KR101587804B1 - Adhesive composition for polarizing plate and polarizing plate using the same - Google Patents
Adhesive composition for polarizing plate and polarizing plate using the same Download PDFInfo
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- KR101587804B1 KR101587804B1 KR1020127003032A KR20127003032A KR101587804B1 KR 101587804 B1 KR101587804 B1 KR 101587804B1 KR 1020127003032 A KR1020127003032 A KR 1020127003032A KR 20127003032 A KR20127003032 A KR 20127003032A KR 101587804 B1 KR101587804 B1 KR 101587804B1
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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
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
- C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- 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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- 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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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
- C09J2301/302—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 the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
Abstract
단기간의 숙성에 의해 우수한 내구성 및 광누설 방지성을 가지는 점착제층을 형성할 수 있는 편광판용 점착제 조성물을 제공하는 것을 과제로 한다. 이 편광판용 점착제 조성물은 다음의 성분(A) 및 (B), (A) 적어도 카르복실기 함유 모노머 1~10질량%를 공중합하여 이루어지는 중량 평균 분자량이 30만~150만인 (메타)아크릴계 폴리머 100질량부 (B) 이소시아누레이트 구조를 가지는 톨릴렌디이소시아네이트계 화합물 4~20질량부를 함유하는 것을 특징으로 한다.It is an object of the present invention to provide a pressure-sensitive adhesive composition for a polarizing plate capable of forming a pressure-sensitive adhesive layer having excellent durability and light leakage prevention property by short-term aging. The pressure-sensitive adhesive composition for a polarizing plate comprises the following components (A) and (B): (A) 100 parts by mass of a (meth) acrylic polymer having a weight average molecular weight of 300,000 to 1,500,000 copolymerized with at least 10% by mass of a carboxyl group- And 4 to 20 parts by mass of a tolylene diisocyanate compound having an isocyanurate structure (B).
Description
본 발명은 편광판용 점착제 조성물에 관한 것으로, 더욱 상세하게는 단기간의 숙성에 의해 우수한 광학적성을 구비한 점착제층을 형성할 수 있는 편광판용 점착제 조성물 및 이것을 사용한 편광판에 관한 것이다.The present invention relates to a pressure-sensitive adhesive composition for a polarizing plate, and more particularly, to a pressure-sensitive adhesive composition for a polarizing plate capable of forming a pressure-sensitive adhesive layer having excellent optical properties due to short-term aging and a polarizing plate using the same.
액정 소자는 액정 재료가 2장의 기판 사이에 끼워진 구조를 가지고 있고, 이 기판의 표면에는 점착제층을 통하여 편광판이 첩착되어 있다. 최근, 액정 소자는 차량 탑재용, 옥외 계기용, 퍼스널 컴퓨터의 디스플레이, 텔레비전 등 용도가 확대되고 있어, 그것에 따라 사용 환경도 매우 가혹하게 되고 있다.A liquid crystal device has a structure in which a liquid crystal material is sandwiched between two substrates, and a polarizer is attached to the surface of the substrate through a pressure-sensitive adhesive layer. BACKGROUND ART In recent years, liquid crystal devices have been used for on-vehicle use, outdoor use, personal computer displays, televisions, and the like.
편광판은 이종 재료의 다층 구조를 가지고 있고, 구성하는 재료의 특성으로부터 치수 안정성이 떨어진다. 특히 고온, 고습열의 사용 환경하에 있어서는, 편광판의 수축에 의해 응력이 집중되어, 편광판의 복굴절을 유발함과 아울러, 점착제 자신도 응력 집중에 의해 배향하여 복굴절이 생기기 때문에, 응력이 집중하는 단부에서 색 불균일(광누설)이 일어나, 표시 품위가 저하한다. 또, 이러한 환경하에서는, 편광판과 유리의 계면에서의 발포나 편광판의 벗겨짐 등의 문제도 생기기 쉽다. 따라서, 편광판용의 점착제에는 우수한 광누설 방지성과 내구성이 요구된다.The polarizing plate has a multilayer structure of different materials, and the dimensional stability is deteriorated due to the characteristics of the constituent materials. Particularly under high temperature and high humidity heat use environments, the stress concentrates due to the shrinkage of the polarizing plate, which causes birefringence of the polarizing plate, and the pressure sensitive adhesive itself is oriented by stress concentration and birefringence occurs. Color irregularity (light leakage) occurs, and the display quality decreases. Under these circumstances, problems such as foaming at the interface between the polarizing plate and the glass and peeling of the polarizing plate are likely to occur. Therefore, the pressure-sensitive adhesive for a polarizing plate is required to have excellent light leakage prevention and durability.
한편, 편광판에 점착제층을 형성함에 있어서, 상기 광누설 방지성과 내구성을 발현시키기 위해서는, 편광판에 점착제 조성물을 도공한 상태에서, 예를 들면 실온에서 1주일정도의 숙성 공정을 두어 경화시킬 필요가 있었지만, 이러한 장기의 숙성 기간에 의해, 생산성이 저하하거나, 재고량이 증대한다는 문제가 생기고 있었다.On the other hand, in order to form the pressure-sensitive adhesive layer on the polarizing plate, it is necessary to cure the polarizing plate by applying a pressure-sensitive adhesive composition on the polarizing plate, for example, , There has been a problem that the productivity is lowered or the inventory amount is increased due to the ripening period of such organ.
이 문제에 대해, 수산기 함유 아크릴 폴리머와 이소시아네이트계 가교제의 혼합물에 있어서, 수산기 함유 아크릴 폴리머 중에 또한 카르복실기를 함유시킴으로써, 경화를 촉진시키는 방법이 제안되어 있다(특허문헌 1). 그러나, 이 기술에서는 이소시아네이트계 가교제의 첨가량이 적고, 단기간의 숙성에 의해 충분한 광누설 방지성이나 내구성을 얻을 수 없었다. 또, 수산기와 카르복실기를 함유하는 아크릴계 폴리머와, 지방족계 또는 지환족계의 다관능 이소시아네이트계 또는 이소시아누레이트계 화합물을 함유하고, 양생 기간이 단축된 표면 보호 필름용 점착제 조성물이 개시되어 있다(특허문헌 2). 그러나, 이 점착제 조성물에서 사용되는 아크릴계 폴리머는 카르복실기의 양이 한정되어 있어, 편광판과 유리의 첩합에 사용하는 용도에는 적합하지 않다. 만일 본 발명의 카르복실기가 1부 이상의 점착제에 상기 지방족계 또는 지환속계의 다관능 이소시아네이트계 또는 이소시아누레이트계 화합물을 첨가한 경우에는, 포트 라이프가 짧아지는 경향이 있어, 실용상 사용할 수 없는 것이었다.To solve this problem, a method of accelerating curing by additionally containing a carboxyl group in a hydroxyl group-containing acrylic polymer in a mixture of a hydroxyl group-containing acrylic polymer and an isocyanate crosslinking agent has been proposed (Patent Document 1). However, in this technique, the amount of the isocyanate-based crosslinking agent to be added is small and sufficient light leakage prevention and durability can not be obtained due to short-term aging. Also disclosed is a pressure-sensitive adhesive composition for a surface protective film containing an acryl-based polymer containing a hydroxyl group and a carboxyl group, and an aliphatic or alicyclic polyfunctional isocyanate-based or isocyanurate-based compound and having a shortened curing period Document 2). However, the acrylic polymer used in this pressure-sensitive adhesive composition has a limited amount of carboxyl groups, and thus is not suitable for use in the conjugation of a polarizing plate and a glass. If the aliphatic or alicyclic polyfunctional isocyanate or isocyanurate compound is added to at least one carboxyl group-containing pressure sensitive adhesive of the present invention, the pot life tends to be shortened, so that it can not be practically used .
그 밖에 카르복실기를 가지는 아크릴계 폴리머에 이소시아네이트계 화합물을 첨가한 광학 필름용의 점착제 조성물이 개시되어 있다(특허문헌 3 및 4). 그러나, 이들 기술은 리워크성이나 광누설 방지성의 향상을 지향하는 것으로서, 숙성 기간의 단축화에 대해서는 전혀 고려하고 있지 않다. 따라서, 이들 문헌에 개시된 점착제 조성물은 모두 단기간의 숙성에 의해 충분한 광학적성을 얻을 수는 없는 것이었다.And a pressure-sensitive adhesive composition for an optical film in which an isocyanate compound is added to an acryl-based polymer having a carboxyl group (Patent Documents 3 and 4). However, these techniques are aimed at improving the reworkability and light leakage prevention property, and do not consider the reduction of the aging period at all. Therefore, all of the pressure-sensitive adhesive compositions disclosed in these documents can not obtain sufficient optical aptitude due to short-term aging.
따라서, 단기간의 숙성에 의해, 우수한 내구성과 광누설 방지성을 구비한 점착제층을 형성할 수 있는 편광판용 점착제 조성물이 요망되고 있고, 본 발명은 그러한 편광판용 점착제 조성물을 제공하는 것을 그 과제로 하는 것이다.Therefore, a pressure-sensitive adhesive composition for a polarizing plate capable of forming a pressure-sensitive adhesive layer having excellent durability and light leakage prevention property by short-term aging has been desired. The present invention provides a pressure-sensitive adhesive composition for a polarizing plate will be.
