WO2015020322A1 - Adhesive composition and composite polarizing plate using same - Google Patents

Adhesive composition and composite polarizing plate using same Download PDF

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Publication number
WO2015020322A1
WO2015020322A1 PCT/KR2014/006577 KR2014006577W WO2015020322A1 WO 2015020322 A1 WO2015020322 A1 WO 2015020322A1 KR 2014006577 W KR2014006577 W KR 2014006577W WO 2015020322 A1 WO2015020322 A1 WO 2015020322A1
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Prior art keywords
meth
acrylate
diisocyanate
polarizing plate
adhesive composition
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PCT/KR2014/006577
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French (fr)
Korean (ko)
Inventor
최한영
문제욱
이도규
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동우화인켐 주식회사
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Publication of WO2015020322A1 publication Critical patent/WO2015020322A1/en

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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
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
    • 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
    • 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • 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

Definitions

  • the patterned retardation film is usually bonded to one side of the polarizing plate through an adhesive or a pressure-sensitive adhesive, and in recent years also bonded to one side of the polyvinyl alcohol polarizer for thinner film weight.
  • Korean Unexamined Patent Publication No. 2013-0028881 discloses a method for producing a film patterned retarder, and a film patterned retarder, and a polarizing plate and an image display device having the same.
  • Patent Document 1 Korean Patent Publication No. 2013-0028881
  • the isocyanate crosslinking agent is an isocyanurate body self-condensed at least one of 3 moles of xylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate, and the isocyanate crosslinking agent is xylene diisocyanate
  • the adhesive composition which is at least 1 sort (s) chosen from the group which consists of an adduct of 3 mol of at least 1 sort (s) of hexamethylene diisocyanate and isophorone diisocyanate, and a trimethylol propane body.
  • crosslinkable functional group is a hydroxyl group, carboxyl group, amide group or tertiary amine group
  • pressure-sensitive adhesive composition is a hydroxyl group, carboxyl group, amide group or tertiary amine group
  • the patterned retardation layer comprises a liquid crystal coating layer containing a reactive liquid crystal monomer including an ester bond.
  • the peel force between the polarizer and the patterned retardation layer is 3 N / 25mm or more, composite polarizing plate.
  • the patterned retardation layer does not include an alignment film, a composite polarizing plate.
  • Image display device including the composite polarizer of the above seven.
  • the composite polarizing plate bonded with the pressure-sensitive adhesive composition of the present invention is excellent in heat resistance and heat-and-moisture resistance, and even when exposed to high temperature and high humidity conditions for a long time, peeling and rolling phenomenon are suppressed.
  • the acrylic copolymer according to the present invention is polymerized to include a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and a monomer having a crosslinkable functional group.
  • (meth) acrylate refers to acrylate, methacrylate or both at the same time.
  • (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate.
  • the production method of the copolymer is not particularly limited, and may be prepared using a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, which are commonly used in the art, and solution polymerization is preferable.
  • a solvent, a polymerization initiator, a chain transfer agent for molecular weight control, and the like, which are usually used in the polymerization may be used.
  • the isocyanate is included in an excessive amount as in the above content range, in which case the unreacted isocyanate group is contacted with moisture to be converted into an amino group (-NH 2 ).
  • the amino group forms a hydrogen bond with the polar group included in the polarizer surface polar group and the liquid crystal coating layer of the patterned retardation layer, and includes a reactive liquid crystal monomer contained on the liquid crystal coating layer.
  • the bonding strength of the polarizer and the patterned retardation layer is significantly improved by the hydrogen bond and the covalent bond.
  • the present invention provides a composite polarizing plate prepared using the pressure-sensitive adhesive composition.
  • the composite polarizing plate of the present invention can be used at a position where a conventional polarizing plate and a patterned retardation layer are stacked.
  • a crosslinking agent was added as shown in Table 2 to prepare a pressure-sensitive adhesive composition.
  • L C Center luminance of left eye image
  • L e Average luminance of peripheral part of left eye image

Abstract

The present invention relates to an adhesive composition and a composite polarizing plate using same, more specifically to an adhesive composition and a composite polarizing plate using same in which the adhesive composition comprises: a polymerized copolymer containing (meth)acrylate monomers having an alkyl group with 1-12 carbons, and monomers having a cross-linkable functional group; and 200-2000 wt% isocynate cross-linking agent with respect to 100 wt% cross-linkable monomers, thereby markedly improving the adhesiveness between a polarizer and a patterned retardation layer when utilized to produce a composite polarizing plate by adhering the polarizer and the patterned retardation layer, and contributing to improving heat resistance and moist-heat resistance, as well as to imparting a superb three-dimensional effect.

Description

점착제 조성물 및 이를 이용한 복합 편광판Adhesive composition and composite polarizing plate using same
본 발명은 점착제 조성물 및 이를 이용한 복합 편광판에 관한 것이다.The present invention relates to an adhesive composition and a composite polarizing plate using the same.
입체 영상 구현용 액정표시장치 등의 디스플레이에는 패턴화된 위상차 필름이 포함되는 경우가 많다. 패턴화된 위상차 필름은 각 패턴 영역의 광축을 서로 다른 방향으로 구성하여 편광 안경을 쓴 시청자의 좌, 우안에 전달되는 영상이 다르게 함으로써 입체 영상을 구현한다.Displays such as liquid crystal displays for stereoscopic image implementation often include a patterned retardation film. The patterned retardation film configures the optical axis of each pattern region in different directions to implement a stereoscopic image by different images transmitted to the left and right eyes of a viewer wearing polarized glasses.
패턴화된 위상차 필름은 통상적으로 유리 기판 상에 배향막을 형성시키고 이 배향막 위에 액정을 코팅 및 배향시켜 형성될 수 있다. 광반응성 액정 물질은 배향막 상에서 배향된 후 자외선 등의 광 조사에 의해 가교되어 고분자 액정 필름의 형태가 된다. 이 때 배향막의 표면 배향에 준하는 액정의 배향 방향에 따라 리타더 패턴의 기능을 하게 된다.The patterned retardation film can typically be formed by forming an alignment film on a glass substrate and coating and aligning the liquid crystal on the alignment film. The photoreactive liquid crystal material is oriented on the alignment film and then crosslinked by light irradiation such as ultraviolet light to form a polymer liquid crystal film. At this time, the retarder pattern functions according to the alignment direction of the liquid crystal corresponding to the surface alignment of the alignment film.
패턴화된 위상차 필름은 통상적으로 편광판의 한 면에 접착제 또는 점착제를 매개로 접합되고, 근래에는 보다 박막 경량화를 위해 폴리비닐알콜 편광자의 한 면에 접합되기도 한다.The patterned retardation film is usually bonded to one side of the polarizing plate through an adhesive or a pressure-sensitive adhesive, and in recent years also bonded to one side of the polyvinyl alcohol polarizer for thinner film weight.
이러한 패턴화된 위상차 필름과 편광판 또는 편광자 사이의 밀착성이 떨어지는 경우에는 공정시 취급 과정 또는 사용 중에 변형이 발생할 수 있으며, 고온 다습한 조건에 장시간 노출되는 경우에 박리되거나 밀림 현상이 발생할 수도 있다. 그리고 통상의 폴리비닐알콜 편광자는 연신 방향으로 수축할 수 있는데, 이에 따라 위상차층의 위치별로 위상차가 상이해져 3D 입체감이 저하될 수 있다.When the adhesion between the patterned retardation film and the polarizing plate or polarizer is poor, deformation may occur during handling or use during the process, and peeling or sliding may occur when exposed to high temperature and high humidity for a long time. In addition, the conventional polyvinyl alcohol polarizer may shrink in the stretching direction. Accordingly, the phase difference may be different for each position of the phase difference layer, thereby reducing the 3D stereoscopic feeling.
