時，可僅於基材膜與一硬化膜之間配置底漆層，或是於基材膜與一硬化膜之間及基材膜與另一硬化膜之間的兩者皆配置底漆層。 In one embodiment of the present invention, the laminate of the present invention may have a primer layer between the base film and the cured film. When hardened films are arranged on both surfaces of the base film, the primer layer may be arranged only between the base film and one hardened film, or between the base film and one hardened film and between the base film and the other hardened A primer layer is provided for both of the films.

底漆層是由底漆劑所形成之層，可提高基材膜與硬化膜之密著性。底漆層所含有之化合物，可與基材膜所含有之高分子，較佳為聚醯亞胺系高分子於界面上形成化學鍵。 The primer layer is a layer formed by a primer, which can improve the adhesion between the base film and the cured film. The compound contained in the primer layer can form a chemical bond at the interface with the polymer contained in the base film, preferably a polyimide-based polymer.

底漆劑例如有紫外線硬化型、熱硬化型或雙液硬化型之環氧系化合物的底漆劑。底漆劑可為聚醯胺酸。此等在基材膜含有聚醯亞胺系高分子而成時，係適合用來提高該基材膜與硬化膜之密著性。 The primer agent is, for example, an epoxy-based compound primer of ultraviolet curing type, thermosetting type or two-liquid curing type. The primer can be polyamide. These are suitable for improving the adhesion between the base film and the cured film when the base film contains a polyimide-based polymer.

底漆劑可含有矽烷偶合劑。矽烷偶合劑亦可與藉由縮合反應而可包含於基材膜之矽化合物化學鍵結。矽烷偶合劑尤其在可包含於基材膜之矽化合物的調配比高時可較佳地使用。 The primer may contain a silane coupling agent. The silane coupling agent may also be chemically bonded to the silicon compound that can be contained in the base film through the condensation reaction. The silane coupling agent can be preferably used particularly when the compounding ratio of the silicon compound that can be contained in the base film is high.

矽烷偶合劑較佳為具有：矽原子、及具有與該矽原子共價鍵結之1至3個烷氧基之烷氧矽基之化合物。尤佳為包含矽原子與2個以上烷氧基共價鍵結而成之結構之化合物，更佳為包含矽原子與3個烷氧基共鍵鍵結而成之結構之化合物。上述烷氧基可列舉例如：甲氧基、 乙氧基、異丙氧基、正丁氧基、第三丁氧基等。此等當中，甲氧基、乙氧基可提高與矽化合物之反應性，故較佳。 The silane coupling agent is preferably a compound having a silicon atom and an alkoxysilyl group having 1 to 3 alkoxy groups covalently bonded to the silicon atom. Particularly preferred is a compound containing a structure in which a silicon atom is covalently bonded with 2 or more alkoxy groups, and more preferably a compound containing a structure in which a silicon atom is co-bonded with 3 alkoxy groups. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, n-butoxy, and third butoxy. Among these, methoxy and ethoxy groups can improve the reactivity with silicon compounds, so it is preferable.

矽烷偶合劑較佳係具有與基材膜及硬化膜之親和性高之取代基。從與基材膜可含有之聚醯亞胺系高分子的親和性之觀點而言，矽烷偶合劑的取代基較佳為環氧基、胺基、脲基或異氰酸基。當硬化膜含有(甲基)丙烯酸酯類時，若底漆層能夠使用之矽烷偶合劑具有環氧基、甲基丙烯酸基、丙烯酸基、胺基或苯乙烯基，則可提高親和性，故較佳。此等當中，當基材膜含有聚醯亞胺系高分子而成時，具有選自甲基丙烯酸基、丙烯酸基、胺基之取代基之矽烷偶合劑顯示出與基材膜及硬化膜之親和性優異之傾向，故較佳。 The silane coupling agent preferably has a substituent having a high affinity with the base film and the cured film. From the viewpoint of affinity with the polyimide-based polymer that the base film can contain, the substituent of the silane coupling agent is preferably an epoxy group, an amine group, a urea group, or an isocyanate group. When the cured film contains (meth) acrylates, if the silane coupling agent that can be used for the primer layer has an epoxy group, a methacrylic group, an acrylic group, an amine group or a styrene group, the affinity can be improved, Better. Among them, when the base film contains a polyimide-based polymer, the silane coupling agent having a substituent selected from a methacrylic group, an acrylic group, and an amine group shows Tendency to have excellent affinity, so it is better.

底漆層的厚度可因應硬化膜來適當地選擇，例如為0.01nm至20μm。使用環氧系化合物的底漆劑時，底漆層的厚度較佳為0.01至20μm，尤佳為0.1至10μm。使用矽烷偶合劑時，底漆層的厚度較佳為0.1nm至1μm，尤佳為0.5nm至0.1μm。 The thickness of the primer layer can be appropriately selected according to the cured film, and is, for example, 0.01 nm to 20 μm. When an epoxy-based compound primer is used, the thickness of the primer layer is preferably 0.01 to 20 μm, and particularly preferably 0.1 to 10 μm. When a silane coupling agent is used, the thickness of the primer layer is preferably 0.1 nm to 1 μm, particularly preferably 0.5 nm to 0.1 μm.

本發明之一實施樣態中，本發明之積層體除了基材膜與硬化膜之外，更可具備功能層。功能層可列舉：紫外線吸收層、黏著層、色相調整層、折射率調整層等具有各種功能者。本發明之積層體可具備單層或複數層的功能層。此外，1層功能層可具有複數種功能。 In one embodiment of the present invention, the laminate of the present invention may include a functional layer in addition to the base film and the cured film. The functional layer can be exemplified by those having various functions such as an ultraviolet absorption layer, an adhesive layer, a hue adjustment layer, and a refractive index adjustment layer. The laminate of the present invention may have a single layer or a plurality of functional layers. In addition, a functional layer can have multiple functions.

紫外線吸收層為具有紫外線吸收的功能之層，例如由選自紫外線硬化型的透明樹脂、電子束硬化型 的透明樹脂及熱硬化型的透明樹脂之主材料，與分散於主材料之紫外線吸收劑所構成。藉由設置紫外線吸收層作為功能層，可容易地抑制因光照射所帶來之黃色度的變化。 The ultraviolet absorbing layer is a layer having a function of absorbing ultraviolet rays. For example, it is composed of a main material selected from an ultraviolet curing transparent resin, an electron beam curing transparent resin, and a thermosetting transparent resin, and an ultraviolet absorbent dispersed in the main material. Posed. By providing an ultraviolet absorbing layer as a functional layer, the change in yellowness caused by light irradiation can be easily suppressed.

黏著層為具有黏著性功能之層，具有使基材膜或積層體與其他構件接著之功能。黏著層的材料可使用通常已知者。例如可使用熱硬化性樹脂組成物或光硬化性樹脂組成物。 The adhesive layer is a layer having an adhesive function, and has a function of attaching a base film or a laminate to other members. As the material of the adhesive layer, generally known ones can be used. For example, a thermosetting resin composition or a photocurable resin composition can be used.

