TW202337936A - Adhesive composition, adhesive sheet, optical member, and display device - Google Patents

Adhesive composition, adhesive sheet, optical member, and display device Download PDF

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TW202337936A
TW202337936A TW112103948A TW112103948A TW202337936A TW 202337936 A TW202337936 A TW 202337936A TW 112103948 A TW112103948 A TW 112103948A TW 112103948 A TW112103948 A TW 112103948A TW 202337936 A TW202337936 A TW 202337936A
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meth
mass
acrylic polymer
adhesive composition
specific
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TW112103948A
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三好陽
池元智拾
長谷川良
守山史朗
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日商日本電石工業股份有限公司
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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
    • 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
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Liquid Crystal (AREA)
  • Adhesive Tapes (AREA)

Abstract

An adhesive composition, adhesive sheet, optical member, and display device include a (meth)acrylic polymer having a carboxy group, a polyisocyanate compound, an alicyclic epoxy compound represented by the following Formula (I), and a silane coupling agent, the polyisocyanate compound being contained in an amount of from 0.1 to 11.0 parts by mass relative to 100 parts by mass of the (meth)acrylic polymer, and the alicyclic epoxy compound being contained in an amount of from 0.1 to 4.0 parts by mass relative to 100 parts by mass of the (meth)acrylic polymer. In Formula (I), R represents a bivalent organic linking group having an ester bond.

Description

黏著劑組成物、黏著片、光學構件、及顯示裝置Adhesive composition, adhesive sheet, optical component, and display device

本揭示係關於黏著劑組成物、黏著片、光學構件及顯示裝置。This disclosure relates to adhesive compositions, adhesive sheets, optical components and display devices.

液晶顯示裝置一般具備在2片支撐基板之間夾入液晶層而成的液晶單元與偏光板、相位差膜、亮度提升膜等光學膜。在將液晶單元與光學膜以及光學膜彼此積層而製造液晶顯示裝置時，此等構件隔著由黏著劑組成物形成之黏著劑層而貼合。液晶顯示裝置中，從確保觀賞性的觀點來看，大多使用(甲基)丙烯酸系的黏著劑組成物。A liquid crystal display device generally includes a liquid crystal cell with a liquid crystal layer sandwiched between two support substrates, and optical films such as a polarizing plate, a retardation film, and a brightness improvement film. When a liquid crystal cell, an optical film, and the optical films are laminated to produce a liquid crystal display device, these components are bonded together via an adhesive layer formed of an adhesive composition. In liquid crystal display devices, (meth)acrylic adhesive compositions are often used from the viewpoint of ensuring viewing quality.

例如，日本專利第6441018號公報揭示了一種黏著劑組成物，其包含具有羧基之(甲基)丙烯酸系聚合物與相對於100質量份的上述(甲基)丙烯酸系聚合物為0.005質量份～2.5質量份的具有特定結構之脂環族環氧改質聚矽氧。For example, Japanese Patent No. 6441018 discloses an adhesive composition including a (meth)acrylic polymer having a carboxyl group and 0.005 parts by mass to 100 parts by mass of the (meth)acrylic polymer. 2.5 parts by mass of alicyclic epoxy modified polysiloxane with a specific structure.

[發明所欲解決之課題][Problem to be solved by the invention]

偏光板等光學膜，通常係將收縮率不同的多個構件積層而構成，容易因為溫度及/或濕度的變化而發生尺寸變化。因此，隔著黏著劑層貼合的光學膜若放置在高溫環境下、重複低溫與高溫的環境下等嚴苛的環境下，可能發生光學膜翹曲、黏著劑層及/或光學膜產生皺褶而黏著劑層從作為被附著體的液晶單元剝離等不良的情形。Optical films such as polarizing plates are usually constructed by laminating a plurality of members with different shrinkage rates, and are prone to dimensional changes due to changes in temperature and/or humidity. Therefore, if an optical film laminated with an adhesive layer is placed in a harsh environment such as a high-temperature environment or repeated exposure to low and high temperatures, the optical film may warp and the adhesive layer and/or the optical film may wrinkle. Defects such as wrinkles and peeling of the adhesive layer from the liquid crystal cell as the adherend.

此外，近年來隨著顯示器的輕量化及小型化的要求提高，亦要求顯示器中所使用的偏光板進一步薄膜化。一般而言，若將偏光板薄膜化，則偏光板整體的剛性降低，因此放置在嚴苛環境下的情況中，偏光板的收縮變大。又，伴隨近年來全螢幕顯示的智慧型手機普及，顯示器中所使用的偏光板中，有時必須在相當於前置相機部分的部位設置穿孔。在這種設有穿孔的偏光板中，若發生收縮，則會發生穿孔的位置偏離這樣的問題。因此要求偏光板中所使用的黏著劑組成物能夠形成可抑制放置在高溫環境下、重複低溫與高溫的環境下等嚴苛環境下時會發生之偏光板收縮的黏著劑層。In addition, in recent years, as the demand for weight reduction and miniaturization of displays has increased, polarizing plates used in displays are also required to be further thinned. Generally speaking, when a polarizing plate is thinned, the rigidity of the entire polarizing plate decreases. Therefore, when the polarizing plate is placed in a harsh environment, the shrinkage of the polarizing plate increases. In addition, as smartphones with full-screen displays have become more popular in recent years, the polarizing plate used in the display sometimes needs to be provided with a perforation in a portion corresponding to the front camera. In such a polarizing plate provided with perforations, if shrinkage occurs, there is a problem that the position of the perforations deviates. Therefore, it is required that the adhesive composition used in the polarizing plate can form an adhesive layer that can suppress the shrinkage of the polarizing plate that occurs when the polarizing plate is placed in a high-temperature environment, repeatedly exposed to low and high temperatures, and other harsh environments.

為了藉由黏著劑層抑制偏光板的收縮，有人想到了提高黏著劑層的凝聚力。然而，若提高黏著劑層的凝聚力，則黏著劑層變硬，反而難以藉由黏著劑層來緩和因偏光板收縮所造成之應力。因此，若偏光板的收縮大，則黏著劑層無法緩和因偏光板的收縮所造成的應力，可能會發生黏著劑層及/或偏光板產生皺褶、黏著劑層從作為被附著體的液晶單元剝離等不良的情形。In order to suppress the shrinkage of the polarizing plate through the adhesive layer, some people thought of increasing the cohesion of the adhesive layer. However, if the cohesion of the adhesive layer is increased, the adhesive layer becomes hard, making it difficult to use the adhesive layer to relieve the stress caused by the shrinkage of the polarizing plate. Therefore, if the shrinkage of the polarizing plate is large, the adhesive layer cannot relieve the stress caused by the shrinkage of the polarizing plate, and the adhesive layer and/or the polarizing plate may become wrinkled, and the adhesive layer may deviate from the liquid crystal as the adherend. Undesirable situations such as unit peeling.

本揭示係鑒於上述狀況而完成。 作為本揭示的一實施形態所欲解決之課題，係提供一種黏著劑組成物，其可形成能夠良好地抑制放置在高溫環境下時會發生的基材收縮並且即使放置在重複低溫與高溫的環境下時亦不易產生皺褶及剝離的黏著劑層。 本揭示的另一實施形態欲解決之課題係提供一種具備可良好地抑制放置在高溫環境下時會發生之基材收縮且即使放置在重複低溫與高溫的環境下時亦不易產生皺褶及剝離之黏著劑層的黏著片、光學構件及顯示裝置。 [解決課題之手段] This disclosure is made in view of the above situation. An object to be solved by one embodiment of the present disclosure is to provide an adhesive composition capable of well suppressing the shrinkage of a base material that occurs when placed in a high temperature environment and even if it is placed in an environment where low and high temperatures are repeated. It is also difficult to produce wrinkles and peeling adhesive layer when applied. Another problem to be solved by another embodiment of the present disclosure is to provide a device that can well suppress the shrinkage of the substrate that occurs when placed in a high-temperature environment and is less likely to cause wrinkles and peeling even when placed in an environment with repeated low and high temperatures. Adhesive sheets, optical components and display devices with adhesive layers. [Means to solve the problem]

用以解決課題的具體手段包含以下的態樣。 ＜1＞一種黏著劑組成物，包含具有羧基之(甲基)丙烯酸系聚合物、多異氰酸酯系化合物、下式(I)表示的脂環族環氧系化合物與矽烷偶聯劑，相對於100質量份的上述(甲基)丙烯酸系聚合物，上述多異氰酸酯系化合物的含量為0.1質量份～11.0質量份，相對於100質量份的上述(甲基)丙烯酸系聚合物，上述脂環族環氧系化合物的含量為0.1質量份～4.0質量份。 Specific means used to solve the problem include the following aspects. <1> An adhesive composition containing a (meth)acrylic polymer having a carboxyl group, a polyisocyanate compound, an alicyclic epoxy compound represented by the following formula (I), and a silane coupling agent, relative to 100 The content of the polyisocyanate compound in the (meth)acrylic polymer is 0.1 to 11.0 parts by mass relative to 100 parts by mass of the (meth)acrylic polymer. The content of the oxygen-based compound is 0.1 parts by mass to 4.0 parts by mass.

[化1] [Chemical 1]

式(I)中，R表示具有酯鍵的2價有機連結基。In formula (I), R represents a divalent organic linking group having an ester bond.

＜2＞如＜1＞之黏著劑組成物，其中上述式(I)中的R表示的2價有機連結基的原子數為3～200。 ＜3＞如＜1＞或＜2＞之黏著劑組成物，其中上述式(I)表示的脂環族環氧系化合物為下式(II)表示的化合物。 <2> The adhesive composition of <1>, wherein the number of atoms of the divalent organic linking group represented by R in the above formula (I) is 3 to 200. <3> The adhesive composition of <1> or <2>, wherein the alicyclic epoxy compound represented by the above formula (I) is a compound represented by the following formula (II).

[化2] [Chemicalization 2]

式(II)中，n表示0～5的整數。In formula (II), n represents an integer from 0 to 5.

＜4＞如＜1＞至＜3＞中任一項之黏著劑組成物，其中上述(甲基)丙烯酸系聚合物的酸價為0.8mgKOH/g～24.0mgKOH/g。 ＜5＞一種黏著片，其具備由如＜1＞至＜4＞中任一項之黏著劑組成物形成的黏著劑層。 ＜6＞如＜5＞之黏著片，其具備：光學膜；及黏著劑層，設於上述光學膜的至少單面，且係由如＜1＞至＜4＞任一項之黏著劑組成物形成。 ＜7＞如＜6＞之黏著片，其中上述光學膜為偏光板。 ＜8＞一種光學構件，其依序具備玻璃基板、由如＜1＞至＜4＞中任一項之黏著劑組成物形成之黏著劑層、及光學膜。 ＜9＞一種顯示裝置，其具備如＜8＞之光學構件。 [發明之效果] <4> The adhesive composition according to any one of <1> to <3>, wherein the (meth)acrylic polymer has an acid value of 0.8 mgKOH/g to 24.0 mgKOH/g. <5> An adhesive sheet provided with an adhesive layer formed of the adhesive composition according to any one of <1> to <4>. <6> The adhesive sheet of <5>, which is provided with: an optical film; and an adhesive layer, which is provided on at least one side of the above-mentioned optical film and is composed of the adhesive of any one of <1> to <4> object formation. <7> The adhesive sheet of <6>, wherein the optical film is a polarizing plate. <8> An optical member provided in this order with a glass substrate, an adhesive layer formed of the adhesive composition according to any one of <1> to <4>, and an optical film. <9> A display device provided with the optical member of <8>. [Effects of the invention]

根據本揭示的一實施形態，可提供一種黏著劑組成物，其可形成能夠良好地抑制放置在高溫環境下時會發生的基材收縮且即使放置在重複低溫與高溫的環境下時亦不易產生皺褶及剝離的黏著劑層。 根據本揭示的另一實施形態，可提供具備能夠良好地抑制放置在高溫環境下時會發生之基材收縮且即使放置在重複低溫與高溫的環境下時亦不易產生皺褶及剝離的黏著劑層的黏著片、光學構件及顯示裝置。 According to one embodiment of the present disclosure, it is possible to provide an adhesive composition that can well suppress shrinkage of a substrate that occurs when placed in a high-temperature environment and is less likely to occur even when placed in an environment where low and high temperatures are repeated. Wrinkled and peeling adhesive layer. According to another embodiment of the present disclosure, it is possible to provide an adhesive that can well suppress the shrinkage of the base material that occurs when placed in a high-temperature environment and is less likely to cause wrinkles and peeling even when placed in environments with repeated low and high temperatures. layers of adhesive sheets, optical components and display devices.

以下詳細說明本揭示的黏著劑組成物、黏著片、光學構件及顯示裝置。以下記載之要件的說明係根據本揭示的代表性實施態樣，但本揭示不限於這樣的實施態樣，在本揭示之目的範圍內可適當施加變化而實施。The adhesive composition, adhesive sheet, optical component and display device of the present disclosure are described in detail below. The description of the requirements described below is based on representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments, and can be implemented with appropriate changes within the scope of the purpose of the present disclosure.

本揭示中使用「～」表示的數值範圍，係指包含記載於「～」之前後的數值並將其分別作為下限值及上限值的範圍。 本揭示階段性記載的數值範圍中，在某數值範圍內記載的上限值或下限值，亦可替代為其他階段性記載的數值範圍之上限值或下限值。又，本揭示記載的數值範圍中，在某數值範圍中記載的上限值或下限值，亦可替換為實施例所示的值。 The numerical range represented by "～" in this disclosure refers to a range including the numerical values before and after "～" as the lower limit and the upper limit respectively. In the numerical ranges described in stages in this disclosure, the upper limit or lower limit stated in a certain numerical range can also be replaced by the upper limit or lower limit of other numerical ranges described in stages. In addition, in the numerical range described in this disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the Example.

本揭示中，2個以上的較佳態樣的組合為更佳的態樣。In this disclosure, a combination of two or more better aspects is a better aspect.

本揭示中，黏著劑組成物中的各成分的量，在黏著劑組成物中存在多種相當於各成分之物質時，若未特別說明，則係指存在於黏著劑組成物中的上述多種物質的總量。In this disclosure, the amount of each component in the adhesive composition, when there are multiple substances equivalent to each component in the adhesive composition, refers to the above-mentioned multiple substances present in the adhesive composition unless otherwise specified. total amount.

本揭示中，所謂的「(甲基)丙烯酸系單體」，係指具有(甲基)丙烯醯基的單體。 本揭示中，所謂的「(甲基)丙烯酸系聚合物」，係指源自具有(甲基)丙烯醯基之單體的構成單元的含有率為所有構成單元[亦即聚合物的所有構成單元]的50質量%以上的聚合物。 In this disclosure, the "(meth)acrylic monomer" refers to a monomer having a (meth)acryl group. In this disclosure, the so-called "(meth)acrylic polymer" means that the content of the structural units derived from the monomer having a (meth)acryl group refers to all the structural units [that is, all the structures of the polymer] unit] of more than 50% by mass of the polymer.

本揭示中，「(甲基)丙烯酸基」係包含「丙烯酸基」及「甲基丙烯酸基」兩者的用語，「(甲基)丙烯酸酯」係包含「丙烯酸酯」及「甲基丙烯酸酯」兩者的用語，「(甲基)丙烯醯基」係包含「丙烯醯基」及「甲基丙烯醯基」兩者的用語，「(甲基)丙烯醯胺」係包含「丙烯醯胺」及「甲基丙烯醯胺」兩者的用語。In this disclosure, "(meth)acrylate" is a term that includes both "acrylate" and "methacrylate", and "(meth)acrylate" includes "acrylate" and "methacrylate". ” are both terms, “(meth)acrylyl” is a term that includes both “acrylyl” and “methacrylamide”, and “(meth)acrylamide” is a term that includes “acrylamide” ” and “methacrylamide”.

本揭示中，「n-」表示正，「i-」表示異，「s-」表示二級，「t-」表示三級。In this disclosure, "n-" means positive, "i-" means opposite, "s-" means second level, and "t-" means third level.

本揭示中，「高分子」與「聚合物」同義。In this disclosure, "polymer" and "polymer" are synonymous.

[黏著劑組成物] 本揭示的黏著劑組成物包含具有羧基之(甲基)丙烯酸系聚合物、多異氰酸酯系化合物、下式(I)表示的脂環族環氧系化合物及矽烷偶聯劑，其中相對於100質量份的上述(甲基)丙烯酸系聚合物，上述多異氰酸酯系化合物的含量為0.1質量份～11.0質量份，相對於100質量份的上述(甲基)丙烯酸系聚合物，上述脂環族環氧系化合物的含量為0.1質量份～4.0質量份。 [Adhesive composition] The adhesive composition of the present disclosure includes a (meth)acrylic polymer having a carboxyl group, a polyisocyanate compound, an alicyclic epoxy compound represented by the following formula (I), and a silane coupling agent, wherein relative to 100 mass parts of the above-mentioned (meth)acrylic polymer, the content of the above-mentioned polyisocyanate compound is 0.1 to 11.0 parts by mass, relative to 100 parts by mass of the above-mentioned (meth)acrylic polymer, the above-mentioned alicyclic epoxy The content of the compound is 0.1 parts by mass to 4.0 parts by mass.

[化3] [Chemical 3]

式(I)中，R表示具有酯鍵的2價有機連結基。In formula (I), R represents a divalent organic linking group having an ester bond.

本揭示的黏著劑組成物可形成能夠良好地抑制放置於高溫環境下時會發生的基材收縮且即使放置於重複低溫與高溫的環境下時亦不易產生皺褶及剝離的黏著劑層。 本揭示的黏著劑組成物可發揮這種效果的理由雖尚未明確，但本案發明人推測如下。惟以下的推測並非限定解釋本揭示的黏著劑組成物，而是作為一例進行說明。 The adhesive composition of the present disclosure can form an adhesive layer that can well suppress the shrinkage of the substrate that occurs when placed in a high-temperature environment and is less likely to wrinkle and peel even when placed in an environment with repeated low and high temperatures. The reason why the adhesive composition of the present disclosure can exert such an effect is not clear yet, but the inventor of the present invention speculates as follows. However, the following speculation is not intended to limit the interpretation of the adhesive composition disclosed in this disclosure, but is provided as an example.

本揭示的黏著劑組成物中，多異氰酸酯系化合物，藉由與具有羧基之(甲基)丙烯酸系聚合物的交聯反應而形成較緻密的三維網狀結構。一般而言，藉由緻密的三維網狀結構形成的黏著劑層具有高凝聚力，具有抑制偏光板收縮的作用，但相反地難以藉由黏著劑層來緩和因偏光板收縮而造成的應力。因此，例如像是薄型的偏光板，放置在嚴苛環境下時收縮變大的偏光板中，黏著劑層無法緩和因收縮所造成的應力，而容易發生在黏著劑層及/或偏光板產生皺褶、黏著劑層從作為被附著體的液晶單元剝離等不良的情形。另一方面，具有特定結構的脂環族環氧系化合物藉由與具有羧基之(甲基)丙烯酸系聚合物的交聯反應而形成三維網狀結構。本揭示的黏著劑組成物所包含的環氧系化合物係具有2個脂環族環氧基的化合物，因為具有體積較大的結構，故形成較鬆散的三維網狀結構。一般而言，由鬆散的三維網狀結構形成的黏著劑層具有適當的柔軟性，因此推測可適當抑制偏光板的收縮，並且緩和因偏光板收縮而造成的應力。In the adhesive composition disclosed in the present disclosure, the polyisocyanate compound forms a relatively dense three-dimensional network structure through a cross-linking reaction with a (meth)acrylic polymer having carboxyl groups. Generally speaking, the adhesive layer formed by a dense three-dimensional network structure has high cohesion and can inhibit the shrinkage of the polarizer. However, on the contrary, it is difficult to use the adhesive layer to relieve the stress caused by the shrinkage of the polarizer. Therefore, for example, if a thin polarizing plate shrinks greatly when it is placed in a harsh environment, the adhesive layer cannot relieve the stress caused by shrinkage, and it is easy to occur in the adhesive layer and/or the polarizing plate. Defects such as wrinkles and peeling of the adhesive layer from the liquid crystal cell as the adherend. On the other hand, an alicyclic epoxy compound having a specific structure forms a three-dimensional network structure through a cross-linking reaction with a (meth)acrylic polymer having a carboxyl group. The epoxy compound contained in the adhesive composition of the present disclosure is a compound with two alicyclic epoxy groups. Because it has a larger structure, it forms a looser three-dimensional network structure. Generally speaking, the adhesive layer formed of a loose three-dimensional network structure has appropriate flexibility, so it is speculated that it can appropriately suppress the shrinkage of the polarizer and relieve the stress caused by the shrinkage of the polarizer.

