TWI642741B - Adhesive composition, adhesive and adhesive sheet - Google Patents

Adhesive composition, adhesive and adhesive sheet Download PDF

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Publication number
TWI642741B
TWI642741B TW103102886A TW103102886A TWI642741B TW I642741 B TWI642741 B TW I642741B TW 103102886 A TW103102886 A TW 103102886A TW 103102886 A TW103102886 A TW 103102886A TW I642741 B TWI642741 B TW I642741B
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adhesive
meth
acrylate
adhesive composition
patent application
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TW103102886A
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TW201431999A (en
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荒井隆行
又野仁
所司悟
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日商琳得科股份有限公司
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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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • C09J2423/00—Presence of polyolefin

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)

Abstract

本發明提供一種適用於偏光板等的光學構件時，耐久性也優異的黏接性組合物、黏接劑以及黏接片。為瞭解決上述課題，提供一種黏接性組合物，包含：作為構成聚合物的單體單元，含有具有脂環式結構的單體的(甲基)丙烯酸酯聚合物(A)，其重量平均分子量為90萬~300萬；活性能量線固化性成分(B)；和矽烷偶聯劑(C)，其具有作為與有機材料反應的官能基的巰基。 The present invention provides an adhesive composition, an adhesive, and an adhesive sheet having excellent durability when applied to an optical member such as a polarizing plate. In order to solve the above-mentioned problems, an adhesive composition is provided which includes, as a monomer unit constituting a polymer, a (meth) acrylate polymer (A) containing a monomer having an alicyclic structure, and having an average weight The molecular weight is 900,000 to 3 million; the active energy ray-curable component (B); and the silane coupling agent (C), which has a mercapto group as a functional group that reacts with an organic material.

Description

黏接性組合物、黏接劑以及黏接片 Adhesive composition, adhesive and adhesive sheet

本發明是關於一種黏接性組合物、黏接劑(使黏接性組合物固化的材料)以及黏接片，特別是關於一種適合作為偏光板等的光學構件用的黏接性組合物、黏接劑以及黏接片。 The present invention relates to an adhesive composition, an adhesive (a material for curing the adhesive composition) and an adhesive sheet, and more particularly to an adhesive composition suitable for use as an optical member such as a polarizing plate, Adhesives and adhesive sheets.

近年在各種電子設備中，多使用兼具顯示裝置與輸入手段的觸控面板。觸控面板的種類主要有電阻式、電容式、光學式以及超聲波式。電阻式觸控面板有模擬數據(analog)電阻式以及母體(matrix)電阻式。電容式觸控面板有表面型以及投影型。 In recent years, in various electronic devices, a touch panel having both a display device and an input means has been used. The types of touch panels are mainly resistive, capacitive, optical, and ultrasonic. The resistive touch panel includes an analog resistive type and a matrix resistive type. Capacitive touch panels are available in surface and projection types.

最近受到注目的智慧手機、平板電腦終端等移動式電子設備的觸控面板，多使用投影型電容式的觸控面板。作為上述移動電子機器的投影型電容式觸控面板，例如，有研究提出了從下向上按順序層疊液晶顯示裝置(LCD)、黏接劑層、透明導電膜(摻雜錫之氧化銦：ITO)、玻璃基板、透明導電膜(ITO)、及強化玻璃等保護層的觸控面板。 Recently, the touch panels of mobile electronic devices such as smartphones and tablet terminals have attracted attention. Projection-type capacitive touch panels are mostly used. As a projection type capacitive touch panel of the above-mentioned mobile electronic device, for example, research has proposed that a liquid crystal display device (LCD), an adhesive layer, and a transparent conductive film (tin-doped indium oxide: ITO) are sequentially stacked from the bottom to the top. ), A glass substrate, a transparent conductive film (ITO), and a touch panel with a protective layer such as tempered glass.

作為上述構成液晶顯示裝置的光學構件，一般使用液晶組件。液晶組件一般是將形成配向層的兩片透明電極基板的配向層作為內側，通過間隔片(spacer)，以形成所定間隔的方式，進行配置，將其周邊密封，在兩片透明電極基板之間 挾持液晶材料的組件。通常，在液晶組件中的兩片透明電極基板的外側，分別介於黏接劑而黏接偏光板。 As the optical member constituting the liquid crystal display device, a liquid crystal module is generally used. A liquid crystal module generally uses an alignment layer of two transparent electrode substrates forming an alignment layer as an inside, and is arranged by a spacer to form a predetermined interval, and the periphery is sealed, between the two transparent electrode substrates. Components that support liquid crystal materials. Generally, polarizers are adhered to the outside of two transparent electrode substrates in a liquid crystal module through an adhesive.

作為在觸控面板中所使用的黏接劑，例如，以知有專利文獻1所示的黏接劑。該黏接劑，作為單體單元，相對於具有碳原子數4~14的烷基的烷基(甲基)丙烯酸酯100重量份，含有將含有羧基的單體0.2重量份~20重量份作為共聚合成分而成的(甲基)丙烯類聚合物，以及相對於(甲基)丙烯類聚合物100重量份，作為架橋劑，含有過氧化物0.02重量份~2重量份，及含有環氧類架橋劑0.005重量份~5重量份。 As an adhesive used for a touch panel, the adhesive shown in patent document 1, for example is known. This adhesive contains, as a monomer unit, 100 parts by weight of an alkyl (meth) acrylate having an alkyl group having 4 to 14 carbon atoms, and contains 0.2 to 20 parts by weight of a carboxyl group-containing monomer as a monomer unit. (Meth) propylene polymer obtained by copolymerizing the components, and as a bridging agent with respect to 100 parts by weight of the (meth) propylene polymer, containing 0.02 to 2 parts by weight of a peroxide and epoxy Cross-linking agent 0.005 parts by weight to 5 parts by weight.

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

【專利文獻1】日本特開2009-242786號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2009-242786

在如上所述的觸控面板中，最近，使用採用了聚環烯烴類保護膜的偏光板的情況在增加，而且，隨著近年的移動電子設備的薄型化，偏光板也被薄型化。但是，聚環烯烴類的材料缺乏與黏接劑的密合性，而且薄型偏光板的收縮率高，因此專利文獻1等以往的黏接劑耐久性低，由於經時或者在高溫條件下、濕熱條件下，有容易發生浮起、剝離這一問題。 In the touch panel as described above, a polarizing plate using a polycycloolefin-based protective film has recently been increasing. In addition, with the reduction in thickness of mobile electronic devices in recent years, the polarizing plate is also becoming thinner. However, polycycloolefin-based materials lack adhesion to the adhesive, and the thin polarizer has a high shrinkage rate. Therefore, conventional adhesives such as Patent Document 1 have low durability. Due to aging or under high temperature conditions, Under the hot and humid conditions, there is a problem that floating and peeling easily occur.

本發明是鑒於這樣的現狀而進行的，目的在於提供一種適用於偏光板等的光學構件時耐久性也優異的黏接性組合物、黏接劑以及黏接片。 The present invention has been made in view of such a situation, and an object thereof is to provide an adhesive composition, an adhesive, and an adhesive sheet that are also excellent in durability when applied to an optical member such as a polarizing plate.

為了達成上述目的，第一，本發明提供一種黏接性組合物，其特徵在於：包含：重量平均分子量為90萬~300萬的(甲基)丙烯酸酯聚合物(A)，其作為構成聚合物的單體單元，含有具有脂環式結構的單體；活性能量線固化性成分(B)；和矽烷偶聯劑(C)，其具有巰基作為與有機材料反應的官能基。 In order to achieve the above object, first, the present invention provides an adhesive composition, comprising: a (meth) acrylate polymer (A) having a weight-average molecular weight of 900,000 to 3 million, and constituting a polymer The monomer unit of the product contains a monomer having an alicyclic structure; an active energy ray-curable component (B); and a silane coupling agent (C), which has a mercapto group as a functional group that reacts with an organic material.

將上述發明(發明1)所述的黏接性組合物固化，則多個活性能量線固化性成分(B)相互結合形成三維網絡結構，據推測在該三維網絡結構上，具有脂環式結構的(甲基)丙烯酸酯聚合物(A)與具有巰基的矽烷偶聯劑(C)形成纏繞的結構。使上述黏接性組合物固化所得到的黏接劑，將偏光板等的光學構件、特別是聚環烯烴類的光學構件、透明導電膜作為被黏物時，耐久性也優異。 When the adhesive composition according to the above invention (Invention 1) is cured, a plurality of active energy ray-curable components (B) are combined with each other to form a three-dimensional network structure. It is estimated that the three-dimensional network structure has an alicyclic structure. The (meth) acrylate polymer (A) and the silane coupling agent (C) having a mercapto group form a entangled structure. The adhesive obtained by curing the above-mentioned adhesive composition is also excellent in durability when an optical member such as a polarizing plate, particularly a polycycloolefin-based optical member, or a transparent conductive film is used as an adherend.

在上述發明(發明1)中，進一步優選含有架橋劑(D)(發明2)。 In the said invention (invention 1), it is more preferable to contain a bridging agent (D) (invention 2).

在上述發明(發明1，發明2)中，上述(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，優選含有0.1質量%~30質量%的具有上述脂環式結構的單體(發明3)。 In the above invention (Invention 1, Invention 2), the (meth) acrylate polymer (A), as a monomer unit constituting the polymer, preferably contains 0.1 to 30% by mass of the alicyclic Structural monomer (Invention 3).

在上述發明(發明1~發明3)中，上述脂環式結構優選含有環己基骨架、雙環戊二烯(dicyclopentadiene)、金剛烷骨架或異冰片骨架(發明4)。 In the above invention (Invention 1 to Invention 3), the alicyclic structure preferably contains a cyclohexyl skeleton, dicyclopentadiene, adamantane skeleton, or isobornyl skeleton (Invention 4).

在上述發明(發明1~發明4)中，上述(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，進一步優選含有0.1質量%~10質量%的具有羥基的單體(發明5)。 In the above invention (Invention 1 to Invention 4), the (meth) acrylate polymer (A), as a monomer unit constituting the polymer, more preferably contains 0.1 to 10% by mass of a monomer having a hydroxyl group.体 (Invention 5).

在上述發明(發明1~發明5)中，上述(甲基)丙烯 酸酯聚合物(A)作為構成該聚合物的單體單元，優選實質上不含有具有羧基的單體(發明6)。 In the above invention (Invention 1 to Invention 5), the (meth) propylene As the monomer unit constituting the polymer, the acid ester polymer (A) preferably does not substantially contain a monomer having a carboxyl group (Invention 6).

在上述發明(發明1~發明6)中，上述活性能量線固化性成分(B)優選為分子量小於1000的多官能丙烯酸酯(acrylate)類單體(發明7)。 In the above invention (Invention 1 to Invention 6), the active energy ray-curable component (B) is preferably a polyfunctional acrylate-based monomer having a molecular weight of less than 1,000 (Invention 7).

在上述發明(發明7)中，上述多官能丙烯酸酯(acrylate)類單體優選具有環狀結構(發明8)。 In the said invention (invention 7), it is preferable that the said polyfunctional acrylate monomer has a cyclic structure (invention 8).

在上述發明(發明1~發明8)中，上述黏接性組合物中上述活性能量線固化性成分(B)的含有量，相對於上述(甲基)丙烯酸酯聚合物(A)100質量份，優選為1質量份~30質量份(發明9)。 In the said invention (invention 1 to invention 8), the content of the said active-energy-ray-curable component (B) in the said adhesive composition is 100 mass parts with respect to the said (meth) acrylate polymer (A) It is preferably 1 to 30 parts by mass (Invention 9).

在上述發明(發明1~發明9)中，上述黏接性組合物中上述矽烷偶聯劑(C)的含有量，相對於上述(甲基)丙烯酸酯聚合物(A)100質量份，優選為0.01質量份~5質量份(發明10)。 In the above invention (Invention 1 to Invention 9), the content of the silane coupling agent (C) in the adhesive composition is preferably based on 100 parts by mass of the (meth) acrylate polymer (A). It is 0.01 to 5 parts by mass (Invention 10).

在上述發明(發明1~發明10)中，上述架橋劑(D)優選為異氰酸酯類架橋劑(發明11)。 In the above invention (Invention 1 to Invention 10), the bridging agent (D) is preferably an isocyanate bridging agent (Invention 11).

在上述發明(發明1~發明11)中，進一步優選含有光聚合起始劑(E)(發明12)。 In the said invention (invention 1 to invention 11), it is more preferable to contain a photoinitiator (E) (invention 12).

第二，本發明提供一種將上述黏接性組合物(發明1~發明12)，通過活性能量線的照射使其固化而成的黏接劑(發明13)。 Second, the present invention provides an adhesive obtained by curing the above-mentioned adhesive composition (Invention 1 to Invention 12) by irradiation with active energy rays (Invention 13).

第三，本發明提供一種黏接片，其特徵在於：為具有基材與黏接劑層的黏接片，上述黏接劑層由上述黏接劑(發明13)構成(發明14)。 Third, the present invention provides an adhesive sheet, which is an adhesive sheet having a substrate and an adhesive layer, and the adhesive layer is composed of the adhesive (invention 13) (invention 14).

上述發明(發明14)中，上述基材優選為光學構件(發明15)。 In the said invention (invention 14), it is preferable that the said base material is an optical member (invention 15).

上述發明(發明15)中，上述光學構件優選為偏光板(發明16)。 In the above invention (Invention 15), the optical member is preferably a polarizing plate (Invention 16).

上述發明(發明15，發明16)中，上述光學構件優選具有聚環烯烴類膜(發明17)。另外，所說的「具有聚環烯烴類膜」為含有「僅由聚環烯烴類膜構成」的概念。 In the above invention (Invention 15, Invention 16), the optical member preferably has a polycycloolefin-based film (Invention 17). In addition, the "having a polycycloolefin-based film" is a concept including "consisting only of a polycycloolefin-based film".

第四，本發明提供一種黏接片，其特徵在於：其具備兩片剝離片和以上述2片剝離片的剝離面相接的方式挾持上述剝離片的黏接劑層，上述黏接劑層由上述黏接劑(發明13)構成(發明18)。 Fourth, the present invention provides an adhesive sheet, which is characterized in that it includes two release sheets and an adhesive layer holding the release sheet so that the release surfaces of the two release sheets are in contact with each other, and the adhesive layer is It consists of the said adhesive agent (invention 13) (invention 18).

本發明所述黏接性組合物通過含有(A)~(C)的成分，則所得到的黏接劑耐久性高，適合用於偏光板等的光學構件使用。 When the adhesive composition according to the present invention contains the components (A) to (C), the obtained adhesive has high durability and is suitable for use in optical members such as polarizing plates.

1A，1B‧‧‧黏接片 1A, 1B ‧‧‧ Adhesive Sheet

11‧‧‧黏接劑層 11‧‧‧Adhesive layer

12，12a，12b‧‧‧剝離片 12, 12a, 12b ‧‧‧ peeling sheet

13‧‧‧基材 13‧‧‧ substrate

圖1為本發明第1實施形態所有關的黏接片的剖面圖。 FIG. 1 is a cross-sectional view of an adhesive sheet according to a first embodiment of the present invention.

圖2為本發明第2實施形態所有關的黏接片的剖面圖。 Fig. 2 is a sectional view of an adhesive sheet according to a second embodiment of the present invention.

以下，關於本發明的實施形態進行說明。 Hereinafter, embodiments of the present invention will be described.

