TW201420718A - Photocuring adhesive agent composition, cured object, adhesive sheet and display panel and producing method thereof - Google Patents

Photocuring adhesive agent composition, cured object, adhesive sheet and display panel and producing method thereof Download PDF

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TW201420718A
TW201420718A TW102133939A TW102133939A TW201420718A TW 201420718 A TW201420718 A TW 201420718A TW 102133939 A TW102133939 A TW 102133939A TW 102133939 A TW102133939 A TW 102133939A TW 201420718 A TW201420718 A TW 201420718A
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meth
acrylate
adhesive composition
component
photocurable
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TW102133939A
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Chinese (zh)
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Akira Satou
Yoshikazu Saito
Youichi Hamano
Kouji Hayama
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Mitsubishi Rayon Co
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Publication of TW201420718A publication Critical patent/TW201420718A/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

A photocuring adhesive agent composition of the invention includes a reactive polymer (constituent A), a monomer (constituent B) having a polymerizable double bond, and a photo polymerization initiator (constituent C). A main chain of the reactive polymer (constituent A) contains a repeated unit derived from a (meth)acrylic monomer and a side chain contains a double bond. A double bond equivalent weight as a polymer mass of every 1 mole double bond ranges from 10, 000 g/mol to 100, 000 g/mol, and a weight average molecule weight (Mw) ranges from 25, 000 to 1, 000, 000. The display panel of the invention has a layer of an adhesive agent obtained by curing the photocuring adhesive agent composition on the display body and has the optical function material on the layer.

Description

光硬化型黏著劑組成物及顯示面板 Photocurable adhesive composition and display panel

本發明是有關於一種具有適度的黏著力、且貼合於顯示體上的光學功能材料的再剝離性(重新加工(rework)性)優異的光硬化型黏著劑組成物，及利用該黏著劑組成物將光學功能材料貼合於顯示體上的顯示面板。 The present invention relates to a photocurable adhesive composition having excellent removability (reworkability) of an optical functional material bonded to a display body and having an appropriate adhesive force, and the use of the adhesive The composition bonds the optical functional material to the display panel on the display body.

通常藉由活性能量線的照射而顯現黏著力的活性能量線硬化型黏著劑因無溶劑，故不會產生揮發性有機化合物(Volatile Organic Compound，VOC)。另外，具有如下等優異的特性，即於顯現黏著力時無需加熱，而可與活性能量線照射大致同時地顯現黏著力，且於製造黏著劑時無需固化期(curing period)，該活性能量線硬化型黏著劑的利用正在擴大。 The active energy ray-curable adhesive which usually exhibits an adhesive force by irradiation with an active energy ray does not generate a volatile organic compound (VOC) because it has no solvent. In addition, it has excellent characteristics such that it does not require heating when the adhesive force is expressed, and the adhesive force can be exhibited substantially simultaneously with the irradiation of the active energy ray, and a curing period is not required in the production of the adhesive, and the active energy ray is not required. The use of hardening adhesives is expanding.

例如，於專利文獻1中揭示有一種光學樹脂黏著劑，其包含側鏈上具有(甲基)丙烯醯基的丙烯酸系聚合物與光聚合起始劑作為必需成分，並填埋作為顯示體的圖像顯示面板與作為光學功能材料的保護蓋板之間的間隙。 For example, Patent Document 1 discloses an optical resin adhesive comprising an acrylic polymer having a (meth)acryl fluorenyl group in a side chain and a photopolymerization initiator as an essential component, and is filled as a display body. A gap between the image display panel and a protective cover as an optical functional material.

當製造包含經由黏著劑而配設於顯示體上的光學功能材料的顯示面板時，有時顯示體與光學功能材料的貼合位置會偏離，於此情況下，為了不浪費昂貴的顯示體，將被接著物彼此剝離並進行修復(重新加工)。於專利文獻1中，因光學樹脂黏著劑中的丙烯酸系聚合物(A)的分子量低，故於重新加工時黏著劑殘留(以下，稱為「殘膠(adhesive residue)」)於圖像顯示面板的表面，因此利用溶劑使其膨潤來進行去除。 When a display panel including an optical functional material disposed on a display body via an adhesive is manufactured, the bonding position of the display body and the optical functional material may be deviated. In this case, in order not to waste an expensive display body, The adherends are peeled off from each other and repaired (reworked). In Patent Document 1, since the molecular weight of the acrylic polymer (A) in the optical resin adhesive is low, the adhesive remains (hereinafter referred to as "adhesive residue") on the image display during reworking. The surface of the panel is thus removed by swelling with a solvent.

於專利文獻2中揭示有一種紫外線硬化型的黏著劑組成物，其含有於(甲基)丙烯酸系聚合物的側鏈上導入具有雙鍵的化合物而成的反應性聚合物。該黏著劑組成物是除上述反應性聚合物以外，含有(甲基)丙烯酸酯單體、可與(甲基)丙烯酸酯單體進行共聚的單官能單體及光聚合起始劑等的組成物，若照射紫外線，則光聚合起始劑發揮作用，上述反應性聚合物與(甲基)丙烯酸酯單體或單官能單體之間進行聚合反應，而顯現黏著力。 Patent Document 2 discloses an ultraviolet curable adhesive composition comprising a reactive polymer obtained by introducing a compound having a double bond to a side chain of a (meth)acrylic polymer. The adhesive composition is a composition containing a (meth) acrylate monomer, a monofunctional monomer copolymerizable with a (meth) acrylate monomer, and a photopolymerization initiator, in addition to the above reactive polymer. When the ultraviolet ray is irradiated, the photopolymerization initiator acts, and the above-mentioned reactive polymer is polymerized with a (meth) acrylate monomer or a monofunctional monomer to exhibit an adhesive force.

但是，於專利文獻2的實施例中具體記載的黏著劑組成物因黏著力高，故存在如下的課題，即若於使被接著物彼此接著後進行剝離，則會產生殘膠。於專利文獻2中，作為黏著劑組成物的用途，並未記載將光學功能材料貼合於顯示體上，但假設當將該黏著劑組成物用於此種用途時，因殘膠而難以重新加工，因此存在不得不廢棄昂貴的顯示體、經濟損失大的課題。 However, since the adhesive composition specifically described in the examples of Patent Document 2 has a high adhesive force, there is a problem that residual glue is generated when the adherends are adhered to each other and then peeled off. In Patent Document 2, as an application of the adhesive composition, there is no description that the optical functional material is bonded to the display body. However, when the adhesive composition is used for such use, it is difficult to regenerate due to the residual adhesive. Since it is processed, there is a problem that an expensive display body has to be discarded and the economic loss is large.

[先前技術文獻] [Previous Technical Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本專利特開2012-117028號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-117028

[專利文獻2]日本專利特開2001-64593號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-64593

本發明是為了解決如上所述的課題而完成的發明，其目的在於提供一種光硬化型黏著劑組成物(以下，有時簡稱為「黏著劑組成物」)，該光硬化型黏著劑組成物當於顯示面板組裝時產生不良情況而進行重新加工時，容易自顯示體上剝離光學功能材料，且於顯示體上殘膠少。另外，本發明的目的在於提供一種此種重新加工性優異的顯示面板。 The present invention has been made to solve the problems as described above, and an object of the invention is to provide a photocurable adhesive composition (hereinafter sometimes referred to simply as "adhesive composition"), which is a photocurable adhesive composition. When a defect occurs in the assembly of the display panel and rework is performed, it is easy to peel off the optical functional material from the display body, and the amount of residual glue on the display body is small. Further, an object of the present invention is to provide a display panel excellent in such reworkability.

[1]一種光硬化型黏著劑組成物，其包括反應性聚合物(A成分)、具有一個聚合性雙鍵的單體(B成分)、及光聚合起始劑(C成分)，上述反應性聚合物(A成分)如下，其主鏈含有源自(甲基)丙烯酸系單體的重複單元，且側鏈含有聚合性雙鍵，其雙鍵當量，即每1mol聚合性雙鍵的聚合物質量，為10,000g/mol~100,000g/mol，其重量平均分子量(Mw)為25,000~1,000,000。 [1] A photocurable adhesive composition comprising a reactive polymer (component A), a monomer having a polymerizable double bond (component B), and a photopolymerization initiator (component C), the above reaction The polymer (component A) is as follows, and its main chain contains a repeating unit derived from a (meth)acrylic monomer, and the side chain contains a polymerizable double bond, and its double bond equivalent, that is, polymerization per 1 mol of the polymerizable double bond The mass of the material is from 10,000 g/mol to 100,000 g/mol, and its weight average molecular weight (Mw) is from 25,000 to 1,000,000.

[2]如[1]所述的光硬化型黏著劑組成物，其中作為上述源自(甲基)丙烯酸系單體的重複單元，上述主鏈含有源自具有醇殘基的(甲基)丙烯酸酯的重複單元，上述醇殘基包含異氰酸基。 [2] The photocurable adhesive composition according to [1], wherein the main chain contains a (meth) group having an alcohol residue as a repeating unit derived from the (meth)acrylic monomer. In the repeating unit of the acrylate, the above alcohol residue contains an isocyanate group.

[3]如[2]所述的光硬化型黏著劑組成物，其中上述具有包含 異氰酸基的醇殘基的(甲基)丙烯酸酯為異氰酸2-(甲基)丙烯醯氧基烷基酯。 [3] The photocurable adhesive composition according to [2], wherein the above has an inclusion The (meth) acrylate of the alcohol residue of the isocyanato group is 2-(meth) propylene oxime alkyl isocyanate.

[4]如[1]所述的光硬化型黏著劑組成物，其中作為上述源自(甲基)丙烯酸系單體的重複單元，上述主鏈含有源自具有碳數為1~14的烷基醇殘基的(甲基)丙烯酸酯的重複單元。 [4] The photocurable adhesive composition according to [1], wherein the main chain contains alkane having a carbon number of 1 to 14 as a repeating unit derived from the (meth)acrylic monomer. A repeating unit of a (meth) acrylate of a base alcohol residue.

[5]如[4]所述的光硬化型黏著劑組成物，其中上述具有碳數為1~14的烷基醇殘基的(甲基)丙烯酸酯為丙烯酸2-乙基己酯。 [5] The photocurable adhesive composition according to [4], wherein the (meth) acrylate having an alkyl alcohol residue having 1 to 14 carbon atoms is 2-ethylhexyl acrylate.

[6]如[1]所述的光硬化型黏著劑組成物，其中作為上述源自(甲基)丙烯酸系單體的重複單元，上述主鏈含有源自具有醇殘基的(甲基)丙烯酸酯的重複單元，上述醇殘基包含異氰酸基，上述側鏈具有如下結構，即將上述異氰酸基與(甲基)丙烯酸羥基烷基酯的羥基進行加成而得的結構。 [6] The photocurable adhesive composition according to [1], wherein the main chain contains a (meth) group having an alcohol residue as a repeating unit derived from the (meth)acrylic monomer. In the repeating unit of the acrylate, the alcohol residue contains an isocyanate group, and the side chain has a structure in which a hydroxyl group of the above-mentioned isocyanate group and a hydroxyalkyl (meth)acrylate are added.

[7]如[6]所述的光硬化型黏著劑組成物，其中上述(甲基)丙烯酸羥基烷基酯為丙烯酸4-羥基丁酯。 [7] The photocurable adhesive composition according to [6], wherein the hydroxyalkyl (meth)acrylate is 4-hydroxybutyl acrylate.

[8]如[1]所述的光硬化型黏著劑組成物，其中A成分的側鏈含有胺基甲酸酯鍵。 [8] The photocurable adhesive composition according to [1], wherein the side chain of the component A contains a urethane bond.

[9]如[1]所述的光硬化型黏著劑組成物，其中相對於A成分及B成分的合計的A成分的含量為5質量%~80質量%。 [9] The photocurable pressure-sensitive adhesive composition according to the above [1], wherein the content of the component A with respect to the total of the component A and the component B is 5% by mass to 80% by mass.

[10]如[1]所述的光硬化型黏著劑組成物，其中相對於A成分及B成分的合計100質量份，包含5質量份以下的含有羧基的單體。 [10] The photocurable adhesive composition according to the above [1], wherein the carboxyl group-containing monomer is contained in an amount of 5 parts by mass or less based on 100 parts by mass of the total of the component A and the component B.

[11]如[1]所述的光硬化型黏著劑組成物，其中相對於A成分及B成分的合計100質量份，含有0.05質量份~10質量份的具有兩個以上的聚合性雙鍵的單體(D成分)。 [1] The photocurable adhesive composition according to the above [1], which contains 0.05 or more by mass of the polymerizable double bond in an amount of 0.05 parts by mass to 10 parts by mass based on 100 parts by mass of the total of the A component and the B component. Monomer (component D).

[12]如[1]所述的光硬化型黏著劑組成物，其中相對於A成分及B成分的合計100質量份，含有10質量份~120質量份的A成分以外的(甲基)丙烯酸系聚合物(F成分)。 [12] The photocurable adhesive composition according to the above [1], which contains 10 parts by mass to 120 parts by mass of (meth)acrylic acid other than the A component, based on 100 parts by mass of the total of the A component and the B component. A polymer (F component).

[13]如[1]所述的光硬化型黏著劑組成物，其依據JIS-Z-0237所測定的黏著保持力為2mm以下。 [13] The photocurable adhesive composition according to [1], which has an adhesive retention force of 2 mm or less as measured according to JIS-Z-0237.

[14]如[1]所述的光硬化型黏著劑組成物，其中針對經硬化而獲得的帶狀物，依據JIS-Z-0237所測定的黏著力為0.1N/24mm~20N/24mm，且於藉由上述測定而將帶剝離後的痕跡上無殘膠。 [14] The photocurable adhesive composition according to [1], wherein the adhesive obtained by hardening has an adhesive force measured according to JIS-Z-0237 of 0.1 N/24 mm to 20 N/24 mm. Further, no residue remained on the trace after peeling off the tape by the above measurement.

[15]如[14]所述的光硬化型黏著劑組成物，其黏著力為10N/24mm~20N/24mm。 [15] The photocurable adhesive composition according to [14], which has an adhesive force of 10 N/24 mm to 20 N/24 mm.

[16]一種硬化物，其是藉由活性能量線來使如[1]所述的光硬化型黏著劑組成物硬化而獲得。 [16] A cured product obtained by hardening a photocurable adhesive composition according to [1] by an active energy ray.

[17]一種黏著片，其是藉由活性能量線來使如[1]所述的光硬化型黏著劑組成物硬化而獲得。 [17] An adhesive sheet obtained by hardening a photocurable adhesive composition according to [1] by an active energy ray.

[18]一種光硬化型黏著劑組成物，其依據JIS-Z-0237所測定的黏著保持力為2mm以下。 [18] A photocurable adhesive composition having an adhesive retention force of 2 mm or less as measured according to JIS-Z-0237.

[19]一種黏著片，其是使如[18]所述的光硬化型黏著劑組成物硬化而獲得。 [19] An adhesive sheet obtained by hardening a photocurable adhesive composition according to [18].

[20]如[19]所述的黏著片，其厚度為25μm~1000μm。 [20] The adhesive sheet according to [19], which has a thickness of from 25 μm to 1000 μm.

[21]一種顯示面板，其是於顯示體上具備黏著劑層，於上述黏著劑層上具備光學功能材料的層的顯示面板，且上述黏著劑層是使如[1]所述的光硬化型黏著劑組成物硬化而獲得。 [21] A display panel comprising a display layer having an adhesive layer on a display body and a layer of an optical functional material on the adhesive layer, wherein the adhesive layer is photohardened as described in [1]. The adhesive composition is obtained by hardening.

[22]一種顯示面板的製造方法，其包括如下的步驟：將如[1]所述的光硬化型黏著劑組成物塗佈於光學功能材料上，於所獲得的塗膜上積層顯示體，自光學功能材料側照射活性能量線來使光硬化型黏著劑組成物硬化，而使上述光學功能材料與上述顯示體接著。 [22] A method of producing a display panel, comprising the steps of: applying a photocurable adhesive composition according to [1] to an optical functional material, and laminating a display on the obtained coating film, The photo-curable adhesive composition is cured by irradiating the active energy ray from the side of the optical functional material, and the optical functional material is followed by the display.

[23]一種顯示面板的製造方法，其包括如下的步驟：將如[1]所述的光硬化型黏著劑組成物注入至分開設置的膜狀或片狀的光學功能材料與膜狀或片狀的顯示體之間，並自光學功能材料側照射活性能量線來使光硬化型黏著劑組成物硬化。 [23] A method of manufacturing a display panel, comprising the steps of: injecting a photocurable adhesive composition according to [1] into a separately provided film-like or sheet-like optical functional material and a film or sheet. The active energy ray is irradiated between the display bodies and the optical functional material side to harden the photocurable adhesive composition.

[24]一種顯示面板的製造方法，其包括如下的步驟：於如[19]所述的黏著片的一面上接著膜狀或片狀的光學功能材料，於另一面上接著膜狀或片狀的顯示體，而使上述光學功能材料與顯示體貼合。 [24] A method of manufacturing a display panel, comprising the steps of: attaching a film-like or sheet-like optical functional material to one side of the adhesive sheet according to [19], and then lining or sheet-like on the other surface. The display body is bonded to the display body.

使本發明的光硬化型黏著劑組成物硬化而獲得的黏著劑當於顯示面板組裝時產生不良情況而進行修復(重新加工)時，容易自顯示體上剝離光學功能材料，另外，於顯示體的表面上殘膠少，因此重新加工性優異。 When the adhesive obtained by curing the photocurable adhesive composition of the present invention is cured when the display panel is assembled and repaired (reworked), the optical functional material is easily peeled off from the display, and the display is removed from the display. The surface has less residual glue and is therefore excellent in reworkability.

另外，使用本發明的光硬化型黏著劑組成物所製造的顯示面 板具有於廢棄時可容易地進行構件的分類作業這一優點。 Further, a display surface produced by using the photocurable adhesive composition of the present invention The board has the advantage that the sorting operation of the components can be easily performed when discarded.

以下，對本發明進行具體說明。但是，本發明包含具備其發明特定事項的所有實施形態，而並不限定於以下所示的實施形態。 Hereinafter, the present invention will be specifically described. However, the present invention includes all embodiments including the matters specific to the invention, and is not limited to the embodiments described below.

於本說明書中，「(甲基)丙烯酸」表示「丙烯酸」及/或「甲基丙烯酸」，「(甲基)丙烯醯基」表示「丙烯醯基」及/或「甲基丙烯醯基」，「(甲基)丙烯酸酯」表示「丙烯酸酯」及/或「甲基丙烯酸酯」，「(甲基)丙烯腈」表示「丙烯腈」及/或「甲基丙烯腈」。 In the present specification, "(meth)acrylic acid" means "acrylic acid" and/or "methacrylic acid", and "(meth)acrylic acid group" means "acrylic acid" and/or "methacrylic acid". "(Meth)acrylate" means "acrylate" and/or "methacrylate", and "(meth)acrylonitrile" means "acrylonitrile" and/or "methacrylonitrile".

本發明的光硬化型黏著劑組成物是含有反應性聚合物(A成分)、具有一個聚合性雙鍵的單體(B成分)、光聚合起始劑(C成分)作為必需成分的光硬化型黏著劑組成物。以下，對各成分進行說明。 The photocurable adhesive composition of the present invention is a photocuring containing a reactive polymer (component A), a monomer having one polymerizable double bond (component B), and a photopolymerization initiator (component C) as essential components. Type of adhesive composition. Hereinafter, each component will be described.

於本發明的組成物中，使用主鏈含有源自(甲基)丙烯酸系單體的重複單元，側鏈含有雙鍵的反應性聚合物作為A成分。 In the composition of the present invention, a reactive polymer derived from a (meth)acrylic monomer in the main chain and a reactive polymer having a double bond in the side chain are used as the component A.

A成分是主鏈含有源自(甲基)丙烯酸系單體的重複單元(以下，有時將「源自單體X的重複單元」僅記作「X單元」)的成分。換言之，A成分是將(甲基)丙烯酸系聚合物作為基本骨架的成分。藉由使主鏈含有(甲基)丙烯酸系單體單元，而可顯現優異的 耐候性、光學性質(透光性、透明性)。再者，於本說明書中，當稱為「主鏈」時，是指於反應性聚合物中碳數最多的碳鏈。 The component A is a component in which the main chain contains a repeating unit derived from a (meth)acrylic monomer (hereinafter, the "repeating unit derived from the monomer X" may be simply referred to as "X unit"). In other words, the component A is a component having a (meth)acrylic polymer as a basic skeleton. Excellent in that the main chain contains a (meth)acrylic monomer unit Weather resistance, optical properties (light transmission, transparency). In the present specification, the term "main chain" means a carbon chain having the largest carbon number in the reactive polymer.

所謂「(甲基)丙烯酸系單體」，是指丙烯酸或甲基丙烯酸或者該些的衍生物。具體而言，除丙烯酸、甲基丙烯酸以外，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸二環戊酯等(甲基)丙烯酸酯類；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯等含有羥基的(甲基)丙烯酸酯類；(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸羥基丁酯縮水甘油醚等含有縮水甘油基的(甲基)丙烯酸酯類；(甲基)丙烯酸苯氧酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、苯氧基聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、壬酚環氧乙烷(ethylene oxide，EO)加成物(甲基)丙烯酸酯、(甲基)丙烯酸鄰聯苯氧基乙酯等含有芳香族環的(甲基)丙烯酸酯類；(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸4-羥基丁酯縮水甘油醚等含有縮水甘油基的(甲基)丙烯酸酯類；(甲基)丙烯酸異氰酸酯、異氰酸2-(甲基)丙烯醯氧基乙酯等含有異氰酸基的(甲基)丙烯酸酯類；(甲基)丙烯酸銨、(甲基)丙烯酸鈉、(甲 基)丙烯酸鉀等(甲基)丙烯酸鹽類；(甲基)丙烯醯胺、(甲基)丙烯醯基嗎啉、二甲基(甲基)丙烯醯胺、二乙基(甲基)丙烯醯胺、二甲胺基丙基丙烯醯胺、異丙基(甲基)丙烯醯胺等(甲基)丙烯醯胺類；丙烯腈、甲基丙烯腈、α-氰基丙烯酸酯、二氰基亞乙烯基、反丁烯二腈(fumaronitrile)等乙烯基氰類等。 The "(meth)acrylic monomer" means acrylic acid or methacrylic acid or a derivative thereof. Specifically, examples of the acrylic acid and methacrylic acid include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. N-butyl methacrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, (meth)acrylic acid n-Hexyl ester, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylates such as dicyclopentenyloxyethyl (meth)acrylate and dicyclopentanyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate and 2-(meth)acrylate Hydroxy-containing (meth) acrylates such as hydroxypropyl ester, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; glycidyl (meth) acrylate, (methyl) a glycidyl group-containing (meth) acrylate such as hydroxybutyl acrylate glycidyl ether; phenoxy (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylate Ester, phenoxy polyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, ethylene oxide (EO) adduct (A Aromatic ring-containing (meth) acrylates such as acrylate, o-phenoxyethyl (meth)acrylate; glycidyl (meth)acrylate; 4-hydroxybutyl (meth)acrylate a glycidyl group-containing (meth) acrylate such as glycidyl ether; (meth)acrylic acid isocyanate or isocyanate 2-(methyl) propylene methoxyethyl ester; Acrylates; ammonium (meth)acrylate, sodium (meth)acrylate, (a (meth)acrylic acid salt such as potassium acrylate; (meth) acrylamide, (meth) propylene decylmorpholine, dimethyl (meth) acrylamide, diethyl (meth) propylene (Methyl) acrylamide, such as decylamine, dimethylaminopropyl acrylamide, isopropyl (meth) acrylamide, acrylonitrile, methacrylonitrile, α-cyanoacrylate, dicyandiamide Vinyl cyanide such as vinylidene or fumaronitrile.

上述(甲基)丙烯酸系單體之中，就發揮良好的黏著性能的觀點而言，較佳為主鏈上含有源自(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸4-羥基乙酯、異氰酸2-(甲基)丙烯醯氧基乙酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯醯基嗎啉、(甲基)丙烯酸苄酯、(甲基)丙烯酸鄰聯苯氧基乙酯的重複單元。 Among the above (meth)acrylic monomers, from the viewpoint of exhibiting good adhesion properties, it is preferred to contain butyl (meth)acrylate or 2-ethylhexyl (meth)acrylate as a main chain. Ester, 2-hydroxyethyl (meth)acrylate, 4-hydroxyethyl (meth)acrylate, 2-(methyl)propenyloxyethyl isocyanate, isobornyl (meth)acrylate, ( a repeating unit of methyl methacryloyl morpholine, benzyl (meth) acrylate, or o-phenoxyethyl (meth) acrylate.