본 발명자들은 상기 과제를 해결하기 위해 예의 검토를 거듭한 결과, 가교제로서, 이소시아누레이트 구조를 가지는 톨릴렌디이소시아네이트계 화합물을 사용하고, 이것을 특정 범위의 분자량을 가지는 카르복실기 함유 아크릴계 폴리머에 대하여 비교적 다량으로 배합함으로써, 단기간의 숙성에서도 우수한 내구성 및 광누설 방지성을 가지는 점착제층을 형성할 수 있는 것을 알아내어 본 발명을 완성시키기에 이르렀다.DISCLOSURE OF THE INVENTION As a result of intensive investigations to solve the above problems, the present inventors have found that a tolylene diisocyanate compound having an isocyanurate structure is used as a cross-linking agent, and that a tolylene diisocyanate compound having a relatively large amount , It has been found that a pressure-sensitive adhesive layer having excellent durability and light leakage-preventing property can be formed even in a short-term aging, thereby completing the present invention.
즉, 본 발명은,That is,
다음의 성분(A) 및 (B)The following components (A) and (B)
(A) 적어도 카르복실기 함유 모노머 1~10질량%를 공중합하여 이루어지는 중량 평균 분자량이 30만~150만인 (메타)아크릴계 폴리머 100질량부(A) 100 parts by mass of a (meth) acryl-based polymer having at least a carboxyl group-containing monomer copolymerized with 1 to 10% by mass and having a weight average molecular weight of 300,000 to 1,500,000
(B) 이소시아누레이트 구조를 가지는 톨릴렌디이소시아네이트계 화합물 4~20질량부(B) 4 to 20 parts by weight of a tolylene diisocyanate compound having an isocyanurate structure
를 함유하는 것을 특징으로 하는 편광판용 점착제 조성물이다., And a pressure-sensitive adhesive composition for a polarizing plate.
또 본 발명은 편광 필름의 적어도 일방의 면에 상기 편광판용 점착제 조성물로 형성되는 점착제층을 마련하여 이루어지는 편광판이다.Further, the present invention is a polarizing plate comprising a polarizing film provided with a pressure-sensitive adhesive layer formed on at least one surface thereof with the above-mentioned pressure-sensitive adhesive composition for a polarizing plate.
본 발명의 점착제 조성물은 이것을 편광판에 사용함으로써, 고온 고습 조건하에서도 광누설의 발생을 유효하게 방지하고, 또 우수한 내구성을 가지고, 점착제층의 발포나 벗겨짐 등의 발생을 억제할 수 있다. 또한, 경화 속도가 빠르고, 숙성 기간의 대폭적인 단축이 가능하기 때문에, 생산성을 현저하게 향상시키고, 재고량을 저감시킬 수 있다.By using the pressure-sensitive adhesive composition of the present invention in a polarizing plate, occurrence of light leakage can be effectively prevented even under high-temperature and high-humidity conditions, and excellent durability and occurrence of foaming and peeling of the pressure-sensitive adhesive layer can be suppressed. In addition, since the curing speed is high and the aging period can be greatly shortened, the productivity can be remarkably improved and the inventory amount can be reduced.
본 발명의 편광판용 점착제 조성물에 사용하는 성분(A)의 아크릴계 폴리머는 적어도 카르복실기 함유 모노머를 공중합하여 얻어지는 것이다.The acrylic polymer of the component (A) used in the pressure-sensitive adhesive composition for a polarizing plate of the present invention is obtained by copolymerizing at least a carboxyl group-containing monomer.
상기 카르복실기 함유 모노머로서는 (메타)아크릴산, 2-카르복시에틸(메타)아크릴레이트, 3-카르복시프로필(메타)아크릴레이트, 4-카르복시부틸(메타)아크릴레이트, 이타콘산, 크로톤산, 말레산, 푸말산 및 무수 말레산 등을 들 수 있다.Examples of the carboxyl group-containing monomer include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, itaconic acid, crotonic acid, Malic acid and maleic anhydride.
성분(A) 아크릴계 폴리머의 구성 모노머 전체에 대한 카르복실기 함유 모노머의 함유량은 1~10질량%(이하,「%」로 나타냄)이며, 바람직하게는 2~8%이며, 보다 바람직하게는 2~6%이다. 1%보다 적으면 응집력이 얻어지기 어렵고, 10%보다 많으면 응집력이 지나치게 높거나 점착력이 상승하기 때문에 바람직하지 않다.Component (A) The content of the carboxyl group-containing monomer in the constituent monomers of the acrylic polymer is 1 to 10 mass% (hereinafter, referred to as "%"), preferably 2 to 8 mass%, more preferably 2 to 6 mass% %to be. If it is less than 1%, it is difficult to obtain a cohesive force, and if it is more than 10%, cohesive force is too high or adhesion increases.
성분(A)의 아크릴계 폴리머의 다른 구성 모노머로서는 (메타)아크릴산알킬에스테르, 수산기 함유 모노머, 벤젠환 함유 모노머, (메타)아크릴산알콕시에스테르, 아미노기 함유 모노머, 아미드 함유 모노머 등을 들 수 있다.Examples of other constituent monomers of the acrylic polymer of the component (A) include (meth) acrylic acid alkyl esters, hydroxyl group-containing monomers, benzene ring-containing monomers, (meth) acrylic acid alkoxy esters, amino group-containing monomers and amide-containing monomers.
상기 (메타)아크릴산알킬에스테르로서는 탄소수 1~12의 분기되어 있어도 되는 알킬기를 가지는 것이 바람직하고, 구체적으로는 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 이소프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트, 이소부틸(메타)아크릴레이트, 펜틸(메타)아크릴레이트, 헥실(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 옥틸(메타)아크릴레이트, 노닐(메타)아크릴레이트, 데실(메타)아크릴레이트, 도데실(메타)아크릴레이트, 라우릴(메타)아크릴레이트를 들 수 있다. 이들 중, 부틸아크릴레이트, 메틸아크릴레이트가 점착력과 내구성의 밸런스가 양호하기 때문에 바람직하게 사용된다.Specific examples of the alkyl (meth) acrylate include alkyl (meth) acrylates, ethyl (meth) acrylates, propyl (meth) acrylates, isopropyl (Meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and lauryl (meth) acrylate. Of these, butyl acrylate and methyl acrylate are preferably used because of good balance of adhesion and durability.
성분(A) 아크릴계 폴리머의 구성 모노머 전체에 대한 (메타)아크릴산알킬에스테르의 함유량은 10~99%이며, 바람직하게는 50~98.5%이다. 10%보다 적으면 점착력과 내구성의 밸런스가 취해지지 않는 경우가 있고, 99%보다 많으면 내구성이 나빠지는 경우가 있다.Component (A) The content of the alkyl (meth) acrylate in the total monomer constituting the acrylic polymer is 10 to 99%, preferably 50 to 98.5%. If it is less than 10%, the adhesive force and durability may not be balanced. If more than 99%, durability may be deteriorated.
상기 수산기 함유 모노머로서는 2-히드록시에틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 6-히드록시헥실(메타)아크릴레이트, 1,4-시클로헥산디메탄올모노(메타)아크릴레이트, 클로로-2-히드록시프로필아크릴레이트, 디에틸렌글리콜모노(메타)아크릴레이트, 알릴알코올 등을 예시할 수 있고, 이러한 수산기 함유 모노머를 공중합시킴으로써 겔 분률을 보다 높게 할 수 있다. 이들 중, 2-히드록시에틸아크릴레이트, 4-히드록시부틸아크릴레이트가 (메타)아크릴산알킬에스테르와의 공중합성이 양호하기 때문에 바람직하게 사용된다.Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- (Meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, chloro-2-hydroxypropyl acrylate, diethylene glycol mono (meth) acrylate and allyl alcohol And the gel fraction can be made higher by copolymerizing such hydroxyl group-containing monomers. Of these, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are preferably used because of their good copolymerization with (meth) acrylic acid alkyl ester.
성분(A) 아크릴계 폴리머의 구성 모노머 전체에 대한 수산기 함유 모노머의 함유량은 0~1%이며, 바람직하게는 0.05~1%이다. 1%보다 많으면 겔 분률이 지나치게 높아져 접착성이 저하되고, 고온, 고습열 조건에서 벗겨짐 등이 생길 우려가 있다.Component (A) The content of the hydroxyl group-containing monomer with respect to the constituent monomers of the acrylic polymer is 0 to 1%, preferably 0.05 to 1%. If it is more than 1%, the gel fraction becomes excessively high, resulting in deterioration of adhesiveness and peeling off under high temperature and high humidity conditions.
상기 벤젠환 함유 모노머는 정의 고유 복굴절을 가지고 있고, 이것을 공중합시킴으로써, (메타)아크릴계 폴리머의 복굴절을 저감할 수 있다. 구체적으로는 페닐아크릴레이트, 페녹시에틸(메타)아크릴레이트, 벤질(메타)아크릴레이트, 페녹시디에틸렌글리콜(메타)아크릴레이트, 에틸렌옥사이드 변성 노닐페놀(메타)아크릴레이트, 히드록시에틸화β-나프톨아크릴레이트, 비페닐(메타)아크릴레이트, 스티렌, 비닐톨루엔, α-메틸스티렌 등을 들 수 있다. 이들 중, 벤질아크릴레이트, 페녹시에틸아크릴레이트가 (메타)아크릴산알킬에스테르와의 상용성, 공중합성이 좋고 투명성을 저하시키지 않기 때문에 바람직하게 사용된다.The benzene ring-containing monomer has a definite intrinsic birefringence, and the birefringence of the (meth) acrylic polymer can be reduced by copolymerizing it. Specific examples thereof include phenylacrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, ethylene oxide modified nonylphenol (meth) acrylate, Naphthol acrylate, biphenyl (meth) acrylate, styrene, vinyltoluene, and? -Methylstyrene. Of these, benzyl acrylate and phenoxyethyl acrylate are preferably used because they have good compatibility with the (meth) acrylic acid alkyl ester, good copolymerization and do not lower transparency.
