TWI490302B - Adhesive layer and adhesive film - Google Patents
Adhesive layer and adhesive film Download PDFInfo
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- TWI490302B TWI490302B TW103100548A TW103100548A TWI490302B TW I490302 B TWI490302 B TW I490302B TW 103100548 A TW103100548 A TW 103100548A TW 103100548 A TW103100548 A TW 103100548A TW I490302 B TWI490302 B TW I490302B
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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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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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
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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
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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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
- C09J7/22—Plastics; Metallised plastics
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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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
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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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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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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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- General Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Human Computer Interaction (AREA)
- Mathematical Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Description
本發明涉及用於光學構件的層間貼合等的黏著劑層以及黏著膜。更詳細而言,本發明提供一種雖然是厚度為1μm~20μm的薄膜但兼備高黏著力、高附著性的性能和抗靜電性能的黏著劑層、以及使用該黏著劑層的黏著膜。The present invention relates to an adhesive layer and an adhesive film for interlayer bonding or the like of an optical member. More specifically, the present invention provides an adhesive layer which has both a high adhesion, a high adhesion property and an antistatic property, and an adhesive film using the adhesive layer, although it is a film having a thickness of 1 μm to 20 μm.
為了藉由黏著劑層將偏光板、相位差板等光學構件貼合在液晶單元等被黏附體上,已提出了各種黏著膜(例如,參照專利文獻1~2)。In order to bond an optical member such as a polarizing plate or a phase difference plate to an adherend such as a liquid crystal cell by an adhesive layer, various adhesive films have been proposed (for example, refer to Patent Documents 1 and 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,並含有丙烯醯胺化合物等的光學用黏著劑組合物。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.
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。Patent Document 2 describes 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. Adhesive composition.
另外,為了提高黏著劑層的折射率,經過反復研究提出了多種黏著膜(例如,參照專利文獻3~8)。Further, in order to increase the refractive index of the adhesive layer, various adhesive films have been proposed through repeated studies (for example, refer to Patent Documents 3 to 8).
專利文獻3中記載了一種具有芳環並含有折射率為1.51~1.75的增黏劑的光學用黏著劑組合物。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.
專利文獻4中記載了一種使用了含共聚合性聚合物的黏著劑組合物的黏著片,該共聚合性聚合物是含芳環的丙烯酸改性單體的共聚合性聚合物。Patent Document 4 describes an adhesive sheet using an adhesive composition containing a copolymerizable polymer which is a copolymerizable polymer of an aromatic ring-containing acrylic modified monomer.
專利文獻5中記載了一種具有含芳環的增黏樹脂和芳香族磷酸酯類增塑劑的光學用黏著劑組合物。Patent Document 5 describes an optical adhesive composition having an aromatic ring-containing tackifying resin and an aromatic phosphate plasticizer.
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。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.
專利文獻7中記載了一種藉由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元件。Patent Document 7 describes an optical element in which a retardation film and a birefringent plate are fixed to each other by an acrylic adhesive containing an aromatic monomer.
專利文獻8中記載了一種含有聚胺酯樹脂的黏著劑組合物,該聚胺酯樹脂是使芳香族二異氰酸酯和芳香族聚酯二醇反應而成。Patent Document 8 describes an adhesive composition containing a polyurethane resin obtained by reacting an aromatic diisocyanate with an aromatic polyester diol.
近年來,為了實現光學構件的薄膜化,要求用於光學構件的層間貼合的黏著膜是黏著劑層為厚度20μm以下薄層的黏著膜。In recent years, in order to achieve thinning of an optical member, an adhesive film for interlayer bonding of an optical member is required to be an adhesive film in which the adhesive layer is a thin layer having a thickness of 20 μm or less.
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,則隨之會降低黏著力。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,也具有與以往的黏著膜(黏著劑層是厚度約為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,也具有與以往的黏著膜同等以上的性能。However, in recent years, it is required that the adhesive film has the same performance as that of the conventional adhesive film (the adhesive layer is a thick layer having a thickness of about 30 μm) even when the thickness of the adhesive layer is reduced, and for high temperature, The durability after standing for a long time in a high-humidity environment also has the same performance as that of the conventional adhesive film.
另外,從能夠將黏著劑層的厚度變薄並能夠形成無需實施時效處理(在恆溫下實施熟化)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,其具有包括去掉了黏著膜的基材後的黏著劑層的“脫模膜/黏著劑層/脫模膜”的構件構成。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 aging treatment (curing at a constant temperature), it is required to form a NCF (Non Carrier Film). It has a member structure of a "release film/adhesive layer/release film" including an adhesive layer from which a substrate of an adhesive film is removed.
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時效處理,因此,能夠提高被黏附體和黏著劑層之間的附著性。Further, in the conventional adhesive film, since the adhesive film is bonded to the adherend, the aging treatment is performed, so that the adhesion between the adherend and the adhesive layer can be improved.
但是,採用NCF形態的黏著膜已經完成了黏著劑層的時效處理,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。However, the adhesive film of the NCF form has been subjected to the aging treatment of the adhesive layer, and thus 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.
因此需要一種滿足這些要求和克服這些問題的黏著膜。There is therefore a need for an adhesive film that meets these requirements and overcomes these problems.
【專利文獻】[Patent Literature]
專利文獻1:日本特開2012-177022號公報Patent Document 1: Japanese Laid-Open Patent Publication No. 2012-177022
專利文獻2:日本特開2012-201734號公報Patent Document 2: JP-A-2012-201734
專利文獻3:日本特開2007-084762號公報Patent Document 3: Japanese Laid-Open Patent Publication No. 2007-084762
專利文獻4:日本特開2011-153169號公報Patent Document 4: Japanese Laid-Open Patent Publication No. 2011-153169
專利文獻5:日本特開2012-167188號公報Patent Document 5: Japanese Laid-Open Patent Publication No. 2012-167188
專利文獻6:日本特開2012-021148號公報Patent Document 6: Japanese Laid-Open Patent Publication No. 2012-021148
專利文獻7:日本特開2006-293281號公報Patent Document 7: Japanese Laid-Open Patent Publication No. 2006-293281
專利文獻8:日本特開2009-091522號公報Patent Document 8: JP-A-2009-091522
本發明是鑒於上述情況而完成的發明,其課題在於,提供一種雖然是厚度為1μm~20μm的薄膜但兼備高黏著力、高附著性的性能和抗靜電性能的黏著劑層、以及使用該黏著劑層的黏著膜。The present invention has been made in view of the above circumstances, and an object of the invention is to provide an adhesive layer having high adhesion, high adhesion property and antistatic property, and a use of the adhesive, which is a film having a thickness of 1 μm to 20 μm. Adhesive film of the agent layer.
為了解決上述課題,本發明的技術思想在於:在使包括丙烯酸類聚合物的黏著劑組合物進行交聯而成的黏著劑層中,將烷基碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種作為主要成分的單體、並含有作為其他共聚合性單體之可共聚的含氮乙烯基單體中的至少一種以上而進行共聚和交聯,藉由含有離子化合物以形成兼備堅韌的黏著力和高附著性的性能和抗靜電性能的黏著劑層。In order to solve the above problems, the technical idea of the present invention is to form a (meth) group having an alkyl group having a carbon number of C1 to C14 in an adhesive layer obtained by crosslinking an adhesive composition comprising an acrylic polymer. Copolymerizing and crosslinking by at least one of a monomer having at least one of an alkyl acrylate monomer as a main component and a copolymerizable nitrogen-containing vinyl monomer as another copolymerizable monomer. An ionic compound containing an ionic compound to form an adhesive layer having both tough adhesion and high adhesion properties and antistatic properties.