本揭示的黏著劑組成物包含具有羧基之(甲基)丙烯酸系聚合物、相對於上述(甲基)丙烯酸系聚合物為特定範圍比例的多異氰酸酯系化合物、以及相對於上述(甲基)丙烯酸系聚合物為特定範圍比例的具有特定結構之脂環族環氧系化合物，因此在黏著劑層中，平衡良好地形成緻密的三維網狀結構部分與鬆散的三維網狀結構部分，黏著劑層兼具高凝聚力與適當的柔軟性。此外，本揭示的黏著劑組成物所包含的環氧系化合物，在分子結構中具有酯鍵，與同樣具有酯鍵的(甲基)丙烯酸系聚合物的相容性良好，因此在黏著劑層中，鬆散的三維網狀結構部分不會分布不均，而可賦予黏著劑層整體柔軟性。 由上述可推測由本揭示的黏著劑組成物形成的黏著劑層，可良好地抑制放置於高溫環境下時會發生的基材收縮且即使放置於重複低溫與高溫的環境下時亦不易產生皺褶及剝離。 The adhesive composition of the present disclosure includes a (meth)acrylic polymer having a carboxyl group, a polyisocyanate compound in a specific range relative to the above-mentioned (meth)acrylic polymer, and a proportion of the above-mentioned (meth)acrylic acid. The polymer is an alicyclic epoxy compound with a specific structure in a specific range of proportions. Therefore, in the adhesive layer, a dense three-dimensional network structure part and a loose three-dimensional network structure part are well balanced. The adhesive layer It has both high cohesion and moderate softness. In addition, the epoxy compound contained in the adhesive composition of the present disclosure has an ester bond in the molecular structure and has good compatibility with a (meth)acrylic polymer that also has an ester bond. Therefore, in the adhesive layer In the adhesive layer, the loose three-dimensional network structure part will not be unevenly distributed, but can give the adhesive layer overall softness. From the above, it can be inferred that the adhesive layer formed by the adhesive composition of the present disclosure can well suppress the shrinkage of the substrate that occurs when placed in a high-temperature environment, and is less likely to produce wrinkles even when placed in an environment with repeated low and high temperatures. and stripping.

本揭示中，亦將「具有羧基之(甲基)丙烯酸系聚合物」稱為「特定(甲基)丙烯酸系聚合物」。又，本揭示中，亦將「式(I)表示的脂環族環氧系化合物」稱為「特定脂環族環氧系化合物」。In this disclosure, the "(meth)acrylic polymer having a carboxyl group" is also called a "specific (meth)acrylic polymer." In addition, in this disclosure, the "alicyclic epoxy compound represented by formula (I)" is also called a "specific alicyclic epoxy compound".

[特定(甲基)丙烯酸系聚合物] 本揭示的黏著劑組成物包含具有羧基之(甲基)丙烯酸系聚合物[亦即特定(甲基)丙烯酸系聚合物]。 特定(甲基)丙烯酸系聚合物中的羧基，可與後述多異氰酸酯系化合物所具有的異氰酸酯基、及式(I)表示的脂環族環氧系化合物[亦即特定脂環族環氧系化合物]所具有的環氧基進行交聯反應。 本揭示的黏著劑組成物可僅包含1種特定(甲基)丙烯酸系聚合物，亦可包含2種以上。 [Specific (meth)acrylic polymer] The adhesive composition of the present disclosure contains a (meth)acrylic polymer having a carboxyl group [that is, a specific (meth)acrylic polymer]. The carboxyl group in the specific (meth)acrylic polymer can be combined with the isocyanate group of the polyisocyanate compound described below and the alicyclic epoxy compound represented by the formula (I) [that is, the specific alicyclic epoxy compound] The epoxy group of the compound] undergoes a cross-linking reaction. The adhesive composition of the present disclosure may contain only one specific (meth)acrylic polymer, or may contain two or more types.

特定(甲基)丙烯酸系聚合物可為均聚物，亦可為共聚物。特定(甲基)丙烯酸系聚合物，例如可為藉由取代將羧基導入到不具有羧基的(甲基)丙烯酸系單體的均聚物或共聚物而成者，亦可為藉由取代將羧基導入到不具有羧基的(甲基)丙烯酸系單體與不具有羧基且為(甲基)丙烯酸系單體以外之單體的共聚物而成者。又，特定(甲基)丙烯酸系聚合物，例如可為具有羧基之(甲基)丙烯酸系單體與不具有羧基之(甲基)丙烯酸系單體的共聚物，亦可為具有羧基之(甲基)丙烯酸系單體與不具有羧基且為(甲基)丙烯酸系單體以外之單體的共聚物，亦可為不具有羧基之(甲基)丙烯酸系單體與具有羧基且為(甲基)丙烯酸系單體以外之單體的共聚物。The specific (meth)acrylic polymer may be a homopolymer or a copolymer. The specific (meth)acrylic polymer may be, for example, a homopolymer or a copolymer in which a carboxyl group is introduced into a (meth)acrylic monomer that does not have a carboxyl group by substitution, or may be a homopolymer or copolymer in which a carboxyl group is introduced through substitution. A carboxyl group is introduced into a copolymer of a (meth)acrylic monomer that does not have a carboxyl group and a monomer that does not have a carboxyl group and is other than a (meth)acrylic monomer. Moreover, the specific (meth)acrylic polymer may be, for example, a copolymer of a (meth)acrylic monomer having a carboxyl group and a (meth)acrylic monomer not having a carboxyl group, or a copolymer of a (meth)acrylic monomer having a carboxyl group. A copolymer of a meth)acrylic monomer and a monomer other than a (meth)acrylic monomer that does not have a carboxyl group may also be a copolymer of a (meth)acrylic monomer that does not have a carboxyl group and a (meth)acrylic monomer that has a carboxyl group and is ( Copolymer of monomers other than meth)acrylic monomers.

特定(甲基)丙烯酸系聚合物的較佳態樣，係特定(甲基)丙烯酸系聚合物藉由含有源自後述具有羧基之單體的構成單元而具有羧基的態樣。A preferred aspect of the specific (meth)acrylic polymer is an aspect in which the specific (meth)acrylic polymer has a carboxyl group by containing a structural unit derived from a monomer having a carboxyl group described below.

＜具有羧基之單體＞ 特定(甲基)丙烯酸系聚合物較佳係包含源自具有羧基之單體的構成單元。 本揭示中，所謂的「源自具有羧基之單體的構成單元」係指具有羧基之單體加成聚合而形成的構成單元。 ＜Monomer having carboxyl group＞ The specific (meth)acrylic polymer preferably contains a structural unit derived from a monomer having a carboxyl group. In the present disclosure, the term "structural unit derived from a monomer having a carboxyl group" refers to a structural unit formed by addition polymerization of a monomer having a carboxyl group.

具有羧基之單體的種類並無特別限定。 作為具有羧基之單體，可列舉例如：1分子中具有至少1個羧基與乙烯屬不飽和基的單體。 作為乙烯屬不飽和基，並無特別限定，可列舉例如：乙烯基、烯丙基、乙烯基苯基、(甲基)丙烯醯胺基及(甲基)丙烯醯基。 作為乙烯屬不飽和基，較佳為(甲基)丙烯醯基。 The type of monomer having a carboxyl group is not particularly limited. Examples of the monomer having a carboxyl group include monomers having at least one carboxyl group and an ethylenically unsaturated group per molecule. The ethylenically unsaturated group is not particularly limited, and examples thereof include vinyl, allyl, vinylphenyl, (meth)acrylamide and (meth)acrylyl. As the ethylenically unsaturated group, a (meth)acrylyl group is preferred.

作為具有羧基之單體的具體例，可列舉：(甲基)丙烯酸、巴豆酸、馬來酸、富馬酸、伊康酸、戊烯二酸、檸康酸、ω-羧基-多己內酯單(甲基)丙烯酸酯[例如ω-羧基-多己內酯(n≒2)單丙烯酸酯]及琥珀酸衍生物(例如，琥珀酸-2-丙烯醯氧基乙酯)。 具有羧基之單體較佳為具有羧基之(甲基)丙烯酸系單體。作為具有羧基之(甲基)丙烯酸系單體，較佳係選自丙烯酸及ω-羧基-多己內酯單丙烯酸酯中的至少1種。 Specific examples of the monomer having a carboxyl group include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, glutaconic acid, citraconic acid, and ω-carboxy-polycaprolactone. Ester mono(meth)acrylates [eg, ω-carboxy-polycaprolactone (n≒2) monoacrylate] and succinic acid derivatives (eg, 2-propenyloxyethyl succinate). The monomer having a carboxyl group is preferably a (meth)acrylic monomer having a carboxyl group. The (meth)acrylic monomer having a carboxyl group is preferably at least one selected from the group consisting of acrylic acid and ω-carboxy-polycaprolactone monoacrylate.

特定(甲基)丙烯酸系聚合物包含源自具有羧基之單體的構成單元時，可僅包含1種源自具有羧基之單體的構成單元，亦可包含2種以上。When the specific (meth)acrylic polymer contains a structural unit derived from a monomer having a carboxyl group, only one type of structural unit derived from a monomer having a carboxyl group may be included, or two or more types may be included.

特定(甲基)丙烯酸系聚合物包含源自具有羧基之單體的構成單元時，特定(甲基)丙烯酸系聚合物中的源自具有羧基之單體的構成單元的含有率並無特別限定。 特定(甲基)丙烯酸系聚合物中的源自具有羧基之單體的構成單元之含有率，例如較佳係因應預期的特定(甲基)丙烯酸系聚合物的酸價適當設定。特定(甲基)丙烯酸系聚合物的酸價於後段中敘述。 When the specific (meth)acrylic polymer contains a structural unit derived from a monomer having a carboxyl group, the content rate of the structural unit derived from a monomer having a carboxyl group in the specific (meth)acrylic polymer is not particularly limited. . The content rate of the structural unit derived from the monomer having a carboxyl group in the specific (meth)acrylic polymer is preferably set appropriately according to the expected acid value of the specific (meth)acrylic polymer, for example. The acid value of the specific (meth)acrylic polymer will be described later.

＜源自(甲基)丙烯酸烷酯單體的構成單元＞ 特定(甲基)丙烯酸系聚合物較佳係包含源自(甲基)丙烯酸烷酯單體的構成單元。 本揭示中，所謂的「源自(甲基)丙烯酸烷酯單體的構成單元」，係指(甲基)丙烯酸烷酯單體加成聚合而形成的構成單元。另外，本揭示中的「(甲基)丙烯酸烷酯單體」不包含與具有羧基之單體相當的單體以及與具有羥基之單體相當的單體。 <Constituting unit derived from (meth)acrylic acid alkyl ester monomer> The specific (meth)acrylic polymer preferably contains a structural unit derived from a (meth)acrylic acid alkyl ester monomer. In this disclosure, the so-called "structural unit derived from (meth)acrylic acid alkyl ester monomer" refers to a structural unit formed by addition polymerization of (meth)acrylic acid alkyl ester monomer. In addition, the "(meth)acrylic acid alkyl ester monomer" in the present disclosure does not include monomers equivalent to monomers having a carboxyl group and monomers equivalent to monomers having a hydroxyl group.

(甲基)丙烯酸烷酯單體的種類並無特別限定。 (甲基)丙烯酸烷酯單體可為丙烯酸烷酯單體，亦可為甲基丙烯酸烷酯單體。 (甲基)丙烯酸烷酯單體所具有的烷基可為未取代，亦可具有取代基(惟羧基及羥基除外)，但較佳為未取代。 (甲基)丙烯酸烷酯單體所具有的烷基可為直鏈狀、分支鏈狀或環狀的任一者。 (甲基)丙烯酸烷酯單體所具有的烷基之碳數，例如較佳為1～18，更佳為1～12，再佳為1～8，特佳為1～4。 The type of alkyl (meth)acrylate monomer is not particularly limited. The (meth)acrylic acid alkyl ester monomer may be an acrylic acid alkyl ester monomer or a methacrylic acid alkyl ester monomer. The alkyl group of the (meth)acrylic acid alkyl ester monomer may be unsubstituted or may have a substituent (except carboxyl group and hydroxyl group), but is preferably unsubstituted. The alkyl group contained in the (meth)acrylic acid alkyl ester monomer may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group of the alkyl (meth)acrylate monomer is, for example, preferably 1 to 18, more preferably 1 to 12, still more preferably 1 to 8, and particularly preferably 1 to 4.

作為(甲基)丙烯酸烷酯單體的具體例，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸環己酯及(甲基)丙烯酸異莰酯。 作為(甲基)丙烯酸烷酯單體，較佳係選自由丙烯酸正丁酯、甲基丙烯酸酯及甲基丙烯酸甲酯構成之群組中的至少1種。 Specific examples of the (meth)acrylic acid alkyl ester monomer include: (meth)acrylic acid methyl ester, (meth)ethyl acrylate, (meth)acrylic acid n-butyl ester, (meth)acrylic acid isobutyl ester , secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylic acid Cyclohexyl ester and isocamphenyl (meth)acrylate. The alkyl (meth)acrylate monomer is preferably at least one selected from the group consisting of n-butyl acrylate, methacrylate, and methyl methacrylate.

特定(甲基)丙烯酸系聚合物包含源自(甲基)丙烯酸烷酯單體之構成單元的情況，可僅包含1種源自(甲基)丙烯酸烷酯單體的構成單元，亦可包含2種以上。When the specific (meth)acrylic polymer contains a structural unit derived from a (meth)acrylic acid alkyl ester monomer, it may contain only one structural unit derived from a (meth)acrylic acid alkyl ester monomer, or it may contain 2 or more types.

特定(甲基)丙烯酸系聚合物包含源自(甲基)丙烯酸烷酯單體的構成單元時，特定(甲基)丙烯酸系聚合物中的源自(甲基)丙烯酸烷酯單體的構成單元之含有率並無特別限定，例如，相對於特定(甲基)丙烯酸系聚合物的所有構成單元，較佳為50.0質量%～99.9質量%，更佳為60.0質量%～99.6質量%，再佳為70.0質量%～99.3質量%，特佳為80.0質量%～99.0質量%。 此處，相對於特定(甲基)丙烯酸系聚合物的所有構成單元，特定(甲基)丙烯酸系聚合物中的源自(甲基)丙烯酸烷酯單體的構成單元的含有率為50.0質量%以上，係指源自(甲基)丙烯酸烷酯單體的構成單元作為構成特定(甲基)丙烯酸系聚合物之構成單元的主成分而包含於其中。 When the specific (meth)acrylic polymer contains a structural unit derived from an alkyl (meth)acrylate monomer, the structure derived from the alkyl (meth)acrylate monomer in the specific (meth)acrylic polymer The unit content is not particularly limited. For example, it is preferably 50.0 mass% to 99.9 mass%, more preferably 60.0 mass% to 99.6 mass%, based on all the constituent units of the specific (meth)acrylic polymer. The optimal range is 70.0 mass% to 99.3 mass%, and the particularly optimal range is 80.0 mass% to 99.0 mass%. Here, the content rate of the structural units derived from the alkyl (meth)acrylate monomer in the specific (meth)acrylic polymer is 50.0 mass with respect to all the structural units of the specific (meth)acrylic polymer. % or more means that the structural unit derived from the (meth)acrylic acid alkyl ester monomer is included as the main component of the structural unit constituting the specific (meth)acrylic polymer.

＜源自具有羥基之單體的構成單元＞ 特定(甲基)丙烯酸系聚合物亦可包含源自具有羥基之單體的構成單元。 本揭示中，所謂的「源自具有羥基之單體的構成單元」係指具有羥基之單體加成聚合而形成的構成單元。 <Constituting unit derived from a monomer having a hydroxyl group> The specific (meth)acrylic polymer may contain a structural unit derived from a monomer having a hydroxyl group. In this disclosure, the so-called "structural unit derived from a monomer having a hydroxyl group" refers to a structural unit formed by addition polymerization of a monomer having a hydroxyl group.

具有羥基之單體的種類並無特別限定。 作為具有羥基之單體，可列舉例如：1分子中具有至少1個羥基與乙烯屬不飽和基的單體。 作為乙烯屬不飽和基，並無特別限定，可列舉例如：乙烯基、烯丙基、乙烯基苯基、(甲基)丙烯醯胺基、及(甲基)丙烯醯基。 作為乙烯屬不飽和基，較佳為(甲基)丙烯醯基。 The type of monomer having a hydroxyl group is not particularly limited. Examples of the monomer having a hydroxyl group include monomers having at least one hydroxyl group and an ethylenically unsaturated group per molecule. The ethylenically unsaturated group is not particularly limited, and examples thereof include vinyl, allyl, vinylphenyl, (meth)acrylamide, and (meth)acrylyl. As the ethylenically unsaturated group, a (meth)acrylyl group is preferred.

作為具有羥基之單體的具體例，可列舉：(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-2-羥丙酯、(甲基)丙烯酸-3-羥丙酯、(甲基)丙烯酸-4-羥丁酯、(甲基)丙烯酸-6-羥己酯、(甲基)丙烯酸-10-羥癸酯、(甲基)丙烯酸-12-羥基月桂酯、3-甲基-3-羥丁基(甲基)丙烯酸酯、1,1-二甲基-3-羥丁基(甲基)丙烯酸酯、1,3-二甲基-3-羥丁基(甲基)丙烯酸酯、2,2,4-三甲基-3-羥戊基(甲基)丙烯酸酯、2-乙基-3-羥己基(甲基)丙烯酸酯、N-羥乙基(甲基)丙烯醯胺、丙三醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯及聚(乙二醇-丙二醇)單(甲基)丙烯酸酯。 具有羥基之單體，例如從與其他單體之共聚合性良好的點來看，較佳為(甲基)丙烯酸羥烷酯。作為(甲基)丙烯酸羥烷酯，較佳為具有碳數為2～4之羥烷基的(甲基)丙烯酸羥烷酯，更佳為丙烯酸2-羥乙酯。 Specific examples of the monomer having a hydroxyl group include: (2-hydroxyethylmeth)acrylate, 2-hydroxypropyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, 3-methyl hydroxy-3-hydroxybutyl (meth)acrylate, 1,1-dimethyl-3-hydroxybutyl (meth)acrylate, 1,3-dimethyl-3-hydroxybutyl (meth)acrylate ) acrylate, 2,2,4-trimethyl-3-hydroxypentyl (meth)acrylate, 2-ethyl-3-hydroxyhexyl (meth)acrylate, N-hydroxyethyl (meth)acrylate ) Acrylamide, glycerol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate and poly(ethylene glycol-propylene glycol) mono(meth)acrylate )Acrylate. The monomer having a hydroxyl group is preferably hydroxyalkyl (meth)acrylate from the viewpoint of good copolymerizability with other monomers. As the hydroxyalkyl (meth)acrylate, a hydroxyalkyl (meth)acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms is preferred, and 2-hydroxyethyl acrylate is more preferred.

特定(甲基)丙烯酸系聚合物包含源自具有羥基之單體的構成單元時，可僅包含1種源自具有羥基之單體的構成單元，亦可包含2種以上。When the specific (meth)acrylic polymer contains a structural unit derived from a monomer having a hydroxyl group, only one type of structural unit derived from a monomer having a hydroxyl group may be included, or two or more types may be included.

特定(甲基)丙烯酸系聚合物包含源自具有羥基之單體的構成單元時，特定(甲基)丙烯酸系聚合物中的源自具有羥基之單體的構成單元之含有率並無特別限定，例如，相對於特定(甲基)丙烯酸系聚合物的所有構成單元，較佳為0.01質量%～3.0質量%，更佳為0.03質量%～1.5質量%，再佳為0.07質量%～0.7質量%，特佳為0.1質量%～0.4質量%。When the specific (meth)acrylic polymer contains a structural unit derived from a monomer having a hydroxyl group, the content rate of the structural unit derived from a monomer having a hydroxyl group in the specific (meth)acrylic polymer is not particularly limited. , for example, based on all the structural units of the specific (meth)acrylic polymer, it is preferably 0.01 mass% to 3.0 mass%, more preferably 0.03 mass% to 1.5 mass%, and still more preferably 0.07 mass% to 0.7 mass%. %, particularly preferably 0.1 mass% to 0.4 mass%.

＜其他構成單元＞ 作為特定(甲基)丙烯酸系聚合物可包含的其他構成單元，可列舉：源自以(甲基)丙烯酸苄酯及(甲基)丙烯酸苯氧基乙酯為代表的具有芳香族環之(甲基)丙烯酸酯的構成單+元；源自以(甲基)丙烯酸甲氧基乙酯及(甲基)丙烯酸乙氧基乙酯為代表的(甲基)丙烯酸烷氧基烷酯的構成單元；源自以苯乙烯、α-甲基苯乙烯、三級丁基苯乙烯、對氯苯乙烯、氯甲基苯乙烯、乙烯基甲苯為代表的芳香族單乙烯基的構成單元；源自以丙烯腈及甲基丙烯腈為代表的氰化乙烯基的構成單元；源自以甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯及新癸酸乙烯酯為代表的乙烯酯的構成單元等。 ＜Other structural units＞ Examples of other structural units that the specific (meth)acrylic polymer may include include those derived from (meth)acrylic acid benzyl ester and (meth)acrylic acid phenoxyethyl ester having an aromatic ring. The constituent unit of meth)acrylate; derived from the composition of alkoxyalkyl (meth)acrylate represented by methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate Unit; a structural unit derived from aromatic monovinyl groups represented by styrene, α-methylstyrene, tertiary butylstyrene, p-chlorostyrene, chloromethylstyrene, and vinyltoluene; derived from Structural units of cyanide vinyl groups represented by acrylonitrile and methacrylonitrile; structural units derived from vinyl esters represented by vinyl formate, vinyl acetate, vinyl propionate and vinyl neodecanoate, etc.

特定(甲基)丙烯酸系聚合物包含其他構成單元時，可僅包含1種其他構成單元，亦可包含2種以上。When the specific (meth)acrylic polymer contains other structural units, only one type of other structural units may be included, or two or more types may be included.

