TW202104504A - Adhesive layer and adhesive film - Google Patents

Adhesive layer and adhesive film Download PDF

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TW202104504A
TW202104504A TW109129507A TW109129507A TW202104504A TW 202104504 A TW202104504 A TW 202104504A TW 109129507 A TW109129507 A TW 109129507A TW 109129507 A TW109129507 A TW 109129507A TW 202104504 A TW202104504 A TW 202104504A
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meth
group
acrylate
adhesive layer
adhesive
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TW109129507A
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Chinese (zh)
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TWI754363B (en
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長倉毅
長谷川良
吉田弘幸
菱沼昌世
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日商藤森工業股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • 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
    • 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
    • C09J133/10—Homopolymers or copolymers of methacrylic 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
    • C09J7/00—Adhesives in the form of films or foils
    • 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
    • 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer

Abstract

An adhesion layer and an adhesion film are provided. The surface hardness of the adhesion layer can be measure without error even when it is adhered to a stacking of an optical component used for adhering of layers in optical components. In addition, the adhesion layer has good durability and reworkability. The optical component is adhered to non-alkali glass by the adhesion layer, and its value of the pencil hardness of the surface and the value of the pencil hardness of the surface of the optical component, which is over 2H. In the adhesion layer, after the acrylic polymer crosslinks with 0.01 to 1.0 parts by weight of the crosslinking agent, isocyanate compound, the gel fraction is 40 to 85%, and the thickness is 1μm-20μm. When the thickness of the adhesion layer is 10μm, the adhesion force is 1.5-8.0N/25m. The acrlic polymer is formed by copolymerizing a total amount of 100 parts by weight of (Methyl) acrylic monomer as the main portion and 0.1 to 10 parts by weight of hydroxyl group-containing copolymerizable vinyl monomer, and its acid value is less than 0.1, and the weight average molecular weight is less than 1,000,000.

Description

黏著劑層及黏著薄膜Adhesive layer and adhesive film

本發明涉及一種用於光學部件的層間貼合等的厚度為1μm~20μm的薄膜的黏著劑層，以及將該黏著劑層夾設在離型膜之間的黏著薄膜。The present invention relates to an adhesive layer of a film with a thickness of 1 μm to 20 μm used for interlayer bonding of optical components, and an adhesive film in which the adhesive layer is sandwiched between release films.

近年來，在液晶面板上外置有靜電電容式的觸控面板的各種顯示裝置被廣泛用於例如智慧手機、平板終端、平板PC等。在這樣的顯示裝置中，液晶面板與觸控面板之間存在有物理的空間。因此，在液晶面板的上面或觸控面板的下面，外部光等發生反射，特別是存在在屋外等明亮環境下的辨識性降低的問題。In recent years, various display devices with capacitive touch panels externally mounted on liquid crystal panels have been widely used, for example, in smartphones, tablet terminals, and tablet PCs. In such a display device, there is a physical space between the liquid crystal panel and the touch panel. Therefore, external light or the like is reflected on the upper surface of the liquid crystal panel or the lower surface of the touch panel, and there is a problem that the visibility in bright environments such as outdoors is reduced.

作為解決該辨識性降低的問題的方法，提出了將觸控面板的功能嵌入液晶圖元中的In-cell方式的顯示裝置（例如，參照專利文獻1）。但是，由於因經過了複雜的製造步驟而使產品的成品率降低、在技術上難以提高畫面的顯示性能等原因而無法實用化。As a method for solving the problem of reduced visibility, an in-cell display device in which the function of a touch panel is embedded in a liquid crystal cell has been proposed (for example, refer to Patent Document 1). However, it cannot be put into practical use due to the reduction in the yield of the product due to the complicated manufacturing steps and the technical difficulty in improving the display performance of the screen.

此外，在最近，提出了一種On-cell方式的顯示裝置（例如，參照專利文獻2）。On-cell方式的顯示裝置為，在彩色濾光片與偏光板之間形成由透明電極圖案構成的觸摸感測器，將觸控面板的功能置於彩色濾光片基板與偏光板之間。On-cell方式具有產品的成品率降低少這一優點。因此，On-cell方式作為嵌入了觸控面板的液晶面板的有前途的製備技術，其今後的發展備受期待。 [先行技術文獻] [專利文獻]In addition, recently, an on-cell display device has been proposed (for example, refer to Patent Document 2). In the on-cell display device, a touch sensor composed of a transparent electrode pattern is formed between the color filter and the polarizing plate, and the function of the touch panel is placed between the color filter substrate and the polarizing plate. The on-cell method has the advantage of less reduction in product yield. Therefore, the on-cell method is a promising manufacturing technology for liquid crystal panels embedded with touch panels, and its future development is highly anticipated. [Advanced Technical Literature] [Patent Literature]

專利文獻1：特開2009-258182號公報 專利文獻2：特開2014-044501號公報Patent Document 1: Japanese Patent Application Publication No. 2009-258182 Patent Document 2: Japanese Patent Application Publication No. 2014-044501

本發明要解決的技術問題Technical problem to be solved by the present invention

在上述各種顯示裝置中，由於對光學部件的層間進行貼合，因此廣泛使用了黏著劑層。但是，在光學部件的至少一個表面經硬塗層等表面處理而提高了表面硬度（例如，表面的鉛筆硬度為2H以上等）的光學部件的情況下，若用於光學部件的貼合的黏著劑層軟，且黏著劑層厚，則在測定貼合了光學部件的層積體的表面硬度時，存在產生測定誤差的問題。 該現象為：在貼合了光學部件的層積體的硬塗層上，用鉛筆觸碰時，即使光學部件本身的表面硬度高，由於光學部件的基材膜的薄膜化使剛性降低及黏著劑層軟，由此引起光學部件的凹陷，表觀上的表面硬度降低。In the various display devices described above, since the layers of optical components are bonded together, adhesive layers are widely used. However, in the case of an optical component whose surface hardness is increased by surface treatment such as a hard coat layer on at least one surface of the optical component (for example, the pencil hardness of the surface is 2H or more), if it is used for the bonding of the optical component If the agent layer is soft and the adhesive agent layer is thick, when measuring the surface hardness of the laminated body to which the optical component is bonded, there is a problem that measurement errors occur. This phenomenon is that even if the surface hardness of the optical component itself is high when touched with a pencil on the hard coat layer of the laminated body on which the optical component is bonded, the rigidity decreases and adhesion due to the thinning of the base film of the optical component The agent layer is soft, which causes dents in the optical component and lowers the apparent surface hardness.

本發明是鑒於上述情況而進行的，其課題在於提供一種即使用於光學部件的層間貼合，貼合了光學部件的層積體的表面硬度的測定值也不產生誤差，並兼具耐久性、再操作性的黏著劑層及黏著薄膜。 [解決技術問題的技術手段]The present invention has been made in view of the above circumstances, and its subject is to provide a method that does not cause errors in the measured value of the surface hardness of the laminated body to which the optical components are bonded, even if it is used for the interlayer bonding of optical components, and has durability. , Re-operable adhesive layer and adhesive film. [Technical means to solve technical problems]

為了解決上述技術課題，本發明與現有技術相比，將黏著劑層薄膜化，使其厚度為1μm~20μm，同時，即使是薄膜化的黏著劑層也具有與以往相同的黏著力。因此，技術思路為：作為主成分（甲基）丙烯酸類單體在選擇自由烷基的碳原子數為C1~C14的烷基（甲基）丙烯酸酯單體、具有芳香族基的（甲基）丙烯酸酯單體、含氮的乙烯基單體、具有脂環族的（甲基）丙烯酸酯單體構成的丙烯酸類單體的群組中的至少一種以上的單體的總量100重量份中，含有至少40重量份以上丙烯酸丁酯，進一步，為了減少黏著劑層的腐蝕性，不含含羧基的共聚性乙烯基單體的丙烯酸類聚合物。In order to solve the above technical problems, compared with the prior art, the present invention thins the adhesive layer to a thickness of 1 μm to 20 μm. At the same time, even the thinned adhesive layer has the same adhesive force as the conventional one. Therefore, the technical idea is as follows: as the main component (meth)acrylic monomers, the alkyl (meth)acrylate monomers with C1~C14 carbon atoms of the free alkyl group and the (meth)acrylate monomers with aromatic groups are selected as the main component (meth)acrylic monomers. ) 100 parts by weight of the total amount of at least one or more monomers in the group of acrylic monomers, nitrogen-containing vinyl monomers, and acrylic monomers composed of alicyclic (meth)acrylate monomers It contains at least 40 parts by weight or more of butyl acrylate, and further, in order to reduce the corrosiveness of the adhesive layer, it does not contain an acrylic polymer containing a carboxyl group-containing copolymerizable vinyl monomer.

