TWI681028B - Active energy ray hardening type adhesive composition for plastic film or sheet - Google Patents

Active energy ray hardening type adhesive composition for plastic film or sheet Download PDF

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TWI681028B
TWI681028B TW105106456A TW105106456A TWI681028B TW I681028 B TWI681028 B TW I681028B TW 105106456 A TW105106456 A TW 105106456A TW 105106456 A TW105106456 A TW 105106456A TW I681028 B TWI681028 B TW I681028B
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energy ray
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TW201638282A (en
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稻田和正
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日商東亞合成股份有限公司
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    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本發明提供一種低黏度且硬化性優異，不論塗佈、硬化時之環境濕度高低，對含有聚甲基丙烯酸甲酯等丙烯酸系樹脂、乙酸纖維素系樹脂、及環烯烴聚合物之各種塑膠薄膜等之接著力優異，且無色透明性亦優異之塑膠薄膜等用活性能量射線硬化型接著劑組成物。 The invention provides a low viscosity and excellent curability, regardless of the environmental humidity during coating and curing, for various plastic films containing acrylic resins such as polymethyl methacrylate, cellulose acetate resins, and cycloolefin polymers Active energy ray-curable adhesive composition for plastic films, etc. with excellent adhesion and colorless transparency.

具體而言，本發明之塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物含有： Specifically, the active energy ray hardening type adhesive composition for plastic films or sheets of the present invention contains:

(A)成分：1分子中具有2個以上之烴環構造及2個以上之縮水甘油醚基或縮水甘油酯基之化合物 (A) Component: a compound having two or more hydrocarbon ring structures and two or more glycidyl ether groups or glycidyl ester groups in one molecule

(B)成分：具有碳數2~10個之多元醇之聚縮水甘油醚 (B) Component: Polyglycidyl ether with a polyhydric alcohol having 2 to 10 carbon atoms

(C)成分：1分子中具有2個以上之氧雜環丁烷基之分子量500以下之化合物 (C) Component: a compound with a molecular weight of 500 or less having 2 or more oxetane groups in 1 molecule

(D)成分：光陽離子聚合起始劑 (D) Component: photo-cationic polymerization initiator

(E)成分：(E1)玻璃轉移溫度20℃以下且重量平均分子量20,000~1,000,000之聚合體、及/或(E2)玻璃轉移溫度20℃以下之具有嵌段單位之重量平均分子量20,000~1,000,000之嵌段共聚合體，且上述(A)~(E)成分之含有比例於組成物整體中， (E) Component: (E1) a polymer having a glass transition temperature of 20°C or lower and a weight average molecular weight of 20,000 to 1,000,000, and/or (E2) a glass transition temperature of 20°C or lower having a block unit weight average molecular weight of 20,000 to 1,000,000 Block copolymer, and the content ratio of the components (A) to (E) in the whole composition,

(A)成分：1~30重量% (A) Ingredient: 1~30% by weight

(B)成分：10~70重量% (B) Ingredient: 10~70% by weight

(C)成分：10~70重量% (C) Ingredient: 10~70% by weight

(D)成分：0.5~10重量% (D) Ingredient: 0.5~10% by weight

(E)成分：1~20重量%。 (E) Ingredients: 1-20% by weight.

Description

塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物 Active energy ray hardening type adhesive composition for plastic film or sheet

本發明係關於一種能夠藉由紫外線、可見光、或電子束等活性能量射線之照射而將各種塑膠製薄膜或片材接著之活性能量射線硬化型接著劑組成物，進而，適宜地使用於液晶顯示器或有機電致發光(EL，Electroluminescence)顯示器等所使用之各種光學薄膜或片材之製造，且能夠較佳用於該等技術領域。再者，於本說明書中，將丙烯酸酯及/或甲基丙烯酸酯表示為(甲基)丙烯酸酯，將丙烯醯基及/或甲基丙烯醯基表示為(甲基)丙烯醯基，將丙烯酸及/或甲基丙烯酸表示為(甲基)丙烯酸。又，以下，在無需特別明示之情形時，將塑膠製薄膜或片材統一表示為「塑膠薄膜等」，將薄膜或片材統一表示為「薄膜等」。 The present invention relates to an active energy ray hardening type adhesive composition capable of bonding various plastic films or sheets by irradiation of active energy rays such as ultraviolet rays, visible light, or electron beams, and is further suitably used in liquid crystal displays Or the manufacture of various optical films or sheets used in organic electroluminescence (EL, Electroluminescence) displays, etc., and can be preferably used in these technical fields. In addition, in this specification, acrylate and/or methacrylate are represented as (meth)acrylate, and acryl and/or methacryl are represented as (meth)acryl, and Acrylic acid and/or methacrylic acid are represented as (meth)acrylic acid. In addition, in the following, when there is no need to express clearly, the plastic film or sheet is collectively referred to as "plastic film, etc.", and the film or sheet is collectively referred to as "film, etc.".

習知，於使塑膠薄膜等薄層被接著體彼此、或塑膠薄膜等薄層被接著體與包含其及其他素材之薄層被接著體貼合之層壓法中，主要進行乾式層壓法，其係將含有乙烯-乙酸乙烯酯共聚合體或聚胺基甲酸酯系聚合體之溶劑型接著劑組成物塗佈於第1薄層被接著體並使之乾燥後，藉由軋輥等將第2薄層被接著體壓合於其上。該方法中所使用之接著劑組成物通常係含有大量溶劑以使組成物之塗佈量均勻者，因此，乾燥時大量之溶劑蒸氣會揮散，毒性、作業安全性及環境污染性成為問題。業界一直研究無溶劑系接著劑 組成物作為解決該等問題之接著劑組成物。 Conventionally, in the lamination method in which thin-film adherends such as plastic films are adhered to each other, or thin-film adherends such as plastic films and thin-layer adherends containing the same and other materials, the dry lamination method is mainly performed. This is to apply a solvent-based adhesive composition containing an ethylene-vinyl acetate copolymer or a polyurethane-based polymer to the first thin-layer adherend and dry it. 2 The thin layer is pressed onto it by the bonding body. The adhesive composition used in this method usually contains a large amount of solvent to make the coating amount of the composition uniform. Therefore, a large amount of solvent vapor will evaporate during drying, and the toxicity, operation safety, and environmental pollution become problems. The industry has been studying solvent-free adhesives The composition serves as an adhesive composition for solving such problems.

作為無溶劑系接著劑組成物，廣泛使用2液型接著劑組成物及藉由紫外線或電子束等活性能量射線而硬化之接著劑組成物。作為2液型接著劑組成物，主要使用將末端具有羥基之聚合物作為主劑，將末端具有異氰酸酯基之聚異氰酸酯化合物作為硬化劑之所謂聚胺基甲酸酯系接著劑組成物。然而，該組成物存在硬化需要長時間之缺點。相對於此，活性能量射線硬化型接著劑組成物因硬化速度較快而生產性優異，因此近年來被使用之情況不斷增加。 As a solventless adhesive composition, a two-component adhesive composition and an adhesive composition hardened by active energy rays such as ultraviolet rays or electron beams are widely used. As a two-component type adhesive composition, a so-called polyurethane adhesive composition mainly using a polymer having a hydroxyl group at the terminal as a main agent and a polyisocyanate compound having an isocyanate group at the terminal as a hardener is used. However, this composition has a disadvantage that it takes a long time to harden. On the other hand, since the active energy ray hardening type adhesive composition has a fast curing speed and is excellent in productivity, it has been increasingly used in recent years.

另一方面，液晶顯示器因薄型、輕量及低耗電等特點，而被廣泛使用於行動電話、智慧型手機、及平板等移動設備。又，亦普及於電腦、電視、汽車導航系統之各種顯示器。又，有機EL顯示器亦以移動設備為中心而被使用之情況不斷增加。活性能量射線硬化型接著劑亦被廣泛使用於液晶顯示器或有機EL顯示器所使用之各種光學薄膜等之貼合。 On the other hand, liquid crystal displays are widely used in mobile devices such as mobile phones, smart phones, and tablets due to their thinness, light weight, and low power consumption. Moreover, it is also popularized in various displays of computers, televisions, and car navigation systems. In addition, the use of organic EL displays is also increasing around mobile devices. Active energy ray-curable adhesives are also widely used for laminating various optical films used in liquid crystal displays or organic EL displays.

作為光學薄膜等，可列舉：賦予防指紋或防眩等功能性之硬塗薄膜、觸控面板之前面板、偏光板、相位差薄膜、視角補償薄膜、增亮薄膜、抗反射薄膜、防眩薄膜、透鏡片材及擴散片材等，並針對該等使用各種塑膠。 Examples of optical films include hard-coated films that provide anti-fingerprint or anti-glare functions, touch panel front panels, polarizing plates, retardation films, viewing angle compensation films, brightness enhancement films, anti-reflection films, and anti-glare films , Lens sheets and diffused sheets, etc., and use a variety of plastics for these.

於該等塑膠中，聚甲基丙烯酸甲酯等(甲基)丙烯酸系樹脂、三乙酸纖維素等乙酸纖維素系樹脂、或環烯烴聚合物由於無色透明性或光學等向性等光學特性尤其優異，故而被廣泛使用。 Among these plastics, (meth)acrylic resins such as polymethyl methacrylate, cellulose acetate resins such as cellulose triacetate, or cycloolefin polymers are particularly colorless, transparent, or optically isotropic. Excellent, so it is widely used.

最近，因靜電容量方式之觸控面板之普及，許多行動電話替換為智慧型手機，或不斷推廣平板等新製品。又，因有機 EL之性能提高，而不斷發展有機EL顯示器。如此，移動設備之顯示器現今亦持續進步，此時，有改變光學薄膜等之構成之情況。此時，存在迫於接著表面特性完全不同之塑膠材料之必要性的情況。例如，(甲基)丙烯酸系樹脂、乙酸纖維素系樹脂、及環烯烴聚合物為廣泛使用於光學用途之塑膠材料，該等之接著性完全不同。業界要求一種即便為此種異種材料亦能夠強力地接著，並且硬化後不產生黃變或渾濁之透明性亦優異之活性能量射線硬化型接著劑。又，針對接著劑要求耐濕熱試驗後之接著力下降較小。 Recently, due to the popularity of electrostatic capacitance touch panels, many mobile phones have been replaced with smart phones, or new products such as tablets have been continuously promoted. Also, due to organic The performance of EL is improved, and organic EL displays are constantly being developed. As such, the display of mobile devices continues to progress today, and at this time, there are cases where the composition of optical films and the like is changed. At this time, there may be cases where it is necessary to adhere to plastic materials having completely different surface characteristics. For example, (meth)acrylic resins, cellulose acetate resins, and cycloolefin polymers are widely used plastic materials for optical applications, and their adhesiveness is completely different. The industry requires an active energy ray hardening type adhesive that can be strongly adhered even if it is such a heterogeneous material, and has excellent transparency without yellowing or turbidity after curing. In addition, the adhesive requires a small decrease in adhesion after a humid heat resistance test.

進而，於移動設備中，薄型、輕量化為重要之課題，因此要求接著劑之厚度亦變薄。為了較薄地塗佈接著劑，接著劑組成物之低黏度化變得重要。然而，若欲使無溶劑之活性能量射線硬化型接著劑低黏度化，則(甲基)丙烯酸酯系活性能量射線硬化型接著劑中所通常使用之(甲基)丙烯酸胺基甲酸酯因其黏度較高而難以使用。因此，(甲基)丙烯酸酯系接著劑難以同時實現低黏度化與較強之接著力。 Furthermore, in mobile devices, thinness and weight reduction are important issues, so the thickness of the adhesive is also required to be thin. In order to apply the adhesive thinly, it is important to reduce the viscosity of the adhesive composition. However, to reduce the viscosity of solvent-free active energy ray-curable adhesives, (meth)acrylate-based active energy ray-curable adhesives are usually Its viscosity is high and difficult to use. Therefore, it is difficult for the (meth)acrylate adhesive to achieve both low viscosity and strong adhesion.

又，於被接著體之至少一者為薄膜之情形時，大多要求較強之剝離接著力，為了增強該剝離接著力，有效的是使接著劑硬化物之動態黏彈性測定之tanδ變大、及使接著劑之厚度變厚(非專利文獻1)。換言之，將接著劑之膜厚設為3μm以下而增強剝離接著力較為困難。 In addition, when at least one of the adherends is a thin film, a strong peeling adhesive force is often required. In order to enhance the peeling adhesive force, it is effective to increase the tan δ of the dynamic viscoelasticity measurement of the adhesive hardened product. And thickening the thickness of the adhesive (Non-Patent Document 1). In other words, it is difficult to increase the peeling adhesive force by setting the thickness of the adhesive to 3 μm or less.

然而，揭示有將多官能之脂肪族環氧單體作為主成分，且包含脂環式環氧單體及/或氧雜環丁烷單體之光陽離子硬化型接著劑，即便接著劑之厚度較薄，對環烯烴聚合物或三乙酸纖維素等塑膠材料之接著力亦優異(專利文獻1)。 However, a photo-cationic hardening type adhesive that uses a multifunctional aliphatic epoxy monomer as a main component and includes an alicyclic epoxy monomer and/or an oxetane monomer is disclosed, even if the thickness of the adhesive It is thinner and has excellent adhesion to plastic materials such as cycloolefin polymer and cellulose triacetate (Patent Document 1).

然而，專利文獻1所揭示之組成物存在陽離子硬化性較差，硬化所需之能量較大之問題。因此，需要使接著步驟之線速變慢，或增加光源之數量。因此，就生產性之觀點而言，期望硬化性亦優異之活性能量射線硬化型接著劑，具體而言，期望一種即便利用UV-B(310nm附近)以200mJ/cm2以下之照射量亦展現充分之接著力之活性能量射線硬化型接著劑。進而，根據本發明者之研究結果，專利文獻1所揭示之組成物為具有以下之問題者。即，存在對聚甲基丙烯酸甲酯及(甲基)丙烯酸烷基酯聚合物等(甲基)丙烯酸系樹脂之接著力不充分之問題。此外，存在若塗佈、硬化接著劑時之環境濕度較高，則接著力大幅下降之問題。 However, the composition disclosed in Patent Document 1 has a problem that the cationic curing property is poor and the energy required for curing is large. Therefore, it is necessary to slow down the line speed of the subsequent steps or increase the number of light sources. Therefore, from the viewpoint of productivity, an active energy ray-curable adhesive with excellent curability is desired, and specifically, a UV-B (near 310 nm) irradiation dose of 200 mJ/cm 2 or less is desired. Active energy ray hardening adhesive with sufficient adhesion. Furthermore, according to the research results of the inventors, the composition disclosed in Patent Document 1 has the following problems. That is, there is a problem of insufficient adhesion to (meth)acrylic resins such as polymethyl methacrylate and alkyl (meth)acrylate polymers. In addition, there is a problem that if the environmental humidity at the time of applying and curing the adhesive is high, the adhesive force greatly decreases.