黏著層亦可由含有具有聚合性官能基之成分之樹脂組成物構成。此時，使積層體與其他構件密著後，進一步使構成黏著層之樹脂組成物聚合，藉此可實踐堅固的接著。其他構件與積層體所含有之黏著層之接著強度，可為0.1N/cm以上或0.5N/cm以上。 The adhesive layer may also be composed of a resin composition containing a component having a polymerizable functional group. At this time, after adhering the laminate to other members, the resin composition constituting the adhesive layer is further polymerized, whereby a firm adhesion can be practiced. The adhesion strength of other members and the adhesive layer contained in the laminate may be 0.1 N / cm or more or 0.5 N / cm or more.

黏著層亦可含有熱硬化性樹脂組成物或光硬化性樹脂組成物作為材料。此時，可藉由在事後供給能量以使樹脂組成物高分子化而硬化。 The adhesive layer may also contain a thermosetting resin composition or a photocurable resin composition as a material. At this time, the resin composition can be polymerized and hardened by supplying energy afterwards.

黏著層亦可為被稱為感壓型黏著劑(Pressure Sensitive Adhesive，PSA)之藉由按壓而貼著於對象物之層。感壓型黏著劑可為「常溫下具有黏著性，於較輕壓力下與被接著材料接著之物質」(JIS K6800)之黏著劑，亦可為「使特定成分內含於保護被膜(微膠囊)，並可保持穩定性直至藉由適當的手段(壓力、熱等)來破壞被膜為止之接著劑」(JIS K6800)之膠囊接著劑。 The adhesive layer may also be a layer called pressure sensitive adhesive (Pressure Sensitive Adhesive, PSA) attached to the object by pressing. The pressure-sensitive adhesive can be "a substance that has adhesiveness at room temperature and adheres to the material to be adhered at a lighter pressure" (JIS K6800), or it can be "containing a specific component in a protective film (microcapsule ), And can maintain stability until the adhesive is destroyed by appropriate means (pressure, heat, etc.) "(JIS K6800) capsule adhesive.

色相調整層為具有色相調整功能之層，可將積層體調整成目的的色相之層。色相調整層例如為含有 樹脂及著色劑之層。著色劑可列舉例如：氧化鈦、氧化鋅、紅色氧化鐵、二氧化鈦系燒成顏料、群青、鋁酸鈷及碳黑等無機顏料；偶氮系化合物、喹吖啶酮(quinacridone)系化合物、蒽醌(anthraquinone)系化合物、苝(perylene)系化合物、異吲哚啉酮(isoindolinone)系化合物、酞菁(phthalocyanine)系化合物、喹啉黃(quinophthalone)系化合物、陰丹士林(indanthrene)系化合物及二酮吡咯并吡咯(diketo pyrrolo pyrrole)系化合物等有機顏料；硫酸鋇及碳酸鈣等體質顏料；以及鹼性染料、酸性染料及媒染染料等。 The hue adjustment layer is a layer having a hue adjustment function, and the layered body can be adjusted to a target hue layer. The hue adjusting layer is, for example, a layer containing resin and coloring agent. Examples of colorants include inorganic pigments such as titanium oxide, zinc oxide, red iron oxide, titanium dioxide-based fired pigments, ultramarine blue, cobalt aluminate, and carbon black; azo-based compounds, quinacridone-based compounds, and anthracene Anthraquinone-based compound, perylene-based compound, isoindolinone-based compound, phthalocyanine-based compound, quinophthaline-based compound, quinophthalone-based compound, indanthrene-based compound Compounds and organic pigments such as diketo pyrrolo pyrrole compounds; constitutional pigments such as barium sulfate and calcium carbonate; and basic dyes, acid dyes and mordant dyes.

折射率調整層為具有折射率調整功能之層，為具有與基材膜不同折射率並可將預定的折射率賦予至積層體之層。折射率調整層例如可為含有經適當選擇之樹脂、及因應情況更含有顏料之樹脂層，亦可為金屬薄膜。 The refractive index adjustment layer is a layer having a refractive index adjustment function, and has a refractive index different from that of the base film and can impart a predetermined refractive index to the laminate. The refractive index adjustment layer may be, for example, a resin layer containing an appropriately selected resin and, if necessary, a pigment, or a metal thin film.

調整折射率之顏料可列舉例如：氧化矽、氧化鋁、氧化銻、氧化錫、氧化鈦、氧化鋯、氧化鉭。顏料的平均一次粒徑可為0.1μm以下。藉由將顏料的平均一次粒徑設為0.1μm以下，可防止穿透折射率調整層之光的散射，而防止透明度的降低。 Examples of the pigments for adjusting the refractive index include silicon oxide, aluminum oxide, antimony oxide, tin oxide, titanium oxide, zirconium oxide, and tantalum oxide. The average primary particle diameter of the pigment may be 0.1 μm or less. By setting the average primary particle diameter of the pigment to 0.1 μm or less, the scattering of light penetrating the refractive index adjustment layer can be prevented, and the decrease in transparency can be prevented.

折射率調整層所使用之金屬可列舉例如：氧化鈦、氧化鉭、氧化鋯、氧化鋅、氧化錫、氧化矽、氧化銦、氮氧化鈦、氮化鈦、氮氧化矽、氮化矽等金屬氧化物、金屬氮化物等。 Examples of the metal used for the refractive index adjustment layer include titanium oxide, tantalum oxide, zirconium oxide, zinc oxide, tin oxide, silicon oxide, indium oxide, titanium oxynitride, titanium nitride, silicon oxynitride, and silicon nitride. Oxides, metal nitrides, etc.

於基材膜與功能層之間亦可配置上述底漆層。 The primer layer can also be arranged between the base film and the functional layer.

本發明之積層體由於含有使前述硬化性組成物硬化而成之硬化膜，所以表面硬度及彎曲性優異。本發明之積層亦具有優異的氧阻隔性及耐翹曲性。因此有用於作為影像顯示裝置等的前面板。 Since the laminate of the present invention contains a cured film obtained by curing the curable composition, it has excellent surface hardness and flexibility. The laminate of the present invention also has excellent oxygen barrier properties and warpage resistance. Therefore, it is used as a front panel of an image display device or the like.

較佳樣態中，本發明之積層體係直接或隔著樹脂層等而積層(或貼合)於光學膜。光學膜(具有光學特性之膜)可為單層構造(例如偏光片、相位差膜、亮度提升膜、防眩膜、抗反射膜、擴散膜、聚光膜等之光學功能膜等)或是多層構造(例如偏光板、相位差板等)。光學膜較佳為偏光板、偏光片、相位差板或相位差膜，特佳為偏光板。樹脂層並無特別限定，例如可由丙烯酸系樹脂、聚碳酸酯系樹脂、聚酯系樹脂、降莰烯系樹脂、纖維素酯系樹脂、環狀烯烴系樹脂、苯乙烯系樹脂、甲基丙烯酸甲酯-苯乙烯系樹脂、丙烯腈-苯乙烯系樹脂及丙烯腈-丁二烯-苯乙烯系樹脂等所構成。此等樹脂可單獨使用或組合兩種以上使用。再者，積層(或貼合)有本發明之積層體之光學膜，可在與積層體為相反側之面(光學膜側的面)積層(或貼合)分離膜(剝離膜)。該分離膜通常是在使用包含光學膜之積層體時剝離去除。分離膜可列舉例如：聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚碳酸酯、聚芳酯等，可於光學膜側與分離膜側中，對光學膜側的面上施以脫模處理。 In a preferred aspect, the layered system of the present invention is laminated (or laminated) on the optical film directly or via a resin layer or the like. The optical film (film with optical characteristics) can be a single-layer structure (such as optical functional films such as polarizers, retardation films, brightness enhancement films, anti-glare films, anti-reflection films, diffusion films, condensing films, etc.) or Multi-layer structure (eg polarizing plate, retardation plate, etc.). The optical film is preferably a polarizing plate, a polarizing plate, a phase difference plate or a phase difference film, particularly preferably a polarizing plate. The resin layer is not particularly limited, and may be, for example, acrylic resin, polycarbonate resin, polyester resin, norbornene resin, cellulose ester resin, cyclic olefin resin, styrene resin, methacrylic acid It is composed of methyl ester-styrene resin, acrylonitrile-styrene resin and acrylonitrile-butadiene-styrene resin. These resins can be used alone or in combination of two or more. Furthermore, the optical film having the layered body of the present invention is laminated (or bonded), and a separation film (release film) can be laminated (or bonded) on the side opposite to the layered body (surface on the optical film side). This separation film is usually peeled off when using a laminate including an optical film. Examples of the separation film include polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyarylate, etc., which can be on the surface of the optical film side between the optical film side and the separation film side Apply release treatment on it.

