TW201516125A - Light-diffusing adhesive layer and light-diffusing adhesive film - Google Patents
Light-diffusing adhesive layer and light-diffusing adhesive film Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0268—Diffusing elements; Afocal elements characterized by the fabrication or manufacturing method
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- 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
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Optics & Photonics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Optical Elements Other Than Lenses (AREA)
- Laminated Bodies (AREA)
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Abstract
Description
本發明係關於一種光擴散黏著劑層，以及使用了該光擴散黏著劑層的光擴散黏著膜。更詳細而言，本發明係關於一種主要作為液晶顯示器內的結構構件的、用於貼合光學構件而進行固定的光擴散黏著膜。尤其提供一種具有層疊於液晶顯示器背光源的可視者一側的光擴散片功能、且因未使用光擴散板而能夠實現薄膜化(顯示器厚度的薄型化)的光擴散黏著劑層，以及使用了該光擴散黏著劑層的光擴散黏著膜。The present invention relates to a light diffusing adhesive layer and a light diffusing adhesive film using the light diffusing adhesive layer. More specifically, the present invention relates to a light-diffusing adhesive film which is mainly used as a structural member in a liquid crystal display for fixing an optical member. In particular, a light-diffusing adhesive layer having a function of a light-diffusing sheet laminated on a visible side of a backlight of a liquid crystal display and capable of being thinned (thickness of a display thickness) without using a light-diffusing sheet is provided, and The light diffusing adhesive layer of the light diffuses the adhesive film.
近年來，以中小型尺寸為中心的液晶顯示器的製造、銷售數量正在逐漸增加。另外，伴隨著對中小型尺寸液晶顯示器需求的增加，不斷要求顯示器結構的進一步簡化以及光學構件的薄膜化，從而減少製造成本並實現顯示面板厚度的薄型化。 對於該等的課題，為了介隔黏著劑層將偏光板、相位差板等光學構件貼合在液晶單元等被黏附體上，已提出了各種具有優良黏著力的黏著膜(例如，參照專利文獻1~2)。 專利文獻1中記載了一種將丙烯酸丁酯等作為主要成分的單體並且含有丙烯醯胺化合物等的光學用黏著劑組合物。 專利文獻2中記載了一種將具有碳原子數為4~8的烷基的(甲基)丙烯酸酯作為主要成分的單體並且具有含羧基的單體及含氮乙烯基單體的光學用黏著劑組合物。 另外，提出了為了提高黏著劑層的折射率而經過反復研究的多種黏著膜(例如，參照專利文獻3~9)。 專利文獻3中記載了一種具有芳香環並含有折射率為1.51~1.75的增黏劑的光學用黏著劑組合物。 專利文獻4中記載了一種包括含共聚合性聚合物的黏著劑組合物的黏著片，該共聚合性聚合物係含芳香環的丙烯酸改質單體的共聚合性聚合物。 專利文獻5中記載了一種包括含芳香環的黏性樹脂和芳香族磷酸酯類可塑劑的光學用黏著劑組合物。 專利文獻6中記載了一種由黏著劑組合物固化而成的黏著劑，該黏著劑組合物包括：丙烯酸類樹脂；以及含一個乙烯性不飽和基團的芳香族化合物。 專利文獻7中記載了一種介隔含芳香族單體的丙烯酸類黏著劑將相位差膜和雙折射板相互固定而成的光學零件。 專利文獻8中記載了一種含有聚氨酯樹脂的黏著劑組合物，該聚氨酯樹脂係使芳香族二異氰酸酯和芳香族聚酯二醇反應而成。 專利文獻9中記載了一種在丙烯酸酯共聚物等黏著性樹脂中添加異氰酸酯等交聯劑和由聚苯乙烯樹脂粒子等樹脂粒子構成的光擴散劑而得到的光擴散性黏著劑組合物。 【先前技術文獻】 【專利文獻】In recent years, the number of manufacturing and sales of liquid crystal displays centering on small and medium-sized sizes is gradually increasing. In addition, with the increase in demand for small and medium-sized liquid crystal displays, further simplification of the display structure and thinning of optical members are required, thereby reducing manufacturing costs and achieving thinning of the thickness of the display panel. In order to adhere such an optical member such as a polarizing plate or a retardation film to an adherend such as a liquid crystal cell, such as an adhesive layer, various adhesive films having excellent adhesion have been proposed (for example, refer to the patent literature). 1~2). Patent Document 1 describes an optical adhesive composition containing a butyl acrylate or the like as a main component and containing an acrylamide compound or the like. Patent Document 2 describes an optical adhesive having a monomer having a (meth) acrylate having an alkyl group having 4 to 8 carbon atoms as a main component and having a carboxyl group-containing monomer and a nitrogen-containing vinyl monomer. Composition. Further, various adhesive films which have been repeatedly studied in order to increase the refractive index of the adhesive layer have been proposed (for example, refer to Patent Documents 3 to 9). Patent Document 3 describes an optical adhesive composition having an aromatic ring and containing a tackifier having a refractive index of 1.51 to 1.75. Patent Document 4 describes an adhesive sheet comprising an adhesive composition containing a copolymerizable polymer, which is a copolymerizable polymer of an aromatic ring-containing acrylic modified monomer. Patent Document 5 describes an optical adhesive composition comprising an aromatic ring-containing adhesive resin and an aromatic phosphate-based plasticizer. Patent Document 6 describes an adhesive formed by curing an adhesive composition comprising: an acrylic resin; and an aromatic compound containing one ethylenically unsaturated group. Patent Document 7 describes an optical component in which a retardation film and a birefringent plate are fixed to each other via an acrylic adhesive containing an aromatic monomer. Patent Document 8 describes an adhesive composition containing a urethane resin obtained by reacting an aromatic diisocyanate with an aromatic polyester diol. Patent Document 9 describes a light-diffusing adhesive composition obtained by adding a crosslinking agent such as an isocyanate or a light-diffusing agent composed of resin particles such as polystyrene resin particles to an adhesive resin such as an acrylate copolymer. [Prior Art Literature] [Patent Literature]
【專利文獻1】日本特開2012-177022號公報 【專利文獻2】日本特開2012-201734號公報 【專利文獻3】日本特開2007-084762號公報 【專利文獻4】日本特開2011-153169號公報 【專利文獻5】日本特開2012-167188號公報 【專利文獻6】日本特開2012-021148號公報 【專利文獻7】日本特開2006-293281號公報 【專利文獻8】日本特開2009-091522號公報 【專利文獻9】日本特開平7-216328號公報[Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A-2012-153762 (Patent Document 3) JP-A-2007-084762 (Patent Document 4) Japanese Patent Laid-Open No. 2011-153169 [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. 2012-021148 (Patent Document 7). Japanese Patent Publication No. Hei 7-216328 (Patent Document 9)
【發明所欲解決之課題】[The subject to be solved by the invention]
近年來，為了實現光學構件的薄膜化，作為用於光學構件的層間貼合的黏著膜，要求其為黏著劑層的厚度薄到20μm以下的黏著膜。 通常，黏著劑層的黏著力與黏著劑層的厚度大致成比例，因此，若將黏著劑層的厚度變薄，則隨之會導致黏著力降低。In recent years, in order to achieve thinning of an optical member, an adhesive film for bonding an interlayer of an optical member is required to be an adhesive film having a thickness of the adhesive layer as thin as 20 μm or less. Generally, the adhesive force of the adhesive layer is approximately proportional to the thickness of the adhesive layer. Therefore, if the thickness of the adhesive layer is made thinner, the adhesive force is lowered.
