TW201610015A - Active-energy-ray-curable resin composition, coating material, coating, and layered film - Google Patents

Active-energy-ray-curable resin composition, coating material, coating, and layered film Download PDF

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TW201610015A
TW201610015A TW104121249A TW104121249A TW201610015A TW 201610015 A TW201610015 A TW 201610015A TW 104121249 A TW104121249 A TW 104121249A TW 104121249 A TW104121249 A TW 104121249A TW 201610015 A TW201610015 A TW 201610015A
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meth
acrylate
resin composition
group
curable resin
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TW104121249A
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Masahiro Ito
Masako Moriya
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Dainippon Ink & Chemicals
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

Provided are an active-energy-ray-curable resin composition whereby excellent workability performance of a cured coating thereof can be demonstrated despite the coating also having extremely high surface hardness, a coating material including the resin composition, a coating comprising the coating material, and a film having a layer of the coating. An active-energy-ray-curable resin composition characterized by containing as an essential component a branched acrylic acrylate resin having a weight-average molecular weight (Mw) in the range of 6,000 to 70,000 in which a plurality of acrylic polymers (a) each having a (meth)acryloyl group in a side chain thereof are connected via a functional group other than the (meth)acryloyl group. A coating material including the active-energy-ray-curable resin composition, and a film having a coating layer obtained by curing the coating material.

Description

活性能量線硬化型樹脂組成物、塗料、塗膜、及積層薄膜 Active energy ray-curable resin composition, coating, coating film, and laminated film

本發明係關於能夠得到：具有非常高的表面硬度的同時，加工性亦優良之塗膜之活性能量線硬化型樹脂組成物；包含該樹脂組成物的塗料；由該塗料構成之塗膜；以及具有該塗膜層的積層薄膜。 The present invention relates to an active energy ray-curable resin composition capable of obtaining a coating film having a very high surface hardness and excellent workability, a coating material containing the resin composition, and a coating film composed of the coating material; A laminated film having the coating layer.

使用聚對酞酸乙二酯樹脂(PET)、丙烯酸樹脂、聚碳酸酯樹脂、乙醯化纖維素樹脂等所製造之塑膠薄膜大多用在工業用途上。這些薄膜被利用作為例如組裝至平板顯示器的內部中之偏光板保護薄膜或表面保護薄膜，但對這些薄膜要求有高的耐刮傷性。 Plastic films produced using polyethylene terephthalate resin (PET), acrylic resin, polycarbonate resin, acetylated cellulose resin, etc. are mostly used for industrial purposes. These films are utilized as, for example, a polarizing plate protective film or a surface protective film incorporated into the interior of a flat panel display, but these films are required to have high scratch resistance.

就提高耐刮傷性的方法而言，已研究探討各種方法，但從硬化所需的能量降低等環境上的優越性的點來看，近年來，已逐漸實施在薄膜上塗布以交聯密度高的多官能丙烯酸酯為主體之活性能量線硬化型樹脂組成物並以紫外線(UV)或電子束(EB)等活性能量線使其硬化形成硬塗層之方法。 In order to improve the scratch resistance, various methods have been studied, but from the viewpoint of environmental advantages such as reduction in energy required for hardening, in recent years, coating on a film has been gradually carried out to crosslink density. A highly polyfunctional acrylate is a main active energy ray-curable resin composition and is cured by an active energy ray such as ultraviolet (UV) or electron beam (EB) to form a hard coat layer.

透過顯示器的輕量化、薄型化的進展，所使用的薄膜亦經薄膜化。於是，塗布、硬化於薄膜上之硬塗劑被要求兼具比以往更高的硬度，且亦對應於要求可 撓性的用途之加工性。就能適用於這樣用途的硬塗劑而言，已知有藉由使丙烯酸與含環氧基的丙烯酸系聚合物反應而得之於側鏈具有雙鍵的丙烯酸系聚合物、與多官能丙烯酸酯而獲得之活性能量線硬化型樹脂組成物(參照例如：專利文獻1)。 Through the progress of weight reduction and thinning of the display, the film used is also thinned. Therefore, the hard coating agent applied and hardened on the film is required to have a higher hardness than before, and also corresponds to the requirements. Processability for flexible applications. In the case of a hard coating agent which can be suitably used for such a use, an acrylic polymer having a double bond in a side chain by reacting acrylic acid with an epoxy group-containing acrylic polymer, and a polyfunctional acrylic acid are known. An active energy ray-curable resin composition obtained by ester (see, for example, Patent Document 1).

然而，在前述專利文獻1所提供之由於側鏈具有雙鍵的丙烯酸系聚合物與多官能丙烯酸酯所得到之活性能量線硬化型樹脂組成物中，由於組成物中所含的雙鍵的反應率不充分，雖然具有一定的加工性，但塗膜硬度還是不足。 However, in the active energy ray-curable resin composition obtained by the acrylic polymer having a double bond in the side chain and the polyfunctional acrylate provided in the aforementioned Patent Document 1, the reaction of the double bond contained in the composition The rate is not sufficient, although it has certain processability, the hardness of the film is still insufficient.

又，相較於僅由有機系材料構成之樹脂組成物，使無機微粒子分散於樹脂成分中而得之無機微粒子分散型活性能量線硬化型樹脂組成物係作為能夠具有硬化塗膜的高硬度化、調整折射率、賦予導電性等之賦予高性能化或新功能之新穎材料而被提供(參照例如：專利文獻2)。雖然由此種使無機微粒子分散而成之樹脂組成物所得到之塗膜具有高硬度這樣的特徵，並能夠作為顯現耐傷性的硬塗層來使用，但是就另一方面來說，其具有加工性差這樣的一面，而且有難以適用於可撓式顯示器用途之情況。 In addition, the inorganic fine particle-dispersed active energy ray-curable resin composition obtained by dispersing inorganic fine particles in a resin component as compared with a resin composition composed only of an organic material has high hardness as a cured coating film. A novel material that imparts high performance or a new function to adjust the refractive index and impart conductivity (see, for example, Patent Document 2). The coating film obtained by dispersing the resin composition in which the inorganic fine particles are dispersed has a high hardness and can be used as a hard coat layer exhibiting scratch resistance, but on the other hand, it has processing. This is a side of poor performance, and it is difficult to apply to flexible display applications.

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

[專利文獻1]日本特開2011-207947號公報 [Patent Document 1] Japanese Laid-Open Patent Publication No. 2011-207947

[專利文獻2]國際公開WO2013/047590號 [Patent Document 2] International Publication WO2013/047590

本發明所欲解決之課題在於提供：於其硬化塗膜具有非常高的表面硬度的同時，亦展現加工性亦優良的性能之活性能量線硬化型樹脂組成物；包含該樹脂組成物的塗料；由該塗料構成之塗膜；以及具有該塗膜層的積層薄膜。 An object of the present invention is to provide an active energy ray-curable resin composition which exhibits excellent surface properties while having a very high surface hardness, and a coating material containing the resin composition; a coating film composed of the coating material; and a laminated film having the coating film layer.

本發明人等為解決上述課題而專心致力於研究，結果發現：包含於側鏈具有(甲基)丙烯醯基的丙烯酸聚合物(a)透過前述(甲基)丙烯醯基以外的官能基而連結複數個而成之重量平均分子量(Mw)在6,000~70,000的範圍之分枝狀丙烯酸丙烯酸酯樹脂(acrylic acrylate resin)(A)之活性能量線硬化型樹脂組成物，在硬化後會展現非常高的表面硬度，同時亦富有於塑膠基材上進行塗布硬化時的加工性(可撓性)，而完成本發明。 The inventors of the present invention have focused their efforts on the above-mentioned problems, and have found that an acrylic polymer (a) having a (meth)acryloyl group in a side chain transmits a functional group other than the (meth)acrylonyl group. A plurality of active energy ray-curable resin compositions of a branched acrylic acrylate resin (A) having a weight average molecular weight (Mw) in the range of 6,000 to 70,000, which are formed by a plurality of The present invention has been accomplished by having a high surface hardness and also being rich in workability (flexibility) at the time of coating hardening on a plastic substrate.

亦即，本發明提供：活性能量線硬化型樹脂組成物及包含其之塗料、使其硬化而成之塗膜、以及具有該塗膜層的積層薄膜，該活性能量線硬化型樹脂組成物之特徵在於含有於側鏈具有(甲基)丙烯醯基的丙烯酸聚合物(a)透過前述(甲基)丙烯醯基以外的官能基而連結複數個而成之重量平均分子量(Mw)在6,000~70,000的範圍之分枝狀丙烯酸丙烯酸酯樹脂(A)作為必要成分。 In other words, the present invention provides an active energy ray-curable resin composition, a coating film containing the same, a coating film obtained by curing the same, and a laminated film having the coating film layer, and the active energy ray-curable resin composition The acrylic polymer (a) having a (meth) acrylonitrile group in a side chain is bonded to a functional group other than the (meth) acryl fluorenyl group to form a weight average molecular weight (Mw) of 6,000 Å. A branched acrylic acrylate resin (A) in the range of 70,000 is an essential component.

若根據本發明，則能夠提供：硬化塗膜，其 在具有非常高的表面硬度、透明性的同時，還具有亦能夠作為可撓式顯示器使用之加工性；能提供該硬化塗膜之活性能量線硬化型樹脂組成物；包含其之塗料。 According to the present invention, it is possible to provide a hardened coating film, which It has a very high surface hardness and transparency, and has workability which can also be used as a flexible display; an active energy ray-curable resin composition capable of providing the cured coating film; and a coating material containing the same.

[實施發明之形態] [Formation of the Invention]

本發明之活性能量線硬化型樹脂組成物之特徵為含有：於側鏈具有(甲基)丙烯醯基的丙烯酸聚合物(a)透過前述(甲基)丙烯醯基以外的官能基而連結複數個而成之重量平均分子量(Mw)在6,000~70,000的範圍之分枝狀丙烯酸丙烯酸酯樹脂(A)作為必要成分。 The active energy ray-curable resin composition of the present invention is characterized in that the acrylic polymer (a) having a (meth)acryl fluorenyl group in a side chain is bonded to a functional group other than the (meth) acryl fluorenyl group As a necessary component, a branched acrylic acrylate resin (A) having a weight average molecular weight (Mw) of 6,000 to 70,000 is obtained.

前述分枝狀丙烯酸丙烯酸酯樹脂(A)係藉由其重量平均分子量(Mw)為6,000~70,000的範圍，而能夠對使其硬化所得到之硬化塗膜賦予高硬度與加工性。從此等的效果更加優良的觀點、以及易於將活性能量線硬化型樹脂組成物的黏度調整成適於塗布者之觀點來看，重量平均分子量(Mw)係以8,000~50,000的範圍為佳，以10,000~40,000的範圍為更佳。 The branched acrylic acrylate resin (A) has a weight average molecular weight (Mw) of 6,000 to 70,000, and can impart high hardness and workability to the cured coating film obtained by curing the cured acrylic film. The weight average molecular weight (Mw) is preferably in the range of 8,000 to 50,000, and the weight average molecular weight (Mw) is preferably from the viewpoint of improving the effect of the above-mentioned effects and the viscosity of the active energy ray-curable resin composition. The range of 10,000 to 40,000 is better.

還有，在本發明中，重量平均分子量(Mw)為使用凝膠滲透層析儀(GPC)且藉由下述條件進行測定而得的值。 Further, in the present invention, the weight average molecular weight (Mw) is a value obtained by measuring using a gel permeation chromatography (GPC) under the following conditions.

測定裝置：TOSOH股份有限公司製HLC-8220 Measuring device: HLC-8220 manufactured by TOSOH Co., Ltd.

管柱：TOSOH股份有限公司製保護管柱HXL-H Pipe column: protection column HXL-H made by TOSOH Co., Ltd.

+TOSOH股份有限公司製TSKgel G5000HXL +TOSOH Co., Ltd. TSKgel G5000HXL

+TOSOH股份有限公司製TSKgel G4000HXL +TOSOH Co., Ltd. TSKgel G4000HXL

+TOSOH股份有限公司製TSKgel G3000HXL +TSKgel G3000HXL made by TOSOH Co., Ltd.

+TOSOH股份有限公司製TSKgel G2000HXL +TOSOH Co., Ltd. TSKgel G2000HXL

偵檢器：RI(示差折射計) Detector: RI (differential refractometer)

數據處理：TOSOH股份有限公司製SC-8010 Data Processing: SC-8010 manufactured by TOSOH Co., Ltd.

測定條件：管柱溫度 40℃ Measurement conditions: column temperature 40 ° C

溶媒 四氫呋喃 Solvent tetrahydrofuran

流速 1.0ml/分鐘 Flow rate 1.0ml/min

標準：聚苯乙烯 Standard: Polystyrene

試料：使用微濾器將以樹脂固體含量換算為0.4質量%的四氫呋喃溶液過濾而得者(100μl) Sample: Filtered by using a microfilter to filter a 0.4% by mass of a resin solid content in tetrahydrofuran (100 μl)

又，就容易得到具有高表面硬度的同時加工性亦優異的硬化塗膜之點來看，前述分枝狀丙烯酸丙烯酸酯樹脂(A)的(甲基)丙烯醯基當量較佳為200g/eq~700g/eq的範圍，更佳為200g/eq~550g/eq的範圍。 Moreover, it is easy to obtain a hardened coating film having high surface hardness and excellent workability, and the (meth)acryl oxime equivalent of the branched acrylic acrylate resin (A) is preferably 200 g/eq. A range of ~700 g/eq, more preferably in the range of 200 g/eq to 550 g/eq.

前述分枝狀丙烯酸丙烯酸酯樹脂(A)係能夠藉由下述方法而得到，該方法為例如藉由將具有羧基與(甲基)丙烯醯基的化合物，與使具有環氧丙基與(甲基)丙烯醯基的化合物進行同元聚合或是使該化合物與(甲基)丙烯酸酯進行共聚合所得到的丙烯酸聚合物的前驅物進行反應，而得到於側鏈具有羥基的丙烯酸聚合物，透過該羥基，使用與羥基具有反應性的化合物，使複數個丙烯酸聚合物連結之方法。 The above branched acrylic acrylate resin (A) can be obtained by, for example, a compound having a carboxyl group and a (meth)acryl fluorenyl group, and having a glycidyl group ( The methyl methacrylate compound is subjected to homopolymerization or a precursor of an acrylic polymer obtained by copolymerizing the compound with a (meth) acrylate to obtain an acrylic polymer having a hydroxyl group in a side chain. A method of linking a plurality of acrylic polymers by using a compound reactive with a hydroxyl group through the hydroxyl group.

更具體而言，可列舉：首先得到具有環氧丙基與(甲基)丙烯醯基的化合物之均聚物、或該化合物與( 甲基)丙烯酸酯之共聚物(以下將此等簡記為「前驅物(1)」。)，使其與具有羧基與(甲基)丙烯醯基的化合物進行反應所得到之丙烯酸聚合物(a1)、與於1分子中具有2個以上的異氰酸酯基之化合物(b1)反應而成之樹脂。藉由使於1分子中具有2個以上的異氰酸酯基之化合物(b1)對因環氧丙基與羧基的反應所生成之羥基反應，而能夠得到可在本發明中使用的分枝狀丙烯酸丙烯酸酯樹脂(A)。 More specifically, a homopolymer of a compound having a glycidyl group and a (meth)acryl fluorenyl group, or a compound and A copolymer of methyl acrylate (hereinafter referred to simply as "precursor (1)"), and an acrylic polymer obtained by reacting a compound having a carboxyl group with a (meth) acryl fluorenyl group (a1) And a resin obtained by reacting a compound (b1) having two or more isocyanate groups in one molecule. By reacting a compound (b1) having two or more isocyanate groups in one molecule with a hydroxyl group formed by a reaction of a glycidyl group and a carboxyl group, a branched acrylic acid which can be used in the present invention can be obtained. Ester resin (A).

在此，成為前驅物(1)的原料之具有環氧丙基與(甲基)丙烯醯基的化合物係可列舉例如：(甲基)丙烯酸環氧丙酯、α-乙基(甲基)丙烯酸環氧丙酯、α-正丙基(甲基)丙烯酸環氧丙酯、α-正丁基(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸-3,4-環氧丁酯、(甲基)丙烯酸-4,5-環氧戊酯、(甲基)丙烯酸-6,7-環氧戊酯、α-乙基(甲基)丙烯酸-6,7-環氧戊酯、β-甲基環氧丙基(甲基)丙烯酸酯、(甲基)丙烯酸-3,4-環氧環己酯、經內酯改質的(甲基)丙烯酸-3,4-環氧環己酯、乙烯基環氧環己烷等。在此等之中，就變得容易將所得到的丙烯酸聚合物(a1)的(甲基)丙烯醯基當量調節成較佳的範圍之點來看，以使用(甲基)丙烯酸環氧丙酯、α-乙基(甲基)丙烯酸環氧丙酯及α-正丙基(甲基)丙烯酸環氧丙酯為佳，以使用(甲基)丙烯酸環氧丙酯為更佳。 Here, examples of the compound having a glycidyl group and a (meth)acryloyl group as a raw material of the precursor (1) include, for example, (meth)acrylic acid propyl acrylate and α-ethyl (methyl). Glycidyl acrylate, g-propyl α-n-propyl (meth) acrylate, g-propyl α-n-butyl (meth) acrylate, 3,4-butyl butyl (meth) acrylate , (meth)acrylic acid-4,5-epoxypentyl ester, (meth)acrylic acid-6,7-epoxypentyl ester, α-ethyl (meth)acrylic acid-6,7-epoxypentyl ester, Β-methylepoxypropyl (meth) acrylate, (meth)acrylic acid-3,4-epoxycyclohexyl ester, lactone-modified (meth)acrylic acid-3,4-epoxy ring Hexyl ester, vinyl epoxy cyclohexane, and the like. Among these, it becomes easy to adjust the (meth)acryl oxime equivalent of the obtained acrylic polymer (a1) to a preferable range to use (meth)acrylic acid propylene-acrylic acid The ester, the epoxypropyl α-ethyl (meth)acrylate and the glycidyl α-n-propyl (meth)acrylate are preferred, and the use of glycidyl (meth)acrylate is more preferred.

製造前述前驅物(1)時，能夠與前述具有環氧丙基與(甲基)丙烯醯基的化合物一起聚合的(甲基)丙烯酸酯亦可使用前述任一者，惟其中，從容易將所得到的丙烯酸聚合物(a1)的(甲基)丙烯醯基當量調節至較佳 範圍之200g/eq~700g/eq的範圍，且在使用使於1分子中具有2個以上的異氰酸酯基之化合物(b1)進一步加成於其上而成之分枝狀丙烯酸丙烯酸酯樹脂(A)所得到的硬化塗膜為高硬度的同時，容易得到亦富有加工性者之觀點來看，較佳為具有碳數1~22的烷基之(甲基)丙烯酸酯及具有脂環式的烷基之(甲基)丙烯酸酯，更佳為具有碳數1~22的烷基之(甲基)丙烯酸酯。尤其是以使用(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、及(甲基)丙烯酸三級丁酯為特佳。 When the precursor (1) is produced, any of the above (meth) acrylate which can be polymerized with the compound having a glycidyl group and a (meth) acryl fluorenyl group may be used, but it is easy to The (meth)acryl oxime equivalent of the obtained acrylic polymer (a1) is adjusted to preferably a branched acrylic acrylate resin (A) obtained by further adding a compound (b1) having two or more isocyanate groups in one molecule to the range of from 200 g/eq to 700 g/eq (A) The hardened coating film obtained has a high hardness and is easy to obtain and has a processability. It is preferably a (meth) acrylate having an alkyl group having 1 to 22 carbon atoms and having an alicyclic structure. The alkyl (meth) acrylate is more preferably a (meth) acrylate having an alkyl group having 1 to 22 carbon atoms. In particular, it is particularly preferred to use methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and tertiary butyl (meth)acrylate. .

在此，為了將所得到的聚合物(a1)的(甲基)丙烯醯基當量調整至適當的範圍，係以將在共聚合時之兩者的質量比[具有環氧丙基與(甲基)丙烯醯基的化合物：(甲基)丙烯酸酯]成為20/80~95/5的範圍之比例下進行共聚合而成的聚合物作為前驅物來使用為佳，以在30/70~90/10的範圍內使用為更佳，以60/40~90/10的範圍為再更佳，以在80/20~90/10的範圍內使用為最佳。 Here, in order to adjust the (meth)acryl oxime equivalent of the obtained polymer (a1) to an appropriate range, the mass ratio of both at the time of copolymerization [having an epoxy propyl group and (a) The compound of the acryl-based fluorenyl group: (meth) acrylate] is preferably used as a precursor in a ratio of 20/80 to 95/5, and is preferably used at 30/70~. It is preferably used in the range of 90/10, and more preferably in the range of 60/40 to 90/10, and is preferably used in the range of 80/20 to 90/10.

前述前驅物(1)係例如能夠藉由在聚合起始劑的存在下，於60℃~180℃的溫度領域中，單獨聚合前述具有環氧丙基與(甲基)丙烯醯基的化合物，或是併用前述化合物與(甲基)丙烯酸酯進行加成聚合來製造，在共聚物的情況下，可為無規共聚物、嵌段共聚物、接枝共聚物等的任一種。聚合方法係能夠利用塊狀聚合法、溶液聚合法、懸浮聚合法、乳化聚合法等。在此等之中，就能夠連續地進行前驅物(1)的製造、接續其之該前驅物(1)與具有羧基與(甲基)丙烯醯基的化合物的反應、以 及與於1分子中具有2個以上的異氰酸酯基之化合物(b1)的反應的點來看，較佳為溶液聚合法。 The precursor (1) can be, for example, polymerized by the above-mentioned compound having a glycidyl group and a (meth)acryl fluorenyl group in the temperature range of 60 ° C to 180 ° C in the presence of a polymerization initiator. Alternatively, it may be produced by addition polymerization of the above compound with (meth) acrylate, and in the case of a copolymer, it may be any of a random copolymer, a block copolymer, a graft copolymer and the like. The polymerization method can utilize a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or the like. Among these, it is possible to continuously carry out the production of the precursor (1), and the reaction of the precursor (1) with a compound having a carboxyl group and a (meth)acryl fluorenyl group, Further, in view of the reaction with the compound (b1) having two or more isocyanate groups in one molecule, a solution polymerization method is preferred.