為了解決上述技術課題，本發明提供一種黏著劑層，其特徵在於，在用於表面的鉛筆硬度為2H以上的光學部件與其他光學部件的層間的、由丙烯酸類聚合物構成的黏著劑組合物交聯而成的黏著劑層中，所述聚丙烯類聚合物在作為（1）主成分（甲基）丙烯酸類單體選擇自由烷基的碳原子數為C1~C14的烷基（甲基）丙烯酸酯單體、具有芳香族基的（甲基）丙烯酸酯單體、含氮的乙烯基單體、具有脂環族的（甲基）丙烯酸酯單體構成的丙烯酸類單體群組中的至少一種以上的單體的總量100重量份中，含有至少40重量份以上丙烯酸丁酯，不含含羧基的共聚性乙烯基單體，所述丙烯酸類聚合物的Tg為-35℃以上，所述黏著劑組合物含有丙烯酸類聚合物與相對於所述主成分（甲基）丙烯酸類單體的總量100重量份為0.01~1.0重量份的（3）作為交聯劑的異氰酸酯化合物，所述丙烯酸類聚合物由所述主成分（甲基）丙烯酸類單體的總量100重量份與0.1~10重量份（2）含羥基的共聚性乙烯基單體共聚而成的、酸值0.1以下、重量平均分子量100萬以上的共聚物構成，所述丙烯酸類聚合物交聯後的凝膠分率為40~85%，所述黏著劑層的厚度為1μm~20μm，厚度10μm的黏著劑層的黏著力為1.5~8.0N/25mm，將所述光學部件經由所述黏著劑層貼合於無鹼玻璃而測定的表面的鉛筆硬度的測定值與所述光學部件的表面的鉛筆硬度同為2H以上。In order to solve the above-mentioned technical problems, the present invention provides an adhesive layer characterized by an adhesive composition composed of an acrylic polymer between the layers of an optical component with a pencil hardness of 2H or more and other optical components used on the surface In the adhesive layer formed by cross-linking, the polypropylene-based polymer is selected as the main component (meth)acrylic monomer of (1) the alkyl group having C1 to C14 carbon atoms (methyl). ) Acrylic monomers, (meth)acrylate monomers with aromatic groups, nitrogen-containing vinyl monomers, and alicyclic (meth)acrylate monomers The total amount of at least one monomer of 100 parts by weight contains at least 40 parts by weight or more of butyl acrylate, and does not contain carboxyl group-containing copolymerizable vinyl monomers. The acrylic polymer has a Tg of -35°C or higher The adhesive composition contains an acrylic polymer and 0.01 to 1.0 parts by weight relative to 100 parts by weight of the main component (meth)acrylic monomer (3) an isocyanate compound as a crosslinking agent , The acrylic polymer is made by copolymerizing 100 parts by weight of the main component (meth)acrylic monomer and 0.1-10 parts by weight (2) a copolymerizable vinyl monomer containing a hydroxyl group. It is composed of a copolymer with a value of 0.1 or less and a weight average molecular weight of 1 million or more, the crosslinked gel fraction of the acrylic polymer is 40-85%, the thickness of the adhesive layer is 1μm-20μm, and the thickness is 10μm. The adhesive force of the adhesive layer is 1.5~8.0N/25mm, and the optical component is bonded to the alkali-free glass via the adhesive layer. The measured value of the pencil hardness of the surface and the pencil on the surface of the optical component are measured The hardness is also above 2H.

所述黏著劑組合物以還含有0.01~0.5重量份矽烷偶聯劑為佳。The adhesive composition preferably further contains 0.01 to 0.5 parts by weight of a silane coupling agent.

所述黏著劑組合物中含有的交聯劑為異氰酸酯化合物，以選擇自含有由甲苯二異氰酸酯的三羥甲基丙烷加成體及六亞甲基二異氰酸酯的異氰脲酸酯體中的至少一種以上為佳。The crosslinking agent contained in the adhesive composition is an isocyanate compound selected from at least one of the trimethylolpropane adduct containing toluene diisocyanate and the isocyanurate body of hexamethylene diisocyanate More than one kind is preferred.

所述黏著劑組合物中的（2）含羥基的共聚性乙烯基單體為選擇自由8-羥基辛基（甲基）丙烯酸酯、6-羥基己基（甲基）丙烯酸酯，4-羥基丁基（甲基）丙烯酸酯，2-羥基乙基（甲基）丙烯酸酯構成的化合物群組中的至少一種以上為佳。The (2) hydroxyl-containing copolymerizable vinyl monomer in the adhesive composition is selected from 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl At least one or more of the group of compounds composed of 2-hydroxyethyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate is preferred.

將所述黏著劑層貼合於黏被黏著體後，經70℃×10天保存後的黏著力為10N/25mm以下為佳。After the adhesive layer is attached to the adherend, the adhesive strength after storage at 70°C for 10 days is preferably 10N/25mm or less.

此外，本發明提供一種黏著薄膜，其特徵在於，所述黏著劑層形成於離型膜的單面上，其為離型膜/黏著劑層/離型膜的結構。In addition, the present invention provides an adhesive film, which is characterized in that the adhesive layer is formed on a single side of the release film, which has a release film/adhesive layer/release film structure.

此外，本發明提供一種黏著薄膜，其特徵在於，在基材的單面上，層積有所述黏著劑層。In addition, the present invention provides an adhesive film characterized in that the adhesive layer is laminated on a single surface of a substrate.

此外，本發明提供一種使用了所述黏著薄膜的、用於貼合偏光板與液晶顯示面板或有機電致發光顯示面板的黏著薄膜。In addition, the present invention provides an adhesive film for bonding a polarizing plate and a liquid crystal display panel or an organic electroluminescence display panel using the adhesive film.

此外，本發明提供一種使用了所述黏著薄膜的、帶有黏著劑層的偏光板。In addition, the present invention provides a polarizing plate with an adhesive layer using the adhesive film.

此外，本發明提供一種帶有黏著劑層的偏光板，其使用了所述黏著薄膜，並使用了具有λ/4及/或λ/2的相位差的相位差膜作為構成材料。In addition, the present invention provides a polarizing plate with an adhesive layer, which uses the adhesive film and uses a retardation film having a retardation of λ/4 and/or λ/2 as a constituent material.

此外，本發明提供一種帶有黏著劑層的光學膜，在該光學膜的至少一個面上層積有所述黏著劑層。 [發明效果]In addition, the present invention provides an optical film with an adhesive layer, and the adhesive layer is laminated on at least one surface of the optical film. [Effects of the invention]

根據本發明，能夠提供即使用於光學部件的層間貼合，也能夠維持表面硬度，並兼具耐久性、再操作性的黏著劑層及黏著薄膜。According to the present invention, it is possible to provide an adhesive layer and an adhesive film that can maintain surface hardness even when used for interlayer bonding of optical components, and have durability and reworkability.

以下，根據較佳的實施方式對本發明進行說明。 本發明的黏著劑層的特徵在於，在用於表面的鉛筆硬度為2H以上的光學部件與其他光學部件的層間的、由丙烯酸類聚合物構成的黏著劑組合物交聯而成的黏著劑層中，所述聚丙烯類聚合物在作為（1）主成分的（甲基）丙烯酸類單體選擇自由烷基的碳原子數為C1~C14的烷基（甲基）丙烯酸酯單體、具有芳香族基的（甲基）丙烯酸酯單體、含氮的乙烯基單體、具有脂環族的（甲基）丙烯酸酯單體構成的丙烯酸類單體群組中的至少一種以上的單體的總量100重量份中，含有至少40重量份以上丙烯酸丁酯，不含含羧基的共聚性乙烯基單體，所述丙烯酸類聚合物的Tg為-35℃以上，所述黏著劑組合物含有丙烯酸類聚合物、相對於總量100重量份的所述主成分的（甲基）丙烯酸類單體為0.01~1.0重量份的（3）作為交聯劑的異氰酸酯化合物，所述丙烯酸類聚合物由總量100重量份的所述主成分的（甲基）丙烯酸類單體與0.1~10重量份（2）含羥基的共聚性乙烯基單體共聚而成的共聚物構成，該共聚物的酸值0.1為以下，重量平均分子量為100萬以上，所述丙烯酸類聚合物交聯後的凝膠分率為40~85%，所述黏著劑層的厚度為1 μm~20μm，厚度10μm的黏著劑層的黏著力為1.5~8.0N/25mm，將所述光學部件經由所述黏著劑層貼合於無鹼玻璃而測定的表面的鉛筆硬度的測定值與所述光學部件的表面的鉛筆硬度同為2H以上。Hereinafter, the present invention will be described based on preferred embodiments. The adhesive layer of the present invention is characterized in that it is an adhesive layer formed by cross-linking an adhesive composition composed of an acrylic polymer between the optical component used on the surface with a pencil hardness of 2H or more and other optical components. In the polypropylene-based polymer, the (meth)acrylic monomer as the main component of (1) is selected from the alkyl (meth)acrylate monomer having C1 to C14 carbon atoms in the alkyl group. At least one monomer from the group of acrylic monomers consisting of aromatic (meth)acrylate monomers, nitrogen-containing vinyl monomers, and alicyclic (meth)acrylate monomers The total amount of 100 parts by weight contains at least 40 parts by weight or more of butyl acrylate and does not contain carboxyl group-containing copolymerizable vinyl monomers. The acrylic polymer has a Tg of -35°C or higher. The adhesive composition Containing an acrylic polymer, 0.01 to 1.0 parts by weight of the (meth)acrylic monomer relative to 100 parts by weight of the total amount of the main component (3) an isocyanate compound as a crosslinking agent, the acrylic polymerizing It is composed of a copolymer of 100 parts by weight of the main component (meth)acrylic monomer and 0.1-10 parts by weight (2) a copolymerizable vinyl monomer containing a hydroxyl group. The copolymer The acid value is less than 0.1, the weight average molecular weight is more than 1 million, the cross-linked gel fraction of the acrylic polymer is 40-85%, the thickness of the adhesive layer is 1 μm-20 μm, and the thickness is 10 μm The adhesive force of the adhesive layer is 1.5~8.0N/25mm, and the measured value of the pencil hardness of the surface measured by bonding the optical component to the alkali-free glass through the adhesive layer and the surface of the optical component The pencil hardness is also above 2H.

本發明的丙烯酸類聚合物為由屬於第一單體組的單體（主成分單體）與屬於第二單體組的單體（官能團單體）的各自一種以上共聚得到的共聚物。作為屬於第一單體組的單體，可使用選自由烷基的碳原子數為C1~C14的烷基（甲基）丙烯酸酯單體、具有芳香族基的丙烯酸酯單體、含氮的乙烯基單體、具有脂環族的（甲基）丙烯酸酯單體構成的單體群組中的至少一種以上。作為屬於第二單體組的單體，可使用含羥基的共聚性乙烯基單體的至少一種以上。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 present invention is a copolymer obtained by copolymerizing one or more types of monomers belonging to the first monomer group (main component monomers) and monomers belonging to the second monomer group (functional monomers). As monomers belonging to the first monomer group, C1-C14 alkyl (meth)acrylate monomers selected from alkyl groups, acrylate monomers having aromatic groups, and nitrogen-containing At least one or more of a monomer group consisting of a vinyl monomer and a (meth)acrylate monomer having an alicyclic group. As the monomer belonging to the second monomer group, at least one kind of hydroxyl group-containing copolymerizable vinyl monomer can be used. In this specification, (meth)acrylate is a general term for acrylate and methacrylate.