이에 따라 접합력이 우수하면서, 내온수성, 내습열성 등의 기능을 고루 갖춘 우수한 접착제 또는 점착제의 개발이 요구되는 실정이다.Accordingly, the development of excellent adhesives or pressure-sensitive adhesives having excellent bonding strength and having functions such as hot water resistance and heat and moisture resistance are required.
한국공개특허 제2013-0028881호에는 필름 패턴드 리타더의 제조 방법, 그리고 필름 패턴드 리타더, 및 그것을 갖는 편광판 및 화상 표시 장치가 개시되어 있다.Korean Unexamined Patent Publication No. 2013-0028881 discloses a method for producing a film patterned retarder, and a film patterned retarder, and a polarizing plate and an image display device having the same.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
(특허문헌 1) 특허문헌 1: 한국공개특허 제2013-0028881호(Patent Document 1) Patent Document 1: Korean Patent Publication No. 2013-0028881
본 발명은 편광자와 패턴화된 위상차층을 접합하여 복합 편광판의 제조하는데 사용될 경우에, 편광자와 패턴화된 위상차층 사이의 접합력을 현저히 개선할 수 있는 점착제 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a pressure-sensitive adhesive composition which, when used to bond a polarizer and a patterned retardation layer to produce a composite polarizing plate, can significantly improve the bonding force between the polarizer and the patterned retardation layer.
본 발명은 상기 점착제 조성물을 통해 접합된 복합 편광판을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a composite polarizing plate bonded through the pressure-sensitive adhesive composition.
1. 탄소수 1 내지 12의 알킬기를 갖는 (메타)아크릴레이트 모노머 및 가교성 관능기를 갖는 모노머를 포함하여 중합된 공중합체; 및 상기 가교성 모노머 100 중량부에 대하여 이소시아네이트 가교제 200 내지 2,000중량부;를 포함하는, 점착제 조성물.1. a copolymer polymerized including a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and a monomer having a crosslinkable functional group; And 200 to 2,000 parts by weight of an isocyanate crosslinking agent based on 100 parts by weight of the crosslinkable monomer.
2. 위 1에 있어서, 상기 이소시아네이트 가교제는 3관능 이상인, 점착제 조성물.2. The above 1, wherein the isocyanate crosslinking agent is trifunctional or more, pressure-sensitive adhesive composition.
3. 위 1에 있어서, 상기 이소시아네이트 가교제는 톨릴렌디이소시아네이트, 자일렌디이소시아네이트, 2,4-디페닐메탄디이소시아네이트, 4,4-디페닐메탄디이소시아네이트, 헥사메틸렌디이소시아네이트, 이소포론디이소시아네이트, 테트라메틸자일렌디이소시아네이트, 나프탈렌디이소시아네이트, 다가 알콜계 화합물 1몰에 디이소시아네이트 화합물 3몰을 반응시킨 부가체, 디이소시아네이트 화합물 3몰을 자기 축합시킨 이소시아누레이트체, 디이소시아네이트 화합물 3몰과 트리메틸올프로판체와의 어덕트체, 디이소시아네이트 화합물 3몰 중 2몰로부터 얻어지는 디이소시아네이트 우레아에 나머지 1몰의 디이소시아네이트가 축합된 뷰렛체, 트리페닐메탄트리이소시아네이트 및 메틸렌비스트리이소시아네이트로 이루어진 군에서 선택되는 적어도 하나인, 점착제 조성물.3. In the above 1, the isocyanate crosslinking agent tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetra Adduct obtained by reacting 3 moles of diisocyanate compound with 1 mole of methyl xylene diisocyanate, naphthalene diisocyanate, polyhydric alcohol compound, isocyanurate body self-condensing 3 moles of diisocyanate compound, 3 moles of diisocyanate compound and trimethylol Adducts with propane, diisocyanate urea obtained from 2 moles of 3 moles of diisocyanate compound, and 1 mole of diisocyanate condensed with a biuret, triphenylmethanetriisocyanate and methylene bistriisocyanate At least A pressure-sensitive adhesive composition.
4. 위 1에 있어서, 상기 이소시아네이트 가교제는 자일렌디이소시아네이트, 헥사메틸렌디이소시아네이트 및 이소포론디이소시아네이트 중 적어도 1종의 3몰을 자기 축합시킨 이소시아누레이트체, 및 상기 이소시아네이트 가교제는 자일렌디이소시아네이트, 헥사메틸렌디이소시아네이트 및 이소포론디이소시아네이트 중 적어도 1종의 3몰과 트리메틸올프로판체와의 어덕트체로 이루어진 군에서 선택되는 적어도 1종인, 점착제 조성물.4. In the above 1, wherein the isocyanate crosslinking agent is an isocyanurate body self-condensed at least one of 3 moles of xylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate, and the isocyanate crosslinking agent is xylene diisocyanate, The adhesive composition which is at least 1 sort (s) chosen from the group which consists of an adduct of 3 mol of at least 1 sort (s) of hexamethylene diisocyanate and isophorone diisocyanate, and a trimethylol propane body.
5. 위 1에 있어서, 상기 탄소수 1 내지 12의 알킬기를 갖는 (메타)아크릴레이트 모노머는, 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, n-프로필 (메타)아크릴레이트, 이소프로필(메타)아크릴레이트, n-부틸 (메타)아크릴레이트, 2-부틸 (메타)아크릴레이트, t-부틸 (메타)아크릴레이트, 2-에틸헥실 (메타)아크릴레이트, 2-에틸부틸 (메타)아크릴레이트, 펜틸 (메타)아크릴레이트, n-옥틸 (메타)아크릴레이트, 이소옥틸 (메타)아크릴레이트, n-노닐 (메타)아크릴레이트, 이소노닐 (메타)아크릴레이트, 데실 (메타)아크릴레이트 및 라우릴 (메타)아크릴레이트로 이루어진 군에서 선택되는 적어도 1종인, 점착제 조성물.5. In the above 1, wherein the (meth) acrylate monomer having an alkyl group of 1 to 12 carbon atoms, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl ( Meta) acrylate, n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylic Latex, pentyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate and Adhesive composition which is at least 1 sort (s) chosen from the group which consists of lauryl (meth) acrylate.
6. 위 1에 있어서, 상기 가교성 관능기는 히드록시기, 카르복시기, 아미드기 또는 3차 아민기인, 점착제 조성물.6. In the above 1, wherein the crosslinkable functional group is a hydroxyl group, carboxyl group, amide group or tertiary amine group, pressure-sensitive adhesive composition.
7. 편광자, 및 상기 편광자의 일면에 위 1 내지 6 중 어느 한 항의 점착제 조성물을 통해 접합된 패턴화된 위상차층을 포함하는, 복합 편광판.7. A composite polarizing plate comprising a polarizer, and a patterned retardation layer bonded to one surface of the polarizer through the pressure-sensitive adhesive composition of any one of 1 to 6 above.
8. 위 7에 있어서, 상기 편광자는 패턴화된 위상차층과 접합되는 면의 반대면에 보호필름 또는 위상차필름의 기능을 가진 필름이 접합된 것인, 복합 편광판.8. In the above 7, the polarizer is a composite polarizing plate is a film having a function of a protective film or a retardation film is bonded on the opposite side of the surface is bonded with the patterned retardation layer.
9. 위 7에 있어서, 상기 패턴화된 위상차층은 에스테르 결합을 포함하는 반응성 액정 모노머를 함유한 액정 코팅층을 포함하는, 복합 편광판.9. The composite polarizing plate of claim 7, wherein the patterned retardation layer comprises a liquid crystal coating layer containing a reactive liquid crystal monomer including an ester bond.