特定(甲基)丙烯酸系聚合物包含其他構成單元時，特定(甲基)丙烯酸系聚合物中的其他構成單元的含有率可在無損本揭示的黏著劑組成物之效果的範圍內適當設定。When the specific (meth)acrylic polymer contains other structural units, the content rate of the other structural units in the specific (meth)acrylic polymer can be appropriately set within a range that does not impair the effect of the adhesive composition of the present disclosure.

-特定(甲基)丙烯酸系聚合物的酸價- 特定(甲基)丙烯酸系聚合物的酸價並無特別限定，例如較佳為0.8mgKOH/g～24.0mgKOH/g，更佳為3.5mgKOH/g～20.0mgKOH/g，再佳為5.0mgKOH/g～15.0mgKOH/g，特佳為5.0mgKOH/g～9.0mgKOH/g。 若特定(甲基)丙烯酸系聚合物的酸價在上述範圍內，則有容易形成即使放置於重複低溫與高溫的環境下時亦不易產生皺褶及剝離的黏著劑層的傾向。其理由推測係藉由特定(甲基)丙烯酸系聚合物與多異氰酸酯系化合物的交聯反應而形成的三維網狀結構部分進一步適當地變得緻密，藉此對於所形成之黏著劑層賦予更適當的硬度。 -Acid value of specific (meth)acrylic polymer- The acid value of the specific (meth)acrylic polymer is not particularly limited, but for example, it is preferably 0.8 mgKOH/g to 24.0 mgKOH/g, more preferably 3.5 mgKOH/g to 20.0 mgKOH/g, and still more preferably 5.0 mgKOH/g. g～15.0mgKOH/g, particularly preferably 5.0mgKOH/g～9.0mgKOH/g. When the acid value of the specific (meth)acrylic polymer is within the above range, there is a tendency to easily form an adhesive layer that is less prone to wrinkles and peeling even when left in an environment where low and high temperatures are repeated. The reason for this is presumed to be that the three-dimensional network structure portion formed by the cross-linking reaction of the specific (meth)acrylic polymer and the polyisocyanate compound becomes more appropriately dense, thereby imparting more strength to the formed adhesive layer. Proper hardness.

特定(甲基)丙烯酸系聚合物的酸價係以下述計算式求出的值。另外，下述計算式中，56.1係KOH的分子量。由計算所得之值，係將小數點以下第2位四捨五入，以作為特定(甲基)丙烯酸系聚合物的酸價。 酸價(單位：mgKOH/g)={(a1/100)÷a2}×56.1×1000×a3 a1：用於製造特定(甲基)丙烯酸系聚合物的所有單體中，具有羧基之單體所占的比例(單位：質量%) a2：用於製造特定(甲基)丙烯酸系聚合物的具有羧基之單體的分子量 a3：具有羧基之單體1分子中所包含的羧基數量 The acid value of a specific (meth)acrylic polymer is a value calculated by the following calculation formula. In addition, in the following calculation formula, 56.1 represents the molecular weight of KOH. The calculated value is rounded off to the second decimal place as the acid value of the specific (meth)acrylic polymer. Acid value (unit: mgKOH/g)={(a1/100)÷a2}×56.1×1000×a3 a1: Proportion of monomers with carboxyl groups among all monomers used to produce specific (meth)acrylic polymers (unit: mass %) a2: Molecular weight of the monomer having a carboxyl group used to produce a specific (meth)acrylic polymer a3: The number of carboxyl groups contained in 1 molecule of the monomer with carboxyl groups

用於製造特定(甲基)丙烯酸系聚合物的具有羧基之單體具有2種以上時，依照上述計算式針對各單體求出酸價後，再將所得的值加總。將所得的加總值作為特定(甲基)丙烯酸系聚合物的酸價。When there are two or more types of monomers having carboxyl groups used to produce a specific (meth)acrylic polymer, the acid value of each monomer is determined according to the above calculation formula, and then the obtained values are added together. The obtained total value was defined as the acid value of the specific (meth)acrylic polymer.

本揭示的黏著劑組成物包含2種以上的特定(甲基)丙烯酸系聚合物時，本揭示的黏著劑組成物中的特定(甲基)丙烯酸系聚合物的酸價係指各特定(甲基)丙烯酸系聚合物之酸價的加權平均值。When the adhesive composition of the present disclosure contains two or more specific (meth)acrylic polymers, the acid value of the specific (meth)acrylic polymers in the adhesive composition of the present disclosure refers to the acid value of each specific (meth)acrylic polymer. The weighted average value of the acid value of the acrylic polymer.

-特定(甲基)丙烯酸系聚合物的玻璃轉移溫度- 特定(甲基)丙烯酸系聚合物的玻璃轉移溫度(亦稱為「Tg」)並無特別限定，例如較佳為-70℃～0℃，更佳為-70℃～-10℃，再佳為-70℃～-20℃，特佳為-70℃～-30℃。 若特定(甲基)丙烯酸系聚合物的玻璃轉移溫度在上述範圍內，則有可形成具有更適當之黏著力的黏著劑層的傾向。 -Glass transition temperature of specific (meth)acrylic polymer- The glass transition temperature (also referred to as "Tg") of a specific (meth)acrylic polymer is not particularly limited. For example, it is preferably -70°C to 0°C, more preferably -70°C to -10°C, and still more preferably -70℃～-20℃, especially -70℃～-30℃. If the glass transition temperature of the specific (meth)acrylic polymer is within the above range, an adhesive layer having more appropriate adhesive force will tend to be formed.

特定(甲基)丙烯酸系聚合物的玻璃轉移溫度，係將由下式1計算而求出的絕對溫度(單位：K)換算成攝氏溫度(單位：℃)所得的值。 1/Tg=m1/Tg1+m2/Tg2+･･･+m(k-1)/Tg(k-1)+mk/Tgk       (式1) The glass transition temperature of a specific (meth)acrylic polymer is a value obtained by converting the absolute temperature (unit: K) calculated by the following formula 1 into a Celsius temperature (unit: °C). 1/Tg=m1/Tg1+m2/Tg2+･･･+m(k-1)/Tg(k-1)+mk/Tgk (Formula 1)

式1中，Tg1、Tg2、･･･、Tg(k-1)及Tgk分別表示以構成特定(甲基)丙烯酸系聚合物的各單體作為均聚物時的絕對溫度所示的玻璃轉移溫度。m1、m2、･･･、m(k-1)及mk分別表示構成特定(甲基)丙烯酸系聚合物的各單體之莫耳分率，m1+m2+･･･+m(k-1)+mk=1。 另外，藉由從絕對溫度減去273，可將絕對溫度換算成攝氏溫度，藉由將攝氏溫度加上273，可將攝氏溫度換算成絕對溫度。 In Formula 1, Tg1, Tg2, ･･･, Tg(k-1), and Tgk respectively represent the glass transition expressed by the absolute temperature when each monomer constituting the specific (meth)acrylic polymer is used as a homopolymer. temperature. m1, m2, ･･･, m(k-1) and mk respectively represent the molar fraction of each monomer constituting a specific (meth)acrylic polymer, m1+m2+･･･+m(k-1 )+mk=1. Additionally, the absolute temperature can be converted to Celsius by subtracting 273 from the absolute temperature, and the Celsius temperature can be converted to absolute temperature by adding 273 to the Celsius temperature.

本揭示中的「作為均聚物時的玻璃轉移溫度」，係採用公知資料中記載的值，或使用差示掃描熱量測量裝置(DSC)測量的值。採用何值，具體如以下所述。The "glass transition temperature when used as a homopolymer" in this disclosure adopts the value described in publicly known materials or the value measured using a differential scanning calorimetry device (DSC). Which value to use is described below.

關於以下所示之單體的「作為均聚物時的玻璃轉移溫度」，分別採用記載的值。 丙烯酸2-乙基己酯：-70℃，甲基丙烯酸2-乙基己酯：-10℃，丙烯酸正丁酯：-54℃，甲基丙烯酸正丁酯：20℃，丙烯酸三級丁酯：43℃，甲基丙烯酸三級丁酯：118℃，甲基丙烯酸異丁酯：53℃，丙烯酸甲酯：10℃，甲基丙烯酸甲酯：105℃，丙烯酸乙酯：-22℃，甲基丙烯酸乙酯：65℃，甲基丙烯酸：228℃，丙烯酸4-羥基丁酯：-80℃，丙烯酸2-羥乙酯：-15℃，甲基丙烯酸2-羥乙酯：85℃，丙烯酸：106℃，丙烯酸正辛酯：-65℃，丙烯酸硬脂酯：30℃，甲基丙烯酸硬脂酯：38℃，丙烯酸月桂酯：-3℃，甲基丙烯酸月桂酯：-65℃，甲基丙烯酸二甲胺基乙酯：18℃，ω-羧基-多己內酯(n≒2)單丙烯酸酯：-30℃，丙烯酸苯氧基乙酯：-22℃。 Regarding the "glass transition temperature when used as a homopolymer" of the monomers shown below, the values described are adopted respectively. 2-ethylhexyl acrylate: -70℃, 2-ethylhexyl methacrylate: -10℃, n-butyl acrylate: -54℃, n-butyl methacrylate: 20℃, tertiary butyl acrylate : 43℃, tertiary butyl methacrylate: 118℃, isobutyl methacrylate: 53℃, methyl acrylate: 10℃, methyl methacrylate: 105℃, ethyl acrylate: -22℃, A Ethyl acrylate: 65℃, methacrylic acid: 228℃, 4-hydroxybutyl acrylate: -80℃, 2-hydroxyethyl acrylate: -15℃, 2-hydroxyethyl methacrylate: 85℃, acrylic acid : 106℃, n-octyl acrylate: -65℃, stearyl acrylate: 30℃, stearyl methacrylate: 38℃, lauryl acrylate: -3℃, lauryl methacrylate: -65℃, Dimethylaminoethyl acrylate: 18°C, ω-carboxy-polycaprolactone (n≒2) monoacrylate: -30°C, phenoxyethyl acrylate: -22°C.

關於上述單體以外之單體的「作為均聚物時的玻璃轉移溫度」，係採用聚合物手冊(第4版，Wiley-Interscience；以下相同)記載的值，聚合物手冊中未記載的情況，則採用以下述測量方法所得之均聚物的玻璃轉移溫度的值。Regarding the "glass transition temperature when used as a homopolymer" of monomers other than the above-mentioned monomers, the values described in the Polymer Handbook (4th edition, Wiley-Interscience; the same applies hereafter) are used, unless otherwise stated in the Polymer Handbook. , the value of the glass transition temperature of the homopolymer obtained by the following measurement method is used.

＜＜均聚物的玻璃轉移溫度的測量＞＞ 使用差示掃描熱量測量裝置(DSC)，在氮氣流中，以測量試料(亦即均聚物)10mg、升溫速度10℃/分鐘的條件進行測量，將所得之DSC曲線的反曲點作為均聚物的玻璃轉移溫度。 作為差示掃描熱量測量裝置，例如可適當地使用TA Instruments Japan股份有限公司製的差示掃描熱量計(商品名稱：Discovery DSC 2500)。惟差示掃描熱量測量裝置不限定於此。 ＜＜Measurement of glass transition temperature of homopolymer＞＞ Use a differential scanning calorimeter (DSC) to measure in a nitrogen flow under the conditions of 10 mg of the sample (i.e., homopolymer) and a heating rate of 10°C/min. The inflection point of the obtained DSC curve is taken as the average. The glass transition temperature of the polymer. As a differential scanning calorimeter measuring device, for example, a differential scanning calorimeter (trade name: Discovery DSC 2500) manufactured by TA Instruments Japan Co., Ltd. can be suitably used. However, the differential scanning calorimetry device is not limited to this.

特定(甲基)丙烯酸系聚合物的玻璃轉移溫度，例如可藉由使用2種以上作為均聚物時的玻璃轉移溫度不同的單體來適當調整。The glass transition temperature of a specific (meth)acrylic polymer can be appropriately adjusted, for example, by using two or more monomers having different glass transition temperatures when used as homopolymers.

-特定(甲基)丙烯酸系聚合物的重量平均分子量- 特定(甲基)丙烯酸系聚合物的重量平均分子量(以下亦稱為「Mw」)並無特別限定，例如較佳為90萬～250萬，更佳為110萬～250萬，再佳為130萬～250萬，特佳為150萬～250萬。 若特定(甲基)丙烯酸系聚合物的重量平均分子量在90萬以上，有容易形成即使放置於重複低溫與高溫的環境下時亦不易產生皺褶及剝離的黏著劑層的傾向。 若特定(甲基)丙烯酸系聚合物的重量平均分子量在250萬以下，有黏著劑組成物的黏度不會過度上升，黏著劑組成物的塗布性變得更良好的傾向。 -Weight average molecular weight of specific (meth)acrylic polymer- The weight average molecular weight (hereinafter also referred to as "Mw") of the specific (meth)acrylic polymer is not particularly limited, but for example, it is preferably 900,000 to 2.5 million, more preferably 1.1 million to 2.5 million, and still more preferably 1.30 Ten thousand to 2.5 million, the best is 1.5 million to 2.5 million. If the weight average molecular weight of the specific (meth)acrylic polymer is 900,000 or more, there is a tendency to form an adhesive layer that is less likely to wrinkle and peel even if it is left in an environment where low and high temperatures are repeated. If the weight average molecular weight of the specific (meth)acrylic polymer is 2.5 million or less, the viscosity of the adhesive composition will not increase excessively, and the coatability of the adhesive composition will tend to become better.

特定(甲基)丙烯酸系聚合物的重量平均分子量係以下述方法測量的值。具體係依照下述(1)～(3)進行測量。 (1)將特定(甲基)丙烯酸系聚合物的溶液塗布於剝離紙，於100℃乾燥1分鐘，得到膜狀的特定(甲基)丙烯酸系聚合物。 (2)使用上述(1)所得之膜狀的特定(甲基)丙烯酸系聚合物與四氫呋喃，得到固體成分濃度為0.2質量%的試料溶液。另外，此處所述的「固體成分濃度」，係指特定(甲基)丙烯酸系聚合物在試料溶液中所占的質量比例。 (3)藉由下述條件的凝膠滲透層析法(GPC)，作為標準聚苯乙烯換算值，求出特定(甲基)丙烯酸系聚合物的重量平均分子量。 The weight average molecular weight of a specific (meth)acrylic polymer is a value measured by the following method. Specifically, the measurement is performed according to the following (1) to (3). (1) A solution of a specific (meth)acrylic polymer is applied to release paper and dried at 100° C. for 1 minute to obtain a film-like specific (meth)acrylic polymer. (2) Using the specific film-like (meth)acrylic polymer obtained in (1) above and tetrahydrofuran, a sample solution having a solid content concentration of 0.2 mass % was obtained. In addition, the "solid content concentration" mentioned here refers to the mass ratio of the specific (meth)acrylic polymer in the sample solution. (3) Determine the weight average molecular weight of the specific (meth)acrylic polymer as a standard polystyrene-converted value by gel permeation chromatography (GPC) under the following conditions.

～條件～ 測量裝置：高速GPC[型號：HLC-8220 GPC，東曹股份有限公司製] 檢測器：差示折射率計(RI)[組裝至HLC-8220，東曹股份有限公司製] 管柱：使用4支TSKgel GMH XL[東曹股份有限公司製] 管柱溫度：40℃ 溶離液：四氫呋喃 試料溶液的注入量：100μL 流量：0.8mL/分鐘 ~Conditions~ Measuring device: High-speed GPC [Model: HLC-8220 GPC, manufactured by Tosoh Corporation] Detector: Differential refractometer (RI) [Assembled into HLC-8220, manufactured by Tosoh Corporation] Column : Use 4 tubes of TSKgel GMH XL [manufactured by Tosoh Co., Ltd.] Column temperature: 40°C Eluate: Injection volume of tetrahydrofuran sample solution: 100 μL Flow rate: 0.8 mL/min

特定(甲基)丙烯酸系聚合物的重量平均分子量，可藉由在使單體聚合時調整聚合溫度、聚合時間、有機溶劑的使用量、聚合起始劑的種類、聚合起始劑的使用量等而成為預期的值。The weight average molecular weight of a specific (meth)acrylic polymer can be determined by adjusting the polymerization temperature, polymerization time, usage amount of organic solvent, type of polymerization initiator, and usage amount of polymerization initiator when polymerizing monomers. etc. to become the expected value.

-特定(甲基)丙烯酸系聚合物的含有率- 本揭示的黏著劑組成物中的特定(甲基)丙烯酸系聚合物的含有率並無特別限定，例如，相對於黏著劑組成物中的所有固體成分量，較佳為80.0質量%～99.9質量%，更佳為85.0質量%～99.7質量%，再佳為89.0質量%～99.5質量%。 -Content rate of specific (meth)acrylic polymer- The content rate of the specific (meth)acrylic polymer in the adhesive composition of the present disclosure is not particularly limited. For example, it is preferably 80.0 mass % to 99.9 mass % based on the total solid content in the adhesive composition. %, more preferably 85.0 mass% to 99.7 mass%, still more preferably 89.0 mass% to 99.5 mass%.

本揭示中，所謂的「黏著劑組成物中的所有固體成分量」，在黏著劑組成物不包含溶劑的情況，係指黏著劑組成物的總質量，在黏著劑組成物包含溶劑的情況，係指從黏著劑組成物去除溶劑而得之殘渣的質量。 本揭示中，所謂的「溶劑」係指水及有機溶劑。 In this disclosure, the so-called "amount of all solid components in the adhesive composition" refers to the total mass of the adhesive composition when the adhesive composition does not contain a solvent. When the adhesive composition contains a solvent, Refers to the mass of the residue obtained by removing the solvent from the adhesive composition. In this disclosure, the so-called "solvent" refers to water and organic solvents.

[特定(甲基)丙烯酸系聚合物的製造方法] 特定(甲基)丙烯酸系聚合物的製造方法並無特別限定。 特定(甲基)丙烯酸系聚合物例如可藉由以溶液聚合法、乳化聚合法、懸浮聚合法及塊狀聚合法為代表的習知聚合方法將上述單體聚合而製造。 作為聚合方法，從在製造後製備黏著劑組成物時處理步驟較簡單且可以短時間進行的觀點來看，較佳為溶液聚合法。 [Production method of specific (meth)acrylic polymer] The production method of the specific (meth)acrylic polymer is not particularly limited. The specific (meth)acrylic polymer can be produced by polymerizing the above-mentioned monomers by a conventional polymerization method represented by solution polymerization, emulsion polymerization, suspension polymerization, and block polymerization. As a polymerization method, a solution polymerization method is preferable from the viewpoint that the processing steps when preparing the adhesive composition after production are simple and can be performed in a short time.

溶液聚合法中，一般係在聚合槽內置入既定的有機溶劑、單體、聚合起始劑、及因應需求使用的鏈轉移劑，例如在有機溶劑的回流溫度下，一邊攪拌一邊使其加熱反應數小時。此情況中，亦可逐次添加有機溶劑、單體、聚合起始劑、及因應需求使用的鏈轉移劑的至少一部分。又，亦可在氮氣流中使其反應。In the solution polymerization method, a predetermined organic solvent, monomer, polymerization initiator, and chain transfer agent are generally put into the polymerization tank, and the chain transfer agent is used according to the needs. For example, the organic solvent is heated at the reflux temperature while stirring. Reaction takes several hours. In this case, at least part of the organic solvent, monomer, polymerization initiator, and chain transfer agent used as required may also be added in sequence. Alternatively, the reaction may be carried out in a nitrogen flow.

作為聚合反應時所使用的有機溶劑，可列舉例如：芳香族烴化合物、脂肪族系烴化合物、脂環族系烴化合物、酯化合物、酮化合物、二醇醚化合物及醇化合物。作為聚合反應時所使用的有機溶劑，更具體而言，可列舉例如：苯、甲苯、乙苯、正丙苯、三級丁苯、鄰二甲苯、間二甲苯、對二甲苯、四氫萘、十氫萘及芳香族石油腦為代表的芳香族烴化合物、正己烷、正庚烷、正辛烷、異辛烷、正癸烷，雙戊烯、石油精(petroleum spirit)、石腦油(naphtha)、及松節油(turpentine)為代表的脂肪族系或脂環族系烴化合物、乙酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸正戊酯、乙酸2-羥乙酯、乙酸2-丁氧基乙酯、乙酸3-甲氧基丁酯、及苯甲酸甲酯為代表的酯化合物、丙酮、甲乙酮、甲基異丁基酮、異佛爾酮、環己酮及甲基環己酮為代表的酮化合物、乙二醇單甲醚、乙二醇單***、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單***及二乙二醇單丁醚為代表的二醇醚化合物及以甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、二級丁醇及三級丁醇為代表的醇化合物。Examples of the organic solvent used in the polymerization reaction include aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, alicyclic hydrocarbon compounds, ester compounds, ketone compounds, glycol ether compounds, and alcohol compounds. More specific examples of the organic solvent used in the polymerization reaction include benzene, toluene, ethylbenzene, n-propylbenzene, tertiary butylbenzene, o-xylene, m-xylene, p-xylene, and tetralin. , aromatic hydrocarbon compounds represented by decalin and aromatic naphtha, n-hexane, n-heptane, n-octane, isooctane, n-decane, dipentene, petroleum spirit (petroleum spirit), naphtha (naphtha), and turpentine (turpentine), aliphatic or alicyclic hydrocarbon compounds, methyl acetate, ethyl acetate, n-butyl acetate, n-amyl acetate, 2-hydroxyethyl acetate, acetic acid 2 -Ester compounds represented by butoxyethyl ester, 3-methoxybutyl acetate, and methyl benzoate, acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, and methyl ring Ketone compounds represented by hexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether Glycol ether compounds represented by and alcohol compounds represented by methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol and tertiary butanol.

