TWI803810B - Adhesive layer and adhesive film - Google Patents

Adhesive layer and adhesive film Download PDF

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TWI803810B
TWI803810B TW110101792A TW110101792A TWI803810B TW I803810 B TWI803810 B TW I803810B TW 110101792 A TW110101792 A TW 110101792A TW 110101792 A TW110101792 A TW 110101792A TW I803810 B TWI803810 B TW I803810B
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acrylate
meth
adhesive layer
adhesive
monomer
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TW202116954A (en
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長倉毅
吉田弘幸
長谷川良
菱沼昌世
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日商藤森工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Human Computer Interaction (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Materials For Medical Uses (AREA)

Abstract

An adhesive layer used for optical unit and an adhesive film used thereof are provided. The adhesive layer has good step-conformability to a frame disposed to a cover glass, and even when the cover glass and a sensor glass are attached, it can still has both excellent step-conformability and durability. The adhesive layer is formed by crosslinking an adhesive composition including an acrylic polymer and a crosslinking agent. The acrylic polymer is an copolymer formed by copolymerizing a hydroxyl group-containing vinyl monomer and a monomer selected from a group of an alkyl acrylate monomer, and alicyclic-containing monomer, a branched- alkyl group containing monomer, and nitrogen-containing vinyl monomer. The gel fraction of the adhesive layer is in a range of 40 to 75%. When the adhesive layers are laminated to a thickness of 1000 µm, the storage elastic modulus measured under 1 Hz at 0.89°C is lower than 100000 Pa. When a shear force 500 Pa with a load of 1N is added continuously for 30 minutes, the distortion is of over 15%, and the distortion-recovery ability afterwards is over 50%.

Description

黏著劑層及黏著膜Adhesive layer and adhesive film

本發明涉及一種用於觸控面板構件的蓋板玻璃（cover glass）（或觸控感測器玻璃）與感測器玻璃（sensor glass）（或感測器膜）之間貼合用的黏著劑層及黏著膜。更詳細而言，涉及一種光學用黏著劑層及使用了該光學用黏著劑層的觸控面板用黏著膜、帶有黏著劑層的光學膜，該光學用黏著劑層對配設於蓋板玻璃上的框架印刷的段差追隨性良好，即使在將蓋板玻璃與感測器玻璃貼合的情況下，仍同時具備優異的段差追隨性與耐久性。The present invention relates to an adhesive used for bonding between cover glass (or touch sensor glass) and sensor glass (sensor glass) (or sensor film) of touch panel components agent layer and adhesive film. More specifically, it relates to an optical adhesive layer, an adhesive film for a touch panel using the optical adhesive layer, and an optical film with the adhesive layer, the optical adhesive layer being arranged on a cover plate. The frame printing on the glass has good step followability, and it has excellent step followability and durability even when the cover glass and sensor glass are bonded together.

作為適用於觸控面板的顯示器（顯示裝置），可列舉出液晶顯示器（LCD）、電致發光顯示器（無機EL、有機EL）等。作為利用觸控面板的具體的電子設備，可列舉出液晶電視、可攜式終端、可攜式電話、電子紙、電子書終端、個人電腦等。As a display (display device) applied to a touch panel, a liquid crystal display (LCD), an electroluminescent display (inorganic EL, organic EL), etc. are mentioned. Examples of specific electronic devices using a touch panel include liquid crystal televisions, portable terminals, mobile phones, electronic paper, electronic book terminals, personal computers, and the like.

例如，在專利文獻1中記載了，在液晶裝置或觸控面板中，為了將具有遮光層的段差的透光構件黏接在顯示面上，同時使用了具有耐衝擊性與厚度的黏著劑層及氣泡難以進入的黏接劑層。 此外，在專利文獻2中記載了，使用含有環狀烯烴類樹脂、飽和聚異丁烯樹脂、丙烯酸樹脂、光起始劑等的透明黏著片，將觸控面板與玻璃板等表面保護層之間貼附的方法。 此外，在專利文獻3中記載了，使用含有具有烯基的聚氧化烯類聚合物、具有氫矽烷基的化合物、氫矽烷化催化劑等的透明黏著片，將觸控面板與保護透明板之間黏接的方法。 [現有技術文獻] [專利文獻]For example, in Patent Document 1, it is described that in a liquid crystal device or a touch panel, an adhesive layer having both impact resistance and thickness is used in order to bond a light-transmitting member having a step of a light-shielding layer to a display surface. And the adhesive layer where air bubbles are difficult to enter. In addition, Patent Document 2 describes that a transparent adhesive sheet containing a cyclic olefin resin, a saturated polyisobutylene resin, an acrylic resin, a photoinitiator, and the like is used to bond a touch panel to a surface protection layer such as a glass plate. attached method. In addition, Patent Document 3 describes that a transparent adhesive sheet containing a polyoxyalkylene-based polymer having an alkenyl group, a compound having a hydrosilyl group, a hydrosilylation catalyst, etc. is used to seal the gap between the touch panel and the protective transparent plate. bonding method. [Prior art literature] [Patent Document]

專利文獻1：日本特開2009-098324號公報 專利文獻2：日本特開2010-072471號公報 專利文獻3：日本特開2010-097070號公報Patent Document 1: Japanese Patent Laid-Open No. 2009-098324 Patent Document 2: Japanese Patent Laid-Open No. 2010-072471 Patent Document 3: Japanese Patent Laid-Open No. 2010-097070

但是，在專利文獻1所述的顯示裝置中，在觸控面板的表面經由黏接劑層及黏著劑層貼合透光構件與僅使用黏著劑層的情況相比，需要過多的操作，因此成為成本提高的原因，存在無法用於廉價的顯示裝置中的問題。此外，專利文獻1所述的顯示裝置中，以包圍液晶裝置的外圍的方式，形成厚度為5~10μm左右的遮光層，但以不影響遮光層的印刷段差的方式，在遮光層的框內配設有黏接劑層及黏著劑層的區域。However, in the display device described in Patent Document 1, bonding the light-transmitting member on the surface of the touch panel through the adhesive layer and the adhesive layer requires too many operations compared with the case where only the adhesive layer is used. There is a problem that it cannot be used in an inexpensive display device due to an increase in cost. In addition, in the display device described in Patent Document 1, a light-shielding layer with a thickness of about 5 to 10 μm is formed so as to surround the periphery of the liquid crystal device, but within the frame of the light-shielding layer so as not to affect the printing steps of the light-shielding layer An area provided with an adhesive layer and an adhesive layer.

此外，專利文獻2中公開了，經由具有特定的存儲彈性模量的黏著劑層，在觸控面板的表面貼合具有遮光層的表面保護層。使用該黏著劑層則不產生氣泡。但是，在將表面保護層貼合於觸控面板後，從表面保護層或觸控面板的相反側照射紫外線，由於黏著劑硬化，存在對遮光層的內側不能充分照射紫外線的問題。In addition, Patent Document 2 discloses that a surface protection layer having a light-shielding layer is bonded to the surface of a touch panel via an adhesive layer having a specific storage elastic modulus. Using this adhesive layer does not generate air bubbles. However, after bonding the surface protection layer to the touch panel, ultraviolet rays are irradiated from the opposite side of the surface protection layer or the touch panel, and the inside of the light-shielding layer cannot be sufficiently irradiated with ultraviolet rays due to hardening of the adhesive.

此外，專利文獻3公開了，經由具有特定剪切儲能模量及凝膠分率的透明黏著片，在觸控面板的表面貼合具有黑色印刷層的保護透明板。若使用專利文獻3的透明黏著片，則在液晶顯示面板與保護透明板的黏接面上不起泡。但是，經由透明黏著片而將由透明塑膠構成的保護透明板黏接於液晶面板上，因此，存在黑色印刷層在產生段差的角落部無法避免氣泡殘留的問題。 In addition, Patent Document 3 discloses that a protective transparent plate having a black printed layer is bonded to the surface of a touch panel via a transparent adhesive sheet having a specific shear storage modulus and gel fraction. When the transparent adhesive sheet of Patent Document 3 is used, no bubbles will occur on the bonding surface between the liquid crystal display panel and the protective transparent plate. However, since the protective transparent plate made of transparent plastic is bonded to the liquid crystal panel through a transparent adhesive sheet, there is a problem that air bubbles cannot be avoided in the corner of the black printed layer where the level difference occurs.

本發明的課題在於提供一種光學用黏著劑層及使用了該光學用黏著劑層的黏著膜，所述光學用黏著劑層對配設在蓋板玻璃上的框架印刷的段差追隨性良好，即使在將蓋板玻璃與感測器玻璃貼合的情況下，也同時具備優異的段差追隨性與耐久性。 An object of the present invention is to provide an optical adhesive layer that has good step followability for frame printing arranged on a cover glass, and an adhesive film using the optical adhesive layer, even if Even when the cover glass and the sensor glass are bonded together, it has excellent step followability and durability at the same time.

為了解決所述技術問題，本申請發明人經過仔細研究後發現，黏著劑層的凝膠分率、及在黏著劑層上施加剪切力時的歪斜值在規定的範圍的情況下，同時具備優異的段差追隨性與耐久性。本發明將下述黏著劑層作為技術構思：黏著劑層的凝膠分率為40~75%，黏著劑層在積層至1000μm的厚度時測定的在1Hz、100℃下的存儲彈性模量為100000(10的5次方)Pa以下，在荷載1N下持續施加30分鐘500Pa剪切力時的歪斜為15%以上，且之後的歪斜回復力為50%以上。 In order to solve the above-mentioned technical problem, the inventors of the present application have found after careful study that when the gel fraction of the adhesive layer and the skew value when a shear force is applied to the adhesive layer are within the specified range, both Excellent step followability and durability. The present invention takes the following adhesive layer as a technical idea: the gel fraction of the adhesive layer is 40-75%, and the storage elastic modulus measured at 1 Hz and 100°C when the adhesive layer is laminated to a thickness of 1000 μm is Below 100000 (10 to the 5th power) Pa, the deflection is 15% or more when a 500Pa shear force is continuously applied under a load of 1N for 30 minutes, and the subsequent deflection recovery force is 50% or more.

為了解決所述技術問題，本發明提供一種黏著劑層，其特徵在於，該黏著劑層由含有丙烯酸類聚合物與交聯劑的黏著劑組合物交聯而成，所述丙烯酸類聚合物為：由烷基的碳原子數為C1~C14的丙烯酸烷基酯單體、含脂環族的單體、含支鏈結構烷基的單體、含氮的乙烯基單體(Vinyl monomer)所構成的單體組中選擇的至少一種以上的單體與含羥基的共聚性乙烯基單體進行共聚而得到的共聚物，相對於從所述單體組中選擇的至少一種以上的單體的總量100重量份，所述丙烯酸類聚合物含有0.1~10.0重量份所述含羥基的共聚性乙烯基單體，所述黏著劑層的凝膠分率為40~75%，黏著劑層在積層至1000μm的厚度時測定的在1Hz、100℃下的存儲彈性模量為100000Pa以下，在荷載1N下持續施加30分鐘500Pa剪切力時的歪斜為15%以上，且之後的歪斜回復力為50%以上。In order to solve the above technical problems, the present invention provides an adhesive layer, which is characterized in that the adhesive layer is formed by cross-linking an adhesive composition containing an acrylic polymer and a cross-linking agent, and the acrylic polymer is : The carbon number of the alkyl group is C 1 ~ C 14 alkyl acrylate monomers, alicyclic monomers, branched chain alkyl monomers, nitrogen-containing vinyl monomers (Vinyl monomers) ) copolymerized with at least one monomer selected from the group of monomers composed of ) and a hydroxyl group-containing copolymerizable vinyl monomer, relative to at least one monomer selected from the group of monomers The total amount of the body is 100 parts by weight, the acrylic polymer contains 0.1-10.0 parts by weight of the hydroxyl-containing copolymerizable vinyl monomer, the gel fraction of the adhesive layer is 40-75%, and the adhesive When the layer is laminated to a thickness of 1000μm, the storage elastic modulus measured at 1Hz and 100°C is 100,000Pa or less, and the deflection is 15% or more when a 500Pa shear force is continuously applied under a load of 1N for 30 minutes, and the subsequent deflection recovery Force is more than 50%.