另外，就提昇折射率的觀點而言，較佳為主鏈上含有源自(甲基)丙烯酸苄酯、(甲基)丙烯酸鄰聯苯氧基乙酯等含有芳香族環的(甲基)丙烯酸酯類的重複單元。 Further, from the viewpoint of increasing the refractive index, it is preferred to contain an aromatic ring-containing (methyl) group derived from benzyl (meth)acrylate or o-phenoxyethyl (meth)acrylate in the main chain. Repeating unit of acrylates.

A成分的主鏈可含有1種(甲基)丙烯酸系單體單元，亦可含有2種以上的(甲基)丙烯酸系單體單元。但是，當製成黏著劑時，就容易精密地調整其塗膜的物性這一理由而言，A成分的主鏈較佳為含有2種以上的(甲基)丙烯酸系單體單元。 The main chain of the component A may contain one type of (meth)acrylic monomer unit, or may contain two or more types of (meth)acrylic monomer units. However, when the adhesive is prepared, it is easy to precisely adjust the physical properties of the coating film. The main chain of the component A preferably contains two or more kinds of (meth)acrylic monomer units.

再者，A成分的主鏈只要是含有(甲基)丙烯酸系單體單元者即可，無需所有重複單元為(甲基)丙烯酸系單體單元。即，只要不妨礙本發明的效果，則亦可為含有(甲基)丙烯酸系單體以外的單體單元者。 Further, the main chain of the component A may be a (meth)acrylic monomer unit as long as it contains a (meth)acrylic monomer unit. That is, as long as the effect of the present invention is not impaired, it may be a monomer unit other than the (meth)acrylic monomer.

「(甲基)丙烯酸系單體以外的單體」的種類並無特別限制，例如可使用具有雙鍵的單體。具體而言，可列舉苯乙烯、α-甲基苯乙烯等芳香族乙烯基類；乙酸乙烯酯、丙酸乙烯酯等羧酸乙烯酯類；順丁烯二酸酐、衣康酸、反丁烯二酸等不飽和二羧酸類；N-乙烯基吡咯啶酮、N-乙烯基己內醯胺等N-乙烯基內醯胺類等。 The type of the "monomer other than the (meth)acrylic monomer" is not particularly limited, and for example, a monomer having a double bond can be used. Specific examples thereof include aromatic vinyls such as styrene and α-methylstyrene; vinyl carboxylates such as vinyl acetate and vinyl propionate; maleic anhydride, itaconic acid, and antibutene. Unsaturated dicarboxylic acids such as diacids; N-vinyl linoleamides such as N-vinylpyrrolidone and N-vinyl caprolactam.

存在如下的傾向：於A成分的主鏈中，(甲基)丙烯酸系單體單元的含有率越多，黏著性能越提昇。當將構成A成分的主鏈的單體單元的合計設為100質量份時，(甲基)丙烯酸系單體單元的含有率較佳為50質量份以上，更佳為90質量份以上，進而更佳為100質量份。即，特佳為主鏈全部由(甲基)丙烯酸系單體單元構成。 There is a tendency that the adhesiveness of the (meth)acrylic monomer unit increases as the content of the (meth)acrylic monomer unit in the main chain of the component A increases. When the total of the monomer units constituting the main chain of the component A is 100 parts by mass, the content of the (meth)acrylic monomer unit is preferably 50 parts by mass or more, more preferably 90 parts by mass or more. More preferably, it is 100 parts by mass. That is, it is preferable that all of the main chains are composed of (meth)acrylic monomer units.

A成分是側鏈具有包含雙鍵的官能基的成分。作為A成分，例如可列舉：針對成為基本骨架的(甲基)丙烯酸系聚合物，藉由化學修飾而導入(甲基)丙烯醯基系官能基及乙烯基等包含雙鍵的官能基來使其改質而成者。作為側鏈上所含有的包含雙鍵的官能基，就聚合性的觀點而言，較佳為丙烯醯氧基。 The component A is a component in which a side chain has a functional group containing a double bond. For the component A, for example, a (meth)acrylic polymer which is a basic skeleton is introduced by chemically modifying a (meth)acrylonyl functional group and a functional group containing a double bond such as a vinyl group. It is a reformer. The functional group containing a double bond contained in the side chain is preferably an acryloxy group from the viewpoint of polymerizability.

側鏈含有雙鍵的聚合物藉由活性能量線而使該聚合物彼此進行交聯，因此顯現對於活性能量線的硬化性。另外，除耐候性高以外，當剝離黏著劑時於顯示體上殘膠少、難以污染顯示體這一較佳的效果亦得以發揮。 The polymer having a double bond in the side chain crosslinks the polymers by the active energy ray, thereby exhibiting hardenability to the active energy ray. Further, in addition to the high weather resistance, when the adhesive is peeled off, the residual effect on the display body is small, and it is difficult to contaminate the display body.

另外，側鏈可為丙烯醯基骨架、甲基丙烯醯基骨架、乙 烯基骨架等含有雙鍵的骨架直接鍵結於主鏈上的結構，亦可為(甲基)丙烯醯氧基等含有雙鍵的骨架經由某個原子或官能基而間接地鍵結於主鏈上的結構。作為使含有雙鍵的骨架間接地鍵結於主鏈上者，較佳為胺基甲酸酯鍵。 In addition, the side chain may be an acrylonitrile skeleton, a methacryl fluorenyl skeleton, or a structure in which a skeleton containing a double bond such as an alkenyl skeleton is directly bonded to a main chain, or a skeleton containing a double bond such as a (meth)acryloxy group may be indirectly bonded to a main group via a certain atom or a functional group. The structure on the chain. As a skeleton in which a double bond-containing skeleton is indirectly bonded to the main chain, a urethane bond is preferred.

較佳為主鏈含有源自具有包含異氰酸基的醇殘基的(甲基)丙烯酸酯的重複單元作為源自(甲基)丙烯酸系單體的重複單元。作為具有包含異氰酸基的醇殘基的(甲基)丙烯酸酯，例如可列舉：異氰酸2-(甲基)丙烯醯氧基乙酯、異氰酸4-(甲基)丙烯醯氧基丁酯、異氰酸5-(甲基)丙烯醯氧基戊酯、異氰酸6-(甲基)丙烯醯氧基己酯等異氰酸(甲基)丙烯醯氧基烷基酯，異氰酸3-(甲基)丙烯醯氧基苯酯等異氰酸(甲基)丙烯醯氧基芳基酯。其中，就聚合時的穩定性這一點而言，較佳為異氰酸(甲基)丙烯醯氧基烷基酯，更佳為異氰酸2-(甲基)丙烯醯氧基乙酯。 It is preferred that the main chain contains a repeating unit derived from a (meth) acrylate having an alcohol residue containing an isocyanate group as a repeating unit derived from a (meth)acrylic monomer. Examples of the (meth) acrylate having an alcohol residue containing an isocyanate group include 2-(meth) propylene methoxyethyl isocyanate and 4-(methyl) propylene hydride isocyanate. (meth) propylene decyloxyalkyl isocyanate, isobutyl 5-(methyl) propylene decyloxy isocyanate, 6-(methyl) propylene oxyhexyl isocyanate An ester, (meth) propylene oxy aryl isocyanate such as 3-(meth) propylene oxy phenyl isocyanate. Among them, in terms of stability at the time of polymerization, a (meth) propylene decyloxyalkyl isocyanate is preferred, and 2-(meth) propylene methoxyethyl isocyanate is more preferred.

進而，較佳為主鏈含有源自具有碳數為1~14的烷基醇殘基的(甲基)丙烯酸酯的重複單元作為源自(甲基)丙烯酸系單體的重複單元。作為具有碳數為1~14的烷基醇殘基的(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲 基)丙烯酸二環戊酯等(甲基)丙烯酸酯類。其中，就發揮良好的黏著性能的觀點而言，較佳為具有碳數為2~12的烷基醇殘基的(甲基)丙烯酸酯，更佳為具有碳數為4~10的烷基醇殘基的(甲基)丙烯酸酯，進而更佳為丙烯酸2-乙基己酯。 Further, a repeating unit containing a (meth) acrylate derived from an alkyl alcohol residue having a carbon number of 1 to 14 as a repeating unit derived from a (meth)acrylic monomer is preferably contained in the main chain. Examples of the (meth) acrylate having an alkyl alcohol residue having 1 to 14 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, and n-propyl (meth)acrylate. , isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, (methyl) ) isoamyl acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclomethacrylate Ester, isobornyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, (A) (meth) acrylate such as dicyclopentanyl acrylate. Among them, from the viewpoint of exhibiting good adhesion properties, a (meth) acrylate having an alkyl alcohol residue having 2 to 12 carbon atoms is preferred, and an alkyl group having 4 to 10 carbon atoms is more preferred. The (meth) acrylate of the alcohol residue is more preferably 2-ethylhexyl acrylate.

較佳為主鏈含有源自具有包含異氰酸基的醇殘基的(甲基)丙烯酸酯的重複單元作為源自(甲基)丙烯酸系單體的重複單元，側鏈具有於該異氰酸基上加成(甲基)丙烯酸羥基烷基酯的羥基而成的結構。作為(甲基)丙烯酸羥基烷基酯，例如可列舉：(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丁酯、(甲基)丙烯酸羥基丙酯等(甲基)丙烯酸單羥基烷基酯類，(甲基)丙烯酸1,2-二羥基乙酯、(甲基)丙烯酸1,2-二羥基丙酯、(甲基)丙烯酸1,2-二羥基丁酯、(甲基)丙烯酸1,2-二羥基-5-乙基己酯、(甲基)丙烯酸1,1-二羥基丙酯、(甲基)丙烯酸1,1-二羥基丁酯、(甲基)丙烯酸1,1-二羥基乙酯等(甲基)丙烯酸二羥基烷基酯類，(甲基)丙烯酸1,2,3-三羥基丙酯、(甲基)丙烯酸1,2,3-三羥基丁酯、(甲基)丙烯酸1,1,2-三羥基丙酯、(甲基)丙烯酸1,1,2-三羥基丁酯等(甲基)丙烯酸三羥基烷基酯類，羥基聚環氧乙烷單(甲基)丙烯酸酯、羥基聚環氧丙烷單(甲基)丙烯酸酯、羥基(聚環氧乙烷-聚環氧丙烷)單(甲基)丙烯酸酯、羥基(聚環氧乙烷-環氧丙烷)單(甲基)丙烯酸酯、羥基(聚環氧乙烷-聚四亞甲基氧化物)單(甲基)丙烯酸酯、羥基(聚環氧乙烷-四亞甲基氧化物)單(甲基)丙烯酸酯、羥基(聚環氧丙烷-聚四亞甲基氧化物)單(甲基)丙烯酸酯、羥基(聚環氧丙烷-四亞甲基氧化物)單(甲基)丙烯酸酯等 含有羥基聚環氧烷基的(甲基)丙烯酸酯類。其中，就與異氰酸基的反應的容易性這一點而言，較佳為(甲基)丙烯酸單羥基烷基酯類，更佳為(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丁酯、(甲基)丙烯酸羥基丙酯，進而更佳為丙烯酸4-羥基丁酯。 Preferably, the main chain contains a repeating unit derived from a (meth) acrylate having an alcohol residue containing an isocyanate group as a repeating unit derived from a (meth)acrylic monomer, and a side chain having the isocyanate A structure in which a hydroxyl group of a hydroxyalkyl (meth)acrylate is added to an acid group. Examples of the hydroxyalkyl (meth)acrylate include (meth)acrylic acid monohydroxyalkane such as hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxypropyl (meth)acrylate. Base esters, 1,2-dihydroxyethyl (meth)acrylate, 1,2-dihydroxypropyl (meth)acrylate, 1,2-dihydroxybutyl (meth)acrylate, (methyl) 1,2-dihydroxy-5-ethylhexyl acrylate, 1,1-dihydroxypropyl (meth)acrylate, 1,1-dihydroxybutyl (meth)acrylate, (meth)acrylic acid 1, Dihydroxyalkyl (meth)acrylates such as 1-dihydroxyethyl ester, 1,2,3-trihydroxypropyl (meth)acrylate, 1,2,3-trihydroxybutyl (meth)acrylate , 1,1,2-trihydroxypropyl (meth)acrylate, 1,1,2-trihydroxybutyl (meth)acrylate, etc., trihydroxyalkyl (meth)acrylate, hydroxypolyepoxy Alkenyl mono (meth) acrylate, hydroxy polypropylene oxide mono (meth) acrylate, hydroxyl (polyethylene oxide - polypropylene oxide) mono (meth) acrylate, hydroxyl (polyethylene oxide) - propylene oxide) mono (meth) acrylate, hydroxy (polyethylene oxide - polytetramethylene oxide) single (a Acrylate, hydroxy (polyethylene oxide-tetramethylene oxide) mono (meth) acrylate, hydroxy (polypropylene oxide - polytetramethylene oxide) mono (meth) acrylate , hydroxy (polypropylene oxide-tetramethylene oxide) mono (meth) acrylate, etc. A (meth) acrylate containing a hydroxy polyalkylene oxide group. Among them, in terms of easiness of reaction with an isocyanate group, preferred are monohydroxyalkyl (meth)acrylates, more preferably hydroxyethyl (meth)acrylate or (meth)acrylic acid. Hydroxybutyl ester, hydroxypropyl (meth)acrylate, and more preferably 4-hydroxybutyl acrylate.

A成分的雙鍵當量必須設為10,000g/mol~100,000g/mol的範圍內，雖然亦根據主鏈的結構、重量平均分子量、玻璃轉移溫度、黏著物性等而不同，但較佳為20,000g/mol~80,000g/mol的範圍內。此處，所謂雙鍵當量，表示每1mol聚合性雙鍵的聚合物質量，且為藉由後述的方法所算出的值。若雙鍵當量未滿10,000g/mol，則黏著劑的凝聚力增加且黏著力變得過高，因此重新加工性下降。另外，若超過100,000g/mol，則黏著劑的凝聚力消失，顯示體上的殘膠變多。 The double bond equivalent of the component A must be in the range of 10,000 g/mol to 100,000 g/mol, and although it varies depending on the structure of the main chain, the weight average molecular weight, the glass transition temperature, the adhesive property, etc., it is preferably 20,000 g. /mol~80,000g/mol range. Here, the double bond equivalent means a polymer mass per 1 mol of the polymerizable double bond, and is a value calculated by a method described later. When the double bond equivalent is less than 10,000 g/mol, the cohesive force of the adhesive increases and the adhesive force becomes too high, so the reworkability is lowered. On the other hand, when it exceeds 100,000 g/mol, the cohesive force of the adhesive disappears, and the amount of residual glue on the display body increases.

A成分的重量平均分子量(Mw)為25,000~1,000,000。藉由將重量平均分子量設為該範圍內，而與稀釋劑的混合性變得良好，組成物的製備變得容易，除此以外，於製成黏著劑時顯示體上的殘膠少、難以污染顯示體這一較佳的效果亦得以發揮。 The weight average molecular weight (Mw) of the component A is 25,000 to 1,000,000. When the weight average molecular weight is within this range, the miscibility with the diluent becomes good, and the preparation of the composition becomes easy. In addition, when the adhesive is prepared, the residual rubber on the display body is small and difficult. The better effect of the pollution display body is also exerted.

A成分的重量平均分子量較佳為25,000~500,000的範圍內，更佳為50,000~300,000的範圍內。若重量平均分子量未滿25,000，則存在顯示體上的殘膠增加而污染顯示體的傾向，故不佳。另一方面，若超過1,000,000，則存在與稀釋劑的混合性變得不良的傾向，故不佳。 The weight average molecular weight of the component A is preferably in the range of 25,000 to 500,000, more preferably in the range of 50,000 to 300,000. When the weight average molecular weight is less than 25,000, there is a tendency that the residual glue on the display body increases to contaminate the display body, which is not preferable. On the other hand, when it exceeds 1,000,000, the miscibility with the diluent tends to be poor, which is not preferable.

重量平均分子量可藉由適當地控制使成為主鏈的(甲基) 丙烯酸系聚合物進行聚合時的聚合條件，例如聚合起始劑的種類及量、溶劑的種類及量、反應溫度、反應時間等來調整。再者，於本說明書中，當稱為「重量平均分子量」時，是指藉由粒徑篩析層析法(Size Exclusion Chromatography，SEC)所測定的聚苯乙烯換算的重量平均分子量。 The weight average molecular weight can be made to be the main chain (methyl) by appropriate control The polymerization conditions at the time of polymerization of the acrylic polymer are adjusted, for example, the type and amount of the polymerization initiator, the kind and amount of the solvent, the reaction temperature, the reaction time, and the like. In the present specification, the term "weight average molecular weight" means a polystyrene-equivalent weight average molecular weight measured by Size Exclusion Chromatography (SEC).

A成分的玻璃轉移溫度(Tg)較佳為-55℃~0℃的範圍內，更佳為-55℃~-10℃的範圍內。藉由將玻璃轉移溫度設為該範圍內，於製成黏著劑時顯現適度的黏著性能。 The glass transition temperature (Tg) of the component A is preferably in the range of -55 ° C to 0 ° C, more preferably in the range of -55 ° C to -10 ° C. By setting the glass transition temperature within this range, moderate adhesion properties are exhibited when the adhesive is formed.

再者，於本說明書中，當稱為「玻璃轉移溫度」時，是指依據JIS K7121(塑膠的轉移溫度測定方法)所測定的玻璃轉移溫度。 In the present specification, the term "glass transition temperature" means a glass transition temperature measured in accordance with JIS K7111 (Method for Measuring Transfer Temperature of Plastics).

A成分的製造方法並無特別限定，例如可藉由如下的方法來製造：針對成為主鏈的(甲基)丙烯酸系聚合物，藉由化學修飾而將(甲基)丙烯醯基系官能基導入至側鏈的方法(化學修飾法)。 The method for producing the component A is not particularly limited. For example, it can be produced by a method in which a (meth)acryloyl group-based functional group is chemically modified with respect to a (meth)acrylic polymer which is a main chain. Method of introduction into a side chain (chemical modification method).

作為化學修飾法的較佳例，例如可列舉如下的方法：將含有源自異氰酸2-(甲基)丙烯醯氧基乙酯等含有異氰酸基的(甲基)丙烯酸酯類的重複單元、且具有源自該重複單元的異氰酸基的(甲基)丙烯酸系聚合物作為基礎聚合物，藉由胺基甲酸酯鍵而使(甲基)丙烯酸羥基烷基酯等具有羥基的(甲基)丙烯酸系化合物鍵結於該基礎聚合物的異氰酸基上，藉此導入(甲基)丙烯醯基系官能基。 As a preferable example of the chemical modification method, for example, a method of containing a (meth) acrylate containing isocyanate groups such as 2-(meth) propylene methoxyethyl isocyanate may be mentioned. a (meth)acrylic polymer having a repeating unit and having an isocyanato group derived from the repeating unit as a base polymer, and having a hydroxyalkyl (meth)acrylate or the like by a urethane bond A (meth)acrylic acid compound having a hydroxyl group is bonded to an isocyanate group of the base polymer, whereby a (meth)acrylonyl group functional group is introduced.

藉由該方法所製造的A成分中，主鏈含有源自異氰酸2-(甲基)丙烯醯氧基乙酯等含有異氰酸基的(甲基)丙烯酸酯類的重 複單元，側鏈具有如下的結構，即藉由胺基甲酸酯鍵而於自上述主鏈中分支出的源自該重複單元的異氰酸基上加成(甲基)丙烯酸羥基烷基酯等具有羥基的(甲基)丙烯酸系化合物的羥基而成的結構。 In the component A produced by the method, the main chain contains a weight derived from a (meth) acrylate containing isocyanate groups such as 2-(meth) propylene methoxyethyl isocyanate. a complex unit having a structure in which a hydroxyalkyl (meth) acrylate is added to an isocyanate group derived from the repeating unit branched from the main chain by a urethane bond A structure having a hydroxyl group of a (meth)acrylic compound having a hydroxyl group such as an ester.

具有異氰酸基的(甲基)丙烯酸系聚合物可藉由使異氰酸2-甲基丙烯醯氧基乙酯(商品名：Karenz MOI，昭和電工公司製造)或異氰酸2-丙烯醯氧基乙酯(商品名：Karenz AOI，昭和電工公司製造)等含有異氰酸基的(甲基)丙烯酸酯類進行均聚、或與其他(甲基)丙烯酸系單體進行共聚而獲得。作為「具有羥基的(甲基)丙烯酸系化合物」，例如可列舉：丙烯酸2-羥基乙酯、丙烯酸4-羥基丁酯等。 The (meth)acrylic polymer having an isocyanate group can be obtained by using 2-methylpropenyloxyethyl isocyanate (trade name: Karenz MOI, manufactured by Showa Denko Co., Ltd.) or 2-propene cyanide. A (meth) acrylate containing an isocyanate group such as a methoxyethyl ester (trade name: Karenz AOI, manufactured by Showa Denko Co., Ltd.) is homopolymerized or copolymerized with another (meth)acrylic monomer. . Examples of the "(meth)acrylic compound having a hydroxyl group" include 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate.

A成分的含量亦根據A成分的聚合物的結構、C成分的種類、顯示體的種類、所要求的黏著特性等而不同，但當將A成分、B成分的合計設為100質量%時，較佳為5質量%~80質量%的範圍內，更佳為20質量%~70質量%的範圍。因存在如下的傾向，即含量越多，黏度變得越高且作為光硬化型黏著劑組成物的塗佈性越良好，含量越低，與用作稀釋劑等的B成分或其他單體的混合性越提昇，故較佳。 The content of the component A is also different depending on the structure of the polymer of the component A, the type of the component C, the type of the display, and the desired adhesive properties. However, when the total of the component A and the component B is 100% by mass, It is preferably in the range of 5 mass% to 80 mass%, more preferably in the range of 20 mass% to 70 mass%. There is a tendency that the higher the content, the higher the viscosity and the better the coating property as a photocurable adhesive composition, and the lower the content, the B component or other monomer used as a diluent or the like. The more the mixing is improved, the better.

本發明的組成物含有作為B成分的具有一個聚合性雙鍵的單體作為構成成分。藉由含有B成分，光硬化型黏著劑組成物的塗佈變得容易，黏著劑的黏著力相對於顯示體得到適度調整，且顯示面板的重新加工性提昇。 The composition of the present invention contains, as a component B, a monomer having one polymerizable double bond as a component B. By containing the B component, the application of the photocurable adhesive composition is facilitated, the adhesive force of the adhesive is appropriately adjusted with respect to the display body, and the reworkability of the display panel is improved.

B成分只要是僅具有1個乙烯基等聚合性雙鍵的單體，則其種類並無特別限制。因此，只要對應於作為光硬化型黏著劑組成物的要求性能而適宜選擇即可。 The B component is not particularly limited as long as it is a monomer having only one polymerizable double bond such as a vinyl group. Therefore, it is suitable as long as it corresponds to the required performance as a photocurable adhesive composition.