但是，近年來要求黏著膜具有如下性能：即使將黏著劑層的厚度變薄，亦具有與以往的黏著膜(黏著劑層係厚度約為30μm的厚層)同等的黏著力，並且對於高溫、高濕環境下長時間放置後的耐久性而言，亦具有與以往的黏著膜同等以上的性能。 另外，從能夠使黏著劑層的厚度變薄並能夠形成無需實施熟成處理(在恒溫下進行固化)的黏著劑層的觀點出發，要求形成為NCF(Non Carrier Film，非承載膜)的形態，其僅由去掉了黏著膜基材後的黏著劑層構成並具有「脫模膜/黏著劑層/脫模膜」的構件結構。However, in recent years, it is required that the adhesive film has the same performance as that of the conventional adhesive film (thick layer having an adhesive layer thickness of about 30 μm) even when the thickness of the adhesive layer is made thin, and for high temperature, In the high-humidity environment, the durability after standing for a long time also has the same performance as the conventional adhesive film. In addition, from the viewpoint of being able to reduce the thickness of the pressure-sensitive adhesive layer and forming an adhesive layer that does not require a aging treatment (curing at a constant temperature), it is required to form a NCF (Non Carrier Film). It is composed only of an adhesive layer from which the adhesive film substrate has been removed, and has a member structure of a "release film/adhesive layer/release film".
另外，在以往的黏著膜中，由於在被黏附體上貼合黏著膜後實施熟成處理，因此，能夠提高被黏附體和黏著劑層之間的附著性。 但是，對採用NCF形態的黏著膜而言，由於已經完成了黏著劑層的熟成處理，因此被黏附體與黏著劑層之間的附著性不足。基於此，存在需要對被黏附體的表面進行電暈處理等表面處理的問題。 因此需要一種滿足這些要求和克服這些問題的黏著膜。Further, in the conventional adhesive film, since the adhesive film is bonded to the adherend and the aging treatment is performed, the adhesion between the adherend and the adhesive layer can be improved. However, in the case of the adhesive film using the NCF form, since the aging process of the adhesive layer has been completed, the adhesion between the adherend and the adhesive layer is insufficient. Based on this, there is a problem that it is necessary to perform surface treatment such as corona treatment on the surface of the adherend. There is therefore a need for an adhesive film that meets these requirements and overcomes these problems.
本發明的課題在於提供一種光擴散黏著劑層、及使用了該光擴散黏著劑層的光擴散黏著膜，其中，該光擴散黏著劑層係能夠替代以往的光擴散板加以使用的光學構件，其具有光擴散片的功能，且能夠實現顯示器厚度的薄型化。 【解決課題之手段】An object of the present invention is to provide a light-diffusing adhesive layer and a light-diffusing adhesive film using the light-diffusing adhesive layer, wherein the light-diffusing adhesive layer can replace an optical member used in a conventional light-diffusing sheet. It has the function of a light diffusion sheet, and can realize thinning of the thickness of the display. [Means for solving the problem]
為了解決上述課題，本發明的光擴散黏著劑層的技術思想在於，藉由包含共聚物和交聯劑以及矽微粒子的黏著劑層來形成光擴散黏著劑層，其中，該共聚物包含：烷基的碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種以上；以及作為含有可共聚的官能基的單體；該單體係選自於含羥基的共聚合性單體、含羧基的共聚合性單體、含氮乙烯基單體、含芳香族的單體構成的群組中至少一種以上。 另外，為了解決上述課題，本發明提供一種光擴散黏著劑層，其係具有光擴散功能的光擴散黏著劑層，該光擴散黏著劑層由含有共聚物和交聯劑以及矽類粒子的黏著劑組合物形成；該共聚物包含：烷基的碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種以上；以及作為含有可共聚的官能基的單體；該單體係選自於由含羥基的共聚合性單體、含羧基的共聚合性單體、含氮乙烯基單體以及含芳香族的單體構成的群組中至少一種以上，而且，該光擴散黏著劑層的透射率為90%以上、霧度值為40%以上、折射率為1.47以上。In order to solve the above problems, the technical idea of the light-diffusing adhesive layer of the present invention is to form a light-diffusing adhesive layer by an adhesive layer containing a copolymer and a crosslinking agent and fine particles, wherein the copolymer contains: an alkane a group having at least one of C1 to C14 alkyl (meth) acrylate monomers; and a monomer having a copolymerizable functional group; the single system is selected from a hydroxyl group-containing copolymerization At least one or more of the group consisting of a monomer, a carboxyl group-containing copolymerizable monomer, a nitrogen-containing vinyl monomer, and an aromatic-containing monomer. Further, in order to solve the above problems, the present invention provides a light-diffusing adhesive layer which is a light-diffusing adhesive layer having a light diffusing function, and the light-diffusing adhesive layer is adhered by a copolymer containing a crosslinking agent and a ruthenium-based particle. a composition comprising: at least one of an alkyl (meth) acrylate monomer having an alkyl group having from C1 to C14; and a monomer having a copolymerizable functional group; The single system is at least one selected from the group consisting of a hydroxyl group-containing copolymerizable monomer, a carboxyl group-containing copolymerizable monomer, a nitrogen-containing vinyl monomer, and an aromatic-containing monomer, and The light-diffusing adhesive layer has a transmittance of 90% or more, a haze value of 40% or more, and a refractive index of 1.47 or more.
另外，該光擴散黏著劑層的厚度為20μm時對於玻璃板的黏著力為2.0N/25 mm以上較為理想。Further, when the thickness of the light-diffusing adhesive layer is 20 μm, the adhesion to the glass plate is preferably 2.0 N/25 mm or more.
另外，該黏著劑組合物係相對於100重量份的共聚物宜含有0.01~5重量份的作為交聯劑的異氰酸酯化合物、0.5~20重量份的矽類粒子而成，其中，該共聚物係由烷基的碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種以上、以及作為含有可共聚的官能基的單體；該單體係選自於含羥基的共聚合性單體、含羧基的共聚合性單體、含氮乙烯基單體和含芳香族的單體構成的群組中至少一種以上所構成的重量平均分子量為20~250萬的共聚物。Further, the adhesive composition is preferably contained in an amount of 0.01 to 5 parts by weight, based on 100 parts by weight of the copolymer, of an isocyanate compound as a crosslinking agent and 0.5 to 20 parts by weight of anthraquinone particles. At least one or more of alkyl (meth) acrylate monomers having an alkyl group having from C1 to C14; and a monomer having a copolymerizable functional group; the single system is selected from the group consisting of hydroxyl groups a copolymer having a weight average molecular weight of 20 to 2.5 million formed by at least one of a group consisting of a copolymerizable monomer, a carboxyl group-containing copolymerizable monomer, a nitrogen-containing vinyl monomer, and an aromatic-containing monomer .
另外，該光擴散黏著劑層的霧度值為40%以上90%以下較為理想。Further, the light diffusing adhesive layer preferably has a haze value of 40% or more and 90% or less.
另外，該矽類粒子係選自於由二氧化矽粒子、二氧化矽三聚氰胺核殼粒子、矽酮粒子所組成的組中的一種以上較為理想。Further, the ruthenium-based particles are preferably one or more selected from the group consisting of cerium oxide particles, cerium oxide melamine core-shell particles, and fluorenone particles.
另外，本發明提供一種在脫模膜的單面形成有該光擴散黏著劑層並具有脫模膜/光擴散黏著劑層/脫模膜的結構的光擴散黏著膜。Further, the present invention provides a light-diffusing adhesive film having a structure in which the light-diffusing adhesive layer is formed on one surface of a release film and has a release film/light-diffusion adhesive layer/release film.
另外，本發明提供一種在基材的單面層疊該光擴散黏著劑層而成的光擴散黏著膜。Further, the present invention provides a light-diffusing adhesive film in which the light-diffusing adhesive layer is laminated on one surface of a substrate.
另外，本發明提供一種使用了該光擴散黏著膜的偏光板週邊構件用黏著膜。Further, the present invention provides an adhesive film for a peripheral member of a polarizing plate using the light-diffusing adhesive film.
另外，本發明提供一種在偏光板與增亮膜之間的層間使用了該光擴散黏著劑層的黏著膜。Further, the present invention provides an adhesive film using the light-diffusing adhesive layer between layers between a polarizing plate and a brightness enhancing film.