성분(A) 아크릴계 폴리머의 구성 모노머 전체에 대한 벤젠환 함유 모노머의 함유량은 0~40%이며, 바람직하게는 0~30%이다. 40%보다 많으면 적절한 점착력을 얻을 수 없는 경우가 있다.Component (A) The content of the benzene ring-containing monomer relative to the constituent monomers of the acrylic polymer is 0 to 40%, preferably 0 to 30%. If it is more than 40%, appropriate adhesive force may not be obtained.
상기 (메타)아크릴산알콕시에스테르로서는 (메타)아크릴산2-메톡시에틸, (메타)아크릴산2-에톡시에틸, (메타)아크릴산2-메톡시프로필, (메타)아크릴산3-메톡시프로필, (메타)아크릴산2-메톡시부틸, (메타)아크릴산4-메톡시부틸 등을 예시할 수 있다. 성분(A) 아크릴계 폴리머의 구성 모노머 전체에 대한 (메타)아크릴산알콕시에스테르의 함유량은 0~90%이며, 바람직하게는 0~80%이다.Examples of the (meth) acrylic acid alkoxy ester include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 3-methoxypropyl ) 2-methoxybutyl acrylate, and 4-methoxybutyl (meth) acrylate. Component (A) The content of the (meth) acrylic acid alkoxy ester in the constituent monomers of the acrylic polymer is 0 to 90%, preferably 0 to 80%.
상기 아미노기 함유 모노머로서는 (메타)아크릴산디메틸아미노에틸, (메타)아크릴산디에틸아미노에틸 등을 예시할 수 있다.Examples of the amino group-containing monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like.
상기 아미드 함유 모노머로서는 (메타)아크릴아미드, (메타)N-메틸올아크릴아미드 등을 예시할 수 있다. 이들 아미노기 함유 모노머, 아미드기 함유 모노머의 사용량은 성분(A) 아크릴계 폴리머의 구성 모노머 전체에 대하여 0~1%정도이다.Examples of the amide-containing monomer include (meth) acrylamide and (meth) N-methylol acrylamide. The amounts of these amino group-containing monomers and amide group-containing monomers to be used are about 0 to 1% with respect to the total monomers of the component (A) acrylic polymer.
본 발명의 성분(A)은 상기 모노머 성분의 혼합물을 용액 중합법, 괴상 중합법, 유화 중합법, 현탁 중합법 등의 종래 공지의 중합법에 의해 중합시킴으로써 제조할 수 있다. 이들 중에서도, 유화제나 현탁제 등의 중합 안정제를 포함하지 않는 용액 중합법이나 괴상 중합법에 의해 제조한 것이 보다 바람직하다.The component (A) of the present invention can be produced by polymerizing a mixture of the above monomer components by a conventionally known polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method and a suspension polymerization method. Among them, those prepared by a solution polymerization method or a bulk polymerization method which do not contain a polymerization stabilizer such as an emulsifier or a suspending agent are more preferable.
상기한 바와 같이 하여 얻어지는 성분(A)의 중량 평균 분자량(Mw)은 30만~150만이며, 바람직하게는 40만~120만이다. 중량 평균 분자량이 30만 미만이면 내구성이 악화되고, 150만보다 크면 점도가 높아져, 취급에 문제가 생긴다. 또한, 본 명세서에 있어서 중량 평균 분자량은 실시예중에 기재한 측정 방법에 의해 구해지는 값을 의미한다.The weight average molecular weight (Mw) of the component (A) obtained as described above is from 300,000 to 1,500,000, preferably from 400,000 to 1,200,000. When the weight average molecular weight is less than 300,000, the durability is deteriorated. When the weight average molecular weight is more than 1.5000,000, the viscosity is increased, which causes problems in handling. In the present specification, the weight average molecular weight means a value obtained by the measuring method described in the Examples.
또, 성분(A)의 아크릴계 폴리머는 유리 전이 온도가 0℃ 이하인 것이 바람직하고, -20℃ 이하인 것이 보다 바람직하며, -80~-30℃가 특히 바람직하다. 유리 전이 온도가 0℃보다 높으면, 얻어지는 점착제의 기재에 대한 밀착성이나 점착제층의 가요성이 저하되고, 기재로부터의 벗겨짐이나 들뜸이 생기는 경우가 있다. 또한, 본 명세서에 있어서, 유리 전이 온도는 하기의 FOX의 식에 의해 산출되는 값이다.The acrylic polymer of the component (A) preferably has a glass transition temperature of 0 ° C or lower, more preferably -20 ° C or lower, particularly preferably -80 ° C to -30 ° C. If the glass transition temperature is higher than 0 占 폚, the adhesiveness of the resultant pressure-sensitive adhesive to the base material and the flexibility of the pressure-sensitive adhesive layer may be deteriorated, resulting in peeling or peeling off from the base material. In the present specification, the glass transition temperature is a value calculated by the following FOX formula.
(FOX의 식)(Expression of FOX)
1/Tg=Wa/Tga+Wb/Tgb+…1 / Tg = Wa / Tga + Wb / Tgb +
Tg : 공중합체의 유리 전이 온도Tg: glass transition temperature of the copolymer
Tga, Tgb,‥ : 단량체 a, 단량체 b,…의 호모 폴리머의 유리 전이 온도Tga, Tgb, ...: monomer a, monomer b, ... Of glass transition temperature
Wa, Wb,‥‥ : 단량체 a, 단량체 b,…의 중량분률Wa, Wb, ..., monomer a, monomer b, ... Weight fraction
본 발명에 사용하는 성분(B)의 이소시아누레이트 구조를 가지는 톨릴렌디이소시아네이트계 화합물은 톨릴렌디이소시아네이트가 3량화하여 형성되는 이소시아누레이트환을 그 구조중에 포함하는 화합물이며 각종의 변성체도 포함된다. 성분(B)의 화합물은 일본 특허 공개 평8-193114호 공보, 국제 공개 제2006/137307호에 기재된 방법 등에 의해 얻을 수 있고, 성분(B)에 해당하는 화합물로서 코로네이트 342, 코로네이트 2030(모두 니혼폴리우레탄코교사제) 등이 시판되고 있다.The tolylene diisocyanate compound having an isocyanurate structure of the component (B) used in the present invention is a compound containing an isocyanurate ring formed by trimerization of tolylene diisocyanate in its structure and also includes various modified products do. The compound of the component (B) can be obtained by the method described in JP-A-8-193114 and WO2006 / 137307, and the compound corresponding to the component (B) is Coronate 342, Coronate 2030 All manufactured by Nippon Polyurethane Co., Ltd.) are commercially available.
본 발명의 편광판용 점착제 조성물에 있어서의 성분(B)의 배합량은 성분(A) 100질량부(이하, 「부」로 나타냄)에 대하여 4~20부이며, 바람직하게는 6~15부이다. 4부보다 적으면 광누설 성능이 좋지 않고, 20부보다 많으면 응집력이 지나치게 높아지기 때문에 바람직하지 않다.The blending amount of the component (B) in the pressure-sensitive adhesive composition for a polarizing plate of the present invention is 4 to 20 parts, preferably 6 to 15 parts, per 100 parts by mass of the component (A). If the amount is less than 4 parts, the light leakage performance is not good, and if it is more than 20 parts, the cohesive force becomes too high.
또 본 발명의 편광판용 점착제 조성물에는 상기 성분(B) 이외의 가교제를 병용할 수 있다(성분(C)). 이러한 가교제로서 톨릴렌디이소시아네이트계 가교제(이소시아누레이트 구조를 가지는 것을 제외함), 에폭시계 가교제, 아지리딘계 가교제를 들 수 있고, 이들의 1종 또는 2종 이상을 사용할 수 있다.Further, a crosslinking agent other than the above-mentioned component (B) may be used in combination with the pressure-sensitive adhesive composition for a polarizing plate of the present invention (component (C)). As such a crosslinking agent, there may be mentioned tolylene diisocyanate crosslinking agent (not having an isocyanurate structure), epoxy crosslinking agent and aziridine crosslinking agent, and one or more of these may be used.
상기 톨릴렌디이소시아네이트계 가교제(이소시아누레이트 구조를 가지는 것을 제외함)로서는 톨릴렌디이소시아네이트 및 이것을 트리메틸올프로판, 펜타에리트리톨 등의 다가 알코올과 부가 반응시킨 이소시아네이트 화합물, 뷰렛형 화합물, 또한 공지의 폴리에테르폴리올이나 폴리에스테르폴리올, 아크릴폴리올, 폴리부타디엔폴리올, 폴리이소프렌폴리올 등과 부가 반응시킨 우레탄 프리폴리머형의 이소시아네이트 화합물 등의 유도체를 들 수 있다. 이러한 톨릴렌디이소시아네이트계 가교제(이소시아누레이트 구조를 가지는 것을 제외함)를 병용함으로써, 기재에 대한 밀착성이 향상되고, 벗겨짐 등을 억제할 수 있다. 이들 중에서도 톨릴렌디이소시아네이트, 트리메틸올프로판톨릴렌디이소시아네이트 등이 바람직하다.Examples of the tolylene diisocyanate crosslinking agent (other than those having an isocyanurate structure) include tolylene diisocyanate and an isocyanate compound, a biuret type compound and a known poly (isocyanurate) compound obtained by reacting the tolylene diisocyanate with a polyhydric alcohol such as trimethylolpropane or pentaerythritol. And derivatives of urethane prepolymer type isocyanate compounds added in reaction with ether polyol, polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol and the like. By using such a tolylene diisocyanate crosslinking agent (excluding those having an isocyanurate structure) in combination, adhesiveness to a substrate can be improved, and peeling and the like can be suppressed. Of these, tolylene diisocyanate and trimethylolpropane tolylene diisocyanate are preferred.