作為B成分，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸異硬脂基酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸三環癸酯、(甲基)丙烯酸二環戊二烯酯、(甲基)丙烯酸二環戊酯等具有烴骨架的(甲基)丙烯酸烷基酯；(甲基)丙烯酸、丁二酸單(2-(甲基)丙烯醯氧基乙基)酯、ω-羧基-聚己內酯單(甲基)丙烯酸酯等含有羧基的(甲基)丙烯酸系單體；(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸甲氧基乙酯、乙氧基二乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、苯氧基二乙二醇(甲基)丙烯酸酯、甲氧基聚環氧乙烷單(甲基)丙烯酸酯、月桂氧基聚環氧乙烷單(甲基)丙烯酸酯、硬脂氧基聚環氧乙烷單(甲基)丙烯酸酯、烯丙氧基聚環氧乙烷單(甲基)丙烯酸酯、壬基苯氧基聚環氧乙烷單(甲基)丙烯酸酯、壬基苯氧基聚環氧丙烷單(甲基)丙烯酸酯、辛氧基(聚環氧乙烷-聚環氧丙烷)單(甲基)丙烯酸酯、壬基苯氧基(聚環氧乙烷-環氧丙烷)單(甲基)丙烯酸酯等含有聚環氧烷基的(甲基)丙烯酸酯 類；(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丁酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸1,2-二羥基乙酯、(甲基)丙烯酸1,2-二羥基丙酯、(甲基)丙烯酸1,2-二羥基丁酯、(甲基)丙烯酸1,2-二羥基-5-乙基己酯、(甲基)丙烯酸1,2,3-三羥基丙酯、(甲基)丙烯酸1,2,3-三羥基丁酯、(甲基)丙烯酸1,1-二羥基乙酯、(甲基)丙烯酸1,1-二羥基丙酯、(甲基)丙烯酸1,1-二羥基丁酯、(甲基)丙烯酸1,1,2-三羥基丙酯、(甲基)丙烯酸1,1,2-三羥基丁酯、(甲基)丙烯酸縮水甘油酯、羥基聚環氧乙烷單(甲基)丙烯酸酯、羥基聚環氧丙烷單(甲基)丙烯酸酯、羥基(聚環氧乙烷-聚環氧丙烷)單(甲基)丙烯酸酯、羥基(聚環氧乙烷-環氧丙烷)單(甲基)丙烯酸酯、羥基(聚環氧乙烷-聚四亞甲基氧化物)單(甲基)丙烯酸酯、羥基(聚環氧乙烷-四亞甲基氧化物)單(甲基)丙烯酸酯、羥基(聚環氧丙烷-聚四亞甲基氧化物)單(甲基)丙烯酸酯、羥基(聚環氧丙烷-四亞甲基氧化物)單(甲基)丙烯酸酯等含有羥基的(甲基)丙烯酸酯；(甲基)丙烯酸N-二甲胺基乙酯、(甲基)丙烯酸N-二乙胺基乙酯等含有胺基的(甲基)丙烯酸酯；(甲基)丙烯醯胺、(甲基)丙烯醯胺二丙酮丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-甲氧基甲基(甲基)丙烯醯胺、N-乙氧基甲基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、(甲基)丙烯醯基嗎啉等(甲基)丙烯醯胺衍生物；2-(甲基)丙烯醯氧基乙基酸式磷酸鹽、2-(甲基)丙烯醯氧基乙基酸式磷酸鹽．單乙醇胺鹽、二苯基((甲基)丙烯醯氧基乙基)磷酸鹽、(甲基)丙烯醯氧基丙基酸式磷酸鹽、(甲基)丙烯酸3-氯-2-酸式．丙酯、酸式． 聚氧乙烯二醇單(甲基)丙烯酸酯、酸式．聚氧丙烯二醇(甲基)丙烯酸酯等含有磷酸基的單體；(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸羥基丁酯縮水甘油醚等含有縮水甘油基的單體；苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、氯苯乙烯等芳香族乙烯基單體；丙烯腈、甲基丙烯腈、α-氰基丙烯酸酯、二氰基亞乙烯基、反丁烯二腈等乙烯基氰單體；巴豆酸、異巴豆酸、桂皮酸、衣康酸、順丁烯二酸、反丁烯二酸、檸康酸、中康酸、戊烯二酸等含有羧基的單體；(甲基)丙烯酸銨、(甲基)丙烯酸鈉、(甲基)丙烯酸鉀等(甲基)丙烯酸鹽類；乙烯基磺酸、2-丙烯醯胺-2-甲基丙磺酸等含有磺酸基的單體；乙酸乙烯酯、丙酸乙烯酯等乙烯系單體；1,3-丁二烯、異戊二烯、2-氯-1,3-丁二烯、氯丁二烯等共軛二烯單體等。該些丙烯酸系單體以外的單體成分可單獨使用1種，亦可併用2種以上。其中，就與A成分的反應的容易性這一點而言，較佳為具有烴骨架的(甲基)丙烯酸烷基酯，更佳為具有碳數為2~25的烴骨架的(甲基)丙烯酸烷基酯，進而更佳為具有碳數為6~20的烷基醇殘基的(甲基)丙烯酸酯。其中，尤其為了顯現透明性、黏著力，較佳為丙烯酸2-乙基己酯、丙烯酸異冰片酯等(甲基)丙烯酸酯類，另外，就透明性、抑制硬化時的收縮的觀點而言，較佳為丙烯酸月桂酯、丙烯酸異硬脂基酯，就與A成分的聚合性，或提昇透明性、折射率的觀點而言，較佳為丙烯酸苄酯，丙烯酸鄰聯苯氧基乙酯等含有芳香族環的(甲基)丙烯酸酯類。 Examples of the component B include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate. , isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, (methyl) N-octyl acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, (methyl) Cyclohexyl acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, (meth)acrylic acid (meth)acrylic acid alkyl ester having a hydrocarbon skeleton such as dicyclopentanyl ester; (meth)acrylic acid, succinic acid mono(2-(methyl)acryloxyethyl)ester, ω-carboxy-polyhexyl a carboxyl group-containing (meth)acrylic monomer such as a lactone mono(meth)acrylate; ethoxyethyl (meth)acrylate; methoxyethyl (meth)acrylate; ethoxydiethylene Alcohol (meth) acrylate, Oxygen triethylene glycol (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, methoxy polyethylene oxide mono (meth) acrylate, lauryloxy poly epoxide Alkenyl mono (meth) acrylate, stearyloxy polyethylene oxide mono (meth) acrylate, allyloxy polyethylene oxide mono (meth) acrylate, nonyl phenoxy polycyclohexane Oxyethane mono(meth)acrylate, nonylphenoxypolypropylene oxide mono(meth)acrylate, octyloxy(polyethylene oxide-polypropylene oxide) mono(meth)acrylate a (meth) acrylate containing a polyalkylene oxide group such as a nonylphenoxy group (polyethylene oxide-propylene oxide) mono(meth)acrylate; a hydroxyethyl (meth)acrylate; Hydroxybutyl methacrylate, hydroxypropyl (meth) acrylate, 1,2-dihydroxyethyl (meth)acrylate, 1,2-dihydroxypropyl (meth)acrylate, (meth)acrylic acid 1,2-dihydroxybutyl ester, 1,2-dihydroxy-5-ethylhexyl (meth)acrylate, 1,2,3-trihydroxypropyl (meth)acrylate, (meth)acrylic acid 1 , 2,3-trihydroxybutyl ester, 1,1-dihydroxyethyl (meth)acrylate, 1,1-(meth)acrylic acid Dihydroxypropyl ester, 1,1-dihydroxybutyl (meth)acrylate, 1,1,2-trihydroxypropyl (meth)acrylate, 1,1,2-trihydroxybutyl (meth)acrylate , glycidyl (meth)acrylate, hydroxypolyethylene oxide mono(meth)acrylate, hydroxypolypropylene oxide mono(meth)acrylate, hydroxyl (polyethylene oxide-polypropylene oxide) Mono(meth)acrylate, hydroxyl (polyethylene oxide-propylene oxide) mono(meth)acrylate, hydroxyl (polyethylene oxide-polytetramethylene oxide) mono(meth)acrylic acid Ester, hydroxy (polyethylene oxide-tetramethylene oxide) mono (meth) acrylate, hydroxy (polypropylene oxide - polytetramethylene oxide) mono (meth) acrylate, hydroxyl ( a hydroxyl group-containing (meth) acrylate such as a polypropylene oxide-tetramethylene oxide) mono(meth)acrylate; N-dimethylaminoethyl (meth)acrylate; (meth)acrylic acid N -Ethyl group-containing (meth) acrylate such as diethylaminoethyl ester; (meth) acrylamide, (meth) acrylamide diacetone acrylamide, N-methylol (meth) propylene Indoleamine, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl ( Methyl) acrylamide, N-butoxymethyl (meth) acrylamide, (meth) acryloyl morpholine (meth) acrylamide derivatives; 2-(methyl) propylene oxime Oxyethylethyl phosphate, 2-(meth)acryloxyethyl phosphate. Monoethanolamine salt, diphenyl ((meth) propylene methoxyethyl) phosphate, (meth) propylene methoxy propyl phosphate, 3-chloro-2-acid (meth) acrylate . Propyl ester, acid type. Polyoxyethylene glycol mono (meth) acrylate, acid type. a monomer containing a phosphate group such as polyoxypropylene diol (meth) acrylate; a glycidyl group-containing monomer such as glycidyl (meth) acrylate or hydroxybutyl methacrylate (glycidyl ether); styrene; , an aromatic vinyl monomer such as α-methylstyrene, p-methylstyrene, vinyl toluene, chlorostyrene; acrylonitrile, methacrylonitrile, α-cyanoacrylate, dicyanovinylidene Vinyl cyanide monomer such as fumaronitrile; crotonic acid, isocrotonic acid, cinnamic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, pentene a monomer having a carboxyl group such as an acid; a (meth)acrylic acid salt such as ammonium (meth)acrylate, sodium (meth)acrylate or potassium (meth)acrylate; vinylsulfonic acid, 2-propenylamine-2- a monomer containing a sulfonic acid group such as methyl propanesulfonic acid; a vinyl monomer such as vinyl acetate or vinyl propionate; 1,3-butadiene, isoprene, 2-chloro-1,3-butyl A conjugated diene monomer such as a diene or a chloroprene. The monomer components other than the acrylic monomers may be used alone or in combination of two or more. Among them, in terms of easiness of the reaction with the component A, an alkyl (meth)acrylate having a hydrocarbon skeleton is preferred, and a (meth) group having a hydrocarbon skeleton having a carbon number of 2 to 25 is more preferred. The alkyl acrylate is more preferably a (meth) acrylate having an alkyl alcohol residue having 6 to 20 carbon atoms. Among them, in particular, in order to exhibit transparency and adhesion, (meth) acrylate such as 2-ethylhexyl acrylate or isobornyl acrylate is preferable, and from the viewpoint of transparency and suppression of shrinkage at the time of curing, Preferably, lauryl acrylate or isostearyl acrylate is preferably benzyl acrylate or o-phenoxyethyl acrylate from the viewpoint of polymerizability with component A or transparency and refractive index. A (meth) acrylate containing an aromatic ring.

另外，就提昇黏著性的觀點而言，較佳為同時調配丙烯 酸2-乙基己酯與丙烯酸異冰片酯，就提昇黏著性與折射率的觀點而言，較佳為同時調配丙烯酸2-乙基己酯、丙烯酸苄酯、丙烯酸鄰聯苯氧基乙酯。 In addition, in terms of improving adhesion, it is preferred to simultaneously mix propylene 2-ethylhexyl acid ester and isobornyl acrylate, in terms of improving adhesion and refractive index, it is preferred to simultaneously formulate 2-ethylhexyl acrylate, benzyl acrylate, and o-phenoxyethyl acrylate. .

B成分的較佳的含量亦根據A成分的聚合物的結構或分子量、B成分的種類、C成分的種類、顯示體的種類、所要求的黏著特性而不同，但當將A成分及B成分的合計設為100質量%時，較佳為20質量%~95質量%的範圍內，更佳為30質量%~80質量%的範圍內。因存在含量越多，與A成分的混合性越提昇的傾向，故較佳。另一方面，因存在含量越少，黏度變得越高且越容易成膜的傾向，故較佳。 The preferred content of the component B is also different depending on the structure or molecular weight of the polymer of the component A, the type of the component B, the type of the component C, the type of the display, and the desired adhesive properties, but the component A and the component B are different. When the total amount is 100% by mass, it is preferably in the range of 20% by mass to 95% by mass, more preferably in the range of 30% by mass to 80% by mass. The more the content is present, the better the mixing property with the component A tends to be. On the other hand, the smaller the content, the higher the viscosity and the easier the film formation tends to be, which is preferable.

於本發明的光硬化型黏著劑組成物中，較佳為相對於A成分及B成分的合計100質量份，以5質量份以下的量包含含有羧基的單體。若相對於A成分及B成分的合計100質量份，本發明的光硬化型黏著劑組成物中所包含的含有羧基的單體的量超過5質量份，則於形成有包含氧化銦錫(Indium Tin Oxide，ITO)等金屬的透明導電性皮膜的光學功能材料的貼合時，有時會腐蝕金屬，而失去導電性。於本發明的光硬化型黏著劑組成物中，更佳為相對於A成分及B成分的合計100質量份，以3質量份以下的量包含含有羧基的單體，進而更佳為1.5質量份以下。 In the photocurable adhesive composition of the present invention, the carboxyl group-containing monomer is preferably contained in an amount of 5 parts by mass or less based on 100 parts by mass of the total of the components A and B. When the amount of the carboxyl group-containing monomer contained in the photocurable pressure-sensitive adhesive composition of the present invention exceeds 5 parts by mass based on 100 parts by mass of the total of the components A and B, the indium tin oxide is contained. When the optical functional material of a transparent conductive film of a metal such as Tin Oxide or ITO is bonded, the metal may be corroded and the conductivity may be lost. In the photocurable adhesive composition of the present invention, the carboxyl group-containing monomer is further contained in an amount of 3 parts by mass or less, and more preferably 1.5 parts by mass, based on 100 parts by mass of the total of the component A and the component B. the following.

作為含有羧基的單體，可列舉：(甲基)丙烯酸、丁二酸單(2-(甲基)丙烯醯氧基乙基)酯、ω-羧基-聚己內酯單(甲基)丙烯酸酯、巴豆酸、異巴豆酸、桂皮酸等一元酸；衣康酸、順丁烯二酸、 反丁烯二酸、檸康酸、中康酸、戊烯二酸等二元酸等具有一個聚合性雙鍵的單體。作為含有羧基的單體，包含具有兩個以上的聚合性雙鍵的單體。該些含有羧基的單體亦可為分子內或分子間的2個羧基脫水而獲得的酸酐。當使用該些含有羧基的單體時，就A成分及B成分的反應的容易性的觀點而言，較佳為一元酸。更佳為(甲基)丙烯酸、丁二酸單(2-(甲基)丙烯醯氧基乙基)酯。 Examples of the carboxyl group-containing monomer include (meth)acrylic acid, succinic acid mono(2-(methyl)acryloxyethyl)ester, and ω-carboxy-polycaprolactone mono(meth)acrylic acid. Monobasic acid such as ester, crotonic acid, isocrotonic acid, cinnamic acid; itaconic acid, maleic acid, A monomer having a polymerizable double bond such as a dibasic acid such as fumaric acid, citraconic acid, mesaconic acid or glutaconic acid. The monomer having a carboxyl group contains a monomer having two or more polymerizable double bonds. The carboxyl group-containing monomer may be an acid anhydride obtained by dehydrating two carboxyl groups in the molecule or in the molecule. When these carboxyl group-containing monomers are used, a monobasic acid is preferred from the viewpoint of easiness of the reaction between the component A and the component B. More preferred is (meth)acrylic acid, succinic acid mono(2-(methyl)acryloxyethyl)ester.

該些含有羧基的單體可單獨使用1種，亦可併用2種以上。 These carboxyl group-containing monomers may be used alone or in combination of two or more.

於本發明的光硬化型黏著劑組成物中，含有光聚合起始劑作為C成分。光聚合起始劑是活性能量線聚合起始劑，且為藉由活性能量線的照射而開裂，並產生使聚合反應開始的自由基的化合物。此處所謂「活性能量線」，例如是指電子束、紫外線、可見光線、電漿、紅外線等熱線等。尤其，就裝置成本或生產性的觀點而言，較佳為使用紫外線。於本發明中，其種類並無特別限制，可使用公知的光聚合起始劑。 The photocurable adhesive composition of the present invention contains a photopolymerization initiator as a component C. The photopolymerization initiator is an active energy ray polymerization initiator, and is a compound which is cleaved by irradiation with an active energy ray and generates a radical which starts a polymerization reaction. Here, the "active energy ray" means, for example, a heat beam such as an electron beam, an ultraviolet ray, a visible ray, a plasma, or an infrared ray. In particular, ultraviolet rays are preferably used from the viewpoint of device cost or productivity. In the present invention, the kind thereof is not particularly limited, and a known photopolymerization initiator can be used.

作為C成分，可列舉：2,2-二甲氧基-1,2-二苯基乙烷-1-酮、1-羥基-環己基-苯基-酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷、2-羥基-1-{4-[4-(2-羥基-2-甲基-丙醯基)-苄基]苯基}-2-甲基-丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮-1,2-甲基-1-(4-甲硫基苯基)-2-嗎啉基丙烷-1-酮、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、2,4,6-三甲基苯甲醯基-二苯基-氧化膦、雙(η5-2,4-環戊二烯-1-基)-雙[2,6-二氟-3(1H-吡咯-1-基)-苯基]鈦、2-羥基-1-{4-[4-(2-羥基-2- 甲基-丙醯基)-苄基]苯基}-2-甲基-丙烷-1-酮等。該些可單獨使用、或併用2種以上。其中，就硬化性的觀點而言，較佳為使用2,2-二甲氧基-1,2-二苯基乙烷-1-酮、1-羥基-環己基-苯基-酮、2-羥基-1-{4-[4-(2-羥基-2-甲基-丙醯基)-苄基]苯基}-2-甲基-丙烷-1-酮。 As the component C, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl group 1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane, 2-hydroxy-1-prop 4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-benzyl-2-dimethylamino- 1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one, bis(2,4 ,6-trimethylbenzylidene)-phenylphosphine oxide, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, bis(η5-2,4-cyclopentadiene -1-yl)-bis[2,6-difluoro-3(1H-pyrrol-1-yl)-phenyl]titanium, 2-hydroxy-1-{4-[4-(2-hydroxy-2- Methyl-propenyl)-benzyl]phenyl}-2-methyl-propan-1-one and the like. These may be used alone or in combination of two or more. Among them, from the viewpoint of hardenability, it is preferred to use 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2 -Hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propan-1-one.

C成分的較佳的含量亦根據A成分的聚合物的結構、B成分的種類、顯示體的種類、所要求的黏著特性而不同，但當將A成分、B成分的合計設為100質量份時，較佳為0.1質量份~10質量份的範圍內，更佳為0.1質量份~5質量份的範圍內，進而更佳為0.3質量份~3質量份的範圍內。若C成分的含量超過10質量份，則硬化物中的殘留量變多，因此有時硬化物的耐候性會下降。若C成分的含量未滿0.1質量份，則有時因硬化不足而導致作為黏著劑的性能下降。 The content of the component A is also different depending on the structure of the polymer of the component A, the type of the component B, the type of the display, and the desired adhesive properties. However, the total amount of the component A and the component B is 100 parts by mass. The amount is preferably in the range of 0.1 part by mass to 10 parts by mass, more preferably 0.1 part by mass to 5 parts by mass, still more preferably 0.3 part by mass to 3 parts by mass. When the content of the component C exceeds 10 parts by mass, the residual amount in the cured product increases, and thus the weather resistance of the cured product may decrease. When the content of the component C is less than 0.1 part by mass, the performance as an adhesive may be deteriorated due to insufficient curing.

另外，於本發明的光硬化型黏著劑組成物中，亦可含有具有兩個以上的聚合性雙鍵的單體作為D成分。作為D成分，例如可列舉：1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、聚丁二醇二(甲基)丙烯酸酯、新戊二醇己二酸酯二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、二(甲基)丙烯酸二環戊酯、己內酯改質二(甲基)丙烯酸二環戊烯酯、環氧乙烷改質二(甲基)丙烯酸酯、異三聚氰酸二(甲基)丙烯醯氧基乙酯、二(甲基)丙烯酸烯丙基化環己酯、三環癸烷二甲醇(甲基)丙烯酸酯、二羥甲基二 環戊烷二(甲基)丙烯酸酯、環氧乙烷改質六氫鄰苯二甲酸二(甲基)丙烯酸酯、三環癸烷二甲醇(甲基)丙烯酸酯、新戊二醇改質三甲基丙烷二(甲基)丙烯酸酯、二(甲基)丙烯酸金剛烷酯或9,9-雙[4-(2-丙烯醯氧基乙氧基)苯基]茀等二官能丙烯酸酯；三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、丙酸改質二季戊四醇三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、環氧丙烷改質三羥甲基丙烷三(甲基)丙烯酸酯、三官能(甲基)丙烯酸胺基甲酸酯或異三聚氰酸三(甲基)丙烯醯氧基乙酯等三官能丙烯酸酯；二甘油四(甲基)丙烯酸酯或季戊四醇四(甲基)丙烯酸酯等四官能丙烯酸酯；丙酸改質二季戊四醇五(甲基)丙烯酸酯等五官能丙烯酸酯；及二季戊四醇六(甲基)丙烯酸酯、己內酯改質二季戊四醇六(甲基)丙烯酸酯或(甲基)丙烯酸胺基甲酸酯(例如異氰酸酯單體及三羥甲基丙烷三(甲基)丙烯酸酯的反應物等)等六官能丙烯酸酯；二乙烯基苯、二乙烯基萘、二乙烯基醚等多官能單體等。該些具有兩個以上的聚合性雙鍵的單體之中，為了顯現黏著力，較佳為二官能丙烯酸酯與三官能丙烯酸酯。就光硬化型黏著劑組成物的塗佈性、及可減少顯示體上的殘膠的觀點而言，更佳為1,6-己二醇二丙烯酸酯、1,9-壬二醇二丙烯酸酯及聚乙二醇二丙烯酸酯。 Further, in the photocurable pressure-sensitive adhesive composition of the present invention, a monomer having two or more polymerizable double bonds may be contained as the component D. Examples of the component D include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol di(methyl). Acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, new Pentandiol adipate di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, dicyclopentyl di(meth)acrylate, caprolactone modified di( Dicyclopentenyl methacrylate, ethylene oxide modified di(meth) acrylate, di(meth) propylene methoxyethyl isophthalate, allyl (meth) acrylate Cyclohexyl ester, tricyclodecane dimethanol (meth) acrylate, dimethylol di Cyclopentane di(meth) acrylate, ethylene oxide modified hexahydrophthalic acid di(meth) acrylate, tricyclodecane dimethanol (meth) acrylate, neopentyl glycol modification Difunctional acrylates such as trimethylpropane di(meth)acrylate, adamantyl di(meth)acrylate or 9,9-bis[4-(2-propenyloxyethoxy)phenyl]indole ; trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide Modifying a trifunctional acrylate such as trimethylolpropane tri(meth)acrylate, trifunctional (meth)acrylic acid urethane or tris(meth)acryloxyethyl ester; a tetrafunctional acrylate such as diglycerin tetra(meth)acrylate or pentaerythritol tetra(meth)acrylate; a pentafunctional acrylate such as propionic acid modified dipentaerythritol penta (meth) acrylate; and dipentaerythritol hexa(methyl) Acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate or (meth) acrylate urethane (such as isocyanate monomer a hexafunctional acrylate such as a reaction product of trimethylolpropane tri(meth)acrylate or the like; a polyfunctional monomer such as divinylbenzene, divinylnaphthalene or divinyl ether. Among these monomers having two or more polymerizable double bonds, a difunctional acrylate and a trifunctional acrylate are preferred in order to exhibit adhesiveness. The 1,6-hexanediol diacrylate and the 1,9-nonanediol diacrylic acid are more preferable from the viewpoints of coatability of the photocurable adhesive composition and reduction of residual glue on the display body. Ester and polyethylene glycol diacrylate.

D成分的較佳的含量亦根據A成分的聚合物的結構、B成分的種類、顯示體的種類、所要求的黏著特性等而不同，但當將A成分、B成分的合計設為100質量份時，就提昇重新加工性的觀點而言，較佳為0.05質量份~10質量份的範圍內，更佳為0.05 質量份~5質量份的範圍內。 The content of the component D is also different depending on the structure of the polymer of the component A, the type of the component B, the type of the display, the desired adhesive properties, etc., but the total of the components A and B is set to 100 mass. In the case of increasing the reworkability, it is preferably in the range of 0.05 parts by mass to 10 parts by mass, more preferably 0.05 part by weight. Within the range of ~5 parts by mass.

另外，於本發明的光硬化型黏著劑組成物中，為了使無法藉由活性能量線而硬化的部分(例如：邊框印刷部分等)硬化，亦可添加熱聚合起始劑作為E成分。作為E成分的具體例，可列舉：甲基酮過氧化物等酮過氧化物，1,1-二(過氧化第三己基)-3,3,5-三甲基環己烷、1,1-二(過氧化第三己基)環己烷、1,1-二(過氧化第三丁基)環己烷等過氧化縮酮，1,1,3,3-四甲基丁基氫過氧化物、枯烯氫過氧化物、對薄荷烷氫過氧化物等氫過氧化物，二枯烯基過氧化物、二-第三丁基過氧化物、二月桂醯基過氧化物、二苯甲醯基過氧化物等二醯基過氧化物，過氧化二碳酸二(4-第三丁基環己基)酯、過氧化二碳酸二(2-乙基己基)酯等過氧化二碳酸酯，過氧化-2-乙基己酸第三丁酯、過氧化異丙基單碳酸第三己酯、過氧化特戊酸第三己酯、過氧化苯甲酸第三丁酯等過氧化酯等。作為偶氮化合物的具體例，可列舉：2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2-甲基丁腈)、2,2'-偶氮雙(2,4-二甲基戊腈)、1,1'-偶氮雙-1-環己碳腈、二甲基-2,2'-偶氮雙異丁酸酯、4,4'-偶氮雙-4-氰基戊酸、2,2'-偶氮雙-(2-甲脒基丙烷)二氫氯化物等。該些之中，就於低溫條件下的硬化性優異的觀點而言，較佳為過氧化特戊酸第三己酯、過氧化二碳酸二(4-第三丁基環己基)酯。 Further, in the photocurable pressure-sensitive adhesive composition of the present invention, a thermal polymerization initiator may be added as the component E in order to cure a portion (for example, a bezel printing portion) which cannot be cured by the active energy ray. Specific examples of the component E include a ketone peroxide such as methyl ketone peroxide, 1,1-di(dihexyl peroxide)-3,3,5-trimethylcyclohexane, and 1, Peroxy ketal such as 1-di(dihexyl peroxide)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 1,1,3,3-tetramethylbutylhydrogen Peroxide, cumene hydroperoxide, hydroperoxide such as p-menthane hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, dilauroyl peroxide, Dimercapto peroxide such as benzoyl hydrazine peroxide, bis(4-tert-butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, etc. Carbonic acid ester, perbutyl-2-ethylhexanoate, third hexyl peroxydicarbonate, third hexyl peroxypivalate, tert-butyl peroxybenzoate, etc. Ester and the like. Specific examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobis (2). , 4-dimethylvaleronitrile, 1,1'-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azo Bis-4-cyanovaleric acid, 2,2'-azobis-(2-methylamidinopropane) dihydrochloride, and the like. Among these, from the viewpoint of excellent curability under low temperature conditions, it is preferably a third hexyl peroxypivalate or a di(4-tert-butylcyclohexyl) peroxydicarbonate.

