TW202309124A - Curable composition, active-energy-ray-curable composition, and active-energy-ray-curable coating composition - Google Patents

Curable composition, active-energy-ray-curable composition, and active-energy-ray-curable coating composition Download PDF

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TW202309124A
TW202309124A TW111115260A TW111115260A TW202309124A TW 202309124 A TW202309124 A TW 202309124A TW 111115260 A TW111115260 A TW 111115260A TW 111115260 A TW111115260 A TW 111115260A TW 202309124 A TW202309124 A TW 202309124A
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meth
acrylate
mixture
composition
component
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大房一樹
橋本直樹
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日商東亞合成股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/147—Polyurethanes; Polyureas
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

To provide a curable composition containing a polyfunctional urethane (meth)acrylate adduct that has a low viscosity, exhibits an excellent balance of surface hardness, scratch resistance, and flexibility as a cured film thereof, and also has exceptional curling properties, preferably to provide an active-energy-ray-curable composition, especially a composition that can be suitably used as a coating. A curable composition containing component (A). Component (A): a reaction product of an organic polyisocyanate and a mixture (a1) of at least one compound selected from the group consisting of glycerin (meth)acrylates and diglycerin (meth)acrylates, the mixture having a hydroxyl value of 20-300 mg KOH/g.

Description

硬化型組成物、活性能量線硬化型組成物及活性能量線硬化型塗佈劑組成物Curing composition, active energy ray curing composition, and active energy ray curing coating agent composition

本發明是有關於一種硬化型組成物，較佳為活性能量線硬化型組成物，其中所述硬化型組成物包含作為具有一個以上的羥基及兩個以上的(甲基)丙烯醯基的化合物與有機聚異氰酸酯的胺基甲酸酯化反應物的胺基甲酸酯(甲基)丙烯酸酯〔以下，稱為「多官能胺基甲酸酯(甲基)丙烯酸酯加成物」〕。 本發明的組成物能夠用於各種用途，特別是與以往的多官能胺基甲酸酯(甲基)丙烯酸酯加成物相比具有低黏度且快速硬化性，在用作硬塗劑的原料的情況下，可獲得所得的硬化膜的彈性係數與彎曲性的平衡良好的組成物，因此，可較佳地用作塗佈劑組成物，屬於該些技術領域。 再者，在本說明書中，將丙烯醯基及/或甲基丙烯醯基稱為(甲基)丙烯醯基，將丙烯酸酯及/或甲基丙烯酸酯稱為(甲基)丙烯酸酯，將丙烯酸及/或甲基丙烯酸稱為(甲基)丙烯酸。 The present invention relates to a curable composition, preferably an active energy ray curable composition, wherein the curable composition contains as a compound having one or more hydroxyl groups and two or more (meth)acryl groups Urethane (meth)acrylate [hereinafter referred to as "polyfunctional urethane (meth)acrylate adduct"] of the urethane-forming reaction product with organic polyisocyanate. The composition of the present invention can be used in various applications, and it is particularly useful as a raw material for hard coating agents because it has low viscosity and rapid curing compared with conventional polyfunctional urethane (meth)acrylate adducts. In the case of the obtained cured film, a composition having a good balance between the modulus of elasticity and flexibility of the obtained cured film can be obtained, so it can be preferably used as a coating agent composition and belongs to these technical fields. Furthermore, in this specification, acryl and/or methacryl are referred to as (meth)acryl, acrylate and/or methacrylate are referred to as (meth)acrylate, and Acrylic acid and/or methacrylic acid are called (meth)acrylic acid.

多官能胺基甲酸酯(甲基)丙烯酸酯加成物是藉由使具有一個以上的羥基及兩個以上的(甲基)丙烯醯基的多官能(甲基)丙烯酸酯與具有兩個以上的異氰酸酯基的有機聚異氰酸酯反應而獲得的化合物，由於硬化性、硬化膜的拉伸強度、伸長率、及強韌性優異，因此用於塗佈劑、油墨、黏著劑、接著劑、及密封劑等各種硬化型組成物，特別是用於活性能量線硬化型組成物。The multifunctional urethane (meth)acrylate adduct is made by combining a multifunctional (meth)acrylate with more than one hydroxyl group and two or more (meth)acryl groups with two The compound obtained by reacting the above isocyanate-based organic polyisocyanate is excellent in curability, tensile strength, elongation, and toughness of the cured film, so it is used in coating agents, inks, adhesives, adhesives, and sealants. Various hardening type compositions such as agents, especially for active energy ray hardening type compositions.

作為廣泛使用所述多官能胺基甲酸酯(甲基)丙烯酸酯加成物的用途，可列舉塑膠用硬塗劑。 塑膠基材輕量，且耐衝擊性及易成形性等優異，但表面容易損傷，硬度低，因此若直接使用，則存在顯著損害外觀的缺點。因此，要求利用塗料組成物塗裝塑膠基材的表面，進行所謂的硬塗層處理，賦予耐擦傷性，提高表面硬度。 以往，作為硬塗劑原料，多官能胺基甲酸酯(甲基)丙烯酸酯加成物中，使用一分子內具有十個以上的(甲基)丙烯醯基的多官能胺基甲酸酯(甲基)丙烯酸酯加成物。 Examples of applications in which the polyfunctional urethane (meth)acrylate adduct is widely used include hard coating agents for plastics. Plastic substrates are lightweight and have excellent impact resistance and formability. However, the surface is easily damaged and the hardness is low. Therefore, if it is used as it is, the appearance will be significantly damaged. Therefore, it is required to coat the surface of the plastic base material with a paint composition to perform a so-called hard coat treatment to impart scratch resistance and increase surface hardness. Conventionally, polyfunctional urethane (meth)acrylate adducts having ten or more (meth)acryl groups in one molecule have been used as raw materials for hard coat agents. (meth)acrylate adducts.

專利文獻1中揭示了一種活性能量線硬化型組成物，其包含二季戊四醇五丙烯酸酯與脂肪族二價異氰酸酯的反應物，即，一分子中具有十個(甲基)丙烯醯基的多官能胺基甲酸酯(甲基)丙烯酸酯加成物。 然而，該專利的組成物雖然硬化膜硬度、耐擦傷性及基材密接性優異，但是當將實施了硬塗層處理的膜基材彎曲時，容易引起破裂或剝離，彎曲性不充分。另一方面，若欲改善耐彎曲性，則硬化膜硬度、及耐擦傷性不充分，難以兼顧該些物性。另外，亦存在實施了硬塗層處理的膜容易捲曲，損害外觀品質的問題。 另外，該專利的多官能胺基甲酸酯(甲基)丙烯酸酯加成物的黏度高，若製成不使用稀釋溶劑的無溶劑的組成物，則黏度變得非常高，亦存在塗佈性差的問題。 Patent Document 1 discloses an active energy ray-curing composition comprising a reaction product of dipentaerythritol pentaacrylate and aliphatic divalent isocyanate, that is, a polyfunctional compound having ten (meth)acryl groups in one molecule. Urethane (meth)acrylate adducts. However, although the composition of this patent is excellent in cured film hardness, scratch resistance, and substrate adhesion, when the hard-coated film substrate is bent, cracks or peeling are likely to occur, and the bendability is insufficient. On the other hand, if the bending resistance is to be improved, the hardness of the cured film and the scratch resistance are not sufficient, and it is difficult to balance these physical properties. In addition, there is also a problem that the hard-coated film tends to curl and impairs the quality of appearance. In addition, the polyfunctional urethane (meth)acrylate adduct of this patent has a high viscosity. If it is made into a solvent-free composition without using a diluent solvent, the viscosity becomes very high, and there are also coating problems. problem of poor sex.

專利文獻2中揭示了一種活性能量線硬化型組成物，其包含二季戊四醇五丙烯酸酯與具有異三聚氰酸基骨架的三價異氰酸酯的反應物，即，一分子中具有15個(甲基)丙烯醯基的胺基甲酸酯(甲基)丙烯酸酯加成物。 然而，該專利的組成物雖然硬化膜硬度、耐擦傷性及復原性優異，但是若將實施了硬塗層處理的膜基材彎曲，則容易引起破裂或剝離，彎曲性不充分。另外，與專利文獻1同樣地，若欲改善彎曲性，則硬化膜硬度及耐擦傷性變得不充分，難以兼顧該些物性。另外，與專利文獻1同樣地，實施了硬塗層處理的膜容易捲曲，亦存在損害外觀品質的問題。進而，該專利的多官能胺基甲酸酯(甲基)丙烯酸酯加成物亦存在黏度高的問題。 Patent Document 2 discloses an active energy ray-curable composition comprising a reactant of dipentaerythritol pentaacrylate and a trivalent isocyanate having an isocyanuric acid group skeleton, that is, a molecule having 15 (methyl ) urethane (meth)acrylate adducts of acryl groups. However, although the composition of this patent has excellent cured film hardness, scratch resistance, and restorability, when the film substrate subjected to the hard coat treatment is bent, cracks or peeling are likely to occur, and the bendability is insufficient. Moreover, similarly to Patent Document 1, if the bendability is to be improved, the hardness of the cured film and the scratch resistance will become insufficient, and it will be difficult to balance these physical properties. Moreover, similarly to Patent Document 1, the hard-coat-treated film tends to curl, and there is also a problem that the appearance quality is impaired. Furthermore, the polyfunctional urethane (meth)acrylate adduct of this patent also has the problem of high viscosity.

如此，作為硬塗劑的原料使用的以往的多官能胺基甲酸酯(甲基)丙烯酸酯加成物若增加分子中的(甲基)丙烯醯基數，則雖然硬化膜硬度提高，但是存在彎曲性變差的問題。另外，由於多官能胺基甲酸酯(甲基)丙烯酸酯加成物的黏度高，因此亦存在塗佈性變差的問題。 [現有技術文獻] [專利文獻] In this way, if the conventional polyfunctional urethane (meth)acrylate adducts used as raw materials for hard coating agents increase the number of (meth)acryl groups in the molecule, the hardness of the cured film will increase, but there will be The problem of poor bendability. In addition, since the polyfunctional urethane (meth)acrylate adduct has a high viscosity, there is also a problem of poor applicability. [Prior art literature] [Patent Document]

[專利文獻1]日本專利特開2011-12099號公報 [專利文獻2]國際公開第2012/86551號手冊 [Patent Document 1] Japanese Patent Laid-Open No. 2011-12099 [Patent Document 2] International Publication No. 2012/86551 Handbook

[發明所欲解決之課題] 本發明者等人為了發現低黏度、且其硬化膜的表面硬度及耐擦傷性與彎曲性的平衡良好，捲曲性亦優異的包含多官能胺基甲酸酯(甲基)丙烯酸酯加成物的硬化型組成物，為了發現較佳為活性能量線硬化型組成物，特別是較佳用作塗佈劑的組成物，進行了深入研究。 [解決課題之手段] [Problem to be Solved by the Invention] The inventors of the present invention have discovered a polyfunctional urethane (meth)acrylate adduct that has a low viscosity, a cured film that has a good balance between surface hardness, scratch resistance, and flexibility, and is excellent in curling properties. Intensive research has been conducted to find a composition that is preferably an active energy ray-curable composition, especially a composition that is preferably used as a coating agent. [Means to solve the problem]

本發明者等人為了解決所述課題，發現含有多官能胺基甲酸酯(甲基)丙烯酸酯加成物作為必須成分的活性能量線硬化型組成物為低黏度，其硬化膜的硬度、耐擦傷性、彎曲性及捲曲性的物性優異，從而完成了本發明，其中所述多官能胺基甲酸酯(甲基)丙烯酸酯是藉由特定的甘油(甲基)丙烯酸酯及/或二甘油(甲基)丙烯酸酯與有機聚異氰酸酯的胺基甲酸酯化反應而獲得。 以下，詳細說明本發明。 [發明的效果] In order to solve the above-mentioned problems, the present inventors have found that an active energy ray-curable composition containing a multifunctional urethane (meth)acrylate adduct as an essential component has a low viscosity, and the hardness of the cured film, The physical properties of scratch resistance, bendability and curling property are excellent, thereby completing the present invention, wherein the polyfunctional urethane (meth)acrylate is obtained by specific glycerin (meth)acrylate and/or It is obtained by the carbamate reaction of diglycerol (meth)acrylate with organic polyisocyanate. Hereinafter, the present invention will be described in detail. [Effect of the invention]

根據本發明的組成物，黏度低，其硬化膜可同時滿足表面硬度及耐擦傷性與彎曲性的平衡，捲曲性亦優異。 因此，本發明的組成物可較佳地用作塗佈劑，可更佳地用作硬塗劑。 According to the composition of the present invention, the viscosity is low, and the cured film thereof satisfies the balance between surface hardness, scratch resistance and flexibility, and is excellent in curling property. Therefore, the composition of the present invention can be preferably used as a coating agent, more preferably as a hard coating agent.

本發明是有關於下述硬化型組成物。The present invention relates to the following hardening type composition.

[1]一種硬化型組成物，包含下述（A）成分， （A）成分：混合物（a1）與有機聚異氰酸酯的反應物，其中所述混合物（a1）為選自由甘油(甲基)丙烯酸酯及二甘油(甲基)丙烯酸酯所組成的群組中的至少一種化合物的混合物，且羥值為20 mgKOH/g～300 mgKOH/g。 [1] A curable composition comprising the following component (A), (A) Component: a reactant of mixture (a1) and organic polyisocyanate, wherein said mixture (a1) is selected from the group consisting of glycerol (meth)acrylate and diglycerol (meth)acrylate A mixture of at least one compound with a hydroxyl value of 20 mgKOH/g to 300 mgKOH/g.

[2]如[1]所述的硬化型組成物，其中有機聚異氰酸酯為脂肪族聚異氰酸酯或脂環式聚異氰酸酯。[2] The curable composition according to [1], wherein the organic polyisocyanate is an aliphatic polyisocyanate or an alicyclic polyisocyanate.

[3]如[1]或[2]所述的硬化型組成物，其中所述混合物（a1）為在下述觸媒X及觸媒Y的存在下，使甘油或二甘油與具有一個(甲基)丙烯醯基的化合物〔以下，稱為單官能(甲基)丙烯酸酯〕進行酯交換反應而得的(甲基)丙烯酸酯混合物，且為羥值為20 mgKOH/g～300 mgKOH/g的混合物。 觸媒X：選自由具有氮雜雙環結構的環狀三級胺或其鹽或者錯合物、脒或其鹽或者錯合物、具有吡啶環的化合物或其鹽或者錯合物、及膦或其鹽或者錯合物所組成的群組中的一種以上的化合物。 觸媒Y：含鋅的化合物。 [3] The curable composition according to [1] or [2], wherein the mixture (a1) is obtained by mixing glycerin or diglycerin with one (a (meth)acrylic ester mixture obtained by transesterification reaction of acrylyl compound [hereinafter referred to as monofunctional (meth)acrylate], and the hydroxyl value is 20 mgKOH/g～300 mgKOH/g mixture. Catalyst X: selected from cyclic tertiary amines with azabicyclic structure or their salts or complexes, amidines or their salts or complexes, compounds with pyridine rings or their salts or complexes, and phosphine or More than one compound in the group consisting of its salt or complex. Catalyst Y: a compound containing zinc.

[4]如[3]所述的硬化型組成物，其中單官能(甲基)丙烯酸酯為烷氧基烷基(甲基)丙烯酸酯。[4] The curable composition according to [3], wherein the monofunctional (meth)acrylate is an alkoxyalkyl (meth)acrylate.

[5]如[3]或[4]所述的硬化型組成物，其中所述觸媒X為選自由具有氮雜雙環結構的環狀三級胺或其鹽或者錯合物、脒或其鹽或者錯合物、及具有吡啶環的化合物或其鹽或者錯合物所組成的群組中的一種以上的化合物。[5] The curable composition as described in [3] or [4], wherein the catalyst X is selected from the group consisting of cyclic tertiary amines having an azabicyclic structure or their salts or complexes, amidines, or One or more compounds in the group consisting of a salt or a complex, and a compound having a pyridine ring or a salt or a complex thereof.

[6]如[3]至[5]中任一項所述的硬化型組成物，其中所述觸媒Y為有機酸鋅或/及二酮烯醇鋅（zinc diketone enolate）。[6] The curable composition according to any one of [3] to [5], wherein the catalyst Y is zinc organic acid or/and zinc diketone enolate.

[7]如[1]至[6]中任一項所述的硬化型組成物，其中（A）成分的重量平均分子量為500～10,000。[7] The curable composition according to any one of [1] to [6], wherein the weight average molecular weight of the component (A) is 500 to 10,000.

[8]如[1]至[7]中任一項所述的硬化型組成物，更包含下述（B）成分， （B）成分：（A）成分以外的具有乙烯性不飽和基的化合物。 [8] The curable composition according to any one of [1] to [7], further comprising the following component (B), (B) Component: a compound having an ethylenically unsaturated group other than the (A) component.

[9]一種活性能量線硬化型組成物，包含如[1]至[8]中任一項所述的組成物。[9] An active energy ray-curing composition comprising the composition according to any one of [1] to [8].

[10]如[9]所述的活性能量線硬化型組成物，更包含相對於（A）成分合計量100重量份，或者相對於（A）成分與（B）成分的合計量100重量份為0.1重量份～10重量份的光聚合起始劑。[10] The active energy ray-curable composition according to [9], further comprising 100 parts by weight relative to the total amount of (A) component, or 100 parts by weight relative to the total amount of (A) component and (B) component It is 0.1 weight part - 10 weight part of photopolymerization initiators.

一種活性能量線硬化型塗佈劑組成物，包含如[9]或[10]所述的組成物。An active energy ray-curable coating composition comprising the composition according to [9] or [10].

以下，對（A）成分、硬化型組成物、使用方法、及用途進行說明。Hereinafter, the (A) component, the curable composition, the method of use, and the application will be described.

1.（A）成分 本發明的（A）成分是混合物（a1）〔以下，稱為「混合物（a1）」〕與有機聚異氰酸酯〔以下，稱為「化合物（a2）」〕的反應物，其中所述混合物（a1）為選自由甘油(甲基)丙烯酸酯及二甘油(甲基)丙烯酸酯所組成的群組中的至少一種化合物的混合物，且羥值為20 mgKOH/g～300 mgKOH/g。 以下，對混合物（a1）、化合物（a2）及（A）成分的製造方法進行說明。 1. (A) Ingredients Component (A) of the present invention is a reaction product of a mixture (a1) [hereinafter referred to as "mixture (a1)"] and an organic polyisocyanate [hereinafter referred to as "compound (a2)"], wherein the mixture (a1 ) is a mixture of at least one compound selected from the group consisting of glycerol (meth)acrylate and diglycerol (meth)acrylate, and has a hydroxyl value of 20 mgKOH/g to 300 mgKOH/g. Hereinafter, methods for producing the mixture (a1), the compound (a2) and the component (A) will be described.

