TWI636106B - Adhesive composition, adhesive and adhesive sheet - Google Patents

Adhesive composition, adhesive and adhesive sheet Download PDF

Info

Publication number
TWI636106B
TWI636106B TW103118215A TW103118215A TWI636106B TW I636106 B TWI636106 B TW I636106B TW 103118215 A TW103118215 A TW 103118215A TW 103118215 A TW103118215 A TW 103118215A TW I636106 B TWI636106 B TW I636106B
Authority
TW
Taiwan
Prior art keywords
adhesive
meth
acrylate
monomer
mass
Prior art date
Application number
TW103118215A
Other languages
Chinese (zh)
Other versions
TW201504376A (en
Inventor
又野仁
荒井隆行
所司悟
Original Assignee
日商琳得科股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商琳得科股份有限公司 filed Critical 日商琳得科股份有限公司
Publication of TW201504376A publication Critical patent/TW201504376A/en
Application granted granted Critical
Publication of TWI636106B publication Critical patent/TWI636106B/en

Links

Classifications

    • 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
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Landscapes

  • 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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

本發明提供一種不會給透明導電膜等的被黏物帶來不良影響，同時耐久性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，其含有重均分子量為100萬~250萬，作為構成聚合物的單體單元，含有具有羥基的單體、具有芳香環的單體和具有羧基的單體的(甲基)丙烯酸酯聚合物(A)、異氰酸酯類架橋劑(B)、具有巰基的矽烷偶聯劑(C)和活性能量線固化性成分(D)，(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，含有1質量%~5質量%具有羥基的單體，5質量%~30質量%具有芳香環的單體，以及0.1質量%~0.8質量%具有羧基的單體。 The present invention provides an adhesive composition, an adhesive, and an adhesive sheet that do not adversely affect adherends such as transparent conductive films and have excellent durability. In order to solve the above-mentioned problems, an adhesive composition is provided which contains a weight average molecular weight of 1 to 2.5 million. As a monomer unit constituting a polymer, a monomer having a hydroxyl group, a monomer having an aromatic ring, and Carboxylic (meth) acrylate polymer (A), isocyanate bridging agent (B), mercapto-containing silane coupling agent (C), active energy ray-curable component (D), (methyl) The acrylate polymer (A), as a monomer unit constituting the polymer, contains 1 to 5 mass% of a monomer having a hydroxyl group, 5 to 30 mass% of a monomer having an aromatic ring, and 0.1 mass%. ~ 0.8% by mass of a monomer having a carboxyl group.

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電阻式以及母體電阻式。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. Resistive touch panels include analog data resistive and matrix resistive. 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。作為上述移動電子設備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積層液晶顯示裝置(LCD)、黏接劑層、透明導電膜(氧化銦錫：ITO)、玻璃基板、透明導電膜(ITO)以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 the 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, a transparent conductive film (indium tin oxide: ITO), and glass are laminated in order from the bottom to the top. Touch panels with protective layers such as substrates, transparent conductive films (ITO), and tempered glass.

作為構成上述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，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夾持液晶材料的組件。通常，在液晶組件中的兩片透明電極基板的外側 ，分別通過黏接劑而黏接偏光板。 As an optical member constituting the liquid crystal display device, a liquid crystal module is generally used. In a liquid crystal module, an alignment layer of two transparent electrode substrates forming an alignment layer is generally used as an inner side, and a spacer is arranged to form a predetermined interval. The periphery is sealed, and liquid crystal is sandwiched between the two transparent electrode substrates. Material components. Usually, the outside of two transparent electrode substrates in a liquid crystal module , Respectively, the polarizing plate is bonded by an adhesive.

在此，如上所述，將液晶顯示裝置的偏光板，通過黏接劑層，在透明導電膜(ITO)上貼合的構成中，黏接劑與ITO直接接觸。因此，在包含大量酸成分的羧基的黏接劑中，會產生ITO被腐蝕或ITO的電阻值發生改變的問題。 Here, as described above, in a configuration in which a polarizing plate of a liquid crystal display device is bonded to a transparent conductive film (ITO) through an adhesive layer, the adhesive directly contacts the ITO. For this reason, in an adhesive containing a large number of carboxyl groups of acid components, there is a problem that ITO is corroded or the resistance value of ITO is changed.

作為光學用的黏接劑，例如，已知有專利文獻1所示的黏接劑。該黏接劑，由含50質量%~90質量%(甲基)丙烯酸的碳原子數為4~12的烷基酯單體、3質量%~10質量%(甲基)丙烯酸的脂環式烷基酯單體、0.1質量%~1.0質量%(甲基)丙烯酸的羥烷基酯單體以及3質量%~10質量%(甲基)丙烯酸的碳原子數為1~3的烷基酯單體(合計100質量%)的共聚物(共聚物中含有羥基，但不含羧基，重均分子量為70萬~120萬)、架橋劑(相對於共聚物100質量份，為0.02質量份~1質量份)以及架橋助劑(相對於共聚物100質量份，為0.5質量份~5.0質量份)所構成。該黏接劑由於不含有酸成分的羧基，不易發生上述問題。 As an adhesive for optics, the adhesive shown in patent document 1, for example is known. The adhesive is an alicyclic type containing an alkyl ester monomer having 4 to 12 carbon atoms and 50 to 90% by mass of (meth) acrylic acid, and 3 to 10% by mass of (meth) acrylic acid. Alkyl ester monomer, 0.1% to 1.0% by mass of (meth) acrylic acid hydroxyalkyl ester monomer, and 3% to 10% by mass of (meth) acrylic acid alkyl ester having 1 to 3 carbon atoms Copolymers of monomers (total 100% by mass) (copolymers contain hydroxyl groups, but do not contain carboxyl groups, weight average molecular weight is 700,000 to 1.2 million), bridging agents (0.02 mass parts to 100 mass parts of copolymers ~ 1 part by mass) and a bridging aid (0.5 to 5.0 parts by mass with respect to 100 parts by mass of the copolymer). Since this adhesive does not contain a carboxyl group of an acid component, the above-mentioned problems are less likely to occur.

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

【專利文獻1】日本特開2012-001647號公報 [Patent Document 1] Japanese Patent Application Publication No. 2012-001647

另一方面，隨著近年移動式電子設備的薄型化，其組成構件偏光板也開始薄型化。具體而言，使用在兩側維持偏光子聚乙烯醇的保護薄膜的厚度減少的偏光板。上述偏光板 ，由於保護薄膜，防止偏光子熱收縮的能力下降，熱收縮有比原來更大的傾向。另外，作為上述保護薄膜的材質，也使用環烯烴聚合物(COP)等容易發生脫氣的光學功能性薄膜等代替三醋酸纖維素。因此，用於這些的黏接劑中，要求具有比現在更高的信賴性(耐久性)。 On the other hand, with the reduction in thickness of mobile electronic devices in recent years, the thickness of polarizing plates of its constituent members has also begun to be reduced. Specifically, a polarizing plate having a reduced thickness of a protective film that maintains polarized polyvinyl alcohol on both sides is used. The above polarizing plate Due to the protective film, the ability to prevent thermal shrinkage of polarized photons is reduced, and the thermal shrinkage tends to be greater than the original. In addition, as the material of the protective film, an optically functional film that is easily degassed, such as a cycloolefin polymer (COP), is used instead of cellulose triacetate. Therefore, it is required to have higher reliability (durability) than those used in these adhesives.

但是，在如上所述的偏光板上使用專利文獻1的黏接劑時，耐久性不充分，在高溫條件下或濕熱條件下，會發生浮起或剝離。 However, when the adhesive of Patent Document 1 is used on the polarizing plate as described above, the durability is insufficient, and floating or peeling may occur under high temperature conditions or wet heat conditions.

本發明是鑒於這樣的現狀而進行的，目的在於提供一種不會給透明導電膜等的被黏物帶來不良影響，同時，耐久性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 having excellent durability without adversely affecting an adherend such as a transparent conductive film. .

為了達成上述目的，第一，本發明提供一種黏接性組合物，其含有重均分子量為100萬~250萬，作為構成聚合物的單體單元，含有具有羥基的單體、具有芳香環的單體和具有羧基的單體的(甲基)丙烯酸酯聚合物(A)、異氰酸酯類架橋劑(B)、具有巰基的矽烷偶聯劑(C)和活性能量線固化性成分(D)，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，含有1質量%~5質量%上述具有羥基的單體，含有5質量%~30質量%上述具有芳香環的單體，含有0.1質量%~0.8質量%上述具有羧基的單體(發明1)。 In order to achieve the above object, first, the present invention provides an adhesive composition containing a weight average molecular weight of 1 to 2.5 million. As a monomer unit constituting a polymer, a monomer having a hydroxyl group and an aromatic ring (Meth) acrylate polymer (A) of monomer and monomer having carboxyl group, isocyanate-based bridging agent (B), mercapto-containing silane coupling agent (C), and active energy ray-curable component (D), The (meth) acrylate polymer (A), as a monomer unit constituting the polymer, contains 1 to 5 mass% of the monomer having a hydroxyl group, and contains 5 to 30 mass% of the monomer having an aromatic ring. The monomer contains 0.1% to 0.8% by mass of the monomer having a carboxyl group described above (Invention 1).

將上述發明(發明1)所述黏接性組合物架橋所得到的黏接劑，通過使(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，分別以所定量含有具有羥基的單體、具有芳香 環的單體以及具有羧基的單體，具有巰基的矽烷偶聯劑(C)發揮優異的偶聯效果，以及活性能量線固化性成分(D)固化，而與(甲基)丙烯酸酯聚合物(A)的架橋體纏繞等，耐久性優異。另外，由於(甲基)丙烯酸酯聚合物(A)包含的羧基的量抑制在較低的程度，因此可抑制由於酸產生的透明導電膜等的被黏物的缺陷。 The adhesive obtained by bridging the adhesive composition according to the above-mentioned invention (Invention 1) is obtained by using a (meth) acrylate polymer (A) as a monomer unit constituting the polymer in a predetermined amount. Contains a monomer with a hydroxyl group and has an aroma A cyclic monomer and a monomer having a carboxyl group, the silane coupling agent (C) having a mercapto group exhibits excellent coupling effect, and the active energy ray-curable component (D) is cured, and the polymer is (meth) acrylate polymer The bridge body of (A) is wound, etc., and is excellent in durability. In addition, since the amount of carboxyl groups contained in the (meth) acrylate polymer (A) is suppressed to a low degree, defects of adherends such as a transparent conductive film due to an acid can be suppressed.

上述發明(發明1)中，上述異氰酸酯類架橋劑(B)，優選為三羥甲基丙烷改性甲次苯基二異氰酸酯(發明2)。 In the above invention (Invention 1), the isocyanate-based bridging agent (B) is preferably trimethylolpropane-modified methylphenyl diisocyanate (Invention 2).

上述發明(發明1，發明2)中，上述黏接性組合物中上述異氰酸酯類架橋劑(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0.01質量份~1質量份(發明3)。 In the above invention (Invention 1, Invention 2), the content of the isocyanate-based bridging agent (B) in the adhesive composition is preferably 100 parts by mass of the (meth) acrylate polymer (A). 0.01 parts by mass to 1 part by mass (Invention 3).

上述發明(發明1~發明3)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~0.5質量份(發明4)。 In the above invention (Invention 1 to Invention 3), the content of the silane coupling agent (C) in the adhesive composition is preferably 100 parts by mass of the (meth) acrylate polymer (A). 0.01 to 0.5 parts by mass (Invention 4).

上述發明(發明1~發明4)中，上述具有芳香環的單體，優選為(甲基)丙烯酸2-苯基乙基酯(發明5)。 In the above invention (Invention 1 to Invention 4), the monomer having an aromatic ring is preferably 2-phenylethyl (meth) acrylate (Invention 5).

上述發明(發明1~發明5)中，上述活性能量線固化性成分(D)，優選為分子量小於1000的多官能丙烯酸酯類單體(發明6)。 In the above invention (Invention 1 to Invention 5), the active energy ray-curable component (D) is preferably a polyfunctional acrylate-based monomer having a molecular weight of less than 1,000 (Invention 6).

上述發明(發明6)中，上述多官能丙烯酸酯類單體，優選為具有環狀結構(發明7)。 In the said invention (invention 6), it is preferable that the said polyfunctional acrylate monomer has a cyclic structure (invention 7).

上述發明(發明1~發明7)中，上述黏接性組合物 中上述活性能量線固化性成分(D)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~50質量份(發明8)。 In the above invention (Invention 1 to Invention 7), the above-mentioned adhesive composition The content of the active energy ray-curable component (D) in the above is preferably 1 to 50 parts by mass based on 100 parts by mass of the (meth) acrylate polymer (A) (Invention 8).

第二，本發明提供一種對上述黏接性組合物(發明1~發明8)照射活性能量線而固化所構成的黏接劑(發明9)。 Secondly, the present invention provides an adhesive composed of the above-mentioned adhesive composition (Invention 1 to Invention 8) irradiated with active energy rays and cured (Invention 9).

上述發明(發明9)中，凝膠分率優選為55%~85%(發明10)。 In the above invention (Invention 9), the gel fraction is preferably 55% to 85% (Invention 10).