另外,為了解決上述課題,本發明提供一種黏著劑層,其是使黏著劑組合物進行交聯而成的黏著劑層,其中,該黏著劑組合物包含共聚物和離子化合物,該共聚物包含:烷基碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種以上;含芳基的(甲基)丙烯酸酯單體中的至少一種以上;以及 其他共聚合性單體,該其他共聚合性單體包含:含氮乙烯基單體中的至少一種以上;以及含羧基的共聚合性乙烯基單體和/或含羥基的共聚合性乙烯基單體中的至少一種以上,該黏著劑層的厚度為1μm~20μm,並且在厚度5μm時的黏著力為3.0(N/25mm)以上。Further, in order to solve the above problems, the present invention provides an adhesive layer which is an adhesive layer obtained by crosslinking an adhesive composition, wherein the adhesive composition contains a copolymer and an ionic compound, and the copolymer contains At least one or more of alkyl (meth) acrylate monomers having an alkyl group having from C1 to C14; at least one or more of aryl group-containing (meth) acrylate monomers; a further copolymerizable monomer, the other copolymerizable monomer comprising: at least one of a nitrogen-containing vinyl monomer; and a carboxyl group-containing copolymerizable vinyl monomer and/or a hydroxyl group-containing copolymerized vinyl group At least one or more of the monomers have a thickness of from 1 μm to 20 μm and an adhesion of 3.0 (N/25 mm) or more at a thickness of 5 μm.
另外,較佳為該黏著劑組合物包含:重均分子量為20萬~200萬的共聚物,其是相對於組合70~95重量份的(A)烷基碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種以上和5~30重量份的(B)含芳基的(甲基)丙烯酸酯單體中的至少一種以上而成的合計100重量份,配合5~50重量份的(C)含氮乙烯基單體中的一種以上和0.1~5重量份的(D)含羧基的共聚合性乙烯基單體和/或含羥基的共聚合性乙烯基單體中的至少一種以上而獲得單體混合物,並使該單體混合物共聚而成;0.1~5.0重量份的(E)熔點為30~50℃的離子化合物;以及0.01~5重量份的(F)交聯劑。Further, it is preferable that the adhesive composition comprises a copolymer having a weight average molecular weight of 200,000 to 2,000,000, which is 70 to 95 parts by weight of the (A) alkyl group having a carbon number of C1 to C14 ( 100 parts by weight of at least one or more of (A) at least one of (B) an aryl group-containing (meth) acrylate monomer in a methyl methacrylate monomer, and a total of 100 parts by weight 5 to 50 parts by weight of one or more of (C) nitrogen-containing vinyl monomers and 0.1 to 5 parts by weight of (D) carboxyl group-containing copolymerizable vinyl monomer and/or hydroxyl group-containing copolymerized vinyl group Obtaining a monomer mixture of at least one of the monomers and copolymerizing the monomer mixture; 0.1 to 5.0 parts by weight of (E) an ionic compound having a melting point of 30 to 50 ° C; and 0.01 to 5 parts by weight ( F) Crosslinker.
另外,在前述黏著劑組合物中,相對於前述(A)和前述(B)的合計100重量份,較佳為含羧基的共聚合性乙烯基單體中的一種以上的含量為2.0重量份以下和/或含羥基的共聚合性乙烯基單體中的一種以上的含量為5.0重量份以下。In addition, it is preferable that the content of one or more of the carboxyl group-containing copolymerizable vinyl monomers is 2.0 parts by weight based on 100 parts by weight of the total of the above (A) and the above (B). The content of one or more of the following and/or hydroxyl group-containing copolymerizable vinyl monomers is 5.0 parts by weight or less.
另外,該黏著劑層的折射率較佳為1.47~1.50。Further, the adhesive layer preferably has a refractive index of 1.47 to 1.50.
另外,本發明提供一種在脫模膜的單面形成有該黏著劑層並具有脫模膜/黏著劑層/脫模膜的構成的黏著膜。Moreover, the present invention provides an adhesive film having a structure in which the adhesive layer is formed on one surface of a release film and has a release film/adhesive layer/release film.
另外,本發明提供一種在基材的單面層疊前述黏著劑層而成的黏著膜。 另外,本發明提供一種使用了前述黏著膜的偏光板和顯示面板貼合用黏著膜。Further, the present invention provides an adhesive film obtained by laminating the above-mentioned adhesive layer on one surface of a substrate. Further, the present invention provides a polarizing plate using the above-mentioned adhesive film and an adhesive film for bonding a display panel.
另外,本發明提供一種使用了黏著膜的觸控面板用膜。Further, the present invention provides a film for a touch panel using an adhesive film.
另外,本發明提供一種使用了上述黏著膜的電子紙用膜。Further, the present invention provides a film for an electronic paper using the above adhesive 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上述黏著劑層。Further, the present invention provides an optical film with an adhesive layer which is laminated on at least one side of an optical film.
根據本發明,能夠滿足以往技術中的要求事項以及克服以往技術中存在的問題,能夠提供一種雖然是厚度1μm~20μm薄膜但兼備高黏著力、高附著性的性能以及抗靜電性能的黏著劑層,還提供使用該黏著劑層的黏著膜。According to the present invention, it is possible to satisfy the requirements in the prior art and overcome the problems in the prior art, and it is possible to provide an adhesive layer having high adhesion, high adhesion property, and antistatic property even in the case of a film having a thickness of 1 μm to 20 μm. An adhesive film using the adhesive layer is also provided.
下面基於較佳的實施方式說明本發明。The invention is illustrated below on the basis of preferred embodiments.
本發明的黏著劑層是使黏著劑組合物進行交聯而成的黏著劑層,其中,該黏著劑組合物包含共聚物和離子化合物,該共聚物包含:烷基碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種以上;含芳基的(甲基)丙烯酸酯單體中的至少一種以上;以及其他共聚合性單體,該其他共聚合性單體包含:含氮乙烯基單體中的一種以上;以及含羧基的共聚合性乙烯基單體和/或含羥基的共聚合性乙烯基單體中的至少一種以上, 該黏著劑層的厚度為1μm~20μm,並且在厚度5μm時的黏著力為3.0(N/25mm)以上。The adhesive layer of the present invention is an adhesive layer obtained by crosslinking an adhesive composition, wherein the adhesive composition comprises a copolymer and an ionic compound, and the copolymer comprises: an alkyl group having a carbon number of C1 to C14 At least one or more of the alkyl (meth) acrylate monomers; at least one of the aryl group-containing (meth) acrylate monomers; and other copolymerizable monomers, the other copolymerizable monomers And comprising: at least one of a nitrogen-containing vinyl monomer; and at least one of a carboxyl group-containing copolymerizable vinyl monomer and/or a hydroxyl group-containing copolymerizable vinyl monomer, The adhesive layer has a thickness of 1 μm to 20 μm and an adhesive force of 3.0 (N/25 mm) or more at a thickness of 5 μm.
另外,在需要更高黏著力的用途中,較佳為本發明的黏著劑層在厚度5μm時的黏著力為4.0(N/25mm)以上。Further, in applications requiring higher adhesion, it is preferred that the adhesive layer of the present invention has an adhesive strength of 4.0 (N/25 mm) or more at a thickness of 5 μm.
作為烷基碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體,可以舉出(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以是直鏈、支鏈、環狀中的任意一種。相對於(A)烷基碳原子數為C1~C14的(甲基)丙烯酸酯單體和(B)含芳基的(甲基)丙烯酸酯單體的合計100重量份,較佳為(A)烷基碳原子數為C1~C14的(甲基)丙烯酸酯單體的含量為70~95重量份。Examples of the (meth)acrylic acid alkyl ester monomer having an alkyl group having C1 to C14 include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. Isopropyl methacrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, ( Octyl methacrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic acid Anthracene ester, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, (methyl) At least one of cyclopentyl acrylate and cyclohexyl (meth)acrylate. The alkyl group in the alkyl (meth) acrylate monomer may be any of a straight chain, a branched chain, and a cyclic group. It is preferably (A) based on 100 parts by weight of the total of (A) a (meth) acrylate monomer having an alkyl group having C1 to C14 and (B) an aryl group-containing (meth) acrylate monomer. The content of the (meth) acrylate monomer having an alkyl group having C1 to C14 is 70 to 95 parts by weight.