在製造特定(甲基)丙烯酸系聚合物時，較佳係使用芳香族烴化合物、酯化合物、酮化合物等不易在聚合反應中發生鏈轉移的有機溶劑，尤其從特定(甲基)丙烯酸系聚合物的溶解性、聚合反應的容易性等觀點來看，較佳係使用乙酸乙酯。When producing specific (meth)acrylic polymers, it is preferable to use aromatic hydrocarbon compounds, ester compounds, ketone compounds and other organic solvents that are difficult to undergo chain transfer during the polymerization reaction, especially from specific (meth)acrylic polymers. From the viewpoint of the solubility of the substance and the ease of polymerization reaction, ethyl acetate is preferably used.

聚合反應時，可僅使用1種有機溶劑，亦可使用2種以上。During the polymerization reaction, only one type of organic solvent may be used, or two or more types may be used.

作為聚合起始劑，可列舉例如：一般溶液聚合法中所使用的有機過氧化物及偶氮化物。 作為有機過氧化物的具體例，可列舉：過氧化-2-乙基己酸三級丁酯、三級丁基過氧化氫、異丙苯過氧化氫、過氧化二異丙苯、過氧化苯甲醯、過氧化月桂醯、過氧化己醯、過氧化二碳酸二異丙酯、過氧化二碳酸二-2-乙基己酯、過氧化三甲基乙酸三級丁酯、2,2-雙(4,4-二-三級丁基過氧基環己基)丙烷、2,2-雙(4,4-二-三級戊基過氧化環己基)丙烷、2,2-雙(4,4-二-三級辛基過氧化環己基)丙烷、2,2-雙(4,4-二-α-異丙苯基過氧化環己基)丙烷、2,2-雙(4,4-二-三級丁基過氧化環己基)丁烷、及2,2-雙(4,4-二-三級辛基過氧化環己基)丁烷。 作為偶氮化物的具體例，可列舉：2,2’-偶氮雙異丁腈[AIBN]、2,2’-偶氮雙(2,4-二甲基戊腈)[ABVN]、2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、1,1’-偶氮雙(環己烷-1-甲腈)及2,2’-偶氮雙(異丁酸)二甲酯。 Examples of the polymerization initiator include organic peroxides and azo compounds used in general solution polymerization methods. Specific examples of organic peroxides include: tertiary butyl peroxy-2-ethylhexanoate, tertiary butyl hydroperoxide, cumene hydroperoxide, dicumyl peroxide, and peroxide. Benzyl peroxide, lauryl peroxide, hexyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, tertiary butyl peroxytrimethylacetate, 2,2 -Bis(4,4-di-tertiary butylperoxycyclohexyl)propane, 2,2-bis(4,4-di-tertiary pentylperoxycyclohexyl)propane, 2,2-bis( 4,4-Di-tertiary octylperoxycyclohexyl)propane, 2,2-bis(4,4-di-α-cumylperoxycyclohexyl)propane, 2,2-bis(4, 4-di-tertiary butylperoxycyclohexyl)butane, and 2,2-bis(4,4-di-tertiary octylperoxycyclohexyl)butane. Specific examples of azo compounds include: 2,2'-azobisisobutyronitrile [AIBN], 2,2'-azobis(2,4-dimethylvaleronitrile) [ABVN], 2 ,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-Azobis(cyclohexane-1-carbonitrile) and 2,2'-Azobis(cyclohexane-1-carbonitrile) Azobis(isobutyrate)dimethyl ester.

聚合反應時，可僅使用1種聚合起始劑，亦可使用2種以上。During the polymerization reaction, only one type of polymerization initiator may be used, or two or more types may be used.

聚合起始劑的使用量並無特別限定，例如可因應目標的特定(甲基)丙烯酸系聚合物之分子量適當設定。The usage amount of the polymerization initiator is not particularly limited, and can be appropriately set according to the molecular weight of the target specific (meth)acrylic polymer, for example.

在製造特定(甲基)丙烯酸系聚合物時，亦可因應需求使用鏈轉移劑。 作為鏈轉移劑，可列舉例如：氰基乙酸、氰基乙酸的碳數1～8的烷酯化合物、溴乙酸、溴乙酸的碳數1～8的烷酯化合物、以α-甲基苯乙烯、蒽、菲、茀及9-苯基茀為代表的芳香族化合物、以對硝基苯胺、硝基苯、二硝基苯、對硝基苯甲酸、對硝基酚及對硝基甲苯為代表的芳香族硝基化合物、苯醌及2,3,5,6-四甲基對苯醌為代表的苯醌衍生物、以三丁基硼烷為代表的硼烷衍生物、以四溴化碳、四氯化碳、1,1,2,2-四溴乙烷、三溴乙烯、三氯乙烯、溴三氯甲烷、三溴甲烷及3-氯-1-丙烯為代表的鹵化烴化合物、以氯醛及呋喃甲醛為代表的醛化合物、碳數1～18的烷基硫醇化合物、以硫苯酚及甲苯硫醇為代表的芳香族硫醇化合物、巰基乙酸、巰基乙酸的碳數1～10之烷酯化合物、碳數1～12的羥基烷基硫醇化合物、以及以蒎烯及萜品油烯(terpinolene)為代表的萜化合物。 When manufacturing specific (meth)acrylic polymers, chain transfer agents can also be used according to needs. Examples of the chain transfer agent include: cyanoacetic acid, alkyl ester compounds having 1 to 8 carbon atoms of cyanoacetic acid, bromoacetic acid, alkyl ester compounds having 1 to 8 carbon atoms of bromoacetic acid, and α-methylstyrene. , anthracene, phenanthrene, fluorine and 9-phenyl fluoride are represented by aromatic compounds, including p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol and p-nitrotoluene. Representative aromatic nitro compounds, benzoquinone derivatives represented by benzoquinone and 2,3,5,6-tetramethylp-benzoquinone, borane derivatives represented by tributylborane, tetrabromoquinone represented by Halogenated hydrocarbon compounds represented by carbon dioxide, carbon tetrachloride, 1,1,2,2-tetrabromoethane, tribromoethylene, trichloroethylene, bromochloroform, tribromoform and 3-chloro-1-propene , aldehyde compounds represented by chloral and furancarbaldehyde, alkyl mercaptan compounds with 1 to 18 carbon atoms, aromatic thiol compounds represented by thiophenol and toluenethiol, thioglycolic acid, carbon number 1 of thioglycolic acid ~10 alkyl ester compounds, hydroxyalkylthiol compounds with 1 to 12 carbon atoms, and terpene compounds represented by pinene and terpinolene.

在製造特定(甲基)丙烯酸系聚合物時使用鏈轉移劑的情況，鏈轉移劑的使用量並無特別限定，例如可因應目標的特定(甲基)丙烯酸系聚合物的分子量適當設定。When a chain transfer agent is used in the production of a specific (meth)acrylic polymer, the amount of the chain transfer agent used is not particularly limited. For example, it can be appropriately set according to the molecular weight of the target specific (meth)acrylic polymer.

聚合溫度並無特別限定，例如可因應目標的特定(甲基)丙烯酸系聚合物的分子量適當設定。The polymerization temperature is not particularly limited, and can be appropriately set according to the molecular weight of the target specific (meth)acrylic polymer, for example.

[多異氰酸酯系化合物] 本揭示的黏著劑組成物包含多異氰酸酯系化合物。 多異氰酸酯系化合物，只要係1分子中具有2個以上之異氰酸酯基的化合物即可，其種類並無特別限定。 作為多異氰酸酯系化合物，可列舉例如：脂肪族多異氰酸酯系化合物、脂環族多異氰酸酯系化合物及芳香族多異氰酸酯系化合物。 [Polyisocyanate compound] The adhesive composition of the present disclosure contains a polyisocyanate compound. The type of the polyisocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups in one molecule. Examples of the polyisocyanate-based compound include aliphatic polyisocyanate-based compounds, alicyclic polyisocyanate-based compounds, and aromatic polyisocyanate-based compounds.

「脂肪族多異氰酸酯系化合物」包含例如脂肪族多異氰酸酯化合物、脂肪族多異氰酸酯化合物的多聚物、脂肪族多異氰酸酯化合物與多元醇系化合物[例如三羥甲基丙烷(TMP)；以下相同]的加成物、及脂肪族多異氰酸酯化合物的縮二脲體。 作為脂肪族多異氰酸酯化合物的具體例，可列舉：六亞甲基二異氰酸酯(HMDI)、五亞甲基二異氰酸酯(PDI)、四亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯及離胺酸二異氰酸酯。 "Aliphatic polyisocyanate compound" includes, for example, an aliphatic polyisocyanate compound, a polymer of an aliphatic polyisocyanate compound, an aliphatic polyisocyanate compound, and a polyol compound [for example, trimethylolpropane (TMP); the same applies below] adducts, and biurets of aliphatic polyisocyanate compounds. Specific examples of aliphatic polyisocyanate compounds include hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate (PDI), tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, and Lysine diisocyanate.

「脂環族多異氰酸酯系化合物」包含例如脂環族多異氰酸酯化合物、脂環族多異氰酸酯化合物的多聚物、脂環族多異氰酸酯化合物與多元醇系化合物的加成物、及脂環族多異氰酸酯化合物的縮二脲體。 作為脂環族多異氰酸酯化合物的具體例，可列舉：異佛爾酮二異氰酸酯(IPDI)、氫化甲苯二異氰酸酯、氫化二甲苯二異氰酸酯、氫化4,4’-二苯基甲烷二異氰酸酯、及4,4’-二環己基甲烷二異氰酸酯。 "Alicyclic polyisocyanate-based compound" includes, for example, alicyclic polyisocyanate compounds, polymers of alicyclic polyisocyanate compounds, adducts of alicyclic polyisocyanate compounds and polyol-based compounds, and alicyclic polyisocyanate compounds. Biuret form of isocyanate compound. Specific examples of the alicyclic polyisocyanate compound include isophorone diisocyanate (IPDI), hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, and 4 ,4'-dicyclohexylmethane diisocyanate.

「芳香族多異氰酸酯系化合物」包含例如芳香族多異氰酸酯化合物、芳香族多異氰酸酯化合物的多聚物、芳香族多異氰酸酯化合物與多元醇系化合物的加成物、及芳香族多異氰酸酯化合物的縮二脲體。 作為芳香族多異氰酸酯化合物的具體例，可列舉：甲苯二異氰酸酯(TDI)、苯二甲基二異氰酸酯(XDI)、及4,4’-二苯基甲烷二異氰酸酯。 "Aromatic polyisocyanate compound" includes, for example, aromatic polyisocyanate compounds, polymers of aromatic polyisocyanate compounds, adducts of aromatic polyisocyanate compounds and polyol compounds, and dicondensates of aromatic polyisocyanate compounds. Urea body. Specific examples of the aromatic polyisocyanate compound include toluene diisocyanate (TDI), xylylene diisocyanate (XDI), and 4,4'-diphenylmethane diisocyanate.

作為多異氰酸酯系化合物，較佳為芳香族多異氰酸酯系化合物，較佳係選自由甲苯二異氰酸酯系化合物及苯二甲基二異氰酸酯系化合物構成之群組中的至少1種。 「甲苯二異氰酸酯系化合物」包含例如TDI、TDI的多聚物、TDI與多元醇系化合物的加成物及TDI的縮二脲體。 作為甲苯二異氰酸酯系化合物，較佳為TDI與TMP的加成物。 「苯二甲基二異氰酸酯系化合物」包含例如XDI、XDI的多聚物、XDI與多元醇系化合物的加成物及XDI的縮二脲體。 作為苯二甲基二異氰酸酯系化合物，較佳為XDI與TMP的加成物。 The polyisocyanate compound is preferably an aromatic polyisocyanate compound, and preferably at least one selected from the group consisting of toluene diisocyanate compounds and xylylene diisocyanate compounds. The "toluene diisocyanate compound" includes, for example, TDI, a polymer of TDI, an adduct of TDI and a polyol compound, and a biuret body of TDI. As the toluene diisocyanate compound, an adduct of TDI and TMP is preferred. The "xylylene diisocyanate compound" includes, for example, XDI, a polymer of XDI, an adduct of XDI and a polyol compound, and a biuret body of XDI. As the xylylene diisocyanate compound, an adduct of XDI and TMP is preferred.

作為多異氰酸酯系化合物，可使用市售產品。 作為多異氰酸酯系化合物之市售產品的例子，可列舉：「CORONATE(註冊商標) HX」、「CORONATE(註冊商標) HL-S」、「CORONATE(註冊商標) L」、「CORONATE(註冊商標) L-45E」、「CORONATE(註冊商標) 2031」、「CORONATE(註冊商標) 2037」、「CORONATE(註冊商標) 2234」、「CORONATE(註冊商標) 2785」、「AQUANATE(註冊商標) 200」及「AQUANATE(註冊商標) 210」[以上為東曹股份有限公司製]、「SUMIDUR(註冊商標) N3300」、「DESMODUR(註冊商標) N3400」、及「SUMIDUR(註冊商標) N75」[以上為SUMIKA COVESTRO URETHANE股份有限公司製]、「DURANATE(註冊商標) D201」、「DURANATE(註冊商標) E405-70B」、「DURANATE(註冊商標) E405-80T」、「DURANATE(註冊商標) AE700-100」、「DURANATE (註冊商標) 24A-100」及「DURANATE (註冊商標)TSE-100」[以上為旭化成股份有限公司製]以及「TAKENATE(註冊商標) D-110N」、「TAKENATE (註冊商標) D-120N」、「TAKENATE (註冊商標)D-140N」、「TAKENATE (註冊商標) M-631N」、「MT-OLESTER(註冊商標) NP1200」及「STABiO(註冊商標) XD-340N」[以上為三井化學股份有限公司製]。 As the polyisocyanate-based compound, commercially available products can be used. Examples of commercially available polyisocyanate compounds include "CORONATE (registered trademark) HX", "CORONATE (registered trademark) HL-S", "CORONATE (registered trademark) L", "CORONATE (registered trademark) L-45E", "CORONATE (Registered Trademark) 2031", "CORONATE (Registered Trademark) 2037", "CORONATE (Registered Trademark) 2234", "CORONATE (Registered Trademark) 2785", "AQUANATE (Registered Trademark) 200" and "AQUANATE (registered trademark) 210" [the above is made by Tosoh Co., Ltd.], "SUMIDUR (registered trademark) N3300", "DESMODUR (registered trademark) N3400", and "SUMIDUR (registered trademark) N75" [the above is SUMIKA Made by COVESTRO URETHANE Co., Ltd.], "DURANATE (registered trademark) D201", "DURANATE (registered trademark) E405-70B", "DURANATE (registered trademark) E405-80T", "DURANATE (registered trademark) AE700-100", "DURANATE (registered trademark) 24A-100" and "DURANATE (registered trademark) TSE-100" [the above are manufactured by Asahi Kasei Co., Ltd.] and "TAKENATE (registered trademark) D-110N", "TAKENATE (registered trademark) D- 120N", "TAKENATE (Registered Trademark) D-140N", "TAKENATE (Registered Trademark) M-631N", "MT-OLESTER (Registered Trademark) NP1200" and "STABiO (Registered Trademark) XD-340N" [The above are Mitsui Chemical Co., Ltd.].

本揭示的黏著劑組成物可僅含1種多異氰酸酯系化合物，亦可包含2種以上。The adhesive composition of the present disclosure may contain only one type of polyisocyanate compound, or may contain two or more types.

相對於100質量份的特定(甲基)丙烯酸系聚合物，本揭示的黏著劑組成物中的多異氰酸酯系化合物的含量為0.1質量份～11.0質量份。 若本揭示的黏著劑組成物中的多異氰酸酯系化合物的含量相對於100質量份的特定(甲基)丙烯酸系聚合物為0.1質量份以上，則可形成能夠良好地抑制放置於高溫環境下時會發生的基材收縮的黏著劑層。其理由據推測係因為特定(甲基)丙烯酸系聚合物與多異氰酸酯系化合物的交聯反應所形成之三維網狀結構部分變得緻密，藉此對於所形成之黏著劑層賦予適當的高凝聚力。從這樣的觀點來看，相對於100質量份的特定(甲基)丙烯酸系聚合物，本揭示的黏著劑組成物中的多異氰酸酯系化合物的含量較佳為0.15質量份以上，更佳為0.3質量份以上，再佳為0.5質量份以上。 若本揭示的黏著劑組成物中的多異氰酸酯系化合物的含量相對於100質量份的特定(甲基)丙烯酸系聚合物為11.0質量份以下，可形成即使放置於重複低溫與高溫的環境下時亦不易產生皺褶及剝離的黏著劑層。推測其理由係因為特定(甲基)丙烯酸系聚合物與多異氰酸酯系化合物的交聯反應形成之三維網狀結構部分並未過度緻密，形成之黏著劑層變得適度柔軟。從這樣的觀點來看，相對於100質量份的特定(甲基)丙烯酸系聚合物，本揭示的黏著劑組成物中的多異氰酸酯系化合物的含量較佳為10.0質量份以下，更佳為8.0質量份以下，再佳為6.0質量份以下。 在一態樣中，相對於100質量份的特定(甲基)丙烯酸系聚合物，本揭示的黏著劑組成物中的多異氰酸酯系化合物的含量亦可為0.15質量份～10.0質量份，亦可為0.15質量份～8.0質量份，亦可為0.5質量份～8.0質量份，亦可為0.5質量份～6.0質量份，亦可為0.8質量份～6.0質量份。 The content of the polyisocyanate compound in the adhesive composition of the present disclosure is 0.1 to 11.0 parts by mass relative to 100 parts by mass of the specific (meth)acrylic polymer. If the content of the polyisocyanate compound in the adhesive composition of the present disclosure is 0.1 parts by mass or more based on 100 parts by mass of the specific (meth)acrylic polymer, the formation of polyisocyanate compound can be well suppressed when placed in a high temperature environment. Shrinkage of the adhesive layer on the substrate will occur. The reason for this is presumed to be that the three-dimensional network structure formed by the cross-linking reaction of a specific (meth)acrylic polymer and a polyisocyanate compound becomes partially dense, thereby imparting appropriately high cohesive force to the formed adhesive layer. . From this point of view, the content of the polyisocyanate compound in the adhesive composition of the present disclosure is preferably 0.15 parts by mass or more, more preferably 0.3 parts per mass part of the specific (meth)acrylic polymer. Parts by mass or more, preferably 0.5 parts by mass or more. If the content of the polyisocyanate compound in the adhesive composition of the present disclosure is 11.0 parts by mass or less based on 100 parts by mass of the specific (meth)acrylic polymer, it can form even when placed in an environment where low and high temperatures are repeated. It is also less likely to produce wrinkles and peeling adhesive layers. The reason is presumed to be that the three-dimensional network structure formed by the cross-linking reaction between the specific (meth)acrylic polymer and the polyisocyanate compound is not too dense, and the formed adhesive layer becomes moderately soft. From this point of view, the content of the polyisocyanate compound in the adhesive composition of the present disclosure is preferably 10.0 parts by mass or less, and more preferably 8.0 parts by mass relative to 100 parts by mass of the specific (meth)acrylic polymer. Parts by mass or less, preferably 6.0 parts by mass or less. In one aspect, the content of the polyisocyanate compound in the adhesive composition of the present disclosure may be 0.15 to 10.0 parts by mass relative to 100 parts by mass of the specific (meth)acrylic polymer. It may be 0.15-8.0 parts by mass, 0.5-8.0 parts by mass, 0.5-6.0 parts by mass, or 0.8-6.0 parts by mass.

[特定脂環族環氧系化合物] 本揭示的黏著劑組成物包含下式(I)表示的脂環族環氧系化合物[亦即特定脂環族環氧系化合物]。 [Specific alicyclic epoxy compound] The adhesive composition of the present disclosure contains an alicyclic epoxy compound represented by the following formula (I) [that is, a specific alicyclic epoxy compound].

[化4] [Chemical 4]

式(I)中，R表示具有酯鍵的2價有機連結基。 作為具有酯鍵的2價有機連結基，並無特別限定，例如除了酯鍵以外，可列舉1或2個以上的酯鍵與1或2個以上的2價烴基連結而成的基。 作為與酯鍵連結的2價烴基，可列舉例如：碳數1～18的直鏈狀或分支鏈狀的伸烷基、及2價的脂環族烴基。 In formula (I), R represents a divalent organic linking group having an ester bond. The divalent organic connecting group having an ester bond is not particularly limited, and examples thereof include, in addition to the ester bond, a group in which one or two or more ester bonds are connected to one or two or more divalent hydrocarbon groups. Examples of the divalent hydrocarbon group connected to the ester bond include a linear or branched alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group.

R表示的2價有機連結基具有酯鍵。 若特定脂環族環氧系化合物具有酯鍵，則特定脂環族環氧系化合物與特定(甲基)丙烯酸系聚合物的相容性提高，可對於黏著劑層的整體賦予因特定(甲基)丙烯酸系聚合物與特定脂環族環氧系化合物的交聯反應所形成的鬆散的三維網狀結構部分而來的柔軟性。結果推測，所形成之黏著劑層，即使放置於重複低溫與高溫的環境下時，亦不易產生皺褶及剝離。 The divalent organic linking group represented by R has an ester bond. If the specific alicyclic epoxy compound has an ester bond, the compatibility between the specific alicyclic epoxy compound and the specific (meth)acrylic polymer is improved, and the specific (meth)acrylic polymer can be imparted to the entire adhesive layer. The softness comes from the loose three-dimensional network structure formed by the cross-linking reaction of acrylic polymer and specific alicyclic epoxy compounds. The results indicate that the formed adhesive layer is not prone to wrinkles and peeling even when placed in environments with repeated low and high temperatures.