在本發明的黏著劑組合物中，作為烷基的碳原子數為C1~C14的烷基（甲基）丙烯酸酯單體，可列舉出（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸異丙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸叔丁酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸異戊酯、（甲基）丙烯酸己酯、（甲基）丙烯酸異己酯、（甲基）丙烯酸庚酯、（甲基）丙烯酸異庚酯、（甲基）丙烯酸辛酯、（甲基）丙烯酸異辛酯、2-乙基己基（甲基）丙烯酸酯、（甲基）丙烯酸壬酯、（甲基）丙烯酸異壬酯、（甲基）丙烯酸癸酯、（甲基）丙烯酸異癸酯、（甲基）丙烯酸十一烷酯、（甲基）丙烯酸異十一烷酯、（甲基）丙烯酸十二烷酯、（甲基）丙烯酸異十二烷酯、（甲基）丙烯酸十三烷酯、（甲基）丙烯酸異十三烷酯、（甲基）丙烯酸十四烷酯、（甲基）丙烯酸異十四烷酯等中的至少一種以上。烷基（甲基）丙烯酸酯單體的烷基可以是直鏈，也可以是分枝狀。 本發明的丙烯酸類聚合物以丙烯酸丁酯作為必要單體。丙烯酸類聚合物在屬於第一單體組的單體的總量100重量份中，含有丙烯酸丁酯的比例至少以40重量份以上為佳、較佳為50重量份以上、特佳為60重量份以上。In the adhesive composition of the present invention, examples of alkyl (meth)acrylate monomers having C1 to C14 carbon atoms in the alkyl group include methyl (meth)acrylate and ethyl (meth)acrylate. Ester, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, (meth)acrylic acid Amyl ester, isoamyl (meth)acrylate, hexyl (meth)acrylate, isohexyl (meth)acrylate, heptyl (meth)acrylate, isoheptyl (meth)acrylate, (meth)acrylic acid Octyl ester, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, ( Isodecyl (meth)acrylate, undecyl (meth)acrylate, isundecyl (meth)acrylate, dodecyl (meth)acrylate, isododecyl (meth)acrylate, At least one or more of tridecyl (meth)acrylate, isotridecan (meth)acrylate, tetradecyl (meth)acrylate, isotridecan (meth)acrylate, and the like. The alkyl group of the alkyl (meth)acrylate monomer may be linear or branched. The acrylic polymer of the present invention uses butyl acrylate as an essential monomer. The acrylic polymer contains at least 40 parts by weight of butyl acrylate in 100 parts by weight of the total amount of monomers belonging to the first monomer group, preferably at least 50 parts by weight, particularly preferably 60 parts by weight Copies or more.

在本發明的黏著劑組合物中，作為具有芳香族基的（甲基）丙烯酸酯單體，可列舉出（甲基）丙烯酸苄酯、（甲基）丙烯酸萘酯、（甲基）丙烯酸苯氧基乙酯、（甲基）丙烯酸苯氧基丁酯、2-(1-萘氧基)乙基（甲基）丙烯酸酯、2-(2-萘氧基)乙基（甲基）丙烯酸酯、6-(1-萘氧基)己基（甲基）丙烯酸酯、6-(2-萘氧基)己基（甲基）丙烯酸酯、8-(1-萘氧基)辛基（甲基）丙烯酸酯、8-(2-萘氧基)辛基（甲基）丙烯酸酯等中的至少一種以上。為了得到折射率高的黏著劑層，以添加至少一種以上具有芳香族基的（甲基）丙烯酸酯單體中為佳。本發明的丙烯酸類聚合物在屬於第一單體組的單體的總量100重量份中，以30重量份以下的比例含有具有芳香族基的（甲基）丙烯酸酯單體為佳。In the adhesive composition of the present invention, examples of the (meth)acrylate monomer having an aromatic group include benzyl (meth)acrylate, naphthyl (meth)acrylate, and benzene (meth)acrylate. Oxyethyl, phenoxybutyl (meth)acrylate, 2-(1-naphthyloxy)ethyl (meth)acrylate, 2-(2-naphthyloxy)ethyl (meth)acrylic acid Ester, 6-(1-naphthyloxy)hexyl(meth)acrylate, 6-(2-naphthyloxy)hexyl(meth)acrylate, 8-(1-naphthyloxy)octyl(methyl) ) At least one of acrylate, 8-(2-naphthyloxy)octyl (meth)acrylate, and the like. In order to obtain an adhesive layer with a high refractive index, it is preferable to add at least one (meth)acrylate monomer having an aromatic group. The acrylic polymer of the present invention preferably contains an aromatic group-containing (meth)acrylate monomer in a ratio of 30 parts by weight or less in 100 parts by weight of the total amount of monomers belonging to the first monomer group.

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。可列舉出含有醯胺鍵的（甲基）丙烯酸類單體、含有胺基的（甲基）丙烯酸類單體等。更具體而言，可列舉出N-（甲基）丙烯醯嗎啉、N-（甲基）丙烯醯呱嗪、N-（甲基）丙烯醯氮丙啶、N-（甲基）丙烯醯氮雜環丁烷、N-（甲基）丙烯醯吡咯烷、N-（甲基）丙烯醯呱啶、N-（甲基）丙烯醯氮雜環庚烷、N-（甲基）丙烯醯氮雜環辛烷等具有N-（甲基）丙烯醯基取代的具有雜環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-二甲胺基甲基（甲基）丙烯酸酯、N,N-二甲胺基乙基（甲基）丙烯酸酯,N,N-二甲胺基丙基（甲基）丙烯酸酯、N,N-二甲胺基異丙基（甲基）丙烯酸酯、N,N-二甲胺基丁基（甲基）丙烯酸酯、N,N-二乙基胺基甲基（甲基）丙烯酸酯、N,N-二乙基胺基乙基（甲基）丙烯酸酯、N-乙基-N-甲胺基乙基（甲基）丙烯酸酯、N-甲基-N-丙基胺基乙基（甲基）丙烯酸酯、N-甲基-N-異丙基胺基乙基（甲基）丙烯酸酯、N,N-二丁基胺基乙基（甲基）丙烯酸酯、叔丁基胺基乙基（甲基）丙烯酸酯等二烷基胺基（甲基）丙烯酸酯；N,N-二甲胺基丙基（甲基）丙烯醯胺、N,N-二乙基胺基丙基（甲基）丙烯醯胺、N,N-二丙基胺基丙基（甲基）丙烯醯胺、N,N-二異丙基胺基丙基（甲基）丙烯醯胺、N-乙基-N-甲胺基丙基（甲基）丙烯醯胺、N-甲基-N-丙基胺基丙基（甲基）丙烯醯胺、N-甲基-N-異丙基胺基丙基（甲基）丙烯醯胺等N,N-二烷基取代胺基丙基（甲基）丙烯醯胺；（甲基）丙烯腈等中的至少一種以上。作為含氮的乙烯基單體，以不含有羥基者為佳，以不含有羥基及羧基者為較佳。本發明的丙烯酸類聚合物在屬於第一單體組的單體的總量100重量份中，以20重量份以下的比例含有含氮的乙烯基單體為佳。In the adhesive composition of the adhesive layer of the present invention, it is used as a nitrogen-containing vinyl monomer. Examples include (meth)acrylic monomers containing amide bonds, (meth)acrylic monomers containing amine groups, and the like. More specifically, N-(meth)acrylic morpholine, N-(meth)acrylic acid, N-(meth)acrylic aziridine, N-(meth)acrylic acid Azetidine, N-(meth)acrylic acid pyrrolidine, N-(meth)acrylic acid pyrrolidine, N-(meth)acrylic acid azepane, N-(meth)acrylic acid Azacyclooctane and other cyclic nitrogen vinyl compounds having a heterocyclic structure substituted with N-(meth)acryloyl groups; (meth)acrylamide, N-methyl(meth)acrylamide, N-isopropyl (meth)acrylamide, N-tert-butyl (meth)acrylamide and other unsubstituted or monoalkyl substituted (meth)acrylamide; N,N-dimethyl( Meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropylacrylamide, N,N-diisopropyl(meth)acrylamide, N ,N-Dibutyl(meth)acrylamide, N-ethyl-N-methyl(meth)acrylamide, N-methyl-N-propyl(meth)acrylamide, N- Dialkyl substituted (meth)acrylamides such as methyl-N-isopropyl(meth)acrylamide; N,N-dimethylaminomethyl(meth)acrylate, N,N-di Methylaminoethyl (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 (meth)acrylate, N-methyl-N-isopropylamine Dialkylamino (meth) acrylate such as methyl ethyl (meth)acrylate, N,N-dibutylaminoethyl (meth)acrylate, tert-butylaminoethyl (meth)acrylate, etc. ) Acrylate; N,N-dimethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, N,N-dipropylamino Propyl (meth)acrylamide, N,N-diisopropylaminopropyl (meth)acrylamide, N-ethyl-N-methylaminopropyl (meth)acrylamide, N-methyl-N-propylaminopropyl(meth)acrylamide, N-methyl-N-isopropylaminopropyl(meth)acrylamide, etc. N,N-dialkyl At least one of substituted aminopropyl (meth)acrylamide; (meth)acrylonitrile, etc. As the nitrogen-containing vinyl monomer, one that does not contain a hydroxyl group is preferred, and one that does not contain a hydroxyl group and a carboxyl group is preferred. The acrylic polymer of the present invention preferably contains a nitrogen-containing vinyl monomer in a ratio of 20 parts by weight or less in 100 parts by weight of the total amount of monomers belonging to the first monomer group.

在本發明的黏著劑組合物中，作為具有脂環族的（甲基）丙烯酸酯單體可列舉出（甲基）丙烯酸環戊酯、（甲基）丙烯酸環己酯、（甲基）丙烯酸異冰片酯、（甲基）丙烯酸二環庚酯、（甲基）丙烯酸二環辛酯、（甲基）丙烯酸二甲基二環庚酯、（甲基）丙烯酸二環戊酯等中的至少一種以上。通過混入像（甲基）丙烯酸環狀烷酯單體那樣在側鏈具有飽和脂環族的（甲基）丙烯酸酯單體，由於降低了丙烯酸類聚合物的極性，故而有助於對於低能量表面的親和性。本發明的丙烯酸類聚合物在屬於第一單體組的單體的總量100重量份中，以30重量份以下的比例含有具有脂環族的（甲基）丙烯酸酯單體為佳。In the adhesive composition of the present invention, examples of the alicyclic (meth)acrylate monomers include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and (meth)acrylic acid. At least one of isobornyl ester, dicycloheptyl (meth)acrylate, dicyclooctyl (meth)acrylate, dimethyldicycloheptyl (meth)acrylate, dicyclopentyl (meth)acrylate, etc. More than one kind. By mixing (meth)acrylate monomers with saturated alicyclic in the side chain like cyclic alkyl (meth)acrylate monomers, the polarity of the acrylic polymer is reduced, which contributes to low energy Surface affinity. The acrylic polymer of the present invention preferably contains an alicyclic (meth)acrylate monomer in a ratio of 30 parts by weight or less in 100 parts by weight of the total amount of monomers belonging to the first monomer group.