另外，本發明提供一種帶有黏著劑層的光學膜，其在光學膜的至少一個面上層疊有該光擴散黏著劑層。 【發明之效果】Further, the present invention provides an optical film with an adhesive layer laminated with a light-diffusing adhesive layer on at least one side of the optical film. [Effects of the Invention]
基於本發明，能夠提供一種光擴散黏著劑層以及使用了該光擴散黏著劑層的光擴散黏著膜，該光擴散黏著劑層係克服了以往的要求事項和問題從而能夠替代以往的光擴散板加以使用的光學構件，具有光擴散片的功能且能夠實現顯示器厚度的薄型化。According to the present invention, it is possible to provide a light-diffusing adhesive layer and a light-diffusing adhesive film using the light-diffusing adhesive layer, which overcomes conventional requirements and problems and can replace the conventional light-diffusing sheet The optical member to be used has a function as a light diffusion sheet and can achieve a reduction in thickness of the display.
下面，基於適當的實施方式說明本發明。 本發明的光擴散黏著劑層係具有光擴散功能的光擴散黏著劑層，該光擴散黏著劑層由含有丙烯酸類聚合物和矽類粒子的黏著劑組合物而形成，該光擴散黏著劑層的透射率為90%以上，霧度值為40%以上，折射率為1.47以上。 另外，該光擴散黏著劑層的霧度值為40%以上90%以下較為理想。另外，該光擴散黏著劑層由含有共聚物(丙烯酸類聚合物)和交聯劑以及矽類粒子的黏著劑組合物來形成較為理想，其中該共聚物包含：烷基的碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種以上；以及作為含有可共聚的官能基的單體的選自於由含羥基的共聚合性單體、含羧基的共聚合性單體、含氮乙烯基單體和含芳香族的單體構成的群組中至少一種以上。 另外，在前述黏著劑組合物中，相對於黏著劑組合物的丙烯酸類聚合物(共聚物)100重量份，含有50~98重量份的烷基的碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種以上、以及2~50重量份作為含有可共聚的官能基的單體；該單體係選自於由含羥基的共聚合性單體、含羧基的共聚合性單體、含氮乙烯基單體和含芳香族的單體構成的群組中至少一種以上的含官能基的單體；並且，對該含官能基的單體的摻合比例而言，相對於100重量份作為主要成分的(甲基)丙烯酸烷基酯單體、烷基的碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體，含有0.1~50重量份的含羥基的共聚合性單體、0~5重量份(當含有時為0.1~5重量份)的含羧基的共聚合性單體、0~50重量份(當含有時為5~50重量份)的含氮乙烯基單體、0~30重量份(當含有時為5~30重量份)的含芳香族的單體較為理想。 另外，相對於100重量份的共聚物，含有0.01~5重量份作為交聯劑的異氰酸酯化合物、0.5~20重量份的矽類粒子較為理想。Hereinafter, the present invention will be described based on appropriate embodiments. The light-diffusing adhesive layer of the present invention is a light-diffusing adhesive layer having a light-diffusing function, and the light-diffusing adhesive layer is formed of an adhesive composition containing an acrylic polymer and cerium-based particles, and the light-diffusing adhesive layer The transmittance is 90% or more, the haze value is 40% or more, and the refractive index is 1.47 or more. Further, the light diffusing adhesive layer preferably has a haze value of 40% or more and 90% or less. Further, the light-diffusing adhesive layer is preferably formed of an adhesive composition containing a copolymer (acrylic polymer) and a crosslinking agent and an anthracene-based particle, wherein the copolymer contains: an alkyl group having a carbon number of C1 At least one or more of ~C14 alkyl (meth) acrylate monomers; and a monomer having a copolymerizable functional group selected from a hydroxyl group-containing copolymerizable monomer, a carboxyl group-containing copolymerization property At least one or more of the group consisting of a monomer, a nitrogen-containing vinyl monomer, and an aromatic-containing monomer. Further, in the above-mentioned adhesive composition, 50 to 98 parts by weight of an alkyl group having a carbon number of C1 to C14 (methyl group) per 100 parts by weight of the acrylic polymer (copolymer) of the adhesive composition At least one or more and 2 to 50 parts by weight of the alkyl acrylate monomer as a monomer having a copolymerizable functional group; the single system is selected from a hydroxyl group-containing copolymerizable monomer, a carboxyl group-containing monomer At least one or more functional group-containing monomers in a group consisting of a copolymerizable monomer, a nitrogen-containing vinyl monomer, and an aromatic-containing monomer; and, a blending ratio of the functional group-containing monomer In an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the alkyl (meth) acrylate monomer as a main component and an alkyl (meth) acrylate monomer having an alkyl group having C1 to C14; The hydroxyl group-containing copolymerizable monomer, 0 to 5 parts by weight (0.1 to 5 parts by weight when contained) of the carboxyl group-containing copolymerizable monomer, 0 to 50 parts by weight (when contained, 5 to 50 parts by weight) The nitrogen-containing vinyl monomer is preferably from 0 to 30 parts by weight (5 to 30 parts by weight when contained) of an aromatic-containing monomer. Further, it is preferable to contain 0.01 to 5 parts by weight of an isocyanate compound as a crosslinking agent and 0.5 to 20 parts by weight of an anthracene particle with respect to 100 parts by weight of the copolymer.
作為烷基的碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體，可列舉：(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)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯等中的至少一種以上。(甲基)丙烯酸烷基酯單體中的烷基可為直鏈狀、支鏈狀、環狀中的任意一種。相對於黏著劑組合物的丙烯酸類聚合物(共聚物)100重量份，烷基的碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體的比例為50~98重量份較為理想。Examples of the (meth)acrylic acid alkyl ester monomer having a C1 to C14 carbon atom in the alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. Isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, Octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, (methyl) Ethyl acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, (a) At least one of cyclopentyl acrylate, cyclohexyl (meth) acrylate, and the like. The alkyl group in the alkyl (meth)acrylate monomer may be any of a linear chain, a branched chain, and a cyclic group. It is preferable that the ratio of the alkyl (meth)acrylic acid alkyl ester monomer having a C1 to C14 alkyl group is 50 to 98 parts by weight based on 100 parts by weight of the acrylic polymer (copolymer) of the adhesive composition. .
作為含芳香基的共聚合性乙烯基單體(含有芳香族的單體)，可列舉：(甲基)丙烯酸酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苯氧乙酯、(甲基)丙烯酸苯氧丁酯、(甲基)丙烯酸2-(1-萘氧基)乙酯、(甲基)丙烯酸2-(2-萘氧基)乙酯、(甲基)丙烯酸6-(1-萘氧基)己酯、(甲基)丙烯酸6-(2-萘氧基)己酯、(甲基)丙烯酸8-(1-萘氧基)辛酯、(甲基)丙烯酸8-(2-萘氧基)辛酯等含芳香族的丙烯酸類單體，苯乙烯等含芳香族的乙烯基單體。為了得到折射率高的黏著劑層，摻合至少一種以上的含芳香族的單體較為理想。 藉由將該等含芳香族的單體與作為主要成分單體的烷基碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體加以混合，能夠使所得到的光擴散黏著劑層的折射率提高而進行調整，減小光學構件間的折射率差，降低全反射，由此能夠提高全光線透射率。在本發明的光擴散黏著劑層中，當黏著劑組合物包括含芳香族的單體時，相對於100重量份作為主要成分的(甲基)丙烯酸烷基酯單體，含芳香族的單體的含量為5~30重量份較為理想。As the aromatic group-containing copolymerizable vinyl monomer (aromatic-containing monomer), (meth)acrylic acid is exemplified. Ester, naphthyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxybutyl (meth)acrylate, 2-(1-naphthyloxy)ethyl (meth)acrylate, (methyl) ) 2-(2-naphthyloxy)ethyl acrylate, 6-(1-naphthalenyloxy)hexyl (meth)acrylate, 6-(2-naphthyloxy)hexyl (meth)acrylate, (A) Aromatic acrylic monomer such as 8-(1-naphthyloxy)octyl acrylate or 8-(2-naphthyloxy)octyl (meth)acrylate, aromatic vinyl such as styrene monomer. In order to obtain an adhesive layer having a high refractive index, it is preferred to blend at least one or more aromatic-containing monomers. The obtained light-diffusing adhesive can be obtained by mixing the aromatic-containing monomer with a (meth)acrylic acid alkyl ester monomer having an alkyl group having a C1 to C14 alkyl group as a main component monomer. The refractive index of the layer is adjusted to be adjusted, the refractive index difference between the optical members is reduced, and total reflection is reduced, whereby the total light transmittance can be improved. In the light-diffusing adhesive layer of the present invention, when the adhesive composition comprises an aromatic-containing monomer, an aromatic-containing single is used with respect to 100 parts by weight of the alkyl (meth)acrylate monomer as a main component. The content of the body is preferably 5 to 30 parts by weight.