另外，E成分的較佳的含量亦根據A成分的聚合物的結構、B成分的種類、顯示體的種類、所要求的黏著特性等而不同，但當將A成分、B成分的合計設為100質量份時，較佳為0.05質 量份~5質量份的範圍內，更佳為0.05質量份~1質量份的範圍內。含量越多，作為熱聚合起始劑的作用越充分地發揮，故較佳。另一方面，含量越少，E成分的殘留變得越少，藉此作為黏著劑的性能下降變少，故較佳。 In addition, the content of the component A is also different depending on the structure of the polymer of the component A, the type of the component B, the type of the display, the desired adhesive properties, etc., but the total of the components A and B is set. When 100 parts by mass, it is preferably 0.05 In the range of parts by mass to 5 parts by mass, more preferably in the range of 0.05 parts by mass to 1 part by mass. The more the content, the more fully the function as a thermal polymerization initiator, and therefore it is preferable. On the other hand, the smaller the content, the less the residue of the component E becomes, and the performance of the adhesive is reduced, which is preferable.

另外，於本發明的光硬化型黏著劑組成物中，就抑制硬化時的收縮的觀點而言，較佳為含有A成分以外的(甲基)丙烯酸系聚合物作為F成分。就與A成分、B成分的相容性的觀點而言，F成分的重量平均分子量較佳為1000~15000。 Moreover, in the photocurable adhesive composition of the present invention, it is preferable to contain a (meth)acrylic polymer other than the A component as the F component from the viewpoint of suppressing shrinkage during curing. The weight average molecular weight of the F component is preferably from 1,000 to 15,000 from the viewpoint of compatibility with the component A and the component B.

另外，F成分的調配量亦根據A成分的聚合物的結構、B成分的種類、顯示體的種類、所要求的黏著特性等而不同，但當將A成分、B成分的合計設為100質量份時，就提昇樹脂強度、及抑制硬化時的收縮的觀點而言，較佳為10質量份~120質量份的範圍內。 In addition, the amount of the component F is different depending on the structure of the polymer of the component A, the type of the component B, the type of the display, and the desired adhesive properties. However, when the total amount of the component A and the component B is 100 mass In the case of the resin, it is preferably in the range of 10 parts by mass to 120 parts by mass from the viewpoint of improving the strength of the resin and suppressing shrinkage during curing.

於本發明的光硬化型黏著劑組成物中，亦可調配紫外線吸收劑。藉由調配紫外線吸收劑，而發揮如下的較佳的效果：遮斷具有強大的化學作用的紫外線，抑制存在於比黏著層更靠下層側的物質的氧化或變質，或者抑制由有機物的分解所引起的變色、退色及脆化等劣化。 In the photocurable adhesive composition of the present invention, an ultraviolet absorber may be formulated. By blending the ultraviolet absorber, the following effects are obtained: the ultraviolet rays having a strong chemical action are blocked, the oxidation or deterioration of the substance existing on the lower layer side than the adhesive layer is suppressed, or the decomposition of the organic substance is suppressed. Deterioration caused by discoloration, discoloration, and embrittlement.

作為紫外線吸收劑，例如除二苯基酮系化合物、苯并***系化合物以外，可列舉水楊酸酯類、三嗪系化合物、氰基丙烯酸酯系化合物等有機系紫外線吸收劑；氧化鋅、氧化鈦等無機系紫外線吸收劑等。 Examples of the ultraviolet absorber include, in addition to the diphenylketone-based compound and the benzotriazole-based compound, an organic ultraviolet absorber such as a salicylate, a triazine-based compound or a cyanoacrylate-based compound; zinc oxide; An inorganic ultraviolet absorber such as titanium oxide.

於本發明的光硬化型黏著劑組成物中，亦可添加黏著性賦予劑、抗老化劑、著色劑、光穩定劑、矽烷偶合劑、熱聚合抑制劑、均染劑、界面活性劑、保存穩定劑、塑化劑、填料、胺化合物、環氧化合物等。 In the photocurable adhesive composition of the present invention, an adhesion imparting agent, an anti-aging agent, a colorant, a light stabilizer, a decane coupling agent, a thermal polymerization inhibitor, a leveling agent, a surfactant, and a preservation may be added. Stabilizers, plasticizers, fillers, amine compounds, epoxy compounds, and the like.

作為保存穩定劑，較佳為對苯二酚、甲氧基苯酚、第三丁基兒茶酚、甲基對苯二酚、二丁基羥基甲苯，就抑制著色的觀點而言，更佳為二丁基羥基甲苯。 As the storage stabilizer, hydroquinone, methoxyphenol, t-butylcatechol, methyl hydroquinone, and dibutylhydroxytoluene are preferred, and from the viewpoint of suppressing coloration, it is more preferable Dibutylhydroxytoluene.

本發明的光硬化型黏著劑組成物可藉由以規定的比率將作為必需成分的A成分、B成分及C成分，以及作為任意成分的D成分、E成分、F成分及其他成分混合而獲得。 The photocurable adhesive composition of the present invention can be obtained by mixing the component A, the component B, and the component C as essential components, and the component D, the component E, the component F, and other components as optional components at a predetermined ratio. .

作為本發明的光硬化型黏著劑組成物的調配方法，例如可列舉如下的方法：向藉由溶液聚合法所製造的丙烯酸系聚合物(A成分)的溶液中添加B成分，充分地攪拌後，進行減壓加熱而將溶劑去除後，添加混合C成分、以及作為任意成分的D成分、E成分、F成分及其他成分。另外，可列舉如下的方法等：向藉由溶液聚合法所製造的丙烯酸系聚合物(A成分)的溶液中添加B成分、C成分、以及作為任意成分的D成分、E成分、F成分及其他成分，充分地攪拌後，進行減壓加熱而將溶劑去除。但是，調配方法並無特別限定。於任何方法中，均必須先將各成分充分地攪拌混合而製成均勻的組成物。 The method of blending the photocurable adhesive composition of the present invention is, for example, a method in which a component B is added to a solution of an acrylic polymer (component A) produced by a solution polymerization method, and the mixture is sufficiently stirred. After the solvent is removed by heating under reduced pressure, the component C and the component D, the component E, the component F, and other components are added as an optional component. In addition, a method of adding a component B, a component C, and a component D, an component E, and an component F as an optional component to a solution of an acrylic polymer (component A) produced by a solution polymerization method may be mentioned. After the other components were sufficiently stirred, the mixture was heated under reduced pressure to remove the solvent. However, the method of blending is not particularly limited. In any method, the components must be thoroughly stirred and mixed to form a uniform composition.

就塗佈性的觀點而言，本發明的光硬化型黏著劑組成物的藉由E型黏度計所測定的25℃下的黏度較佳為1mPa．s以上， 更佳為10mPa．s以上。另外，就減少氣泡的混入及塗膜的厚度的不均這一觀點而言，較佳為10,000mPa．s以下，更佳為5000mPa．s以下。 From the viewpoint of coatability, the viscosity of the photocurable adhesive composition of the present invention at 25 ° C as measured by an E-type viscometer is preferably 1 mPa. s above, More preferably 10mPa. s above. Further, from the viewpoint of reducing the incorporation of bubbles and the uneven thickness of the coating film, it is preferably 10,000 mPa. Below s, more preferably 5000mPa. s below.

本發明的組成物可不溶解於有機溶劑中，而以原本的狀態供於塗佈。例如，可利用敷料器(applicator)等公知的塗佈裝置將本發明的組成物塗佈於顯示體的表面，貼附光學功能材料後，藉由活性能量線來進行硬化而製作顯示面板。另外，亦可將本發明的組成物注入至顯示體與光學功能材料的間隙中後，進行光硬化而製作顯示面板。如上述般注入來使用時的組成物的黏度較佳為低。 The composition of the present invention can be applied to the coating in an original state without being dissolved in an organic solvent. For example, the composition of the present invention can be applied to the surface of a display body by a known coating device such as an applicator, and after attaching the optical functional material, it can be cured by an active energy ray to produce a display panel. Further, the composition of the present invention may be injected into a gap between the display body and the optical functional material, and then light-cured to form a display panel. The viscosity of the composition when injected and used as described above is preferably low.

再者，本發明的光硬化型黏著劑組成物亦可包含有機溶劑。有機溶劑的含量只要對應於塗佈性而適宜調整即可，但相對於反應性聚合物(A成分)100質量份，較佳為100質量份以下，更佳為50質量份以下，進而更佳為5質量份以下。 Furthermore, the photocurable adhesive composition of the present invention may also contain an organic solvent. The content of the organic solvent is appropriately adjusted in accordance with the coating property, and is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 100 parts by mass of the reactive polymer (component A). It is 5 parts by mass or less.

作為有機溶劑，具體而言，可列舉乙酸乙酯、乙酸丁酯等酯系溶劑；丙酮、甲基乙基酮、甲基異丁基酮等酮系溶劑；庚烷、己烷、環己烷等脂肪族烴系溶劑；甲苯、二甲苯等芳香族烴系溶劑；甲醇(沸點為65℃)、乙醇、異丙醇、異丁醇等醇系溶劑等，但並不限於該些溶劑。 Specific examples of the organic solvent include ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; heptane, hexane, and cyclohexane. An aliphatic hydrocarbon-based solvent; an aromatic hydrocarbon solvent such as toluene or xylene; an alcohol solvent such as methanol (boiling point: 65 ° C), ethanol, isopropyl alcohol or isobutanol, but is not limited thereto.

本發明的光硬化型黏著劑組成物可藉由照射活性能量線而硬化。作為活性能量線，例如可列舉：α射線、β射線、γ射線、X射線、紫外線及可見光線。就作業性及硬化性的觀點而言， 特佳為紫外線。作為照射紫外線的光源，可列舉：高壓水銀燈、金屬鹵化物燈、氙氣閃光燈、發光二極體(Light Emitting Diode，LED)燈等。 The photocurable adhesive composition of the present invention can be cured by irradiation with an active energy ray. Examples of the active energy rays include α rays, β rays, γ rays, X rays, ultraviolet rays, and visible rays. From the viewpoint of workability and hardenability, Particularly good for ultraviolet light. Examples of the light source that emits ultraviolet light include a high pressure mercury lamp, a metal halide lamp, a Xenon flash lamp, and a Light Emitting Diode (LED) lamp.

使本發明的光硬化型黏著劑組成物硬化而成的黏著劑可用於使顯示體與光學功能材料貼合。作為顯示體，可列舉：於玻璃上貼附有偏向板的液晶顯示器(Liquid Crystal Display，LCD)、電致發光(Electroluminescence，EL)顯示器、EL照明、電子紙或電漿顯示器等顯示元件。作為光學功能材料，可列舉：以提昇視認性或防止顯示元件因外部衝擊而破損為目的之壓克力板(可進行單面或雙面硬塗處理、或者抗反射(Anti-Reflection，AR)塗佈)、聚碳酸酯板、聚對苯二甲酸乙二酯(Polyethylene terephthalate，PET)板、聚萘二甲酸乙二酯(Polyethylene naphthalate，PEN)板等透明塑膠板，強化玻璃(可附有防飛散膜)及觸控面板輸入感測器等。 The adhesive which hardened the photocurable adhesive composition of this invention can be used for bonding a display body and an optical functional material. Examples of the display body include display elements such as a liquid crystal display (LCD), an electroluminescence (EL) display, an EL illumination, an electronic paper, or a plasma display in which a deflecting plate is attached to the glass. As the optical functional material, an acrylic sheet for improving the visibility or preventing the display element from being damaged by an external impact (can be subjected to single-sided or double-sided hard coating treatment, or anti-reflection (AR)). Coated), polycarbonate plate, polyethylene terephthalate (PET) plate, polyethylene naphthalate (PEN) plate and other transparent plastic plates, tempered glass (can be attached) Anti-flying film) and touch panel input sensors.

作為利用使本發明的光硬化型黏著劑組成物硬化而成的黏著劑，使顯示體與光學功能材料貼合的方法，例如可列舉以下的方法。將本發明的光硬化型黏著劑組成物塗佈於光學功能材料上，於所獲得的塗膜上積層顯示體，自光學功能材料側照射活性能量線來使光硬化型黏著劑組成物硬化，而使上述光學功能材料與上述顯示體接著的方法(方法1)；將本發明的組成物注入至分開設置的膜狀或片狀的光學功能材料與膜狀或片狀的顯示體之間，並自光學功能材料側照射活性能量線來使光硬化型黏著劑組 成物硬化，而使顯示體與光學功能材料貼合併一體化的方法(方法2)；於使本發明的黏著劑組成物硬化而獲得的黏著片的一面上接著膜狀或片狀的光學功能材料，於另一面上接著膜狀或片狀的顯示體，而使上述光學功能材料與顯示體貼合的方法(方法3)。但是，上述方法並不限定於此。 The method of bonding the display body and the optical functional material to the adhesive which hardened the photocurable adhesive composition of this invention, for example, the following methods are mentioned. The photocurable adhesive composition of the present invention is applied onto an optical functional material, and a display body is laminated on the obtained coating film, and an active energy ray is irradiated from the side of the optical functional material to cure the photocurable adhesive composition. a method of adhering the optical functional material to the display body (method 1); and injecting the composition of the present invention between a separately provided film-like or sheet-shaped optical functional material and a film-like or sheet-like display body, And the active energy ray is irradiated from the side of the optical functional material to make the photo-curing adhesive group A method in which the object is hardened, and the display body and the optical functional material are bonded and integrated (method 2); the optical function of the film or sheet on the one side of the adhesive sheet obtained by hardening the adhesive composition of the present invention A method in which the above-mentioned optical functional material is bonded to a display body on the other surface, followed by a film-like or sheet-like display body (Method 3). However, the above method is not limited to this.

作為上述記載的方法1及方法2的具體的程序，例如可藉由如下的方法來製造：將本組成物直接塗佈於圖像顯示面板等顯示體的表面，於本組成物未硬化的狀態下將光學片或光學膜等光學功能材料載置於其上後，照射活性能量線來使本組成物硬化，而在顯示體與光學功能材料之間事後形成本片材。 The specific procedure of the method 1 and the method 2 described above can be produced, for example, by applying the composition directly to the surface of a display body such as an image display panel, in a state in which the composition is not cured. After the optical functional material such as an optical sheet or an optical film is placed thereon, the active energy ray is irradiated to harden the composition, and the sheet is formed after the display body and the optical functional material.

作為上述記載的方法3中所使用的黏著片的具體的製造方法，例如可列舉如下的方法，但並不限定於此。 The specific method for producing the pressure-sensitive adhesive sheet used in the method 3 described above is, for example, the following method, but is not limited thereto.

可藉由如下的方法來製造：將本發明的光硬化型黏著劑組成物塗佈於間隔片上，藉由活性能量線的照射來進行硬化反應而形成黏著劑層後，使間隔片貼合併捲繞成卷狀的方法；將本組成物塗佈於間隔片上，利用間隔片夾持未硬化的本組成物後，進行光硬化反應，然後捲繞成卷狀的方法。間隔片可使用利用三聚氰胺或矽酮等進行了表面處理的PET膜、或烯烴系膜等樹脂膜，利用矽酮或剝離性丙烯酸樹脂等進行了表面處理的玻璃紙(glassine paper)、塗佈紙、積層紙等脫模紙。尤其，較佳為PET膜等樹脂膜。進而，可對間隔片進行防密接等背面處理、或賦予抗靜電性，亦可完全不進行任何處理。本組成物的塗佈可適宜選擇敷料器、 模塗佈機、模唇塗佈機、反向輥塗機、接觸輥塗機、逗號輥塗機、浸漬輥塗機、凹版輥塗機、棒式塗佈機、刮刀塗佈機、氣刀式塗佈機、簾幕式塗佈機、旋轉塗佈機、噴霧塗佈機等公知的方法來使用。再者，當光硬化型黏著劑組成物中包含有機溶劑時，亦可於光硬化反應前、或光硬化反應後將有機溶劑乾燥去除。有機溶劑的乾燥去除方法並無特別限制，例如可列舉：吹風乾燥、暖風乾燥、紅外線加熱、遠紅外線加熱、真空乾燥等。乾燥溫度只要對應於組成物中所含有的溶劑的沸點而適宜選擇即可。 It can be produced by applying the photocurable pressure-sensitive adhesive composition of the present invention to a spacer, and performing a curing reaction by irradiation with an active energy ray to form an adhesive layer, and then affixing the spacer sheet to a roll. A method of winding into a roll; applying the composition to a spacer, sandwiching the unhardened composition with a spacer, and performing a photohardening reaction, and then winding into a roll. As the spacer, a PET film such as a melamine or an anthrone or a resin film such as an olefin film, or a glass paper or a coated paper which has been surface-treated with an fluorenone or a release acrylic resin can be used. Release paper such as laminated paper. In particular, a resin film such as a PET film is preferred. Further, the spacer may be subjected to back treatment such as adhesion prevention or the like, or antistatic property may be imparted, and no treatment may be performed at all. The coating of the composition can be suitably selected as an applicator, Mold coater, lip coater, reverse roll coater, contact roll coater, comma roll coater, dip roll coater, gravure roll coater, bar coater, knife coater, air knife A known method such as a coater, a curtain coater, a spin coater, or a spray coater is used. Further, when the photocurable adhesive composition contains an organic solvent, the organic solvent may be dried and removed before the photocuring reaction or after the photohardening reaction. The method for drying and drying the organic solvent is not particularly limited, and examples thereof include air drying, warm air drying, infrared heating, far infrared heating, vacuum drying, and the like. The drying temperature may be appropriately selected in accordance with the boiling point of the solvent contained in the composition.

作為上述記載的方法3的使光學功能材料與顯示體貼合的具體的程序，可例示如下的方法：當於圖像顯示面板等顯示體上積層光學片或光學膜等光學功能材料時，首先，將作為本片材的雙面黏著片的一面貼附於光學功能材料上，製作於光學功能材料上積層有雙面黏著片的積層體，繼而將雙面黏著片的另一面貼附於顯示體上。亦可與該方法相反，先將雙面黏著片貼附於顯示體上，其後貼附光學功能材料。根據該些方法，可製造於圖像顯示面板等顯示體上具有本片材的層，於該層上具有光學片或光學膜等光學功能材料的層的圖像顯示裝置等顯示裝置。 As a specific procedure for bonding the optical functional material to the display body of the method 3 described above, a method of laminating an optical functional material such as an optical sheet or an optical film on a display body such as an image display panel, first, One side of the double-sided adhesive sheet as the sheet is attached to the optical functional material, and a laminated body having a double-sided adhesive sheet laminated on the optical functional material is produced, and then the other side of the double-sided adhesive sheet is attached to the display body. on. Contrary to this method, the double-sided adhesive sheet is attached to the display body, and then the optical functional material is attached. According to these methods, a display device such as an image display device having a layer of the present sheet on a display body such as an image display panel and having a layer of an optical functional material such as an optical sheet or an optical film can be manufactured.

關於使本發明的光硬化型黏著劑組成物硬化而獲得的帶狀物，較佳為依據JIS-Z-0237所測定的黏著力為0.1N/24mm~20N/24mm，且於藉由該測定而將黏著劑剝離後的被黏著體上無殘膠。黏著力的具體的測定方法如下：將黏著劑組成物滴在厚度為100μm的透明聚酯膜(東麗公司製造，商品名：Lumirror#100) 上。進而，自其上方覆蓋利用矽酮進行了表面處理的厚度為50μm的透明聚酯膜(琳得科(Lintec)公司製造，商品名：P501031)，以硬化後的硬化物厚度變成200μm的方式，以固定速度於間隙固定的輥間滑動。其後，藉由照射活性能量線來進行硬化，而獲得帶狀物。將所獲得的帶狀物切斷成寬度為24mm、長度為250mm，剝離利用矽酮進行了表面處理的厚度為50μm的透明聚酯膜，然後與不鏽鋼板(工程試驗服務(Engineering Test Service)股份有限公司製造，商品名：SUS304BA處理品，厚度為1.5mm，寬度為50mm，長度為125mm)貼合。再者，於貼合時，在23℃、50%RH的環境下使2kg的橡膠輥往返2次來進行加壓貼付。其後，於23℃×50%RH的條件下，在180度方向上以300mm/min的速度剝離所貼合的黏著劑片，並測定黏著力。另外，針對剝離黏著劑片後的不鏽鋼板，以目視確認有無殘膠。 The tape obtained by curing the photocurable adhesive composition of the present invention preferably has an adhesive force measured according to JIS-Z-0237 of 0.1 N/24 mm to 20 N/24 mm, and is determined by the measurement. On the adhesive body after peeling off the adhesive, there is no residual glue. The specific measurement method of the adhesive force is as follows: The adhesive composition is dropped on a transparent polyester film having a thickness of 100 μm (manufactured by Toray Industries, Inc., trade name: Lumirror #100) on. Furthermore, a transparent polyester film (manufactured by Lintec Co., Ltd., trade name: P501031) having a thickness of 50 μm which was surface-treated with an anthrone was coated thereon, and the thickness of the cured product after hardening was changed to 200 μm. Sliding between rollers fixed at a fixed speed at the gap. Thereafter, hardening is performed by irradiating the active energy ray to obtain a ribbon. The obtained ribbon was cut into a width of 24 mm and a length of 250 mm, and a transparent polyester film having a thickness of 50 μm which was surface-treated with an anthrone was peeled off, and then with a stainless steel plate (Engineering Test Service) Co., Ltd. manufactured, trade name: SUS304BA treated product, thickness 1.5mm, width 50mm, length 125mm). Further, at the time of bonding, a 2 kg rubber roller was reciprocated twice in an environment of 23° C. and 50% RH to perform pressure bonding. Thereafter, the adhered adhesive sheet was peeled off at a rate of 300 mm/min in a 180-degree direction under conditions of 23 ° C × 50% RH, and the adhesive force was measured. Further, the presence or absence of residual glue was visually observed for the stainless steel sheet after peeling off the adhesive sheet.

藉由上述記載的測定方法所求出的黏著力較佳為0.1N/24mm~20N/24mm。若黏著力未滿0.1N/24mm，則有時無法使被黏著物彼此充分地貼合。另外，若黏著力超過20N/24mm，則有時於將被黏著物彼此剝離時，需要大的力量，因此重新加工性會下降。尤其於上述記載的方法3中，為了使被黏著物彼此充分地貼合，黏著力更佳為10N/24mm~20N/24mm。 The adhesive force obtained by the above-described measurement method is preferably from 0.1 N/24 mm to 20 N/24 mm. If the adhesive force is less than 0.1 N/24 mm, the adherends may not be sufficiently bonded to each other. Further, when the adhesive force exceeds 20 N/24 mm, a large force is required when the adherends are peeled off from each other, and thus the reworkability is lowered. In particular, in the method 3 described above, in order to sufficiently bond the adherends to each other, the adhesive force is preferably from 10 N/24 mm to 20 N/24 mm.

較佳為於上述記載的測定後的不鏽鋼板上無殘膠。當有殘膠時，有時於將被黏著物彼此剝離時黏著劑殘留，而無法獲得充分的重新加工性。 Preferably, there is no residual glue on the stainless steel plate after the measurement described above. When there is a residual glue, the adhesive may remain when the adherends are peeled off from each other, and sufficient reworkability cannot be obtained.