1-1.混合物（a1） 混合物（a1）為選自由甘油(甲基)丙烯酸酯及二甘油(甲基)丙烯酸酯所組成的群組中的至少一種化合物的混合物，且為羥值為20 mgKOH/g～300 mgKOH/g的混合物。 1-1. Mixture (a1) The mixture (a1) is a mixture of at least one compound selected from the group consisting of glycerin (meth)acrylate and diglycerol (meth)acrylate, and has a hydroxyl value of 20 mgKOH/g to 300 mgKOH/g mixture.

作為混合物（a1），在為甘油(甲基)丙烯酸酯的混合物的情況下，就與化合物（a2）的反應性優異的方面而言，較佳為以甘油二丙烯酸酯為主要成分的混合物。 在為二甘油(甲基)丙烯酸酯的混合物的情況下，就與化合物（a2）的反應性優異的方面而言，較佳為以二甘油三丙烯酸酯為主要成分的混合物。 As the mixture (a1), when it is a mixture of glycerin (meth)acrylate, it is preferably a mixture containing glycerin diacrylate as a main component in terms of excellent reactivity with the compound (a2). In the case of a mixture of diglycerol (meth)acrylate, a mixture containing diglycerol triacrylate as a main component is preferable at the point that the reactivity with the compound (a2) is excellent.

混合物（a1）可藉由甘油及/或二甘油（以下，將該些亦統稱為「(聚)甘油」）與單官能(甲基)丙烯酸酯〔具有一個(甲基)丙烯醯基的化合物〕的酯交換反應而獲得。另外，混合物（a1）亦可藉由(聚)甘油與(甲基)丙烯酸的脫水酯化反應而獲得。 在使用甘油作為原料的情況下，混合物（a1）是甘油的單(甲基)丙烯酸酯、二(甲基)丙烯酸酯、及三(甲基)丙烯酸酯的混合物。在使用二甘油作為原料的情況下，混合物（a1）是二甘油的單(甲基)丙烯酸酯、以及二甘油的二(甲基)丙烯酸酯、三(甲基)丙烯酸酯、及四(甲基)丙烯酸酯的混合物。 混合物（a1）是選自由甘油(甲基)丙烯酸酯及二甘油(甲基)丙烯酸酯所組成的群組中的至少一種化合物的混合物，且羥值為20 mgKOH/g～300 mgKOH/g。作為混合物（a1）的羥值，較佳為30 mgKOH/g～290 mgKOH/g，更佳為40 mgKOH/g～280 mgKOH/g。 在混合物（a1）的羥值小於20 mgKOH/g的情況下，包含所獲得的（A）成分的組成物的硬化膜的硬度降低。另外，若羥值超過300 mgKOH/g，則所獲得的（A）成分成為高黏度。 再者，本發明中羥值是指根據日本工業標準（Japanese Industrial Standards，JIS）K0070-1992中規定的方法測定的值。 The mixture (a1) can be obtained by combining glycerin and/or diglycerin (hereinafter, these are also collectively referred to as "(poly)glycerin") and monofunctional (meth)acrylate [a compound having one (meth)acryl group]. ] obtained by the transesterification reaction. In addition, the mixture (a1) can also be obtained by the dehydration esterification reaction of (poly)glycerol and (meth)acrylic acid. When glycerin is used as a raw material, the mixture (a1) is a mixture of mono(meth)acrylate, di(meth)acrylate, and tri(meth)acrylate of glycerin. In the case of using diglycerol as a raw material, the mixture (a1) is mono(meth)acrylate of diglycerol, di(meth)acrylate, tri(meth)acrylate, and tetra(meth)acrylate of diglycerol Base) a mixture of acrylates. The mixture (a1) is a mixture of at least one compound selected from the group consisting of glycerin (meth)acrylate and diglycerol (meth)acrylate, and has a hydroxyl value of 20 mgKOH/g to 300 mgKOH/g. The hydroxyl value of the mixture (a1) is preferably from 30 mgKOH/g to 290 mgKOH/g, more preferably from 40 mgKOH/g to 280 mgKOH/g. When the hydroxyl value of a mixture (a1) is less than 20 mgKOH/g, the hardness of the cured film of the obtained composition containing (A) component will fall. Moreover, when a hydroxyl value exceeds 300 mgKOH/g, the obtained (A) component becomes high viscosity. In addition, the hydroxyl value in this invention means the value measured by the method prescribed|regulated by Japanese Industrial Standards (Japanese Industrial Standards, JIS) K0070-1992.

進而，作為甘油(甲基)丙烯酸酯的混合物，更佳為包含甘油二(甲基)丙烯酸酯（以下，亦稱為「GLY-DA」）的混合物。 GLY-DA是下述式（1）或式（2）所表示的化合物。 Furthermore, as a mixture of glycerin (meth)acrylates, a mixture containing glycerin di(meth)acrylate (hereinafter also referred to as "GLY-DA") is more preferable. GLY-DA is a compound represented by the following formula (1) or formula (2).

[化1]

Figure 02_image001
[chemical 1]
Figure 02_image001

〔所述式（1）中，R 1及R 2分別獨立地表示氫原子或甲基。〕 [In the formula (1), R 1 and R 2 each independently represent a hydrogen atom or a methyl group. 〕

[化2]

Figure 02_image003
[Chem 2]
Figure 02_image003

〔所述式（2）中，R 3及R 4分別獨立地表示氫原子或甲基。〕 [In the above-mentioned formula (2), R 3 and R 4 each independently represent a hydrogen atom or a methyl group. 〕

GLY-DA只要不特別精製，則在製造時作為式（1）所表示的化合物與式（2）所表示的化合物的混合物獲得，因此直接使用該些即可，特別是式（1）所表示的化合物與式（2）所表示的化合物的混合比率並無限制，以任意的比例使用亦沒有問題。GLY-DA is obtained as a mixture of the compound represented by the formula (1) and the compound represented by the formula (2) at the time of production unless it is particularly purified, so these can be used as they are, especially those represented by the formula (1). The mixing ratio of the compound represented by the formula (2) is not limited, and it can be used in any ratio without any problem.

關於混合物（a1）中所含的GLY-DA的純度，在使用下述式（3）求出的情況下，較佳為30%以上，更佳為40%以上，進而佳為50%以上。藉由將GLY-DA的純度設為30%以上，可使作為與化合物（a2）的反應物的（A）成分的表面硬度及彎曲率優異。The purity of GLY-DA contained in the mixture (a1) is preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more when calculated using the following formula (3). By setting the purity of GLY-DA to 30% or more, the surface hardness and curvature of the component (A) which is a reactant with the compound (a2) can be made excellent.

GLY-DA的純度（%） =〔（D×2）/M+D/2＋T/3）〕×100 ···式（3） 計算式（3）中的D、M、T是指使用包括紫外線（Ultraviolet，UV）檢測器的高效液相層析儀（以下，亦稱為「HPLC（high performance liquid chromatograph）」）對混合物（a1）進行分析而獲得的下述值。 ·D：GLY-DA在210 nm處的峰值面積 ·M：甘油單(甲基)丙烯酸酯在210 nm處的峰值面積 ·T：甘油三(甲基)丙烯酸酯在210 nm處的峰值面積 藉由HPLC測定的峰值面積是指在以下條件下測定而得的值。 ·檢測器：UV檢測器，檢測波長210 nm ·管柱的種類：填充有經碳數18的烷基修飾的矽膠的管柱 具體而言，沃特世（Waters）（股）製造的阿奎提（ACQUITY）UPLC BEH C18（零件號（Part No.）186002350，管柱內徑2.1 mm，管柱長度50 mm） ·管柱的溫度：40℃ ·洗脫液的組成：0.03重量%三氟乙酸水溶液與甲醇的混合溶液 ·洗脫液的流量：0.3 mL/分鐘 Purity of GLY-DA (%) =[(D×2)/M+D/2+T/3)]×100 ···Formula (3) D, M, and T in the calculation formula (3) refer to using a high-performance liquid chromatography (hereinafter, also referred to as "HPLC (high performance liquid chromatograph)") including an ultraviolet (Ultraviolet, UV) detector to analyze the mixture ( a1) The following values obtained by analysis. D: Peak area of GLY-DA at 210 nm M: The peak area of glycerol mono(meth)acrylate at 210 nm T: Glycerol tri(meth)acrylate peak area at 210 nm The peak area measured by HPLC means the value measured under the following conditions. Detector: UV detector, detection wavelength 210 nm ・Column type: A column filled with silica gel modified with an alkyl group having 18 carbon atoms Specifically, ACQUITY UPLC BEH C18 (Part No. (Part No.) 186002350, string inner diameter 2.1 mm, string length 50 mm) manufactured by Waters Co., Ltd. ·Column temperature: 40°C ・Composition of eluent: Mixed solution of 0.03% by weight trifluoroacetic acid aqueous solution and methanol ·Eluent flow rate: 0.3 mL/min

作為混合物（a1），可使用藉由各種製造方法獲得的混合物。 例如，可列舉藉由在酯交換觸媒的存在下的、(聚)甘油與單官能(甲基)丙烯酸酯的酯交換反應而得者，或者藉由在酸性觸媒的存在下的、(聚)甘油與(甲基)丙烯酸的脫水酯化而得者等。 As the mixture (a1), those obtained by various production methods can be used. For example, those obtained by transesterification of (poly)glycerol and monofunctional (meth)acrylate in the presence of a transesterification catalyst, or by transesterification in the presence of an acidic catalyst, ( Those obtained by dehydrating esterification of poly)glycerol and (meth)acrylic acid, etc.

作為混合物（a1），在所述製造方法中，藉由(聚)甘油與單官能(甲基)丙烯酸酯的酯交換反應而得者由於雜質少，可獲得目標(甲基)丙烯酸酯，因此較佳。As the mixture (a1), in the above production method, the target (meth)acrylate can be obtained by transesterification reaction of (poly)glycerin and monofunctional (meth)acrylate since there are few impurities. better.

進而，作為酯交換反應，較佳為下述觸媒X及觸媒Y的存在下的(聚)甘油與單官能(甲基)丙烯酸酯的酯交換反應。 觸媒X：選自由具有氮雜雙環結構的環狀三級胺或其鹽或者錯合物（以下，亦稱為「氮雜雙環系化合物」）、脒或其鹽或者錯合物（以下，亦稱為「脒系化合物」）、具有吡啶環的化合物或其鹽或者錯合物（以下，亦稱為「吡啶系化合物」）、及膦或其鹽或者錯合物（以下，亦稱為「膦系化合物」）所組成的群組中的一種以上的化合物。 觸媒Y：含鋅的化合物。 Furthermore, as a transesterification reaction, the transesterification reaction of (poly)glycerin and a monofunctional (meth)acrylate in presence of the following catalyst X and catalyst Y is preferable. Catalyst X: selected from cyclic tertiary amines having an azabicyclic structure or their salts or complexes (hereinafter also referred to as "azabicyclic compounds"), amidines or their salts or complexes (hereinafter, Also called "amidine compounds"), compounds having a pyridine ring or their salts or complexes (hereinafter also called "pyridine compounds"), and phosphines or their salts or complexes (hereinafter also called "Phosphine-based compounds") consisting of one or more compounds. Catalyst Y: a compound containing zinc.

作為單官能(甲基)丙烯酸酯，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯及(甲基)丙烯酸2-乙基己酯等具有碳數1～8的烷基的(甲基)丙烯酸烷基酯，丙烯酸2-甲氧基乙酯等(甲基)丙烯酸烷氧基烷基酯，以及N,N-二甲基胺基乙基(甲基)丙烯酸酯等。 作為單官能(甲基)丙烯酸酯，較佳為促進(聚)甘油的溶解，顯示極其良好的反應性的具有碳數1～2的烷基的(甲基)丙烯酸烷氧基烷基酯，更佳為(甲基)丙烯酸2-甲氧基乙酯。 另外，作為單官能(甲基)丙烯酸酯，由於丙烯酸酯的反應性優異，因此特佳。 Examples of monofunctional (meth)acrylates include: methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylate ) Alkyl (meth)acrylates having an alkyl group having 1 to 8 carbon atoms such as 2-ethylhexyl acrylate, alkoxyalkyl (meth)acrylates such as 2-methoxyethyl acrylate, and N,N-Dimethylaminoethyl (meth)acrylate, etc. As the monofunctional (meth)acrylate, an alkoxyalkyl (meth)acrylate having an alkyl group having 1 to 2 carbon atoms, which promotes the dissolution of (poly)glycerin and exhibits extremely good reactivity, is preferred. More preferred is 2-methoxyethyl (meth)acrylate. Moreover, since the reactivity of an acrylate is excellent as a monofunctional (meth)acrylate, it is especially preferable.

作為觸媒X，所述的化合物群組中，較佳為選自由氮雜雙環系化合物、脒系化合物及吡啶系化合物所組成的群組中的一種以上的化合物。該些化合物的觸媒活性優異，可較佳地製造混合物（a1），此外於反應結束後與後述的觸媒Y形成錯合物，從而該錯合物可利用基於吸附等的簡便的方法而自反應結束後的反應液容易地去除。尤其，氮雜雙環系化合物與觸媒Y的錯合物於反應液中為難溶解性，因而藉由過濾及吸附等而可更容易地去除。As the catalyst X, among the above compound groups, preferably one or more compounds selected from the group consisting of azabicyclic compounds, amidine compounds and pyridine compounds. These compounds are excellent in catalytic activity, and the mixture (a1) can be preferably produced. In addition, after the completion of the reaction, they form a complex with the catalyst Y described later, so that the complex can be produced by a simple method based on adsorption or the like. The reaction liquid after completion of the reaction is easily removed. In particular, the complex compound of the azabicyclic compound and the catalyst Y is poorly soluble in the reaction liquid, and thus can be removed more easily by filtration, adsorption, and the like.

作為觸媒X，較佳為作為氮雜雙環系化合物的例子的奎寧環（quinuclidine）、3-奎寧環酮、3-羥基奎寧環、三乙二胺（別名：1,4-二氮雜雙環[2.2.2]辛烷；以下，亦稱為「DABCO」）、N-甲基咪唑、1,8-二氮雜雙環[5.4.0]十一碳-7-烯（以下，亦稱為「DBU」）、及1,5-二氮雜雙環[4.3.0]壬-5-烯（以下，亦稱為「DBN」）、以及作為脒系化合物的例子的N,N-二甲基-4-胺基吡啶（以下，亦稱為「DMAP」）。 該些化合物中，更佳為對大部分多元醇顯示良好的反應性，容易獲取的3-羥基奎寧環、DABCO、N-甲基咪唑、DBU及DMAP。 As the catalyst X, quinuclidine (quinuclidine), 3-quinuclidone, 3-hydroxyquinuclidine, triethylenediamine (another name: 1,4-di Azabicyclo[2.2.2]octane; hereinafter, also referred to as "DABCO"), N-methylimidazole, 1,8-diazabicyclo[5.4.0]undec-7-ene (hereinafter, Also referred to as "DBU"), and 1,5-diazabicyclo[4.3.0]non-5-ene (hereinafter also referred to as "DBN"), and N,N- Dimethyl-4-aminopyridine (hereinafter also referred to as "DMAP"). Among these compounds, 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU, and DMAP, which show good reactivity with most polyols and are readily available, are more preferable.

作為觸媒Y，若為含鋅的化合物則可使用各種化合物，就反應性優異的方面而言，較佳為有機酸鋅及二酮烯醇鋅。 作為觸媒Y，較佳為作為有機酸鋅的例子的乙酸鋅、丙酸鋅、丙烯酸鋅及甲基丙烯酸鋅，較佳為作為二酮烯醇鋅的例子的乙醯丙酮鋅。 該些化合物中，作為觸媒Y，特佳為對大部分多元醇顯示良好的反應性，容易獲取的乙酸鋅、丙烯酸鋅及乙醯丙酮鋅。 As the catalyst Y, various compounds can be used as long as they are zinc-containing compounds, but organic acid zinc and diketone enol zinc are preferable because they are excellent in reactivity. As the catalyst Y, zinc acetate, zinc propionate, zinc acrylate, and zinc methacrylate are preferable as examples of zinc organic acids, and zinc acetylacetonate is preferable as an example of zinc diketone enol. Among these compounds, as the catalyst Y, zinc acetate, zinc acrylate, and zinc acetylacetonate, which exhibit good reactivity with most polyols and are readily available, are particularly preferable.

混合物（a1）的製造方法中的觸媒X及觸媒Y的使用比例並無特別限制，相對於觸媒Y的1莫耳，較佳使用0.005莫耳～10.0莫耳的觸媒X，更佳使用0.05莫耳～5.0莫耳。藉由相對於觸媒Y的1莫耳使用0.005莫耳以上的觸媒X，可增加目標多官能(甲基)丙烯酸酯的生成量，藉由設為10.0莫耳以下，可抑制副產物的生成及反應液的著色，使反應結束後的精製步驟簡便。The proportion of catalyst X and catalyst Y used in the method for producing the mixture (a1) is not particularly limited, and relative to 1 mole of catalyst Y, it is preferable to use 0.005 moles to 10.0 moles of catalyst X, and more preferably It is best to use 0.05 mole to 5.0 mole. By using 0.005 mol or more of catalyst X with respect to 1 mol of catalyst Y, the production amount of the target polyfunctional (meth)acrylate can be increased, and by-products can be suppressed by setting it to 10.0 mol or less. The formation and coloring of the reaction solution make the purification steps after the reaction easy.

作為觸媒X與觸媒Y的組合，較佳為觸媒X為氮雜雙環系化合物、觸媒Y為有機酸鋅的組合，特佳為氮雜雙環系化合物為DABCO、有機酸鋅為乙酸鋅及/或丙烯酸鋅的組合。 該組合除了可產率良好地獲得混合物（a1）以外，反應結束後的色調優異（例如，黃色感小），因此可較佳地用於透明清漆及硬塗層等重視無色透明性的用途。進而所述觸媒可較廉價地獲取，因此為經濟上有利的製造方法。 As the combination of catalyst X and catalyst Y, it is preferable that catalyst X is an azabicyclic compound, and catalyst Y is a combination of organic acid zinc, and it is particularly preferred that the azabicyclic compound is DABCO, and the organic acid zinc is acetic acid. A combination of zinc and/or zinc acrylate. In addition to obtaining the mixture (a1) with good yield, this combination has an excellent color tone after the reaction (for example, little yellowness), so it can be preferably used in applications where colorless transparency is important, such as clear varnishes and hard coats. Furthermore, the catalyst can be obtained relatively cheaply, so it is an economically advantageous production method.

混合物（a1）的製造方法中的反應溫度較佳為40℃～180℃，更佳為60℃～160℃。藉由將反應溫度設為40℃以上，可加快反應速度，藉由設為180℃以下，可抑制原料或產物中的(甲基)丙烯醯基的熱聚合，抑制反應液的著色，從而可簡化反應結束後的精製步驟。The reaction temperature in the method for producing the mixture (a1) is preferably from 40°C to 180°C, more preferably from 60°C to 160°C. By setting the reaction temperature above 40°C, the reaction speed can be accelerated, and by setting it below 180°C, thermal polymerization of (meth)acryloyl groups in the raw materials or products can be suppressed, and coloring of the reaction solution can be suppressed, thereby enabling Simplify the refining steps after the reaction.