本發明之積層體中，氧穿透度較佳為800cc/(m2‧24h‧atm)以下，尤佳為600cc/(m2‧24h‧atm)以下，更佳為400cc/(m2‧24h‧atm)以下，特佳為300cc/(m2‧24h‧ atm)以下。氧穿透度於前述範圍時，在將積層體適用在影像顯示裝置等時可有效地抑制顯示元件或偏光板等的劣化。此外，氧穿透度可藉由實施例所記載之方法來測定。 In the layered product of the present invention, the oxygen permeability is preferably less than 800cc / (m 2 ‧24h‧atm), particularly preferably less than 600cc / (m 2 ‧24h‧atm), and more preferably 400cc / (m 2 ‧ 24h‧atm) or less, the best is 300cc / (m 2 ‧24h‧atm) or less. When the oxygen permeability is within the aforementioned range, the deterioration of the display element, the polarizing plate, etc. can be effectively suppressed when the laminate is applied to an image display device or the like. In addition, the oxygen permeability can be measured by the method described in the examples.

本發明之積層體，較佳係於心軸試驗中以彎曲半徑3mm連續彎折10次時不會產生破裂。特佳樣態中，即使以彎曲半徑2mm連續彎折10次時亦不會產生破裂。本發明之積層體由於具有如此優異的彎曲性，故可較佳地使用在可撓性顯示器。心軸試驗可藉由實施例所記載之方法來測定。 In the laminate of the present invention, it is preferred that the mandrel test does not cause cracking when it is continuously bent 10 times with a bending radius of 3 mm. In the best mode, even if it is continuously bent 10 times with a bending radius of 2 mm, it will not break. Since the laminate of the present invention has such excellent flexibility, it can be preferably used in flexible displays. The mandrel test can be measured by the method described in the examples.

本發明之積層體的鉛筆硬度較佳為H以上，尤佳為2H以上，更佳為3H以上，又更佳為4H以上，特佳為5H以上。本發明之積層體由於具有如此優異的鉛筆硬度，所以在作為影像顯示裝置等的前面板使用時，可有效地抑制影像顯示裝置表面的損傷。 The pencil hardness of the laminate of the present invention is preferably H or higher, particularly preferably 2H or higher, more preferably 3H or higher, still more preferably 4H or higher, and particularly preferably 5H or higher. Since the laminate of the present invention has such excellent pencil hardness, when used as a front panel of an image display device or the like, damage to the surface of the image display device can be effectively suppressed.

本發明之積層體，即使在將積層體裁切為預定大小並放置長時間後，翹曲量小，具有優異的耐翹曲性。翹曲量較佳為±8mm以下，尤佳為±6mm以下，更佳為±5mm以下，更佳為±4mm以下，特佳為±3mm以下。該翹曲量可藉由實施例所記載之方法來測定。 The laminate of the present invention has a small amount of warpage even after the laminate is cut to a predetermined size and left for a long time, and has excellent warpage resistance. The amount of warpage is preferably ± 8 mm or less, particularly preferably ± 6 mm or less, more preferably ± 5 mm or less, more preferably ± 4 mm or less, and particularly preferably ± 3 mm or less. The amount of warpage can be measured by the method described in the examples.

(2)積層體的製造方法 (2) Manufacturing method of laminate

本發明之積層體例如可藉由包含以下步驟之方法來製造：(d)將本發明之硬化性組成物塗佈於基材膜上而形成塗膜之步驟(塗膜形成步驟)， (e)對塗膜照射高能量線使塗膜硬化而形成硬化膜之步驟(硬化步驟)。 The layered product of the present invention can be produced by, for example, a method including the following steps: (d) a step of applying a curable composition of the present invention to a base film to form a coating film (coating film forming step), ) The step of irradiating the coating film with high energy rays to harden the coating film to form a cured film (hardening step).

於塗膜形成步驟中，可將溶解於溶劑之硬化性組成物塗佈於基材膜。溶劑只要是可溶解硬化性組成物即可，可列舉例如：甲醇、乙醇、1-丙醇、2-丙醇(異丙醇)、1-丁醇、2-丁醇(第二丁醇)、2-甲基-1-丙醇(異丁醇)、2-甲基-2-丙醇(第三丁醇)等醇溶劑；2-乙氧基乙醇、2-丁氧基乙醇、3-甲氧基-1-丙醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇等烷氧基醇溶劑；二丙酮醇等縮酮溶劑；丙酮、丁酮、甲基異丁酮等酮溶劑；甲苯、二甲苯等芳香族烴溶劑；乙酸乙酯、乙酸丁酯等酯溶劑等。此等溶劑可單獨使用或組合兩種以上使用。 In the coating film forming step, the curable composition dissolved in the solvent may be applied to the base film. The solvent may be any one that dissolves the hardenable composition, and examples include methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 1-butanol, and 2-butanol (second butanol). , 2-methyl-1-propanol (isobutanol), 2-methyl-2-propanol (third butanol) and other alcohol solvents; 2-ethoxyethanol, 2-butoxyethanol, 3 -Alkoxy alcohol solvents such as methoxy-1-propanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol; ketal solvents such as diacetone alcohol; acetone, butanone , Methyl isobutyl ketone and other ketone solvents; toluene, xylene and other aromatic hydrocarbon solvents; ethyl acetate, butyl acetate and other ester solvents. These solvents can be used alone or in combination of two or more.

亦可進行形成於基材膜上之塗膜的乾燥。塗膜的乾燥可藉由在溫度50至150℃下使溶劑蒸發而進行，乾燥時間通常為30至180秒。亦可在大氣下、惰性環境下或減壓的條件下進行乾燥。 The coating film formed on the base film can also be dried. The coating film can be dried by evaporating the solvent at a temperature of 50 to 150 ° C. The drying time is usually 30 to 180 seconds. It can also be dried in the atmosphere, in an inert environment or under reduced pressure.