此外，較佳的是，所述丙烯酸類聚合物的酸價為1以下，相對於從所述單體組中選擇的至少一種以上的單體的總量100重量份，所述黏著劑組合物含有0.01~3.0重量份作為所述交聯劑的異氰酸酯化合物，將交聯所述黏著劑組合物後的黏著劑層在基材的單面上積層至175μm的厚度時的黏著力為20N/25mm以上，總透光率為90%以上，霧度值為1.0%以下。In addition, preferably, the acid value of the acrylic polymer is 1 or less, and the adhesive composition Containing 0.01 to 3.0 parts by weight of an isocyanate compound as the crosslinking agent, the adhesive force when the adhesive layer after crosslinking the adhesive composition is laminated on one side of the substrate to a thickness of 175 μm is 20N/25mm Above, the total light transmittance is above 90%, and the haze value is below 1.0%.

此外，相對於從所述單體組中選擇的至少一種以上的單體的總量100重量份，所述黏著劑組合物較佳進一步含有0.01~2.0重量份矽烷偶聯劑。In addition, the adhesive composition preferably further contains 0.01 to 2.0 parts by weight of a silane coupling agent based on 100 parts by weight of the total amount of at least one or more monomers selected from the group of monomers.

此外，所述含羥基的共聚性乙烯基單體以從（甲基）丙烯酸8-羥基辛酯、（甲基）丙烯酸6-羥基己酯、（甲基）丙烯酸4-羥基丁酯、（甲基）丙烯酸2-羥基乙酯所構成的化合物組中選擇的至少一種以上為佳。In addition, the hydroxyl group-containing copolymerizable vinyl monomer is derived from 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylate It is preferable to select at least one kind or more from the compound group consisting of 2-hydroxyethyl acrylate.

此外，較佳的是，相對於從所述單體組中選擇的至少一種以上的單體的總量100重量份，所述黏著劑組合物進一步含有0.1~10重量份在一分子中具有2~3個丙烯醯基的多官能基丙烯酸酯單體及0.01~2.0重量份光聚合起始劑，在將使所述黏著劑組合物交聯後的所述黏著劑層貼合於被黏著體之後，更進一步，經紫外線照射而進行紫外線硬化後的所述黏著劑層的凝膠分率為50~95%。In addition, preferably, the adhesive composition further contains 0.1 to 10 parts by weight of monomers having 2 A polyfunctional acrylate monomer with ~3 acryl groups and 0.01 to 2.0 parts by weight of a photopolymerization initiator, the adhesive layer after crosslinking the adhesive composition is pasted on the adherend After that, further, the gel fraction of the adhesive layer cured by ultraviolet irradiation is 50-95%.

此外，較佳的是，所述黏著劑層是將作為所述黏著劑組合物交聯而成的黏著劑層的所述黏著劑層貼合於被黏著體後，進一步經紫外線照射而進行紫外線硬化後的黏著劑層，相對於從所述單體組中選擇的至少一種以上的單體的總量100重量份，所述黏著劑組合物進一步含有0.1~10重量份在一分子中具有2~3個丙烯醯基的多官能基丙烯酸酯單體及0.01~2.0重量份光聚合起始劑，在進行所述紫外線硬化後的所述黏著劑層的凝膠分率為50~95%。In addition, it is preferable that the adhesive layer is formed by attaching the adhesive layer, which is an adhesive layer obtained by crosslinking the adhesive composition, to an adherend, and then irradiating with ultraviolet rays to irradiate ultraviolet rays. In the hardened adhesive layer, relative to 100 parts by weight of the total amount of at least one or more monomers selected from the monomer group, the adhesive composition further contains 0.1 to 10 parts by weight having 2 A multifunctional acrylate monomer with ~3 acryl groups and 0.01~2.0 parts by weight of a photopolymerization initiator, the gel fraction of the adhesive layer after the ultraviolet curing is 50~95%.

此外，本發明提供一種觸控面板用黏著膜，其由在基材的單面上積層所述黏著劑層而成。In addition, the present invention provides an adhesive film for a touch panel, which is formed by laminating the adhesive layer on one side of a base material.

此外，本發明提供一種帶有黏著劑層的光學膜，其由在光學膜的至少單面上積層所述黏著劑層而成。Furthermore, the present invention provides an optical film with an adhesive layer, which is formed by laminating the adhesive layer on at least one side of the optical film.

根據本發明的黏著劑層，黏著劑層的凝膠分率及對黏著劑層施加剪切力時的歪斜值在規定的範圍內。因此，對配設於蓋板玻璃的框架印刷的段差追隨性良好，即使在將蓋板玻璃與感測器玻璃貼合的情況下，也能夠提供同時具備優異段差追隨性與耐久性的光學用黏著劑層及使用該光學用黏著劑層的黏著膜。According to the adhesive layer of the present invention, the gel fraction of the adhesive layer and the deflection value when a shear force is applied to the adhesive layer are within predetermined ranges. Therefore, the step followability of the frame printed on the cover glass is good, and even when the cover glass and the sensor glass are bonded together, it is possible to provide optical products with excellent step followability and durability. An adhesive layer and an adhesive film using the optical adhesive layer.

以下，基於較佳實施方式對本發明進行說明。 本發明的黏著劑層由含有丙烯酸類聚合物與交聯劑的黏著劑組合物交聯而成，其特徵在於，所述丙烯酸類聚合物為：由烷基的碳原子數為C1 ~C14 的丙烯酸烷基酯單體、含脂環族的單體、含支鏈結構烷基的單體、含氮的乙烯基單體所構成的單體組中選擇的至少一種以上的單體與含羥基的共聚性乙烯基單體進行共聚而得到的共聚物，相對於從所述單體組中選擇的至少一種以上的單體的總量100重量份，所述丙烯酸類聚合物含有0.1~10.0重量份所述含羥基的共聚性乙烯基單體，所述黏著劑層的凝膠分率為40~75%，黏著劑層在積層至1000μm的厚度時測定的在1Hz、100℃下的存儲彈性模量為100000Pa以下，在荷載1N下持續施加30分鐘500Pa剪切力時的歪斜為15%以上，且之後的歪斜回復力為50%以上。Hereinafter, the present invention will be described based on preferred embodiments. The adhesive layer of the present invention is formed by cross - linking an adhesive composition containing an acrylic polymer and a cross-linking agent. 14. At least one or more monomers selected from the monomer group consisting of alkyl acrylate monomers, alicyclic-containing monomers, branched-chain alkyl-containing monomers, and nitrogen-containing vinyl monomers and A copolymer obtained by copolymerizing a hydroxyl group-containing copolymerizable vinyl monomer, wherein the acrylic polymer contains 0.1- 10.0 parts by weight of the hydroxyl-containing copolymerizable vinyl monomer, the gel fraction of the adhesive layer is 40-75%, and the adhesive layer is measured at 1 Hz and 100 °C when the thickness is 1000 μm. The storage elastic modulus is 100,000 Pa or less, the deflection when a 500 Pa shear force is continuously applied under a load of 1 N for 30 minutes is 15% or more, and the subsequent deflection recovery force is 50% or more.

本發明的黏著劑層的丙烯酸類聚合物為：作為屬於第一單體組的單體，使用由烷基的碳原子數為C1 ~C14 的丙烯酸烷基酯單體、含脂環族的單體、含支鏈結構烷基的單體、含氮的乙烯基單體所構成的單體組中選擇的至少一種以上的單體，作為屬於第二單體組的單體，使用含羥基的共聚性乙烯基單體，將分別屬於第一單體組的單體與屬於第二單體組的單體的一種以上進行共聚而得到的共聚物。在本說明書中，（甲基）丙烯酸酯為丙烯酸酯及甲基丙烯酸酯的總稱。The acrylic polymer of the adhesive layer of the present invention is: as the monomer belonging to the first monomer group, an alkyl acrylate monomer with an alkyl group having C 1 to C 14 carbon atoms, an alicyclic At least one or more monomers selected from the monomer group consisting of monomers containing branched chain structure alkyl monomers and nitrogen-containing vinyl monomers, as monomers belonging to the second monomer group, use The hydroxyl copolymerizable vinyl monomer is a copolymer obtained by copolymerizing a monomer belonging to the first monomer group and one or more monomers belonging to the second monomer group. In this specification, (meth)acrylate is a generic term for acrylate and methacrylate.

在本發明的黏著劑層的黏著劑組合物中，作為烷基的碳原子數為C1 ~C14 的丙烯酸烷基酯單體，可列舉丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸戊酯、丙烯酸己酯、丙烯酸庚酯、丙烯酸辛酯、丙烯酸壬基酯、丙烯酸癸基酯、丙烯酸十一烷基酯、丙烯酸十二烷基酯、丙烯酸十三烷基酯、丙烯酸十四烷基酯等中的至少一種以上。丙烯酸烷基酯單體的烷基可為直鏈狀、分支狀、環狀的任一種，這裡的烷基為直鏈狀。具有分支狀烷基的丙烯酸酯單體屬於含支鏈結構烷基的單體。此外，具有環狀烷基的丙烯酸酯單體屬於含脂環族的單體。In the adhesive composition of the adhesive layer of the present invention, as an alkyl acrylate monomer having C 1 to C 14 carbon atoms, methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid Butyl, Amyl Acrylate, Hexyl Acrylate, Heptyl Acrylate, Octyl Acrylate, Nonyl Acrylate, Decyl Acrylate, Undecyl Acrylate, Lauryl Acrylate, Tridecyl Acrylate, At least one or more of myristyl acrylate and the like. The alkyl group of the alkyl acrylate monomer may be linear, branched, or cyclic, and the alkyl group here is linear. Acrylate monomers with branched alkyl groups are monomers containing branched alkyl groups. In addition, acrylate monomers having a cyclic alkyl group are alicyclic-containing monomers.

在本發明的黏著劑層的黏著劑組合物中，作為含脂環族的單體，可列舉（甲基）丙烯酸環戊基酯、（甲基）丙烯酸環己基酯、（甲基）丙烯酸異冰片酯、（甲基）丙烯酸二環庚基酯、（甲基）丙烯酸二環辛基酯、（甲基）丙烯酸二甲基二環庚基酯、（甲基）丙烯酸二環戊基酯等中的至少一種以上。含脂環族的單體可以是烷基的碳原子數為C1 ~C18 的（甲基）丙烯酸脂環族烷基酯單體。In the adhesive composition of the adhesive layer of the present invention, examples of the alicyclic-containing monomer include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, iso(meth)acrylate, Bornyl ester, dicycloheptyl (meth)acrylate, dicycloctyl (meth)acrylate, dimethyldicycloheptyl (meth)acrylate, dicyclopentyl (meth)acrylate, etc. at least one of the above. The alicyclic-containing monomer may be an alicyclic alkyl (meth)acrylate monomer whose alkyl group has C 1 -C 18 carbon atoms.