本發明的光硬化型黏著劑組成物較佳為依據JIS-Z-0237所測定的黏著保持力為2mm以下。黏著保持力的具體的測定方法如下：將黏著劑組成物滴在厚度為100μm的透明聚酯膜(東麗公司製造，商品名：Lumirror#100)上。進而，自其上方覆蓋利用矽酮進行了表面處理的厚度為50μm的透明聚酯膜(琳得科公司製造，商品名：P501031)，以硬化後的硬化物厚度變成175μm的方式，以固定速度於間隙固定的輥間滑動。其後，藉由照射活性能量線來進行硬化，而獲得帶狀物。自所獲得的帶狀物中剝離利用矽酮進行了表面處理的厚度為50μm的透明聚酯膜，然後以貼合面積變成25mm×25mm的方式，使帶狀物與不鏽鋼板(工程試驗服務股份有限公司製造，商品名：SUS304BA處理品，厚度為1.5mm，寬度為50mm，長度為125mm)貼合。再者，於貼合時，在23℃、50%RH的環境下使2kg的橡膠輥往返2次來進行加壓貼付。於垂直方向上對上述帶狀物施加9.8N的負荷，並測定於60℃、40%RH的環境下靜置24小時後的黏著位置的偏移量。 The photocurable adhesive composition of the present invention preferably has an adhesive retention force of 2 mm or less as measured according to JIS-Z-0237. The specific measurement method of the adhesive retention force was as follows: The adhesive composition was dropped on a transparent polyester film (manufactured by Toray Industries, Inc., trade name: Lumirror #100) having a thickness of 100 μm. Furthermore, a transparent polyester film (manufactured by Linde Co., Ltd., trade name: P501031) having a thickness of 50 μm which was surface-treated with an anthrone was coated thereon, and the thickness of the cured product after hardening was changed to 175 μm at a fixed speed. Slide between the rollers with fixed clearance. Thereafter, hardening is performed by irradiating the active energy ray to obtain a ribbon. A transparent polyester film having a thickness of 50 μm which was surface-treated with an anthrone was peeled off from the obtained ribbon, and then the ribbon and the stainless steel plate (engineering test service shares) were formed in such a manner that the bonding area became 25 mm × 25 mm. Co., Ltd. manufactured, trade name: SUS304BA treated product, thickness 1.5mm, width 50mm, length 125mm). Further, at the time of bonding, a 2 kg rubber roller was reciprocated twice in an environment of 23° C. and 50% RH to perform pressure bonding. A load of 9.8 N was applied to the above-mentioned ribbon in the vertical direction, and the amount of shift of the adhesive position after standing for 24 hours in an environment of 60 ° C and 40% RH was measured.

藉由上述記載的測定方法所求出的黏著保持力較佳為2mm以下。更佳為1mm以下。當黏著保持力超過2mm時，硬化物的凝聚力低，因此有時於將被黏著物彼此剝離時黏著劑殘留，而無法獲得充分的重新加工性。 The adhesive holding force obtained by the above-described measuring method is preferably 2 mm or less. More preferably, it is 1 mm or less. When the adhesive retention force exceeds 2 mm, the cohesive force of the cured product is low, and thus the adhesive remains in the case where the adherends are peeled off from each other, and sufficient reworkability cannot be obtained.

使本發明的光硬化型黏著劑組成物硬化而獲得的黏著片的黏著劑層部分的厚度較佳為25μm以上、1000μm以下。若為25μm以上，則可填埋20μm左右的段差，若為1000μm以下， 則可應對薄型化的要求。進而，就填埋20μm左右的段差的觀點而言，更佳為50μm以上，進而更佳為75μm以上。另外，就應對薄型化的要求的觀點而言，更佳為500μm以下，進而更佳為350μm以下。 The thickness of the adhesive layer portion of the pressure-sensitive adhesive sheet obtained by curing the photocurable pressure-sensitive adhesive composition of the present invention is preferably 25 μm or more and 1000 μm or less. When it is 25 μm or more, a step of about 20 μm can be filled, and if it is 1000 μm or less, It can meet the requirements of thinning. Further, from the viewpoint of filling a step of about 20 μm, it is more preferably 50 μm or more, and still more preferably 75 μm or more. Moreover, from the viewpoint of the requirement for the reduction in thickness, it is more preferably 500 μm or less, and still more preferably 350 μm or less.

使本發明的光硬化型黏著劑組成物硬化而成的黏著劑可用於使顯示體與光學功能材料貼合。作為顯示體，可列舉：於玻璃上貼附有偏向板的LCD、EL顯示器、EL照明、電子紙或電漿顯示器等顯示元件。作為光學功能材料，可列舉：以提昇視認性或防止顯示元件因外部衝擊而破損為目的之壓克力板(可進行單面或雙面硬塗處理、或者AR塗佈)、聚碳酸酯板、PET板、PEN板等透明塑膠板，強化玻璃(可附有防飛散膜)及觸控面板輸入感測器等。 The adhesive which hardened the photocurable adhesive composition of this invention can be used for bonding a display body and an optical functional material. Examples of the display body include display elements such as an LCD, an EL display, an EL illumination, an electronic paper, or a plasma display to which a deflecting plate is attached to the glass. Examples of the optical functional material include an acrylic sheet for improving visibility or preventing damage of the display element due to external impact (single-sided or double-sided hard coating treatment, or AR coating), and polycarbonate sheet. Transparent plastic plates such as PET plates and PEN plates, tempered glass (with anti-scatter film) and touch panel input sensors.

[實施例] [Examples]

以下，藉由實施例來具體地說明本發明。 Hereinafter, the present invention will be specifically described by way of examples.

於實施例及比較例中，製造各種光硬化型黏著劑組成物，繼而製作使該些光硬化型黏著劑組成物硬化而成的黏著劑，並進行各種評價。具體而言，對光硬化型黏著劑組成物測定黏度，對作為其構成成分的A成分測定重量平均分子量，並藉由理論計算來算出雙鍵當量。進而，對黏著劑測定黏著力、被黏著體上的殘膠、黏著保持力、折射率(nD)。 In the examples and the comparative examples, various photocurable adhesive compositions were produced, and then an adhesive obtained by curing the photocurable adhesive compositions was prepared and evaluated. Specifically, the photocurable adhesive composition was measured for viscosity, and the weight average molecular weight of the component A as a constituent component thereof was measured, and the double bond equivalent was calculated by theoretical calculation. Further, the adhesive was measured for adhesion, residual glue on the adherend, adhesion retention, and refractive index (nD).

[A成分的重量平均分子量] [Weight average molecular weight of component A]

A成分的重量平均分子量藉由粒徑篩析層析法(SEC)來測 定。管柱使用聚苯乙烯凝膠，流動相使用四氫呋喃(Tetrahydrofuran，THF)，並使用自聚苯乙烯標準物質的換算值。將結果示於表1。 The weight average molecular weight of component A is determined by particle size exclusion chromatography (SEC). set. The column used was a polystyrene gel, and the mobile phase was tetrahydrofuran (THF) using a conversion value from a polystyrene standard. The results are shown in Table 1.

[A成分的雙鍵當量] [Double bond equivalent of component A]

雙鍵當量是作為每1mol雙鍵的反應性聚合物的質量來算出。將結果示於表1。下式為後述的反應性聚合物(A-1)的雙鍵當量的計算例。 The double bond equivalent is calculated as the mass of the reactive polymer per 1 mol of the double bond. The results are shown in Table 1. The following formula is a calculation example of the double bond equivalent of the reactive polymer (A-1) to be described later.

[光硬化型黏著劑組成物的黏度] [Viscosity of light-curing adhesive composition]

光硬化型黏著劑組成物的黏度是依據JIS-K-7117-1，使用E型黏度計(東機美(TOKIMEC)(股份)製造)，於將試樣約1ml保持為25℃的狀態下進行測定。 The viscosity of the photocurable adhesive composition is in accordance with JIS-K-7117-1, using an E-type viscometer (manufactured by TOKIMEC Co., Ltd.), and maintaining about 1 ml of the sample at 25 ° C. The measurement was carried out.

[黏著力] [adhesion]

黏著力是依據JIS-Z-0237來測定。將黏著劑組成物滴在厚度為100μm的透明聚酯膜(東麗公司製造，商品名：Lumirror#100)上。進而，自其上方覆蓋利用矽酮進行了表面處理的厚度為50μm的透明聚酯膜(琳得科公司製造，商品名：P501031)，以硬化後的硬化物厚度變成200μm的方式，以固定速度於間隙固定的輥間 滑動。其後，藉由照射活性能量線來進行硬化，而獲得帶狀物。將所獲得的帶狀物切斷成寬度為24mm、長度為250mm，剝離利用矽酮進行了表面處理的厚度為50μm的透明聚酯膜，然後與不鏽鋼板(工程試驗服務股份有限公司製造，商品名：SUS304BA處理品，厚度為1.5mm，寬度為50mm，長度為125mm)貼合。再者，於貼合時，在23℃、50%RH的環境下使2kg的橡膠輥往返2次來進行加壓貼付。於23℃×50%RH的條件下，使用小型台式試驗機EZ-S(商品名，島津製作所股份有限公司製造)，在180度方向上以300mm/min的速度剝離所貼合的黏著劑片，並測定黏著力。將黏著力為0.1N/24mm~20N/24mm的情況評價為「○」，將黏著力未滿0.1N/24mm或超過20N/24mm的情況評價為「×」。 The adhesion was measured in accordance with JIS-Z-0237. The adhesive composition was dropped on a transparent polyester film (manufactured by Toray Industries, Inc., trade name: Lumirror #100) having a thickness of 100 μm. Furthermore, a transparent polyester film (manufactured by Linde Co., Ltd., trade name: P501031) having a thickness of 50 μm which was surface-treated with an anthrone was coated thereon, and the thickness of the cured product after hardening was changed to 200 μm at a fixed speed. Between the rollers with fixed clearance slide. Thereafter, hardening is performed by irradiating the active energy ray to obtain a ribbon. The obtained ribbon was cut into a width of 24 mm and a length of 250 mm, and a transparent polyester film having a thickness of 50 μm which was surface-treated with an fluorenone was peeled off, and then manufactured with a stainless steel plate (manufactured by Engineering Testing Services Co., Ltd.). Name: SUS304BA treated product, thickness 1.5mm, width 50mm, length 125mm). Further, at the time of bonding, a 2 kg rubber roller was reciprocated twice in an environment of 23° C. and 50% RH to perform pressure bonding. The laminated adhesive sheet was peeled off at a speed of 300 mm/min in a 180-degree direction using a small bench tester EZ-S (trade name, manufactured by Shimadzu Corporation) under conditions of 23 ° C × 50% RH. And determine the adhesion. The case where the adhesive force was 0.1 N/24 mm to 20 N/24 mm was evaluated as "○", and the case where the adhesive force was less than 0.1 N/24 mm or more than 20 N/24 mm was evaluated as "X".

[被黏著體上的殘膠] [Residual glue on the body]

於上述黏著力的評價後，以「○」來評價被黏著體(不鏽鋼板)上無黏著劑的殘膠的情況，以「×」來評價有殘膠的情況。 After the evaluation of the adhesion, the residual adhesive of the adhesive (stainless steel plate) was evaluated by "○", and the residual rubber was evaluated by "x".

[黏著保持力] [Adhesive retention]

黏著保持力是依據JIS-Z-0237來測定。將黏著劑組成物滴在厚度為100μm的透明聚酯膜(東麗公司製造，商品名：Lumirror#100)上。進而，自其上方覆蓋利用矽酮進行了表面處理的厚度為50μm的透明聚酯膜(琳得科公司製造，商品名：P501031)，以硬化後的硬化物厚度變成175μm的方式，以固定速度於間隙固定的輥間滑動。其後，藉由照射活性能量線來進行硬化，而獲得帶狀物。自所獲得的帶狀物中剝離利用矽酮進行了表 面處理的厚度為50μm的透明聚酯膜，然後以貼合面積變成25mm×25mm的方式，使帶狀物與不鏽鋼板(工程試驗服務股份有限公司製造，商品名：SUS304BA處理品，厚度為1.5mm，寬度為50mm，長度為125mm)貼合。再者，於貼合時，在23℃、50%RH的環境下使2kg的橡膠輥往返2次來進行加壓貼付。使用帶有恆溫恆濕槽的保持力試驗機No145-D(商品名，安田精機製作所股份有限公司製造)，於垂直方向上對上述帶狀物施加9.8N的負荷，並測定於60℃、40%RH的環境下靜置24小時後的黏著位置的偏移量。將黏著保持力為2mm以下的情況評價為「○」，將黏著保持力超過2mm且帶狀物未自被黏著體上落下的情況評價為「△」，將帶狀物自被黏著體落下的情況評價為「×]。 Adhesion retention is measured in accordance with JIS-Z-0237. The adhesive composition was dropped on a transparent polyester film (manufactured by Toray Industries, Inc., trade name: Lumirror #100) having a thickness of 100 μm. Furthermore, a transparent polyester film (manufactured by Linde Co., Ltd., trade name: P501031) having a thickness of 50 μm which was surface-treated with an anthrone was coated thereon, and the thickness of the cured product after hardening was changed to 175 μm at a fixed speed. Slide between the rollers with fixed clearance. Thereafter, hardening is performed by irradiating the active energy ray to obtain a ribbon. Peeling from the obtained ribbon was carried out using an anthrone The surface of the transparent polyester film having a thickness of 50 μm was used, and the strip and the stainless steel plate (manufactured by Engineering Testing Services Co., Ltd., trade name: SUS304BA, thickness 1.5) were used in such a manner that the bonding area became 25 mm × 25 mm. Mm, width 50mm, length 125mm) fit. Further, at the time of bonding, a 2 kg rubber roller was reciprocated twice in an environment of 23° C. and 50% RH to perform pressure bonding. Using a holding force tester No 145-D (trade name, manufactured by Yasuda Seiki Seisakusho Co., Ltd.) equipped with a constant temperature and humidity chamber, a load of 9.8 N was applied to the above-mentioned belt in the vertical direction, and measured at 60 ° C, 40 The offset of the adhesive position after standing for 24 hours in the environment of %RH. When the adhesion retention force was 2 mm or less, it was evaluated as "○", and when the adhesion retention force exceeded 2 mm and the ribbon was not dropped from the adherend, it was evaluated as "△", and the ribbon was dropped from the adherend. The situation is evaluated as "x].

[黏著劑的折射率] [The refractive index of the adhesive]

針對根據上述[黏著力]中記載的方法所獲得的硬化物，使用愛拓(Atago)公司製造的阿貝折射計，測定25℃下的折射率(nD)來作為黏著劑的折射率。 The refractive index (nD) at 25 ° C was measured using the Abbe refractometer manufactured by Atago Co., Ltd. as the cured product obtained by the method described in the above [Adhesive Force] as the refractive index of the adhesive.

[光硬化型黏著劑組成物中的雙鍵量] [Amount of double bond in photohardenable adhesive composition]

光硬化型黏著劑組成物中的雙鍵量表示黏著劑組成物中所含有的雙鍵的數量，存在如下的傾向：雙鍵量越少，硬化時的收縮越少，於填充至顯示體與顯示面板間後，當進行了硬化時難以產生縮痕(sink mark)等現象。下式為實施例1的黏著劑組成物中所含有的雙鍵量的計算例。 The amount of double bonds in the photocurable adhesive composition indicates the number of double bonds contained in the adhesive composition, and there is a tendency that the smaller the amount of double bonds, the less the shrinkage at the time of hardening, and the filling into the display body and After the display panel is in place, it is difficult to cause a sink mark or the like when hardening is performed. The following formula is a calculation example of the amount of double bonds contained in the adhesive composition of Example 1.

[數式2] [Expression 2]

[實施例1] [Example 1]

向具備冷卻器、滴加漏斗及溫度計的3升的四口燒瓶中添加甲苯(720g)，繼而於80℃下，透過滴加漏斗歷時約3小時滴加丙烯酸2-乙基己酯(897.8g)、異氰酸2-甲基丙烯醯氧基乙酯(昭和電工製造，商品名：Karenz MOI)(2.25g)、2,2'-偶氮雙-2-甲基丁腈(AMBN)(0.45g)的混合液。滴加結束約1小時後，添加AMBN(0.45g)、甲苯(90g)的混合液，於80℃下反應7小時後，於90℃下反應3小時。繼而，添加丙烯酸4-羥基丁酯(2.09g)、二月桂酸二丁基錫(0.27g)、甲苯(92.1g)、二丁基羥基甲苯(0.45g)，然後於50℃下進行約3小時加成反應。將藉由異氰酸酯值測定，反應率變成99%以上的時間設為反應的終點。繼而，添加丙烯酸2-乙基己酯(602g)，將甲苯去除至系統外，使殘留溶劑變成1%以下，而獲得反應性聚合物(A-1)903g與丙烯酸2-乙基己酯(B-1)602g的混合溶液1505g。該反應性聚合物的重量平均分子量為175,000(SEC：聚苯乙烯換算)，雙鍵當量為62321g/mol。向上述混合溶液中添加1-羥基-環己基-苯基-酮(汽巴精化(Ciba Specialty Chemicals)公司製造，商品名：Irgacure184)(C) (15.1g)來進行混合，而獲得光硬化型黏著劑組成物。該組成物的黏度為3753mPa．s/25℃。另外，組成物的雙鍵量為2.18×10-3mol。 Toluene (720 g) was added to a 3-liter four-necked flask equipped with a cooler, a dropping funnel and a thermometer, and then 2-ethylhexyl acrylate (897.8 g) was added dropwise at 80 ° C through a dropping funnel over a period of about 3 hours. ), 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko, trade name: Karenz MOI) (2.25 g), 2,2'-azobis-2-methylbutyronitrile (AMBN) ( Mixture of 0.45 g). After about 1 hour from the completion of the dropwise addition, a mixed liquid of AMBN (0.45 g) and toluene (90 g) was added, and the mixture was reacted at 80 ° C for 7 hours, and then reacted at 90 ° C for 3 hours. Then, 4-hydroxybutyl acrylate (2.09 g), dibutyltin dilaurate (0.27 g), toluene (92.1 g), dibutylhydroxytoluene (0.45 g) were added, followed by addition at 50 ° C for about 3 hours. Into a reaction. The time at which the reaction rate became 99% or more by the isocyanate value was taken as the end point of the reaction. Then, 2-ethylhexyl acrylate (602 g) was added, and toluene was removed to the outside of the system to make the residual solvent 1% or less, and 903 g of a reactive polymer (A-1) and 2-ethylhexyl acrylate were obtained ( B-1) 1505 g of a mixed solution of 602 g. The reactive polymer had a weight average molecular weight of 175,000 (SEC: polystyrene equivalent) and a double bond equivalent of 62321 g/mol. To the above mixed solution, 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 184) (C) (15.1 g) was added for mixing to obtain photohardening. Type of adhesive composition. The viscosity of the composition is 3753 mPa. s / 25 ° C. Further, the amount of the double bond of the composition was 2.18 × 10 -3 mol.

使用高壓水銀燈(照射強度為250mW/cm2，照射量為5000mJ/cm2)作為活性能量線，根據上述記載的試驗方法進行黏著力、被黏著體上的殘膠、折射率(nD)的測定。將結果示於表2。 Using a high-pressure mercury lamp (irradiation intensity: 250 mW/cm 2 , irradiation amount: 5000 mJ/cm 2 ) as an active energy ray, the adhesion, the residual glue on the adherend, and the refractive index (nD) were measured according to the test method described above. . The results are shown in Table 2.

[實施例2] [Embodiment 2]

向實施例1的光硬化型黏著劑組成物中追加添加過氧化特戊酸第三己酯(E)(日本油脂製造，商品名：PERHEXYL PV)0.1g，不利用高壓水銀燈進行照射，而於80℃下進行1小時硬化，除此以外，以與實施例1相同的方法進行評價。將結果示於表2。再者，該例是設想顯示面板的一部分的表面藉由邊框印刷等來覆蓋，並藉由熱硬化來使無法對黏著劑組成物進行光照射的部分硬化的例子。 To the photocurable adhesive composition of Example 1, 0.1 g of peroxidic pivalic acid trihexyl ester (E) (manufactured by Nippon Oil Co., Ltd., trade name: PERHEXYL PV) was added, and the film was not irradiated with a high pressure mercury lamp. Evaluation was carried out in the same manner as in Example 1 except that the curing was performed at 80 ° C for 1 hour. The results are shown in Table 2. In this example, it is assumed that the surface of a part of the display panel is covered by a bezel printing or the like, and is hardened by heat hardening to partially cure the adhesive composition.

[實施例3] [Example 3]

向具備冷卻器、滴加漏斗及溫度計的3升的四口燒瓶中添加甲苯(720g)，繼而於80℃下，透過滴加漏斗歷時約3小時滴加丙烯酸2-乙基己酯(861.9g)、甲基丙烯酸縮水甘油酯(35.9g)、異氰酸2-甲基丙烯醯氧基乙酯(昭和電工製造，商品名：Karenz MOI)(2.25g)、2,2'-偶氮雙-2-甲基丁腈(AMBN)(0.45g)的混合液。滴加結束約1小時後，添加AMBN(0.45g)、甲苯(90g)的混合液，於80℃下反應7小時後，於90℃下反應3小時。繼而， 添加丙烯酸4-羥基丁酯(2.09g)、二月桂酸二丁基錫(0.27g)、甲苯(92.1g)、二丁基羥基甲苯(0.45g)，然後於50℃下進行約3小時加成反應。將藉由異氰酸酯值測定，反應率變成99%以上的時間設為反應的終點。繼而，添加丙烯酸2-乙基己酯(903g)，將甲苯去除至系統外，使殘留溶劑變成1%以下，而獲得反應性聚合物(A-2)903g與丙烯酸2-乙基己酯(B-1)903g的混合溶液1806g。該反應性聚合物(A-2)的重量平均分子量為189,000(SEC：聚苯乙烯換算)，雙鍵當量為62321g/mol。向上述混合溶液中添加1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(18.1g)來進行混合，而獲得光硬化型黏著劑組成物。該組成物的黏度為2700mPa．s/25℃。使用高壓水銀燈(照射強度為250mW/cm2，照射量為5000mJ/cm2)作為活性能量線，根據上述記載的試驗方法進行黏著力、被黏著體上的殘膠、折射率(nD)的測定。將結果示於表2。 Toluene (720 g) was added to a 3-liter four-necked flask equipped with a cooler, a dropping funnel, and a thermometer, followed by dropwise addition of 2-ethylhexyl acrylate (861.9 g) at 80 ° C through a dropping funnel over a period of about 3 hours. ), glycidyl methacrylate (35.9g), 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko, trade name: Karenz MOI) (2.25g), 2,2'-azo double A mixture of -2-methylbutyronitrile (AMBN) (0.45 g). After about 1 hour from the completion of the dropwise addition, a mixed liquid of AMBN (0.45 g) and toluene (90 g) was added, and the mixture was reacted at 80 ° C for 7 hours, and then reacted at 90 ° C for 3 hours. Then, 4-hydroxybutyl acrylate (2.09 g), dibutyltin dilaurate (0.27 g), toluene (92.1 g), dibutylhydroxytoluene (0.45 g) were added, followed by addition at 50 ° C for about 3 hours. Into a reaction. The time at which the reaction rate became 99% or more by the isocyanate value was taken as the end point of the reaction. Then, 2-ethylhexyl acrylate (903 g) was added, and toluene was removed to the outside of the system to make the residual solvent 1% or less, and 903 g of a reactive polymer (A-2) and 2-ethylhexyl acrylate were obtained ( B-1) 1806 g of a mixed solution of 903 g. The reactive polymer (A-2) had a weight average molecular weight of 189,000 (SEC: polystyrene equivalent) and a double bond equivalent of 62321 g/mol. To the above mixed solution, 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (18.1 g) was added and mixed to obtain a photocurable adhesive composition. . The composition has a viscosity of 2700 mPa. s / 25 ° C. Using a high-pressure mercury lamp (irradiation intensity: 250 mW/cm 2 , irradiation amount: 5000 mJ/cm 2 ) as an active energy ray, the adhesion, the residual glue on the adherend, and the refractive index (nD) were measured according to the test method described above. . The results are shown in Table 2.