作為含芳基的(甲基)丙烯酸酯單體,可以舉出(甲基)丙烯酸苄酯、(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。為了得到折射率高的黏著劑層,較佳為配合至少一種以上的含芳基的(甲基)丙烯酸酯單體。Examples of the aryl group-containing (meth) acrylate monomer include benzyl (meth) acrylate, naphthyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxy (meth) acrylate. Butyl ester, 2-(1-naphthalenyloxy)ethyl (meth)acrylate, 2-(2-naphthalenyloxy)ethyl (meth)acrylate, 6-(1-naphthyloxy)(meth)acrylate Hexyl ester, 6-(2-naphthyloxy)hexyl (meth)acrylate, 8-(1-naphthalenyloxy)octyl (meth)acrylate, 8-(2-naphthyloxy)(meth)acrylate Base) octyl ester and the like. In order to obtain an adhesive layer having a high refractive index, at least one or more aryl group-containing (meth) acrylate monomers are preferably blended.
藉由將這些含芳基的(甲基)丙烯酸酯單體與作為主要成分的單體即烷基碳原子數為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過率。By mixing these aryl group-containing (meth) acrylate monomers with a monomer as a main component, that is, an alkyl (meth) acrylate monomer having an alkyl group having C1 to C14, it is possible to The refractive index of the obtained adhesive 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.
另外,在本發明的黏著劑層中,相對於組合前述(A)和前述(B)而成的主要成分即(甲基)丙烯酸酯單體100重量份,較佳為(B)含芳基的(甲基)丙烯酸 酯單體的含量為5~30重量份。Further, in the pressure-sensitive adhesive layer of the present invention, (B) an aryl group is preferred, based on 100 parts by weight of the (meth) acrylate monomer which is a main component obtained by combining the above (A) and (B). (meth)acrylic acid The content of the ester monomer is 5 to 30 parts by weight.
作為含氮乙烯基單體,例如可以舉出N-乙烯基吡咯烷酮、N-乙烯基己內醯胺、(甲基)丙烯醯啉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-vinylcaprolactam, and (meth)acryl oxime. Cyclic nitrogen vinyl compound such as porphyrin; 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) acrylamide, N, N-dipropyl (A a dialkyl-substituted (meth) acrylamide such as acrylamide, N,N-diisopropyl(meth)acrylamide or N,N-dibutyl(meth)acrylamide; N-ethyl-N-methylamine ethyl methacrylate, N-methyl-N-propylamine ethyl (meth) acrylate, N-methyl-N-isopropyl (meth) acrylate Amine ethyl ester, N,N-dimethylamine methyl (meth)acrylate, N,N-dimethylamine ethyl (meth)acrylate, N,N-dimethylamine (meth)acrylate Ester, N,N-dimethylamine butyl (meth)acrylate, N,N-dipropylamine ethyl (meth)acrylate, N,N-dibutylamineethyl (meth)acrylate, etc. Dialkylamine (meth)acrylate; N-ethyl-N-methylaminopropyl (meth) acrylamide, N-methyl-N-propylaminopropyl (meth) acrylamide , N-methyl-N-isopropylaminopropyl (meth) acrylamide, N,N-dimethylaminopropyl (meth) acrylamide , N,N-diethylaminopropyl (meth) acrylamide, N,N-dipropylaminopropyl (meth) acrylamide, N,N-dimethylamine ethyl (methyl And at least one of a dialkyl-substituted aminoalkyl (meth) acrylamide such as acrylamide or N,N-diethylamineethyl(meth)acrylamide.
為了能夠與後述(D)的化合物區別,作為上述含氮乙烯基單體,較佳為不含有羥基,更佳為不含有羥基和羧基。作為這種單體,較佳為上述例示的單體,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-乙烯基吡咯烷酮、N-乙烯基己內醯胺等N-乙烯基取代內醯胺類;N-(甲基)丙烯醯啉等N-(甲基)丙烯醯基取代環狀胺類。In order to distinguish it from the compound (D) described later, it is preferred that the nitrogen-containing vinyl monomer does not contain a hydroxyl group, and more preferably does not contain a hydroxyl group or a carboxyl group. As such a monomer, preferred are the above-exemplified monomers, for example, an acrylic monomer containing an N,N-dialkyl substituted amine group or an N,N-dialkyl substituted decylamino group; N-vinyl group N-vinyl substituted indoleamines such as pyrrolidone and N-vinyl caprolactam; N-(methyl) propylene oxime An N-(meth)acrylinyl group such as a phenyl group is substituted with a cyclic amine.
另外,在本發明的黏著劑層中,黏著劑組合物所含有的含氮乙烯基單體,能夠賦予黏著劑層必要的黏著力和耐久性。在本發明的黏著劑層中,相對於100重量份的組合前述(A)和前述(B)而成的作為主要成分的(甲基)丙烯酸酯單體,較佳為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。Further, in the 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 adhesive layer. In the adhesive layer of the present invention, the (meth) acrylate monomer as a main component obtained by combining the above (A) and the above (B) is preferably contained in the adhesive composition. The content of the nitrogen-containing vinyl monomer is 5 to 50 parts by weight.
另外,在本發明的黏著劑層中,作為黏著劑組合物含有的含氮乙烯基 單體,特別較佳為使用N-乙烯基吡咯烷酮、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。Further, in the adhesive layer of the present invention, the nitrogen-containing vinyl contained as the adhesive composition Monomer, particularly preferably 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-dimethylamine ethyl (meth) acrylamide, N-vinyl ene Amidoxime and the like.
作為含有羧基的共聚合性乙烯基單體(含有羧基的單體),例如可以舉出(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、羧基聚己酸內酯單(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。Examples of the carboxyl group-containing copolymerizable vinyl monomer (carboxyl group-containing monomer) include (meth)acrylic acid, (meth)acrylic acid carboxyethyl ester, (meth)acrylic acid carboxypentyl ester, and 2-((). Methyl) propylene methoxyethyl hexahydrophthalic acid, 2-(methyl) propylene methoxy propyl hexahydrophthalic acid, 2-(methyl) propylene methoxyethyl phthalate Formic acid, 2-(methyl)propenyloxyethyl succinic acid, 2-(methyl) propylene oxiranyl ethyl maleic acid, carboxy polycaprolactone mono(meth) acrylate, 2-( At least one of methyl group acryloxyethyltetrahydrophthalic acid and the like.
另外,在本發明的黏著劑層中,黏著劑組合物所含有的含羧基的單體能夠賦予黏著劑層必要的凝聚力。在本發明的黏著劑層中,相對於100重量份的組合前述(A)和前述(B)而成的作為主要成分的(甲基)丙烯酸酯單體,較佳為黏著劑組合物中含有的含羧基的單體的含量為0.1~5重量份。Further, in the adhesive layer of the present invention, the carboxyl group-containing monomer contained in the adhesive composition can impart the necessary cohesive force to the adhesive layer. In the adhesive layer of the present invention, the (meth) acrylate monomer as a main component obtained by combining the above (A) and the above (B) is preferably contained in the adhesive composition. The content of the carboxyl group-containing monomer is 0.1 to 5 parts by weight.
作為含羥基的共聚合性乙烯基單體(含羥基的單體),例如可以舉出(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。Examples of the hydroxyl group-containing copolymerizable vinyl monomer (hydroxyl group-containing monomer) include 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and (meth)acrylic acid. Hydroxyalkyl (meth)acrylates such as 4-hydroxybutyl ester and hydroxyethyl (meth)acrylate, N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, At least one or more of hydroxyl group-containing (meth) acrylamides such as N-hydroxyethyl (meth) acrylamide.