作為含氮乙烯基單體，可列舉例如：N-乙烯基吡咯啶酮(N-vinylpyrrolidone)、N-乙烯基己內醯胺、(甲基)丙烯醯啉((meth) acryloyl morpholine)等環狀氮乙烯基化合物；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、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(甲基)丙烯醯胺、N,N-二異丙基(甲基)丙烯醯胺、N,N-二丁基(甲基)丙烯醯胺等二烷基取代(甲基)丙烯醯胺；(甲基)丙烯酸N-乙基-N-甲基胺乙酯、(甲基)丙烯酸N-甲基-N-丙基胺乙酯、(甲基)丙烯酸N-甲基-N-異丙基胺乙酯、(甲基)丙烯酸N,N-二甲基胺甲酯、(甲基)丙烯酸N,N-二甲基胺乙酯、(甲基)丙烯酸N,N-二甲基胺丙酯、(甲基)丙烯酸N,N-二甲基胺丁酯、(甲基)丙烯酸N,N-二丙基胺乙酯、(甲基)丙烯酸N,N-二丁基胺乙酯等(甲基)丙烯酸二烷基胺酯；N-乙基-N-甲基胺丙基(甲基)丙烯醯胺、N-甲基-N-丙基胺丙基(甲基)丙烯醯胺、N-甲基-N-異丙基胺丙基(甲基)丙烯醯胺、N,N-二甲基胺丙基(甲基)丙烯醯胺、N,N-二乙基胺丙基(甲基)丙烯醯胺、N,N-二丙基胺丙基(甲基)丙烯醯胺、N,N-二甲基胺乙基(甲基)丙烯醯胺、N,N-二乙基胺乙基(甲基)丙烯醯胺等二烷基取代胺基烷基(甲基)丙烯醯胺等中的至少一種以上。Examples of the nitrogen-containing vinyl monomer include N-vinylpyrrolidone, N-vinyl caprolactam, and (meth)acryl oxime. a cyclic nitrogen-vinyl compound such as (meth) acryloyl morpholine; N-ethyl-N-methyl (meth) acrylamide, N-methyl-N-propyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide, N,N-dimethyl(meth) acrylamide, N,N-diethyl(meth) decylamine, N, Dialkyl substitutions such as N-dipropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-dibutyl(meth)acrylamide Acrylamide; N-ethyl-N-methylamine ethyl (meth)acrylate, N-methyl-N-propylamine ethyl (meth)acrylate, N-methyl (meth)acrylate Base-N-isopropylamine ethyl ester, N,N-dimethylamine methyl (meth)acrylate, N,N-dimethylamine ethyl (meth)acrylate, N (meth)acrylate N-dimethylaminopropyl propyl ester, N,N-dimethylamine butyl (meth)acrylate, N,N-dipropylamine ethyl (meth)acrylate, N,N-(meth)acrylate Dialkylamine (meth)acrylate such as dibutylamine ethyl ester; N-ethyl-N-methylaminopropyl (meth) acrylamide, N-methyl-N-propylaminopropyl (Meth) acrylamide, N-methyl-N-isopropylamine propyl (meth) acrylamide, N, N-dimethyl Propyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dipropylaminopropyl (meth) acrylamide, N, N- a dialkyl substituted aminoalkyl (meth) acrylamide such as dimethylamine ethyl (meth) acrylamide or N,N-diethylamine ethyl (meth) acrylamide At least one or more.
為了能夠區別於後述的含羥基的共聚合性單體，作為該含氮乙烯基單體宜為不含有羥基的單體，不含有羥基和羧基的單體更佳。作為這樣的單體，於上述例示的單體，例如，含有N,N-二烷基取代胺基或N,N-二烷基取代醯胺基的丙烯酸類單體；N-乙烯基吡咯啶酮、N-乙烯基己內醯胺等的N-乙烯基取代內醯胺類；N-(甲基)丙烯醯啉等的N-(甲基)丙烯醯基取代環狀胺類較為理想。In order to distinguish it from the hydroxyl group-containing copolymerizable monomer to be described later, the nitrogen-containing vinyl monomer is preferably a monomer having no hydroxyl group, and the monomer having no hydroxyl group or carboxyl group is more preferable. As such a monomer, the monomer exemplified above, for example, an acrylic monomer containing an N,N-dialkyl substituted amine group or an N,N-dialkyl substituted decylamino group; N-vinylpyrrolidine N-vinyl substituted indolamines such as ketones, N-vinyl caprolactam, etc.; N-(methyl) propylene oxime An N-(meth)acryloyl group-substituted cyclic amine such as a phenyl group is preferred.
另外，在本發明的光擴散黏著劑層中，黏著劑組合物所含有的含氮乙烯基單體，能夠賦予光擴散黏著劑層必要的黏著力和耐久性。在本發明的光擴散黏著劑層中，相對於100重量份作為主要成分的(甲基)丙烯酸烷基酯單體，黏著劑組合物中含有的含氮乙烯基單體的含量為5~50重量份較為理想。 另外，在本發明的光擴散黏著劑層中，作為黏著劑組合物所含的含氮乙烯基單體，N-乙烯基吡咯啶酮、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(甲基)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,N-二甲基胺丙基(甲基)丙烯醯胺、N,N-二乙基胺丙基(甲基)丙烯醯胺、N,N-二甲基胺乙基(甲基)丙烯醯胺、N-乙烯基己內醯胺等特別適用。Further, in the light-diffusing adhesive layer of the present invention, the nitrogen-containing vinyl monomer contained in the adhesive composition can impart the necessary adhesive force and durability to the light-diffusing adhesive layer. In the light-diffusing adhesive layer of the present invention, the content of the nitrogen-containing vinyl monomer contained in the adhesive composition is 5 to 50 with respect to 100 parts by weight of the alkyl (meth)acrylate monomer as a main component. The weight is ideal. Further, in the light-diffusing adhesive layer of the present invention, as a nitrogen-containing vinyl monomer contained in the adhesive composition, N-vinylpyrrolidone, N,N-dimethyl(meth)acrylamide , N,N-Diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N -dibutyl(meth)acrylamide, N,N-dimethylaminopropyl (meth) acrylamide, N,N-diethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N-vinyl caprolactam, and the like are particularly suitable.
作為含有羧基的共聚性乙烯基單體(含羧基的共聚合性單體)，可列舉例如：(甲基)丙烯酸、(甲基)丙烯酸羧乙酯、甲基丙烯酸羧戊酯、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基馬來酸、羧基聚己內酯單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基四氫鄰苯二甲酸等中的至少一種以上。 另外，在本發明的光擴散黏著劑層中，黏著劑組合物所含有的含羧基的共聚合性單體能夠賦予光擴散黏著劑層必要的凝聚力。在本發明的光擴散黏著劑層中，黏著劑組合物亦可不含有含羧基的共聚合性單體，但當含有時，相對於100重量份作為主要成分的(甲基)丙烯酸烷基酯單體，含羧基的共聚合性單體的含量為0.1~5重量份較為理想。Examples of the carboxyl group-containing copolymerizable vinyl monomer (carboxyl group-containing copolymerizable monomer) include (meth)acrylic acid, (meth)acrylic acid carboxyethyl ester, carboxy amyl methacrylate, and 2-( Methyl) propylene methoxyethyl hexahydrophthalic acid, 2-(methyl) propylene methoxy propyl hexahydrophthalic acid, 2-(methyl) propylene methoxyethyl phthalate Formic acid, 2-(methyl) propylene methoxyethyl succinic acid, 2-(methyl) propylene oxiranyl ethyl maleic acid, carboxy polycaprolactone mono (meth) acrylate, 2- (A) At least one of acryloxyethyltetrahydrophthalic acid and the like. Further, in the light-diffusing adhesive layer of the present invention, the carboxyl group-containing copolymerizable monomer contained in the adhesive composition can impart a necessary cohesive force to the light-diffusing adhesive layer. In the light-diffusing adhesive layer of the present invention, the adhesive composition may not contain a carboxyl group-containing copolymerizable monomer, but when it is contained, relative to 100 parts by weight of the alkyl (meth)acrylate as a main component The content of the carboxyl group-containing copolymerizable monomer is preferably 0.1 to 5 parts by weight.