以溶液聚合法進行前述前驅物(1)的製造時所使用的溶媒，若考慮反應溫度，則以沸點在80℃以上者為理想，可列舉例如：甲基乙基酮、甲基正丙基酮、甲基異丙基酮、甲基正丁基酮、甲基異丁基酮、甲基正戊基酮、甲基正己基酮、二乙基酮、乙基正丁基酮、二正丙基酮、二異丁基酮、環己酮、佛耳酮等酮溶劑；正丁基醚、二異戊基醚、二烷等醚溶劑；醋酸正丙酯、醋酸異丙酯、醋酸正丁酯、醋酸正戊酯、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙酸乙基-3-乙氧酯等酯溶劑；甲苯、二甲苯、SOLVESSO 100、SOLVESSO 150、SWASOL 1800、SWASOL 310、ISOPAR E、ISOPAR G、Exxon naphtha 5號、Exxon naphtha 6號等烴溶劑等。此等係可單獨使用，亦可併用2種以上。 The solvent used in the production of the precursor (1) by the solution polymerization method is preferably a boiling point of 80 ° C or higher in consideration of the reaction temperature, and examples thereof include methyl ethyl ketone and methyl n-propyl group. Ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl n-hexyl ketone, diethyl ketone, ethyl n-butyl ketone, di-n-butyl Ketone solvents such as propyl ketone, diisobutyl ketone, cyclohexanone, and phorbol; n-butyl ether, diisoamyl ether, and Ether solvent such as alkane; n-propyl acetate, isopropyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Ester monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxylate propionate ester solvent; toluene, xylene, SOLVESSO 100, SOLVESSO 150, SWASOL 1800, SWASOL 310, ISOPAR E, ISOPAR G, Exxon naphtha 5, Exxon naphtha 6 and other hydrocarbon solvents. These may be used singly or in combination of two or more.

在前述溶媒之中，從所得到的前驅物(1)的溶解性為優異的點來看，較佳為甲基乙基酮或甲基異丁基酮等酮溶劑、或醋酸異丙酯、醋酸正丁酯等酯溶劑。 Among the above solvents, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone or isopropyl acetate is preferred from the viewpoint that the solubility of the obtained precursor (1) is excellent. An ester solvent such as n-butyl acetate.

在此，前驅物(1)的製造中使用的觸媒係可列舉例如：2,2'-偶氮雙異丁腈、2,2'-偶氮雙-(2,4-二甲基戊腈)、2,2'-偶氮雙-(4-甲氧基-2,4-二甲基戊腈)等偶氮化合物；過氧化苯甲醯基(benzoyl peroxide)、過氧化月桂醯基(lauroyl peroxide)、過氧三甲基乙酸三級丁酯、過 氧乙基己酸三級丁酯、1,1'-雙(三級丁基過氧)環己烷、過氧-2-乙基己酸三級戊酯、過氧-2-乙基己酸三級己酯等有機過氧化物及過氧化氫等。 Here, the catalyst system used in the production of the precursor (1) may, for example, be 2,2'-azobisisobutyronitrile or 2,2'-azobis-(2,4-dimethylpentyl) Azo compound such as nitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauric acid peroxide (lauroyl peroxide), tertiary butyl peroxytrimethylacetate, Tert-butyl oxyethylhexanoate, 1,1'-bis(tri-butylperoxy)cyclohexane, peroxy-pentyl 2-ethylhexanoate, peroxy-2-ethyl Organic peroxides such as acid tertiary hexyl ester and hydrogen peroxide.

在使用過氧化物作為觸媒的情況下，亦可將過氧化物與還原劑一起使用而作成氧化還原型起始劑。 In the case where a peroxide is used as a catalyst, a peroxide may be used together with a reducing agent to form a redox type initiator.

如此進行所得到的前驅物(1)係能夠進一步與具有羧基與(甲基)丙烯醯基的化合物進行反應而作成丙烯酸聚合物(a1)。該反應方法係可列舉例如：以溶液聚合法將前驅物(1)聚合，在該反應系統中加入具有羧基與(甲基)丙烯醯基的化合物，於60~150℃的溫度範圍下，適當使用三苯膦等觸媒等之方法。丙烯酸聚合物(a1)的(甲基)丙烯醯基當量較佳為200eq~700g/eq的範圍，但其係能夠藉由前述前驅物(1)與前述具有羧基與(甲基)丙烯醯基的化合物之反應比率來調節。通常，藉由以羧基相對於1莫耳的前驅物(1)具有的環氧丙基成為0.9~1.2莫耳的範圍之方式進行反應，而易於將所得到的丙烯酸聚合物(a1)的(甲基)丙烯醯基當量調整至上述較佳的範圍。 The precursor (1) thus obtained can be further reacted with a compound having a carboxyl group and a (meth)acryl fluorenyl group to form an acrylic polymer (a1). The reaction method may, for example, be a method of polymerizing a precursor (1) by a solution polymerization method, and adding a compound having a carboxyl group and a (meth)acryl fluorenyl group to the reaction system at a temperature of 60 to 150 ° C, suitably A method such as a catalyst such as triphenylphosphine is used. The (meth) acrylonitrile group equivalent of the acrylic polymer (a1) is preferably in the range of from 200 eq to 700 g/eq, but it is capable of having a carboxyl group and a (meth) acrylonitrile group by the aforementioned precursor (1) and the foregoing. The reaction ratio of the compound is adjusted. In general, it is easy to carry out the reaction of the obtained acrylic polymer (a1) by reacting the carboxyl group with respect to the epoxy group of the 1 mol precursor (1) in the range of 0.9 to 1.2 mol. The methyl methacrylate oxime equivalent is adjusted to the above preferred range.

此處所使用之具有羧基與(甲基)丙烯醯基的化合物係可列舉例如：(甲基)丙烯酸、(丙烯醯氧基)醋酸、丙烯酸-2-羧基乙酯、丙烯酸-3-羧基丙酯、琥珀酸-1-[2-(丙烯醯氧基)乙酯]、酞酸-1-(2-丙烯醯氧乙酯)、六氫酞酸氫-2-(丙烯醯氧基)乙酯及此等的內酯改質物等不飽和單羧酸；順丁烯二酸等不飽和二羧酸；使琥珀酸酐或順丁烯二酐等酸酐與新戊四醇三丙烯酸酯等含羥基的多官能 (甲基)丙烯酸酯單體反應所得到之含羧基的多官能(甲基)丙烯酸酯等。此等係可單獨使用，亦可併用2種以上。在此等之中，就易於將所得到的丙烯酸聚合物(a2)的(甲基)丙烯醯基當量調節至前述較佳的範圍的點來看，較佳為(甲基)丙烯酸、(丙烯醯氧基)醋酸、丙烯酸-2-羧基乙酯、丙烯酸-3-羧基丙酯，特佳為(甲基)丙烯酸。 The compound having a carboxyl group and a (meth)acrylinyl group used herein may, for example, be (meth)acrylic acid, (acryloxy)acetic acid, 2-carboxyethyl acrylate or 3-carboxypropyl acrylate. , succinic acid-1-[2-(propylene decyloxy)ethyl ester], decanoic acid-1-(2-propenyl oxime), hydrogen hexahydrophthalate-2-(propylene decyloxy) ethyl ester And an unsaturated monocarboxylic acid such as a lactone modified product; an unsaturated dicarboxylic acid such as maleic acid; an acid anhydride such as succinic anhydride or maleic anhydride; and a hydroxyl group such as neopentyl alcohol triacrylate. Multifunctional A carboxyl group-containing polyfunctional (meth) acrylate obtained by reacting a (meth) acrylate monomer. These may be used singly or in combination of two or more. Among these, from the viewpoint of easily adjusting the (meth)acrylonitrile group equivalent of the obtained acrylic polymer (a2) to the above preferred range, (meth)acrylic acid, (propylene) is preferred.醯oxy)acetic acid, 2-carboxyethyl acrylate, 3-carboxypropyl acrylate, particularly preferably (meth)acrylic acid.

如此進行所得到的丙烯酸聚合物(a1)係在其分子結構中具有因環氧基與羧基的反應所產生的羥基。藉由使此羥基與於1分子中具有2個以上的異氰酸酯基之化合物(b1)進一步反應，而得到本發明中使用的分枝狀丙烯酸丙烯酸酯樹脂(A)。 The acrylic polymer (a1) thus obtained has a hydroxyl group which is produced by a reaction of an epoxy group and a carboxyl group in its molecular structure. The branched acrylic acrylate resin (A) used in the present invention is obtained by further reacting the hydroxyl group with the compound (b1) having two or more isocyanate groups in one molecule.

再者，從能夠以合成更簡便的方法來製造的點來看，係以尤其是使用(甲基)丙烯酸環氧丙酯，使其與(甲基)丙烯酸酯共聚合而得到前驅物(1)，使用(甲基)丙烯酸而與該前驅物(1)反應所得到之丙烯酸聚合物(a1)為特佳。 Further, from the viewpoint of being able to be produced by a simpler method of synthesis, a precursor (1) is obtained by copolymerizing a (meth) acrylate with a glycidyl (meth) acrylate in particular. The acrylic polymer (a1) obtained by reacting the precursor (1) with (meth)acrylic acid is particularly preferred.

就如此進行所得到的丙烯酸聚合物(a1)的重量平均分子量而言，較佳為3,000~15,000的範圍。亦即，藉由使用此範圍內的丙烯酸聚合物(a1)，而使所得到的分枝狀丙烯酸丙烯酸酯樹脂(A)的分枝度變得合適，容易以平衡的方式使所得到的硬化塗膜的硬度與加工性更展現。從更加提高該效果的點來看，就丙烯酸聚合物(a1)的重量平均分子量而言，較佳為4,000~13,000的範圍，特佳為5,000~10,000的範圍。 The weight average molecular weight of the obtained acrylic polymer (a1) thus obtained is preferably in the range of 3,000 to 15,000. That is, by using the acrylic polymer (a1) in this range, the branching degree of the obtained branched acrylic acrylate resin (A) becomes appropriate, and the obtained hardening is easily performed in a balanced manner. The hardness and processability of the coating film are more exhibited. From the viewpoint of further improving the effect, the weight average molecular weight of the acrylic polymer (a1) is preferably in the range of 4,000 to 13,000, particularly preferably in the range of 5,000 to 10,000.

假設本發明之活性能量線硬化型樹脂組成物 能夠藉由使前述的丙烯酸聚合物(a1)中的羥基與於1分子中具有2個以上的異氰酸酯基之化合物(b1)中的異氰酸酯基反應而將分枝結構導入至樹脂，並且藉由使用增加分子量分布範圍而成的分枝狀丙烯酸丙烯酸酯樹脂(A)來提高所得到的塗膜的表面硬度，同時藉由含有胺基甲酸酯鍵結而使塗膜的加工性提升。因此，就化合物(b1)而言，只要是具有2個以上的異氰酸酯基的化合物即可，並沒有特殊的限定，但從更有效地提高分枝度並且使硬化塗膜的加工性更為顯現之觀點來看，較佳為具有在1分子中具有3個以上的異氰酸酯基的化合物之化合物。 It is assumed that the active energy ray-curable resin composition of the present invention The branching structure can be introduced into the resin by reacting the hydroxyl group in the acrylic polymer (a1) with an isocyanate group in the compound (b1) having two or more isocyanate groups in one molecule, and by using The branched acrylic acrylate resin (A) having a molecular weight distribution range is increased to increase the surface hardness of the obtained coating film, and the workability of the coating film is improved by bonding with a urethane. Therefore, the compound (b1) is not particularly limited as long as it is a compound having two or more isocyanate groups, but the branching degree is more effectively improved and the processability of the cured coating film is more apparent. From the viewpoint of the above, a compound having a compound having three or more isocyanate groups in one molecule is preferred.

就前述於1分子中具有2個以上的異氰酸酯基之化合物(b1)而言，可列舉例如：六亞甲二異氰酸酯、2,2,4-三甲基己烷二異氰酸酯、2,4,4-三甲基六亞甲二異氰酸酯、離胺酸二異氰酸基甲酯、離胺酸三異氰酸酯、間苯二甲基二異氰酸酯、α,α,α',α'-四甲基苯二甲基二異氰酸酯、雙(異氰酸基甲基)萘、1,3,5-三甲苯(mesitylene)三異氰酸酯、雙(異氰酸基甲基)硫化物、雙(異氰酸基乙基)硫化物、雙(異氰酸基甲基)二硫化物、雙(異氰酸基乙基)二硫化物、雙(異氰酸基甲硫基)甲烷、雙(異氰酸基乙硫基)甲烷、雙(異氰酸基乙硫基)乙烷、雙(異氰酸基甲硫基)乙烷等脂肪族聚異氰酸酯化合物；異佛酮二異氰酸酯、雙(異氰酸基甲基)環己烷、二環己基甲烷二異氰酸酯、環己烷二異氰酸酯、甲基環己烷二異氰酸酯、二環己基二甲基甲烷異氰酸酯、2,5-雙(異氰酸基甲基)雙環-[2.2.1]-庚烷、2,6-雙(異氰酸基甲基)雙環-[2.2.1]-庚烷 、3,8-雙(異氰酸基甲基)三環癸烷、3,9-雙(異氰酸基甲基)三環癸烷、4,8-雙(異氰酸基甲基)三環癸烷、4,9-雙(異氰酸基甲基)三環癸烷等脂環族聚異氰酸酯化合物；硫化二苯基-4,4-二異氰酸酯等芳香族聚異氰酸酯化合物；2,5-二異氰酸基噻吩、2,5-雙(異氰酸基甲基)噻吩、2,5-二異氰酸基四氫噻吩、2,5-雙(異氰酸基甲基)四氫噻吩、3,4-雙(異氰酸基甲基)四氫噻吩、2,5-二異氰酸基-1,4-二噻、2,5-雙(異氰酸基甲基)-1,4-二噻、4,5-二異氰酸基-1,3-二噻、4,5-雙(異氰酸基甲基)-1,3-二噻等雜環聚異氰酸酯化合物、及此等異氰酸酯化合物衍生物之縮二脲(biuret)體、三聚氰酸酯(nurate)體、脲甲酸酯體、多元醇加成體等，可為單獨，亦可併用2種以上。 The compound (b1) having two or more isocyanate groups in one molecule may, for example, be hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, or 2,4,4. -trimethylhexamethylene diisocyanate, diisocyanate methyl amide, triisocyanate, m-xylylene diisocyanate, α,α,α',α'-tetramethylbenzene Methyl diisocyanate, bis(isocyanatomethyl)naphthalene, mesitylene triisocyanate, bis(isocyanatomethyl) sulfide, bis(isocyanatoethyl) Sulfide, bis(isocyanatomethyl)disulfide, bis(isocyanatoethyl)disulfide, bis(isocyanatomethylthio)methane, bis(isocyanatoethylthio) An aliphatic polyisocyanate compound such as methane, bis(isocyanatoethylthio)ethane or bis(isocyanatomethylthio)ethane; isophorone diisocyanate, bis(isocyanatomethyl) Cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane isocyanate, 2,5-bis(isocyanatomethyl)bicyclo- [2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 3,8-bis(isocyanatomethyl)tricyclodecane, 3,9-bis(isocyanocyanate Alicyclic polycondensation such as acid methyl)tricyclodecane, 4,8-bis(isocyanatomethyl)tricyclodecane, 4,9-bis(isocyanatomethyl)tricyclodecane Isocyanate compound; aromatic polyisocyanate compound such as diphenyl-4,4-diisocyanate; 2,5-diisocyanatothiophene, 2,5-bis(isocyanatomethyl)thiophene, 2,5 -diisocyanatotetrahydrothiophene, 2,5-bis(isocyanatomethyl)tetrahydrothiophene, 3,4-bis(isocyanatomethyl)tetrahydrothiophene, 2,5-diiso Cyanate-1,4-dithiazide 2,5-bis(isocyanatomethyl)-1,4-dithiazide 4,5-diisocyanato-1,3-dithiazide , 4,5-bis(isocyanatomethyl)-1,3-dithiazide The heterocyclic polyisocyanate compound, and the biuret, the nurate, the ureacarboxylate, the polyol adduct, etc. of the isocyanate compound derivative may be used alone. Two or more types may be used in combination.

在此等之中，從所得到的塗膜的加工性優異並且不損及透明性以及不易黃變的觀點來看，係以使用六亞甲異氰酸酯、六亞甲異氰酸酯的縮二脲體、六亞甲異氰酸酯的三聚氰酸酯體為佳。 Among these, from the viewpoint of excellent workability of the obtained coating film and not impairing transparency and yellowing, a biuret body using hexamethylene isocyanate or hexamethylene isocyanate is used. A cyanurate body of methylene isocyanate is preferred.

就如此之於1分子中具有2個以上的異氰酸酯基之化合物(b1)的使用比例而言，較佳為以所得到的分枝狀丙烯酸丙烯酸酯樹脂(A)的重量平均分子量(Mw)成為6,000~70,000的範圍的方式來使用，特佳為以成為8,000~50,000的範圍的方式來使用，進一步更佳為以成為10,000~40,000的範圍的方式來使用。具體而言，相對於具有羥基與(甲基)丙烯醯基的重量平均分子量(Mw)在3,000~15,000的範圍之丙烯酸聚合物(a1)中的羥基1莫耳而言，較佳為以化合物(B)中的異氰酸酯基成為0.002 ~0.25莫耳的方式來使用，特佳為以成為0.01~0.18莫耳的方式來使用，進一步更佳為以成為0.02~0.12莫耳的方式來使用。 In the case where the compound (b1) having two or more isocyanate groups in one molecule is used, the weight average molecular weight (Mw) of the obtained branched acrylic acrylate resin (A) is preferably It is used in a range of 6,000 to 70,000, particularly preferably in a range of 8,000 to 50,000, and more preferably in a range of 10,000 to 40,000. Specifically, it is preferably a compound with respect to the hydroxyl group 1 mol in the acrylic polymer (a1) having a weight average molecular weight (Mw) of a hydroxyl group and a (meth)acryl fluorenyl group in the range of 3,000 to 15,000. The isocyanate group in (B) becomes 0.002 It is preferably used in a form of ~0.25 m. It is preferably used in a form of 0.01 to 0.18 mol, and more preferably used in a form of 0.02 to 0.12 mol.

還有，在此反應中，能夠使用各種的胺基甲酸酯化反應觸媒，其使用比例係以使用相對於丙烯酸聚合物(a1)的100質量份而言為0.001~1.0質量份左右為佳。 In addition, in the reaction, various urethanation catalysts can be used, and the ratio of use is 0.001 to 1.0 part by mass based on 100 parts by mass of the acrylic polymer (a1). good.

又，在此胺基甲酸酯化反應中，亦可直接使用前述丙烯酸聚合物(a1)的合成時使用的有機溶媒，在溶媒中進行反應，例如藉由在40~120℃的溫度下反應1~20小時左右而能輕易得到。再者，亦可併用用於抑制(甲基)丙烯醯基的聚合之聚合抑制劑。 Further, in the urethanation reaction, the organic solvent used in the synthesis of the acrylic polymer (a1) may be used as it is, and the reaction may be carried out in a solvent, for example, by reacting at a temperature of 40 to 120 °C. It can be easily obtained in about 1~20 hours. Further, a polymerization inhibitor for suppressing polymerization of a (meth) acrylonitrile group may also be used in combination.

又，本發明中使用的分枝狀丙烯酸丙烯酸酯樹脂(A)亦能夠使具有環氧丙基之重量平均分子量(Mw)在2,000~14,000的範圍之丙烯酸聚合物(a2)、於1分子中具有(甲基)丙烯醯基與羧基的化合物(b2)與於1分子中具有2個以上的羧基的化合物(b3)反應而得到。 Further, the branched acrylic acrylate resin (A) used in the present invention can also have an acrylic polymer (a2) having a weight average molecular weight (Mw) of a propylene group in the range of 2,000 to 14,000, in one molecule. The compound (b2) having a (meth)acryl fluorenyl group and a carboxyl group is obtained by reacting a compound (b3) having two or more carboxyl groups in one molecule.

具體而言，得到具有環氧丙基與(甲基)丙烯醯基的化合物之均聚物、或該化合物與(甲基)丙烯酸酯之共聚物(以下將此等簡記為「前驅物(2)」。)，使其與於1分子中具有(甲基)丙烯醯基與羧基的化合物(b2)及於1分子中具有2個以上的羧基的化合物(b3)反應，而進行於前驅物(2)的側鏈導入(甲基)丙烯醯基之反應、以及連結複數個具有該反應中所導入之(甲基)丙烯醯基的丙烯酸聚合物(a2)之反應。 Specifically, a homopolymer of a compound having a glycidyl group and a (meth)acryl fluorenyl group, or a copolymer of the compound and a (meth) acrylate is obtained (hereinafter, these are simply referred to as "precursors (2). And a compound (b2) having a (meth)acryloyl group and a carboxyl group in one molecule and a compound (b3) having two or more carboxyl groups in one molecule, and reacting with the precursor The side chain of (2) introduces a reaction of a (meth)acryl fluorenyl group, and a reaction of coupling a plurality of acrylic polymers (a2) having a (meth) acrylonitrile group introduced in the reaction.

在此，成為前驅物(2)的原料之具有環氧丙 基與(甲基)丙烯醯基的化合物係可列舉例如：(甲基)丙烯酸環氧丙酯、α-乙基(甲基)丙烯酸環氧丙酯、α-正丙基(甲基)丙烯酸環氧丙酯、α-正丁基(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸-3,4-環氧丁酯、(甲基)丙烯酸-4,5-環氧戊酯、(甲基)丙烯酸-6,7-環氧戊酯、α-乙基(甲基)丙烯酸-6,7-環氧戊酯、β-甲基環氧丙基(甲基)丙烯酸酯、(甲基)丙烯酸-3,4-環氧環己酯、經內酯改質的(甲基)丙烯酸-3,4-環氧環己酯、乙烯基環氧環己烷等。在此等之中，就易於將所得到的丙烯酸聚合物(a1-2)的(甲基)丙烯醯基當量調節至前述較佳的範圍的點來看，係以使用(甲基)丙烯酸環氧丙酯、α-乙基(甲基)丙烯酸環氧丙酯及α-正丙基(甲基)丙烯酸環氧丙酯為佳，以使用(甲基)丙烯酸環氧丙酯為更佳。 Here, the raw material of the precursor (2) has a propylene oxide Examples of the compound of the (meth)acryl fluorenyl group include glycidyl (meth)acrylate, glycidyl α-ethyl (meth)acrylate, and α-n-propyl (meth)acrylic acid. Glycidyl propyl ester, glycidyl α-n-butyl (meth) acrylate, 3,4-butyl butyl (meth) acrylate, 4,5-epoxypentyl (meth) acrylate, (meth)acrylic acid-6,7-epoxypentyl ester, α-ethyl (meth)acrylic acid-6,7-epoxypentyl ester, β-methylepoxypropyl (meth) acrylate, ( Methyl)acrylic acid-3,4-epoxycyclohexyl ester, lactone-modified (meth)acrylic acid-3,4-epoxycyclohexyl ester, vinyl epoxycyclohexane, and the like. Among these, it is easy to adjust the (meth)acryl oxime equivalent of the obtained acrylic polymer (a1-2) to the above preferred range, using a (meth)acrylic acid ring. Oxypropyl propyl ester, α-ethyl (meth) acrylate propyl acrylate and α-n-propyl (meth) acrylate propyl acrylate are preferred, and glycidyl (meth) acrylate is more preferred.