〔黏接性組合物〕 [Adhesive composition]

本實施形態所有關的黏接性組合物(以下稱為「黏接性組合物P」)，作為構成聚合物的單體單元，含有(甲基)丙烯酸酯 聚合物(A)、活性能量線固化性成分(B)、具有作為與有機材料反應的官能基的巰基的矽烷偶聯劑(C)，優選進一步含有架橋劑(D)及/或光聚合起始劑(E)，上述(甲基)丙烯酸酯聚合物(A)的重量平均分子量為90萬~300萬，其含有具有脂環式結構的單體(含有脂環式結構單體)。另外，本說明書中，所說的(甲基)丙烯酸酯，指丙烯酸酯以及甲基丙烯酸酯的兩方。其他的類似用語也同樣。另外，在「聚合物」中，也包括「共聚物」的概念。 The adhesive composition (hereinafter referred to as "adhesive composition P") according to this embodiment contains a (meth) acrylate as a monomer unit constituting a polymer. The polymer (A), the active energy ray-curable component (B), and the silane coupling agent (C) having a mercapto group as a functional group that reacts with an organic material, preferably further contain a bridging agent (D) and / or photopolymerization. As the initiator (E), the weight average molecular weight of the (meth) acrylate polymer (A) is 900,000 to 3 million, and it contains a monomer having an alicyclic structure (containing an alicyclic structure monomer). In addition, in this specification, a (meth) acrylate means both an acrylate and a methacrylate. The same applies to other similar terms. In addition, the term "copolymer" is also included in "polymer".

使上述黏接性組合物P固化，則複數個活性能量線固化性成分(B)相互結合形成三維網絡結構，據推測在該三維網絡結構上，具有脂環式結構的(甲基)丙烯酸酯聚合物(A)和具有巰基的矽烷偶聯劑(C)形成纏繞的結構。這樣所得到的黏接劑，在將偏光板等的光學構件、特別是將聚環烯烴類的光學構件(例如，由聚環烯烴類膜所構成的光學構件、一部分具有聚環烯烴類膜的光學構件)、透明導電膜作為被黏物時，耐久性也優異。 When the adhesive composition P is cured, a plurality of active energy ray-curable components (B) are combined with each other to form a three-dimensional network structure. It is estimated that the (meth) acrylate having an alicyclic structure on the three-dimensional network structure. The polymer (A) and the silane coupling agent (C) having a mercapto group form a entangled structure. The adhesive obtained in this way can be used for an optical member such as a polarizing plate, particularly a polycycloolefin-based optical member (for example, an optical member composed of a polycycloolefin-based film, Optical members) and transparent conductive films are excellent in durability.

(1)(甲基)丙烯酸酯聚合物(A) (1) (meth) acrylate polymer (A)

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，具有含有脂環式結構的單體。由此，所得到的黏接劑，如前所述成為耐久性優異的黏接劑。可以認為該効果是由於脂環式結構與光學構件或透明導電膜的親和性、相互作用比較強，密合性等提高的原因。 The (meth) acrylate polymer (A) has a monomer having an alicyclic structure as a monomer unit constituting the polymer. Thereby, the obtained adhesive becomes the adhesive excellent in durability as mentioned above. It is considered that this effect is due to the relatively strong affinity and interaction between the alicyclic structure and the optical member or the transparent conductive film, and the increase in adhesion and the like.

脂環式結構的碳原子環，即可以為飽和結構的碳原子環，也可以為含有不飽和鍵的碳原子環。而且，脂環式結 構即可以是單環的脂環式結構，也可以是二環、三環等的多環脂環式結構。脂環式結構的碳原子數優選為5~20，特別優選為6~15，進一步優選為7~12。 The carbon atom ring of the alicyclic structure may be a carbon atom ring of a saturated structure or a carbon atom ring containing an unsaturated bond. Moreover, alicyclic knots The configuration may be a monocyclic alicyclic structure, or a bicyclic, tricyclic, or other polycyclic alicyclic structure. The number of carbon atoms of the alicyclic structure is preferably 5 to 20, particularly preferably 6 to 15, and even more preferably 7 to 12.

作為脂環式結構，例如可以列舉含有環己基骨架、雙環戊二烯骨架、金剛烷骨架、異冰片骨架、環烷烴骨架(環庚烷骨架、環辛烷骨架、環壬烷骨架、環癸烷骨架、環十一烷骨架、環十二烷骨架等)、環烯烴骨架(環庚烯骨架、環辛烯骨架等)、降冰片烯骨架、降冰片二烯骨架、多環式骨架(立方烷骨架、五環癸烷(Basketane)骨架、房烷(housane)骨架等)、螺環(spiro)骨架等的脂環式結構，其中，優選發揮更優異的耐久性向上効果的含有環己基骨架、雙環戊二烯骨架、金剛烷骨架或異冰片骨架的脂環式結構。 Examples of the alicyclic structure include a cyclohexyl skeleton, a dicyclopentadiene skeleton, an adamantane skeleton, an isobornyl skeleton, a cycloalkane skeleton (cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane). Skeleton, cycloundecane skeleton, cyclododecane skeleton, etc.), cyclic olefin skeleton (cycloheptene skeleton, cyclooctene skeleton, etc.), norbornene skeleton, norbornadiene skeleton, polycyclic skeleton (cubane Among the alicyclic structures such as a skeleton, a pentacyclodecane (Basketane skeleton, a housane skeleton, etc.), and a spiro skeleton, a cyclohexyl skeleton including a cyclohexyl skeleton, which exhibits superior durability upward effect, is preferred. An alicyclic structure of a dicyclopentadiene skeleton, an adamantane skeleton, or an isobornyl skeleton.

作為上述含有脂環式結構的單體，優選含有上述骨架的(甲基)丙烯酸酯單體，具體而言，可以舉出(甲基)丙烯酸環己基酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊烯基酯、(甲基)丙烯酸二環戊烯氧乙基酯等，其中，優選發揮更優異的提高耐久性効果的(甲基)丙烯酸環己基酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷基酯或(甲基)丙烯酸異冰片酯。這些可以單獨使用1種，也可以組合兩種以上使用。 As the alicyclic structure-containing monomer, a (meth) acrylate monomer containing the above-mentioned skeleton is preferable, and specifically, cyclohexyl (meth) acrylate and dicyclopentyl (meth) acrylate are mentioned. , Adamantyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, etc., among them, preferred Cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, adamantyl (meth) acrylate, or isobornyl (meth) acrylate exhibiting more excellent durability-improving effects. These may be used individually by 1 type, and may be used in combination of 2 or more type.

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，優選含有0.1質量%~30質量%的上述含有脂環式結構的單體，特別是優選含有0.2質量%~25質量%，進一步優選含有0.5質量%~20質量%。含有脂環式結構單體的含有 量如果小於0.1質量%，則難以得到上述的提高耐久性的効果。脂環式結構含有單體的含有量如果超過30質量%，則作為光學用途有得不到優選的黏接性的情況。 The (meth) acrylate polymer (A), as a monomer unit constituting the polymer, preferably contains 0.1 to 30% by mass of the above-mentioned alicyclic structure-containing monomer, and particularly preferably contains 0.2% by mass to 25 mass%, more preferably 0.5 mass% to 20 mass%. Containing alicyclic structural monomers If the amount is less than 0.1% by mass, it is difficult to obtain the aforementioned effect of improving durability. When the content of the alicyclic structure-containing monomer exceeds 30% by mass, the adhesiveness may not be obtained for optical applications.

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，除上述含有脂環式結構單體之外，還優選含有烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯，特別是優選作為主成分而含有。 The (meth) acrylic acid ester polymer (A), as the monomer unit constituting the polymer, in addition to the alicyclic structure-containing monomer described above, it is also preferable that the Alkyl) acrylate is particularly preferably contained as a main component.

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，通過含有烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯，可以表現優選的黏接性。作為烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯，例如，可以列舉出(甲基)丙烯酸甲基酯、(甲基)丙烯酸乙基酯、(甲基)丙烯酸丙基酯、(甲基)丙烯酸正丁基酯、(甲基)丙烯酸正戊基酯、(甲基)丙烯酸正己基酯、(甲基)丙烯酸2-乙基己基酯、(甲基)丙烯酸異辛基酯、(甲基)丙烯酸正癸基酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸肉豆蔻基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸硬脂基等。其中，從更加提高黏接性的觀點考慮，優選烷基的碳原子數為1~8的(甲基)丙烯酸酯，特別優選(甲基)丙烯酸甲酯及(甲基)丙烯酸正丁酯。而且，這些可以單獨使用，也可以組合兩種以上使用。 The (meth) acrylic acid ester polymer (A), as a monomer unit constituting the polymer, can exhibit preferable adhesion by an alkyl (meth) acrylic acid ester having 1 to 20 carbon atoms in the alkyl group. Sex. Examples of the alkyl (meth) acrylate having 1 to 20 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. Ester, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isomethacrylate Octyl ester, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, (methyl) ) Acrylic stearyl and the like. Among them, (meth) acrylates having 1 to 8 carbon atoms in the alkyl group are preferable from the viewpoint of further improving the adhesiveness, and methyl (meth) acrylate and n-butyl (meth) acrylate are particularly preferable. These may be used alone or in combination of two or more.

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，優選含有20質量%~99.8質量%的烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯，特別優選含有50質量%~90.5質量%，進一步優選含有60質量%~99質量%。 The (meth) acrylic acid ester polymer (A) is preferably a (meth) acrylic acid alkyl group having 1 to 20 carbon atoms having 20 to 99.8% by mass of an alkyl group as a monomer unit constituting the polymer. The ester particularly preferably contains 50% to 90.5% by mass, and more preferably 60% to 99% by mass.

另外，(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，優選含有具有羥基的單體(含有羥基單體)。黏接性組合物P含有架橋劑(D)的情況時，羥基與該架橋劑(D)的反應性官能基、特別是與異氰酸酯類架橋劑的異氰酸酯基反應性高，由於這些反應，(甲基)丙烯酸酯聚合物(A)由於架橋劑(D)被有效地架橋，形成良好的架橋結構。由此，所得到的黏接劑耐久性更優異。 The (meth) acrylate polymer (A) preferably contains a monomer having a hydroxyl group (a hydroxyl-containing monomer) as a monomer unit constituting the polymer. When the adhesive composition P contains a bridging agent (D), the reactive functional group of the hydroxyl group and the bridging agent (D), especially the isocyanate group of the isocyanate bridging agent is highly reactive. Base) acrylic polymer (A) is effectively bridged by the bridging agent (D), forming a good bridging structure. Thereby, the obtained adhesive is more excellent in durability.

作為含羥基單體，例如，可以例舉(甲基)丙烯酸2-羥基乙基酯、(甲基)丙烯酸2-羥基丙基酯、(甲基)丙烯酸3-羥基丙基酯、(甲基)丙烯酸2-羥基丁基酯、(甲基)丙烯酸3-羥基丁基酯、(甲基)丙烯酸4-羥基丁基酯等的(甲基)丙烯酸羥基烷基酯等，其中，與所得到的(甲基)丙烯酸酯聚合物(A)中的羥基的架橋劑(B)的反應性以及與其他單體的共聚合性的觀點考慮，優選(甲基)丙烯酸2-羥基乙基酯。這些可以單獨使用，也可以組合兩種以上使用。 Examples of the hydroxyl-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (methyl) ) 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. From the viewpoint of the reactivity of the hydroxy bridging agent (B) in the (meth) acrylate polymer (A) and the copolymerizability with other monomers, 2-hydroxyethyl (meth) acrylate is preferred. These may be used alone or in combination of two or more.

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，優選含有0.1質量%~10質量%的含有羥基單體，特別是優選含有0.2質量%~8質量%，進一步優選含有0.3質量%~5質量%。含有羥基單體的含有量在上述範圍，則所形成的架橋結構良好，所得到的黏接劑具有更優異的耐久性。含有羥基單體的含有量如果小於0.1質量%，則架橋點過少，難以得到提高耐久性的効果。另一方面，含有羥基單體的含有量如果超過10質量%，則架橋點過多，所得到的黏接劑有不柔軟，應力緩和性降低的可能性。 The (meth) acrylate polymer (A), as a monomer unit constituting the polymer, preferably contains 0.1 to 10% by mass of a hydroxyl group-containing monomer, and particularly preferably contains 0.2 to 8% by mass. Further, It is preferably contained in an amount of 0.3 to 5% by mass. When the content of the hydroxyl group-containing monomer is within the above range, the formed bridging structure is good, and the obtained adhesive has more excellent durability. When the content of the hydroxyl-containing monomer is less than 0.1% by mass, the number of bridge points is too small, and it is difficult to obtain the effect of improving durability. On the other hand, if the content of the hydroxyl-containing monomer exceeds 10% by mass, there will be too many bridging points, and the resulting adhesive may not be soft and the stress relaxation may be reduced.

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，優選實質上不含有具有羧基的單體(含有羧基單體)。通過實質上不含有具有酸成分的羧基的單體，可以抑制所得到的黏接劑的貼附對象由於酸所產生的不良，例如即使為透明導電膜或金屬膜等的情況，也可以抑制它們由於酸所產生的不良。特別是，在貼附對象為透明導電膜的情況時，可以抑制該透明導電膜被腐食或該透明導電膜的電阻值發生變化。而且，像後述的矽烷偶聯劑(C)那樣，不受酸影響的聚合物也有效地發揮作用。另外，通過實質上不含有具有羧基的單體，可以防止該羧基阻礙上述含有羥基單體的羥基與架橋劑(D)，特別是與異氰酸酯類架橋劑的反應。 The (meth) acrylate polymer (A), as a monomer unit constituting the polymer, preferably does not substantially contain a monomer having a carboxyl group (a carboxyl group-containing monomer). By substantially not containing a monomer having a carboxyl group having an acid component, it is possible to suppress defects caused by the acid due to the adhered object of the adhesive, for example, even in the case of a transparent conductive film or a metal film. Defects due to acids. In particular, when the object to be attached is a transparent conductive film, it is possible to suppress the transparent conductive film from being rotten or to change the resistance value of the transparent conductive film. In addition, like the silane coupling agent (C) described later, polymers that are not affected by acids also effectively function. In addition, by not substantially containing a monomer having a carboxyl group, it is possible to prevent the carboxyl group from hindering the reaction between the hydroxyl group of the hydroxyl group-containing monomer and the bridging agent (D), and in particular with an isocyanate-based bridging agent.

(甲基)丙烯酸酯聚合物(A)除上述單體以外，根據需要，還可以含有其他的單體。作為其他單體，可以為具有羥基以外的反應性官能基的單體(含有反應性官能基單體)，也可以為非反應性的單體。 The (meth) acrylate polymer (A) may contain other monomers in addition to the above-mentioned monomers as necessary. The other monomer may be a monomer having a reactive functional group other than a hydroxyl group (a reactive functional group-containing monomer), or may be a non-reactive monomer.

作為含有反應性官能基的單體，例如，可以舉出具有氨基的單體(含有氨基單體)等。作為含有氨基的單體，例如，可以舉出(甲基)丙烯酸氨基乙基酯、(甲基)丙烯酸正丁基氨基乙基酯等。這些可以單獨使用，也可以組合兩種以上使用。 Examples of the reactive functional group-containing monomer include a monomer having an amino group (amino-containing monomer) and the like. Examples of the amino group-containing monomer include aminoethyl (meth) acrylate and n-butylaminoethyl (meth) acrylate. These may be used alone or in combination of two or more.

作為非反應性單體，例如，可以舉出(甲基)丙烯酸甲氧基甲基酯、(甲基)丙烯酸甲氧基乙基酯、(甲基)丙烯酸乙氧基甲基酯、(甲基)丙烯酸乙氧基乙基酯等的含有烷氧基烷基(甲基)丙烯酸酯、(甲基)丙烯酸苯基等的具有芳香族環的(甲基)丙烯酸酯、丙烯醯胺、甲基丙烯醯胺等的非架橋性的丙烯醯 胺、(甲基)丙烯酸N，N-二甲基氨基乙基酯、(甲基)丙烯酸N，N-二甲基氨基丙基酯等的具有非架橋性的3級氨基的(甲基)丙烯酸酯、乙酸乙烯酯、苯乙烯等。這些可以單獨使用，也可以組合兩種以上使用。 Examples of the non-reactive monomer include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and (meth) (Meth) acrylate containing alkoxyalkyl (meth) acrylate, (meth) acrylic phenyl, and the like having aromatic rings (meth) acrylate, acrylamido, and methyl Non-bridged acrylamide (Methyl) having a non-bridged tertiary amino group such as amine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate Acrylate, vinyl acetate, styrene, etc. These may be used alone or in combination of two or more.