[實施例4] [Example 4]

與實施例1同樣地進行至異氰酸酯化反應為止後，添加丙烯酸2-乙基己酯(301g)，將甲苯去除至系統外，使殘留溶劑變成1%以下，而獲得反應性聚合物(A-1)903g與丙烯酸2-乙基己酯(B-1)301g的混合溶液1204g。向上述混合溶液中添加丙烯酸2-乙基己酯(B-1)(274g)、丙烯酸異冰片酯(B-2)(164g)、1,9-壬二醇二丙烯酸酯(D-1)(1.6g)、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(16.4g)來進行混合， 而取得光硬化型黏著劑組成物。黏著劑的製造方法、評價是與實施例1同樣地進行。將結果示於表2。 After the isocyanation reaction was carried out in the same manner as in Example 1, 2-ethylhexyl acrylate (301 g) was added to remove the toluene to the outside of the system, and the residual solvent was changed to 1% or less to obtain a reactive polymer (A- 1) 1204 g of a mixed solution of 903 g and 301 g of 2-ethylhexyl acrylate (B-1). To the above mixed solution, 2-ethylhexyl acrylate (B-1) (274 g), isobornyl acrylate (B-2) (164 g), and 1,9-nonanediol diacrylate (D-1) were added. (1.6 g), 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (16.4 g) for mixing, A photocurable adhesive composition is obtained. The manufacturing method and evaluation of the adhesive were carried out in the same manner as in Example 1. The results are shown in Table 2.

[實施例5] [Example 5]

向具備冷卻器、滴加漏斗及溫度計的3升的四口燒瓶中添加甲苯(720g)，繼而於80℃下，透過滴加漏斗歷時約3小時滴加丙烯酸2-乙基己酯(717.8g)、丙烯酸苄酯(180g)、異氰酸2-甲基丙烯醯氧基乙酯(昭和電工製造，商品名：Karenz MOI)(2.25g)、2,2'-偶氮雙-2-甲基丁腈(AMBN)(0.45g)的混合液。滴加結束約1小時後，添加AMBN(0.45g)、甲苯(90g)的混合液，於80℃下反應7小時後，於90℃下反應3小時。繼而，添加丙烯酸4-羥基丁酯(2.09g)、二月桂酸二丁基錫(0.27g)、甲苯(92.1g)、二丁基羥基甲苯(0.45g)，然後於50℃下進行約3小時加成反應。將藉由異氰酸酯值測定，反應率變成99%以上的時間設為反應的終點。 Toluene (720 g) was added to a 3-liter four-necked flask equipped with a cooler, a dropping funnel, and a thermometer, followed by dropwise addition of 2-ethylhexyl acrylate (717.8 g) at 80 ° C through a dropping funnel over a period of about 3 hours. Benzyl acrylate (180g), 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko, trade name: Karenz MOI) (2.25g), 2,2'-azobis-2- A mixture of butyronitrile (AMBN) (0.45 g). After about 1 hour from the completion of the dropwise addition, a mixed liquid of AMBN (0.45 g) and toluene (90 g) was added, and the mixture was reacted at 80 ° C for 7 hours, and then reacted at 90 ° C for 3 hours. Then, 4-hydroxybutyl acrylate (2.09 g), dibutyltin dilaurate (0.27 g), toluene (92.1 g), dibutylhydroxytoluene (0.45 g) were added, followed by addition at 50 ° C for about 3 hours. Into a reaction. The time at which the reaction rate became 99% or more by the isocyanate value was taken as the end point of the reaction.

繼而，添加丙烯酸2-乙基己酯(301g)，將甲苯去除至系統外，使殘留溶劑變成1%以下，而獲得反應性聚合物(A-3)903g與丙烯酸2-乙基己酯(B-1)301g的混合溶液1204g。該反應性聚合物(A-3)的重量平均分子量為161,000(SEC：聚苯乙烯換算)，雙鍵當量為62321g/mol。向上述混合溶液中添加丙烯酸2-乙基己酯(B-1)(239g)、丙烯酸鄰聯苯氧基乙酯(B-3)(361g)、1,9-壬二醇二丙烯酸酯(D-1)(1.8g)、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(18.1g)來進行混 合，而獲得光硬化型黏著劑組成物。黏著劑的製造方法、評價是與實施例1同樣地進行。將結果示於表2。 Then, 2-ethylhexyl acrylate (301 g) was added, and toluene was removed to the outside of the system to make the residual solvent 1% or less, and 903 g of the reactive polymer (A-3) and 2-ethylhexyl acrylate were obtained ( B-1) 1204 g of a mixed solution of 301 g. The reactive polymer (A-3) had a weight average molecular weight of 161,000 (SEC: polystyrene equivalent) and a double bond equivalent of 62321 g/mol. To the above mixed solution, 2-ethylhexyl acrylate (B-1) (239 g), o-phenoxyethyl acrylate (B-3) (361 g), and 1,9-nonanediol diacrylate ( D-1) (1.8 g), 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (18.1 g) for mixing In combination, a photocurable adhesive composition is obtained. The manufacturing method and evaluation of the adhesive were carried out in the same manner as in Example 1. The results are shown in Table 2.

[實施例6] [Embodiment 6]

使用甲基丙烯酸異冰片酯來代替丙烯酸苄酯，除此以外，以與實施例5相同的方法進行聚合、單體的添加、黏著劑的製造、評價。所取得的反應性聚合物(A-4)的重量平均分子量為220,000(SEC：聚苯乙烯換算)，雙鍵當量為62321g/mol。將結果示於表2。 Polymerization, addition of a monomer, production of an adhesive, and evaluation were carried out in the same manner as in Example 5 except that isobornyl methacrylate was used instead of benzyl acrylate. The obtained reactive polymer (A-4) had a weight average molecular weight of 220,000 (SEC: polystyrene equivalent) and a double bond equivalent of 62321 g/mol. The results are shown in Table 2.

[實施例7] [Embodiment 7]

使用丙烯酸鄰聯苯氧基乙酯來代替丙烯酸苄酯，除此以外，以與實施例5相同的方法進行聚合、單體的添加、黏著劑的製造、評價。所取得的反應性聚合物(A-5)的重量平均分子量為190,000(SEC：聚苯乙烯換算)，雙鍵當量為62321g/mol。將結果示於表2。 Polymerization, addition of a monomer, production of an adhesive, and evaluation were carried out in the same manner as in Example 5 except that o-phenoxyethyl acrylate was used instead of benzyl acrylate. The weight average molecular weight of the obtained reactive polymer (A-5) was 190,000 (SEC: polystyrene equivalent), and the double bond equivalent was 62321 g/mol. The results are shown in Table 2.

[實施例8] [Embodiment 8]

向具備冷卻器、滴加漏斗及溫度計的3升的四口燒瓶中添加甲基乙基酮(750g)，繼而於85℃下，並於回流條件下，透過滴加漏斗歷時約3小時滴加丙烯酸2-乙基己酯(1496g)、異氰酸2-甲基丙烯醯氧基乙酯(昭和電工製造，商品名：Karenz MOI)(3.75g)、2,2'-偶氮雙-2-甲基丁腈(AMBN)(0.75g)的混合液。滴加結束約1小時後，添加AIBN(0.75g)、甲基乙基酮(30g)的混合液，並於85℃下反應6小時。繼而，添加丙烯酸4-羥基丁酯(3.49 g)、二月桂酸二丁基錫(0.45g)、甲基乙基酮(30g)、二丁基羥基甲苯(0.75g)，然後於70℃下進行約5小時加成反應。將藉由異氰酸酯值測定，反應率變成99%以上的時間設為反應的終點。繼而，添加丙烯酸2-乙基己酯(645g)，將甲基乙基酮去除至系統外，使殘留溶劑變成1%以下，而獲得反應性聚合物(A-8)1505g與丙烯酸2-乙基己酯(B-1)645g的聚合物/丙烯酸2-乙基己酯混合溶液(2150g)。該反應性聚合物(A-8)的重量平均分子量為90,000(SEC：聚苯乙烯換算)，雙鍵當量為62179g/mol。向上述混合溶液21.4g中添加丙烯酸2-乙基己酯(B-1)23.6g、聚丙二醇二丙烯酸酯(東亞合成製造，商品名：Aronix M-270)(D-3)5g、丙烯酸系塑化劑(東亞合成製造，商品名：Arufon UP-1020)(F-1)50g、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(1g)、二丁基羥基甲苯(0.05g)來進行混合，而獲得光硬化型黏著劑組成物。該組成物的黏度為150mPa．s/25℃。使用化學燈(照射強度為1.9mW/cm2，照射量為4000mJ/cm2)作為活性能量線，根據上述記載的試驗方法進行黏著力、黏著保持力、被黏著體上的殘膠、折射率(nD)的測定。將結果示於表2。 Methyl ethyl ketone (750 g) was added to a 3-liter four-necked flask equipped with a cooler, a dropping funnel and a thermometer, and then dropped at 85 ° C under reflux conditions through a dropping funnel for about 3 hours. 2-ethylhexyl acrylate (1496g), 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko, trade name: Karenz MOI) (3.75g), 2,2'-azobis-2 a mixture of methylbutyronitrile (AMBN) (0.75 g). About 1 hour after the completion of the dropwise addition, a mixed solution of AIBN (0.75 g) and methyl ethyl ketone (30 g) was added, and the mixture was reacted at 85 ° C for 6 hours. Then, 4-hydroxybutyl acrylate (3.49 g), dibutyltin dilaurate (0.45 g), methyl ethyl ketone (30 g), and dibutylhydroxytoluene (0.75 g) were added, followed by about 70 ° C. 5 hours addition reaction. The time at which the reaction rate became 99% or more by the isocyanate value was taken as the end point of the reaction. Then, 2-ethylhexyl acrylate (645 g) was added, and methyl ethyl ketone was removed to the outside of the system to make the residual solvent 1% or less, and 1505 g of reactive polymer (A-8) and 2-B of acrylic acid were obtained. Hexyl hexyl ester (B-1) 645 g of a polymer / 2-ethylhexyl acrylate mixed solution (2150 g). The reactive polymer (A-8) had a weight average molecular weight of 90,000 (SEC: polystyrene equivalent) and a double bond equivalent of 62,179 g/mol. To 21.4 g of the above mixed solution, 23.6 g of 2-ethylhexyl acrylate (B-1) and polypropylene glycol diacrylate (manufactured by Toagosei Co., Ltd., trade name: Aronix M-270) (D-3), 5 g, acrylic acid were added. Plasticizer (made by East Asia Synthetic, trade name: Arufon UP-1020) (F-1) 50g, 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (1 g) and dibutylhydroxytoluene (0.05 g) were mixed to obtain a photocurable adhesive composition. The composition has a viscosity of 150 mPa. s / 25 ° C. Using a chemical lamp (irradiation intensity: 1.9 mW/cm 2 , irradiation amount: 4000 mJ/cm 2 ) as an active energy ray, adhesion, adhesion retention force, residual glue on the adherend, and refractive index were measured according to the test method described above. Determination of (nD). The results are shown in Table 2.

[實施例9] [Embodiment 9]

與實施例8同樣地進行至加成反應為止後，繼而添加丙烯酸月桂酯(645g)，將甲基乙基酮去除至系統外，使殘留溶劑變成1%以下，而獲得反應性聚合物(A-8)1505g與丙烯酸月桂酯(B-6) 645g的反應性聚合物(A-8)/丙烯酸月桂酯混合溶液(2150g)。向上述混合液(21.4g)中添加丙烯酸月桂酯(B-6)(23.6g)、聚丙二醇二丙烯酸酯(東亞合成製造，商品名：Aronix M-270)(D-3)(5g)、丙烯酸系塑化劑(東亞合成製造，商品名：Arufon UP-1020)(F-1)(50g)、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(1g)、二丁基羥基甲苯(0.05g)來進行混合，而獲得光硬化型黏著劑組成物。黏著劑的製造方法、評價是與實施例8同樣地進行。將結果示於表2。 After the addition reaction was carried out in the same manner as in Example 8, then, lauryl acrylate (645 g) was added, and methyl ethyl ketone was removed to the outside of the system, and the residual solvent was changed to 1% or less to obtain a reactive polymer (A). -8) 1505g and lauryl acrylate (B-6) 645 g of a reactive polymer (A-8) / lauryl acrylate mixed solution (2150 g). To the above mixed liquid (21.4 g), lauryl acrylate (B-6) (23.6 g), polypropylene glycol diacrylate (manufactured by Toagosei Co., Ltd., trade name: Aronix M-270) (D-3) (5 g), Acrylic plasticizer (made by East Asia Synthetic, trade name: Arufon UP-1020) (F-1) (50g), 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure184 (C) (1 g) and dibutylhydroxytoluene (0.05 g) were mixed to obtain a photocurable adhesive composition. The method and evaluation of the production of the adhesive were carried out in the same manner as in Example 8. The results are shown in Table 2.

[實施例10] [Embodiment 10]

向實施例8中所取得的反應性聚合物(A-8)/丙烯酸2-乙基己酯混合溶液(21.4g)中添加丙烯酸2-乙基己酯(B-1)(8.6g)、聚丙二醇二丙烯酸酯(東亞合成製造，商品名：Aronix M-270)(D-3)(2g)、丙烯酸系塑化劑(東亞合成製造，商品名：Arufon UP-1020)(F-1)(50g)、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(1g)、二丁基羥基甲苯(0.05g)來進行混合，而獲得光硬化型黏著劑組成物。黏著劑的製造方法、評價是與實施例8同樣地進行。將結果示於表2。 2-ethylhexyl acrylate (B-1) (8.6 g) was added to the mixed solution (21.4 g) of the reactive polymer (A-8) / 2-ethylhexyl acrylate obtained in Example 8, Polypropylene glycol diacrylate (manufactured by Toagosei, trade name: Aronix M-270) (D-3) (2g), acrylic plasticizer (manufactured by Toagosei, trade name: Arufon UP-1020) (F-1) (50 g), 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (1 g), dibutylhydroxytoluene (0.05 g), and mixed A photocurable adhesive composition. The method and evaluation of the production of the adhesive were carried out in the same manner as in Example 8. The results are shown in Table 2.

[實施例11] [Example 11]

向實施例8中所取得的反應性聚合物(A-8)/丙烯酸2-乙基己酯混合溶液(21.4g)中添加丙烯酸2-乙基己酯(B-1)(33.6g)、聚丙二醇二丙烯酸酯(東亞合成製造，商品名：Aronix M-270)(D-3)(5g)、丙烯酸系塑化劑(東亞合成製造，商品名：Arufon UP-1020)(F-1)(40g)、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(1g)、二丁基羥基甲苯(0.05g)來進行混合，而獲得光硬化型黏著劑組成物。黏著劑的製造方法、評價是與實施例8同樣地進行。將結果示於表2。 2-ethylhexyl acrylate (B-1) (33.6 g) was added to the mixed solution (21.4 g) of the reactive polymer (A-8) / 2-ethylhexyl acrylate obtained in Example 8, Polypropylene glycol diacrylate (manufactured by Toagos Corporation, trade name: Aronix M-270) (D-3) (5g), acrylic plasticizer (manufactured by Toagos Corporation, trade name: Arufon UP-1020) (F-1) (40 g), 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (1 g), dibutylhydroxytoluene ( 0.05 g) was mixed to obtain a photocurable adhesive composition. The method and evaluation of the production of the adhesive were carried out in the same manner as in Example 8. The results are shown in Table 2.

[實施例12] [Embodiment 12]

向實施例9中所取得的反應性聚合物(A-8)/丙烯酸月桂酯混合溶液(21.4g)中添加丙烯酸月桂酯(B-6)(33.6g)、聚丙二醇二丙烯酸酯(東亞合成製造，商品名：Aronix M-270)(D-3)(5g)、丙烯酸系塑化劑(東亞合成製造，商品名：Arufon UP-1020)(F-1)(40g)、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(1g)、二丁基羥基甲苯(0.05g)來進行混合，而獲得光硬化型黏著劑組成物。黏著劑的製造方法、評價是與實施例8同樣地進行。將結果示於表2。 To the reactive polymer (A-8) / lauryl acrylate mixed solution (21.4 g) obtained in Example 9, lauryl acrylate (B-6) (33.6 g) and polypropylene glycol diacrylate (eastern synthesis) were added. Manufactured, trade name: Aronix M-270) (D-3) (5g), acrylic plasticizer (made by East Asia Synthetic, trade name: Arufon UP-1020) (F-1) (40g), 1-hydroxy- A cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (1 g) and dibutylhydroxytoluene (0.05 g) were mixed to obtain a photocurable adhesive composition. The method and evaluation of the production of the adhesive were carried out in the same manner as in Example 8. The results are shown in Table 2.

[實施例13] [Example 13]

向實施例9中所取得的反應性聚合物(A-8)/丙烯酸月桂酯混合溶液(21.4g)中添加丙烯酸月桂酯(B-6)(36.6g)、聚丙二醇二丙烯酸酯(東亞合成製造，商品名：Aronix M-270)(D-3)(2g)、丙烯酸系塑化劑(東亞合成製造，商品名：Arufon UP-1020)(F-1)(40g)、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(1g)、二丁基羥基甲苯(0.05g)來進行混合，而獲得光硬化型黏著劑組成物。黏著劑的製造方法、評價是與實施例8同樣地進行。將結果示於表2。 To the reactive polymer (A-8) / lauryl acrylate mixed solution (21.4 g) obtained in Example 9, lauryl acrylate (B-6) (36.6 g) and polypropylene glycol diacrylate (eastern synthesis) were added. Manufactured, trade name: Aronix M-270) (D-3) (2g), acrylic plasticizer (made by East Asia Synthetic, trade name: Arufon UP-1020) (F-1) (40g), 1-hydroxy- A cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (1 g) and dibutylhydroxytoluene (0.05 g) were mixed to obtain a photocurable adhesive composition. The method and evaluation of the production of the adhesive were carried out in the same manner as in Example 8. The results are shown in Table 2.

[實施例14] [Embodiment 14]

向實施例8中所取得的反應性聚合物(A-8)/丙烯酸2-乙基己酯混合溶液(71.4g)中添加丙烯酸2-乙基己酯(B-1)(8.6g)、聚丙二醇二丙烯酸酯(東亞合成製造，商品名：Aronix M-270)(D-3)(5g)、丙烯酸系塑化劑(東亞合成製造，商品名：Arufon UP-1020)(F-1)(15g)、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(1g)、二丁基羥基甲苯(0.05g)來進行混合，而獲得光硬化型黏著劑組成物。黏著劑的製造方法、評價是與實施例8同樣地進行。將結果示於表3。 2-ethylhexyl acrylate (B-1) (8.6 g) was added to the mixed solution (71.4 g) of the reactive polymer (A-8) / 2-ethylhexyl acrylate obtained in Example 8, Polypropylene glycol diacrylate (manufactured by East Asia Synthetic, trade name: Aronix M-270) (D-3) (5g), acrylic plasticizer (manufactured by Toagosei, trade name: Arufon UP-1020) (F-1) (15 g), 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (1 g), dibutylhydroxytoluene (0.05 g), and mixed A photocurable adhesive composition. The method and evaluation of the production of the adhesive were carried out in the same manner as in Example 8. The results are shown in Table 3.

[實施例15] [Example 15]

向實施例8中所取得的反應性聚合物(A-8)/丙烯酸2-乙基己酯混合溶液(57.1g)中添加丙烯酸2-乙基己酯(B-1)(12.9g)、聚丙二醇二丙烯酸酯(東亞合成製造，商品名：Aronix M-270)(D-3)(5g)、丙烯酸系塑化劑(東亞合成製造，商品名：Arufon UP-1020)(F-1)(25g)、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(1g)、二丁基羥基甲苯(0.05g)來進行混合，而獲得光硬化型黏著劑組成物。黏著劑的製造方法、評價是與實施例8同樣地進行。將結果示於表3。 2-ethylhexyl acrylate (B-1) (12.9 g) was added to the mixed solution (57.1 g) of the reactive polymer (A-8) / 2-ethylhexyl acrylate obtained in Example 8, Polypropylene glycol diacrylate (manufactured by East Asia Synthetic, trade name: Aronix M-270) (D-3) (5g), acrylic plasticizer (manufactured by Toagosei, trade name: Arufon UP-1020) (F-1) (25 g), 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (1 g), dibutylhydroxytoluene (0.05 g), and mixed A photocurable adhesive composition. The method and evaluation of the production of the adhesive were carried out in the same manner as in Example 8. The results are shown in Table 3.

[實施例16] [Example 16]

向具備冷卻器、滴加漏斗及溫度計的3升的四口燒瓶中添加甲基乙基酮(750g)，繼而於85℃下，並於回流條件下，透過滴加漏斗歷時約3小時滴加丙烯酸2-乙基己酯(1496g)、異氰酸2- 甲基丙烯醯氧基乙酯(昭和電工製造，商品名：Karenz MOI)(2.81g)、2,2'-偶氮雙-2-甲基丁腈(AMBN)(0.75g)的混合液。滴加結束約1小時後，添加AIBN(0.75g)、甲基乙基酮(30g)的混合液，並於85℃下反應6小時。繼而，添加丙烯酸4-羥基丁酯(2.58g)、二月桂酸二丁基錫(0.45g)、甲基乙基酮(30g)、二丁基羥基甲苯(0.75g)，然後於70℃下進行約5小時加成反應。將藉由異氰酸酯值測定，反應率變成99%以上的時間設為反應的終點。繼而，添加丙烯酸2-乙基己酯(645g)，將甲基乙基酮去除至系統外，使殘留溶劑變成1%以下，而獲得反應性聚合物(A-9)1505g與丙烯酸2-乙基己酯(B-1)645g的聚合物/丙烯酸2-乙基己酯混合溶液(2150g)。該反應性聚合物的重量平均分子量為88,000(SEC：聚苯乙烯換算)，雙鍵當量為90200g/mol。向上述混合溶液21.4g中添加丙烯酸2-乙基己酯(B-1)33.6g、聚丙二醇二丙烯酸酯(東亞合成製造，商品名：Aronix M-270)(D-3)5g、丙烯酸系塑化劑(東亞合成製造，商品名：Arufon UP-1020)(F-1)40g、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(1g)、二丁基羥基甲苯(0.05g)來進行混合，而獲得光硬化型黏著劑組成物。該組成物的黏度為75mPa．s/25℃。使用化學燈(照射強度為1.9mW/cm2，照射量為4000mJ/cm2)作為活性能量線，根據上述記載的試驗方法進行黏著力、黏著保持力、被黏著體上的殘膠、折射率(nD)的測定。將結果示於表3。 Methyl ethyl ketone (750 g) was added to a 3-liter four-necked flask equipped with a cooler, a dropping funnel and a thermometer, and then dropped at 85 ° C under reflux conditions through a dropping funnel for about 3 hours. 2-ethylhexyl acrylate (1496g), 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko, trade name: Karenz MOI) (2.81g), 2,2'-azobis-2 a mixture of methylbutyronitrile (AMBN) (0.75 g). About 1 hour after the completion of the dropwise addition, a mixed solution of AIBN (0.75 g) and methyl ethyl ketone (30 g) was added, and the mixture was reacted at 85 ° C for 6 hours. Then, 4-hydroxybutyl acrylate (2.58 g), dibutyltin dilaurate (0.45 g), methyl ethyl ketone (30 g), dibutylhydroxytoluene (0.75 g) were added, and then about 70 ° C was carried out. 5 hours addition reaction. The time at which the reaction rate became 99% or more by the isocyanate value was taken as the end point of the reaction. Then, 2-ethylhexyl acrylate (645 g) was added, and methyl ethyl ketone was removed to the outside of the system to make the residual solvent 1% or less, and 1505 g of reactive polymer (A-9) and 2-B of acrylic acid were obtained. Hexyl hexyl ester (B-1) 645 g of a polymer / 2-ethylhexyl acrylate mixed solution (2150 g). The reactive polymer had a weight average molecular weight of 88,000 (SEC: polystyrene equivalent) and a double bond equivalent of 90200 g/mol. To 21.4 g of the above mixed solution, 33.6 g of 2-ethylhexyl acrylate (B-1) and polypropylene glycol diacrylate (manufactured by Toagosei Co., Ltd., trade name: Aronix M-270) (D-3), 5 g, acrylic acid were added. Plasticizer (made by East Asia Synthetic, trade name: Arufon UP-1020) (F-1) 40g, 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (1 g) and dibutylhydroxytoluene (0.05 g) were mixed to obtain a photocurable adhesive composition. The composition has a viscosity of 75 mPa. s / 25 ° C. Using a chemical lamp (irradiation intensity: 1.9 mW/cm 2 , irradiation amount: 4000 mJ/cm 2 ) as an active energy ray, adhesion, adhesion retention force, residual glue on the adherend, and refractive index were measured according to the test method described above. Determination of (nD). The results are shown in Table 3.