在本發明的黏著劑層的黏著劑組合物中，作為含支鏈結構烷基的單體，可列舉（甲基）丙烯酸異丙酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸叔丁酯、（甲基）丙烯酸異戊酯、（甲基）丙烯酸異辛酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸異壬酯、（甲基）丙烯酸異癸酯、（甲基）丙烯酸異十一烷基酯、（甲基）丙烯酸異十二烷基酯、（甲基）丙烯酸異十三烷基酯、（甲基）丙烯酸異十四烷基酯、（甲基）丙烯酸異十五烷基酯、（甲基）丙烯酸異十六烷基酯、（甲基）丙烯酸異十七烷基酯、（甲基）丙烯酸異十八烷基酯、（甲基）丙烯酸異肉豆蔻酯、（甲基）丙烯酸異硬脂基酯等中的至少一種以上。含支鏈結構烷基的單體可以是烷基的碳原子數為C1 ~C18 的支鏈結構（甲基）丙烯酸烷基酯單體。含支鏈結構烷基的單體可以像叔丁基一樣，烷基含有2個以上的支鏈結構（例如相對主鏈的2個以上的側鏈）。In the adhesive composition of the adhesive layer of the present invention, examples of monomers containing an alkyl group of a branched chain structure include isopropyl (meth)acrylate, isobutyl (meth)acrylate, Tert-butyl ester, Isoamyl (meth)acrylate, Isooctyl (meth)acrylate, 2-Ethylhexyl (meth)acrylate, Isononyl (meth)acrylate, Isodecyl (meth)acrylate ester, isoundecyl (meth)acrylate, isododecyl (meth)acrylate, isotridecyl (meth)acrylate, isotetradecyl (meth)acrylate, Isopentadecyl (meth)acrylate, Isohexadecyl (meth)acrylate, Isoheptadecyl (meth)acrylate, Isostearyl (meth)acrylate, (meth)acrylate base) at least one of isomyristyl acrylate, isostearyl (meth)acrylate, and the like. The monomer containing an alkyl group with a branched chain structure may be an alkyl (meth)acrylate monomer with a branched chain structure with C 1 -C 18 carbon atoms in the alkyl group. The monomer containing a branched chain structure alkyl group can be like tert-butyl, and the alkyl group contains more than two branched chain structures (for example, two or more side chains relative to the main chain).

在本發明的黏著劑層的黏著劑組合物中，作為含氮的乙烯基單體，可列舉含醯胺鍵的乙烯基單體、含氨基的乙烯基單體、含氮的具有雜環式結構的乙烯基單體等。更具體而言，可列舉N-乙烯基-2-吡咯烷酮、N-乙烯基吡咯烷酮、甲基乙烯基吡咯烷酮、N-乙烯基吡啶、N-乙烯基呱啶酮、N-乙烯基嘧啶、N-乙烯基呱嗪、N-乙烯基吡嗪、N-乙烯基吡咯、N-乙烯基咪唑、N-乙烯基噁唑、N-乙烯基嗎啉、N-乙烯基己內醯胺、N-乙烯基月桂內醯胺等具有N-乙烯基取代的雜環式結構的環狀氮乙烯基化合物；N-（甲基）丙烯醯基嗎啉、N-（甲基）丙烯醯基呱嗪、N-（甲基）丙烯醯基氮丙啶、N-（甲基）丙烯醯基氮雜環丁烷、N-（甲基）丙烯醯基吡咯烷、N-（甲基）丙烯醯呱啶、N-（甲基）丙烯醯基氮雜環庚烷、N-（甲基）丙烯醯基氮雜環辛烷等具有N-（甲基）丙烯醯取代的雜環式結構的環狀氮乙烯基化合物；N-環己基馬來醯亞胺、N-苯基馬來醯亞胺等在環內具有氮原子及烯屬不飽和鍵的具有雜環式結構的環狀氮乙烯基化合物；（甲基）丙烯醯胺、N-甲基（甲基）丙烯醯胺、N-異丙基（甲基）丙烯醯胺、N-叔丁基（甲基）丙烯醯胺等無取代或單烷基取代的（甲基）丙烯醯胺；N,N-二甲基（甲基）丙烯醯胺、N,N-二乙基（甲基）丙烯醯胺、N,N-二丙基丙烯醯胺、N,N-二異丙基（甲基）丙烯醯胺、N,N-二丁基（甲基）丙烯醯胺、N-乙基-N-甲基（甲基）丙烯醯胺、N-甲基-N-丙基（甲基）丙烯醯胺、N-甲基-N-異丙基（甲基）丙烯醯胺等二烷基取代（甲基）丙烯醯胺；N,N-二甲基氨基甲基（甲基）丙烯酸酯、N,N-二甲基氨基乙基（甲基）丙烯酸酯、N,N-二甲基氨基丙基（甲基）丙烯酸酯、N,N-二甲基氨基異丙基（甲基）丙烯酸酯、N,N-二甲基氨基丁基（甲基）丙烯酸酯、N,N-二乙基氨基甲基（甲基）丙烯酸酯、N,N-二乙基氨基乙基（甲基）丙烯酸酯、N-乙基-N-甲基氨基乙基（甲基）丙烯酸酯、N-甲基-N-丙基氨基乙基（甲基）丙烯酸酯、N-甲基-N-異丙基氨基乙基（甲基）丙烯酸酯、N,N-二丁基氨基乙基（甲基）丙烯酸酯、叔丁基氨基乙基（甲基）丙烯酸酯等二烷基氨基（甲基）丙烯酸酯；N,N-二甲基氨基丙基（甲基）丙烯醯胺、N,N-二乙基氨基丙基（甲基）丙烯醯胺、N,N-二丙基氨基丙基（甲基）丙烯醯胺、N,N-二異丙基氨基丙基（甲基）丙烯醯胺、N-乙基-N-甲基氨基丙基（甲基）丙烯醯胺、N-甲基-N-丙基氨基丙基（甲基）丙烯醯胺、N-甲基-N-異丙基氨基丙基（甲基）丙烯醯胺等N,N-二烷基取代氨基丙基（甲基）丙烯醯胺；N-乙烯基甲醯胺、N-乙烯基乙醯胺、N-乙烯基-N-甲基乙醯胺等N-乙烯基羧酸醯胺類；N-甲氧基甲基（甲基）丙烯醯胺、N-乙氧基乙基（甲基）丙烯醯胺、N-丁氧基甲基（甲基）丙烯醯胺、二丙酮丙烯醯胺、N,N-亞甲基雙（甲基）丙烯醯胺等（甲基）丙烯醯胺類；（甲基）丙烯腈等不飽和羧酸腈類等。 作為含氮的乙烯基單體，較佳不含羥基，更較佳不含羥基及羧基。作為這樣的單體，較佳為以上列舉的單體，例如較佳為含有N,N-二烷基取代氨基或N,N-二烷基取代醯胺基的丙烯酸類單體；N-乙烯基-2-吡咯烷酮、N-乙烯基己內醯胺、N-乙烯基-2-呱啶酮等N-乙烯基取代內醯胺類；N-（甲基）丙烯醯基嗎啉或N-（甲基）丙烯醯基吡咯烷等N-（甲基）丙烯醯取代環狀胺類。In the adhesive composition of the adhesive layer of the present invention, examples of nitrogen-containing vinyl monomers include amide bond-containing vinyl monomers, amino-containing vinyl monomers, nitrogen-containing vinyl monomers having a heterocyclic formula Structured vinyl monomers, etc. More specifically, N-vinyl-2-pyrrolidone, N-vinylpyrrolidone, methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N- Vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, N-vinylcaprolactam, N-vinyl Cyclic nitrogen vinyl compounds with N-vinyl substituted heterocyclic structures such as laurolactamyl; N-(meth)acryl morpholine, N-(meth)acryl piperazine, N -(Meth)acryloyl aziridine, N-(meth)acryloyl azetidine, N-(meth)acryloyl pyrrolidine, N-(meth)acryloyl piperidine, N-(meth)acryloylazacycloheptane, N-(meth)acryloylazacycloctane and other cyclic nitrogen ethylenes with heterocyclic structure substituted by N-(meth)acryloyl N-cyclohexylmaleimide, N-phenylmaleimide, etc. have nitrogen atoms and ethylenically unsaturated bonds in the ring, and have heterocyclic nitrogen vinyl compounds with a heterocyclic structure; ( Meth)acrylamide, N-methyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-tert-butyl(meth)acrylamide etc. unsubstituted or monoalkane N,N-Dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropylacrylamide Amine, N,N-diisopropyl(meth)acrylamide, N,N-dibutyl(meth)acrylamide, N-ethyl-N-methyl(meth)acrylamide, Dialkyl-substituted (meth)acrylamides such as N-methyl-N-propyl(meth)acrylamide, N-methyl-N-isopropyl(meth)acrylamide; N,N -Dimethylaminomethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N, N-Dimethylaminoisopropyl (meth)acrylate, N,N-Dimethylaminobutyl (meth)acrylate, N,N-diethylaminomethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N-ethyl-N-methylaminoethyl (meth)acrylate, N-methyl-N-propylaminoethyl (methyl) base) acrylate, N-methyl-N-isopropylaminoethyl (meth)acrylate, N,N-dibutylaminoethyl (meth)acrylate, tert-butylaminoethyl (meth)acrylate Dialkylamino(meth)acrylates such as acrylates; N,N-dimethylaminopropyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide Amine, N,N-dipropylaminopropyl(meth)acrylamide, N,N-diisopropylaminopropyl(meth)acrylamide, N-ethyl-N-methylaminopropyl N-methyl-N-propylaminopropyl (meth)acrylamide, N-methyl-N-isopropylaminopropyl (meth)acrylamide, etc. N,N-dialkyl substituted aminopropyl (meth)acrylamide; N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, etc. Vinyl carboxamides; N-methoxymethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide (meth)acrylamides such as amide, diacetone acrylamide, N,N-methylenebis(meth)acrylamide, etc.; unsaturated carboxylic acid nitriles such as (meth)acrylonitrile, etc. The nitrogen-containing vinyl monomer preferably does not contain a hydroxyl group, more preferably does not contain a hydroxyl group or a carboxyl group. Such monomers are preferably those listed above, for example, acrylic monomers containing N,N-dialkyl-substituted amino groups or N,N-dialkyl-substituted amido groups; N-ethylene N-vinyl-2-pyrrolidone, N-vinylcaprolactam, N-vinyl-2-piperidone and other N-vinyl substituted lactams; N-(meth)acryl morpholine or N- N-(meth)acrylyl substituted cyclic amines such as (meth)acrylpyrrolidine.

在本發明的黏著劑層的黏著劑組合物中，作為含羥基的共聚性乙烯基單體，可列舉（甲基）丙烯酸8-羥基辛酯、（甲基）丙烯酸6-羥基己酯、（甲基）丙烯酸4-羥基丁酯、（甲基）丙烯酸2-羥基乙酯等（甲基）丙烯酸的含羥基烷基酯類，或N-羥基（甲基）丙烯醯胺、N-羥基甲基（甲基）丙烯醯胺、N-羥基乙基（甲基）丙烯醯胺等含羥基的（甲基）丙烯醯胺類等中的至少一種以上。其中，含羥基的共聚性乙烯基單體較佳為從（甲基）丙烯酸8-羥基辛酯、（甲基）丙烯酸6-羥基己酯、（甲基）丙烯酸4-羥基丁酯、（甲基）丙烯酸2-羥基乙酯所構成的化合物組中選擇的至少一種以上。本發明的丙烯酸類聚合物，相對於屬於所述第一單體組的單體的總量100重量份，較佳含有0.1~10.0重量份的含羥基的共聚性乙烯基單體，更佳含有0.2~5.0重量份，特佳含有0.2~4.0重量份。In the adhesive composition of the adhesive layer of the present invention, examples of the hydroxyl-containing copolymerizable vinyl monomer include 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, ( Hydroxyl-containing alkyl esters of (meth)acrylic acid such as 4-hydroxybutyl methacrylate, 2-hydroxyethyl (meth)acrylate, or N-hydroxy (meth)acrylamide, N-hydroxyformyl At least one or more of hydroxyl group-containing (meth)acrylamides such as N-hydroxyl (meth)acrylamide and N-hydroxyethyl (meth)acrylamide. Among them, the hydroxyl-containing copolymerizable vinyl monomer is preferably from 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylate base) at least one selected from the compound group consisting of 2-hydroxyethyl acrylate. The acrylic polymer of the present invention preferably contains 0.1 to 10.0 parts by weight of a hydroxyl-containing copolymerizable vinyl monomer, more preferably 0.2~5.0 parts by weight, preferably 0.2~4.0 parts by weight.