10. 위 7에 있어서, 편광자와 패턴화된 위상차층 사이의 박리력이 3 N/25mm 이상인, 복합 편광판.10. In the above 7, the peel force between the polarizer and the patterned retardation layer is 3 N / 25mm or more, composite polarizing plate.
11. 위 7에 있어서, 상기 패턴화된 위상차층은 배향막을 포함하지 않는, 복합 편광판.11. In the above 7, wherein the patterned retardation layer does not include an alignment film, a composite polarizing plate.
12. 위 7에 있어서, 60℃에 250시간 동안 노출된 경우에 패턴화된 위상차층의 단위 패턴 간격 변화율이 0.13%이하인, 복합 편광판.12. In the above 7, the rate of change of the unit pattern interval of the patterned retardation layer when exposed to 250 ℃ for 250 hours, 0.13% or less, the composite polarizing plate.
13. 위 7의 복합 편광판을 포함하는 화상표시장치.13. Image display device including the composite polarizer of the above seven.
본 발명의 점착제 조성물은 편광자와 패턴화된 위상차층을 접합하여 복합 편광판의 제조하는데 사용될 경우에, 편광자와 패턴화된 위상차층 사이의 접합력을 현저히 개선한다.The pressure-sensitive adhesive composition of the present invention significantly improves the bonding force between the polarizer and the patterned retardation layer when used to bond the polarizer and the patterned retardation layer to produce a composite polarizing plate.
본 발명의 점착제 조성물로 접합된 복합 편광판은 내열성 및 내습열성이 우수하여 고온 다습 조건에 장시간 노출된 경우에도 박리 및 밀림 현상이 억제된다.The composite polarizing plate bonded with the pressure-sensitive adhesive composition of the present invention is excellent in heat resistance and heat-and-moisture resistance, and even when exposed to high temperature and high humidity conditions for a long time, peeling and rolling phenomenon are suppressed.
본 발명의 점착제 조성물로 접합된 복합 편광판은 편광 기능 및 개선된 3D 입체효과를 동시에 갖는다.The composite polarizing plate bonded with the pressure-sensitive adhesive composition of the present invention simultaneously has a polarizing function and an improved 3D stereoscopic effect.
본 발명은, 탄소수 1 내지 12의 알킬기를 갖는 (메타)아크릴레이트 모노머 및 가교성 관능기를 갖는 모노머를 포함하여 중합된 공중합체; 및 상기 가교성 모노머 100 중량부에 대하여 이소시아네이트 가교제 200 내지 2,000중량부;를 포함함으로써, 편광자와 패턴화된 위상차층을 접합하여 복합 편광판을 제조하는데 사용될 경우에, 편광자와 패턴화된 위상차층 사이의 접합력을 현저히 개선하고, 내열성 및 내습열성을 개선할 뿐만 아니라 우수한 3D 입체효과를 갖도록 하는 점착제 조성물 및 이를 이용한 복합 편광판에 관한 것이다.The present invention is a copolymer copolymerized with a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and a monomer having a crosslinkable functional group; And 200 to 2,000 parts by weight of an isocyanate crosslinking agent with respect to 100 parts by weight of the crosslinkable monomer; when used to bond the polarizer and the patterned retardation layer to produce a composite polarizing plate, between the polarizer and the patterned retardation layer. The present invention relates to a pressure-sensitive adhesive composition and a composite polarizing plate using the same, which significantly improve bonding strength, improve heat resistance and heat-and-moisture resistance, and have an excellent 3D stereoscopic effect.
이하, 본 발명을 상세하게 설명하도록 한다.Hereinafter, the present invention will be described in detail.
점착제 조성물Pressure-sensitive adhesive composition
본 발명의 점착제 조성물은 아크릴레이트계 공중합체를 포함한다.The pressure-sensitive adhesive composition of the present invention includes an acrylate copolymer.
본 발명에 따른 아크릴계 공중합체는 탄소수 1 내지 12의 알킬기를 갖는 (메타)아크릴레이트 모노머 및 가교성 관능기를 갖는 모노머를 포함하여 중합된다. 본 발명에 있어서, (메타)아크릴레이트란 아크릴레이트, 메타아크릴레이트 또는 이 둘을 동시에 지칭한다.The acrylic copolymer according to the present invention is polymerized to include a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and a monomer having a crosslinkable functional group. In the present invention, (meth) acrylate refers to acrylate, methacrylate or both at the same time.
탄소수 1 내지 12의 알킬기를 갖는 (메타)아크릴레이트 모노머의 구체적인 예시로는, 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, n-프로필 (메타)아크릴레이트, 이소프로필(메타)아크릴레이트, n-부틸 (메타)아크릴레이트, 2-부틸 (메타)아크릴레이트, t-부틸 (메타)아크릴레이트, 2-에틸헥실 (메타)아크릴레이트, 2-에틸부틸 (메타)아크릴레이트, 펜틸 (메타)아크릴레이트, n-옥틸 (메타)아크릴레이트, 이소옥틸 (메타)아크릴레이트, n-노닐 (메타)아크릴레이트, 이소노닐 (메타)아크릴레이트, 데실 (메타)아크릴레이트, 라우릴 (메타)아크릴레이트 등을 들 수 있으며, 이들은 각각 단독으로 또는 2종 이상 혼합되어 사용될 수 있다.Specific examples of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. , n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, pentyl ( Meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) ) Acrylates and the like, and these may be used alone or in combination of two or more.
가교성 관능기를 갖는 모노머는 화학 결합에 의해 점착제 조성물의 응집력 또는 점착 강도를 보강하여 내구성과 절단성을 부여하기 위한 성분으로서, 예컨대 히드록시기를 갖는 모노머, 카르복시기를 갖는 모노머, 아미드기를 갖는 모노머, 3차 아민기를 갖는 모노머 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있고, 바람직하게는 히드록시기를 갖는 모노머를 사용할 수 있다.The monomer having a crosslinkable functional group is a component for reinforcing the cohesive force or adhesive strength of the pressure-sensitive adhesive composition by chemical bonding and imparting durability and cutting property, such as a monomer having a hydroxy group, a monomer having a carboxyl group, a monomer having an amide group, and a tertiary The monomer etc. which have an amine group are mentioned, These can be used individually or in mixture of 2 or more types, Preferably, the monomer which has a hydroxyl group can be used.
히드록시기를 갖는 모노머로는 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 6-히드록시헥실(메타)아크릴레이트, 2-히드록시에틸렌글리콜(메타)아크릴레이트, 2-히드록시프로필렌글리콜(메타)아크릴레이트, 알킬렌기의 탄소수가 2-4인 히드록시알킬렌글리콜(메타)아크릴레이트, 4-히드록시부틸비닐에테르, 5-히드록시펜틸비닐에테르, 6-히드록시헥실비닐에테르, 7-히드록시헵틸비닐에테르, 8-히드록시옥틸비닐에테르, 9-히드록시노닐비닐에테르, 10-히드록시데실비닐에테르 등을 들 수 있으며, 이들 중에서 4-히드록시부틸비닐에테르가 바람직하다.As a monomer which has a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, 2-hydroxypropylene glycol (meth) acrylate, hydroxyalkylene glycol having 2 to 4 carbon atoms of an alkylene group ( Meta) acrylate, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 7-hydroxyheptyl vinyl ether, 8-hydroxyoctyl vinyl ether, 9-hydroxynonyl Vinyl ether, 10-hydroxydecyl vinyl ether, etc. are mentioned, Among these, 4-hydroxybutyl vinyl ether is preferable.