[實施例17] [Example 17]

向具備冷卻器、滴加漏斗及溫度計的3升的四口燒瓶中投入乙酸乙酯(1000g)、丙烯酸2-乙基己酯(1496g)、異氰酸2-甲基丙烯醯氧基乙酯(昭和電工製造，商品名：Karenz MOI)(5.48g)、2,2'-偶氮雙-2-甲基丁腈(AMBN)(0.02g)，於80℃下並於回流條件下進行聚合。回流開始2小時後添加2,2'-偶氮雙-2-甲基丁腈(AMBN)(0.12g)、乙酸乙酯(30g)的混合液，並於80℃下反應6小時。繼而，添加丙烯酸4-羥基丁酯(5.04g)、二月桂酸二丁基錫(0.45g)、甲基乙基酮(30g)、二丁基羥基甲苯(0.75g)，並於70℃下進行約5小時加成反應。將藉由異氰酸酯值測定，反應率變成99%以上的時間設為反應的終點。繼而，添加丙烯酸2-乙基己酯(645g)，將甲基乙基酮去除至系統外，使殘留溶劑變成1%以下，而獲得反應性聚合物(A-10)1505g與丙烯酸2-乙基己酯(B-1)645g的聚合物/丙烯酸2-乙基己酯混合溶液(2150g)。該反應性聚合物(A-10)的重量平均分子量為440,000(SEC：聚苯乙烯換算)，雙鍵當量為46400g/mol。向上述混合溶液21.4g中添加丙烯酸2-乙基己酯(B-1)33.6g、聚丙二醇二丙烯酸酯(東亞合成製造，商品名：Aronix M-270)(D-3)5g、丙烯酸系塑化劑(東亞合成製造，商品名：Arufon UP-1020)(F-1)40g、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(1g)、二丁基羥基甲苯(0.05g)來進行混合，而獲得光硬化型黏著劑組成物。該組成物的黏度為700mPa．s/25℃。使用化學燈(照 射強度為1.9mW/cm2，照射量為4000mJ/cm2)作為活性能量線，根據上述記載的試驗方法進行黏著力、黏著保持力、被黏著體上的殘膠、折射率(nD)的測定。將結果示於表3。 Ethyl acetate (1000 g), 2-ethylhexyl acrylate (1496 g), 2-methylpropenyloxyethyl isocyanate were placed in a 3-liter four-necked flask equipped with a cooler, a dropping funnel and a thermometer. (manufactured by Showa Denko, trade name: Karenz MOI) (5.48g), 2,2'-azobis-2-methylbutyronitrile (AMBN) (0.02g), polymerized at 80 ° C under reflux conditions . Two hours after the start of the reflux, a mixed liquid of 2,2'-azobis-2-methylbutyronitrile (AMBN) (0.12 g) and ethyl acetate (30 g) was added, and the mixture was reacted at 80 ° C for 6 hours. Then, 4-hydroxybutyl acrylate (5.04 g), dibutyltin dilaurate (0.45 g), methyl ethyl ketone (30 g), dibutylhydroxytoluene (0.75 g) were added, and about 70 ° C was carried out. 5 hours addition reaction. The time at which the reaction rate became 99% or more by the isocyanate value was taken as the end point of the reaction. Then, 2-ethylhexyl acrylate (645 g) was added, and methyl ethyl ketone was removed to the outside of the system to make the residual solvent 1% or less, and 1505 g of reactive polymer (A-10) and 2-B of acrylic acid were obtained. Hexyl hexyl ester (B-1) 645 g of a polymer / 2-ethylhexyl acrylate mixed solution (2150 g). The reactive polymer (A-10) had a weight average molecular weight of 440,000 (SEC: polystyrene) and a double bond equivalent of 46,400 g/mol. To 21.4 g of the above mixed solution, 33.6 g of 2-ethylhexyl acrylate (B-1) and polypropylene glycol diacrylate (manufactured by Toagosei Co., Ltd., trade name: Aronix M-270) (D-3), 5 g, acrylic acid were added. Plasticizer (made by East Asia Synthetic, trade name: Arufon UP-1020) (F-1) 40g, 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (1 g) and dibutylhydroxytoluene (0.05 g) were mixed to obtain a photocurable adhesive composition. The composition has a viscosity of 700 mPa. s / 25 ° C. Using a chemical lamp (irradiation intensity: 1.9 mW/cm 2 , irradiation amount: 4000 mJ/cm 2 ) as an active energy ray, adhesion, adhesion retention force, residual glue on the adherend, and refractive index were measured according to the test method described above. Determination of (nD). The results are shown in Table 3.

[實施例18] [Embodiment 18]

向實施例17中所取得的反應性聚合物(A-10)/丙烯酸2-乙基己酯混合溶液(42.9g)中添加丙烯酸2-乙基己酯(B-1)(17.1g)、丙烯酸異冰片酯(B-2)(40g)、1,9-壬二醇二丙烯酸酯(D-1)(0.2g)、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(1g)、二丁基羥基甲苯(0.05g)來進行混合，而獲得光硬化型黏著劑組成物。黏著劑的製造方法、評價是與實施例16同樣地進行。將結果示於表3。 2-ethylhexyl acrylate (B-1) (17.1 g) was added to the mixed solution (42.9 g) of the reactive polymer (A-10) / 2-ethylhexyl acrylate obtained in Example 17, Isobornyl acrylate (B-2) (40g), 1,9-nonanediol diacrylate (D-1) (0.2g), 1-hydroxy-cyclohexyl-phenyl-one (Ciba Specialty Chemicals) Manufactured, trade name: Irgacure 184) (C) (1 g) and dibutylhydroxytoluene (0.05 g) were mixed to obtain a photocurable adhesive composition. The manufacturing method and evaluation of the adhesive were carried out in the same manner as in Example 16. The results are shown in Table 3.

[實施例19] [Embodiment 19]

向具備冷卻器、滴加漏斗及溫度計的3升的四口燒瓶中添加甲基乙基酮(750g)，繼而於85℃下，並於回流條件下，透過滴加漏斗歷時約3小時滴加丙烯酸2-乙基己酯(1496g)、異氰酸2-甲基丙烯醯氧基乙酯(昭和電工製造，商品名：Karenz MOI)(17.20g)、2,2'-偶氮雙-2-甲基丁腈(AMBN)(0.75g)的混合液。滴加結束約1小時後，添加AIBN(0.75g)、甲基乙基酮(30g)的混合液，並於85℃下反應6小時。繼而，添加丙烯酸4-羥基丁酯(15.82g)、二月桂酸二丁基錫(0.45g)、甲基乙基酮(30g)、二丁基羥基甲苯(0.75g)，然後於70℃下進行約5小時加成反應。將藉由異氰酸酯值測定，反應率變成99%以上的時間設為反應的終點。 繼而，添加丙烯酸2-乙基己酯(645g)，將甲基乙基酮去除至系統外，使殘留溶劑變成1%以下，而獲得反應性聚合物(A-11)1505g與丙烯酸2-乙基己酯(B-1)645g的聚合物/丙烯酸2-乙基己酯混合溶液(2150g)。該反應性聚合物(A-11)的重量平均分子量為90,000(SEC：聚苯乙烯換算)，雙鍵當量為15000g/mol。向上述混合溶液21.4g中添加丙烯酸2-乙基己酯(B-1)33.6g、聚丙二醇二丙烯酸酯(東亞合成製造，商品名：Aronix M-270)(D-3)5g、丙烯酸系塑化劑(東亞合成製造，商品名：Arufon UP-1020)(F-1)40g、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(1g)、二丁基羥基甲苯(0.05g)來進行混合，而獲得光硬化型黏著劑組成物。該組成物的黏度為110mPa．s/25℃。使用化學燈(照射強度為1.9mW/cm2，照射量為4000mJ/cm2)作為活性能量線，根據上述記載的試驗方法進行黏著力、黏著保持力、被黏著體上的殘膠、折射率(nD)的測定。將結果示於表3。 Methyl ethyl ketone (750 g) was added to a 3-liter four-necked flask equipped with a cooler, a dropping funnel and a thermometer, and then dropped at 85 ° C under reflux conditions through a dropping funnel for about 3 hours. 2-ethylhexyl acrylate (1496g), 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko, trade name: Karenz MOI) (17.20g), 2,2'-azobis-2 a mixture of methylbutyronitrile (AMBN) (0.75 g). About 1 hour after the completion of the dropwise addition, a mixed solution of AIBN (0.75 g) and methyl ethyl ketone (30 g) was added, and the mixture was reacted at 85 ° C for 6 hours. Then, 4-hydroxybutyl acrylate (15.82 g), dibutyltin dilaurate (0.45 g), methyl ethyl ketone (30 g), dibutylhydroxytoluene (0.75 g) were added, and then about 70 ° C was carried out. 5 hours addition reaction. The time at which the reaction rate became 99% or more by the isocyanate value was taken as the end point of the reaction. Then, 2-ethylhexyl acrylate (645 g) was added, and methyl ethyl ketone was removed to the outside of the system, and the residual solvent was changed to 1% or less to obtain 1505 g of reactive polymer (A-11) and 2-ethyl acrylate. Hexyl hexyl ester (B-1) 645 g of a polymer / 2-ethylhexyl acrylate mixed solution (2150 g). The reactive polymer (A-11) had a weight average molecular weight of 90,000 (SEC: polystyrene) and a double bond equivalent of 15,000 g/mol. To 21.4 g of the above mixed solution, 33.6 g of 2-ethylhexyl acrylate (B-1) and polypropylene glycol diacrylate (manufactured by Toagosei Co., Ltd., trade name: Aronix M-270) (D-3), 5 g, acrylic acid were added. Plasticizer (made by East Asia Synthetic, trade name: Arufon UP-1020) (F-1) 40g, 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (1 g) and dibutylhydroxytoluene (0.05 g) were mixed to obtain a photocurable adhesive composition. The composition has a viscosity of 110 mPa. s / 25 ° C. Using a chemical lamp (irradiation intensity: 1.9 mW/cm 2 , irradiation amount: 4000 mJ/cm 2 ) as an active energy ray, adhesion, adhesion retention force, residual glue on the adherend, and refractive index were measured according to the test method described above. Determination of (nD). The results are shown in Table 3.

[實施例20] [Example 20]

向具備冷卻器、滴加漏斗及溫度計的5升的四口燒瓶中添加甲基乙基酮(1500g)，繼而於85℃下，並於回流條件下，透過滴加漏斗歷時約3小時滴加丙烯酸2-乙基己酯(1496g)、異氰酸2-甲基丙烯醯氧基乙酯(昭和電工製造，商品名：Karenz MOI)(3.75g)、2,2'-偶氮雙-2-甲基丁腈(AMBN)(0.75g)的混合液。滴加結束約1小時後，添加AIBN(0.75g)、甲基乙基酮(30g)的混 合液，並於85℃下反應6小時。繼而，添加丙烯酸4-羥基丁酯(3.49g)、二月桂酸二丁基錫(0.45g)、甲基乙基酮(30g)、二丁基羥基甲苯(0.75g)，然後於70℃下進行約5小時加成反應。將藉由異氰酸酯值測定，反應率變成99%以上的時間設為反應的終點。繼而，添加丙烯酸2-乙基己酯(645g)，將甲基乙基酮去除至系統外，使殘留溶劑變成1%以下，而獲得反應性聚合物(A-12)1505g與丙烯酸2-乙基己酯(B-1)645g的聚合物/丙烯酸2-乙基己酯混合溶液(2150g)。該反應性聚合物(A-12)的重量平均分子量為57,000(SEC：聚苯乙烯換算)，雙鍵當量為62000g/mol。向上述混合溶液21.4g中添加丙烯酸2-乙基己酯(B-1)33.6g、聚丙二醇二丙烯酸酯(東亞合成製造，商品名：Aronix M-270)(D-3)5g、丙烯酸系塑化劑(東亞合成製造，商品名：Arufon UP-1020)(F-1)40g、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(1g)、二丁基羥基甲苯(0.05g)來進行混合，而獲得光硬化型黏著劑組成物。該組成物的黏度為90mPa．s/25℃。使用化學燈(照射強度為1.9mW/cm2，照射量為4000mJ/cm2)作為活性能量線，根據上述記載的試驗方法進行黏著力、黏著保持力、被黏著體上的殘膠、折射率(nD)的測定。將結果示於表3。 Methyl ethyl ketone (1500 g) was added to a 5-liter four-necked flask equipped with a cooler, a dropping funnel and a thermometer, followed by dropwise addition at 85 ° C under reflux for about 3 hours through a dropping funnel. 2-ethylhexyl acrylate (1496g), 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko, trade name: Karenz MOI) (3.75g), 2,2'-azobis-2 a mixture of methylbutyronitrile (AMBN) (0.75 g). About 1 hour after the completion of the dropwise addition, a mixed solution of AIBN (0.75 g) and methyl ethyl ketone (30 g) was added, and the mixture was reacted at 85 ° C for 6 hours. Then, 4-hydroxybutyl acrylate (3.49 g), dibutyltin dilaurate (0.45 g), methyl ethyl ketone (30 g), and dibutylhydroxytoluene (0.75 g) were added, followed by about 70 ° C. 5 hours addition reaction. The time at which the reaction rate became 99% or more by the isocyanate value was taken as the end point of the reaction. Then, 2-ethylhexyl acrylate (645 g) was added, and methyl ethyl ketone was removed to the outside of the system to make the residual solvent 1% or less, and 1505 g of reactive polymer (A-12) and 2-B of acrylic acid were obtained. Hexyl hexyl ester (B-1) 645 g of a polymer / 2-ethylhexyl acrylate mixed solution (2150 g). The reactive polymer (A-12) had a weight average molecular weight of 57,000 (SEC: polystyrene equivalent) and a double bond equivalent of 62000 g/mol. To 21.4 g of the above mixed solution, 33.6 g of 2-ethylhexyl acrylate (B-1) and polypropylene glycol diacrylate (manufactured by Toagosei Co., Ltd., trade name: Aronix M-270) (D-3), 5 g, acrylic acid were added. Plasticizer (made by East Asia Synthetic, trade name: Arufon UP-1020) (F-1) 40g, 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (1 g) and dibutylhydroxytoluene (0.05 g) were mixed to obtain a photocurable adhesive composition. The composition has a viscosity of 90 mPa. s / 25 ° C. Using a chemical lamp (irradiation intensity: 1.9 mW/cm 2 , irradiation amount: 4000 mJ/cm 2 ) as an active energy ray, adhesion, adhesion retention force, residual glue on the adherend, and refractive index were measured according to the test method described above. Determination of (nD). The results are shown in Table 3.

[實施例21] [Example 21]

向具備冷卻器、滴加漏斗及溫度計的5升的四口燒瓶中添加甲基乙基酮(2250g)，繼而於85℃下，並於回流條件下，透過滴 加漏斗歷時約3小時滴加丙烯酸2-乙基己酯(1496g)、異氰酸2-甲基丙烯醯氧基乙酯(昭和電工製造，商品名：Karenz MOI)(3.75g)、2,2'-偶氮雙-2-甲基丁腈(AMBN)(0.75g)的混合液。滴加結束約1小時後，添加AIBN(0.75g)、甲基乙基酮(30g)的混合液，並於85℃下反應6小時。繼而，添加丙烯酸4-羥基丁酯(3.49g)、二月桂酸二丁基錫(0.45g)、甲基乙基酮(30g)、二丁基羥基甲苯(0.75g)，然後於70℃下進行約5小時加成反應。將藉由異氰酸酯值測定，反應率變成99%以上的時間設為反應的終點。繼而，添加丙烯酸2-乙基己酯(645g)，將甲基乙基酮去除至系統外，使殘留溶劑變成1%以下，而獲得反應性聚合物(A-13)1505g與丙烯酸2-乙基己酯(B-1)645g的聚合物/丙烯酸2-乙基己酯混合溶液(2150g)。該反應性聚合物(A-13)的重量平均分子量為35,000(SEC：聚苯乙烯換算)，雙鍵當量為62000g/mol。向上述混合溶液21.4g中添加丙烯酸2-乙基己酯(B-1)33.6g、聚丙二醇二丙烯酸酯(東亞合成製造，商品名：Aronix M-270)(D-3)5g、丙烯酸系塑化劑(東亞合成製造，商品名：Arufon UP-1020)(F-1)40g、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(1g)、二丁基羥基甲苯(0.05g)來進行混合，而獲得光硬化型黏著劑組成物。該組成物的黏度為70mPa．s/25℃。使用化學燈(照射強度為1.9mW/cm2，照射量為4000mJ/cm2)作為活性能量線，根據上述記載的試驗方法進行黏著力、黏著保持力、被黏著體上的殘膠、折射率(nD)的測定。將結果 示於表3。 Methyl ethyl ketone (2250 g) was added to a 5-liter four-necked flask equipped with a chiller, a dropping funnel and a thermometer, and then dropped at 85 ° C under reflux conditions through a dropping funnel for about 3 hours. 2-ethylhexyl acrylate (1496g), 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko, trade name: Karenz MOI) (3.75g), 2,2'-azobis-2 a mixture of methylbutyronitrile (AMBN) (0.75 g). About 1 hour after the completion of the dropwise addition, a mixed solution of AIBN (0.75 g) and methyl ethyl ketone (30 g) was added, and the mixture was reacted at 85 ° C for 6 hours. Then, 4-hydroxybutyl acrylate (3.49 g), dibutyltin dilaurate (0.45 g), methyl ethyl ketone (30 g), and dibutylhydroxytoluene (0.75 g) were added, followed by about 70 ° C. 5 hours addition reaction. The time at which the reaction rate became 99% or more by the isocyanate value was taken as the end point of the reaction. Then, 2-ethylhexyl acrylate (645 g) was added, and methyl ethyl ketone was removed to the outside of the system to make the residual solvent 1% or less, and 1505 g of the reactive polymer (A-13) and 2-B of acrylic acid were obtained. Hexyl hexyl ester (B-1) 645 g of a polymer / 2-ethylhexyl acrylate mixed solution (2150 g). The reactive polymer (A-13) had a weight average molecular weight of 35,000 (SEC: polystyrene equivalent) and a double bond equivalent of 62000 g/mol. To 21.4 g of the above mixed solution, 33.6 g of 2-ethylhexyl acrylate (B-1) and polypropylene glycol diacrylate (manufactured by Toagosei Co., Ltd., trade name: Aronix M-270) (D-3), 5 g, acrylic acid were added. Plasticizer (made by East Asia Synthetic, trade name: Arufon UP-1020) (F-1) 40g, 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (1 g) and dibutylhydroxytoluene (0.05 g) were mixed to obtain a photocurable adhesive composition. The composition has a viscosity of 70 mPa. s / 25 ° C. Using a chemical lamp (irradiation intensity: 1.9 mW/cm 2 , irradiation amount: 4000 mJ/cm 2 ) as an active energy ray, adhesion, adhesion retention force, residual glue on the adherend, and refractive index were measured according to the test method described above. Determination of (nD). The results are shown in Table 3.

[比較例1] [Comparative Example 1]

向具備冷卻器、滴加漏斗及溫度計的3升的四口燒瓶中添加甲苯(720g)，繼而一面透過滴加漏斗歷時約2小時滴加丙烯酸2-乙基己酯(702g)、丙烯酸2-羥基乙酯(10.8g)、丙烯酸(7.2g)、偶氮雙異丁腈(AIBN)(14.4g)的混合液，一面於100℃~110℃下反應8小時。繼而，添加異氰酸2-甲基丙烯醯氧基乙酯(昭和電工製造，商品名：Karenz MOI)(14.4g)、對苯二酚(0.29g)、及二丁基錫月桂酸酯(0.29g)，並於相同溫度下進行8小時加成反應。將藉由異氰酸酯值測定，反應率變成99%以上的時間設為反應的終點。繼而，將甲苯去除至系統外，使殘留溶劑變成1%以下，而獲得反應性聚合物(A-6)734.3g。該反應性聚合物(A-6)的重量平均分子量為530,000(SEC：聚苯乙烯換算)，雙鍵當量為8068g/mol。向該反應性聚合物(A-6)734.3g中添加丙烯酸2-乙基己酯(B-1)(1447g)、丙烯酸(B-4)(22g)、1,6-己二醇二丙烯酸酯(D-2)(22g)、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(22.3g)來進行混合，而獲得光硬化型黏著劑組成物。黏著劑的製造方法、評價是與實施例1同樣地進行。將結果示於表3。 Toluene (720 g) was added to a 3-liter four-necked flask equipped with a cooler, a dropping funnel and a thermometer, and then 2-ethylhexyl acrylate (702 g) and acrylic acid 2- were added dropwise over a period of about 2 hours through a dropping funnel. A mixture of hydroxyethyl ester (10.8 g), acrylic acid (7.2 g), and azobisisobutyronitrile (AIBN) (14.4 g) was reacted at 100 ° C to 110 ° C for 8 hours. Then, 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko, trade name: Karenz MOI) (14.4 g), hydroquinone (0.29 g), and dibutyltin laurate (0.29 g) were added. ) and an 8 hour addition reaction was carried out at the same temperature. The time at which the reaction rate became 99% or more by the isocyanate value was taken as the end point of the reaction. Then, toluene was removed to the outside of the system, and the residual solvent was changed to 1% or less to obtain 734.3 g of a reactive polymer (A-6). The reactive polymer (A-6) had a weight average molecular weight of 530,000 (SEC: polystyrene equivalent) and a double bond equivalent of 8068 g/mol. To 734.3 g of the reactive polymer (A-6), 2-ethylhexyl acrylate (B-1) (1447 g), acrylic acid (B-4) (22 g), and 1,6-hexanediol diacrylic acid were added. Ester (D-2) (22 g), 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (22.3 g) were mixed to obtain a photocuring type. Adhesive composition. The manufacturing method and evaluation of the adhesive were carried out in the same manner as in Example 1. The results are shown in Table 3.

[比較例2] [Comparative Example 2]

向具備冷卻器、滴加漏斗及溫度計的2升的四口燒瓶分別投入黏度為14000mPa．s、重量平均分子量為11000、羥基當量(OHV) 為20mgKOH/g的含有羥基的乙烯基聚合物(東亞合成製造，商品名：Arufon UH-2000)(800g)，異氰酸2-甲基丙烯醯氧基乙酯(昭和電工製造，商品名：Karenz MOI)(53g)，於氮氣氣流下，利用熱水浴保持為50℃。其後，添加二月桂酸二丁基錫(0.12g)，並進行8小時加成反應，而獲得反應性聚合物(A-7)853g。將藉由異氰酸酯值測定，反應率變成99%以上的時間設為反應的終點。該反應性聚合物(A-7)的重量平均分子量為12,000(SEC：聚苯乙烯換算)，雙鍵當量為2497g/mol。向該反應性聚合物(A-7)835g中添加丙烯酸四氫糠酯(B-5)(45g)、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(8.8g)來進行混合，而獲得光硬化型黏著劑組成物。黏著劑的製造方法、評價是與實施例1同樣地進行。將結果示於表3。 The viscosity of the 2 liter four-necked flask with a cooler, a dropping funnel and a thermometer was set to 14000 mPa. s, weight average molecular weight is 11000, hydroxyl equivalent (OHV) 20 mg KOH/g of a hydroxyl group-containing vinyl polymer (manufactured by Toagos Corporation, trade name: Arufon UH-2000) (800 g), 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko, trade name: Karenz MOI) (53 g) was kept at 50 ° C with a hot water bath under a stream of nitrogen. Thereafter, dibutyltin dilaurate (0.12 g) was added, and an addition reaction was carried out for 8 hours to obtain 853 g of a reactive polymer (A-7). The time at which the reaction rate became 99% or more by the isocyanate value was taken as the end point of the reaction. The reactive polymer (A-7) had a weight average molecular weight of 12,000 (SEC: polystyrene) and a double bond equivalent of 2,497 g/mol. To 835 g of the reactive polymer (A-7), tetrahydrofurfuryl acrylate (B-5) (45 g) and 1-hydroxy-cyclohexyl-phenyl-one (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (8.8 g) was mixed to obtain a photocurable adhesive composition. The manufacturing method and evaluation of the adhesive were carried out in the same manner as in Example 1. The results are shown in Table 3.