上述發明(發明9，發明10)中，在23℃下的儲能模量優選為0.15MPa~0.3MPa，在80℃下的儲能模量優選為0.05MPa~0.2MPa(發明11)。 In the above invention (Invention 9, Invention 10), the storage modulus at 23 ° C is preferably 0.15 MPa to 0.3 MPa, and the storage modulus at 80 ° C is preferably 0.05 MPa to 0.2 MPa (Invention 11).

第三，本發明提供一種黏接片，其特徵在於：其具備基材和黏接劑層，上述黏接劑層由上述黏接劑(發明9~發明11)構成(發明12)。 Third, the present invention provides an adhesive sheet, which is characterized in that it includes a base material and an adhesive layer, and the adhesive layer is composed of the adhesive (Invention 9 to Invention 11) (Invention 12).

上述發明(發明12)中，上述基材優選為光學構件(發明13)。 In the said invention (invention 12), it is preferable that the said base material is an optical member (invention 13).

上述發明(發明13)中，上述光學構件優選為偏光板(發明14)。 In the above invention (Invention 13), the optical member is preferably a polarizing plate (Invention 14).

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與上述兩片剝離片的剝離面相接的方式夾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9~發明11)構成(發明15)。 Fourth, the present invention provides an adhesive sheet, comprising: two release sheets; and an adhesive layer for sandwiching the release sheet so as to contact the release surfaces of the two release sheets. The adhesive layer is composed of the above-mentioned adhesive (Invention 9 to Invention 11) (Invention 15).

上述發明(發明12~發明15)中，對上述黏接劑層和透明導電膜的積層體，在65℃、95%RH的氣氛下，進行曝露500小時的濕熱促進試驗時，上述透明導電膜根據以下算式 算出的電阻值增加率優選為15%以下(發明16)。 In the above invention (Invention 12 to Invention 15), when the laminated body of the adhesive layer and the transparent conductive film is subjected to a humid heat promotion test in an atmosphere of 65 ° C and 95% RH for 500 hours, the transparent conductive film is According to the following formula The calculated resistance value increase rate is preferably 15% or less (Invention 16).

電阻值增加率(%)={(R-R0)/R0}×100(算式中，R0為濕熱促進試驗前的初始電阻值，R為濕熱促進試驗後的電阻值。) Resistance value increase rate (%) = {(RR 0 ) / R 0 } × 100 (In the formula, R 0 is the initial resistance value before the moist heat promotion test, and R is the resistance value after the moist heat promotion test.)

根據本發明所述黏接性組合物、黏接劑以及黏接片，不會給透明導電膜等的被黏物帶來不良影響，同時，耐久性優異。 The adhesive composition, the adhesive, and the adhesive sheet according to the present invention do not adversely affect adherends such as a transparent conductive film, and are excellent in durability.

1A，1B‧‧‧黏接片 1A, 1B ‧‧‧ Adhesive Sheet

1A’‧‧‧附有黏接劑層的偏光板 1A’‧‧‧ polarizer with adhesive layer

11‧‧‧黏接劑層 11‧‧‧Adhesive layer

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

13‧‧‧基材 13‧‧‧ substrate

13’‧‧‧偏光板 13’‧‧‧ polarizing plate

21‧‧‧PET薄膜 21‧‧‧PET film

21a，21b‧‧‧面 21a, 21b

22‧‧‧ITO膜 22‧‧‧ITO film

22a‧‧‧面 22a‧‧‧

23‧‧‧玻璃板 23‧‧‧ glass plate

23a‧‧‧面 23a‧‧‧face

24‧‧‧黏接膠帶 24‧‧‧ Adhesive Tape

25‧‧‧電極 25‧‧‧ electrode

30‧‧‧數字測高儀 30‧‧‧ Digital Altimeter

S‧‧‧電阻值測定用樣品 S‧‧‧Samples for resistance value measurement

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.

圖3為試驗例3中製作的電阻值測定樣品的剖面圖。 3 is a cross-sectional view of a resistance value measurement sample prepared in Test Example 3. FIG.

圖4為對試驗例3的試驗方法進行說明的斜視圖。 FIG. 4 is a perspective view illustrating a test method of Test Example 3. FIG.

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]

本實施形態所述黏接性組合物(以下稱為「黏接性組合物P」。)，含有重均分子量為100萬~250萬，作為構成聚合物的單體單元，含有具有羥基的單體(含羥基單體)、具有芳香環的單體(含芳香環單體)和具有羧基的單體(含羧基單體)的(甲基)丙烯酸酯聚合物(A)、異氰酸酯類架橋劑(B)、具有巰基的矽烷偶聯劑(C)和活性能量線固化性成分(D)，優選為進一步含有光聚合起始劑(E)。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，含有1質量%~5質量%含羥基單體，含有5質量%~30質量%含芳香環單體，含有0.1質量%~0.8質量%含羧基單體。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 according to this embodiment (hereinafter referred to as "adhesive composition P") contains a weight average molecular weight of 1 to 2.5 million, and as a monomer unit constituting a polymer, a monomer having a hydroxyl group is contained. (Meth) acrylic polymer (A), isocyanate-based bridging agent (hydroxyl-containing monomer), monomer having aromatic ring (aromatic ring-containing monomer), and monomer having carboxyl group (carboxyl-containing monomer) (B) The silane coupling agent (C) having a mercapto group and the active energy ray-curable component (D) preferably further contain a photopolymerization initiator (E). In addition, a (meth) acrylate polymer (A) is used as a constitution The monomer unit of the polymer contains 1 to 5 mass% of a hydroxyl-containing monomer, 5 to 30 mass% of an aromatic ring-containing monomer, and 0.1 to 0.8 mass% of a carboxyl-containing 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".

在上述黏接性組合物P中，(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，通過分別以所定量含有含羥基單體、含芳香環單體以及含羧基單體，將該黏接性組合物P固化所得到的黏接劑，兼具凝集力和應力緩和性，耐久性優異。 In the adhesive composition P, the (meth) acrylate polymer (A), as a monomer unit constituting the polymer, contains a hydroxyl group-containing monomer, an aromatic ring-containing monomer, and A carboxyl monomer, an adhesive obtained by curing the adhesive composition P, has both cohesive force and stress relaxation, and is excellent in durability.

【0032】另外，如果將上述黏接性組合物P固化，則矽烷偶聯劑(C)的巰基，與異氰酸酯類架橋劑(B)的異氰酸酯基容易形成硫代氨基甲酸酯鍵，該異氰酸酯類架橋劑(B)的其他異氰酸酯基，與(甲基)丙烯酸酯聚合物(A)的羥基反應，將(甲基)丙烯酸酯聚合物(A)架橋，形成第1三維網絡結構。而且，據推測矽烷偶聯劑(C)的烷氧基甲矽烷，與(甲基)丙烯酸酯聚合物(A)保持適宜距離，懸掛在(甲基)丙烯酸酯聚合物(A)上。由此，發揮優異的偶聯效果。另一方面，複數的活性能量線固化性成分(D)相互結合，形成第2三維網絡結構。據推測上述第1三維網絡結構以及第2三維網絡結構相互纏繞，形成整體的三維網絡結構(以下將該結構稱為「結構X」。)。通過該結構X以及上述偶聯效果，所得到的黏接劑，在高溫條件下或濕熱條件下，黏接耐久性也優異。 [0032] When the adhesive composition P is cured, the mercapto group of the silane coupling agent (C) and the isocyanate group of the isocyanate-based bridging agent (B) easily form a thiourethane bond, and the isocyanate The other isocyanate groups of the bridging agent (B) react with the hydroxyl group of the (meth) acrylate polymer (A) to bridge the (meth) acrylate polymer (A) to form a first three-dimensional network structure. Further, it is estimated that the alkoxysilane of the silane coupling agent (C) is suspended from the (meth) acrylate polymer (A) at a suitable distance from the (meth) acrylate polymer (A). Thereby, an excellent coupling effect is exhibited. On the other hand, a plurality of active energy ray-curable components (D) are combined with each other to form a second three-dimensional network structure. It is presumed that the first three-dimensional network structure and the second three-dimensional network structure are intertwined with each other to form an overall three-dimensional network structure (hereinafter, this structure is referred to as "structure X"). By the structure X and the coupling effect described above, the obtained adhesive is also excellent in adhesion durability under high temperature conditions or wet heat conditions.

另外，上述黏接性組合物P中，由於(甲基)丙烯酸 酯聚合物(A)，作為單體單元，含有的含羧基單體的含有量抑制在較低的程度，所得到的黏接劑的貼附對象，可抑制由於酸產生的缺陷，例如，在為透明導電膜及金屬膜等的情況時，也能抑制由於酸產生的這些缺陷。特別是貼附對象為透明導電膜的情況時，可抑制該透明導電膜被腐蝕或該透明導電膜的電阻值發生改變。 Moreover, in the said adhesive composition P, (meth) acrylic acid The ester polymer (A), as a monomer unit, has a low content of a carboxyl group-containing monomer, and the target of the obtained adhesive can suppress defects due to an acid. For example, In the case of a transparent conductive film, a metal film, or the like, these defects due to an acid can be suppressed. In particular, when the object to be attached is a transparent conductive film, it is possible to suppress the transparent conductive film from being corroded or changing the resistance value of the transparent conductive film.

(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，除上述含羥基單體、含芳香環單體以及含羧基單體外，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。另外，根據需要，還可以含有其他的單體。 The (meth) acrylate polymer (A), as a monomer unit constituting the polymer, preferably has the number of carbon atoms containing an alkyl group in addition to the above-mentioned hydroxyl-containing monomer, aromatic ring-containing monomer, and carboxyl-containing monomer. The 1 to 20 alkyl (meth) acrylate is particularly preferably contained as a main component. In addition, if necessary, other monomers may be contained.

(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，可以表現優異的黏接性。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)丙烯酸硬脂基酯等。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)丙烯酸甲基酯以及(甲基)丙烯酸正丁基酯。而且，這些可以單獨使用，也可 以組合兩種以上使用。 The (meth) acrylate polymer (A), as a monomer unit constituting the polymer, can exhibit excellent adhesion by containing an alkyl (meth) acrylate 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) ) Stearyl acrylate and the like. Among these, from the viewpoint of further improving the adhesion, (meth) acrylates having 1 to 8 carbon atoms in the alkyl group are preferred, and methyl (meth) acrylate and n-butyl (meth) acrylate are particularly preferred. ester. Moreover, these can be used alone or Use 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50質量%~93.9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64.2質量%~93質量%，進一步優選含有80質量%~90質量%。另外，如果含有50質量%以上的(甲基)丙烯酸烷基酯，則(甲基)丙烯酸酯聚合物(A)可被賦予優異的黏接性。另外，通過含有93.9質量%以下的(甲基)丙烯酸烷基酯，可在(甲基)丙烯酸酯聚合物(A)中以優選的量導入其他單體成分。 The (meth) acrylic acid ester polymer (A) is preferably a (meth) acrylic acid alkyl group having 1 to 20 carbon atoms having 50 to 93.9% by mass of an alkyl group as a monomer unit constituting the polymer. The ester particularly preferably contains 64.2% to 93% by mass, and more preferably 80% to 90% by mass. In addition, if the (meth) acrylic acid alkyl ester is contained in an amount of 50% by mass or more, the (meth) acrylic acid ester polymer (A) can be provided with excellent adhesiveness. In addition, when the (meth) acrylic acid alkyl ester is contained in an amount of 93.9% by mass or less, other monomer components can be introduced into the (meth) acrylic acid ester polymer (A) in a preferable amount.

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，含有含羥基單體。該羥基與異氰酸酯類架橋劑(B)的異氰酸酯基反應性高，通過它們的反應，(甲基)丙烯酸酯聚合物(A)通過異氰酸酯類架橋劑(B)而架橋。通過該架橋結構所得到的黏接劑，耐久性優異。 The (meth) acrylate polymer (A) contains a hydroxyl-containing monomer as a monomer unit constituting the polymer. This hydroxyl group has high reactivity with the isocyanate group of the isocyanate-based bridging agent (B), and through their reaction, the (meth) acrylate polymer (A) is bridged by the isocyanate-based bridging agent (B). The adhesive obtained by this bridge structure is excellent in durability.

作為含羥基單體，例如可以列舉出(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，從與異氰酸酯類架橋劑(B)的反應性觀點考慮，優選(甲基)丙烯酸2-羥基乙基酯或(甲基)丙烯酸4-羥基丁基酯。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 (meth) 2-hydroxybutyl (meth) acrylate, hydroxyalkyl (meth) acrylate, and the like, such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Among these, from the viewpoint of reactivity with the isocyanate-based bridging agent (B), 2-hydroxyethyl (meth) acrylate or 4-hydroxybutyl (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，含有1質量%~5質量%的含羥基單體，優選含有2質量%~4質量%。含羥基單體的含有量在上述範圍，則形成的 架橋結構變得良好，所得到的黏接劑具有優異的耐久性。含羥基單體的含有量如果小於1質量%，則架橋點過少，凝集力降低，所得到的黏接劑無法發揮優異的耐久性。另一方面，含羥基單體的含有量如果超過5質量%，則架橋點過多，所得到的黏接劑無法變得柔軟，應力緩和性下降，由此，無法應對基材的收縮，耐久性變差。 The (meth) acrylate polymer (A), as a monomer unit constituting the polymer, contains 1 to 5 mass% of a hydroxyl-containing monomer, and preferably contains 2 to 4 mass%. If the content of hydroxyl-containing monomer is in the above range, The bridge structure becomes good, and the obtained adhesive has excellent durability. When the content of the hydroxyl-containing monomer is less than 1% by mass, the number of bridge points is too small, the cohesive force is reduced, and the obtained adhesive cannot exhibit excellent durability. On the other hand, if the content of the hydroxyl-containing monomer exceeds 5% by mass, there will be too many bridging points, and the resulting adhesive will not be soft and the stress relaxation will be reduced. As a result, it will not be able to deal with shrinkage of the substrate and durability Worse.