混合物（a1）的製造方法中的反應壓力只要可維持規定的反應溫度則並無特別限制，可於減壓狀態下實施，另外亦可於加壓狀態下實施。反應壓力較佳為0.000001 MPa～10 MPa（絕對壓力）。The reaction pressure in the method for producing the mixture (a1) is not particularly limited as long as the predetermined reaction temperature can be maintained, and the reaction may be carried out under reduced pressure or under increased pressure. The reaction pressure is preferably from 0.000001 MPa to 10 MPa (absolute pressure).

混合物（a1）的製造方法中，隨著酯交換反應的進行而副產出源自單官能(甲基)丙烯酸酯的一元醇。 在將(聚)甘油的羥基的一部分（例如50莫耳%左右）(甲基)丙烯酸酯化的情況下，使該一元醇共存於反應體系內而成為平衡狀態，對觸媒進行吸附除去或失活操作後，蒸餾去除該一元醇及作為原料的單官能(甲基)丙烯酸酯，藉此可穩定地製造丙烯酸酯化率得到控制的產物。 In the method for producing the mixture (a1), monofunctional (meth)acrylate-derived monohydric alcohol is byproduced as the transesterification reaction progresses. When a part (for example, about 50 mol%) of the hydroxyl group of (poly)glycerin is (meth)acrylicated, the monohydric alcohol is allowed to coexist in the reaction system to achieve an equilibrium state, and the catalyst is adsorbed and removed or After the deactivation operation, the monofunctional (meth)acrylate used as a raw material is distilled off, whereby a product with a controlled acrylate rate can be stably produced.

混合物（a1）的製造方法中，不使用溶媒亦可進行反應，亦可視需要而使用溶媒。 作為溶媒的具體例，可列舉：烴類、醚類、冠醚類、酯類、酮類、碳酸酯化合物、碸類、亞碸類、脲類或其衍生物、氧化膦類、離子液體、矽油及水等。 該些溶媒中，較佳為烴類、醚類、碳酸酯化合物及離子液體。 該些溶媒可單獨使用，亦可將兩種以上任意組合而作為混合溶媒來使用。 In the method for producing the mixture (a1), the reaction may be performed without using a solvent, and a solvent may be used as needed. Specific examples of the solvent include hydrocarbons, ethers, crown ethers, esters, ketones, carbonate compounds, ureas, sulfides, ureas or derivatives thereof, phosphine oxides, ionic liquids, Silicon oil and water etc. Among these solvents, hydrocarbons, ethers, carbonate compounds, and ionic liquids are preferred. These solvents may be used alone, or two or more of them may be combined arbitrarily and used as a mixed solvent.

混合物（a1）的製造方法中，出於良好地維持反應液的色調的目的可於系統內導入氬、氦、氮、或二氧化碳氣體等惰性氣體，出於防止(甲基)丙烯醯基聚合的目的亦可於系統內導入含氧氣體。作為含氧氣體的具體例，可列舉空氣、氧與氮的混合氣體、及氧與氦的混合氣體等。作為該含氧氣體的導入方法，可列舉溶存於反應液中、或吹入反應液中（所謂的鼓泡（bubbling））的方法。In the method for producing the mixture (a1), an inert gas such as argon, helium, nitrogen, or carbon dioxide gas may be introduced into the system for the purpose of maintaining the color tone of the reaction liquid well, and for preventing polymerization of (meth)acryl groups Purpose It is also possible to introduce oxygen-containing gas into the system. Specific examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and helium. As a method for introducing the oxygen-containing gas, a method of dissolving it in the reaction liquid or blowing it into the reaction liquid (so-called bubbling) may be mentioned.

混合物（a1）的製造方法中，出於防止(甲基)丙烯醯基聚合的目的較佳為於反應液中添加聚合抑制劑。 作為聚合抑制劑，可列舉有機系聚合抑制劑、無機系聚合抑制劑及有機鹽系聚合抑制劑。 作為有機系聚合抑制劑的具體例，可列舉：對苯二酚、第三丁基對苯二酚、對苯二酚單甲醚、2,6-二-第三丁基-4-甲基苯酚、2,4,6-三-第三丁基苯酚及4-第三丁基鄰苯二酚等酚系化合物；苯醌等醌化合物；啡噻嗪；N-亞硝基-N-苯基羥胺銨、以及N-氧基化合物等。 作為N-氧基化合物，可列舉：2,2,6,6-四甲基哌啶-1-氧自由基、4-羥基-2,2,6,6-四甲基哌啶-1-氧基、4-氧代-2,2,6,6-四甲基哌啶-1-氧基及4-甲氧基-2,2,6,6-四甲基哌啶-1-氧基等。 作為聚合抑制劑，所述化合物中，較佳使用N-氧基化合物。作為N-氧基化合物，較佳為所述化合物。 進而，作為聚合抑制劑，較佳為併用N-氧基化合物及除此以外的聚合抑制劑。作為此時的N-氧基化合物以外的聚合抑制劑，較佳為酚系化合物及啡噻嗪，更佳為酚系化合物。 聚合抑制劑可單獨添加一種，或亦可將兩種以上任意組合來添加，可自混合物（a1）的製造方法的最初添加，亦可自中途添加。另外，可一次性添加所期望的使用量，亦可分開添加。另外，亦可經由精餾塔而連續地添加。 作為聚合抑制劑的添加比例，較佳為相對於反應液的總重量為5 wtppm～30,000 wtppm，更佳為25 wtppm～10,000 wtppm。藉由將聚合抑制劑的添加比例設為5 wtppm以上，可發揮聚合抑制效果，藉由設為30,000 wtppm以下，可抑制反應液的著色、可簡化反應結束後的精製步驟、或可抑制混合物（a1）的硬化速度降低。 In the method for producing the mixture (a1), it is preferable to add a polymerization inhibitor to the reaction liquid for the purpose of preventing (meth)acryl groups from polymerizing. Examples of the polymerization inhibitor include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors. Specific examples of organic polymerization inhibitors include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methyl Phenol compounds such as phenol, 2,4,6-tri-tert-butylphenol and 4-tert-butylcatechol; quinone compounds such as benzoquinone; phenthiazine; N-nitroso-N-benzene Hydroxylammonium, and N-oxyl compounds. Examples of N-oxyl compounds include: 2,2,6,6-tetramethylpiperidine-1-oxyl radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1- Oxygen, 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl and 4-methoxy-2,2,6,6-tetramethylpiperidin-1-oxyl Base etc. As the polymerization inhibitor, among the above-mentioned compounds, N-oxyl compounds are preferably used. As the N-oxyl compound, the above-mentioned compounds are preferred. Furthermore, as a polymerization inhibitor, it is preferable to use an N-oxyl compound and other polymerization inhibitors together. As the polymerization inhibitor other than the N-oxyl compound in this case, a phenolic compound and a phenthiazine are preferable, and a phenolic compound is more preferable. One type of polymerization inhibitor may be added alone, or two or more types may be added in any combination, and may be added from the beginning of the production method of the mixture (a1) or may be added from the middle. In addition, the desired usage amount may be added at once, or may be added separately. Moreover, it can also add continuously via a rectification column. The addition ratio of the polymerization inhibitor is preferably 5 wtppm to 30,000 wtppm, more preferably 25 wtppm to 10,000 wtppm, based on the total weight of the reaction solution. By setting the addition ratio of the polymerization inhibitor to 5 wtppm or more, the polymerization inhibitory effect can be exerted, and by setting it to 30,000 wtppm or less, it is possible to suppress the coloring of the reaction solution, simplify the purification step after the reaction, or suppress the mixture ( a1) The hardening rate is reduced.

1-2.化合物（a2） 作為（A）成分的另一種原料化合物即化合物（a2）〔有機聚異氰酸酯〕，可使用各種化合物。 1-2. Compound (a2) As the compound (a2) [organic polyisocyanate] which is another raw material compound of the component (A), various compounds can be used.

作為化合物（a2），可列舉二異氰酸酯及三異氰酸酯等。 作為化合物（a2），可列舉脂肪族聚異氰酸酯、脂環式聚異氰酸酯、及芳香族聚異氰酸酯。 作為脂肪族聚異氰酸酯的具體例，可列舉：六亞甲基二異氰酸酯、四亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、及離胺酸二異氰酸酯等，以及該些化合物的縮二脲體、異氰脲酸酯體、及與三羥甲基丙烷等多元醇的反應物等。 作為脂環式異氰酸酯的具體例，可列舉：異佛爾酮二異氰酸酯、降冰片烷二異氰酸酯、2,5(2,6)-雙(異氰酸酯甲基)雙環[2,2,1]庚烷、氫化甲苯二異氰酸酯、氫化4,4'-二苯基甲烷二異氰酸酯、氫化伸二甲苯基二異氰酸酯、及1,3-雙(異氰酸酯甲基)環己烷等，以及該些化合物的縮二脲體、氰脲酸酯體、及與三羥甲基丙烷等多元醇的反應物等。 作為芳香族異氰酸酯的具體例，可列舉：甲苯二異氰酸酯、萘二異氰酸酯、伸二甲苯基二異氰酸酯、及二苯基甲烷二異氰酸酯等，以及該些化合物的縮二脲體、異氰脲酸酯體、及與三羥甲基丙烷等多元醇的反應物等。 另外，作為化合物（a2），出於耐光性優異的理由，較佳為脂肪族聚異氰酸酯及脂環式聚異氰酸酯。 作為化合物（a2），更佳為脂肪族聚異氰酸酯，就組成物為低黏度且硬化膜的硬度及彎曲性優異的方面而言，特佳為六亞甲基二異氰酸酯。 As a compound (a2), a diisocyanate, a triisocyanate, etc. are mentioned. Examples of the compound (a2) include aliphatic polyisocyanate, alicyclic polyisocyanate, and aromatic polyisocyanate. Specific examples of aliphatic polyisocyanates include hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate, as well as condensed compounds of these compounds. Diurea body, isocyanurate body, and reactants with polyols such as trimethylolpropane, etc. Specific examples of alicyclic isocyanate include: isophorone diisocyanate, norbornane diisocyanate, 2,5(2,6)-bis(isocyanatomethyl)bicyclo[2,2,1]heptane , hydrogenated toluene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and 1,3-bis(isocyanate methyl)cyclohexane, etc., and biurets of these compounds body, cyanurate body, and reactants with polyols such as trimethylolpropane, etc. Specific examples of aromatic isocyanates include toluene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and biuret and isocyanurate forms of these compounds. , and reactants with polyols such as trimethylolpropane, etc. In addition, as the compound (a2), aliphatic polyisocyanate and alicyclic polyisocyanate are preferable because of excellent light resistance. As the compound (a2), aliphatic polyisocyanate is more preferable, and hexamethylene diisocyanate is particularly preferable at the point that the composition has low viscosity and is excellent in hardness and flexibility of a cured film.

1-3.（A）成分的製造方法 （A）成分可將混合物（a1）及化合物（a2）視需要在觸媒、溶媒的存在下進行加熱、攪拌而進行胺基甲酸酯化來製造。 1-3. (A) Manufacturing method of component (A) Component can be manufactured by heating and stirring a mixture (a1) and a compound (a2) in presence of a catalyst and a solvent as needed, and performing urethanization.

作為化合物（a2）相對於混合物（a1）的反應比例，相對於混合物（a1）的羥基合計1莫耳，化合物（a2）的異氰酸酯基的合計較佳為0.3莫耳～1.3莫耳的比例，更佳為0.5莫耳～1.2莫耳的比例，特佳為0.9莫耳～1.1莫耳的比例。As the reaction ratio of the compound (a2) to the mixture (a1), the total isocyanate group of the compound (a2) is preferably a ratio of 0.3 mol to 1.3 mol with respect to 1 mol of the total hydroxyl groups of the mixture (a1), More preferably, it is a ratio of 0.5 mol to 1.2 mol, and particularly preferably, it is a ratio of 0.9 mol to 1.1 mol.

在此情況下，亦能夠一併加入混合物（a1）及化合物（a2）使其反應，但由於存在反應中的放熱增大的問題，因此較佳為在混合物（a1）的存在下，逐次添加化合物（a2）使其反應。另外，同樣較佳為在化合物（a2）的存在下逐次添加混合物（a1）。In this case, it is also possible to add the mixture (a1) and the compound (a2) together to make it react, but since there is a problem that the heat generation during the reaction increases, it is preferable to add the compound (a1) one by one in the presence of the mixture (a1). Compound (a2) reacts it. In addition, it is also preferred to add the mixture (a1) successively in the presence of the compound (a2).

所述反應即使在無觸媒的情況下亦進行，但為了在短時間內效率良好地推進反應，在合成時，作為觸媒，可使用胺基甲酸酯化反應中通常使用的觸媒。 作為觸媒的具體例，可列舉：二月桂酸二丁基錫、二乙酸二丁基錫、二辛酸二丁基錫及二乙醯丙酮二丁基錫等錫化合物；二辛酸鉍等鉍化合物；乙醯丙酮鐵等鐵化合物；乙醯丙酮鋅等鋅化合物；三乙胺等胺化合物等。 所述觸媒可僅使用一種，亦可併用兩種以上。 The reaction proceeds even without a catalyst, but in order to efficiently advance the reaction in a short period of time, a catalyst generally used in a urethanization reaction can be used as a catalyst at the time of synthesis. Specific examples of the catalyst include: tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, and dibutyltin diacetylacetonate; bismuth compounds such as bismuth dioctoate; iron compounds such as iron acetylacetonate ; zinc compounds such as zinc acetylacetonate; amine compounds such as triethylamine, etc. These catalysts may be used alone or in combination of two or more.

關於觸媒的調配量，可為觸媒量，例如，相對於反應溶液，較佳為0.01 wtppm～1,000 wtppm，更佳為0.1 wtppm～1,000 wtppm。藉由將觸媒的調配量設為0.01 wtppm以上，可較佳地進行胺基甲酸酯化反應，藉由設為1,000 wtppm以下，可抑制所獲得的（A）成分的著色。The compounding quantity of a catalyst may be a catalyst quantity, for example, Preferably it is 0.01 wtppm-1,000 wtppm with respect to a reaction solution, More preferably, it is 0.1 wtppm-1,000 wtppm. When the compounding quantity of a catalyst is 0.01 wtppm or more, a urethanization reaction can progress preferably, and when it is 1,000 wtppm or less, the coloring of the obtained (A) component can be suppressed.

包含（A）成分的反應混合物成為高黏度，有時難以攪拌，因此，亦可在反應成分中調配溶媒。 作為溶媒，較佳為不參與胺基甲酸酯化反應的溶媒，例如可列舉：甲苯及二甲苯等芳香族系溶劑、甲基乙基酮及甲基異丁基酮等酮系溶劑等有機溶媒。 使用有機溶媒時的調配量只要根據生成的（A）成分的黏度等適當設定即可，較佳設定為在反應溶液中為0質量%～70質量%。 此處，所謂反應溶液，在僅使用原料化合物的情況下，是指原料化合物的合計量，在除了使用原料化合物之外亦使用反應溶媒等的情況下，是指包括該些的合計量。具體而言，以混合有混合物（a1）、化合物（a2）、及視需要使用的觸媒、溶媒、聚合抑制劑等的溶液的含義使用。 Since the reaction mixture containing the component (A) becomes highly viscous and sometimes difficult to stir, a solvent may also be prepared in the reaction components. The solvent is preferably a solvent that does not participate in the urethanization reaction, and examples thereof include organic solvents such as aromatic solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, etc. solvent. When using an organic solvent, the compounding quantity should just be set suitably according to the viscosity etc. of the (A) component produced|generated, and it is preferable to set it as 0 mass % - 70 mass % in a reaction solution. Here, the reaction solution refers to the total amount of the raw material compounds when only the raw material compounds are used, and the total amount including these when the reaction solvent and the like are used in addition to the raw material compounds. Specifically, it is used in the meaning of a solution in which a mixture (a1), a compound (a2), and optionally a catalyst, a solvent, a polymerization inhibitor, and the like are mixed.

作為溶媒，亦可與所述有機溶媒一起或者代替所述有機溶媒而調配(甲基)丙烯酸酯。 作為(甲基)丙烯酸酯，可列舉後述的（A）成分以外的具有乙烯性不飽和基的化合物〔以下，稱為「（B）」成分〕。 在該些(甲基)丙烯酸酯的存在下進行胺基甲酸酯化反應，可製造包含所獲得的（A）成分及(甲基)丙烯酸酯的硬化型組成物。該組成物與調配所述有機溶媒的情況不同，塗佈該組成物後，不需要乾燥，因此較佳。 關於在反應溶液中調配作為溶媒使用的(甲基)丙烯酸酯時的調配量，只要根據最終在組成物中調配的其他(甲基)丙烯酸酯的比例適當設定即可，例如，較佳設定為在反應溶液中為0質量%～70質量%，進而為0質量%～50質量%。 As a solvent, (meth)acrylate can also be compounded together with or instead of the above-mentioned organic solvent. As (meth)acrylic acid ester, the compound which has an ethylenically unsaturated group other than (A) component mentioned later [henceforth "(B)" component] is mentioned. Urethane reaction is performed in the presence of these (meth)acrylates, and the curable composition containing the obtained (A) component and a (meth)acrylate can be manufactured. Unlike the case of preparing the above-mentioned organic solvent, this composition is preferable because it does not require drying after application. As for the compounding amount when compounding the (meth)acrylate used as a solvent in the reaction solution, it may be appropriately set according to the ratio of other (meth)acrylates finally compounded in the composition. For example, it is preferably set as It is 0 mass % - 70 mass % in a reaction solution, and it is 0 mass % - 50 mass % further.