屬於第二單體組的單體（官能團單體）具有可與用作交聯劑的異氰酸酯化合物反應的官能團。作為這樣的官能團，除羥基之外，還有羧基等。但是，從避免對於透明導電性膜的ITO表面等容易腐蝕的黏被黏著體的腐蝕性的影響的角度考慮，丙烯酸類聚合物為不含有含羧基的共聚性乙烯基單體為佳。丙烯酸類聚合物的酸值較佳為0.1以下。The monomers (functional monomers) belonging to the second monomer group have functional groups that can react with the isocyanate compound used as a crosslinking agent. As such functional groups, in addition to hydroxyl groups, there are carboxyl groups and the like. However, from the viewpoint of avoiding the corrosive influence on the adherend which is easily corroded such as the ITO surface of the transparent conductive film, it is preferable that the acrylic polymer does not contain a carboxyl group-containing copolymerizable vinyl monomer. The acid value of the acrylic polymer is preferably 0.1 or less.

在本發明的黏著劑組合物中，作為含羥基的共聚性乙烯基單體，可列舉出8-羥基辛基（甲基）丙烯酸酯、6-羥基己基（甲基）丙烯酸酯，4-羥基丁基（甲基）丙烯酸酯、2-羥基乙基（甲基）丙烯酸酯等含羥基的烷基（甲基）丙烯酸酯類，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為以選擇自由8-羥基辛基（甲基）丙烯酸酯、6-羥基己基（甲基）丙烯酸酯、4-羥基丁基（甲基）丙烯酸酯、2-羥基乙基（甲基）丙烯酸酯所構成的化合物群組中的至少一種以上為佳。本發明的丙烯酸類聚合物相對於屬於第一單體組的單體的總量100重量份，以含有0.1~10重量份含羥基的共聚性乙烯基單體為佳，含有0.2~5.0重量份為較佳，含有0.2~4.0重量份為特佳。In the adhesive composition of the present invention, examples of the hydroxyl-containing copolymerizable vinyl monomers include 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxy Hydroxy-containing alkyl (meth)acrylates such as butyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate, or N-hydroxy (meth)acrylamide, N-hydroxymethyl At least one or more of hydroxyl group-containing (meth)acrylamides, such as N-hydroxyethyl (meth)acrylamide and N-hydroxyethyl (meth)acrylamide. Among them, the hydroxyl-containing copolymerizable vinyl monomer is selected from 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, At least one or more of the compound group consisting of 2-hydroxyethyl (meth)acrylate is preferable. The acrylic polymer of the present invention preferably contains 0.1 to 10 parts by weight of a copolymerizable vinyl monomer containing a hydroxyl group with respect to 100 parts by weight of the total amount of monomers belonging to the first monomer group, and contains 0.2 to 5.0 parts by weight Preferably, it is particularly preferable to contain 0.2 to 4.0 parts by weight.

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以含有50~100重量%（甲基）丙烯酸酯單體等丙烯酸類單體為佳。在本發明中，丙烯酸類聚合物的玻璃化轉變溫度（以下，記為Tg）以-35℃以上為佳。Tg若未滿-35℃，則再操作性及耐久性降低，故而不佳。更進一步，Tg為-35℃~-10℃為較佳。Tg若超過-10℃，則無法獲得本發明需要的黏著力，故而不佳。此外，所述丙烯酸類聚合物的重量平均分子量為100萬以上為佳，100萬~200萬的範圍為較佳。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 and 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. In the present invention, the glass transition temperature (hereinafter referred to as Tg) of the acrylic polymer is preferably -35°C or higher. If the Tg is less than -35°C, the reworkability and durability will decrease, which is not good. Furthermore, Tg is preferably -35°C to -10°C. If the Tg exceeds -10°C, the adhesive force required by the present invention cannot be obtained, which is not good. In addition, the weight average molecular weight of the acrylic polymer is preferably 1 million or more, preferably in the range of 1 million to 2 million.

所述黏著劑組合物可通過向上述的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理性質等特性。The adhesive composition can adjust the required physical properties and other characteristics by adding a crosslinking agent or any suitable additives to the above-mentioned acrylic polymer.

作為交聯劑，例如可列舉出六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、二苯甲烷二異氰酸酯、甲苯二異氰酸酯、苯二亞甲基二異氰酸酯等的二異氰酸酯類的縮二脲（biuret）改性體或異氰脲酸酯改性體、與三羥甲基丙烷或甘油等3元以上多元醇的加成體等聚異氰酸酯化合物中的至少一種以上。Examples of the crosslinking agent include diisocyanate-based biurets such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and xylylene diisocyanate. biuret) At least one of polyisocyanate compounds such as a modified product, an isocyanurate modified product, and an adduct with a trivalent or higher polyol such as trimethylolpropane or glycerin.

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以0.01~1.0重量份為佳。作為交聯劑，可以僅使用異氰酸酯化合物。作為異氰酸酯化合物，以選擇自含有由甲苯二異氰酸酯的三羥甲基丙烷加成體及六亞甲基二異氰酸酯的異氰脲酸酯體中的至少一種以上為佳。The content of the isocyanate compound used as the crosslinking agent is preferably 0.01 to 1.0 part by weight relative to 100 parts by weight of the total amount of monomers belonging to the first monomer group. As the crosslinking agent, only an isocyanate compound can be used. As the isocyanate compound, it is preferable to select at least one or more selected from the group consisting of a trimethylolpropane adduct containing toluene diisocyanate and an isocyanurate containing hexamethylene diisocyanate.

所述黏著劑組合物進一步以含有矽烷偶聯劑為佳。作為矽烷偶聯劑，可列舉出如下的化合物：在1個分子中具有至少一個有機官能團與至少一個水解性基團，所述水解性基團為鍵合於矽原子的烷氧基等。所述矽烷偶聯劑選擇自含有由環氧基、（甲基）丙烯醯氧基、巰基、胺基構成的群組中的至少一種有機官能團。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, and the hydrolyzable group is an alkoxy group bonded to a silicon atom or the like. The silane coupling agent is selected from at least one organic functional group selected from the group consisting of an epoxy group, a (meth)acryloxy group, a mercapto group, and an amine group. Here, the (meth)acryloyloxy group refers to an allyloxy group (CH 2 =CHCOO-) or a methacryloyloxy group (CH 2 =C(CH 3 )COO-).

作為具有環氧基的矽烷偶聯劑，例如可列舉出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。作為具有（甲基）丙烯醯氧基的矽烷偶聯劑，例如可列舉出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。作為具有巰基的矽烷偶聯劑，例如可列舉出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。作為具有胺基的矽烷偶聯劑，例如可列舉出3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二乙氧基矽烷，N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三乙氧基矽烷、3-(甲胺基)丙基三甲氧基矽烷、3-(甲胺基)丙基三乙氧基矽烷等。此外，含有所述有機官能團、經過低聚物化的烷氧基低聚物（有機矽（silicone）烷氧基低聚物）等也可作為矽烷偶聯劑使用。As the silane coupling agent having an epoxy group, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidol Etheroxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-( 3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 2-(3,4-epoxy Cyclohexyl) ethyltriethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 5,6-epoxyhexylmethyldimethoxysilane, 5,6-epoxyhexylmethyldiethoxy Silane, 5,6-epoxyhexyl triethoxy silane, etc. As the silane coupling agent having a (meth)acryloxy group, for example, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyl Dimethoxysilane, 3-(meth)acryloxypropyl triethoxysilane, 3-(meth)acryloxypropylmethyl diethoxysilane, 3-(methyl) ) Acrylic oxypropyl dimethyl ethoxy silane, 3-(meth) acryloxy propyl dimethyl methoxy silane, etc. As the silane coupling agent having a mercapto group, for example, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3 -Mercaptopropyl triethoxysilane, etc. As the silane coupling agent having an amino group, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane can be cited. N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxy N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3- (Methylamino)propyltrimethoxysilane, 3-(methylamino)propyltriethoxysilane, etc. In addition, oligomerized alkoxy oligomers (silicone alkoxy oligomers) containing the organic functional group and oligomerization can also be used as a silane coupling agent.

矽烷偶聯劑的含量相對於除了含羥基的共聚性乙烯基單體以外的單體（屬於第一單體組的單體）的總量100重量份，以0.01~0.5重量份為佳。The content of the silane coupling agent is preferably 0.01 to 0.5 parts by weight relative to 100 parts by weight of the total amount of monomers (monomers belonging to the first monomer group) other than the hydroxyl-containing copolymerizable vinyl monomer.

作為其他任選成分，可適當添加抗氧化劑、抗靜電劑、表面活性劑、固化促進劑、增塑劑、填充劑、交聯催化劑、交聯延遲劑、加工助劑、抗老化劑等公知的添加劑。這些物質可以單獨使用，或者也可兩種以上同時使用。As other optional ingredients, well-known antioxidants, antistatic agents, surfactants, curing accelerators, plasticizers, fillers, crosslinking catalysts, crosslinking retarders, processing aids, anti-aging agents, etc. can be appropriately added. additive. These substances may be used alone, or two or more of them may be used simultaneously.

本發明的黏著劑層可通過將所述黏著劑組合物塗布於基材或離型膜後，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以40~85%為佳。The adhesive layer of the present invention can be obtained by coating the adhesive composition on a substrate or a release film, and then crosslinking the adhesive composition. The gel fraction of the crosslinked adhesive layer is preferably 40-85%.

在將本發明的黏著劑層用於光學部件的層間的貼合等的情況下，最好為薄的黏著劑層。黏著劑層的厚度以1μm~20μm為佳。此外，厚度10μm的黏著劑層的黏著力以1.5~8.0N/25mm為佳。此外，黏著劑層的黏著力通常基本上與黏著劑層的厚度成比例。作為用於黏著力試驗的黏被黏著體，可列舉出無鹼玻璃等玻璃板、樹脂膜等。When the adhesive layer of the present invention is used for bonding between layers of optical components, etc., it is preferably a thin adhesive layer. The thickness of the adhesive layer is preferably 1 μm to 20 μm. In addition, the adhesive strength of the adhesive layer with a thickness of 10μm is preferably 1.5~8.0N/25mm. In addition, the adhesive force of the adhesive layer is generally basically proportional to the thickness of the adhesive layer. Examples of the adherend used for the adhesion test include glass plates such as alkali-free glass, resin films, and the like.