카르복시기를 갖는 모노머로는 (메타)아크릴산, 크로톤산, 3-(아크릴로일옥시)프로파노익산, 4-(2-(아크릴로일옥시)에톡시)-4-옥소부타노익산, 3-((2-(아크릴로일옥시)에톡시)카보닐)시클로헥산카복시산, 4-(2-아크릴아미도에톡시)-4-옥소부타노익산 등의 1가산; 말레인산, 이타콘산, 푸마르산 등의 2가산 및 이들의 모노알킬에스테르; 3-(메타)아크릴로일프로피온산; 알킬기의 탄소수가 2-3인 2-히드록시알킬(메타)아크릴레이트의 무수호박산 개환 부가체, 알킬렌기의 탄소수가 2-4인 히드록시알킬렌글리콜(메타)아크릴레이트의 무수 호박산 개환 부가체, 알킬기의 탄소수가 2-3인 2-히드록시알킬(메타)아크릴레이트의 카프로락톤 부가체에 무수 호박산을 개환 부가시킨 화합물 등을 들 수 있으며, 이들 중에서 (메타)아크릴산이 바람직하다.Examples of the monomer having a carboxy group include (meth) acrylic acid, crotonic acid, 3- (acryloyloxy) propanoic acid, 4- (2- (acryloyloxy) ethoxy) -4-oxobutanoic acid, 3- Monovalent acids such as ((2- (acryloyloxy) ethoxy) carbonyl) cyclohexanecarboxylic acid and 4- (2-acrylamidoethoxy) -4-oxobutanoic acid; Diacids such as maleic acid, itaconic acid and fumaric acid, and monoalkyl esters thereof; 3- (meth) acryloylpropionic acid; Succinic anhydride ring-opening adduct of 2-hydroxyalkyl (meth) acrylate with 2-3 carbon atoms of an alkyl group, Succinic anhydride ring opening adduct of hydroxyalkylene glycol (meth) acrylate with 2-4 carbon atoms of an alkylene group And a compound obtained by ring-opening addition of succinic anhydride to a caprolactone adduct of 2-hydroxyalkyl (meth) acrylate having 2 to 3 carbon atoms of an alkyl group, among which (meth) acrylic acid is preferred.
아미드기를 갖는 모노머로는 (메타)아크릴아미드, N-이소프로필아크릴아미드, N-3차부틸아크릴아미드, 3-히드록시프로필(메타)아크릴아미드, 4-히드록시부틸(메타)아크릴아미드, 6-히드록시헥실(메타)아크릴아미드, 8-히드록시옥틸(메타)아크릴아미드, 2-히드록시에틸헥실(메타)아크릴아미드 등을 들 수 있으며, 이들 중에서 (메타)아크릴아미드가 바람직하다.Examples of the monomer having an amide group include (meth) acrylamide, N-isopropylacrylamide, N-tert-butylacrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (meth) acrylamide, 6 -Hydroxyhexyl (meth) acrylamide, 8-hydroxyoctyl (meth) acrylamide, 2-hydroxyethylhexyl (meth) acrylamide, etc. are mentioned, Among these, (meth) acrylamide is preferable.
3차 아민기를 갖는 모노머로는 N,N-(디메틸아미노)에틸(메타)아크릴레이트, N,N-(디에틸아미노)에틸(메타)아크릴레이트, N,N-(디메틸아미노)프로필(메타)아크릴레이트 등을 들 수 있다.Monomers having a tertiary amine group include N, N- (dimethylamino) ethyl (meth) acrylate, N, N- (diethylamino) ethyl (meth) acrylate, and N, N- (dimethylamino) propyl (meth ) Acrylates and the like.
가교성 관능기를 갖는 모노머는 전체 모노머 총 중량에 대하여 0.1 내지 15중량%로 포함될 수 있고, 보다 바람직하게는 1 내지 10중량%로 포함될 수 있다. 함량이 0.1중량% 미만인 경우 점착제의 응집력이 작아지게 되어 내구성이 저하될 수 있으며, 10중량% 초과인 경우 높은 겔분율에 의해 점착력이 떨어지고 내구성에 문제를 야기할 수 있다.The monomer having a crosslinkable functional group may be included in an amount of 0.1 to 15% by weight, and more preferably 1 to 10% by weight, based on the total weight of the monomers. If the content is less than 0.1% by weight, the cohesive force of the pressure-sensitive adhesive may be reduced, the durability may be lowered. When the content is more than 10% by weight, the adhesive strength may be degraded by a high gel fraction and may cause a problem in durability.
선택적으로, 본 발명에 따른 공중합체는 공중합이 가능한 모노머를 추가적으로 포함하여 중합될 수도 있다. 공중합이 가능한 모노머로는, 스티렌, 클로로 스티렌, α-메틸스티렌, 비닐톨루엔, 벤질(메타)아크릴레이트, 디메틸아미노에틸(메타)아크릴레이트, 2-페녹시에틸(메타)아크릴레이트, 아실옥틸옥시-2-히드록시프로필(메타)아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 3-메톡시부틸(메타)아크릴레이트, 에톡시디에틸렌글리콜(메타)아크릴레이트, 메톡시트리에틸렌글리콜(메타)아크릴레이트, 메톡시트리프로필렌글리콜(메타)아크릴레이트, 메톡시폴리에틸렌글리콜(메타)아크릴레이트, 페녹시디에틸렌글리콜(메타)아크릴레이트, p-노닐페녹시폴리에틸렌글리콜(메타)아크릴레이트, p-노닐페녹시폴리프로필렌글리콜(메타)아크릴레이트, 테트라플루오로프로필(메타)아크릴레이트, 1,1,1,3,3,3-헥사플루오로이소프로필(메타)아크릴레이트, 옥타플루오로펜틸(메타)아크릴레이트, 헵타데카플루오로데실(메타)아크릴레이트, 트리브로모페닐(메타)아크릴레이트, β-(메타)아실올옥시에틸히드로겐석시네이트, 메틸α-히드록시메틸아크릴레이트, 에틸α-히드록시메틸아크릴레이트, 프로필α-히드록시메틸아크릴레이트, 부틸α-히드록시메틸아크릴레이트 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Alternatively, the copolymer according to the present invention may be polymerized by additionally including a copolymerizable monomer. As a monomer which can be copolymerized, styrene, chloro styrene, (alpha) -methylstyrene, vinyltoluene, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, and acyl octyloxy 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol ( Meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxy polyethylene glycol (meth) acrylate, p Nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl ( Ta) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, β- (meth) acyloloxyethylhydrogensuccinate, methylα-hydroxymethylacrylate, ethyl (alpha) -hydroxymethylacrylate, propyl (alpha)-hydroxymethylacrylate, butyl (alpha)-hydroxymethyl acrylate, etc. are mentioned, These can be used individually or in mixture of 2 or more types.
공중합체의 제조방법은 특별히 한정되지 않으며, 당 분야에서 통상적으로 사용되는 괴상중합, 용액중합, 유화중합 또는 현탁중합 등의 방법을 이용하여 제조할 수 있으며, 용액중합이 바람직하다. 또한, 중합 시 통상 사용되는 용매, 중합개시제, 분자량 제어를 위한 연쇄이동제 등을 사용할 수 있다.The production method of the copolymer is not particularly limited, and may be prepared using a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, which are commonly used in the art, and solution polymerization is preferable. In addition, a solvent, a polymerization initiator, a chain transfer agent for molecular weight control, and the like, which are usually used in the polymerization, may be used.
공중합체는 겔투과크로마토그래피(Gel permeation chromatography, GPC)에 의해 측정된 중량평균 분자량(폴리스티렌 환산, Mw)이 20만 내지 150만, 바람직하게 40만 내지 120만일 수 있다. 분자량이 20만 미만이면 공중합체 간의 응집력이 부족하여 점착 내구성에 문제를 야기할 수 있고, 150만 초과이면 도공 시 공정성을 확보하기 위하여 다량의 희석 용매를 필요로 하는 문제가 있다.The copolymer may have a weight average molecular weight (polystyrene equivalent, Mw) measured by gel permeation chromatography (GPC) of 200,000 to 1.50,000, preferably 400,000 to 1.2 million. When the molecular weight is less than 200,000, cohesion between copolymers may be insufficient, which may cause problems in adhesion durability. When the molecular weight is more than 1.5 million, a large amount of diluting solvent is required to ensure fairness during coating.