在胺基甲酸酯化反應中，為了防止原料或產物的(甲基)丙烯醯基的聚合，較佳為使用聚合抑制劑，進而亦可將含氧氣體導入至反應液中。作為含氧氣體，例如可列舉空氣、氧氣與氮氣的混合氣體、氧氣與氦氣的混合氣體等。 作為聚合抑制劑，可列舉有機系聚合抑制劑、無機系聚合抑制劑、有機鹽系聚合抑制劑。作為有機系聚合抑制劑的具體例，可列舉：對苯二酚、第三丁基對苯二酚、對苯二酚單甲醚、2,6-二-第三丁基-4-甲基苯酚、2,4,6-三-第三丁基苯酚、4-第三丁基鄰苯二酚等酚化合物；苯醌等醌化合物；加爾萬氧基自由基（Galvinoxyl）；2,2,6,6-四甲基哌啶-1-氧基、4-羥基-2,2,6,6-四甲基哌啶-1-氧基等穩定自由基、啡噻嗪、N-亞硝基-N-苯基羥胺銨等。作為無機系聚合抑制劑的具體例，可列舉：氯化銅、硫酸銅及硫酸鐵。作為有機鹽系聚合抑制劑的具體例，可列舉：N-亞硝基-N-苯基羥胺-鋁鹽、銨N-亞硝基苯基羥基胺等亞硝基化合物、二丁基二硫胺甲酸銅。該些可僅單獨使用一種，亦可併用兩種以上。 作為聚合抑制劑的比例，在反應液中較佳為5 wtppm～20,000 wtppm，更佳為25 wtppm～3,000 wtppm。 In the urethanization reaction, in order to prevent the polymerization of (meth)acryl groups in raw materials or products, it is preferable to use a polymerization inhibitor, and further, an oxygen-containing gas may also be introduced into the reaction liquid. Examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and helium. Examples of the polymerization inhibitor include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors. Specific examples of organic polymerization inhibitors include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methyl Phenol compounds such as phenol, 2,4,6-tri-tert-butylphenol, 4-tert-butylcatechol; quinone compounds such as benzoquinone; Galvinoxyl; 2,2, 6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl and other stable free radicals, phenthiazine, N-nitroso Base-N-phenylhydroxylamine ammonium, etc. Specific examples of the inorganic polymerization inhibitor include copper chloride, copper sulfate, and iron sulfate. Specific examples of organic salt-based polymerization inhibitors include: N-nitroso-N-phenylhydroxylamine-aluminum salts, nitroso compounds such as ammonium N-nitrosophenylhydroxylamine, dibutyl disulfide Copper urethane. These may be used alone or in combination of two or more. The ratio of the polymerization inhibitor in the reaction solution is preferably 5 wtppm to 20,000 wtppm, more preferably 25 wtppm to 3,000 wtppm.

反應溫度只要根據所使用的原料及目標（A）成分的結構或分子量等適當設定即可，通常較佳為25℃～150℃，更佳為30℃～120℃。反應時間亦只要根據所使用的原料及目標（A）成分的結構或分子量等適當設定即可，通常較佳為1小時～70小時，更佳為2小時～30小時。The reaction temperature may be appropriately set according to the raw materials used and the structure or molecular weight of the target (A) component, etc., but usually, it is preferably 25°C to 150°C, more preferably 30°C to 120°C. The reaction time may also be appropriately set according to the raw materials used and the structure and molecular weight of the target (A) component, etc., but usually, it is preferably 1 hour to 70 hours, and more preferably 2 hours to 30 hours.

就組成物的塗佈性及接著力提高的觀點而言，本發明中的（A）成分的重量平均分子量（以下，稱為「Mw」）較佳為500～10,000，更佳為500～5,000，進而佳為500～2,000。The weight average molecular weight (hereinafter referred to as "Mw") of component (A) in the present invention is preferably from 500 to 10,000, more preferably from 500 to 5,000, from the viewpoint of improving the coatability and adhesive force of the composition. , and more preferably 500 to 2,000.

再者，在本發明中，所謂Mw，是將藉由凝膠滲透層析法（以下，稱為「GPC（Gel Permeation Chromatography）」）測定的分子量聚苯乙烯換算而得的值，且是指在以下條件下測定而得的值。 ·檢測器：示差折射系（折射率（refractive index，RI）檢測器） ·管柱的種類：交聯聚苯乙烯系管柱 ·管柱的溫度：40℃ ·洗脫液：四氫呋喃 ·分子量標準物質：聚苯乙烯 In addition, in the present invention, Mw is a value obtained in terms of molecular weight polystyrene measured by gel permeation chromatography (hereinafter referred to as "GPC (Gel Permeation Chromatography)"), and means Values measured under the following conditions. Detector: Differential refractive system (refractive index (RI) detector) The type of column: cross-linked polystyrene column ·Column temperature: 40°C ·Eluent: tetrahydrofuran ・Molecular weight standard material: polystyrene

作為（A）成分，可僅單獨使用一種，亦可併用兩種以上。As (A) component, only 1 type may be used individually, and 2 or more types may be used together.

2.硬化型組成物 本發明是有關於一種包含所述（A）成分的硬化型組成物。 作為組成物的製造方法，只要按照常規方法即可，例如可將（A）成分與視需要的其他成分進行攪拌、混合來製造。 在此情況下，亦可視需要進行加熱。作為加熱溫度，只要根據所使用的組成物所含的成分、塗佈組成物的基材及使用目的等適當設定即可，較佳為30℃～80℃。 2. Hardening type composition This invention relates to the hardening type composition containing the said (A) component. What is necessary is just to follow a conventional method as a manufacturing method of a composition, For example, it can manufacture by stirring and mixing (A) component and other components as needed. In this case, heating may also be performed as needed. The heating temperature may be appropriately set according to the components contained in the composition to be used, the substrate on which the composition is applied, the purpose of use, and the like, and is preferably 30°C to 80°C.

作為組成物中的（A）成分的含有比例，在含有後述的（B）成分〔（A）成分以外的具有乙烯性不飽和基的化合物〕的情況下，在（A）成分與（B）成分的合計量100重量%中，較佳為1重量%～90重量%，更佳為10重量%～80重量%，進而佳為20重量%～60重量%。 藉由將（A）成分的比例設為1重量%以上，可防止組成物的硬化膜發生翹曲（捲曲），並且可使組成物的硬化膜的接著力優異，藉由設為90重量%以下，可抑制組成物成為高黏度，可使塗敷性較佳。 As the content ratio of the (A) component in the composition, when the (B) component [compound having an ethylenically unsaturated group other than the (A) component] mentioned later is contained, the ratio between (A) component and (B) The total amount of components is 100% by weight, preferably 1% by weight to 90% by weight, more preferably 10% by weight to 80% by weight, still more preferably 20% by weight to 60% by weight. By setting the ratio of component (A) to 1% by weight or more, warpage (curling) of the cured film of the composition can be prevented, and the adhesive force of the cured film of the composition can be made excellent. By setting it to 90% by weight Next, the composition can be suppressed from becoming high-viscosity, and the applicability can be improved.

組成物的黏度只要根據目的適當設定即可，較佳為1 mPa·s～100,000 mPa·s。 再者，本發明中所謂黏度，是指使用E型黏度計（錐板型黏度計）在25℃下測定而得的值。 The viscosity of the composition may be appropriately set according to the purpose, but is preferably 1 mPa·s to 100,000 mPa·s. In addition, the viscosity as used in this invention means the value measured at 25 degreeC using the E-type viscometer (cone and plate type viscometer).

本發明的組成物可作為活性能量線硬化型組成物及熱硬化型組成物使用，可較佳地用作活性能量線硬化型組成物使用。The composition of the present invention can be used as an active energy ray-curable composition and a thermosetting composition, and can be preferably used as an active energy ray-curable composition.

本發明的組成物以所述（A）為必須成分，可根據目的調配各種成分。 作為其他成分，可列舉（B）成分〔（A）成分以外的具有乙烯性不飽和基的化合物〕、光聚合起始劑〔以下，稱為〔（C）成分〕、熱聚合起始劑、有機溶劑、抗氧化劑、紫外線吸收劑、顏料及染料、調平劑、矽烷偶合劑、表面改質劑及聚合物等。 以下，對該些成分進行說明。 再者，後述的其他成分可僅使用例示的化合物的一種，亦可併用兩種以上。 The composition of the present invention contains the above-mentioned (A) as an essential component, and various components can be formulated according to the purpose. Examples of other components include (B) component [a compound having an ethylenically unsaturated group other than (A) component], a photopolymerization initiator [hereinafter referred to as [(C) component], a thermal polymerization initiator, Organic solvents, antioxidants, UV absorbers, pigments and dyes, leveling agents, silane coupling agents, surface modifiers and polymers, etc. Hereinafter, these components are demonstrated. In addition, the other component mentioned later may use only 1 type of compound illustrated, and may use 2 or more types together.

1）（B）成分 （B）成分是所述（A）成分以外的乙烯性不飽和化合物，是出於對組成物的硬化膜賦予各種物性的目的而調配。 作為（B）成分中的乙烯性不飽和基，可列舉(甲基)丙烯醯基、(甲基)丙烯醯胺基、乙烯基及(甲基)烯丙基等，較佳為(甲基)丙烯醯基。 再者，下述中，所謂「單官能」，是指具有一個乙烯性不飽和基的化合物，所謂「○官能」，是指具有○個乙烯性不飽和基的化合物，所謂「多官能」，是指具有兩個以上乙烯性不飽和基的化合物。 作為（B）成分，可列舉具有一個乙烯性不飽和基的化合物（以下，稱為「單官能不飽和化合物」）、具有兩個(甲基)丙烯醯基的化合物（以下，稱為「二官能(甲基)丙烯酸酯」）、及具有三個以上(甲基)丙烯醯基的化合物（以下，稱為「三官能以上(甲基)丙烯酸酯」）等。 1) (B) ingredients The (B) component is an ethylenically unsaturated compound other than the above-mentioned (A) component, and is formulated for the purpose of imparting various physical properties to the cured film of the composition. Examples of the ethylenically unsaturated group in component (B) include (meth)acryl, (meth)acrylamide, vinyl, and (meth)allyl, and are preferably (methyl) ) acryl group. Furthermore, in the following, the so-called "monofunctional" refers to a compound having one ethylenically unsaturated group, the so-called "○ functional" refers to a compound having ○ ethylenically unsaturated groups, and the so-called "multifunctional", It refers to a compound having two or more ethylenically unsaturated groups. Examples of the component (B) include a compound having one ethylenically unsaturated group (hereinafter referred to as "monofunctional unsaturated compound"), a compound having two (meth)acryl groups (hereinafter referred to as "difunctional unsaturated compound"), Functional (meth)acrylates"), compounds having three or more (meth)acryl groups (hereinafter referred to as "more than trifunctional (meth)acrylates"), etc.

（B）成分中，作為單官能不飽和化合物的具體例，可列舉：含有(甲基)丙烯醯基的化合物、含有單官能(甲基)丙烯醯胺及乙烯基的化合物。 作為含有(甲基)丙烯醯基的化合物的例子，可列舉： (甲基)丙烯酸、丙烯酸邁克爾加成型的二聚物、ω-羧基-聚己內酯單(甲基)丙烯酸酯、及(甲基)丙烯酸鄰苯二甲酸單羥基乙酯等含有羧基及乙烯性不飽和基的化合物； (甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、及(甲基)丙烯酸2-乙基己酯等(甲基)丙烯酸烷基酯； (甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、及(甲基)丙烯酸4-羥基丁酯等具有羥基的(甲基)丙烯酸酯； 乙基卡必醇(甲基)丙烯酸酯、丁基卡必醇(甲基)丙烯酸酯及2-乙基己基卡必醇(甲基)丙烯酸酯等卡必醇(甲基)丙烯酸酯； (甲基)丙烯酸苄酯、苯酚的環氧烷加成物的(甲基)丙烯酸酯、烷基苯酚的環氧烷加成物的(甲基)丙烯酸酯、對枯基苯酚的環氧烷加成物的(甲基)丙烯酸酯、鄰苯基苯酚(甲基)丙烯酸酯、鄰苯基苯酚的環氧烷加成物的(甲基)丙烯酸酯、及(甲基)丙烯酸2-羥基-3-苯氧基丙酯等具有芳香族基的單官能(甲基)丙烯酸酯； (甲基)丙烯酸環己酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、及(甲基)丙烯酸三環癸烷三羥甲酯等具有脂環式基的單官能(甲基)丙烯酸酯；以及 (甲基)丙烯酸四氫糠酯、(甲基)丙烯醯嗎啉、N-(2-(甲基)丙烯醯氧基乙基)六氫鄰苯二甲醯亞胺及N-(2-(甲基)丙烯醯氧基乙基)四氫鄰苯二甲醯亞胺等具有雜環的單官能(甲基)丙烯酸酯等。 (B) In the component, as a specific example of a monofunctional unsaturated compound, the compound containing a (meth)acryl group, the compound containing a monofunctional (meth)acrylamide, and a vinyl group is mentioned. Examples of compounds containing (meth)acryloyl groups include: (Meth)acrylic acid, dimer of acrylic Michael addition type, ω-carboxy-polycaprolactone mono(meth)acrylate, and (meth)acrylic acid monohydroxyethyl phthalate contain carboxyl and vinyl Compounds with sexually unsaturated groups; Alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; (meth)acrylates with hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Carbitol (meth)acrylates such as ethyl carbitol (meth)acrylate, butyl carbitol (meth)acrylate and 2-ethylhexyl carbitol (meth)acrylate; Benzyl (meth)acrylate, (meth)acrylate of phenol alkylene oxide adduct, (meth)acrylate of alkylphenol alkylene oxide adduct, p-cumylphenol alkylene oxide Adducted (meth)acrylate, o-phenylphenol (meth)acrylate, (meth)acrylate of o-phenylphenol alkylene oxide adduct, and (meth)acrylic acid 2-hydroxy -Monofunctional (meth)acrylates with aromatic groups such as 3-phenoxypropyl ester; Cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate Monofunctional (meth)acrylates with alicyclic groups such as alkenyloxyethyl ester and tricyclodecane trimethylol (meth)acrylate; and Tetrahydrofurfuryl (meth)acrylate, (meth)acrylmorpholine, N-(2-(meth)acryloxyethyl)hexahydrophthalimide and N-(2- Monofunctional (meth)acrylates having a heterocycle such as (meth)acryloxyethyl)tetrahydrophthalimide and the like.

作為單官能(甲基)丙烯醯胺，可列舉： N,N-二甲基(甲基)丙烯醯胺、(甲基)丙烯醯基嗎啉、N-甲基(甲基)丙烯醯胺、N-正丙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-正丁基(甲基)丙烯醯胺、N-第二丁基(甲基)丙烯醯胺、N-第三丁基(甲基)丙烯醯胺、及N-正己基(甲基)丙烯醯胺等N-烷基(甲基)丙烯醯胺； N-羥基乙基(甲基)丙烯醯胺等N-羥基烷基(甲基)丙烯醯胺；以及 N,N-二甲基胺基乙基(甲基)丙烯醯胺、N,N-二甲基胺基丙基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N,N-二-正丙基(甲基)丙烯醯胺、N,N-二異丙基(甲基)丙烯醯胺、N,N-二-正丁基(甲基)丙烯醯胺及N,N-二己基(甲基)丙烯醯胺等N,N-二烷基(甲基)丙烯醯胺等。 Examples of monofunctional (meth)acrylamide include: N,N-Dimethyl(meth)acrylamide, (meth)acrylmorpholine, N-methyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl (meth)acrylamide, N-n-butyl (meth)acrylamide, N-second butyl (meth)acrylamide, N-tert-butyl (methyl) Acrylamide, and N-alkyl (meth)acrylamide such as N-n-hexyl (meth)acrylamide; N-hydroxyalkyl(meth)acrylamides such as N-hydroxyethyl(meth)acrylamide; and N,N-Dimethylaminoethyl(meth)acrylamide, N,N-Dimethylaminopropyl(meth)acrylamide, N,N-Dimethyl(meth)acrylamide Amide, N,N-diethyl(meth)acrylamide, N,N-di-n-propyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide , N,N-di-n-butyl(meth)acrylamide and N,N-dihexyl(meth)acrylamide, etc. N,N-dialkyl(meth)acrylamide etc.

作為含有乙烯基的化合物，可列舉N-乙烯基吡咯啶酮、及N-乙烯基己內醯胺等。As a compound containing a vinyl group, N-vinylpyrrolidone, N-vinylcaprolactam, etc. are mentioned.

作為二官能(甲基)丙烯酸酯，具體而言可列舉：乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、及四亞甲基二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、及壬二醇二(甲基)丙烯酸酯等脂肪族二醇的二(甲基)丙烯酸酯； 聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、及聚四亞甲基二醇二(甲基)丙烯酸酯等聚烷二醇二(甲基)丙烯酸酯；以及 雙酚A的環氧烷烴加成物的二(甲基)丙烯酸酯、及雙酚F的環氧烷加成物的二(甲基)丙烯酸酯等具有雙酚骨架的二醇的環氧烷加成物的二(甲基)丙烯酸酯等。 Specific examples of the difunctional (meth)acrylate include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and tetramethylene glycol di(meth)acrylate. Di(meth)acrylates of aliphatic diols such as hexanediol di(meth)acrylate, and nonanediol di(meth)acrylate; Polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate and other polyalkylene glycol di(meth)acrylates; as well as Alkylene oxides of diols having a bisphenol skeleton, such as di(meth)acrylate of alkylene oxide adducts of bisphenol A and di(meth)acrylate of alkylene oxide adducts of bisphenol F Adducted di(meth)acrylate, etc.

作為二官能(甲基)丙烯酸酯，除了所述化合物以外，亦可使用具有雙酚骨架、或聚醚骨架、聚亞烷基骨架的環氧(甲基)丙烯酸酯，具有聚酯骨架、聚醚骨架或聚碳酸酯骨架的胺基甲酸酯(甲基)丙烯酸酯，以及聚酯(甲基)丙烯酸酯等寡聚物。As the difunctional (meth)acrylate, in addition to the above-mentioned compounds, epoxy (meth)acrylates having a bisphenol skeleton, a polyether skeleton, or a polyalkylene skeleton can also be used, and epoxy (meth)acrylates having a polyester skeleton, poly Oligomers such as urethane (meth)acrylate with ether backbone or polycarbonate backbone, and polyester (meth)acrylate.

作為三官能以上(甲基)丙烯酸酯，只要為含有三個以上的(甲基)丙烯醯基的化合物則可列舉各種化合物，例如可列舉：甘油三(甲基)丙烯酸酯、二甘油四(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇的三或四(甲基)丙烯酸酯、二-三羥甲基丙烷的三或四(甲基)丙烯酸酯、及二季戊四醇的三、四、五、或六(甲基)丙烯酸酯等多元醇聚(甲基)丙烯酸酯； 季戊四醇環氧烷加成物的三或四(甲基)丙烯酸酯、二-三羥甲基丙烷環氧烷加成物的三或四(甲基)丙烯酸酯、二季戊四醇環氧烷加成物的三、四、五或六(甲基)丙烯酸酯等多元醇環氧烷加成物的聚(甲基)丙烯酸酯； 異三聚氰酸環氧烷加成物的三(甲基)丙烯酸酯；以及 作為季戊四醇三(甲基)丙烯酸酯等具有羥基且具有三個以上的(甲基)丙烯醯基的化合物與有機聚異氰酸酯的反應物的胺基甲酸酯(甲基)丙烯酸酯等。 作為所述的環氧烷加成物的例子，可列舉：環氧乙烷加成物、環氧丙烷加成物、以及環氧乙烷及環氧丙烷加成物等。 另外，作為所述有機聚異氰酸酯，可列舉：六亞甲基二異氰酸酯、四亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、離胺酸二異氰酸酯、異佛爾酮二異氰酸酯、降冰片烷二異氰酸酯、氫化甲苯二異氰酸酯、氫化4,4'-二苯基甲烷二異氰酸酯、氫化伸二甲苯基二異氰酸酯、4,4'-二環己基甲烷二異氰酸酯、六亞甲基二異氰酸酯的三聚體等。 As the trifunctional or higher (meth)acrylate, as long as it is a compound containing three or more (meth)acryloyl groups, various compounds can be cited, for example: glycerol tri(meth)acrylate, diglyceryl tetra( Meth)acrylates, trimethylolpropane tri(meth)acrylates, tri- or tetra(meth)acrylates of pentaerythritol, tri- or tetra(meth)acrylates of di-trimethylolpropane, and Polyol poly(meth)acrylates such as tri-, tetra-, penta-, or hexa-(meth)acrylates of dipentaerythritol; Tri- or tetra(meth)acrylates of pentaerythritol alkylene oxide adducts, tri- or tetra(meth)acrylates of di-trimethylolpropane alkylene oxide adducts, dipentaerythritol alkylene oxide adducts Poly(meth)acrylates of polyol alkylene oxide adducts such as three, four, five or hexa(meth)acrylates; Tri(meth)acrylates of alkylene oxide adducts of isocyanuric acid; and Urethane (meth)acrylate etc. which are a reaction product of the compound which has a hydroxyl group and three or more (meth)acryl groups, such as pentaerythritol tri(meth)acrylate, and organic polyisocyanate. Examples of the above-mentioned alkylene oxide adducts include ethylene oxide adducts, propylene oxide adducts, ethylene oxide and propylene oxide adducts, and the like. In addition, examples of the organic polyisocyanate include hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, and Bornane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, three of hexamethylene diisocyanate aggregates etc.