[先前技術文獻] [Prior Technical Literature] [非專利文獻] [Non-patent literature]

[非專利文獻1]三刀基鄉，接著，47卷，8號，12~15頁(2003年) [Non-Patent Document 1] Sandaoji Township, then, Volume 47, No. 8, pages 12-15 (2003)

[專利文獻] [Patent Literature]

[專利文獻1]日本專利特開2008-63397號公報(申請專利範圍) [Patent Document 1] Japanese Patent Laid-Open No. 2008-63397 (Patent Application Range)

本發明係鑒於上述問題而成者，其目的在於提供一種低黏度且硬化性優異，不論塗佈、硬化時之環境濕度高低，對包含聚甲基丙烯酸甲酯等丙烯酸系樹脂、乙酸纖維素系樹脂、及環烯烴聚合物之各種塑膠薄膜等之接著力優異，且無色透明性亦優異之塑 膠薄膜等用活性能量射線硬化型接著劑組成物。進而，其目的在於提供一種耐濕熱試驗後之接著力下降較小之接著劑組成物。 The present invention was made in view of the above-mentioned problems, and its object is to provide a low viscosity and excellent curability, regardless of the environmental humidity at the time of coating and curing, for acrylic resins such as polymethyl methacrylate and cellulose acetate Plastics such as resins and cycloolefin polymers have excellent adhesion and colorless transparency. Adhesive composition hardened with active energy rays for adhesive films, etc. Furthermore, the object is to provide an adhesive composition having a small decrease in adhesive strength after a humid heat resistance test.

本發明者等人根據各種研究之結果發現：分別以特定之比例含有(A)1分子中具有2個以上之烴環構造及2個以上之縮水甘油醚基或縮水甘油酯基之環氧樹脂、(B)具有碳數2~10個之多元醇之聚縮水甘油醚、(C)1分子中具有2個以上之氧雜環丁烷基之分子量500以下之化合物、(D)光陽離子聚合起始劑、及(E)玻璃轉移溫度(Tg)20℃以下之聚合體(嵌段共聚合體之情形時為Tg20℃以下之具有嵌段者)的活性能量射線硬化型接著劑組成物可解決上述課題，從而完成本發明。 Based on the results of various studies, the inventors found that: (A) 1 molecule containing two or more hydrocarbon ring structures and two or more glycidyl ether groups or glycidyl ester groups in an epoxy resin in a specific ratio. , (B) Polyglycidyl ether with a polyhydric alcohol having 2 to 10 carbon atoms, (C) A compound having a molecular weight of 500 or less with 2 or more oxetanyl groups in 1 molecule, (D) Photocationic polymerization The active energy ray-curable adhesive composition of the initiator and (E) a polymer with a glass transition temperature (Tg) of 20°C or lower (in the case of a block copolymer) having a Tg of 20°C or lower can be solved The above problems complete the present invention.

本發明係關於一種塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物，其含有： The present invention relates to an active energy ray hardening type adhesive composition for plastic films or sheets, which contains:

(A)成分：1分子中具有2個以上之烴環構造及2個以上之縮水甘油醚基或縮水甘油酯基之化合物 (A) Component: a compound having two or more hydrocarbon ring structures and two or more glycidyl ether groups or glycidyl ester groups in one molecule

(B)成分：具有碳數2~10個多元醇之聚縮水甘油醚 (B) Component: Polyglycidyl ether with 2 to 10 polyalcohols

(C)成分：1分子中具有2個以上之氧雜環丁烷基之分子量500以下之化合物 (C) Component: a compound with a molecular weight of 500 or less having 2 or more oxetane groups in 1 molecule

(D)成分：光陽離子聚合起始劑 (D) Component: photo-cationic polymerization initiator

(E)成分：(E1)玻璃轉移溫度(以下，稱為「Tg」)20℃以下且重量平均分子量20,000~1,000,000之聚合體、及/或(E2)Tg20℃以下之具有嵌段單位之重量平均分子量20,000~1,000,000的嵌段共聚合體，且上述(A)~(E)成分之含有比例於組成物整體中， (E) Component: (E1) Glass transition temperature (hereinafter referred to as "Tg") polymer below 20°C and weight average molecular weight of 20,000 to 1,000,000, and/or (E2) weight with block unit below Tg20°C Block copolymers with an average molecular weight of 20,000 to 1,000,000, and the content ratio of the components (A) to (E) in the entire composition,

(A)成分：1~30重量% (A) Ingredient: 1~30% by weight

(B)成分：10~70重量% (B) Ingredient: 10~70% by weight

(C)成分：10~70重量% (C) Ingredient: 10~70% by weight

(D)成分：0.5~10重量% (D) Ingredient: 0.5~10% by weight

(E)成分：1~20重量%。 (E) Ingredients: 1-20% by weight.

作為(A)成分，較佳為下述2種化合物。 As the component (A), the following two compounds are preferred.

(A1)成分：1分子中具有2個以上之芳香環及2個以上之縮水甘油醚基或縮水甘油酯基的芳香族環氧樹脂、及/或上述芳香族環氧樹脂之氫化型環氧樹脂 (A1) Component: an aromatic epoxy resin having two or more aromatic rings and two or more glycidyl ether groups or glycidyl ester groups in one molecule, and/or a hydrogenated epoxy resin of the above aromatic epoxy resin Resin

(A2)成分：以含有烴環構造之自由基聚合性單體及含有縮水甘油基之自由基聚合性單體作為必需構成單體之重量平均分子量1,000~1,000,000之聚合體 (A2) Component: a polymer having a weight-average molecular weight of 1,000 to 1,000,000, which has a radical polymerizable monomer containing a hydrocarbon ring structure and a radical polymerizable monomer containing a glycidyl group, as essential constituent monomers

作為(B)成分，較佳為具有碳數2~6個之二醇之二縮水甘油醚，更佳為具有碳數4~6個之烷二醇之二縮水甘油醚。作為(C)成分，較佳為下述式(1)所表示之氧雜環丁烷化合物。 The component (B) is preferably a diglycidyl ether having a diol having 2 to 6 carbon atoms, and more preferably a diglycidyl ether having an alkylene glycol having 4 to 6 carbon atoms. The component (C) is preferably an oxetane compound represented by the following formula (1).

Figure 105106456-A0101-12-0006-1
Figure 105106456-A0101-12-0006-1

作為(D)成分，較佳為鋶鹽系光陽離子聚合起始劑。作為(E)成分，較佳為以丙烯酸烷基酯作為必需構成單體之重量平均分子量20,000~500,000之聚合體。 The component (D) is preferably a cerium salt-based photocationic polymerization initiator. The component (E) is preferably a polymer having a weight-average molecular weight of 20,000 to 500,000 using alkyl acrylate as an essential constituent monomer.

作為(A)~(D)成分之含有比例，較佳為於組成物整體中含有1~20重量%之(A)成分、25~65重量%之(B)成分、20~60重量%之(C)成分、1~5重量%之(D)成分、及3~15重量%之(E)成 分。進而，較佳為於組成物整體中含有0.05~3重量%之水。又，較佳為塑膠製薄膜或片材之至少一者為(甲基)丙烯酸系樹脂、乙酸纖維素系樹脂或環烯烴聚合物。 As the content ratio of the components (A) to (D), it is preferable to contain 1 to 20% by weight of the (A) component, 25 to 65% by weight of the (B) component, and 20 to 60% by weight of the entire composition (C) component, 1 to 5 wt% (D) component, and 3 to 15 wt% (E) component Minute. Furthermore, it is preferable to contain 0.05 to 3% by weight of water in the entire composition. Furthermore, it is preferable that at least one of the plastic film or sheet is (meth)acrylic resin, cellulose acetate resin or cycloolefin polymer.

又，本發明係關於一種積層體，其係由基材、上述塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物之硬化物、及其他基材所構成者，其中，上述基材及上述其他基材之兩者或一者為塑膠製薄膜或片材。作為塑膠製薄膜或片材，較佳為其至少一者為(甲基)丙烯酸系樹脂、乙酸纖維素系樹脂或環烯烴聚合物。 Furthermore, the present invention relates to a layered product comprising a substrate, a cured product of the above-mentioned plastic film or active energy ray-curable adhesive composition for sheets, and other substrates, wherein the substrate Two or one of the other substrates mentioned above are plastic films or sheets. As the plastic film or sheet, at least one of them is preferably (meth)acrylic resin, cellulose acetate resin or cycloolefin polymer.

又，本發明係關於一種積層體之製造方法，其係將上述組成物塗佈於基材，將其他基材貼合於塗佈面，並自上述基材或上述其他基材之任一側照射活性能量射線，其中，上述基材及上述其他基材之兩者或一者為塑膠製薄膜或片材。 In addition, the present invention relates to a method for manufacturing a laminate, which is to apply the above composition to a substrate, attach another substrate to the coated surface, and from either side of the substrate or the other substrate Active energy rays are irradiated, wherein either or both of the above substrate and the other substrate are plastic films or sheets.

根據本發明，可提供一種低黏度且硬化性亦優異，不論塗佈、硬化時之環境濕度高低，對聚甲基丙烯酸甲酯等(甲基)丙烯酸系樹脂、乙酸纖維素、及環烯烴聚合物等各種塑膠薄膜等之接著力優異、且無色透明性亦優異之活性能量射線硬化型接著劑組成物。因此，可適宜地使用於液晶顯示器或有機EL顯示器等所使用之各種光學薄膜等之製造。又，對於除顯示器以外之用途例如窗或建材等、抑或對要求低黏度、硬化性、接著力、及透明性之各種用途均可適宜地使用。 According to the present invention, it is possible to provide a polymer with low viscosity and excellent curability, regardless of the environmental humidity during coating and curing, for the polymerization of (meth)acrylic resins such as polymethyl methacrylate, cellulose acetate, and cycloolefins It is an active energy ray-curable adhesive composition with excellent adhesion of various plastic films, etc., and colorless transparency. Therefore, it can be suitably used for the production of various optical films used in liquid crystal displays, organic EL displays, and the like. In addition, it can be suitably used for applications other than displays, such as windows and building materials, or for various applications requiring low viscosity, curability, adhesion, and transparency.

本發明係關於一種塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物，其含有： The present invention relates to an active energy ray hardening type adhesive composition for plastic films or sheets, which contains:

(A)成分：1分子中具有2個以上之烴環構造及2個以上之縮水甘油醚基或縮水甘油酯基之化合物 (A) Component: a compound having two or more hydrocarbon ring structures and two or more glycidyl ether groups or glycidyl ester groups in one molecule

(B)成分：具有碳數2~10個之多元醇之聚縮水甘油醚 (B) Component: Polyglycidyl ether with a polyhydric alcohol having 2 to 10 carbon atoms

(C)成分：1分子中具有2個以上之氧雜環丁烷基之分子量500以下之化合物 (C) Component: a compound with a molecular weight of 500 or less having 2 or more oxetane groups in 1 molecule

(D)成分：光陽離子聚合起始劑 (D) Component: photo-cationic polymerization initiator

(E)成分：(E1)Tg20℃以下且重量平均分子量20,000~1,000,000之聚合體、及/或(E2)Tg20℃以下之具有嵌段單位之重量平均分子量20,000~1,000,000之嵌段共聚合體，且上述(A)~(E)成分之含有比例於組成物整體中， (E) Component: (E1) a polymer having a Tg of 20°C or lower and a weight average molecular weight of 20,000 to 1,000,000, and/or (E2) a block copolymer having a Tg of 20 or less and a block unit weight average molecular weight of 20,000 to 1,000,000, and The content ratio of the components (A) to (E) in the entire composition,

(A)成分：1~30重量% (A) Ingredient: 1~30% by weight

(B)成分：10~70重量% (B) Ingredient: 10~70% by weight

(C)成分：10~70重量% (C) Ingredient: 10~70% by weight

(D)成分：0.5~10重量% (D) Ingredient: 0.5~10% by weight

(E)成分：1~20重量%。以下，對(A)~(E)成分、其他成分、及本發明之組成物之較佳使用方法進行詳細說明。 (E) Ingredients: 1-20% by weight. Hereinafter, (A) to (E) components, other components, and preferred methods of using the composition of the present invention will be described in detail.

1.(A)成分 1. (A) Ingredients

(A)成分為1分子中具有2個以上之烴環構造及2個以上之縮水甘油醚基或縮水甘油酯基之化合物。(A)成分中之2個以上之烴環構造、及2個以上之縮水甘油醚基或縮水甘油酯基具有強化組成物對塑膠基材之接著力之效果。尤其是對乙酸纖維素系基材，藉由 與下述(E)成分之協同效應而強化接著力。作為(A)成分，具有縮水甘油醚基之化合物與具有縮水甘油酯基之化合物相比，組成物之硬化性優異，故而較佳。作為(A)成分中之烴環構造，可列舉芳香族烴環及脂肪族烴環。作為芳香族烴環之較佳例，可列舉苯環及萘環等，作為脂肪族烴環之較佳例，可列舉環己基環及異

Figure 105106456-A0101-12-0009-6
基環等。作為烴環構造，該等之中，尤佳為苯環。 The component (A) is a compound having two or more hydrocarbon ring structures and two or more glycidyl ether groups or glycidyl ester groups in one molecule. (A) Two or more hydrocarbon ring structures in the component and two or more glycidyl ether groups or glycidyl ester groups have the effect of enhancing the adhesion of the composition to the plastic substrate. Especially for the cellulose acetate-based substrate, the synergistic effect with the following (E) component enhances the adhesion. As the component (A), a compound having a glycidyl ether group is preferable to a compound having a glycidyl ester group because the composition has excellent curability. Examples of the hydrocarbon ring structure in the component (A) include aromatic hydrocarbon rings and aliphatic hydrocarbon rings. Preferred examples of aromatic hydrocarbon rings include benzene ring and naphthalene ring, and preferred examples of aliphatic hydrocarbon rings include cyclohexyl ring and isocyanate ring.
Figure 105106456-A0101-12-0009-6
Base ring, etc. As a hydrocarbon ring structure, among these, a benzene ring is particularly preferable.

作為(A)成分，只要為1分子中具有2個以上之烴環構造及2個以上之縮水甘油醚基或縮水甘油酯基之化合物，則低分子量之化合物及高分子量之化合物均可使用。 As the component (A), as long as it is a compound having two or more hydrocarbon ring structures and two or more glycidyl ether groups or glycidyl ester groups in one molecule, both low molecular weight compounds and high molecular weight compounds can be used.