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，含有含芳香環單體。由此，(甲基)丙烯酸酯聚合物(A)具有適宜的硬度，所得到的黏接劑，容易兼具凝集力與應力緩和性，耐久性優異。 The (meth) acrylate polymer (A) contains an aromatic ring-containing monomer as a monomer unit constituting the polymer. Accordingly, the (meth) acrylate polymer (A) has a suitable hardness, and the obtained adhesive easily has both cohesive force and stress relaxation properties and is excellent in durability.

作為含芳香環單體，例如可以舉出(甲基)丙烯酸苯基、(甲基)丙烯酸2-苯基乙基酯、(甲基)丙烯酸苄基、(甲基)丙烯酸萘基、(甲基)丙烯酸苯氧基乙基、(甲基)丙烯酸苯氧基丁基、乙氧基化鄰苯基苯酚丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、環氧乙烷改性甲酚(甲基)丙烯酸酯、環氧乙烷(EO)改性壬基苯酚(甲基)丙烯酸酯等，其中，從提高凝集力的觀點考慮，優選(甲基)丙烯酸2-苯基乙基酯。這些可以單獨使用，也可以組合兩種以上使用。 Examples of the aromatic ring-containing monomer include phenyl (meth) acrylate, 2-phenylethyl (meth) acrylate, benzyl (meth) acrylate, naphthyl (meth) acrylate, and (methyl) Group) phenoxyethyl acrylate, phenoxybutyl (meth) acrylate, ethoxylated o-phenylphenol acrylate, phenoxy polyethylene glycol (meth) acrylate, ethylene oxide modified Among the cresol (meth) acrylates and ethylene oxide (EO) -modified nonylphenol (meth) acrylates, 2-phenyl (meth) acrylate is preferred from the viewpoint of improving the cohesive force. Ethyl ester. 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，含有5質量%~30質量%含芳香環單體，優選為含有7質量%~25質量%，特別優選為含有10質量%~20質量%。含芳香環單體的含有量在上述範圍，則所得到的黏接劑具有優異的應力緩和性以及優異的耐久性。含芳香環單體的含有量如果小於5質量%，則所得到的黏接劑的耐久性變差。另一方 面，含芳香環單體的含有量如果超過30質量%，則其他成分的搭配量減少，所得到的黏接劑的耐久性變差。 The (meth) acrylate polymer (A) contains, as a monomer unit constituting the polymer, 5 to 30% by mass of an aromatic ring-containing monomer, preferably 7 to 25% by mass, and particularly preferably Contains 10% to 20% by mass. When the content of the aromatic ring-containing monomer is within the above range, the obtained adhesive has excellent stress relaxation properties and excellent durability. When the content of the aromatic ring-containing monomer is less than 5% by mass, the durability of the obtained adhesive will be deteriorated. The other side On the other hand, if the content of the aromatic ring-containing monomer exceeds 30% by mass, the blending amount of other components will decrease, and the durability of the obtained adhesive will be deteriorated.

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，含有含羧基單體。該羧基可促進(甲基)丙烯酸酯聚合物(A)中的羥基與異氰酸酯類架橋劑(B)的架橋反應，同時，羧基本身也與異氰酸酯類架橋劑(B)發生架橋反應。由此所得到的黏接劑，架橋的程度適當，在(甲基)丙烯酸酯聚合物(A)之間的架橋程度均勻，從而耐久性優異。 The (meth) acrylate polymer (A) contains a carboxyl group-containing monomer as a monomer unit constituting the polymer. The carboxyl group can promote a bridging reaction between the hydroxyl group in the (meth) acrylate polymer (A) and the isocyanate-based bridging agent (B), and at the same time, the carboxyl group itself can also cross-link with the isocyanate-based bridging agent (B). The adhesive thus obtained has an appropriate degree of bridging, has a uniform degree of bridging between (meth) acrylate polymers (A), and is excellent in durability.

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，含有0.1質量%~0.8質量%的含羧基單體，優選為含有0.1質量%~0.5質量%，特別優選為含有0.1質量%~0.3質量%。含羧基單體在上述範圍，則所得到的黏接劑具有優異的耐久性。含羧基單體的含有量如果小於0.1質量%，則所得到的黏接劑的耐久性變差。另一方面，含羧基單體的含有量如果超過0.8質量%，則所得到的黏接劑，在貼附對象為透明導電膜等的情況時，透明導電膜等會被腐蝕，或透明導電膜的電阻值發生大的變化。 The (meth) acrylate polymer (A), as a monomer unit constituting the polymer, contains 0.1 to 0.8% by mass of a carboxyl group-containing monomer, preferably 0.1 to 0.5% by mass, and particularly preferably Contains 0.1% to 0.3% by mass. When the carboxyl group-containing monomer is in the above range, the obtained adhesive has excellent durability. When the content of the carboxyl group-containing monomer is less than 0.1% by mass, the durability of the obtained adhesive is deteriorated. On the other hand, if the content of the carboxyl group-containing monomer exceeds 0.8% by mass, the transparent conductive film or the like will be corroded or the transparent conductive film will be corroded when the adhered object is a transparent conductive film or the like. The resistance value changes greatly.

作為上述其他的單體，即使是為了不妨礙上述含羥基單體的羥基以及含羧基單體的羧基與異氰酸酯類架橋劑(B)的反應，也優選不包含與異氰酸酯類架橋劑(B)具有反應性的官能基的單體。作為這樣的其他單體，例如可以列舉(甲基)丙烯酸甲氧基乙基酯、(甲基)丙烯酸乙氧基乙基酯等的(甲基)丙烯酸烷氧基烷基酯；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、(甲基)丙 烯酸N，N-二甲基氨基丙基等的具有非架橋性的具有3級氨基的(甲基)丙烯酸酯；乙酸乙烯酯等。這些可以單獨使用，也可以組合兩種以上使用。 As the other monomer, it is preferable not to contain the isocyanate-based bridging agent (B) even if it does not hinder the reaction of the hydroxyl group of the hydroxyl-containing monomer and the carboxyl group of the carboxyl-containing monomer with the isocyanate-based bridging agent (B). Reactive functional monomer. Examples of such other monomers include alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; acrylamide Non-bridged acrylamide, such as methacrylamide; N, N-dimethylaminoethyl (meth) acrylate, (meth) acrylic acid Non-bridged (meth) acrylates having tertiary amino groups such as enoic acid N, N-dimethylaminopropyl; vinyl acetate and the like. 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)的重均分子量為100萬~250萬，優選為140萬~220萬，特別優選為180萬~200萬。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 1 to 2.5 million, preferably 1.4 to 2.2 million, and particularly preferably 1.8 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)的重均分子量如果小於100萬，則所得到的黏接劑耐久性變差。(甲基)丙烯酸酯聚合物(A)的重均分子量如果超過250萬，則所得到的黏接劑加工性降低。 When the weight average molecular weight of the (meth) acrylate polymer (A) is less than 1 million, the durability of the obtained adhesive will be deteriorated. When the weight average molecular weight of the (meth) acrylate polymer (A) exceeds 2.5 million, the workability of the obtained adhesive will fall.

另外，在黏接性組合物P中，(甲基)丙烯酸酯聚合物(A)可以單獨使用一種，也可以組合兩種以上使用。另外，黏接性組合物P還可進一步含有不含有含羥基單體、含芳香環單體或含羧基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. The adhesive composition P may further contain a (meth) acrylic acid ester polymer that does not contain a hydroxyl-containing monomer, an aromatic ring-containing monomer, or a carboxyl-containing monomer as a constituent monomer unit.

(2)異氰酸酯類架橋劑(B) (2) Isocyanate bridging agent (B)

異氰酸酯類架橋劑(B)具有與(甲基)丙烯酸酯聚合物(A)所具有的羥基的反應性以及與矽烷偶聯劑(C)所具有的巰基的反應性優異的好處。 The isocyanate-based bridging agent (B) has the advantages of being highly reactive with the hydroxyl group of the (meth) acrylate polymer (A) and with the mercapto group of the silane coupling agent (C).

異氰酸酯類架橋劑(B)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、二苯甲烷二異氰酸酯、伸二甲苯二異氰酸酯等的 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，以及這些的雙縮脲體、異氰酸酯體，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。其中在用於偏光板的情況時，從耐久性以及加工性的觀點考慮，優選為三羥甲基丙烷改性芳香族聚異氰酸酯，特別優選為三羥甲基丙烷改性甲次苯基二異氰酸酯。上述異氰酸酯類架橋劑(B)可以單獨使用一種，或者也可以組合兩種以上使用。 The isocyanate-based bridging agent (B) is a bridging agent containing at least a polyisocyanate compound. Examples of the polyisocyanate compound include methylenediphenyl diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate. Aromatic polyisocyanates; aliphatic polyisocyanates such as hexamethylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate; hydrogenated diphenylmethane diisocyanate; etc .; and bisuretons and isocyanates of these Further, examples include ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, and the like as an addition substance with a reactant containing a low-molecular active hydrogen compound. Among them, when it is used for a polarizing plate, from the viewpoints of durability and processability, trimethylolpropane-modified aromatic polyisocyanate is preferable, and trimethylolpropane-modified methylenephenyl diisocyanate is particularly preferable. . The isocyanate-based bridging agent (B) may be used alone or in combination of two or more.

黏接性組合物P中，異氰酸酯類架橋劑(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0.01質量份~1質量份，特別優選為0.05質量份~0.5質量份，進一步優選為0.1質量份~0.3質量份。異氰酸酯類架橋劑(B)的含有量在上述範圍，則所得到的黏接劑中，可形成應力緩和性以及耐久性優異的架橋結構。 The content of the isocyanate-based bridging agent (B) in the adhesive composition P is preferably 0.01 to 1 part by mass, and particularly preferably 0.05 to 100 parts by mass of the (meth) acrylate polymer (A). Part by mass to 0.5 part by mass, more preferably 0.1 part by mass to 0.3 part by mass. When the content of the isocyanate-based bridging agent (B) is within the above range, a bridging structure having excellent stress relaxation properties and durability can be formed in the obtained adhesive.

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

本實施形態中的矽烷偶聯劑(C)具有巰基。該巰基與異氰酸酯類架橋劑(B)的異氰酸酯基容易反應。如前所述，據推測將黏接性組合物P固化的黏接劑中，矽烷偶聯劑(C)的烷氧基甲矽烷，與(甲基)丙烯酸酯聚合物(A)保持適宜距離，即，異氰酸酯類架橋劑(B)中複數的異氰酸酯基相互間保持距離，懸掛於(甲基)丙烯酸酯聚合物(A)上。像這樣，烷氧基甲矽烷通過與(架橋的)(甲基)丙烯酸酯聚合物(A)保持適宜距離而存在，可發揮優異的偶聯效果，由此所得到的黏接劑，黏接性優異，即使 在高溫條件下以及濕熱條件下，黏接耐久性也優異。該效果，在黏接劑的貼附對象為玻璃或金屬等無機材料的情況時，發揮得尤其顯著。 The silane coupling agent (C) in this embodiment has a mercapto group. This mercapto group easily reacts with the isocyanate group of the isocyanate-based bridging agent (B). As described above, in the adhesive for curing the adhesive composition P, it is estimated that the alkoxysilane of the silane coupling agent (C) is kept at a suitable distance from the (meth) acrylate polymer (A). That is, a plurality of isocyanate groups in the isocyanate-based bridging agent (B) maintain a distance from each other, and are suspended from the (meth) acrylate polymer (A). In this manner, the alkoxysilane exists by maintaining an appropriate distance from the (bridged) (meth) acrylate polymer (A), and can exhibit an excellent coupling effect. The adhesive thus obtained adheres to the adhesive. Excellent sex, even It also has excellent adhesion durability under high temperature conditions and wet heat conditions. This effect is particularly remarkable when the object to which the adhesive is applied is an inorganic material such as glass or metal.

作為矽烷偶聯劑(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。 The silane coupling agent (C) is an organosilicon compound having at least one mercapto group and at least one alkoxysilane in the molecule. It has good compatibility with the adhesive component and has light permeability. For example, it is preferably substantially Be transparent.