在本發明的黏著劑層的黏著劑組合物中，從降低黏著劑層的介電常數的角度考慮，丙烯酸類聚合物較佳不含有具有芳香族基的（甲基）丙烯酸酯單體。同樣的，不僅是具有芳香族基的（甲基）丙烯酸酯，還可以不含有具有芳香族基的共聚性乙烯基單體（苯乙烯等）。此外，從避免對透明導電性膜的ITO表面等易腐蝕的被黏著體的腐蝕性的影響的角度考慮，丙烯酸類聚合物的酸價較佳為1以下。In the adhesive composition of the adhesive layer of the present invention, it is preferable that the acrylic polymer does not contain a (meth)acrylate monomer having an aromatic group from the viewpoint of reducing the dielectric constant of the adhesive layer. Similarly, not only the (meth)acrylate having an aromatic group, but also a copolymerizable vinyl monomer (styrene, etc.) having an aromatic group may not be contained. In addition, the acid value of the acrylic polymer is preferably 1 or less from the viewpoint of avoiding the influence of corrosion on easily corroded adherends such as the ITO surface of the transparent conductive film.

作為所述丙烯酸類聚合物而使用的共聚物的聚合方法沒有特別的限定，可使用溶液聚合法、乳化聚合法等適當的公知聚合方法。所述丙烯酸類聚合物較佳含有50~100重量%的（甲基）丙烯酸酯單體等丙烯酸類單體。The polymerization method of the copolymer used as the acrylic polymer is not particularly limited, and an appropriate known polymerization method such as a solution polymerization method or an emulsion polymerization method can be used. The acrylic polymer preferably contains 50 to 100% by weight of acrylic monomers such as (meth)acrylate monomers.

所述黏著劑組合物可通過在上述丙烯酸類聚合物中添加交聯劑或適宜的任意添加劑來調整所需的物性值等特性。The adhesive composition can be adjusted to desired properties such as physical properties by adding a crosslinking agent or appropriate arbitrary additives to the above-mentioned acrylic polymer.

作為交聯劑，例如可列舉六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、二苯基甲烷二異氰酸酯、甲苯二異氰酸酯、苯二亞甲基二異氰酸酯等二異氰酸酯類的縮二脲改性體或異氰脲酸酯改性體、與三羥甲基丙烷或甘油等3元以上的多元醇的加成體等聚異氰酸酯化合物中的至少一種以上。作為可與交聯劑的異氰酸酯化合物進行交聯反應的官能基團，丙烯酸類聚合物較佳具有羥基，此外，較佳含有在側鏈具有這些官能基團的單體。 相對於屬於第一單體組的單體的總量100重量份，作為交聯劑而使用的異氰酸酯化合物的含量較佳為0.01~3.0重量份。作為交聯劑，可僅使用異氰酸酯化合物。Examples of crosslinking agents include biuret modification of diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and xylylene diisocyanate. At least one or more of polyisocyanate compounds such as trimethylolpropane or glycerin or trimethylol propane or glycerin or the like trimethylol propane or glycerin etc. trimethylol propane or glycerin etc. The acrylic polymer preferably has a hydroxyl group as a functional group capable of a crosslinking reaction with the isocyanate compound of the crosslinking agent, and further preferably contains a monomer having such a functional group in a side chain. The content of the isocyanate compound used as the crosslinking agent is preferably 0.01 to 3.0 parts by weight relative to 100 parts by weight of the total amount of monomers belonging to the first monomer group. As a crosslinking agent, only isocyanate compounds can be used.

所述黏著劑組合物進一步較佳含有矽烷偶聯劑。作為矽烷偶聯劑，可列舉在1分子中具有至少一個有機官能基團和至少一個水解性基團、所述水解性基團為與矽原子鍵合的烷氧基等的化合物。所述矽烷偶聯劑較佳具有從環氧基、（甲基）丙烯醯氧基、巰基、氨基所構成的組中選擇的至少一種有機官能基團。在此，（甲基）丙烯醯氧基是指丙烯醯氧基（CH2 ＝CHCOO-）或甲基丙烯醯氧基（CH2 ＝C(CH3 )COO-）。The adhesive composition further preferably contains a silane coupling agent. Examples of the silane coupling agent include compounds having at least one organic functional group and at least one hydrolyzable group in one molecule, wherein the hydrolyzable group is an alkoxy group bonded to a silicon atom, or the like. The silane coupling agent preferably has at least one organic functional group selected from the group consisting of epoxy group, (meth)acryloxy group, mercapto group, and amino group. Here, (meth)acryloxy means acryloxy (CH 2 ═CHCOO—) or methacryloxy (CH 2 ═C(CH 3 )COO—).

作為具有環氧基的矽烷偶聯劑，例如可列舉3-縮水甘油醚氧基丙基三甲氧基矽烷、3-縮水甘油醚氧基丙基甲基二乙氧基矽烷、3-縮水甘油醚氧基丙基甲基二甲氧基矽烷、3-縮水甘油醚氧基丙基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧基矽烷、5,6-環氧己基三甲氧基矽烷、5,6-環氧己基甲基二甲氧基矽烷、5,6-環氧己基甲基二乙氧基矽烷、5,6-環氧己基三乙氧基矽烷等。 作為含有（甲基）丙烯醯氧基的矽烷偶聯劑，例如可列舉3-（甲基）丙烯醯氧基丙基三甲氧基矽烷、3-（甲基）丙烯醯氧基丙基甲基二甲氧基矽烷、3-（甲基）丙烯醯氧基丙基三乙氧基矽烷、3-（甲基）丙烯醯氧基丙基甲基二乙氧基矽烷、3-（甲基）丙烯醯氧基丙基二甲基乙氧基矽烷、3-（甲基）丙烯醯氧基丙基二甲基甲氧基矽烷等。 作為含有巰基的矽烷偶聯劑，例如可列舉3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基甲基二乙氧基矽烷、3-巰基丙基三乙氧基矽烷等。 作為含有氨基的矽烷偶聯劑，例如可列舉3-氨基丙基三甲氧基矽烷、3-氨基丙基三乙氧基矽烷、N-苯基-3-氨基丙基三甲氧基矽烷、N-2-(氨基乙基)-3-氨基丙基甲基二甲氧基矽烷、N-2-(氨基乙基)-3-氨基丙基甲基二乙氧基矽烷、N-2-(氨基乙基)-3-氨基丙基三甲氧基矽烷、N-2-(氨基乙基)-3-氨基丙基三乙氧基矽烷、3-(甲基氨基)丙基三甲氧基矽烷、3-(甲基氨基)丙基三乙氧基矽烷等。 此外，含有所述有機官能基團的經過寡聚物化的烷氧基寡聚物（矽氧烷氧基寡聚物）等也可作為矽烷偶聯劑使用。Examples of the silane coupling agent having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyl ether Oxypropylmethyldimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3 ,4-Epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl Hexyl)ethyltriethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 5,6-epoxyhexylmethyldimethoxysilane, 5,6-epoxyhexylmethyldiethoxysilane Silane, 5,6-epoxyhexyltriethoxysilane, etc. Examples of silane coupling agents containing a (meth)acryloxy group include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyl Dimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(methyl) Acryloxypropyldimethylethoxysilane, 3-(meth)acryloxypropyldimethylmethoxysilane, etc. As a mercapto-containing silane coupling agent, for example, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropylmethyldiethoxysilane, Mercaptopropyltriethoxysilane, etc. As the silane coupling agent containing an amino group, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(amino Ethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-(methylamino)propyltrimethoxysilane, 3 -(methylamino)propyltriethoxysilane, etc. In addition, an oligomerized alkoxy oligomer (siloxaneoxy oligomer) containing the organic functional group can also be used as a silane coupling agent.

相對於屬於第一單體組的單體的總量100重量份，矽烷偶聯劑的含量較佳為0.01~2.0重量份。The content of the silane coupling agent is preferably 0.01 to 2.0 parts by weight relative to 100 parts by weight of the total amount of monomers belonging to the first monomer group.

作為其他任選成分，可適當添加抗氧化劑、表面活性劑、硬化促進劑、增塑劑、填充劑、交聯催化劑、交聯延遲劑、硬化延遲劑、加工助劑、抗老化劑等已知的添加劑。它們可單獨或兩種以上同時使用。As other optional components, antioxidants, surfactants, hardening accelerators, plasticizers, fillers, crosslinking catalysts, crosslinking retarders, hardening retarders, processing aids, antiaging agents, etc. additives. They can be used alone or in combination of two or more.

本發明的黏著劑層可通過將所述黏著劑組合物塗佈在基材或離型膜上之後，使黏著劑組合物交聯而獲得。交聯後的黏著劑層的凝膠分率較佳為40~75%。此外，對蓋板玻璃的框架印刷的段差追隨性良好，即使在貼合蓋板玻璃及感測器玻璃的情況下，為了使光學用黏著劑層同時具備優異段差追隨性與耐久性，較佳黏著劑層在積層至1000μm的厚度時測定的在1Hz、100℃下的存儲彈性模量為100000Pa以下，在荷載1N下持續施加30分鐘500Pa剪切力時的歪斜為15%以上，且之後的歪斜回復力為50%以上。The adhesive layer of the present invention can be obtained by crosslinking the adhesive composition after coating the adhesive composition on a substrate or a release film. The gel fraction of the cross-linked adhesive layer is preferably 40-75%. In addition, since the frame printing on the cover glass has good step followability, even when the cover glass and the sensor glass are bonded together, it is preferable to provide the optical adhesive layer with excellent step followability and durability. When the adhesive layer is laminated to a thickness of 1000 μm, the storage elastic modulus measured at 1 Hz and 100 °C is 100,000 Pa or less, and the deflection when a 500 Pa shear force is continuously applied under a load of 1 N for 30 minutes is 15% or more, and the subsequent Skew recovery force is 50% or more.

在用於光學構件的層間貼合等的情況下，將使所述黏著劑組合物交聯後的黏著劑層以175μm的厚度積層於基材的單面時的黏著力較佳為20N/25mm以上，總透光率較佳為90%以上，霧度值較佳為1.0%以下。作為用於黏著力的試驗的被黏著體，可列舉出無鹼玻璃等玻璃板、樹脂膜等。When used for interlayer bonding of optical members, etc., the adhesive force when the adhesive layer obtained by crosslinking the adhesive composition is laminated on one side of the substrate with a thickness of 175 μm is preferably 20N/25mm. Above, the total light transmittance is preferably 90% or more, and the haze value is preferably 1.0% or less. As an adherend used for the test of adhesive force, glass plates, such as an alkali-free glass, a resin film, etc. are mentioned.

本發明的黏著劑層在使所述黏著劑組合物交聯而獲得後，貼合於被黏著體，可進一步經紫外線照射進行紫外線硬化，形成黏著劑層。在該情況下，所述黏著劑組合物較佳含有作為必要成分的丙烯酸類聚合物、交聯劑、多官能基丙烯酸酯單體、光聚合起始劑。該黏著劑組合物可進一步含有上述矽烷偶聯劑等作為任選成分。The adhesive layer of the present invention is obtained by cross-linking the adhesive composition, and then attached to an adherend, and further cured by ultraviolet rays to form an adhesive layer. In this case, the adhesive composition preferably contains an acrylic polymer, a crosslinking agent, a polyfunctional acrylate monomer, and a photopolymerization initiator as essential components. This adhesive composition may further contain the above-mentioned silane coupling agent etc. as an optional component.