作為(A)成分，較佳為下述2種化合物。 As the component (A), the following two compounds are preferred.

(A1)成分：1分子中具有2個以上之芳香環及2個以上之縮水甘油醚基或縮水甘油酯基之芳香族環氧樹脂、及/或上述芳香族環氧樹脂之氫化型環氧樹脂 (A1) Component: an aromatic epoxy resin having two or more aromatic rings and two or more glycidyl ether groups or glycidyl ester groups in one molecule, and/or a hydrogenated epoxy resin of the above aromatic epoxy resin Resin

(A2)成分：以含有烴環構造之自由基聚合性單體及含有縮水甘油基之自由基聚合性單體作為必需構成單體之重量平均分子量1,000~1,000,000之聚合體 (A2) Component: a polymer having a weight-average molecular weight of 1,000 to 1,000,000, which has a radical polymerizable monomer containing a hydrocarbon ring structure and a radical polymerizable monomer containing a glycidyl group, as essential constituent monomers

以下，對(A1)及(A2)成分之各者進行說明。 Hereinafter, each of the components (A1) and (A2) will be described.

1-1.(A1)成分 1-1. (A1) Ingredients

(A1)成分為1分子中具有2個以上之芳香環及2個以上之縮水甘油醚基或縮水甘油酯基之芳香族環氧樹脂、及/或上述芳香族環氧樹脂之氫化型環氧樹脂。此處，環氧樹脂係即便為低分子量之化合物亦被慣用地稱為「環氧樹脂」之化合物。作為(A1)成分，具有縮水甘油醚基之化合物與具有縮水甘油酯基之化合物相比，組成物之硬 化性優異，故而較佳。 (A1) The component is an aromatic epoxy resin having two or more aromatic rings and two or more glycidyl ether groups or glycidyl ester groups in one molecule, and/or a hydrogenated epoxy resin of the above aromatic epoxy resin Resin. Here, the epoxy resin is a compound commonly referred to as "epoxy resin" even if it is a low molecular weight compound. As the component (A1), the compound having a glycidyl ether group is harder than the compound having a glycidyl ester group. It has excellent chemical properties and is therefore preferred.

作為(A1)成分之具體例，可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、使雙酚A與雙酚F及表氯醇縮聚合而成之環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、雙酚F酚醛清漆型環氧樹脂、聯苯型環氧樹脂、氫化雙酚A型環氧樹脂、氫化雙酚F型環氧樹脂等。作為(A1)成分，低分子量體及高分子量體均可使用。 Specific examples of the component (A1) include bisphenol A epoxy resins, bisphenol F epoxy resins, epoxy resins and phenols obtained by polycondensation of bisphenol A with bisphenol F and epichlorohydrin. Novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, biphenyl epoxy resin, hydrogenated bisphenol A epoxy resin Resin, hydrogenated bisphenol F type epoxy resin, etc. As the component (A1), both low molecular weight bodies and high molecular weight bodies can be used.

作為(A1)成分，可單獨使用上述化合物、或使用兩種以上。 As the component (A1), the above compounds may be used alone, or two or more kinds may be used.

1-2.(A2)成分 1-2. (A2) Ingredients

(A2)成分係以含有烴環構造之自由基聚合性單體(以下，稱為「單體(a2-1)」)及含有縮水甘油基之自由基聚合性單體(以下，稱為「單體(a2-2)」)作為必需構成單體之重量平均分子量(以下，稱為「Mw」)1,000~1,000,000的聚合體。藉由將(A2)成分之Mw設為1,000以上，可提高組成物對塑膠基材、尤其是對乙酸纖維素系基材之接著力。另一方面，藉由將Mw設為1,000,000以下，可防止組成物之拉絲等，使塗佈性良好。(A2)成分之更佳Mw為1,000~100,000，進而較佳為2,000~50,000，特佳為3,000~20,000。再者，於本發明中，Mw意指對藉由凝膠滲透層析法(GPC，Gel Permeation Chromatography)測得之分子量進行聚苯乙烯換算而得之值。 (A2) The component is a radical polymerizable monomer containing a hydrocarbon ring structure (hereinafter, referred to as "monomer (a2-1)") and a radical polymerizable monomer containing a glycidyl group (hereinafter, referred to as " The monomer (a2-2)") is a polymer having a weight-average molecular weight (hereinafter, referred to as "Mw") of 1,000 to 1,000,000, which must constitute the monomer. By setting the Mw of the (A2) component to 1,000 or more, the adhesion of the composition to the plastic substrate, especially to the cellulose acetate-based substrate, can be improved. On the other hand, by setting Mw to 1,000,000 or less, it is possible to prevent drawing of the composition and the like, and to improve the applicability. (A2) The Mw of the component is more preferably 1,000 to 100,000, further preferably 2,000 to 50,000, and particularly preferably 3,000 to 20,000. In addition, in the present invention, Mw means a value obtained by converting polystyrene to the molecular weight measured by gel permeation chromatography (GPC, Gel Permeation Chromatography).

作為單體(a2-1)之具體例，可列舉：苯乙烯、α-甲基苯乙烯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸異

Figure 105106456-A0101-12-0010-7
基酯等。又，作為單體(a2-2)之具體例， 可列舉(甲基)丙烯酸縮水甘油酯。 Specific examples of the monomer (a2-1) include styrene, α-methylstyrene, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and phenoxy (meth)acrylate Ethyl ester, (meth)acrylic acid
Figure 105106456-A0101-12-0010-7
基ester etc. In addition, as a specific example of the monomer (a2-2), glycidyl (meth)acrylate may be mentioned.

作為構成(A2)成分之單體，亦可使用除單體(a2-1)及(a2-2)以外之單體。作為該單體之例，可列舉具有碳數1~10之烴基及1個(甲基)丙烯醯基之化合物。作為該化合物之例，可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯及(甲基)丙烯酸異癸酯等。進而，作為該單體，較佳為具有碳數1~10之烴基及1個甲基丙烯醯基之化合物(以下，稱為「單體(a2-3)」)，其具體例可列舉上述化合物之甲基丙烯酸酯。作為(A2)成分中之各單體之共聚合比例，較佳為於全部構成單體中單體(a2-1)為10~60重量%、單體(a2-2)為1~50重量%及單體(a2-3)為10~80重量%。 As the monomer constituting the (A2) component, monomers other than the monomers (a2-1) and (a2-2) can also be used. As an example of this monomer, the compound which has a C1-C10 hydrocarbon group and one (meth)acryloyl group is mentioned. Examples of the compound include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, ( Second butyl methacrylate, third butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (A Group) octyl acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, and isodecyl (meth) acrylate. Furthermore, the monomer is preferably a compound having a hydrocarbon group having 1 to 10 carbon atoms and one methacryl group (hereinafter, referred to as "monomer (a2-3)"), and specific examples thereof include the above. Methacrylate of the compound. As the copolymerization ratio of each monomer in the component (A2), it is preferable that the monomer (a2-1) is 10 to 60% by weight and the monomer (a2-2) is 1 to 50% by weight in all constituent monomers % And monomer (a2-3) are 10 to 80% by weight.

(A2)成分較佳為藉由高溫聚合所獲得者。高溫聚合時之較佳溫度為160℃以上，更佳為160~350℃，特佳為180~300℃。(A2)成分較佳為Tg(玻璃轉移溫度)為30℃以上，更佳為40℃以上。再者，於本發明中，Tg意指使用示差掃描熱量計(DSC)以10℃/min之升溫速度所測得之值，於△T-溫度曲線中意指玻璃轉移溫度中間點(Tmg)下之值。 (A2) The component is preferably obtained by high-temperature polymerization. The preferred temperature during high temperature polymerization is above 160°C, more preferably 160 to 350°C, and particularly preferably 180 to 300°C. (A2) The component preferably has a Tg (glass transition temperature) of 30°C or higher, and more preferably 40°C or higher. Furthermore, in the present invention, Tg means the value measured using a differential scanning calorimeter (DSC) at a heating rate of 10°C/min, and in the △T-temperature curve means the midpoint of the glass transition temperature (Tmg) Value.

作為(A)成分，可併用上述(A1)成分與(A2)成分，亦可單獨使用任一者。(A)成分之含有比例於組成物整體中為1~30重量%。若(A)成分未滿1重量%，則組成物對各種塑膠基材之接著力下降。又，若(A)成分之含有比例超過30重量%，則組成物之黏度 過高，而塗佈性變差。(A)成分之較佳含有比例於組成物整體中為1~20重量%，更佳為3~15重量%。 As the (A) component, the aforementioned (A1) component and (A2) component may be used in combination, or any one of them may be used alone. (A) The content ratio of the component is 1 to 30% by weight in the entire composition. If the (A) component is less than 1% by weight, the adhesion of the composition to various plastic substrates will decrease. Also, if the content of (A) component exceeds 30% by weight, the viscosity of the composition If it is too high, the coatability becomes poor. (A) The preferable content ratio of the component is 1 to 20% by weight in the entire composition, and more preferably 3 to 15% by weight.

2.(B)成分 2. (B) Ingredients

(B)成分為具有碳數2~10個之多元醇之聚縮水甘油醚。再者，具有碳數2~10個之多元醇中之「碳數」意指構成自多元醇中除去羥基的部位之碳之數目。 (B) The component is a polyglycidyl ether having a polyhydric alcohol having 2 to 10 carbon atoms. In addition, the "carbon number" in a polyol having 2 to 10 carbon atoms means the number of carbons constituting the site from which the hydroxyl group is removed from the polyol.

作為(B)成分，可列舉：烷烴多元醇之聚縮水甘油醚、具有1個環構造之環烷烴多元醇之聚縮水甘油醚、聚伸烷基二醇聚縮水甘油醚、及具有1個環構造之芳香族多元醇之聚縮水甘油醚等。(B)成分較佳為具有碳數2~6個之二醇之二縮水甘油醚，更佳為具有碳數4~6個之烷二醇之二縮水甘油醚。 Examples of the component (B) include polyglycidyl ethers of alkane polyols, polyglycidyl ethers of cycloalkane polyols having one ring structure, polyalkylene glycol polyglycidyl ethers, and one ring Structured polyglycidyl ether of aromatic polyol, etc. (B) The component is preferably a diglycidyl ether having a diol having 2 to 6 carbon atoms, and more preferably a diglycidyl ether having an alkylene glycol having 4 to 6 carbon atoms.

作為(B)成分之具體例，可列舉：乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、1,4-丁二醇二縮水甘油醚、新戊二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、環己烷二羥甲基二縮水甘油醚、1,9-壬二醇二縮水甘油醚、二乙二醇二縮水甘油醚、三乙二醇二縮水甘油醚、二丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、對苯二酚二縮水甘油醚、間苯二酚二縮水甘油醚、三羥甲基丙烷二縮水甘油醚、三羥甲基丙烷三縮水甘油醚、季戊四醇聚縮水甘油醚及二季戊四醇聚縮水甘油醚等。 Specific examples of the component (B) include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 -Hexanediol diglycidyl ether, cyclohexane dimethylol diglycidyl ether, 1,9-nonanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether , Dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, hydroquinone diglycidyl ether, resorcinol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether Glycerol ether, pentaerythritol polyglycidyl ether and dipentaerythritol polyglycidyl ether, etc.

作為(B)成分，更佳為乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、1,4-丁二醇二縮水甘油醚、新戊二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、對苯二酚二縮水甘油醚、間苯二酚二縮水甘油醚、二乙二醇二縮水甘油醚、二丙二醇二縮水甘油醚等所例 示之具有碳數2~6個之二醇之二縮水甘油醚。 As component (B), ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanedione are more preferable Examples of alcohol diglycidyl ether, hydroquinone diglycidyl ether, resorcinol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, etc. Shown are diglycidyl ethers of diols with 2 to 6 carbon atoms.

作為(B)成分，於所獲得之組成物成為低黏度，硬化物接著力優異，進而為無色透明之方面而言，特佳為1,4-丁二醇二縮水甘油醚、新戊二醇二縮水甘油醚及1,6-己二醇二縮水甘油醚等所例示之具有碳數4~6個之烷二醇之二縮水甘油醚。 As the component (B), in view of the low viscosity of the obtained composition, excellent adhesion of the hardened material, and further colorless and transparent, 1,4-butanediol diglycidyl ether and neopentyl glycol are particularly preferred. Examples of diglycidyl ethers such as diglycidyl ether, 1,6-hexanediol diglycidyl ether, and the like are alkylene glycols having 4 to 6 carbon atoms.

作為(B)成分，可單獨使用上述化合物、或使用兩種以上。(B)成分之含有比例於組成物整體中為10~70重量%。若(B)成分未滿10重量%，則組成物對大多塑膠基材之接著力下降。又，若(B)成分之含有比例超過70重量%，則組成物之硬化性惡化，接著力亦惡化。(B)成分之較佳含有比例於組成物整體中為25~65重量%，更佳為30~60重量%。 As the component (B), the above compounds can be used alone, or two or more kinds can be used. (B) The content ratio of the component is 10 to 70% by weight in the entire composition. If the (B) component is less than 10% by weight, the adhesion of the composition to most plastic substrates will decrease. In addition, if the content of the component (B) exceeds 70% by weight, the curability of the composition deteriorates, and the adhesion also deteriorates. (B) The preferable content ratio of the component is 25 to 65% by weight in the entire composition, and more preferably 30 to 60% by weight.

3.(C)成分 3. (C) ingredients

(C)成分為1分子中具有2個以上之氧雜環丁烷基之分子量500以下之化合物。作為(C)成分，於所獲得之組成物成為低黏度之方面、及硬化物接著力優異之方面而言，更佳為分子量150~400之化合物，進而較佳之分子量為150~300之範圍。 The component (C) is a compound having a molecular weight of 500 or less having 2 or more oxetanyl groups in 1 molecule. The component (C) is more preferably a compound having a molecular weight of 150 to 400, and further preferably has a molecular weight in the range of 150 to 300, in terms of the obtained composition having a low viscosity and excellent adhesion of the cured product.