另外,在本發明的黏著劑層中,黏著劑組合物所含的含羥基的單體,能夠作為用於減少含羧基的單體含量的共聚合性單體來使用,該含羧基的單體使所得到的黏著劑層對透明導電性膜的ITO表面等易腐蝕的被黏附體的腐蝕性產生影響。因此,含羥基的單體能夠有助於提高黏著劑層的黏著力並且減少腐蝕性。在本發明的黏著劑層中,相對於100重量份的組合前述(A)和前述(B)而成的作為主要成分的(甲基)丙烯酸酯單體,較佳為黏著劑組合物中含有的含羥基的單體的含量為0.1~5重量份。Further, in the adhesive layer of the present invention, the hydroxyl group-containing monomer contained in the adhesive composition can be used as a copolymerizable monomer for reducing the content of a carboxyl group-containing monomer, the carboxyl group-containing monomer. The obtained adhesive layer is affected by the corrosiveness of the adherend which is easily corroded, such as the ITO surface of the transparent conductive film. Therefore, the hydroxyl group-containing monomer can contribute to the adhesion of the adhesive layer and reduce corrosion. In the adhesive layer of the present invention, the (meth) acrylate monomer as a main component obtained by combining the above (A) and the above (B) is preferably contained in the adhesive composition. The content of the hydroxyl group-containing monomer is 0.1 to 5 parts by weight.
對用於本發明的黏著劑層的黏著劑組合物的共聚物而言,較佳為使下述單體混合物共聚而成,該單體混合物是:相對於100重量份的作為主要成分的(甲基)丙烯酸酯單體,配合5~50重量份的(C)含氮乙烯基單體中的一種以上和0.1~5重量份的(D)含羧基的共聚合性乙烯基單體和/或含羥基的共聚合性乙烯基單體中的至少一種以上而成的單體混合物,其中,該作為主要成分的(甲基)丙烯酸酯單體含有70~95重量份的(A)烷基碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種以上和5~30重量份的(B)含芳基的(甲基)丙烯酸酯單體中的至少一種以上。The copolymer of the adhesive composition used in the adhesive layer of the present invention is preferably obtained by copolymerizing a monomer mixture which is as a main component with respect to 100 parts by weight ( a methyl acrylate monomer, which is blended with 5 to 50 parts by weight of one or more of (C) nitrogen-containing vinyl monomers and 0.1 to 5 parts by weight of (D) a carboxyl group-containing copolymerizable vinyl monomer and/or Or a monomer mixture of at least one of a hydroxyl group-containing copolymerizable vinyl monomer, wherein the (meth) acrylate monomer as a main component contains 70 to 95 parts by weight of (A) alkyl group At least one or more of (B) aryl group-containing (meth) acrylate monomers having at least one of C1 to C14 alkyl (meth) acrylate monomers and 5 to 30 parts by weight of (B) aryl group-containing (meth) acrylate monomers .
另外,相對於100重量份的組合前述(A)和前述(B)而成的作為主要成分的(甲基)丙烯酸酯單體,較佳為含有0.1~5.0重量份的(E)熔點為30~50℃的離子化合物以及0.01~5重量份的(F)交聯劑。Further, the (meth) acrylate monomer as a main component obtained by combining the above (A) and the above (B) is preferably contained in an amount of 0.1 to 5.0 parts by weight per (E) melting point of 30. An ionic compound of ~50 ° C and 0.01 to 5 parts by weight of a (F) crosslinking agent.
另外,相對於100重量份的組合前述(A)和前述(B)而成的作為主要成分的(甲基)丙烯酸酯單體,較佳為含羧基的共聚合性乙烯基單體中的一種以上的含量為2.0重量份以下和/或含羥基的共聚合性乙烯基單體中的一種以上的含量為5.0重量份以下。Further, the (meth) acrylate monomer as a main component obtained by combining the above (A) and the above (B) is preferably one of carboxyl group-containing copolymerizable vinyl monomers. The content of one or more of the above content of 2.0 parts by weight or less and/or the hydroxyl group-containing copolymerizable vinyl monomer is 5.0 parts by weight or less.
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、乳液聚合法等適宜的公知的聚合方法。共聚物的重均分子量較佳為20萬~200萬。The polymerization method of the copolymer is not particularly limited, and a suitable 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 2,000,000.
上述共聚物較佳為丙烯酸類聚合物,較佳為含有(甲基)丙烯酸酯單體或(甲基)丙烯酸、(甲基)丙烯醯胺類等丙烯酸類單體50~100重量%。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 a (meth)acrylic acid or a (meth) acrylamide.
在上述黏著劑組合物中,藉由對上述共聚物配合交聯劑、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 adhesive composition, characteristics such as desired physical properties can be adjusted by blending the above-mentioned copolymer with a crosslinking agent and a suitable optional additive.
作為交聯劑,例如可以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、苯二甲基二異氰酸酯等二異氰酸酯類的縮二脲改性體或異氰脲酸酯改性體;與三羥甲基丙烷或甘油等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,也可以藉由紫外線等光交聯來使黏著劑進行交聯。Examples of the crosslinking agent include biuret modified diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and benzodimethyl diisocyanate. Or an isocyanurate-modified product; at least one of a polyisocyanate compound such as an adduct of a trivalent or higher polyhydric alcohol such as trimethylolpropane or glycerin; a metal chelate compound; an epoxy compound; . Further, the adhesive may be crosslinked by photocrosslinking such as ultraviolet rays.
在使用交聯劑來使共聚物交聯的情況下,較佳為共聚物具有能夠與交 聯劑進行交聯反應的官能團(根據交聯劑的種類可以選擇羥基或羧基等),而且較佳為含有在側鏈具有這些官能團的單體。另外,較佳為黏著劑組合物含有0.01~5重量份的(F)交聯劑。另外,重量份的基準與上述共聚物中的(A)至(D)相同。In the case where a crosslinking agent is used to crosslink the copolymer, it is preferred that the copolymer has the ability to The functional group in which the crosslinking agent is subjected to a crosslinking reaction (a hydroxyl group or a carboxyl group may be selected depending on the kind of the crosslinking agent), and preferably a monomer having these functional groups in a side chain. Further, it is preferred that the adhesive composition contains 0.01 to 5 parts by weight of the (F) crosslinking agent. Further, the basis of the parts by weight is the same as (A) to (D) in the above copolymer.
本發明的黏著劑組合物,為了賦予其抗靜電性,較佳為含有抗靜電劑。對抗靜電劑而言,較佳為在常溫(例如30℃)下是固體。更具體而言,抗靜電劑是熔點為30~50℃的離子化合物。抗靜電劑可以是含有丙烯醯基的4級銨鹽型離子化合物。The adhesive composition of the present invention preferably contains an antistatic agent in order to impart antistatic properties. The antistatic agent is preferably a solid at normal temperature (for example, 30 ° C). More specifically, the antistatic agent is an ionic compound having a melting point of 30 to 50 °C. The antistatic agent may be a 4-stage ammonium salt type ionic compound containing an acrylonitrile group.
由於這些抗靜電劑的熔點低且具有長鏈烷基的緣故,推測它們與丙烯酸類聚合物的親和性高。Since these antistatic agents have a low melting point and a long-chain alkyl group, they are presumed to have high affinity with an acrylic polymer.