作為多官能基丙烯酸酯單體，只要是在一分子中具有2~3個丙烯醯基的化合物則沒有特別的限定，例如可列舉2元醇（二醇）的二丙烯酸酯、3元醇（三醇）的二丙烯酸酯或三丙烯酸酯、4元醇（四醇）的二丙烯酸酯或三丙烯酸酯等。作為具體例，可列舉乙二醇二丙烯酸酯、二乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、丙二醇二丙烯酸酯、二丙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、1,3-丙二醇二丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,5-戊二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、甘油三丙烯酸酯、三羥甲基乙烷三丙烯酸酯、三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、二季戊四醇三丙烯酸酯等中的一種或2種以上。與多官能基丙烯酸酯單體相同，可使用在一分子中具有2~3個甲基丙烯醯基的多官能基甲基丙烯酸酯單體。這些多官能基單體可在黏著劑組合物中使用一種或2種以上。用於本發明的黏著劑組合物的多官能基單體較佳為在一分子中具有2~3個（甲基）丙烯醯基等的聚合性官能基團。所述黏著劑組合物可不含在一分子中具有4個以上聚合性官能基團的單體。The polyfunctional acrylate monomer is not particularly limited as long as it is a compound having 2 to 3 acryl groups in one molecule, for example, diacrylates of diols (diols), triols ( Triol) diacrylate or triacrylate, 4 alcohol (tetraol) diacrylate or triacrylate, etc. Specific examples include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol Diacrylate, 1,3-Propanediol Diacrylate, 1,4-Butanediol Diacrylate, 1,5-Pentanediol Diacrylate, 1,6-Hexanediol Diacrylate, Glycerin Triacrylate , trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol triacrylate, or two or more. As with the polyfunctional acrylate monomer, a polyfunctional methacrylate monomer having 2 to 3 methacryl groups in one molecule can be used. These polyfunctional monomers may be used alone or in combination of two or more in the adhesive composition. The polyfunctional monomer used in the adhesive composition of the present invention is preferably a polymerizable functional group having 2 to 3 (meth)acryloyl groups or the like in one molecule. The adhesive composition may not contain a monomer having four or more polymerizable functional groups in one molecule.

光聚合起始劑沒有特別的限定，例如可列舉苯乙酮類光聚合起始劑、安息香類光聚合起始劑、苯甲酮類光聚合起始劑、噻噸酮類光聚合起始劑等。 作為苯乙酮類光聚合起始劑，可列舉苯乙酮、對(叔丁基)1’,1’,1’-三氯苯乙酮、氯苯乙酮、2’,2’-二乙氧基苯乙酮、羥基苯乙酮、2,2-二甲氧基-2’-苯基苯乙酮、2-氨基苯乙酮、二烷基氨基苯乙酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮等。 作為安息香類光聚合起始劑，可列舉苯偶醯、安息香、安息香甲醚、安息香***、安息香異丙醚、安息香異丁醚、1-羥基環己基苯基酮、2-羥基- 2-甲基-1-苯基-2-甲基丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、苯偶醯二甲基縮酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等。 作為苯甲酮類光聚合起始劑，可列舉苯甲酮、苯甲醯基安息香酸、苯甲醯基安息香酸甲酯、甲基鄰苯甲醯基苯甲酸酯、4-苯基苯甲酮、羥基苯甲酮、羥基丙基苯甲酮、丙烯酸苯甲酮、4,4'-雙(二甲基氨基)苯甲酮等。 作為噻噸酮類光聚合起始劑，可列舉噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、二乙基噻噸酮、二甲基噻噸酮等。 作為其它光聚合起始劑，可列舉α-醯基肟酯、芐基-(鄰乙氧基羰基)-α-單肟、醯基氧化膦、苯基乙醛酸酯、3-香豆素酮、2-乙基蒽醌、樟腦醌、硫化四甲基秋蘭姆、偶氮二異丁腈、過氧化苯甲醯、二烷基過氧化物、過氧化新戊酸叔丁酯等。The photopolymerization initiator is not particularly limited, and examples thereof include acetophenone-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzophenone-based photopolymerization initiators, and thioxanthone-based photopolymerization initiators. wait. Examples of the acetophenone-based photopolymerization initiator include acetophenone, p-(tert-butyl) 1',1',1'-trichloroacetophenone, chloroacetophenone, 2',2'-bis Ethoxyacetophenone, hydroxyacetophenone, 2,2-dimethoxy-2'-phenylacetophenone, 2-aminoacetophenone, dialkylaminoacetophenone, 2-hydroxy-2 -Methyl-1-phenyl-propan-1-one and the like. As the benzoin photopolymerization initiator, benzoyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl Base-1-phenyl-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzoyl dimethyl acetal Ketones, 2,2-dimethoxy-1,2-diphenylethan-1-one, etc. Examples of benzophenone-based photopolymerization initiators include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, methyl o-benzoylbenzoate, 4-phenylbenzene Methanone, hydroxybenzophenone, hydroxypropyl benzophenone, acrylic benzophenone, 4,4'-bis(dimethylamino)benzophenone, etc. Examples of the thioxanthone-based photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, diethylthioxanthone, and dimethylthioxanthone. Examples of other photopolymerization initiators include α-acyl oxime ester, benzyl-(o-ethoxycarbonyl)-α-monoxime, acyl phosphine oxide, phenylglyoxylate, 3-coumarin Ketones, 2-ethylanthraquinone, camphorquinone, tetramethylthiuram sulfide, azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, tert-butyl peroxypivalate, etc.

通過使用多官能基丙烯酸酯單體、光聚合起始劑、紫外線照射，可使經過交聯劑交聯的丙烯酸類聚合物進一步紫外線硬化，使耐久性提高。相對於屬於第一單體組的單體的總量100重量份，交聯前的黏著劑組合物中多官能基丙烯酸酯單體的含量較佳為0.1~10重量份。此外，相對於屬於第一單體組的單體的總量100重量份，光聚合起始劑的含量較佳為0.01~2.0重量份。在進行紫外線硬化後的黏著劑層的凝膠分率較佳為50~95%。By using a polyfunctional acrylate monomer, a photopolymerization initiator, and ultraviolet irradiation, the acrylic polymer crosslinked by a crosslinking agent can be further cured by ultraviolet light, thereby improving durability. With respect to 100 parts by weight of the total amount of monomers belonging to the first monomer group, the content of the multifunctional acrylate monomer in the adhesive composition before crosslinking is preferably 0.1-10 parts by weight. Moreover, it is preferable that content of a photoinitiator is 0.01-2.0 weight part with respect to 100 weight part of total amounts of the monomer which belongs to a 1st monomer group. The gel fraction of the adhesive layer after ultraviolet curing is preferably 50-95%.

在將本發明的黏著劑層用於光學構件層間的貼合等的情況下，由於降低了在黏著劑層與光學構件的介面的光線反射，因此有望使兩者的折射率差盡可能小。因此，所述黏著劑層的折射率較佳為1.47~1.50。When the adhesive layer of the present invention is used for bonding between layers of optical members, etc., since the reflection of light at the interface between the adhesive layer and the optical member is reduced, it is expected to minimize the difference in refractive index between the two. Therefore, the refractive index of the adhesive layer is preferably 1.47-1.50.

將本發明的黏著劑層用於觸控面板等電子設備的情況下，從降低電磁場噪音的角度考慮，在將黏著劑層積層至1000μm的厚度時測定的頻率100kHz的相對介電常數較佳為1.50~5.50，且介電損耗較佳為0.01~0.09。When the adhesive layer of the present invention is used in electronic devices such as touch panels, from the viewpoint of reducing electromagnetic field noise, the relative permittivity at a frequency of 100 kHz measured when the adhesive layer is laminated to a thickness of 1000 μm is preferably 1.50~5.50, and the dielectric loss is preferably 0.01~0.09.

本發明的黏著膜可以通過在基材或離型膜的單面上形成本發明的黏著劑層而製備。 作為用於形成黏著劑層的基材膜或保護黏著面的離型膜（分離膜（separator）），可使用聚酯膜等的樹脂膜等。 在基材膜上，可在樹脂膜的形成黏著劑層一側的相反面上，通過矽氧氧（silicone）類、氟類的離型劑或塗佈劑、二氧化矽微粒等施加防汙處理，通過塗佈或摻雜抗靜電劑等施加抗靜電處理。The adhesive film of the present invention can be produced by forming the adhesive layer of the present invention on one side of a substrate or a release film. A resin film such as a polyester film or the like can be used as a base film for forming an adhesive layer or a release film (separator) for protecting an adhesive surface. On the base film, anti-fouling can be applied on the opposite side of the resin film to the side where the adhesive layer is formed, using a silicone-based, fluorine-based release agent or coating agent, silica particles, etc. Treatment, antistatic treatment is applied by coating or doping with antistatic agents, etc.

在離型膜上，可在與黏著劑層的黏著面貼合的一側的面上，通過矽氧類、氟類的離型劑等施加離型處理。 通過在一個黏著劑層的兩面上分別合上離型膜的經過離型處理的面，形成“離型膜/黏著劑層/離型膜”的結構。在該情況下，可以通過將兩側的離型膜依次或同時剝離，露出黏著面，與光學膜等光學構件進行貼合。作為光學膜，可列舉偏光膜、相位差膜、防反射膜、防眩（Anti-glare）膜、紫外線吸收膜、紅外線吸收膜、光學補償膜、亮度提高膜等。On the release film, a release treatment can be applied to the surface on the side that is bonded to the adhesive surface of the adhesive layer with a silicone-based, fluorine-based release agent, or the like. The structure of "release film/adhesive layer/release film" is formed by closing the release-treated surface of the release film on both sides of an adhesive layer. In this case, the release films on both sides can be peeled off sequentially or simultaneously to expose the adhesive surface, and can be bonded to optical members such as optical films. Examples of the optical film include polarizing films, retardation films, antireflection films, anti-glare (anti-glare) films, ultraviolet absorbing films, infrared absorbing films, optical compensation films, brightness enhancement films, and the like.

本發明的黏著劑層即使在如將蓋板玻璃與感測器玻璃等玻璃與玻璃貼合的情況下，也能獲得良好的段差追隨性，因此可適用於觸控面板的蓋板玻璃與感測器玻璃的貼合。此外，在進行膜構件與玻璃構件的貼合的情況下，在膜構件的單面上積層本發明的黏著劑層而得到的本發明的黏著膜，也可貼合於蓋板玻璃、感測器玻璃等玻璃構件上。本發明的黏著劑層及黏著膜適合作為觸控面板用黏著劑層及觸控面板用黏著膜。作為段差追隨性，例如黏著劑層的厚度為175μm時，對42μm的印刷段差具有良好的段差追隨性。Even when the adhesive layer of the present invention is bonded to glass such as cover glass and sensor glass, it can obtain good step followability, so it can be applied to the cover glass and sensor of the touch panel. Bonding of the detector glass. In addition, when bonding a film member and a glass member, the adhesive film of the present invention obtained by laminating the adhesive layer of the present invention on one surface of the film member can be bonded to a cover glass, sensor on glass components such as glassware. The adhesive layer and adhesive film of this invention are suitable as an adhesive layer for touch panels and an adhesive film for touch panels. As for step followability, for example, when the adhesive layer has a thickness of 175 μm, it has good step followability to a printing step of 42 μm.