作為(C)成分之具體例，可列舉：雙[(3-乙基氧雜環丁烷-3-基)甲基]醚、雙[(3-甲基氧雜環丁烷-3-基)甲基]醚、雙[(氧雜環丁烷-3-基)甲基]醚、1,4-雙{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}苯、1,4-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]苯、1,3-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]苯、1,2-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]苯、4,4'-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]聯苯、2,2'-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]聯苯、1,1,1-叁[(3-乙基氧雜環丁烷-3-基) 甲氧基甲基]丙烷、1,2-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]乙烷、1,2-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]丙烷、1,4-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]丁烷及1,6-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]己烷等。 Specific examples of the component (C) include bis[(3-ethyloxetane-3-yl)methyl]ether and bis[(3-methyloxetane-3-yl )Methyl]ether, bis[(oxetane-3-yl)methyl]ether, 1,4-bis{[(3-ethyloxetan-3-yl)methoxy] Methyl}benzene, 1,4-bis[(3-ethyloxetane-3-yl)methoxy]benzene, 1,3-bis[(3-ethyloxetane-3 -Yl)methoxy]benzene, 1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene, 4,4'-bis[(3-ethyloxa Cyclobutane-3-yl)methoxy]biphenyl, 2,2'-bis[(3-ethyloxetan-3-yl)methoxy]biphenyl, 1,1,1- Tris((3-ethyloxetan-3-yl) Methoxymethyl]propane, 1,2-bis[(3-ethyloxetan-3-yl)methoxy]ethane, 1,2-bis[(3-ethyloxetane Butane-3-yl)methoxy]propane, 1,4-bis[(3-ethyloxetan-3-yl)methoxy]butane and 1,6-bis[(3- Ethyloxetane-3-yl)methoxy]hexane and the like.

作為(C)成分，特佳為雙[(3-乙基氧雜環丁烷-3-基)甲基]醚，即下述式(1)所表示之氧雜環丁烷化合物。 The component (C) is particularly preferably bis[(3-ethyloxetane-3-yl)methyl] ether, that is, an oxetane compound represented by the following formula (1).

Figure 105106456-A0101-12-0014-2
Figure 105106456-A0101-12-0014-2

於(C)成分之分子量為500以下之情形時，較佳為150~400，更佳為150~300，特佳為上述式(1)所表示之化合物，於該情形時，組成物之硬化物即便於Tg以上之溫度，亦可提高彈性模數。因此，可提高組成物之硬化物之耐熱性。 When the molecular weight of the component (C) is 500 or less, it is preferably 150 to 400, more preferably 150 to 300, and particularly preferably the compound represented by the above formula (1). In this case, the composition is hardened Even at temperatures above Tg, the modulus of elasticity can be increased. Therefore, the heat resistance of the cured product of the composition can be improved.

作為(C)成分，可單獨使用上述化合物、或使用兩種以上。(C)成分之含有比例於組成物整體中為10~70重量%。若(C)成分未滿10重量%，則硬化性惡化，接著力亦惡化。又，若(C)成分之含有比例超過70重量%，則對大多塑膠基材接著力降低。(C)成分之較佳含有比例於組成物整體中為20~60重量%，更佳為25~55重量%。 As the component (C), the above compounds can be used alone, or two or more kinds can be used. (C) The content of the component is 10 to 70% by weight in the entire composition. If the (C) component is less than 10% by weight, the hardenability deteriorates, and the adhesion also deteriorates. In addition, if the content of the component (C) exceeds 70% by weight, the adhesion to most plastic substrates will decrease. (C) The preferable content ratio of the component is 20 to 60% by weight in the entire composition, and more preferably 25 to 55% by weight.

4.(D)成分 4. (D) ingredients

(D)成分為光陽離子聚合起始劑。即，其係藉由紫外線或電子束等活性能量射線之照射而產生陽離子或路易斯酸，使環氧化合物或氧雜環丁烷化合物等陽離子硬化性成分之聚合開始的化合物。作 為(D)成分之具體例，可列舉鋶鹽系光陽離子聚合起始劑、錪鹽系光陽離子聚合起始劑及重氮鹽系光陽離子聚合起始劑等。 (D) The component is a photo-cationic polymerization initiator. That is, it is a compound that generates a cation or a Lewis acid by irradiation of active energy rays such as ultraviolet rays or electron beams, and starts polymerization of a cationic hardening component such as an epoxy compound or an oxetane compound. Make As specific examples of the component (D), a cerium salt-based photo-cationic polymerization initiator, a gallium salt-based photo-cationic polymerization initiator, a diazonium salt-based photo-cationic polymerization initiator, etc. may be mentioned.

作為鋶鹽系光陽離子聚合起始劑之例，例如可列舉：三苯基鋶六氟磷酸鹽、三苯基鋶六氟銻酸鹽、三苯基鋶肆(五氟苯基)硼酸鹽、二苯基-4-(苯硫基)苯基鋶六氟磷酸鹽、二苯基-4-(苯硫基)苯基鋶六氟銻酸鹽、4,4'-雙(二苯基鋶基)二苯基硫醚雙六氟磷酸鹽、4,4'-雙[二(β-羥基乙氧基)苯基二氫硫基]二苯基硫醚雙六氟銻酸鹽、4,4'-雙[二(β-羥基乙氧基)苯基二氫硫基]二苯基硫醚雙六氟磷酸鹽、7-[二(對甲苯甲醯基)二氫硫基]-2-異丙基9-氧硫

Figure 105106456-A0101-12-0015-8
六氟銻酸鹽、7-[二(對甲苯甲醯基)二氫硫基]-2-異丙基9-氧硫
Figure 105106456-A0101-12-0015-9
肆(五氟苯基)硼酸鹽、4-苯基羰基-4'-二苯基二氫硫基-二苯基硫醚六氟磷酸鹽、4-(對第三丁基苯基羰基)-4'-二苯基二氫硫基-二苯基硫醚六氟銻酸鹽、4-(對第三丁基苯基羰基)-4'-二(對甲苯甲醯基)二氫硫基-二苯基硫醚肆(五氟苯基)硼酸鹽等三芳基鋶鹽。 Examples of the cerium salt-based photo-cationic polymerization initiator include, for example, triphenylammonium hexafluorophosphate, triphenylammonium hexafluoroantimonate, triphenylammonium (pentafluorophenyl) borate, Diphenyl-4-(phenylthio) phenyl alkane hexafluorophosphate, diphenyl-4-(phenylthio) phenyl alkane hexafluoroantimonate, 4,4'-bis(diphenyl alkane Group) diphenyl sulfide bishexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxy)phenyl dihydrothio]diphenyl sulfide bishexafluoroantimonate, 4, 4'-bis[bis(β-hydroxyethoxy)phenyldihydrothio]diphenyl sulfide bishexafluorophosphate, 7-[bis(p-tolylmethyl)dihydrothio]-2 -Isopropyl 9-oxysulfur
Figure 105106456-A0101-12-0015-8
Hexafluoroantimonate, 7-[bis(p-tolylmethyl)dihydrosulfanyl]-2-isopropyl 9-oxysulfide
Figure 105106456-A0101-12-0015-9
(Pentafluorophenyl) borate, 4-phenylcarbonyl-4'-diphenyldihydrothio-diphenylsulfide hexafluorophosphate, 4-(p-third butylphenylcarbonyl)- 4'-diphenyldihydrosulfanyl-diphenylsulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-bis(p-tolylmethyl)dihydrothio -Triarylsulfonium salts such as diphenyl sulfide (pentafluorophenyl) borate.

作為錪鹽系光陽離子聚合起始劑之例，例如可列舉：二苯基錪肆(五氟苯基)硼酸鹽、二苯基錪六氟磷酸鹽、二苯基錪六氟銻酸鹽、二(4-第三丁基苯基)錪六氟磷酸鹽、二(4-第三丁基苯基)錪六氟銻酸鹽、甲苯基

Figure 105106456-A0101-12-0015-10
基錪肆(五氟苯基)硼酸鹽、(4-甲基苯基)[4-(2-甲基丙基)苯基]-六氟磷酸鹽、二(4-壬基苯基)錪六氟磷酸鹽、二(4-烷基苯基)錪六氟磷酸鹽等二芳基錪鹽。 As examples of the photocationic polymerization initiators of the antimony salt system, for example, there can be mentioned: diphenylphosphonium (pentafluorophenyl) borate, diphenylphosphonium hexafluorophosphate, diphenylphosphonium hexafluoroantimonate, Di(4-tert-butylphenyl) hexafluorophosphate, bis(4-tert-butylphenyl) hexafluoroantimonate, tolyl
Figure 105106456-A0101-12-0015-10
Phenylphosphonium (pentafluorophenyl) borate, (4-methylphenyl) [4-(2-methylpropyl)phenyl]-hexafluorophosphate, bis(4-nonylphenyl)phosphonium Diaryl phosphonium salts such as hexafluorophosphate, bis (4-alkylphenyl) hexafluorophosphate.

作為重氮鹽系光陽離子聚合起始劑之例，例如可列舉：重氮苯六氟銻酸鹽、重氮苯六氟磷酸鹽等。 Examples of the diazonium salt-based photocationic polymerization initiator include diazobenzene hexafluoroantimonate, diazobenzene hexafluorophosphate, and the like.

(D)成分有市售，可列舉：Adeka Optomer SP-100、SP-150、SP-152、SP-170、SP-172[ADEKA(股)製造]、Photoinitiator 2074(RHODIA公司製造)、Kayarad PCI-220、PCI-620[日本化藥(股)製造]、Irgacure 250(日本汽巴公司製造)、CPI-100P、CPI-110P、CPI-101A、CPI-200K、CPI-210S[SAN-APRO(股)製造]、WPI-113、WPI-116[和光純藥工業(股)製造]、BBI-102、BBI-103、TPS-102、TPS-103、DTS-102、DTS-103[Midori化學(股)製造]等。 (D) Ingredients are commercially available, and examples include: Adeka Optomer SP-100, SP-150, SP-152, SP-170, SP-172 [made by ADEKA Corporation], Photoinitiator 2074 (manufactured by Rhodia), Kayarad PCI-220, PCI-620 [manufactured by Nippon Kayaku Co., Ltd.], Irgacure 250 (manufactured by Nippon Ciba), CPI-100P, CPI-110P, CPI-101A, CPI-200K , CPI-210S [manufactured by SAN-APRO], WPI-113, WPI-116 [manufactured by Wako Pure Chemical Industries, Ltd.], BBI-102, BBI-103, TPS-102, TPS-103, DTS- 102. DTS-103 [Midori Chemicals Co., Ltd.] etc.

該等之中，由於活性能量射線硬化性優異，無色透明性亦優異，故而較佳為鋶鹽系光陽離子聚合起始劑，更佳為三芳基鋶鹽。作為三芳基鋶鹽，上述之中，較佳為三苯基鋶六氟磷酸鹽及二苯基-4-(苯硫基)苯基鋶六氟磷酸鹽。 Among these, since the active energy ray has excellent curability and colorless transparency, it is preferably a cerium salt-based photo-cationic polymerization initiator, and more preferably a triaryl cerium salt. As the triaryl alkoxide salt, among the above, triphenyl alkoxide hexafluorophosphate and diphenyl-4-(phenylthio)phenyl alkoxide hexafluorophosphate are preferred.

作為(D)成分，可單獨使用上述化合物、或使用兩種以上。 As the component (D), the above compounds can be used alone, or two or more kinds can be used.

(D)成分之含有比例於組成物整體中為0.5~10重量%，較佳為1~5重量%。若(D)成分之含有比例未滿0.5重量%，則組成物之硬化性惡化，若超過10重量%，則組成物之接著力下降，或硬化物發生黃變。 (D) The content ratio of the component is 0.5 to 10% by weight in the entire composition, preferably 1 to 5% by weight. If the content ratio of the component (D) is less than 0.5% by weight, the curability of the composition deteriorates, and if it exceeds 10% by weight, the adhesion of the composition decreases, or the cured product becomes yellow.

5.(E)成分 5. (E) ingredients

(E)成分為(E1)Tg20℃以下且Mw20,000~1,000,000之聚合體[以下，稱為「(E1)成分」]、及/或(E2)Tg20℃以下之具有嵌段單位之Mw20,000~1,000,000之嵌段共聚合體[以下，稱為「(E2)成分」]。於(E1)成分為Tg超過20℃之聚合體之情形時、或當(E2)成分為Tg20℃以下之無嵌段單位之嵌段共聚合體時，組成物對乙酸纖維素系塑膠之接著力會下降。若(E)成分之Mw未滿20,000，則組成物對乙酸纖維素系塑膠之接著力會下降，若超過1,000,000，則產生組成物 之拉絲等，塗佈性變差。 (E) A polymer whose component is (E1) Tg20°C or lower and Mw20,000 to 1,000,000 [hereinafter, referred to as "(E1) component"], and/or (E2) Mw20 having a block unit below Tg20°C, 000-1,000,000 block copolymer [hereinafter, referred to as "(E2) component"]. When the component (E1) is a polymer with a Tg exceeding 20°C, or when the component (E2) is a block copolymer without a block unit having a Tg of 20°C or lower, the adhesion of the composition to the cellulose acetate-based plastic Will fall. If the Mw of the (E) component is less than 20,000, the adhesion of the composition to the cellulose acetate plastic will decrease. If it exceeds 1,000,000, the composition will be produced. Wire drawing, etc., the coating properties become poor.

作為(E)成分，較佳為以丙烯酸烷基酯作為必需構成單體之Mw20,000~500,000之聚合體。又，較佳為以丙烯酸烷基酯與甲基丙烯酸烷基酯之兩者作為構成單體之聚合體。 The component (E) is preferably a polymer of Mw 20,000 to 500,000 having alkyl acrylate as an essential constituent monomer. In addition, it is preferably a polymer having both alkyl acrylate and alkyl methacrylate as constituent monomers.

作為(E)成分，較佳為(E2)成分，更佳為具有丙烯酸烷基酯之嵌段及甲基丙烯酸烷基酯之嵌段的嵌段共聚合體，進而較佳為包含Tg為20℃以下之成為嵌段單位之碳數1~10的烷基之丙烯酸酯、及甲基丙烯酸甲酯之嵌段共聚合體。於(E2)成分中，在組成物成為接著力優異者之方面而言，較佳為Tg為20℃以下之嵌段單位之質量大於Tg超過20℃之嵌段之質量的共聚合體。 The component (E) is preferably the component (E2), more preferably a block copolymer having a block of alkyl acrylate and a block of alkyl methacrylate, and further preferably contains Tg of 20°C The following are block copolymers of C 1-10 alkyl acrylates in block units and methyl methacrylate. The component (E2) is preferably a copolymer having a mass of block units with a Tg of 20° C. or less than a mass of blocks having a Tg of more than 20° C. in terms of the composition having excellent adhesion.