본 발명의 편광판용 점착제 조성물에 있어서, 톨릴렌디이소시아네이트계 가교제(이소시아누레이트 구조를 가지는 것을 제외함)는 성분(B)에 대한 배합비가 1:3~3:1이 되도록 배합하는 것이 바람직하다. 배합비가 이 범위 밖이면, 숙성에 장기간을 필요로 하고, 또 고온, 고습열 조건에서 벗겨짐 등이 생기는 경우가 있다.In the pressure-sensitive adhesive composition for a polarizing plate of the present invention, it is preferable that the tolylene diisocyanate crosslinking agent (excluding those having an isocyanurate structure) is blended so that the blending ratio to the component (B) is 1: 3 to 3: 1 . If the compounding ratio is out of this range, aging may take a long period of time, and peeling may occur at high temperature and high humidity.
상기 에폭시 가교제로서는 비스페놀A 에피클로르히드린형의 에폭시계 수지, 에틸렌디글리시딜에테르, 폴리에틸렌글리콜디글리시딜에테르, 글리세린디글리시딜에테르, 글리세린트리글리시딜에테르, 1,6-헥산디올디글리시딜에테르, 트리메틸올프로판트리글리시딜에테르, 디글리시딜아닐린, 디아민글리시딜아민, N,N,N',N'-테트라글리시딜-m-크실릴렌디아민, 1,3-비스(N,N'-디아민글리시딜아미노메틸)시클로헥산 등의 분자 중에 2개 이상의 에폭시기를 가지는 화합물을 들 수 있다. 이들 에폭시계 가교제를 병용함으로써, 겔 분률을 보다 높게 할 수 있다. 이들 중에서도 N,N,N',N'-테트라글리시딜-m-크실릴렌디아민, 1,3-비스(N,N'-디아민글리시딜아미노메틸)시클로헥산이 바람직하게 사용된다.Examples of the epoxy crosslinking agent include bisphenol A epichlorohydrin type epoxy resin, ethylene diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol N, N ', N'-tetraglycidyl-m-xylylenediamine, 1, 2, 3, 4, And 3-bis (N, N'-diamine glycidylaminomethyl) cyclohexane. By using these epoxy crosslinking agents in combination, the gel fraction can be increased. Among these, N, N, N ', N'-tetraglycidyl-m-xylylenediamine and 1,3-bis (N, N'-diamine glycidylaminomethyl) cyclohexane are preferably used.
본 발명의 편광판용 점착제 조성물에 있어서의 에폭시 가교제의 배합량은 성분(B)에 대하여 0~1%이며, 바람직하게는 0.05~0.5%이다. 배합량이 이 범위 밖이면, 숙성에 장기간을 필요로 하고, 또 고온, 고습열 조건에서 벗겨짐 등이 생기는 경우가 있다.The blending amount of the epoxy cross-linking agent in the pressure-sensitive adhesive composition for a polarizing plate of the present invention is 0 to 1%, preferably 0.05 to 0.5% based on the component (B). If the blending amount is outside this range, a long period of time is required for aging, and peeling may occur at high temperature and high humidity.
상기 아지리딘계 가교제로서는 1,1'-(메틸렌-디p-페닐렌)비스-3,3-아지리딜요소, 1,1'-(헥사메틸렌)비스-3,3-아지리딜요소, 2,4,6-트리아지리디닐-1,3,5-트리아진, 트리메틸올프로판-트리스-(2-아지리디닐프로피오네이트) 등을 들 수 있다. 이들 아지리딘계 가교제를 병용함으로써, 겔 분률을 보다 높게 할 수 있다.Examples of the aziridine crosslinking agent include 1,1 '- (methylene-di p-phenylene) bis-3,3-aziridyl element, 1,1' - (hexamethylene) 4,6-triaziridinyl-1,3,5-triazine, and trimethylolpropane-tris- (2-aziridinyl propionate). By using these aziridine crosslinking agents in combination, the gel fraction can be increased.
본 발명의 편광판용 점착제 조성물에 있어서의 아지리딘계 가교제의 배합량은 성분(B)에 대하여 0~1%이며, 바람직하게는 0.05~0.5%이다. 배합량이 이 범위 밖이면, 숙성 기간이 길어지고, 또 고온, 고습열 조건에서 벗겨짐 등이 생기는 경우가 있다.The blending amount of the aziridine crosslinking agent in the pressure-sensitive adhesive composition for a polarizing plate of the present invention is 0 to 1%, preferably 0.05 to 0.5% based on the component (B). If the blending amount is out of this range, the aging period becomes long, and peeling may occur at high temperature and high humidity heat conditions.
본 발명의 편광판용 점착제 조성물에는, 또한 성분(A)의 아크릴계 폴리머 중에 포함되는 카르복실기와 반응하는 기를 함유하는 실란커플링제(D)를 배합하는 것이 바람직하다. 이것을 사용함으로써, 점착제를 유리에 대하여 강고하게 접착할 수 있고, 습열 환경하에서 벗겨짐을 방지할 수 있다. 구체적으로는, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필트리에톡시실란, 3-글리시독시프로필메틸디에톡시실란, 2-(3,4에폭시시클로헥실)에틸트리메톡시실란 등의 에폭시 함유 실란커플링제, 3-아미노프로필트리메톡시실란, N-2(아미노에틸)3-아미노프로필트리메톡시실란 등의 아미노기 함유 실란커플링제 등을 들 수 있다.The pressure-sensitive adhesive composition for a polarizing plate of the present invention is preferably blended with a silane coupling agent (D) containing a group reactive with a carboxyl group contained in the acrylic polymer of the component (A). By using this, the pressure-sensitive adhesive can be firmly adhered to the glass, and peeling can be prevented in a moist heat environment. Specific examples thereof include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Containing silane coupling agents such as 3-aminopropyltrimethoxysilane and N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, and the like.
본 발명의 편광판용 점착제 조성물에 있어서의 실란커플링제(D)의 배합량은 성분(A) 100부에 대하여 0.05~1부이며, 바람직하게는 0.1~0.5부이다. 0.05부보다 적으면 습열 환경하에 있어서 벗겨짐이 발생하기 쉬워지고, 1부보다 많으면 고온 환경하에 있어서 실란커플링제가 블리드하여, 반대로 벗겨짐이 생기기 쉬워져버리기 때문에 바람직하지 않다.The blending amount of the silane coupling agent (D) in the pressure-sensitive adhesive composition for a polarizing plate of the present invention is 0.05 to 1 part, preferably 0.1 to 0.5 part, per 100 parts of the component (A). When the amount is less than 0.05 part, peeling easily occurs under a humid environment. If it is more than 1 part, the silane coupling agent bleeds under high temperature environment, and peeling easily occurs, which is not preferable.
본 발명의 편광판용 점착제 조성물의 조제는, 상기 성분(A), (B)와 필요에 의해 성분(C), (D)이나 그 밖의 임의 성분을 배합하고, 이들을 상법에 따라 혼합함으로써 행해진다. 사용 가능한 임의 성분으로서는 산화 방지제, 자외선 흡수제, 가소제, 대전 방지제 등을 들 수 있고, 이들은 본 발명의 효과를 해치지 않는 범위에서 배합할 수 있다.The pressure-sensitive adhesive composition for a polarizing plate of the present invention is prepared by blending the components (A) and (B) with components (C) and (D) or other optional components as necessary and mixing them according to a conventional method. Examples of optional components that can be used include antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, and the like, and they can be compounded within a range that does not impair the effects of the present invention.
이렇게 하여 얻어진 편광판용 점착제 조성물로부터 본 발명의 편광판용 점착 시트를 얻기 위해서는, 지지체 상의 적어도 일방의 면에 상법에 따라 당해 점착제 조성물을 도포하고, 도공 후, 건조, 숙성하여 점착제층을 형성시킨다. 건조는 통상 80~110℃, 2~10분정도로 행해진다. 한편, 본 발명의 점착제 조성물은 종래의 것보다 대폭 숙성 기간을 단축하는 것이 가능하며, 예를 들면, 23℃, 50%RH의 조건에서 1~3일정도의 숙성에 의해 충분히 경화가 행해지고, 양호한 점착력과 광학적성을 구비한 점착제층이 얻어진다. 숙성 후의 점착제층의 겔 분률은 60~90%인 것이 바람직하고, 65~85%이이면 보다 바람직하다. 이 범위 밖이면 내구성이 떨어져 벗겨지기 쉬운 경우가 있다. 또한, 본 명세서에 있어서 겔 분률은 실시예 중에 기재한 측정 방법에 의해 구해지는 값을 의미한다. 지지체로서는 표면에 박리 처리된 폴리에스테르 필름을 사용할 수 있다. 점착제층의 두께는 통상 10~30μm, 바람직하게는 15~25μm정도이다.In order to obtain the pressure-sensitive adhesive sheet for a polarizing plate of the present invention from the pressure-sensitive adhesive composition for a polarizing plate thus obtained, the pressure-sensitive adhesive composition is applied to at least one surface of a support according to a conventional method, followed by drying and aging to form a pressure-sensitive adhesive layer. Drying is usually carried out at 80 to 110 ° C for 2 to 10 minutes. On the other hand, the pressure-sensitive adhesive composition of the present invention can significantly shorten the aging time as compared with the conventional one. For example, the pressure-sensitive adhesive composition is sufficiently cured at a temperature of 23 캜 and 50% RH under aging of 1 to 3 days, A pressure-sensitive adhesive layer having an adhesive property and an optical property can be obtained. The gel fraction of the pressure-sensitive adhesive layer after aging is preferably 60 to 90%, more preferably 65 to 85%. If it is outside this range, durability may be deteriorated and it may be easily peeled off. In the present specification, the gel fraction means a value obtained by the measuring method described in the examples. As the support, a polyester film that has been peeled off the surface may be used. The thickness of the pressure-sensitive adhesive layer is usually about 10 to 30 占 퐉, preferably about 15 to 25 占 퐉.