將本發明的黏著劑層用於光學部件的層間的貼合等的情況下，為了降低在黏著劑層與光學部件的介面的光線的反射，折射率的差最好盡可能小。因此所述黏著劑層的折射率以1.47~1.50為佳。When the adhesive layer of the present invention is used for bonding between layers of optical components, etc., in order to reduce the reflection of light at the interface between the adhesive layer and the optical component, the difference in refractive index is preferably as small as possible. Therefore, the refractive index of the adhesive layer is preferably 1.47 to 1.50.

本發明的黏著薄膜可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是保護黏著面的離型膜（隔離物），可使用聚酯膜等的樹脂膜等。在基材膜中，在樹脂膜的形成黏著劑層一側的相反面上，可通過有機矽類、氟類的離型劑或塗布劑、二氧化矽微粒等施加防汙處理，通過塗布或摻混抗靜電劑等施加抗靜電處理。The adhesive film of the present invention can be prepared by forming the adhesive layer of the present invention on one side of a substrate or a release film. As the base film for forming the adhesive layer or the release film (separator) for protecting the adhesive surface, a resin film such as a polyester film or the like can be used. In the base film, on the opposite side of the resin film on the side where the adhesive layer is formed, antifouling treatment can be applied with silicone, fluorine-based release agents or coating agents, silica particles, etc., by coating or Antistatic treatment is applied by blending antistatic agents and the like.

離型膜中，在與黏著劑層的黏著面貼合的一側的面上，通過有機矽類、氟類的離型劑等而實施離型處理。通過在一個黏著劑層的兩面分別貼合實施了離型膜的離型處理的面，可形成「離型膜/黏著劑層/離型膜」的結構。在該情況下，通過依次或同時剝離兩側的離型膜，露出黏著面，從而可與光學膜等光學部件貼合。作為光學膜，可列舉出偏光膜、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、光補償膜、亮度提高膜等。In the release film, a release treatment is performed on the surface of the side to be bonded to the adhesive surface of the adhesive layer with a silicone-based, fluorine-based release agent, or the like. By laminating the surface of the release film on both sides of one adhesive layer, the structure of "release film/adhesive layer/release film" can be formed. In this case, by peeling off the release films on both sides sequentially or at the same time to expose the adhesive surface, it can be bonded to optical components such as optical films. As an optical film, a polarizing film, a retardation film, an anti-reflection film, an anti-glare film, an ultraviolet absorption film, an infrared absorption film, a light compensation film, a brightness improvement film, etc. are mentioned.

本發明的黏著劑層即使黏著劑層厚也能夠維持黏被黏著體的表面硬度，因此在至少一個黏被黏著體為通過硬塗層等提高了表面硬度的（例如，表面的鉛筆硬度為2H以上等）光學部件的情況下，能夠適宜地使用。從再操作性的角度考慮，將黏著劑層貼合於黏被黏著體後經70℃×10天保存後的黏著力以10N/25mm以下為佳。The adhesive layer of the present invention can maintain the surface hardness of the adherend even if the adhesive layer is thick. Therefore, at least one adherend has a surface hardness that is increased by a hard coating or the like (for example, the pencil hardness of the surface is 2H The above etc.) In the case of an optical component, it can be suitably used. From the perspective of reworkability, the adhesive strength after the adhesive layer is attached to the adherend and stored at 70°C for 10 days is preferably 10N/25mm or less.

本發明的黏著劑層及黏著薄膜可用於以偏光板為主的液晶顯示裝置的周邊部件用的各種光學膜、觸控面板用的各種光學膜、電子書用的各種光學膜、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層積有所述黏著劑層的帶有黏著劑層的光學膜。在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」那樣露出黏著劑層，貼合其他光學膜，能夠獲得在層間的貼合中使用了黏著劑層的「光學膜/黏著劑層/光學膜」這樣的結構。The adhesive layer and adhesive film of the present invention can be used for various optical films for peripheral parts of liquid crystal display devices, mainly polarizing plates, various optical films for touch panels, various optical films for electronic books, and organic EL Bonding of various optical films, etc. In addition, an optical film with an adhesive layer in which the adhesive layer is laminated on at least one surface of these optical films can be formed. In the case of an adhesive layer protected by a release film, by peeling off the release film, the adhesive layer is exposed like an "optical film/adhesive layer", and other optical films can be bonded together. The structure of "optical film/adhesive layer/optical film" using adhesive layer.

本發明的黏著薄膜可適用於偏光板與顯示面板的貼合。作為顯示面板，例如可列舉出液晶面板或有機EL（電致發光）面板。本發明的黏著薄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。可在相位差膜與偏光板的貼合中使用本發明的黏著劑層。 [實施例]The adhesive film of the present invention can be suitable for bonding a polarizing plate and a display panel. As the display panel, for example, a liquid crystal panel or an organic EL (electroluminescence) panel can be cited. The adhesive film of the present invention can be suitably used as an adhesive layer of a polarizing plate with an adhesive 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 this invention can be used for bonding of a retardation film and a polarizing plate. [Example]

以下，通過實施例對本發明進行具體的說明。Hereinafter, the present invention will be specifically explained through examples.

＜丙烯酸類聚合物的製備＞ ［實施例1］ 向帶有攪拌機、溫度計、回流冷卻器及氮氣導入管的反應裝置中導入氮氣，用氮氣置換反應裝置內的空氣。之後，向反應裝置中加入75重量份丙烯酸丁酯、25重量份丙烯酸叔丁酯、1.0重量份8-羥基辛基丙烯酸酯，同時加入60重量份溶劑（醋酸乙酯）。之後用2小時滴入0.1重量份作為聚合引發劑的偶氮二異丁腈，在65℃下反應6小時，得到用於實施例1的丙烯酸類聚合物溶液。 ［實施例2~5及比較例1~3］ 除了將單體的組成分別設定為表1的（1）組及（2）組所述以外，以與上述用於實施例1的丙烯酸類聚合物溶液1相同的方式，得到用於實施例2~5及比較例1~3的丙烯酸類聚合物溶液。＜Preparation of acrylic polymer＞ [Example 1] Nitrogen was introduced into the reaction device equipped with a stirrer, a thermometer, a reflux cooler, and a nitrogen introduction pipe, and the air in the reaction device was replaced with nitrogen. After that, 75 parts by weight of butyl acrylate, 25 parts by weight of t-butyl acrylate, and 1.0 part by weight of 8-hydroxyoctyl acrylate were added to the reaction device, and 60 parts by weight of solvent (ethyl acetate) were added at the same time. 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 the acrylic polymer solution used in Example 1. [Examples 2 to 5 and Comparative Examples 1 to 3] Except that the composition of the monomers was set as described in the groups (1) and (2) of Table 1, in the same manner as in the acrylic polymer solution 1 used in Example 1, the results were used in Example 2. ~5 and the acrylic polymer solutions of Comparative Examples 1 to 3.

＜黏著劑組合物、黏著劑層及黏著薄膜的製備＞ ［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0.2重量份CORONATE HX（HDI的異氰脲酸酯體）、0.05重量份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布於離型膜（塗布有有機矽樹脂的聚對苯二甲酸乙二醇酯（PET）膜）上之後，通過在90℃下乾燥去除溶劑，然後在23℃、50%RH的氣氛下熟化7天，由此獲得在離型膜的單面上具有經黏著劑組合物交聯而成的黏著劑層的實施例1的黏著薄膜。 ［實施例2~5及比較例1~3］ 除了將添加劑的組成分別設定為表1的（3）組及（4）組所述以外，以與上述的實施例1的黏著薄膜同樣的方式，獲得實施例2~5及比較例1~3的黏著薄膜。<Preparation of adhesive composition, adhesive layer and adhesive film> [Example 1] To the acrylic polymer solution of Example 1 prepared as described above, 0.2 parts by weight of CORONATE HX (isocyanurate body of HDI) and 0.05 parts by weight of KBM-803 (3-mercaptopropyltrimethoxysilane) were added. , Stir and mix to obtain the adhesive composition of Example 1. After coating the adhesive composition on a release film (polyethylene terephthalate (PET) film coated with silicone resin), the solvent was removed by drying at 90°C, and then at 23°C, 50°C and 50°C. After curing for 7 days in an atmosphere of %RH, the adhesive film of Example 1 having an adhesive layer crosslinked by the adhesive composition on one side of the release film was obtained. [Examples 2 to 5 and Comparative Examples 1 to 3] Except that the composition of the additives was set as described in the groups (3) and (4) of Table 1, in the same manner as the adhesive film of the above-mentioned Example 1, Examples 2 to 5 and Comparative Examples 1 to 3 were obtained. The adhesive film.