作為含羥基的共聚合性乙烯基單體(含羥基的共聚合性單體)，可列舉例如：(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)丙烯酸羥基乙酯等(甲基)丙烯酸羥基烷基酯類，N-羥基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥乙基(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。 另外，在本發明的光擴散黏著劑層中，黏著劑組合物所含的含羥基的共聚合性單體，能夠作為用於減少含羧基的共聚合性單體的含量的共聚合性單體來使用，而該含羧基的單體使所得到的光擴散黏著劑層對透明導電性膜的ITO表面等易腐蝕的被黏附體產生腐蝕性影響。因此，含羥基的共聚合性單體能夠有助於提高光擴散黏著劑層的黏著力並且減少腐蝕性。在本發明的光擴散黏著劑層中，相對於100重量份作為主要成分的(甲基)丙烯酸烷基酯單體，黏著劑組合物中含有的含羥基的共聚合性單體的含量為0.1~50重量份較為理想。Examples of the hydroxyl group-containing copolymerizable vinyl monomer (hydroxy group-containing copolymerizable monomer) include 8-hydroxyoctyl (meth)acrylate and 6-hydroxyhexyl (meth)acrylate. (hydroxy) hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl acrylate or hydroxyethyl (meth) acrylate, N-hydroxy(meth) acrylamide, N-methylol (meth) propylene At least one or more of hydroxyl group-containing (meth) acrylamides such as guanamine and N-hydroxyethyl (meth) acrylamide. Further, in the light-diffusing adhesive layer of the present invention, the hydroxyl group-containing copolymerizable monomer contained in the adhesive composition can be used as a copolymerizable monomer for reducing the content of the carboxyl group-containing copolymerizable monomer. The carboxyl group-containing monomer causes the obtained light-diffusing adhesive layer to have a corrosive effect on the easily corroded adherend such as the ITO surface of the transparent conductive film. Therefore, the hydroxyl group-containing copolymerizable monomer can contribute to the improvement of the adhesion of the light-diffusing adhesive layer and the reduction of corrosion. In the light-diffusing adhesive layer of the present invention, the content of the hydroxyl group-containing copolymerizable monomer contained in the adhesive composition is 0.1 with respect to 100 parts by weight of the alkyl (meth)acrylate monomer as a main component. ~50 parts by weight is preferred.
本發明的光擴散黏著劑層中使用的黏著劑組合物的丙烯酸類聚合物，宜為由烷基的碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種以上、與作為含有可共聚的官能基的單體；該單體係選自於含羥基的共聚合性單體、含羧基的共聚合性單體、含氮乙烯基單體和含芳香族的單體構成的群組中至少一種以上所構成的重量平均分子量為20~250萬的共聚物。The acrylic polymer of the adhesive composition used in the light-diffusing adhesive layer of the present invention is preferably at least one selected from the group consisting of alkyl (meth) acrylate monomers having an alkyl group having from C1 to C14. And as a monomer having a copolymerizable functional group; the single system is selected from a hydroxyl group-containing copolymerizable monomer, a carboxyl group-containing copolymerizable monomer, a nitrogen-containing vinyl monomer, and an aromatic-containing single A copolymer having at least one or more of the group consisting of a weight average molecular weight of from 2 to 2.5 million.
對共聚物的聚合方法沒有特別的限定，可以使用溶液聚合法、乳化聚合法等合適、已知的聚合方法。共聚物的重量平均分子量宜為20萬~250萬。 該共聚物宜為丙烯酸類聚合物，含有(甲基)丙烯酸酯單體或(甲基)丙烯酸、(甲基)丙烯醯胺類等的丙烯酸類單體50~100重量%較為理想。The polymerization method of the copolymer is not particularly limited, and a suitable and known polymerization method such as a solution polymerization method or an emulsion polymerization method can be used. The weight average molecular weight of the copolymer is preferably from 200,000 to 2.5 million. The copolymer is preferably an acrylic polymer, and preferably contains 50 to 100% by weight of an acrylic monomer such as a (meth) acrylate monomer or (meth)acrylic acid or (meth) acrylamide.
前述黏著劑組合物中，藉由在該共聚物(丙烯酸類聚合物)中摻合作為光擴散劑的矽類粒子，能夠賦予所需的光學特性(透射率、霧度值)。進而，藉由摻合交聯劑、適宜的任意添加劑，能夠調整所需的物理性質等特性。In the above-mentioned adhesive composition, desired optical characteristics (transmittance, haze value) can be imparted by incorporating the ruthenium-based particles which are a light diffusing agent in the copolymer (acrylic polymer). Further, by blending a crosslinking agent and a suitable optional additive, properties such as desired physical properties can be adjusted.
作為矽類粒子，可以選自含矽化合物的單個粒子或複合粒子中，具體而言，可列舉：二氧化矽粒子、二氧化矽三聚氰胺核殼粒子、矽酮粒子、矽酸鹽玻璃粒子等。宜為選自於由二氧化矽粒子、二氧化矽三聚氰胺核殼粒子、矽酮粒子所組成的組中的一種以上。二氧化矽三聚氰胺核殼粒子，係具有三聚氰胺的核和二氧化矽的殼的複合粒子。該複合粒子具有將膠體二氧化矽的微小粒子(奈米粒子)緊密地填充於三聚氰胺粒子的表面而成的結構。作為矽酮粒子，可列舉矽酮樹脂粒子、矽酮橡膠粒子、交聯矽酮粒子等。 本發明的光擴散黏著劑層使用的黏著劑組合物中，相對於100重量份的丙烯酸類聚合物，含有0.5~20重量份的矽類粒子較為理想。The ruthenium-based particles may be selected from individual particles or composite particles containing a ruthenium compound, and specific examples thereof include ruthenium dioxide particles, cerium oxide melamine core-shell particles, anthrone particles, and silicate glass particles. It is preferably one or more selected from the group consisting of cerium oxide particles, cerium oxide melamine core-shell particles, and anthrone particles. The cerium oxide melamine core-shell particle is a composite particle having a core of melamine and a shell of cerium oxide. This composite particle has a structure in which fine particles (nanoparticles) of colloidal cerium oxide are closely packed on the surface of melamine particles. Examples of the anthrone particles include an anthrone resin particle, an anthrone rubber particle, and a crosslinked anthrone particle. The adhesive composition used in the light-diffusing adhesive layer of the present invention preferably contains 0.5 to 20 parts by weight of anthraquinone particles per 100 parts by weight of the acrylic polymer.