作為成為(E)成分之構成單體之丙烯酸烷基酯的烷基，可列舉：甲基、乙基、丙基、丁基、己基、正辛基、2-乙基己基、癸基、十二烷基等。作為成為(E)成分之構成單體之甲基丙烯酸烷基酯之烷基亦可列舉相同之基。但是，於甲基丙烯酸酯之情形時，特佳為甲基。又，作為(E)成分，較佳為不具有環氧基者。 Examples of the alkyl group of the alkyl acrylate which is the constituent monomer of the component (E) include methyl, ethyl, propyl, butyl, hexyl, n-octyl, 2-ethylhexyl, decyl, and decyl. Dialkyl and so on. The alkyl group of the alkyl methacrylate which is the constituent monomer of (E) component can also be the same group. However, in the case of methacrylate, methyl is particularly preferred. Moreover, as (E) component, what does not have an epoxy group is preferable.

(E)成分之含有比例於組成物整體中為1~20重量%，較佳為3~15重量%。若(E)成分之含有比例未滿1重量%，則組成物對乙酸纖維素系樹脂之接著力下降，若超過20重量%，則組成物之黏度變高而塗佈性下降，或硬化物白濁而透明性下降。 (E) The content ratio of the component is 1 to 20% by weight in the entire composition, preferably 3 to 15% by weight. If the content of the (E) component is less than 1% by weight, the adhesion of the composition to the cellulose acetate resin will decrease. If it exceeds 20% by weight, the viscosity of the composition will increase and the coating properties will decrease, or the cured product White turbidity and decreased transparency.

6.其他成分 6. Other ingredients

本發明之組成物係以上述(A)~(E)成分作為必需者，但可根據目的調配各種成分(稱為「其他成分」)。 The composition of the present invention requires the aforementioned components (A) to (E) as essential, but various components (referred to as "other components") can be formulated according to the purpose.

作為其他成分，亦可含有除上述(A)成分、(B)成分、 及(C)成分以外之陽離子硬化性化合物(以下，稱為「其他陽離子硬化性成分」)。於包含其他陽離子硬化性成分之情形時，該等之含有比例之合計於陽離子硬化性成分之合計量100重量%中，較佳為設為30重量%以下，更佳為設為20重量%以下，進而較佳為設為10重量%以下。作為陽離子硬化性成分，可列舉除(A)成分及(B)成分以外之含有環氧基之化合物、除(C)成分以外之含有氧雜環丁烷基之化合物、及含有乙烯醚基之化合物等。 As other components, components (A), (B), and And a cation-curable compound other than the component (C) (hereinafter, referred to as "other cation-curable components"). When other cationic hardening components are included, the total content of these components is 100% by weight of the total cationic hardening components, preferably 30% by weight or less, more preferably 20% by weight or less It is more preferably 10% by weight or less. Examples of the cationic hardening component include compounds containing epoxy groups other than the components (A) and (B), compounds containing oxetane groups other than the component (C), and compounds containing vinyl ether groups Compounds etc.

作為除(A)成分及(B)成分以外之含有環氧基之化合物的具體例，可列舉：3,4-環氧環己烷羧酸3,4-環氧環己基甲酯、己二酸雙(3,4-環氧環己基甲基)酯、3,4-環氧環己烷羧酸3,4-環氧環己基甲酯之己內酯改質物、多元羧酸與3,4-環氧環己基甲基醇之酯化物或己內酯改質物、二氧化二環戊二烯、二氧化檸檬烯、2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧基矽烷及二氧化4-乙烯環己烷等脂環式環氧化合物；以及聚乙二醇(重複數6以上)二縮水甘油醚、聚丙二醇(重複數4以上)二縮水甘油醚、聚四亞甲基二醇(重複數3以上)二縮水甘油醚、兩末端羥基之聚丁二烯二縮水甘油醚等碳數11以上之二醇之二縮水甘油醚等。除該等以外，亦可列舉：環氧化植物油、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、聚丁二烯之內部環氧化物、苯乙烯-丁二烯共聚合體之雙鍵經一部分環氧化而得之化合物[例如，大賽璐化學工業(股)製造之「Epofriend」]、及乙烯-丁烯共聚合體與聚異戊二烯之嵌段共聚合物之異戊二烯單位經一部分環氧化而得之化合物[例如，科騰(KRATON)公司製造之「L-207」]等。 Specific examples of the epoxy group-containing compound other than the component (A) and the component (B) include 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyl methyl ester and hexanedi Acid bis(3,4-epoxycyclohexylmethyl) ester, 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyl methyl ester caprolactone modified product, polycarboxylic acid and 3, 4-Epoxycyclohexyl methyl alcohol ester or caprolactone modified product, dicyclopentadiene dioxide, limonene dioxide, 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane, Alicyclic epoxy compounds such as 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane and 4-ethylenecyclohexane dioxide; and polyethylene glycol (repeating number 6 or more) diglycidyl Ether, polypropylene glycol (repeating number 4 or more) diglycidyl ether, polytetramethylene glycol (repeating number 3 or more) diglycidyl ether, polybutadiene diglycidyl ether of both terminal hydroxyl groups, etc. with a carbon number of 11 or more Glycidyl ether of glycol II, etc. In addition to these, epoxidized vegetable oil, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, internal epoxy of polybutadiene Compound, a compound obtained by partially epoxidizing the double bond of styrene-butadiene copolymer [for example, "Epofriend" manufactured by Daicel Chemical Industry Co., Ltd.], and ethylene-butene copolymer and polyisoprene A compound obtained by partially epoxidizing the isoprene unit of the block copolymer of ene [for example, "L-207" manufactured by KRATON Co., Ltd.], etc.

作為除(C)成分以外之氧雜環丁烷化合物之具體例，可列舉：如3-乙基-3-(2-乙基己氧基甲基)氧雜環丁烷、含有烷氧基烷基之單官能氧雜環丁烷、如3-乙基-3-苯氧甲基氧雜環丁烷、含有芳香族基之單官能氧雜環丁烷、3-乙基-3-羥甲基氧雜環丁烷、酚醛清漆型苯酚-甲醛樹脂之3-氯甲基-3-乙基氧雜環丁烷之醚化改質物、3-[(3-乙基氧雜環丁烷-3-基)甲氧基]丙基三甲氧基矽烷、3-[(3-乙基氧雜環丁烷-3-基)甲氧基]丙基三乙氧基矽烷、3-[(3-乙基氧雜環丁烷-3-基)甲氧基]丙基三烷氧基矽烷之水解縮合物、3-乙基氧雜環丁烷-3-基甲醇與矽烷四醇縮聚物之縮合反應生成物等。 Specific examples of oxetane compounds other than the component (C) include, for example, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane and alkoxy-containing Alkyl monofunctional oxetane, such as 3-ethyl-3-phenoxymethyloxetane, monofunctional oxetane containing aromatic group, 3-ethyl-3-hydroxy Ether-modified 3-chloromethyl-3-ethyloxetane of methyl oxetane, novolak type phenol-formaldehyde resin, 3-[(3-ethyloxetane -3-yl)methoxy]propyltrimethoxysilane, 3-[(3-ethyloxetan-3-yl)methoxy]propyltriethoxysilane, 3-[( 3-ethyloxetane-3-yl)methoxy]propyltrialkoxysilane hydrolyzed condensate, 3-ethyloxetane-3-ylmethanol and silanetetraol polycondensate The condensation reaction product and so on.

作為乙烯醚化合物之具體例，可列舉：環己基乙烯醚、2-乙基己基乙烯醚、十二烷基乙烯醚、4-羥基丁基乙烯醚、二乙二醇單乙烯醚、三乙二醇二乙烯醚、環己烷二甲醇二乙烯醚等。 Specific examples of vinyl ether compounds include cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and triethylene dioxide. Alcohol divinyl ether, cyclohexane dimethanol divinyl ether, etc.

本發明之組成物較佳為於組成物整體中含有0.05~3重量%之水。藉由將水之含有比例設為0.05%以上，可防止陽離子硬化變得過快，導致接著力下降。另一方面，藉由將水之含量設為3重量%以下，可提高組成物之硬化性或接著力。 The composition of the present invention preferably contains 0.05 to 3% by weight of water in the entire composition. By setting the water content to 0.05% or more, the cation hardening can be prevented from becoming too fast, resulting in a decrease in adhesion. On the other hand, by setting the water content to 3% by weight or less, the hardenability or adhesion of the composition can be improved.

本發明之組成物亦可含有自由基硬化性成分。於含有自由基硬化性成分之情形時，該等之合計量相對於陽離子硬化性成分之合計量100重量份，較佳為100重量份以下，更佳為50重量份以下。作為其他自由基硬化性成分，可列舉含有(甲基)丙烯醯基之化合物等。又，作為該等之分子量，可選擇各種分子量，且可為單體、寡聚物、及聚合物之任一者。 The composition of the present invention may contain a radical hardening component. In the case of containing a radical hardening component, the total amount of these is 100 parts by weight relative to the total amount of the cationic hardening component, preferably 100 parts by weight or less, and more preferably 50 parts by weight or less. Examples of other radical-curable components include compounds containing (meth)acryloyl groups. In addition, as these molecular weights, various molecular weights may be selected, and may be any of monomers, oligomers, and polymers.

作為含有(甲基)丙烯醯基之化合物，可列舉分子內具有1個(甲基)丙烯醯基之化合物[以下，稱為「單官能(甲基)丙烯酸酯 」]及分子內具有2個以上之(甲基)丙烯醯基之化合物[以下，稱為「多官能(甲基)丙烯酸酯」]。 Examples of compounds containing (meth)acryloyl groups include compounds having one (meth)acryloyl group in the molecule [hereinafter, referred to as "monofunctional (meth)acrylates "] and compounds having more than two (meth)acryloyl groups in the molecule [hereinafter, referred to as "multifunctional (meth)acrylate"].

作為單官能(甲基)丙烯酸酯之具體例，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異

Figure 105106456-A0101-12-0020-11
基酯、單(甲基)丙烯酸1,4-環己烷二羥甲酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸苄酯、苯酚環氧烷加成物之(甲基)丙烯酸酯、對
Figure 105106456-A0101-12-0020-12
基苯酚環氧烷加成物之(甲基)丙烯酸酯、鄰苯基苯酚環氧烷加成物之(甲基)丙烯酸酯、壬基苯酚環氧烷加成物之(甲基)丙烯酸酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸乙氧基乙氧基乙酯、2-乙基己醇之環氧烷加成物之(甲基)丙烯酸酯、戊二醇單(甲基)丙烯酸酯、己二醇單(甲基)丙烯酸酯、二乙二醇之單(甲基)丙烯酸酯、三乙二醇之單(甲基)丙烯酸酯、四乙二醇之單(甲基)丙烯酸酯、聚乙二醇之單(甲基)丙烯酸酯、二丙二醇之單(甲基)丙烯酸酯、三丙二醇之單(甲基)丙烯酸酯、聚丙二醇之單(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸2-羥基-3-丁氧基丙酯、(甲基)丙烯酸四氫糠酯、己內酯改質(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸(2-乙基-2-甲基-1,3-二氧雜環戊烷-4-基)甲酯、(甲基)丙烯酸(2-異丁基-2-甲基-1,3-二氧雜環戊烷-4-基)甲酯、(甲基)丙烯酸(1,4-二氧雜螺[4,5]癸烷-2-基)甲酯、(甲基)丙烯酸縮水甘油酯、(甲 基)丙烯酸3,4-環氧環己基甲酯、(甲基)丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯、異氰酸2-(甲基)丙烯醯氧基乙酯、(甲基)丙烯酸烯丙酯、N-(甲基)丙烯醯氧基乙基六氫鄰苯二甲醯亞胺、N-(甲基)丙烯醯氧基乙基四氫鄰苯二甲醯亞胺、六氫鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯、琥珀酸2-(甲基)丙烯醯氧基乙酯、ω-羧基-聚己內酯單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基酸式磷酸酯、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基二甲氧基甲基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷等。於上述環氧烷加成物中，作為環氧烷，可列舉環氧乙烷及環氧丙烷等。 Specific examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, ( Butyl meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylic acid Lauryl ester, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylic acid Cyclohexyl, (meth)acrylic acid
Figure 105106456-A0101-12-0020-11
Esters, 1,4-cyclohexane dihydroxymethyl mono(meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate Ethoxylated ethyl ester, benzyl (meth)acrylate, (meth)acrylic acid ester of phenol alkylene oxide adduct,
Figure 105106456-A0101-12-0020-12
(Meth) acrylate of alkylphenol alkylene oxide adduct, (meth)acrylate of o-phenylphenol alkylene oxide adduct, (meth)acrylate of nonylphenol alkylene oxide adduct , (Meth)acrylic acid 2-methoxyethyl ester, (meth)acrylic acid ethoxyethoxyethyl ester, 2-ethylhexanol alkylene oxide adduct (meth)acrylic acid ester, pentyl Glycol mono(meth)acrylate, hexylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylenedioxide Mono(meth)acrylate of alcohol, mono(meth)acrylate of polyethylene glycol, mono(meth)acrylate of dipropylene glycol, mono(meth)acrylate of tripropylene glycol, mono(meth)acrylate of polypropylene ( Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, Modification of caprolactone tetrahydrofurfuryl (meth)acrylate, (2-ethyl-2-methyl-1,3-dioxol-4-yl)methyl (meth)acrylate, ( (2-Isobutyl-2-methyl-1,3-dioxol-4-yl)methyl methacrylate, (meth)acrylic acid (1,4-dioxaspiro[4 ,5]decane-2-yl)methyl ester, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, (3-ethyloxa) (meth)acrylic acid Cyclobutane-3-yl) methyl ester, 2-(meth)acryloyloxyethyl isocyanate, allyl (meth)acrylate, N-(meth)acryloyloxyethyl hexahydro Phthalimide, N-(meth)acryloyloxyethyltetrahydrophthalimide, hexahydrophthalic acid 2-(meth)acryloyloxyethyl, amber Acid 2-(meth)acryloyloxyethyl, ω-carboxy-polycaprolactone mono(meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, 3-( Meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyldimethoxymethylsilane, 3-(meth)acryloxypropyltriethoxy Silane, etc. In the above-mentioned alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