(甲基)丙烯酸酯聚合物(A)的聚合方式，可以為無規共聚物，也可以為嵌段共聚物。 The polymerization method of the (meth) acrylate polymer (A) may be a random copolymer or a block copolymer.

(甲基)丙烯酸酯聚合物(A)的重量平均分子量為90萬~300萬，優選為100萬~250萬，特別優選為110萬~200萬。另外，本說明書中的重均分子量，為根據凝膠滲透色譜法(GPC)法所測定的聚苯乙烯換算的值。 The weight average molecular weight of the (meth) acrylate polymer (A) is 900,000 to 3 million, preferably 1 to 2.5 million, and particularly preferably 1.1 to 2 million. In addition, the weight average molecular weight in this specification is a polystyrene conversion value measured by the gel permeation chromatography (GPC) method.

(甲基)丙烯酸酯聚合物(A)重量平均分子量如果小於90萬，則所得到的黏接劑的耐久性差。而且，(甲基)丙烯酸酯聚合物(A)的重量平均分子量如果超過300萬，則所得到的黏接劑的黏接力降低。 When the weight average molecular weight of the (meth) acrylate polymer (A) is less than 900,000, the durability of the obtained adhesive is poor. When the weight average molecular weight of the (meth) acrylate polymer (A) exceeds 3 million, the adhesive force of the obtained adhesive is reduced.

另外，在黏接性組合物P中，(甲基)丙烯酸酯聚合物(A)可以單獨使用1種，也可以組合兩種以上使用。而且，黏接性組合物P可以進一步含有不含有上述含有脂環式結構單體作為構成單體單元的(甲基)丙烯酸酯聚合物。 In addition, in the adhesive composition P, a (meth) acrylate polymer (A) may be used individually by 1 type, and may be used in combination of 2 or more type. Further, the adhesive composition P may further contain a (meth) acrylate polymer that does not contain the alicyclic structure-containing monomer as a constituent monomer unit.

(2)活性能量線固化性成分(B) (2) Active energy ray curable component (B)

活性能量線固化性成分(B)，只要為不防礙本發明的効果，通過活性能量線的照射固化的成分，就沒有特別的制限，既可以為單體、低聚物或聚合物的任意一種，也可以為它們的混合物。其中，可以優選列舉出與(甲基)丙烯酸酯聚合物(A)等的相溶性優異的分子量小於1000的多官能丙烯酸酯 (acrylate)類單體。 The active energy ray-curable component (B) is not particularly limited as long as it is a component that does not prevent the effects of the present invention and is cured by irradiation of the active energy ray, and may be any monomer, oligomer, or polymer. One kind or a mixture of them. Among these, polyfunctional acrylates having a molecular weight of less than 1,000 and having excellent compatibility with the (meth) acrylate polymer (A) and the like can be cited. (acrylate) type monomer.

作為分子量小於1000的多官能丙烯酸酯(acrylate)類單體，例如可以舉出1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、新戊二醇己二酸酯二(甲基)丙烯酸酯(neopentylglycol adipate di(meth)acrylate)、羥基新戊酸新戊二醇二(甲基)丙烯酸酯(hydroxypivalic acid neopentylglycol di(meth)acrylate)、二環戊基二(甲基)丙烯酸酯(dicyclopentanyl di(meth)acrylate)、己內酯改性二環戊烯基二(甲基)丙烯酸酯(caprolactone-modified dicyclopentenyl di(meth)acrylate)、環氧乙烷改性磷酸二(甲基)丙烯酸酯、二(丙烯酰氧基乙基)異氰酸酯(di(acryloxy ethyl)isocyanurate)、烯丙基化環己基二(甲基)丙烯酸酯(allylated cyclohexyl di(meth)acrylate)等的2官能型；三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、丙酸改性二季戊四醇三(甲基)丙烯酸酯(propionic acid-modified dipentaerythritol tri(meth)acrylate)、季戊四醇三(甲基)丙烯酸酯、環氧丙烯改性三羥甲基丙烷三(甲基)丙烯酸酯(propyleneoxide-modified trimethylolpropane tri(meth)acrylate)、三(丙烯酰氧基乙基)異氰酸酯等的3官能型；二甘油四(甲基)丙烯酸酯(diglycerin tetra(meth)acrylate)、季戊四醇四(甲基)丙烯酸酯等的4官能型；丙酸改性二季戊四醇五(甲基)丙烯酸酯等的5官能型；二季戊四醇六(甲基)丙烯酸酯、己內酯(caprolactone)改性二季戊四醇六(甲基)丙烯酸酯等的6官能型等。這些可以單獨使用1種，也可以組合兩種以上使用。 Examples of the polyfunctional acrylate monomer having a molecular weight of less than 1,000 include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxyl Pivalic acid neopentylglycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modification Dicyclopentenyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified phosphate di (meth) acrylate, bis (acryloyloxyethyl) isocyanate ( di (acryloxy ethyl) isocyanurate), allylated cyclohexyl di (meth) acrylate, and other bifunctional types; trimethylolpropane tri (meth) acrylate, di Pentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate (propionic aci d-modified dipentaerythritol tri (meth) acrylate), pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, three 3-functional types such as (acryloyloxyethyl) isocyanate; 4-functional types such as diglycerin tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate; etc. 5-functional types such as dipentaerythritol penta (meth) acrylate, etc .; 6-functional types such as dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, etc. These may be used individually by 1 type, and may be used in combination of 2 or more type.

上述多官能丙烯酸酯類單體中，在骨架中具有環狀結構的多官能丙烯酸酯類單體由於耐久性能更優異，因此優選。環狀結構即可以為碳環結構也可以為雜環結構，此外，即可以為單環結構也可以為多環結構。作為像這樣的多官能丙烯酸酯類單體，例如可以舉出二(丙烯醯氧基乙基)異氰酸酯(di(acryloxy ethyl)isocyanurate)、三(丙烯醯氧基乙基)異氰酸酯等的具有異氰酸酯結構的多官能丙烯酸酯類單體、二羥甲基二環戊烷二丙烯酸酯、環氧乙烷改性六氫鄰苯二甲酸二丙烯酸酯、三環二甲醇丙烯酸酯、金剛烷二丙烯酸酯等。 Among the above-mentioned polyfunctional acrylate monomers, a polyfunctional acrylate monomer having a cyclic structure in the skeleton is more preferable because it has superior durability. The cyclic structure may be a carbocyclic structure or a heterocyclic structure, and may be a monocyclic structure or a polycyclic structure. Examples of such a polyfunctional acrylate-based monomer include an isocyanate structure such as di (acryloxy ethyl) isocyanurate, tri (acryloxy ethyl) isocyanurate, and the like. Polyfunctional acrylate monomer, dimethylol dicyclopentane diacrylate, ethylene oxide modified hexahydrophthalic acid diacrylate, tricyclic dimethanol acrylate, adamantane diacrylate, etc. .

作為活性能量線固化性成分(B)，也可以使用活性能量線固化型的丙烯酸酯類低聚物。該丙烯酸酯類低聚物優選重均分子量為50,000以下。作為像這樣的丙烯酸酯類低聚物的例子，可以舉出聚酯丙烯酸酯類、環氧丙烯酸酯類、胺基甲酸酯丙烯酸酯(urethane acrylate)類、聚醚丙烯酸酯類、聚丁二烯丙烯酸酯類、矽酮丙烯酸酯(silicone acrylate)類等。 As the active energy ray-curable component (B), an active energy ray-curable acrylate-based oligomer may be used. The acrylate oligomer preferably has a weight average molecular weight of 50,000 or less. Examples of such acrylate-based oligomers include polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates, and polybutadiene Acrylic acrylates, silicone acrylates, etc.

在此，聚酯丙烯酸酯類低聚物，例如可以通過用(甲基)丙烯酸，使由多元羧酸與多元醇的縮聚而得到的在兩末端具有羥基的聚酯低聚物的羥基，酯化而得到；或者，可以通過用(甲基)丙烯酸，使在多元羧酸上附加氧化亞烴所得的低聚物末端的羥基，酯化而得到。環氧丙烯酸酯類低聚物，例如，可以通過在分子量比較低的雙酚型環氧樹脂、酚醛清漆型環氧樹脂的環氧乙烷環上，使(甲基)丙烯酸反應，且酯化而得到。另外，也可以使用將該環氧丙烯酸酯類低聚物，用二鹽基性(dibasic character)羧酸酐(carboxylic acid anhydride)，進行部 分地改性所得的羧改性型環氧丙烯酸酯低聚物。胺基甲酸酯丙烯酸酯(urethane acrylate)類低聚物，例如，可以通過用(甲基)丙烯酸，使由聚醚多醇或聚酯多元醇與聚異氰酸酯(polyisocyanate)的反應所得到的聚氨酯低聚物，酯化而得到。多醇丙烯酸酯類低聚物，可以通過用(甲基)丙烯酸、使聚醚多醇的羥基，酯化而得到。 Here, the polyester acrylate-based oligomer can be obtained by, for example, using (meth) acrylic acid and polycondensing a polycarboxylic acid and a polyhydric alcohol to obtain a hydroxyl group and an ester of a polyester oligomer having hydroxyl groups at both ends. Alternatively, it can be obtained by esterifying a hydroxy group at the end of an oligomer obtained by oxidizing an alkylene with a polycarboxylic acid using (meth) acrylic acid. The epoxy acrylate-based oligomer can be reacted with, for example, esterification of (meth) acrylic acid on the ethylene oxide ring of a relatively low molecular weight bisphenol epoxy resin or novolac epoxy resin. And get. Alternatively, the epoxy acrylate-based oligomer may be prepared by using a dibasic character carboxylic acid anhydride. Separate modification of the obtained carboxy-modified epoxy acrylate oligomer. Urethane acrylate-based oligomers, for example, can be obtained by reacting a polyether polyol or polyester polyol with a polyisocyanate using (meth) acrylic acid. Oligomers, obtained by esterification. The polyol acrylate oligomer can be obtained by esterifying a hydroxyl group of a polyether polyol with (meth) acrylic acid.

上述丙烯酸酯類低聚物的重量平均分子量優選為50,000以下，特別優選為500~50,000，進一步又選為3,000~40,000。這些丙烯酸酯類低聚物可以單獨使用1種，也可組合兩種以上使用。 The weight average molecular weight of the acrylate-based oligomer is preferably 50,000 or less, particularly preferably 500 to 50,000, and still more preferably 3,000 to 40,000. These acrylate oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.

另外，作為活性能量線固化性成分(B)，也可以使用在側鏈導入了具有(甲基)丙烯醯基((meta)acryloyl)的基團所得的加成物丙烯酸酯(adduct acrylate)類聚合物。這樣的加成物丙烯酸酯類聚合物，可以通過使用(甲基)丙烯酸酯與分子內具有架橋性官能基的單體的共聚物，使具有與(甲基)丙烯醯基及架橋性官能基反應的基團的化合物，與該共聚物的架橋性官能基的一部分，進行反應而得到。 In addition, as the active energy ray-curable component (B), adduct acrylates obtained by introducing a group having a (meth) acryloyl group into a side chain may be used. polymer. Such an adduct acrylate polymer can have a copolymer with a (meth) acrylfluorene group and a bridging functional group by using a copolymer of (meth) acrylate and a monomer having a bridging functional group in the molecule. A compound of a reactive group is obtained by reacting with a part of the bridging functional group of the copolymer.

作為上述(甲基)丙烯酸酯，優選含有烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯，例如可以舉出(甲基)丙烯酸甲基酯、(甲基)丙烯酸乙基酯、(甲基)丙烯酸丙基酯、(甲基)丙烯酸丁基酯、(甲基)丙烯酸戊基酯、(甲基)丙烯酸己基酯、(甲基)丙烯酸環己基酯、(甲基)丙烯酸2-乙基己基酯、(甲基)丙烯酸異辛基酯、(甲基)丙烯酸癸基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸肉豆蔻基酯、(甲基)丙烯酸十六烷基酯、(甲 基)丙烯酸硬脂基酯等。這些可以單獨使用，也可以組合兩種以上使用。 The (meth) acrylate is preferably an alkyl (meth) acrylate containing 1 to 20 carbon atoms in the alkyl group, and examples thereof include methyl (meth) acrylate and ethyl (meth) acrylate Ester, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) ) 2-ethylhexyl acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, ( Cetyl meth) acrylate, Base) stearyl acrylate and the like. These may be used alone or in combination of two or more.

上述分子內具有架橋性官能基的單體，作為官能基，優選含有選自羥基、羧基、氨基以及醯胺基的至少1種。作為上述單體，例如可以列舉(甲基)丙烯酸2-羥基乙基酯、(甲基)丙烯酸2-羥基丙基酯、(甲基)丙烯酸3-羥基丙基酯、(甲基)丙烯酸2-羥基丁基酯、(甲基)丙烯酸3-羥基丁基酯、(甲基)丙烯酸4-羥基丁基酯等的(甲基)丙烯酸羥基烷基酯；丙烯醯胺、甲基丙烯醯胺、N-甲基丙烯醯胺、N-甲基甲丙烯醯胺、N-羥甲基丙烯醯胺、N-羥甲基甲基丙烯醯胺等的丙烯醯胺類；(甲基)丙烯酸單甲基氨基乙基酯、(甲基)丙烯酸單乙基氨基乙基酯、(甲基)丙烯酸單甲基氨基丙基酯、(甲基)丙烯酸單乙基氨基丙基酯等的(甲基)丙烯酸單烷基氨基烷基酯；丙烯酸、甲基丙烯酸、巴豆酸、馬來酸、衣康酸以及檸康酸等的乙烯性不飽和羧酸等。這些單體可以單獨使用，也可以組合兩種以上使用。 The monomer having a bridging functional group in the molecule preferably contains at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a fluorenyl group as a functional group. Examples of the monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid 2 -Hydroxyalkyl (meth) acrylates such as hydroxybutyl ester, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; acrylamide, methacrylamide Acrylamides such as N-methacrylamide, N-methacrylamide, N-methylolpropanamine, N-methylolmethacrylamine; (meth) acrylic acid monoamine (Methylaminoethyl ester, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoethylaminopropyl (meth) acrylate, etc. ) Monoalkylaminoalkyl acrylates; ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. These monomers may be used alone or in combination of two or more.

作為具有與(甲基)丙烯醯基((meta)acryloyl)以及架橋性官能基進行反應的基團的化合物，例如，可以優選舉出2-甲基丙烯醯氧乙基異氰酸酯、甲基丙烯酸2-(0-〔1'-甲基亞丙烷氨基〕羧氨基)乙基、2-〔(3，5-二甲基吡唑)羰基氨基〕乙基甲基丙烯酸酯、1，1-(雙丙烯醯氧甲基)乙基異氰酸酯、2-丙烯醯氧乙基異氰酸酯、2-丙烯醯氧乙基琥珀酸鹽(succinate)、2-丙烯醯氧乙基六氫鄰苯二甲酸醯亞胺、ω-羧基-聚己內酯單丙烯酸酯、鄰苯二甲酸單羥乙基丙烯酸酯、 2-羥基-3-苯氧基丙基丙烯酸酯等。這些化合物可以單獨使用，也可以組合兩種以上使用。 Examples of the compound having a group that reacts with (meta) acryloyl and a bridging functional group include, for example, 2-methacryloxyethyl isocyanate and methacrylic acid 2 -(0- [1'-methylpropaneamino] carboxyamino) ethyl, 2-[(3,5-dimethylpyrazole) carbonylamino] ethyl methacrylate, 1,1- (bis Propylene oxomethyl) ethyl isocyanate, 2-propylene oxo ethyl isocyanate, 2-propylene oxo ethyl succinate, 2-propylene oxo ethyl hexahydrophthalimide, imine, ω-carboxy-polycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate and the like. These compounds may be used alone or in combination of two or more.