본 발명의 공중합체는 이소시아네이트 가교제와 함께 혼합되어 점착제 조성물로 사용된다.The copolymer of the present invention is mixed with an isocyanate crosslinking agent and used as the pressure-sensitive adhesive composition.
본 발명에 따른 이소시아네이트 가교제는 공중합체를 적절히 가교함으로써 점착제의 응집력을 강화할 뿐만 아니라, 공중합체를 형성하는 가교성 관능기를 갖는 모노머 100 중량부에 대하여 200 내지 2,000 중량부로 포함되어 편광자와 패턴화된 위상차층을 접합하는데 사용되는 경우 그 접합력을 현저하게 향상시킨다.The isocyanate crosslinking agent according to the present invention not only reinforces the cohesive force of the pressure-sensitive adhesive by appropriately crosslinking the copolymer, but is also included in an amount of 200 to 2,000 parts by weight based on 100 parts by weight of the monomer having a crosslinkable functional group to form a copolymer, thereby reversing the patterned phase difference. When used to bond layers, the bond strength is significantly improved.
구체적으로 본 발명의 점착제 조성물에서 이소시아네이트는 상기 함량 범위와 같이 과량으로 포함되는데, 이 경우 미반응된 이소시아네이트기가 수분과 접촉하여 아미노기(-NH2)로 변환된다. 이와 같이 점착제 조성물 내에 아미노기가 형성되게 되면, 상기 아미노기는 편광자 표면 극성기 및 패턴화된 위상차층의 액정 코팅층 내에 포함되어 있는 극성기와의 수소결합을 형성하며, 액정 코팅층 상에 함유되는 반응성 액정 모노머가 포함하는 에스테르 결합과 아미드화 반응을 하여 공유 결합을 형성하게 되는데, 이러한 수소결합 및 공유결합에 의해 편광자와 패턴화된 위상차층의 접합력이 현저히 개선되는 것으로 판단된다.Specifically, in the pressure-sensitive adhesive composition of the present invention, the isocyanate is included in an excessive amount as in the above content range, in which case the unreacted isocyanate group is contacted with moisture to be converted into an amino group (-NH 2 ). As such, when the amino group is formed in the pressure-sensitive adhesive composition, the amino group forms a hydrogen bond with the polar group included in the polarizer surface polar group and the liquid crystal coating layer of the patterned retardation layer, and includes a reactive liquid crystal monomer contained on the liquid crystal coating layer. To form a covalent bond by an amidation reaction with an ester bond, it is believed that the bonding strength of the polarizer and the patterned retardation layer is significantly improved by the hydrogen bond and the covalent bond.
이소시아네이트 가교제의 함량이 200 중량부 미만이면 점착제 조성물의 접합력이 불충분하며, 2,000 중량부를 초과하면 과다 가교반응에 의해 잔류응력 완화에 문제가 발생할 수 있다.If the content of the isocyanate crosslinking agent is less than 200 parts by weight, the adhesive strength of the pressure-sensitive adhesive composition is insufficient. If the content of the isocyanate crosslinking agent is more than 2,000 parts, the problem of relaxation of residual stress may be caused by an excessive crosslinking reaction.
본 발명에 따른 이소시아네이트 가교제로는 예를 들면, 이소시아네이트계 화합물로는 톨릴렌디이소시아네이트, 자일렌디이소시아네이트, 2,4-디페닐메탄디이소시아네트, 4,4-디페닐메탄디이소시아네트, 헥사메틸렌디이소시아네이트, 이소포론디이소시아네이트, 테트라메틸자일렌디이소시아네이트, 나프탈렌디이소시아네이트 등의 디이소시아네이트 화합물; 트리메틸올프로판 등의 다가 알콜계 화합물 1몰에 디이소시아네이트 화합물 3몰을 반응시킨 부가체, 디이소시아네이트 화합물 3몰을 자기 축합시킨 이소시아누레이트체, 디이소시아네이트 화합물 3몰과 트리메틸올프로판체와의 어덕트체, 디이소시아네이트 화합물 3몰 중 2몰로부터 얻어지는 디이소시아네이트 우레아에 나머지 1몰의 디이소시아네이트가 축합된 뷰렛체, 트리페닐메탄트리이소시아네이트, 메틸렌비스트리이소시아네이트 등의 3개의 관능기를 함유하는 다관능 이소시아네이트 화합물 등을 들 수 있다. 이들은 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있다.As the isocyanate crosslinking agent according to the present invention, for example, tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene di Diisocyanate compounds such as isocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate and naphthalene diisocyanate; An adduct obtained by reacting 3 moles of a diisocyanate compound with 1 mole of a polyhydric alcohol compound such as trimethylolpropane, an isocyanurate obtained by self-condensing 3 moles of the diisocyanate compound, 3 moles of the diisocyanate compound and trimethylolpropane Multifunctional containing three functional groups, such as an adduct body, the biuret body which remaining 1 mol diisocyanate condensed to the diisocyanate urea obtained from 2 mol of 3 mol of diisocyanate compounds, triphenylmethane triisocyanate, and methylene bistriisocyanate, etc. Isocyanate compounds etc. are mentioned. These can be used individually or in mixture of 2 or more types, respectively.
바람직하게는 3관능 이상의 다관능 이소시아네이트 가교제를 사용할 수 있으며, 예를 들면, 3관능, 4관능, 5관능, 6관능의 이소시아네이트 가교제를 사용할 수 있다.Preferably, trifunctional or more than trifunctional isocyanate crosslinking agent can be used, For example, a trifunctional, tetrafunctional, 5-functional, and 6-functional isocyanate crosslinking agent can be used.
3관능 이소시아네이트 가교제로는 자일렌디이소시아네이트, 헥사메틸렌디이소시아네이트 및 이소포론디이소시아네이트 중 적어도 1종의 3몰을 자기 축합시킨 이소시아누레이트체; 및 자일렌디이소시아네이트, 헥사메틸렌디이소시아네이트 및 이소포론디이소시아네이트 중 적어도 1종의 3몰과 트리메틸올프로판체와의 어덕트체로 이루어진 군에서 선택되는 적어도 1종을 들 수 있다.As a trifunctional isocyanate crosslinking agent, the isocyanurate body which self-condensed at least 3 mol of xylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate; And at least one selected from the group consisting of at least one of 3 moles of xylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate and an adduct of trimethylolpropane.
상기와 같은 성분 이외에, 본 발명에 따른 점착제 조성물은 용도에 따라 요구되는 점착력, 응집력, 점성, 탄성률, 유리전이온도, 대전방지성 등을 조절하기 위하여, 점착성 부여 수지, 산화방지제, 부식방지제, 레벨링제, 표면윤활제, 염료, 안료, 소포제, 충전제, 광안정제, 대전방지제 등의 첨가제를 더 포함할 수 있다.In addition to the components as described above, the pressure-sensitive adhesive composition according to the present invention, in order to adjust the adhesion, cohesion, viscosity, elastic modulus, glass transition temperature, antistatic properties, etc. required according to the use, tackifying resin, antioxidant, corrosion inhibitor, leveling Agents may further include additives such as surface lubricants, dyes, pigments, antifoams, fillers, light stabilizers, antistatic agents and the like.