作為多官能(甲基)丙烯酸酯之具體例，可列舉：乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、3-甲基-1,5-戊二醇二(甲基)丙烯酸酯、2-丁基-2-乙基-1,3-丙二醇二(甲基)丙烯酸酯及1,9-壬二醇二(甲基)丙烯酸酯等脂肪族二醇之二(甲基)丙烯酸酯；環己烷二羥甲基二(甲基)丙烯酸酯及三環癸烷二羥甲基二(甲基)丙烯酸酯等脂環族二醇之二(甲基)丙烯酸酯；二乙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯及三丙二醇二(甲基)丙烯酸酯等伸烷基二醇二(甲基)丙烯酸酯；新戊二醇與羥基三甲基乙酸與(甲基)丙烯酸之酯化反應生成物；雙酚A環氧烷加成物之二(甲基)丙烯酸酯等雙酚系化合物之環氧烷加成物之二(甲基)丙烯酸酯；氫化雙酚A之二(甲基)丙烯酸酯等氫化雙酚系化合物之二(甲基)丙烯酸酯；三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、季戊四醇三或四(甲基)丙烯酸酯、二季戊四醇五或六(甲基)丙烯酸酯 等多元醇聚(甲基)丙烯酸酯；三羥甲基丙烷環氧烷加成物之三(甲基)丙烯酸酯、二-三羥甲基丙烷環氧烷加成物之四(甲基)丙烯酸酯、季戊四醇環氧烷加成物之三或四(甲基)丙烯酸酯、二季戊四醇環氧烷加成物之五或六(甲基)丙烯酸酯等多元醇環氧烷加成物之聚(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯；環氧(甲基)丙烯酸酯；以及聚酯(甲基)丙烯酸酯等。聚酯(甲基)丙烯酸酯亦可為樹枝狀聚合物型(甲基)丙烯酸酯。於上述環氧烷加成物中，作為環氧烷，可列舉環氧乙烷及環氧丙烷等。 Specific examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and 1,4-butanediol di(meth)acrylate. , Neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2- Di(meth)acrylates of aliphatic diols such as butyl-2-ethyl-1,3-propanediol di(meth)acrylate and 1,9-nonanediol di(meth)acrylate; Di(meth)acrylates of cycloaliphatic diols such as hexane dimethylol di(meth)acrylate and tricyclodecane dimethylol di(meth)acrylate; diethylene glycol di(meth)acrylate Alkylene glycol di(meth)acrylates such as meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate and tripropylene glycol di(meth)acrylate ; The esterification reaction product of neopentyl glycol, hydroxytrimethylacetic acid and (meth)acrylic acid; the alkylene oxide of bisphenol compounds such as di(meth)acrylate of bisphenol A alkylene oxide adduct Adduct bis(meth)acrylate; hydrogenated bisphenol A bis(meth)acrylate and other hydrogenated bisphenol-based compounds bis(meth)acrylate; trimethylolpropane tri(meth)acrylic acid Ester, di-trimethylolpropane tetra (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate, di pentaerythritol penta or hexa (meth) acrylate Poly(meth)acrylates such as polyols; tri(meth)acrylates of trimethylolpropane alkylene oxide adducts, and tetrakis(methyl) of di-trimethylolpropane alkylene oxide adducts Polymerization of polyhydric alcohol alkylene oxide adducts such as acrylates, pentaerythritol alkylene oxide adducts three or four (meth)acrylates, dipentaerythritol alkylene oxide adducts five or six (meth)acrylates (Meth) acrylate; (meth) acrylate urethane; epoxy (meth) acrylate; and polyester (meth) acrylate. The polyester (meth)acrylate may also be a dendrimer (meth)acrylate. In the above-mentioned alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

於本發明之組成物含有自由基硬化性成分之情形時，較佳為以組成物整體作為基準，含有0.1~10重量%之光自由基聚合起始劑。作為光自由基聚合起始劑，可使用一般可獲得者。 When the composition of the present invention contains a radical hardening component, it is preferable to contain 0.1 to 10% by weight of a photoradical polymerization initiator based on the entire composition. As the photo radical polymerization initiator, generally available ones can be used.

本發明之組成物除該等以外，只要不損害本發明之效果，亦可含有除硬化性成分以外之各種添加劑。作為各種添加劑，可列舉熱陽離子聚合起始劑、光敏劑、紫外線吸收劑、光穩定劑、抗氧化劑、聚合抑制劑、矽烷偶合劑、多元醇化合物、聚合物、黏著賦予劑、填料、金屬微粒子、金屬氧化物微粒子、離子捕捉劑、消泡劑、均染劑、色素及顏料等。 In addition to these, the composition of the present invention may contain various additives other than the curable component as long as the effect of the present invention is not impaired. Examples of various additives include thermal cationic polymerization initiators, photosensitizers, ultraviolet absorbers, light stabilizers, antioxidants, polymerization inhibitors, silane coupling agents, polyol compounds, polymers, adhesion-imparting agents, fillers, and metal fine particles. , Metal oxide particles, ion trapping agent, defoaming agent, leveling agent, pigment and pigment, etc.

7.塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物 7. Active energy ray hardening type adhesive composition for plastic film or sheet

本發明係關於一種含有上述(A)~(E)成分作為必需成分之塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物。 The present invention relates to an active energy ray-curable adhesive composition for plastic films or sheets containing the aforementioned components (A) to (E) as essential components.

本發明之組成物較佳為組成物中之總氯含量為0.1重量%以下。作為減少組成物中之總氯含量之方法，例如可列舉使用蒸餾精製品作為(B)成分及/或(C)成分之全部或一部分之方法等。 In the composition of the present invention, the total chlorine content in the composition is preferably 0.1% by weight or less. As a method of reducing the total chlorine content in the composition, for example, a method of using a distilled refined product as all or part of the (B) component and/or (C) component can be cited.

作為本發明之組成物之製造方法，按照常規方法即可，可藉由按照常規方法將上述(A)~(E)成分、進而視需要之其他成分進行攪拌、混合而製造。於該情形時，可視需要進行加熱或加溫。 The method for producing the composition of the present invention may be a conventional method, which can be produced by stirring and mixing the above-mentioned components (A) to (E) and further other components as necessary according to a conventional method. In this case, heating or heating may be performed as necessary.

作為本發明之組成物之黏度，只要根據使用目的適當設定即可。為了獲得能夠使用於利用塑膠薄膜等之積層體之製造步驟之塗佈性、即便為薄膜而平滑性亦優異之塗佈面，較佳為25℃下之黏度為1,000mPa‧s以下，更佳為10~500mPa‧s，特佳為20~100mPa‧s。於本發明中，組成物之黏度意指藉由E型黏度計所測得之測定值。 The viscosity of the composition of the present invention may be appropriately set according to the purpose of use. In order to obtain a coating surface that can be used in the manufacturing process of a laminate using a plastic film or the like and has excellent smoothness even if it is a thin film, the viscosity at 25°C is preferably 1,000 mPa‧s or less, more preferably It is 10~500mPa‧s, especially good is 20~100mPa‧s. In the present invention, the viscosity of the composition means the measured value measured by an E-type viscometer.

本發明之組成物可使用於塑膠薄膜等彼此之接著、塑膠薄膜等與除此以外之各種基材(以下，稱為「其他基材」)之接著。即，可用於至少一者為塑膠薄膜等之2個基材之接著。再者，以下，在僅記載為「基材」之情形時，意指塑膠薄膜等及其他基材之總稱。作為其他基材，可列舉玻璃、金屬氧化物、金屬、木、紙等。 The composition of the present invention can be used for bonding of plastic films and the like, bonding of plastic films and the like to various other substrates (hereinafter, referred to as "other substrates"). That is, it can be used for bonding at least one of two substrates such as plastic films. In addition, hereinafter, when it is only described as "substrate", it means the general term for plastic films and other substrates. Examples of other substrates include glass, metal oxides, metals, wood, and paper.

作為塑膠薄膜等之材質，例如可列舉：環烯烴聚合物、(甲基)丙烯酸系樹脂、聚苯乙烯、丙烯酸/苯乙烯共聚合體、三乙酸纖維素、乙酸丁酸纖維素、聚氯乙烯、聚偏二氯乙烯、聚乙烯、聚丙烯、丙烯腈-丁二烯-苯乙烯(ABS，acrylonitrile-butadiene-styrene)樹脂、聚醯胺、聚酯、聚碳酸酯、聚胺基甲酸酯、及氯化聚丙烯等。作為(甲基)丙烯酸系樹脂，可列舉：聚甲基丙烯酸甲酯、以甲基丙烯酸甲酯作為主成分之共聚合體之(甲基)丙烯酸系樹脂、不含甲基丙烯酸甲酯作為聚合單體之(甲基)丙烯酸系樹脂等。於該等塑膠薄膜等中，本發明之組成物亦可較佳地應用於環烯烴聚合物、乙酸纖 維素系樹脂、及(甲基)丙烯酸系樹脂。 Examples of materials for plastic films include cycloolefin polymers, (meth)acrylic resins, polystyrene, acrylic/styrene copolymers, cellulose triacetate, cellulose acetate butyrate, polyvinyl chloride, Polyvinylidene chloride, polyethylene, polypropylene, acrylonitrile-butadiene-styrene (ABS, acrylonitrile-butadiene-styrene) resin, polyamide, polyester, polycarbonate, polyurethane, And chlorinated polypropylene. Examples of the (meth)acrylic resin include polymethyl methacrylate, a copolymer of (meth)acrylic resin containing methyl methacrylate as a main component, and no methyl methacrylate as a polymerization monomer. (Meth)acrylic resin. In these plastic films, etc., the composition of the present invention can also be preferably applied to cycloolefin polymer, acetate fiber Vitamin resin and (meth)acrylic resin.

作為金屬氧化物，例如可列舉氧化錫、氧化銦、氧化鈦、氧化鋅等。作為金屬，例如可列舉金、銀、銅、鋁、鐵、鎳、鈦等。該等之中，於藉由蒸鍍或濺鍍等形成之透明性薄膜為基材的情形時，大多要求屬於本發明之組成物之特徵之一的透明性，因此被更好地應用。 Examples of metal oxides include tin oxide, indium oxide, titanium oxide, and zinc oxide. Examples of metals include gold, silver, copper, aluminum, iron, nickel, and titanium. Among these, when a transparent film formed by evaporation, sputtering, or the like is used as a base material, most of them require transparency, which is one of the characteristics of the composition of the present invention, and therefore are better used.

再者，於塑膠薄膜等為難接著性之材質之情形時，可於塗佈本發明之組成物之前，對一者或兩者之表面進行活化處理。作為表面活化處理，可列舉電漿處理、電暈放電處理、藥液處理、粗面化處理及蝕刻處理、火焰處理等，亦可併用該等。 Furthermore, in the case where plastic films and other materials are difficult to adhere to, the surface of one or both of them can be activated before coating the composition of the present invention. Examples of the surface activation treatment include plasma treatment, corona discharge treatment, chemical treatment, roughening treatment, etching treatment, flame treatment, etc., and these may be used in combination.

8.使用方法 8. How to use

作為本發明之組成物之使用方法，按照常規方法即可，可列舉在將組成物塗佈於基材後，與另一基材貼合，並照射活性能量射線之方法等。本發明之組成物適合於接著作為基材之薄層被接著體之情形。於接著薄層被接著體之情形時之使用方法按照層壓之製造中通常所進行之方法即可。例如，可列舉將組成物塗佈於第1薄層被接著體，將第2薄層被接著體貼合於其上，並進行活性能量射線之照射之方法等。 The method for using the composition of the present invention may be a conventional method, and a method of applying the composition to a substrate, bonding it to another substrate, and irradiating an active energy ray, etc. may be mentioned. The composition of the present invention is suitable for a case where a thin layer to be bonded as a substrate is attached. In the case where the thin layer is adhered, the method of use may be a method generally performed in the manufacture of lamination. For example, a method of applying the composition to the first thin-layer adherend, bonding the second thin-layer adherend to it, and irradiating the active energy ray, etc. may be mentioned.

對基材之塗佈按照習知所知之方法即可，例如可列舉：自然式塗佈機、刮刀帶式塗佈機、浮動刮刀法、輥襯刮刀法、墊襯刮刀法、噴霧法、浸漬法、接觸輥法、壓輥法、逆轉輥法、氣刀法、淋幕式塗佈機、缺角輪塗佈機、凹版塗佈機、微凹版塗佈機、模具塗佈機及簾幕式塗佈機等方法。 The coating of the substrate may be performed according to a conventionally known method, and examples thereof include a natural coater, a blade belt coater, a floating blade method, a roll liner blade method, a liner blade method, and a spray method. Dipping method, contact roller method, pressure roller method, reverse roller method, air knife method, shower coater, notched wheel coater, gravure coater, micro gravure coater, die coater and curtain Screen coating machine and other methods.

又，本發明之組成物之塗佈厚度根據使用之基材及用途進行選擇即可，較佳為0.1~10μm，更佳為1~5μm。 In addition, the coating thickness of the composition of the present invention may be selected according to the base material and application to be used, preferably 0.1 to 10 μm, more preferably 1 to 5 μm.

作為活性能量射線，可列舉可見光線、紫外線、X射線及電子束等，由於可使用廉價之裝置，因此較佳為紫外線。 Examples of active energy rays include visible rays, ultraviolet rays, X-rays, and electron beams. Since inexpensive devices can be used, ultraviolet rays are preferred.

作為於藉由紫外線使其硬化之情形之光源，可使用各種光源，例如可列舉：加壓或高壓水銀燈、金屬鹵素燈、氙氣燈、無電極放電燈、碳弧燈及發光二極體(LED，Light Emitting Diode)等。該等之中，特佳為高壓水銀燈及金屬鹵素燈。紫外線之照射量於UV-B區域(310nm附近)中，較佳為10~1,000mJ/cm2，更佳為20~500mJ/cm2，進而較佳為50~200mJ/cm2。 As a light source for curing by ultraviolet rays, various light sources can be used, and examples include pressurized or high-pressure mercury lamps, metal halide lamps, xenon lamps, electrodeless discharge lamps, carbon arc lamps, and light emitting diodes (LED , Light Emitting Diode), etc. Among these, Tejia are high-pressure mercury lamps and metal halogen lamps. The irradiation amount of ultraviolet rays in the UV-B region (near 310 nm) is preferably 10 to 1,000 mJ/cm 2 , more preferably 20 to 500 mJ/cm 2 , and still more preferably 50 to 200 mJ/cm 2 .

於藉由電子束使其硬化之情形時，作為可使用之電子束(EB，electron beam)照射裝置可使用各種裝置，例如可列舉柯克勞夫-沃耳吞(Cockcroft-Walton)型、凡德格拉夫型及共振變壓器型裝置等，作為電子束，較佳為具有50~1000eV之能量者，更佳為100~300eV。 In the case of hardening by an electron beam, various devices can be used as the electron beam (EB) irradiation device that can be used, for example, a Cockcroft-Walton type, ordinary De Graf type and resonance transformer type devices, etc., as the electron beam, preferably have an energy of 50~1000eV, more preferably 100~300eV.