作為交聯劑，可列舉：六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯(isophorone diisocyanate)、二苯基甲烷二異氰酸酯、甲苯二異氰酸酯、苯二甲基二異氰酸酯等的二異氰酸酯類的縮二脲改質體(burette-modified products)或異氰脲酸酯改質體、與三羥甲基丙烷或丙三醇等三價以上的多元醇的加成物等的聚異氰酸酯化合物、金屬類螯合物、環氧化合物等中的至少一種以上。另外，亦可藉由紫外線等光交聯來使黏著劑進行交聯。 在使用交聯劑來使共聚物交聯的情況下，共聚物具有能夠與交聯劑進行交聯反應的官能基(根據交聯劑的種類可以選擇羥基或羧基等)較為理想，而且宜為含有在側鏈具有該等官能基的單體。另外，相對於100重量份的共聚物，黏著劑組合物含有0.01~5重量份作為交聯劑的異氰酸酯化合物較為理想。Examples of the crosslinking agent include diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and benzodimethyl diisocyanate. A polyisocyanate compound or a metal such as a burette-modified product, an isocyanurate modified product, or an adduct of a trivalent or higher polyhydric alcohol such as trimethylolpropane or glycerin At least one of a chelate compound, an epoxy compound, and the like. Further, the adhesive may be crosslinked by photocrosslinking such as ultraviolet rays. When a crosslinking agent is used to crosslink the copolymer, the copolymer has a functional group capable of crosslinking reaction with a crosslinking agent (a hydroxyl group or a carboxyl group may be selected depending on the kind of the crosslinking agent), and is preferably A monomer having such functional groups in a side chain. Further, it is preferred that the adhesive composition contains 0.01 to 5 parts by weight of an isocyanate compound as a crosslinking agent with respect to 100 parts by weight of the copolymer.
作為其它任意成分，可以適宜地摻合矽烷偶聯劑、抗氧化劑、界面活性劑、固化促進劑、可塑劑、填充劑、交聯催化劑、交聯抑制劑、固化抑制劑、加工助劑、抗老化劑等已知的添加劑。這些既可單獨使用，亦可組合兩種以上使用。As other optional components, a decane coupling agent, an antioxidant, a surfactant, a curing accelerator, a plasticizer, a filler, a crosslinking catalyst, a crosslinking inhibitor, a curing inhibitor, a processing aid, and an antibiotic may be suitably blended. A known additive such as an aging agent. These may be used alone or in combination of two or more.
本發明的光擴散黏著劑層可以藉由在基材或脫模膜上塗布該黏著劑組合物後，使黏著劑組合物交聯而得到。The light-diffusing 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.
用於光學構件的層間貼合等的黏著劑層，希望為薄的黏著劑層，該光擴散黏著劑層的厚度為1µm~20µm較為理想。另外，通常黏著劑層的黏著力與黏著劑層的厚度大致成比例，但光擴散黏著劑層的厚度為20μm時對玻璃板的黏著力為2.0N/25mm以上較為理想。另外，當黏著劑層的厚度不為20µm的情況下，「厚度20µm時的黏著力」(N/25mm)係將黏著劑層的厚度設定為T(µm)、將黏著劑層的黏著力設定為F(N/25mm)，並可藉由算式「(厚度20µm時的黏著力)=20F/T」來推算。The adhesive layer used for the interlayer bonding of the optical member is desirably a thin adhesive layer, and the thickness of the light-diffusing adhesive layer is preferably 1 μm to 20 μm. Further, in general, the adhesive force of the adhesive layer is substantially proportional to the thickness of the adhesive layer. However, when the thickness of the light-diffusing adhesive layer is 20 μm, the adhesion to the glass plate is preferably 2.0 N/25 mm or more. In addition, when the thickness of the adhesive layer is not 20 μm, the "adhesion at a thickness of 20 μm" (N/25 mm) is set such that the thickness of the adhesive layer is T (μm), and the adhesive force of the adhesive layer is set. It is F (N/25 mm) and can be estimated by the formula "(adhesion at thickness 20 μm) = 20 F/T".
當將本發明的光擴散黏著劑層用於光學構件的層間貼合等中時，光擴散黏著劑層的透射率為90%以上、霧度值為40%以上、折射率為1.47以上較為理想。霧度值宜為40%以上90%以下。為了減少光擴散黏著劑層與光學構件之間介面上的光線反射，希望折射率差盡可能小。因此，該光擴散黏著劑層的折射率宜為1.47~1.50。When the light-diffusing adhesive layer of the present invention is used for interlayer bonding or the like of an optical member, the light-diffusing adhesive layer has a transmittance of 90% or more, a haze value of 40% or more, and a refractive index of 1.47 or more. . The haze value is preferably 40% or more and 90% or less. In order to reduce light reflection on the interface between the light-diffusing adhesive layer and the optical member, it is desirable that the refractive index difference be as small as possible. Therefore, the refractive index of the light-diffusing adhesive layer is preferably 1.47 to 1.50.
本發明的光擴散黏著膜可藉由在基材或脫模膜的單面形成本發明的光擴散黏著劑層來製造。 作為用於形成光擴散黏著劑層的基材膜或保護黏著面的脫模膜(隔膜)，可以使用聚酯膜等樹脂膜等。 對基材膜而言，可在樹脂膜的與形成有光擴散黏著劑層一側相反的面上，實施藉由矽酮類、氟類的脫模劑或塗層劑、二氧化矽微粒等進行的防汙處理，可實施藉由抗靜電劑的塗布或混入等進行的抗靜電處理。The light-diffusing adhesive film of the present invention can be produced by forming the light-diffusing adhesive layer of the present invention on one side of a substrate or a release film. As the release film (separator) for forming the base film of the light-diffusing adhesive layer or the protective adhesive surface, a resin film such as a polyester film or the like can be used. In the base film, a release agent, a coating agent, a cerium oxide particle, or the like by an anthrone or a fluorine-based release agent may be applied to a surface of the resin film opposite to the side on which the light-diffusing adhesive layer is formed. The antifouling treatment to be carried out can be carried out by an antistatic treatment by application or mixing of an antistatic agent.
對脫模膜而言，在與光擴散黏著劑層的黏著面進行貼合一側的面上，實施藉由矽酮類、氟類的脫模劑等進行的脫模處理。 藉由在一個光擴散黏著劑層的兩面分別與脫模膜的脫模處理實施面貼合，能夠形成「脫模膜/光擴散黏著劑層/脫模膜」的結構。在該情況下，藉由將兩側的脫模膜依次或同時剝離而露出黏著面，能夠與光學膜等光學構件貼合。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、增亮膜等。例如，在偏光板與增亮膜的層間使用光擴散黏著劑層較為理想。In the release film, a release treatment by an anthrone or a fluorine release agent is performed on the surface on the side where the adhesion surface of the light-diffusing adhesive layer is bonded. The structure of the "release film/light diffusion adhesive layer/release film" can be formed by bonding the surface of each of the light-diffusing adhesive layers to the mold release film. In this case, the release film on both sides can be peeled off sequentially or simultaneously to expose the adhesive surface, and can be bonded to an optical member such as an optical film. Examples of the optical film include a polarizing film, a retardation film, an antireflection film, an anti-glare film, an ultraviolet absorbing film, an infrared absorbing film, an optical compensation film, and a brightness enhancement film. For example, it is preferred to use a light-diffusing adhesive layer between the layers of the polarizing plate and the brightness enhancing film.