作為上述矽烷偶聯劑(C)，例如，可以列舉出3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-巰基丙基甲基二甲氧基矽烷等的含巰基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-巰基丙基甲基二甲氧基矽烷等的含巰基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烷基矽烷化合物的共縮合物等的含巰基低聚物型矽烷偶聯劑等。其中，從提高耐久性的觀點考慮，優選為含巰基低聚物型矽烷偶聯劑，特別是優選含巰基矽烷化合物與含烷基矽烷化合物的共縮合物，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合物。這些可以單獨使用一種，也可以組合兩種以上使用。 Examples of the silane coupling agent (C) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and the like. Mercapto-containing low-molecular-weight silane coupling agent; mercapto-containing silane compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and the like Mercapto group-containing oligomer-type silane couplers such as methyltriethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane-containing cocondensates of alkylsilane compounds, and the like联 剂 Such as. Among them, from the viewpoint of improving durability, a mercapto-containing oligomer-type silane coupling agent is preferred, and a co-condensate of a mercapto-containing silane compound and an alkyl-containing silane compound is particularly preferred, and 3-mercaptopropyltrimethyl is more preferred. Co-condensate of oxysilane and methyltriethoxysilane. These may be used alone or in combination of two or more.

黏接性組合物P中矽烷偶聯劑(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~0.5質量份，特別優選為0.1質量份~0.4質量份。矽烷偶聯劑(C)的含有量如果小於0.01質量份，則有難以得到通過該矽烷偶聯劑(C)產生的效果的情況。另一方面，矽烷偶聯劑(C)的含有量如果超過0.5質量份，則異氰酸酯類架橋劑(B)與(甲基)丙 烯酸酯聚合物(A)的反應有受到阻礙的情況。 The content of the silane coupling agent (C) in the adhesive composition P is preferably 0.01 to 0.5 parts by mass, and particularly preferably 0.1 part by mass based on 100 parts by mass of the (meth) acrylate polymer (A). Parts ~ 0.4 parts by mass. When the content of the silane coupling agent (C) is less than 0.01 parts by mass, it may be difficult to obtain the effect by the silane coupling agent (C). On the other hand, if the content of the silane coupling agent (C) exceeds 0.5 parts by mass, the isocyanate-based bridging agent (B) and (meth) propyl The reaction of the acrylate polymer (A) may be hindered.

(4)活性能量線固化性成分(D) (4) Active energy ray curable component (D)

活性能量線固化性成分(D)，只要為不妨礙本發明的效果，通過活性能量線的照射而固化的成分，就沒有特別的限制，可以為單體、低聚物或聚合物中的任意一種，也可以為這些的混合物。其中，可優選列舉與(甲基)丙烯酸酯聚合物(A)等的相溶性優異的分子量小於1000的多官能丙烯酸酯類單體。 The active energy ray-curable component (D) is not particularly limited as long as it is a component that is cured by irradiation with active energy rays without impeding the effects of the present invention, and may be any of monomers, oligomers, and polymers. One kind may be a mixture of these. Among them, preferred are polyfunctional acrylate monomers having a molecular weight of less than 1,000 and having excellent compatibility with the (meth) acrylate polymer (A) and the like.

作為分子量小於1000的多官能丙烯酸酯類單體，例如可以列舉出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、羥基新戊酸新戊二醇二(甲基)丙烯酸酯、二環戊基二(甲基)丙烯酸酯、己內酯改性二環戊烯基二(甲基)丙烯酸酯、環氧乙烷改性磷酸二(甲基)丙烯酸酯、二(丙烯醯氧基乙基)異氰酸酯、烯丙基化環己基二(甲基)丙烯酸酯等的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、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、三(丙烯醯氧基乙基)異氰酸酯等的3官能型；二甘油四(甲基)丙烯酸酯、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。這些可以單獨使用一種，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, and neopentyl Alcohol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) Acrylate, dicyclopentyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphate di (meth) acrylate, di ( 2-functional types such as propylene ethoxyethyl) isocyanate, allyl cyclohexyl di (meth) acrylate; trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate , Propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (propyleneoxyethyl) ) 3-functional types such as isocyanate; 4-functional types such as diglycerol tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate; propionic acid-modified dipentaerythritol Penta (meth) acrylate functional type 5; dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate and hexafunctional type. These may be used alone or in combination of two or more.

在上述多官能丙烯酸酯類單體中，也由於骨架中 具有環狀結構者耐久性能優異所以優選。環狀結構可以為碳環式結構，也可以為雜環式結構，另外，可以為單環式結構，也可以為多環式結構。作為上述多官能丙烯酸酯類單體，例如可以列舉出二(丙烯醯氧基乙基)異氰酸酯、三(丙烯醯氧基乙基)異氰酸酯等具有異氰酸酯結構，或二羥甲基環戊烷二丙烯酸酯、環氧乙烷改性六氫鄰苯二甲酸二丙烯酸酯、三環癸烷二丙烯酸酯、金剛烷二醇二丙烯酸酯等。 Among the above-mentioned multifunctional acrylate monomers, A ring structure is preferred because it has excellent 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 the polyfunctional acrylate-based monomer include an isocyanate structure such as bis (propenyloxyethyl) isocyanate, tris (propenyloxyethyl) isocyanate, or dimethylolcyclopentanediacrylic acid. Esters, ethylene oxide-modified hexahydrophthalic acid diacrylate, tricyclodecane diacrylate, adamantanediol diacrylate, and the like.

作為活性能量線固化性成分(D)，也可以利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為重均分子量為50,000以下。作為上述丙烯酸酯類低聚物，例如可以舉出聚酯丙烯酸酯類、環氧丙烯酸酯類、聚氨酯丙烯酸酯類、聚醚丙烯酸酯類、聚丁二烯丙烯酸酯類、矽酮丙烯酸酯類等。 As the active energy ray-curable component (D), an active energy ray-curable acrylate-based oligomer may be used. The acrylic oligomer preferably has a weight average molecular weight of 50,000 or less. Examples of the acrylate oligomer include polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates, polybutadiene acrylates, and silicone acrylates. .

在此，聚酯丙烯酸酯類低聚物，例如可以通過使用(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環氧烷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，可以通過在分子量較低的雙酚型環氧樹脂以及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，用二鹽基性羧酸酐，進行部分地改性所得的羧改性型環氧丙烯酸酯低聚物。聚氨酯丙烯酸酯類低聚物，例如，可以通過用(甲基)丙烯酸，使由聚醚多元醇以及聚酯多元醇與聚異氰酸酯的反應所得到 的聚氨酯低聚物，酯化而得到。多元醇丙烯酸酯類低聚物，可以通過用(甲基)丙烯酸，使聚醚多元醇的羥基，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 terminal of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid with (meth) acrylic acid. The epoxy acrylate oligomer can be reacted and esterified with, for example, an ethylene oxide ring of a bisphenol epoxy resin and a novolac epoxy resin having a low molecular weight. And get. A carboxy-modified epoxy acrylate oligomer obtained by partially modifying the epoxy acrylate-based oligomer with a dibasic carboxylic anhydride may also be used. The urethane acrylate oligomer can be obtained by, for example, using (meth) acrylic acid by reacting a polyether polyol and a polyester polyol with a polyisocyanate. Polyurethane oligomer 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均分子量優選為50,000以下，特別優選為500~50,000，進一步優選為3,000~40,000。這些丙烯酸酯類低聚物可以單獨使用一種，也可以組合兩種以上使用。 The weight average molecular weight of the acrylate 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 singly or in combination of two or more kinds.

另外，作為活性能量線固化性成分(D)，也可以使用在側鏈導入了具有(甲基)丙烯醯基的基團所得的加和物丙烯酸酯類聚合物。這樣的加和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)丙烯醯基以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 (D), an adduct acrylate polymer obtained by introducing a group having a (meth) acrylfluorenyl group into a side chain may be used. Such an additive acrylate polymer can have a copolymer with a (meth) acrylfluorenyl 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、(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, amyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, (formyl) Hexadecyl acrylate, stearyl (meth) 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一種。 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-甲基甲基丙烯醯胺、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、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, as a functional group, at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and an amido 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 Monomethylaminoethyl ester, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoethylaminopropyl (meth) acrylate, etc. Group) monoalkylaminoalkyl acrylates; ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid, and the like. These monomers may be used alone or in combination of two or more.

作為具有與(甲基)丙烯醯基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-〔(3，5-二甲基吡坐)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、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。 As the compound having a group that reacts with a (meth) acrylfluorenyl group and a bridging functional group, for example, 2-methacrylfluorenyloxyethyl isocyanate and methacrylic acid 2- (0- [1 '-Methylpropaneamino] carboxyamino) ethyl, 2-[(3,5-dimethylpyridine) carbonylamino] ethyl methacrylate, 1,1- (bispropenyloxymethyl) Ethyl isocyanate, 2-propenyloxyethyl isocyanate, 2-propenyloxyethyl succinate, 2-propenyloxyethylhexahydrophthalimide, imine, ω-carboxy-polycaprolactone mono Acrylate, 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類聚合物的重均分子量，優選為30萬~200萬左右，特別優選為50萬~85萬。 The weight-average molecular weight of the adduct acrylic polymer is preferably about 300,000 to 2 million, and particularly preferably 500,000 to 850,000.

活性能量線固化性成分(D)，既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類 聚合物中選擇一種使用，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 (D) can be selected from the above-mentioned multifunctional acrylate monomers, acrylate oligomers, and additive acrylates. One kind of polymer is selected and used, two or more kinds may be used in combination, and other active energy ray-curable components other than these may be used in combination.

黏接性組合物P中的活性能量線固化性成分(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1質量份~50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~10質量份。據推測從在此範圍含有活性能量線固化性成分(D)的黏接性組合物P所得到的黏接劑，可良好地形成上述結構X。特別是，通過使活性能量線固化性成分(D)的含有量為3質量份~10質量份，據推測上述結構X可在較高水準上兼具柔軟性和凝集力，特別是成為耐久性優異的黏接劑。 The content of the active energy ray-curable component (D) in the adhesive composition P is preferably 1 to 50 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 10 parts by mass. It is presumed that the adhesive obtained from the adhesive composition P containing the active energy ray-curable component (D) in this range can form the above-mentioned structure X satisfactorily. In particular, by setting the content of the active energy ray-curable component (D) to 3 to 10 parts by mass, it is estimated that the structure X can have both flexibility and cohesive power at a relatively high level, and particularly has durability. Excellent adhesive.

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

作為向黏接性組合物P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進一步優選含有光聚合起始劑(E)。像這樣，通過含有光聚合起始劑(E)，可有效地將活性能量線固化性成分(D)固化，另外，可以減少聚合固化時間以及活性能量線的照射量。 As an active energy ray irradiated to the adhesive composition P, when an ultraviolet ray is used, it is more preferable that the adhesive composition P contains a photopolymerization initiator (E). In this manner, by containing the photopolymerization initiator (E), the active energy ray-curable component (D) can be effectively cured, and the polymerization curing time and the amount of irradiation of the active energy ray can be reduced.

作為上述光聚合起始劑(E)，例如可以舉出苯偶姻、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-嗎琳-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-甲基塞噸酮、2-乙基塞噸酮、2-氯塞噸酮、2，4-二甲基塞噸酮、2，4-二乙基塞噸酮、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〔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 the photopolymerization initiator (E) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, and benzene. Diethyl isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone Ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morphine-propane-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) one, benzophenone, p-phenylbenzophenone, 4,4'-diethylamino Benzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylxanthone, 2- Ethylxanthone, 2-chloroxanthone, 2,4-dimethylxanthone, 2,4-diethylxanthone, benzyldimethylketal, acetophenonedimethylketal Ketone, p-dimethylaminobenzoate, oligo [2-hydroxy-2-methyl-1 [4- (1-methylvinyl) benzene] acetone], 2,4,6-trimethylbenzene Formamyl-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(D)100質量份，優選為2質量份~15質量份，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 used in an amount ranging from 2 parts by mass to 15 parts by mass with respect to 100 parts by mass of the active energy ray-curable component (D), and particularly in an amount ranging from 5 parts by mass to 12 parts by mass.

(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、阻燃劑、充填劑、折射率調整劑等。 The adhesive composition P may be added with various additives commonly used in acrylic adhesives, such as an antistatic agent, an adhesion-imparting agent, an oxidation preventive agent, an ultraviolet absorber, a light stabilizer, and a barrier agent, as needed. Fuel, filler, refractive index adjuster, etc.

作為帶電防止劑的具體例子，可以列舉N-丁基-4-甲基吡啶鎓六氟磷酸鹽、N-己基-4-甲基吡啶鎓六氟磷酸鹽、N-丁基-2-己基吡啶高氯酸鹽、雙(氟磺醯亞胺)鉀(KFSI)、雙(三氟甲磺醯亞胺)鉀(KTFSI)、雙(氟磺醯亞胺)鋰(LIFSI)、雙(三氟甲磺醯氯醯亞胺)鋰(LITFSI)、N-丁基-2-己基吡啶鎓雙(三氟甲磺醯基)亞胺等。這些帶電防止劑，可以單獨使用一種，也可以組合兩種以上使用。 Specific examples of the antistatic agent include N-butyl-4-methylpyridinium hexafluorophosphate, N-hexyl-4-methylpyridinium hexafluorophosphate, and N-butyl-2-hexylpyridine. Perchlorate, potassium bis (fluorosulphenimide) potassium (KFSI), potassium bis (trifluorosulphenimide) (KTFSI), lithium bis (fluorosulphenimide) (LIFSI), bis (trifluoro Methanesulfonylchlorosulfonylimide) lithium (LITFSI), N-butyl-2-hexylpyridinium bis (trifluoromethanesulfonyl) imine, and the like. These antistatic agents may be used alone or in combination of two or more.