再者，於塗膜形成步驟後，可設置將基材膜延伸之延伸步驟。延伸可為單軸延伸或雙軸延伸，從面內相位差分布均一性之觀點而言，較佳是藉由單軸延伸進行基材膜的延伸。進行雙軸延伸時，雙軸延伸可為同步雙軸延伸或逐次雙軸延伸。 Furthermore, after the coating film forming step, an extension step of extending the base film may be provided. The stretching may be uniaxial stretching or biaxial stretching. From the viewpoint of the uniformity of the in-plane retardation distribution, it is preferable to uniaxially stretch the base film. When performing biaxial extension, the biaxial extension may be simultaneous biaxial extension or successive biaxial extension.

於硬化步驟中，對塗膜照射高能量線(例如活化能射線)使塗膜硬化而形成硬化膜。照射強度可因應硬化性組成物的組成來適當地決定，並無特別限定，較佳為 對光陽離子聚合起始劑及光自由基聚合起始劑的活化有效之波長區域的照射。照射強度較佳為0.1至6,000mW/cm2，尤佳為10至1,000mW/cm2，更佳為20至500mW/cm2。照射強度為前述範圍內時，可確保適當的反應時間，並可抑制因從光源所輻射之熱及硬化反應時的熱所導致之黃變或劣化。照射時間可因應硬化性組成物的組成來適當地決定，並無特別限制，可設定為由前述照射強度與照射時間之積所表示之積算光量較佳成為10至10,000mJ/cm2，尤佳成為50至1,000mJ/cm2，更佳成為80至500mJ/cm2。積算光量為前述範圍內時，可產生充分量之來自光陽離子聚合起始劑或光自由基聚合起始劑的活化種，而更確實地進行硬化反應，再者，照射時間不會過長，可維持良好的生產性。又，藉由在此範圍中進行照射步驟，可更為提高硬化膜的硬度，故為有用。 In the curing step, the coating film is irradiated with high energy rays (for example, activation energy rays) to harden the coating film to form a cured film. The irradiation intensity can be appropriately determined according to the composition of the curable composition, and is not particularly limited. Preferably, it is irradiation in a wavelength region effective for activation of the photocationic polymerization initiator and the photoradical polymerization initiator. The irradiation intensity is preferably 0.1 to 6,000 mW / cm 2 , particularly preferably 10 to 1,000 mW / cm 2 , and more preferably 20 to 500 mW / cm 2 . When the irradiation intensity is within the aforementioned range, an appropriate reaction time can be ensured, and yellowing or deterioration due to the heat radiated from the light source and the heat during the hardening reaction can be suppressed. The irradiation time can be appropriately determined according to the composition of the hardenable composition, and is not particularly limited. It can be set to the cumulative light amount expressed by the product of the aforementioned irradiation intensity and irradiation time, preferably 10 to 10,000 mJ / cm 2 , particularly It becomes 50 to 1,000 mJ / cm 2 , more preferably 80 to 500 mJ / cm 2 . When the total amount of light is within the aforementioned range, a sufficient amount of activated species from the photocationic polymerization initiator or photoradical polymerization initiator can be generated, and the hardening reaction can be more reliably performed. Furthermore, the irradiation time will not be too long Can maintain good productivity. In addition, by performing the irradiation step in this range, the hardness of the cured film can be further increased, which is useful.

[3]影像顯示裝置 [3] Video display device

本發明之積層體係有用於作為影像顯示裝置的前面板，尤其是可撓性顯示器的前面板(觸控膜)。本發明中，亦可提供包含本發明之積層體之影像顯示裝置，尤其是可撓性顯示器。本實施形態之可撓性顯示器，例如具有可撓性功能層與積層於可撓性功能層之本發明之積層體(發揮前面板的功能)。亦即，可撓性顯示器的前面板配置在可撓性功能層上的觀看側。此前面板具有保護可撓性功能層之功能。 The layered system of the present invention is useful as a front panel of an image display device, especially a front panel (touch film) of a flexible display. In the present invention, an image display device including the laminate of the present invention, especially a flexible display, can also be provided. The flexible display of the present embodiment includes, for example, the laminated body of the present invention (which functions as a front panel) having a flexible functional layer and a flexible functional layer laminated on it. That is, the front panel of the flexible display is arranged on the viewing side on the flexible functional layer. The front panel has the function of protecting the flexible functional layer.

影像顯示裝置可列舉：電視、智慧型手機、 行動電話、車用導航、平板PC、可攜式遊戲機、電子紙、指示器、告示牌、鐘錶及智慧型手錶等可穿戴式裝置。可撓性顯示器為包含所有具有可撓特性之影像顯示裝置之涵義。 Examples of image display devices include wearable devices such as TVs, smart phones, mobile phones, car navigation, tablet PCs, portable game consoles, electronic paper, indicators, billboards, clocks, and smart watches. Flexible display is meant to include all image display devices with flexible characteristics.

[實施例]     [Example]    

以下顯示實施例及比較例來更具體地說明本發明，但本發明並不限定於此等例子。以下，表示用量、含量之份及%，在無特別言明時為質量基準。 The following shows examples and comparative examples to explain the present invention more specifically, but the present invention is not limited to these examples. In the following, the dosage and content parts and% are indicated, and the quality standard is used unless otherwise specified.

[1-1]製造例1：基材膜1的製造 [1-1] Production Example 1: Production of base film 1

將DMAc添加入至聚醯亞胺的粉末(「KPI-MX300F(100)」、河村產業股份有限公司製、經聚苯乙烯換算重量平均分子量(Mw)=280,000)並溶解後，加入分散介質為GBL之氧化矽溶膠，而調製出以純份基礎計，聚醯亞胺與氧化矽之質量比為1：1之聚醯亞胺清漆。聚醯亞胺清漆中聚醯亞胺樹脂與氧化矽所佔有之合計質量為17質量%。將該聚醯亞胺清漆流體澆注成形後進行乾燥，而得到厚度50μm的基材膜1。 After adding DMAc to the powder of polyimide ("KPI-MX300F (100)", manufactured by Kawamura Industries Co., Ltd., weight average molecular weight (Mw) = 280,000 in terms of polystyrene) and dissolving, the dispersion medium GBL's silica sol is prepared on a pure basis, with a polyimide to silica mass ratio of 1: 1 polyimide varnish. The total mass of polyimide resin and silicon oxide in the polyimide varnish is 17% by mass. This polyimide varnish fluid was cast-molded and dried to obtain a base film 1 with a thickness of 50 μm.

[1-2]製造例2：基材膜2的製造 [1-2] Production Example 2: Production of base film 2

(氧化矽溶膠A的調製) (Modulation of silica sol A)

以藉由溶膠凝膠法所製作之BET徑(以BET法所測定之平均粒徑)27nm的非晶質氧化矽溶膠作為原料，並藉由溶劑置換而調製出經GBL置換之氧化矽溶膠A。 Amorphous silica sol A with BET diameter (average particle diameter measured by BET method) of 27 nm produced by the sol-gel method is used as a raw material, and GBL-substituted silica sol A is prepared by solvent replacement .