上述加和物丙烯酸酯(adduct acrylate)類聚合物的重量平均分子量，優選為30萬~200萬左右，特別優選為50萬~85萬左右。 The weight average molecular weight of the adduct acrylate-based polymer is preferably about 300,000 to 2 million, and particularly preferably about 500,000 to 850,000.

活性能量線固化性成分(B)，即可以從上述的多官能丙烯酸酯類單體、丙烯酸酯類低聚物以及加和物丙烯酸酯(adduct acrylate)類聚合物中，選擇1種使用，也可以將兩種以上組合起來使用，還可以與這些以外的活性能量線固化性成分組合起來使用。 The active energy ray-curable component (B) can be selected from one of the above-mentioned multifunctional acrylate monomers, acrylate oligomers, and adduct acrylate polymers. These can be used in combination of two or more kinds, and can also be used in combination with active energy ray-curable components other than these.

黏接性組合物P中的活性能量線固化性成分(B)的含有量，相對於(甲基)丙烯酸酯聚合物(A)100質量份，優選為1質量份~30質量份，特別優選為2質量份~20質量份，進一步優選為3質量份~9質量份。從在該範圍含有活性能量線固化性成分(B)的黏接性組合物P所得到的黏接劑，據推測為良好地形成上述的三維網絡結構的黏接劑。 The content of the active energy ray-curable component (B) in the adhesive composition P is preferably 1 to 30 parts by mass based on 100 parts by mass of the (meth) acrylate polymer (A), and particularly preferably It is 2 to 20 parts by mass, and more preferably 3 to 9 parts by mass. The adhesive obtained from the adhesive composition P containing the active energy ray-curable component (B) in this range is presumed to be an adhesive that satisfactorily forms the three-dimensional network structure described above.

(3)矽烷偶聯劑(C) (3) Silane coupling agent (C)

黏接性組合物P，作為與有機材料反應的官能基，如果含有具有巰基的矽烷偶聯劑(C)，則通過矽烷偶聯劑(C)與活性能量線固化性成分(B)的反應、矽烷偶聯劑(C)與被黏物的反應、以及矽烷偶聯劑(C)彼此的縮聚反應，呈現密合性提高的効果。另外，關於黏接性組合物P含有架橋劑(D)的情況時的作用効果，在下文闡述。 The adhesive composition P, as a functional group that reacts with an organic material, contains a silane coupling agent (C) having a mercapto group, and then reacts with the active energy ray-curable component (B) through the silane coupling agent (C). , The reaction between the silane coupling agent (C) and the adherend, and the polycondensation reaction between the silane coupling agent (C), exhibiting the effect of improving adhesion. The effect when the adhesive composition P contains a bridging agent (D) will be described below.

作為矽烷偶合劑(C)，為分子內至少具有一個巰 基，至少具有一個烷氧基甲矽烷基(alkoxysilyl)的有機矽化合物，與黏接劑成分的相溶性良好，且具有光透過性，例如優選實質上為透明者。 As the silane coupling agent (C), it has at least one thiol in the molecule Group, an organosilicon compound having at least one alkoxysilyl group, has good compatibility with the adhesive component, and has light permeability, and is preferably substantially transparent, for example.

作為上述的矽烷偶聯劑(C)的具體例，可以舉出3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-巰基丙基二甲氧基甲基矽烷等的含有巰基的低分子型矽烷偶聯劑；3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-巰基丙基二甲氧基甲基矽烷等的含有巰基的矽烷化合物與甲基三乙氧基矽烷、乙基三乙氧基矽烷、甲基三甲氧基矽烷、乙基三甲氧基矽烷等的含有烷基的矽烷化合物的共縮聚物等的含有巰基的低聚物型矽烷偶聯劑等。其中，從提高耐久性的觀點考慮，優選為含有巰基的低聚物型矽烷偶聯劑，特別優選為含有巰基的矽烷化合物與含有烷基矽烷化合物的共縮聚物，進一步優選為3-巰基丙基三甲氧基矽烷與甲基三乙氧基矽烷的共縮聚物。這些可以單獨使用1種，也可以組合兩種以上使用。 Specific examples of the silane coupling agent (C) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane Mercapto-containing low-molecular-weight silane coupling agents; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane, etc. Copolycondensates of silane compounds such as methyltriethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, and other alkyl group-containing silane compounds Oligomer type silane coupling agent. Among these, from the viewpoint of improving durability, an oligomeric silane coupling agent containing a mercapto group is preferred, a copolycondensate of a mercapto group-containing silane compound and an alkylsilane compound is particularly preferred, and 3-mercaptopropyl is more preferred. Copolymer of methyltrimethoxysilane and methyltriethoxysilane. These may be used individually by 1 type, and may be used in combination of 2 or more type.

矽烷偶聯劑(C)優選為低聚物。上述低聚物的矽烷偶聯劑(C)中，低聚物中的巰基當量優選為100g/mol~1000g/mol，特別優選為200g/mol~900g/mol，進一步優選為300g/mol~700g/mol。巰基當量如果小於100g/mol，則提高耐久性的効果有可能降低。巰基當量如果超過1000g/mol，則有發生黏接力降低或剝離不良的可能性。 The silane coupling agent (C) is preferably an oligomer. In the silane coupling agent (C) of the oligomer, the thiol equivalent in the oligomer is preferably 100 g / mol to 1000 g / mol, particularly preferably 200 g / mol to 900 g / mol, and more preferably 300 g / mol to 700 g / mol. If the mercapto equivalent is less than 100 g / mol, the effect of improving durability may be reduced. When the mercapto equivalent is more than 1000 g / mol, there is a possibility that a decrease in adhesive strength or poor peeling may occur.

在黏接性組合物P中的矽烷偶聯劑(C)的含有量，相對於(甲基)丙烯酸酯聚合物(A)100質量份，優選為0.01質量 份~5質量份，特別優選為0.02質量份~3質量份，進一步優選為0.05質量份~2質量份。矽烷偶聯劑(C)的含有量，如果小於0.01質量份，則難於得到由該矽烷偶聯劑(C)所帶來的効果。另一方面，矽烷偶聯劑(C)的含有量如果超過5質量份，則有可能發生黏接力的極端降低或凝集力不足的情況。 The content of the silane coupling agent (C) in the adhesive composition P is preferably 0.01 mass based on 100 mass parts of the (meth) acrylate polymer (A). Parts to 5 parts by mass, particularly preferably 0.02 parts by mass to 3 parts by mass, and more preferably 0.05 parts by mass to 2 parts by mass. When the content of the silane coupling agent (C) is less than 0.01 parts by mass, it is difficult to obtain the effect by the silane coupling agent (C). On the other hand, when the content of the silane coupling agent (C) exceeds 5 parts by mass, there may be a case where the adhesive force is extremely reduced or the cohesive force is insufficient.

(4)架橋劑(D) (4) bridging agent (D)

黏接性組合物P優選為含有架橋劑(D)。在此，矽烷偶聯劑(C)如前所述，通過與活性能量線固化性成分(B)的反應或其自身的縮聚反應等，有助於耐久性的提高。而且，如果黏接性組合物P含有架橋劑(D)，則在使黏接性組合物P固化時，矽烷偶聯劑(C)的巰基，據推測也與架橋劑(D)的反應性官能基發生反應。特別是在架橋劑(D)為異氰酸酯類架橋劑的情況時，矽烷偶聯劑(C)的巰基，與異氰酸酯類架橋劑的異氰酸酯基容易形成硫代氨基甲酸酯鍵。另一方面，架橋劑(D)的其它的反應性官能基(異氰酸酯類架橋劑的異氰酸酯基)，與(甲基)丙烯酸酯聚合物(A)的反應性官能基(羥基、氨基等)進行反應，將(甲基)丙烯酸酯聚合物(A)架橋，形成第2三維網絡結構。據推測該第2三維網絡結構，與由上述活性能量線固化性成分(B)形成的三維網絡結構互相纏繞，形成一體的三維網絡結構。根據上述結構，所得到的黏接劑成為耐久性更優異的黏接劑。而且，矽烷偶聯劑(C)的烷氧基甲矽烷基(alkoxysilyl)，與(被架橋的)(甲基)丙烯酸酯聚合物(A)保持適宜的距離，成為懸掛在(甲基)丙烯酸酯聚合物(A)上的形狀，由此而發揮優異的偶聯効果。如上所得到的黏接劑，黏接性優異，即使在高溫條件下或 濕熱條件下，也成為耐久性更優異的黏接劑。 The adhesive composition P preferably contains a bridging agent (D). Here, as described above, the silane coupling agent (C) contributes to the improvement of durability by a reaction with the active energy ray-curable component (B) or its own polycondensation reaction. When the adhesive composition P contains a bridging agent (D), the mercapto group of the silane coupling agent (C) is presumed to be reactive with the bridging agent (D) when the adhesive composition P is cured. Functional groups react. In particular, when the bridging agent (D) is an isocyanate-based bridging agent, the mercapto group of the silane coupling agent (C) and the isocyanate group of the isocyanate-based bridging agent easily form a thiourethane bond. On the other hand, the other reactive functional groups of the bridging agent (D) (isocyanate groups of the isocyanate-based bridging agent) are performed with the reactive functional groups (such as a hydroxyl group and an amino group) of the (meth) acrylate polymer (A). The reaction bridges the (meth) acrylate polymer (A) to form a second three-dimensional network structure. It is estimated that this second three-dimensional network structure is intertwined with the three-dimensional network structure formed of the active energy ray-curable component (B) to form an integrated three-dimensional network structure. According to the said structure, the obtained adhesive becomes an adhesive with more durability. In addition, the alkoxysilyl of the silane coupling agent (C) is kept at a proper distance from the (bridged) (meth) acrylate polymer (A), and is suspended from (meth) acrylic acid. The shape on the ester polymer (A) thereby exhibits an excellent coupling effect. The adhesive obtained as above has excellent adhesion, even under high temperature conditions or Under hot and humid conditions, it also becomes an adhesive with better durability.

在架橋劑(D)為異氰酸酯類架橋劑的情況時，具有矽烷偶聯劑(C)的巰基，由於容易與異氰酸酯類架橋劑的異氰酸酯基發生反應，因此(甲基)丙烯酸酯聚合物(A)的反應性官能基，即使僅為在一般的的矽烷偶聯劑中難以發揮作用的羥基((甲基)丙烯酸酯聚合物(A)作為反應性官能基可以不含有羧基)，也能得到來自矽烷偶聯劑(C)的偶聯効果。 When the bridging agent (D) is an isocyanate-based bridging agent, the thiol group having a silane coupling agent (C) easily reacts with the isocyanate group of the isocyanate-based bridging agent, so the (meth) acrylate polymer (A Reactive functional group) can be obtained even if it is only a hydroxyl group ((meth) acrylate polymer (A) which does not contain a carboxyl group as a reactive functional group) which is difficult to function in a general silane coupling agent. Coupling effect from silane coupling agent (C).

作為架橋劑(D)，只要為對於(甲基)丙烯酸酯聚合物(A)所具有的反應性官能基(羥基、氨基等)，具有反應性的架橋劑即可，例如可以舉出異氰酸酯類架橋劑、環氧類架橋劑、胺類架橋劑、三聚氰胺類架橋劑、氮丙啶(aziridine)類架橋劑、肼(hydrazine)類架橋劑、醛類架橋劑、惡唑啉類架橋劑、金屬醇鹽類架橋劑、金屬螯合物類架橋劑、金屬鹽類架橋劑、銨鹽類架橋劑等。其中，異氰酸酯類架橋劑與矽烷偶聯劑(C)所具有的巰基的反應性優異，而且，在(甲基)丙烯酸酯聚合物(A)具有羥基的情況時，具有與該羥基的反應性優異的長處。架橋劑(D)可以單獨使用1種，或者也可以組合兩種以上使用。 The bridging agent (D) may be a reactive bridging agent with respect to a reactive functional group (such as a hydroxyl group and an amino group) of the (meth) acrylate polymer (A), and examples thereof include isocyanates. Bridging agent, epoxy bridging agent, amine bridging agent, melamine bridging agent, aziridine bridging agent, hydrazine bridging agent, aldehyde bridging agent, oxazoline bridging agent, metal Alkoxide bridging agent, metal chelate bridging agent, metal salt bridging agent, ammonium salt bridging agent, etc. Among them, the isocyanate-based bridging agent has excellent reactivity with the mercapto group of the silane coupling agent (C), and when the (meth) acrylate polymer (A) has a hydroxyl group, it has reactivity with the hydroxyl group. Excellent strengths. The bridging agent (D) may be used singly or in combination of two or more kinds.

異氰酸酯類架橋劑為至少含有聚異氰酸酯化合物的架橋劑。作為聚異氰酸酯化合物，例如，可以舉出甲次苯基二異氰酸酯(tolylene diisocyanate)、二苯甲烷二異氰酸酯、伸二甲苯二異氰酸酯(xylylene diisocyanate)等的芳香族聚異氰酸酯、六亞甲基二異氰酸酯等的脂肪族聚異氰酸酯、異佛爾酮二異氰酸酯、氫化二苯甲烷二異氰酸酯等的脂環式聚異氰酸酯等、及這些的雙縮脲體、異氰酸酯(isocyanurate)體、進一步可 以列舉乙二醇、丙二醇、新戊二醇、三羥甲基丙烷、蓖麻油等的作為與含有低分子活性氫化合物的反應物的加和物體等。其中，從與(甲基)丙烯酸酯聚合物(A)的羥基的反應性方面考慮，優選三羥甲基丙烷改性的芳香族聚異氰酸酯，特別是優選三羥甲基丙烷改性伸二甲苯二異氰酸酯以及三羥甲基丙烷改性甲次苯基二異氰酸酯。 The isocyanate-based bridging agent is a bridging agent containing at least a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate. Aliphatic polyisocyanates, such as aliphatic polyisocyanates, isophorone diisocyanates, hydrogenated diphenylmethane diisocyanates, etc., and these bisureton bodies, isocyanurates, Examples thereof include ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, and the like as addition substances and reactants containing a low-molecular active hydrogen compound. Among these, from the viewpoint of reactivity with the hydroxyl group of the (meth) acrylate polymer (A), trimethylolpropane-modified aromatic polyisocyanate is preferred, and trimethylolpropane-modified xylene is particularly preferred. Isocyanate and trimethylolpropane modified methylenediphenyl diisocyanate.

黏接性組合物P中架橋劑(D)的含有量，相對於(甲基)丙烯酸酯聚合物(A)100質量份，優選為0.05質量份~3質量份，特別優選為0.08質量份~1.5質量份，進一步優選為0.1質量份~1質量份。架橋劑(D)的含有量如果為0.05質量份以上，則能夠得到由該架橋劑(D)所產生的耐久性提高的効果。架橋劑(D)的含有量如果超過3質量份，則架橋的程度過度，所得到的黏接劑的黏接力有可能降低。 The content of the bridging agent (D) in the adhesive composition P is preferably 0.05 to 3 parts by mass, and particularly preferably 0.08 to parts by mass, relative to 100 parts by mass of the (meth) acrylate polymer (A). 1.5 parts by mass, and more preferably 0.1 to 1 part by mass. When the content of the bridging agent (D) is 0.05 parts by mass or more, the effect of improving the durability by the bridging agent (D) can be obtained. When the content of the bridging agent (D) exceeds 3 parts by mass, the degree of bridging is excessive, and the adhesive force of the obtained adhesive may be reduced.