〔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) ，將所得到的(甲基)丙烯酸酯聚合物(A)與異氰酸酯類架橋劑(B)、矽烷偶聯劑(C)、活性能量線固化性成分(D)進行混合，同時，根據需要，在任意階段添加光聚合起始劑(E)、添加劑等來製造。 The adhesive composition P can be produced by (meth) acrylate polymer (A) , Mixing the obtained (meth) acrylate polymer (A) with an isocyanate-based bridging agent (B), a silane coupling agent (C), and an active energy ray-curable component (D), and, if necessary, It is manufactured by adding a photopolymerization initiator (E), an additive, etc. at an arbitrary stage.

(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單元的混合物來製造。(甲基)丙烯酸酯聚合物(A)的聚合，可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 a mixture of monomer units constituting the polymer by a general 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，可以列舉偶氮類化合物、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，可以列舉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)、2，2’-偶氮雙(2，4-二甲基戊腈)、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-咪坐琳-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), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), Dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxy Methylpropionitrile), 2,2'-azobis [2- (2-imidoline-2-yl) propane], and the like.

作為有機過氧化物，例如，可以列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均分子量進行調節。 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，添加異氰酸酯類架橋劑(B)、矽烷偶聯劑(C)、活性能量線固化性成分(D)以及根據需要添加光聚合起始劑(E)、稀釋溶劑、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, an isocyanate-based bridging agent (B), a silane coupling agent (C), and an active energy ray are added to the solution of the (meth) acrylate polymer (A). The curable component (D) and, if necessary, a photopolymerization initiator (E), a diluent solvent, an additive, and the like are added and sufficiently mixed to obtain an adhesive composition P (coating solution) diluted with a 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，例如可以使用己烷、庚烷、環己烷等的脂肪族烴；甲苯、二甲苯等的芳香族烴；二氯甲烷、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、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, for example, aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; methylene chloride, Halogenated hydrocarbons such as dichloroethane; alcohols such as methanol, ethanol, propanol, butanol, 1-methoxy-2-propanol; acetone, methyl ethyl ketone, 2-pentanone, isophor Ketones such as ketones and 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即可，沒有特別的限制，可以根據情況進行適宜選定。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，將(甲基)丙烯酸酯聚合物(A)的聚合溶劑直接作為稀釋溶劑的塗布溶液。 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 they can be appropriately selected according to circumstances. For example, the concentration of the adhesive composition P may be diluted to 10% 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 uses a polymerization solvent of the (meth) acrylate polymer (A) as a coating solution for a diluting solvent as it is.

〔黏接劑〕 [Adhesive]

本實施形態所述黏接劑，可通過將黏接性組合物P在所希望的對象物上進行塗布、乾燥後，通過活性能量線的照射，將黏接性組合物P固化而優選得到。進行這些處理後，根據需要 ，可在常溫(例如，23℃、50%RH)下保留1~2周左右的熟成期間。需要該熟成期間的情況時，在熟成期間經過後；不需要熟成期間的情況時，在活性能量線照射後形成黏接劑(層)。 The adhesive agent according to this embodiment is preferably obtained by coating the adhesive composition P on a desired object, drying it, and then curing the adhesive composition P by irradiation with active energy rays. After performing these processes, as needed , Can be kept at room temperature (for example, 23 ° C, 50% RH) for about 1 to 2 weeks of ripening period. When the ripening period is required, after the ripening period has elapsed; when the ripening period is not required, an adhesive (layer) is formed after irradiation with active energy rays.

黏接性組合物P的乾燥，通過風乾而進行，但通常通過加熱處理(優選為熱風乾燥)而進行。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，特別優選50秒~2分。 Drying of the adhesive composition P is 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, and particularly preferably 50 seconds to 2 minutes.

作為活性能量線，通常使用紫外線、電子束等。活性能量線的照射量根據能量線的種類有所不同，例如，使用紫外線的情況時，光量優選為50mJ/cm2~1000mJ/cm2，特別優選為100mJ/cm2~500mJ/cm2。另外，使用電子束的情況時，優選為1()krad~1000krad左右。 As the active energy ray, ultraviolet rays, electron beams, and the like are generally used. The irradiation amount of the active energy ray varies depending on the type of the energy ray. For example, when using ultraviolet rays, the light amount is preferably 50 mJ / cm 2 to 1000 mJ / cm 2 , and particularly preferably 100 mJ / cm 2 to 500 mJ / cm 2 . When an electron beam is used, it is preferably about 1 to 1000 krad.

通過上述加熱處理(以及熟成)，通過異氰酸酯類架橋劑(B)，(甲基)丙烯酸酯聚合物(A)架橋，形成第1三維網絡結構。另外，矽烷偶聯劑(C)的巰基，與異氰酸酯類架橋劑(B)的異氰酸酯基容易反應，據推測該矽烷偶聯劑(C)的烷氧基甲矽烷，通過該異氰酸酯類架橋劑(B)，與(甲基)丙烯酸酯聚合物(A)，進一步與上述三維網絡結構保持適宜距離而存在，發揮優異的偶聯效果。另一方面，通過活性能量線的照射，複數的活性能量線固化性成分(D)相互結合，形成第2三維網絡結構。據推測該第2三維網絡結構與上述第1三維網絡結構相互纏繞，形成上述結構X。具有上述結構X的黏接劑，具有適當的黏接力力與應力緩和性，由於具有高凝集力，因此具有優異的 耐久性。 Through the heat treatment (and maturation) described above, the isocyanate-based bridging agent (B) and the (meth) acrylate polymer (A) are bridged to form a first three-dimensional network structure. In addition, the mercapto group of the silane coupling agent (C) easily reacts with the isocyanate group of the isocyanate-based bridging agent (B), and it is estimated that the alkoxysilane of the silane coupling agent (C) passes through the isocyanate-based bridging agent ( B), and (meth) acrylate polymer (A), further exists at an appropriate distance from the above-mentioned three-dimensional network structure, and exhibits excellent coupling effect. On the other hand, a plurality of active energy ray-curable components (D) are combined with each other by irradiation with active energy rays to form a second three-dimensional network structure. It is estimated that the second three-dimensional network structure and the first three-dimensional network structure are intertwined with each other to form the structure X. The adhesive having the above-mentioned structure X has suitable adhesive force and stress relaxation property, and has high cohesive force, so it has excellent Durability.

另外，將黏接性組合物P固化所得到的黏接劑，即使在上述第1三維網絡結構呈現較為鬆散的狀態時，也通過含有芳香環，而具有適宜的凝集力。由此，不會使凝集力降低，即可提高應力緩和性，因此，黏接劑的耐久性高。另外，憑借通過矽烷偶聯劑(C)得到的優異的偶聯效果，對玻璃表面等的黏接性優異，在高溫條件下或濕熱條件下，也可發揮優異的黏接耐久性。上述黏接劑，例如，在85℃的高溫條件下或60℃‧90%RH的濕熱條件下放置250小時的情況時，也能防止和抑制浮起、剝離、氣泡等的發生。 The adhesive obtained by curing the adhesive composition P has an appropriate cohesive force by including an aromatic ring even when the first three-dimensional network structure is in a relatively loose state. Accordingly, the stress relaxation property can be improved without reducing the cohesive force, and therefore, the durability of the adhesive is high. In addition, due to the excellent coupling effect obtained by the silane coupling agent (C), it has excellent adhesion to glass surfaces and the like, and can exhibit excellent adhesion durability under high temperature conditions or wet heat conditions. The above-mentioned adhesive can prevent and suppress the occurrence of floating, peeling, and air bubbles, for example, when left for 250 hours under a high temperature condition of 85 ° C or a humid heat condition of 60 ° C‧90% RH.

本實施形態所述黏接劑的凝膠分率，優選為55%~85%，特別優選為60%~80%。凝膠分率如果小於55%，則黏接劑的凝集力不足，有耐久性以及再加工性降低的情況。特別是用於COP偏光板的情況時，在高溫下，有得不到充分黏接耐久性的情況。另一方面，凝膠分率如果超過85%，則應力緩和性變得過低，有耐久性降低的情況。 The gel fraction of the adhesive according to this embodiment is preferably 55% to 85%, and particularly preferably 60% to 80%. When the gel fraction is less than 55%, the cohesive force of the adhesive is insufficient, and durability and reworkability may be reduced. In particular, when it is used for a COP polarizing plate, sufficient adhesion durability may not be obtained at high temperatures. On the other hand, when the gel fraction exceeds 85%, the stress relaxation property becomes too low, and the durability may decrease.

本實施形態所述黏接劑在23℃下的儲能模量(G’)，從耐久性觀點考慮，優選為0.15MPa~0.3MPa，特別優選為0.18MPa~0.28MPa，從使霧度值更加優異的觀點考慮，進一步優選為0.20MPa~0.26MPa。另外，在80℃下的儲能模量(G’)，從耐久性觀點考慮，優選為0.05MPa~0.2MPa，特別優選為0.08MPa~0.18MPa，從使霧度值更加優異的觀點考慮，進一步優選為0.1MPa~0.14MPa。另外，上述儲能模量(G’)為根據後述的扭剪法所測定的值。 The storage modulus (G ') of the adhesive according to this embodiment at 23 ° C is preferably from 0.15 MPa to 0.3 MPa, and particularly preferably from 0.18 MPa to 0.28 MPa from the viewpoint of durability. From a more excellent viewpoint, it is more preferably 0.20 MPa to 0.26 MPa. In addition, the storage modulus (G ') at 80 ° C is preferably from 0.05 MPa to 0.2 MPa, and particularly preferably from 0.08 MPa to 0.18 MPa from the viewpoint of durability. From the viewpoint of making the haze value more excellent, It is more preferably 0.1 MPa to 0.14 MPa. The storage modulus (G ') is a value measured by a torsional shear method described later.

〔黏接片〕 [Adhesive sheet]

如圖1所示，第1實施形態所述黏接片1A，按照從下往上的順序，由剝離片12、積層於剝離片12的剝離面上的黏接劑層11、以及積層於黏接劑層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 an adhesive layer in order from bottom to top. 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所夾持的黏接劑層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 connected to the peeling surfaces of the two peeling sheets 12 a and 12 b. The peeling sheet 12a, 12b is comprised by the adhesive layer 11 sandwiched. 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P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 adhesive composition P described above.

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 depending on 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，還可以列舉出人造絲、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；聚氨酯發泡體、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、三醋酸纖維素等的纖維素薄膜；聚氯乙烯薄膜、聚偏二氯乙烯薄膜、聚乙烯醇薄膜、乙烯-乙酸乙烯酯共聚物薄膜、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；這些的兩種以上的積層體等。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 the 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 foils such as aluminum and copper; foams such as polyurethane foam and polyethylene foam; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate Polyester films such as alcohol esters; polyurethane films, polyethylene films Film, polypropylene film, cellulose triacetate, etc .; polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate Plastic films such as films, 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，例如可以列舉出偏光板(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，偏光板(偏光薄膜)容易收縮，尺寸變化大，因此從要求耐久性的觀點考慮，適宜作為形成本實施形態的黏接劑(上述黏接劑層11)的基材。另外，特別是聚環烯烴類薄膜或具備該薄膜的偏光板(COP偏光板)，容易收縮，尺寸變化大，而且接觸角大，密合性低，因此從要求黏接性、黏接耐久性的觀點考慮，適宜作為形成本實施形態的黏接劑(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 semi-transmissive film. Reflective film, etc. Among them, a polarizing plate (polarizing film) is easy to shrink and has a large dimensional change. Therefore, it is suitable as a base material for forming the adhesive (the above-mentioned adhesive layer 11) of the present embodiment from the viewpoint of durability. In addition, in particular, polycycloolefin-based films or polarizing plates (COP polarizing plates) having the films are easy to shrink, have large dimensional changes, have large contact angles, and have low adhesion. Therefore, adhesiveness and adhesion durability are required. From a viewpoint of this point, it is suitable as a base material which forms the adhesive agent (the said adhesive agent layer 11) of this embodiment.

基材13的厚度，根據其種類而有所不同，例如，在光學構件的情況時，通常為10μm~500μm，優選為50μm~300μm，特別優選為80μm~150μm。 The thickness of the substrate 13 varies depending on the type thereof. For example, in the case of an optical member, 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、聚氯乙烯薄膜、氯乙烯共聚物薄膜、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，也可使用這些的架橋薄膜。進一步，也可以為這些的積層薄膜。 As the release sheets 12, 12a, 12b, for example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, or a polyethylene film can be used. Polyethylene terephthalate film, Polyethylene naphthalate film, Polybutylene terephthalate film, Polyurethane film, Vinyl acetate film, Ionomer resin film, B An olefin- (meth) acrylic copolymer film, an ethylene- (meth) acrylate copolymer film, a polystyrene film, a polycarbonate film, a polyimide film, a fluororesin film, and the like. These bridge films can also be used. Furthermore, these laminated films may be used.