[表1]   (1)組 (2)組 (3)組 (4)組 實施例1 BA (75) TBA (25) 8HOA (1.0) HX (0.1) KBM-803 (0.05) 實施例2 BA (50) MA (30) PHEA (20) 6HHA (0.5) 4HBA (0.5) HX (0.2) KBM-803 (0.03) 實施例3 BA (70) IBXA (20) TBA (10) 4HBA (0.5) HEA (1.0) L (0.2) KBM-802 (0.03) 實施例4 BA (70) TBA (20) DEAA (10) 6HHA (1.0) HX (0.5) KBM-803 (0.1) 實施例5 BA (70) BZA (20) DEAA (10) HEA (2.0) L (0.1) KBM-803 (0.04) 比較例1 2EHA (80) MA (20) AAc (2.5) L (1.5) KBM-403 (1.0) 比較例2 2EHA (100) HEA (10.0) HX (2.0) KBM-803 (0.5) 比較例3 BA (90) MA (10) - L (0.5) - [Table 1] (Group 1 (2 teams (3) Group (4) Group Example 1 BA (75) TBA (25) 8HOA (1.0) HX (0.1) KBM-803 (0.05) Example 2 BA (50) MA (30) PHEA (20) 6HHA (0.5) 4HBA (0.5) HX (0.2) KBM-803 (0.03) Example 3 BA (70) IBXA (20) TBA (10) 4HBA (0.5) HEA (1.0) L (0.2) KBM-802 (0.03) Example 4 BA (70) TBA (20) DEAA (10) 6HHA (1.0) HX (0.5) KBM-803 (0.1) Example 5 BA (70) BZA (20) DEAA (10) HEA (2.0) L (0.1) KBM-803 (0.04) Comparative example 1 2EHA (80) MA (20) AAc (2.5) L (1.5) KBM-403 (1.0) Comparative example 2 2EHA (100) HEA (10.0) HX (2.0) KBM-803 (0.5) Comparative example 3 BA (90) MA (10) - L (0.5) -

在表1中，要求（1）組的由烷基的碳原子數為C1~C14的烷基（甲基）丙烯酸酯單體、具有芳香族基的（甲基）丙烯酸酯單體、含氮的乙烯基單體、具有脂環族的（甲基）丙烯酸酯單體所構成的單體群組的總量為100重量份。此外，作為（2）組~（4）組的添加比例，重量份的數值在括弧內示出。此外，（2）組為含官能團的單體，即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群組。（3）組為交聯劑。（4）組為矽烷偶聯劑。In Table 1, the requirement (1) group consists of alkyl (meth)acrylate monomers with C1-C14 carbon atoms, (meth)acrylate monomers with aromatic groups, and nitrogen-containing The total amount of the monomer group composed of vinyl monomers and (meth)acrylate monomers having alicyclic groups is 100 parts by weight. In addition, as the addition ratio of the group (2) to the group (4), the numerical value of parts by weight is shown in parentheses. In addition, the group (2) is a functional group-containing monomer, that is, a monomer group composed of a hydroxyl group-containing copolymerizable vinyl monomer and a carboxyl group-containing copolymerizable vinyl monomer. (3) Group is a crosslinking agent. (4) Group is silane coupling agent.

此外，用於表1的各成分的縮寫符號的化合物名如表2所示。此外，CORONATE（註冊商標）HX及L為日本聚胺酯工業株式會社的商品名，KBM-403、KBM-802及KBM- 803為信越化學工業株式會社的商品名。TDI表示甲苯二異氰酸酯，TMP表示三羥甲基丙烷，HDI表示六亞甲基二異氰酸酯。In addition, the compound name used for the abbreviation of each component in Table 1 is as shown in Table 2. In addition, CORONATE (registered trademark) HX and L are trade names of Japan Polyurethane Industry Co., Ltd., and KBM-403, KBM-802 and KBM-803 are trade names of Shin-Etsu Chemical Co., Ltd. TDI means toluene diisocyanate, TMP means trimethylolpropane, and HDI means hexamethylene diisocyanate.

[表2] 組 縮寫符號 化合物名 (1)組 2EHA 2-乙基己基丙烯酸酯   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 PHEA 苯氧基乙基丙烯酸酯 BZA 丙烯酸苄酯 DEAA 二乙基丙烯醯胺 (2)組 8HOA 8-羥基辛基丙烯酸酯   6HHA 6-羥基己基丙烯酸酯 4HBA 4-羥基丙烯酸丁酯 HEA 2-羥基乙基丙烯酸酯 AAc 丙烯酸酸 (3)組 HX CORONATE HX HDI的異氰脲酸酯體   L CORONATE L TDI的TMP加成體（75%醋酸乙酯溶液） (4)組 KBM-403 信越化學製　3-縮水甘油醚氧基丙基三甲氧基矽烷   KBM-802 信越化學製　3-巰基丙基甲基二甲氧基矽烷 KBM-803 信越化學製　3-巰基丙基三甲氧基矽烷 [Table 2] group Abbreviation Compound name (Group 1 2EHA 2-ethylhexyl acrylate BA Butyl acrylate MA Methyl acrylate IBXA Isobornyl acrylate TBA Tert-butyl acrylate PHEA Phenoxyethyl acrylate BZA Benzyl acrylate DEAA Diethyl acrylamide (2 teams 8HOA 8-hydroxyoctyl acrylate 6HHA 6-hydroxyhexyl acrylate 4HBA 4-hydroxy butyl acrylate HEA 2-hydroxyethyl acrylate AAc Acrylic acid (3) Group HX CORONATE HX HDI isocyanurate body L TMP adduct of CORONATE L TDI (75% ethyl acetate solution) (4) Group KBM-403 Shin-Etsu Chemical's 3-glycidoxypropyltrimethoxysilane KBM-802 Shin-Etsu Chemical's 3-mercaptopropylmethyldimethoxysilane KBM-803 Shin-Etsu Chemical's 3-mercaptopropyltrimethoxysilane

＜試驗方法及評價＞ 從實施例1~5及比較例1~3的黏著薄膜上剝離離型膜（塗布有有機矽樹脂的PET膜），露出黏著劑層，將黏著劑層轉印到偏光板（膜）的單面上。＜Test method and evaluation＞ Peel the release film (PET film coated with silicone resin) from the adhesive films of Examples 1 to 5 and Comparative Examples 1 to 3 to expose the adhesive layer, and transfer the adhesive layer to the sheet of the polarizing plate (film). Surface.

＜黏著力的測定方法＞ 在厚度180μm的偏光板（膜）的單面上轉印厚度10μm的黏著劑層，得到成為試樣的黏著薄膜（帶有黏著劑層的光學膜）。將所得到的黏著薄膜用壓輥貼合於用丙酮清洗過的無鹼玻璃的非錫面上，在50℃、0.5MPa×20分鐘的條件下進行高壓釜處理後，回到23℃×50%RH的氣氛下，經過1小時。之後通過拉伸試驗機，以JIS Z0237「黏著帶·黏著片試驗方法」為標準測定黏著薄膜的剝離強度，將在180°方向上以300mm/分鐘的速度剝離時的剝離強度設為黏著薄膜的黏著劑層的黏著力（N/25mm）。＜Measurement method of adhesive force＞ An adhesive layer with a thickness of 10 μm was transferred on one side of a polarizing plate (film) with a thickness of 180 μm to obtain an adhesive film (optical film with an adhesive layer) as a sample. The obtained adhesive film was pasted on the non-tin surface of alkali-free glass cleaned with acetone with a pressure roller, and then autoclaved at 50°C, 0.5MPa×20 minutes, and then returned to 23°C×50 Under the atmosphere of %RH, after 1 hour. After that, the peel strength of the adhesive film was measured by a tensile testing machine in accordance with JIS Z0237 "Testing Methods for Adhesive Tapes and Adhesive Sheets". The peel strength of the adhesive film when peeled in the 180° direction at a speed of 300 mm/min was set as that of the adhesive film. Adhesion of the adhesive layer (N/25mm).

＜酸值的測定方法＞ 將丙烯酸類聚合物的試樣溶於溶劑（乙醚與乙醇以體積比2:1混合），作為測定試樣。使用電位差自動滴定裝置（京都電子工業製，AT-610），通過濃度約0.1mol/l的氫氧化鉀乙醇溶液對該測定試樣進行電位差滴定，測定為了中和試樣所需要的氫氧化鉀乙醇溶液的量。然後，通過下述式子求出丙烯酸類聚合物的酸值。 酸值=（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） f=0.1mol/l氫氧化鉀乙醇溶液的因數 S=試樣的固體成分的品質（g）＜Method of measuring acid value＞ A sample of acrylic polymer is dissolved in a solvent (diethyl ether and ethanol are mixed at a volume ratio of 2:1), and used as a measurement sample. Use a potentiometric automatic titration device (manufactured by Kyoto Electronics Industry, AT-610) to perform potentiometric titration on the measurement sample with a potassium hydroxide ethanol solution with a concentration of about 0.1 mol/l, and measure the potassium hydroxide required to neutralize the sample The amount of ethanol solution. Then, the acid value of the acrylic polymer was obtained by the following formula. Acid value=(B×f×5.611)/S B=Amount of 0.1mol/l potassium hydroxide ethanol solution used for titration (ml) f=0.1mol/l potassium hydroxide ethanol solution factor S = the quality of the solid content of the sample (g)

＜凝膠分率的測定方法＞ 在熟化完成後，正確測定貼合於偏光板前的測定試樣的黏著劑層的品質，在甲苯中浸漬24小時後，使用200目的金屬網過濾。之後，將濾除物在100℃下乾燥1小時後，正確測定殘渣的品質，通過以下的公式計算黏著劑層（交聯後的黏著劑層）的凝膠分率。 凝膠分率（%）=不溶部分品質（g）/黏著劑層的品質（g）×100＜Measuring method of gel fraction＞ After the aging is completed, the quality of the adhesive layer of the measurement sample before being attached to the polarizing plate is accurately measured, and after immersing in toluene for 24 hours, it is filtered with a 200-mesh metal mesh. After that, the filtered matter was dried at 100°C for 1 hour, and then the quality of the residue was accurately measured, and the gel fraction of the adhesive layer (crosslinked adhesive layer) was calculated by the following formula. Gel fraction (%)=quality of insoluble part (g)/quality of adhesive layer (g)×100

＜耐久性的試驗方法＞ 將用與黏著力的測定方法相同的方法製作的10cm見方的黏著薄膜用壓輥貼合在無鹼玻璃的經過丙酮清洗的非錫面上，製成測定樣品。將製成的測定樣品在規定的氣氛（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薄膜的狀態，判斷耐久性。目視觀察的判定標準如下所述。 ○：完全沒有黏著薄膜的剝落及起泡。 △：黏著薄膜的一部分發生剝落及起泡。 ╳：黏著薄膜的整體發生剝落及起泡。＜Durability test method＞ A 10 cm square adhesive film made by the same method as the adhesive force measurement method was applied to the non-tin surface of alkali-free glass washed with acetone with a pressure roller to prepare a measurement sample. Place the prepared measurement sample in a specified atmosphere (80°C dry atmosphere or 60°C×90%RH atmosphere) for 250 hours, then take it out and place it in a 23°C×50%RH atmosphere, and observe the adhesion visually after 1 hour The state of the film determines the durability. The criteria for visual observation are as follows. ○: There is no peeling and blistering of the adhesive film at all. △: Peeling and blistering occurred in a part of the adhesive film. ╳: The whole adhesive film peeled off and blistered.