(5)光聚合起始劑(E) (5) Photopolymerization initiator (E)

作為對黏接性組合物P所照射的活性能量線，在使用紫外線的情況時，黏接性組合物P優選進一步含有光聚合起始劑(E)。像這樣通過含有光聚合起始劑(E)，可以有效的使活性能量線固化性成分(B)固化，而且可以減少聚合固化時間以及活性能量線的照射量。 As the active energy ray irradiated to the adhesive composition P, when ultraviolet rays are used, the adhesive composition P preferably further contains a photopolymerization initiator (E). By containing the photopolymerization initiator (E) as described above, the active energy ray-curable component (B) can be effectively cured, and the polymerization curing time and the amount of active energy ray irradiation can be reduced.

作為這樣的光聚合起始劑(E)，例如可以列舉出苯 偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚、苯偶姻正丁基醚、苯偶姻異丁基醚、苯乙酮、二甲氨基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-羥環己基苯基酮、2-甲基-1- 〔4-(甲基硫代)苯基〕-2-嗎啉-丙烷-1-酮、4-(2-羥基乙氧基)苯基-2-(羥基-2-丙基)酮、二苯甲酮、p-苯基二苯甲酮、4，4’-二乙氨基二苯甲酮、二氯二苯甲酮、2-甲基蒽醌、2-乙基蒽醌、2-叔丁基蒽醌、2-氨基蒽醌、2-甲基噻噸酮、2-乙基噻噸酮、2-氯噻噸酮、2，4-二甲基噻噸酮、2，4-二乙基噻噸酮、苄基二甲基縮酮、苯乙酮二甲基縮酮、p-二甲基氨基安息香酸酯、寡(oligo)〔2-羥基-2-甲基-1〔4-(1-甲基乙烯基)苯〕丙酮〕、2，4，6-三甲基苯甲醯基-二苯基-氧化膦等。這些可以單獨使用，也可以組合兩種以上使用。 Examples of such a photopolymerization initiator (E) include benzene Acetoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminophenethyl Ketone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane -1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholin-propane-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) one, di Benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert Butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-bis Ethylthioxanthone, benzyldimethylketal, acetophenonedimethylketal, p-dimethylaminobenzoate, oligo [2-hydroxy-2-methyl-1 [4 -(1-methylvinyl) benzene] acetone], 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, and the like. These may be used alone or in combination of two or more.

光聚合起始劑(E)，相對於活性能量線固化性成分(B)100質量份，優選為以2質量份~15質量份範圍的量，特別是以5質量份~12質量份範圍的量來使用。 The photopolymerization initiator (E) is preferably in an amount in the range of 2 to 15 parts by mass, particularly in the range of 5 to 12 parts by mass, with respect to 100 parts by mass of the active energy ray-curable component (B). Amount to use.

(6)各種添加劑 (6) Various additives

黏接性組合物P，根據需要，可以添加在丙烯酸類黏接劑中通常使用的各種添加劑，例如帶電防止劑、黏接賦予劑、氧化防止劑、紫外線吸收劑、光穩定劑、軟化劑、充填劑、折射率調整劑等。 The adhesive composition P may be added with various additives generally used in acrylic adhesives, such as an antistatic agent, an adhesion-imparting agent, an oxidation inhibitor, an ultraviolet absorber, a light stabilizer, a softener, and the like, as necessary. Fillers, refractive index modifiers, etc.

作為帶電防止劑，例如可以舉出離子性液體、離子性固體、陰離子類介面活性劑、堿金屬鹽、陽離子類表面活性劑、非離子類表面活性劑等，其中優選使用從離子性液體、離子性固體以及堿金屬鹽所選出的至少1種。 Examples of the antistatic agent include ionic liquids, ionic solids, anionic surfactants, sulfonium metal salts, cationic surfactants, and nonionic surfactants. Among them, ionic liquids and ions are preferably used. At least one selected from solid solids and rhenium metal salts.

作為離子性液體以及離子性固體，優選為含氮翁鹽、含硫黃翁鹽、含磷翁鹽等。另外，作為堿金屬鹽優選為 鋰鹽、鉀鹽等。這些可以單獨使用，也可以組合兩種以上使用。 As the ionic liquid and the ionic solid, a nitrogen-containing onium salt, a sulfur-containing xanthium salt, a phosphorus-onium salt, and the like are preferable. In addition, the rhenium metal salt is preferably Lithium and potassium salts. These may be used alone or in combination of two or more.

黏接性組合物P中的帶電防止劑的含有量，優選為0.5質量%~8質量%，特別優選為1質量%~5質量%。通過帶電防止劑的含有量在上述範圍內，則帶電防止性能與黏接劑的耐久性的平衡變得良好。 The content of the antistatic agent in the adhesive composition P is preferably 0.5% to 8% by mass, and particularly preferably 1% to 5% by mass. When the content of the antistatic agent is within the above range, the balance between the antistatic property and the durability of the adhesive becomes good.

〔黏接性組合物的製造方法〕 [Manufacturing method of adhesive composition]

黏接性組合物P可以通過製造(甲基)丙烯酸酯聚合物(A)，將所得的(甲基)丙烯酸酯聚合物(A)、活性能量線固化性成分(B)和矽烷偶聯劑(C)進行混合，同時，根據需要，在任意的階段，添加架橋劑(D)、光聚合起始劑(E)、添加劑等來製造。 The adhesive composition P can be produced by (meth) acrylate polymer (A), and the obtained (meth) acrylate polymer (A), an active energy ray-curable component (B), and a silane coupling agent can be produced. (C) It mixes and manufactures by adding a bridge | crosslinking agent (D), a photoinitiator (E), an additive, etc. at arbitrary stages at the same time as needed.

(甲基)丙烯酸酯聚合物(A)，可以通過用通常的自由基聚合法，聚合構成聚合物的單體(共聚合物的情況為單體的混合物)來製造。(甲基)丙烯酸酯聚合物(A)的聚合，可以根據需要，使用聚合引發劑，由溶液聚合法等進行。作為聚合溶劑，例如可以舉出乙酸乙酯、乙酸正丁基酯、乙酸異丁基酯、甲苯、丙酮、己烷、甲基乙基酮等，可以並用兩種以上。 The (meth) acrylate polymer (A) can be produced by polymerizing monomers (in the case of a copolymer, a mixture of monomers) constituting a polymer by a usual radical polymerization method. The polymerization of the (meth) acrylate polymer (A) can be performed by a solution polymerization method or the like using a polymerization initiator as necessary. Examples of the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, and methyl ethyl ketone, and two or more of them may be used in combination.

作為聚合引發劑，可以例舉偶氮類化合物、有機過氧化物等，可以同時使用兩種以上。作為偶氮類化合物，可以例舉2，2’-偶氮雙異丁腈、2，2’-偶氮雙(2-甲基丁腈)、1，1’-偶氮雙(環己烷1-腈)(1,1-azobis(cyclo-hexane-1-carbonitrile))、2，2’-偶氮雙(2，4-二甲基戊腈)(2,2-azobis(2,4-dimethylvaleronitrile))、2，2’-偶氮雙(2，4-二甲基-4-甲氧基戊腈)、二甲基2，2’-偶氮雙(2-甲基丙酸酯)、4，4’-偶氮雙(4-氰基纈草酸)、2，2’-偶氮雙(2-羥 基甲基丙腈)、2，2’-偶氮雙〔2-(2-咪唑琳-2-基)丙烷〕等。 Examples of the polymerization initiator include an azo compound, an organic peroxide, and the like, and two or more of them may be used simultaneously. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), and 1,1'-azobis (cyclohexane). 1-nitrile) (1,1-azobis (cyclo-hexane-1-carbonitrile)), 2,2'-azobis (2,4-dimethylvaleronitrile) (2,2-azobis (2,4 -dimethylvaleronitrile)), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl2,2'-azobis (2-methylpropionate) ), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxy Methylmethylpropionitrile), 2,2'-azobis [2- (2-imidazolin-2-yl) propane] and the like.

作為有機過氧化物，例如可以例舉出苯甲醯過氧化物、過氧苯甲酸叔丁基酯、異丙苯過氧化氫、二異丙基過氧二碳酸酯、二正丙基過氧二碳酸酯、二(2-乙氧基乙基)過氧二碳酸酯、過氧新葵酸叔丁基酯、過氧特戊酸叔丁基酯、(3，5，5-三甲基己醯基)過氧化物、二丙醯過氧化物、二乙醯過氧化物等。 Examples of the organic peroxide include benzamidine peroxide, tert-butyl peroxybenzoate, cumene hydrogen peroxide, diisopropylperoxydicarbonate, and di-n-propylperoxy. Dicarbonate, bis (2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxynecaprylate, tert-butyl peroxypivalate, (3,5,5-trimethyl Hexamethylene) peroxide, dipropylhydrazone peroxide, diethylhydrazone peroxide, and the like.

另外，在上述聚合步驟中，通過搭配2-巰基乙醇等的鏈移動劑，可以對得到的聚合物的重量平均分子量進行調解。 Moreover, in the said polymerization process, the weight average molecular weight of the obtained polymer can be adjusted by mix | blending a chain shifting agent, such as 2-mercaptoethanol.

得到(甲基)丙烯酸酯聚合物(A)後，在(甲基)丙烯酸酯聚合物(A)的溶液中，添加活性能量線固化性成分(B)、矽烷偶聯劑(C)以及根據需要加入架橋劑(D)、光聚合起始劑(E)、添加劑等，進行充分混合，得到用溶劑稀釋了的黏接性組合物P(塗布溶液)。 After the (meth) acrylate polymer (A) is obtained, to the solution of the (meth) acrylate polymer (A), an active energy ray-curable component (B), a silane coupling agent (C), and It is necessary to add a bridging agent (D), a photopolymerization initiator (E), an additive, etc., and mix well, and obtain the adhesive composition P (coating solution) diluted with the solvent.

作為對黏接性組合物P進行稀釋，得到塗布溶液的稀釋溶劑，可以使用己烷、庚烷、環己烷等的脂肪族烴；甲苯以及二甲苯等的芳香族烴；二氯甲烷以及二氯乙烷等的鹵代烴；甲醇、乙醇、丙醇、丁醇、1-甲氧基-2-丙醇等的醇；丙酮、甲基乙基酮、2-戊酮、異佛爾酮、環己酮等的酮類；乙酸乙酯以及乙酸丁基酯等的酯、乙基溶纖劑等的溶纖劑類溶劑等。 As a diluent for diluting the adhesive composition P to obtain a coating solution, aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; dichloromethane and two Halogenated hydrocarbons such as ethyl chloride; alcohols such as methanol, ethanol, propanol, butanol, 1-methoxy-2-propanol; acetone, methyl ethyl ketone, 2-pentanone, isophorone , Ketones such as cyclohexanone; esters such as ethyl acetate and butyl acetate; solvents such as ethyl cellosolve;

作為如此調制的塗布溶液的濃度、黏度，只要為在塗布可能的範圍內即可，沒有特別的限制，可以根據情況進行適宜選擇。例如，黏接性組合物P的濃度可以稀釋到10質 量%~40質量%。另外，得到塗布溶液時，稀釋溶劑等的添加不是必要條件，黏接性組合物P只要是塗布可能的黏度等，稀釋溶劑不添加也可。該情況時黏接性組合物P可以直接作為塗布溶液。 The concentration and viscosity of the coating solution prepared in this manner are not particularly limited as long as they are within the range possible for coating, and can be appropriately selected according to circumstances. For example, the concentration of the adhesive composition P can be diluted to 10 Amount% to 40% by mass. In addition, when a coating solution is obtained, the addition of a diluent solvent and the like is not necessary, and the adhesive composition P may not be added as long as the viscosity is possible for coating. In this case, the adhesive composition P can be used as a coating solution as it is.

〔黏接劑〕 [Adhesive]

本實施形態所述的黏接劑，可以優選將黏接性組合物P，塗布乾燥成所希望的對象物後，通過活性能量線的照射，使黏接性組合物P固化而得到。 The adhesive agent according to this embodiment can be preferably obtained by applying and drying the adhesive composition P to a desired object, and then curing the adhesive composition P by irradiation with active energy rays.

黏接性組合物P的幹燥可以用風乾來進行，但是，通常用加熱處理(優選用熱風乾燥)來進行。在進行加熱處理的情況時，加熱溫度優選為50℃~150℃，特別優選為70℃~120℃。另外，加熱時間優選為10秒~10分，特別優選為50秒~2分。 Drying of the adhesive composition P can be performed by air-drying, but it is usually performed by heat treatment (preferably hot-air drying). When the heat treatment is performed, the heating temperature is preferably 50 ° C to 150 ° C, and particularly preferably 70 ° C to 120 ° C. The heating time is preferably 10 seconds to 10 minutes, and particularly preferably 50 seconds to 2 minutes.

作為活性能量線通常使用紫外線、電子線等。活性能量線的照射量根據能量線的種類而有所不同，但是例如為紫外線的情況時，優選以光量計為50mJ/cm2~1000mJ/cm2，特別優選為100mJ/cm2~500mJ/cm2。另外，為電子線的情況時優選為10krad~1000krad左右。 As the active energy rays, ultraviolet rays, electron rays, and the like are generally used. The amount of active energy ray irradiation varies depending on the type of energy ray, but in the case of ultraviolet rays, for example, it is preferably 50 mJ / cm 2 to 1000 mJ / cm 2 in terms of light amount, and particularly preferably 100 mJ / cm 2 to 500 mJ / cm 2 . In the case of an electron beam, it is preferably about 10 krad to 1000 krad.

通過黏接性組合物P的乾燥及活性能量線的照射，複數個活性能量線固化性成分(B)相互結合而形成三維網絡結構，據推測在該三維網絡結構上，形成(甲基)丙烯酸酯聚合物(A)和矽烷偶聯劑(C)纏繞的結構。 By drying the adhesive composition P and irradiating the active energy rays, a plurality of active energy ray-curable components (B) are combined with each other to form a three-dimensional network structure. It is estimated that (meth) acrylic acid is formed on the three-dimensional network structure Structure in which the ester polymer (A) and the silane coupling agent (C) are entangled.

使黏接性組合物P固化而得到的黏接劑，通過與上述結構、與具有(甲基)丙烯酸酯聚合物(A)的脂環式結構的作 用、與矽烷偶聯劑(C)的活性能量線固化性成分(B)的反應或其自身的縮聚反應等的作用，在將偏光板等的光學構件，特別是將聚環烯烴類的光學構件、或透明導電膜當作被黏物時，耐久性也高，特別是即使在高溫條件下或濕熱條件下，也發揮優異的耐久性。 The adhesive obtained by curing the adhesive composition P works with the above-mentioned structure and an alicyclic structure having a (meth) acrylate polymer (A). By reacting with the active energy ray-curable component (B) of the silane coupling agent (C) or its own polycondensation reaction, it is used for optical members such as polarizing plates, especially for When a member or a transparent conductive film is used as an adherend, the durability is also high, and in particular, it exhibits excellent durability even under high-temperature conditions or wet heat conditions.