(聚醯胺醯亞胺A的合成) (Synthesis of Polyamide Amide A)

於氮氣環境下，將2,2’-雙(三氟甲基)聯苯胺(TFMB)45 質量份及二甲基乙醯胺(DMAc)768.55質量份添加至具備攪拌機之反應容器，一面於室溫下攪拌一面使TFMB溶解於DMAc。接著，將4,4’-(六氟異亞丙基)二鄰苯二甲酸二酐(6FDA)18.92質量份(0.3莫耳倍[相對於TFMB])添加至反應容器，於室溫下攪拌3小時。然後，將4,4’-氧基雙(氯化苯甲醯)(OBBC)4.19質量份(0.1莫耳倍[相對於TFMB])添加至反應容器，接著將對苯二甲醯氯(TPC)17.29質量份(0.6莫耳倍[相對於TFMB])添加至反應容器，於室溫下攪拌1小時。接著，將4-甲基吡啶4.63質量份(0.35莫耳倍[相對於TFMB])與乙酸酐13.04質量份(0.9莫耳倍[相對於TFMB])添加至反應容器，於室溫下攪拌30分鐘，升溫至70℃並更攪拌3.5小時而得到反應液。 Under a nitrogen atmosphere, add 45 parts by mass of 2,2'-bis (trifluoromethyl) benzidine (TFMB) and 768.55 parts by mass of dimethylacetamide (DMAc) to a reaction vessel equipped with a stirrer, on the side The TFMB was dissolved in DMAc while stirring at a warm temperature. Next, 18.92 parts by mass of 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA) (0.3 mole times [relative to TFMB]) was added to the reaction vessel, and stirred at room temperature 3 hours. Then, 4.19 parts by mass of 4,4'-oxybis (benzoyl chloroform) (OBBC) (0.1 mole times [relative to TFMB]) was added to the reaction vessel, followed by terephthaloyl chloride (TPC) ) 17.29 parts by mass (0.6 mole times [relative to TFMB]) was added to the reaction vessel, and stirred at room temperature for 1 hour. Next, 4.63 parts by mass of 4-picoline (0.35 mole times [relative to TFMB]) and 13.04 parts by mass of acetic anhydride (0.9 mole times [relative to TFMB]) were added to the reaction vessel, and stirred at room temperature for 30 The temperature was raised to 70 ° C. in minutes, and the mixture was further stirred for 3.5 hours to obtain a reaction liquid.

將所得到之反應液冷卻至室溫，以絲狀投入於大量的甲醇中並取出所析出之沉澱物，浸漬在甲醇6小時後以甲醇洗淨。接著，於100℃進行沉澱物的減壓乾燥，而得到聚醯胺醯亞胺A。聚醯胺醯亞胺A的重量平均分子量為455,000。 The obtained reaction liquid was cooled to room temperature, put into a large amount of methanol in a filament form, and the deposited precipitate was taken out, immersed in methanol for 6 hours, and washed with methanol. Next, the precipitate was dried under reduced pressure at 100 ° C to obtain polyamidoamide imine A. The weight average molecular weight of polyamidoamide imine A was 455,000.

(聚醯胺醯亞胺清漆A的製造) (Manufacture of Polyamide Amide Imine Varnish A)

將聚醯胺醯亞胺A溶解於GBL後，以成為聚醯胺醯亞胺A：氧化矽粒子=60：40(質量比)之方式添加氧化矽溶膠A，而製造聚醯胺醯亞胺清漆A。以使聚醯胺醯亞胺清漆A中的固形份濃度成為10質量%之方式進行調製。 After dissolving polyimide amide imine A in GBL, silica sol A is added in such a way that it becomes polyimide amide imide A: silica particles = 60:40 (mass ratio), and polyimide amide imide is manufactured Varnish A. It was prepared so that the solid content concentration in the polyamidoamide imine varnish A would be 10% by mass.

以網目開口10μm的過濾器過濾聚醯胺醯亞胺清漆A後，以使自立膜的膜厚成為55μm之方式，使用 施用機(applicator)塗佈於聚酯基材(東洋紡股份有限公司製、商品名稱「A4100」)的平滑面上，於50℃乾燥30分鐘，接著於140℃乾燥15分鐘後，將所得到之塗膜從聚酯基材中剝離，而得到自立膜。將自立膜固定在金屬框，進一步於大氣下以200℃乾燥40分鐘，而得到具有50μm的厚度之基材膜2。 After filtering the polyamidoamide imide varnish A through a filter with a mesh opening of 10 μm, it was applied to a polyester substrate (manufactured by Toyobo Co., Ltd.) using an applicator so that the thickness of the free-standing film became 55 μm. The smooth surface of the trade name "A4100") was dried at 50 ° C for 30 minutes and then at 140 ° C for 15 minutes, and the resulting coating film was peeled from the polyester substrate to obtain a free-standing film. The self-supporting film was fixed to a metal frame, and further dried at 200 ° C. for 40 minutes in the atmosphere to obtain a base film 2 having a thickness of 50 μm.

[2-1]實施例1至25及比較例1 [2-1] Examples 1 to 25 and Comparative Example 1

量秤表1及表2所示之成分後，藉由攪拌而調製出硬化性組成物。使用棒塗佈機將硬化性組成物塗佈於製造例1中所得到之基材膜1，於80℃乾燥3分鐘後，於氮氣環境下使用UV照射裝置「Eye Graphics公司製6KWI燈輸送帶」，以下述硬化條件進行UV硬化，藉此得到於基材膜1之一面之積層有硬化膜積層體。硬化膜的厚度為9μm。在所使用之商品含有溶劑等時，表1及表2所示之各調配成分的調配量為該商品所包含之有效成分的質量份數。 After weighing the ingredients shown in Table 1 and Table 2, the curable composition was prepared by stirring. Using a bar coater, the curable composition was applied to the base film 1 obtained in Production Example 1, and after drying at 80 ° C for 3 minutes, a UV irradiation device "6KWI lamp conveyor belt manufactured by Eye Graphics Corporation" was used under a nitrogen atmosphere. "Using the UV curing under the following curing conditions, thereby obtaining a laminate having a cured film laminated on one surface of the base film 1. The thickness of the cured film was 9 μm. When the product used contains a solvent, etc., the formulation amount of each formulation component shown in Table 1 and Table 2 is the mass part of the active ingredient contained in the product.

(硬化條件) (Hardening conditions)

光源燈：高壓汞燈 Light source lamp: high pressure mercury lamp

積算光量：500mJ/cm2 Total light quantity: 500mJ / cm 2

峰值強度：200mW/cm2 Peak intensity: 200mW / cm 2

此外，積算光量為使用上述UV照射裝置的積層光量計(365nm)所測定之值。 In addition, the integrated light quantity is the value measured using the laminated light meter (365 nm) of the said UV irradiation apparatus.

[2-2]實施例26至29 [2-2] Examples 26 to 29

量秤表3所示之成分後，藉由攪拌而調製出硬化性組成物。除了使用製造例2中所得到之基材膜2取代製造例 1中所得到之基材膜1，並且以使硬化膜的厚度成為16μm之方式調整之外，其他與實施例1至25相同地施作而得到於基材膜2之一面積層有硬化膜之積層體。硬化膜的厚度為16μm。所使用之商品含有溶劑等時，表3所示之各調配成分的調配量為該商品所包含之有效成分的質量份數。 After weighing the ingredients shown in Table 3, a curable composition was prepared by stirring. It is the same as that of Examples 1 to 25 except that the base film 2 obtained in Production Example 2 is used instead of the base film 1 obtained in Production Example 1, and the thickness of the cured film is adjusted to 16 μm. As a result, a laminate having a cured film layered on an area of the base film 2 is obtained. The thickness of the cured film was 16 μm. When the product used contains a solvent, etc., the formulation amount of each formulation component shown in Table 3 is the mass part of the active ingredient contained in the product.