製造前述前驅物(2)時，能夠與前述具有環氧丙基與(甲基)丙烯醯基的化合物一起聚合的(甲基)丙烯酸酯亦可使用前述任一者，惟其中，從容易將所得到的分枝狀丙烯酸丙烯酸酯樹脂(A)的(甲基)丙烯醯基當量調節至前述較佳的範圍，且在所得到的硬化塗膜為高硬度的同時，容易得到亦富有加工性者之觀點來看，較佳為具有碳數1~22的烷基之(甲基)丙烯酸酯及具有脂環式的烷基之(甲基)丙烯酸酯，更佳為具有碳數1~22的烷基之(甲基)丙烯酸酯。尤其是以使用(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯為特佳。 When the precursor (2) is produced, any of the above (meth) acrylate which can be polymerized with the compound having a glycidyl group and a (meth) acryl fluorenyl group may be used, but it is easy to The (meth)acryl oxime equivalent of the obtained branched acrylic acrylate resin (A) is adjusted to the above preferred range, and the obtained hardened coating film is high in hardness and easy to obtain and processable. From the viewpoint of the above, it is preferably a (meth) acrylate having an alkyl group having 1 to 22 carbon atoms and a (meth) acrylate having an alicyclic alkyl group, more preferably having a carbon number of 1 to 22 Alkyl (meth) acrylate. In particular, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, tertiary butyl (meth)acrylate, (methyl) ) Cyclohexyl acrylate and isodecyl (meth) acrylate are particularly preferred.

在此，從易於將所得到的分枝狀丙烯酸丙烯酸酯樹脂(A)的(甲基)丙烯醯基當量調整至適當的範圍、得到具有高表面硬度且硬化時的耐捲曲性亦優異的硬化塗膜之點來看，係以在共聚合時之兩者的質量比[具有環氧丙基與(甲基)丙烯醯基的化合物]：[(甲基)丙烯酸酯]成為20/80~95/5的範圍之比例下使用為佳，尤其是以在成為30/70~95/5的範圍之比例下使用為更佳。再者，從得到在低照射量下的硬化性為優異的活性能量線硬化型樹脂組成物之點來看，較佳為60/40~90/10的範圍，特佳為80/20~90/10的範圍。 Here, the (meth) acrylonitrile base equivalent of the obtained branched acrylic acrylate resin (A) is easily adjusted to an appropriate range, and hardening having excellent surface hardness and excellent curl resistance at the time of curing is obtained. From the point of film coating, the mass ratio of the two at the time of copolymerization [compound having a glycidyl group and a (meth) acrylonitrile group]: [(meth) acrylate] becomes 20/80~ It is preferably used at a ratio of 95/5, especially at a ratio of 30/70 to 95/5. In addition, from the viewpoint of obtaining an active energy ray-curable resin composition having excellent curability at a low irradiation amount, it is preferably in the range of 60/40 to 90/10, particularly preferably 80/20 to 90. /10 range.

前述前驅物(2)雖具有源自前述具有環氧丙基與(甲基)丙烯醯基的化合物之環氧基，但就易於將最終所得到的分枝狀丙烯酸丙烯酸酯樹脂(A)的丙烯醯基當量調節至200~700g/eq的範圍之點來看，該前驅物(2)的環氧基當量較佳為140~720g/eq的範圍，更佳為150~480g/eq的範圍，再更佳為150~240g/eq的範圍，特佳為150~180g/eq的範圍。 Although the precursor (2) has an epoxy group derived from the above compound having a glycidyl group and a (meth)acryl fluorenyl group, it is easy to obtain the finally obtained branched acrylic acrylate resin (A). The epoxy equivalent of the precursor (2) is preferably in the range of from 140 to 720 g/eq, more preferably in the range of from 150 to 480 g/eq, from the viewpoint that the propylene group equivalent is adjusted to a range of from 200 to 700 g/eq. More preferably, it is in the range of 150 to 240 g/eq, and particularly preferably in the range of 150 to 180 g/eq.

前述前驅物(2)係例如能夠藉由在聚合起始劑的存在下，於60℃~180℃的溫度領域中，單獨聚合前述具有環氧丙基與(甲基)丙烯醯基的化合物，或是與前述(甲基)丙烯酸酯併用進行聚合來製造，但就能夠連續地進行前述前驅物(2)的製造、以及接續其之前述前驅物(2)、於1分子中具有(甲基)丙烯醯基與羧基的化合物(b2)與於1分子中具有2個以上的羧基的化合物(b3)的反應的點來看，較佳為以溶液聚合進行製造。 The precursor (2) can be, for example, polymerized by the above-mentioned compound having a glycidyl group and a (meth)acryl fluorenyl group in the temperature range of 60 ° C to 180 ° C in the presence of a polymerization initiator. Alternatively, it may be produced by polymerization in combination with the above (meth) acrylate, but the precursor (2) may be continuously produced, and the precursor (2) may be successively formed in one molecule (methyl group). When the compound (b2) of the acryloyl group and the carboxyl group is reacted with the compound (b3) having two or more carboxyl groups in one molecule, it is preferably produced by solution polymerization.

以溶液聚合法進行前述前驅物(2)的製造時所使用的溶媒，若考慮反應溫度，則以沸點在80℃以上者為理想，可列舉例如：甲基乙基酮、甲基正丙基酮、甲基異丙基酮、甲基正丁基酮、甲基異丁基酮、甲基正戊基酮、甲基正己基酮、二乙基酮、乙基正丁基酮、二正丙基酮、二異丁基酮、環己酮、佛耳酮等酮溶媒；正丁基醚、二異戊基醚、二烷等醚溶媒；乙二醇單甲基醚、乙二醇二甲基醚、乙二醇單乙基醚、乙二醇二乙基醚、乙二醇單丙基醚、乙二醇單異丙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、二乙二醇二甲基醚、二乙二醇單乙基醚、二乙二醇二乙基醚、二乙二醇單異丙基醚、二乙二醇單丁基醚、三乙二醇單甲基醚、三乙二醇二甲基醚、丙二醇單甲基醚、丙二醇二甲基醚、丙二醇單丙基醚、丙二醇單丁基醚、二丙二醇單甲基醚、二丙二醇二甲基醚等二醇醚溶劑；醋酸正丙酯、醋酸異丙酯、醋酸正丁酯、醋酸正戊酯、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙酸乙基-3-乙氧酯等酯溶媒；異丙醇、正丁醇、異丁醇、二丙酮醇、3-甲氧基-1-丙醇、3-甲氧基-1-丁醇、3-甲基-3-甲氧基丁醇等醇溶媒；甲苯、二甲苯、SOLVESSO 100、SOLVESSO 150、SWASOL 1800、SWASOL 310、ISOPAR E、ISOPAR G、Exxon naphtha 5號、Exxon naphtha 6號等烴溶媒等。此等係可單獨使用，亦可併用2種以上。 The solvent to be used in the production of the precursor (2) by the solution polymerization method is preferably a boiling point of 80 ° C or higher in consideration of the reaction temperature, and examples thereof include methyl ethyl ketone and methyl n-propyl group. Ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl n-hexyl ketone, diethyl ketone, ethyl n-butyl ketone, di-n-butyl a ketone solvent such as propyl ketone, diisobutyl ketone, cyclohexanone or phorbolone; n-butyl ether, diisoamyl ether, two Ether solvent such as alkane; ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoiso Propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethyl Glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl Glycol ether solvent such as phenyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether; n-propyl acetate, isopropyl acetate, n-butyl acetate, n-amyl acetate, ethylene Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether An ester solvent such as an acid ester or ethyl-3-ethoxylate propionate; isopropanol, n-butanol, isobutanol, diacetone alcohol, 3-methoxy-1-propanol, 3-methoxy- Alcohol solvent such as 1-butanol or 3-methyl-3-methoxybutanol; , Xylene, SOLVESSO 100, SOLVESSO 150, SWASOL 1800, SWASOL 310, ISOPAR E, ISOPAR G, Exxon naphtha No. 5, Exxon naphtha No. 6 hydrocarbons and other solvents. These may be used singly or in combination of two or more.

在前述溶媒之中，從所得到的前驅物(2)的 溶解性為優異的點來看，較佳為甲基乙基酮或甲基異丁基酮等酮溶劑、或醋酸異丙酯、醋酸正丁酯等酯溶劑。 Among the aforementioned solvents, from the obtained precursor (2) The solvent is preferably a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone or an ester solvent such as isopropyl acetate or n-butyl acetate.

前述前驅物(2)的製造中使用的觸媒係可列舉例如：2,2'-偶氮雙異丁腈、2,2'-偶氮雙-(2,4-二甲基戊腈)、2,2'-偶氮雙-(4-甲氧基-2,4-二甲基戊腈)等偶氮化合物；過氧化苯甲醯基、過氧化月桂醯基、過氧三甲基乙酸三級丁酯、過氧乙基己酸三級丁酯、1,1'-雙(三級丁基過氧)環己烷、過氧-2-乙基己酸三級戊酯、過氧-2-乙基己酸三級己酯等有機過氧化物及過氧化氫等。 The catalyst system used in the production of the aforementioned precursor (2) may, for example, be 2,2'-azobisisobutyronitrile or 2,2'-azobis-(2,4-dimethylvaleronitrile). , 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds; benzammonium peroxide, lauryl peroxide, peroxytrimethyl Tertiary butyl acetate, tert-butyl peroxyethylhexanoate, 1,1'-bis(tri-butylperoxy)cyclohexane, peroxy-penta-ethylhexanoate, and An organic peroxide such as oxy-2-ethylhexanoic acid hexahexyl ester or hydrogen peroxide.

在使用過氧化物作為觸媒的情況下，亦可將過氧化物與還原劑一起使用而作成氧化還原型起始劑。 In the case where a peroxide is used as a catalyst, a peroxide may be used together with a reducing agent to form a redox type initiator.

就如此進行所得到的前驅物(2)的重量平均分子量而言，從能易於將接下來進行的與化合物(b2)、(b3)的反應所得到的分枝狀丙烯酸丙烯酸酯樹脂(A)的分子量調製至6,000~70,000的範圍之點來看，較佳為2,000~14,000的範圍。 The branched acrylic acrylate resin (A) obtained by reacting the compound (b2) and (b3) which can be easily carried out in the weight average molecular weight of the obtained precursor (2) The molecular weight is adjusted to a range of 6,000 to 70,000, preferably in the range of 2,000 to 14,000.

接著，使於1分子中具有(甲基)丙烯醯基與羧基的化合物(b2)以及於1分子中具有2個以上的羧基的化合物(b3)與此前驅物(2)反應。該反應方法係可列舉例如：以溶液聚合法將前驅物(2)聚合，在該反應系統中加入化合物(b2)、(b3)，於60~150℃的溫度範圍下，適當使用三苯膦等觸媒等之方法。所得到的分枝狀丙烯酸丙烯酸酯樹脂(A)的(甲基)丙烯醯基當量較佳為200~700g/eq的範圍，但其係能夠藉由前述前驅物(2)、於1分子中具有(甲基)丙烯醯基與羧基的化合物(b2)與於1分子 中具有2個以上的羧基的化合物(b3)之使用比例來調節。通常較佳為以於1分子中具有(甲基)丙烯醯基與羧基的化合物(b2)中的羧基以及於1分子中具有2個以上的羧基的化合物(b3)中的羧基之合計莫耳數相對於前述前驅物(2)具有的環氧丙基1莫耳成為0.9~1.2莫耳的方式來使用，特佳為在0.95~1.1莫耳的範圍內使用。 Next, the compound (b2) having a (meth)acryloyl group and a carboxyl group in one molecule and the compound (b3) having two or more carboxyl groups in one molecule are allowed to react with the precursor (2). The reaction method may, for example, polymerize the precursor (2) by a solution polymerization method, and add the compounds (b2) and (b3) to the reaction system, and suitably use triphenylphosphine at a temperature of 60 to 150 ° C. Such as catalysts and other methods. The (meth)acryl oxime equivalent of the branched acrylic acrylate resin (A) is preferably in the range of 200 to 700 g/eq, but it can be used in one molecule by the aforementioned precursor (2). a compound having a (meth)acryl fluorenyl group and a carboxyl group (b2) and one molecule The ratio of use of the compound (b3) having two or more carboxyl groups is adjusted. It is generally preferred to use a total of carboxyl groups in the compound (b2) having a (meth)acryloyl group and a carboxyl group in one molecule and a carboxyl group in a compound (b3) having two or more carboxyl groups in one molecule. The number is used in such a manner that the epoxypropyl group 1 mol of the precursor (2) is 0.9 to 1.2 mol, and particularly preferably used in the range of 0.95 to 1.1 mol.

又，在前述反應中，前述化合物(b2)與(b3)的使用比例係鑑於所得到的分枝狀丙烯酸丙烯酸酯樹脂(A)的分枝度、重量平均分子量，就(b3)/(b2)(莫耳比)而言，以在0.3/99.7~30/70的比例下使用為佳，尤其是以在1/99~20/80的比例下使用為佳，還有以在5/95~12/88的比例下使用為更佳。 Further, in the above reaction, the ratio of use of the above compounds (b2) and (b3) is (b3)/(b2) in view of the branching degree and weight average molecular weight of the obtained branched acrylic acrylate resin (A). (Morby), it is better to use at a ratio of 0.3/99.7~30/70, especially at a ratio of 1/99~20/80, and at 5/95. It is better to use at a ratio of ~12/88.

此處所使用之於1分子中具有(甲基)丙烯醯基與羧基的化合物(b2)係可列舉例如：(甲基)丙烯酸、(丙烯醯氧基)醋酸、丙烯酸-2-羧基乙酯、丙烯酸-3-羧基丙酯、琥珀酸-1-[2-(丙烯醯氧基)乙酯]、酞酸-1-(2-丙烯醯氧乙酯)、六氫酞酸氫-2-(丙烯醯氧基)乙酯及此等的內酯改質物等不飽和單羧酸；順丁烯二酸等不飽和二羧酸；使琥珀酸酐或順丁烯二酐等酸酐與新戊四醇三丙烯酸酯等含羥基的多官能(甲基)丙烯酸酯單體反應所得到之含羧基的多官能(甲基)丙烯酸酯等。此等係可單獨使用，亦可併用2種以上。在此等之中，就易於將所得到的分枝狀丙烯酸丙烯酸酯樹脂(A)的(甲基)丙烯醯基當量調節至前述較佳的範圍的點來看，較佳為(甲基)丙烯酸、(丙烯醯氧基)醋酸、丙烯酸-2-羧基乙酯、丙烯酸-3-羧基 丙酯，特佳為(甲基)丙烯酸。 The compound (b2) having a (meth)acryl fluorenyl group and a carboxyl group in one molecule used herein may, for example, be (meth)acrylic acid, (acryloxycarbonyl)acetic acid or 2-carboxyethyl acrylate. 3-carboxypropyl acrylate, 1-[2-(acryloxy)ethyl succinate], 1-(2-propenyloxyethyl) phthalate, hydrogen-2- hexahydrophthalate An unsaturated monocarboxylic acid such as acryloxy)ethyl ester and such a lactone modified product; an unsaturated dicarboxylic acid such as maleic acid; an acid anhydride such as succinic anhydride or maleic anhydride; and neopentyl alcohol A carboxyl group-containing polyfunctional (meth) acrylate obtained by reacting a hydroxyl group-containing polyfunctional (meth) acrylate monomer such as a triacrylate. These may be used singly or in combination of two or more. Among these, it is preferable that the (meth)acryl oxime equivalent of the obtained branched acrylic acrylate resin (A) is adjusted to the above preferred range, and it is preferably (methyl). Acrylic acid, (acryloxy)acetic acid, 2-carboxyethyl acrylate, 3-carboxy carboxylate Propyl ester, particularly preferably (meth)acrylic acid.

又，就於1分子中具有2個以上的羧基的化合物(b3)而言，可列舉例如：草酸、丙二酸、順丁烯二酸、反丁烯二酸、中康酸、檸康酸、伊康酸、氯化順丁烯二酸、氯橋酸、琥珀酸、己二酸、壬二酸、癸二酸、戊二酸、2,4-二乙基戊二酸、1,10-癸二酸(decamethylene dicarboxylic acid)等碳數2~50的脂肪族二羧酸；酞酸、異酞酸、對酞酸、二氯酞酸、二氯異酞酸、四氯酞酸、四氯異酞酸、四氯對酞酸等芳香族二羧酸；四氫酞酸、六氫酞酸、甲基六氫酞酸、六氫異酞酸、六氫對酞酸等脂環式二羧酸、二聚酸等。 In addition, examples of the compound (b3) having two or more carboxyl groups in one molecule include oxalic acid, malonic acid, maleic acid, fumaric acid, mesaconic acid, and citraconic acid. , itaconic acid, chlorinated maleic acid, chlorhexidine acid, succinic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, 2,4-diethylglutaric acid, 1,10 - an aliphatic dicarboxylic acid having 2 to 50 carbon atoms such as decamethylene dicarboxylic acid; citric acid, isophthalic acid, p-nonanoic acid, dichlorodecanoic acid, dichloroisodecanoic acid, tetrachlorodecanoic acid, and tetra An aromatic dicarboxylic acid such as chloroisophthalic acid or tetrachloro-p-citric acid; an alicyclic two such as tetrahydrofurfuric acid, hexahydrofurfuric acid, methyl hexahydrophthalic acid, hexahydroisodecanoic acid or hexahydropyridinic acid Carboxylic acid, dimer acid, and the like.

再者，能夠使用由1莫耳的二醇與2莫耳的酸酐的加成反應所得到的二羧酸的半酯體。就這樣的二醇而言，可列舉例如：乙二醇、二乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,6-己二醇、戊二醇、二甲基丁二醇、氫化雙酚A、雙酚A、新戊二醇、1,8-辛二醇、1,4-環己二醇、1,4-環己烷二甲醇、2-甲基-1,3-丙二醇等。就半酯體所使用的酸酐而言，可列舉例如：琥珀酸、戊二酸、2,4-二乙基戊二酸、酞酸、順丁烯二酸、二氯酞酸、四氯酞酸、四氫酞酸、六氫酞酸、甲基六氫酞酸等之二羧酸的酸酐。除此之外，只要是具有具聚酯結構、聚丁二烯結構的末端二羧酸等二羧酸結構者，亦可以使用任何化合物。 Further, a half ester of a dicarboxylic acid obtained by an addition reaction of a 1 molar diol and a 2 mole anhydride can be used. Examples of such a diol include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, and 1,4-butanediol. , 3-butanediol, 1,6-hexanediol, pentanediol, dimethylbutanediol, hydrogenated bisphenol A, bisphenol A, neopentyl glycol, 1,8-octanediol, 1, 4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-methyl-1,3-propanediol, and the like. Examples of the acid anhydride used in the half ester body include succinic acid, glutaric acid, 2,4-diethylglutaric acid, citric acid, maleic acid, dichlorodecanoic acid, and tetrachloroguanidine. An acid anhydride of a dicarboxylic acid such as an acid, tetrahydrofurfuric acid, hexahydrophthalic acid or methylhexahydrophthalic acid. Other than this, any compound may be used as long as it has a dicarboxylic acid structure such as a terminal dicarboxylic acid having a polyester structure or a polybutadiene structure.

就三羧酸化合物而言，可列舉例如：丙烷-1,2,3-三羧酸、丙烯-1,2,3-三羧酸、丁烷-1,2,3-三羧酸、 戊烷-1,2,3-三羧酸、己烷-1,2,3-三羧酸等碳數2~50的脂肪族三羧酸；1,3,5-苯三羧酸、1,2,4-苯三羧酸、1,3,5-苯三醋酸等芳香族三羧酸；1,3,5-環己烷三羧酸、1,2,4-環己烷三羧酸等脂環式三羧酸等。 Examples of the tricarboxylic acid compound include propane-1,2,3-tricarboxylic acid, propylene-1,2,3-tricarboxylic acid, and butane-1,2,3-tricarboxylic acid. An aliphatic tricarboxylic acid having 2 to 50 carbon atoms such as pentane-1,2,3-tricarboxylic acid or hexane-1,2,3-tricarboxylic acid; 1,3,5-benzenetricarboxylic acid, 1 , an aromatic tricarboxylic acid such as 2,4-benzenetricarboxylic acid or 1,3,5-benzenetriacetic acid; 1,3,5-cyclohexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid An alicyclic tricarboxylic acid or the like such as an acid.

又，能夠使用藉由1莫耳的三醇與3莫耳的酸酐的加成反應所得到的三羧酸的半酯體來代替這些三羧酸。就這樣的三醇而言，可列舉例如：甘油、1,2,4-丁三醇、1,2,5-戊三醇、1,2,6-己三醇、1,2,7-庚三醇、1,2,8-辛三醇、1,2,9-壬三醇、1,2,10-癸三醇、1,3,5-環己三醇、1,2,4-環己三醇、1,3,5-苯三醇、1,2,4-苯三醇、2,6-雙(羥基甲基)-4-甲酚、三羥甲丙烷、三羥甲乙烷等。就半酯體所使用的酸酐而言，可列舉例如：琥珀酸、戊二酸、酞酸、順丁烯二酸、二氯酞酸、四氯酞酸、四氫酞酸、六氫酞酸甲基六氫酞酸等的酸酐。 Further, instead of these tricarboxylic acids, a half ester of a tricarboxylic acid obtained by an addition reaction of a 1 mol of a triol and a 3 mol of an acid anhydride can be used. Examples of such a triol include glycerin, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, 1,2,7- Glycerol, 1,2,8-octanetriol, 1,2,9-nonanetriol, 1,2,10-triol, 1,3,5-cyclohexanetriol, 1,2,4 -cyclohexanetriol, 1,3,5-benzenetriol, 1,2,4-benzenetriol, 2,6-bis(hydroxymethyl)-4-cresol, trimethylolpropane, trishydroxyl Ethane and the like. Examples of the acid anhydride used in the half ester body include succinic acid, glutaric acid, decanoic acid, maleic acid, dichlorodecanoic acid, tetrachlorodecanoic acid, tetrahydrofurfuric acid, and hexahydroabietic acid. An acid anhydride such as methyl hexahydrophthalic acid.