另外，據推測在黏接性組合物P含有架橋劑(D)的情況時，通過上述加熱處理，(甲基)丙烯酸酯聚合物(A)通過架橋劑(D)而被架橋，也形成第2三維網絡結構，與通過活性能量線固化性成分(B)而形成的三維網絡結構相互纏繞，形成一體化的三維網絡結構。矽烷偶聯劑(C)的巰基與架橋劑(D)的反應性官能基反應，該矽烷偶聯劑(C)的烷氧基介於該架橋劑(D)，從(甲基)丙烯酸酯聚合物(A)，進而從上述三維網絡結構具有適當的距離而存在，發揮優異的偶聯効果。像這樣所得到的黏接劑的黏接性優異，即使在高溫條件下或濕熱條件下，也成為耐久性更優異的黏接劑。例如，在85℃的高溫條件下或60℃、90% RH的濕熱條件下，放置500小時也可以防止和抑制浮起、剝離、氣泡等的發生。 In addition, when the adhesive composition P contains a bridging agent (D), it is estimated that the (meth) acrylate polymer (A) is bridged by the bridging agent (D) by the above-mentioned heat treatment, and the first 2 The three-dimensional network structure is intertwined with the three-dimensional network structure formed by the active energy ray-curable component (B) to form an integrated three-dimensional network structure. The mercapto group of the silane coupling agent (C) reacts with the reactive functional group of the bridging agent (D). The alkoxy group of the silane coupling agent (C) is interposed between the bridging agent (D) and the (meth) acrylate. The polymer (A) further exists at an appropriate distance from the three-dimensional network structure described above, and exhibits an excellent coupling effect. The adhesive obtained in this way is excellent in adhesiveness, and becomes an adhesive with more excellent durability even under high temperature conditions or wet heat conditions. For example, under high temperature conditions of 85 ° C or humid conditions of 60 ° C and 90% RH, 500 hours of standing can also prevent and suppress the occurrence of floating, peeling, and bubbles.

本實施形態所述的黏接劑的凝膠分率，優選為30%~99% %，特別優選為40%~95%，進一步優選為50%~90%。如果凝膠分率小於30%，則黏接劑的凝集力不足，有耐久性以及再加工(rework)性降低的情況。另一方面，如果凝膠分率大於99%，則黏接力變得過低，有耐久性降低的情況。另外，上述凝膠分率是從黏接劑層形成時起，在23℃、50% RH的環境下，保管7天(熟成期間經過後)後的值。在不明是否為熟成 期間的情況時，只要重新在23℃、50% RH的環境下保管7天後，如果凝膠分率在上述範圍內即可。 The gel fraction of the adhesive according to this embodiment is preferably 30% to 99%, particularly preferably 40% to 95%, and still more preferably 50% to 90%. When the gel fraction is less than 30%, the cohesive force of the adhesive is insufficient, and durability and reworkability may be reduced. On the other hand, if the gel fraction is more than 99%, the adhesive force becomes too low, and the durability may be reduced. The above-mentioned gel fraction is a value after storage for 7 days (after the maturation period has elapsed) under the environment of 23 ° C. and 50% RH from the time of formation of the adhesive layer. Unknown whether it is ripe In the case of a period, the gel fraction should be within the above range after re-storing for 7 days in an environment of 23 ° C and 50% RH.

〔黏接片〕 [Adhesive sheet]

如圖1所示，第1實施形態所述的黏接片1A，按照從下往上的順序，由剝離片12、層疊於剝離片12的剝離面上的黏接劑層11、及層疊於黏接劑層11上的基材13所構成。 As shown in FIG. 1, the adhesive sheet 1A according to the first embodiment is composed of a release sheet 12, an adhesive layer 11 laminated on a release surface of the release sheet 12, and The base material 13 on the adhesive layer 11 is configured.

另外，如圖2所示，第2實施形態所述的黏接片1B，由兩片剝離片12a、12b，以及以與這兩片剝離片12a、12b的剝離面相接的方式，被這兩片剝離片12a、12b所挾持的黏接劑層11所構成。另外，本說明書中所謂的剝離片的剝離面，是指剝離片中具有剝離性的面，包括實施了剝離處理的面以及即使未實施剝離處理也顯示出剝離性的面的兩者。 In addition, as shown in FIG. 2, the adhesive sheet 1B according to the second embodiment is composed of two peeling sheets 12 a and 12 b and is in contact with the peeling surfaces of the two peeling sheets 12 a and 12 b. The adhesive layer 11 held by the two release sheets 12a and 12b is configured. The release surface of the release sheet in the present specification refers to a surface having releasability in the release sheet, and includes both a surface subjected to a release treatment and a surface that exhibits releasability even without a release treatment.

在黏接片1A、1B的兩者中，黏接劑層11都是由固化上述黏接性組合物所成的黏接劑構成。 In both of the adhesive sheets 1A and 1B, the adhesive layer 11 is composed of an adhesive formed by curing the above-mentioned adhesive composition.

黏接劑層11的厚度，根據黏接片1A、1B的使用目的而適宜決定，但是通常為5μm~100μm，優選為10μm~60μm的範圍。例如，在作為光學構件，特別是作為偏光板用的黏接劑層使用的情況時，優選為10μm~50μm，特別優選為15μm~30μm。 The thickness of the adhesive layer 11 is appropriately determined according to the purpose of use of the adhesive sheets 1A and 1B, but it is usually 5 μm to 100 μm, and preferably 10 μm to 60 μm. For example, when it is used as an optical member, especially as an adhesive layer for polarizing plates, it is preferable that it is 10 micrometers-50 micrometers, and it is especially preferable that it is 15 micrometers-30 micrometers.

作為基材13，沒有特別的限制，作為通常的黏接片的基材片所使用的基材都可以使用。例如，除所希望的光學構件之外，可以例舉出人造絲、丙烯以及聚酯等使用了纖維的織布或者不織布；合成紙；上質紙、玻璃紙、含浸紙、銅板紙等的紙類；鋁、銅等的金屬箔；氨基甲酸酯發泡體、聚乙烯發 泡體等的發泡體；聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚萘二酸乙二醇酯等的聚酯薄膜；聚氨酯薄膜、聚乙烯薄膜、聚丙烯薄膜、三乙醯纖維素等的纖維素薄膜；聚氯乙烯薄膜、聚偏氯乙烯薄膜、聚乙烯基醇薄膜、乙烯-乙酸乙烯基共聚物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、丙烯酸樹脂薄膜、降冰片烯類樹脂薄膜、環烯烴樹脂薄膜等的塑膠薄膜；這些的兩種以上的層疊體等。塑膠薄膜可以為單軸壓延的薄膜或者雙軸壓延的薄膜。 The base material 13 is not particularly limited, and any base material used as a base material sheet of a general adhesive sheet can be used. For example, in addition to desired optical members, woven or non-woven fabrics using fibers such as rayon, acrylic, and polyester; synthetic paper; high-quality paper, cellophane, impregnated paper, and coated paper; Metal foil of aluminum, copper, etc .; urethane foam, polyethylene hair Foams such as foams; polyester films such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polyurethane films, polyethylene films, polymer films Cellulose films such as acrylic films, triethyl cellulose, etc .; polyvinyl chloride films, polyvinylidene chloride films, polyvinyl alcohol films, ethylene-vinyl acetate copolymer films, polystyrene films, polycarbonate films, Plastic films such as acrylic resin films, norbornene-based resin films, and cycloolefin resin films; and laminates of two or more of these. The plastic film may be a uniaxially rolled film or a biaxially rolled film.

作為光學構件，例如可以例舉出偏光板(偏光薄膜)、偏光子、相位差板(相位差薄膜)、視野角補償薄膜、提高輝度薄膜、提高對比度薄膜、液晶聚合物薄膜、擴散薄膜、半透過反射薄膜等。其中，由於偏光板易於收縮，尺寸變化大，所以從耐久性的觀點考慮，優選作為形成本實施形態所述的黏接劑(上述黏接劑層11)的基材。特別是一方的保護膜由聚環烯烴類薄摸所構成的偏光板(以下有稱為「COP偏光板」的情況)，不僅容易收縮，寸法變化也大，而且接觸角大，密合性低，因此從耐久性的觀點考慮，更優選作為形成本實施形態所述的黏接劑(上述黏接劑層11)的基材。 Examples of the optical member include a polarizing plate (polarizing film), a polarizer, a retardation plate (a retardation film), a viewing angle compensation film, a brightness enhancement film, a contrast enhancement film, a liquid crystal polymer film, a diffusion film, and a half Transmissive reflective film, etc. Among them, since the polarizing plate is easy to shrink and has a large dimensional change, it is preferably used as a base material for forming the adhesive (the above-mentioned adhesive layer 11) according to this embodiment from the viewpoint of durability. In particular, a polarizing plate made of a thin polycyclic olefin-based protective film (hereinafter referred to as a "COP polarizing plate") is not only easy to shrink, but also has a large change in inch method, and has a large contact angle and low adhesion. Therefore, from the viewpoint of durability, it is more preferable as a base material for forming the adhesive (the above-mentioned adhesive layer 11) according to this embodiment.

基材13的厚度，根據其種類而有所不同，但是，在例如為光學構件的情況時，通常為10μm~500μm，優選為50μm~300μm，特別是優選為80μm~150μm。 The thickness of the base material 13 varies depending on the type, but in the case of an optical member, for example, it is usually 10 μm to 500 μm, preferably 50 μm to 300 μm, and particularly preferably 80 μm to 150 μm.

作為剝離片12，12a，12b可以使用例如聚乙烯薄膜、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯乙烯基薄膜、氯乙烯基共聚物薄膜、聚對苯二甲酸乙 二醇酯薄膜、聚萘二酸乙二醇酯薄膜、聚對苯二甲酸丁二醇酯薄膜、聚氨酯薄膜、乙烯乙酸乙烯基薄膜、離聚物樹脂薄膜、乙烯-(甲基)丙烯酸共聚物薄膜、乙烯-(甲基)丙烯酸酯共聚物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、聚醯亞胺薄膜、氟樹脂薄膜等。另外，也可以使用這些的架橋薄膜。進一步，也可以為這些的疊層薄膜。另外，剝離片12，12a，12b優選為具有活性能量線透過性。 As the release sheets 12, 12a, 12b, for example, polyethylene films, polypropylene films, polybutene films, polybutadiene films, polymethylpentene films, polyvinyl chloride films, vinyl chloride copolymer films, Polyethylene terephthalate Glycol ester film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene- (meth) acrylic acid copolymer Film, ethylene- (meth) acrylate copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, etc. Moreover, these bridge films can also be used. Furthermore, these laminated films may be used. The release sheets 12, 12a, and 12b preferably have active energy ray permeability.

上述剝離片的剝離面(特別是與黏接劑層11相接的面)，優選為實施有剝離處理。作為剝離處理所使用的剝離劑，例如可以列舉出醇酸類、矽酮(silicone)類、氟類、不飽和聚酯類、聚烯烴類以及蠟類的剝離劑。 It is preferable that the peeling surface (especially the surface which contacts the adhesive layer 11) of the said peeling sheet is peeled. Examples of the release agent used in the release treatment include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents.

關於剝離片12，12a，12b的厚度，沒有特別的限制，通常為20μm~150μm左右。 The thickness of the release sheets 12, 12a, and 12b is not particularly limited, but is usually about 20 μm to 150 μm.

在製造上述黏接片1A中，在剝離片12的剝離面上，將含有黏接性組合物P的溶液(塗布溶液)進行塗布乾燥，在形成黏接性組合物P的塗膜層之後，在其塗膜層上，將基材13進行層疊。並且，隔著剝離片12，向上述塗膜層照射活性能量線，由此形成黏接劑層11。另外，關於活性能量線的照射條件如上所述。 In the production of the above-mentioned adhesive sheet 1A, the solution (coating solution) containing the adhesive composition P was coated and dried on the release surface of the release sheet 12, and after the coating film layer of the adhesive composition P was formed, The base material 13 is laminated on the coating film layer. Then, the coating film layer is irradiated with active energy rays through the release sheet 12 to form an adhesive layer 11. The irradiation conditions of the active energy rays are as described above.

另外，在製造上述黏接片1B中，在一個剝離片12a(或者12b)的剝離面上，將含有上述黏接性組合物的塗布溶液進行塗布乾燥，在形成黏接性組合物P的塗膜層之後，在其塗膜層上，將另一個剝離片12b(或者12a)進行層疊。並且，隔著剝離片12a(或者12b)，向上述塗膜層照射活性能量線，由此 形成黏接劑層11。 In addition, in the production of the adhesive sheet 1B, a coating solution containing the adhesive composition is applied and dried on the release surface of one release sheet 12a (or 12b), and then the adhesive composition P is applied. After the film layer, another peeling sheet 12b (or 12a) is laminated on the coating film layer. Then, the coating film layer is irradiated with active energy rays through the release sheet 12a (or 12b), whereby Forming an adhesive layer 11.

另外，代替如上所述那樣隔著剝離片照射活性能量線形成黏接劑層11，也可以在剝離片上形成黏接性組合物P的塗膜層，在該塗膜層露出的狀態下，照射活性能量線形成黏接劑層11，其後，在該黏接劑層11上，疊層基材或剝離片。進而，也可以在基材上，直接形成黏接性組合物P的塗膜層，向該塗膜層照射活性能量線，形成黏接劑層11。 In addition, instead of irradiating the active energy ray to form the adhesive layer 11 through the release sheet as described above, a coating film layer of the adhesive composition P may be formed on the release sheet, and the coating film layer is exposed and irradiated. The active energy ray forms an adhesive layer 11, and thereafter, a base material or a release sheet is laminated on the adhesive layer 11. Furthermore, a coating film layer of the adhesive composition P may be directly formed on the substrate, and the coating film layer may be irradiated with active energy rays to form the adhesive layer 11.

作為塗布上述塗布溶液的方法，例如可以利用棒塗布法、刮刀塗布法、輥塗布法、板塗布法、模具塗布法、凹板塗布法等。 As a method of applying the coating solution, for example, a bar coating method, a blade coating method, a roll coating method, a plate coating method, a mold coating method, a gravure coating method, or the like can be used.

在此，例如，在製造由液晶組件和偏光板所構成的液晶顯示裝置中，作為黏接片1A的基材13，使用偏光板，將該黏接片1A的剝離片12剝離，將露出的黏接劑層11和液晶組件進行貼合即可。 Here, for example, in manufacturing a liquid crystal display device composed of a liquid crystal module and a polarizing plate, as the base material 13 of the adhesive sheet 1A, a polarizing plate is used, and the release sheet 12 of the adhesive sheet 1A is peeled off to expose the exposed The adhesive layer 11 may be bonded to the liquid crystal module.

另外，例如，製造在液晶組件和偏光板之間配置有相位差板的液晶顯示裝置中，作為一例，首先，將黏接片1B的一個剝離片12a(或者12b)剝離，將黏接片1B露出的黏接劑層11和相位差板進行貼合。然後，將作為基材13使用偏光板的黏接片1A的剝離片12剝離，將黏接片1A露出的黏接劑層11和上述相位差板進行貼合。進一步，從上述黏接片B的黏接劑層11，將另一個剝離片12b(或者12a)剝離，將黏接片B露出的黏接劑層11和液晶組件貼合。 In addition, for example, in a liquid crystal display device in which a retardation plate is disposed between a liquid crystal module and a polarizing plate, as an example, first, one peeling sheet 12a (or 12b) of the adhesive sheet 1B is peeled off, and the adhesive sheet 1B The exposed adhesive layer 11 and the retardation plate are bonded together. Then, the release sheet 12 of the adhesive sheet 1A using a polarizing plate as the base material 13 is peeled off, and the adhesive layer 11 exposed by the adhesive sheet 1A and the retardation plate are bonded together. Furthermore, the other peeling sheet 12b (or 12a) is peeled from the adhesive layer 11 of the said adhesive sheet B, and the adhesive layer 11 exposed by the adhesive sheet B and a liquid crystal element are bonded.

根據以上的黏接片1A，1B，黏接劑層11的耐久性優異，因此即使在高溫條件下或者濕熱條件下，也可以防止 抑制在與COP偏光板等的基材13或與被黏物之間產生浮起、剝離、發泡等。 According to the above-mentioned pressure-sensitive adhesive sheets 1A and 1B, the durability of the pressure-sensitive adhesive layer 11 is excellent, and therefore it can be prevented even under high-temperature conditions or wet-heat conditions. Swelling, peeling, foaming, and the like with the substrate 13 such as the COP polarizing plate or the adherend are suppressed.