9.積層體之製造方法 9. Manufacturing method of laminate

本發明之組成物可較佳地使用於積層體之製造。作為積層體之構成，係由基材、上述組成物之硬化物、及其他基材所構成之積層體，其中，上述基材及其他基材之兩者或一者為塑膠製薄膜或片材者。作為塑膠薄膜等，較佳為至少一者為(甲基)丙烯酸系樹脂、乙酸纖維素系樹脂、或環烯烴聚合物者。作為積層體之製造方法，具體而言，可列舉將上述組成物塗佈於基材，將其他基材貼合於該塗佈面，並自上述基材或其他基材之任一側照射活性能量射線之方法 等。於該情形時，作為上述基材及上述其他基材之兩者之基材、或至少一基材，使用塑膠薄膜等。基材之具體例及較佳例係如上所述。組成物之塗佈方法、組成物之膜厚、活性能量射線之種類之照射條件等亦如上所述。 The composition of the present invention can be preferably used in the production of laminates. The structure of the layered body is a layered body composed of a base material, a cured product of the above composition, and other base materials, wherein either or one of the above base materials and other base materials is a plastic film or sheet By. As the plastic film or the like, it is preferable that at least one is (meth)acrylic resin, cellulose acetate resin, or cycloolefin polymer. As a method of manufacturing the laminate, specifically, the above composition is applied to a substrate, another substrate is bonded to the coated surface, and the activity is irradiated from either side of the above substrate or other substrate Energy ray method Wait. In this case, a plastic film or the like is used as the substrate of both the aforementioned substrate and the aforementioned other substrate, or at least one substrate. Specific examples and preferred examples of the substrate are as described above. The coating method of the composition, the film thickness of the composition, the irradiation conditions of the type of active energy rays, etc. are also as described above.

作為所獲得之積層體之用途，可列舉於液晶顯示器、有機EL顯示器等中所使用之各種光學薄膜等，具體而言，可列舉：賦予防指紋或防眩等功能性之硬塗薄膜、觸控面板之前面板、偏光板、相位差薄膜、視角補償薄膜、增亮薄膜、抗反射薄膜、防眩薄膜、透鏡片材及擴散片材等。 Examples of applications of the obtained laminate include various optical films used in liquid crystal displays, organic EL displays, and the like, and specific examples include hard-coated films that provide functionality such as anti-fingerprint or anti-glare, touch Front panel of control panel, polarizing plate, retardation film, viewing angle compensation film, brightening film, anti-reflection film, anti-glare film, lens sheet and diffusion sheet, etc.

[實施例] [Example]

以下列舉實施例及比較例，對本發明進行更具體地說明。但是，本發明並不受該等例所限定。再者，以下，「份」意指重量份，表中之表示調配比例之數值意指重量%。 Examples and comparative examples are listed below to explain the present invention more specifically. However, the present invention is not limited by these examples. In addition, in the following, "parts" means parts by weight, and the values in the table indicating the blending ratio mean% by weight.

於實施例及比較例中，用於製備組成物之各成分係如下所述，以下，如下般簡略記述。 In the examples and comparative examples, the components used to prepare the composition are as follows, and are briefly described below.

(A)成分 (A) Ingredients (A1)成分 (A1) Ingredients

‧J-1004：雙酚A型固形環氧樹脂，三菱化學(股)製造之「jER-1004」 ‧J-1004: Bisphenol A type solid epoxy resin, "jER-1004" manufactured by Mitsubishi Chemical Corporation

‧850CRP：雙酚A型環氧樹脂之蒸餾精製品(分子量340)，DIC(股)製造之「EPICLON 850-CRP」 ‧850CRP: Distilled refined product of bisphenol A epoxy resin (molecular weight 340), "EPICLON 850-CRP" manufactured by DIC Corporation

‧Y-8000：氫化雙酚A型環氧樹脂，三菱化學(股)製造之「YX-8000」 ‧Y-8000: Hydrogenated bisphenol A epoxy resin, "YX-8000" manufactured by Mitsubishi Chemical Corporation

‧J-157S70：雙酚A酚醛清漆型環氧榭脂，三菱化學(股)製造之「jER-157S70」 ‧J-157S70: Bisphenol A novolac epoxy resin, "jER-157S70" manufactured by Mitsubishi Chemical Corporation

(A2)成分 (A2) Ingredients

‧聚合物X：製造例1之生成物甲基丙烯酸縮水甘油酯、甲基丙烯酸甲酯、及苯乙烯之共聚合體 ‧Polymer X: copolymer of glycidyl methacrylate, methyl methacrylate, and styrene

(B)成分 (B) Ingredients

‧BD-DGE：1,4-丁二醇二縮水甘油醚(蒸餾精製品)，阪本藥品工業(股)製造之「SR-14BJ」 BD-DGE: 1,4-butanediol diglycidyl ether (distilled refined product), "SR-14BJ" manufactured by Sakamoto Pharmaceutical Co., Ltd.

‧HD-DGE：1,6-己二醇二縮水甘油醚(蒸餾精製品)，四日市合成(股)製造之「Epogosey HD(D)」 ‧HD-DGE: 1,6-Hexanediol diglycidyl ether (distilled refined product), "Epogosey HD(D)" manufactured by Yokkaichi Synthetic Co., Ltd.

(C)成分 (C) Ingredients

‧OXT-221：雙[(3-乙基氧雜環丁烷-3-基)甲基]醚，東亞合成(股)製造之「Aron oxetane OXT-221」 ‧OXT-221: bis[(3-ethyloxetan-3-yl)methyl] ether, "Aron oxetane OXT-221" manufactured by East Asia Synthetic Co., Ltd.

(D)成分 (D) Ingredients

‧110P：三芳基鋶六氟磷酸鹽(有效成分100%)，SAN-APRO(股)製造之「CPI-110P」 ‧110P: Triaryl hexafluorophosphate (100% active ingredient), "CPI-110P" manufactured by SAN-APRO Co., Ltd.

(E)成分 (E) Ingredient

‧LA-1114：聚丙烯酸丁酯與聚甲基丙烯酸甲酯之嵌段共聚合體(構成單體單位之主成分為丙烯酸丁酯，單末端PMMA)(聚丙烯酸丁酯嵌段單位之Tg：-50℃，Mw：80,000，室溫下為液狀)，可樂 麗(股)製造之「Clarity LA1114」 ‧LA-1114: block copolymer of polybutyl acrylate and polymethyl methacrylate (the main component of the monomer unit is butyl acrylate, single-terminal PMMA) (Tg of polybutyl acrylate block unit:- 50℃, Mw: 80,000, liquid at room temperature), Coke "Clarity LA1114" manufactured by Lai

‧LA-2140：聚丙烯酸丁酯與聚甲基丙烯酸甲酯之嵌段共聚合體(構成單體單位之主成分為丙烯酸丁酯，兩末端PMMA)(聚丙烯酸丁酯嵌段單位之Tg：-50℃，Mw：80,000)，可樂麗(股)製造之「Clarity LA2140e」 ‧LA-2140: block copolymer of polybutyl acrylate and polymethyl methacrylate (the main component of the monomer unit is butyl acrylate, PMMA at both ends) (Tg of polybutyl acrylate block unit:- 50°C, Mw: 80,000), "Clarity LA2140e" manufactured by Kuraray Co., Ltd.

(其他)[其他成分] (Other) [other ingredients]

‧2N-220S：聚酯二醇(數量平均分子量2,000，熔點0℃)，豐國製油(股)製造之「HS2N-220S」 ‧2N-220S: Polyester diol (quantity average molecular weight 2,000, melting point 0°C), "HS2N-220S" manufactured by Feng Guo Oil Co., Ltd.

‧BR-83：聚甲基丙烯酸甲酯(Mw：40,000，Tg=105℃)，三菱麗陽(股)製造之「Dianal BR-83」 ‧BR-83: Polymethyl methacrylate (Mw: 40,000, Tg=105℃), "Dianal BR-83" manufactured by Mitsubishi Rayon Co., Ltd.

‧聚合物Y：製造例2之生成物 ‧Polymer Y: Product of Production Example 2

1.製造例 1. Manufacturing Example 1)製造例1 1) Manufacturing example 1

將具備油夾套之容量1000mL之加壓式攪拌槽型反應器的夾套溫度保持為190℃。繼而，一邊將反應器之壓力保持固定，一邊開始以固定之供給速度(48g/min，滯留時間：12分鐘)將包含甲基丙烯酸縮水甘油酯(30份)、甲基丙烯酸甲酯(以下，稱為「MMA」)(45份)、苯乙烯(25份)、作為聚合溶劑之甲基乙基酮(18份)、作為聚合起始劑之二-第三丁基過氧化物(0.25份)之單體混合物自原料罐連續供給至反應器，將相當於單體混合物之供給量之反應液自出口連續地抽出。反應剛開始後，暫時降低反應溫度後，確認出因聚合熱引起之溫度上升，但藉由控制油夾套溫度，而使反應器之內溫保持 為192~194℃。將反應器內溫穩定後以36分鐘後之時間點作為反應液之採集時間點，此後繼續反應25分鐘，結果供給1.2kg之單體混合液，回收1.2kg之反應液。其後，將反應液導入至薄膜蒸發器，分離未反應單體等揮發成分，去除未反應單體等揮發成分，而獲得聚合體「聚合物X」。測定GPC，結果聚苯乙烯換算之數量平均分子量(Mn)為3,500，Mw(重量平均分子量)為9,900，Tg(DSC測定，升溫速度10℃/min)為65℃。 The jacket temperature of the pressurized stirred tank reactor with an oil jacket capacity of 1000 mL was maintained at 190°C. Then, while keeping the pressure of the reactor fixed, the glycidyl methacrylate (30 parts) and methyl methacrylate (below, at a fixed supply rate (48 g/min, residence time: 12 minutes) (Referred to as "MMA") (45 parts), styrene (25 parts), methyl ethyl ketone (18 parts) as a polymerization solvent, di-tert-butyl peroxide (0.25 parts) as a polymerization initiator ) The monomer mixture is continuously supplied from the raw material tank to the reactor, and the reaction liquid corresponding to the supply amount of the monomer mixture is continuously withdrawn from the outlet. Immediately after the start of the reaction, after temporarily lowering the reaction temperature, it was confirmed that the temperature rise due to the heat of polymerization, but by controlling the temperature of the oil jacket, the internal temperature of the reactor was maintained It is 192~194℃. After the internal temperature of the reactor was stabilized, the time point after 36 minutes was taken as the collection time point of the reaction liquid, and then the reaction was continued for 25 minutes. As a result, 1.2 kg of the monomer mixed liquid was supplied, and 1.2 kg of the reaction liquid was recovered. Thereafter, the reaction liquid is introduced into a thin-film evaporator, and volatile components such as unreacted monomers are separated, and volatile components such as unreacted monomers are removed to obtain a polymer "Polymer X". When GPC was measured, the number-average molecular weight (Mn) in terms of polystyrene was 3,500, Mw (weight average molecular weight) was 9,900, and Tg (DSC measurement, temperature increase rate 10°C/min) was 65°C.

2)製造例2 2) Manufacturing example 2

將與製造例1相同之反應器之夾套溫度保持為181℃。 The jacket temperature of the same reactor as in Production Example 1 was maintained at 181°C.

繼而，一邊將反應器之壓力保持固定，一邊開始以與製造例1相同之固定之供給速度將包含丙烯酸丁酯(45份)、丙烯酸2-乙基己酯(45份)、MMA(10份)、作為聚合溶劑之異丙醇(9份)、甲基乙基酮(MEK，methyl ethyl ketone)(9份)、作為聚合起始劑之鄰苯二甲酸二丁酯(DBP，Dibutyl phthalate)(0.25份)之單體混合物自原料罐連續供給至反應器，將相當於單體混合物之供給量之反應液自出口連續地抽出。反應剛開始後，暫時降低反應溫度後，確認出因聚合熱引起之溫度上升，但藉由控制油夾套溫度，而使反應器之內溫保持為183~185℃。將反應器內溫穩定後以36分鐘後之時間點作為反應液之採集開始點，此後繼續反應25分鐘，結果供給1.2kg之單體混合液，回收1.2kg之反應液。其後，將反應液導入至薄膜蒸發器，分離未反應單體等揮發成分，去除未反應單體等揮發成分，而獲得聚合體「聚合物Y」。藉由與製造例1相同之方法對所獲得之聚合物Y進行評價，結果Mn為2,500，Mw為7,500，Tg為-55℃， 黏度於25℃下為20,000mPa‧s。 Then, while keeping the pressure of the reactor fixed, the butyl acrylate (45 parts), 2-ethylhexyl acrylate (45 parts), and MMA (10 parts) were started at the same fixed supply rate as in Production Example 1. ), isopropyl alcohol (9 parts) as a polymerization solvent, methyl ethyl ketone (MEK) (9 parts), dibutyl phthalate (DBP) as a polymerization initiator (0.25 parts) of the monomer mixture is continuously supplied from the raw material tank to the reactor, and the reaction liquid corresponding to the supply amount of the monomer mixture is continuously withdrawn from the outlet. Immediately after the start of the reaction, after temporarily lowering the reaction temperature, it was confirmed that the temperature rise due to the heat of polymerization, but by controlling the temperature of the oil jacket, the internal temperature of the reactor was maintained at 183 to 185°C. After the internal temperature of the reactor was stabilized, the time point after 36 minutes was taken as the starting point for collecting the reaction liquid, and then the reaction was continued for 25 minutes. As a result, 1.2 kg of the monomer mixture liquid was supplied, and 1.2 kg of the reaction liquid was recovered. Thereafter, the reaction solution was introduced into a thin-film evaporator, and volatile components such as unreacted monomers were separated, and volatile components such as unreacted monomers were removed to obtain a polymer "Polymer Y". The obtained polymer Y was evaluated by the same method as in Production Example 1. As a result, Mn was 2,500, Mw was 7,500, and Tg was -55°C. The viscosity is 20,000mPa‧s at 25℃.

2.實施例1~實施例5、比較例1~比較例7 2. Example 1 to Example 5, Comparative Example 1 to Comparative Example 7 1)組成物之製造 1) Manufacture of composition

以各者之比例調配表1~表3所示之各成分，按照常規方法進行攪拌混合，製備活性能量射線硬化型接著劑組成物。利用東機產業(股)製造之E型黏度計對所獲得之組成物測定25℃下之黏度。 The components shown in Table 1 to Table 3 are blended in proportions of each, and stirred and mixed according to a conventional method to prepare an active energy ray-curable adhesive composition. Using an E-type viscometer manufactured by Toki Industries Co., Ltd., the viscosity of the obtained composition was measured at 25°C.