또, 상기 편광판용 점착제 조성물로부터 형성되는 점착제층을 편광 필름의 적어도 일방의 면에 마련함으로써, 본 발명의 편광판을 얻을 수 있다. 편광 필름 상에 마련되는 점착제층의 두께는 통상 10~30μm, 바람직하게는 15~25μm정도이다.The polarizing plate of the present invention can be obtained by providing a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition for a polarizing plate on at least one surface of the polarizing film. The thickness of the pressure-sensitive adhesive layer provided on the polarizing film is usually about 10 to 30 占 퐉, preferably about 15 to 25 占 퐉.
편광 필름 상에 점착제층을 마련함에 있어서는, 편광 필름 상에 점착제 조성물을 도공하고, 건조, 숙성시키거나, 또는 지지체에 도공하여 건조시킨 도막을 편광 필름 상에 맞붙여, 이것을 숙성시킴으로써 점착제층을 형성시킬 수 있다. 건조, 숙성의 조건이나 겔 분률의 범위 등은 상기와 마찬가지이다.When a pressure-sensitive adhesive layer is provided on a polarizing film, a pressure-sensitive adhesive composition is coated on a polarizing film, dried, aged, or coated on a support to form a pressure-sensitive adhesive layer . The conditions for drying, aging, and the range of the gel fraction are the same as described above.
또, 본 발명에 사용되는 편광 필름으로서는 다른 기능을 가지는 층이 적층 되어 있어도 되고, 구체적으로는 타원편광 필름, 위상차 필름 등도 포함된다.As the polarizing film used in the present invention, layers having different functions may be laminated, and specifically, an elliptically polarizing film and a retardation film are also included.
상기한 바와 같이 하여 얻어지는 본 발명의 편광판을 액정 셀의 기판표면에 마련함으로써 액정 소자가 제조된다. 본 발명의 편광판이 사용되는 액정 소자의 타입으로서는 특별히 한정되는 것은 아니며, TN 모드, VA 모드, IPS 모드, OCB 모드 등의 어느 것이어도 된다. 이 액정 소자에 백라이트 등의 구성 부품을 적당히 부착함으로써, 광누설을 저감한 액정 표시 장치가 제조된다.A liquid crystal device is produced by providing the polarizing plate of the present invention obtained as described above on the surface of a substrate of a liquid crystal cell. The type of liquid crystal device in which the polarizing plate of the present invention is used is not particularly limited, and TN mode, VA mode, IPS mode, and OCB mode may be used. By appropriately attaching a component such as a backlight to the liquid crystal device, a liquid crystal display device with reduced light leakage is manufactured.
본 발명의 편광판 점착제 조성물은 단기간의 숙성에 의해 우수한 광누설 방지성과 내구성을 구비하는 점착제층을 형성할 수 있는 것인데, 그 이유는 다음과 같이 생각된다.The polarizer-type pressure-sensitive adhesive composition of the present invention is capable of forming a pressure-sensitive adhesive layer having excellent light leakage prevention and durability due to short-term aging, for the following reasons.
즉, 점착제에 이소시아네이트계 화합물을 과잉량 첨가하면, 이소시아네이트계 화합물 유래의 폴리요소가 생성된다고 일컬어지고 있다. 이 폴리요소가 점착제의 주폴리머와 서로 얽혀서 물리적 결합을 발생시키고, 일반의 점착제와 마찬가지의 그물코 구조를 가지는데, 이소시아누레이트 구조를 가지는 톨릴렌디이소시아네이트계 화합물의 경우에도 마찬가지의 서로 얽힘에 의한 그물코 구조를 가진다고 생각된다. 이소시아누레이트 구조를 가지는 톨릴렌디이소시아네이트계 화합물 유래의 폴리요소에 의해 고탄성이 되고, 아울러 복굴절도 제어할 수 있기 때문에, 광누설 방지성이 양호하게 되고, 또한, 이소시아누레이트 구조를 가지는 톨릴렌디이소시아네이트계 화합물은 다른 이소시아네이트계 화합물과 비교하여 반응성이 높고, 가교 반응이나 폴리요소의 생성 반응이 빠른 점에서, 숙성 기간을 대폭 단축할 수 있는 것이라고 생각된다.That is, it is said that when an isocyanate compound is added to an adhesive in an excessive amount, a polyurethane originating from an isocyanate compound is produced. This polyolefin is intertwined with the main polymer of the pressure-sensitive adhesive to cause physical bonding and has a mesh structure similar to that of a general pressure-sensitive adhesive. In the case of a tolylene diisocyanate compound having an isocyanurate structure, It is thought to have a mesh structure. The polyolefins derived from a tolylene diisocyanate compound having an isocyanurate structure are highly elastic and can control the birefringence, so that the light leakage preventing property is improved, and the tolylene diisocyanate compound having an isocyanurate structure It is considered that the radical-isocyanate-based compound has a higher reactivity than other isocyanate-based compounds, and is quick in the cross-linking reaction and poly-urea formation reaction, thereby greatly shortening the aging period.
(실시예)(Example)
다음에 실시예를 들어 본 발명을 더욱 상세하게 설명하는데, 본 발명은 이들 실시예에 전혀 제약되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples at all.
(제조예 1)(Production Example 1)
아크릴계 폴리머의 제조 :Preparation of acrylic polymer:
교반기, 질소 가스 도입관, 온도계 및 환류 냉각관을 구비한 플라스크에, 부틸아크릴레이트 97질량부, 아크릴산 3질량부, 아세트산에틸 100질량부, 노르말도데실메르캅탄(NDM) 0.04질량부를 넣고 플라스크 내에 질소 가스를 도입하면서 플라스크의 내용물을 60℃로 가열했다. 다음에 충분히 질소 가스 치환한 중합 개시제 아조비스이소부티로니트릴(AIBN) 0.1질량부를 교반하에 플라스크 내에 첨가했다. 플라스크 내의 내용물의 온도를 60℃로 유지할 수 있도록, 가열 및 냉각을 10시간 행하고 마지막으로 아세트산에틸 100부를 첨가하여 아크릴계 폴리머 A1 용액을 얻었다. 이 아크릴계 폴리머 A1에 대해서, 중량 평균 분자량(Mw), 수 평균 분자량(Mn)을 하기 GPC 측정 조건에 따라 측정하고, 분산도(Mw/Mn)를 구했다. 또, 불휘발 분(nV) 및 점도에 대해서도 하기 방법에 의해 측정했다. 측정 결과를 모노머 조성과 아울러 표 1에 나타낸다.97 parts by mass of butyl acrylate, 3 parts by mass of acrylic acid, 100 parts by mass of ethyl acetate and 0.04 parts by mass of n-dodecyl mercaptan (NDM) were placed in a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer and a reflux condenser, The contents of the flask were heated to 60 DEG C while introducing nitrogen gas. Then, 0.1 part by mass of a polymerization initiator azobisisobutyronitrile (AIBN) sufficiently purged with nitrogen gas was added to the flask under stirring. Heating and cooling were performed for 10 hours so that the temperature of the contents in the flask could be maintained at 60 DEG C, and finally 100 parts of ethyl acetate was added to obtain an acrylic polymer A1 solution. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of this acrylic polymer A1 were measured according to the following GPC measurement conditions and the degree of dispersion (Mw / Mn) was determined. The nonvolatile fraction (nV) and viscosity were also measured by the following methods. The measurement results are shown in Table 1 together with the monomer composition.
<GPC 측정 조건>≪ GPC measurement condition >
측정 장치 : HLC-8120GPC(토소사제)Measurement apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
GPC 칼럼 구성 : 이하의 5연속 칼럼(모두 토소사제)GPC Column Composition: The following five continuous columns (all Tosoh Corporation)
(1) TSK-GEL HXL-H(가드 칼럼)(1) TSK-GEL HXL-H (Guard column)
(2) TSK-GEL G7000HXL(2) TSK-GEL G7000HXL
(3) TSK-GEL GMHXL(3) TSK-GEL GMHXL
(4) TSK-GEL GMHXL(4) TSK-GEL GMHXL
(5) TSK-GEL G2500HXL(5) TSK-GEL G2500HXL
샘플 농도 : 1.0mg/cm3가 되도록, 테트라히드로푸란으로 희석Sample concentration: 1.0 mg / cm < 3 >, diluted with tetrahydrofuran
이동상 용매 : 테트라히드로푸란Mobile phase solvent: tetrahydrofuran
유량 : 1ml/minFlow rate: 1 ml / min
칼럼 온도 : 40℃Column temperature: 40 DEG C
<불휘발분의 측정 방법><Method of measuring non-volatile matter>
정밀하게 칭량한 함석 샤알레(n1)에 아크릴계 공중합체 용액을 1g정도 넣고, 합계 중량(n2)을 정밀하게 칭량한 후, 105℃에서 3시간 가열했다. 그 후, 이 함석 샤알레를 실온의 데시케이터 내에 1시간 정치하고, 이어서 다시 정밀하게 칭량하여 가열 후의 합계 중량(n3)을 측정했다. 얻어진 중량 측정값(n1~n3)을 사용하여 하기식으로부터 불휘발분을 산출했다.Approximately 1 g of the acrylic copolymer solution was placed in a precisely weighed quartz crystal (n1), and the total weight (n2) was precisely weighed and then heated at 105 DEG C for 3 hours. Thereafter, the quartz crystal was allowed to stand in a desiccator at room temperature for one hour, and then precisely weighed again to measure the total weight (n3) after heating. Using the obtained weight measurement values (n1 to n3), the non-volatile content was calculated from the following formula.