本發明的光擴散黏著膜可用於以偏光板為主的液晶顯示器的週邊構件用各種光學膜、觸控面板用各種光學膜、電子紙用各種光學膜、有機EL用各種光學膜等的貼合中。 另外，可在這些光學膜的至少一個面上層疊該光擴散黏著劑層而製備帶有黏著劑層的光學膜。具體來說，可列舉：「光學膜/光擴散黏著劑層/光學膜」、「光學膜/光擴散黏著劑層/脫模膜」、「光學膜/光擴散黏著劑層」、「光學膜/光擴散黏著劑層/光學膜/光擴散黏著劑層/光學膜」、「光學膜/光擴散黏著劑層/光學膜/光擴散黏著劑層/脫模膜」、「脫模膜/光擴散黏著劑層/光學膜/光擴散黏著劑層/脫模膜」等的結構。當在光學膜的雙面上設置黏著劑層時，亦可僅將其單面設置成光擴散黏著劑層。 例如，如「光學膜/光擴散黏著劑層/脫模膜」具有以脫模膜進行保護的光擴散黏著劑層的情況下，剝掉脫模膜而露出如「光學膜/光擴散黏著劑層」的光擴散黏著劑層，並且與其它光學膜進行貼合，由此能夠得到將光擴散黏著劑層用於層間貼合的如「光學膜/光擴散黏著劑層/光學膜」的結構。 【實施例】The light-diffusing adhesive film of the present invention can be used for bonding various optical films, various optical films for touch panels, various optical films for electronic paper, various optical films for organic EL, and the like for peripheral members of liquid crystal displays mainly including polarizing plates. in. Further, the optical diffusion adhesive layer may be laminated on at least one surface of these optical films to prepare an optical film with an adhesive layer. Specifically, "optical film / light diffusing adhesive layer / optical film", "optical film / light diffusing adhesive layer / release film", "optical film / light diffusing adhesive layer", "optical film" /Light diffusing adhesive layer / optical film / light diffusing adhesive layer / optical film", "optical film / light diffusing adhesive layer / optical film / light diffusing adhesive layer / release film", "release film / light A structure such as a diffusion adhesive layer/optical film/light diffusion adhesive layer/release film. When the adhesive layer is provided on both sides of the optical film, it is also possible to provide only one side of the optical diffusing adhesive layer. For example, when the "optical film/light diffusion adhesive layer/release film" has a light-diffusing adhesive layer protected by a release film, the release film is peeled off to expose an "optical film/light diffusion adhesive". The light-diffusion adhesive layer of the layer is bonded to other optical films, whereby a structure in which a light-diffusing adhesive layer is used for interlayer bonding such as "optical film/light diffusion adhesive layer/optical film" can be obtained. . [Examples]
下面，基於實施例具體說明本發明。Hereinafter, the present invention will be specifically described based on examples.
＜丙烯酸共聚物的製造＞ [實施例1] 向配有攪拌器、溫度計、回流冷凝器和氮導入管的反應裝置中導入氮氣，從而用氮氣置換了反應裝置內的空氣。然後，向反應裝置中加入了90重量份的丙烯酸丁酯、1.0重量份的丙烯酸4-羥基丁酯、9重量份的二乙基丙烯醯胺，並同時加入60重量份的溶劑(乙酸乙酯)。然後，用2小時時間滴入0.1重量份的作為聚合引發劑的偶氮二異丁腈，在65℃下使其反應6小時，獲得了重量平均分子量為70萬的、用於實施例1的丙烯酸共聚物溶液1。取丙烯酸共聚物的一部分，作為後述的酸價測定試樣使用。 [實施例2~5和比較例1~3] 除了如表1的(A)、(B)、(C)、(D)、(E)中所述地分別調整了各單體的組成以外，與上述用於實施例1的丙烯酸共聚物溶液1同樣地進行操作，得到了用於實施例2~5和比較例1~3的丙烯酸共聚物溶液。<Manufacture of Acrylic Copolymer> [Example 1] Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, thereby replacing the air in the reaction apparatus with nitrogen. Then, 90 parts by weight of butyl acrylate, 1.0 part by weight of 4-hydroxybutyl acrylate, and 9 parts by weight of diethyl acrylamide were added to the reaction apparatus, and 60 parts by weight of a solvent (ethyl acetate) was simultaneously added. ). Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and the mixture was reacted at 65 ° C for 6 hours to obtain a weight average molecular weight of 700,000 for use in Example 1. Acrylic copolymer solution 1. A part of the acrylic copolymer was used as an acid value measurement sample to be described later. [Examples 2 to 5 and Comparative Examples 1 to 3] Except that the compositions of the respective monomers were adjusted as described in (A), (B), (C), (D), and (E) of Table 1, The acrylic copolymer solution used in Examples 2 to 5 and Comparative Examples 1 to 3 was obtained in the same manner as in the above-described acrylic copolymer solution 1 used in Example 1.
＜黏著劑組合物、光擴散黏著劑層及光擴散黏著膜的製備＞ [實施例1] 在如上所述製造的實施例1的丙烯酸共聚物溶液1中，加入0.1重量份的Coronate L-45(甲苯二異氰酸酯(TDI)化合物的加成物)和3.0重量份的二氧化矽三聚氰胺核殼粒子(粒徑2μm)並進行攪拌混合，得到了實施例1的黏著劑組合物。將該黏著劑組合物，塗布在由已塗有矽酮樹脂的聚對苯二甲酸乙二酯(PET)膜構成的剝離膜上後，在90℃溫度下進行乾燥而去除溶劑，然後，在23℃、50%RH的環境下熟成7天，從而獲得了在剝離膜的單面上具有使黏著劑組合物交聯而成的光擴散黏著劑層(厚度20μm)的實施例1的光擴散黏著膜。 [實施例2~5和比較例1~3] 除了如表1的(F)、(G)所述地分別調整了添加劑的組成以外，與上述實施例1的光擴散黏著膜同樣地進行操作，得到了實施例2~5和比較例1~3的光擴散黏著膜。<Preparation of Adhesive Composition, Light-Diffusion Adhesive Layer, and Light-Diffusing Adhesive Film> [Example 1] In the acrylic copolymer solution 1 of Example 1 produced as described above, 0.1 part by weight of Coronate L-45 was added. (Adduct of toluene diisocyanate (TDI) compound) and 3.0 parts by weight of cerium oxide melamine core-shell particles (particle diameter: 2 μm) were stirred and mixed to obtain an adhesive composition of Example 1. The adhesive composition is applied onto a release film composed of a polyethylene terephthalate (PET) film coated with an fluorenone resin, and then dried at a temperature of 90 ° C to remove the solvent, and then, The film was aged for 7 days in an environment of 23° C. and 50% RH to obtain a light diffusion of Example 1 having a light-diffusing adhesive layer (thickness: 20 μm) obtained by crosslinking the adhesive composition on one surface of the release film. Adhesive film. [Examples 2 to 5 and Comparative Examples 1 to 3] Operations were carried out in the same manner as in the light-diffusing adhesive film of Example 1 except that the composition of the additive was adjusted as described in (F) and (G) of Table 1, respectively. The light-diffusing adhesive films of Examples 2 to 5 and Comparative Examples 1 to 3 were obtained.
在表1中，括弧內的數值表示各成分的重量份摻合比。重量份係以設定單體總量、即(A)~(E)組的合計為約100重量份的方式來求出。其中，實施例2的單體總量為105重量份、實施例3的單體總量為92重量份、比較例2的單體總量為110.5重量份、比較例3的單體總量為110重量份。 另外，將表1中使用的各成分的縮寫對應的化合物名稱顯示於表2中。在此，Coronate(註冊商標)L-45為日本聚氨酯工業股份有限公司的商品名稱，D-110N為三井化學股份有限公司的商品名稱。TDI指甲苯二異氰酸酯，XDI指苯二甲基二異氰酸酯。In Table 1, the numerical values in parentheses indicate the blending ratio by weight of each component. The parts by weight are determined in such a manner that the total amount of the monomers is set, that is, the total of the groups (A) to (E) is about 100 parts by weight. The total amount of the monomers of Example 2 was 105 parts by weight, the total amount of the monomers of Example 3 was 92 parts by weight, the total amount of the monomers of Comparative Example 2 was 110.5 parts by weight, and the total amount of the monomers of Comparative Example 3 was 110 parts by weight. Further, the compound names corresponding to the abbreviations of the respective components used in Table 1 are shown in Table 2. Here, Coronate (registered trademark) L-45 is the trade name of Japan Polyurethane Industry Co., Ltd., and D-110N is the trade name of Mitsui Chemicals Co., Ltd. TDI refers to toluene diisocyanate and XDI refers to benzenedimethyl diisocyanate.
＜試驗方法和評價＞ 從實施例1~5和比較例1~3的光擴散黏著膜剝掉剝離膜(塗有矽酮樹脂的PET膜)而露出光擴散黏著劑層，並將光擴散黏著劑層轉印至偏光板(膜)的單面上。<Test Method and Evaluation> The release film (PET film coated with an oxime resin) was peeled off from the light-diffusing adhesive films of Examples 1 to 5 and Comparative Examples 1 to 3 to expose the light-diffusing adhesive layer, and the light was diffused and adhered. The agent layer is transferred to one side of the polarizing plate (film).