關於（B）成分的含有比例，較佳為在（A）成分與（B）成分（以下，將（A）成分及（B）成分統稱為「硬化性成分」）的合計量100重量份中包含0重量%～60重量%，更佳為0重量%～30重量%。 若（B）成分的含有比例超過60重量%，則特別是在多官能乙烯性不飽和化合物的情況下，硬化膜有時變脆。 The content ratio of (B) component is preferably within 100 parts by weight of the total amount of (A) component and (B) component (hereinafter, (A) component and (B) component are collectively referred to as "hardening components") It contains 0% by weight to 60% by weight, more preferably 0% by weight to 30% by weight. When the content rate of (B) component exceeds 60 weight%, especially in the case of a polyfunctional ethylenically unsaturated compound, a cured film may become brittle.

2）（C）成分 在將本發明的組成物作為活性能量線硬化型組成物使用，進而作為電子束硬化型組成物使用的情況下，亦能夠不含有（C）成分（光聚合起始劑），而藉由電子束使其硬化。 在將本發明的組成物作為活性能量線硬化型組成物使用的情況下，特別是使用紫外線及可見光線作為活性能量線時，就硬化的容易性或成本的觀點而言，較佳為進一步含有（C）成分。 在使用電子束作為活性能量線的情況下，未必需要調配，但為了改善硬化性，亦可視需要少量調配。 2) (C) Components When the composition of the present invention is used as an active energy ray-curable composition and further as an electron beam-curable composition, it can be used without the component (C) (photopolymerization initiator) and can be cured by electrons. bundle to harden. When using the composition of the present invention as an active energy ray-curable composition, especially when using ultraviolet rays or visible rays as active energy rays, it is preferable to further contain (C) INGREDIENTS. When using an electron beam as an active energy ray, it does not necessarily need to mix|blend, but it may mix|blend in a small amount as needed in order to improve curability.

作為（C）成分的具體例，可列舉：苄基二甲基縮酮、苄基、安息香、安息香***、安息香異丙醚、安息香異丁醚、1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮、寡聚[2-羥基-2-甲基-1-[4-1-(甲基乙烯基)苯基]丙酮、2-羥基-1-{4-[4-(2-羥基-2-甲基-丙醯基)-苄基]-苯基}-2-甲基丙烷-1-酮、2-甲基-1-[4-(甲基硫代)]苯基]-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)丁烷-1-酮、2-二甲基胺基-2-(4-甲基苄基)-1-(4-嗎啉-4-基-苯基)丁烷-1-酮、3,6-雙(2-甲基-2-嗎啉代丙醯基)-9-正辛基咔唑、苯基乙醛酸甲酯、乙基蒽醌及菲醌等芳香族酮化合物； 二苯甲酮、2-甲基二苯甲酮、3-甲基二苯甲酮、4-甲基二苯甲酮、2,4,6-三甲基二苯甲酮、4-苯基二苯甲酮、4-(甲基苯基硫代)苯基苯基甲烷、甲基-2-二苯甲酮、1-[4-(4-苯甲醯基苯基巰基)苯基]-2-甲基-2-(4-甲基苯基巰基)丙烷-1-酮、4,4'-雙(二甲基胺基)二苯甲酮、4,4'-雙(二乙基胺基)二苯甲酮、及4-甲氧基-4'-二甲基胺基二苯甲酮等二苯甲酮系化合物； 雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦、乙基(2,4,6-三甲基苯甲醯基)苯基次膦酸酯及雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基氧化膦等醯基氧化膦化合物； 噻噸酮、2-氯噻噸酮、2,4-二乙基噻噸酮、異丙基噻噸酮、1-氯-4-丙基噻噸酮、3-[3,4-二甲基-9-氧代-9H-噻噸酮-2-基-氧基]-2-羥基丙基-N,N,N-三甲基氯化銨及氟噻噸酮等噻噸酮系化合物等。 Specific examples of component (C) include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy -2-Methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one , oligo[2-hydroxy-2-methyl-1-[4-1-(methylvinyl)phenyl]acetone, 2-hydroxy-1-{4-[4-(2-hydroxy-2- Methyl-propionyl)-benzyl]-phenyl}-2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)]phenyl]-2-mol Linyl propane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-( 4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butan-1-one, 3,6-bis(2-methyl-2-morpholinopropionyl) -Aromatic ketone compounds such as 9-n-octylcarbazole, methyl phenylglyoxylate, ethylanthraquinone and phenanthrenequinone; Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenyl Benzophenone, 4-(methylphenylthio)phenylphenylmethane, methyl-2-benzophenone, 1-[4-(4-benzoylphenylmercapto)phenyl] -2-Methyl-2-(4-methylphenylmercapto)propan-1-one, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethyl Amino) benzophenone, and benzophenone-based compounds such as 4-methoxy-4'-dimethylamino benzophenone; Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl(2,4,6-tris Acylphosphine oxide compounds such as methylbenzoyl)phenylphosphinate and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3-[3,4-dimethyl Thioxanthone series compounds such as -9-oxo-9H-thioxanthone-2-yl-oxyl]-2-hydroxypropyl-N,N,N-trimethylammonium chloride and fluorothioxanthone wait.

該些化合物中，α-羥基苯基酮類在大氣下即使是薄膜的塗層，表面硬化性亦良好，而較佳，具體而言，更佳為1-羥基環己基苯基酮、及2-羥基-2-甲基-1-苯基-丙烷-1-酮。 另外，在需要增厚硬化膜的膜厚的情況下，例如需要設為50 μm以上的情況下，出於提高硬化膜內部的硬化性的目的、或者在併用紫外線吸收劑或顏料的情況下，較佳為併用雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦、乙基-(2,4,6-三甲基苯甲醯基)苯基次膦酸酯及雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基氧化膦等醯基氧化膦化合物、或2-甲基-1-[4-(甲硫基)]苯基]-2-嗎啉代丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉代苯基)丁烷-1-酮、2-二甲基胺基-2-(4-甲基苄基)-1-(4-嗎啉-4-基-苯基)-丁烷-1-酮等。 Among these compounds, α-hydroxyphenyl ketones have good surface hardening properties even in thin-film coatings in the atmosphere, and are preferred. Specifically, 1-hydroxycyclohexyl phenyl ketone and 2 -Hydroxy-2-methyl-1-phenyl-propan-1-one. In addition, when it is necessary to increase the film thickness of the cured film, for example, when it is necessary to set it to 50 μm or more, for the purpose of improving the curability inside the cured film, or when using an ultraviolet absorber or a pigment in combination, Preferably bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-(2 ,4,6-trimethylbenzoyl)phenylphosphinate and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, etc. Acyl phosphine oxide compound, or 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl- Phenyl)-butan-1-one, etc.

相對於硬化性成分合計量100重量份，（C）成分的含有比例較佳為0.1重量份～10重量份，更佳為0.5重量份～8重量份。藉由將（C）成分的比例設為0.1重量份以上，可使組成物的光硬化性良好，密接性優異，藉由設為10重量份以下，可使硬化膜的內部硬化性良好，可使與基材的密接性良好。The content of the component (C) is preferably from 0.1 to 10 parts by weight, more preferably from 0.5 to 8 parts by weight, based on 100 parts by weight of the total curable components. By setting the proportion of the component (C) to 0.1 parts by weight or more, the photocurability of the composition can be improved and the adhesiveness can be excellent. By setting it to 10 parts by weight or less, the internal curability of the cured film can be improved, and it is possible to Make good adhesion with the base material.

3）熱聚合起始劑 在使用組成物作為熱硬化型組成物的情況下，可調配熱聚合起始劑。 本發明的組成物亦可調配熱聚合起始劑，使其加熱硬化。 作為熱聚合起始劑，可使用各種化合物，較佳為有機過氧化物及偶氮系起始劑。 作為有機過氧化物的具體例，可列舉：1,1-雙(第三丁基過氧化)2-甲基環己烷、1,1-雙(第三己基過氧化)-3,3,5-三甲基環己烷、1,1-雙(第三己基過氧化)環己烷、1,1-雙(第三丁基過氧化)-3,3,5-三甲基環己烷、1,1-雙(第三丁基過氧化)環己烷、2,2-雙(4,4-二-丁基過氧化環己基)丙烷、1,1-雙(第三丁基過氧化)環十二烷、過氧化異丙基單碳酸第三己酯、過氧化馬來酸第三丁酯、過氧化-3,5,5-三甲基己酸第三丁酯、過氧化月桂酸第三丁酯、2,5-二甲基-2,5-二(間甲苯甲醯基過氧化)己烷、過氧化異丙基單碳酸第三丁酯、過氧化2-乙基己基單碳酸第三丁酯、過氧化苯甲酸第三己酯、2,5-二-甲基-2,5-二(苯甲醯基過氧化)己烷、過氧化乙酸第三丁酯、2,2-雙(第三丁基過氧化)丁烷、過氧化苯甲酸第三丁酯、正丁基-4,4-雙(第三丁基過氧化)戊酸酯、過氧化間苯二甲酸二-第三丁酯、α,α'-雙(第三丁基過氧化)二異丙基苯、過氧化二枯基、2,5-二甲基-2,5-二(第三丁基過氧化)己烷、過氧化第三丁基枯基、過氧化二-第三丁基、對薄荷烷過氧化氫、2,5-二甲基-2,5-二(第三丁基過氧化)己炔-3、二異丙基苯過氧化氫、過氧化第三丁基三甲基矽烷基、1,1,3,3-四甲基丁基過氧化氫、枯烯過氧化氫、第三己基過氧化氫、第三丁基過氧化氫等。 作為偶氮系化合物的具體例，可列舉：1,1'-偶氮雙(環己烷-1-甲腈)、2-(胺甲醯基偶氮)異丁腈、2-苯基偶氮-4-甲氧基-2,4-二甲基戊腈、偶氮二-第三辛烷、偶氮二-第三丁烷等。 該些可單獨使用，亦可併用兩種以上。另外，有機過氧化物藉由與還原劑組合，亦可進行氧化還原反應。 3) Thermal polymerization initiator In the case of using the composition as a thermosetting composition, a thermopolymerization initiator may be formulated. The composition of the present invention can also be formulated with a thermal polymerization initiator to be cured by heating. As the thermal polymerization initiator, various compounds can be used, and organic peroxides and azo-based initiators are preferable. Specific examples of organic peroxides include: 1,1-bis(tertiary butyl peroxide) 2-methylcyclohexane, 1,1-bis(tertiary hexyl peroxide)-3,3, 5-trimethylcyclohexane, 1,1-bis(tertiary hexylperoxy)cyclohexane, 1,1-bis(tertiary butylperoxy)-3,3,5-trimethylcyclohexane alkane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(4,4-di-butylperoxycyclohexyl)propane, 1,1-bis(tert-butylperoxy) peroxy)cyclododecane, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxymaleate, tert-butyl peroxy-3,5,5-trimethylhexanoate, peroxy-3,5,5-trimethylhexanoate tertiary butyl laurate, 2,5-dimethyl-2,5-bis(m-cresyl peroxy)hexane, tertiary butyl peroxyisopropyl monocarbonate, 2-ethyl peroxide tert-butyl hexyl monocarbonate, tert-hexyl peroxybenzoate, 2,5-di-methyl-2,5-bis(benzoylperoxy)hexane, tert-butyl peroxyacetate , 2,2-bis(tertiary butyl peroxy)butane, tertiary butyl peroxybenzoate, n-butyl-4,4-bis(tertiary butyl peroxy)valerate, m-peroxy Di-tert-butyl phthalate, α,α'-bis(tert-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di( tert-butyl peroxy)hexane, tert-butyl cumyl peroxide, di-tert-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-bis( Tributyl peroxide) hexyne-3, diisopropylbenzene hydroperoxide, tert-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene Alkene hydroperoxide, tertiary hexyl hydroperoxide, tertiary butyl hydroperoxide, etc. Specific examples of azo compounds include: 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(aminoformylazo)isobutyronitrile, 2-phenylazo Nitrogen-4-methoxy-2,4-dimethylvaleronitrile, azobis-tertiary octane, azobis-tertiary butane, etc. These may be used alone or in combination of two or more. In addition, organic peroxides can also undergo oxidation-reduction reactions by combining them with reducing agents.

作為該些熱聚合起始劑的使用量，較佳為相對於硬化性成分合計量100重量份不超過10重量份。 在單獨使用熱聚合起始劑的情況下，按照通常的自由基熱聚合的慣用方法進行即可，根據情況，亦可與光聚合起始劑併用，出於在光硬化後進一步提高反應率的目的而進行熱硬化。 The amount of these thermal polymerization initiators used is preferably not more than 10 parts by weight with respect to 100 parts by weight of the total amount of curable components. In the case of using a thermal polymerization initiator alone, it can be carried out according to the usual method of free radical thermal polymerization. Depending on the situation, it can also be used in combination with a photopolymerization initiator. In order to further increase the reaction rate after photohardening purpose for thermal hardening.

4）有機溶劑 出於改善對基材的塗敷性等目的，本發明的組成物可使用包含有機溶劑的組成物。 4) Organic solvents A composition containing an organic solvent may be used for the composition of the present invention for the purpose of improving coatability to a substrate or the like.

作為有機溶劑的具體例，可列舉：甲醇、乙醇、異丙醇及丁醇等醇化合物；乙二醇單甲醚及丙二醇單甲醚等烷二醇單醚化合物；雙丙酮醇等丙酮醇；苯、甲苯及二甲苯等芳香族化合物；丙二醇單甲醚乙酸酯、乙酸乙酯、乙酸丁酯等酯化合物；丙酮、甲基乙基酮及甲基異丁基酮等酮化合物；二丁基醚等醚化合物；以及N-甲基吡咯啶酮等。 該些中，較佳為烷二醇單醚化合物、酮化合物，更佳為烷二醇單醚化合物。 Specific examples of organic solvents include alcohol compounds such as methanol, ethanol, isopropanol, and butanol; alkanediol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetol alcohols such as diacetone alcohol; Aromatic compounds such as benzene, toluene, and xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate, and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; dibutyl Ether compounds such as base ethers; and N-methylpyrrolidone, etc. Among these, alkanediol monoether compounds and ketone compounds are preferable, and alkanediol monoether compounds are more preferable.

相對於硬化性成分的合計量100重量份，有機溶劑的含有比例較佳為10重量份～1,000重量份，更佳為50重量份～500重量份，進而佳為50重量份～300重量份。若為所述範圍，則可使組成物為適合於塗敷的黏度，可利用後述的公知的塗佈方法容易地塗佈組成物。The content of the organic solvent is preferably from 10 to 1,000 parts by weight, more preferably from 50 to 500 parts by weight, and still more preferably from 50 to 300 parts by weight, based on 100 parts by weight of the total curable components. If it is within the above-mentioned range, the viscosity of the composition can be made suitable for coating, and the composition can be easily coated by a known coating method described later.

5）抗氧化劑 抗氧化劑是出於提高硬化膜的耐熱性、耐候性等耐久性的目的而調配。 作為抗氧化劑，可列舉例如酚系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑等。 作為酚系抗氧化劑，可列舉例如二第三丁基羥基甲苯等受阻酚類。作為市售品，可列舉（股）艾迪科（ADEKA）製造的AO-20、AO-30、AO-40、AO-50、AO-60、AO-70、AO-80等。 作為磷系抗氧化劑，可列舉三烷基膦、三芳基膦等膦類；亞磷酸三烷基酯、亞磷酸三芳基酯等。該些衍生物中，作為市售品，可列舉例如（股）艾迪科（ADEKA）製造的艾迪科斯塔伯（ADEKASTAB）PEP-4C、PEP-8、PEP-24G、PEP-36、HP-10、260、522A、329K、1178、1500、135A、3010等。 作為硫系抗氧化劑，可列舉硫醚系化合物，作為市售品，可列舉（股）艾迪科（ADEKA）製造的AO-23、AO-412S、AO-503A等。 該些可使用一種，亦可使用兩種以上。作為該些抗氧化劑的較佳的組合，可列舉酚系抗氧化劑與磷系抗氧化劑的組合使用、以及酚系抗氧化劑與硫系抗氧化劑的組合使用。 作為抗氧化劑的含有比例，根據目的來適當設定即可，相對於硬化性成分的合計量100重量份，較佳為0.01重量份～5重量份、更佳為0.1重量份～1重量份。 藉由將含有比例設為0.1重量份以上，能夠提高組成物的耐久性，另一方面，藉由設為5重量份以下，能夠使硬化性、密接性良好。 5) Antioxidant Antioxidants are formulated for the purpose of improving durability such as heat resistance and weather resistance of the cured film. As an antioxidant, a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant etc. are mentioned, for example. Examples of the phenolic antioxidant include hindered phenols such as di-tert-butylhydroxytoluene. As a commercial item, AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80 etc. made by ADEKA (stock) are mentioned. Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine; trialkyl phosphite, triaryl phosphite, and the like. Among these derivatives, commercially available products include, for example, Adekastab (ADEKASTAB) PEP-4C, PEP-8, PEP-24G, PEP-36, HP- 10, 260, 522A, 329K, 1178, 1500, 135A, 3010, etc. Examples of sulfur-based antioxidants include thioether-based compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by ADEKA Co., Ltd., and the like. One of these may be used, or two or more may be used. As a preferable combination of these antioxidants, the combined use of a phenolic antioxidant and a phosphorus antioxidant, and the combined use of a phenolic antioxidant and a sulfur antioxidant are mentioned. The content ratio of the antioxidant may be appropriately set depending on the purpose, but is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of curable components. By making the content rate 0.1 weight part or more, the durability of a composition can be improved, and on the other hand, by making it 5 weight part or less, curability and adhesiveness can be made favorable.