就四羧酸化合物而言，可列舉例如：1,2,3,4-丁烷四羧酸等碳數2~50的脂肪族四羧酸；苯四羧酸等芳香族四羧酸；環己烷四羧酸等脂環式四羧酸等。 The tetracarboxylic acid compound may, for example, be an aliphatic tetracarboxylic acid having 2 to 50 carbon atoms such as 1,2,3,4-butanetetracarboxylic acid or an aromatic tetracarboxylic acid such as benzenetetracarboxylic acid; An alicyclic tetracarboxylic acid or the like such as hexanetetracarboxylic acid.

又，能夠使用藉由1莫耳的四醇與4莫耳的酸酐的加成反應所得到的四羧酸的半酯體來代替這些四羧酸。就這樣的四醇而言，可列舉例如：新戊四醇等。就半酯體所使用的酸酐而言，可列舉例如：琥珀酸、戊二酸、酞酸、順丁烯二酸、二氯酞酸、四氯酞酸、四氫酞酸、六氫酞酸、甲基六氫酞酸等的酸酐。除此之外，只要是具有四羧酸結構者，亦可以使用任何化合物。此等的四羧酸型化合物的原料係可單獨使用1種，或是亦可摻 合2種以上來使用。在前述的四羧酸之中，較佳可列舉新戊四醇與甲基六氫酞酸酐等。再者，就具有5官能基以上的官能基的化合物而言，可列舉例如：二-三羥甲丙烷之與二羧酸的半酯(5官能)、二新戊四醇之與二羧酸的半酯(6官能)，還有5官能以上的多元醇之與二羧酸的半酯(多官能)等。 Further, instead of these tetracarboxylic acids, a half ester of a tetracarboxylic acid obtained by an addition reaction of 1 mole of tetraol and 4 moles of an acid anhydride can be used. Examples of such a tetraol include pentaerythritol and the like. Examples of the acid anhydride used in the half ester body include succinic acid, glutaric acid, decanoic acid, maleic acid, dichlorodecanoic acid, tetrachlorodecanoic acid, tetrahydrofurfuric acid, and hexahydroabietic acid. An acid anhydride such as methyl hexahydrophthalic acid. Besides, any compound can be used as long as it has a tetracarboxylic acid structure. The raw materials of the tetracarboxylic acid type compounds may be used alone or in combination. Use in combination of two or more. Among the above tetracarboxylic acids, preferred are neopentyltetraol and methylhexahydrophthalic anhydride. Further, examples of the compound having a functional group having a functional group of 5 or more include, for example, a half ester of di-trimethylolpropane with a dicarboxylic acid (5-functional), dipentaerythritol and a dicarboxylic acid. The half ester (hexafunctional), and a half ester (polyfunctional) of a difunctional or higher polyhydric alcohol with a dicarboxylic acid.

還有，在此反應中，能夠使用三苯膦等反應觸媒，其使用比例係以使用相對於丙烯酸聚合物(a1)的100質量份而言為0.1~5.0質量份左右為佳。 In addition, in the reaction, a reaction catalyst such as triphenylphosphine can be used, and the use ratio is preferably from 0.1 to 5.0 parts by mass based on 100 parts by mass of the acrylic polymer (a1).

又，在此反應中，亦可直接使用前述前驅物(2)的合成時使用的有機溶媒，在溶媒中進行反應，例如藉由在80~130℃的溫度下反應1~20小時而能輕易得到。再者，亦可併用用於抑制(甲基)丙烯醯基的聚合之聚合抑制劑。 Further, in this reaction, the organic solvent used in the synthesis of the precursor (2) may be used as it is, and the reaction may be carried out in a solvent, for example, by reacting at a temperature of 80 to 130 ° C for 1 to 20 hours. get. Further, a polymerization inhibitor for suppressing polymerization of a (meth) acrylonitrile group may also be used in combination.

在前述的分枝狀丙烯酸丙烯酸酯樹脂(A)的製造方法之中，從合成更簡便的點來看，係以使用前述前驅物(1)的方法為佳，尤其是以使用(甲基)丙烯酸環氧丙酯，使其與(甲基)丙烯酸酯共聚合而得到前驅物(1)，使(甲基)丙烯酸與該前驅物(1)反應而得到丙烯酸聚合物(a)，使其與六亞甲異氰酸酯的縮二脲體反應所得到之分枝狀丙烯酸丙烯酸酯樹脂為特佳。 Among the above-described methods for producing the branched acrylic acrylate resin (A), it is preferred to use the above-mentioned precursor (1) from the viewpoint of more convenient synthesis, especially in the use of (methyl). Glycidyl acrylate is copolymerized with (meth) acrylate to obtain a precursor (1), and (meth)acrylic acid is reacted with the precursor (1) to obtain an acrylic polymer (a). A branched acrylic acrylate resin obtained by reacting with a biuret of hexamethylene isocyanate is particularly preferred.

又，在本發明中，從容易調製作為塗料的黏度、硬化性良好之觀點、以及所得到的塗膜的表面硬度變高之觀點來看，亦可併用前述分枝狀丙烯酸丙烯酸酯樹脂(A)以外的(甲基)丙烯酸酯(C)。 Moreover, in the present invention, the branched acrylic acrylate resin (A) may be used in combination from the viewpoint of easy preparation of a viscosity and a hardenability of a coating material, and a surface hardness of the obtained coating film. (Meth) acrylate (C) other than ).

就能夠在本案中使用的(甲基)丙烯酸酯而言，並沒有特殊的限定，可列舉例如：各種(甲基)丙烯酸酯單體、或胺基甲酸酯(甲基)丙烯酸酯等。 The (meth) acrylate which can be used in the present invention is not particularly limited, and examples thereof include various (meth) acrylate monomers or urethane (meth) acrylates.

前述(甲基)丙烯酸酯單體係可列舉例如：(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-2-羥基丁酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸環氧丙酯、丙烯醯基啉、N-乙烯吡咯啶酮、丙烯酸四氫糠酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十三烷酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸-2-乙氧基乙酯、(甲基)丙烯酸-3-甲氧基丁酯、乙基卡必醇(甲基)丙烯酸酯、磷酸(甲基)丙烯酸酯、經環氧乙烷(ethylene oxide)改質之磷酸(甲基)丙烯酸酯、(甲基)丙烯酸苯氧酯、經環氧乙烷改質之(甲基)丙烯酸苯氧酯、經環氧丙烷(propylene oxide)改質之(甲基)丙烯酸苯氧酯、壬基苯酚(甲基)丙烯酸酯、經環氧乙烷改質之壬基苯酚(甲基)丙烯酸酯、經環氧丙烷改質之壬基苯酚(甲基)丙烯酸酯、甲氧基二乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基丙二醇(甲基)丙烯酸酯、酞酸-2-(甲基)丙烯醯氧基乙基-2-羥基丙酯、(甲基)丙烯酸-2-羥基-3-苯氧基丙酯、酞酸氫-2-(甲基)丙烯醯氧基乙酯、酞酸氫-2-(甲基)丙烯醯氧基丙酯、六氫酞酸氫-2-(甲基)丙烯醯氧基丙酯、四氫酞酸氫-2-(甲基)丙烯醯氧基 丙酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸四氟丙酯、(甲基)丙烯酸六氟丙酯、(甲基)丙烯酸八氟丙酯、(甲基)丙烯酸八氟丙酯、單(甲基)丙烯酸金剛烷酯等單(甲基)丙烯酸酯；丁二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、乙氧基化己二醇二(甲基)丙烯酸酯、丙氧基化己二醇二(甲基)丙烯酸酯、二乙二醇二(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、新戊二醇二(甲基)丙烯酸酯、乙氧基化新戊二醇二(甲基)丙烯酸酯、羥三甲基乙酸新戊二醇二(甲基)丙烯酸酯等二(甲基)丙烯酸酯；三羥甲丙烷三(甲基)丙烯酸酯、乙氧基化三羥甲丙烷三(甲基)丙烯酸酯、丙氧基化三羥甲丙烷三(甲基)丙烯酸酯、參2-羥乙基異三聚氰酸酯三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯等三(甲基)丙烯酸酯；新戊四醇三(甲基)丙烯酸酯、二新戊四醇三(甲基)丙烯酸酯、二-三羥甲丙烷三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二-三羥甲丙烷四(甲基)丙烯酸酯、二新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二-三羥甲丙烷五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、二-三羥甲丙烷六(甲基)丙烯酸酯等4官能以上的(甲基)丙烯酸酯；及將上述之各種多官能(甲基)丙烯酸酯的一部分以烷基取代而成之(甲基)丙烯酸酯等。 Examples of the (meth) acrylate single system include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. N-butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, glycidyl (meth)acrylate, propylene fluorenyl Porphyrin, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, (methyl) Isodecyl acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, 2-Ethyl ethyl methacrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth) acrylate, phosphoric acid (meth) acrylate, epoxy Ethylene oxide modified phosphoric acid (meth) acrylate, (meth) acrylate phenoxylate, ethylene oxide modified phenoxy methacrylate, propylene oxide Modified phenoxy (meth) acrylate, nonyl phenol (meth) acrylate, ethylene oxide modified nonyl phenol (meth) acrylate, propylene oxide modified sulfhydryl Phenol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy propylene glycol (meth) acrylate, citric acid - 2-(methyl)propenyloxy 2-hydroxypropyl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(methyl)propenyloxyethyl phthalate, hydrogen-2-carboxylate Methyl) propylene methoxy propyl ester, hydrogen hexahydrophthalate-2-(methyl) propylene methoxy propyl ester, hydrogen tetrahydro phthalate-2-(methyl) propylene methoxy propyl ester, (A) Dimethylaminoethyl acrylate, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoropropyl (meth)acrylate, octafluoropropyl (meth)acrylate Mono(meth)acrylate such as octafluoropropyl (meth)acrylate or adamantyl mono(meth)acrylate; butanediol di(meth)acrylate, hexanediol di(meth)acrylate Ethoxylated hexanediol di(meth)acrylate, propoxylated hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(a) Acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, hydroxytrimethylacetate Di(meth) acrylate such as diol di(meth) acrylate; trimethylolpropane tri(methyl) propylene Ester, ethoxylated trimethylolpropane tri(meth) acrylate, propoxylated trimethylolpropane tri(meth) acrylate, ginsyl 2-hydroxyethyl isocyanurate tris(methyl) Tris(meth)acrylate such as acrylate or tris(meth)acrylate; pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, di-trishydroxyl Methylpropane tri (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, two Pentaerythritol penta (meth) acrylate, di-trimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di-trimethylolpropane hexa(methyl) A tetrafunctional or higher (meth) acrylate such as an acrylate; and a (meth) acrylate obtained by substituting a part of the above various polyfunctional (meth) acrylates with an alkyl group.

前述胺基甲酸酯(甲基)丙烯酸酯舉例來說， 可列舉例如：使聚異氰酸酯化合物與含羥基的(甲基)丙烯酸酯化合物反應而得到之胺基甲酸酯(甲基)丙烯酸酯。 The aforementioned urethane (meth) acrylate, for example, For example, a urethane (meth) acrylate obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate compound can be mentioned.

前述胺基甲酸酯(甲基)丙烯酸酯的原料中使用之前述聚異氰酸酯化合物係可列舉：各種二異氰酸酯單體、或於分子內具有異三聚氰酸酯環結構的三聚氰酸酯型聚異氰酸酯化合物等。 The polyisocyanate compound used in the raw material of the urethane (meth) acrylate may be exemplified by various diisocyanate monomers or cyanurates having an isomeric cyanate ring structure in the molecule. Type polyisocyanate compound or the like.

前述二異氰酸酯單體係可列舉例如：丁烷 -1,4-二異氰酸酯、六亞甲二異氰酸酯、2,2,4-三甲基六亞甲二異氰酸酯、2,4,4-三甲基六亞甲二異氰酸酯、苯二甲基二異氰酸酯、間四甲基苯二甲基二異氰酸酯等脂肪族二異氰酸酯；環己烷-1,4-二異氰酸酯、異佛酮二異氰酸酯、離胺酸二異氰酸酯、二環己基甲烷-4,4'-二異氰酸酯、1,3-雙(異氰酸酯甲基)環己烷、甲基環己烷二異氰酸酯等脂環式二異氰酸酯；二異氰酸-1,5-伸萘酯、4,4'-二苯基甲烷二異氰酸酯、4,4'-二苯基二甲基甲烷二異氰酸酯、二異氰酸-4,4'-二苄酯、二烷基二苯基甲烷二異氰酸酯、四烷基二苯基甲烷二異氰酸酯、二異氰酸-1,3-伸苯酯、二異氰酸-1,4-伸苯酯、甲苯二異氰酸酯(tolylene diisocyanate)等芳香族二異氰酸酯等。 The aforementioned diisocyanate single system may, for example, be butane -1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, benzodimethyl diisocyanate , an aliphatic diisocyanate such as m-tetramethyl dimethyl diisocyanate; cyclohexane-1,4-diisocyanate, isophorone diisocyanate, leucine diisocyanate, dicyclohexylmethane-4, 4'- An alicyclic diisocyanate such as diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane or methylcyclohexane diisocyanate; diisocyanate-1,5-naphthyl ester, 4,4'-di Phenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenyl An aromatic diisocyanate such as methane diisocyanate, diisocyanate-1,3-phenylene ester, diisocyanate-1,4-phenylene ester or tolylene diisocyanate.

前述於分子內具有異三聚氰酸酯環結構的三聚氰酸酯型聚異氰酸酯化合物係可列舉例如：使二異氰酸酯單體與單醇及/或二醇反應而得者。就該反應中使用的二異氰酸酯單體而言，可列舉前述各種二異氰酸酯單 體，可各自單獨使用，亦可併用二種以上。又，該反應中使用的單醇係可列舉己醇、辛醇、正癸醇、正十一醇、正十二醇、正十三醇、正十四醇、正十五醇、正十七醇、正十八醇、正十九醇等，二醇係可列舉乙二醇、二乙二醇、丙二醇、1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、3-甲基-1,3-丁二醇、1,5-戊二醇、新戊二醇、1,6-己二醇等。此等單醇或二醇係可各自單獨使用，亦可併用二種以上。 The polycyanate type polyisocyanate compound having a hetero-cyanate ring structure in the molecule may, for example, be obtained by reacting a diisocyanate monomer with a monool and/or a diol. As the diisocyanate monomer used in the reaction, various kinds of the above-mentioned diisocyanate may be mentioned. The bodies may be used singly or in combination of two or more. Further, the monool used in the reaction may, for example, be hexanol, octanol, n-decyl alcohol, n-undecyl alcohol, n-dodecyl alcohol, n-tridecyl alcohol, n-tetradecyl alcohol, n-pentadecanol or n. Alcohol, n-octadecanol, n-nonadecanol, etc., and the diol type may, for example, be ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, or 1,3-butanediol. , 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and the like. These monools or diols may be used alone or in combination of two or more.

在此等聚異氰酸酯化合物之中，就得到加工性更優良的硬化塗膜之點而言，較佳為前述二異氰酸酯單體，更佳為前述脂肪族二異氰酸酯及前述脂環式二異氰酸酯。 Among these polyisocyanate compounds, the diisocyanate monomer is more preferred as the hardened coating film having more excellent workability, and the aliphatic diisocyanate and the alicyclic diisocyanate are more preferred.

前述胺基甲酸酯(甲基)丙烯酸酯的原料中使用之前述含羥基的(甲基)丙烯酸酯化合物係可列舉例如：丙烯酸-2-羥基乙酯、丙烯酸-2-羥基丙酯、丙烯酸-4-羥基丁酯、甘油二丙烯酸酯、三羥甲丙烷二丙烯酸酯、新戊四醇三丙烯酸酯、二新戊四醇五丙烯酸酯等脂肪族(甲基)丙烯酸酯化合物；丙烯酸-4-羥基苯酯、丙烯酸-β-羥基苯乙酯、丙烯酸-4-羥基苯乙酯、丙烯酸-1-苯基-2-羥基乙酯、丙烯酸-3-羥基-4-乙醯基苯酯、丙烯酸-2-羥基-3-苯氧基丙酯等於分子結構中具有芳香環的(甲基)丙烯酸酯化合物等。此等係可各自單獨使用，亦可併用二種以上。 The hydroxyl group-containing (meth) acrylate compound used in the raw material of the urethane (meth) acrylate may, for example, be 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate or acrylic acid. Aliphatic (meth) acrylate compound such as 4-hydroxybutyl ester, glycerin diacrylate, trimethylolpropane diacrylate, neopentyl alcohol triacrylate, dipentaerythritol pentaacrylate; acrylic acid-4 -hydroxyphenyl ester, β-hydroxyphenylethyl acrylate, 4-hydroxyphenylethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, 3-hydroxy-4-ethenyl phenyl acrylate, 2-Hydroxy-3-phenoxypropyl acrylate is equivalent to a (meth) acrylate compound having an aromatic ring in a molecular structure. These may be used singly or in combination of two or more.

在此等羥基(甲基)丙烯酸酯化合物之中，就得到加工性優良且具有高表面硬度的硬化塗膜之點而言 ，較佳為甘油二丙烯酸酯、三羥甲丙烷二丙烯酸酯、新戊四醇三丙烯酸酯、二新戊四醇五丙烯酸酯等於分子結構中具有2個以上的(甲基)丙烯醯基之脂肪族(甲基)丙烯酸酯化合物。再者，就得到顯現更高表面硬度的硬化塗膜之點而言，更佳為新戊四醇三丙烯酸酯、二新戊四醇五丙烯酸酯等於分子結構中具有3個以上的(甲基)丙烯醯基之脂肪族(甲基)丙烯酸酯化合物。 Among these hydroxy (meth) acrylate compounds, in terms of obtaining a cured film having excellent workability and high surface hardness, Preferably, glycerin diacrylate, trimethylolpropane diacrylate, neopentyl alcohol triacrylate, and dipentaerythritol pentaacrylate are equal to two or more (meth) acrylonitrile groups in the molecular structure. Aliphatic (meth) acrylate compound. Further, in terms of obtaining a cured coating film exhibiting a higher surface hardness, it is more preferable that neopentyl alcohol triacrylate and dipentaerythritol pentaacrylate have three or more (methyl groups) in a molecular structure. An aliphatic (meth) acrylate compound of an acrylonitrile group.

製造前述胺基甲酸酯(甲基)丙烯酸酯的方法係可列舉例如：以前述聚異氰酸酯化合物具有的異氰酸酯基與前述含羥基的(甲基)丙烯酸酯化合物具有的羥基之莫耳比[(NCO)/(OH)]成為1/0.95~1/1.05的範圍之比例來使用前述聚異氰酸酯化合物與前述含羥基的(甲基)丙烯酸酯化合物，在20~120℃的溫度範圍內，視需要地使用各種胺基甲酸酯化觸媒來進行之方法等。 The method of producing the aforementioned urethane (meth) acrylate is, for example, a molar ratio of a hydroxyl group having an isocyanate group of the polyisocyanate compound to a hydroxyl group-containing (meth) acrylate compound [( NCO)/(OH)] is a ratio of 1/0.95 to 1/1.05, and the polyisocyanate compound and the hydroxyl group-containing (meth) acrylate compound are used in a temperature range of 20 to 120 ° C, as needed. A method of using various urethane-catalyzed catalysts, and the like.

由前述聚異氰酸酯化合物與於前述分子結構中具有一個羥基的(甲基)丙烯酸酯化合物製造前述胺基甲酸酯(甲基)丙烯酸酯時，該反應亦可在包含新戊四醇四(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等丙烯酸酯化合物的系統中進行。具體而言，以這樣的方法所得到的胺基甲酸酯(甲基)丙烯酸酯係可列舉：使含有前述聚異氰酸酯化合物、新戊四醇三(甲基)丙烯酸酯與新戊四醇四(甲基)丙烯酸酯的原料反應而得到之胺基甲酸酯(甲基)丙烯酸酯；或使含有前述聚異氰酸酯化合物、二新戊四醇五(甲基)丙烯酸酯與二新戊四醇六(甲基)丙烯酸酯的原料反應而得到之胺基甲酸酯丙烯酸酯等。 When the above-mentioned urethane (meth) acrylate is produced from the above polyisocyanate compound and a (meth) acrylate compound having a hydroxyl group in the above molecular structure, the reaction may also be carried out in the presence of pentaerythritol IV (A) The system is carried out in a system of an acrylate compound such as acrylate or dipentaerythritol hexa(meth)acrylate. Specifically, the urethane (meth) acrylate obtained by such a method is exemplified by containing the above polyisocyanate compound, pentaerythritol tri(meth)acrylate, and pentaerythritol. a urethane (meth) acrylate obtained by reacting a raw material of (meth) acrylate; or containing the aforementioned polyisocyanate compound, dipentaerythritol penta (meth) acrylate and dipentaerythritol A urethane acrylate obtained by reacting a raw material of hexa(meth) acrylate or the like.

就與前述分枝狀丙烯酸丙烯酸酯樹脂(A)的相溶性優異的點而言，如此進行所得到之胺基甲酸酯(甲基)丙烯酸酯的重量平均分子量(Mw)較佳為800~20,000的範圍，更佳為900~1,000的範圍。 The weight average molecular weight (Mw) of the obtained urethane (meth) acrylate is preferably 800 to be obtained from the point that the compatibility with the branched acrylic acrylate resin (A) is excellent. The range of 20,000 is better than the range of 900 to 1,000.