[比較例3] [Comparative Example 3]

向具備冷卻器、滴加漏斗及溫度計的5升的四口燒瓶中添加甲基乙基酮(2250g)，繼而於85℃下，並於回流條件下，透過滴加漏斗歷時約3小時滴加丙烯酸2-乙基己酯(1496g)、異氰酸2-甲基丙烯醯氧基乙酯(昭和電工製造，商品名：Karenz MOI)(3.75g)、2,2'-偶氮雙-2-甲基丁腈(AMBN)(3.5g)的混合液。滴加結束約1小時後，添加AIBN(0.75g)、甲基乙基酮(30g)的混合液，並於85℃下反應6小時。繼而，添加丙烯酸4-羥基丁酯(3.49g)、二月桂酸二丁基錫(0.45g)、甲基乙基酮(30g)、二丁基羥基甲苯(0.75g)，然後於70℃下進行約5小時加成反應。將藉由 異氰酸酯值測定，反應率變成99%以上的時間設為反應的終點。繼而，添加丙烯酸2-乙基己酯(645g)，將甲基乙基酮去除至系統外，使殘留溶劑變成1%以下，而獲得反應性聚合物(A-14)1505g與丙烯酸2-乙基己酯(B-1)645g的聚合物/丙烯酸2-乙基己酯混合溶液(2150g)。該反應性聚合物(A-14)的重量平均分子量為18,000(SEC：聚苯乙烯換算)，雙鍵當量為62000g/mol。向上述混合溶液21.4g中添加丙烯酸2-乙基己酯(B-1)33.6g、聚丙二醇二丙烯酸酯(東亞合成製造，商品名：Aronix M-270)(D-3)5g、丙烯酸系塑化劑(東亞合成製造，商品名：Arufon UP-1020)(F-1)40g、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(1g)、二丁基羥基甲苯(0.05g)來進行混合，而獲得光硬化型黏著劑組成物。該組成物的黏度為50mPa．s/25℃。使用化學燈(照射強度為1.9mW/cm2，照射量為4000mJ/cm2)作為活性能量線，根據上述記載的試驗方法進行黏著力、黏著保持力、被黏著體上的殘膠、折射率(nD)的測定。將結果示於表3。 Methyl ethyl ketone (2250 g) was added to a 5-liter four-necked flask equipped with a chiller, a dropping funnel and a thermometer, and then dropped at 85 ° C under reflux conditions through a dropping funnel for about 3 hours. 2-ethylhexyl acrylate (1496g), 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko, trade name: Karenz MOI) (3.75g), 2,2'-azobis-2 a mixture of methylbutyronitrile (AMBN) (3.5 g). About 1 hour after the completion of the dropwise addition, a mixed solution of AIBN (0.75 g) and methyl ethyl ketone (30 g) was added, and the mixture was reacted at 85 ° C for 6 hours. Then, 4-hydroxybutyl acrylate (3.49 g), dibutyltin dilaurate (0.45 g), methyl ethyl ketone (30 g), and dibutylhydroxytoluene (0.75 g) were added, followed by about 70 ° C. 5 hours addition reaction. The time at which the reaction rate became 99% or more by the isocyanate value was taken as the end point of the reaction. Then, 2-ethylhexyl acrylate (645 g) was added, and methyl ethyl ketone was removed to the outside of the system to make the residual solvent 1% or less, and 1505 g of reactive polymer (A-14) and 2-B of acrylic acid were obtained. Hexyl hexyl ester (B-1) 645 g of a polymer / 2-ethylhexyl acrylate mixed solution (2150 g). The reactive polymer (A-14) had a weight average molecular weight of 18,000 (SEC: polystyrene equivalent) and a double bond equivalent of 62000 g/mol. To 21.4 g of the above mixed solution, 33.6 g of 2-ethylhexyl acrylate (B-1) and polypropylene glycol diacrylate (manufactured by Toagosei Co., Ltd., trade name: Aronix M-270) (D-3), 5 g, acrylic acid were added. Plasticizer (made by East Asia Synthetic, trade name: Arufon UP-1020) (F-1) 40g, 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (1 g) and dibutylhydroxytoluene (0.05 g) were mixed to obtain a photocurable adhesive composition. The composition has a viscosity of 50 mPa. s / 25 ° C. Using a chemical lamp (irradiation intensity: 1.9 mW/cm 2 , irradiation amount: 4000 mJ/cm 2 ) as an active energy ray, adhesion, adhesion retention force, residual glue on the adherend, and refractive index were measured according to the test method described above. Determination of (nD). The results are shown in Table 3.

[比較例4] [Comparative Example 4]

向具備冷卻器、滴加漏斗及溫度計的5升的四口燒瓶中添加甲基乙基酮(750g)，繼而於85℃下，並於回流條件下，透過滴加漏斗歷時約3小時滴加丙烯酸2-乙基己酯(1496g)、異氰酸2-甲基丙烯醯氧基乙酯(昭和電工製造，商品名：Karenz MOI)(2.11g)、2,2'-偶氮雙-2-甲基丁腈(AMBN)(0.75g)的混合液。滴加 結束約1小時後，添加AIBN(0.75g)、甲基乙基酮(30g)的混合液，並於85℃下反應6小時。繼而，添加丙烯酸4-羥基丁酯(1.94g)、二月桂酸二丁基錫(0.45g)、甲基乙基酮(30g)、二丁基羥基甲苯(0.75g)，然後於70℃下進行約5小時加成反應。將藉由異氰酸酯值測定，反應率變成99%以上的時間設為反應的終點。繼而，添加丙烯酸2-乙基己酯(645g)，將甲基乙基酮去除至系統外，使殘留溶劑變成1%以下，而獲得反應性聚合物(A-15)1505g與丙烯酸2-乙基己酯(B-1)645g的聚合物/丙烯酸2-乙基己酯混合溶液(2150g)。該反應性聚合物(A-15)的重量平均分子量為91,000(SEC：聚苯乙烯換算)，雙鍵當量為120000g/mol。向上述混合溶液21.4g中添加丙烯酸2-乙基己酯(B-1)33.6g、聚丙二醇二丙烯酸酯(東亞合成製造，商品名：Aronix M-270)(D-3)5g、丙烯酸系塑化劑(東亞合成製造，商品名：Arufon UP-1020)(F-1)40g、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(1g)、二丁基羥基甲苯(0.05g)來進行混合，而獲得光硬化型黏著劑組成物。該組成物的黏度為110mPa．s/25℃。使用化學燈(照射強度為1.9mW/cm2，照射量為4000mJ/cm2)作為活性能量線，根據上述記載的試驗方法進行黏著力、黏著保持力、被黏著體上的殘膠、折射率(nD)的測定。將結果示於表3。 Methyl ethyl ketone (750 g) was added to a 5-liter four-necked flask equipped with a chiller, a dropping funnel, and a thermometer, followed by dropwise addition at 85 ° C under reflux for about 3 hours through a dropping funnel. 2-ethylhexyl acrylate (1496g), 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko, trade name: Karenz MOI) (2.11g), 2,2'-azobis-2 a mixture of methylbutyronitrile (AMBN) (0.75 g). About 1 hour after the completion of the dropwise addition, a mixed solution of AIBN (0.75 g) and methyl ethyl ketone (30 g) was added, and the mixture was reacted at 85 ° C for 6 hours. Then, 4-hydroxybutyl acrylate (1.94 g), dibutyltin dilaurate (0.45 g), methyl ethyl ketone (30 g), and dibutylhydroxytoluene (0.75 g) were added, followed by about 70 ° C. 5 hours addition reaction. The time at which the reaction rate became 99% or more by the isocyanate value was taken as the end point of the reaction. Then, 2-ethylhexyl acrylate (645 g) was added, and methyl ethyl ketone was removed to the outside of the system to make the residual solvent 1% or less, and 1505 g of reactive polymer (A-15) and 2-B of acrylic acid were obtained. Hexyl hexyl ester (B-1) 645 g of a polymer / 2-ethylhexyl acrylate mixed solution (2150 g). The reactive polymer (A-15) had a weight average molecular weight of 91,000 (SEC: polystyrene equivalent) and a double bond equivalent of 120,000 g/mol. To 21.4 g of the above mixed solution, 33.6 g of 2-ethylhexyl acrylate (B-1) and polypropylene glycol diacrylate (manufactured by Toagosei Co., Ltd., trade name: Aronix M-270) (D-3), 5 g, acrylic acid were added. Plasticizer (made by East Asia Synthetic, trade name: Arufon UP-1020) (F-1) 40g, 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (1 g) and dibutylhydroxytoluene (0.05 g) were mixed to obtain a photocurable adhesive composition. The composition has a viscosity of 110 mPa. s / 25 ° C. Using a chemical lamp (irradiation intensity: 1.9 mW/cm 2 , irradiation amount: 4000 mJ/cm 2 ) as an active energy ray, adhesion, adhesion retention force, residual glue on the adherend, and refractive index were measured according to the test method described above. Determination of (nD). The results are shown in Table 3.

[比較例5] [Comparative Example 5]

向具備冷卻器、滴加漏斗及溫度計的5升的四口燒瓶中添加 甲基乙基酮(2250g)，繼而於85℃下，並於回流條件下，透過滴加漏斗歷時約3小時滴加丙烯酸2-乙基己酯(1496g)、異氰酸2-甲基丙烯醯氧基乙酯(昭和電工製造，商品名：Karenz MOI)(32.9g)、2,2'-偶氮雙-2-甲基丁腈(AMBN)(3.5g)的混合液。滴加結束約1小時後，添加AIBN(0.75g)、甲基乙基酮(30g)的混合液，並於85℃下反應6小時。繼而，添加丙烯酸4-羥基丁酯(30.27g)、二月桂酸二丁基錫(0.45g)、甲基乙基酮(30g)、二丁基羥基甲苯(0.75g)，然後於70℃下進行約5小時加成反應。將藉由異氰酸酯值測定，反應率變成99%以上的時間設為反應的終點。繼而，添加丙烯酸2-乙基己酯(645g)，將甲基乙基酮去除至系統外，使殘留溶劑變成1%以下，而獲得反應性聚合物(A-16)1505g與丙烯酸2-乙基己酯(B-1)645g的聚合物/丙烯酸2-乙基己酯混合溶液(2150g)。該反應性聚合物(A-16)的重量平均分子量為20,000(SEC：聚苯乙烯換算)，雙鍵當量為8000g/mol。向上述混合溶液21.4g中添加丙烯酸2-乙基己酯(B-1)33.6g、聚丙二醇二丙烯酸酯(東亞合成製造，商品名：Aronix M-270)(D-3)5g、丙烯酸系塑化劑(東亞合成製造，商品名：Arufon UP-1020)(F-1)40g、1-羥基-環己基-苯基-酮(汽巴精化公司製造，商品名：Irgacure184)(C)(1g)、二丁基羥基甲苯(0.05g)來進行混合，而獲得光硬化型黏著劑組成物。該組成物的黏度為55mPa．s/25℃。使用化學燈(照射強度為1.9mW/cm2，照射量為4000mJ/cm2)作為活性能量線，根據上述記載的試驗方法進行黏著力、 黏著保持力、被黏著體上的殘膠、折射率(nD)的測定。將結果示於表3。 Methyl ethyl ketone (2250 g) was added to a 5-liter four-necked flask equipped with a chiller, a dropping funnel and a thermometer, and then dropped at 85 ° C under reflux conditions through a dropping funnel for about 3 hours. 2-ethylhexyl acrylate (1496g), 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko, trade name: Karenz MOI) (32.9g), 2,2'-azobis-2 a mixture of methylbutyronitrile (AMBN) (3.5 g). About 1 hour after the completion of the dropwise addition, a mixed solution of AIBN (0.75 g) and methyl ethyl ketone (30 g) was added, and the mixture was reacted at 85 ° C for 6 hours. Then, 4-hydroxybutyl acrylate (30.27 g), dibutyltin dilaurate (0.45 g), methyl ethyl ketone (30 g), dibutylhydroxytoluene (0.75 g) were added, and then about 70 ° C was carried out. 5 hours addition reaction. The time at which the reaction rate became 99% or more by the isocyanate value was taken as the end point of the reaction. Then, 2-ethylhexyl acrylate (645 g) was added, and methyl ethyl ketone was removed to the outside of the system to make the residual solvent 1% or less, and 1505 g of reactive polymer (A-16) and 2-B of acrylic acid were obtained. Hexyl hexyl ester (B-1) 645 g of a polymer / 2-ethylhexyl acrylate mixed solution (2150 g). The reactive polymer (A-16) had a weight average molecular weight of 20,000 (SEC: polystyrene equivalent) and a double bond equivalent of 8000 g/mol. To 21.4 g of the above mixed solution, 33.6 g of 2-ethylhexyl acrylate (B-1) and polypropylene glycol diacrylate (manufactured by Toagosei Co., Ltd., trade name: Aronix M-270) (D-3), 5 g, acrylic acid were added. Plasticizer (made by East Asia Synthetic, trade name: Arufon UP-1020) (F-1) 40g, 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) (C) (1 g) and dibutylhydroxytoluene (0.05 g) were mixed to obtain a photocurable adhesive composition. The composition has a viscosity of 55 mPa. s / 25 ° C. Using a chemical lamp (irradiation intensity of 1.9 mW/cm 2 and an irradiation amount of 4000 mJ/cm 2 ) as an active energy ray, adhesion, adhesion retention force, residual glue on the adherend, and refractive index were measured according to the test method described above. Determination of (nD). The results are shown in Table 3.

使實施例1~實施例21的光硬化型黏著劑組成物硬化而獲得的黏著劑的黏著力及殘膠的評價均為「○」。根據該結果可知顯示面板組裝時的重新加工性優異。另一方面，可知使用雙鍵當量未滿10000g/mol的A成分的比較例1變成黏著力過高的結果，因此重新加工性低，另外，使用重量平均分子量未滿50000、雙鍵當量未滿10000g/mol的A成分的比較例2有殘膠，因此重新加工性低。關於比較例3、比較例4、比較例5，因不具有充分的黏著保持力，故硬化物的凝聚力低，將被黏著物彼此剝離時黏著劑容易殘留，無法獲得充分的重新加工性。 The adhesion of the adhesive obtained by curing the photocurable adhesive compositions of Examples 1 to 21 and the evaluation of the residual adhesive were all "○". From this result, it is understood that the reworkability at the time of assembly of the display panel is excellent. On the other hand, in Comparative Example 1 in which the component A having a double bond equivalent of less than 10000 g/mol was used, the adhesiveness was too high, so that the reworkability was low, and the weight average molecular weight was less than 50,000 and the double bond equivalent was not satisfied. In Comparative Example 2 of the A component of 10000 g/mol, there was a residual rubber, and thus the reworkability was low. In Comparative Example 3, Comparative Example 4, and Comparative Example 5, since the adhesive retention force was not sufficient, the cohesive force of the cured product was low, and the adhesive was likely to remain when the adherends were peeled off from each other, and sufficient reworkability could not be obtained.

本申請主張以於2012年9月20日申請的日本申請特願2012-206835為基礎的優先權，並將其所揭示的全部內容編入至本申請中。 The present application claims priority based on Japanese Patent Application No. 2012-206835, filed on Sep. 20, 2012, the entire disclosure of which is incorporated herein.

以上，參照實施形態及實施例對本申請案發明進行了說明，但本申請案發明並不限定於上述實施形態及實施例。可於本申請案發明的範圍內，對本申請案發明的構成或詳細內容進行本領域從業人員可理解的各種變更。 The invention of the present application has been described above with reference to the embodiments and examples, but the invention is not limited to the embodiments and examples described above. Various changes that can be understood by those skilled in the art can be made to the constitution or details of the invention of the present application within the scope of the invention.

Claims (24)

一種光硬化型黏著劑組成物，其包括反應性聚合物(A成分)、具有一個聚合性雙鍵的單體(B成分)、及光聚合起始劑(C成分)，上述反應性聚合物(A成分)如下，其主鏈含有源自(甲基)丙烯酸系單體的重複單元，且側鏈含有聚合性雙鍵，其雙鍵當量，即每1mol聚合性雙鍵的聚合物質量，為10,000g/mol~100,000g/mol，其重量平均分子量(Mw)為25,000~1,000,000。 A photocurable adhesive composition comprising a reactive polymer (component A), a monomer having a polymerizable double bond (component B), and a photopolymerization initiator (component C), the above reactive polymer (Component A) wherein the main chain contains a repeating unit derived from a (meth)acrylic monomer, and the side chain contains a polymerizable double bond, and the double bond equivalent thereof, that is, the polymer mass per 1 mol of the polymerizable double bond, It has a weight average molecular weight (Mw) of from 5,000 g/mol to 100,000 g/mol of from 25,000 to 1,000,000. 如申請專利範圍第1項所述的光硬化型黏著劑組成物，其中作為上述源自(甲基)丙烯酸系單體的重複單元，上述主鏈含有源自具有醇殘基的(甲基)丙烯酸酯的重複單元，上述醇殘基包含異氰酸基。 The photocurable pressure-sensitive adhesive composition according to claim 1, wherein the main chain contains a (meth) group having an alcohol residue as a repeating unit derived from the (meth)acrylic monomer. In the repeating unit of the acrylate, the above alcohol residue contains an isocyanate group. 如申請專利範圍第2項所述的光硬化型黏著劑組成物，其中上述具有包含異氰酸基的醇殘基的(甲基)丙烯酸酯為異氰酸2-(甲基)丙烯醯氧基烷基酯。 The photocurable adhesive composition according to claim 2, wherein the (meth) acrylate having an alcohol residue containing an isocyanate group is 2-(methyl) propylene isocyanate Alkyl ester. 如申請專利範圍第1項所述的光硬化型黏著劑組成物，其中作為上述源自(甲基)丙烯酸系單體的重複單元，上述主鏈含有源自具有碳數為1~14的烷基醇殘基的(甲基)丙烯酸酯的重複單元。 The photocurable adhesive composition according to claim 1, wherein the main chain contains alkane having a carbon number of 1 to 14 as a repeating unit derived from the (meth)acrylic monomer. A repeating unit of a (meth) acrylate of a base alcohol residue. 如申請專利範圍第4項所述的光硬化型黏著劑組成物，其中上述具有碳數為1~14的烷基醇殘基的(甲基)丙烯酸酯為丙烯 酸2-乙基己酯。 The photocurable adhesive composition according to claim 4, wherein the (meth) acrylate having an alkyl alcohol residue having 1 to 14 carbon atoms is propylene. 2-ethylhexyl acid. 如申請專利範圍第1項所述的光硬化型黏著劑組成物，其中作為上述源自(甲基)丙烯酸系單體的重複單元，上述主鏈含有源自具有醇殘基的(甲基)丙烯酸酯的重複單元，上述醇殘基包含異氰酸基，上述側鏈具有如下結構，即將上述異氰酸基與(甲基)丙烯酸羥基烷基酯的羥基進行加成而得的結構。 The photocurable pressure-sensitive adhesive composition according to claim 1, wherein the main chain contains a (meth) group having an alcohol residue as a repeating unit derived from the (meth)acrylic monomer. In the repeating unit of the acrylate, the alcohol residue contains an isocyanate group, and the side chain has a structure in which a hydroxyl group of the above-mentioned isocyanate group and a hydroxyalkyl (meth)acrylate are added. 如申請專利範圍第6項所述的光硬化型黏著劑組成物，其中上述(甲基)丙烯酸羥基烷基酯為丙烯酸4-羥基丁酯。 The photocurable adhesive composition according to claim 6, wherein the hydroxyalkyl (meth)acrylate is 4-hydroxybutyl acrylate. 如申請專利範圍第1項所述的光硬化型黏著劑組成物，其中上述A成分的側鏈含有胺基甲酸酯鍵。 The photocurable adhesive composition according to claim 1, wherein the side chain of the component A contains a urethane bond. 如申請專利範圍第1項所述的光硬化型黏著劑組成物，其中相對於上述A成分及上述B成分的合計的上述A成分的含量為5質量%~80質量%。 The photocurable adhesive composition according to the first aspect of the invention, wherein the content of the component A is 5% by mass to 80% by mass based on the total of the component A and the component B. 如申請專利範圍第1項所述的光硬化型黏著劑組成物，其中相對於上述A成分及上述B成分的合計100質量份，包含5質量份以下的含有羧基的單體。 The photocurable adhesive composition according to the first aspect of the invention, wherein the carboxyl group-containing monomer is contained in an amount of 5 parts by mass or less based on 100 parts by mass of the total of the component A and the component B. 如申請專利範圍第1項所述的光硬化型黏著劑組成物，其中相對於上述A成分及上述B成分的合計100質量份，含有0.05質量份~10質量份的具有兩個以上的聚合性雙鍵的單體(D成分)。 The photocurable pressure-sensitive adhesive composition according to the first aspect of the invention, wherein the polymer component is contained in an amount of from 0.05 part by mass to 10 parts by mass per 100 parts by mass of the total of the component A and the component B. Double bond monomer (component D). 如申請專利範圍第1項所述的光硬化型黏著劑組成物，其中相對於上述A成分及上述B成分的合計100質量份，含有10質量份~120質量份的上述A成分以外的(甲基)丙烯酸系聚合物(F成分)。 The photocurable adhesive composition according to the first aspect of the invention, wherein the component A is contained in an amount of 10 parts by mass to 120 parts by mass based on 100 parts by mass of the total of the component A and the component B (a) Base) acrylic polymer (component F). 如申請專利範圍第1項所述的光硬化型黏著劑組成物，其依據JIS-Z-0237所測定的黏著保持力為2mm以下。 The photocurable adhesive composition according to the first aspect of the invention is characterized in that the adhesive retention force measured according to JIS-Z-0237 is 2 mm or less. 如申請專利範圍第1項所述的光硬化型黏著劑組成物，其中針對經硬化而獲得的帶狀物，依據JIS-Z-0237所測定的黏著力為0.1N/24mm~20N/24mm，且於藉由上述測定而將帶剝離後的痕跡上無殘膠。 The photocurable adhesive composition according to claim 1, wherein the adhesive obtained by hardening has an adhesive force of 0.1 N/24 mm to 20 N/24 mm as measured according to JIS-Z-0237. Further, no residue remained on the trace after peeling off the tape by the above measurement. 如申請專利範圍第14項所述的光硬化型黏著劑組成物，其黏著力為10N/24mm~20N/24mm。 The photocurable adhesive composition according to Item 14 of the patent application has an adhesive force of 10 N/24 mm to 20 N/24 mm. 一種硬化物，其是藉由活性能量線來使如申請專利範圍第1項所述的光硬化型黏著劑組成物硬化而獲得。 A cured product obtained by curing a photocurable adhesive composition according to item 1 of the patent application by an active energy ray. 一種黏著片，其是藉由活性能量線來使如申請專利範圍第1項所述的光硬化型黏著劑組成物硬化而獲得。 An adhesive sheet obtained by hardening a photocurable adhesive composition as described in claim 1 by an active energy ray. 一種光硬化型黏著劑組成物，其依據JIS-Z-0237所測定的黏著保持力為2mm以下。 A photocurable adhesive composition having an adhesive retention force of 2 mm or less as measured according to JIS-Z-0237. 一種黏著片，其是使如申請專利範圍第18項所述的光硬化型黏著劑組成物硬化而獲得。 An adhesive sheet obtained by hardening a photocurable adhesive composition as described in claim 18 of the patent application. 如申請專利範圍第19項所述的黏著片，其厚度為25μm~1000μm。 The adhesive sheet according to claim 19, which has a thickness of 25 μm to 1000 μm. 一種顯示面板，其是於顯示體上具備黏著劑層，於上述黏著劑層上具備光學功能材料的層的顯示面板，且上述黏著劑層是使如申請專利範圍第1項所述的光硬化型黏著劑組成物硬化而獲得。 A display panel which is provided with an adhesive layer on a display body, and a display panel having a layer of an optical functional material on the adhesive layer, and the adhesive layer is photohardened as described in claim 1 The adhesive composition is obtained by hardening. 一種顯示面板的製造方法，其包括如下的步驟：將如申請專利範圍第1項所述的光硬化型黏著劑組成物塗佈於光學功能材料上，於所獲得的塗膜上積層顯示體，自光學功能材料側照射活性能量線來使上述光硬化型黏著劑組成物硬化，而使上述光學功能材料與上述顯示體接著。 A method for producing a display panel, comprising the steps of: applying a photocurable adhesive composition according to claim 1 of the invention to an optical functional material, and laminating the display on the obtained coating film, The photo-curable adhesive composition is cured by irradiating the active energy ray from the side of the optical functional material, and the optical functional material is followed by the display. 一種顯示面板的製造方法，其包括如下的步驟：將如申請專利範圍第1項所述的光硬化型黏著劑組成物注入至分開設置的膜狀或片狀的光學功能材料與膜狀或片狀的顯示體之間，並自光學功能材料側照射活性能量線來使上述光硬化型黏著劑組成物硬化。 A method of manufacturing a display panel, comprising the steps of: injecting a photocurable adhesive composition according to claim 1 of the invention into a separately provided film-like or sheet-like optical functional material and a film or sheet The photocurable adhesive composition is cured between the display bodies and the active energy rays from the side of the optical functional material. 一種顯示面板的製造方法，其包括如下的步驟：於如申請專利範圍第19項所述的黏著片的一面上接著膜狀或片狀的光學功能材料，於另一面上接著膜狀或片狀的顯示體，而使上述光學功能材料與上述顯示體貼合。 A manufacturing method of a display panel, comprising the steps of: attaching a film-like or sheet-like optical functional material on one side of the adhesive sheet according to claim 19, and then membranous or sheet-like on the other surface The display body is bonded to the display body.
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