6）紫外線吸收劑 紫外線吸收劑是出於提高硬化膜的耐光性的目的而調配。 作為紫外線吸收劑，可列舉巴斯夫（BASF）公司製造的啼努穩（TINUVIN）400、啼努穩（TINUVIN）405、啼努穩（TINUVIN）460、啼努穩（TINUVIN）479等三嗪系紫外線吸收劑；啼努穩（TINUVIN）900、啼努穩（TINUVIN）928、啼努穩（TINUVIN）1130等苯並***系紫外線吸收劑。 作為紫外線吸收劑的含有比例，根據目的來適當設定即可，相對於硬化性成分的合計量100重量份，較佳為0.01重量份～5重量份、更佳為0.1重量份～1重量份。藉由將含有比例設為0.01重量%以上，能夠使硬化膜的耐光性保持良好，另一方面，藉由設為5重量%以下，能夠製成組成物的硬化性優異者。 6) UV absorber The ultraviolet absorber is formulated for the purpose of improving the light resistance of the cured film. Examples of the ultraviolet absorber include triazine-based ultraviolet rays such as TINUVIN 400, TINUVIN 405, TINUVIN 460, and TINUVIN 479 manufactured by BASF. Absorbents; benzotriazole-based ultraviolet absorbers such as TINUVIN 900, TINUVIN 928, and TINUVIN 1130. The content ratio of the ultraviolet absorber may be appropriately set depending on the purpose, but is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total curable components. By making the content rate 0.01 weight% or more, the light resistance of a cured film can be maintained favorable, and on the other hand, by making it 5 weight% or less, the curability of a composition can be made excellent.

7）顏料-染料 作為顏料，可列舉有機顏料及無機顏料等。 作為有機顏料的具體例，可列舉：甲苯胺紅、甲苯胺栗、漢薩黃（Hansa Yellow）、聯苯胺黃及吡唑啉酮紅等不溶性偶氮顏料；立索紅（Lithol Red）、棗紅（Helio Bordeaux）、顏料猩紅及永久紅2B等溶性偶氮顏料；源自茜素、陰丹士林（indanthrone）及硫靛栗等建築染料的衍生物；酞菁藍及酞菁綠等酞菁系有機顏料；喹吖啶酮紅及喹吖啶酮品紅等喹吖啶酮系有機顏料、苝紅及苝猩紅等苝系有機顏料；異吲哚啉酮黃及異吲哚啉酮橙等異吲哚啉酮系有機顏料；皮蒽酮紅（Pyranthrone Red）及皮蒽酮橙等皮蒽酮系有機顏料；硫靛系有機顏料；縮合偶氮系有機顏料；苯並咪唑酮系有機顏料；喹酞酮黃等喹酞酮系有機顏料、異吲哚啉黃等異吲哚啉系有機顏料；以及作為其他顏料的黃士酮黃、醯基醯胺黃、鎳偶氮黃、銅偶氮次甲基黃、紫環酮橙、蒽酮橙、二蒽醌基紅及二噁嗪紫（dioxazine violet）等。 另外，作為所述無機顏料的具體例，可列舉氧化鈦、硫酸鋇、碳酸鈣、鋅華、硫酸鉛、黃色鉛、鋅黃、鐵丹（紅色氧化鐵（III））、鎘紅、群青、普魯士藍、氧化鉻綠、鈷綠、赭色顏料、鈦黑及合成鐵黑等。再者，所述填料中例示的碳黑亦可作為無機顏料使用。 作為染料，可使用先前已知的各種化合物。 7) Pigment-dye As a pigment, an organic pigment, an inorganic pigment, etc. are mentioned. Specific examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine chestnut, Hansa yellow, benzidine yellow, and pyrazolone red; Soluble azo pigments such as Helio Bordeaux, pigment scarlet and permanent red 2B; derivatives of architectural dyes such as alizarin, indanthrone and thioindigo chestnut; phthalocyanines such as phthalocyanine blue and phthalocyanine green Organic pigments; quinacridone-based organic pigments such as quinacridone red and quinacridone magenta, perylene-based organic pigments such as perylene red and perylene scarlet; isoindolinone yellow and isoindolinone orange, etc. Isoindolinone-based organic pigments; pyranthrone-based organic pigments such as Pyranthrone Red and Pyranthrone Orange; thioindigo-based organic pigments; condensed azo-based organic pigments; benzimidazolone-based organic pigments ; quinophthalone-based organic pigments such as quinophthalone yellow, isoindoline-based organic pigments such as isoindoline yellow; Nitromethine yellow, perionone orange, anthrone orange, dianthraquinone red and dioxazine violet, etc. In addition, specific examples of the above-mentioned inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron (red iron (III) oxide), cadmium red, ultramarine blue, Prussian blue, chromium oxide green, cobalt green, ocher pigment, titanium black and synthetic iron black, etc. In addition, the carbon black exemplified among the above-mentioned fillers can also be used as an inorganic pigment. As the dye, various compounds previously known can be used.

8）矽烷偶合劑 矽烷偶合劑是出於改善硬化膜與基材的界面接著強度的目的而調配。 作為矽烷偶合劑，只要能夠有助於提高與基材的接著性，則並無特別限定。 8) Silane coupling agent The silane coupling agent is formulated for the purpose of improving the interface bonding strength between the cured film and the substrate. The silane coupling agent is not particularly limited as long as it contributes to the improvement of the adhesiveness with the substrate.

作為矽烷偶合劑，具體而言，可列舉2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙胺、N-苯基-3-胺基丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷等。Specific examples of the silane coupling agent include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyl Methyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N- 2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane Oxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-amino Propyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.

矽烷偶合劑的調配比例根據目的來適當設定即可，相對於硬化性成分的合計量100重量份，較佳為0.1重量份～10重量份、更佳為1重量份～5重量份。 藉由將調配比例設為0.1重量份以上，可提高組成物的接著力，另一方面，藉由設為10重量份以下，可防止接著力的經時變化。 The blending ratio of the silane coupling agent may be appropriately set depending on the purpose, and is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the total curable components. By making the compounding ratio 0.1 weight part or more, the adhesive force of a composition can be improved, and on the other hand, by making it 10 weight part or less, the temporal change of adhesive force can be prevented.

9）表面改質劑 本發明的組成物中，出於提高塗佈時的調平性的目的、或為了提高硬化物的平滑性而提高耐擦傷性的目的等，可添加表面改質劑。 作為表面改質劑，可列舉表面調整劑、界面活性劑、調平劑、消泡劑、滑動性賦予劑、防污性賦予劑等，可使用該些公知的表面改質劑。 該些之中，可較佳地列舉矽酮系表面改質劑及氟系表面改質劑。作為具體例，可列舉具有矽酮鏈及聚環氧烷鏈的矽酮系聚合物及寡聚物、具有矽酮鏈及聚酯鏈的矽酮系聚合物及寡聚物、具有全氟烷基及聚環氧烷鏈的氟系聚合物及寡聚物、以及具有全氟烷基醚鏈及聚環氧烷鏈的氟系聚合物及寡聚物等。 另外，出於提高平滑性的持續力等的目的，亦可使用分子中具有乙烯性不飽和基、較佳為具有(甲基)丙烯醯基的表面改質劑。 9) Surface modifier In the composition of the present invention, a surface modifying agent may be added for the purpose of improving the leveling property at the time of coating, or for the purpose of improving the smoothness of the cured product to improve scratch resistance. Examples of the surface modifying agent include surface modifiers, surfactants, leveling agents, antifoaming agents, slipperiness imparting agents, antifouling property imparting agents, and the like, and these known surface modifying agents can be used. Among these, silicone-based surface modifiers and fluorine-based surface modifiers are preferably mentioned. Specific examples include silicone-based polymers and oligomers having silicone chains and polyalkylene oxide chains, silicone-based polymers and oligomers having silicone chains and polyester chains, perfluoroalkane Fluorine-based polymers and oligomers with polyalkylene oxide chains, and fluorine-based polymers and oligomers with perfluoroalkyl ether chains and polyalkylene oxide chains. In addition, for the purpose of improving the durability of smoothness, etc., a surface modifier having an ethylenically unsaturated group, preferably a (meth)acryl group, in the molecule may also be used.

相對於硬化性成分的合計量100重量份，表面改質劑的含有比例較佳為0.01重量份～1.0重量份。若為所述範圍，則塗膜的表面平滑性優異。The content of the surface modifying agent is preferably 0.01 to 1.0 parts by weight relative to 100 parts by weight of the total amount of curable components. If it is the said range, the surface smoothness of a coating film will be excellent.

10）聚合物 出於進一步改善所獲得的硬化膜的耐捲曲性的目的等，本發明的組成物可更含有聚合物。 作為較佳的聚合物，可列舉(甲基)丙烯酸系聚合物，作為較佳的構成單體，可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸、(甲基)丙烯酸縮水甘油酯、N-(2-(甲基)丙烯醯氧基乙基)四氫鄰苯二甲醯亞胺等。在對(甲基)丙烯酸的聚合物進行共聚的聚合物的情況下，可加成(甲基)丙烯酸縮水甘油酯而將(甲基)丙烯醯基導入至聚合物鏈。 相對於硬化性成分的合計量100重量份，聚合物的含有比例較佳為0.01重量份～10重量份。若為所述範圍，則所獲得的硬化膜的耐捲曲性更優異。 10) Polymer The composition of the present invention may further contain a polymer for the purpose of further improving the curl resistance of the obtained cured film. Preferred polymers include (meth)acrylic polymers, and preferred constituent monomers include methyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid , glycidyl (meth)acrylate, N-(2-(meth)acryloxyethyl)tetrahydrophthalimide, etc. In the case of a polymer obtained by copolymerizing a (meth)acrylic acid polymer, glycidyl (meth)acrylate may be added to introduce (meth)acryl groups into the polymer chain. The content ratio of the polymer is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of curable components. If it is the said range, the curl resistance of the cured film obtained will be more excellent.

3.使用方法 作為本發明的組成物的使用方法，只要按照常規方法即可。 例如，可列舉在對基材塗佈組成物後，照射活性能量線或者進行加熱而使其硬化的方法等。 具體而言，在塗佈劑及接著劑等的用途的情況下，可列舉藉由通常的塗裝方法在所應用的基材上塗佈組成物後，在活性能量線硬化型組成物的情況下照射活性能量線而使其硬化的方法，或者在熱硬化型組成物的情況下進行加熱而使其硬化的方法等。在成形材料等的用途的情況下，可列舉：將組成物注入至規定的模框中，然後在活性能量線硬化型組成物的情況下，藉由照射活性能量線而使其硬化的方法，或者在熱硬化型組成物的情況下，進行加熱而使其硬化的方法等。 活性能量線的照射方法或加熱方法只要採用作為現有硬化方法而已知的一般方法即可。 另外，亦可採用如下的方法：藉由在組成物中併用（C）成分（光聚合起始劑）及熱聚合起始劑，對其照射活性能量線後，使其加熱硬化來提高與基材的密接性的方法。 3. How to use As a usage method of the composition of this invention, what is necessary is just to follow a conventional method. For example, the method of hardening by irradiating active energy rays or heating after applying a composition to a base material etc. is mentioned. Concretely, in the case of the use of coating agents and adhesives, etc., the case where the active energy ray-curable composition is applied after the composition is applied to the substrate to be applied by a normal coating method A method of curing by irradiating active energy rays downward, or a method of curing by heating in the case of a thermosetting composition. In the case of applications such as molding materials, a method in which the composition is poured into a predetermined frame and then cured by irradiating active energy rays in the case of an active energy ray-curable composition, Or, in the case of a thermosetting type composition, a method of heating and hardening it, etc. As a method of irradiating active energy rays or a method of heating, a general method known as a conventional hardening method may be used. In addition, the following method can also be adopted: by using (C) component (photopolymerization initiator) and thermal polymerization initiator together in the composition, after irradiating it with active energy rays, it is heated and hardened to improve the compatibility with the radical. The method of material adhesion.

作為可應用本發明的組成物的基材，可應用於各種材料，可列舉塑膠、木材、金屬、無機材料及紙等。 作為塑膠的具體例，可列舉：聚乙烯醇、三乙醯基纖維素及二乙醯基纖維素等纖維素乙酸酯樹脂；丙烯酸樹脂；以聚對苯二甲酸乙二酯、聚碳酸酯、聚芳酯、聚醚碸、降冰片烯等環狀烯烴作為單體的環狀聚烯烴樹脂；聚氯乙烯、環氧樹脂及聚胺基甲酸酯樹脂等。 作為木材，可列舉天然木材及合成木材等。 作為金屬，可列舉鋼板、鋁及鉻等金屬；氧化鋅（ZnO）及氧化銦錫（ITO）等金屬氧化物等。 作為無機材料，可列舉玻璃、灰漿、混凝土及石材等。 該些中，特佳為塑膠基材。 Various materials can be used as the substrate to which the composition of the present invention can be applied, and examples thereof include plastics, wood, metals, inorganic materials, and paper. Specific examples of plastics include: cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose, and diacetyl cellulose; acrylic resins; polyethylene terephthalate, polycarbonate , polyarylate, polyether sulfide, norbornene and other cyclic olefins as monomers of cyclic polyolefin resin; polyvinyl chloride, epoxy resin and polyurethane resin, etc. Examples of wood include natural wood, synthetic wood, and the like. Examples of the metal include metals such as steel sheets, aluminum, and chromium; metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO); and the like. Examples of inorganic materials include glass, mortar, concrete, and stone materials. Among these, plastic substrates are particularly preferred.

組成物硬化膜相對於基材的膜厚只要根據目的適當設定即可。作為硬化膜的厚度，只要根據所使用的基材或具有所製造的硬化膜的基材的用途進行選擇即可，較佳為1 μm～500 μm，更佳為5 μm～200 μm。The film thickness of the composition cured film with respect to a base material should just be set suitably according to the objective. The thickness of the cured film may be selected according to the substrate used or the application of the substrate having the produced cured film, but is preferably 1 μm to 500 μm, more preferably 5 μm to 200 μm.

作為將本發明的組成物塗佈於基材的方法，根據目的來適當設定即可，可列舉利用棒塗機、塗抹器、刮板、浸塗機、輥塗機、旋塗機、流塗機、刮刀塗佈機、逗點塗佈機、逆輥塗佈機、模塗機、唇塗機、凹版塗佈機及微型凹版塗佈機等進行塗佈的方法。The method for applying the composition of the present invention to a base material may be appropriately set according to the purpose, and examples include bar coater, applicator, doctor blade, dip coater, roll coater, spin coater, flow coater, etc. Machine, blade coater, comma coater, reverse roll coater, die coater, lip coater, gravure coater and micro gravure coater etc. for coating methods.

作為用於使本發明的組成物硬化的活性能量線，可列舉紫外線、可見光線及電子束等，較佳為紫外線。 作為紫外線照射裝置，可列舉高壓汞燈、金屬鹵化物燈、紫外線（UV）無電極燈、發光二極體（LED）等。 照射能量應根據活性能量線的種類、或調配組成來適當設定，作為一例而列舉使用高壓汞燈的情況時，以UV-A區域的照射能量計較佳為10 mJ/cm 2～10,000 mJ/cm 2、更佳為100 mJ/cm 2～2,000 mJ/cm 2。 Examples of the active energy rays for curing the composition of the present invention include ultraviolet rays, visible rays, and electron beams, among which ultraviolet rays are preferred. Examples of the ultraviolet irradiation device include high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, light emitting diodes (LEDs), and the like. Irradiation energy should be appropriately set according to the type of active energy ray or the compounding composition. When using a high-pressure mercury lamp as an example, the irradiation energy in the UV-A region is preferably 10 mJ/cm 2 to 10,000 mJ/cm 2. More preferably 100 mJ/cm 2 to 2,000 mJ/cm 2 .

4.用途 本發明的組成物可用於各種用途，具體而言，可列舉：硬塗層等塗佈劑、平板印刷等的油墨、黏著劑、接著劑及密封劑等用途。 4. Purpose The composition of the present invention can be used in various applications, and specific examples include applications such as coating agents such as hard coats, inks such as offset printing, adhesives, adhesives, and sealants.

本發明的組成物可較佳地用作活性能量線硬化型組成物，其硬化膜由於表面硬度及耐擦傷性與彎曲性的平衡優異，因此捲曲性亦優異，因此可更佳地用作硬塗劑。 作為硬塗劑的較佳用途，例如可列舉顯示板用前表面板、建材用途、照明器具、行動電話、智慧型手機、平板終端的顯示器或殼體、家電製品的殼體、及眼鏡等各種鏡片。 作為顯示板用前表面板的具體例，可列舉電光公告板、顯示器、看板、廣告以及標識等。 作為使用木材作為基材的例子，可列舉樓梯、地板及家具等木製品。作為使用金屬作為基材的例子，可列舉廚房用廚房面板及不鏽鋼水槽等金屬製品等。 [實施例] The composition of the present invention can be preferably used as an active energy ray-curable composition. Since the cured film is excellent in surface hardness and a good balance between scratch resistance and bendability, it is also excellent in curling properties, so it can be used more preferably as a hardened film. lotion. Examples of preferred uses of the hard coating agent include front panels for display panels, building materials, lighting fixtures, mobile phones, smartphones, displays or housings for tablet terminals, housings for home appliances, and eyeglasses. lens. Specific examples of the front panel for a display panel include a bulletin board, a display, a signboard, an advertisement, a sign, and the like. As an example of using wood as a base material, wood products, such as a staircase, a floor, and furniture, are mentioned. As an example using a metal as a base material, metal products, such as a kitchen panel and a stainless steel sink, etc. are mentioned. [Example]

以下示出實施例及比較例，更具體地說明本發明。 再者，以下中所謂「份」，是指重量份。 Examples and comparative examples are shown below to describe the present invention more specifically. In addition, "part" in the following is a weight part.