本發明的黏著膜可用於以偏光板為主的液晶顯示裝置的周邊構件用的各種光學膜、觸控面板用的各種光學膜、電子紙用的各種光學膜、有機EL用的各種光學膜等的貼合。 此外，可形成在這些光學膜的至少一個面上積層有所述黏著劑層的帶有黏著劑層的光學膜。具體而言，可列舉「光學膜/黏著劑層/光學膜」、「光學膜/黏著劑層/離型膜」、「光學膜/黏著劑層」、「光學膜/黏著劑層/光學膜/黏著劑層/光學膜」、「光學膜/黏著劑層/光學膜/黏著劑層/離型膜」、「離型膜/黏著劑層/光學膜/黏著劑層/離型膜」等結構。 例如，在如「光學膜/黏著劑層/離型膜」具有通過離型膜保護的黏著劑層的情況下，通過剝離離型膜，如「光學膜/黏著劑層」露出黏著劑層，貼合其他光學膜，能夠得到將黏著劑層用於層間貼合的如「光學膜/黏著劑層/光學膜」的結構。The adhesive film of the present invention can be used for various optical films for peripheral members of liquid crystal display devices including polarizing plates, various optical films for touch panels, various optical films for electronic paper, various optical films for organic EL, etc. fit. In addition, an optical film with an adhesive layer in which the above-mentioned adhesive layer is laminated on at least one surface of these optical films can be formed. Specifically, "optical film/adhesive layer/optical film", "optical film/adhesive layer/release film", "optical film/adhesive layer", "optical film/adhesive layer/optical film /adhesive layer/optical film", "optical film/adhesive layer/optical film/adhesive layer/release film", "release film/adhesive layer/optical film/adhesive layer/release film", etc. structure. For example, in the case of having an adhesive layer protected by a release film such as "optical film/adhesive layer/release film", by peeling off the release film such as "optical film/adhesive layer" to expose the adhesive layer, By laminating other optical films, a structure such as "optical film/adhesive layer/optical film" can be obtained using an adhesive layer for lamination between layers.

本發明的黏著膜適用於偏光板與顯示器面板的貼合。作為顯示器面板，例如可列舉液晶面板或有機EL面板。本發明的黏著膜可適宜地用作帶有黏著劑層的偏光板的黏著劑層。作為偏光板的構成材料，可使用具有λ/4或λ/2的相位差的相位差膜。本發明的黏著劑層可用於相位差膜與偏光板的貼合。根據本發明的黏著膜，由於黏著劑層為低介電常數，因此在彩色濾光片（color filter）與偏光板之間設有觸控感測器的On Cell式顯示裝置中，可適用於偏光板與背光單元之間的光學構件的貼合。 [實施例]The adhesive film of the present invention is suitable for bonding polarizers and display panels. As a display panel, a liquid crystal panel or an organic electroluminescence panel is mentioned, for example. The adhesive film of this invention can be used suitably as the adhesive agent layer of the polarizing plate with an adhesive agent layer. As a constituent material of the polarizing plate, a retardation film having a retardation of λ/4 or λ/2 can be used. The adhesive layer of the present invention can be used for bonding the phase difference film and the polarizing plate. According to the adhesive film of the present invention, since the adhesive layer has a low dielectric constant, it can be used in an on-cell display device in which a touch sensor is provided between a color filter (color filter) and a polarizing plate. Bonding of optical members between a polarizing plate and a backlight unit. [Example]

以下通過實施例對本發明進行具體的說明。The present invention will be specifically described below through examples.

＜丙烯酸類聚合物的製備＞ [實施例1] 向具有攪拌機、溫度計、回流冷卻器及氮氣導入管的反應裝置中導入氮氣，用氮氣置換掉反應裝置內的空氣，然後，向反應裝置中加入80重量份的丙烯酸丁酯、20重量份的丙烯酸甲酯、1.0重量份的丙烯酸8-羥基辛酯、60重量份的溶劑（醋酸乙酯）。然後，用2小時滴入0.1重量份的作為聚合起始劑的偶氮二異丁腈，在65℃下反應6小時，得到實施例1中使用的丙烯酸類聚合物溶液。取部分丙烯酸類聚合物用作後述的酸價的測定試樣。 [實施例2~5及比較例1~3] 單體的組成分別如表1的（1）組及（2）組所示，除此之外，以與上述實施例1中使用的丙烯酸類聚合物溶液相同的方式得到實施例2~5及比較例1~3中使用的丙烯酸類聚合物溶液。＜Preparation of acrylic polymer＞ [Example 1] Introduce nitrogen into the reaction device with stirrer, thermometer, reflux cooler and nitrogen inlet pipe, replace the air in the reaction device with nitrogen, then add 80 parts by weight of butyl acrylate, 20 parts by weight of acrylic acid in the reaction device Methyl ester, 1.0 parts by weight of 8-hydroxyoctyl acrylate, and 60 parts by weight of solvent (ethyl acetate). Then, 0.1 parts by weight of azobisisobutyronitrile as a polymerization initiator was dropped over 2 hours, and reacted at 65° C. for 6 hours to obtain an acrylic polymer solution used in Example 1. Part of the acrylic polymer was used as a sample for measuring the acid value described later. [Examples 2 to 5 and Comparative Examples 1 to 3] The compositions of the monomers are shown in Group (1) and Group (2) of Table 1, respectively. Examples 2 to 5 and Acrylic polymer solutions used in Comparative Examples 1 to 3.

＜黏著劑組合物、黏著劑層及黏著膜的製備＞ [實施例1] 對於如上所述製備的實施例1的丙烯酸類聚合物溶液，加入0.5重量份的CORONATE L（甲苯二異氰酸酯（TDI）化合物的三羥甲基丙烷（TMP）加成體的75%醋酸乙酯溶液）、0.2重量份的KBM-803（3-巰基丙基三甲氧基矽烷），攪拌混合，得到實施例1的黏著劑組合物。將該黏著劑組合物塗佈於離型膜（經矽氧樹脂塗佈的聚對苯二甲酸乙二醇酯（PET）膜）上後，通過在90℃下進行乾燥去除溶劑後，在23℃、50%RH的氣氛下，進行7天熟化，由此得到在離型膜的單面上具有由黏著劑組合物交聯而成的黏著劑層的實施例1的黏著膜。 [實施例2~5及比較例1~3] 添加劑的組成分別如表1的（3）組~（6）組所示，除此之外，以與上述實施例1的黏著膜相同地方式，得到實施例2~5及比較例1~3的黏著膜。在實施例3~5及比較例2的黏著膜中，對黏著劑組合物交聯而成的黏著劑層照射紫外線，進一步進行紫外線硬化。<Preparation of Adhesive Composition, Adhesive Layer and Adhesive Film> [Example 1] To the acrylic polymer solution of Example 1 prepared as described above, 0.5 parts by weight of CORONATE L (trimethylolpropane (TMP) adduct of toluene diisocyanate (TDI) compound) in 75% ethyl acetate solution was added ), 0.2 parts by weight of KBM-803 (3-mercaptopropyltrimethoxysilane), stirred and mixed to obtain the adhesive composition of Example 1. After coating this adhesive composition on a release film (polyethylene terephthalate (PET) film coated with silicone resin), after removing the solvent by drying at 90°C, ° C and 50% RH atmosphere, aging was performed for 7 days to obtain the adhesive film of Example 1 having an adhesive layer crosslinked from the adhesive composition on one side of the release film. [Examples 2 to 5 and Comparative Examples 1 to 3] The compositions of the additives are shown in Groups (3) to (6) of Table 1, respectively. Examples 2 to 5 and Comparative Examples 1 to 3 were obtained in the same manner as the adhesive film of Example 1 above. of adhesive film. In the adhesive films of Examples 3 to 5 and Comparative Example 2, the adhesive layer obtained by crosslinking the adhesive composition was irradiated with ultraviolet rays to further perform ultraviolet curing.

[表1]   (1)組 (2)組 (3)組 (4)組 (5)組 (6)組 實施例1 BA (80) MA (20) 8HOA (1.0) L (0.5) KBM-803 (0.2) - - 實施例2 IOA (60) TBA (30) DEAA (10) 6HHA (0.5) 4HBA (0.5) D-110N (0.5) KBE-9007 (0.2) - - 實施例3 BA (60) 2EHA (30) IBXA (10) 4HBA (0.2) HEA (0.3) D-170N (1.0) X-41-1805 (0.15) TPGDA (1) BDDA (1) Irg651 (0.1) 實施例4 2EHA (70) TBA (25) DEAA (5) 6HHA (0.5) HEA (2.0) Aac (0.1) D-170N (0.5) KBM-803 (0.1) TEGDA (1) HDDA (3) Irg184 (0.2) 實施例5 IOA (80) MA (10) IBXA (10) HEA (2.5) D-110N (0.1) D-170N (0.2) KBM-803 (0.15) TMPTA (3) Dar1173 (0.2) 比較例1 2EHA (80) TBA (20) 6HHA (0.05) D-110N (0.2) - - - 比較例2 BA (90) MA (10) HEA (4) L (1.0) KBM-803 (0.2) PETA (3) Irg184 (2.2) 比較例3 IOA (90) MA (10) 4HBA (0.5) - - - - [Table 1] (Group 1 (2 teams (3) group (4) group (5) group (6) group Example 1 BA (80) MA (20) 8HOA (1.0) L (0.5) KBM-803 (0.2) - - Example 2 IOA (60) TBA (30) DEAA (10) 6HHA (0.5) 4HBA (0.5) D-110N (0.5) KBE-9007 (0.2) - - Example 3 BA (60) 2EHA (30) IBXA (10) 4HBA (0.2) HEA (0.3) D-170N (1.0) X-41-1805 (0.15) TPGDA (1) BDDA (1) Irg651 (0.1) Example 4 2EHA (70) TBA (25) DEAA (5) 6HHA (0.5) HEA (2.0) Aac (0.1) D-170N (0.5) KBM-803 (0.1) TEGDA (1) HDDA (3) Irg184 (0.2) Example 5 IOA (80) MA (10) IBXA (10) HEA (2.5) D-110N (0.1) D-170N (0.2) KBM-803 (0.15) TMPTA (3) Dar1173 (0.2) Comparative example 1 2EHA (80) TBA (20) 6HHA (0.05) D-110N (0.2) - - - Comparative example 2 BA (90) MA (10) HEA (4) L (1.0) KBM-803 (0.2) PETA (3) Irg184 (2.2) Comparative example 3 IOA (90) MA (10) 4HBA (0.5) - - - -

在表1中，要求（1）組的烷基的碳原子數為C1 ~C14 的（甲基）丙烯酸烷基酯單體、含脂環族的單體、含支鏈結構烷基的單體所構成的單體組的總量為100重量份。此外，作為（2）組~（6）組的添加比例，用括弧將重量份的數值括出表示。 此外，（2）組為由含羥基的共聚性乙烯基單體及含羧基的共聚性乙烯基單體構成的單體組。（3）組為交聯劑。（4）組為矽烷偶聯劑。（5）組為多官能基丙烯酸酯單體。（6）組為光聚合起始劑。In Table 1, the alkyl (meth)acrylate monomers, alicyclic-containing monomers, and branched-chain alkyl-containing monomers are required to have the carbon atoms of the alkyl groups in group (1) ranging from C 1 to C 14 . The total amount of the monomer group composed of monomers is 100 parts by weight. In addition, as the addition ratio of the (2) group to (6) group, the numerical values of parts by weight are enclosed in parentheses and shown. In addition, group (2) is a monomer group composed of a hydroxyl group-containing copolymerizable vinyl monomer and a carboxyl group-containing copolymerizable vinyl monomer. (3) The group is a cross-linking agent. (4) Group is silane coupling agent. (5) The group is multifunctional acrylate monomer. (6) The group is a photopolymerization initiator.