作為熔點是30~50℃的離子化合物的抗靜電劑,是具有陽離子和陰離子的離子化合物,可以舉出:陽離子為吡啶鎓陽離子、咪唑鎓陽離子、嘧啶鎓陽離子、吡唑鎓陽離子、吡咯鎓陽離子、銨基陽離子等的含氮鎓陽離子、或者磷鎓陽離子、硫鎓陽離子等的化合物;陰離子為六氟磷酸根(PF6 - )、硫氰酸根(SCN- )、烷基苯磺酸根(RC6 H4 SO3 - )、高氯酸根(ClO4 - )、四氟硼酸根(BF4 - )等的無機或有機陰離子的化合物。藉由對烷基的鏈長或取代基的位置、個數等的選擇,能夠得到熔點為30~50℃的物質。較佳為陽離子為含4級氮鎓陽離子,可以舉出:1-烷基吡啶鎓(2~6位的碳原子既可以具有取代基也可以是未取代)等的4級吡啶鎓陽離子、1,3-二烷基咪唑鎓(2、4、5位的碳原子既可以具有取代基也可以是未取代)等的4級咪唑鎓陽離子、四烷基銨等的4級銨陽離子等。The antistatic agent having an ionic compound having a melting point of 30 to 50 ° C is an ionic compound having a cation and an anion, and examples of the cation include a pyridinium cation, an imidazolium cation, a pyrimidine cation, a pyrazolium cation, and a pyrrole cation. a nitrogen-containing phosphonium cation such as an ammonium cation or a compound such as a phosphonium cation or a sulfonium cation; the anion is hexafluorophosphate (PF 6 - ), thiocyanate (SCN - ), alkyl benzene sulfonate (RC) A compound of an inorganic or organic anion such as 6 H 4 SO 3 - ), perchlorate (ClO 4 - ) or tetrafluoroborate (BF 4 - ). A material having a melting point of 30 to 50 ° C can be obtained by selecting the chain length of the alkyl group or the position and number of the substituent. Preferably, the cation is a 4-stage nitrogen sulfonium cation, and a 4-stage pyridinium cation such as 1-alkylpyridinium (a carbon atom at the 2nd to 6th position may have a substituent or an unsubstituted) may be mentioned. a 4-diimidazolium cation such as a 3-dialkylimidazolium (a carbon atom at the 2, 4, or 5 position may have a substituent or an unsubstituted), or a 4-stage ammonium cation such as a tetraalkylammonium.
作為前述含有丙烯醯基的4級銨鹽型離子化合物,是具有陽離子和陰離子的離子化合物,可以舉出:陽離子為(甲基)丙烯醯氧基烷基三烷基銨(R3 N+ -Cn H2n -OCOCQ=CH2 ,其中,Q=H或CH3 ,R=烷基)等的含有(甲基)丙烯醯基的4級銨;陰離子為六氟磷酸根(PF6 - )、硫氰酸根(SCN- )、有機磺酸根(RSO3 - )、高氯酸根(ClO4 - )、四氟硼酸根(BF4 - )、含有F的醯亞胺根(RF 2 N- )等的無機或有機陰離子的化合物。作為含有F的醯亞胺根(RF 2 N- )的RF ,可 以舉出三氟甲磺醯基、五氟乙磺醯基等的全氟烷基磺醯基、氟磺醯基。作為含有F的醯亞胺根,可以舉出雙(氟磺醯基)醯亞胺根[(FSO2 )2 N- ]、雙(三氟甲磺醯基)醯亞胺根[(CF3 SO2 )2 N- ]、雙(五氟乙磺醯基)醯亞胺根[(C2 F5 SO2 )2 N- ]等的雙磺醯基醯亞胺根。The quaternary ammonium salt-type ionic compound containing an acrylonitrile group is an ionic compound having a cation and an anion, and the cation is a (meth) propylene decyloxyalkyltrialkylammonium (R 3 N + - C n H 2n -OCOCQ=CH 2 , wherein Q=H or CH 3 , R=alkyl), etc., contains 4-methylammonium (meth)acryloyl group; anion is hexafluorophosphate (PF 6 - ) , thiocyanate (SCN - ), organic sulfonate (RSO 3 - ), perchlorate (ClO 4 - ), tetrafluoroborate (BF 4 - ), quinone imine containing F (R F 2 N - Or a compound of an inorganic or organic anion. Examples of R F of the ruthenium root (R F 2 N - ) containing F include a perfluoroalkylsulfonyl group such as a trifluoromethanesulfonyl group or a pentafluoroethanesulfonyl group, and a fluorosulfonyl group. Examples of the ruthenium root containing F include bis(fluorosulfonyl) quinone imide [(FSO 2 ) 2 N - ], bis(trifluoromethanesulfonyl) quinone imide [(CF 3 ) SO 2 ) 2 N - ], bis(sulfonyl sulfonyl) ruthenium [(C 2 F 5 SO 2 ) 2 N - ] and the like.
對熔點為30~50℃的離子化合物的抗靜電劑並沒有特別的限制。作為具有吡啶鎓陽離子的熔點為30~50℃的離子化合物的具體例子,可以舉出1-辛基吡啶鎓十二烷基苯磺酸鹽、1-十二烷基吡啶鎓硫氰酸鹽、3-甲基-1-十二烷基吡啶鎓六氟磷酸鹽、1-十二烷基吡啶鎓十二烷基苯磺酸鹽、4-甲基-1-辛基吡啶鎓六氟磷酸鹽等。The antistatic agent for the ionic compound having a melting point of 30 to 50 ° C is not particularly limited. Specific examples of the ionic compound having a pyridinium cation having a melting point of 30 to 50 ° C include 1-octylpyridinium dodecylbenzenesulfonate and 1-dodecylpyridinium thiocyanate. 3-methyl-1-dodecylpyridinium hexafluorophosphate, 1-dodecylpyridinium dodecylbenzenesulfonate, 4-methyl-1-octylpyridinium hexafluorophosphate Wait.
另外,作為前述含有丙烯醯基的4級銨鹽型離子化合物的具體例子,可以舉出(甲基)丙烯酸二甲胺基甲酯六氟磷酸甲基鹽[(CH3 )3 N+ CH2 OCOCQ=CH2 .PF6 - 、其中,Q=H或CH3 ]、(甲基)丙烯酸二甲胺基乙酯雙(三氟甲磺醯基)醯亞胺甲基鹽[(CH3 )3 N+ (CH2 )2 OCOCQ=CH2 .(CF3 SO2 )2 N- ,其中,Q=H或CH3 ]、(甲基)丙烯酸二甲胺基甲酯雙(氟磺醯基)醯亞胺甲基鹽[(CH3 )3 N+ CH2 OCOCQ=CH2 .(FSO2 )2 N- ,其中,Q=H或CH3 ]等。Further, specific examples of the quaternary ammonium salt type ionic compound containing an acrylonitrile group include dimethylaminomethyl (meth) methacrylate hexafluorophosphate methyl salt [(CH 3 ) 3 N + CH 2 OCOCQ=CH 2 . PF 6 - , wherein, Q = H or CH 3 ], dimethylaminoethyl (meth) acrylate bis(trifluoromethanesulfonyl) quinone imine methyl salt [(CH 3 ) 3 N + (CH 2 ) 2 OCOCQ=CH 2 . (CF 3 SO 2 ) 2 N - , wherein, Q = H or CH 3 ], dimethylaminomethyl (meth) acrylate bis(fluorosulfonyl) quinone imine methyl salt [(CH 3 ) 3 N + CH 2 OCOCQ=CH 2 . (FSO 2 ) 2 N - , wherein Q = H or CH 3 ] and the like.
另外,相對於100重量份的組合前述(A)和前述(B)而成的作為主要成分的(甲基)丙烯酸酯單體,較佳為熔點為30~50℃的離子化合物的含量是0.1~5.0重量份。Further, the content of the ionic compound having a melting point of 30 to 50 ° C is preferably 0.1 based on 100 parts by weight of the (meth) acrylate monomer as a main component obtained by combining the above (A) and the above (B). ~5.0 parts by weight.