式(I)中的R表示的2價有機連結基的原子數並無特別限定，例如較佳為3以上，更佳為3～200，再佳為3～100，再更佳為，特佳為3～10。 若式(I)中的R表示的2價有機連結基的原子數為3以上，可形成放置於重複低溫與高溫的環境下時更不易產生皺褶及剝離的黏著劑層。推測其理由係因為特定(甲基)丙烯酸系聚合物與特定脂環族環氧系化合物的交聯反應形成的三維網狀結構部分更適當地變得鬆散，而對於所形成之黏著劑層賦予更適當的柔軟性。 本揭示中，「有機連結基的原子數」係指有機連結基中的主鏈之原子數。所謂「主鏈的原子數」，係指將式(I)中的2個脂環族環氧基彼此連結之原子鏈的原子數，並不包含取代基的原子數。例如，有機連結基中的主鏈包含「環己烷環」的情況，環己烷環部分的原子數係計算為「6」。 The number of atoms of the divalent organic linking group represented by R in formula (I) is not particularly limited. For example, it is preferably 3 or more, more preferably 3 to 200, still more preferably 3 to 100, still more preferably, and particularly preferably It is 3~10. If the number of atoms of the divalent organic linking group represented by R in formula (I) is 3 or more, an adhesive layer can be formed that is less likely to wrinkle and peel when placed in an environment where low and high temperatures are repeated. The reason for this is presumed to be that the three-dimensional network structure formed by the cross-linking reaction of the specific (meth)acrylic polymer and the specific alicyclic epoxy compound becomes looser more appropriately, and the formed adhesive layer is imparted with More appropriate softness. In this disclosure, "the number of atoms of the organic linking group" refers to the number of atoms of the main chain in the organic linking group. The so-called "number of atoms in the main chain" refers to the number of atoms in the atomic chain connecting the two alicyclic epoxy groups in formula (I), and does not include the number of atoms in the substituent. For example, when the main chain of the organic linking group contains a "cyclohexane ring", the number of atoms in the cyclohexane ring part is calculated as "6".

作為特定脂環族環氧系化合物，較佳為下式(II)表示的化合物。As the specific alicyclic epoxy compound, a compound represented by the following formula (II) is preferred.

[化5] [Chemistry 5]

式(II)中，n表示0～5的整數，較佳為0～4的整數，更佳為0～3的整數，再佳為0～2的整數，特佳為0或1。In formula (II), n represents an integer of 0 to 5, preferably an integer of 0 to 4, more preferably an integer of 0 to 3, still more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

作為特定脂環族環氧系化合物，可使用市售產品。 作為特定脂環族環氧系化合物的市售產品的例子，可列舉「CELLOXIDE(註冊商標) 2021P」及「CELLOXIDE(註冊商標) 2081」[以上為Daicel股份有限公司製]。 As the specific alicyclic epoxy compound, commercially available products can be used. Examples of commercially available products of specific alicyclic epoxy compounds include "CELLOXIDE (registered trademark) 2021P" and "CELLOXIDE (registered trademark) 2081" [the above products are manufactured by Daicel Co., Ltd.].

本揭示的黏著劑組成物可僅包含1種特定脂環族環氧系化合物，亦可包含2種以上。The adhesive composition of the present disclosure may contain only one specific alicyclic epoxy compound, or may contain two or more types.

相對於100質量份的特定(甲基)丙烯酸系聚合物，本揭示的黏著劑組成物中的特定脂環族環氧系化合物的含量較佳為0.1質量份～4.0質量份。 若本揭示的黏著劑組成物中的特定脂環族環氧系化合物的含量相對於100質量份的特定(甲基)丙烯酸系聚合物在上述範圍內，則可形成即使放置於重複低溫與高溫的環境下時亦不易產生皺褶及剝離的黏著劑層。推測其理由係因為特定(甲基)丙烯酸系聚合物與特定脂環族環氧系化合物的交聯反應而形成的三維網狀結構部分變得鬆散，對於所形成之黏著劑層賦予適當的柔軟性。 相對於100質量份的特定(甲基)丙烯酸系聚合物，本揭示的黏著劑組成物中的多異氰酸酯系化合物的含量較佳為0.15質量份以上，更佳為0.2質量份以上，再佳為0.25質量份以上，特佳為0.3質量份以上。又，相對於100質量份的特定(甲基)丙烯酸系聚合物，本揭示的黏著劑組成物中的特定脂環族環氧系化合物的含量較佳為3.5質量份以下，更佳為3.0質量份以下，再佳為2.5質量份以下，特佳為2.0質量份以下。 在一態樣中，相對於100質量份的特定(甲基)丙烯酸系聚合物，本揭示的黏著劑組成物中的特定脂環族環氧系化合物的含量可為0.15質量份～3.8質量份，亦可為0.2質量份～3.8質量份，亦可為0.25質量份～3.5質量份，亦可為0.3質量份～3.0質量份，亦可為0.5質量份～2.5質量份，亦可為0.5質量份～2.0質量份。 The content of the specific alicyclic epoxy compound in the adhesive composition of the present disclosure is preferably 0.1 to 4.0 parts by mass relative to 100 parts by mass of the specific (meth)acrylic polymer. If the content of the specific alicyclic epoxy compound in the adhesive composition of the present disclosure is within the above range relative to 100 parts by mass of the specific (meth)acrylic polymer, it can form an adhesive even if it is placed at repeated low and high temperatures. It is not easy to produce wrinkles and peeling adhesive layer even under the environment. The reason is presumed to be that the three-dimensional network structure formed by the cross-linking reaction of the specific (meth)acrylic polymer and the specific alicyclic epoxy compound becomes partially loose, imparting appropriate softness to the formed adhesive layer. sex. Relative to 100 parts by mass of the specific (meth)acrylic polymer, the content of the polyisocyanate compound in the adhesive composition of the present disclosure is preferably 0.15 parts by mass or more, more preferably 0.2 parts by mass or more, and still more preferably 0.25 parts by mass or more, particularly preferably 0.3 parts by mass or more. Furthermore, the content of the specific alicyclic epoxy compound in the adhesive composition of the present disclosure is preferably 3.5 parts by mass or less, more preferably 3.0 parts by mass, based on 100 parts by mass of the specific (meth)acrylic polymer. parts by mass or less, preferably 2.5 parts by mass or less, and particularly preferably 2.0 parts by mass or less. In one aspect, the content of the specific alicyclic epoxy compound in the adhesive composition of the present disclosure may be 0.15 parts by mass to 3.8 parts by mass relative to 100 parts by mass of the specific (meth)acrylic polymer. , it can be 0.2 parts by mass to 3.8 parts by mass, it can be 0.25 parts by mass - 3.5 parts by mass, it can be 0.3 parts by mass - 3.0 parts by mass, it can be 0.5 parts by mass - 2.5 parts by mass, it can also be 0.5 parts by mass parts ~ 2.0 parts by mass.

[矽烷偶聯劑] 本揭示的黏著劑組成物包含矽烷偶聯劑。 若本揭示的黏著劑組成物包含矽烷偶聯劑，可形成即使放置於重複低溫與高溫的環境下時亦不易產生皺褶及剝離的黏著劑層。 [Silane coupling agent] The adhesive composition of the present disclosure includes a silane coupling agent. If the adhesive composition of the present disclosure includes a silane coupling agent, an adhesive layer that is less likely to wrinkle and peel even when placed in environments with repeated low and high temperatures can be formed.

矽烷偶聯劑的種類並無特別限定。 作為矽烷偶聯劑，可列舉例如：以乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷及3-甲基丙烯醯氧基丙基三甲氧基矽烷為代表的含聚合性不飽和基之矽烷化合物、以3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷及3-巰基丙基二甲氧基甲基矽烷為代表的含硫醇基之矽烷系化合物、以3-環氧丙氧基丙基三甲氧基矽烷及2-(3,4-環氧環己基)乙基三甲氧基矽烷為代表的含環氧基之矽烷化合物、以3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷及N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷為代表的含胺基之矽烷化合物、以及參-(3-三甲氧基矽基丙基)三聚異氰酸酯。 The type of silane coupling agent is not particularly limited. Examples of silane coupling agents include polymerizable unsaturated group-containing compounds represented by vinyltrimethoxysilane, vinyltriethoxysilane, and 3-methacryloxypropyltrimethoxysilane. Silane compounds, silane compounds containing thiol groups represented by 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane and 3-mercaptopropyldimethoxymethylsilane, Silane compounds containing epoxy groups represented by 3-glycidoxypropyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyl Trimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Silane is represented by amine-containing silane compounds and ginseng-(3-trimethoxysilylpropyl)tripolyisocyanate.

作為矽烷偶聯劑，可使用市售產品。 作為矽烷偶聯劑之市售產品的例子，可列舉：信越化學工業股份有限公司製的「KBM-803」、「KBM-802」、「X-41-1810」、「X-41-1811」、「X-41-1805」、「X-41-1818」、「KBM-403」、「KBM-303」、「KBM-402」、「KBE-402」、「KBE-403」、「X-41-1053」、「X-41-1056」、「KBM-9659」、「KBE-9007N」及「KBM-573」(皆為商品名稱)。 As the silane coupling agent, commercially available products can be used. Examples of commercially available silane coupling agents include "KBM-803", "KBM-802", "X-41-1810", and "X-41-1811" manufactured by Shin-Etsu Chemical Industry Co., Ltd. , "X-41-1805", "X-41-1818", "KBM-403", "KBM-303", "KBM-402", "KBE-402", "KBE-403", "X- 41-1053", "X-41-1056", "KBM-9659", "KBE-9007N" and "KBM-573" (all are product names).

本揭示的黏著劑組成物可僅包含1種矽烷偶聯劑，亦可包含2種以上。The adhesive composition of the present disclosure may contain only one type of silane coupling agent, or may contain two or more types.

本揭示的黏著劑組成物中的矽烷偶聯劑的含量並無特別限定，例如，相對於100質量份的特定(甲基)丙烯酸系聚合物，較佳為0.1質量份～1質量份，更佳為0.1質量份～0.8質量份，再佳為0.1質量份～0.5質量份。 若本揭示的黏著劑組成物中的矽烷偶聯劑的含量相對於100質量份的特定(甲基)丙烯酸系聚合物在上述範圍內，則所形成之黏著劑層，例如在與玻璃貼合的狀態下，表現出放置於重複低溫與高溫的環境下時更不易產生皺褶及剝離的傾向。推測其理由係因為與玻璃的相互作用更適當地提高。 The content of the silane coupling agent in the adhesive composition of the present disclosure is not particularly limited. For example, relative to 100 parts by mass of the specific (meth)acrylic polymer, it is preferably 0.1 to 1 part by mass, more preferably 0.1 part by mass to 1 part by mass. Preferably, it is 0.1-0.8 parts by mass, and more preferably, it is 0.1-0.5 parts by mass. If the content of the silane coupling agent in the adhesive composition of the present disclosure is within the above range relative to 100 parts by mass of the specific (meth)acrylic polymer, the formed adhesive layer will, for example, be bonded to glass. In this state, it shows a tendency to become less prone to wrinkles and peeling when placed in environments with repeated low and high temperatures. The reason for this is presumed to be that the interaction with glass is more appropriately improved.

[有機溶劑] 本揭示的黏著劑組成物亦可包含有機溶劑。 若本揭示的黏著劑組成物包含有機溶劑，則可提升塗布性。 作為有機溶劑，可列舉例如：與上述特定(甲基)丙烯酸系聚合物的聚合反應時所使用的有機溶劑相同者。 [Organic solvent] The adhesive composition of the present disclosure may also contain organic solvents. If the adhesive composition of the present disclosure contains an organic solvent, the coating property can be improved. Examples of the organic solvent include the same organic solvents used in the polymerization reaction of the above-mentioned specific (meth)acrylic polymer.

本揭示的黏著劑組成物包含有機溶劑的情況，可僅包含1種有機溶劑，亦可包含2種以上。When the adhesive composition of the present disclosure contains an organic solvent, it may contain only one type of organic solvent or two or more types.

本揭示的黏著劑組成物包含有機溶劑的情況，有機溶劑的含量並無特別限定，可因應目的適當設定。When the adhesive composition of the present disclosure contains an organic solvent, the content of the organic solvent is not particularly limited and can be appropriately set according to the purpose.

[其他成分] 本揭示的黏著劑組成物，在無損其效果的範圍內，亦可因應需求包含上述成分以外的成分(所謂其他成分)。 作為其他成分，可列舉：特定(甲基)丙烯酸系聚合物以外的聚合物、交聯觸媒、抗氧化劑、著色劑(例如染料及顏料)、光穩定劑(例如紫外線吸收劑)、抗靜電劑等各種添加劑。 [Other ingredients] The adhesive composition of the present disclosure may also contain components other than the above-mentioned components (so-called other components) according to needs within the scope that does not impair its effect. Examples of other components include polymers other than specific (meth)acrylic polymers, cross-linking catalysts, antioxidants, colorants (such as dyes and pigments), light stabilizers (such as ultraviolet absorbers), antistatic agents and various additives.

本揭示的黏著劑組成物包含其他成分時，其他成分的含量可在無損本揭示之黏著劑組成物之效果的範圍內適當設定。When the adhesive composition of the present disclosure contains other components, the content of the other components can be appropriately set within the range that does not impair the effect of the adhesive composition of the present disclosure.

＜黏著劑組成物的用途＞ 本揭示的黏著劑組成物的用途並無特別限定。 本揭示的黏著劑組成物，可形成能夠良好地抑制放置於高溫環境下時會發生的基材收縮且即使放置於重複低溫與高溫的環境下時亦不易產生皺褶及剝離的黏著劑層，因此宜作為用於放置在高溫環境下及/或重複低溫與高溫的環境下時容易收縮的膜厚較薄之基材的黏著劑組成物。 從更有效地發揮本揭示之黏著劑組成物的效果之觀點來看，本揭示的黏著劑組成物特佳係使用於近年要求進一步薄膜化的光學膜(特別是偏光板)。 作為本揭示的黏著劑組成物的具體用途，可列舉：將偏光板與液晶單元的玻璃基板貼合的用途、將光學膜彼此(例：偏光板與相位差膜)貼合的用途等。 ＜Use of adhesive composition＞ The use of the adhesive composition of the present disclosure is not particularly limited. The adhesive composition disclosed in the present disclosure can form an adhesive layer that can well suppress the shrinkage of the substrate that occurs when placed in a high-temperature environment, and is not prone to wrinkles and peeling even when placed in environments with repeated low and high temperatures. Therefore, it is suitable as an adhesive composition for base materials with a thin film thickness that are prone to shrinkage when placed in a high-temperature environment and/or repeated exposure to low and high temperatures. From the viewpoint of more effectively exerting the effects of the adhesive composition of the present disclosure, the adhesive composition of the present disclosure is particularly preferably used in optical films (especially polarizing plates) that require further thinning in recent years. Specific uses of the adhesive composition disclosed in the present disclosure include bonding a polarizing plate and a glass substrate of a liquid crystal cell, bonding optical films (for example, a polarizing plate and a retardation film) to each other, and the like.

[黏著片] 本揭示的黏著片，因為具備由上述本揭示之黏著劑組成物所形成之黏著劑層，因此放置在高溫環境下時亦可良好地抑制基材收縮且即使放置於重複低溫與高溫的環境下時黏著劑層(黏著片具有基材的情況為基材及黏著劑層)不易產生皺褶，而且亦不易發生黏著劑層從被附著體剝離。 本揭示的黏著片所具備之黏著劑層，包含本揭示的黏著劑組成物的硬化物。硬化物包含例如由多異氰酸酯化合物及特定脂環族環氧系化合物交聯硬化而成的特定(甲基)丙烯酸系聚合物之交聯物。 [adhesive sheet] Since the adhesive sheet of the present disclosure has an adhesive layer formed of the adhesive composition of the present disclosure, it can well suppress the shrinkage of the base material when placed in a high-temperature environment and even if it is placed in an environment of repeated low and high temperatures. The adhesive layer (the base material and the adhesive layer when the adhesive sheet has a base material) is less likely to wrinkle, and the adhesive layer is less likely to peel off from the adherend. The adhesive layer of the adhesive sheet of the present disclosure includes a hardened product of the adhesive composition of the present disclosure. The cured product includes, for example, a cross-linked product of a specific (meth)acrylic polymer that is cross-linked and cured by a polyisocyanate compound and a specific alicyclic epoxy compound.

本揭示的黏著片所具備之黏著劑層的厚度並無特別限定。 黏著劑層的厚度一般為1μm～100μm，較佳為5μm～50μm，更佳為10μm～30μm。 The thickness of the adhesive layer included in the adhesive sheet of the present disclosure is not particularly limited. The thickness of the adhesive layer is generally 1 μm to 100 μm, preferably 5 μm to 50 μm, and more preferably 10 μm to 30 μm.

本揭示中的「黏著劑層的厚度」係指黏著劑層的平均厚度。 黏著劑層的平均厚度係由以下的方法求出的值。 使用膜厚計，在黏著劑層的厚度方向上隨機選擇的10處測量其厚度。求出測量值的算術平均值，將所得之值作為黏著劑層的平均厚度。 The "thickness of the adhesive layer" in this disclosure refers to the average thickness of the adhesive layer. The average thickness of the adhesive layer is a value calculated by the following method. Using a film thickness meter, measure the thickness of the adhesive layer at 10 randomly selected places in the thickness direction. Calculate the arithmetic mean of the measured values and use the resulting value as the average thickness of the adhesive layer.

本揭示的黏著片可為不具有基材的無基材型黏著片，亦可為在基材的單面或兩面具備黏著劑層的有基材型黏著片。 本揭示的黏著片在不具有基材的無基材型黏著片的情況或是在基材的單面具備黏著劑層的有基材型黏著片的情況，本揭示的黏著片中，露出的黏著劑層的面，亦可由剝離片所保護。 一般而言，剝離片在黏著片提供至實用為止的期間保護黏著劑層的表面，而在使用時剝離。 The adhesive sheet disclosed in the present disclosure may be a base-material-free adhesive sheet without a base material, or may be a base-material-type adhesive sheet having an adhesive layer on one or both sides of the base material. The adhesive sheet of the present disclosure is a base-material-free adhesive sheet that does not have a base material or a base-material type adhesive sheet that has an adhesive layer on one side of the base material. In the adhesive sheet of the present disclosure, the exposed The surface of the adhesive layer can also be protected by a release sheet. Generally speaking, the release sheet protects the surface of the adhesive layer while the adhesive sheet is provided until practical use, and is peeled off during use.

剝離片只要是可從黏著劑層輕易剝離者，則無特別限定。 作為剝離片，可列舉例如：單面或兩面經由剝離處理劑實施表面處理(所謂易剝離處理)的樹脂膜、紙、合成紙及將此等2種以上積層而成的複合片。 本揭示中，將樹脂膜的單面或兩面經由剝離處理劑實施表面處理(所謂易剝離處理)之態樣的剝離片稱為「剝離膜」。 作為剝離處理劑，可列舉例如：聚矽氧系剝離處理劑(例：聚矽氧)、蠟系剝離處理劑(例：石蠟)、及氟系剝離處理劑(例：氟系樹脂)。 作為樹脂膜，可列舉例如：以聚對苯二甲酸乙二酯(PET)膜為代表的聚酯膜。 作為紙，可列舉例如：高級紙及塗布紙。 剝離片的膜厚並無特別限定，一般為20μm～180μm。 The peeling sheet is not particularly limited as long as it can be easily peeled off from the adhesive layer. Examples of the release sheet include a resin film, paper, synthetic paper, and a composite sheet in which two or more of these are laminated, and one or both surfaces are surface-treated with a release treatment agent (so-called easy-release treatment). In this disclosure, a release sheet in which one or both sides of a resin film is surface-treated (so-called easy-release treatment) with a release treatment agent is called a "release film." Examples of the release treatment agent include polysilicone release treatment agents (eg, polysilicone), wax-based release treatment agents (eg, paraffin wax), and fluorine-based release treatment agents (eg, fluorine-based resin). Examples of the resin film include polyester films represented by polyethylene terephthalate (PET) films. Examples of paper include high-quality paper and coated paper. The film thickness of the release sheet is not particularly limited, but is generally 20 μm to 180 μm.

本揭示的黏著片具備基材時，基材只要是可在其上形成黏著劑層者，則無特別限定，較佳係放置於高溫環境下及/或重複低溫與高溫的環境下時會收縮者。 作為基材，可列舉例如：包含聚烯烴系樹脂[例如聚乙烯(PE)及聚丙烯(PP)]、聚酯系樹脂[例如聚對苯二甲酸乙二酯(PET)]、乙酸酯系樹脂(例如三乙醯基纖維素)、聚醚碸系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚胺基甲酸酯系樹脂、丙烯酸系樹脂、氯化乙烯系樹脂、ABS(Acrylonitrile Butadiene Styrene)樹脂、氟系樹脂等樹脂的膜。 When the adhesive sheet of the present disclosure has a base material, the base material is not particularly limited as long as an adhesive layer can be formed thereon. Preferably, the base material shrinks when placed in a high temperature environment and/or in repeated low and high temperature environments. By. Examples of the base material include polyolefin-based resins [such as polyethylene (PE) and polypropylene (PP)], polyester-based resins [such as polyethylene terephthalate (PET)], and acetate. Resins (such as triacetyl cellulose), polyether resins, polycarbonate resins, polyamide resins, polyimide resins, polyurethane resins, acrylic resins, Films made of resins such as chlorinated vinyl resin, ABS (Acrylonitrile Butadiene Styrene) resin, and fluorine resin.