[2-3]實施例30 [2-3] Example 30

量秤表3所示之成分後，藉由攪拌而調製硬化性組成物。除了使用製造例2中所得到之基材膜2取代製造例1中所得到之基材膜1之外，其他與實施例1至25相同地施作，而得到於基材膜2之一面積層有硬化膜之積層體。硬化膜的厚度為9μm。所使用之商品含有溶劑等時，表3所示之各調配成分的調配量為該商品所包含之有效成分的質量份數。 After weighing the ingredients shown in Table 3, the curable composition was prepared by stirring. Except that the substrate film 2 obtained in Production Example 2 was used instead of the substrate film 1 obtained in Production Example 1, the same procedure as in Examples 1 to 25 was carried out to obtain an area layer on the substrate film 2 A laminate with a hardened film. The thickness of the cured film was 9 μm. When the product used contains a solvent, etc., the formulation amount of each formulation component shown in Table 3 is the mass part of the active ingredient contained in the product.

[鉛筆硬度的測定] [Measurement of pencil hardness]

依據JIS K 5600-5-4：1999對實施例1至30及比較例1中所得到之積層體測定硬化膜表面的鉛筆硬度。荷重設為750g。測定結果如表1至表3所示。 The pencil hardness of the surface of the cured film was measured for the laminates obtained in Examples 1 to 30 and Comparative Example 1 according to JIS K 5600-5-4: 1999. The load is set to 750g. The measurement results are shown in Tables 1 to 3.

[心軸試驗] [Spindle test]

依據JIS K 5600-5-1：1999對實施例1至30及比較例1中所得到之積層體進行彎曲試驗，並藉由以下的評估方法進行評估。評估結果如表1至表3所示。 The laminates obtained in Examples 1 to 30 and Comparative Example 1 were subjected to a bending test according to JIS K 5600-5-1: 1999, and evaluated by the following evaluation method. The evaluation results are shown in Tables 1 to 3.

將實施例1至30及比較例1中所得到之積層體裁切為1cm×8cm而得到測定樣本。以使硬化膜成為朝向外側之方式，進行將測定樣本分別捲繞於6mm(半徑R=3mm)或4mm (半徑R=2mm)的輥之操作，並連續進行此操作10次。 The laminates obtained in Examples 1 to 30 and Comparative Example 1 were cut into 1 cm × 8 cm to obtain measurement samples. The measurement sample was wound around a roll of 6 mm (radius R = 3 mm) or 4 mm (radius R = 2 mm) so that the cured film was oriented outward, and this operation was continuously performed 10 times.

根據硬化膜有無產生破損(龜裂)，以下列方式判定彎曲性。判定結果如表1至表3所示。 Based on the presence or absence of damage (cracking) of the cured film, the bendability was determined in the following manner. The judgment results are shown in Table 1 to Table 3.

(彎曲性的判定) (Judgment of flexibility)

◎：無龜裂，外觀良好。 ◎: No cracks and good appearance.

○：產生1至4處的龜裂。 ○: Cracks at 1 to 4 places occurred.

△：產生5處以上的龜裂。 △: Five or more cracks occurred.

[氧穿透度的測定] [Measurement of oxygen permeability]

依據JIS K 7126-1(差壓法)，使用GTR TEC股份有限公司製的差壓式氣體穿透率測定裝置「GTR-30AS型」對實施例1至30及比較例1中所得到之積層體測定氧穿透度。測定結果如表1至表3所示。 In accordance with JIS K 7126-1 (differential pressure method), the laminates obtained in Examples 1 to 30 and Comparative Example 1 were formed using a differential pressure gas permeability measuring device "GTR-30AS type" manufactured by GTR TEC Corporation Determination of oxygen permeability. The measurement results are shown in Tables 1 to 3.

[翹曲測定] [Warpage measurement]

將實施例1至30及比較例1中所得到之積層體裁切為3.5cm×4.0cm，在23℃/50%RH的恆溫恆濕條件下進行24小時狀態調整後得到測定樣本。以使下側成為凸側之方式將測定樣本靜置於平面上，使用數位尺寸測定裝置LS-7600(KEYENCE公司製)，分別測量從平面至測定樣本的4個角落部為止之高度，將所得到之4點之值的平均值設為翹曲量。 The laminates obtained in Examples 1 to 30 and Comparative Example 1 were cut to 3.5 cm × 4.0 cm, and the measurement samples were obtained after 24 hours of state adjustment under a constant temperature and humidity condition of 23 ° C / 50% RH. Place the measurement sample on a flat surface so that the lower side is convex, and measure the height from the flat surface to the four corners of the measurement sample using a digital size measuring device LS-7600 (manufactured by KEYENCE). The average value of the obtained four points was defined as the amount of warpage.

表1至表3所示之各調配成分的詳細內容如下所述。 The details of each formulation component shown in Table 1 to Table 3 are as follows.

〈3官能A(丙烯酸酯)單體〉 <3-functional A (acrylate) monomer>

三丙烯酸三羥甲基丙烷酯(「A-TMPT」、新中村化學工業股份有限公司製) Trimethylolpropane triacrylate ("A-TMPT", manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

〈4官能A(丙烯酸酯)單體〉 <4-functional A (acrylate) monomer>

四丙烯酸新戊四醇酯(「A-TMMT」、新中村化學工業 股份有限公司製) Neopentaerythritol tetraacrylate ("A-TMMT", manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

〈6官能A(丙烯酸酯)單體〉 <6 functional A (acrylate) monomer>

六丙烯酸二新戊四醇酯(「A-DPH」、新中村化學工業股份有限公司製) Dipentaerythritol hexaacrylate ("A-DPH", manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

〈8官能A(丙烯酸酯)單體〉 <8-functional A (acrylate) monomer>

八丙烯酸三新戊四醇酯(「A-TPE-H-NS」、新中村化學工業股份有限公司製) Tripentaerythritol octaacrylate ("A-TPE-H-NS", manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

〈雙環狀醚化合物1〉 <Bicyclic Ether Compound 1>

3,4-環氧基環己基甲基3,4-環氧基環己烷羧酸酯(「Celloxide(註冊商標)2021P」、Daicel化學股份有限公司製) 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate ("Celloxide (registered trademark) 2021P", manufactured by Daicel Chemical Co., Ltd.)

〈雙環狀醚化合物2〉 <Bicyclic Ether Compound 2>

3-乙基-3[{(3-乙基氧雜環丁烷-3-基)甲氧基}甲基]氧雜環丁烷(「OXT-221」、東亞合成股份有限公司製) 3-ethyl-3 [{(3-ethyloxetane-3-yl) methoxy} methyl] oxetane ("OXT-221", manufactured by East Asia Synthesis Co., Ltd.)

〈雙環狀醚化合物3〉 <Bicyclic Ether Compound 3>

二甲苯雙氧雜環丁烷之混合物(二甲苯骨架的重複單元數為1、2或3之混合物)(「OXT-121」、東亞合成股份有限公司製) A mixture of xylene dioxetane (a mixture of 1, 2 or 3 repeating units of the xylene skeleton) ("OXT-121", manufactured by East Asia Synthetic Co., Ltd.)