＜再操作性的試驗方法＞ 將用與黏著力的測定相同的方法製作的10cm見方的黏著薄膜用相同的方法貼合於無鹼玻璃的非錫面，製成試樣，將其在70℃的氣氛下放置10天後，取出置於23℃的氣氛下，測定放置1小時後的黏著薄膜的黏著力，判斷再操作性。再操作性的判定標準如下所述。 ○：70℃×10天後的黏著力為1.5~10N/25mm。 △：70℃×10天後的黏著力大於10N/25mm、20N/25mm以下。 ╳：70℃×10天後的黏著力大於20N/25mm（無法剝離）。＜Re-operability test method＞ A 10cm-square adhesive film made by the same method as the measurement of the adhesive force was attached to the non-tin surface of the alkali-free glass by the same method to prepare a sample. After placing it in an atmosphere of 70°C for 10 days, Take it out and place it in an atmosphere of 23°C, measure the adhesive force of the adhesive film after leaving it for 1 hour, and judge the reoperability. The criteria for determining reoperability are as follows. ○: The adhesive force after 70°C × 10 days is 1.5-10N/25mm. △: The adhesive force after 70°C×10 days is greater than 10N/25mm, 20N/25mm or less. ╳: The adhesive force after 70℃×10 days is greater than 20N/25mm (cannot be peeled).

＜鉛筆硬度的測定方法＞ 在表面具有鉛筆硬度為2H的硬塗層的偏光板上，轉印規定厚度（表4）的黏著劑層，作為試樣。經由試樣的黏著劑層在無鹼玻璃上貼合偏光板後，以JIS K5600的劃痕硬度（鉛筆法）為標準，進行試樣表面的鉛筆硬度試驗，測定「硬塗層/偏光板/黏著劑層/無鹼玻璃」的層結構中的硬塗層的表面的鉛筆硬度。＜Measuring method of pencil hardness＞ On a polarizing plate with a hard coat of 2H pencil hardness on the surface, an adhesive layer of a predetermined thickness (Table 4) was transferred as a sample. After bonding the polarizing plate to the alkali-free glass via the adhesive layer of the sample, perform a pencil hardness test on the surface of the sample according to the scratch hardness of JIS K5600 (pencil method) to measure the "hard coating/polarizing plate/ The pencil hardness of the surface of the hard coat layer in the layer structure of "adhesive layer/alkali-free glass".

評價結果示於表3及表4。此外，雖未特別示出結果，在未使用含羧基的共聚性乙烯基單體的實施例1~5及比較例2~3中，丙烯酸類聚合物的酸值為0.1以下。此外，丙烯酸類聚合物的重量平均分子量均為100萬以上。The evaluation results are shown in Table 3 and Table 4. In addition, although the results are not particularly shown, in Examples 1 to 5 and Comparative Examples 2 to 3 in which a carboxyl group-containing copolymerizable vinyl monomer is not used, the acid value of the acrylic polymer is 0.1 or less. In addition, the weight average molecular weight of acrylic polymers is 1 million or more.

[表3]   共聚物 Tg (℃) 10μm 黏著力 (N/25mm) 10天後 黏著力 (N/25mm) 再操作性 凝膠分率 (%) 耐久性 耐玻璃 80℃乾燥 耐久性 耐玻璃 60℃90%RH 實施例1 -34 6.5 7.8 ○ 75 ○ ○ 實施例2 -31 6.0 8.5 ○ 65 ○ ○ 實施例3 -25 5.3 8.6 ○ 70 ○ ○ 實施例4 -28 4.5 9.0 ○ 75 ○ ○ 實施例5 -33 6.8 7.6 ○ 65 ○ ○ 比較例1 -58 4.0 14.6 △ 55 ○ ╳ 比較例2 -66 1.1 1.5 ○ 97 △ ╳ 比較例3 -47 25.0 30.0 ╳ 0 ╳ ╳ [table 3] Copolymer Tg (℃) 10μm adhesion (N/25mm) Adhesion after 10 days (N/25mm) Reoperability Gel fraction (%) Durable glass drying at 80℃ Durable glass resistant 60℃90%RH Example 1 -34 6.5 7.8 ○ 75 ○ ○ Example 2 -31 6.0 8.5 ○ 65 ○ ○ Example 3 -25 5.3 8.6 ○ 70 ○ ○ Example 4 -28 4.5 9.0 ○ 75 ○ ○ Example 5 -33 6.8 7.6 ○ 65 ○ ○ Comparative example 1 -58 4.0 14.6 △ 55 ○ ╳ Comparative example 2 -66 1.1 1.5 ○ 97 △ ╳ Comparative example 3 -47 25.0 30.0 ╳ 0 ╳ ╳

[表4]   硬塗層表面的 鉛筆硬度 試驗時的 黏著劑層厚度 實施例1 2H 10μm 實施例2 2H 10μm 實施例3 2H 20μm 實施例4 2H 15μm 實施例5 2H 10μm 比較例1 H 15μm 比較例2 H 20μm 比較例3 H 25μm [Table 4] Pencil hardness of hard coat surface Adhesive layer thickness during test Example 1 2H 10μm Example 2 2H 10μm Example 3 2H 20μm Example 4 2H 15μm Example 5 2H 10μm Comparative example 1 H 15μm Comparative example 2 H 20μm Comparative example 3 H 25μm

作為本發明的黏著薄膜的實施例1~5的黏著薄膜，丙烯酸類聚合物在主成分（甲基）丙烯酸類單體的總量100重量份中，至少含有40重量份以上丙烯酸丁酯。此外，實施例1~5的丙烯酸類聚合物不含有含羧基的共聚性乙烯基單體，丙烯酸類聚合物的Tg為-35℃以上，酸值為0.1以下，重量平均分子量為100萬以上，交聯後的凝膠分率為40~85%。此外，經由黏著劑層而貼合於無鹼玻璃的偏光板的表面的鉛筆硬度，在表觀上仍為2H。由此，若使用本發明的黏著薄膜，貼合了光學部件的層積體的表面硬度的測定值不產生誤差。 此外，實施例1~5的黏著劑層的厚度為10μm的黏著劑層的黏著力為1.5~8.0N/25mm，且耐久性優異。此外，將實施例1~5的黏著薄膜貼合於黏被黏著體後，70℃×10天保存後的黏著力為10N/25mm以下，由此，再操作性也優異。即，根據實施例1~5的黏著薄膜，能夠克服現有技術中的要求事項及問題。As the adhesive films of Examples 1 to 5 of the adhesive film of the present invention, the acrylic polymer contains at least 40 parts by weight or more of butyl acrylate in 100 parts by weight of the total amount of the main component (meth)acrylic monomers. In addition, the acrylic polymers of Examples 1 to 5 do not contain a carboxyl group-containing copolymerizable vinyl monomer. The acrylic polymer has a Tg of -35°C or more, an acid value of 0.1 or less, and a weight average molecular weight of 1 million or more. The gel fraction after crosslinking is 40-85%. In addition, the pencil hardness of the surface of the polarizing plate bonded to the alkali-free glass via the adhesive layer was still 2H in appearance. Therefore, when the adhesive film of the present invention is used, no error occurs in the measured value of the surface hardness of the laminate to which the optical component is bonded. In addition, in Examples 1 to 5, the adhesive layer having a thickness of 10 μm has an adhesive force of 1.5 to 8.0 N/25 mm, and is excellent in durability. In addition, after bonding the adhesive films of Examples 1 to 5 to the adherend, the adhesive force after storage at 70° C. for 10 days was 10 N/25 mm or less, and thus the reworkability was also excellent. That is, according to the adhesive films of Examples 1 to 5, the requirements and problems in the prior art can be overcome.

比較例1的黏著薄膜在丙烯酸類聚合物中含有含羧基的共聚性乙烯基單體，因此丙烯酸類聚合物的酸值大於0.1。此外，由於比較例1的黏著薄膜在丙烯酸類聚合物中不含丙烯酸丁酯，交聯劑的含量過多，丙烯酸類聚合物的Tg低於-35℃，因此再操作性稍差，60℃×90%RH的耐久性差。此外，經由黏著劑層貼合於無鹼玻璃的偏光板的表面的鉛筆硬度，在表觀上從2H降低至H。The adhesive film of Comparative Example 1 contains a carboxyl group-containing copolymerizable vinyl monomer in the acrylic polymer, so the acid value of the acrylic polymer is greater than 0.1. In addition, since the adhesive film of Comparative Example 1 does not contain butyl acrylate in the acrylic polymer, the content of the crosslinking agent is too much, and the Tg of the acrylic polymer is lower than -35°C, so the reworkability is slightly worse, 60°C× The durability of 90%RH is poor. In addition, the pencil hardness of the surface of the polarizing plate bonded to the alkali-free glass through the adhesive layer decreased from 2H to H in appearance.

比較例2的黏著薄膜在丙烯酸類聚合物中不含有丙烯酸丁酯，丙烯酸類聚合物的Tg低於-35℃，交聯劑的含量過多。此外，交聯後的凝膠分率高，因此厚度10μm的黏著劑層的黏著力小於1.5N/25mm，80℃乾燥的耐久性稍差，60℃×90%RH的耐久性差。此外，經由黏著劑層貼合於無鹼玻璃的偏光板的表面的鉛筆硬度，在表觀上從2H降低至H。The adhesive film of Comparative Example 2 does not contain butyl acrylate in the acrylic polymer, the Tg of the acrylic polymer is lower than -35°C, and the content of the crosslinking agent is too much. In addition, the gel fraction after crosslinking is high, so the adhesive strength of the adhesive layer with a thickness of 10μm is less than 1.5N/25mm, the durability of drying at 80°C is slightly worse, and the durability of 60°C×90%RH is poor. In addition, the pencil hardness of the surface of the polarizing plate bonded to the alkali-free glass through the adhesive layer decreased from 2H to H in appearance.

比較例3的黏著薄膜在丙烯酸類聚合物中不含有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，因此即使使用交聯劑，交聯後的凝膠分率為0%（實質上不發生交聯）。此外，丙烯酸類聚合物的Tg低於-35℃，黏著力非常大，再操作性及耐久性差。此外，經由黏著劑層貼合於無鹼玻璃的偏光板的表面的鉛筆硬度，在表觀上從2H降低至H。The adhesive film of Comparative Example 3 does not contain a hydroxyl group-containing copolymerizable vinyl monomer and a carboxyl group-containing copolymerizable vinyl monomer in the acrylic polymer. Therefore, even if a crosslinking agent is used, the gel fraction after crosslinking is 0% (substantially no crosslinking occurs). In addition, the Tg of acrylic polymer is lower than -35°C, the adhesive force is very large, and the reworkability and durability are poor. In addition, the pencil hardness of the surface of the polarizing plate bonded to the alkali-free glass through the adhesive layer decreased from 2H to H in appearance.