복합 편광판Composite polarizer
또한, 본 발명은 상기 점착제 조성물을 사용하여 제조된 복합 편광판을 제공한다.In addition, the present invention provides a composite polarizing plate prepared using the pressure-sensitive adhesive composition.
본 발명의 복합 편광판은 편광자 및 상기 편광자의 일면에 상기 점착제 조성물을 통해 접합된 패턴화된 위상차층을 포함한다.The composite polarizing plate of the present invention includes a polarizer and a patterned retardation layer bonded to one surface of the polarizer through the pressure-sensitive adhesive composition.
본 발명의 복합 편광판은 상기 점착제 조성물을 통해 편광자와 패턴화된 위상차층이 접합되어, 그 접합력이 우수하다. 이 경우 전술한 바와 같이, 점착제 조성물층은 편광자와는 수소 결합을 형성하며, 패턴화된 위상차층과는 아미드화 반응에 의한 공유결합을 형성할 수 있다.In the composite polarizing plate of the present invention, the polarizer and the patterned retardation layer are bonded through the pressure-sensitive adhesive composition, and the bonding strength is excellent. In this case, as described above, the pressure-sensitive adhesive composition layer may form a hydrogen bond with the polarizer, and may form a covalent bond with the patterned retardation layer by an amidation reaction.
편광자는 디스플레이 분야에서 일반적으로 사용되는 것으로서 입사되는 빛을 편광시킬 수 있는 것이라면 특정의 것으로 한정되지 않는다. 예컨대 폴리 비닐알코올(PVA)로 이루어진 필름에 요오드나 이색성 염료를 염색시키고 이를 일정 방향으로 연신시켜 제조된 것을 사용할 수 있다. 패턴화된 위상차층과 접합되는 면의 반대면에는 보호필름 또는 위상차필름의 기능을 가진 필름이 접합된 것일 수 있다.The polarizer is generally used in the display field, and the polarizer is not limited as long as it can polarize incident light. For example, a film made of polyvinyl alcohol (PVA) may be used by dyeing iodine or dichroic dye and drawing it in a predetermined direction. On the opposite side of the surface to be bonded to the patterned retardation layer may be a film having a function of a protective film or retardation film is bonded.
패턴화된 위상차층의 구성은 특별히 한정되지 않고 당 분야에서 일반적으로 사용되는 구성을 포함하는 것일 수 있다. 예를 들어, 기재, 배향막 및 액정코팅층의 순서로 적층된 구조를 가질 수 있고, 또는 배향막을 포함하지 않는 구조일 수도 있다.The configuration of the patterned retardation layer is not particularly limited and may include a configuration generally used in the art. For example, it may have a structure laminated in the order of the substrate, the alignment film and the liquid crystal coating layer, or may be a structure that does not include the alignment film.
패턴화된 위상차층은 액정 코팅층이 편광자쪽을 향하도록 접합된다.The patterned retardation layer is bonded so that the liquid crystal coating layer faces the polarizer.
기재는 투명성, 기계적 강도, 열 안정성, 수분 차폐성, 위상차 균일성, 등방성 등이 우수한 소재로 형성된 것이라면 특별히 한정되지 않으며, 예를 들면 폴리올레핀계 수지, 폴리에스테르계 수지, 셀룰로오스계 수지, 폴리카보네이트계 수지, 아크릴계 수지, 스티렌계 수지, 염화비닐계 수지, 아미드계 수지, 이미드계 수지, 폴리에테르술폰계 수지, 술폰계 수지, 폴리에테르술폰계 수지, 폴리에테르에테르케톤계 수지, 황화 폴리페닐렌계 수지, 비닐알코올계 수지, 염화비닐리덴계 수지, 비닐부티랄계 수지, 알릴레이트계 수지, 폴리옥시메틸렌계 수지 및 에폭시계 수지로 이루어진 군에서 선택된 적어도 하나의 소재로 형성된 기재를 사용할 수 있다.The base material is not particularly limited as long as it is formed of a material having excellent transparency, mechanical strength, thermal stability, moisture shielding property, retardation uniformity, and isotropy. For example, the polyolefin resin, polyester resin, cellulose resin, and polycarbonate resin , Acrylic resin, styrene resin, vinyl chloride resin, amide resin, imide resin, polyether sulfone resin, sulfone resin, polyether sulfone resin, polyether ether ketone resin, sulfonated polyphenylene resin, A substrate formed of at least one material selected from the group consisting of vinyl alcohol resin, vinylidene chloride resin, vinyl butyral resin, allylate resin, polyoxymethylene resin and epoxy resin can be used.
패턴화된 위상차층이 배향막을 포함하는 경우, 상기 배향막은 기재 상에 당 분야에서 통상적으로 사용되는 배향막 형성용 조성물을 코팅하고 배향성을 부여한 후에, 서로 다른 배향 방향을 갖도록 패턴화하는 방법에 의해 형성될 수 있다.When the patterned retardation layer includes an alignment layer, the alignment layer is formed by coating a composition for forming an alignment layer commonly used in the art on the substrate and imparting orientation, and then patterning the substrate to have different orientation directions. Can be.
상기 배향성 부여 방법은 러빙 방식, 광 배향 방식 등을 들 수 있고, 패턴화 방법은 포토마스크를 이용한 복수의 노광 공정에 의할 수 있으나 이에 한정되는 것은 아니다.The orientation providing method may include a rubbing method, a photo alignment method, and the like, and the patterning method may be based on a plurality of exposure processes using a photomask, but is not limited thereto.
노광에 사용되는 광은 특별히 한정하지는 않으나, 예를 들면 편광된 자외선 조사, 소정의 각도로 이온빔 또는 플라즈마빔 조사 및 방사선 조사 등을 사용할 수 있다. 예컨대 편광된 자외선을 조사하는 것이 바람직하다.The light used for the exposure is not particularly limited, but for example, polarized ultraviolet irradiation, ion beam or plasma beam irradiation, radiation irradiation, or the like can be used. For example, it is preferable to irradiate polarized ultraviolet rays.
액정 코팅층은 당 분야에 통상적으로 사용되는 반응성 액정 모노머(RM) 등을 포함하는 액정 코팅층 형성용 조성물을 배향막 상에 도포하고, 가교시켜 형성된 것일 수 있다.The liquid crystal coating layer may be formed by applying a composition for forming a liquid crystal coating layer including a reactive liquid crystal monomer (RM) or the like commonly used in the art on an alignment layer and crosslinking the same.
반응성 액정 모노머는 특별히 한정되지 않고 당 분야에서 통상적으로 사용되는 모노머가 사용될 수 있으나, 바람직하게는 에스테르 결합을 갖는 모노머일 수 있다.The reactive liquid crystal monomer is not particularly limited and may be a monomer commonly used in the art, but preferably may be a monomer having an ester bond.
패턴화된 위상차층이 배향막을 포함하지 않는 경우에는, 배향막 없이 기재 상에 액정 코팅층 형성용 조성물을 도포하고, 노광시켜 패턴화 및 배향을 동시에 수행하여 패턴화된 위상차층을 형성할 수 있다.When the patterned retardation layer does not include an alignment layer, the composition for forming a liquid crystal coating layer may be applied onto the substrate without the alignment layer, and may be exposed to simultaneously perform patterning and orientation to form a patterned retardation layer.
이러한 경우에 액정 코팅층 형성용 조성물은 배향을 위해, 직선 광중합성 폴리머 등의 편광 자외선 광에 의해 배향이 가능한 화합물을 더 포함할 수도 있다.In this case, the composition for forming a liquid crystal coating layer may further include a compound which can be aligned by polarized ultraviolet light such as a linear photopolymerizable polymer for alignment.
패턴화된 위상차층이 배향막을 포함하지 않는 경우에는 보다 박막의 디스플레이를 구현할 수 있다.When the patterned retardation layer does not include an alignment layer, a thinner display can be realized.