〈自由基聚合性環狀醚化合物〉 <Free radical polymerizable cyclic ether compound>

甲基丙烯酸3,4-環氧基環己基甲酯(「Cyclomer(註冊商標)M100」、Daicel化學股份有限公司製) 3,4-epoxycyclohexyl methyl methacrylate ("Cyclomer (registered trademark) M100", manufactured by Daicel Chemical Co., Ltd.)

〈乙烯氧基化合物〉 <Vinyloxy compound>

環己烷二甲醇二乙烯醚(SIGMA-ALDRICH公司製) Cyclohexane dimethanol divinyl ether (manufactured by SIGMA-ALDRICH)

〈無機粒子〉 <Inorganic particles>

經丙烯醯基修飾之氧化矽粒子(「PGM-AC-2140Y」、日產化學股份有限公司製、粒徑10至15nm) Silica particles modified with acrylamide ("PGM-AC-2140Y", manufactured by Nissan Chemical Co., Ltd., with a particle size of 10 to 15 nm)

〈陽離子聚合起始劑〉 <Cationic polymerization initiator>

錪鹽(4-甲基苯基)[4-(2-甲基丙基)苯基]-六氟磷酸鹽與碳酸丙烯酯之3：1(質量比)的混合物(「IRGACURE(註冊商標)250」、BASF Japan股份有限公司製) Podium salt (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate and propylene carbonate 3: 1 (mass ratio) mixture ("IRGACURE (registered trademark) 250 '', manufactured by BASF Japan Co., Ltd.)

〈自由基聚合起始劑〉 <Free radical polymerization initiator>

1-羥基-環己基-苯基-酮(「IRGACURE 184」、BASF Japan股份有限公司製) 1-hydroxy-cyclohexyl-phenyl-one ("IRGACURE 184", manufactured by BASF Japan Co., Ltd.)

〈勻染劑〉 <Levelling agent>

聚矽氧系勻染劑(「BYK(註冊商標)-307」、BYK Chemie Japan股份有限公司製) Polysilicone leveling agent ("BYK (registered trademark) -307", manufactured by BYK Chemie Japan Co., Ltd.)

相較於比較例1之積層體，實施例1至30之積層體可確認到鉛筆硬度高且於R=3的心軸試驗中不會產生外觀不良。進一步，可確認到氧穿透度低且翹曲量小。在如此實施例1至30中所得到之積層體，具有優異的表面硬度及彎曲性。再者，亦具有優異的氧阻隔性及耐翹曲性。 Compared with the laminate of Comparative Example 1, the laminates of Examples 1 to 30 can be confirmed to have a high pencil hardness and no appearance defect in the mandrel test of R = 3. Furthermore, it was confirmed that the oxygen permeability is low and the amount of warpage is small. The laminates thus obtained in Examples 1 to 30 have excellent surface hardness and flexibility. Furthermore, it also has excellent oxygen barrier properties and warpage resistance.

關於彎曲性，實施例4、8、9、10、14、16、17、22及25中所得到之積層體，即使於R=2的心軸試驗中，亦僅產生1至4mm的龜裂。再者，實施例6、12、15、18至21、23、24及26至30中所得到之積層體，即使於在R=2下所進行之心軸試驗中，外觀亦良好。 Regarding flexibility, the laminates obtained in Examples 4, 8, 9, 10, 14, 16, 17, 22, and 25 produced only 1 to 4 mm cracks even in the mandrel test with R = 2 . In addition, the laminates obtained in Examples 6, 12, 15, 18 to 21, 23, 24, and 26 to 30 had good appearance even in the mandrel test conducted at R = 2.

Claims (18)

一種硬化性組成物，其係含有：包含選自由3官能(甲基)丙烯酸酯單體、4官能(甲基)丙烯酸酯單體及8官能(甲基)丙烯酸酯單體所組成之群組的至少2種之多官能(甲基)丙烯酸酯單體(A)，以及陽離子聚合性單體(B)，其中，相對於多官能(甲基)丙烯酸酯單體(A)100質量份，3官能(甲基)丙烯酸酯單體、4官能(甲基)丙烯酸酯單體及8官能(甲基)丙烯酸酯單體的總質量為50質量份以上。     A hardening composition comprising: a group selected from the group consisting of 3-functional (meth) acrylate monomers, 4-functional (meth) acrylate monomers and 8-functional (meth) acrylate monomers At least two kinds of multifunctional (meth) acrylate monomers (A) and cation polymerizable monomers (B), wherein, relative to 100 parts by mass of the multifunctional (meth) acrylate monomer (A), The total mass of the trifunctional (meth) acrylate monomer, the 4-functional (meth) acrylate monomer, and the 8-functional (meth) acrylate monomer is 50 parts by mass or more.     如申請專利範圍第1項所述之硬化性組成物，其中，陽離子聚合性單體(B)含有具有1個以上環氧基及/或1個以上氧雜環丁烷基之環狀醚化合物(B-1)。     The curable composition as described in item 1 of the patent application scope, wherein the cationic polymerizable monomer (B) contains a cyclic ether compound having one or more epoxy groups and / or one or more oxetanyl groups (B-1).     如申請專利範圍第2項所述之硬化性組成物，其中，環狀醚化合物(B-1)含有具有2個以上環氧基及/或2個以上氧雜環丁烷基之雙環狀醚化合物(B-1-1)。     The curable composition as described in item 2 of the patent application, wherein the cyclic ether compound (B-1) contains a bicyclic ring having two or more epoxy groups and / or two or more oxetanyl groups Ether compound (B-1-1).     如申請專利範圍第1至3項中任一項所述之硬化性組成物，其中，陽離子聚合性單體(B)更含有乙烯氧基化合物(B-2)。     The hardenable composition as described in any one of claims 1 to 3, wherein the cationic polymerizable monomer (B) further contains an ethyleneoxy compound (B-2).     如申請專利範圍第4項所述之硬化性組成物，其中，相對於硬化性組成物100質量份，多官能(甲基)丙烯酸酯單體(A)的含量為5至80質量份，環狀醚化合物(B-1)的含量為5至80質量份，乙烯氧基化合物(B-2)的含量為3至60質量份。     The curable composition as described in item 4 of the patent application scope, wherein the content of the polyfunctional (meth) acrylate monomer (A) is 5 to 80 parts by mass relative to 100 parts by mass of the curable composition. The content of the ether compound (B-1) is 5 to 80 parts by mass, and the content of the vinyloxy compound (B-2) is 3 to 60 parts by mass.     如申請專利範圍第4或5項所述之硬化性組成物，其 中，相對於多官能(甲基)丙烯酸酯單體(A)及陽離子聚合性單體(B)的總量100質量份，乙烯氧基化合物(B-2)的含量為3至50質量份。     The curable composition as described in item 4 or 5 of the patent application scope, wherein, relative to the total amount of 100 parts by mass of the polyfunctional (meth) acrylate monomer (A) and the cationic polymerizable monomer (B) The content of the vinyloxy compound (B-2) is 3 to 50 parts by mass.     如申請專利範圍第2至6項中任一項所述之硬化性組成物，其中，環狀醚化合物(B-1)含有具有1個以上自由基聚合性官能基之自由基聚合性環狀醚化合物(B-1-2)。     The curable composition according to any one of claims 2 to 6, wherein the cyclic ether compound (B-1) contains a radically polymerizable cyclic group having one or more radically polymerizable functional groups Ether compound (B-1-2).     如申請專利範圍第7項所述之硬化性組成物，其中，相對於硬化性組成物100質量份，多官能(甲基)丙烯酸酯單體(A)的含量為5至50質量份，雙環狀醚化合物(B-1-1)的含量為3至30質量份，自由基聚合性環狀醚化合物(B-1-2)的含量為5至40質量份。     The curable composition as described in item 7 of the patent application scope, wherein the content of the polyfunctional (meth) acrylate monomer (A) is 5 to 50 parts by mass relative to 100 parts by mass of the curable composition, the double The content of the cyclic ether compound (B-1-1) is 3 to 30 parts by mass, and the content of the radically polymerizable cyclic ether compound (B-1-2) is 5 to 40 parts by mass.     如申請專利範圍第7或8項所述之硬化性組成物，其中，相對於雙環狀醚化合物(B-1-1)1質量份，自由基聚合性環狀醚化合物(B-1-2)的含量為0.1至10質量份。     The curable composition according to item 7 or 8 of the patent application scope, wherein the radically polymerizable cyclic ether compound (B-1- The content of 2) is 0.1 to 10 parts by mass.     如申請專利範圍第1至9項中任一項所述之硬化性組成物，其更含有自由基聚合起始劑(C)及陽離子聚合起始劑(D)。     The hardenable composition according to any one of items 1 to 9 of the patent application scope further contains a radical polymerization initiator (C) and a cationic polymerization initiator (D).     如申請專利範圍第10項所述之硬化性組成物，其中，相對於多官能(甲基)丙烯酸酯單體(A)100質量份，自由基聚合起始劑(C)的含量為1至15質量份；相對於陽離子聚合性單體(B)100質量份，陽離子聚合起始劑(D)的含量為1至15質量份。     The curable composition as described in item 10 of the patent application scope, wherein the content of the radical polymerization initiator (C) is 1 to 100 parts by mass of the multifunctional (meth) acrylate monomer (A) 15 parts by mass; the content of the cationic polymerization initiator (D) is 1 to 15 parts by mass relative to 100 parts by mass of the cationic polymerizable monomer (B).     如申請專利範圍第1至11項中任一項所述之硬化性組 成物，其更含有無機粒子。     The curable composition as described in any one of claims 1 to 11 further contains inorganic particles.     如申請專利範圍第12項所述之硬化性組成物，其中，無機粒子為反應性氧化矽粒子時，相對於硬化性組成物的質量，反應性氧化矽粒子的含量為1至70質量%。     The curable composition as described in item 12 of the patent application range, wherein when the inorganic particles are reactive silica particles, the content of the reactive silica particles is 1 to 70% by mass relative to the mass of the curable composition.     一種硬化膜，其係使申請專利範圍第1至13項中任一項所述之硬化性組成物硬化而成者。     A cured film obtained by curing the curable composition as described in any one of patent application items 1 to 13.     一種積層體，其係於基材膜之至少一面積層有申請專利範圍第14項所述之硬化膜。     A laminate having a cured film as described in item 14 of the patent application scope on at least one area layer of a base film.     如申請專利範圍第15項所述之積層體，其中，基材膜係含有聚醯亞胺系高分子而成者。     The laminate as described in item 15 of the patent application, wherein the base film is made of a polyimide-based polymer.     如申請專利範圍第15或16項所述之積層體，其中，氧穿透度為800cc/(m 2‧24h‧atm)以下。 The laminate as described in item 15 or 16 of the patent application, wherein the oxygen permeability is less than 800cc / (m 2 ‧24h‧atm). 一種可撓性顯示器，其係包含申請專利範圍第15至17項中任一項所述之積層體。     A flexible display comprising the laminate as described in any one of claims 15 to 17.    
TW107132438A 2017-09-15 2018-09-14 Curable composition TWI786185B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017178243 2017-09-15
JP2017-178243 2017-09-15