2)積層體之製造 2) Manufacturing of laminates

對厚度100μm之環烯烴聚合物[商品名ZEONOR ZF-14，日本瑞翁(股)製造，以下稱為「ZEONOR」]、及厚度75μm之加有UV吸收劑之丙烯酸系樹脂[商品名HI50-75KT-UV，可樂麗(股)製造，以下稱為「PMMA」]實施作為易接著處理之電暈處理。繼而，於藉由棒式塗佈機將所獲得之組成物塗佈於PMMA之電暈處理面至厚度3μm之後，層壓ZEONOR。此時，以使ZEONOR之電暈處理面與塗佈面接觸之方式配置。最後，藉由EYE GRAPHICS(股)製造之附有帶式輸送機之紫外線照射裝置(使用金屬鹵素燈)，以累計光量100mJ/cm2(UV-B)自ZEONOR之表面照射紫外線，而使接著劑組成物硬化(23℃、50%環境)。按照與上述相同之順序，亦製作將PMMA變更為厚度80μm之三乙酸纖維素[商品名富士TAC，富士軟片(股)製造，以下稱為「TAC」]之積層體。所獲得之積層體於23℃、相對濕度50%之條件下放置1天後，按照下述方法，對無色透明性及接著力進行評價。將該等之結果示於表1~表3。 For cyclic olefin polymers with a thickness of 100 μm [trade name ZEONOR ZF-14, manufactured by Japan Ruion Co., Ltd., hereinafter referred to as “ZEONOR”], and acrylic resin with a UV absorber thickness of 75 μm [trade name HI50- 75KT-UV, manufactured by Kuraray Co., Ltd., hereinafter referred to as "PMMA"] is implemented as a corona treatment as an easy adhesion process. Then, after applying the obtained composition to the corona-treated surface of PMMA by a bar coater to a thickness of 3 μm, ZEONOR was laminated. At this time, the corona treatment surface of ZEONOR is arranged so as to be in contact with the coating surface. Finally, the ultraviolet irradiation device (using a metal halide lamp) with a belt conveyor manufactured by EYE GRAPHICS Co., Ltd. irradiates ultraviolet rays from the surface of ZEONOR with a cumulative light amount of 100mJ/cm 2 (UV-B), and then The agent composition hardens (23°C, 50% environment). In the same order as above, a layered body of cellulose triacetate [trade name Fuji TAC, manufactured by Fuji Film (share), hereinafter referred to as "TAC"] with PMMA changed to a thickness of 80 μm was also produced. After the obtained laminate was allowed to stand for 1 day under the conditions of 23° C. and 50% relative humidity, the colorless transparency and the adhesion were evaluated according to the following method. The results are shown in Table 1 to Table 3.

3.評價方法 3. Evaluation method 1)無色透明性之評價 1) Evaluation of colorless transparency

將5片所獲得之積層體重疊並進行目視觀察，按照以下之基準進行判定。 The laminates obtained by stacking 5 sheets were visually observed and judged according to the following criteria.

A：完全未感到渾濁或黃變 A: No turbidity or yellowing at all

B：感到些許渾濁或黃變 B: I feel a little cloudy or yellow

C：明顯感到渾濁或黃變 C: Obviously feel cloudy or yellow

2)接著力之評價 2) Evaluation of adhesion

○常溫保管後 ○After storage at room temperature

將所獲得之積層體切割為寬度1英吋、長度15cm，藉由雙面膠帶將PMMA或TAC側貼附於鋁板。繼而，以剝離速度200mm/min將ZEONOR進行90°剝離，測定接著力。此時，將薄膜立刻破裂而無法測定者評價為「材料破裂」。於能夠剝離之情形時，剝離止於5cm，進行以下所示之耐濕熱試驗。 The obtained laminate was cut to a width of 1 inch and a length of 15 cm, and the PMMA or TAC side was attached to an aluminum plate with double-sided tape. Then, ZEONOR was peeled at 90° at a peeling speed of 200 mm/min, and the adhesive force was measured. At this time, the film was immediately broken and the person who could not measure it was evaluated as "material breakage". When peeling is possible, the peeling stops at 5 cm, and the humidity and heat resistance test shown below is performed.

○耐濕熱試驗後 ○After humidity and heat resistance test

將測定過常溫保管後之接著力之試驗片投入至85℃、85%之恆溫恆濕槽2天後，與「常溫保管後」之測定同樣地測定接著力。 After putting the test piece which measured the adhesive force after storage at normal temperature into a constant temperature and humidity tank at 85°C and 85% for 2 days, the adhesive force was measured in the same manner as the measurement after "normal temperature storage".

Figure 105106456-A0101-12-0032-13
Figure 105106456-A0101-12-0032-13

Figure 105106456-A0101-12-0032-14
Figure 105106456-A0101-12-0032-14

Figure 105106456-A0101-12-0033-4
Figure 105106456-A0101-12-0033-4

本發明之實施例1~實施例5之組成物對ZEONOR、TAC、及PMMA之任一者均顯示較強之接著力，該接著力於85℃、85%下保持2天後仍較強。另一方面，除去實施例1之作為(E)成分之LA-1114而替換為J-1004的比較例1之組成物雖對ZEONOR及PMMA之接著力較為強力，但對TAC之接著力較低。反之，除去實施例1之作為(A)成分之J-1004而替換為LA-1114的比較例2之組成物對TAC及PMMA之接著力下降。藉此可知：實施例1之對TAC之較強之接著力係基於藉由包含(A)成分與(E)成分兩者而得之協同效應。又，除去實施例5之作為(E)成分之LA-2140而替換為聚合物X的比較例3之組成物對ZEONOR及PMMA之接著力較為強力，但對TAC之接著力較低。將實施例1之LA-1114替換為作為聚酯二醇之2N-220S的比較例4之組成物、及將實施例1之 LA-1114替換為分子量較低之(甲基)丙烯酸系聚合物的比較例5之組成物雖對ZEONOR及PMMA之接著力較強，但對TAC之接著力較低。將實施例5之組成物之LA-2140替換為Tg較高的作為PMMA系聚合物之BR-83之比較例6之組成物亦對ZEONOR及PMMA之接著力較為強力，但對TAC之接著力較低。雖按照本發明中規定之比例含有(A)、(C)、(D)、及(E)成分，但以未滿本發明之下限10重量%之6重量%含有(B)成分的比較例7之組成物對ZEONOR及PMMA之接著力較強，但對TAC之接著力較低。 The compositions of Examples 1 to 5 of the present invention showed strong adhesion to any of ZEONOR, TAC, and PMMA, and the adhesion was still strong after being maintained at 85°C and 85% for 2 days. On the other hand, the composition of Comparative Example 1 except that the LA-1114 of Example 1 was replaced with J-1004 and replaced with J-1004 was stronger in adhesion to ZEONOR and PMMA, but lower in adhesion to TAC . On the contrary, the composition of Comparative Example 2 in which the J-1004 as the component (A) of Example 1 was removed and replaced with LA-1114 had lower adhesion to TAC and PMMA. From this, it can be seen that the stronger adhesion to TAC of Example 1 is based on the synergistic effect obtained by including both the (A) component and the (E) component. In addition, the composition of Comparative Example 3, in which the LA-2140 as the component (E) of Example 5 was removed and replaced with the polymer X, had stronger adhesion to ZEONOR and PMMA, but lower adhesion to TAC. The composition of Comparative Example 4 which replaced LA-1114 of Example 1 with 2N-220S which is polyester diol, and the Although the composition of Comparative Example 5 in which LA-1114 was replaced with a (meth)acrylic polymer having a lower molecular weight, the adhesion to ZEONOR and PMMA was stronger, but the adhesion to TAC was lower. The composition of Comparative Example 6 in which LA-2140 of the composition of Example 5 was replaced by BR-83 which is a PMMA-based polymer with a higher Tg was also stronger for the adhesion of ZEONOR and PMMA, but the adhesion of TAC Lower. Although the components (A), (C), (D), and (E) are contained in the ratio specified in the present invention, the comparative example containing the component (B) at 6% by weight which is less than the lower limit of 10% by weight of the present invention The composition of 7 has stronger adhesion to ZEONOR and PMMA, but lower adhesion to TAC.

(產業上之可利用性) (Industry availability)

本發明之組成物可使用作為塑膠製薄膜等之接著劑，尤其是可適宜地使用於液晶顯示器或有機EL顯示器所使用之光學薄膜之接著。 The composition of the present invention can be used as an adhesive for plastic films or the like, and in particular, it can be suitably used for the bonding of optical films used in liquid crystal displays or organic EL displays.

Claims (13)

一種塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物，其含有：(A)成分：1分子中具有2個以上之芳香環及2個以上之縮水甘油醚基之芳香族環氧樹脂、及/或上述芳香族環氧樹脂之氫化型環氧樹脂(B)成分：具有碳數2~10個之多元醇之聚縮水甘油醚(C)成分：1分子中具有2個以上之氧雜環丁烷基之分子量500以下之化合物(D)成分：光陽離子聚合起始劑(E)成分：(E1)玻璃轉移溫度20℃以下且重量平均分子量20,000~1,000,000之聚合體、及/或(E2)玻璃轉移溫度20℃以下之具有嵌段單位之重量平均分子量20,000~1,000,000之嵌段共聚合體，且上述(A)~(E)成分之含有比例係於組成物整體中，(A)成分：1~30重量%(B)成分：10~70重量%(C)成分：10~70重量%(D)成分：0.5~10重量%(E)成分：1~20重量%。 An active energy ray-curable adhesive composition for plastic films or sheets, comprising: (A) component: an aromatic epoxy having 2 or more aromatic rings and 2 or more glycidyl ether groups in 1 molecule Resin, and/or the hydrogenated epoxy resin (B) component of the above-mentioned aromatic epoxy resin: polyglycidyl ether (C) component having a polyhydric alcohol having 2 to 10 carbon atoms: 2 or more in one molecule Compound (D) component of oxetanyl group with molecular weight below 500: photo-cationic polymerization initiator (E) component: (E1) polymer with glass transition temperature below 20°C and weight average molecular weight of 20,000-1,000,000, and/ Or (E2) a block copolymer having a block-average weight average molecular weight of 20,000 to 1,000,000 with a glass transition temperature of 20°C or less, and the content ratio of the above components (A) to (E) is in the entire composition, (A ) Ingredients: 1 to 30% by weight (B) Ingredients: 10 to 70% by weight (C) Ingredients: 10 to 70% by weight (D) Ingredients: 0.5 to 10% by weight (E) Ingredients: 1 to 20% by weight. 如請求項1之塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物，其中，(E)成分係以丙烯酸烷基酯作為必需構成單體，且重量平均分子量20,000~500,000之聚合體。 The active energy ray-curable adhesive composition for plastic films or sheets as claimed in claim 1, wherein (E) component is a polymer having alkyl acrylate as an essential constituent monomer and having a weight average molecular weight of 20,000 to 500,000 . 如請求項1之塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物，其中，(A)成分為以含有烴環構造之自由基聚合性單體 及含有縮水甘油基之自由基聚合性單體作為必需構成單體之重量平均分子量1,000~1,000,000之聚合體。 The active energy ray-curable adhesive composition for plastic films or sheets according to claim 1, wherein component (A) is a radical polymerizable monomer having a hydrocarbon ring structure And a radical polymerizable monomer containing a glycidyl group is a polymer having a weight average molecular weight of 1,000 to 1,000,000, which is necessary to constitute the monomer. 如請求項1之塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物，其中，(B)成分為具有碳數2~6個之二醇之二縮水甘油醚。 The active energy ray-curable adhesive composition for plastic films or sheets according to claim 1, wherein component (B) is diglycidyl ether of a diol having 2 to 6 carbon atoms. 如請求項1之塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物，其中，(B)成分為具有碳數4~6個之烷二醇之二縮水甘油醚。 The active energy ray-curable adhesive composition for plastic films or sheets according to claim 1, wherein the component (B) is a diglycidyl ether having an alkylene glycol having 4 to 6 carbon atoms. 如請求項1之塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物，其中，(C)成分為下述式(1)所表示之氧雜環丁烷化合物，
Figure 105106456-A0305-02-0039-1
 The active energy ray-curable adhesive composition for plastic films or sheets according to claim 1, wherein component (C) is an oxetane compound represented by the following formula (1),
Figure 105106456-A0305-02-0039-1
 如請求項1之塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物，其中，(D)成分為鋶鹽系光陽離子聚合起始劑。 The active energy ray hardening type adhesive composition for plastic films or sheets according to claim 1, wherein the component (D) is a photo salt cationic polymerization initiator. 如請求項1之塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物，其中，於組成物整體中含有1~20重量%之(A)成分、25~65重量%之(B)成分、20~60重量%之(C)成分、1~5重量%之(D)成分、及3~15重量%之(E)成分。 The active energy ray-curable adhesive composition for plastic films or sheets according to claim 1, which contains 1 to 20% by weight of (A) component and 25 to 65% by weight of (B) in the entire composition Ingredients, 20 to 60% by weight of (C) ingredient, 1 to 5% by weight of (D) ingredient, and 3 to 15% by weight of (E) ingredient. 如請求項1之塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物，其中，於組成物整體中含有0.05~3重量%之水。 The active energy ray-curable adhesive composition for plastic films or sheets according to claim 1, wherein the entire composition contains 0.05 to 3% by weight of water. 如請求項1之塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物，其中，塑膠製薄膜或片材之至少一者為(甲基)丙烯酸系 樹脂、乙酸纖維素系樹脂、或環烯烴聚合物。 The active energy ray-curable adhesive composition for plastic films or sheets according to claim 1, wherein at least one of the plastic films or sheets is (meth)acrylic Resin, cellulose acetate resin, or cycloolefin polymer. 一種積層體，其係由基材、請求項1至10中任一項之塑膠製薄膜或片材用活性能量射線硬化型接著劑組成物之硬化物、及其他基材所構成者，其中，上述基材及上述其他基材之兩者或一者為塑膠製薄膜或片材。 A laminate comprising a substrate, a cured product of an active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 10, and other substrates, wherein, Two or one of the above substrates and the other substrates are plastic films or sheets. 如請求項11之積層體，其中，塑膠製薄膜或片材之至少一者為(甲基)丙烯酸系樹脂、乙酸纖維素系樹脂、或環烯烴聚合物。 The laminate according to claim 11, wherein at least one of the plastic film or sheet is (meth)acrylic resin, cellulose acetate resin, or cycloolefin polymer. 一種積層體之製造方法，其係將請求項1至10中任一項之組成物塗佈於基材，將其他基材貼合於塗佈面，並自上述基材或上述其他基材之任一側照射活性能量射線者，其中，上述基材及上述其他基材之兩者或一者為塑膠製薄膜或片材。 A method for manufacturing a laminate, which is to apply the composition of any one of claims 1 to 10 to a substrate, and to adhere the other substrate to the coated surface, and to obtain the composition from the above substrate or the other substrate The active energy ray is irradiated on either side, wherein both or one of the above substrate and the other substrate is a plastic film or sheet.
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