본 발명의 복합 편광판은 전술한 본 발명의 점착제 조성물을 사용함으로써, 고온 다습한 조건에 오래 노출되는 경우에도 편광자의 수축으로 발생한 응력에 의해 패턴화된 위상차층이 수축하는 것이 억제된다. 예를 들면, 60℃에서 250시간 동안 노출된 경우에 패턴화된 위상차층의 단위 패턴 간격 변화율이 0.13% 이하일 수 있다. 이에 따라 3D 입체감 저하를 억제할 수 있다.By using the pressure-sensitive adhesive composition of the present invention described above, the composite polarizing plate of the present invention suppresses the shrinkage of the patterned retardation layer due to the stress caused by the shrinkage of the polarizer even when exposed to high temperature and high humidity for a long time. For example, the unit pattern interval change rate of the patterned retardation layer may be 0.13% or less when exposed to 250 hours at 60 ° C. Thereby, 3D stereoscopic fall can be suppressed.
또한, 본 발명의 점착제 조성물을 사용하여 제조된 본 발명의 복합 편광판은 편광자와 패턴화된 위상차층 간의 접합력이 매우 우수하다. 예를 들면, 편광자와 패턴화된 위상차층 사이의 박리력이 3 N/25mm 이상일 수 있고, 바람직하게는 3 내지 6 N/25mm일 수 있다.In addition, the composite polarizing plate of the present invention produced using the pressure-sensitive adhesive composition of the present invention is very excellent in bonding strength between the polarizer and the patterned retardation layer. For example, the peel force between the polarizer and the patterned retardation layer may be 3 N / 25 mm or more, preferably 3 to 6 N / 25 mm.
화상표시장치Image display device
또한, 본 발명은 상기 복합 편광판을 포함하는 화상표시장치를 제공한다.In addition, the present invention provides an image display device including the composite polarizing plate.
화상표시장치는 특별히 한정되지 않고, 예를 들면 입체화상구현용 또는 반투과형 액정디스플레이 장치, 플라즈마 디스플레이 장치, 유기 EL 디스플레이 장치 등을 들 수 있다.The image display device is not particularly limited, and examples thereof include stereoscopic image implementation or semi-transmissive liquid crystal display device, plasma display device, organic EL display device, and the like.
본 발명의 복합 편광판은 종래 편광판과 패턴화된 위상차층이 적층되는 위치에 사용될 수 있다.The composite polarizing plate of the present invention can be used at a position where a conventional polarizing plate and a patterned retardation layer are stacked.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 이들 실시예는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 이들 실시예는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다. Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.
제조예 1-3Preparation Example 1-3
질소가스가 환류되고 온도조절이 용이하도록 냉각장치를 설치한 1L의 반응기에 n-부틸아크릴레이트(BA) 89.5부, 벤질메타크릴레이트(BzMA) 10 중량부, 히드록시에틸아크릴레이트(HEA) 0.2중량부, 아크릴산(AA) 0.3중량부와 용제로 에틸아세테이트(아세톤) 100중량부를 투입하였다. 그 다음 산소를 제거하기 위하여 질소가스를 1시간 동안 퍼징한 후, 62℃로 유지하였다. 상기 혼합물을 균일하게 한 후, 반응개시제로 아조비스이소부티로니트릴(AIBN) 0.07중량부를 투입하고, 6시간 동안 반응시켜 중량평균분자량 약 1,000,000인 아크릴계 공중합체를 제조하였다(제조예 1).89.5 parts of n-butyl acrylate (BA), 10 parts by weight of benzyl methacrylate (BzMA), hydroxyethyl acrylate (HEA) 0.2 in a 1L reactor equipped with a refrigeration system for easy reflux of nitrogen gas By weight, 0.3 parts by weight of acrylic acid (AA) and 100 parts by weight of ethyl acetate (acetone) were added. Then, after purging nitrogen gas for 1 hour to remove oxygen, it was maintained at 62 ℃. After homogenizing the mixture, 0.07 parts by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator, and reacted for 6 hours to prepare an acrylic copolymer having a weight average molecular weight of about 1,000,000 (Preparation Example 1).
제조예 2 및 3은 하기 표 1의 조성 및 함량으로 상기 제조예 1과 동일한 방법으로 제조하였다.Preparation Examples 2 and 3 were prepared in the same manner as in Preparation Example 1, using the compositions and contents shown in Table 1 below.
표 1
Figure PCTKR2014006577-appb-T000001
 Table 1
Figure PCTKR2014006577-appb-T000001
실시예 및 비교예Examples and Comparative Examples
상기 제조예에서 제조된 아크릴계 공중합체의 고형분 100중량부 대비, 가교제를 하기 표 2와 같이 첨가하여, 점착제 조성물을 제조하였다.Compared to 100 parts by weight of the solid content of the acrylic copolymer prepared in Preparation Example, a crosslinking agent was added as shown in Table 2 to prepare a pressure-sensitive adhesive composition.
표 2
Figure PCTKR2014006577-appb-T000002
 TABLE 2
Figure PCTKR2014006577-appb-T000002
비교예 3Comparative Example 3
일면에 TAC(40㎛)가 접합되어 있는 PVA편광자의 PVA면이, 패턴화된 위상차층(MPR32, DNP사)의 위상차 액정층 코팅면과 접촉하도록 위치시키고, 그 사이에 폴리비닐알콜 2% 수용액과 가교제로서 글리옥살 0.2부를 녹인 수계 접착제를 이용하여, 접합한 뒤, 100℃ 건조오븐에서 3분 간 건조한 뒤 상온에서 24시간 방치하여, 복합 편광판을 제조하였다.The PVA surface of the PVA polarizer having TAC (40 μm) bonded to one surface thereof is placed in contact with the retardation liquid crystal layer coating surface of the patterned retardation layer (MPR32, DNP), and a polyvinyl alcohol 2% aqueous solution therebetween. After bonding using an aqueous adhesive obtained by dissolving 0.2 parts of glyoxal as a crosslinking agent, the mixture was dried in a 100 ° C. drying oven for 3 minutes and left at room temperature for 24 hours to prepare a composite polarizing plate.
실험예Experimental Example
점착제 조성물을 고형분 20%의 농도로 희석한 뒤에, 실리콘 이형처리된 PET필름에 건조 후 두께가 20㎛가 되로록 코팅하고, 100℃ 오븐에서 1분간 건조한 뒤, 일면에 TAC(40um)가 접합되어 있는 PVA편광자의 PVA면이 점착제에 접촉되로록 하여 접합한 뒤, 상온에서 7일 보관하여 양생하였다.After diluting the pressure-sensitive adhesive composition to a concentration of 20% solids, coated on a silicone release-treated PET film to a thickness of 20㎛, dried for 1 minute in an oven at 100 ℃, TAC (40um) is bonded to one side The PVA surface of the PVA polarizer in contact with the adhesive was bonded to each other, and then cured by storing at room temperature for 7 days.
양생이 완료된 뒤, 패턴화된 위상차층(MPR32, DNP사)의 위상차코팅면이 점착제와 접촉하도록, 점착제면의 이형필름의 제거한 뒤, 접합하여 복합 편광판을 제조하였다.After curing was completed, the release film on the pressure-sensitive adhesive side was removed so that the phase difference coating surface of the patterned retardation layer (MPR32, DNP Co., Ltd.) was in contact with the pressure-sensitive adhesive, followed by bonding to prepare a composite polarizing plate.