基材中設有黏著劑層之一側的面，從提升基材與黏著劑層之密合性的觀點來看，亦可實施電暈放電處理、電漿放電處理等表面處理(所謂易接著處理)。From the perspective of improving the adhesion between the base material and the adhesive layer, the surface of the base material on which the adhesive layer is provided can also be subjected to surface treatment such as corona discharge treatment and plasma discharge treatment (so-called easy adhesion). handle).

基材亦可包含塑化劑、著色劑(例如染料及顏料)、熱穩定劑、光穩定劑、抗靜電劑、阻燃劑、抗氧化劑、填充劑等各種添加劑。 可對於基材的一部分或整體賦予圖樣。 The base material may also contain various additives such as plasticizers, colorants (such as dyes and pigments), heat stabilizers, light stabilizers, antistatic agents, flame retardants, antioxidants, fillers, etc. A pattern can be given to a part or the entire base material.

本揭示的黏著片具備基材的情況，基材較佳為光學膜。此情況中，作為本揭示的黏著片的態樣，較佳係具備光學膜與設於光學膜的至少單面且由本揭示的黏著劑組成物所形成之黏著劑層的態樣。The adhesive sheet of the present disclosure has a base material, and the base material is preferably an optical film. In this case, the adhesive sheet of the present disclosure preferably has an optical film and an adhesive layer provided on at least one side of the optical film and formed of the adhesive composition of the present disclosure.

光學膜的種類並無特別限定。 作為光學膜的具體例，可列舉：包含偏光板、防眩光(AG，Anti-Glare)偏光板、波長板、1/2、1/4等波長板的相位差膜、視角補償膜、光學補償膜、亮度提升膜、導光板、反射膜、抗反射膜、稜鏡片、透鏡片、擴散板、透明導電性膜等。 The type of optical film is not particularly limited. Specific examples of the optical film include retardation films including polarizing plates, anti-glare (AG, Anti-Glare) polarizing plates, wavelength plates, 1/2, 1/4 and other wavelength plates, viewing angle compensation films, and optical compensation films. Film, brightness enhancement film, light guide plate, reflective film, anti-reflective film, lens sheet, lens sheet, diffusion plate, transparent conductive film, etc.

作為光學膜，較佳為偏光板。 偏光板係至少包含偏光鏡而構成者，可為偏光鏡單體，亦可為將偏光鏡與保護膜積層而成者。亦即，偏光板可為偏光鏡單獨的1層結構，亦可為偏光鏡的單面具有保護膜的2層結構，亦可為偏光鏡的兩面具有保護膜的3層結構。 As the optical film, a polarizing plate is preferred. The polarizing plate is composed of at least a polarizer, and may be a polarizer alone or a laminate of a polarizer and a protective film. That is, the polarizing plate may have a single-layer structure with a polarizer, a two-layer structure with a protective film on one side of the polarizer, or a three-layer structure with a protective film on both sides of the polarizer.

作為本揭示的黏著片具備基材且基材為偏光板之情況中的層構成，可列舉例如：黏著劑層/偏光鏡、黏著劑層/偏光鏡/保護膜、黏著劑層/保護膜/偏光鏡/保護膜及黏著劑層/保護膜/偏光鏡。又，偏光鏡與保護膜之間、保護膜與黏著劑層之間、及偏光鏡與黏著劑層之間，例如亦可具有相位差膜。 偏光鏡例如係使用含浸有碘的聚乙烯醇(PVA)膜。 作為保護膜，可列舉例如：三乙醯基纖維素(TAC)膜、聚環烯烴(COP)膜、聚對苯二甲酸乙二酯(PET)膜及丙烯酸膜。 Examples of the layer composition when the adhesive sheet of the present disclosure includes a base material and the base material is a polarizing plate include: adhesive layer/polarizer, adhesive layer/polarizer/protective film, adhesive layer/protective film/ Polarizer/protective film and adhesive layer/protective film/polarizer. Furthermore, for example, a retardation film may be provided between the polarizer and the protective film, between the protective film and the adhesive layer, and between the polarizer and the adhesive layer. For example, a polyvinyl alcohol (PVA) film impregnated with iodine is used as the polarizer. Examples of the protective film include triacetyl cellulose (TAC) film, polycycloolefin (COP) film, polyethylene terephthalate (PET) film, and acrylic film.

基材的厚度並無特別限定，例如較佳為100μm以下，更佳為50μm～100μm，再佳為70μm～100μm。 若基材的厚度為100μm以下，有更有效地發揮由本揭示之黏著劑組成物形成之黏著劑層之效果的傾向。 The thickness of the base material is not particularly limited, but for example, it is preferably 100 μm or less, more preferably 50 μm to 100 μm, and still more preferably 70 μm to 100 μm. If the thickness of the base material is 100 μm or less, the effect of the adhesive layer formed of the adhesive composition of the present disclosure tends to be exerted more effectively.

本揭示中的「基材的厚度」係指基材的平均厚度。基材的平均厚度係由與上述黏著劑層之平均厚度相同的方法求出的值。The "thickness of the substrate" in this disclosure refers to the average thickness of the substrate. The average thickness of the base material is a value calculated by the same method as the average thickness of the above-mentioned adhesive layer.

[黏著片的製作方法] 本揭示的黏著片的製作方法並無特別限定。 本揭示的黏著片可藉由習知的方法製作。 作為製作本揭示之黏著片的方法，可列舉例如以下的方法。 [How to make adhesive sheets] The manufacturing method of the adhesive sheet disclosed in this disclosure is not particularly limited. The adhesive sheet of the present disclosure can be produced by conventional methods. As a method of producing the adhesive sheet of this disclosure, the following method is mentioned, for example.

本揭示的黏著片為無基材型黏著片的情況，首先藉由將本揭示的黏著劑組成物塗布於剝離片的易剝離處理面，在剝離片上形成塗布膜。然後，藉由使所形成之塗布膜乾燥，而在剝離片上形成黏著膜。然後，將所形成之黏著膜露出的面重合於另外準備的剝離片之易剝離處理面並進行貼合後進行養護，藉此可製作具有剝離片/黏著劑層/剝離片之積層結構的無基材型黏著片。When the adhesive sheet of the present disclosure is a substrate-less adhesive sheet, first, the adhesive composition of the present disclosure is applied to the easily peelable surface of the release sheet to form a coating film on the release sheet. Then, the formed coating film is dried to form an adhesive film on the release sheet. Then, the exposed surface of the formed adhesive film is superimposed on the easily peelable surface of a separately prepared release sheet, bonded, and cured. This makes it possible to produce a non-woven fabric with a laminated structure of release sheet/adhesive layer/release sheet. Base material adhesive sheet.

本揭示的黏著片為有基材型黏著片的情況，首先將本揭示的黏著劑組成物塗布於基材的易接著處理面，藉此在基材上形成塗布膜。然後，藉由使所形成之塗布膜乾燥，而在基材上形成黏著膜。然後，將所形成之黏著膜的露出面重合於剝離片的易剝離處理面並進行貼合後進行養護，藉此可製作具有基材/黏著劑層/剝離片之積層結構的有基材型黏著片。When the adhesive sheet of the present disclosure has a base material type adhesive sheet, the adhesive composition of the present disclosure is first coated on the easy-adhesion surface of the base material, thereby forming a coating film on the base material. Then, the formed coating film is dried to form an adhesive film on the base material. Then, the exposed surface of the formed adhesive film is superimposed on the easy-to-releasable surface of the release sheet, bonded and then cured. This makes it possible to produce a base material type with a laminated structure of base material/adhesive layer/release sheet. Adhesive sheet.

本揭示的黏著片為有基材型之黏著片的情況，作為另一方法，亦可列舉例如以下的方法。藉由將本揭示的黏著劑組成物塗布於剝離片的易剝離處理面，在剝離片上形成塗布膜。然後，藉由將所形成之塗布膜乾燥，在剝離片上形成黏著膜。然後，將所形成之黏著膜的露出面重合於基材的易接著處理面並將其貼合後進行養護，藉此可製作具有基材/黏著劑層/剝離片之積層結構的有基材型黏著片。When the adhesive sheet of the present disclosure is a base material-type adhesive sheet, another method may include the following method. By applying the adhesive composition of the present disclosure to the easily peelable surface of the release sheet, a coating film is formed on the release sheet. Then, the formed coating film is dried to form an adhesive film on the release sheet. Then, the exposed surface of the formed adhesive film is superimposed on the easy-adhesion surface of the base material, and the two are bonded and cured. This makes it possible to produce a base material having a laminated structure of base material/adhesive layer/release sheet. type adhesive sheet.

黏著劑組成物的塗布方法並無特別限定。 作為黏著劑組成物的塗布方法，可列舉例如：使用凹版輥塗法、逆式輥塗法、吻合式輥塗法、浸漬式輥塗法、刀塗法、噴塗法、棒塗法、塗抹器等習知方法。 黏著劑組成物的塗布量並無特別限定，例如可因應所形成之黏著劑層的厚度適當設定。 The method of applying the adhesive composition is not particularly limited. Examples of the coating method of the adhesive composition include gravure roller coating, reverse roller coating, matching roller coating, dip roller coating, knife coating, spray coating, rod coating, and applicator Wait for familiar methods. The coating amount of the adhesive composition is not particularly limited. For example, it can be appropriately set according to the thickness of the adhesive layer formed.

塗布膜的乾燥方法並無特別限定。 作為塗布膜的乾燥方法，可列舉例如：自然乾燥、加熱乾燥、熱風乾燥、真空乾燥等的方法。 塗布膜的乾燥溫度及乾燥時間並無特別限定，可因應塗布膜的厚度、塗布膜中的有機溶劑的量等適當設定。 作為乾燥條件的一例，可列舉使用熱風循環式乾燥機於60℃～120℃乾燥30秒～180秒的條件。 The drying method of the coating film is not particularly limited. Examples of methods for drying the coating film include natural drying, heat drying, hot air drying, and vacuum drying. The drying temperature and drying time of the coating film are not particularly limited, and can be appropriately set according to the thickness of the coating film, the amount of organic solvent in the coating film, and the like. An example of the drying conditions is drying at 60°C to 120°C for 30 seconds to 180 seconds using a hot air circulation dryer.

作為養護的方法，可列舉例如：在環境溫度20℃～35℃及相對濕度45%～55%的環境下靜置2天～7天的方法。An example of a curing method is a method of leaving it alone for 2 to 7 days in an environment with an ambient temperature of 20°C to 35°C and a relative humidity of 45% to 55%.

[光學構件] 本揭示的光學構件依序具備玻璃基板、由上述本揭示之黏著劑組成物形成的黏著劑層與光學膜。 本揭示的光學構件因為具備由本揭示的黏著劑組成物形成的黏著劑層，故即使在放置於高溫環境下時亦可抑制光學膜的收縮，且即使放置於重複低溫與高溫的環境下時，光學膜及黏著劑層中亦不易產生皺褶，而且不易發生黏著劑層從玻璃基板剝離。 [Optical components] The optical component of the present disclosure includes a glass substrate, an adhesive layer formed of the adhesive composition of the present disclosure, and an optical film in this order. Since the optical member of the present disclosure has an adhesive layer formed of the adhesive composition of the present disclosure, the shrinkage of the optical film can be suppressed even when placed in a high-temperature environment, and even when placed in an environment of repeated low and high temperatures, Wrinkles are also less likely to occur in the optical film and adhesive layer, and the adhesive layer is less likely to peel off from the glass substrate.

玻璃基板的厚度並無特別限定，一般為0.3mm～0.7mm，較佳為0.3mm～0.5mm。The thickness of the glass substrate is not particularly limited, but is generally 0.3 mm to 0.7 mm, preferably 0.3 mm to 0.5 mm.

作為玻璃基板，可列舉例如：鈉玻璃、無鹼玻璃及附ITO(Indium Tin Oxide)膜之玻璃。Examples of the glass substrate include soda glass, alkali-free glass, and glass with an ITO (Indium Tin Oxide) film.

本揭示的光學構件中的黏著劑層及光學膜與本揭示的黏著片中的黏著劑層及光學膜同義，較佳的態樣亦相同，故此處省略說明。The adhesive layer and optical film in the optical component of the present disclosure have the same meaning as the adhesive layer and optical film in the adhesive sheet of the present disclosure, and the preferred aspects are also the same, so the description is omitted here.

本揭示的光學構件，例如可適當地作為顯示裝置的構件使用。 作為顯示裝置，可列舉例如：液晶顯示器及有機EL(Electro-Luminescence)顯示器。 The optical member of the present disclosure can be suitably used as a member of a display device, for example. Examples of display devices include liquid crystal displays and organic EL (Electro-Luminescence) displays.

本揭示的光學構件之製造方法並無特別限定。 本揭示的光學構件，例如可藉由使用光學膜作為基材，以上述方法製作本揭示的黏著片後，將黏著片的黏著劑層與玻璃基板貼合而製造。 The manufacturing method of the optical component of the present disclosure is not particularly limited. The optical component of the present disclosure can be manufactured, for example, by using an optical film as a base material, preparing the adhesive sheet of the present disclosure by the above method, and then laminating the adhesive layer of the adhesive sheet to a glass substrate.

[顯示裝置] 本揭示的顯示裝置具備上述本揭示的光學構件。 本揭示的顯示裝置具備本揭示的光學構件，因此即使放置於高溫環境下時亦可抑制光學膜的收縮，且即使放置於重複低溫與高溫的環境下時光學膜及黏著劑層中亦不易產生皺褶，而且亦不易發生黏著劑層從玻璃基板剝離。 [display device] The display device of the present disclosure includes the optical member of the present disclosure described above. The display device of the present disclosure is equipped with the optical member of the present disclosure, so it can suppress the shrinkage of the optical film even when placed in a high-temperature environment, and is less likely to occur in the optical film and the adhesive layer even if it is placed in an environment with repeated low and high temperatures. Wrinkles, and it is not easy for the adhesive layer to peel off from the glass substrate.

顯示裝置的具體例如上所述。 [實施例] Specific examples of the display device are as described above. [Example]

以下，藉由實施例更具體說明本揭示的黏著劑組成物。本揭示只要不超出其主旨，則不限於以下的實施例。Hereinafter, the adhesive composition of the present disclosure will be described in more detail through examples. The present disclosure is not limited to the following examples unless the gist thereof is exceeded.

[(甲基)丙烯酸系聚合物的製造] [製造例A-1] 在具備溫度計、攪拌機、氮氣導入管及迴流冷卻器的反應器內放入87.6質量份的丙烯酸正丁酯[n-BA；丙烯酸烷酯單體]、12.0質量份的丙烯酸苯氧基乙酯[PHEA；其他單體]、0.4質量份的丙烯酸2-羥乙酯[2HEA；具有羥基之單體]及70.0質量份的乙酸乙酯[有機溶劑]並進行混合，得到混合物後，對於反應器內進行氮氣取代。然後，一邊攪拌反應器內的混合物，一邊升溫至70℃後，對於反應器內的混合物逐次添加0.02質量份的2,2’-偶氮雙(2,4-二甲基戊腈)[ABVN；聚合起始劑]與120.0質量份的乙酸乙酯，添加結束後保持6小時，結束聚合反應。然後，使用乙酸乙酯將由聚合反應結束所得之溶液稀釋成固體成分濃度18.5質量%後進行冷卻，得到(甲基)丙烯酸系聚合物A-1的溶液。 [Production of (meth)acrylic polymer] [Manufacturing Example A-1] 87.6 parts by mass of n-butyl acrylate [n-BA; alkyl acrylate monomer] and 12.0 parts by mass of phenoxyethyl acrylate [ PHEA; other monomers], 0.4 parts by mass of 2-hydroxyethyl acrylate [2HEA; monomer with hydroxyl groups] and 70.0 parts by mass of ethyl acetate [organic solvent] and mix them to obtain the mixture. Perform nitrogen substitution. Then, the temperature of the mixture in the reactor was raised to 70°C while stirring, and then 0.02 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) [ABVN] was gradually added to the mixture in the reactor. ; Polymerization initiator] and 120.0 parts by mass of ethyl acetate, and keep for 6 hours after the addition to complete the polymerization reaction. Then, the solution obtained after the completion of the polymerization reaction was diluted with ethyl acetate to a solid content concentration of 18.5% by mass, and then cooled to obtain a solution of (meth)acrylic polymer A-1.

此處所述的「固體成分濃度」，係指在(甲基)丙烯酸系聚合物A-1的溶液中，(甲基)丙烯酸系聚合物A-1所占的質量比例。針對以下製造的(甲基)丙烯酸系聚合物A-2～A-10的各溶液皆相同。The "solid content concentration" here refers to the mass ratio of (meth)acrylic polymer A-1 in the solution of (meth)acrylic polymer A-1. The solutions of (meth)acrylic polymers A-2 to A-10 produced below are all the same.

[製造例A-2～A-10] 製造例A-2～A-10中，將(甲基)丙烯酸系聚合物的單體組成變更為表1所示的單體組成，除此之外，進行與製造例A-1相同的操作，得到固體成分濃度18.5質量%的(甲基)丙烯酸系聚合物A-2～A-10的各溶液。 [Manufacturing Examples A-2 to A-10] In Production Examples A-2 to A-10, the same operations as Production Example A-1 were performed except that the monomer composition of the (meth)acrylic polymer was changed to the monomer composition shown in Table 1. , each solution of (meth)acrylic polymers A-2 to A-10 with a solid content concentration of 18.5% by mass was obtained.

(甲基)丙烯酸系聚合物A-1～A-10的單體組成[單位：質量%]、酸價[單位：mgKOH/g]、玻璃轉移溫度(Tg)[單位：℃]及重量平均分子量(Mw)顯示於表1。Monomer composition [unit: mass %], acid value [unit: mgKOH/g], glass transition temperature (Tg) [unit: ℃] and weight average of (meth)acrylic polymers A-1 to A-10 Molecular weight (Mw) is shown in Table 1.

(甲基)丙烯酸系聚合物A-1～A-10的酸價係以與上述特定(甲基)丙烯酸系聚合物之酸價的求法相同的方法求出。 (甲基)丙烯酸系聚合物A-1～A-10的玻璃轉移溫度(Tg)係藉由與上述特定(甲基)丙烯酸系聚合物的玻璃轉移溫度的求法相同的方法求出。 (甲基)丙烯酸系聚合物A-1～A-10的重量平均分子量(Mw)係以與上述特定(甲基)丙烯酸系聚合物的重量平均分子量的測量方法相同的方法進行測量。 The acid value of (meth)acrylic polymers A-1 to A-10 is determined by the same method as the acid value of the above-mentioned specific (meth)acrylic polymer. The glass transition temperature (Tg) of the (meth)acrylic polymers A-1 to A-10 is determined by the same method as the glass transition temperature of the specific (meth)acrylic polymer described above. The weight average molecular weight (Mw) of the (meth)acrylic polymers A-1 to A-10 is measured in the same manner as the weight average molecular weight of the specific (meth)acrylic polymer described above.

(甲基)丙烯酸系聚合物A-1～A-10之中，(甲基)丙烯酸系聚合物A-2～A-10相當於本揭示中的特定(甲基)丙烯酸系聚合物。Among the (meth)acrylic polymers A-1 to A-10, the (meth)acrylic polymers A-2 to A-10 correspond to the specific (meth)acrylic polymers in this disclosure.