另外，黏接片1A，1B中的黏接劑層11，霧度值(依據JIS K7136：2000測定而得到的值)優選為2.0%以下，特別是優選為1.8%以下，進一步優選為1.0%以下。如果霧度值為1.0%以下，則透明性非常高，成為適宜作為光學用途的黏接劑層。 The haze value (value measured in accordance with JIS K7136: 2000) of the adhesive layer 11 in the adhesive sheets 1A and 1B is preferably 2.0% or less, particularly preferably 1.8% or less, and further preferably 1.0%. the following. When the haze value is 1.0% or less, the transparency is very high, and it becomes an adhesive layer suitable for optical applications.

另一方面，本實施形態所述的黏接片1A，1B，優選將透明導電膜作為被黏物。該種情況時，黏接性組合物P中的(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，優選為不含有含羧基單體。由此，可以抑制由於酸成分對透明導電膜帶來不良影響。具體而言，為可以抑制透明導電膜發生腐食，或透明導電膜的電阻值發生變化。 On the other hand, in the adhesive sheets 1A and 1B according to this embodiment, it is preferable to use a transparent conductive film as an adherend. In this case, the (meth) acrylate polymer (A) in the adhesive composition P preferably does not contain a carboxyl group-containing monomer as a monomer unit constituting the polymer. Thereby, it is possible to suppress the adverse effect of the acid component on the transparent conductive film. Specifically, it is possible to suppress rottenness of the transparent conductive film or change in the resistance value of the transparent conductive film.

作為上述透明導電膜，例如可以列舉出鉑、金、銀、銅等的金屬；氧化錫、氧化銦、氧化鎘、氧化鋅、二氧化鋅等的氧化物；摻雜錫之氧化銦(ITO)、摻雜氧化鋅之氧化銦、摻雜氟之氧化銦、摻雜銻之氧化錫、摻雜氟之氧化錫、摻雜鋁之氧化鋅等的複合氧化物；硫化物、六硼化鑭、氨化鈦、碳化鈦等的非氧化化合物等所構成的透明導電膜。 Examples of the transparent conductive film include metals such as platinum, gold, silver, and copper; oxides of tin oxide, indium oxide, cadmium oxide, zinc oxide, and zinc dioxide; and tin-doped indium oxide (ITO) Compound oxides of zinc oxide-doped indium oxide, fluorine-doped indium oxide, antimony-doped tin oxide, fluorine-doped tin oxide, aluminum-doped zinc oxide, etc .; sulfide, lanthanum hexaboride, A transparent conductive film made of a non-oxidizing compound such as titanium amide or titanium carbide.

而且，作為基材13使用了偏光板的黏接片1A(以下有稱為「帶黏接劑層偏光板」的情況。)，黏接力相對於無鹼玻璃，優選為0.1N/25mm~25N/25mm，特別優選為2N/25mm~20N/25mm。通過使黏接力在上述的範圍內，則在與玻璃板等的被黏物之間，可以防止浮起或剝離等。另外，在此所說的 黏接力，基本上是指通過基於JIS Z0237：2009的180°剝離法所測定的黏接力，但是將測定樣品切成寬25mm、長100mm，使該測定樣品相對於被黏物(無鹼玻璃)，在0.5MPa、50℃，加壓20分貼附之後，以常壓23℃、50% RH的條件下放置24小時之後，以剝離速度300mm/min進行測定所得到的黏接力。 Further, an adhesive sheet 1A (hereinafter referred to as a “polarizer with an adhesive layer layer”) is used as a base material 13 for a polarizing plate, and the adhesive force is preferably 0.1N / 25mm to 25N relative to alkali-free glass. / 25mm, particularly preferably 2N / 25mm to 20N / 25mm. When the adhesive force is within the above range, it is possible to prevent floating, peeling, and the like from being adhered to a glass plate or the like. In addition, what is said here Adhesive force is basically the adhesive force measured by the 180 ° peeling method based on JIS Z0237: 2009, but the measurement sample is cut into a width of 25mm and a length of 100mm to make the measurement sample relative to the adherend (alkali-free glass). After attaching at 0.5 MPa, 50 ° C for 20 minutes under pressure, and leaving it for 24 hours under the conditions of normal pressure 23 ° C and 50% RH, the obtained adhesion force was measured at a peeling speed of 300 mm / min.

而且，上述帶黏接劑層的偏光板貼附於上述無堿玻璃，放置14天之後的黏接力(貼附14天後的黏接力)，優選為0.5N/25mm~30N/25mm，特別是優選為1N/25mm~25N/25mm，進一步優選為2N/25mm~20N/25mm。像這樣由於經時所產生的黏接力的上升被抑制，由此可以將上述帶黏接劑層的偏光板評價為再加工(rework)性優異的偏光板。此外，這裏所說的黏接力也基本上是指通過基於JIS Z0237：2009的180°剝離法所測定的黏接力，但是將測定樣品切成寬25mm、長100mm，使該測定樣品相對於被黏物(無堿玻璃)，在0.5MPa、50℃，加壓20分貼附之後，以常壓23℃、50% RH的條件下放置14天之後，以剝離速度300mm/min進行測定所得到的黏接力。 Moreover, the above-mentioned polarizing plate with an adhesive layer is adhered to the above-mentioned non-glass, and the adhesion force after being left for 14 days (adhesion force after being adhered for 14 days) is preferably 0.5N / 25mm ~ 30N / 25mm, especially It is preferably 1N / 25mm to 25N / 25mm, and more preferably 2N / 25mm to 20N / 25mm. As described above, the increase in the adhesive force due to the passage of time is suppressed, so that the above-mentioned polarizing plate with an adhesive layer can be evaluated as a polarizing plate having excellent reworkability. In addition, the adhesive force referred to here basically refers to the adhesive force measured by the 180 ° peeling method based on JIS Z0237: 2009, but the measurement sample is cut into a width of 25 mm and a length of 100 mm to make the measurement sample relatively adhered. (Glass-free glass), after attaching at 0.5 MPa, 50 ° C for 20 minutes under pressure, leaving it under normal pressure at 23 ° C and 50% RH for 14 days, and measuring at a peeling rate of 300 mm / min Adhesion.

以上說明的實施形態，是為了易於對本發明的理解而記述的，並不是對本發明進行限定而進行的記述。因此，上述實施形態中所公開的各要素，也包括屬於本發明的技術範圍的所有設計變更以及均等物。 The embodiments described above are described for easy understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above embodiment includes all design changes and equivalents belonging to the technical scope of the present invention.

例如，黏接片1A的剝離片12可以省略，黏接片1B中的剝離片12a，12b的任意一方也可以省略。 For example, the release sheet 12 of the adhesive sheet 1A may be omitted, and any of the release sheets 12a and 12b in the adhesive sheet 1B may be omitted.

【實施例】 [Example]

以下，通過實施例等進一步對本發明進行具體說明，但是本發明的範圍並不受這些實施例等的限定。 Hereinafter, the present invention will be described in more detail through examples and the like, but the scope of the present invention is not limited by these examples and the like.

〔實施例1〕 [Example 1]

1.(甲基)丙烯酸酯聚合物的調製 1. Preparation of (meth) acrylate polymer

向包括攪拌機、溫度計、回流冷卻器、滴下裝置及氮氣導入管的反應容器中，裝入丙烯酸正丁基酯74質量份、丙烯酸甲基酯5質量份、丙烯酸異冰片酯(acrylic acid isobornyl)20質量份、丙烯酸2-羥乙基酯1質量份、乙酸乙酯(ethyl acetate)200質量份、及2，2'-偶氮二異丁腈0.08質量份，將上述反應容器內的空氣置換成氮氣。在該氮氣氣氛下一邊攪拌，一邊將反應溶液升溫至60℃，使反應進行16小時後、冷卻至室溫。在此，將所得的溶液的一部分，用後述的方法測定分子量，確認到生成有重均分子量(Mw)185萬的(甲基)丙烯酸酯聚合物(A)。 Into a reaction vessel including a stirrer, a thermometer, a reflux cooler, a dropping device, and a nitrogen introduction tube, 74 parts by mass of n-butyl acrylate, 5 parts by mass of methyl acrylate, and acrylic acid isobornyl 20 were charged. Parts by mass, 1 part by mass of 2-hydroxyethyl acrylate, 200 parts by mass of ethyl acetate, and 0.08 parts by mass of 2,2'-azobisisobutyronitrile, replacing the air in the reaction vessel with Nitrogen. The reaction solution was heated to 60 ° C. while stirring under this nitrogen atmosphere, and the reaction was allowed to proceed for 16 hours, followed by cooling to room temperature. Here, a part of the obtained solution was measured for molecular weight by a method described later, and it was confirmed that a (meth) acrylate polymer (A) having a weight average molecular weight (Mw) of 1.85 million was formed.

2.黏接性組合物的調製 2. Preparation of adhesive composition

將在上述步驟(1)中獲得的(甲基)丙烯酸酯聚合物(A)100質量份(固體成分換算值；以下同)；作為活性能量線固化性成分(B)，將三(丙烯醯氧基乙基)異氰酸酯(東亞合成公司製，商品名「ARONIX M-315」)5質量份；作為矽烷偶聯劑(C)，其具有作為與有機材料反應的官能基的巰基，將3-巰基丙基三甲氧基矽烷與甲基三乙氧基矽烷的共縮聚物(信越化學公司製，商品名「X41-1810」)0.3質量份；作為架橋劑(D)，將三羥甲基丙烷改性伸二甲苯二異氰酸酯(xylylene diisocyanate)(綜研化學公司製，商品名「TD-75」)0.4質量份；作為光聚合起始劑(E)，將把二苯甲酮(Benzophenone)及1-羥 基環己基二苯甲酮以1：1的質量比混合所得的聚合物(公司製，Irgacure500)0.5質量份，進行混合，充分地攪拌，通過用乙酸乙酯進行稀釋，獲得黏接性組合物的塗布溶液。 100 parts by mass of the (meth) acrylate polymer (A) obtained in the above step (1) (solid content conversion value; the same applies hereinafter); as the active energy ray-curable component (B), 5 parts by mass of oxyethyl) isocyanate (manufactured by Toa Kosei, trade name "ARONIX M-315 " ); as a silane coupling agent (C), it has a mercapto group as a functional group that reacts with an organic material, 0.3 parts by mass of a copolycondensate of mercaptopropyltrimethoxysilane and methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. under the trade name "X41-1810"); as a bridging agent (D), trimethylolpropane 0.4 parts by mass of modified xylylene diisocyanate (manufactured by Soken Chemical Co., Ltd. under the trade name "TD-75 " ); as the photopolymerization initiator (E), benzophenone (Benzophenone) and 1- 0.5 mass parts of the polymer (Irgacure 500) manufactured by mixing hydroxycyclohexylbenzophenone at a mass ratio of 1: 1 was mixed, stirred sufficiently, and diluted with ethyl acetate to obtain an adhesive composition Coating solution.

在此，將該黏接性組合物的搭配表示於表1。另外，表1所記載的縮寫符號等的詳細情況如下所述。 Here, the combination of this adhesive composition is shown in Table 1. The details of the abbreviations and the like described in Table 1 are as follows.

[(甲基)丙烯酸酯聚合物(A)] [(Meth) acrylate polymer (A)]

BA：丙烯酸正丁基酯 BA: n-butyl acrylate

MA：丙烯酸甲基酯 MA: methyl acrylate

HEA：丙烯酸2-羥基乙基酯 HEA: 2-hydroxyethyl acrylate

IBXA：丙烯酸異冰片酯 IBXA: Isobornyl Acrylate

ADMMA：甲基丙烯酸金剛烷基酯 ADMMA: Adamantyl Methacrylate

DCPA：丙烯酸二環戊酯(acrylic acid dicyclopentanyl) DCPA: acrylic acid dicyclopentanyl

CHA：丙烯酸環己基酯 CHA: cyclohexyl acrylate

PhEA：丙烯酸2-苯氧基乙基酯 PhEA: 2-phenoxyethyl acrylate

AA：丙烯酸 AA: Acrylic

〔矽烷偶聯劑(C)〕 [Silane coupling agent (C)]

C1：3-巰基丙基三甲氧基矽烷和甲基三乙氧基矽烷的共縮聚物(信越化學工業公司制，商品名「X41-1810」，巰基當量：450g/mol) C1: Co-condensation product of 3-mercaptopropyltrimethoxysilane and methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X41-1810", mercapto equivalent: 450 g / mol)

C2：3-巰基丙基三甲氧基矽烷(信越化學工業公司制，商品名「KBM-803」) C2: 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-803")

C3：3-環氧丙氧基丙基三甲氧基矽烷(3-glycidoxypropyltrimethoxysilane)(信越化學工業公司製，商品名「KBM-403」) C3: 3-glycidoxypropyltrimethoxysilane (made by Shin-Etsu Chemical Industry Co., Ltd., trade name "KBM-403")

〔架橋劑(D)〕 〔Cross-linking agent (D)〕

XDI：三羥甲基丙烷改性伸二甲苯二異氰酸酯(xylylene diisocyanate)(綜研化學公司製，商品名「TD-75」) XDI: Trimethylolpropane modified xylylene diisocyanate (manufactured by Soken Chemical Co., Ltd., trade name "TD-75")

TDI：三羥甲基丙烷改性甲次苯基二異氰酸酯(tolylene diisocyanate)(綜研化學公司製，商品名「L-45」) TDI: trimethylolpropane modified tolylene diisocyanate (manufactured by Soken Chemical Co., Ltd., trade name "L-45")

3.帶有黏接劑層偏光板的製造 3. Manufacturing of polarizing plate with adhesive layer

將所得到的黏接性組合物的塗布溶液，在將聚對苯二甲酸乙二醇酯薄膜的一個面，用矽酮(silicone)類剝離劑進行了剝離處理的剝離片(琳得科株式公司制，SP-PET3811，厚度：38μm)的剝離處理面上，用刮刀塗布器進行塗布之後，用90℃進行1分鍾加熱處理而形成黏接性組合物的塗膜層。 The obtained coating solution of the adhesive composition was a peeling sheet (lintec type) which had been peeled with a silicone release agent on one side of a polyethylene terephthalate film. SP-PET3811 (manufactured by the company, SP-PET3811, thickness: 38 μm) was coated with a doctor blade applicator and then heat-treated at 90 ° C. for 1 minute to form a coating film layer of the adhesive composition.

接著，用三乙醯纖維素薄膜，保護聚乙烯基醇薄膜所構成的偏光子的一個面，用環烯烴聚合物薄膜保護另一個面所得的厚度為100μm的COP偏光板，貼合於上述塗膜層的露出面側。之後，透過剝離片用以下的條件照射紫外線，使上述塗膜層成為黏接劑層，由此而得到帶有黏接劑層的偏光板。另外，黏接劑層的厚度為20μm。 Next, a one-sided polarizer made of a polyvinyl alcohol film was protected with a triethylammonium cellulose film, and a COP polarizing plate having a thickness of 100 μm obtained by protecting the other surface with a cycloolefin polymer film was bonded to the above coating. The exposed side of the film layer. Thereafter, ultraviolet rays were irradiated through the release sheet under the following conditions to make the coating film layer into an adhesive layer, thereby obtaining a polarizing plate with an adhesive layer. The thickness of the adhesive layer was 20 μm.