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、矽酮類、氟類、不飽和聚酯類、聚烯烴類、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 peeling 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，形成黏接劑組合物P的塗膜後，在其塗膜上將基材13進行積層。然後，越過剝離片12在上述塗膜上照射活性能量線。上述塗膜，在不需要熟成期間的情況時，直接成為黏接劑層11，在需要熟成期間的情況時，經過熟成期間後成為黏接劑層11。關於乾燥以及熟成條件如上所述。 In the production of the above-mentioned adhesive sheet 1A, a solution (coating solution) containing the adhesive composition P is applied and dried on the release surface of the release sheet 12 to form a coating film of the adhesive composition P, and then The substrate 13 is laminated on the coating film. Then, the coating film is irradiated with active energy rays over the release sheet 12. When the coating film is not required to be matured, the coating film is directly used as the adhesive layer 11. When the coating film is required to be matured, the coating film is used as the adhesive layer 11. The drying and ripening conditions 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，形成黏接劑組合物P的塗膜後，在其塗膜上，將另一個剝離片12b(或者12a)的剝離面聚合。然後，越過剝離片12a(或者12b)，在上述塗膜上照射活性能量線。上述塗膜，在不需要熟成期間的情況時，直接成為黏接劑層11，在需要熟成期間的情況時，經過熟成期間後成為黏接劑層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) to form a coating of the adhesive composition P. After the film is formed, the release surface of the other release sheet 12b (or 12a) is polymerized on the coating film. Then, the coating film is irradiated with active energy rays over the release sheet 12a (or 12b). When the coating film is not required to be matured, the coating film is directly used as the adhesive layer 11. When the coating film is required to be matured, the coating film is used as 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.

黏接片1A、1B中的黏接劑層11，霧度值(基於JIS K7136：2000測定的值)優選為1.0%以下，特別優選為0.9%以下，進一步優選為0.8%以下。霧度值如果為1.0%以下，則透明性極高，適宜用作光學用途。 The haze value (value measured based on JIS K7136: 2000) of the adhesive layer 11 in the adhesive sheets 1A and 1B is preferably 1.0% or less, particularly preferably 0.9% or less, and still more preferably 0.8% or less. When the haze value is 1.0% or less, the transparency is extremely high, and it is suitable for optical applications.

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。另外，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和液晶組件進行貼合。 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. In addition, the other release sheet 12b (or 12a) is peeled from the adhesive layer 11 of the adhesive sheet B, and the adhesive layer 11 exposed by the adhesive sheet B and the liquid crystal module 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濕熱條件下，也可防止和抑制基材13與被黏物之間產生浮起、剝離、氣泡等。特別是將COP偏光板作為基材13的情況時，也能將由於COP偏光板的變形而可能產生的應力，在黏接劑層11上吸收、緩和，由此 發揮優異的耐久性。 According to the above-mentioned pressure-sensitive adhesive sheets 1A and 1B, the durability of the pressure-sensitive adhesive layer 11 is excellent. Therefore, it is possible to prevent and suppress floating and peeling between the substrate 13 and the adherend even under high-temperature conditions or wet heat conditions. , Bubbles, etc. In particular, when a COP polarizing plate is used as the base material 13, the stress that may occur due to the deformation of the COP polarizing plate can be absorbed and relaxed on the adhesive layer 11, thereby Show excellent durability.

本實施形態所述黏接片1A、1B，也優選將透明導電膜作為被黏物。黏接性組合物P中的(甲基)丙烯酸酯聚合物(A)，作為單體單元，所包含的含羧基單體的量如上所述為少量，因此可以抑制由於酸成分對透明導電膜帶來的不良影響。具體而言，為可抑制透明導電膜被腐蝕，或透明導電膜的電阻值發生變化。 In the adhesive sheets 1A and 1B according to the present embodiment, it is also preferable to use a transparent conductive film as an adherend. As described above, the (meth) acrylate polymer (A) in the adhesive composition P contains a small amount of a carboxyl group-containing monomer as a monomer unit, so that it is possible to suppress the transparent conductive film due to an acid component. Brought about bad effects. Specifically, the transparent conductive film can be prevented from being corroded or the resistance value of the transparent conductive film can be changed.

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；錫之氧化銦錫(ITO)、氧化鋅之氧化銦、氟之氧化銦、銻之氧化錫、氟之氧化錫、鋁之氧化鋅等的複合氧化物；硫化物、六硼化鑭、氮化鈦、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; indium tin oxide (ITO) of tin, Compound oxides of zinc oxide indium oxide, fluorine indium oxide, antimony tin oxide, fluorine tin oxide, aluminum zinc oxide, etc .; non-oxidizing compounds such as sulfide, lanthanum hexaboride, titanium nitride, and titanium carbide And other transparent conductive films.

對上述透明導電膜的電阻值變化進行具體說明，使用本實施形態所述黏接片1A或黏接片1B，將黏接劑層11與透明導電膜貼合，對所得到的積層體，在65℃、95%RH的氣氛下，進行曝露500小時的濕熱促進試驗時，透明導電膜根據以下算式算出的電阻值增加率優選為15%以下，特別優選為10%以下。 The change in the resistance value of the transparent conductive film is described in detail. Using the adhesive sheet 1A or the adhesive sheet 1B described in this embodiment, the adhesive layer 11 and the transparent conductive film are bonded together. When the humidity and heat acceleration test is performed in an atmosphere of 65 ° C. and 95% RH for 500 hours, the resistance increase rate of the transparent conductive film calculated from the following formula is preferably 15% or less, and particularly preferably 10% or less.

電阻值增加率(%)={(R-R0)/R0}×100(算式中，R0為濕熱促進試驗前的初始電阻值(Ω)，R為濕熱促進試驗後的電阻值(Ω)。) Resistance increase rate (%) = {(RR 0 ) / R 0 } × 100 (In the formula, R 0 is the initial resistance value (Ω) before the moist heat promotion test, and R is the resistance value (Ω) after the moist heat promotion test. .)

另外，關於透明導電膜電阻值增加率測定方法的詳細情況如後所述。 The details of the method for measuring the resistance increase rate of the transparent conductive film will be described later.

作為基材13使用了偏光板的黏接片1A(以下有稱為「附有黏接劑層的偏光板」的情況。)，相對於無堿玻璃的黏接力，優選為0.1N/25mm~20N/25mm，特別優選為0.5N/25mm~10N/25mm，進一步優選為1N/25mm~5N/25mm。黏接力通過在上述範圍內，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，這裏所說的黏接力，基本上是指通過基於JIS Z0237：2009的180°剝離法所測定的黏接力，但是將測定樣品裁成寬25mm、長100mm，使該測定樣品相對於被黏物，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。 As the base material 13, an adhesive sheet 1A of a polarizing plate is used (hereinafter referred to as a "polarizing plate with an adhesive layer"). The adhesive force to the glass without glass is preferably 0.1N / 25mm ~ 20N / 25mm, particularly preferably 0.5N / 25mm to 10N / 25mm, and still more preferably 1N / 25mm to 5N / 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, 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 25mm and a length of 100mm, so that the measurement sample is relatively adhered to The object was adhered at 0.5 MPa and 50 ° C. for 20 minutes under pressure, and then left to stand for 24 hours under the conditions of normal pressure 23 ° C. and 50% RH. Then, the obtained adhesion force was measured at a peeling speed of 300 mm / min.

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中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 one 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制 1. Preparation of (meth) acrylate polymer

將丙烯酸正丁基酯76.9質量份、丙烯酸甲基酯10質量份、丙烯酸2-苯基乙基10質量份、丙烯酸2-羥基乙基酯3質量 份以及丙烯酸0.1質量份共聚合，調制(甲基)丙烯酸酯聚合物(A)。將該(甲基)丙烯酸酯聚合物(A)的分子量，用後述方法測定的結果，重均分子量為150萬。 76.9 parts by mass of n-butyl acrylate, 10 parts by mass of methyl acrylate, 10 parts by mass of 2-phenylethyl acrylate, and 3 parts by mass of 2-hydroxyethyl acrylate And 0.1 mass parts of acrylic acid were copolymerized to prepare a (meth) acrylate polymer (A). As a result of measuring the molecular weight of this (meth) acrylate polymer (A) by the method mentioned later, the weight average molecular weight was 1.5 million.

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

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)；作為異氰酸酯類架橋劑(B)，將三羥甲基丙烷改性甲次苯基二異氰酸酯(日本聚氨酯工業公司製，商品名「CORONATE L」)0.1質量份；作為具有巰基的矽烷偶聯劑(C)，將3-巰基丙基三甲氧基矽烷與甲基三乙氧基矽烷的共縮合物(信越化學工業公司製，商品名「X-411-1810」，巰基當量：450g/摩爾)0.3質量份；作為活性能量線固化性成分(D)，將三(丙烯醯氧基乙基)異氰酸酯(東亞合成公司製，商品名「ARONIXM-315」，分子量：423，三官能型)5質量份；作為光聚合起始劑(E)，將二苯甲酮以及1-羥環己基苯基酮以1：1的質量比混合的混合物(千葉特殊化學品公司製，IRUGACURE 500)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 step (1) (solid content conversion value; the same applies hereinafter); as an isocyanate-based bridging agent (B), trimethylolpropane is modified 0.1 parts by mass of methylenediphenyl diisocyanate (manufactured by Japan Polyurethane Industry Corporation, trade name "CORONATE L"); as a mercapto-containing silane coupling agent (C), 3-mercaptopropyltrimethoxysilane and methyltris 0.3 parts by mass of a co-condensate of ethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., "X-411-1810", mercapto equivalent: 450 g / mole); as the active energy ray-curable component (D), three ( 5 parts by mass of acryloxyethyl) isocyanate (manufactured by Toa Kosei, trade name "ARONIXM-315", molecular weight: 423, trifunctional type); as a photopolymerization initiator (E), benzophenone and 1-hydroxycyclohexylphenyl ketone was mixed at a mass ratio of 1: 1 (0.5 parts by mass, manufactured by Chiba Specialty Chemicals Co., Ltd., IRUGACURE 500), thoroughly stirred, and diluted with ethyl acetate to obtain adhesion A coating solution of a sexual composition.

在此，該黏接性組合物的搭配示於表1。另外，表1所記載的縮寫符號等的詳細情況如下所述。 The composition 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] [(Meth) acrylate polymer]

BA：丙烯酸正丁基酯 BA: n-butyl acrylate

MA：丙烯酸甲基酯 MA: methyl acrylate

PhEA：丙烯酸2-苯基乙基 PhEA: 2-phenylethyl acrylate

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

AA：丙烯酸 AA: Acrylic

〔矽烷偶聯劑〕 [Silane coupling agent]

C1：3-巰基丙基三甲氧基矽烷和甲基三乙氧基矽烷的共縮合物(信越化學工業公司製，商品名「X-411-1810」) C1: Co-condensate of 3-mercaptopropyltrimethoxysilane and methyltriethoxysilane (produced by Shin-Etsu Chemical Co., Ltd., trade name "X-411-1810")

C2：3-環氧丙氧基三甲氧基矽烷(信越化學工業公司製，商品名「KBM-403」) C2: 3-glycidoxytrimethoxysilane (made by Shin-Etsu Chemical Industry Co., Ltd., trade name "KBM-403")

3.附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，用矽酮類剝離劑進行了剝離處理的剝離片(琳得科株式公司製，SP-PET3811，厚度：38μm)的剝離處理面上，用刮刀塗布器進行塗布，使乾燥後的厚度為20μm後，用90℃進行1分鐘加熱處理而形成黏接性組合物的塗膜。 The obtained coating solution of the adhesive composition was a peeling sheet (manufactured by Lindec Corporation, peeled off) on one side of a polyethylene terephthalate film with a silicone release agent, SP-PET3811 (thickness: 38 μm) was applied on a peeled surface with a doctor blade applicator so that the thickness after drying was 20 μm, and then heat-treated at 90 ° C. for 1 minute to form a coating film of an adhesive composition.

接著，用三醋酸纖維素薄膜，保護聚乙烯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，使上述塗膜的露出面與環烯烴聚合物薄膜的表面相接觸，之後，越過剝離片按照以下條件向上述塗膜照射紫外線，在23℃、50%RH下放置7天熟成，由此得到附有黏接劑層的偏光板。 Next, a one-sided polarizer made of a polyvinyl alcohol film is protected with a cellulose triacetate film, and a COP polarizing plate having a thickness of 100 μm obtained by protecting the other surface with a cycloolefin polymer film is bonded to the coating film. The exposed surface of the coating film was brought into contact with the surface of the cycloolefin polymer film, and then the coating film was irradiated with ultraviolet rays over the release sheet under the following conditions, and was left to mature at 23 ° C and 50% RH for 7 days to obtain Polarizer with adhesive layer.