此等化合物(C)係可各自單獨使用，亦可併用二種以上。其中，從得到更高硬度的塗膜來看，較佳為於1分子中具有3個以上的(甲基)丙烯醯基之多官能(甲基)丙烯酸酯。就前述具有3個以上的(甲基)丙烯醯基之多官能(甲基)丙烯酸酯而言，較佳為新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯。又，就作為具有3個以上的(甲基)丙烯醯基之多官能(甲基)丙烯酸酯之胺基甲酸酯(甲基)丙烯酸酯而言，較佳為使二異氰酸酯化合物、與甘油二丙烯酸酯、三羥甲丙烷二丙烯酸酯、新戊四醇三丙烯酸酯、二新戊四醇五丙烯酸酯等於分子結構中具有2個以上的(甲基)丙烯醯基之含羥基的(甲基)丙烯酸酯化合物反應所得到之胺基甲酸酯(甲基)丙烯酸酯，更佳為使二異氰酸酯化合物與具有3個以上的(甲基)丙烯醯基之含羥基的(甲基)丙烯酸酯化合物反應所得到之胺基甲酸酯(甲基)丙烯酸酯。 These compounds (C) may be used alone or in combination of two or more. Among them, from the viewpoint of obtaining a coating film having a higher hardness, a polyfunctional (meth) acrylate having three or more (meth) acrylonitrile groups in one molecule is preferred. In the above polyfunctional (meth) acrylate having three or more (meth) acrylonitrile groups, pentaerythritol tri(meth) acrylate, neopentyl alcohol tetra (methyl) is preferred. Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate. Further, as the urethane (meth) acrylate having a polyfunctional (meth) acrylate having three or more (meth) acrylonitrile groups, a diisocyanate compound and glycerin are preferred. Diacrylate, trimethylolpropane diacrylate, neopentyl alcohol triacrylate, and dipentaerythritol pentaacrylate are equivalent to hydroxyl groups having two or more (meth) acrylonitrile groups in the molecular structure (A) A urethane (meth) acrylate obtained by reacting an acrylate compound, more preferably a diisocyanate compound and a hydroxyl group-containing (meth)acrylic acid having 3 or more (meth) acrylonitrile groups The urethane compound (meth) acrylate obtained by the reaction of the ester compound.

又，就能夠在本發明中使用的(甲基)丙烯酸酯(C)而言，可為多分枝狀的(甲基)丙烯酸酯。就這樣的多分枝狀的(甲基)丙烯酸酯而言，係可使用以樹枝狀聚合物(dendrimer)、核-殼、高分歧(hyperbranch)等的名稱所提供者之任一者，例如可適當地使用任何在 WO08/047620號公報、日本特開2012-111963號公報、日本特表平10-508052號公報等中與其製造方法一起所提供者。又，就作為這樣的多分枝狀的(甲基)丙烯酸酯所市售者而言，可列舉大阪有機公司製的SIRIUS501等。 Further, the (meth) acrylate (C) which can be used in the present invention may be a multi-branched (meth) acrylate. In the case of such a multi-branched (meth) acrylate, any one of a name provided by a dendrimer, a core-shell, a hyperbranch, or the like can be used, for example, Use whatever is appropriate Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In addition, as a commercial product of such a multi-branched (meth) acrylate, SIRIUS 501 manufactured by Osaka Organic Co., Ltd., etc. are mentioned.

在本發明中，就前述分枝狀丙烯酸丙烯酸酯樹脂(A)與其他的(甲基)丙烯酸酯(C)之使用比例而言，並沒有特殊的限定，雖能夠依據目標之硬化塗膜的硬度及加工性、還有透明性或耐傷性等進行適當設定，但從易於得到表面硬度特別高且加工性亦良好的塗膜之觀點來看，就前述分枝狀丙烯酸丙烯酸酯樹脂(A)與(甲基)丙烯酸酯(C)的質量比(A)/(C)而言，較佳為10/90~100/0的範圍，特佳為30/70~90/10的範圍，更佳為60/40~80/20。 In the present invention, the ratio of use of the branched acrylic acrylate resin (A) to other (meth) acrylate (C) is not particularly limited, and the coating film can be cured according to the target. Though the hardness and the workability, and the transparency and the scratch resistance are appropriately set, the branched acrylic acrylate resin (A) is obtained from the viewpoint of easily obtaining a coating film having a particularly high surface hardness and good workability. The mass ratio (A)/(C) to the (meth) acrylate (C) is preferably in the range of 10/90 to 100/0, particularly preferably in the range of 30/70 to 90/10, and more preferably Good for 60/40~80/20.

在本發明中，為了進一步提高塗膜的表面硬度或是賦予其他性能、例如耐黏結(anti-blocking)性等之目的，可併用無機微粒子(D)。 In the present invention, inorganic fine particles (D) may be used in combination for the purpose of further improving the surface hardness of the coating film or imparting other properties such as anti-blocking properties and the like.

就前述無機微粒子(D)的摻合比例而言，因應目標之性能而能夠適當地設定，但從得到透明性高的硬化塗膜的點來看，以在相對於活性能量線硬化型樹脂組成物中的非揮發性物質100質量份而言為30~55質量份的範圍內含有無機微粒子(D)為佳。亦即，前述無機微粒子(D)的含量在30質量份以上的情況下，硬化時的硬度或耐刮傷性的改善效果會變顯著。又，於前述無機微粒子(D)的含量在55質量份以下的情況下，活性能量線硬化型樹脂組成物的保存安定性或透明性會變良好。其中，就樹脂組成物的保存安定性優異且能得到兼具高表面硬 度與透明性、耐捲曲性之硬化塗膜的點來看，以在相對於該組成物中的非揮發性物質100質量份而言為35~50質量份的範圍內含有無機微粒子(D)為更佳。 The blending ratio of the inorganic fine particles (D) can be appropriately set in accordance with the performance of the target, but from the viewpoint of obtaining a cured film having high transparency, it is composed of a resin which is hardened with respect to the active energy ray. It is preferable that the inorganic fine particles (D) are contained in the range of 30 to 55 parts by mass in 100 parts by mass of the nonvolatile matter in the product. In other words, when the content of the inorganic fine particles (D) is 30 parts by mass or more, the effect of improving the hardness or the scratch resistance at the time of curing becomes remarkable. In addition, when the content of the inorganic fine particles (D) is 55 parts by mass or less, the storage stability or transparency of the active energy ray-curable resin composition is improved. Among them, the resin composition is excellent in storage stability and can be obtained with high surface hardness. In the range of 35 to 50 parts by mass with respect to 100 parts by mass of the nonvolatile matter in the composition, the inorganic fine particles (D) are contained in the range of 35 to 50 parts by mass with respect to 100 parts by mass of the nonvolatile matter in the composition. For better.

前述無機微粒子(D)的平均粒徑係作為在分散於組成物中的狀態下以動態光散射法進行測定而得的值，從塗膜的表面硬度與透明性之平衡優良的點來看，以95~250nm的範圍為佳。亦即，於平均粒徑在95nm以上的情況下，所得到的塗膜的表面硬度變得更高；另一方面，在250nm以下的情況下，所得到的塗膜的透明性變良好。其中，就能夠以更高水準兼具所得到的塗膜的硬度與透明性之點來看，平均粒徑係以在100~130nm的範圍內為更佳。 The average particle diameter of the inorganic fine particles (D) is a value measured by a dynamic light scattering method in a state of being dispersed in a composition, and is excellent in that the balance between the surface hardness and the transparency of the coating film is excellent. It is preferably in the range of 95 to 250 nm. In other words, when the average particle diameter is 95 nm or more, the surface hardness of the obtained coating film becomes higher. On the other hand, when it is 250 nm or less, the transparency of the obtained coating film becomes good. Among them, the average particle diameter is preferably in the range of 100 to 130 nm from the viewpoint of the hardness and transparency of the obtained coating film at a higher level.

還有，本案發明中之前述無機微粒子(D)之以動態光散射法測得之平均粒徑是指依照「ISO 13321」進行測定並根據累積量法所算出者，具體而言，其為以MIBK稀釋活性能量線硬化型樹脂組成物，調整成濃度1.0%的MIBK溶液後，使用此MIBK溶液，以粒徑測定裝置(大塚電子股份有限公司製「ELSZ-2」)所測定的值。 Further, the average particle diameter of the inorganic fine particles (D) measured by the dynamic light scattering method in the present invention is measured according to "ISO 13321" and is calculated according to the cumulative amount method. Specifically, it is After MIBK was diluted with the active energy ray-curable resin composition, the MIBK solution was adjusted to a concentration of 1.0%, and the value measured by the particle size measuring device ("ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.) was used.

具體而言，此處所使用之無機微粒子(D)係可列舉二氧化矽、氧化鋁、氧化鋯、氧化鈦、鈦酸鋇、三氧化銻等無機微粒子。此等係可各自單獨使用，亦可併用二種以上。在此等無機微粒子(D)之中，就易於取得且操作簡便的點來看，較佳為二氧化矽微粒子，該二氧化矽微粒子係可列舉例如：濕式二氧化矽及乾式二氧化矽。前述濕式二氧化矽係可列舉例如：使矽酸鈉與礦酸 反應所得到之所謂沉降法二氧化矽或凝膠法二氧化矽。又，在使用該濕式二氧化矽的情況下，就易於將分散於最終所得到的樹脂組成物中之該無機微粒子的平均粒徑調節至前述較佳的數值之點來看，在其乾燥狀態下的平均粒徑係以95~250nm的範圍為佳。 Specifically, examples of the inorganic fine particles (D) used herein include inorganic fine particles such as cerium oxide, aluminum oxide, zirconium oxide, titanium oxide, barium titanate, and antimony trioxide. These may be used singly or in combination of two or more. Among the inorganic fine particles (D), preferred are cerium oxide fine particles, and examples of the cerium oxide fine particles include wet cerium oxide and dry cerium oxide. . The wet cerium oxide system may, for example, be a sodium citrate and a mineral acid. The so-called sedimentation method of cerium oxide or gelled cerium oxide obtained by the reaction. Further, in the case of using the wet cerium oxide, it is easy to adjust the average particle diameter of the inorganic fine particles dispersed in the finally obtained resin composition to the above-mentioned preferable value. The average particle diameter in the state is preferably in the range of 95 to 250 nm.

另一方面，乾式二氧化矽微粒子為例如藉由在氧或氫火焰中燃燒四氯化矽而得到者，從易於將最終所得到的樹脂組成物中的無機微粒子(D)的平均粒徑調節至前述95~250nm的範圍之點來看，較佳為在分散前的狀態下其平均一次粒徑為3~100nm、尤其是為5~50nm的範圍之乾式二氧化矽微粒子凝集而成的二次粒子。 On the other hand, the dry cerium oxide fine particles are obtained, for example, by burning ruthenium tetrachloride in an oxygen or hydrogen flame, and are easily adjusted from the average particle diameter of the inorganic fine particles (D) in the finally obtained resin composition. From the point of the range of 95 to 250 nm, it is preferred that the dry cerium oxide microparticles having an average primary particle diameter of 3 to 100 nm, particularly 5 to 50 nm, are agglomerated in a state before dispersion. Secondary particles.

在上述的二氧化矽微粒子之中，就得到表面硬度更高的硬化塗膜之點來看，較佳為乾式二氧化矽微粒子。 Among the above-mentioned cerium oxide fine particles, dry cerium oxide fine particles are preferred from the viewpoint of obtaining a cured coating film having a higher surface hardness.

在本發明中，前述無機微粒子(D)係能夠使用對上述各種無機微粒子使用矽烷偶合劑並於前述無機微粒子的表面導入反應性官能基而成者。藉由在無機微粒子(D)的表面導入反應性官能基，而使與前述分枝狀丙烯酸丙烯酸酯樹脂(A)、其他的(甲基)丙烯酸酯(C)等的有機成分之混合性提高，使分散安定性、保存安定性提升。 In the present invention, the inorganic fine particles (D) can be obtained by introducing a reactive functional group onto the surface of the inorganic fine particles by using a decane coupling agent for each of the above inorganic fine particles. By introducing a reactive functional group on the surface of the inorganic fine particles (D), the mixing property with the organic components such as the branched acrylic acrylate resin (A) and other (meth) acrylate (C) is improved. To improve dispersion stability and preservation stability.

此處所使用之矽烷偶合劑係可列舉例如：乙烯基三氯矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-環氧丙氧丙基三甲氧基矽烷、3-環氧丙氧丙基甲基二乙氧基矽 烷、3-環氧丙氧丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧丙基三甲氧基矽烷、3-甲基丙烯醯氧丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧丙基三乙氧基矽烷、3-丙烯醯氧丙基三甲氧基矽烷、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)丙基胺、N-苯基-3-胺基丙基三甲氧基矽烷、N-(乙烯基苄基)-2-胺基乙基-3-胺基丙基三甲氧基矽烷的鹽酸鹽、特殊胺基矽烷、3-脲丙基三乙氧基矽烷、3-氯丙基三甲氧基矽烷、3-巰丙基甲基二甲氧基矽烷、3-巰丙基三甲氧基矽烷、雙(三乙氧基矽烷基丙基)四硫化物、3-異氰酸酯丙基三乙氧基矽烷、烯丙基三氯矽烷、烯丙基三乙氧基矽烷、烯丙基三甲氧基矽烷、二乙氧基甲基乙烯基矽烷、三氯乙烯基矽烷、乙烯基三氯矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷等、乙烯基系的矽烷偶合劑；二乙氧基(環氧丙氧基丙基)甲基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-環氧丙氧丙基三甲氧基矽烷、3-環氧丙氧丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷等、環氧系的矽烷偶合劑；對苯乙烯基三甲氧基矽烷等、苯乙烯系的矽烷偶合劑； 3-甲基丙烯醯氧丙基甲基二甲氧基矽烷、3-丙烯醯氧丙基三甲氧基矽烷、3-甲基丙烯醯氧丙基三甲氧基矽烷、3-甲基丙烯醯氧丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧丙基三乙氧基矽烷等、(甲基)丙烯醯氧基系的矽烷偶合劑；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)丙基胺、N-苯基-3-胺基丙基三甲氧基矽烷等、胺基系的矽烷偶合劑；3-脲丙基三乙氧基矽烷等、脲基系的矽烷偶合劑；3-氯丙基三甲氧基矽烷等、氯丙基系的矽烷偶合劑；3-巰丙基甲基二甲氧基矽烷、3-巰丙基三甲氧基矽烷等、巰基系的矽烷偶合劑；雙(三乙氧基矽烷基丙基)四硫化物等、硫化物系的矽烷偶合劑；3-異氰酸酯丙基三乙氧基矽烷等、異氰酸酯系的矽烷偶合劑。此等矽烷偶合劑係可各自單獨使用，亦可併用2種以上。在此等之中，就與有機成分的混合性優異並能夠得到表面硬度高且透明性亦優異之硬化塗膜之點來看，較佳為(甲基)丙烯醯氧基系的矽烷偶合劑，更佳為3-丙烯醯氧丙基三甲氧基矽烷、3-甲基丙烯醯氧 丙基三甲氧基矽烷。 The decane coupling agent used herein may, for example, be vinyl trichloromethane, vinyl trimethoxy decane, vinyl triethoxy decane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxy. Decane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxyhydrazine Alkane, 3-glycidoxypropyltriethoxydecane, p-styryltrimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropane Trimethoxy decane, 3-methyl propylene methoxypropyl methyl diethoxy decane, 3-methyl propylene oxypropyl triethoxy decane, 3- propylene oxypropyl trimethoxy decane, N-2-(Aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2 -(Aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxydecane -N-(1,3-dimethyl.butylene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane, N-(vinylbenzyl)-2-aminoethyl Hydrochloride of 3-aminopropyltrimethoxydecane, special aminodecane, 3-ureidopropyltriethoxydecane, 3-chloropropyltrimethoxydecane, 3-mercaptomethylmethyl Dimethoxydecane, 3-mercaptopropyltrimethoxydecane, bis(triethoxydecylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxydecane, alkene Trichloromethane, allyl triethoxy decane, allyl trimethoxy decane, diethoxymethyl vinyl decane, trichlorovinyl decane, vinyl trichloro decane, vinyl trimethoxy decane , vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, etc., vinyl decane coupling agent; diethoxy (glycidoxypropyl) methyl decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3- An epoxy-based decane coupling agent such as glycidoxypropyltriethoxysilane; a styrene-based decane coupling agent such as p-styryltrimethoxydecane; 3-Methyl propylene methoxypropyl methyl dimethoxy decane, 3-propenyl methoxypropyl trimethoxy decane, 3-methyl propylene oxypropyl trimethoxy decane, 3-methyl propylene oxime a (meth)acryloxyl-type decane coupling agent such as propylmethyldiethoxydecane, 3-methacryloxypropyltriethoxydecane, or the like; N-2 (aminoethyl)3 -Aminopropylmethyldimethoxydecane, N-2(aminoethyl)3-aminopropyltrimethoxydecane, N-2(aminoethyl)3-aminopropyltriethyl Oxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxydecyl-N-(1,3-dimethyl-butylene) a propylamine, N-phenyl-3-aminopropyltrimethoxydecane, an amine-based decane coupling agent, a 3-ureidotriethoxysilane, or the like, a urea-based decane coupling agent; a chloropropyl decane coupling agent such as chloropropyltrimethoxydecane; a fluorenyl decane coupling agent such as 3-mercaptopropylmethyldimethoxydecane or 3-mercaptopropyltrimethoxydecane; Sulfide-based decane coupling agent such as bis(triethoxydecylpropyl)tetrasulfide; 3-isocyanate Triethoxy etc. Silane, silane-based coupling agent is an isocyanate. These decane coupling agents may be used alone or in combination of two or more. Among these, a (meth)acryloxy-based decane coupling agent is preferred because it has excellent miscibility with an organic component and can obtain a cured coating film having high surface hardness and excellent transparency. More preferably 3-propenyloxypropyltrimethoxydecane, 3-methylpropene oxime Propyltrimethoxydecane.

本發明之樹脂組成物亦可視需要地含有分散助劑。該分散助劑係可列舉例如：酸式磷酸異丙酯、亞磷酸三異癸酯、經環氧乙烷改質之磷酸二甲基丙烯酸酯等磷酸酯化合物等。此等係可各自單獨使用，亦可併用二種以上。在此等之中，就分散補助性能優異之點來看，較佳為經環氧乙烷改質之磷酸二甲基丙烯酸酯。 The resin composition of the present invention may optionally contain a dispersing aid. Examples of the dispersing aid include phosphate ester compounds such as acid isopropyl phosphate, triisodecyl phosphite, and ethylene oxide-modified phosphoric acid dimethacrylate. These may be used singly or in combination of two or more. Among these, in view of excellent dispersibility and subsidence performance, phosphoric acid dimethacrylate modified with ethylene oxide is preferred.

前述分散助劑的市售品係可列舉例如：日本化藥股份有限公司製「KAYAMER PM-21」、「KAYAMER PM-2」、共榮社化學股份有限公司製「Light Ester P-2M」等。 For example, "KAYAMER PM-21" manufactured by Nippon Kayaku Co., Ltd., "KAYAMER PM-2", and "Light Ester P-2M" manufactured by Kyoeisha Chemical Co., Ltd., etc., may be mentioned. .

在使用前述分散助劑的情況下，就成為保存安定性更高的樹脂組成物之點來看，係以在本發明之樹脂組成物100質量份中含有0.5~5.0質量份的範圍為佳。 In the case of using the above-mentioned dispersing aid, it is preferable that the resin composition of the present invention contains 0.5 to 5.0 parts by mass in 100 parts by mass of the resin composition of the present invention.

又，本發明之樹脂組成物亦可含有有機溶劑。該有機溶劑係例如在以溶液聚合法製造前述分枝狀丙烯酸丙烯酸酯樹脂(A)的情況下，可直接含有此時使用的溶劑，亦可進一步以追加的方式添加其他的溶劑。或是亦可一次將前述分枝狀丙烯酸丙烯酸酯樹脂(A)製造時使用的有機溶劑除去後，再使用其他的溶劑。使用的溶劑的具體例係可列舉：丙酮、甲基乙基酮、甲基異丁基酮等酮溶劑；四氫呋喃、二氧戊環(dioxolane)等環狀醚溶劑；醋酸甲酯、醋酸乙酯、醋酸丁酯等酯；甲苯、二甲苯等芳香族溶劑；卡必醇、賽路蘇、甲醇、異丙醇、丁醇、丙二醇單甲基醚等醇溶劑；乙二醇單乙基醚、乙 二醇單丁基醚、丙二醇單甲基醚、丙二醇單丙基醚等二醇醚系溶劑。此等係可各自單獨使用，亦可併用2種以上。在此等之中，就成為保存安定性優異且作為塗料使用時的塗布性優異的樹脂組成物之點來看，較佳為酮溶劑，更佳為甲基異丁基酮。 Further, the resin composition of the present invention may contain an organic solvent. In the case of producing the branched acrylic acrylate resin (A) by a solution polymerization method, for example, the organic solvent may directly contain the solvent used at this time, and may further add another solvent in an additional manner. Alternatively, the organic solvent used in the production of the branched acrylic acrylate resin (A) may be removed at a time, and then another solvent may be used. Specific examples of the solvent to be used include a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; a cyclic ether solvent such as tetrahydrofuran or dioxolane; methyl acetate or ethyl acetate; An ester such as butyl acetate; an aromatic solvent such as toluene or xylene; an alcohol solvent such as carbitol, celecoxime, methanol, isopropanol, butanol or propylene glycol monomethyl ether; ethylene glycol monoethyl ether; B A glycol ether solvent such as diol monobutyl ether, propylene glycol monomethyl ether or propylene glycol monopropyl ether. These may be used alone or in combination of two or more. Among these, a ketone solvent, more preferably methyl isobutyl ketone, is preferred as a resin composition which is excellent in storage stability and excellent in coatability when used as a coating material.

本發明之樹脂組成物亦可進一步含有紫外線吸收劑、抗氧化劑、聚矽氧系添加劑、有機珠、氟系添加劑、流變控制劑、消泡劑、脫膜劑、抗靜電劑、防霧劑、著色劑、有機溶劑、無機填料等添加劑。 The resin composition of the present invention may further contain an ultraviolet absorber, an antioxidant, a polyoxonium additive, an organic bead, a fluorine-based additive, a rheology control agent, an antifoaming agent, a release agent, an antistatic agent, and an antifogging agent. Additives such as colorants, organic solvents, and inorganic fillers.

前述紫外線吸收劑係可列舉例如：2-[4-{(2-羥基-3-十二烷氧基丙基)氧基}-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三、2-[4-{(2-羥基-3-十三烷氧基丙基)氧基}-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三等三衍生物、2-(2'-二苯并哌喃羧基-5'-甲基苯基)苯并***、2-(2'-鄰硝基苄氧基-5'-甲基苯基)苯并***、2-二苯并哌喃羧基-4-十二烷氧基二苯基酮、2-鄰硝基苄氧基-4-十二烷氧基二苯基酮等。 The above ultraviolet absorber may, for example, be 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis (2,4) -dimethylphenyl)-1,3,5-three ,2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)- 1,3,5-three Wait three Derivative, 2-(2'-dibenzopyranocarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl) Benzotriazole, 2-dibenzopyranylcarboxy-4-dodecyloxydiphenyl ketone, 2-o-nitrobenzyloxy-4-dodecyloxydiphenyl ketone, and the like.