불휘발분(%)=100×[가열후 중량(n3-n1)/가열전 중량(n2-n1)]Nonvolatile matter (%) = 100 x [weight after heating (n3-n1) / weight before heating (n2-n1)]
<점도의 측정 방법><Method of measuring viscosity>
B형 점도계를 사용하여, 실온에서 측정했다.B type viscometer at room temperature.
(제조예 2~6)(Production Examples 2 to 6)
표 1에 나타내는 모노머 조성으로 바꾼 것 이외에는 제조예 1과 마찬가지로 하여 아크릴계 폴리머 A2~A6 용액을 얻었다. 이 폴리머의 Mw, Mn, 불휘발분, 점도를 제조예 1과 마찬가지로 하여 측정했다. 결과를 표 1에 나타낸다.Acrylic polymers A2 to A6 were obtained in the same manner as in Preparation Example 1 except that the monomer compositions shown in Table 1 were used. The Mw, Mn, non-volatile content and viscosity of the polymer were measured in the same manner as in Production Example 1. The results are shown in Table 1.
(비교 제조예 1~4)(Comparative Production Examples 1 to 4)
표 1에 나타내는 모노머 조성으로 바꾼 것 이외에는 제조예 1과 마찬가지로 하여 아크릴계 폴리머 B1~B4 용액을 얻었다. 이 폴리머의 Mw, Mn, 불휘발분, 점도를 제조예 1과 마찬가지로 하여 측정했다. 결과를 표 1에 나타낸다.Acrylic polymers B1 to B4 were obtained in the same manner as in Preparation Example 1 except that the monomer compositions shown in Table 1 were used. The Mw, Mn, non-volatile content and viscosity of the polymer were measured in the same manner as in Production Example 1. The results are shown in Table 1.
표 중의 약호는 다음과 같다.The abbreviations in the table are as follows.
BA : 부틸아크릴레이트BA: butyl acrylate
AA : 아크릴산AA: Acrylic acid
HEA : 2-히드록시에틸아크릴레이트HEA: 2-hydroxyethyl acrylate
BzA : 벤질아크릴레이트BzA: benzyl acrylate
POA : 페녹시에틸아크릴레이트POA: phenoxyethyl acrylate
MEA : 아크릴산메톡시에틸MEA: methoxyethyl acrylate
(실시예 1)(Example 1)
점착제층을 가지는 편광판의 제작 :Preparation of a polarizing plate having a pressure-sensitive adhesive layer:
(점착제 조성물의 조제)(Preparation of pressure-sensitive adhesive composition)
제조예 1에 의해 얻어진 아크릴계 폴리머 A1 용액의 아크릴계 폴리머 A1(고형분) 100질량부에 대하여, 톨릴렌디이소시아네이트(TDI)계의 이소시아누레이트 변성체인 코로네이트 342(니혼폴리우레탄사제) 5질량부, 실란커플링제로서 KBM-403(신에츠카가쿠코교 가부시키가이샤제) 0.2질량부를 첨가하고, 이들을 충분히 혼합하여 점착제 조성물을 얻었다.5 parts by mass of Coronate 342 (manufactured by Nippon Polyurethane Industry Co., Ltd.), which is an isocyanurate modification of tolylene diisocyanate (TDI), was added to 100 parts by mass of the acrylic polymer A1 (solid content) of the acrylic polymer A1 solution obtained in Production Example 1, And 0.2 parts by mass of KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent were added and thoroughly mixed to obtain a pressure-sensitive adhesive composition.
(편광판의 제작)(Production of polarizing plate)
기포가 빠진 후, 닥터 블레이드를 사용하여 박리 처리된 폴리에스테르 필름에 도공하고, 바로 90℃에서 3분간 건조했다. 건조 후, 편광판에 맞붙여, 실온 23℃, 습도 50%의 조건으로 정치하여 숙성시켜 점착제층을 가지는 편광판을 얻었다. 숙성 기간은 1일, 3일, 7일로 했다.After the bubbles had disappeared, the coated film was applied to a peeled polyester film using a doctor blade, and dried at 90 ° C for 3 minutes. Dried, adhered to a polarizing plate, allowed to stand at a room temperature of 23 캜 and a humidity of 50%, and aged to obtain a polarizing plate having a pressure-sensitive adhesive layer. The aging period was 1 day, 3 days, and 7 days.
(실시예 2~12)(Examples 2 to 12)
아크릴계 폴리머 및 가교제를 하기 표 2와 같이 바꾼 것 이외에는 실시예 1과 마찬가지로 하여 점착제 조성물을 얻었다. 또, 얻어진 점착제 조성물을 사용하고, 실시예 1과 마찬가지로 하여 점착제층을 가지는 편광판을 제작했다.A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that the acrylic polymer and the crosslinking agent were changed as shown in Table 2 below. Using the obtained pressure-sensitive adhesive composition, a polarizing plate having a pressure-sensitive adhesive layer was produced in the same manner as in Example 1.
(비교예 1~11)(Comparative Examples 1 to 11)
아크릴계 폴리머 및 가교제를 하기 표 3과 같이 바꾼 것 이외에는 실시예 1과 마찬가지로 하여 점착제 조성물을 얻었다. 또, 얻어진 점착제 조성물을 사용하고, 실시예 1과 마찬가지로 하여 점착제층을 가지는 편광판을 제작했다.A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that the acrylic polymer and the crosslinking agent were changed as shown in Table 3 below. Using the obtained pressure-sensitive adhesive composition, a polarizing plate having a pressure-sensitive adhesive layer was produced in the same manner as in Example 1.
(시험예 1)(Test Example 1)
실시예 1~12 및 비교예 1~11에서 얻은 편광판 중, 숙성 기간이 1일과 7일인 것에 대해, 내구성, 광누설 방지성을 이하의 방법에 의해 평가했다. 이들의 결과를 표 2 및 3에 정리하여 나타낸다.Among the polarizers obtained in Examples 1 to 12 and Comparative Examples 1 to 11, the durability and the light leakage preventing property were evaluated by the following methods, with the aging period being one day and seven days. The results are summarized in Tables 2 and 3.
<내구성의 평가 방법><Evaluation method of durability>
점착제층을 가지는 편광판을 150mm×250mm의 크기로 재단하고, 유리판의 편면에 라미네이터 롤을 사용하여 첩착하고, 이어서 50℃, 5기압으로 조정된 오토클레이브에 20분간 유지하여, 시험판을 작성했다. 마찬가지의 시험판을 2장 작성하고, 온도 60℃, 습도 95%RH의 조건하(내습열성) 및 온도 85℃의 조건하(내열성)에서 500시간 방치하고, 이하의 기준으로 벗겨짐의 발생 등을 육안으로 관찰하여 평가했다.A polarizing plate having a pressure-sensitive adhesive layer was cut to a size of 150 mm x 250 mm, and the glass plate was attached to one side of the glass plate using a laminator roll and then maintained in an autoclave adjusted at 50 캜 and 5 atm for 20 minutes to prepare a test plate. Two sheets of the same test plates were prepared and left for 500 hours under the conditions of a temperature of 60 ° C and a humidity of 95% RH (humid heat resistance) and a temperature of 85 ° C (heat resistance), and the occurrence of peeling .
(기준)(standard)
○ : 발포, 벗겨짐, 균열은 보이지 않음○: No foaming, peeling, or cracks observed
△ : 발포, 벗겨짐, 균열이 다소 보임△: Foaming, peeling, and cracks are somewhat visible
× : 발포, 벗겨짐, 균열이 전면에 보임X: Foam, peeling, and crack appear on the front side
<광누설 방지성의 평가 방법>≪ Evaluation method of light leakage prevention property &
점착제층을 가지는 편광판 2장을 19인치 와이드 TN 모니터(형번:BenQ FP93VW)의 표리면에 서로 직교 니콜위가 되도록 라미네이터 롤을 사용하여 첩착하고, 이어서 50℃, 5기압으로 조정된 오토클레이브에 20분간 유지하여, 시험판을 작성했다. 작성한 시험판을 70℃의 조건하에서 500시간 방치하고, 광누설을 육안으로 관찰하고, 이하의 기준으로 평가했다.Two polarizer plates each having a pressure-sensitive adhesive layer were laminated on the front and back surfaces of a 19-inch wide TN monitor (model number: BenQ FP93VW) by using a laminator roll so as to be perpendicular to each other, and then placed in an autoclave Minute, and a trial version was prepared. The prepared test plate was allowed to stand under the condition of 70 캜 for 500 hours, and light leakage was visually observed and evaluated according to the following criteria.
(기준)(standard)
○ : 광누설이 보이지 않음○: No light leakage observed
△ : 광누설이 일부 보임△: Light leakage partially observed
× : 광누설이 전면에 보임X: Light leakage is seen on the front side
표 중의 약호는 이하와 같다.The abbreviations in the table are as follows.
L-45 : TDI계 이소시아네이트(소켄카가쿠사제)L-45: TDI-based isocyanate (manufactured by Soekenkagaku Co., Ltd.)
코로네이트 342 : TDI계 이소시아누레이트 변성체(니혼폴리우레탄사제)Coronate 342: TDI isocyanurate-modified product (manufactured by Nippon Polyurethane Industry Co., Ltd.)
코로네이트 2030 : TDI계 이소시아누레이트(니혼폴리우레탄사제)Coronate 2030: TDI isocyanurate (manufactured by Nippon Polyurethane Industry Co., Ltd.)