此外，表1中使用的各成分的縮寫符號的化合物名如表2所示。另外，CORONATE （註冊商標）L為日本聚氨酯工業股份公司的商品名，D-110N及D-170N為三井化學股份公司的商品名，KBM-803（上述）、KBE-9007（3-異氰酸酯丙基三乙氧基矽烷）及X-41-1805（含巰基的矽氧烷氧基寡聚物）為信越化學工業股份公司的商品名。TDI表示甲苯二異氰酸酯，TMP表示三羥甲基丙烷，XDI表示苯二亞甲基二異氰酸酯，HDI表示六亞甲基二異氰酸酯。IRGACURE（註冊商標）651（2,2-二甲氧基-1,2-二苯基乙烷-1-酮）、IRGACURE（註冊商標）184（1-羥基-環己基-苯基-酮）、DAROCUR（註冊商標）1173（2-羥基-2-甲基-1-苯基-丙烷-1-酮）為BASF社的商品名。In addition, the compound names of the abbreviated symbols of each component used in Table 1 are as shown in Table 2. In addition, CORONATE (registered trademark) L is a trade name of Japan Polyurethane Industry Co., Ltd., D-110N and D-170N are trade names of Mitsui Chemicals Co., Ltd., KBM-803 (above), KBE-9007 (3-isocyanate propyl Triethoxysilane) and X-41-1805 (mercapto-containing siloxaneoxy oligomer) are trade names of Shin-Etsu Chemical Co., Ltd. TDI means toluene diisocyanate, TMP means trimethylolpropane, XDI means xylylene diisocyanate, HDI means hexamethylene diisocyanate. IRGACURE (registered trademark) 651 (2,2-dimethoxy-1,2-diphenylethan-1-one), IRGACURE (registered trademark) 184 (1-hydroxy-cyclohexyl-phenyl-one) , DAROCUR (registered trademark) 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one) are trade names of BASF Corporation.

[表2] 組 縮寫符號 化合物名 (1)組 2EHA 丙烯酸2-乙基己酯 IOA 丙烯酸異辛酯 BA 丙烯酸丁酯 MA 丙烯酸甲酯 IBXA 丙烯酸異冰片酯 TBA 丙烯酸叔丁酯 DEAA 二乙基丙烯醯胺 (2)組 8HOA 丙烯酸8-羥基辛酯 6HHA 丙烯酸6-羥基己酯 4HBA 丙烯酸4-羥基丁酯 HEA 丙烯酸2-羥基乙酯 Aac 丙烯酸 (3)組 L CORONATE L：TDI的TMP加成體（75%醋酸乙酯溶液） D-110N D-110N：XDI加成體 D-170N D-170N：HDI的異氰脲酸酯 (4)組 KBM-803 KBM-803：信越化學制 KBE-9007 KBE-9007：信越化學制 X-41-1805 X-41-1805：信越化學制 (5)組 TPGDA 三丙二醇二丙烯酸酯 TEGDA 四乙二醇二丙烯酸酯 BDDA 1,4-丁二醇二丙烯酸酯 HDDA 1,6-己二醇二丙烯酸酯 TMPTA 三羥甲基丙烷三丙烯酸酯 PETA 季戊四醇四丙烯酸酯 (6)組 Irg651 IRGACURE　651：BASF制 Irg184 IRGACURE　184：BASF制 Dar1173 DAROCUR　1173：BASF制 [Table 2] Group Abbreviation Compound name (Group 1 2EHA 2-Ethylhexyl Acrylate IOA Isooctyl acrylate BA Butyl acrylate MA Methyl acrylate IBXA Isobornyl Acrylate TBA tert-butyl acrylate DEAA Diethylacrylamide (2 teams 8HOA 8-Hydroxyoctyl Acrylate 6HHA 6-Hydroxyhexyl Acrylate 4HBA 4-Hydroxybutyl Acrylate HEA 2-Hydroxyethyl Acrylate Aac acrylic acid (3) group L CORONATE L: TMP adduct of TDI (75% ethyl acetate solution) D-110N D-110N: XDI adduct D-170N D-170N: Isocyanurate of HDI (4) group KBM-803 KBM-803: Shin-Etsu Chemical KBE-9007 KBE-9007: Shin-Etsu Chemical X-41-1805 X-41-1805: Shin-Etsu Chemical (5) group TPGDA Tripropylene glycol diacrylate TEGDA Tetraethylene glycol diacrylate BDDA 1,4-Butanediol diacrylate HDDA 1,6-Hexanediol diacrylate TMPTA trimethylolpropane triacrylate PETA pentaerythritol tetraacrylate (6) group Irg651 IRGACURE 651: Made by BASF Irg184 IRGACURE 184: Made by BASF Dar1173 DAROCUR 1173: Made by BASF

＜試驗方法及評估＞ 從實施例1~5及比較例1~3的黏著膜上剝離離型膜（經過矽氧樹脂塗佈的PET膜），露出黏著劑層，按照下述的試驗方法及測定方法進行評估。＜Test method and evaluation＞ The release film (PET film coated with silicone resin) was peeled off from the adhesive films of Examples 1-5 and Comparative Examples 1-3 to expose the adhesive layer, and evaluated according to the following test methods and measurement methods.

<黏著力的測定方法> <Measuring method of adhesion>

在厚度50μm的聚酯膜的單面上，轉印厚度175μm的黏著劑層，得到試樣黏著膜(帶有黏著劑層的光學膜)。 On one side of a polyester film with a thickness of 50 μm, an adhesive layer with a thickness of 175 μm was transferred to obtain a sample adhesive film (optical film with an adhesive layer).

用壓輥將得到的黏著膜貼合在經丙酮清洗過的無鹼玻璃的非錫面上，在50℃、0.5MPa×20分鐘的條件下經過高壓釜處理後，回到23℃×50%RH的氣氛下，經過1小時。然後，通過拉伸試驗機，以JIS Z0237“黏著帶．黏著片試驗方法”為標準測定黏著膜的剝離強度，以在180°方向以300mm/分鐘的速度進行剝離時的剝離強度為黏著膜的黏著劑層的黏著力(N/25mm)。 Use a pressure roller to attach the obtained adhesive film to the non-tin surface of the alkali-free glass cleaned with acetone. Under the atmosphere of RH, 1 hour passed. Then, the peel strength of the adhesive film is measured by a tensile testing machine in accordance with JIS Z0237 "Adhesive tape. Adhesive sheet test method" as the standard, and the peel strength of the adhesive film is defined as the peel strength when peeled at a speed of 300mm/min in the 180° direction. Adhesive force of the adhesive layer (N/25mm).

<凝膠分率的測定方法> <Measuring method of gel fraction>

正確測定黏著劑層的、測定試樣的質量，在甲苯中浸漬24小時後，使用200目的金屬網過濾。然後，將濾出物在100℃下乾燥1小時後，正確測定殘渣的質量，通過以下的公式計算黏著劑層(交聯後的黏著劑)的凝膠分率。 To accurately measure the adhesive layer, measure the mass of the sample, immerse in toluene for 24 hours, and filter through a 200-mesh metal mesh. Then, after drying the filtrate at 100° C. for 1 hour, the mass of the residue was accurately measured, and the gel fraction of the adhesive layer (crosslinked adhesive) was calculated by the following formula.

凝膠分率(%)=不溶部分質量(g)/黏著劑質量(g)×100 Gel fraction (%)=insoluble part mass (g)/adhesive mass (g)×100

在實施例3~5及比較例2的黏著膜中，在通過熟化進行交聯後，分別測定紫外線照射前與紫外線照射後的黏著劑層的凝膠分率，向右箭頭(

Figure 110101792-A0305-02-0022-2
)的左側記載紫外線照射前的值，右側記載紫外線照射後的值。 In the adhesive films of Examples 3 to 5 and Comparative Example 2, after crosslinking by aging, the gel fractions of the adhesive layers before and after ultraviolet irradiation were measured respectively, and the right arrow (
Figure 110101792-A0305-02-0022-2
) shows the value before ultraviolet irradiation on the left side, and the value after ultraviolet irradiation on the right side.

<耐久性的試驗方法> <Durability test method>

將以黏著力的測定方法相同的方法製作的10cm見方的黏著膜通過相同的方法貼合在無鹼玻璃的非錫面上，製成試樣，將其在規定的氣氛(80℃乾燥氣氛或60℃×90%RH的氣氛)下放置250小時後，取出置於23℃×50%RH氣氛下，在1小時後目視觀察黏著膜的狀態，判斷耐久性。 A 10cm square adhesive film made in the same way as the method for measuring the adhesion is attached to the non-tin surface of the alkali-free glass by the same method to make a sample, and it is placed in a specified atmosphere (80°C dry atmosphere or (60°C x 90%RH atmosphere) for 250 hours, then take it out and place it in a 23°C x 50%RH atmosphere, and observe the state of the adhesive film visually after 1 hour to judge the durability.

○：完全沒有黏著膜的剝落及起泡。 ◯: No peeling and blistering of the adhesive film at all.

△：部分黏著膜發生剝落及起泡。 △: Partial peeling and blistering of the adhesive film occurred.

×：黏著膜的整體發生剝落及起泡。x: Peeling and blistering occurred in the whole adhesive film.

＜存儲彈性模量的測定方法＞ 將厚度為1000μm的黏著劑層作為試樣，用剪切型流變儀（Anton Paar公司，裝置名 MCR301）在頻率1Hz的條件下實施動態黏彈性試驗。存儲彈性模量的測定值為100℃下的值。<Measurement method of storage elastic modulus> The adhesive layer having a thickness of 1000 μm was used as a sample, and a dynamic viscoelasticity test was carried out at a frequency of 1 Hz using a shear rheometer (Anton Paar, device name MCR301). The measured value of the storage elastic modulus is a value at 100°C.

＜剪切力導致的歪斜及回復力的試驗方法＞ 將厚度為1000μm的黏著劑層作為試樣，測定在荷載1N下保持30分鐘500Pa剪切力時的歪斜A（%）及之後使剪切力為0時的歪斜B（%）。使黏著劑層的厚度為y，剪切方向（垂直於厚度的方向）的位移為Δx時，通過下式求出剪切導致的歪斜。 剪切歪斜＝（Δx/ｙ）×100（%） 歪斜B若為0%（回到施加荷載前的形狀），則回復力為100%，歪斜B若等於歪斜A（歪斜永久殘留），則回復力為0%，以此方式通過下式求出歪斜的回復力。 回復力＝（A-B）/A×100（%）<Test method for deflection and restoring force due to shear force> The adhesive layer with a thickness of 1000 μm was used as a sample, and the deflection A (%) when the shear force of 500 Pa was maintained under a load of 1 N for 30 minutes and the deflection B (%) when the shear force was made to 0 were measured. When the thickness of the adhesive layer is y and the displacement in the shearing direction (direction perpendicular to the thickness) is Δx, the distortion caused by shearing can be obtained from the following formula. Shear skew = (Δx/y) × 100 (%) If the skew B is 0% (returns to the shape before the load is applied), the restoring force is 100%, and if the skew B is equal to the skew A (the skew remains permanently), the restoring force is 0%. In this way, it can be obtained by the following formula Skew resilience. Resilience = (A-B)/A×100 (%)

＜段差追隨性的試驗方法＞ 在0.7mm的玻璃板的表面上貼合厚度175μm的黏著劑層，然後，用真空貼合裝置，在真空度為-100kPa的條件下，從其上以壓力80kPa貼合具有印刷段差42μm的厚度1.1mm的蓋板玻璃。進一步，在溫度60℃、6個大氣壓、30分鐘的條件下，進行高壓釜處理，以目視確認段差追隨性。目視確認的判定標準如下所述。 ○：追隨印刷段差，印刷段差的周圍完全不起泡。 △：印刷段差的周圍少許起泡。 ×：印刷段差的周圍起泡。＜Test method for step followability＞ Bond an adhesive layer with a thickness of 175 μm on the surface of a 0.7 mm glass plate, and then, use a vacuum bonding device to bond a thickness of 42 μm with a printing step at a pressure of 80 kPa under a vacuum of -100 kPa 1.1mm cover glass. Further, autoclave treatment was performed under the conditions of a temperature of 60° C., a pressure of 6 atmospheres, and 30 minutes, and step followability was visually confirmed. Judgment criteria for visual confirmation are as follows. ◯: Follows the printing step, and there is no blistering around the printing step. Δ: Slight blistering around the printing steps. ×: Blisters around the printing steps.