前述抗氧化劑係可列舉例如：受阻酚系抗氧化劑、受阻胺系抗氧化劑、有機硫系抗氧化劑、磷酸酯系抗氧化劑等。此等係可各自單獨使用，亦可併用二種以上。 Examples of the antioxidant include a hindered phenol-based antioxidant, a hindered amine-based antioxidant, an organic sulfur-based antioxidant, and a phosphate-based antioxidant. These may be used singly or in combination of two or more.

前述聚矽氧系添加劑係可列舉例如：如二甲基聚矽氧烷、甲基苯基聚矽氧烷、環狀二甲基聚矽氧烷、甲基氫聚矽氧烷、經聚醚改質之二甲基聚矽氧烷共聚物、經聚酯改質之二甲基聚矽氧烷共聚物、經氟改質之 二甲基聚矽氧烷共聚物、經胺基改質之二甲基聚矽氧烷共聚物等之具有烷基或苯基的聚有機矽氧烷、經聚醚改質之具有丙烯酸基的聚二甲基矽氧烷、經聚酯改質之具有丙烯酸基的聚二甲基矽氧烷等。此等係可各自單獨使用，亦可併用二種以上。 Examples of the polyfluorene-based additive include, for example, dimethyl polyoxyalkylene, methylphenyl polyoxyalkylene, cyclic dimethyl polyoxyalkylene, methyl hydrogen polyoxyalkylene, and polyether. Modified dimethyl polyoxyalkylene copolymer, polyester modified dimethyl polyoxyalkylene copolymer, modified with fluorine a polyorganosiloxane having an alkyl group or a phenyl group such as a dimethyl polyoxyalkylene copolymer, an amino group-modified dimethyl polyoxyalkylene copolymer, or the like, and a polyether-modified acrylic group Polydimethyl methoxy oxane, polydimethyl methoxide having an acrylic group modified by polyester, and the like. These may be used singly or in combination of two or more.

前述有機珠係可列舉例如：聚甲基丙烯酸甲酯珠、聚碳酸酯珠、聚苯乙烯珠、聚丙烯酸苯乙烯珠、聚矽氧珠、玻璃珠、丙烯酸珠、苯并胍胺系樹脂珠、三聚氰胺系樹脂珠、聚烯烴系樹脂珠、聚酯系樹脂珠、聚醯胺樹脂珠、聚醯亞胺系樹脂珠、聚氟乙烯樹脂珠、聚乙烯樹脂珠等。此等有機珠的平均粒徑的較佳值為1~10μm的範圍。此等係可各自單獨使用，亦可併用二種以上。 Examples of the organic bead include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacrylic acid styrene beads, polyoxyn beads, glass beads, acrylic beads, and benzoguanamine resin beads. And melamine resin beads, polyolefin resin beads, polyester resin beads, polyamide resin beads, polyimide resin beads, polyvinyl fluoride resin beads, polyethylene resin beads, and the like. The average particle diameter of these organic beads is preferably in the range of 1 to 10 μm. These may be used singly or in combination of two or more.

前述氟系添加劑係可列舉例如：DIC股份有限公司「MEGAFAC」系列等。此等係可各自單獨使用，亦可併用二種以上。 Examples of the fluorine-based additive include a DIC Corporation "MEGAFAC" series and the like. These may be used singly or in combination of two or more.

前述脫膜劑係可列舉例如：EVONIK DEGUSSA公司製「TEGO Rad 2200N」、「TEGO Rad 2300」、「TEGO Rad 2100」、BYK Chemie公司製「UV3500」、Toray Dow Corning公司製「Peintadd 8526」、「SH-29PA」等。此等係可各自單獨使用，亦可併用二種以上。 Examples of the release agent include "TEGO Rad 2200N" manufactured by EVONIK DEGUSSA, "TEGO Rad 2300", "TEGO Rad 2100", "UV3500" manufactured by BYK Chemie Co., Ltd., and "Peintadd 8526" manufactured by Toray Dow Corning Co., Ltd., SH-29PA" and so on. These may be used singly or in combination of two or more.

前述抗靜電劑係可列舉例如：雙(三氟甲烷磺醯基)醯亞胺或雙(氟磺醯基)醯亞胺的吡啶鎓、咪唑鎓、鏻、銨、或鋰鹽。此等係可各自單獨使用，亦可併用二種以上。 Examples of the antistatic agent include pyridinium, imidazolium, sulfonium, ammonium, or a lithium salt of bis(trifluoromethanesulfonyl) quinone imine or bis(fluorosulfonyl) quinone imine. These may be used singly or in combination of two or more.

前述各種添加劑的使用量係以充分發揮其效果並且不會阻礙紫外線硬化的範圍為佳，具體而言，以在本案發明樹脂組成物100質量份中分別以0.01~40質量份的範圍來使用為佳。 The amount of the above-mentioned various additives is preferably in the range of 0.01 to 40 parts by mass per 100 parts by mass of the resin composition of the present invention. good.

本發明之樹脂組成物係以進一步含有光聚合起始劑為佳。該光聚合起始劑係可列舉例如：二苯基酮、3,3'-二甲基-4-甲氧基二苯基酮、4,4'-雙二甲基胺基二苯基酮、4,4'-雙二乙基胺基二苯基酮、4,4'-二氯二苯基酮、米其勒酮、3,3',4,4'-四(三級丁基過氧羰基)二苯基酮等各種的二苯基酮；酮、9-氧硫(thioxanthone)、2-甲基-9-氧硫、2-氯-9-氧硫、2,4-二乙基-9-氧硫等的酮、9-氧硫類；苯偶姻(benzoin)、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚等各種的醯偶姻(acyloin)醚；二苯乙二酮、2,3-丁二酮(diacetyl)等α-二酮類；四甲胺硫甲醯基二硫化物(tetramethyl thiuram disulfide)、對甲苯基二硫化物等硫化物類；4-二甲基胺基安息香酸、4-二甲基胺基安息香酸乙酯等各種的安息香酸；3,3'-羰基-雙(7-二乙基胺基)香豆素、1-羥基環己基苯基酮、2,2'-二甲氧基-1,2-二苯基乙烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-N-啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-N-啉基苯基)-丁烷-1-酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、氧化-2,4,6-三甲基苯甲醯基二 苯基膦、氧化雙(2,4,6-三甲基苯甲醯基)苯基膦、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、1-(4-十二基苯基)-2-羥基-2-甲基丙烷-1-酮、4-苯甲醯基-4'-甲基二甲基硫化物、2,2'-二乙氧基苯乙酮、苄基二甲基縮酮、苄基-β-甲氧基乙基縮醛、鄰苯甲醯基安息香酸甲酯、雙(4-二甲基胺基苯基)酮、對二甲基胺基苯乙酮、α,α-二氯-4-苯氧基苯乙酮、苄酸戊基4-二甲基胺基酯、2-(鄰氯苯基)-4,5-二苯基咪唑基二聚物、2,4-雙-三氯甲基-6-[二(乙氧基羰基甲基)胺基]苯基-S-三、2,4-雙-三氯甲基-6-(4-乙氧基)苯基-S-三、2,4-雙-三氯甲基-6-(3-溴-4-乙氧基)苯基-S-三蒽醌、2-三級丁基蒽醌、2-戊基蒽醌、β-氯蒽醌等。此等係可各自單獨使用，亦可併用二種以上。 The resin composition of the present invention is preferably further contained in a photopolymerization initiator. The photopolymerization initiator may, for example, be diphenyl ketone, 3,3'-dimethyl-4-methoxydiphenyl ketone or 4,4'-bisdimethylaminodiphenyl ketone. , 4,4'-bisdiethylaminodiphenyl ketone, 4,4'-dichlorodiphenyl ketone, mischrone, 3,3',4,4'-tetra (tributyl) Various diphenyl ketones such as peroxycarbonyl)diphenyl ketone; Ketone, 9-oxosulfur (thioxanthone), 2-methyl-9-oxosulfur 2-chloro-9-oxosulfur 2,4-diethyl-9-oxosulfur Wait Ketone, 9-oxosulfur a variety of acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; diphenylethylenedione, 2, 3 - α-diketones such as diacetyl; tetramethyl thiuram disulfide, sulfides such as p-tolyl disulfide; 4-dimethylamino benzoic acid , various benzoic acid such as 4-dimethylamino benzoic acid ethyl ester; 3,3'-carbonyl-bis(7-diethylamino)coumarin, 1-hydroxycyclohexyl phenyl ketone, 2, 2'-Dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-N- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-N- Phenylphenyl)-butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oxidized-2,4,6-trimethylbenzimidyl diphenyl Phosphine, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1 -propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2 -methylpropan-1-one, 4-benzylidene-4'-methyldimethyl sulfide, 2,2'-diethoxyacetophenone, benzyldimethylketal, benzyl -β-methoxyethyl acetal, methyl benzylidene benzoate, bis(4-dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α,α-di Chloro-4-phenoxyacetophenone, pentyl 4-dimethylamino benzylate, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer, 2,4- Bis-trichloromethyl-6-[bis(ethoxycarbonylmethyl)amino]phenyl-S-three 2,4-bis-trichloromethyl-6-(4-ethoxy)phenyl-S-three 2,4-bis-trichloromethyl-6-(3-bromo-4-ethoxy)phenyl-S-three 蒽醌, 2-tertiary butyl hydrazine, 2-pentyl hydrazine, β-chloropurine, and the like. These may be used singly or in combination of two or more.

在前述光聚合起始劑之中，藉由使用選自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、9-氧硫及9-氧硫衍生物、2,2'-二甲氧基-1,2-二苯基乙烷-1-酮、氧化-2,4,6-三甲基苯甲醯基二苯基膦、氧化雙(2,4,6-三甲基苯甲醯基)苯基膦、2-甲基-1-[4-(甲硫基)苯基]-2-N-啉基-1-丙酮、2-苄基-2-二甲基胺基-1-(4-N-啉基苯基)-丁烷-1-酮之群組中之1種或2種以上的混合系，而能夠得到對更廣範圍的波長的光顯示活性且硬化性高的塗料，故而較佳。 Among the above photopolymerization initiators, by using 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2) -hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 9-oxosulfur And 9-oxosulfur Derivative, 2,2'-dimethoxy-1,2-diphenylethane-1-one, oxidized-2,4,6-trimethylbenzhydryldiphenylphosphine, oxidized double 2,4,6-Trimethylbenzylidene)phenylphosphine, 2-methyl-1-[4-(methylthio)phenyl]-2-N- Lolinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4-N- It is preferred to use one or a mixture of two or more of the group of morphylphenyl)-butan-1-one to obtain a coating exhibiting light activity over a wider range of wavelengths and having high curability. .

前述光聚合起始劑的市售品係可列舉例如：Ciba Specialty Chemicals公司製「IRGACURE-184」、「 IRGACURE-149」、「IRGACURE-261」、「IRGACURE-369」、「IRGACURE-500」、「IRGACURE-651」、「IRGACURE-754」、「IRGACURE-784」、「IRGACURE-819」、「IRGACURE-907」、「IRGACURE-1116」、「IRGACURE-1664」、「IRGACURE-1700」、「IRGACURE-1800」、「IRGACURE-1850」、「IRGACURE-2959」、「IRGACURE-4043」、「DAROCUR-1173」；BASF公司製「LUCIRIN TPO」；日本化藥股份有限公司製「KAYACURE-DETX」、「KAYACURE-MBP」、「KAYACURE-DMBI」、「KAYACURE-EPA」、「KAYACURE-OA」；Sutoufa Chemical公司製「VICURE-10」、「VICURE-55」；AKZO公司製「TRIGONAL P1」；SANDOZ公司製「SANDORAY 1000」；APJOHN公司製「DEAP」；WARD BLEKINSOP公司製「QUANTACURE-PDO」、「QUANTACURE-ITX」、「QUANTACURE-EPD」等。 The commercially available product of the photopolymerization initiator is, for example, "IRGACURE-184" manufactured by Ciba Specialty Chemicals Co., Ltd., " IRGACURE-149", "IRGACURE-261", "IRGACURE-369", "IRGACURE-500", "IRGACURE-651", "IRGACURE-754", "IRGACURE-784", "IRGACURE-819", "IRGACURE- 907", "IRGACURE-1116", "IRGACURE-1664", "IRGACURE-1700", "IRGACURE-1800", "IRGACURE-1850", "IRGACURE-2959", "IRGACURE-4043", "DAROCUR-1173" "LUCIRIN TPO" manufactured by BASF Corporation; "KAYACURE-DETX", "KAYACURE-MBP", "KAYACURE-DMBI", "KAYACURE-EPA", "KAYACURE-OA" manufactured by Nippon Kayaku Co., Ltd.; manufactured by Sutoufa Chemical Co., Ltd. "VICURE-10" and "VICURE-55"; "TRIGONAL P1" manufactured by AKZO Co., Ltd.; "SANDORAY 1000" manufactured by SANDOZ; "DEAP" manufactured by APJOHN; "QUANTACURE-PDO" and "QUANTACURE-ITX" manufactured by WARD BLEKINSOP , "QUANTACURE-EPD", etc.

前述光聚合起始劑的使用量為能充分發揮作為光聚合起始劑的功能之量，而且以不產生結晶析出或塗膜物性劣化的範圍為佳，具體而言，以在相對於樹脂組成物100質量份為0.05~20質量份的範圍內使用為佳，其中以在0.1~10質量份的範圍內使用為特佳。 The amount of the photopolymerization initiator to be used is such an amount that the function as a photopolymerization initiator can be sufficiently exhibited, and it is preferably in a range in which no crystal precipitation or physical properties of the coating film are deteriorated, specifically, in composition with respect to the resin. It is preferably used in the range of 0.05 to 20 parts by mass, and particularly preferably used in the range of 0.1 to 10 parts by mass.

本發明之樹脂組成物亦可進一步與前述光聚合起始劑一起使用各種的光增感劑。光增感劑係可列舉例如：胺類、尿素類、含硫化合物、含磷化合物、含氯化合物或腈類或是其他的含氮化合物等。 Further, the resin composition of the present invention may further use various photo sensitizers together with the above photopolymerization initiator. Examples of the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds or nitriles, and other nitrogen-containing compounds.

在本發明中，亦能夠進一步使用熱聚合起始劑。就熱聚合起始劑而言，可列舉例如：2,2'-偶氮雙異丁腈、2,2'-偶氮雙-(2,4-二甲基戊腈)、2,2'-偶氮雙-(4-甲氧基-2,4-二甲基戊腈)等偶氮化合物；過氧化苯甲醯基、過氧化月桂醯基、過氧三甲基乙酸三級丁酯、過氧乙基己酸三級丁酯、1,1'-雙(三級丁基過氧)環己烷、過氧-2-乙基己酸三級戊酯、過氧-2-乙基己酸三級己酯等有機過氧化物及過氧化氫等，以在相對於樹脂組成物100質量份為0.05~20質量份的範圍下使用為佳。 In the present invention, a thermal polymerization initiator can also be further used. The thermal polymerization initiator may, for example, be 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2' -Azo compound such as azobis-(4-methoxy-2,4-dimethylvaleronitrile); benzamidine peroxide, lauryl peroxide, tertiary butyl peroxytrimethylacetate , tert-butyl peroxyethylhexanoate, 1,1'-bis(tri-butylperoxy)cyclohexane, per-pentyl peroxy-2-ethylhexanoate, peroxy-2-ethyl An organic peroxide such as hexyl hexanoate or a hydrogen peroxide or the like is preferably used in an amount of 0.05 to 20 parts by mass based on 100 parts by mass of the resin composition.

製造本發明之活性能量線硬化型樹脂組成物的方法在併用無機微粒子(D)的情況下，可列舉例如：使用分散器、具有渦輪葉片等攪拌葉片的分散機、顏料振動器、輥磨機、球磨機、磨碎機、碾砂機、珠磨機等分散機，將前述無機微粒子(D)混合分散在前述分枝狀丙烯酸丙烯酸酯樹脂(A)中之方法；或是將前述無機微粒子(D)混合分散在包含前述分枝狀丙烯酸丙烯酸酯樹脂(A)、前述(甲基)丙烯酸酯(C)的樹脂成分中之方法。在前述無機微粒子(D)為濕式二氧化矽微粒子的情況下，於使用上述任一分散機時皆能得到均一且穩定的分散體。另一方面，在前述無機微粒子(C)為乾式二氧化矽微粒子的情況下，為了得到均一且穩定的分散體，以使用球磨機或珠磨機為佳。 In the method of producing the active energy ray-curable resin composition of the present invention, when the inorganic fine particles (D) are used in combination, for example, a disperser using a disperser, a stirring blade such as a turbine blade, a pigment shaker, and a roll mill may be mentioned. a disperser such as a ball mill, an attritor, a sand mill, a bead mill, or the like, wherein the inorganic fine particles (D) are mixed and dispersed in the branched acrylic acrylate resin (A); or the inorganic fine particles ( D) A method of mixing and dispersing in a resin component containing the above branched acrylic acrylate resin (A) and the above (meth) acrylate (C). In the case where the inorganic fine particles (D) are wet cerium oxide fine particles, a uniform and stable dispersion can be obtained by using any of the above dispersers. On the other hand, in the case where the inorganic fine particles (C) are dry cerium oxide fine particles, in order to obtain a uniform and stable dispersion, it is preferred to use a ball mill or a bead mill.

製造本發明之活性能量線硬化型樹脂組成物時所能夠適用的球磨機係可列舉例如濕式球磨機，其具有：內部填充有介質的容器、轉動軸承、具有與前述轉 動軸承為同軸狀的旋轉軸且藉由前述轉動軸承的旋轉驅動而旋轉的攪拌葉片、設置於前述容器的原料供給口、設置於前述容器的分散體排出口、及配置在前述轉動軸承貫通容器的部分的軸封裝置，其中前述軸封裝置為具有2組機械密封單元且具有該2組機械密封單元的密封部分經外部密封液密封的結構之軸封裝置。 The ball mill to which the active energy ray-curable resin composition of the present invention is applied may, for example, be a wet ball mill having a container filled with a medium, a rotary bearing, and having the above-described rotation. The moving bearing is a coaxial rotating shaft, and the stirring blade that rotates by the rotation of the rotating bearing, the raw material supply port provided in the container, the dispersion discharge port provided in the container, and the rotating bearing through container A part of the shaft sealing device, wherein the shaft sealing device is a shaft sealing device having two sets of mechanical sealing units and having a sealing portion of the two sets of mechanical sealing units sealed by an external sealing liquid.

亦即，製造含有無機微粒子(D)的活性能量線硬化型樹脂組成物之方法係可列舉例如：從濕式球磨機的前述供給口，將以前述無機微粒子(D)、前述樹脂(A)、前述(甲基)丙烯酸酯(C)為成分的樹脂成分供給至前述容器，藉由在前述容器內使轉動軸承及攪拌葉片旋轉來攪拌混合介質與原料，而進行前述無機微粒子(D)的粉碎與該無機微粒子(D)對前述樹脂成分的分散，接著再從前述排出口排出之方法，其中該濕式球磨機具有：內部填充有介質的容器、轉動軸承、具有與前述轉動軸承為同軸狀的旋轉軸且藉由前述轉動軸承的旋轉驅動而旋轉的攪拌葉片、設置於前述容器的原料供給口、設置於前述容器的分散體排出口、及配置在前述轉動軸承貫通容器的部分的軸封裝置，前述軸封裝置為具有2組機械密封單元且具有該2組機械密封單元的密封部分經外部密封液密封的結構之軸封裝置。 In other words, the method of producing the active energy ray-curable resin composition containing the inorganic fine particles (D) includes, for example, the inorganic fine particles (D) and the resin (A) from the supply port of the wet ball mill. The resin component containing the component (meth) acrylate (C) is supplied to the container, and the mixed medium and the raw material are stirred by rotating the rotary bearing and the stirring blade in the container to pulverize the inorganic fine particles (D). Dispersing the resin component with the inorganic fine particles (D), and then discharging the resin component from the discharge port, wherein the wet ball mill has a container filled with a medium, a rotary bearing, and has a coaxial shape with the rotary bearing a rotating blade, a stirring blade that is rotated by the rotation of the rotating bearing, a material supply port provided in the container, a dispersion discharge port provided in the container, and a shaft sealing device disposed in a portion of the rotating bearing penetrating the container The shaft sealing device is a knot having two sets of mechanical sealing units and having a sealing portion of the two sets of mechanical sealing units sealed by an external sealing liquid Shaft seal device.

本發明之活性能量線硬化型樹脂組成物係能夠使用在塗料用途上。該塗料係能夠藉由塗布在各種基材上並照射活性能量線使其硬化，而作為保護基材表面的塗布層來使用。在此情況下，可將本發明之塗料直接 塗布在被表面保護構件上來使用，亦可將塗布在塑膠薄膜上而成者作為保護薄膜來使用。或是亦可將本發明之塗料塗布在塑膠薄膜上，將形成塗膜者作為抗反射薄膜、擴散薄膜及稜鏡片等光學薄膜來使用。使用本發明之塗料所得到的塗膜由於具有表面硬度高且透明性亦優異的特徵，因此能夠以視用途而定的膜厚塗布在各式各樣的塑膠薄膜上而作為保護薄膜用途或薄膜狀成形品來使用。 The active energy ray-curable resin composition of the present invention can be used for coating applications. The coating can be used as a coating layer for protecting the surface of a substrate by being applied to various substrates and irradiated with an active energy ray to be cured. In this case, the coating of the present invention can be directly It can be used by being applied to a surface protection member, and it can also be used as a protective film by coating on a plastic film. Alternatively, the coating material of the present invention may be applied to a plastic film, and the film-forming film may be used as an optical film such as an antireflection film, a diffusion film, and a ruthenium film. Since the coating film obtained by using the coating material of the present invention has a high surface hardness and excellent transparency, it can be applied to various plastic films in a film thickness depending on the intended use as a protective film or film. Shaped products are used.