<紫外線照射條件> <UV irradiation conditions>

‧使用FUSION公司製，無電極燈H BULB ‧Using electrodeless lamp H BULB made by FUSION

‧照度600mW/cm2，光量150mJ/cm2 ‧Illumination 600mW / cm 2 , 150mJ / cm 2

‧UV照度‧光量計使用EYE GRAPHIC公司製，「UVPF-36」 ‧UV illuminance‧Light meter uses "UVPF-36" manufactured by EYE GRAPHIC

〔實施例2~13，比較例1~4〕 [Examples 2 to 13, Comparative Examples 1 to 4]

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)的重均分子量、異氰酸酯類架橋劑(B)的搭配量、矽烷偶聯劑(C)的種類以及搭配量、活性能量線固化性成分(D)的搭配量以及光聚合起始劑(E)的搭配量，按照表1所示進行變更外，與實施例1同樣地進行操作，製造附有黏接劑層的偏光板。另外，實施例7中，在黏接性組合物的調制時，作為帶電防止劑，搭配了1.8質量份雙(三氟甲磺醯氯醯亞胺)鋰和四乙二醇二甲醚的等摩爾混合品(三光化學工業公司製，商品名「SANKONOL TGR」)。 In addition to the types and proportions of each monomer constituting the (meth) acrylate polymer (A), the weight average molecular weight of the (meth) acrylate polymer (A), the blending amount of the isocyanate-based bridging agent (B), The types and blending amounts of the silane coupling agent (C), the blending amount of the active energy ray-curable component (D), and the blending amount of the photopolymerization initiator (E) were changed as shown in Table 1. 1 In the same manner, a polarizing plate with an adhesive layer was manufactured. In addition, in Example 7, when preparing the adhesive composition, 1.8 parts by mass of lithium bis (trifluoromethanesulfonylchloroimide), tetraethylene glycol dimethyl ether, and the like were blended as an antistatic agent. Mole mixture (manufactured by Sanko Chemical Industries, Ltd., trade name "SANKONOL TGR").

在此，上述的重均分子量(MW)，為使用凝膠滲透色譜法(GPC)在以下的條件下測定(GPC測定)的聚苯乙烯換算的重均分子量。 Here, the above-mentioned 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℃ ‧Measuring temperature: 40 ℃

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

在實施例或比較例中，代替製作附有黏接劑層的偏光板所使用的偏光板，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，在用實施例或比較例的製造過程所得到的剝離片/黏接性組合物的塗膜所構成的構成體的露出的塗膜上，以使剝離處理面側相接的方式，將上述剝離片進行積層，在23℃、50%RH的條件下進行7天熟成。由此，來製作由剝離片(SP-PET3801)/黏接劑層(厚度：20μm)/剝離片(SP-PET3811)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 peeled with a silicone-based release agent. Treated release sheet (manufactured by Lindec Corporation) , SP-PET3801, thickness: 38 μm), for the production of adhesive sheets. Specifically, on the exposed coating film of the structure composed of the release sheet / adhesive composition coating film obtained by the manufacturing process of the example or comparative example, the peeling treatment surface side is brought into contact with each other. The above-mentioned release sheet was laminated, and aged for 7 days under the conditions of 23 ° C. and 50% RH. Thereby, an adhesive sheet formed by a configuration of a release sheet (SP-PET3801) / adhesive layer (thickness: 20 μm) / release sheet (SP-PET3811) was produced.

將得到的黏接片製成80mm×80mm尺寸的樣品，將其黏接劑層用聚酯制網(網尺寸200)包裹，僅將黏接劑的質量用精密天秤進行稱量。將此時的質量作為M1。 The obtained 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 (net size 200). Only the quality of the adhesive was weighed with a precision balance. Let the mass at this time be M1.

接著，將上述聚酯制網包裹的黏接劑，在室溫(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秤進行稱量。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. Weigh only the weight of the dried adhesive 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，准備與測定凝膠分率所用的黏接片同樣的黏接片。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. 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〕(電阻值增加率的測定) [Test Example 3] (Measurement of resistance value increase rate)

將在實施例或比較例中得到的附有黏接劑層的偏光板，按照以下的試驗方法，測定ITO膜的電力電阻值，計算電阻值增 加率。 Using the polarizing plate with an adhesive layer obtained in the examples or comparative examples, the electric resistance value of the ITO film was measured according to the following test method, and the resistance value increase was calculated. Increase rate.

如圖3所示，為電阻值測定樣品S的剖面圖。通過濺射，准備在一個面21a上形成有ITO膜22的聚對苯二甲酸乙二醇酯(PET)薄膜21，用黏接膠帶24(琳得科株式公司製，商品名「TACKLINER TL-70」)，將沒有形成PET薄膜21的ITO膜22的面21b與玻璃板23的一個面23a接合。 As shown in FIG. 3, it is a sectional view of the resistance value measurement sample S. A polyethylene terephthalate (PET) film 21 having an ITO film 22 formed on one surface 21a was prepared by sputtering, and an adhesive tape 24 (manufactured by Lindec Corporation, trade name "TACKLINER TL- 70 ″), the surface 21b of the ITO film 22 on which the PET film 21 is not formed is bonded to one surface 23a of the glass plate 23.

然後，在與ITO膜22的PET薄膜21相接的面的反面(以下稱為「一個面」。)22a上，使含有銀的導電性樹脂材料(藤倉化成公司製，商品名「FA-301CA」，DOTITE觸控面板回路型)呈20mm×5mm的長方形電極形狀，進行塗布後，在溫度80℃下加熱20分鐘乾燥，形成兩個成為電阻值測定點的電極25。此時，調整兩個電極25，25的位置，使其之間的距離略大於20mm。 Then, a conductive resin material (manufactured by Fujikura Kasei Co., Ltd., under the trade name "FA-301CA") containing silver was formed on the reverse side (hereinafter referred to as "one side") of the surface that is in contact with the PET film 21 of the ITO film 22. ", DOTITE touch panel circuit type) has a rectangular electrode shape of 20 mm x 5 mm. After coating, it is dried by heating at a temperature of 80 ° C for 20 minutes to form two electrodes 25 serving as resistance measurement points. At this time, adjust the positions of the two electrodes 25, 25 so that the distance between them is slightly greater than 20 mm.

另一方面，將實施例或比較例中所得到的附有黏接劑層的偏光板1A’，裁成20mm×250mm尺寸，將剝離片剝離(此時，附有黏接劑層的偏光板1A’，為由偏光板13’和黏接劑層11所構成的積層體)。之後，附有黏接劑層的偏光板1A’的黏接劑層11緊貼兩個電極25，25的邊(剛好沒有與之接觸到)，在ITO膜22的一個面22a上，貼附附有黏接劑層的偏光板1A’，製作如圖3所示的電阻值測定用樣品S。 On the other hand, the polarizing plate 1A ′ with an adhesive layer obtained in Examples or Comparative Examples was cut into a size of 20 mm × 250 mm, and the release sheet was peeled off (in this case, the polarizing plate with an adhesive layer was attached). 1A ′ is a laminated body composed of a polarizing plate 13 ′ and an adhesive layer 11). After that, the adhesive layer 11 of the polarizing plate 1A ′ with the adhesive layer is in close contact with the sides of the two electrodes 25 and 25 (just not in contact with them), and is attached to one surface 22 a of the ITO film 22. A polarizing plate 1A ′ with an adhesive layer was prepared as a sample S for measuring resistance value as shown in FIG. 3.

之後，如圖4所示，利用數字測高儀(HIOKI.E公司製，商品名「3802-50」)30，測定電極25、25之間的初始電阻值R0(Ω)。並且將電阻值測定用樣品S，在60℃、90%RH的環境下放置500小時後，測定濕熱促進後的電阻值R(Ω)。根 據所得到的初始電阻值R0以及濕熱促進後的電阻值R，按以下公式算出電阻值測定用樣品S的電阻值增加率。將結果示於表2。 Thereafter, as shown in FIG. 4, an initial resistance value R 0 (Ω) between the electrodes 25 and 25 was measured using a digital altimeter (trade name “3802-50” manufactured by HIOKI.E Corporation) 30. In addition, the resistance value measurement sample S was left in an environment of 60 ° C. and 90% RH for 500 hours, and then the resistance value R (Ω) after the moist heat promotion was measured. From the obtained initial resistance value R 0 and the resistance value R after the moist heat promotion, the resistance value increase rate of the resistance value measurement sample S was calculated according to the following formula. The results are shown in Table 2.

電阻值增加率(%)={(R-R0)/R0}×100 Resistance increase rate (%) = ((RR 0 ) / R 0 ) × 100

〔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附有黏接劑層的偏光板裁斷，製作200mm×150mm尺寸的樣品。從該樣品上將剝離片剝離，通過露出的黏接劑層，在無堿玻璃(康寧公司製，鷹XG)上進行貼附之後，用栗原製作所公司製的高壓鍋，在0.5MPa、50℃，加壓20分鐘。 The polarizing plate with an adhesive layer obtained in the example or the comparative example was cut to produce a sample having a size of 200 mm × 150 mm. The release sheet was peeled from this sample, and the exposed adhesive layer was pasted on a glassless glass (made by Corning, Eagle XG), and then a pressure cooker made by Kurihara Seisakusho was used at 0.5 MPa and 50 ° C. Press for 20 minutes.

之後，投入到以下耐久條件的環境中，250小時後，利用10倍放大鏡，對浮起或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 placed in an environment with the following durability conditions. After 250 hours, the presence or absence of floating or peeling was confirmed using a 10-times 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以下大小的浮起或剝離。 ○: Floating or peeling of a size of 0.5 mm or less was confirmed.

△：確認到0.5mm以上1.0mm以下大小的浮起或剝離。 Δ: Floating or peeling of a size of 0.5 mm to 1.0 mm was confirmed.

×：確認到1.0mm以上大小的浮起或剝離。 ×: Floating or peeling of a size of 1.0 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

〔試驗例5〕(黏接劑層的表面電阻值測定) [Test Example 5] (Surface Resistance Measurement of Adhesive Layer)

將在實施例7中所得到的附有黏接劑層的偏光板，裁斷成50mm×50mm大小，將所得到的樣品在溫度23℃、濕度50%RH下放置24小時。之後，將剝離片剝離，對露出的黏接劑層表 面，用電阻率儀(三菱化學ANALYTECH公司製，HIRESTAUP MCP-HT450型)，基於JIS K6911，測定表面電阻值(Ω/Sq)。將結果示於表2。 The polarizing plate with an adhesive layer obtained in Example 7 was cut into a size of 50 mm × 50 mm, and the obtained sample was left at a temperature of 23 ° C. and a humidity of 50% RH for 24 hours. After that, the release sheet was peeled, and the exposed adhesive layer surface The surface was measured for surface resistivity (Ω / Sq) using a resistivity meter (HIRESTAUP MCP-HT450, manufactured by ANALYTECH Corporation, Mitsubishi Chemical Corporation) based on JIS K6911. The results are shown in Table 2.

另外，表面電阻值優選為3.0×1011Ω/Sq以下，特別優選為1.0×1011Ω/Sq以下，進一步優選為8.0×1010Ω/Sq以下。表面電阻值在上述值以下，則可發揮良好的帶電防止性。 The surface resistance value is preferably 3.0 × 10 11 Ω / Sq or less, particularly preferably 1.0 × 10 11 Ω / Sq or less, and still more preferably 8.0 × 10 10 Ω / Sq or less. When the surface resistance value is equal to or less than the above value, good antistatic properties can be exhibited.

〔試驗例6〕(儲能模量的測定) [Test Example 6] (Measurement of storage modulus)

作為測定樣品，準備與凝膠分率測定中使用的黏接片同樣的黏接片。對該黏接片的黏接劑層(厚度：20μm)，積層該黏接劑層，製作直徑8mm×厚度3mm的圓柱狀試驗片，依據扭剪法在以下條件測定儲能模量(G’)。將結果示於表2。 As a measurement sample, an adhesive sheet similar to the adhesive sheet used in the gel fraction measurement was prepared. An adhesive layer (thickness: 20 μm) of the adhesive sheet was laminated, and a cylindrical test piece having a diameter of 8 mm × thickness 3 mm was produced, and the storage modulus (G ′) was measured according to the torsional shear method under the following conditions. ). The results are shown in Table 2.

‧測定裝置：Rheometric Scientific公司製，動態黏彈性測定裝置「DYNAMIC ANALYZER RDAII」 ‧Measuring device: Dynamic viscoelasticity measuring device "DYNAMIC ANALYZER RDAII" manufactured by Rheometric Scientific

‧頻率：1Hz ‧Frequency: 1Hz

‧溫度：23℃以及80℃ ‧Temperature: 23 ℃ and 80 ℃

【表2】 【Table 2】

由表2可知，在實施例中所得到的黏接劑層的黏接劑，耐久性優異，同時，被黏物透明導電膜的電阻值不易被改變。 As can be seen from Table 2, the adhesive of the adhesive layer obtained in the examples is excellent in durability, and at the same time, the resistance value of the adherend transparent conductive film is not easily changed.

【產業上可利用性】 [Industrial availability]

本發明的黏接劑以及黏接片，適宜於透明導電膜，特別是由氧化銦錫(ITO)所構成的透明導電膜與光學構件，特別是與偏光板的黏接。 The adhesive and the adhesive sheet of the present invention are suitable for the adhesion of a transparent conductive film, particularly a transparent conductive film composed of indium tin oxide (ITO), and an optical member, and particularly to a polarizing plate.