＜黏著力的測定方法＞ 將光擴散黏著劑層轉印至厚度180μm的偏光板(膜)的單面，從而得到了作為試樣的光擴散黏著膜(帶有黏著劑層的光學膜)。 用壓合輥將光擴散黏著膜貼合在用丙酮清洗過的鈉鈣玻璃的非錫面上，在50℃、0.5MPa×20分鐘的條件下進行高壓釜處理。然後，恢復至23℃×50%RH的環境，用拉伸試驗機並根據JIS Z0237「黏著帶、黏著片試驗方法」，測定經過1小時後的光擴散黏著膜的剝離強度，將以300mm/min的速度向180°方向剝離時的剝離強度作為光擴散黏著膜的光擴散黏著劑層的黏著力。<Measurement Method of Adhesive Force> The light-diffusing adhesive layer was transferred onto one surface of a polarizing plate (film) having a thickness of 180 μm to obtain a light-diffusing adhesive film (an optical film with an adhesive layer) as a sample. The light-diffusing adhesive film was bonded to a non-tin surface of soda lime glass washed with acetone using a pressure roller, and autoclaved at 50 ° C and 0.5 MPa × 20 minutes. Then, the film was returned to an environment of 23 ° C × 50% RH, and the peeling strength of the light-diffusing adhesive film after one hour passed was measured by a tensile tester in accordance with JIS Z0237 "Adhesive tape and adhesive sheet test method", and was 300 mm/ The peel strength at the time when the speed of min is peeled off in the 180° direction serves as the adhesion of the light-diffusing adhesive layer of the light-diffusing adhesive film.
＜折射率的測定方法＞ 用阿貝折射儀(製造商：ERMA，型號：ER-2S)測定23℃下的光擴散黏著劑層的折射率。<Method for Measuring Refractive Index> The refractive index of the light-diffusing adhesive layer at 23 ° C was measured by an Abbe refractometer (manufacturer: ERMA, model: ER-2S).
＜透射率的測定方法＞ 透光率的測定方法：根據JIS K7105、「塑膠的光學特性試驗方法」測定光擴散黏著劑層的透射率。<Method for Measuring Transmittance> Method for Measuring Light Transmittance: The transmittance of the light-diffusing adhesive layer was measured in accordance with JIS K7105 and "Test Method for Optical Properties of Plastics".
＜霧度值的測定方法＞ 霧度值的測定方法：根據JIS K7136、「塑膠-透明材料的霧度計算方法」測定光擴散黏著劑層的霧度值。<Method for Measuring Haze Value> Method for Measuring Haze Value: The haze value of the light-diffusing adhesive layer was measured in accordance with JIS K7136, "Method for Calculating Haze of Plastic-Transparent Material".
＜耐久性的試驗方法＞ 將採用與黏著力的測定同樣的方法製備的10cm見方的黏著膜，貼合在鈉鈣玻璃的非錫面上而製備試樣，將該試樣放置在60℃×90%RH的環境下250小時後，取出至23℃×50%RH的環境，用目視觀察1小時後的光擴散黏著膜的狀態，從而判斷耐久性。 ○：完全沒有產生光擴散黏著膜的剝離和起泡 △：光擴散黏著膜的一部分產生了剝離和起泡。 ×：光擴散黏著膜的整體產生了剝離和起泡。<Test method for durability> A 10 cm square adhesive film prepared in the same manner as the measurement of the adhesion force was applied to a non-tin surface of soda lime glass to prepare a sample, and the sample was placed at 60 ° C × After 250 hours in an environment of 90% RH, the mixture was taken out to an environment of 23 ° C × 50% RH, and the state of the light-diffusing adhesive film after 1 hour was visually observed to determine the durability. ○: Peeling and foaming of the light-diffusing adhesive film were not produced at all Δ: Part of the light-diffusing adhesive film was peeled off and foamed. X: Peeling and foaming occurred in the entirety of the light-diffusing adhesive film.
將實施例1~5和比較例1~3的測定結果顯示於表3中。The measurement results of Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 3.
對實施例1~5的光擴散黏著膜而言，當光擴散黏著劑層的厚度為20μm時對玻璃板的黏著力為2.0N/25mm以上。另外，光擴散黏著劑層的折射率為1.47以上、透射率為90%以上、且霧度值為40%以上、耐久性亦優良。即，實施例1~5的光擴散黏著膜能夠滿足所需要求及克服問題。In the light-diffusing adhesive films of Examples 1 to 5, when the thickness of the light-diffusing adhesive layer was 20 μm, the adhesion to the glass plate was 2.0 N/25 mm or more. Further, the light-diffusing adhesive layer has a refractive index of 1.47 or more, a transmittance of 90% or more, a haze value of 40% or more, and excellent durability. That is, the light-diffusing adhesive films of Examples 1 to 5 can satisfy the required requirements and overcome the problems.
作為參考，使用與實施例1~5相同的光擴散黏著劑組合物並以相同的方法製備光擴散黏著劑層厚度分別為10μm、13μm、15μm、20μm的光擴散黏著膜，分別測定了光擴散黏著劑層的透射率和霧度值，並將其結果顯示於表4中。對使用了光擴散黏著劑組合物的光擴散黏著劑層的透射率而言，雖然不相關於黏著劑層的膜厚，但可知霧度值在黏著劑層的膜厚變薄的情況下降低。For reference, using the same light-diffusing adhesive composition as in Examples 1 to 5, a light-diffusing adhesive film having a thickness of a light-diffusing adhesive layer of 10 μm, 13 μm, 15 μm, and 20 μm was prepared in the same manner, and light diffusion was measured. The transmittance and haze values of the adhesive layer are shown in Table 4. The transmittance of the light-diffusing adhesive layer using the light-diffusing adhesive composition is not related to the film thickness of the adhesive layer, but it is understood that the haze value is lowered in the case where the thickness of the adhesive layer is reduced. .
比較例1的黏著膜，由於丙烯酸類聚合物的單體組成為單一的2EHA的緣故，折射率低；由於不含矽類粒子的緣故，霧度值低。而且，耐久性亦差。 比較例2的黏著膜，可能由於矽類粒子的含量多的緣故，黏著力低、透射率低、耐久性亦差。 比較例3的黏著膜，由於矽類粒子的含量少的緣故，霧度值低；由於黏著劑組合物未發生交聯的緣故，黏合性和耐久性亦差。 如此，比較例1~3的黏著膜無法滿足以往所提出的要求以及克服以往存在的問題。In the adhesive film of Comparative Example 1, since the monomer composition of the acrylic polymer was a single 2EHA, the refractive index was low, and the haze value was low because the ruthenium-free particles were not contained. Moreover, the durability is also poor. The adhesive film of Comparative Example 2 may have a low adhesive force, a low transmittance, and a poor durability due to a large content of the ruthenium-based particles. In the adhesive film of Comparative Example 3, since the content of the cerium-based particles was small, the haze value was low, and the adhesive composition was not crosslinked, and the adhesiveness and durability were also inferior. Thus, the adhesive films of Comparative Examples 1 to 3 could not satisfy the requirements set forth in the prior art and overcome the problems existing in the past.
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| JP6644971B2 (en) * | 2014-08-06 | 2020-02-12 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| JP6520483B2 (en) * | 2015-06-30 | 2019-05-29 | 日本ゼオン株式会社 | Adhesive composition for optical member, optical laminate, and surface light source device |
| WO2017010502A1 (en) * | 2015-07-13 | 2017-01-19 | 王子ホールディングス株式会社 | Adhesive sheet, laminate, and method for producing same |
| JP6140774B2 (en) * | 2015-07-22 | 2017-05-31 | 日東電工株式会社 | Polarizing film laminate having a transparent adhesive layer and display panel |
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| JP6805014B2 (en) | 2017-02-09 | 2020-12-23 | リンテック株式会社 | Adhesive sheet |
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| TWI545172B (en) | 2016-08-11 |
| JP2015086297A (en) | 2015-05-07 |
| JP6343836B2 (en) | 2018-06-20 |
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