코로네이트 2041 : 폴리머릭 MDI(니혼폴리우레탄사제)Coronate 2041: Polymeric MDI (manufactured by Nippon Polyurethane Industry Co., Ltd.)
TD-75 : XDI계(소켄카가쿠사제)TD-75: XDI system (manufactured by Soweki Kagaku Co., Ltd.)
E-5XM : 에폭시계 가교제(소켄카가쿠사제)E-5XM: epoxy cross-linking agent (manufactured by Soekenkagaku Co., Ltd.)
듀라네이트 TPA-100 : HDI계 이소시아누레이트(아사히카세이사제)Dyuranate TPA-100: HDI isocyanurate (manufactured by Asahi Chemical Industry Co., Ltd.)
KBM-403 : 실란커플링제(신에츠카가쿠코교사제)KBM-403: Silane coupling agent (Shin-Etsu Chemical Co., Ltd.)
(시험예 2)(Test Example 2)
실시예 1~12 및 비교예 1~11에서 얻어진 숙성 1, 3, 7일의 점착제층을 가지는 편광판에 대해서, 이하의 방법에 의해 점착력을 평가했다. 또 실시예 1~12 및 비교예 1~11에서 얻어진 점착제 조성물에 의해 형성되는 점착제층에 대해서, 이하의 방법에 의해 숙성 1, 3, 7일에 있어서의 겔 분률을 평가했다. 이들의 결과를 표 4에 나타낸다.The polarizing plates having the pressure-sensitive adhesive layers of aged 1, 3 and 7 days obtained in Examples 1 to 12 and Comparative Examples 1 to 11 were evaluated for adhesion by the following method. The pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 11 was evaluated for gel fraction on aging 1, 3 and 7 by the following method. The results are shown in Table 4.
<점착력의 측정 방법>≪ Measurement method of adhesive force >
점착제층을 가지는 편광판을 70mm×25mm의 크기로 재단하여 시험편을 작성했다. 시험편으로부터 폴리에스테르 필름을 박리하고, 유리판의 편면에 라미네이터 롤을 사용하여 첩착한 후, 50℃, 5기압으로 조정된 오토클레이브 중에 20분간 유지했다. 다음에 23℃, 50%RH 환경하에 1시간 방치한 후, 90°방향으로 300mm/min의 속도로 잡아당겨, 박리 강도를 측정했다.A polarizing plate having a pressure-sensitive adhesive layer was cut into a size of 70 mm x 25 mm to prepare a test piece. The polyester film was peeled off from the test piece and attached to one side of the glass plate using a laminator roll, and then held in an autoclave adjusted to 5 atmospheric pressure at 50 캜 for 20 minutes. Next, the substrate was left for one hour under an environment of 23 ° C and 50% RH, and pulled at a speed of 300 mm / min in a 90 ° direction to measure the peel strength.
<겔 분률의 측정 방법><Method of measuring gel fraction>
얻어진 점착제 조성물을 건조 후의 두께가 20μm가 되도록 박리 처리한 폴리에스테르의 표면에 도포하고, 건조시킨 후, 다른 일방의 면에 박리 처리한 폴리에스테르 필름을 맞붙여, 23℃, 50%RH에서 1, 3, 7일간 숙성시켜, 시험편을 제작했다. 시험편으로부터 점착제 약0.1g을 샘플 병에 채취하고, 아세트산에틸 30cc를 가하여 24시간 진탕한 후, 이 샘플 병의 내용물을 200메시의 스테인레스제 금망으로 여별하고, 금망 상의 잔류물을 100℃에서 2시간 건조시켜, 건조 중량을 측정하고, 다음식으로부터 구했다.The obtained pressure-sensitive adhesive composition was coated on the surface of the polyester subjected to the peeling treatment so as to have a thickness of 20 탆 after drying, and then the polyester film peeled off on the other surface was stuck together and dried at 23 캜 and 50% Aged for 3 or 7 days to prepare a test piece. Approximately 0.1 g of a pressure sensitive adhesive was taken from the test piece into a sample bottle, and 30 cc of ethyl acetate was added and shaken for 24 hours. The content of the sample bottle was filtered with a 200 mesh stainless steel net, Dried, and the dry weight was measured.
겔 분률(%)=(건조 중량/채취한 점착제 중량)×100Gel fraction (%) = (dry weight / weight of the pressure-sensitive adhesive) x 100
비교예 1~11의 편광판은 상온 숙성 1일에서는 광누설 방지성 및 내구성이 충분한 것이 얻어지지 않은 것에 대해, 실시예 1~12에서는 숙성 1일에서 광누설 방지성 및 내구성이 양호한 것이 되고, 또 점착력 및 겔 분률도 숙성 1일에서 안정되고, 이들 성능이 안정적으로 유지되는 것이 나타났다.In the polarizing plates of Comparative Examples 1 to 11, light leakage preventing properties and durability were not sufficient at one day of maturing at room temperature, whereas light leakage preventing properties and durability of the polarizing plates of Examples 1 to 12 were good at 1 day of maturing, Adhesion and gel fraction were also stable at 1 day of aging, and these performances remained stable.
본 발명의 점착제 조성물은 단기간의 숙성에 의해 광누설을 유효하게 방지함과 아울러, 우수한 내구성을 가지고, 고온 고습 조건에 있어서도 발포나 벗겨짐 등의 발생을 억제할 수 있는 점착제층을 형성할 수 있다. 따라서, 이것은 편광판용의 점착제 조성물로서 적합하게 이용 가능하다.The pressure-sensitive adhesive composition of the present invention can effectively prevent light leakage by aging in a short period of time, and can form a pressure-sensitive adhesive layer having excellent durability and capable of suppressing the occurrence of foaming and peeling even under high temperature and high humidity conditions. Therefore, it can be suitably used as a pressure-sensitive adhesive composition for a polarizing plate.
Claims (8)
(A) 적어도 카르복실기 함유 모노머 1~8질량% 및 수산기 함유 (메타)아크릴계 모노머 0.05~1질량%를 공중합하여 이루어지는 중량 평균 분자량이 30만~150만인 (메타)아크릴계 폴리머 100질량부
(B) 이소시아누레이트 구조를 가지는 톨릴렌디이소시아네이트계 화합물 6~20질량부
를 함유하고, 이하의 측정 방법에 의해 구해지는 겔 분률이 75~90%인 편광판용 점착제 조성물.
<겔 분률의 측정 방법>
편광판용 점착제 조성물을 건조 후의 두께가 20μm가 되도록 박리 처리한 폴리에스테르의 표면에 도포하고, 건조시킨 후, 다른 일방의 면에 박리 처리한 폴리에스테르 필름을 맞붙여, 23℃, 50%RH에서 1일간 숙성시켜, 시험편을 제작했다. 시험편으로부터 점착제 약0.1g을 샘플 병에 채취하고, 아세트산에틸 30cc를 가하여 24시간 진탕한 후, 이 샘플 병의 내용물을 200메시의 스테인레스제 금망으로 여별하고, 금망 상의 잔류물을 100℃에서 2시간 건조시켜, 건조 중량을 측정하고, 다음식으로부터 구했다.
겔 분률(%)=(건조 중량/채취한 점착제 중량)×100The following components (A) and (B)
(A) 100 parts by mass of a (meth) acrylic polymer having a weight average molecular weight of 300,000 to 1,500,000 copolymerized with at least 1% by mass of a carboxyl group-containing monomer and 0.05-1% by mass of a hydroxyl group-
(B) a tolylene diisocyanate compound having an isocyanurate structure in an amount of 6 to 20 parts by weight
And a gel fraction of 75 to 90% as determined by the following measuring method.
<Method of measuring gel fraction>
The pressure-sensitive adhesive composition for a polarizing plate was coated on the surface of the polyester which had been peeled to a thickness of 20 mu m after drying, and then the polyester film peeled off from the other surface was stuck to the surface of the polyester and dried at 23 DEG C and 50% The test pieces were aged for a day. Approximately 0.1 g of a pressure sensitive adhesive was taken from the test piece into a sample bottle, and 30 cc of ethyl acetate was added and shaken for 24 hours. The content of the sample bottle was filtered with a 200 mesh stainless steel net, Dried, and the dry weight was measured.
Gel fraction (%) = (dry weight / weight of the pressure-sensitive adhesive) x 100
(A) 적어도 카르복실기 함유 모노머 1~8질량% 및 수산기 함유 (메타)아크릴계 모노머 0.05~1질량%를 공중합하여 이루어지는 중량 평균 분자량이 30만~150만인 (메타)아크릴계 폴리머 100질량부
(B) 이소시아누레이트 구조를 가지는 톨릴렌디이소시아네이트계 화합물 6~20질량부
를 함유하는 점착제 조성물로 형성되는 이하의 측정 방법에 의해 구해지는 겔 분률이 75~90%인 점착제층을 편광 필름의 적어도 일방의 면에 마련한 편광판을 액정 셀의 기판 표면에 마련하는 것을 특징으로 하는 액정 소자의 제조 방법.
<겔 분률의 측정 방법>
편광판용 점착제 조성물을 건조 후의 두께가 20μm가 되도록 박리 처리한 폴리에스테르의 표면에 도포하고, 건조시킨 후, 다른 일방의 면에 박리 처리한 폴리에스테르 필름을 맞붙여, 23℃, 50%RH에서 1일간 숙성시켜, 시험편을 제작했다. 시험편으로부터 점착제 약0.1g을 샘플 병에 채취하고, 아세트산에틸 30cc를 가하여 24시간 진탕한 후, 이 샘플 병의 내용물을 200메시의 스테인레스제 금망으로 여별하고, 금망 상의 잔류물을 100℃에서 2시간 건조시켜, 건조 중량을 측정하고, 다음식으로부터 구했다.