Publications (2)

Publication Number Publication Date
TW201925367A true TW201925367A (en) 2019-07-01
TWI786185B TWI786185B (en) 2022-12-11

Family

ID=65723719

Family Applications (1)

Application Number Title Priority Date Filing Date
TW107132438A TWI786185B (en) 2017-09-15 2018-09-14 Curable composition

Country Status (5)

Country Link
JP (1) JPWO2019054412A1 (en)
KR (1) KR20200052948A (en)
CN (1) CN111065669B (en)
TW (1) TWI786185B (en)
WO (1) WO2019054412A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI706012B (en) * 2019-09-12 2020-10-01 明基材料股份有限公司 A high hardness flexible hard coating film

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110669423B (en) * 2019-09-23 2023-01-24 明基材料有限公司 High-hardness flexible hard coating film and display

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4055427B2 (en) * 2001-02-23 2008-03-05 富士フイルム株式会社 CURABLE COMPOSITION, HARD COAT TREATED ARTICLE USING THE SAME, AND IMAGE DISPLAY DEVICE
JP2002287356A (en) * 2001-03-28 2002-10-03 Nippon Paint Co Ltd Photosensitive solder resist composition
JP2009202456A (en) 2008-02-28 2009-09-10 Toray Ind Inc Laminate sheet
JP2012047787A (en) * 2010-08-24 2012-03-08 Daicel Corp Photosensitive composition for volume hologram recording and method for manufacturing medium
US9527994B2 (en) * 2010-10-29 2016-12-27 Kuraray Co., Ltd. Methacrylic resin composition, resin modifier, and molded article
JP2014043506A (en) * 2012-08-27 2014-03-13 Toyo Ink Sc Holdings Co Ltd Resin composition and coating film using the same
JP2014051601A (en) * 2012-09-07 2014-03-20 Nippon Shokubai Co Ltd Optical formed body
JP6167090B2 (en) * 2014-09-30 2017-07-19 富士フイルム株式会社 Hard coat film, method for producing hard coat film, polarizing plate, and liquid crystal display device
CN107406690B (en) * 2015-04-21 2020-06-09 株式会社大赛璐 Resin composition for forming hard coat layer and cured product thereof
JP7199790B2 (en) * 2021-01-28 2023-01-06 日東電工株式会社 Active energy ray-curable adhesive composition, laminated polarizing film and method for producing the same, laminated optical film and image display device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI706012B (en) * 2019-09-12 2020-10-01 明基材料股份有限公司 A high hardness flexible hard coating film
US11326072B2 (en) 2019-09-12 2022-05-10 Benq Materials Corporation High hardness flexible hard coating film

Also Published As

Publication number Publication date
TWI786185B (en) 2022-12-11
CN111065669A (en) 2020-04-24
KR20200052948A (en) 2020-05-15
JPWO2019054412A1 (en) 2020-11-19
WO2019054412A1 (en) 2019-03-21
CN111065669B (en) 2022-07-15

Similar Documents

Publication Publication Date Title
TWI773728B (en) Polyimide film
CN110234687B (en) Polyimide film and laminate
KR102042677B1 (en) Optical multilayer body
JP6936206B2 (en) Optical laminate
JP6952735B2 (en) Optical film, optical laminate and flexible image display device
CN112041708B (en) Optical film, optical laminate, and flexible image display device
CN110031920B (en) Optical laminate
TWI786185B (en) Curable composition
TW202003256A (en) Optical film having excellent impact resistance
WO2020230663A1 (en) Varnish, optical film, and method for manufacturing optical film
JP2020111750A (en) Optical film
JP6799182B2 (en) Optical film, flexible display device, and resin composition