再者，為了得到塗膜，能夠在照射活性能量線之前或之後包含加熱處理步驟。藉由進行加熱處理，而能夠得到更高硬度的塗膜。就此時的加熱溫度而言，能夠根據使用的基材(塑膠薄膜)的耐熱性等而適當地選擇，但從更加提高表面硬度的觀點來看，以在80~200℃的範圍下進行1~180分鐘左右的處理為佳。 Further, in order to obtain a coating film, a heat treatment step may be included before or after the irradiation of the active energy ray. By performing heat treatment, a coating film of higher hardness can be obtained. The heating temperature at this time can be appropriately selected depending on the heat resistance of the substrate (plastic film) to be used, etc., but from the viewpoint of further improving the surface hardness, it is carried out at a temperature of 80 to 200 ° C. The treatment of about 180 minutes is better.

前述塑膠薄膜係可列舉例如：由聚碳酸酯、聚甲基丙烯酸甲酯、聚苯乙烯、聚酯、聚烯烴、環氧樹脂、三聚氰胺樹脂、三乙醯纖維素樹脂、ABS樹脂、AS樹脂、降莰烯系樹脂、環狀烯烴、聚醯亞胺樹脂等所構成的塑膠薄膜或塑膠薄片。 Examples of the plastic film include polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, and AS resin. A plastic film or a plastic sheet made of a decene-based resin, a cyclic olefin, or a polyimide resin.

在上述塑膠薄膜之中，三乙醯纖維素薄膜為特別適用於液晶顯示器的偏光板用途的薄膜，但由於通常厚度為40~100μm這樣的薄，因此有即使在設置硬塗層的情況下也難以充分地提高表面硬度並且易於產生大幅捲曲的特徵。包含本案發明之樹脂組成物之塗膜即使在將三乙醯纖維素薄膜作為基材使用的情況下，還是能 夠達到表面硬度高、耐捲曲性或加工性、透明性亦優異的效果，因而相當適用。在將該三乙醯纖維素薄膜作為基材使用的情況下，塗布本案發明之塗料時的塗布量係以乾燥後的膜厚成為1~20μm的範圍、較佳成為2~15μm的範圍之方式進行塗布為佳。此時的塗布方法係可列舉例如：棒塗布機塗布、邁耶棒(Meyer bar)塗布、氣刀塗布、凹版塗布、逆轉凹版(reverse gravure)塗布、平版印刷(offset printing)、柔版印刷(flexo printing)、網版印刷法等。 Among the above plastic films, the triacetyl cellulose film is a film which is particularly suitable for use in a polarizing plate of a liquid crystal display, but since it is usually thinner than 40 to 100 μm, it is possible even in the case of providing a hard coat layer. It is difficult to sufficiently increase the surface hardness and to easily produce a characteristic of large curl. The coating film containing the resin composition of the invention of the present invention can be used even when the triethylene fluorene cellulose film is used as a substrate. It is suitable for achieving high surface hardness, curl resistance, workability, and transparency. When the triethylene fluorene cellulose film is used as a substrate, the coating amount in the coating of the present invention is such that the film thickness after drying is in the range of 1 to 20 μm, preferably in the range of 2 to 15 μm. Coating is preferred. The coating method at this time may, for example, be a bar coater coating, a Meyer bar coating, an air knife coating, a gravure coating, a reverse gravure coating, an offset printing, or a flexographic printing ( Flexo printing), screen printing method, etc.

在上述塑膠薄膜之中，聚酯薄膜係可列舉例如：聚對酞酸乙二酯，其厚度通常為100~300μm左右。由於容易以低成本進行加工，因而為可用於觸控面板顯示器等各式各樣用途的薄膜，但具有非常柔軟而即使在設置硬塗層的情況下也難以充分地提高表面硬度之特徵。在將該聚乙烯薄膜作為基材使用的情況下，塗布本案發明之塗料時的塗布量係以配合其用途而以乾燥後的膜厚成為5~100μm的範圍、較佳成為7~80μm的範圍之方式進行塗布為佳。通常以如超過20μm之膜厚塗布塗料的情況，比起以較薄的膜厚進行塗布的情況具有容易產生較大的捲曲的傾向，但由於本案發明之塗料具有耐捲曲性優異的特徵，即使在以超過20μm之較高的膜厚進行塗布的情況下也不易產生捲曲，而相當適用。此時的塗布方法係可列舉例如：棒塗布機塗布、邁耶棒塗布、氣刀塗布、凹版塗布、逆轉凹版塗布、平版印刷、柔版印刷、網版印刷法等。 Among the above-mentioned plastic films, the polyester film may, for example, be polyethylene terephthalate, and its thickness is usually about 100 to 300 μm. Since it is easy to process at a low cost, it is a film which can be used for various uses, such as a touch panel display, but it is very soft, and it is difficult to fully improve surface hardness even if a hard-coat layer is provided. When the polyethylene film is used as a substrate, the coating amount when the coating material of the present invention is applied is in a range of 5 to 100 μm, preferably 7 to 80 μm, in accordance with the use thereof. It is preferred to carry out the coating in the same manner. In general, when the coating material is applied at a film thickness of more than 20 μm, it tends to cause a large curl when coated with a thin film thickness. However, since the coating material of the present invention has a characteristic of excellent curl resistance, even In the case of coating at a film thickness of more than 20 μm, curling is less likely to occur, and it is quite suitable. The coating method at this time may, for example, be a bar coater coating, a Meyer bar coating, an air knife coating, a gravure coating, a reverse gravure coating, a lithography, a flexographic printing, a screen printing method, or the like.

在上述塑膠薄膜之中，由於聚甲基丙烯酸甲酯薄膜通常厚度在100~2,000μm左右，而比較厚且堅固，因此是適用於液晶顯示器的前面板用途等要求特別高的表面硬度之用途的薄膜。在將該聚甲基丙烯酸甲酯薄膜作為基材使用的情況下，塗布本案發明之塗料時的塗布量係以配合其用途而以乾燥後的膜厚成為1~100μm的範圍、較佳成為7~80μm的範圍之方式進行塗布為佳。通常在如聚甲基丙烯酸甲酯薄膜之比較厚的薄膜之上以超過30μm的膜厚塗布塗料的情況下，其成為表面硬度高的積層薄膜，反之也有透明性下降的傾向，但本案發明之塗料比起以往的塗料具有非常高的透明性，因此能夠得到兼具高表面硬度與透明性的積層薄膜。此時的塗布方法係可列舉例如：棒塗布機塗布、邁耶棒塗布、氣刀塗布、凹版塗布、逆轉凹版塗布、平版印刷、柔版印刷、網版印刷法等。 Among the above-mentioned plastic films, since the polymethyl methacrylate film is usually thick and strong in thickness of about 100 to 2,000 μm, it is suitable for use in a front panel application such as a liquid crystal display, which requires a particularly high surface hardness. film. When the polymethyl methacrylate film is used as a substrate, the coating amount when the coating material of the present invention is applied is preferably in the range of 1 to 100 μm, preferably 7 in terms of the film thickness after drying. Coating is preferably carried out in a range of ~80 μm. In general, when a coating material is applied over a relatively thick film such as a polymethyl methacrylate film over a film thickness of more than 30 μm, it becomes a laminated film having a high surface hardness, and conversely, transparency tends to decrease, but the present invention The coating has a very high transparency compared to the conventional coating, so that a laminated film having high surface hardness and transparency can be obtained. The coating method at this time may, for example, be a bar coater coating, a Meyer bar coating, an air knife coating, a gravure coating, a reverse gravure coating, a lithography, a flexographic printing, a screen printing method, or the like.

使本發明之塗料硬化製成塗膜時照射的活性能量線係可列舉例如：紫外線或電子束。在使用紫外線進行硬化的情況下，使用具有氙燈、高壓水銀燈、金屬鹵素燈、LED燈作為光源的紫外線照射裝置，可視需要地調整光量、光源的配置等。在使用高壓水銀燈的情況下，通常以在搬運速度對1盞具有80~160W/cm的範圍之光量的燈為5~50m/分鐘的範圍內進行硬化為佳。另一方面，在使用電子束進行硬化的情況下，通常以使用具有10~300kV的範圍之加速電壓之電子束加速裝置在搬運速度5~50m/分鐘的範圍內進行硬化為佳。 Examples of the active energy ray which is irradiated when the coating material of the present invention is cured into a coating film include ultraviolet rays or electron beams. In the case of curing using ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high pressure mercury lamp, a metal halide lamp, or an LED lamp as a light source is used, and the amount of light, the arrangement of the light source, and the like can be adjusted as needed. In the case of using a high-pressure mercury lamp, it is usually preferably cured in a range of 5 to 50 m/min in a lamp having a light amount in the range of 80 to 160 W/cm at a conveyance speed. On the other hand, in the case of hardening using an electron beam, it is usually preferably performed by using an electron beam accelerator having an acceleration voltage in the range of 10 to 300 kV at a conveyance speed of 5 to 50 m/min.

又，塗布本發明之塗料之基材不僅可適合作為塑膠薄膜來使用，亦能適合作為各種塑膠成形品、例如行動電話、家電製品、汽車保險槓等的表面塗布劑來使用。在此情況下，就其塗膜的行程方法而言，可列舉例如：塗布法、轉印法、片材接著法等。 Further, the substrate coated with the coating material of the present invention can be suitably used not only as a plastic film but also as a surface coating agent for various plastic molded articles such as mobile phones, home electric appliances, automobile bumpers, and the like. In this case, examples of the stroke method of the coating film include a coating method, a transfer method, a sheet joining method, and the like.

前述塗布法為將前述塗料噴灑塗布、或是使用簾幕式塗布機、輥塗布機、凹版塗布機等印刷機器塗布在成形品上方後，照射活性能量線並使其硬化之方法。 The coating method is a method in which the coating material is spray-coated or coated on a molded article by a printing machine such as a curtain coater, a roll coater, or a gravure coater, and then the active energy ray is irradiated and cured.

前述轉印法係可列舉：使在具有脫模性的基體片材上塗布前述本發明之塗料所得到之轉印材料接著於成形品表面後，將基體片材剝離並將頂塗層(top coat)轉印在成型品表面，接著照射活性能量線使其硬化之方法；或是使該轉印材料接著於成形品表面後，照射活性能量線使其硬化，接著藉由將基體片材剝離而將頂塗層轉印在成型品表面之方法。 In the transfer method, the transfer material obtained by applying the coating material of the present invention onto the base sheet having mold release property is applied to the surface of the molded article, and then the base material sheet is peeled off and the top coat layer is applied (top). Coat) a method of transferring onto the surface of a molded article and then irradiating the active energy ray to harden it; or after the transfer material is applied to the surface of the molded article, irradiating the active energy ray to harden it, and then peeling off the base sheet The method of transferring the top coat to the surface of the molded article.

另一方面，前述片材接著法為藉由將於基體片材上具有由前述本發明之塗料構成之塗膜之保護片材、或於基體片材上具有由前述塗料構成之塗膜與裝飾層之保護片材接著於塑膠成形品，而在成形品表面形成保護層之方法。 On the other hand, the sheet joining method is a protective sheet having a coating film comprising the coating material of the present invention on the base sheet, or a coating film and decoration composed of the coating material on the base sheet. The protective sheet of the layer is then applied to a plastic molded article to form a protective layer on the surface of the molded article.

在此等之中，本發明之塗料係能夠較佳地使用在轉印法及片材接著法用途上。 Among these, the coating of the present invention can be preferably used in the transfer method and the sheet joining method.

在前述轉印法中，首先製作轉印材料。該轉印材料係例如能夠將前述塗料單獨、或是將與聚異氰酸酯化合物混合而成者塗布在基材片材上並進行加熱使塗 膜半硬化(B-階段化)而製造。 In the above transfer method, a transfer material is first produced. The transfer material can be applied, for example, by coating the above-mentioned coating material alone or by mixing with a polyisocyanate compound on a substrate sheet and heating it. It is manufactured by film semi-hardening (B-staged).

為了製造轉印材料，首先在基材片材上塗布前述本發明之塗料。塗布前述塗料的方法係可列舉例如：凹版塗布法、輥塗布法、噴灑塗布法、唇塗布(lip coat)法、缺角輪塗布(comma coat)法等塗布法；凹版印刷法、網版印刷法等印刷法等。從耐磨耗性及耐藥品性變良好來看，塗布時的膜厚係以硬化後的塗膜的厚度成為1~50μm之方式進行塗布為佳，以成為3~40μm之方式進行塗布為更佳。 In order to manufacture a transfer material, the aforementioned coating material of the present invention is first coated on a substrate sheet. Examples of the method of applying the coating material include a gravure coating method, a roll coating method, a spray coating method, a lip coating method, a comma coat method, and the like; a gravure printing method, screen printing, and the like. Printing methods such as law. In view of the improvement in abrasion resistance and chemical resistance, the film thickness at the time of application is preferably such that the thickness of the coating film after curing is 1 to 50 μm, and coating is performed at 3 to 40 μm. good.

以前述方法將前述塗料塗布在基材片材上之後，進行加熱乾燥將塗膜半硬化(B-階段化)。加熱通常為55~160℃，較佳為100~140℃。加熱時間通常為30秒鐘~30分鐘，較佳為1~10分鐘，更佳為1~5分鐘。 After the coating material is applied onto the substrate sheet by the above method, the coating film is semi-cured (B-staged) by heat drying. The heating is usually 55 to 160 ° C, preferably 100 to 140 ° C. The heating time is usually from 30 seconds to 30 minutes, preferably from 1 to 10 minutes, more preferably from 1 to 5 minutes.

使用前述轉印材料而成的成形品的表面保護層的形成係例如在將前述轉印材料之經B-階段化的樹脂層與成形品接著後，照射活性能量線使樹脂層硬化而進行。具體而言，可列舉例如：使轉印材料之經B-階段化的樹脂層接著於成形品表面，之後藉由將轉印材料的基體片材剝離，而使轉印材料之經B-階段化的樹脂層轉印在成形品表面上之後，藉由活性能量線照射使其能量線硬化來進行樹脂層的交聯硬化之方法(轉印法)；或將前述轉印材料***成形模具內，使樹脂射出充滿模槽內，在得到樹脂成形品的同時，使轉印材料接著在其表面上，將基體片材剝離並轉印至成形品上之後，藉由活性能量線照射使其能量線硬化來進行樹脂層的交聯硬化之方 法(成形同時轉印法)等。 The formation of the surface protective layer of the molded article using the transfer material is performed, for example, after the B-staged resin layer of the transfer material is bonded to the molded article, and then the active energy ray is irradiated to cure the resin layer. Specifically, for example, a B-staged resin layer of the transfer material is attached to the surface of the molded article, and then the B-stage of the transfer material is caused by peeling off the base sheet of the transfer material. After the resin layer is transferred onto the surface of the molded article, the energy beam is hardened by irradiation with an active energy ray to perform cross-linking hardening of the resin layer (transfer method); or the transfer material is inserted into the forming mold The resin is injected into the cavity, and the resin material is obtained, and the transfer material is subsequently peeled off on the surface of the substrate and transferred to the molded article, and then the energy is irradiated by the active energy ray. Wire hardening to carry out cross-linking hardening of the resin layer Method (formation simultaneous transfer method) and the like.

接著，具體而言，片材接著法係可列舉：使預先製成的保護層形成用片材的基體片材與成形品接著後，進行藉由加熱使其熱硬化而進行B-階段化而成之樹脂層的交聯硬化之方法(後接著法)；或將前述保護層形成用片材***成形模具內，使樹脂射出充滿模槽內，在得到樹脂成形品的同時，使其表面與保護層形成用片材接著後，藉由加熱使其熱硬化來進行樹脂層的交聯硬化之方法(成形同時接著法)等。 In the sheet-following method, the base sheet and the molded article of the sheet for forming a protective layer prepared in advance are then subjected to heat-hardening by heating to be B-staged. a method of crosslinking hardening of a resin layer (follow-up method); or inserting the sheet for forming a protective layer into a molding die, and ejecting the resin into the cavity, and obtaining a resin molded article while making the surface thereof After the protective layer forming sheet is subsequently heated and thermally cured by heating, a method of crosslinking and curing the resin layer (forming simultaneous bonding method) or the like is performed.

接著，本發明之塗膜為將本發明之塗料塗布在前述的塑膠薄膜上並使其硬化所形成的塗膜、或是將本發明之塗料作為塑膠成形品的表面保護劑進行塗布並硬化所形成的塗膜，而且本發明之積層薄膜為在塑膠薄膜上形成有塗膜之薄膜。 Next, the coating film of the present invention is a coating film formed by applying the coating material of the present invention to the above-mentioned plastic film and hardening it, or coating and hardening the coating material of the present invention as a surface protective agent for a plastic molded article. The formed coating film, and the laminated film of the present invention is a film in which a coating film is formed on a plastic film.

在前述薄膜的各種用途之中，如前面所述，從塗膜硬度優異的點來看，以將在塑膠薄膜上塗布本發明之塗料並照射活性能量線所得到的薄膜作為液晶顯示器或觸控面板顯示器等所使用之偏光板用保護薄膜來使用為佳。具體而言，在製成將本發明之塗料塗布在液晶顯示器或觸控面板顯示器等所使用的偏光板的保護薄膜上並照射活性能量線使其硬化而成之薄膜的情況下，硬化塗膜會成為兼具高硬度與高透明性的保護薄膜。在偏光板的保護薄膜用途中，亦可在塗布本發明之塗料而成的塗布層的另一側的面上形成黏著劑層。 Among the various uses of the above-mentioned film, as described above, a film obtained by applying the coating of the present invention to a plastic film and irradiating an active energy ray is used as a liquid crystal display or touch from the viewpoint of excellent hardness of the coating film. It is preferable to use a polarizing plate for a panel display or the like with a protective film. Specifically, in the case of producing a film obtained by applying the coating material of the present invention to a protective film of a polarizing plate used in a liquid crystal display or a touch panel display, and irradiating an active energy ray to cure the film, the cured film is formed. It will become a protective film with high hardness and high transparency. In the use of the protective film of the polarizing plate, an adhesive layer may be formed on the other side of the coating layer on which the coating of the present invention is applied.

[實施例] [Examples]

以下列舉具體的製造例、實施例，更具體地說明本發明，惟本發明未受到此等實施例的限定。例中的份及%只要未特別記載，皆為質量基準。 The present invention will be more specifically described by the following specific examples and examples, but the present invention is not limited by the examples. The parts and % in the examples are all based on quality unless otherwise specified.

在本發明之實施例中，重量平均分子量(Mw)係使用凝膠滲透層析儀(GPC)並依據下述條件進行測定而得的值。 In the examples of the present invention, the weight average molecular weight (Mw) is a value obtained by using a gel permeation chromatography (GPC) and measuring according to the following conditions.

測定裝置：TOSOH股份有限公司製HLC-8220 Measuring device: HLC-8220 manufactured by TOSOH Co., Ltd.

管柱：TOSOH股份有限公司製保護管柱HXL-H Pipe column: protection column HXL-H made by TOSOH Co., Ltd.

+TOSOH股份有限公司製TSKgel G5000HXL +TOSOH Co., Ltd. TSKgel G5000HXL

+TOSOH股份有限公司製TSKgel G4000HXL +TOSOH Co., Ltd. TSKgel G4000HXL

+TOSOH股份有限公司製TSKgel G3000HXL +TSKgel G3000HXL made by TOSOH Co., Ltd.

+TOSOH股份有限公司製TSKgel G2000HXL +TOSOH Co., Ltd. TSKgel G2000HXL

偵檢器：RI(示差折射計) Detector: RI (differential refractometer)

數據處理：TOSOH股份有限公司製SC-8010 Data Processing: SC-8010 manufactured by TOSOH Co., Ltd.

測定條件：管柱溫度 40℃ Measurement conditions: column temperature 40 ° C

溶媒 四氫呋喃 Solvent tetrahydrofuran

流速 1.0ml/分鐘 Flow rate 1.0ml/min

標準：聚苯乙烯 Standard: Polystyrene

試料：使用微濾器將以樹脂固體含量換算為0.4質量%的四氫呋喃溶液過濾而得者(100μl) Sample: Filtered by using a microfilter to filter a 0.4% by mass of a resin solid content in tetrahydrofuran (100 μl)

[鉛筆硬度試驗] [Pencil hardness test]

1.試驗片的作成方法 1. Method for preparing test piece

使用棒塗布機，將各實施例及比較例所得到的活性能量線硬化型樹脂組成物以在硬化後成為指定的膜厚之方式塗布在薄膜上，藉由活性能量線照射及加熱處理 而得到具有硬化塗膜的積層薄膜。 The active energy ray-curable resin composition obtained in each of the examples and the comparative examples was applied onto the film by a bar coater so as to have a predetermined film thickness after curing, by active energy ray irradiation and heat treatment. A laminated film having a cured coating film was obtained.

2.鉛筆硬度試驗方法 2. Pencil hardness test method

按照JIS K 5400，將上述所得到的硬化塗膜的表面透過負重500g的鉛筆刮痕試驗進行評定。進行試驗5次，將比刮傷1次以上的硬度低一級的硬度作為其塗膜的鉛筆硬度。 The surface of the hardened coating film obtained above was passed through a pencil scratch test of a load of 500 g in accordance with JIS K 5400. The test was performed 5 times, and the hardness lower than the hardness of one or more scratches was used as the pencil hardness of the coating film.

[耐磨耗性試驗] [Abrasion resistance test]

1.硬化塗膜的作成方法 1. Method for preparing hardened coating film

以與上述鉛筆硬度試驗的情況同樣的方法作成塗膜。 A coating film was produced in the same manner as in the case of the pencil hardness test described above.

2.耐鋼絲絨性試驗 2. Steel wool resistance test

以0.5g的鋼絲絨(NIPPON STEEL WOOL股份有限公司製「BONSTAR #0000」包裹直徑2.4公分的圓盤狀的壓頭，對該壓頭施加1kg重的負重，來回薄膜的塗膜表面100次。使用SUGA試驗機股份有限公司製「HAZE COMPUTER HZ-2」測定試驗前後的塗膜的霧度值，以該等的差δH進行評定。δH值越小，為耐刮傷性越優異的硬化塗膜。 A disk-shaped indenter having a diameter of 2.4 cm was wrapped in 0.5 g of steel wool ("BONSTAR #0000" manufactured by NIPPON STEEL WOOL Co., Ltd.), and a load of 1 kg was applied to the indenter, and the surface of the coating film of the film was returned 100 times. The haze value of the coating film before and after the test was measured by "HAZE COMPUTER HZ-2" manufactured by SUGA Testing Machine Co., Ltd., and the difference was evaluated by the difference δH. The smaller the δH value, the harder the coating is excellent in scratch resistance. membrane.