Claims (17)

一種黏接性組合物，其含有重均分子量為100萬~250萬，作為構成聚合物的單體單元，含有具有羥基的單體、具有芳香環的單體和具有羧基的單體的(甲基)丙烯酸酯聚合物(A)、異氰酸酯類架橋劑(B)、具有巰基的矽烷偶聯劑(C)和活性能量線固化性成分(D)，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，含有1質量%~5質量%上述具有羥基的單體，5質量%~30質量%上述具有芳香環的單體，以及0.1質量%~0.8質量%上述具有羧基的單體。An adhesive composition containing a monomer having a weight average molecular weight of 1 to 2.5 million and comprising a monomer having a hydroxyl group, a monomer having an aromatic ring, and a monomer having a carboxyl group as a monomer unit constituting a polymer. Base) acrylate polymer (A), isocyanate-based bridging agent (B), mercapto-containing silane coupling agent (C), and active energy ray-curable component (D), the (meth) acrylate polymer (A ), As a monomer unit constituting the polymer, containing 1 to 5 mass% of the monomer having a hydroxyl group, 5 to 30 mass% of the monomer having an aromatic ring, and 0.1 to 0.8 mass% The monomer having a carboxyl group as described above. 根據申請專利範圍第1項所述的黏接性組合物，其中上述異氰酸酯類架橋劑(B)為三羥甲基丙烷改性甲次苯基二異氰酸酯。The adhesive composition according to item 1 of the scope of the patent application, wherein the isocyanate bridging agent (B) is trimethylolpropane-modified methylphenyl diisocyanate. 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，上述異氰酸酯類架橋劑(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0.01質量份~1質量份。The adhesive composition according to item 1 of the scope of patent application, wherein the content of the isocyanate-based bridging agent (B) in the adhesive composition is greater than that of the (meth) acrylate polymer (A ) 100 parts by mass, 0.01 to 1 part 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，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~0.5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 0.5 parts by mass. 根據申請專利範圍第1項所述的黏接性組合物，其中上述具有芳香環的單體為(甲基)丙烯酸2-苯基乙基酯。The adhesive composition according to item 1 of the scope of patent application, wherein the monomer having an aromatic ring is 2-phenylethyl (meth) acrylate. 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(D)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 patent application, wherein the active energy ray-curable component (D) 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，上述活性能量線固化性成分(D)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~50質量份。The adhesive composition according to item 1 of the patent application scope, wherein the content of the active energy ray-curable component (D) in the adhesive composition is relative to the (meth) acrylate polymer. (A) 100 parts by mass, 1 to 50 parts by mass. 一種黏接劑，為將申請專利範圍第1至8項中任一項所述的黏接性組合物經活性能量線照射固化所構成。An adhesive is formed by curing the adhesive composition according to any one of claims 1 to 8 by applying active energy rays. 根據申請專利範圍第9項所述的黏接劑，其中凝膠分率為55%~85%。According to the adhesive according to item 9 of the scope of patent application, the gel fraction is 55% to 85%. 根據申請專利範圍第9項所述的黏接劑，其中在23℃下的儲能模量為0.15MPa~0.3MPa，在80℃下的儲能模量為0.05MPa~0.2MPa。The adhesive according to item 9 of the scope of the patent application, wherein the storage modulus at 23 ° C is 0.15 MPa to 0.3 MPa, and the storage modulus at 80 ° C is 0.05 MPa to 0.2 MPa. 一種黏接片，其特徵在於：具備基材和黏接劑層，上述黏接劑層由申請專利範圍第9項所述黏接劑所構成。An adhesive sheet is characterized in that it includes a substrate and an adhesive layer, and the adhesive layer is composed of the adhesive described in item 9 of the scope of patent application. 根據申請專利範圍第12項所述的黏接片，其中上述基材為光學構件。The adhesive sheet according to item 12 of the application, wherein the substrate is an optical member. 根據申請專利範圍第13項所述的黏接片，其中上述光學構件的厚度為10μm~150μm。The adhesive sheet according to item 13 of the scope of the patent application, wherein the thickness of the optical member is 10 μm to 150 μm. 根據申請專利範圍第13或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 13 or 14 of the scope of patent application, wherein the optical member is a polarizing plate. 一種黏接片，其特徵在於：其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夾持的黏接劑層，上述黏接劑層由申請專利範圍第9項所述黏接劑所構成。An adhesive sheet is characterized in that it comprises two release sheets and an adhesive layer sandwiched by the release sheet so as to be in contact with the release surfaces of the two release sheets. The adhesive layer is applied for by a patent. It consists of the adhesive as described in the range item 9. 根據申請專利範圍第12項所述的黏接片，其中對上述黏接劑層和透明導電膜的積層體，在65℃、95%RH的氣氛下進行曝露500小時的濕熱促進試驗時，上述透明導電膜根據以下算式算出的電阻值增加率為15%以下：電阻值增加率(%)={(R-R0)/R0}×100算式中，R0為濕熱促進試驗前的初始電阻值，R為濕熱促進試驗後的電阻值。The adhesive sheet according to item 12 of the scope of application for patent, wherein when the laminated body of the adhesive layer and the transparent conductive film is subjected to a humid heat promotion test in an atmosphere of 65 ° C and 95% RH for 500 hours, the above The resistance increase rate of the transparent conductive film calculated according to the following formula is 15% or less: the resistance value increase rate (%) = {(RR 0 ) / R 0 } × 100 In the formula, R 0 is the initial resistance value before the moist heat promotion test , R is the resistance value after the damp heat promotion test.
TW103118215A 2013-06-28 2014-05-26 Adhesive composition, adhesive and adhesive sheet TWI636106B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-137538 2013-06-28
JP2013137538A JP6114648B2 (en) 2013-06-28 2013-06-28 Adhesive composition, adhesive and adhesive sheet

Publications (2)

Publication Number Publication Date
TW201504376A TW201504376A (en) 2015-02-01
TWI636106B true TWI636106B (en) 2018-09-21

Family

ID=52185788

Family Applications (1)

Application Number Title Priority Date Filing Date
TW103118215A TWI636106B (en) 2013-06-28 2014-05-26 Adhesive composition, adhesive and adhesive sheet

Country Status (4)

Country Link
JP (1) JP6114648B2 (en)
KR (1) KR102281768B1 (en)
CN (1) CN104250524B (en)
TW (1) TWI636106B (en)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6463192B2 (en) * 2015-03-03 2019-01-30 リンテック株式会社 Optical film with adhesive layer
KR102557510B1 (en) * 2015-03-03 2023-07-19 린텍 가부시키가이샤 Polarizing plate with adhesive layer
JP6438817B2 (en) * 2015-03-27 2018-12-19 リンテック株式会社 Adhesive composition, adhesive, adhesive sheet and optical film with adhesive layer
JP6554344B2 (en) * 2015-06-30 2019-07-31 リンテック株式会社 Adhesive sheet and display
KR101780547B1 (en) 2015-07-31 2017-09-22 삼성에스디아이 주식회사 Adhesive film for polarizing plate, polarizing plate comprising the same and optical display apparatus comprising the same
TWI562892B (en) * 2015-10-28 2016-12-21 Sumika Technology Co Ltd Touch display device
KR101908175B1 (en) * 2015-11-24 2018-10-15 삼성에스디아이 주식회사 Adhesive film for polarizing plate, polarizing plate and display deviece comprising the same
TWI642742B (en) 2015-11-24 2018-12-01 三星Ｓｄｉ股份有限公司 Adhesive film for polarizing plate, polarizing plate and optical display comprising the same
CN107163867B (en) * 2016-03-07 2021-10-26 日东电工株式会社 Optical adhesive sheet, polarizing film with adhesive layer, and liquid crystal display device
TW201825583A (en) * 2016-11-16 2018-07-16 日商東亞合成股份有限公司 Curable composition for producing resin sheet
JP7112828B2 (en) * 2016-12-16 2022-08-04 大王製紙株式会社 Adhesive sheet
KR102158871B1 (en) * 2017-07-04 2020-09-22 삼성에스디아이 주식회사 Adhesive composition for polarizing plate, adhesive film for polarizing plate prepared using the same, polarizing plate comprising the same and optical display apparatus comprising the same
CN109237434A (en) * 2018-09-29 2019-01-18 江苏锐阳照明电器设备有限公司 A kind of dust-proof coating of mining illuminating lamp tool
CN110387193A (en) * 2019-08-09 2019-10-29 苏州凡赛特材料科技有限公司 A kind of nano metal conductive film optics Adhesive composition and its glue film
KR102635555B1 (en) * 2021-06-18 2024-02-08 (주)이녹스첨단소재 Adhesive sheet for display and display comprising the same
CN113956423B (en) * 2021-08-19 2023-05-26 Oppo广东移动通信有限公司 Composition, polymer dispersed liquid crystal, film and electronic device
WO2023136052A1 (en) * 2022-01-12 2023-07-20 綜研化学株式会社 Pressure-sensitive adhesive composition for polarizing plate, and polarizing plate with pressure-sensitive adhesive layer
JP7327700B1 (en) * 2023-04-05 2023-08-16 東洋インキＳｃホールディングス株式会社 Rolled conductive bonding sheet, wiring board with metal reinforcing plate, and electronic device

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103168083A (en) * 2010-10-12 2013-06-19 日本合成化学工业株式会社 Adhesive composition for optical components, adhesive for optical components, optical component with adhesive layer, and image display device

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3997270B2 (en) * 2005-11-21 2007-10-24 綜研化学株式会社 Optical film pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet, and optical member using the same
JP2007169329A (en) * 2005-12-19 2007-07-05 Saiden Chemical Industry Co Ltd Adhesive composition for optical use and adhesive sheet
JP5047556B2 (en) * 2006-07-26 2012-10-10 リンテック株式会社 Adhesive for bonding optical functional film, optical functional film with adhesive, and method for producing the same
JP5015648B2 (en) * 2007-04-11 2012-08-29 サイデン化学株式会社 Optical pressure-sensitive adhesive composition and optical functional film
JP5649276B2 (en) * 2007-12-25 2015-01-07 日本合成化学工業株式会社 Optical member pressure-sensitive adhesive and optical member
JP5379409B2 (en) * 2008-02-15 2013-12-25 日東電工株式会社 Adhesive composition for optical film, adhesive optical film, and image display device
JP2009221324A (en) * 2008-03-14 2009-10-01 Soken Chem & Eng Co Ltd Pressure-sensitive adhesive for optical member and protection film for optical member using the same
JP5616652B2 (en) * 2010-02-24 2014-10-29 リンテック株式会社 Adhesive composition and adhesive sheet
JP5683229B2 (en) * 2009-11-27 2015-03-11 日本合成化学工業株式会社 Adhesive, adhesive for optical member, optical member with adhesive layer, image display device, and adhesive composition
CN102181244B (en) * 2009-12-29 2014-02-12 第一毛织株式会社 Adhesive binder and preparation method thereof, composition, method for manufacturing adhesive binder layer and optical member
JP5729973B2 (en) * 2010-11-11 2015-06-03 日本合成化学工業株式会社 Acrylic adhesive, adhesive for optical members, optical member with adhesive layer, image display device
JP5552338B2 (en) * 2010-03-12 2014-07-16 リンテック株式会社 Adhesive composition, adhesive and adhesive sheet
KR20120001647A (en) 2010-06-28 2012-01-04 주식회사 누마스타세척기 Hand washing device
JP2012077299A (en) * 2010-09-10 2012-04-19 Nippon Synthetic Chem Ind Co Ltd:The Pressure-sensitive adhesive composition, pressure-sensitive adhesive, pressure-sensitive adhesive for optical member, optical member with pressure-sensitive adhesive layer, image display device
KR101459124B1 (en) * 2011-12-07 2014-11-07 제일모직주식회사 Photo-curable adhesive composition and display device comprising the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103168083A (en) * 2010-10-12 2013-06-19 日本合成化学工业株式会社 Adhesive composition for optical components, adhesive for optical components, optical component with adhesive layer, and image display device

Also Published As

Publication number Publication date
TW201504376A (en) 2015-02-01
CN104250524B (en) 2020-02-21
JP6114648B2 (en) 2017-04-12
CN104250524A (en) 2014-12-31
JP2015010192A (en) 2015-01-19
KR102281768B1 (en) 2021-07-27
KR20150002459A (en) 2015-01-07

Similar Documents

Publication Publication Date Title
TWI636106B (en) Adhesive composition, adhesive and adhesive sheet
TWI652321B (en) Adhesive composition, adhesive and adhesive sheet
TWI618767B (en) Adhesive composition, adhesive and adhesive sheet
TWI623599B (en) Adhesive composition, adhesive and adhesive sheet
JP6196781B2 (en) Adhesive composition, adhesive and adhesive sheet
JP6097589B2 (en) Adhesive composition, adhesive and adhesive sheet
KR102246041B1 (en) adhesion composition, an adhesive and adhesion sheet
KR102314959B1 (en) adhesion composition, an adhesive and adhesion sheet
TWI642741B (en) Adhesive composition, adhesive and adhesive sheet
JP6039451B2 (en) Adhesive for sticking transparent conductive film and adhesive sheet
JP6290466B2 (en) Adhesive sheet
JP6502999B2 (en) Adhesive composition, adhesive and adhesive sheet