由此，在比較例1~3的黏著薄膜中，無法克服現有技術中的要求事項及問題。Therefore, in the adhesive films of Comparative Examples 1 to 3, the requirements and problems in the prior art could not be overcome.

無。no.

無。no.

無。no.

Claims (5)

一種黏著劑層，其特徵在於，為用於光學部件的貼合之黏著劑層， 所述黏著劑層為將包含丙烯酸類聚合物及交聯劑的黏著劑組合物交聯而成， 所述丙烯酸類聚合物是將 選自由（A）烷基的碳原子數為C1~C14的烷基（甲基）丙烯酸酯單體、（B）具有芳香族基的（甲基）丙烯酸酯單體、（C）不含有羥基及羧基的含氮的乙烯基單體、及（D）具有脂環族的（甲基）丙烯酸酯單體所構成的丙烯酸類單體的群組中的至少一種以上的單體、以及 （E）含羥基的共聚性乙烯基單體中的至少一種以上、 在不含含羧基的共聚性乙烯基單體下共聚而成的、由重量平均分子量為100萬以上的共聚體所構成之丙烯酸類聚合物， 所述丙烯酸類聚合物為相對於總量100重量份的所述（A）~（D），以含有至少40重量份以上的比例的丙烯酸丁酯， 以含有0.01~1.0重量份的比例的所述（E）含羥基的共聚性乙烯基單體中的至少一種以上所構成， 所述（C）不含有羥基及羧基的含氮的乙烯基單體為選自由含有醯胺鍵的（甲基）丙烯酸類單體、以及含有胺基的（甲基）丙烯酸類單體所構成之群組中的至少一種以上的化合物， 所述丙烯酸類聚合物的酸價為0.1以下， 所述丙烯酸類聚合物的Tg為-35℃以上， 所述黏著劑組合物為相對於總量100重量份的所述（A）~（D），以含有0.01~1.0重量份的比例的作為所述交聯劑的異氰酸酯化合物所構成， 所述黏著劑組合物為相對於總量100重量份的所述（A）~（D），以更含有0.01~0.5重量份的比例的具有選自由環氧基、（甲基）丙烯醯氧基、巰基、胺基構成的群組中的至少一種的有機官能團的矽烷偶聯劑所構成， 所述黏著劑組合物在交聯後的黏著劑層的凝膠分率為40~85%， 所述黏著劑層的厚度為1μm~20μm，將厚度10μm的黏著劑層轉印至厚度180μm的偏光板膜的單面而得到的黏著薄膜對無鹼玻璃的剝離試驗，以JIS Z0237為標準，在180°方向上以300mm/分鐘的速度進行，所得的厚度10μm的黏著劑層的黏著力為1.5~8.0N/25mm。An adhesive layer, characterized by being an adhesive layer for bonding optical components, The adhesive layer is formed by cross-linking an adhesive composition containing an acrylic polymer and a cross-linking agent, The acrylic polymer is (A) C1-C14 alkyl (meth)acrylate monomers with carbon atoms selected from the alkyl group, (B) (meth)acrylate monomers having an aromatic group, (C) no hydroxyl group And a nitrogen-containing vinyl monomer with a carboxyl group, and (D) at least one monomer from the group of acrylic monomers composed of an alicyclic (meth)acrylate monomer, and (E) At least one of the hydroxyl-containing copolymerizable vinyl monomers, An acrylic polymer composed of a copolymer with a weight average molecular weight of 1 million or more, which is copolymerized without a carboxyl group-containing copolymerizable vinyl monomer, The acrylic polymer contains butyl acrylate in a proportion of at least 40 parts by weight or more with respect to the total amount of 100 parts by weight of the (A) to (D), It is composed of at least one of the (E) hydroxyl-containing copolymerizable vinyl monomers in a ratio of 0.01 to 1.0 parts by weight, The (C) nitrogen-containing vinyl monomer that does not contain a hydroxyl group and a carboxyl group is selected from the group consisting of (meth)acrylic monomers containing amide bonds and (meth)acrylic monomers containing amine groups At least one compound in the group, The acid value of the acrylic polymer is 0.1 or less, The Tg of the acrylic polymer is above -35°C, The adhesive composition is composed of an isocyanate compound as the crosslinking agent in a ratio of 0.01 to 1.0 parts by weight relative to the total amount of 100 parts by weight of the (A) to (D), The adhesive composition is based on the total amount of 100 parts by weight of the (A) to (D), with a ratio of 0.01 to 0.5 parts by weight selected from the group consisting of epoxy and (meth)acrylic acid Is composed of a silane coupling agent with at least one organic functional group from the group consisting of a sulfhydryl group, a sulfhydryl group, and an amine group, The gel fraction of the adhesive layer after crosslinking of the adhesive composition is 40-85%, The adhesive layer has a thickness of 1 μm to 20 μm. The adhesive film obtained by transferring the adhesive layer with a thickness of 10 μm to a single side of a polarizing film with a thickness of 180 μm has a peeling test on alkali-free glass according to JIS Z0237. It is carried out at a speed of 300 mm/min in the 180° direction, and the adhesive force of the resulting adhesive layer with a thickness of 10 μm is 1.5 to 8.0 N/25 mm. 如請求項1所述之黏著劑層，其中，所述（E）含羥基的共聚性乙烯基單體為選自由8-羥基辛基（甲基）丙烯酸酯、6-羥基己基（甲基）丙烯酸酯、4-羥基丁基（甲基）丙烯酸酯、2-羥基乙基（甲基）丙烯酸酯所構成的化合物群組中的至少一種以上。The adhesive layer according to claim 1, wherein the (E) hydroxyl-containing copolymerizable vinyl monomer is selected from 8-hydroxyoctyl (meth)acrylate and 6-hydroxyhexyl (methyl) At least one or more of the compound group consisting of acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. 一種黏著薄膜，其特徵在於，如請求項1或2所述之黏著劑層形成於離型膜的單面上，其為離型膜/黏著劑層/離型膜的結構。An adhesive film, characterized in that the adhesive layer as described in claim 1 or 2 is formed on a single side of the release film, and it has a release film/adhesive layer/release film structure. 一種黏著薄膜，其特徵在於，在基材的單面上，層積有如請求項1或2所述之黏著劑層。An adhesive film characterized in that an adhesive layer as described in claim 1 or 2 is laminated on a single side of a substrate. 一種帶有黏著劑層的偏光板，其使用了如請求項3所述之黏著薄膜。A polarizing plate with an adhesive layer, which uses the adhesive film as described in claim 3.
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JP2019031660A (en) * 2017-08-04 2019-02-28 日本合成化学工業株式会社 Adhesive composition, adhesive using the same, adhesive for polarizing plate, and image display device
US11024831B2 (en) * 2017-11-08 2021-06-01 Sakai Display Products Corporation Display apparatus and method for manufacturing display apparatus
JP7159764B2 (en) * 2018-10-03 2022-10-25 東洋インキＳｃホールディングス株式会社 foam adhesive tape
KR102188402B1 (en) * 2018-11-23 2020-12-08 주식회사 엘엠에스 Adhesive sheet and adhesive material using the same
JP6792657B2 (en) * 2019-02-27 2020-11-25 住友化学株式会社 Laminates, adhesive compositions and adhesive sheets
JP2022530928A (en) 2019-03-07 2022-07-05 ダウ グローバル テクノロジーズ エルエルシー Formaldehyde-free adhesive composition
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Family Cites Families (22)

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JP5082354B2 (en) * 2006-09-11 2012-11-28 Ｄｉｃ株式会社 Protective adhesive film
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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
JP5481040B2 (en) 2008-04-11 2014-04-23 株式会社ジャパンディスプレイ Display device and driving method thereof
JP5472685B2 (en) * 2009-05-27 2014-04-16 Ｄｉｃ株式会社 Anti-scattering adhesive sheet
WO2011040422A1 (en) * 2009-09-29 2011-04-07 リンテック株式会社 Adhesive agent and adhesive sheet
JP5474673B2 (en) * 2010-06-16 2014-04-16 日本合成化学工業株式会社 Emulsion-type pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and pressure-sensitive adhesive sheet peeling method
JP5760571B2 (en) * 2011-03-24 2015-08-12 Dic株式会社 Colored adhesive tape for fixing polarizing film
US20120327510A1 (en) * 2011-06-23 2012-12-27 Nitto Denko Corporation Polarizing plate having pressure-sensitive adhesive layer and image display device
KR20130013995A (en) * 2011-07-29 2013-02-06 동우 화인켐 주식회사 Adhesive composition, polarizing plate and liquid crystal display device comprising the same
JP2013212657A (en) * 2012-04-03 2013-10-17 Dainippon Printing Co Ltd Triacetylcellulose laminate, optical film using the same, and optical member
WO2013176457A1 (en) * 2012-05-21 2013-11-28 주식회사 엘지화학 Optical member, adhesive composition and liquid crystal display device
JP2015525368A (en) * 2012-05-21 2015-09-03 エルジー・ケム・リミテッド Optical member, pressure-sensitive adhesive composition, and liquid crystal display device
JP2014044501A (en) 2012-08-24 2014-03-13 Toppan Printing Co Ltd Manufacturing method of on-cell capacitive touch panel substrate, on-cell capacitive touch panel substrate, and display device
JP6057693B2 (en) * 2012-12-17 2017-01-11 藤森工業株式会社 Adhesive layer and adhesive film
JP6039451B2 (en) * 2013-02-12 2016-12-07 リンテック株式会社 Adhesive for sticking transparent conductive film and adhesive sheet
JP6196781B2 (en) * 2013-02-13 2017-09-13 リンテック株式会社 Adhesive composition, adhesive and adhesive sheet
JP5988889B2 (en) * 2013-02-15 2016-09-07 リンテック株式会社 Adhesive composition, adhesive and adhesive sheet
JP6356383B2 (en) * 2013-02-15 2018-07-11 リンテック株式会社 Adhesive composition, adhesive and adhesive sheet
JP6229926B2 (en) * 2013-06-03 2017-11-15 大日本印刷株式会社 Adhesive composition and adhesive sheet using the same
JP6570266B2 (en) * 2015-03-06 2019-09-04 綜研化学株式会社 Optical laminate
JP6570280B2 (en) * 2015-03-17 2019-09-04 綜研化学株式会社 Adhesive for optical member and optical laminate

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