[表1]    (甲基)丙烯酸系聚合物 單體組成[質量%] 酸價 [mgKOH/g] Tg [℃] Mw n-BA PHEA MA MMA AA M-5300 2HEA A-1 87.6 12.0 - - - - 0.4 0.0 -52 172萬 A-2 87.2 12.0 - - 0.4 - 0.4 3.1 -51 168萬 A-3 86.6 12.0 - - 1.0 - 0.4 7.8 -50 172萬 A-4 86.6 - 12.0 - 1.0 - 0.4 7.8 -44 167萬 A-5 86.6 10.0 - 2.0 1.0 - 0.4 7.8 -48 154萬 A-6 87.0 12.0 - - 1.0 - - 7.8 -50 170萬 A-7 84.6 12.0 - - 3.0 - 0.4 23.4 -46 171萬 A-8 85.6 12.0 - - - 2.0 0.4 3.7 -51 171萬 A-9 98.8 - - - 1.2 - - 9.4 -52 173萬 A-10 88.5 - 10.0 - 1.4 - 0.1 10.9 -44 175萬 [Table 1] (meth)acrylic polymer Monomer composition [mass %] Acid value [mgKOH/g] Tg [℃] Mw n-BA PHEA MA MMA AA M-5300 2HEA A-1 87.6 12.0 - - - - 0.4 0.0 -52 1.72 million A-2 87.2 12.0 - - 0.4 - 0.4 3.1 -51 1.68 million A-3 86.6 12.0 - - 1.0 - 0.4 7.8 -50 1.72 million A-4 86.6 - 12.0 - 1.0 - 0.4 7.8 -44 1.67 million A-5 86.6 10.0 - 2.0 1.0 - 0.4 7.8 -48 1.54 million A-6 87.0 12.0 - - 1.0 - - 7.8 -50 1.7 million A-7 84.6 12.0 - - 3.0 - 0.4 23.4 -46 1.71 million A-8 85.6 12.0 - - - 2.0 0.4 3.7 -51 1.71 million A-9 98.8 - - - 1.2 - - 9.4 -52 1.73 million A-10 88.5 - 10.0 - 1.4 - 0.1 10.9 -44 1.75 million

表1中記載的各單體之詳細內容如以下所示。 ＜(甲基)丙烯酸烷酯單體＞ 「n-BA」：丙烯酸正丁酯[作為均聚物時的Tg：-54℃] 「MA」：丙烯酸甲酯[作為均聚物時的Tg：10℃] 「MMA」：甲基丙烯酸甲酯[作為均聚物時的Tg：105℃] ＜具有羧基之單體＞ 「AA」：丙烯酸[作為均聚物時的Tg：106℃，分子量：72，1分子中所包含的羧基的數：1] 「M-5300」：ω-羧基-多己內酯(n≒2)單丙烯酸酯[作為均聚物時的Tg：-30℃，分子量：300，1分子中所包含的羧基的數：1] ＜具有羥基之單體＞ 「2HEA」：丙烯酸2-羥乙酯[作為均聚物時的Tg：-15℃] ＜其他單體＞ 「PHEA」：苯氧基乙基丙烯酸酯[作為均聚物時的Tg：-22℃] The details of each monomer described in Table 1 are as follows. ＜(Meth)acrylic acid alkyl ester monomer＞ "n-BA": n-butyl acrylate [Tg as homopolymer: -54°C] "MA": Methyl acrylate [Tg as homopolymer: 10°C] "MMA": methyl methacrylate [Tg as homopolymer: 105°C] ＜Monomer having carboxyl group＞ "AA": Acrylic acid [Tg as homopolymer: 106°C, molecular weight: 72, number of carboxyl groups contained in 1 molecule: 1] "M-5300": ω-carboxy-polycaprolactone (n≒2) monoacrylate [Tg when used as a homopolymer: -30°C, molecular weight: 300, number of carboxyl groups contained in 1 molecule: 1 ] ＜Monomer having hydroxyl group＞ "2HEA": 2-hydroxyethyl acrylate [Tg as homopolymer: -15°C] ＜Other monomers＞ "PHEA": phenoxyethyl acrylate [Tg as homopolymer: -22°C]

表1中，單體組成的欄位中記載的「-」表示並未使用相當於該欄位的單體。In Table 1, "-" written in the column of monomer composition indicates that the monomer corresponding to that column is not used.

[黏著劑組成物的製備] [實施例1] 將540.5質量份(作為固體成分為100質量份)的(甲基)丙烯酸系聚合物A-3的溶液、1.78質量份(作為固體成分為0.80質量份)的作為多異氰酸酯系化合物之CORONATE(註冊商標) L-45E[商品名稱，甲苯二異氰酸酯(TDI)與三羥甲基丙烷(TMP)的加成物，固體成分濃度：45質量%，東曹股份有限公司製]、0.50質量份(作為固體成分為0.50質量份)的作為特定脂環族環氧系化合物之CELLOXIDE(註冊商標) 2021P[商品名稱，3’,4’-環氧環己基甲基3,4-環氧環己烷羧酸酯、固體成分濃度：100質量%，Daicel股份有限公司製]、0.20質量份(作為固體成分為0.20質量份)的作為矽烷偶聯劑之X-41-1810[商品名稱，含有甲基/巰基之烷氧基聚矽氧寡聚物、固體成分濃度：100質量%，信越化學工業股份有限公司]及適量的乙酸乙酯[有機溶劑]充分混合，得到實施例1的黏著劑組成物。 [Preparation of adhesive composition] [Example 1] 540.5 parts by mass (100 parts by mass as solid content) of a solution of (meth)acrylic polymer A-3, 1.78 parts by mass (0.80 parts by mass as solid content) of CORONATE (registered polyisocyanate compound) Trademark) L-45E [trade name, adduct of toluene diisocyanate (TDI) and trimethylolpropane (TMP), solid content concentration: 45% by mass, manufactured by Tosoh Co., Ltd.], 0.50 parts by mass (as CELLOXIDE (registered trademark) 2021P [trade name, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylic acid, a specific alicyclic epoxy compound with a solid content of 0.50 parts by mass) Acid ester, solid content concentration: 100 mass %, manufactured by Daicel Co., Ltd.], 0.20 mass parts (0.20 mass parts as solid content) of X-41-1810 [trade name, containing methyl/ Mercapto alkoxy polysiloxy oligomer, solid content concentration: 100 mass%, Shin-Etsu Chemical Industry Co., Ltd.] and an appropriate amount of ethyl acetate [organic solvent] were thoroughly mixed to obtain the adhesive composition of Example 1.

[實施例2～17] 實施例1中，將黏著劑組成物的組成變更為表2所示的組成，除此之外，進行與實施例1相同的操作，得到實施例2～17的各黏著劑組成物。 [Examples 2 to 17] In Example 1, the same operation as Example 1 was performed except that the composition of the adhesive composition was changed to the composition shown in Table 2, and each adhesive composition of Examples 2 to 17 was obtained.

[比較例1～14] 實施例1中，將黏著劑組成物的組成變更為表3所示的組成，除此之外，進行與實施例1相同的操作，得到比較例1～14的各黏著劑組成物。 [Comparative Examples 1 to 14] In Example 1, the same operation as Example 1 was performed except that the composition of the adhesive composition was changed to the composition shown in Table 3, and each adhesive composition of Comparative Examples 1 to 14 was obtained.

[附黏著劑層的偏光板之製作] 在經由聚矽氧系剝離處理劑進行表面處理(所謂易剝離處理)的剝離膜[型：MRF，厚度：38μm，三菱化學股份有限公司製]的易剝離處理面塗布上述製備的黏著劑組成物，形成塗布膜。另外，黏著劑組成物的塗布量係使後述黏著膜的厚度成為15μm的量。然後，對於所形成之塗布膜，使用熱風循環式乾燥機，以風速3m/秒吹附100℃的空氣60秒，藉此使塗布膜乾燥，在剝離膜上形成厚度15μm的黏著膜。然後，將所形成之黏著膜的露出面與具有三乙醯基纖維素(TAC)層/包含偏光鏡的聚乙烯醇(PVA)層/TAC層之構成的偏光板(厚度：75μm)一邊之TAC層的面重合並進行貼合後，在環境溫度23℃及50%RH的環境下靜置7天以使黏著膜進行養護，製作具有剝離膜/黏著劑層/偏光板(TAC層/PVA層/TAC層)之構成的附黏著劑層之偏光板。 [Production of polarizing plate with adhesive layer] The adhesive composition prepared above is applied to the easy-releasable surface of a release film [type: MRF, thickness: 38 μm, manufactured by Mitsubishi Chemical Co., Ltd.] that has been surface-treated (so-called easy-releasable treatment) with a polysiloxane-based release treatment agent. , forming a coating film. In addition, the coating amount of the adhesive composition is an amount such that the thickness of the adhesive film described below becomes 15 μm. Then, the formed coating film was dried using a hot air circulation dryer to blow 100°C air at a wind speed of 3 m/sec for 60 seconds, thereby forming an adhesive film with a thickness of 15 μm on the release film. Then, the exposed surface of the formed adhesive film was placed on one side of a polarizing plate (thickness: 75 μm) composed of a triacetyl cellulose (TAC) layer/polyvinyl alcohol (PVA) layer including a polarizer/TAC layer. After the surfaces of the TAC layer are overlapped and bonded, the adhesive film is left to rest for 7 days at an ambient temperature of 23°C and 50% RH to allow the adhesive film to cure, and a peeling film/adhesive layer/polarizing plate (TAC layer/PVA Polarizing plate with adhesive layer composed of layer/TAC layer).

[評價用樣本的製作] 將上述製作的附黏著劑層之偏光板以長邊相對於偏光板之吸收軸成為0°的方式裁斷，以準備多片尺寸為62mm×110mm(長邊)的試片。然後，將試片的剝離膜剝離，將因剝離而露出之黏著劑層的面與玻璃板[種類：鈉玻璃，松浪硝子工業股份有限公司製]的一面接觸而重合後，使用層合機進行壓接，將試片與玻璃板貼合，藉此製作具有玻璃板/黏著劑層/偏光板(TAC層/PVA層/TAC層)之構成的評價用樣本。 [Preparation of samples for evaluation] Cut the polarizing plate with the adhesive layer produced above so that the long side becomes 0° with respect to the absorption axis of the polarizing plate, to prepare multiple test pieces with a size of 62 mm × 110 mm (long side). Then, the peeling film of the test piece was peeled off, and the surface of the adhesive layer exposed by peeling was brought into contact with the surface of the glass plate [type: soda glass, manufactured by Matsunami Glass Industry Co., Ltd.] and then overlapped using a laminator. Press and bond the test piece to the glass plate to prepare an evaluation sample composed of the glass plate/adhesive layer/polarizing plate (TAC layer/PVA layer/TAC layer).

[測量及評價] 1.耐久性 (1)高溫低濕環境 將上述製作的評價用樣本於處理溫度50℃及處理壓力5kg/cm 2的條件下進行高壓釜處理20分鐘後，靜置於環境溫度23℃及50%RH的環境下24小時。將該靜置24小時後的評價用樣本靜置於環境溫度85℃及10%RH以下的環境(所謂的高溫低濕環境下)150小時。以目視觀察該靜置150小時後的評價用樣本的狀態，根據下述評價基準進行評價。結果顯示於表2及表3。 下述的評價基準中，「A」、「B」及「C」為實用等級，最佳為「A」。 [Measurement and Evaluation] 1. Durability (1) High-temperature and low-humidity environment. The above-prepared evaluation sample was subjected to autoclave treatment for 20 minutes under the conditions of a processing temperature of 50°C and a processing pressure of 5kg/ cm2 , and then left to stand in the environment. 24 hours in an environment of 23℃ and 50%RH. The evaluation sample that had been left to stand for 24 hours was left to stand for 150 hours in an environment with an ambient temperature of 85° C. and 10% RH or less (a so-called high temperature and low humidity environment). The state of the evaluation sample after leaving it still for 150 hours was visually observed, and evaluation was performed based on the following evaluation criteria. The results are shown in Table 2 and Table 3. Among the following evaluation criteria, "A", "B", and "C" are practical grades, and "A" is the best.

-評價基準- A：評價用樣本中完全未確認到皺褶及剝離。 B：評價用樣本中確認到些許皺褶及剝離，但係實用上沒有問題的等級。 C：評價用樣本中確認到皺褶及剝離，但係實用上可允許的等級。 D：評價用樣本明顯確認到皺褶及剝離，係實用上不允許的等級。 -Evaluation criteria- A: No wrinkles or peeling were observed in the evaluation sample. B: Slight wrinkles and peeling were observed in the evaluation sample, but this was a level with no practical problems. C: Wrinkling and peeling were observed in the evaluation sample, but it is a practically acceptable level. D: Wrinkling and peeling were clearly observed in the evaluation sample, which is a grade that is not allowed for practical use.

(2)熱震環境 將上述製作之評價用樣本在處理溫度50℃及處理壓力5kg/cm 2的條件下進行高壓釜處理20分鐘後，在環境溫度23℃及50%RH的環境下靜置24小時。對於該靜置24小時後的評價用樣本，使用冷熱衝擊裝置[型號：TSA-301L-W，ESPEC股份有限公司製]進行下述試驗：在環境溫度-40℃的環境下靜置0.5小時後，在環境溫度85℃的環境下靜置0.5小時，將此操作設為1循環，重複此操作300個循環。以目視觀察此試驗後的評價用樣本的狀態，根據下述評價基準進行評價。結果顯示於表2及表3。 下述的評價基準中，「A」、「B」及「C」為可實用的等級，最佳為「A」。 (2) Thermal shock environment: The above-prepared evaluation sample is subjected to autoclave treatment at a processing temperature of 50°C and a processing pressure of 5kg/ cm2 for 20 minutes, and then left to stand in an environment with an ambient temperature of 23°C and 50% RH. 24 hours. The evaluation sample after being left to stand for 24 hours was subjected to the following test using a thermal shock device [Model: TSA-301L-W, manufactured by ESPEC Co., Ltd.]: After being left to stand for 0.5 hours in an environment with an ambient temperature of -40°C , let it stand for 0.5 hours at an ambient temperature of 85°C, set this operation to 1 cycle, and repeat this operation for 300 cycles. The state of the evaluation sample after this test was visually observed and evaluated based on the following evaluation criteria. The results are shown in Table 2 and Table 3. Among the following evaluation criteria, "A", "B" and "C" are practical grades, and "A" is the best.

-評價基準- A：評價用樣本中完全未確認到皺褶及剝離。 B：評價用樣本中確認到些許皺褶及剝離，但係實用上沒有問題的等級。 C：評價用樣本中確認到皺褶及剝離，但係實用上可允許的等級。 D：評價用樣本中明顯確認到皺褶及剝離，係實用上不允許的等級。 -Evaluation criteria- A: No wrinkles or peeling were observed in the evaluation sample. B: Slight wrinkles and peeling were observed in the evaluation sample, but this was a level with no practical problems. C: Wrinkling and peeling were observed in the evaluation sample, but it is a practically acceptable level. D: Wrinkles and peeling were clearly observed in the evaluation sample, which is a grade that is not allowed for practical use.

2.收縮抑制 將上述製作的評價用樣本在處理溫度50℃及處理壓力5kg/cm 2的條件下進行高壓釜處理20分鐘後，在環境溫度23℃及50%RH的環境下靜置24小時。將該靜置24小時後的評價用樣本靜置於環境溫度85℃及10%RH以下的環境中(所謂的高溫低濕環境下)150小時。使用數位顯微鏡[型號：VHX-100F，KEYENCE股份有限公司製]，測量該靜置150小時後的評價用樣本之長邊(亦即相對吸收軸成為0°的邊)的長度，由下述算式算出收縮率。算出的值係將小數點以下第3位四捨五入。 收縮率(單位：%)=[[靜置前的評價用樣本之長邊的長度(單位：mm)]-[靜置後的評價用樣本之長邊的長度(單位：mm)]]/靜置前的評價用樣本之長邊的長度(單位：mm)×100 2. Shrinkage inhibition: The above-prepared evaluation sample was subjected to autoclave treatment at a processing temperature of 50°C and a processing pressure of 5kg/ cm2 for 20 minutes, and then left to stand for 24 hours in an environment with an ambient temperature of 23°C and 50% RH. . The evaluation sample left to stand for 24 hours was left to stand for 150 hours in an environment with an ambient temperature of 85° C. and 10% RH or less (a so-called high temperature and low humidity environment). Using a digital microscope [Model: VHX-100F, manufactured by KEYENCE Co., Ltd.], the length of the long side (that is, the side at 0° relative to the absorption axis) of the evaluation sample after being left to stand for 150 hours was measured, and the length was calculated by the following formula Calculate the shrinkage rate. The calculated value is rounded to the third decimal place. Shrinkage rate (unit: %) = [[The length of the long side of the evaluation sample before resting (unit: mm)] - [The length of the long side of the evaluation sample after resting (unit: mm)]]/ The length of the long side of the evaluation sample before standing (unit: mm) × 100

根據計算出來的收縮率，依照下述評價基準進行評價。結果顯示於表2及表3。下述的評價基準中，「A」、「B」及「C」為可實用的等級，最佳為「A」。Based on the calculated shrinkage rate, evaluation was performed according to the following evaluation criteria. The results are shown in Table 2 and Table 3. Among the following evaluation criteria, "A", "B" and "C" are practical grades, and "A" is the best.

-評價基準- A：評價用樣本的收縮率小於0.20%。 B：評價用樣本的收縮率為0.20%以上且小於0.35%的範圍。 C：評價用樣本的收縮率為0.35%以上且小於0.50%的範圍。 D：評價用樣本的收縮率為0.50%以上。 -Evaluation criteria- A: The shrinkage rate of the evaluation sample is less than 0.20%. B: The shrinkage rate of the sample for evaluation is in the range of 0.20% or more and less than 0.35%. C: The shrinkage rate of the sample for evaluation is in the range of 0.35% or more and less than 0.50%. D: The shrinkage rate of the evaluation sample is 0.50% or more.

[表2]    黏著性組成物的組成 測定及評價 (甲基)丙烯酸系聚合物 多異氰酸酯系化合物 特定脂環族環氧系化合物 矽烷偶聯劑 耐久性 收縮抑制 高溫低溫環境 熱震環境 種類 摻合量 [質量份] 種類 摻合量 [質量份] 種類 摻合量 [質量份] 種類 摻合量 [質量份] 種類 摻合量 [質量份] 85℃,10%RH以下 (150小時) -40℃⇔85℃ (300循環) 收縮率 [%] 評價 實施例1 A-3 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 X-41-1810 0.20 A A 0.18 A 實施例2 A-3 100 - - CORONATE L-45E 0.80 CELLOXIDE 2081 0.50 X-41-1810 0.20 A A 0.19 A 實施例3 A-3 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.15 X-41-1810 0.20 B C 0.22 B 實施例4 A-3 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 3.8 X-41-1810 0.20 B C 0.13 A 實施例5 A-3 100 - - CORONATE L-45E 0.15 CELLOXIDE 2021P 0.50 X-41-1810 0.20 A A 0.46 C 實施例6 A-9 80 A-10 20 CORONATE L-45E 8.0 CELLOXIDE 2021P 0.15 X-41-1810 0.20 B C 0.20 B 實施例7 A-9 80 A-10 20 CORONATE L-45E 8.0 CELLOXIDE 2021P 0.50 X-41-1810 0.20 B B 0.14 A 實施例8 A-9 80 A-10 20 CORONATE L-45E 8.0 CELLOXIDE 2021P 3.8 X-41-1810 0.20 B C 0.11 A 實施例9 A-3 100 - - CORONATE L-45E 10.0 CELLOXIDE 2021P 0.50 X-41-1810 0.20 B C 0.12 A 實施例10 A-4 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 X-41-1810 0.20 A A 0.18 A 實施例11 A-5 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 X-41-1810 0.20 A A 0.18 A 實施例12 A-6 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 X-41-1810 0.20 A A 0.19 A 實施例13 A-2 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 X-41-1810 0.20 B C 0.23 B 實施例14 A-7 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 X-41-1810 0.20 B C 0.17 A 實施例15 A-3 100 - - TAKENATE D-110N 0.50 CELLOXIDE 2021P 0.50 X-41-1810 0.20 A B 0.18 A 實施例16 A-3 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 KBM-403 0.20 A A 0.18 A 實施例17 A-8 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 X-41-1810 0.20 B B 0.19 A [Table 2] Composition of adhesive composition Measurement and evaluation (meth)acrylic polymer Polyisocyanate compounds Specific alicyclic epoxy compounds Silane coupling agent Durability contraction inhibition High and low temperature environment thermal shock environment Kind Blending amount [mass parts] Kind Blending amount [mass parts] Kind Blending amount [mass parts] Kind Blending amount [mass parts] Kind Blending amount [mass parts] 85℃, below 10%RH (150 hours) -40℃⇔85℃ (300 cycles) Shrinkage [%] Evaluation Example 1 A-3 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 X-41-1810 0.20 A A 0.18 A Example 2 A-3 100 - - CORONATE L-45E 0.80 CELLOXIDE 2081 0.50 X-41-1810 0.20 A A 0.19 A Example 3 A-3 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.15 X-41-1810 0.20 B C 0.22 B Example 4 A-3 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 3.8 X-41-1810 0.20 B C 0.13 A Example 5 A-3 100 - - CORONATE L-45E 0.15 CELLOXIDE 2021P 0.50 X-41-1810 0.20 A A 0.46 C Example 6 A-9 80 A-10 20 CORONATE L-45E 8.0 CELLOXIDE 2021P 0.15 X-41-1810 0.20 B C 0.20 B Example 7 A-9 80 A-10 20 CORONATE L-45E 8.0 CELLOXIDE 2021P 0.50 X-41-1810 0.20 B B 0.14 A Example 8 A-9 80 A-10 20 CORONATE L-45E 8.0 CELLOXIDE 2021P 3.8 X-41-1810 0.20 B C 0.11 A Example 9 A-3 100 - - CORONATE L-45E 10.0 CELLOXIDE 2021P 0.50 X-41-1810 0.20 B C 0.12 A Example 10 A-4 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 X-41-1810 0.20 A A 0.18 A Example 11 A-5 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 X-41-1810 0.20 A A 0.18 A Example 12 A-6 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 X-41-1810 0.20 A A 0.19 A Example 13 A-2 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 X-41-1810 0.20 B C 0.23 B Example 14 A-7 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 X-41-1810 0.20 B C 0.17 A Example 15 A-3 100 - - TAKENATE D-110N 0.50 CELLOXIDE 2021P 0.50 X-41-1810 0.20 A B 0.18 A Example 16 A-3 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 KBM-403 0.20 A A 0.18 A Example 17 A-8 100 - - CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 X-41-1810 0.20 B B 0.19 A