[撓曲性試驗] [Flexibility test]

1.硬化塗膜的作成方法 1. Method for preparing hardened coating film

以與上述鉛筆硬度試驗的情況同樣的方法在聚酯薄膜(膜厚75μm)上作成塗膜(硬化後的膜厚：18μm)。 A coating film (thickness after curing: 18 μm) was formed on a polyester film (film thickness: 75 μm) in the same manner as in the above pencil hardness test.

2.撓曲性試驗 2. Flexibility test

使用心軸試驗機(TP技研公司製「彎曲試驗機」)，將積層薄膜捲繞在試驗棒上，進行以目視確認薄膜的 硬化塗膜層有無產生裂痕之試驗，將未產生裂痕之試驗棒的最小直徑作為評定結果。最小直徑越小，為撓曲性越優異的塗膜。 The laminated film was wound on a test bar using a mandrel tester ("Bending Tester" manufactured by TP Technik Co., Ltd.), and the film was visually confirmed. The hardened coating layer was tested for cracks, and the minimum diameter of the test rod without cracks was used as the evaluation result. The smaller the minimum diameter, the more excellent the coating film is.

合成例1：分枝狀丙烯酸丙烯酸酯樹脂(A-1)的製造 Synthesis Example 1: Production of Branched Acrylic Acrylate Resin (A-1)

在具備攪拌裝置、冷卻管、滴液漏斗及氮氣導入管的高壓密閉反應裝置中裝入甲基異丁基酮254質量份，一面攪拌，一面將系統內溫度升溫至150℃為止，接著花費3小時從滴液漏斗滴下包含甲基丙烯酸環氧丙酯229質量份、甲基丙烯酸甲酯153質量份及三級丁基過氧-2-乙基己酸酯(日本油脂股份有限公司製「PERBUTYL O」)23質量份與1,1'-雙(三級丁基過氧)環己烷(日本油脂股份有限公司製「PERHEXA C」)12質量份的混合液後，在150℃下保持2小時。接著，降溫至90℃後，裝入4-甲氧基苯酚(methoquinone)0.1質量份及丙烯酸118質量份後，添加3質量份的三苯膦後，再升溫至110℃，確認酸價為3mgKOH/g以下，得到丙烯酸聚合物(a-1)。該丙烯酸聚合物(a-1)的性狀值係如下所述。 254 parts by mass of methyl isobutyl ketone was placed in a high-pressure sealed reactor equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, and the temperature in the system was raised to 150 ° C while stirring, and then it was taken 3 229 parts by mass of glycidyl methacrylate, 153 parts by mass of methyl methacrylate, and tert-butylperoxy-2-ethylhexanoate ("Breakfast" made by Nippon Oil & Fat Co., Ltd. O") a mixture of 23 parts by mass and 12 parts by mass of 1,1'-bis(tri-butylperoxy)cyclohexane ("PERHEXA C" manufactured by Nippon Oil & Fat Co., Ltd.), and kept at 150 ° C for 2 hour. Then, after cooling to 90 ° C, 0.1 parts by mass of 4-methoxyphenol (methoquinone) and 118 parts by mass of acrylic acid were charged, and after adding 3 parts by mass of triphenylphosphine, the temperature was further raised to 110 ° C, and the acid value was confirmed to be 3 mg KOH. Below /g, an acrylic polymer (a-1) is obtained. The property values of the acrylic polymer (a-1) are as follows.

重量平均分子量(Mw)：6,500、 固體含量換算之源自丙烯酸的理論丙烯醯基當量：309g/eq。 Weight average molecular weight (Mw): 6,500, The theoretical propylene oxime equivalent derived from acrylic acid in terms of solid content: 309 g/eq.

接著，加入HDI10質量份、辛酸錫0.1質量份，在80℃下保持5小時，確認NCO%在0.3以下。接著使用甲基異丁基酮進行稀釋，得到分枝狀丙烯酸丙烯酸酯樹脂(A-1)的甲基異丁基酮溶液(非揮發性物質50.0質量%)。該分枝狀 丙烯酸丙烯酸酯樹脂(A-1)的各性狀值係如下所述。 Next, 10 parts by mass of HDI and 0.1 parts by mass of tin octylate were added, and the mixture was kept at 80 ° C for 5 hours, and it was confirmed that the NCO% was 0.3 or less. Subsequently, the mixture was diluted with methyl isobutyl ketone to obtain a methyl isobutyl ketone solution of a branched acrylic acrylate resin (A-1) (nonvolatile matter: 50.0% by mass). Branched The properties of each of the acrylic acrylate resin (A-1) are as follows.

重量平均分子量(Mw)：20,600、 固體含量換算之源自丙烯酸的理論丙烯醯基當量：316g/eq。 Weight average molecular weight (Mw): 20,600, The theoretical propylene oxime equivalent derived from acrylic acid in terms of solid content: 316 g/eq.

合成例2~4、比較合成例7、8 Synthesis Examples 2 to 4, Comparative Synthesis Examples 7 and 8

在合成例1中，除了將甲基丙烯酸環氧丙酯(GMA)、甲基丙烯酸甲酯(MMA)、丙烯酸(AA)的使用量、及與所得到的丙烯酸聚合物反應之化合物作成表1所記載者以外，係與合成例1同樣地進行，得到分枝狀丙烯酸丙烯酸酯樹脂(A-2)~(A-4)、及比較用的丙烯酸聚合物(A'-1)。比較用的分枝狀丙烯酸丙烯酸酯樹脂(A'-2)由於在加入HDI 17.5質量份、辛酸錫0.1質量份並在80℃下保持1小時後產生凝膠化，因而停止反應。 In Synthesis Example 1, except that the amount of glycidyl methacrylate (GMA), methyl methacrylate (MMA), acrylic acid (AA) used, and the compound reacted with the obtained acrylic polymer were made in Table 1. In the same manner as in Synthesis Example 1, the branched acrylic acrylate resins (A-2) to (A-4) and the comparative acrylic polymer (A'-1) were obtained. The branched acrylic acrylate resin (A'-2) for comparison was gelled after the addition of 17.5 parts by mass of HDI and 0.1 parts by mass of tin octoate and maintained at 80 ° C for 1 hour, thereby stopping the reaction.

合成例5：分枝狀丙烯酸丙烯酸酯樹脂(A-5)的製造 Synthesis Example 5: Production of Branched Acrylic Acrylate Resin (A-5)

在具備攪拌裝置、冷卻管、滴液漏斗及氮氣導入管的高壓密閉反應裝置中，裝入甲基異丁基酮254質量份，一面攪拌，一面將系統內溫度升溫至150℃為止，接著花費3小時從滴液漏斗滴下包含甲基丙烯酸環氧丙酯229質量份、甲基丙烯酸甲酯153質量份及三級丁基過氧-2-乙基己酸酯(日本油脂股份有限公司製「PERBUTYL O」)23質量份與1,1'-雙(三級丁基過氧)環己烷(日本油脂股份有限公司製「PERHEXA C」)12質量份的混合液後，在150℃下保持2小時，得到前驅物(2-5)。該前驅物(2-5)的性狀值係如下所述。 254 parts by mass of methyl isobutyl ketone was placed in a high-pressure sealed reactor equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen gas introducing tube, and the temperature in the system was raised to 150 ° C while stirring, and then it was taken. 229 parts by mass of glycidyl methacrylate, 153 parts by mass of methyl methacrylate, and tertiary butyl peroxy-2-ethylhexanoate (manufactured by Nippon Oil & Fats Co., Ltd.) were dropped from the dropping funnel for 3 hours. PERBUTYL O") A mixture of 23 parts by mass and 12 parts by mass of 1,1'-bis(tri-butylperoxy)cyclohexane ("PERHEXA C" manufactured by Nippon Oil & Fat Co., Ltd.), and maintained at 150 ° C After 2 hours, the precursor (2-5) was obtained. The trait values of the precursor (2-5) are as follows.

重量平均分子量(Mw)：4,000、接著，降溫至90℃後，裝入4-甲氧基苯酚0.1質量份及丙烯酸111質量份、己二酸10質量份後，添加3質量份的三苯膦，在升溫至110℃，確認酸價為3mgKOH/g以下，得到分枝狀丙烯酸丙烯酸酯(A-5)。該丙烯酸丙烯酸酯(A-5)的性狀值係如下所述。 Weight average molecular weight (Mw): 4,000, and then, after cooling to 90 ° C, 0.1 parts by mass of 4-methoxyphenol, 111 parts by mass of acrylic acid, and 10 parts by mass of adipic acid were added, and then 3 parts by mass of triphenylphosphine was added. The temperature was raised to 110 ° C, and the acid value was confirmed to be 3 mgKOH/g or less to obtain a branched acrylic acrylate (A-5). The properties of the acrylic acrylate (A-5) are as follows.

重量平均分子量(Mw)：22,000、固體含量換算之源自丙烯酸的理論丙烯醯基當量：312g/eq。 Weight average molecular weight (Mw): 22,000, theoretical propylene oxime equivalent derived from acrylic acid in terms of solid content: 312 g/eq.

合成例6、比較合成例9 Synthesis Example 6 Comparative Synthesis Example 9

在合成例5中，除了將甲基丙烯酸環氧丙酯(GMA)、甲基丙烯酸甲酯(MMA)的使用量、及與所得到的前驅物反應之丙烯酸(AA)作成表1所記載者以外，係與合成例5同樣地進行，得到分枝狀丙烯酸丙烯酸酯樹脂(A-5)~(A-6)。比較用的分枝狀丙烯酸丙烯酸酯樹脂(A'-3)由於在110℃下保持1小時後產生凝膠化，因而停止反應。 In Synthesis Example 5, the amount of use of glycidyl methacrylate (GMA), methyl methacrylate (MMA), and acrylic acid (AA) reacted with the obtained precursor were as shown in Table 1. The same procedure as in Synthesis Example 5 was carried out to obtain branched acrylic acrylate resins (A-5) to (A-6). The branched acrylic acrylate resin (A'-3) for comparison was gelled after being kept at 110 ° C for 1 hour, and thus the reaction was stopped.

表1的附註： HDI：六亞甲二異氰酸酯 Notes to Table 1: HDI: hexamethylene diisocyanate

24A-100：ASAHI KASEI CHEMICALS股份有限公司製六亞甲二異氰酸酯的縮二脲體 24A-100: Biuret body of hexamethylene diisocyanate manufactured by ASAHI KASEI CHEMICALS Co., Ltd.

AdA：己二酸 AdA: adipic acid

SeA：癸二酸 SeA: azelaic acid

實施例1 Example 1

在前述合成例1中所得到的分枝狀丙烯酸丙烯酸酯樹脂(A-1)120質量份中加入DPHA(ARONIX M-404)40質量份、IRGACURE 184 4質量份，得到活性能量線硬化型樹脂組成物。 40 parts by mass of DPHA (ARONIX M-404) and 4 parts by mass of IRGACURE 184 were added to 120 parts by mass of the branched acrylic acrylate resin (A-1) obtained in the above Synthesis Example 1, to obtain an active energy ray-curable resin. Composition.

將此活性能量線硬化型樹脂組成物以乾燥膜厚成為18μ的方式塗布在PET薄膜上(東洋紡製75μA4300)，使用具備高壓水銀燈的照射機，以500mJ/cm2進行硬化，得到積層薄膜。 The active energy ray-curable resin composition was applied onto a PET film (75 μA 4300 manufactured by Toyobo Co., Ltd.) so as to have a dry film thickness of 18 μ, and was cured at 500 mJ/cm 2 using an irradiation machine equipped with a high-pressure mercury lamp to obtain a laminated film.

實施例2~9及比較例1 Examples 2 to 9 and Comparative Example 1

藉由與實施例1同樣地進行並以表2所記載的摻合量(質量基準)摻合各材料，來調製活性能量線硬化型樹脂組成物。還有，實施例8係進一步對硬化塗膜進行150℃、30分鐘的加熱處理。實施例9為摻合無機微粒子(D)而成者，其調製方法係進行使用濕式球磨機的分散。將結果示於表2。 The active energy ray-curable resin composition was prepared by blending each material in the same manner as in Example 1 and blending the amounts (mass basis) described in Table 2. Further, in Example 8, the cured coating film was further subjected to heat treatment at 150 ° C for 30 minutes. Example 9 is a method in which inorganic fine particles (D) were blended, and the preparation method was carried out by dispersion using a wet ball mill. The results are shown in Table 2.

前述使用濕式球磨機的分散的各條件係如下所述。 The above various conditions for dispersion using a wet ball mill are as follows.

介質：中位直徑100μm的氧化鋯珠 Medium: zirconia beads with a median diameter of 100 μm

樹脂組成物對磨機內容積的填充率：70體積% Filling ratio of the resin composition to the inner volume of the mill: 70% by volume

攪拌葉片尖端部的周速：11m/sec Peripheral speed of the tip end of the stirring blade: 11m/sec

樹脂組成物的流速：200ml/min Flow rate of resin composition: 200 ml/min

分散時間：60分鐘 Dispersion time: 60 minutes

還有，表2中的縮寫係如下所述。 Also, the abbreviations in Table 2 are as follows.

ARONIX M-404：東亞合成股份有限公司製二新戊四醇六丙烯酸酯/二新戊四醇五丙烯酸酯 ARONIX M-404: East New Synthetic Co., Ltd. dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate

AEROSIL R7200：NIPPON AEROSIL股份有限公司製「AEROSIL R7200」一次平均粒徑為12nm且在粒子表面具有(甲基)丙烯醯基之二氧化矽微粒子 AEROSIL R7200: "AEROSIL R7200" manufactured by NIPPON AEROSIL Co., Ltd. has a primary particle diameter of 12 nm and has (meth)acrylonitrile-based cerium oxide microparticles on the surface of the particle.

Claims (20)

一種活性能量線硬化型樹脂組成物，其特徵為含有：於側鏈具有(甲基)丙烯醯基的丙烯酸聚合物(a)透過該(甲基)丙烯醯基以外的官能基而連結複數個而成之重量平均分子量(Mw)在6,000~70,000的範圍之分枝狀丙烯酸丙烯酸酯樹脂(acrylic acrylate resin)(A)作為必要成分。 An active energy ray-curable resin composition comprising an acrylic polymer having a (meth) acrylonitrile group in a side chain (a) and a plurality of functional groups other than the (meth) acryl fluorenyl group A branched acrylic acrylate resin (A) having a weight average molecular weight (Mw) in the range of 6,000 to 70,000 is formed as an essential component. 如請求項1之活性能量線硬化型樹脂組成物，其中該分枝狀丙烯酸丙烯酸酯樹脂(A)的(甲基)丙烯醯基當量在200~700eq/g的範圍。 The active energy ray-curable resin composition of claim 1, wherein the (meth)acryl oxime equivalent of the branched acrylic acrylate resin (A) is in the range of 200 to 700 eq/g. 如請求項1或2之活性能量線硬化型樹脂組成物，其中該分枝狀丙烯酸丙烯酸酯樹脂(A)為使具有羥基與(甲基)丙烯醯基的重量平均分子量(Mw)在3,000~15,000的範圍之丙烯酸聚合物(a1)與於1分子中具有2個以上的異氰酸酯基之化合物(b1)反應而得者。 The active energy ray-curable resin composition according to claim 1 or 2, wherein the branched acrylic acrylate resin (A) has a weight average molecular weight (Mw) having a hydroxyl group and a (meth)acryl fluorenyl group at 3,000 Å. The acrylic polymer (a1) in the range of 15,000 is reacted with a compound (b1) having two or more isocyanate groups in one molecule. 如請求項3之活性能量線硬化型樹脂組成物，其中該分枝狀丙烯酸丙烯酸酯樹脂(A)為以該具有異氰酸酯基的化合物(b1)中的異氰酸酯基相對於該具有羥基與(甲基)丙烯醯基的重量平均分子量(Mw)在3,000~15,000的範圍之線型丙烯酸聚合物(a1)中的羥基1莫耳成為0.002~0.25莫耳的方式來使用而使其進行反應而成者。 The active energy ray-curable resin composition of claim 3, wherein the branched acrylic acrylate resin (A) is an isocyanate group in the compound (b1) having an isocyanate group with respect to the hydroxyl group and (methyl group) The weight average molecular weight (Mw) of the acrylonitrile group in the linear acrylic polymer (a1) in the range of 3,000 to 15,000 is used in such a manner that the hydroxyl group 1 molar is 0.002 to 0.25 mol. 如請求項3或4之活性能量線硬化型樹脂組成物，其中該於1分子中具有2個以上的異氰酸酯基之化合物(b1)為六亞甲二異氰酸酯、六亞甲二異氰酸酯的縮二脲體或六亞甲二異氰酸酯的三聚氰酸酯(nurate)體。 The active energy ray-curable resin composition of claim 3 or 4, wherein the compound (b1) having two or more isocyanate groups in one molecule is hexapethylene diisocyanate or hexamethylene diisocyanate biuret Or a nurate body of hexamethylene diisocyanate. 如請求項1或2之活性能量線硬化型樹脂組成物，其中該分枝狀丙烯酸丙烯酸酯樹脂(A)為使具有環氧丙基之重量平均分子量(Mw)在2,000~14,000的範圍之丙烯酸聚合物(a2)、於1分子中具有(甲基)丙烯醯基與羧基的化合物(b2)與於1分子中具有2個以上的羧基的化合物(b3)反應而得者。 The active energy ray-curable resin composition according to claim 1 or 2, wherein the branched acrylic acrylate resin (A) is acrylic acid having a weight average molecular weight (Mw) of a propylene group of from 2,000 to 14,000. The polymer (a2) and the compound (b2) having a (meth)acryloyl group and a carboxyl group in one molecule are reacted with a compound (b3) having two or more carboxyl groups in one molecule. 如請求項6之活性能量線硬化型樹脂組成物，其中該分枝狀丙烯酸丙烯酸酯樹脂(A)為以於1分子中具有(甲基)丙烯醯基與羧基的化合物(b2)中的羧基以及於1分子中具有2個以上的羧基的化合物(b3)中的羧基之合計莫耳數相對於具有環氧丙基、羥基與(甲基)丙烯醯基之重量平均分子量(Mw)在2,000~14,000的範圍之丙烯酸聚合物(a2)中的環氧丙基1莫耳成為0.9~1.2莫耳的方式來使用而使其進行反應而成者。 The active energy ray-curable resin composition of claim 6, wherein the branched acrylic acrylate resin (A) is a carboxyl group in the compound (b2) having a (meth) acrylonitrile group and a carboxyl group in one molecule. And the total number of moles of the carboxyl groups in the compound (b3) having two or more carboxyl groups in one molecule is 2,000 with respect to the weight average molecular weight (Mw) having a glycidyl group, a hydroxyl group and a (meth)acryl fluorenyl group. The epoxy propylene 1 mol in the acrylic polymer (a2) in the range of ~14,000 is used in a manner of 0.9 to 1.2 mol to cause it to react. 如請求項6或7之活性能量線硬化型樹脂組成物，其中該於1分子中具有(甲基)丙烯醯基與羧基的化合物(b2)為(甲基)丙烯酸。 The active energy ray-curable resin composition according to claim 6 or 7, wherein the compound (b2) having a (meth) acrylonitrile group and a carboxyl group in one molecule is (meth)acrylic acid. 如請求項6至8中任一項之活性能量線硬化型樹脂組成物，其中該於1分子中具有2個以上的羧基的化合物(b3)為己二酸、癸二酸或二聚酸。 The active energy ray-curable resin composition according to any one of claims 6 to 8, wherein the compound (b3) having two or more carboxyl groups in one molecule is adipic acid, sebacic acid or dimer acid. 如請求項1至9中任一項之活性能量線硬化型樹脂組成物，其進一步含有該分枝狀丙烯酸丙烯酸酯樹脂(A)以外的(甲基)丙烯酸酯(C)。 The active energy ray-curable resin composition according to any one of claims 1 to 9, which further comprises a (meth) acrylate (C) other than the branched acrylic acrylate resin (A). 如請求項10之活性能量線硬化型樹脂組成物，其中該(甲基)丙烯酸酯(C)為於1分子中具有3個以上的(甲基) 丙烯醯基之多官能(甲基)丙烯酸酯。 The active energy ray-curable resin composition of claim 10, wherein the (meth) acrylate (C) has three or more (meth) groups in one molecule. A polyfunctional (meth) acrylate of acrylonitrile. 如請求項10之活性能量線硬化型樹脂組成物，其中該(甲基)丙烯酸酯(C)具有羥基。 The active energy ray-curable resin composition of claim 10, wherein the (meth) acrylate (C) has a hydroxyl group. 如請求項10之活性能量線硬化型樹脂組成物，其中該(甲基)丙烯酸酯(C)為二新戊四醇六丙烯酸酯、二新戊四醇五丙烯酸酯、二新戊四醇四丙烯酸酯、新戊四醇四丙烯酸酯、新戊四醇三丙烯酸酯或新戊四醇二丙烯酸酯。 The active energy ray-curable resin composition of claim 10, wherein the (meth) acrylate (C) is dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol IV Acrylate, neopentyl alcohol tetraacrylate, neopentyl alcohol triacrylate or neopentyl alcohol diacrylate. 如請求項1至13中任一項之活性能量線硬化型樹脂組成物，其進一步含有無機微粒子(D)。 The active energy ray-curable resin composition according to any one of claims 1 to 13, which further contains inorganic fine particles (D). 如請求項14之活性能量線硬化型樹脂組成物，其中該無機微粒子(D)為乾式二氧化矽。 The active energy ray-curable resin composition of claim 14, wherein the inorganic fine particles (D) are dry cerium oxide. 一種塗料，其特徵為包含如請求項1至15中任一項之活性能量線硬化型樹脂組成物。 A coating comprising the active energy ray-curable resin composition according to any one of claims 1 to 15. 一種塗膜，其特徵在於其係使如請求項16之塗料硬化而成。 A coating film characterized in that it is obtained by hardening a coating material as claimed in claim 16. 如請求項17之塗膜，其中該硬化包含60℃以上的加熱處理步驟。 The coating film of claim 17, wherein the hardening comprises a heat treatment step of 60 ° C or higher. 一種積層薄膜，其特徵為在塑膠薄膜的一面或兩面具有如請求項17或18之塗膜。 A laminated film characterized by having a coating film as claimed in claim 17 or 18 on one or both sides of a plastic film. 如請求項19之積層薄膜，其中該塗膜的膜厚在1~100μm的範圍。 The laminated film according to claim 19, wherein the film thickness of the coating film is in the range of 1 to 100 μm.
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