<紫外線照射條件> <UV irradiation conditions>

．FUSION公司製無電極燈使用H燈泡 ． H bulb made of FUSION electrodeless lamp

．照度600mW/cm2，光量150mJ/cm2 ． Illumination 600mW / cm 2 , light quantity 150mJ / cm 2

．UV照度．光量計使用EYE GRAPHICS公司製“UVPF-36” ． UV illumination. The light meter uses "UVPF-36" manufactured by EYE GRAPHICS

〔實施例2~22，比較例1~5〕 [Examples 2 to 22, Comparative Examples 1 to 5]

除將構成(甲基)丙烯酸酯聚合物(A)的各單體的種類以及比例、(甲基)丙烯酸酯聚合物(A)的重量平均分子量、以及活性 能量線固化性成分(B)、矽烷偶聯劑(C)、架橋劑(D)以及光聚合起始劑(E)的種類及/或配合量，按造表1所示進行變更外，與實施例1同樣地進行操作，製造帶有黏接劑層的偏光板。另外，在實施例7中，作為帶電防止劑，使用進一步搭配有吡啶鹽類離子性液體(廣榮化學公司製，商品名「IL-P18」)的黏接性組合物。 In addition to the types and proportions of the monomers that constitute the (meth) acrylate polymer (A), the weight average molecular weight of the (meth) acrylate polymer (A), and the activity The types and / or blending amounts of the energy ray-curable component (B), the silane coupling agent (C), the bridging agent (D), and the photopolymerization initiator (E) are changed as shown in Table 1, and In Example 1, a polarizing plate with an adhesive layer was produced in the same manner. Moreover, in Example 7, as a charge preventive agent, the adhesive composition further mix | blended with the pyridinium-type ionic liquid (made by Kwong Young Chemical Co., Ltd., brand name "IL-P18") was used.

在此，上述的重量平均分子量(Mw)，為使用凝膠滲透色譜(GPC)在以下的條件下測定(GPC測定)的聚苯乙烯換算的重量平均分子量。 Here, the weight average molecular weight (Mw) is a polystyrene equivalent weight average molecular weight measured (GPC measurement) under the following conditions using gel permeation chromatography (GPC).

<測定條件> <Measurement conditions>

．GPC測定裝置：TOSOH公司製，HLC-8020 ． GPC measuring device: manufactured by TOSOH, HLC-8020

．GPC柱(以下的順序通過)：TOSOH公司製 ． GPC column (passed in the following order): made by TOSOH

TSK guard column HXL-H TSK guard column HXL-H

TSK gel GMHXL(×2) TSK gel GMHXL (× 2)

TSK gel G2000HXL TSK gel G2000HXL

．測定熔劑：四氫呋喃 ． Determination of flux: tetrahydrofuran

．測定溫度：40℃ ． Measurement temperature: 40 ° C

〔試驗例1〕(凝膠分率的測定) [Test Example 1] (Measurement of gel fraction)

在實施例或者比較例中，代替製作帶有黏接劑層的偏光板所使用的的偏光板，使用將聚對苯二甲酸乙二醇酯薄膜的一個面，用矽酮(silicone)類剝離劑進行了剝離處理的剝離片(琳得科株式公司製，SP-PET3801，厚度：38μm)，進行黏接片的製作。具體而言，在用實施例或者比表例的製造過程所得到的剝離片/黏接劑層(厚度：20μm)所構成的構成體的露出的黏接劑 層上，以剝離處理面側相接的方式，將上述剝離片進行層疊。由此，來製作由剝離片/黏接劑層/剝離片的構成所形成的黏接片。 In Examples or Comparative Examples, instead of the polarizing plate used for the production of the polarizing plate with an adhesive layer, one surface of a polyethylene terephthalate film was used, and a silicone type was used to peel it off. A release sheet (SP-PET3801, manufactured by Lindec Corporation, thickness: 38 μm) subjected to a release treatment with an adhesive agent was used to produce an adhesive sheet. Specifically, the exposed adhesive of the structure composed of the release sheet / adhesive layer (thickness: 20 μm) obtained in the manufacturing process of the example or the comparative example is used. The release sheet is laminated on the layer so that the release treatment surface side is in contact with each other. Thereby, the adhesive sheet which consists of a peeling sheet / adhesive layer / peeling sheet structure was produced.

將得到的黏接片，在23℃，50%RH的條件下進行7天熟成。之後，將該黏接片製成80mm×80mm尺寸的樣品，將其黏接劑層用聚酯製網(網尺寸200)包裹，僅將黏接劑的質量用精密天平進行稱量。將此時的質量作為M1。 The obtained adhesive sheet was aged for 7 days under the conditions of 23 ° C. and 50% RH. Then, the adhesive sheet was made into a sample having a size of 80 mm × 80 mm, and the adhesive layer was wrapped with a polyester mesh (mesh size 200), and only the mass of the adhesive was weighed with a precision balance. Let the mass at this time be M1.

接著，將上述聚酯製網包裹的黏接劑，在室溫下(23℃)下，在乙酸乙酯中進行24小時浸漬。之後將黏接劑取出，在溫度23℃、相對濕度50%的環境下，進行24小時風乾，進一步在80℃的烘箱中進行12小時乾燥。僅將乾燥後的黏接劑的質量用精密天平進行稱量。將此時的質量作為M2。凝膠分率(%)用(M2/M1)×100來表示。將結果示於表2。 Next, the polyester mesh-wrapped adhesive was impregnated in ethyl acetate at room temperature (23 ° C) for 24 hours. After that, the adhesive was taken out and air-dried for 24 hours under an environment of a temperature of 23 ° C and a relative humidity of 50%, and further dried in an oven at 80 ° C for 12 hours. Only the mass of the dried adhesive was weighed with a precision balance. Let the mass at this time be M2. The gel fraction (%) is represented by (M2 / M1) × 100. The results are shown in Table 2.

〔試驗例2〕(霧度值的測定) [Test Example 2] (Measurement of Haze Value)

作為測定樣品，準備與測定凝膠分率所用的黏接片同樣的黏接片(已經熟成7天)。關於該黏接片的黏接劑層(厚度：20μm)，使用霧度測量計(日本電色工業公司製，NDH2000)，基於JIS K7136：2000，對霧度值(%)進行測定。將結果示於表2。 As a measurement sample, an adhesive sheet similar to the adhesive sheet used for measuring the gel fraction was prepared (aged for 7 days). About the adhesive layer (thickness: 20 micrometers) of this adhesive sheet, the haze value (%) was measured based on JIS K7136: 2000 using the haze meter (made by Nippon Denshoku Industries, NDH2000). The results are shown in Table 2.

〔試驗例3〕(黏接力的測定) [Test Example 3] (Measurement of Adhesive Strength)

將在實施例或比較例中所得到的帶有黏接劑層的偏光板裁斷，製作寬25mm、長100mm的樣品。從該樣品上將剝離片剝離，介於露出的黏接劑層，在無鹼玻璃(康寧公司製，鷹XG)上進行該樣品的貼附之後，用栗原製作所公司製的高壓鍋，在 0.5MPa、50℃，加壓20分鍾。其後，在23℃、50% RH的條件下，放置24小時(1天)或放置14天後，使用拉伸試驗機(奧瑞公司製，TENSILON)，基於JIS Z0237：2009，以剝離速度300mm/min、剝離角度180°的條件，測定黏接力(貼附1天後及貼附14天後的黏接力；N/25mm)。將結果分別示於表2。 The polarizing plate with an adhesive layer obtained in the examples or comparative examples was cut to produce samples having a width of 25 mm and a length of 100 mm. The release sheet was peeled from the sample, and the sample was attached to an alkali-free glass (Korning Corporation, Eagle XG) through the exposed adhesive layer, and then a pressure cooker manufactured by Kurihara Seisakusho was used. 0.5 MPa, 50 ° C, and pressure for 20 minutes. Thereafter, under conditions of 23 ° C. and 50% RH, it was left for 24 hours (1 day) or after 14 days, and then a tensile tester (Tensilon, manufactured by Orin Co., Ltd.) was used at a peeling speed based on JIS Z0237: 2009. At 300 mm / min and a peeling angle of 180 °, the adhesive force (adhesive force after 1 day and 14 days after application; N / 25 mm) was measured. The results are shown in Table 2.

〔試驗例4〕(耐久性評價) [Test Example 4] (Durability Evaluation)

將在實施例或比較例中所得到的帶有黏接劑層的偏光板裁斷，製作233mm×309mm大小的樣品。作為樣品，從製作帶有黏接劑層的偏光板(形成黏接劑層)中，準備在23℃、50% RH的環境下保管7天後的樣品。從該樣品把剝離片剝離，介於露出的黏接劑層，在無鹼玻璃(康寧公司製，鷹XG)上進行貼附之後，用栗原製作所製的高壓鍋，在0.5MPa、50℃，加壓20分鍾。 The polarizing plate with an adhesive layer obtained in the examples or comparative examples was cut to produce a sample having a size of 233 mm × 309 mm. As a sample, from the production of a polarizing plate with an adhesive layer (adhesive layer formation), a sample was stored for 7 days in an environment of 23 ° C. and 50% RH. The release sheet was peeled from the sample, and the exposed adhesive layer was adhered to an alkali-free glass (Corning Co., Eagle XG), and then a pressure cooker made by Kurihara Seisakusho was applied at 0.5 MPa and 50 ° C. Press for 20 minutes.

之後，投入到下述的耐久條件的環境下，500小時後，使用10倍放大鏡，對浮起或者剝離的有無進行確認。評價基準如下。將結果示於表2。 After that, it was put into an environment with the following durable conditions, and 500 hours later, the presence or absence of floating or peeling was confirmed using a 10-fold magnifying glass. The evaluation criteria are as follows. The results are shown in Table 2.

◎：沒有確認到浮起或者剝離。 ：: No floating or peeling was observed.

○：確認到0.5mm以下大小的浮起或者剝離。 ○: Floating or peeling of a size of 0.5 mm or less was confirmed.

×：確認到0.6mm以上大小的浮起或者剝離。 ×: Floating or peeling of a size of 0.6 mm or more was confirmed.

<耐久條件> <Durable conditions>

．85℃ dry ． 85 ℃ dry

．60℃，相對濕度90% RH ． 60 ℃, relative humidity 90% RH

【表1】 【Table 1】

【表2】 【Table 2】

由表2可知，在實施例所得到的黏接劑層的黏接劑，具有高黏接力，耐久性也優異。 As can be seen from Table 2, the adhesive of the adhesive layer obtained in the examples has high adhesive strength and excellent durability.

【產業上可利用性】 [Industrial availability]

本發明的黏接劑適宜於光學構件，特別是適宜於偏光板的黏接，而且，本發明的黏接片適宜作為光學構件用， 特別是適宜作為偏光板用的黏接片。 The adhesive of the present invention is suitable for optical members, especially for the adhesion of polarizing plates, and the adhesive sheet of the present invention is suitable for optical members. In particular, it is suitable as an adhesive sheet for polarizing plates.

Claims (17)

一種黏接性組合物，其特徵在於：包含：重量平均分子量為90萬~300萬的(甲基)丙烯酸酯聚合物(A)，其作為構成聚合物的單體單元，含有0.1質量%~30質量%的具有脂環式結構的單體；活性能量線固化性成分(B)；和矽烷偶聯劑(C)，其具有巰基作為與有機材料反應的官能基。An adhesive composition, comprising: a (meth) acrylate polymer (A) having a weight-average molecular weight of 900,000 to 3 million, and as a monomer unit constituting the polymer, containing 0.1% by mass to 30% by mass of a monomer having an alicyclic structure; an active energy ray-curable component (B); and a silane coupling agent (C) having a mercapto group as a functional group that reacts with an organic material. 根據申請專利範圍第1項所述的黏接性組合物，其中其進一步含有架橋劑(D)。The adhesive composition according to item 1 of the patent application scope, further comprising a bridging agent (D). 根據申請專利範圍第1項所述的黏接性組合物，其中上述脂環式結構含有環己基骨架、雙環戊二烯(dicyclopentadiene)骨架、金剛烷骨架或者異冰片骨架。The adhesive composition according to item 1 of the scope of the patent application, wherein the alicyclic structure contains a cyclohexyl skeleton, a dicyclopentadiene skeleton, an adamantane skeleton, or an isobornyl skeleton. 根據申請專利範圍第1項所述的黏接性組合物，其中上述(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，進一步含有0.1質量%~10質量%的具有羥基的單體。The adhesive composition according to item 1 of the scope of patent application, wherein the (meth) acrylate polymer (A), as a monomer unit constituting the polymer, further contains 0.1% to 10% by mass of A monomer having a hydroxyl group. 根據申請專利範圍第1項所述的黏接性組合物，其中上述(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，實質上不含有具有羧基的單體。The adhesive composition according to claim 1, wherein the (meth) acrylate polymer (A) does not substantially contain a monomer having a carboxyl group as a monomer unit constituting the polymer. 根據申請專利範圍第1項所述的黏接性組合物，其中上述活性能量線固化性成分(B)為分子量小於1000的多官能丙烯酸酯類單體。The adhesive composition according to item 1 of the scope of the patent application, wherein the active energy ray-curable component (B) is a polyfunctional acrylate monomer having a molecular weight of less than 1,000. 根據申請專利範圍第6項所述的黏接性組合物，其中上述多官能丙烯酸酯類單體具有環狀結構。The adhesive composition according to item 6 of the patent application scope, wherein the polyfunctional acrylate monomer has a cyclic structure. 根據申請專利範圍第1項所述的黏接性組合物，其中上述黏接性組合物中的上述活性能量線固化性成分(B)的含有量，相對於上述(甲基)丙烯酸酯聚合物(A)100質量份，為1質量份~30質量份。The adhesive composition according to item 1 of the scope of patent application, wherein the content of the active energy ray-curable component (B) in the adhesive composition is relative to the (meth) acrylate polymer (A) 100 parts by mass, 1 to 30 parts by mass. 根據申請專利範圍第1項所述的黏接性組合物，其中上述黏接性組合物中的上述矽烷偶聯劑(C)的含有量，相對於上述(甲基)丙烯酸酯聚合物(A)100質量份，為0.01質量份~5質量份。The adhesive composition according to item 1 of the scope of patent application, wherein the content of the silane coupling agent (C) in the adhesive composition is greater than that of the (meth) acrylate polymer (A ) 100 parts by mass, 0.01 to 5 parts by mass. 根據申請專利範圍第2項所述的黏接性組合物，其中上述架橋劑(D)為異氰酸酯類架橋劑。The adhesive composition according to item 2 of the scope of patent application, wherein the bridging agent (D) is an isocyanate bridging agent. 根據申請專利範圍第1項所述的黏接性組合物，其中其進一步含有光聚合起始劑(E)。The adhesive composition according to item 1 of the patent application scope, further comprising a photopolymerization initiator (E). 一種黏接劑，其是通過活性能量線的照射，使申請專利範圍第1至11項中任一項所述的黏接性組合物固化所成的黏接劑。An adhesive is an adhesive formed by curing the adhesive composition described in any one of the claims 1 to 11 of the scope of patent application by irradiation of active energy rays. 一種黏接片，其特徵在於：其為具備基材和黏接劑層的黏接片，上述黏接劑層由申請專利範圍第12項所述的黏接劑構成。An adhesive sheet is characterized in that it is an adhesive sheet provided with a substrate and an adhesive layer, and the adhesive layer is composed of the adhesive described in item 12 of the scope of patent application. 根據申請專利範圍第13項所述的黏接片，其中上述基材為光學構件。The adhesive sheet according to item 13 of the patent application scope, wherein the substrate is an optical member. 根據申請專利範圍第14項所述的黏接片，其中上述光學構件為偏光板。The adhesive sheet according to item 14 of the scope of patent application, wherein the optical member is a polarizing plate. 根據申請專利範圍第14項所述的黏接片，其中上述光學構件具有聚環烯烴類薄膜。The pressure-sensitive adhesive sheet according to item 14 of the scope of patent application, wherein the optical member has a polycycloolefin-based film. 一種黏接片，其特徵在於：其為具備兩片剝離片和以與上述兩片剝離片的剝離面相接的方式被上述剝離片挾持的黏接劑層的黏接片，上述黏接劑層由申請專利範圍第12項所述的黏接劑構成。An adhesive sheet is characterized in that it is an adhesive sheet comprising two release sheets and an adhesive layer held by the release sheet so as to be in contact with the release surfaces of the two release sheets, and the adhesive The layer is composed of the adhesive described in item 12 of the scope of patent application.
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