겔 분률(%)=(건조 중량/채취한 점착제 중량)×100The following components (A) and (B)
(A) 100 parts by mass of a (meth) acrylic polymer having a weight average molecular weight of 300,000 to 1,500,000 copolymerized with at least 1% by mass of a carboxyl group-containing monomer and 0.05-1% by mass of a hydroxyl group-
(B) a tolylene diisocyanate compound having an isocyanurate structure in an amount of 6 to 20 parts by weight
And a polarizing plate provided on at least one surface of the polarizing film with a pressure-sensitive adhesive layer having a gel fraction of 75 to 90% determined by the following measuring method is formed on the substrate surface of the liquid crystal cell A method of manufacturing a liquid crystal device.
<Method of measuring gel fraction>
The pressure-sensitive adhesive composition for a polarizing plate was coated on the surface of the polyester which had been peeled to a thickness of 20 mu m after drying, and then the polyester film peeled off from the other surface was stuck to the surface of the polyester and dried at 23 DEG C and 50% The test pieces were aged for a day. Approximately 0.1 g of a pressure sensitive adhesive was taken from the test piece into a sample bottle, and 30 cc of ethyl acetate was added and shaken for 24 hours. The content of the sample bottle was filtered with a 200 mesh stainless steel net, Dried, and the dry weight was measured.
Gel fraction (%) = (dry weight / weight of the pressure-sensitive adhesive) x 100
(A) 적어도 카르복실기 함유 모노머 1~8질량% 및 수산기 함유 (메타)아크릴계 모노머 0.05~1질량%를 공중합하여 이루어지는 중량 평균 분자량이 30만~150만인 (메타)아크릴계 폴리머 100질량부
(B) 이소시아누레이트 구조를 가지는 톨릴렌디이소시아네이트계 화합물 6~20질량부
를 함유하는 점착제 조성물로 형성되는 이하의 측정 방법에 의해 구해지는 겔 분률이 75~90%인 점착제층을 편광 필름의 적어도 일방의 면에 마련한 편광판을 액정 셀의 기판 표면에 마련하는 것을 특징으로 하는 액정 표시 장치의 광누설 저감 방법.
<겔 분률의 측정 방법>
편광판용 점착제 조성물을 건조 후의 두께가 20μm가 되도록 박리 처리한 폴리에스테르의 표면에 도포하고, 건조시킨 후, 다른 일방의 면에 박리 처리한 폴리에스테르 필름을 맞붙여, 23℃, 50%RH에서 1일간 숙성시켜, 시험편을 제작했다. 시험편으로부터 점착제 약0.1g을 샘플 병에 채취하고, 아세트산에틸 30cc를 가하여 24시간 진탕한 후, 이 샘플 병의 내용물을 200메시의 스테인레스제 금망으로 여별하고, 금망 상의 잔류물을 100℃에서 2시간 건조시켜, 건조 중량을 측정하고, 다음식으로부터 구했다.
겔 분률(%)=(건조 중량/채취한 점착제 중량)×100The following components (A) and (B)
(A) 100 parts by mass of a (meth) acrylic polymer having a weight average molecular weight of 300,000 to 1,500,000 copolymerized with at least 1% by mass of a carboxyl group-containing monomer and 0.05-1% by mass of a hydroxyl group-
(B) a tolylene diisocyanate compound having an isocyanurate structure in an amount of 6 to 20 parts by weight
And a polarizing plate provided on at least one surface of the polarizing film with a pressure-sensitive adhesive layer having a gel fraction of 75 to 90% determined by the following measuring method is formed on the substrate surface of the liquid crystal cell (Method for Reducing Light Leakage in a Liquid Crystal Display).
<Method of measuring gel fraction>
The pressure-sensitive adhesive composition for a polarizing plate was coated on the surface of the polyester which had been peeled to a thickness of 20 mu m after drying, and then the polyester film peeled off from the other surface was stuck to the surface of the polyester and dried at 23 DEG C and 50% The test pieces were aged for a day. Approximately 0.1 g of a pressure sensitive adhesive was taken from the test piece into a sample bottle, and 30 cc of ethyl acetate was added and shaken for 24 hours. The content of the sample bottle was filtered with a 200 mesh stainless steel net, Dried, and the dry weight was measured.
Gel fraction (%) = (dry weight / weight of the pressure-sensitive adhesive) x 100
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| JP2009261506 | 2009-11-17 | ||
| JPJP-P-2009-261506 | 2009-11-17 |
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| JP (1) | JP5764496B2 (en) |
| KR (1) | KR101587804B1 (en) |
| CN (1) | CN102686689B (en) |
| TW (1) | TWI486417B (en) |
| WO (1) | WO2011062127A1 (en) |
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| JP5777416B2 (en) * | 2011-06-13 | 2015-09-09 | 日本カーバイド工業株式会社 | Adhesive composition, optical film using the same, and liquid crystal display device |
| JP5949013B2 (en) * | 2012-03-21 | 2016-07-06 | 住友化学株式会社 | Adhesive sheet, optical film with adhesive, and optical laminate |
| JP5949014B2 (en) * | 2012-03-21 | 2016-07-06 | 住友化学株式会社 | Adhesive sheet, optical film with adhesive, and optical laminate |
| JP6024382B2 (en) * | 2012-10-23 | 2016-11-16 | 大日本印刷株式会社 | Adhesive composition, adhesive sheet and image display device |
| JP6013898B2 (en) * | 2012-12-17 | 2016-10-25 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| CN107148587B (en) * | 2014-11-04 | 2020-07-07 | 综研化学株式会社 | Adhesive composition for polarizing plate and polarizing plate with adhesive layer |
| JP6390661B2 (en) * | 2016-04-19 | 2018-09-19 | 東洋インキＳｃホールディングス株式会社 | Adhesive and adhesive sheet |
| JP6160743B2 (en) * | 2016-06-08 | 2017-07-12 | 住友化学株式会社 | Adhesive sheet, optical film with adhesive, and optical laminate |
| JP6197919B2 (en) * | 2016-06-08 | 2017-09-20 | 住友化学株式会社 | Adhesive sheet, optical film with adhesive, and optical laminate |
| KR102294142B1 (en) * | 2018-06-22 | 2021-08-26 | 산진 옵토일렉트로닉스 (쑤저우) 컴퍼니 리미티드 | Quantitative method for polarizer adhesive leakage |
| CN111548761B (en) * | 2019-02-08 | 2023-08-18 | 日本电石工业株式会社 | Adhesive composition for polarizing plate, polarizing plate with adhesive layer, and in-vehicle display device |
| CN113755101A (en) * | 2021-09-07 | 2021-12-07 | 常州都铂高分子有限公司 | Glue composition with good re-peeling property |
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| JPH04136524A (en) | 1990-09-27 | 1992-05-11 | Nissan Motor Co Ltd | Wet type frictional engagement plate |
| JP3830375B2 (en) * | 2001-11-07 | 2006-10-04 | リンテック株式会社 | Adhesive sheet primer, adhesive sheet affixed product and method for producing the same |
| JP2003154797A (en) * | 2001-11-26 | 2003-05-27 | Toppan Printing Co Ltd | Transfer sheet |
| JP4134350B2 (en) * | 2002-08-29 | 2008-08-20 | 綜研化学株式会社 | Optical member pressure-sensitive adhesive and optical member using the pressure-sensitive adhesive |
| JP4623485B2 (en) | 2004-03-02 | 2011-02-02 | サイデン化学株式会社 | Adhesive composition and surface protective film |
| JP2007119667A (en) * | 2005-10-31 | 2007-05-17 | Sumitomo Chemical Co Ltd | Adhesive |
| JP4976075B2 (en) * | 2005-12-26 | 2012-07-18 | リンテック株式会社 | Adhesive for polarizing plate, polarizing plate with adhesive and method for producing the same |
| JP2008144126A (en) | 2006-11-17 | 2008-06-26 | Fujifilm Corp | Acrylate-based pressure-sensitive adhesive, and polarizing plate and liquid crystal display device obtained using the same |
| JP5717940B2 (en) | 2006-12-25 | 2015-05-13 | 日東電工株式会社 | Method for accelerating curing of mixture and method for accelerating curing of pressure-sensitive adhesive composition |
| JP2009132751A (en) * | 2007-11-28 | 2009-06-18 | Cheil Industries Inc | Adhesive composition and optical member |
| JP2009132752A (en) * | 2007-11-28 | 2009-06-18 | Cheil Industries Inc | Adhesive composition and optical member |
| JP4963485B2 (en) * | 2008-04-07 | 2012-06-27 | 綜研化学株式会社 | Adhesive composition for polarizing plate and method for producing the same |
| JP5304339B2 (en) * | 2009-03-11 | 2013-10-02 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition and adhesive laminate comprising the same |
| JP5526645B2 (en) * | 2009-08-07 | 2014-06-18 | 東洋インキＳｃホールディングス株式会社 | Optical pressure-sensitive adhesive and optical pressure-sensitive adhesive sheet using the optical pressure-sensitive adhesive |
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2010
- 2010-11-12 TW TW099139043A patent/TWI486417B/en not_active IP Right Cessation
- 2010-11-15 KR KR1020127003032A patent/KR101587804B1/en active IP Right Grant
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| JP5764496B2 (en) | 2015-08-19 |
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| TW201132723A (en) | 2011-10-01 |
| KR20120115203A (en) | 2012-10-17 |
| TWI486417B (en) | 2015-06-01 |
| CN102686689B (en) | 2015-12-16 |
| WO2011062127A1 (en) | 2011-05-26 |
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