＜酸價的測定方法＞ 丙烯酸類聚合物的酸價為，將試樣溶於溶劑（***與乙醇以體積比2:1混合的物質)，使用電位差自動滴定裝置(京都電子工業製，AT-610)，用濃度約0.1mol/l的氫氧化鉀乙醇溶液進行電位差滴定，測定用於中和試樣所需的氫氧化鉀乙醇溶液的量。然後，通過下式求出酸價。 ＜Measuring method of acid value＞ The acid value of the acrylic polymer is: Dissolve the sample in a solvent (diethyl ether and ethanol mixed at a volume ratio of 2:1), and use a potentiometric automatic titration device (manufactured by Kyoto Denshi Kogyo, AT-610) with a concentration of about 0.1 Potentiometric titration with mol/l potassium hydroxide ethanol solution to determine the amount of potassium hydroxide ethanol solution needed to neutralize the sample. Then, the acid value was calculated|required by the following formula.

酸價=(B×f×5.611)/S Acid value=(B×f×5.611)/S

B=用於滴定的0.1mol/l氫氧化鉀乙醇溶液的量(ml) B = the amount of 0.1mol/l potassium hydroxide ethanol solution used for titration (ml)

f=0.1mol/l氫氧化鉀乙醇溶液的因數 f=factor of 0.1mol/l potassium hydroxide ethanol solution

S=試樣的固體成分的質量(g) S=mass of the solid content of the sample (g)

<總透光率的測定方法> <Measurement method of total light transmittance>

透光率的測定方法：JIS K7105，根據“塑膠的光學特性試驗方法”測定總透光率。 Measuring method of light transmittance: JIS K7105, according to "Test method for optical properties of plastics", measure total light transmittance.

<霧度值的測定方法> <Measurement method of haze value>

霧度值的測定方法：JIS K7136，根據“塑膠-透明材料的霧度的計算方法”測定霧度值。 Measuring method of haze value: According to JIS K7136, the haze value is measured in accordance with "Calculation method of haze of plastic-transparent material".

在表3及表4中，表示出實施例1~5及比較例1~3的評估結果。在表3的存儲彈性模量的測定結果中，100000Pa表示為1.0E+05(1.0×105)。 In Table 3 and Table 4, the evaluation results of Examples 1-5 and Comparative Examples 1-3 are shown. In the measurement results of the storage elastic modulus in Table 3, 100000 Pa is expressed as 1.0E+05 (1.0×10 5 ).

Figure 110101792-A0305-02-0024-1
Figure 110101792-A0305-02-0024-1

[表4]   剪切力 歪斜 (%) 剪切力 回復力 (%) 段差 追隨性 酸價 全光線 穿透率 (%) 霧度值 (%) 實施例1 20.5 58.0 ○ 0.0 92.50 0.2 實施例2 25.0 54.4 ○ 0.0 92.50 0.2 實施例3 39.5 62.5 ○ 0.0 93.50 0.2 實施例4 39.1 69.5 ○ 0.4 92.60 0.3 實施例5 28.5 63.6 ○ 0.0 91.50 0.2 比較例1 16.0 8.5 × 0.0 91.60 0.2 比較例2 5.3 52.0 × 0.0 90.50 0.3 比較例3 45.5 2.5 × 0.0 91.00 0.2 [Table 4] Shear skew (%) Shear force recovery force (%) Follow-up acid value Total light transmittance (%) Haze value (%) Example 1 20.5 58.0 ○ 0.0 92.50 0.2 Example 2 25.0 54.4 ○ 0.0 92.50 0.2 Example 3 39.5 62.5 ○ 0.0 93.50 0.2 Example 4 39.1 69.5 ○ 0.4 92.60 0.3 Example 5 28.5 63.6 ○ 0.0 91.50 0.2 Comparative example 1 16.0 8.5 x 0.0 91.60 0.2 Comparative example 2 5.3 52.0 x 0.0 90.50 0.3 Comparative example 3 45.5 2.5 x 0.0 91.00 0.2

對於本發明的實施例1~5的黏著劑層，交聯後的黏著劑層的凝膠分率為40~75%，黏著劑層在積層至1000μm的厚度時測定的1Hz、100℃下的存儲彈性模量為100000Pa以下，在荷載1N下持續施加30分鐘500Pa剪切力時的歪斜為15%以上，且之後的歪斜回復力為50%以上，耐久性及段差追隨性優異。此外，在基材的單面上積層至175μm的厚度時的黏著力為20N/25mm以上，黏著力優異。此外，總透光率為90%以上，且霧度值為1.0%以下，光學特性也優異。即根據本發明的實施例1~5的黏著劑層，能夠克服現有技術中的要求事項及問題。For the adhesive layers of Examples 1 to 5 of the present invention, the gel fraction of the crosslinked adhesive layer is 40 to 75%, and the adhesive layer is laminated to a thickness of 1000 μm at 1 Hz and 100 ° C. The storage elastic modulus is 100,000 Pa or less, and the deflection when a 500 Pa shear force is continuously applied under a load of 1N for 30 minutes is 15% or more, and the subsequent deflection recovery force is 50% or more, and the durability and step followability are excellent. In addition, the adhesive force when laminated on one side of the base material to a thickness of 175 μm was 20 N/25 mm or more, and the adhesive force was excellent. In addition, the total light transmittance is 90% or more, the haze value is 1.0% or less, and the optical properties are also excellent. That is, according to the adhesive layers of Examples 1 to 5 of the present invention, the requirements and problems in the prior art can be overcome.

比較例1的黏著劑層使用在丙烯酸類聚合物中含羥基的共聚性乙烯基單體的含量少的黏著劑組合物而製備，黏著劑層的凝膠分率為1%，歪斜回復力低，耐久性及段差追隨性差。 比較例2的黏著劑層使用在一分子中具有4個丙烯醯基的多官能基丙烯酸酯單體並使其紫外線硬化，因此在1Hz、100℃下的存儲彈性模量高，耐久性及段差追隨性差。 比較例3的黏著劑層使用不含交聯劑的黏著劑組合物製備，由於黏著劑組合物不交聯，黏著劑層的凝膠分率為0%，歪斜回復力低，耐久性及段差追隨性差。 因此，比較例1~3的黏著劑層沒能夠克服現有技術中的要求事項及問題。The adhesive layer of Comparative Example 1 was prepared using an adhesive composition containing a small amount of a hydroxyl group-containing copolymerizable vinyl monomer in the acrylic polymer, and the gel fraction of the adhesive layer was 1%, and the skew recovery force was low. , poor durability and step difference followability. The adhesive layer of Comparative Example 2 uses a polyfunctional acrylate monomer having 4 acryl groups in one molecule and hardens it with ultraviolet rays, so the storage elastic modulus at 1Hz and 100°C is high, and the durability and step difference are high. Poor followability. The adhesive layer of Comparative Example 3 was prepared using an adhesive composition that did not contain a cross-linking agent. Since the adhesive composition was not cross-linked, the gel fraction of the adhesive layer was 0%, the skew recovery force was low, and the durability and step difference were low. Poor followability. Therefore, the adhesive layers of Comparative Examples 1 to 3 could not overcome the requirements and problems in the prior art.

無。none.

無。none.

Claims (3)

一種黏著劑組合物，其特徵在於，其為含有丙烯酸類聚合物、交聯劑、多官能基丙烯酸酯單體、光聚合起始劑與矽烷偶聯劑的黏著劑組合物，所述丙烯酸類聚合物為由從(A)烷基的碳原子數C1~C14的丙烯酸烷基酯單體、(C)含支鏈結構烷基的單體和(D)含氮的乙烯基單體所構成的單體組中選擇的至少一種以上的單體的總量100重量份與(E)含羥基的共聚性乙烯基單體的至少一種以上的總量0.1~10.0重量份，不包含含脂環族的單體進行共聚而得到的共聚物，所述(A)烷基的碳原子數為C1~C14的丙烯酸烷基酯單體為從丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸戊酯、丙烯酸己酯、丙烯酸庚酯、丙烯酸辛酯、及丙烯酸壬基酯所構成的組中選擇的至少一種以上，所述(C)含支鏈結構烷基的單體為從(甲基)丙烯酸異丙酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、及(甲基)丙烯酸異壬酯所構成的組中選擇的至少一種以上，所述(E)含羥基的共聚性乙烯基單體為由(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基乙酯所構成的化合物組中選擇的至少一種以上，所述多官能基丙烯酸酯單體為在一分子中具有2~3個丙烯醯基的化合物且為由乙二醇二丙烯酸酯、二乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、丙二醇二丙烯酸酯、二丙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、1,3-丙二醇二丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,5-戊二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、甘油三丙烯酸酯、三羥甲基乙烷三丙烯酸酯、三羥甲基丙 烷三丙烯酸酯、季戊四醇三丙烯酸酯、二季戊四醇三丙烯酸酯所構成的化合物組中選擇的至少一種，所述丙烯酸類聚合物的酸價為1以下，相對於從所述單體組中選擇的至少一種以上的總量100重量份，所述黏著劑組合物含有0.01~3.0重量份的作為所述交聯劑的異氰酸酯化合物、0.1~10重量份的所述多官能基丙烯酸酯單體、0.01~2.0重量份的所述光聚合起始劑與0.01~2.0重量份的所述矽烷偶聯劑。 An adhesive composition, characterized in that it is an adhesive composition containing an acrylic polymer, a crosslinking agent, a multifunctional acrylate monomer, a photopolymerization initiator and a silane coupling agent, and the acrylic The polymer is composed of (A) alkyl acrylate monomers with C 1 ~C 14 carbon atoms, (C) monomers containing branched alkyl groups and (D) nitrogen-containing vinyl monomers The total amount of 100 parts by weight of at least one or more monomers selected in the constituted monomer group and the total amount of 0.1 to 10.0 parts by weight of at least one or more of (E) hydroxyl-containing copolymerizable vinyl monomers, excluding A copolymer obtained by copolymerizing alicyclic monomers, the (A) alkyl acrylate monomer having C 1 to C 14 carbon atoms is selected from methyl acrylate, ethyl acrylate, propylene acrylate At least one selected from the group consisting of ester, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, and nonyl acrylate. The monomer is from isopropyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isopentyl (meth)acrylate, isooctyl (meth)acrylate, ( At least one or more selected from the group consisting of 2-ethylhexyl methacrylate and isononyl (meth)acrylate, the (E) hydroxyl-containing copolymerizable vinyl monomer is composed of (methyl ) At least one selected from the compound group consisting of 8-hydroxyoctyl acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate Above, the multifunctional acrylate monomer is a compound having 2 to 3 acryl groups in one molecule and is composed of ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate ester, tetraethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1,3-propylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5 -Pentylene Glycol Diacrylate, 1,6-Hexanediol Diacrylate, Glycerin Triacrylate, Trimethylolethane Triacrylate, Trimethylolpropane Triacrylate, Pentaerythritol Triacrylate, Dipentaerythritol At least one selected from the compound group consisting of triacrylate, the acid value of the acrylic polymer is 1 or less, relative to 100 parts by weight of the total amount of at least one selected from the monomer group, the The adhesive composition contains 0.01-3.0 parts by weight of the isocyanate compound as the crosslinking agent, 0.1-10 parts by weight of the multifunctional acrylate monomer, and 0.01-2.0 parts by weight of the photopolymerization initiator and 0.01-2.0 parts by weight of the silane coupling agent. 一種觸控面板用黏著膜，其通過在基材的單面上積層由如申請專利範圍第1項所述之黏著劑組成物交聯而成的黏著劑層而成。 An adhesive film for a touch panel, which is formed by laminating an adhesive layer formed by cross-linking the adhesive composition described in item 1 of the patent application on one side of a base material. 一種帶有黏著劑層的光學膜，其由在光學膜的至少一個面上積層由如申請專利範圍第1項所述之黏著劑組成物交聯而成的黏著劑層而成。An optical film with an adhesive layer, which is formed by laminating an adhesive layer formed by cross-linking the adhesive composition described in item 1 of the scope of the patent application on at least one surface of the optical film.
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