作為其他任意成分,可以適宜地配合矽烷偶聯劑、抗氧化劑、表面活性劑、固化促進劑、增塑劑、填充劑、交聯催化劑、交聯抑制劑、固化抑制劑、加工助劑、防老化劑等公知的添加劑。這些添加劑可以單獨使用或並用兩種以上使用。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 anti-proof agent can be suitably blended. A well-known additive such as an aging agent. These additives may be used singly or in combination of two or more.
本發明的黏著劑層可以藉由在基材或脫模膜上塗布上述黏著劑組合物後,使黏著劑組合物交聯而得到。The pressure-sensitive adhesive layer of the present invention can be obtained by coating the above-mentioned pressure-sensitive adhesive composition on a substrate or a release film, and then crosslinking the pressure-sensitive adhesive composition.
在用於光學構件的層間貼合等情況下,希望黏著劑層是厚度薄的黏著劑層,較佳為前述黏著劑層的厚度為1μm~20μm。而且,通常黏著劑層的黏著力與黏著劑層的厚度大致成比例,但較佳為厚度5μm時的黏著力為 3.0(N/25mm)以上。另外,在需要更高黏著力的用途中,較佳為本發明的黏著劑層在厚度5μm時的黏著力為4.0(N/25mm)以上。另外,當黏著劑層的厚度不為5μm的情況下,“厚度5μm時的黏著力”(N/25mm)是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),並藉由算式“(厚度5μm時的黏著力)=5F/T”來推算。In the case of bonding between layers for an optical member, etc., it is desirable that the adhesive layer is a thin adhesive layer, and it is preferable that the thickness of the adhesive layer is 1 μm to 20 μm. Further, usually, the adhesive force of the adhesive layer is substantially proportional to the thickness of the adhesive layer, but the adhesive force at a thickness of 5 μm is preferably 3.0 (N/25mm) or more. Further, in applications requiring higher adhesion, it is preferred that the adhesive layer of the present invention has an adhesive strength of 4.0 (N/25 mm) or more at a thickness of 5 μm. Further, when the thickness of the adhesive layer is not 5 μm, the "adhesion at a thickness of 5 μm" (N/25 mm) is set to a thickness of T (μm) of the adhesive layer, and the adhesive force of the adhesive layer is set. It is F (N/25 mm) and is estimated by the formula "(adhesion at thickness 5 μm) = 5F/T".
在將本發明的黏著劑層作為光學構件貼合在例如偏光板(偏光膜)時,希望黏著劑層對偏光板的黏著力為上述下限值以上。通常,偏光膜是以吸附了碘的聚乙烯醇(PVA)的膜作為主體,並在其表面設置了經過皂化處理過的三乙醯基纖維素(TAC)、聚對苯二甲酸乙二醇酯(PET)等的保護層而成。因此,希望本發明的黏著劑層對皂化處理過的三乙醯基纖維素(TAC)等的被黏附體的黏著力是上述下限值以上。When the pressure-sensitive adhesive layer of the present invention is bonded to, for example, a polarizing plate (polarizing film) as an optical member, the adhesive force of the pressure-sensitive adhesive layer to the polarizing plate is desirably equal to or higher than the lower limit value. Usually, the polarizing film is mainly composed of a film of polyvinyl alcohol (PVA) to which iodine is adsorbed, and a saponified triethylenesulfonyl cellulose (TAC) or polyethylene terephthalate is provided on the surface thereof. A protective layer such as an ester (PET). Therefore, the adhesive strength of the adhesive layer of the present invention to the adherend of saponified triacetyl cellulose (TAC) or the like is desirably equal to or higher than the above lower limit value.
當將本發明的黏著劑層用於光學構件的層間貼合等的情況下,為了減少黏著劑層與光學構件的介面上的光線反射,希望折射率差盡可能小。因此,上述黏著劑層的折射率較佳為1.47~1.50。When the adhesive layer of the present invention is used for interlayer bonding or the like of an optical member, in order to reduce light reflection on the interface between the 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 above adhesive layer is preferably from 1.47 to 1.50.
較佳為使前述黏著劑組合物交聯而成的黏著劑層的表面電阻率為5.0×10+11 Ω/□以下。另外,較佳為使前述黏著劑組合物交聯而成的黏著劑層的剝離靜電壓為±0~0.5kV。另外,在本發明中,所謂“±0~0.5kV”的意思是指“0~-0.5kV”和“0~+0.5kV”、即“-0.5~+0.5kV”。若表面電阻率大則對剝離時因帶電而產生的靜電進行釋放的性能差,因此,藉由使表面電阻率足夠小,能夠降低伴隨從被黏附體剝離黏著劑層時發生的靜電所產生的剝離靜電壓,能夠抑制對被黏附體的電控制電路等的影響。It is preferred that the adhesive layer obtained by crosslinking the above-mentioned adhesive composition has a surface resistivity of 5.0 × 10 + 11 Ω / □ or less. Further, it is preferable that the adhesive layer of the adhesive composition obtained by crosslinking the adhesive composition has a peeling static voltage of ±0 to 0.5 kV. Further, in the present invention, "±0 to 0.5 kV" means "0 to -0.5 kV" and "0 to +0.5 kV", that is, "-0.5 to +0.5 kV". When the surface resistivity is large, the performance of releasing static electricity due to charging at the time of peeling is inferior. Therefore, by making the surface resistivity sufficiently small, it is possible to reduce the static electricity generated when the adhesive layer is peeled off from the adherend. By peeling off the static voltage, it is possible to suppress the influence on the electric control circuit or the like of the adherend.
本發明的黏著膜可藉由在基材或脫模膜的單面形成本發明的黏著劑層來製備。The adhesive film of the present invention can be produced by forming the adhesive layer of the present invention on one side of a substrate or a release film.
作為用於形成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。A resin film such as a polyester film or the like can be used as the release film (separator) for forming the base film of the pressure-sensitive adhesive layer or the protective adhesive surface.
對基材膜而言,可在樹脂膜的與形成有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污處理, 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 base film can be formed on the surface of the resin film opposite to the side on which the adhesive layer is formed by an anthrone or a fluorine-based release agent, a coating agent, cerium oxide particles or the like. Antifouling treatment, Antistatic treatment by application or mixing of an antistatic agent or the like can be performed.
對剝離膜而言,在與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。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 adhesive surface of the adhesive layer is bonded.
藉由在一個黏著劑層的兩面分別貼合脫模膜的實施了脫模處理的面,能夠形成“脫模膜/黏著劑層/脫模膜”的構成。在此情況下,藉由將兩側的脫模膜依次或同時剝離而露出黏著面,從而能夠與光學膜等光學構件貼合。作為光學膜,可以舉出偏光膜、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、光學補償膜、增亮膜等。The "release film/adhesive layer/release film" can be formed by bonding the surface of the release film to the mold release film on both surfaces of one adhesive layer. 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.
本發明的黏著膜能夠用於偏光板和顯示面板的貼合。作為顯示面板可以舉出液晶顯示裝置、有機EL等,但並不局限於這些。The adhesive film of the present invention can be used for bonding of a polarizing plate and a display panel. Examples of the display panel include a liquid crystal display device, an organic EL, and the like, but are not limited thereto.
另外,本發明的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。In addition, the 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.
另外,可在這些光學膜的至少單面上層疊上述黏著劑層而製備帶有黏著劑層的光學膜。具體地,可以舉出“光學膜/黏著劑層/光學膜”、“光學膜/黏著劑層/脫模膜”、“光學膜/黏著劑層”、“光學膜/黏著劑層/光學膜/黏著劑層/光學膜”、“光學膜/黏著劑層/光學膜/黏著劑層/脫模膜”、“脫模膜/黏著劑層/光學膜/黏著劑層/脫模膜”等的構成。Further, the above-mentioned adhesive layer may be laminated on at least one side of these optical films to prepare an optical film with an adhesive layer. Specifically, “optical film/adhesive layer/optical film”, “optical film/adhesive layer/release film”, “optical film/adhesive layer”, “optical film/adhesive layer/optical film” /Adhesive layer / optical film", "optical film / adhesive layer / optical film / adhesive layer / release film", "release film / adhesive layer / optical film / adhesive layer / release film", etc. Composition.