1.製造例 1）製造例1〔混合物（a1）的製造〕 於安裝有攪拌機、溫度計、氣體導入管、精餾塔及冷卻管的3升燒瓶中，加入302.75份（3.29莫耳）的甘油〔阪本藥品工業（股）製造的精製甘油（商品名）。以下，稱為「GLY」〕、2312.84份（17.77莫耳）的丙烯酸2-甲氧基乙酯（以下，稱為「MCA」）、6.51份（0.06莫耳）的作為觸媒X的DABCO、24.07份（0.12莫耳）的作為觸媒Y的丙烯酸鋅、1.19份（0.01莫耳）的對苯二酚單甲醚（以下，稱為「MEHQ」）、0.21份（0.02莫耳）的啡噻嗪，使含氧氣體（氧為5體積%、氮為95體積%）於液體中鼓泡。 一邊以反應液溫度100℃～130℃的範圍進行加熱攪拌，一邊以110 mmHg～760 mmHg的範圍調整反應系統內的壓力，經由精餾塔及冷卻管自反應系統提取出MCA與隨著酯交換反應的進行而副產出的2-甲氧基乙醇（以下，稱為「MEL」）的混合液。另外，於反應系統中隨時追加與該提取液相同重量的MCA。自加熱攪拌開始18小時後，使反應系統內的壓力返回至常壓而結束提取。 由MEL的生成量求出GLY的羥基的丙烯酸酯化率，結果為57莫耳%。 將反應液冷卻至室溫，過濾分離沈澱物後，為了吸附除去濾液中所含的觸媒X及觸媒Y，投入58.7份的矽酸鋁〔協和化學工業（股）製造的喬瓦德（Kyoward）700SEN-S（商品名）。以下稱為「700SEN-S」。〕並攪拌，進而在70℃～100℃的範圍內加熱攪拌1小時。將吸附處理後的矽酸鋁過濾分離後，將濾液放入連接有攪拌機、溫度計、氣體導入管、餾出用冷卻管、及減壓用管的燒瓶中，在溫度70℃～100℃、壓力0.001 mmHg～100 mmHg的範圍內，一邊使乾燥空氣鼓泡一邊進行10小時的減壓蒸餾，將包含未反應的MCA的餾出液分離。向釜液中添加5.0份的矽藻土（昭和化學工業（股）製造的瑞迪歐萊特（Radiolite）（商品名）。以下稱為「瑞迪歐萊特（Radiolite）」。）進行加壓過濾，將所獲得的濾液作為混合物（a1）。混合物（a1）的產量為647份。以下，將其稱為混合物（a1-1）。 裝入的GLY 302.75份全部轉換為甘油二丙烯酸酯（以下，稱為「GLY-DA」）時的產量為658份，以此為基準算出的所述混合物（a1-1）的產率為98%。 使用包括UV檢測器的HPLC，根據下述計算式（3）算出混合物（a1-1）中所含的GLY-DA的純度，結果為63%，甘油三丙烯酸酯（以下，稱為「GLY-TA」）為23%，甘油單丙烯酸酯（以下，稱為「GLY-MA」）為14%。 所獲得的混合物（a1-1）的黏度為41 mPa·s（25℃），羥值為240 mgKOH/g。藉由GPC測定的Mw為309。 1. Manufacturing example 1) Production example 1 [production of mixture (a1)] 302.75 parts (3.29 moles) of glycerin (purified glycerin (trade name) manufactured by Sakamoto Pharmaceutical Co., Ltd.) was added to a 3-liter flask equipped with a stirrer, a thermometer, a gas inlet pipe, a rectification tower, and a cooling pipe. Hereinafter, referred to as "GLY"], 2312.84 parts (17.77 moles) of 2-methoxyethyl acrylate (hereinafter referred to as "MCA"), 6.51 parts (0.06 moles) of DABCO as catalyst X, 24.07 parts (0.12 moles) of zinc acrylate as catalyst Y, 1.19 parts (0.01 moles) of hydroquinone monomethyl ether (hereinafter referred to as "MEHQ"), 0.21 parts (0.02 moles) of For thiazide, an oxygen-containing gas (5% by volume of oxygen and 95% by volume of nitrogen) was bubbled into the liquid. While heating and stirring at the temperature of the reaction solution in the range of 100°C to 130°C, the pressure in the reaction system is adjusted in the range of 110 mmHg to 760 mmHg, and the MCA is extracted from the reaction system through the rectification tower and the cooling pipe, followed by transesterification. A mixed solution of 2-methoxyethanol (hereinafter referred to as "MEL") is produced as a by-product during the reaction. In addition, MCA of the same weight as the extract was added to the reaction system at any time. After 18 hours from the start of heating and stirring, the pressure in the reaction system was returned to normal pressure to complete the extraction. The acrylate ratio of the hydroxyl group of GLY was calculated from the amount of MEL produced, and it was 57 mol%. The reaction solution was cooled to room temperature, and the precipitate was separated by filtration. In order to adsorb and remove the catalyst X and catalyst Y contained in the filtrate, 58.7 parts of aluminum silicate [Joward (manufactured by Kyowa Chemical Industry Co., Ltd.) Kyoward) 700SEN-S (trade name). Hereinafter referred to as "700SEN-S". ] and stirred, and further heated and stirred in the range of 70° C. to 100° C. for 1 hour. After the adsorption treatment of aluminum silicate is separated by filtration, the filtrate is put into a flask connected with a stirrer, a thermometer, a gas inlet tube, a cooling tube for distillation, and a tube for decompression, at a temperature of 70°C to 100°C and a pressure of In the range of 0.001 mmHg to 100 mmHg, vacuum distillation was performed for 10 hours while bubbling dry air, and the distillate containing unreacted MCA was separated. Add 5.0 parts of diatomaceous earth (Radiolite (trade name) manufactured by Showa Chemical Industry Co., Ltd., hereinafter referred to as "Radiolite") to the pot liquid, and perform pressure filtration , and the obtained filtrate was referred to as mixture (a1). The yield of mixture (a1) was 647 parts. Hereinafter, this is called a mixture (a1-1). When all 302.75 parts of GLY charged were converted into glycerol diacrylate (hereinafter referred to as "GLY-DA"), the yield was 658 parts, and the yield of the mixture (a1-1) calculated on this basis was 98 %. Using HPLC including a UV detector, the purity of GLY-DA contained in the mixture (a1-1) was calculated according to the following calculation formula (3), and the result was 63%. Glyceryl triacrylate (hereinafter referred to as "GLY-DA TA") was 23%, and glycerin monoacrylate (hereinafter referred to as "GLY-MA") was 14%. The obtained mixture (a1-1) had a viscosity of 41 mPa·s (25°C) and a hydroxyl value of 240 mgKOH/g. The Mw determined by GPC was 309.

再者，HPLC、黏度、羥值及GPC按照下述的方法來測定。 ◆HPLC測定條件 ·裝置：沃特世（Waters）（股）製造的阿奎提（ACQUITY）超高效液相層析儀（ultra-high performance liquid chromatograph，UPLC） ·檢測器：UV檢測器 ·檢測波長：210 nm ·管柱：沃特世（Waters）（股）製造的阿奎提（ACQUITY）UPLC BEH C18（貨號（Part No.）186002350，管柱內徑2.1 mm，管柱長度50 mm） ·管柱溫度：40℃ ·洗脫液的組成：0.03重量%三氟乙酸水溶液與甲醇的混合溶液 ·洗脫液的流量：0.3 mL/分鐘 In addition, HPLC, viscosity, a hydroxyl value, and GPC were measured by the following method. ◆HPLC determination conditions ·Device: ACQUITY ultra-high performance liquid chromatograph (UPLC) manufactured by Waters Co., Ltd. Detector: UV detector · Detection wavelength: 210 nm String: ACQUITY UPLC BEH C18 manufactured by Waters (Part No. 186002350, inner diameter of the string is 2.1 mm, length of the string is 50 mm) ·Column temperature: 40℃ ・Composition of eluent: Mixed solution of 0.03% by weight trifluoroacetic acid aqueous solution and methanol ·Eluent flow rate: 0.3 mL/min

◆混合物（a1-1）中所含的GLY-DA的純度算出方法 GLY-DA的純度% =〔（D/2）/（M＋D/2＋T/3）〕×100  ··式（3） 計算式（1）中的符號及用語是指以下的含義。 ·D：GLY-DA在210 nm處的峰值面積 ·M：GLY-MA在210 nm處的峰值面積 ·T：GLY-TA在210 nm處的峰值面積 ◆How to calculate the purity of GLY-DA contained in the mixture (a1-1) Purity % of GLY-DA =[(D/2)/(M+D/2+T/3)]×100 Formula (3) The symbols and terms in the calculation formula (1) have the following meanings. D: Peak area of GLY-DA at 210 nm M: Peak area of GLY-MA at 210 nm T: Peak area of GLY-TA at 210 nm

◆黏度測定條件 使用E型黏度計，測定25℃下的黏度。 ◆Viscosity measurement conditions Using an E-type viscometer, the viscosity at 25° C. was measured.

◆羥值測定條件 根據JIS K0070-1992進行測定。即，在試樣中加入乙醯化試劑，在熱水浴槽中進行加熱處理。放置冷卻後，將酚酞溶液作為指示劑，利用氫氧化鉀乙醇溶液滴定酸，而求出羥值。 再者，使用JIS K0070-1992中記載的方法的5倍量的吡啶。 ◆Hydroxyl value determination conditions Measurement was performed in accordance with JIS K0070-1992. That is, an acetylation reagent is added to the sample, and heat treatment is performed in a hot water bath. After standing to cool, the phenolphthalein solution was used as an indicator, and the acid was titrated with potassium hydroxide ethanol solution to obtain the hydroxyl value. In addition, pyridine was used in an amount five times that of the method described in JIS K0070-1992.

◆GPC測定條件 ·裝置：沃特世（Waters）（股）製造的GPC 系統名為1515 2414 717P RI ·檢測器：RI檢測器 ·管柱：保護管柱 昭和電工（股）製造 昭和（Shodex）KFG（8 μm 4.6×10 mm）、主管柱兩種 沃特世（Waters）（股）製造的斯特瑞格爾（styragel） HR 4E THF（7.8×300 mm）+斯特瑞格爾（styragel） HR 1THF（7.8×300 mm） ·管柱溫度：40℃ ·洗脫液的組成：THF（作為內部標準而包含0.03%的硫）、流量為0.75 mL/分鐘 再者，製造例2～製造例5中，亦在同樣的條件下進行GPC測定。 ◆GPC measurement conditions ·Device: GPC system manufactured by Waters (stock) named 1515 2414 717P RI Detector: RI detector ・Tube string: Two kinds of protective strings: Shodex KFG (8 μm 4.6×10 mm) manufactured by Showa Denko Co., Ltd., and two kinds of main pipe strings: styragel manufactured by Waters Co., Ltd. HR 4E THF (7.8×300 mm) + Strygel (styragel) HR 1THF (7.8×300 mm) ·Column temperature: 40℃ ・Eluent composition: THF (contains 0.03% sulfur as internal standard), flow rate 0.75 mL/min In addition, also in manufacture example 2 - manufacture example 5, GPC measurement was performed on the same conditions.

2）製造例2（混合物（a1）的製造） 於安裝有攪拌機、溫度計、氣體導入管、精餾塔及冷卻管的3升燒瓶中，加入249.92份（1.50莫耳）的甘油〔阪本藥品工業（股）製造的甘油801（商品名）。以下，稱為「DGLY」〕、1410.92份（10.84莫耳）的MCA、5.95份（0.05莫耳）的作為觸媒X的DABCO、22.03份（0.11莫耳）的作為觸媒Y的丙烯酸鋅、0.99份（0.01莫耳）的MEHQ、0.45份（0.003莫耳）的4-羥基-2,2,6,6-四甲基哌啶-1-氧基，使含氧氣體（氧為5體積%、氮為95體積%）於液體中鼓泡。 一邊以反應液溫度100℃～130℃的範圍進行加熱攪拌，一邊以150 mmHg～760 mmHg的範圍調整反應系統內的壓力，經由精餾塔及冷卻管自反應系統提取出MCA與隨著酯交換反應的進行而副產出的MEL的混合液。另外，隨時追加包含聚合抑制劑的MCA，使其與該提取液的重量平衡。自加熱攪拌開始20小時後，使反應系統內的壓力返回至常壓而結束提取。 由MEL的生成量求出DGLY的羥基的丙烯酸酯化率，結果為82莫耳%。 將反應液冷卻至室溫，過濾分離沈澱物後，為了吸附除去濾液中所含的觸媒X及觸媒Y，投入25.0份的矽酸鋁（700SEN-S）並攪拌，進而在70℃～100℃的範圍內加熱攪拌1小時。其後，在內溫20℃～40℃的範圍內投入3.7份的氫氧化鈣，在常壓下攪拌1小時，藉由加壓過濾來分離不溶物。 在所獲得的濾液中投入2.0份的矽酸鋁（700SEN-S），並放入連接有攪拌機、溫度計、氣體導入管、餾出用冷卻管、及減壓用管的燒瓶中，在溫度70℃～100℃、壓力0.001 mmHg～100 mmHg的範圍內，一邊使乾燥空氣鼓泡一邊進行10小時的減壓蒸餾，將包含未反應的MCA的餾出液分離。 向所獲得的釜液中添加0.33份的DEHA，並在內溫70℃～90℃的範圍內在常壓下攪拌3小時。其後，在釜液中添加5.0份的矽藻土（瑞迪歐萊特（Radiolite））並進行加壓過濾，獲得濾液。將所獲得的濾液作為混合物（a1）。混合物（a1）的產量為502份。以下，將其稱為混合物（a1-2）。 使用包括UV檢測器的HPLC，根據下述計算式（4）算出混合物（a1-2）中所含的二甘油三丙烯酸酯（以下，稱為「DGLY-TA」）的純度，結果為41%。 關於所獲得的混合物（a1-2），黏度：223 mPa·s（25℃），羥值：80 mgKOH/g。 2) Production example 2 (production of mixture (a1)) 249.92 parts (1.50 mol) of glycerin [Glycerol 801 (trade name) manufactured by Sakamoto Pharmaceutical Co., Ltd., manufactured by Sakamoto Pharmaceutical Co., Ltd. was added to a 3-liter flask equipped with a stirrer, a thermometer, a gas introduction pipe, a rectification tower, and a cooling pipe. Hereinafter, referred to as "DGLY"], 1410.92 parts (10.84 moles) of MCA, 5.95 parts (0.05 moles) of DABCO as catalyst X, 22.03 parts (0.11 moles) of zinc acrylate as catalyst Y, 0.99 parts (0.01 mol) of MEHQ, 0.45 parts (0.003 mol) of 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, make oxygen-containing gas (oxygen is 5 volumes %, nitrogen is 95% by volume) bubbled in the liquid. While heating and stirring the temperature of the reaction solution in the range of 100°C to 130°C, the pressure in the reaction system is adjusted in the range of 150 mmHg to 760 mmHg, and the MCA is extracted from the reaction system through the rectification tower and the cooling pipe. A mixed liquid of MEL is produced as a by-product during the progress of the reaction. In addition, MCA containing a polymerization inhibitor was added as needed to balance the weight of the extract. After 20 hours from the start of heating and stirring, the pressure in the reaction system was returned to normal pressure to complete the extraction. The acrylate ratio of the hydroxyl group in DGLY was calculated from the amount of MEL produced, and it was 82 mol%. Cool the reaction liquid to room temperature, filter and separate the precipitate, in order to adsorb and remove the catalyst X and catalyst Y contained in the filtrate, add 25.0 parts of aluminum silicate (700SEN-S) and stir, and then at 70 ° C ~ It heated and stirred in the range of 100 degreeC for 1 hour. Thereafter, 3.7 parts of calcium hydroxide were injected within the range of an internal temperature of 20°C to 40°C, stirred for 1 hour under normal pressure, and insoluble matter was separated by pressure filtration. Add 2.0 parts of aluminum silicate (700SEN-S) to the obtained filtrate, put it into a flask connected with a stirrer, a thermometer, a gas inlet tube, a cooling tube for distillation, and a tube for decompression, and set the temperature at 70 In the range of 0.001 mmHg to 100 mmHg at a pressure of 0.001 mmHg to 100 mmHg, vacuum distillation was performed for 10 hours while bubbling dry air to separate the distillate containing unreacted MCA. 0.33 parts of DEHA were added to the obtained pot liquid, and it stirred for 3 hours under normal pressure in the range of internal temperature 70 degreeC - 90 degreeC. Thereafter, 5.0 parts of diatomaceous earth (Radiolite) were added to the pot liquid, and pressure filtration was performed to obtain a filtrate. The obtained filtrate was referred to as a mixture (a1). The yield of mixture (a1) was 502 parts. Hereinafter, this is called a mixture (a1-2). Using HPLC including a UV detector, the purity of diglyceryl triacrylate (hereinafter referred to as "DGLY-TA") contained in the mixture (a1-2) was calculated according to the following calculation formula (4), and the result was 41% . Regarding the obtained mixture (a1-2), viscosity: 223 mPa·s (25° C.), hydroxyl value: 80 mgKOH/g.

◆混合物（a1-2）中所含的DGLY-TA的純度算出方法 DGLY-TA的純度% =〔（Tri/3）/（M+D/2+Tri/3+Tetra/4）〕×100 ···式（4） 計算式（1）中的符號及用語是指以下的含義。 ·Tri：DGLY-TA的210 nm處的峰值面積 ·M：二甘油單丙烯酸酯的210 nm處的峰值面積 ·D：二甘油二丙烯酸酯的210 nm處的峰值面積 ·Tetra：二甘油四丙烯酸酯的210 nm處的峰值面積 ◆How to calculate the purity of DGLY-TA contained in the mixture (a1-2) Purity % of DGLY-TA =[(Tri/3)/(M+D/2+Tri/3+Tetra/4)]×100 ···Formula (4) The symbols and terms in the calculation formula (1) have the following meanings. Tri: Peak area of DGLY-TA at 210 nm M: Peak area at 210 nm of diglycerol monoacrylate D: Peak area at 210 nm of diglycerol diacrylate Tetra: peak area at 210 nm of diglyceryl tetraacrylate

3）製造例3〔（A）成分的製造〕 在裝備有攪拌機、溫度計、氧濃度為5%的氧氣/氮氣混合氣體（以下，稱為5%ON）配管的1L燒瓶中，加入93.52 g的混合物（a1-1）、0.064 g的2,6-二-第三丁基-4-甲基苯酚（以下，稱為BHT）、0.064g的二月桂酸二正丁基錫〔富士軟片和光純藥（股）製造的試劑。以下，稱為DBTDL〕。 一邊吹入5%ON一邊攪拌內容物，使燒瓶內達到70℃。其後，緩慢添加六亞甲基二異氰酸酯（以下，稱為HDI），最終加入33.6 g的HDI〔相對於混合物（a1-1）的羥基合計1莫耳，異氰酸酯基的合計為0.98莫耳的比例〕。其後，將燒瓶內的溫度升溫至90℃，保持5小時，結束反應。 藉由其後的IR測量，確認到異氰酸酯基消失，結束合成。 所獲得的反應混合物為藉由GPC的Mw為0.4萬的四官能胺基甲酸酯丙烯酸酯加成物（以下，稱為「A-1」）。 3) Manufacturing Example 3 [Manufacturing of Component (A)] 93.52 g of the mixture (a1-1), 0.064 g of 2,6 - Di-tert-butyl-4-methylphenol (hereinafter referred to as BHT), 0.064 g of di-n-butyltin dilaurate [a reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]. Hereinafter, it is referred to as DBTDL]. The contents were stirred while blowing in 5% ON, and the inside of the flask was brought to 70°C. Thereafter, hexamethylene diisocyanate (hereinafter referred to as HDI) was slowly added, and finally 33.6 g of HDI [1 mol of total hydroxyl groups and 0.98 mol of isocyanate groups were added to the mixture (a1-1) Proportion〕. Thereafter, the temperature in the flask was raised to 90° C. and maintained for 5 hours to complete the reaction. The disappearance of the isocyanate group was confirmed by subsequent IR measurement, and the synthesis was completed. The obtained reaction mixture was a tetrafunctional urethane acrylate adduct (hereinafter referred to as "A-1") whose Mw by GPC was 4,000.