[表3]    黏著性組成物的組成 測定及評價 (甲基)丙烯酸系 聚合物 多異氰酸酯系 化合物 特定脂環族 環氧系化合物 特定脂環族環氧系化合物 以外的環氧系化合物 矽烷偶聯劑 耐久性 收縮抑制 高溫低溫環境 熱震環境 種類 摻合量 [質量份] 種類 摻合量 [質量份] 種類 摻合量 [質量份] 種類 摻合量 [質量份] 種類 摻合量 [質量份] 85℃,10%RH以下 (150小時) -40℃⇔85℃ (300循環) 收縮率 [%] 評價 比較例1 A-3 100 CORONATE L-45E 0.80 - - CELLOXIDE 2000 0.50 X-41-1810 0.20 C D 0.32 B 比較例2 A-3 100 CORONATE L-45E 0.80 - - CELLOXIDE 8010 0.50 X-41-1810 0.20 B D 0.32 B 比較例3 A-3 100 CORONATE L-45E 0.80 - - EPOCHALIC THI-DE 0.50 X-41-1810 0.20 C D 0.34 B 比較例4 A-3 100 CORONATE L-45E 0.80 - - EPOCHALIC DE-102 0.50 X-41-1810 0.20 C D 0.33 B 比較例5 A-3 100 CORONATE L-45E 0.80 - - EPOCHALIC DE-103 0.50 X-41-1810 0.20 C D 0.33 B 比較例6 A-3 100 CORONATE L-45E 0.80 - - X-22-2046 0.50 X-41-1810 0.20 C D 0.32 B 比較例7 A-3 100 CORONATE L-45E 0.80 - - - - X-41-1810 0.20 C D 0.32 B 比較例8 A-3 100 CORONATE L-45E 0.80 CELLOXIDE 2021P 0.07 - - X-41-1810 0.20 B D 0.27 B 比較例9 A-3 100 CORONATE L-45E 0.80 CELLOXIDE 2021P 4.3 - - X-41-1810 0.20 C D 0.09 A 比較例10 A-3 100 CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 - - X-41-1810 0.20 A A 0.83 D 比較例11 A-3 100 CORONATE L-45E 12.0 CELLOXIDE 2021P 0.50 - - X-41-1810 0.20 C D 0.09 A 比較例12 A-1 100 CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 - - X-41-1810 0.20 C D 0.47 C 比較例13 A-3 100 CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 - - - - C D 0.25 B 比較例14 A-3 100 CORONATE L-45E 0.80 - - TETRAD-X 0.50 X-41-1810 0.20 C D 0.28 B [table 3] Composition of adhesive composition Measurement and evaluation (meth)acrylic polymer Polyisocyanate compounds Specific alicyclic epoxy compounds Epoxy compounds other than specific alicyclic epoxy compounds Silane coupling agent Durability contraction inhibition High and low temperature environment thermal shock environment Kind Blending amount [mass parts] Kind Blending amount [mass parts] Kind Blending amount [mass parts] Kind Blending amount [mass parts] Kind Blending amount [mass parts] 85℃, below 10%RH (150 hours) -40℃⇔85℃ (300 cycles) Shrinkage [%] Evaluation Comparative example 1 A-3 100 CORONATE L-45E 0.80 - - CELLOXIDE 2000 0.50 X-41-1810 0.20 C D 0.32 B Comparative example 2 A-3 100 CORONATE L-45E 0.80 - - CELLOXIDE 8010 0.50 X-41-1810 0.20 B D 0.32 B Comparative example 3 A-3 100 CORONATE L-45E 0.80 - - EPOCHALIC THI-DE 0.50 X-41-1810 0.20 C D 0.34 B Comparative example 4 A-3 100 CORONATE L-45E 0.80 - - EPOCHALIC DE-102 0.50 X-41-1810 0.20 C D 0.33 B Comparative example 5 A-3 100 CORONATE L-45E 0.80 - - EPOCHALIC DE-103 0.50 X-41-1810 0.20 C D 0.33 B Comparative example 6 A-3 100 CORONATE L-45E 0.80 - - X-22-2046 0.50 X-41-1810 0.20 C D 0.32 B Comparative example 7 A-3 100 CORONATE L-45E 0.80 - - - - X-41-1810 0.20 C D 0.32 B Comparative example 8 A-3 100 CORONATE L-45E 0.80 CELLOXIDE 2021P 0.07 - - X-41-1810 0.20 B D 0.27 B Comparative example 9 A-3 100 CORONATE L-45E 0.80 CELLOXIDE 2021P 4.3 - - X-41-1810 0.20 C D 0.09 A Comparative example 10 A-3 100 CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 - - X-41-1810 0.20 A A 0.83 D Comparative example 11 A-3 100 CORONATE L-45E 12.0 CELLOXIDE 2021P 0.50 - - X-41-1810 0.20 C D 0.09 A Comparative example 12 A-1 100 CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 - - X-41-1810 0.20 C D 0.47 C Comparative example 13 A-3 100 CORONATE L-45E 0.80 CELLOXIDE 2021P 0.50 - - - - C D 0.25 B Comparative example 14 A-3 100 CORONATE L-45E 0.80 - - TETRAD-X 0.50 X-41-1810 0.20 C D 0.28 B

表2及/或表3記載之成分的詳細內容如以下所示。 ＜多異氰酸酯系化合物＞ 「CORONATE L-45E」[商品名稱，TDI與TMP的加成物，固體成分濃度：45質量%，東曹股份有限公司製]「TAKENATE D-110N」[商品名稱，XDI與TMP的加成物，固體成分濃度：75質量%，三井化學股份有限公司製]上述「CORONATE」及「TAKENATE」皆為註冊商標。 The details of the ingredients described in Table 2 and/or Table 3 are as follows. ＜Polyisocyanate compounds＞ "CORONATE L-45E" [trade name, adduct of TDI and TMP, solid content concentration: 45% by mass, manufactured by Tosoh Co., Ltd.] "TAKENATE D-110N" [trade name, adduct of XDI and TMP , solid content concentration: 75% by mass, manufactured by Mitsui Chemicals Co., Ltd.] The above "CORONATE" and "TAKENATE" are registered trademarks.

＜特定脂環族環氧系化合物＞ 「CELLOXIDE 2021P」[商品名稱，化學名：3’,4’-環氧環己基甲基3,4-環氧環己烷羧酸酯，固體成分濃度：100質量%，Daicel股份有限公司製]、「CELLOXIDE 2081」[商品名稱，化學名：ε-己內酯改質3’,4’-環氧環己基甲基3,4-環氧環己烷羧酸酯，固體成分濃度：100質量%，Daicel股份有限公司製]上述「CELLOXIDE」為註冊商標。 ＜Specific alicyclic epoxy compounds＞ "CELLOXIDE 2021P" [trade name, chemical name: 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, solid content concentration: 100 mass%, manufactured by Daicel Co., Ltd.] , "CELLOXIDE 2081" [trade name, chemical name: ε-caprolactone modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, solid content concentration: 100 mass %, made by Daicel Co., Ltd.] The above "CELLOXIDE" is a registered trademark.

「CELLOXIDE 2021P」具有下式(A)表示的結構。與式(I)中的R相當的2價有機連結基之原子數為3。"CELLOXIDE 2021P" has a structure represented by the following formula (A). The number of atoms of the divalent organic linking group corresponding to R in formula (I) is 3.

[化6] [Chemical 6]

「CELLOXIDE 2081」具有下式(B)表示之結構。與式(I)中的R相當的2價有機連結基的原子數為10。"CELLOXIDE 2081" has a structure represented by the following formula (B). The number of atoms of the divalent organic linking group corresponding to R in formula (I) is 10.

[化7] [Chemical 7]

＜特定脂環族環氧系化合物以外的環氧系化合物＞ 「CELLOXIDE 2000」[商品名稱，化學名：1,2-環氧-4-乙烯基環己烷，固體成分濃度：100質量%，Daicel股份有限公司製] 「CELLOXIDE 8010」[商品名稱，化學名：雙(7-氧雜雙環[4.1.0]庚烷)，固體成分濃度：100質量%，Daicel股份有限公司製] 「EPOCHALIC THI-DE」[商品名稱，化學名：四氫茚二環氧化物，固體成分濃度：100質量%，ENEOS股份有限公司製] 「EPOCHALIC DE-102」[商品名稱，化學名：5,12-二氧雜六環[7.6.1.0(2,8).0(4,6).0(10,15).0(11,13)]十六烷，固體成分濃度：100質量%，ENEOS股份有限公司製] 「EPOCHALIC DE-103」[商品名稱，化學名：5,12-二氧雜七環[7.6.1.1(3,7).0(2,8).0(4,6).0(10,15).0(11,13)]十七烷，固體成分濃度：100質量%，ENEOS股份有限公司製] 「X-22-2046」[商品名稱，化學名：側鏈脂環族環氧改質聚矽氧油，固體成分濃度：100質量%，信越化學工業股份有限公司製] 「TETRAD-X」[商品名稱，化學名：N,N,N’,N’-四環氧丙基間二甲苯二胺、固體成分濃度：100質量%，三菱瓦斯化學股份有限公司製] 上述「CELLOXIDE」、「EPOCHALIC」及「TETRAD」皆為註冊商標。 ＜Epoxy compounds other than specific alicyclic epoxy compounds＞ "CELLOXIDE 2000" [trade name, chemical name: 1,2-epoxy-4-vinylcyclohexane, solid content concentration: 100 mass%, manufactured by Daicel Co., Ltd.] "CELLOXIDE 8010" [trade name, chemical name: bis(7-oxabicyclo[4.1.0]heptane), solid content concentration: 100 mass%, manufactured by Daicel Co., Ltd.] "EPOCHALIC THI-DE" [trade name, chemical name: tetrahydroindene diepoxide, solid content concentration: 100 mass%, manufactured by ENEOS Co., Ltd.] "EPOCHALIC DE-102" [Trade name, chemical name: 5,12-dioxane[7.6.1.0(2,8).0(4,6).0(10,15).0(11, 13)]Hexadecane, solid content concentration: 100% by mass, manufactured by ENEOS Co., Ltd.] "EPOCHALIC DE-103" [Trade name, chemical name: 5,12-dioxacyclo[7.6.1.1(3,7).0(2,8).0(4,6).0(10, 15).0(11,13)] Heptadecane, solid content concentration: 100% by mass, manufactured by ENEOS Co., Ltd.] "X-22-2046" [Trade name, chemical name: Side chain alicyclic epoxy modified polysiloxane oil, solid content concentration: 100 mass%, manufactured by Shin-Etsu Chemical Industry Co., Ltd.] "TETRAD-X" [trade name, chemical name: N,N,N’,N’-tetraepoxypropyl meta-xylylenediamine, solid content concentration: 100 mass%, manufactured by Mitsubishi Gas Chemical Co., Ltd.] The above "CELLOXIDE", "EPOCHALIC" and "TETRAD" are registered trademarks.

「CELLOXIDE 8010」具有下式(X)表示的結構，「CELLOXIDE 2000」具有下式(Y)表示的結構。"CELLOXIDE 8010" has a structure represented by the following formula (X), and "CELLOXIDE 2000" has a structure represented by the following formula (Y).

[化8] [Chemical 8]

「EPOCHALIC THI-DE」、「EPOCHALIC DE-102」及「EPOCHALIC DE-103」分別具有下述結構。"EPOCHALIC THI-DE", "EPOCHALIC DE-102" and "EPOCHALIC DE-103" each have the following structure.

[化9] [Chemical 9]

＜矽烷偶聯劑＞ 「X-41-1810」[商品名稱，含硫醇基之矽烷化合物，固體成分濃度：100質量%，信越化學工業股份有限公司] 「KBM-403」[商品名稱，含環氧基之矽烷化合物，固體成分濃度：100質量%，信越化學工業股份有限公司] ＜Silane coupling agent＞ "X-41-1810" [trade name, thiol group-containing silane compound, solid content concentration: 100 mass%, Shin-Etsu Chemical Industry Co., Ltd.] "KBM-403" [trade name, epoxy group-containing silane compound, solid content concentration: 100 mass%, Shin-Etsu Chemical Industry Co., Ltd.]

表2及表3中，「摻合量」的欄位中記載的數值皆為固體成分換算值。 表2及表3中，「-」表示並未摻合相當於該欄位的成分。 In Tables 2 and 3, the values stated in the "Blending Amount" column are all solid content conversion values. In Tables 2 and 3, "-" indicates that the ingredient corresponding to that column is not blended.

如表2所示，確認由實施例1～17的黏著劑組成物形成的黏著劑層，可良好地抑制放置於高溫環境下時產生的基材收縮。又，確認由實施例1～17的黏著劑組成物形成的黏著劑層，即使放置於重複低溫與高溫的環境下時亦不易產生皺褶及剝離。又，確認由實施例1～17的黏著劑組成物形成的黏著劑層，即使放置於高溫環境下時亦不易產生皺褶及剝離。As shown in Table 2, it was confirmed that the adhesive layer formed of the adhesive compositions of Examples 1 to 17 can well suppress the shrinkage of the base material when placed in a high temperature environment. In addition, it was confirmed that the adhesive layer formed of the adhesive compositions of Examples 1 to 17 is less likely to wrinkle and peel even when placed in an environment where low and high temperatures are repeated. In addition, it was confirmed that the adhesive layer formed of the adhesive compositions of Examples 1 to 17 is less likely to wrinkle and peel even when placed in a high temperature environment.

另一方面，如表3所示，確認由包含特定脂環族環氧系化合物以外的環氧系化合物以代替特定脂環族環氧系化合物的比較例1～6及14的黏著劑組成物所形成的黏著劑層，放置在重複低溫與高溫的環境下時，相較於由實施例的黏著劑組成物所形成之黏著劑層，容易產生皺褶及剝離。 確認由不含特定脂環族環氧系化合物的比較例7之黏著劑組成物所形成之黏著劑層，放置於重複低溫與高溫的環境下時，相較於由實施例的黏著劑組成物形成之黏著劑層，容易產生皺褶及剝離。 確認由特定脂環族環氧系化合物含量相對於100質量份的特定(甲基)丙烯酸系聚合物小於0.1質量份的比較例8的黏著劑組成物所形成之黏著劑層，放置在重複低溫與高溫的環境下時，相較於由實施例的黏著劑組成物所形成之黏著劑層，容易產生皺褶及剝離。 確認由特定脂環族環氧系化合物含量相對於100質量份的特定(甲基)丙烯酸系聚合物超過4.0質量份的比較例9之黏著劑組成物所形成之黏著劑層，放置於重複低溫與高溫的環境下時，相較於由實施例的黏著劑組成物所形成之黏著劑層，容易產生皺褶及剝離。 確認由多異氰酸酯系化合物的含量相對於100質量份的特定(甲基)丙烯酸系聚合物小於0.1質量份的比較例10之黏著劑組成物所形成之黏著劑層，相較於由實施例的黏著劑組成物所形成之黏著劑層，並無法良好地抑制放置在高溫環境下時產生的基材收縮。 確認由多異氰酸酯系化合物的含量相對於100質量份的特定(甲基)丙烯酸系聚合物超過11.0質量份的比較例11的黏著劑組成物所形成之黏著劑層，放置於重複低溫與高溫的環境下時，比由實施例的黏著劑組成物所形成之黏著劑層容易產生皺褶及剝離。 確認由(甲基)丙烯酸系聚合物不具有羧基的比較例12之黏著劑組成物所形成之黏著劑層，放置在重複低溫與高溫的環境下時，相較於實施例的黏著劑組成物所形成之黏著劑層，容易產生皺褶及剝離。 確認由不包含矽烷偶聯劑的比較例13的黏著劑組成物所形成之黏著劑層，放置於重複低溫與高溫的環境下時，相較於由實施例的黏著劑組成物所形成之黏著劑層，容易產生皺褶及剝離。 On the other hand, as shown in Table 3, it was confirmed that the adhesive compositions of Comparative Examples 1 to 6 and 14 contained epoxy compounds other than the specific alicyclic epoxy compound in place of the specific alicyclic epoxy compound. When the formed adhesive layer is placed in an environment with repeated low and high temperatures, it is more likely to wrinkle and peel than the adhesive layer formed from the adhesive composition of the embodiment. It was confirmed that the adhesive layer formed from the adhesive composition of Comparative Example 7 that does not contain a specific alicyclic epoxy compound is better than the adhesive composition of the Example when placed in an environment where low and high temperatures are repeated. The adhesive layer formed is prone to wrinkles and peeling. It was confirmed that the adhesive layer formed of the adhesive composition of Comparative Example 8 with a specific alicyclic epoxy compound content of less than 0.1 parts by mass relative to 100 parts by mass of the specific (meth)acrylic polymer was placed at repeated low temperatures. When exposed to a high temperature environment, the adhesive layer formed by the adhesive composition of the embodiment is more prone to wrinkles and peeling. It was confirmed that the adhesive layer formed of the adhesive composition of Comparative Example 9 in which the content of the specific alicyclic epoxy compound exceeds 4.0 parts by mass relative to 100 parts by mass of the specific (meth)acrylic polymer was placed at repeated low temperatures. When exposed to a high temperature environment, the adhesive layer formed by the adhesive composition of the embodiment is more prone to wrinkles and peeling. It was confirmed that the adhesive layer formed from the adhesive composition of Comparative Example 10 in which the content of the polyisocyanate compound is less than 0.1 parts by mass relative to 100 parts by mass of the specific (meth)acrylic polymer is better than that of the example. The adhesive layer formed by the adhesive composition cannot well inhibit the shrinkage of the substrate when placed in a high temperature environment. It was confirmed that the adhesive layer formed from the adhesive composition of Comparative Example 11 in which the content of the polyisocyanate compound exceeds 11.0 parts by mass relative to 100 parts by mass of the specific (meth)acrylic polymer was placed in a state where low and high temperatures were repeated. When exposed to environmental conditions, the adhesive layer formed by the adhesive composition of the embodiment is more likely to wrinkle and peel than that formed by the adhesive composition of the embodiment. It was confirmed that the adhesive layer formed from the adhesive composition of Comparative Example 12 in which the (meth)acrylic polymer does not have a carboxyl group was placed in an environment where low and high temperatures were repeated, compared with the adhesive composition of the Example. The adhesive layer formed is prone to wrinkles and peeling. It was confirmed that the adhesive layer formed by the adhesive composition of Comparative Example 13 that does not contain a silane coupling agent, when placed in an environment with repeated low and high temperatures, is better than the adhesive layer formed by the adhesive composition of the Example. The agent layer is prone to wrinkles and peeling.

Claims (9)

一種黏著劑組成物，包含： 具有羧基之(甲基)丙烯酸系聚合物； 多異氰酸酯系化合物； 下式(I)表示的脂環族環氧系化合物；及 矽烷偶聯劑； 其中，相對於100質量份的該(甲基)丙烯酸系聚合物，該多異氰酸酯系化合物的含量為0.1質量份～11.0質量份； 相對於100質量份的該(甲基)丙烯酸系聚合物，該脂環族環氧系化合物的含量為0.1質量份～4.0質量份； 式(I)中，R表示具有酯鍵的2價有機連結基。 An adhesive composition, including: a (meth)acrylic polymer having a carboxyl group; a polyisocyanate compound; an alicyclic epoxy compound represented by the following formula (I); and a silane coupling agent; wherein, relative to For 100 parts by mass of the (meth)acrylic polymer, the content of the polyisocyanate compound is 0.1 to 11.0 parts by mass; relative to 100 parts by mass of the (meth)acrylic polymer, the alicyclic compound The content of the epoxy compound is 0.1 to 4.0 parts by mass; In formula (I), R represents a divalent organic linking group having an ester bond. 如請求項1之黏著劑組成物，其中，該式(I)中的R表示之2價有機連結基的原子數為3～200。The adhesive composition of claim 1, wherein the number of atoms of the divalent organic linking group represented by R in the formula (I) is 3 to 200. 如請求項1之黏著劑組成物，其中，該式(I)表示的脂環族環氧系化合物為下式(II)表示的化合物， 式(II)中，n表示0～5的整數。 The adhesive composition of claim 1, wherein the alicyclic epoxy compound represented by formula (I) is a compound represented by the following formula (II), In formula (II), n represents an integer from 0 to 5. 如請求項1之黏著劑組成物，其中，該(甲基)丙烯酸系聚合物的酸價為0.8mgKOH/g～24.0mgKOH/g。The adhesive composition of claim 1, wherein the (meth)acrylic polymer has an acid value of 0.8 mgKOH/g to 24.0 mgKOH/g. 一種黏著片，其具備由如請求項1至4中任一項之黏著劑組成物所形成之黏著劑層。An adhesive sheet having an adhesive layer formed of the adhesive composition according to any one of claims 1 to 4. 如請求項5之黏著片，其具備光學膜與設於該光學膜的至少單面且由如請求項1至4中任一項之黏著劑組成物所形成之黏著劑層。The adhesive sheet according to Claim 5, which includes an optical film and an adhesive layer provided on at least one side of the optical film and formed of the adhesive composition according to any one of Claims 1 to 4. 如請求項6之黏著片，其中該光學膜為偏光板。The adhesive sheet of claim 6, wherein the optical film is a polarizing plate. 一種光學構件，其依序具備： 玻璃基板； 黏著劑層，其係由如請求項1至4中任一項之黏著劑組成物所形成；及 光學膜。 An optical component, which has in order: Glass base board; An adhesive layer formed from the adhesive composition of any one of claims 1 to 4; and Optical film. 一種顯示裝置，其具備如請求項8之光學構件。A display device provided with the optical component of claim 8.
TW112103948A 2022-02-08 2023-02-04 Adhesive composition, adhesive sheet, optical member, and display device TW202337936A (en)

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