例如,如“光學膜/黏著劑層/脫模膜”,在具有由脫模膜保護的黏著劑層的情況下,藉由剝掉脫模膜而露出像“光學膜/黏著劑層”那樣的黏著劑層,並與其他光學膜進行貼合,能夠得到將黏著劑層用於層間貼合的如“光學膜/黏著劑層/光學膜”的構成。For example, in the case of an "optical film/adhesive layer/release film", in the case of having an adhesive layer protected by a release film, the release film is peeled off to expose an "optical film/adhesive layer". The adhesive layer is bonded to other optical films to obtain a structure in which an adhesive layer is used for interlayer bonding such as "optical film/adhesive layer/optical film".
下面,藉由實施例具體說明本發明。Hereinafter, the present invention will be specifically described by way of examples.
<丙烯酸共聚物的製造><Manufacture of Acrylic Copolymer>
[實施例1][Example 1]
向具有攪拌機、溫度計、回流冷凝器和氮導入管的反應裝置中導入氮氣,從而將反應裝置內的空氣置換為氮氣。然後,向反應裝置內加入丙烯酸丁酯90重量份、丙烯酸苯氧乙酯10重量份、二乙基丙烯醯胺10重量份、丙烯酸1.0重量份、丙烯酸4-羥基丁酯1.0重量份和溶劑(乙酸乙酯)60重量份。然後,經過2小時滴入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,得到了重均分子量為50萬的用於實施例1的丙烯酸共聚物溶液1。取丙烯酸共聚物的一部分,用作後述的酸值測定試樣。Nitrogen gas was introduced into a reaction apparatus having a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube to replace the air in the reaction device with nitrogen. Then, 90 parts by weight of butyl acrylate, 10 parts by weight of phenoxyethyl acrylate, 10 parts by weight of diethyl acrylamide, 1.0 part by weight of acrylic acid, 1.0 part by weight of 4-hydroxybutyl acrylate, and a solvent were added to the reaction apparatus. Ethyl acetate) 60 parts by weight. Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise thereto over 2 hours, and the mixture was reacted at 65 ° C for 6 hours to obtain an acrylic acid copolymer of Example 1 having a weight average molecular weight of 500,000. Solution 1. A part of the acrylic copolymer was taken and used as an acid value measurement sample described later.
[實施例2~5和比較例1~3][Examples 2 to 5 and Comparative Examples 1 to 3]
除了如表1的(A)、(B)、(C)、(D-1)(D-2)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。在此,雖沒有特別示出測定結果,但實施例2~5和比較例1~3的丙烯酸共聚物溶液中含有的共聚物的重均分子量在20萬~200萬的範圍內。The acrylic acid used in the above Example 1 was adjusted except that the composition of each monomer was adjusted as described in (A), (B), (C), (D-1) (D-2) of Table 1, respectively. The copolymer solution 1 was treated in the same manner to obtain acrylic acid copolymer solutions for Examples 2 to 5 and Comparative Examples 1 to 3. Here, the measurement results are not particularly shown, but the copolymers contained in the acrylic copolymer solutions of Examples 2 to 5 and Comparative Examples 1 to 3 have a weight average molecular weight of 200,000 to 2,000,000.
<黏著劑組合物、黏著劑層和黏著膜的製備><Preparation of Adhesive Composition, Adhesive Layer and Adhesive Film>
[實施例1][Example 1]
在如上述製造的實施例1的丙烯酸共聚物溶液1中,加入1.5重量份的1-辛基吡啶鎓十二烷基苯磺酸鹽、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0.1重量份的鋁螯合物(三乙醯丙酮鋁)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於由塗有矽酮樹脂的聚對苯二甲酸乙二醇酯(PET)膜構成的剝離膜上,然後在90℃下進行乾燥而去除溶劑。然後,藉由在23℃、50%RH的環境下實施7天的時效處理,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黏著劑層的實施例1的黏著膜。In the acrylic copolymer solution 1 of Example 1 produced as described above, 1.5 parts by weight of 1-octylpyridinium dodecylbenzenesulfonate and 0.1 part by weight of Coronate L-45 (toluene diisocyanate (TDI) were added. The adduct of the compound) and 0.1 part by weight of an aluminum chelate compound (aluminum triethylacetonate) were stirred and mixed to obtain an adhesive composition of Example 1. This adhesive composition was applied onto a release film composed of a polyethylene terephthalate (PET) film coated with an anthrone resin, and then dried at 90 ° C to remove the solvent. Then, by performing an aging treatment for 7 days in an environment of 23 ° C and 50% RH, the adhesion of Example 1 having an adhesive layer obtained by crosslinking the adhesive composition on one side of the release film was obtained. membrane.
[實施例2~5和比較例1~3][Examples 2 to 5 and Comparative Examples 1 to 3]
除了如表1的(E)、(F)所述地分別調整了添加劑的組成以外,與上述實施例1的黏著膜同樣地進行操作,得到了實施例2~5和比較例1~3的黏著膜。Except that the composition of the additive was adjusted as described in (E) and (F) of Table 1, the operation was carried out in the same manner as in the above-described adhesive film of Example 1, and Examples 2 to 5 and Comparative Examples 1 to 3 were obtained. Adhesive film.
【表1】
表1中,括弧內的數值表示以(A)組和(B)組的合計重量設為100重量份而求出的(C)組~(F)組的重量份的數值,以作為(C)組~(F)組的添加比例。In Table 1, the numerical value in parentheses indicates the numerical value of the weight of the (C) group to the (F) group obtained by setting the total weight of the group (A) and the group (B) to 100 parts by weight (C). The proportion of the group ~ (F) group added.
並且,表2中顯示了與表1中使用的各成分的簡稱對應的化合物名稱。在此,Coronate(註冊商標)L-45為日本聚胺酯工業(股)公司的商品名稱,D-110N為三井化學(股)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。Further, in Table 2, the compound names corresponding to the abbreviations of the respective components used in Table 1 are shown. 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.
【表2】
<試驗方法和評價><Test method and evaluation>
從實施例1~5和比較例1~3的黏著膜剝掉剝離膜(塗有矽酮樹脂的 PET膜)而露出黏著劑層,並將黏著劑層轉移至偏光板(膜)的單面上。The release film was peeled off from the adhesive films of Examples 1 to 5 and Comparative Examples 1 to 3 (coated with an anthrone resin) The PET film) exposes the adhesive layer and transfers the adhesive layer to one side of the polarizing plate (film).
<黏著力的測定方法><Method for measuring adhesion>
將黏著劑層轉移至厚度180μm的偏光板(膜)的單面,從而得到了作為試樣的黏著膜(帶有黏著劑層的光學膜)。The adhesive layer was transferred to one side of a polarizing plate (film) having a thickness of 180 μm to obtain an adhesive film (an optical film with an adhesive layer) as a sample.
用壓緊輥將該黏著膜貼合在用丙酮清洗過的鈉鈣玻璃的非錫面上。然後,在50℃、0.5MPa×20分鐘的條件下進行高壓鍋處理後,回到23℃×50%RH的環境,藉由拉伸試驗機測定經過1小時後的黏著膜的剝離強度。根據JIS Z0237《黏著帶、黏著片試驗方法》進行測定,將以300mm/min的速度向180°方向剝離時的剝離強度作為黏著膜的黏著劑層的黏著力。The adhesive film was attached to a non-tin surface of soda lime glass washed with acetone using a pinch roller. Then, the autoclave treatment was carried out under the conditions of 50 ° C and 0.5 MPa × 20 minutes, and then returned to an environment of 23 ° C × 50% RH, and the peeling strength of the adhesive film after one hour passed was measured by a tensile tester. According to JIS Z0237 "Adhesive tape and adhesive sheet test method", the peel strength at the time of peeling at 180 mm/min in the 180° direction was used as the adhesive force of the adhesive layer of the adhesive film.