4）製造例4〔（A）成分的製造〕 在裝備有攪拌機、溫度計、5%ON配管的1L燒瓶中，加入112.22 g的混合物（a1-2）、0.063 g的BHT、0.064 g的DBTDL。 一邊吹入5%ON一邊攪拌內容物，使燒瓶內達到70℃。其後，緩慢添加HDI，最終加入13.5 g的HDI〔相對於混合物（a1-2）的羥基合計1莫耳，異氰酸酯基的合計為0.98莫耳的比例〕。其後，將燒瓶內的溫度升溫至90℃，保持5小時，結束反應。 藉由其後的IR測量，確認到異氰酸酯基消失，結束合成。 所獲得的反應混合物為藉由GPC的Mw為0.4萬的六官能胺基甲酸酯丙烯酸酯加成物（以下，稱為「A-2」）。 4) Manufacturing Example 4 [Manufacturing of Component (A)] In a 1 L flask equipped with a stirrer, a thermometer, and a 5% ON tubing, 112.22 g of the mixture (a1-2), 0.063 g of BHT, and 0.064 g of DBTDL were charged. The contents were stirred while blowing in 5% ON, and the inside of the flask was brought to 70°C. Thereafter, HDI was slowly added, and finally 13.5 g of HDI [a ratio of 0.98 mol of total isocyanate groups to 1 mol of hydroxyl groups in the mixture (a1-2)] was finally added. Thereafter, the temperature in the flask was raised to 90° C. and maintained for 5 hours to complete the reaction. The disappearance of the isocyanate group was confirmed by subsequent IR measurement, and the synthesis was completed. The obtained reaction mixture was a hexafunctional urethane acrylate adduct (hereinafter referred to as "A-2") whose Mw by GPC was 0.40 thousand.

5）製造例5〔（A）成分的製造〕 在裝備有攪拌機、溫度計、5%ON配管的1L燒瓶中，加入278.3 g的混合物（a1-1）、0.50 g的BHT、0.10g的DBTDL。 一邊吹入5%ON一邊攪拌內容物，使燒瓶內達到70℃。其後，緩慢添加TAP-100〔旭化成化學（股）製造的異氰酸酯。以下，稱為TPA-100〕，最終加入221.7 g的TPA-100〔相對於混合物（a1-1）的羥基合計1莫耳，異氰酸酯基的合計為0.98莫耳的比例〕。其後，將燒瓶內的溫度升溫至90℃，保持5小時，結束反應。 藉由其後的IR測量，確認到異氰酸酯基消失，結束合成。 所獲得的反應混合物為藉由GPC的Mw為0.6萬的六官能胺基甲酸酯丙烯酸酯加成物（以下，稱為「A-3」）。 5) Manufacturing Example 5 [Manufacturing of Component (A)] Into a 1 L flask equipped with a stirrer, a thermometer, and a 5% ON pipe, 278.3 g of the mixture (a1-1), 0.50 g of BHT, and 0.10 g of DBTDL were charged. The contents were stirred while blowing in 5% ON, and the inside of the flask was brought to 70°C. Thereafter, TAP-100 [isocyanate manufactured by Asahi Kasei Chemical Co., Ltd.] was slowly added. Hereinafter, it will be referred to as TPA-100], and finally 221.7 g of TPA-100 [a ratio of 0.98 moles of total isocyanate groups to 1 mole of hydroxyl groups in the mixture (a1-1)] was finally added. Thereafter, the temperature in the flask was raised to 90° C. and maintained for 5 hours to complete the reaction. The disappearance of the isocyanate group was confirmed by subsequent IR measurement, and the synthesis was completed. The obtained reaction mixture was a hexafunctional urethane acrylate adduct (hereinafter referred to as "A-3") whose Mw by GPC was 6,000.

6）比較製造例1〔（A）成分以外的胺基甲酸酯丙烯酸酯加成物的製造〕 在裝備有攪拌機、溫度計、5%ON配管的1L燒瓶中，加入599.4 g的阿羅尼斯（Aronix）M-305〔東亞合成（股）製造的季戊四醇三/四丙烯酸酯。羥值115 mgKOH/g。以下，稱為M-305〕、0.50 g的BHT、0.10 g的DBTDL。 一邊吹入5%ON一邊攪拌內容物，使燒瓶內達到70℃。其後，緩慢添加TAP-100，最終加入221.7 g的TPA-100〔相對於M-305的羥基合計1莫耳，異氰酸酯基的合計為0.98莫耳的比例〕。其後，將燒瓶內的溫度升溫至90℃，保持5小時，結束反應。 藉由其後的IR測量，確認到異氰酸酯基消失，結束合成。 所獲得的反應混合物為藉由GPC的Mw為0.8萬的九官能胺基甲酸酯丙烯酸酯加成物（以下，稱為「A'-1」）。 6) Comparative Production Example 1 [Manufacture of urethane acrylate adducts other than (A) component] Into a 1 L flask equipped with a stirrer, a thermometer, and a 5% ON pipe, 599.4 g of pentaerythritol tri/tetraacrylate of Aronix M-305 (manufactured by Toagosei Co., Ltd.) was charged. The hydroxyl value is 115 mgKOH/g. Hereinafter, it is referred to as M-305], 0.50 g of BHT, and 0.10 g of DBTDL. The contents were stirred while blowing in 5% ON, and the inside of the flask was brought to 70°C. Thereafter, TAP-100 was gradually added, and finally 221.7 g of TPA-100 [a ratio of 0.98 mol of total isocyanate groups to 1 mol of hydroxyl groups in M-305] was finally added. Thereafter, the temperature in the flask was raised to 90° C. and maintained for 5 hours to complete the reaction. The disappearance of the isocyanate group was confirmed by subsequent IR measurement, and the synthesis was completed. The obtained reaction mixture was a non-functional urethane acrylate adduct (hereinafter, referred to as "A'-1") whose Mw by GPC was 8,000.

2.實施例及比較例 1）活性能量線硬化型組成物的製造 將下述表1所示的化合物以表1所示的比例進行攪拌、混合，製造活性能量線硬化型組成物。 使用所獲得的組成物，進行後述的評價。將該些的結果示於表2。 2. Examples and Comparative Examples 1) Manufacture of active energy ray hardening type composition The compounds shown in Table 1 below were stirred and mixed at the ratios shown in Table 1 to prepare an active energy ray-curable composition. The evaluation described later was performed using the obtained composition. These results are shown in Table 2.

[表1]    （A） （B） （C） 實施例1 A-1 （50） M-930 （30） ACMO （20） HCPK （2） 實施例2 A-2 （50） M-930 （30） ACMO （20） HCPK （2） 實施例3 A-3 （50） M-930 （30） ACMO （20） HCPK （2） 比較例1 UA-306H （50） M-930 （30） ACMO （20） HCPK （2） 比較例2 A'-1 （50） M-930 （30） ACMO （20） HCPK （2） [Table 1] (A) (B) (C) Example 1 A-1 (50) M-930 (30) ACMO (20) HCPK (2) Example 2 A-2 (50) M-930 (30) ACMO (20) HCPK (2) Example 3 A-3 (50) M-930 (30) ACMO (20) HCPK (2) Comparative example 1 UA-306H (50) M-930 (30) ACMO (20) HCPK (2) Comparative example 2 A'-1 (50) M-930 (30) ACMO (20) HCPK (2)

再者，表1中的數字是指份數，縮寫是指下述含義。 ·M-930：甘油三丙烯酸酯，東亞合成製造的「阿羅尼斯（Aronix）M-930」 ·ACMO：丙烯醯嗎啉，KJ化學製造的「ACMO」 ·UA306H：由季戊四醇三丙烯酸酯與六亞甲基二異氰酸酯構成的四官能胺基甲酸酯丙烯酸酯加成物，共榮社化學製造的「UA-306H」 ·HCPK：1-羥基環己基苯基酮，艾堅蒙樹脂（IGM RESINS）公司製造的歐米拉得（Omnirad）184 In addition, the number in Table 1 means the number of parts, and the abbreviation means the following meaning. ・M-930: Glycerin triacrylate, "Aronix M-930" manufactured by Toyasei ・ACMO: Acryloylmorpholine, "ACMO" manufactured by KJ Chemicals ・UA306H: Tetrafunctional urethane acrylate adduct composed of pentaerythritol triacrylate and hexamethylene diisocyanate, "UA-306H" manufactured by Kyoeisha Chemical Co., Ltd. HCPK: 1-hydroxycyclohexyl phenyl ketone, Omnirad 184 manufactured by IGM RESINS

2）組成物的評價方法 （1）黏度 利用E型黏度計，在25℃下對表1中獲得的組成物測定黏度。將該些的結果示於表2。 2) Evaluation method of composition (1) Viscosity Viscosities of the compositions obtained in Table 1 were measured at 25° C. using an E-type viscometer. These results are shown in Table 2.

3）硬化膜物性 在以下的評價中，調整為在UV-A強度500 mW/cm 2下，每1道次為800 mJ/cm 2的照射能量，除此之外，按照與硬化性試驗相同的條件，使用使組成物硬化的樣品。 3) In the following evaluation, the physical properties of the cured film were adjusted to an irradiation energy of 800 mJ/cm 2 per pass at a UV-A intensity of 500 mW/cm 2 , except that, the same as the curability test conditions, a sample in which the composition was hardened was used.

（2）鉛筆硬度 按照JIS K5600-5-4，以750 g荷重進行評價。 (2) Pencil hardness Evaluation was performed with a load of 750 g in accordance with JIS K5600-5-4.

（3）耐擦傷性 使用鋼絲棉#0000以荷重500 g往復100次後，按照以下2個等級進行評價。 ○：在硬化膜上未見傷痕，×：在硬化膜上可見傷痕 (3) Scratch resistance After reciprocating 100 times with a load of 500 g using steel wool #0000, the following two grades were used for evaluation. ○: No scratches are seen on the cured film, ×: Scars are seen on the cured film

（4）彎曲性 按照心軸試驗（JIS K5600-5-1），在直徑2 mm、4 mm或6 mm的芯棒上捲繞形成有硬化膜的聚對苯二甲酸乙二醇酯（Polyethylene Terephthalate，PET）膜，按照以下2個等級進行評價。 ○：無硬化膜的破裂或剝離，×：可見硬化膜的破裂或剝離 (4) Flexibility According to the mandrel test (JIS K5600-5-1), a polyethylene terephthalate (PET) film with a hardened film is wound around a mandrel with a diameter of 2 mm, 4 mm, or 6 mm , and evaluated according to the following two levels. ○: No cracking or peeling of the cured film, ×: Cracking or peeling of the cured film was observed

（5）捲曲性 將樣品切成6 cm×6 cm，測定其四角翹起的高度，以平均值進行評價。值越小表示變形越小。 (5) Curly Cut the sample into 6 cm x 6 cm, measure the height of its four corners, and use the average value for evaluation. Smaller values indicate less deformation.

[表2]    黏度 （mPa·s） 鉛筆硬度 耐擦傷性 彎曲性 捲曲性 （mm） 直徑 2 mm 直徑 4 mm 直徑 6 mm 實施例1 120 3H ○ ○ ○ ○ 2 實施例2 160 3H ○ ○ ○ ○ 2 實施例3 3,560 5H ○ × ○ ○ 6 比較例1 300 3H ○ × × ○ 8 比較例2 9,730 5H 〇 × × × 12 [Table 2] Viscosity (mPa·s) pencil hardness Scratch resistance Flexibility Curlability (mm) diameter 2 mm 4 mm in diameter 6 mm in diameter Example 1 120 3H ○ ○ ○ ○ 2 Example 2 160 3H ○ ○ ○ ○ 2 Example 3 3,560 5H ○ x ○ ○ 6 Comparative example 1 300 3H ○ x x ○ 8 Comparative example 2 9,730 5H 〇 x x x 12

由實施例1及實施例2的結果可知，該些組成物為低黏度，其硬化膜的硬度、耐擦傷性、彎曲性、及捲曲性優異。 與此相對，比較例1中，是不含（A）成分，以六官能胺基甲酸酯丙烯酸酯加成物為主成分的組成物，但黏度高，且彎曲性與捲曲性差。 另外，實施例3中，是以由三官能的異氰酸酯、即，TPA-100合成的多官能胺基甲酸酯丙烯酸酯加成物、即，A-3為主成分的組成物，但與同樣以由TPA-100合成的多官能胺基甲酸酯丙烯酸酯加成物、即，A'-1為主成分的比較例2相比，黏度低，且彎曲性與捲曲性優異。 [產業上之可利用性] From the results of Examples 1 and 2, it can be seen that these compositions have low viscosity, and their cured films are excellent in hardness, scratch resistance, flexibility, and curlability. On the other hand, in Comparative Example 1, the component (A) was not included and the hexafunctional urethane acrylate adduct was the main component, but the viscosity was high, and the bendability and curlability were poor. In addition, in Example 3, the polyfunctional urethane acrylate adduct synthesized from trifunctional isocyanate, that is, TPA-100, that is, A-3 is the main component of the composition, but the same Compared with Comparative Example 2, which is a polyfunctional urethane acrylate adduct synthesized from TPA-100, that is, A'-1, the main component has low viscosity and excellent bendability and curlability. [Industrial availability]

本發明是有關於一種硬化型組成物，可較佳地用作活性能量線硬化型組成物。 進而，作為本發明的組成物的具體用途，能夠用於硬塗層等的塗佈劑、平板印刷等的油墨的各種用途，特別是低黏度，所獲得的硬化膜可同時滿足硬度、耐擦傷性、彎曲性及捲曲性，因此可較佳地用作塗佈劑組成物。 The present invention relates to a curable composition which can be preferably used as an active energy ray curable composition. Furthermore, as a specific use of the composition of the present invention, it can be used in various applications such as coating agents such as hard coats and inks such as lithographic printing, especially low viscosity, and the obtained cured film can satisfy both hardness and scratch resistance. Sexuality, flexibility and curling properties, so it can be preferably used as a coating agent composition.

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Claims (11)

一種硬化型組成物，包含下述（A）成分， （A）成分：混合物（a1）與有機聚異氰酸酯的反應物，其中所述混合物（a1）為選自由甘油(甲基)丙烯酸酯及二甘油(甲基)丙烯酸酯所組成的群組中的至少一種化合物的混合物，且羥值為20 mgKOH/g～300 mgKOH/g。 A curable composition comprising the following (A) component, (A) Component: a reactant of mixture (a1) and organic polyisocyanate, wherein said mixture (a1) is selected from the group consisting of glycerol (meth)acrylate and diglycerol (meth)acrylate A mixture of at least one compound with a hydroxyl value of 20 mgKOH/g to 300 mgKOH/g. 如請求項1所述的硬化型組成物，其中有機聚異氰酸酯為脂肪族聚異氰酸酯或脂環式聚異氰酸酯。The curable composition according to claim 1, wherein the organic polyisocyanate is aliphatic polyisocyanate or alicyclic polyisocyanate. 如請求項1或請求項2所述的硬化型組成物，其中所述混合物（a1）為在下述觸媒X及觸媒Y的存在下，使甘油或二甘油與具有一個(甲基)丙烯醯基的化合物進行酯交換反應而得的(甲基)丙烯酸酯混合物，且為羥值為20 mgKOH/g～300 mgKOH/g的混合物， 觸媒X：選自由具有氮雜雙環結構的環狀三級胺或其鹽或者錯合物、脒或其鹽或者錯合物、具有吡啶環的化合物或其鹽或者錯合物、及膦或其鹽或者錯合物所組成的群組中的一種以上的化合物； 觸媒Y：包含鋅的化合物。 The hardening composition according to claim 1 or claim 2, wherein the mixture (a1) is obtained by mixing glycerin or diglycerin with one (meth)propylene in the presence of the following catalysts X and Y. (Meth)acrylic acid ester mixture obtained by transesterification of acyl compound, and is a mixture with a hydroxyl value of 20 mgKOH/g to 300 mgKOH/g, Catalyst X: selected from cyclic tertiary amines with azabicyclic structure or their salts or complexes, amidines or their salts or complexes, compounds with pyridine rings or their salts or complexes, and phosphine or More than one compound in the group consisting of its salt or complex; Catalyst Y: a compound containing zinc. 如請求項3所述的硬化型組成物，其中所述具有一個(甲基)丙烯醯基的化合物為烷氧基烷基(甲基)丙烯酸酯。The curable composition according to claim 3, wherein the compound having one (meth)acryl group is an alkoxyalkyl (meth)acrylate. 如請求項3所述的硬化型組成物，其中所述觸媒X為選自由具有氮雜雙環結構的環狀三級胺或其鹽或者錯合物、脒或其鹽或者錯合物、及具有吡啶環的化合物或其鹽或者錯合物所組成的群組中的一種以上的化合物。The hardening composition according to claim 3, wherein the catalyst X is selected from cyclic tertiary amines having an azabicyclic structure or their salts or complexes, amidines or their salts or complexes, and One or more compounds in the group consisting of compounds having a pyridine ring or salts or complexes thereof. 如請求項3所述的硬化型組成物，其中所述觸媒Y為有機酸鋅或/及二酮烯醇鋅。The curable composition according to claim 3, wherein the catalyst Y is zinc organic acid or/and zinc diketone enolate. 如請求項1或請求項2所述的硬化型組成物，其中（A）成分的重量平均分子量為500～10,000。The curable composition according to claim 1 or claim 2, wherein the weight average molecular weight of the component (A) is 500 to 10,000. 如請求項1或請求項2所述的硬化型組成物，其中更包含下述（B）成分， （B）成分：（A）成分以外的具有乙烯性不飽和基的化合物。 The hardening type composition as described in claim 1 or claim 2, which further comprises the following (B) component, (B) Component: a compound having an ethylenically unsaturated group other than the (A) component. 一種活性能量線硬化型組成物，包含如請求項1至請求項8中任一項所述的組成物。An active energy ray-curing composition comprising the composition described in any one of claim 1 to claim 8. 如請求項9所述的活性能量線硬化型組成物，更包含相對於（A）成分合計量100重量份，或者相對於（A）成分與（B）成分的合計量100重量份為0.1重量份～10重量份的光聚合起始劑。The active energy ray-curing composition according to claim 9, further comprising 0.1 parts by weight relative to 100 parts by weight of the total amount of the components (A) or 100 parts by weight of the total amount of the components (A) and (B) 10 parts by weight of photopolymerization initiator. 一種活性能量線硬化型塗佈劑組成物，包含如請求項9或請求項10所述的組成物。An active energy ray-curable coating composition comprising the composition described in Claim 9 or Claim 10.
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JP6927233B2 (en) * 2016-11-17 2021-08-25 東亞合成株式会社 Active energy ray-curable composition
TW201835029A (en) * 2016-12-20 2018-10-01 日商東亞合成股份有限公司 Curable composition
JP2018100371A (en) * 2016-12-21 2018-06-28 東亞合成株式会社 Curable composition
JP7119553B2 (en) * 2018-05-11 2022-08-17 東亞合成株式会社 Active energy ray-curable composition

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