<附著性的試驗方法><Test method for adhesion>
用目視確認測定黏著力後的試樣的黏著膜的黏著劑層,並以從基材層的偏光板(膜)脫落的狀態,判斷其附著性。The adhesive layer of the adhesive film of the sample after the measurement of the adhesive force was visually confirmed, and the adhesion was judged in a state of being peeled off from the polarizing plate (film) of the base material layer.
○:黏著劑層完全沒有從基材層脫落。○: The adhesive layer was not peeled off from the substrate layer at all.
△:黏著劑層的一部分從基材層分離而脫落。△: A part of the adhesive layer was separated from the substrate layer and peeled off.
×:黏著劑層從基材層脫落而附著在被黏附體的玻璃上。X: The adhesive layer was peeled off from the base material layer and adhered to the glass of the adherend.
<耐久性的試驗方法><Test method for durability>
將藉由與黏著力的測定同樣的方法製備的10cm見方的黏著膜,用同樣的方法貼合在鈉鈣玻璃的非錫面上,從而獲得了試樣。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小時後的黏著膜的狀態,從而判斷耐久性。A 10 cm square adhesive film prepared by the same method as the measurement of the adhesive force was applied to the non-tin surface of the soda lime glass in the same manner to obtain a sample. The sample was placed in an environment of 60° C.×90% RH for 250 hours, and then taken out to an environment of 23° C.×50% RH, and the state of the adhesive film after 1 hour was visually observed to determine the durability.
○:黏著膜完全沒有產生剝離和發泡○: The adhesive film did not peel and foam at all.
△:黏著膜的一部分產生了剝離和發泡。△: Part of the adhesive film was peeled off and foamed.
×:黏著膜的整體產生了剝離和發泡。×: Peeling and foaming occurred in the entire adhesive film.
<折射率的測定方法><Method for Measuring Refractive Index>
用阿貝折射儀(製造商:ERMA,型號:ER-2S)測定23℃下的黏著劑層的折射率。The refractive index of the adhesive layer at 23 ° C was measured using an Abbe refractometer (manufacturer: ERMA, model: ER-2S).
<表面電阻率的測定方法><Method for Measuring Surface Resistivity>
在老化後、貼合偏光板之前,剝掉剝離膜(塗有矽酮樹脂的PET膜)而使黏著劑層外露,採用電阻率儀(商品名稱為“Hiresta UP-HT450”,(股)公司三菱化學分析技術(Mitsubishi Chemical Analytech Co.,Ltd.)製造),測定了黏著劑層的表面電阻率。After aging, before peeling off the polarizing plate, peeling off the peeling film (PET film coated with fluorenone resin) to expose the adhesive layer, using a resistivity meter (trade name "Hiresta UP-HT450", (share) company The surface resistivity of the adhesive layer was measured by Mitsubishi Chemical Analytech Co., Ltd.).
將評價結果示於表3中。另外,在表面電阻率中,藉由“mE+n”來表示“m×10+n ”(其中,m為任意的實數,n為正整數)。The evaluation results are shown in Table 3. Further, in the surface resistivity, by "mE + n" to represent "m × 10 + n" (where, m is an arbitrary real numbers, n-is a positive integer).
在實施例1~5的黏著膜中,5μm厚度的黏著劑層的黏著力為4.0N/25mm以上,黏著劑層的折射率在1.47~1.50的範圍內,並具有足以發揮抗靜電性能的5.0×10+11 Ω/□以下的表面電阻率,而且附著性和耐久性也優異。即,實施例1~5的黏著膜能夠滿足所需要求及克服問題。In the adhesive films of Examples 1 to 5, the adhesive layer having a thickness of 5 μm has an adhesive force of 4.0 N/25 mm or more, and the refractive index of the adhesive layer is in the range of 1.47 to 1.50, and has an antistatic property of 5.0. The surface resistivity of ×10 +11 Ω/□ or less is excellent also in adhesion and durability. That is, the adhesive films of Examples 1 to 5 can satisfy the required requirements and overcome the problems.
使用實施例1和實施例3的黏著劑組合物,並用相同的方法製備了黏著劑層厚度為3μm、5μm、10μm、15μm、20μm的黏著膜,並測定了黏著劑層的黏著力,將其結果示於表4中。可知使用了實施例1和實施例3的 黏著劑組合物的黏著劑層的黏著力如眾所周知的那樣與黏著劑層的厚度大致成比例。Using the adhesive compositions of Example 1 and Example 3, an adhesive film having an adhesive layer thickness of 3 μm, 5 μm, 10 μm, 15 μm, and 20 μm was prepared in the same manner, and the adhesive force of the adhesive layer was measured. The results are shown in Table 4. It can be seen that the use of the embodiment 1 and the embodiment 3 The adhesion of the adhesive layer of the adhesive composition is substantially proportional to the thickness of the adhesive layer as is well known.
比較例1的黏著膜也許是因為黏著劑組合物中不具有含氮的單體,其厚度5μm的黏著劑層的黏著力弱。另外,由於不具有含芳基的(甲基)丙烯酸酯單體,黏著劑層的折射率低。另外,由於不含有離子化合物,因此表面電阻率高。而且,附著性和耐久性也差。The adhesive film of Comparative Example 1 may be because the adhesive composition does not have a nitrogen-containing monomer, and the adhesive layer having a thickness of 5 μm has a weak adhesive force. Further, since the (meth) acrylate monomer having no aryl group is not contained, the adhesive layer has a low refractive index. In addition, since it does not contain an ionic compound, the surface resistivity is high. Moreover, adhesion and durability are also poor.
比較例2的黏著膜也許是因為黏著劑組合物中含有羧基的共聚合性乙烯基單體的配合量過多,厚度5μm的黏著劑層的黏著力弱。另外,由於不具有含芳基的(甲基)丙烯酸酯單體,黏著劑層的折射率低。另外,由於離子化合物不是熔點為30~50℃的離子化合物,因此表面電阻率稍高。而且,附著力和耐久性也差。The adhesive film of Comparative Example 2 may be because the amount of the copolymerizable vinyl monomer having a carboxyl group in the adhesive composition is too large, and the adhesive layer having a thickness of 5 μm is weak. Further, since the (meth) acrylate monomer having no aryl group is not contained, the adhesive layer has a low refractive index. Further, since the ionic compound is not an ionic compound having a melting point of 30 to 50 ° C, the surface resistivity is slightly higher. Moreover, adhesion and durability are also poor.
比較例3的黏著膜也許是因為黏著劑組合物中既不具有含羧基的共聚合性乙烯基單體也不具有含羥基的共聚合性乙烯基單體,其厚度5μm的黏著劑層的黏著力弱。另外,由於不含有離子化合物,因此表面電阻率高。而且,附著性和耐久性也差。The adhesive film of Comparative Example 3 may be because the adhesive composition has neither a carboxyl group-containing copolymerizable vinyl monomer nor a hydroxyl group-containing copolymerizable vinyl monomer, and the adhesive layer having a thickness of 5 μm is adhered. Weak. In addition, since it does not contain an ionic compound, the surface resistivity is high. Moreover, adhesion and durability are also poor.
如此地,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。As described above, the adhesive films of Comparative Examples 1 to 3 could not satisfy the conventionally proposed requirements and overcome the problems existing in the past.
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