(1) 박리력 측정(1) Peel force measurement
상기 복합 편광판 제조시, 샘플의 끝단 부분에 이형필름을 삽입하여 점착제 면이 FPR 필름과 접촉하지 못하도록 접합한 뒤, 샘플을 25mm 폭으로 절단한 뒤, 180도 박리방향으로 300mm/min의 속도로 박리하여 측정하였다.In the manufacturing of the composite polarizing plate, the release film is inserted into the end of the sample to be bonded so that the adhesive surface does not come into contact with the FPR film, and the sample is cut to 25 mm width, and then peeled at a speed of 300 mm / min in a 180 degree peeling direction. It was measured by.
(2) 내열성, 내습열성 평가(2) Heat resistance and heat and humidity resistance evaluation
복합 편광판의 TAC면에 미리 양생하여 준비된 점착제를 접합한 뒤, 소다글라스에 접합하고, 오토클레이브 처리하였다.After bonding the adhesive prepared by curing previously to the TAC surface of a composite polarizing plate, it bonded to soda glass and autoclave-processed.
이후에 각각 80℃에서 500시간, 60℃, 90% RH에서 500시간 방치한 후에, 액정 코팅층과 편광자의 접합면에서의 기포나 박리 발생 여부를 확인하여, 하기 기준에 따라 내열성 및 내습열성을 평가하였다.Thereafter, after 500 hours at 80 ° C., 60 ° C., and 500% at 90% RH, it was confirmed whether bubbles or peeling occurred at the bonding surface of the liquid crystal coating layer and the polarizer, respectively, and evaluated heat resistance and moisture heat resistance according to the following criteria. It was.
○: 기포나 박리가 없음○: no bubbles or peeling
△: 기포나 박리가 있으나, 매우 작은 부분에 한정하여 확인됨(Triangle | delta): Although there exist bubble or peeling, it is confirmed only to a very small part.
X: 기포나 박리가 육안으로 쉽게 확인됨X: Bubbles or peeling are easily visually confirmed
○의 경우, 내열성 및 내습열성 모두 상기 기준에 해당하는 경우에만 ○로 평가하였다. △ 및 X의 경우 내열성 및 내습열성 중 하나만 상기 기준에 해당하는 경우에도 △ 또는 X로 평가하였다.In the case of ○, the heat resistance and the moist heat resistance were evaluated as ○ only when the above criteria were met. In the case of Δ and X, only one of the heat resistance and the heat and humidity resistance was evaluated as Δ or X even when the criteria were met.
(3) 입체감 평가(3) three-dimensional evaluation
3D TV(47LA7400, LG 전자사)의 표시부 정중앙 부분을 15cm X 25cm로 절단하여 편광판 및 패턴화된 위상차층을 제거한 후에, 상기 실험예 2와 동일하게 제조되어 소다글래스에 접합된 복합 편광판을 동일 크기로 절단하여 해당 부위에 접합하고, 80℃에서 250시간 방치하였다.After cutting the center portion of the display of the 3D TV (47LA7400, LG Electronics Co., Ltd.) to 15 cm x 25 cm to remove the polarizing plate and the patterned retardation layer, the composite polarizing plate manufactured in the same manner as Experimental Example 2 and bonded to soda glass was the same size. It cut | disconnected and bonded to this site | part, and was left to stand at 80 degreeC for 250 hours.
이후에 TV 전원을 키고, 3D 안경(상기 3DTV의 부속품)을 착용하고 영상을 시청하여 하기 기준에 따라 입체감의 균일성을 평가하였다. After that, the TV was turned on, and the 3D glasses (the accessories of the 3DTV) were worn and the images were viewed to evaluate the uniformity of the stereoscopic effect according to the following criteria.
○: 전면에서 3D 입체감의 위치별 차이가 확인되지 않음○: no positional differences in 3D depth from the front
△: 수직방향(TD방향) 말단 부분에서 입체감의 저하가 미미하게 시인됨(Triangle | delta): Deterioration of a three-dimensional feeling is visually recognized in the vertical part (TD direction) terminal part.
X: 샘플의 수직방향(TD방향) 말단 부분에서 입체감의 저하가 확실히 시인됨X: The deterioration of a three-dimensional effect is clearly recognized by the vertical (TD direction) terminal part of a sample.
(4) 입체감 평가(4) three-dimensional evaluation
실험예 (2)와 동일한 방법으로 복합편광판을 제조하고, 32인치 3D TV 픽셀과 복합 편광판(MPR32, DNP사)의 패턴화된 위상차층의 단위 패턴을 맞추어 접합하였다.A composite polarizing plate was manufactured in the same manner as in Experimental Example (2), and the unit patterns of the patterned retardation layer of the 32-inch 3D TV pixel and the composite polarizing plate (MPR32, DNP) were matched to each other.
다음으로, 3D TV 단위 픽셀에 Red/Blue색상이 교차되어있는 이미지를 띄우고 좌원편광 또는 우원편광만으로 구현되는 영상의 초기 휘도를 화면의 중앙을 포함한 9 지점에서 측정하여 중앙부분과 나머지 주변 부분의 휘도차를 계산하고, 그로부터 좌안 영상 전체 휘도차와 우안 영상 전체 휘도차로부터, 전체 평균 휘도차를 산출하였다(하기 수학식 참조).Next, display the image where the red / blue color is intersected on the 3D TV unit pixel, and measure the initial luminance of the image realized by the left circular polarization or the right circular polarization only at 9 points including the center of the screen. The difference was calculated, and the total average luminance difference was calculated from the left eye image total luminance difference and the right eye image total luminance difference therefrom (see the following equation).
D=(DL+DR)/2D = (D L + D R ) / 2
DL=|( LC - Le)|, DR=|( RC - Re)|, D L = | (L C -L e ) |, D R = | (R C -R e ) |,
Le=(Le1+Le2+…+Le8)/8, Re=(Re1+Re2+…+Re8)/8,L e = (L e 1 + L e 2 +… + L e 8) / 8, R e = (R e 1 + R e 2 +… + R e 8) / 8,
(식 중, (In the meal,
D: 전체 평균 휘도 차, D: overall average luminance difference,
DL: 좌안 영상 전체 휘도차, DR: 우안 영상 전체 휘도차, D L : Total luminance difference of left eye image, D R : Total luminance difference of right eye image,
LC : 좌안 영상 중앙부분 휘도, Le: 좌안 영상 주변부분 평균 휘도, L C : Center luminance of left eye image, L e : Average luminance of peripheral part of left eye image,
RC : 우안 영상 중앙부분 휘도, Re: 우안 영상 주변부분 평균 휘도, R C : luminance at center of right eye image, R e : average luminance at edge of right eye image,
Le1, Le2, …, Le8 : 좌안 영상 주변부분 8 지점의 각 지점별 휘도L e 1, L e 2,... , L e 8: Luminance of each point of 8 points around the left eye image
Re1, Re2, …, Re8 : 우안 영상 주변부분 8 지점의 각 지점별 휘도)R e 1, R e 2,... , R e 8: luminance at each point of 8 points around the right eye image)
이후, 60℃ 250시간 방치한 후 다시 영상을 띄워 휘도를 측정하여 초기 D값과 방치후 D값의 휘도 변화율을 하기 기준에 따라 평가하였다.Thereafter, the image was floated again after being left at 60 ° C. for 250 hours to measure luminance to evaluate the luminance change rate of the initial D value and the D value after standing according to the following criteria.
[휘도 변화율에 따든 입체감 판정 기준][Dimensional Decision Based on Luminance Change Rate]
○: D값 변화율이 0%이상 30%미만일 때 3D 입체감의 위치별 차이가 확인되지 않음○: When the D value change rate is more than 0% and less than 30%, the positional difference of 3D stereoscopic effect is not confirmed
△: D값이 30%이상~60%미만일 때 입체감의 저하가 미미하게 시인됨(Triangle | delta): When the D value is more than 30%-less than 60%, the fall of a three-dimensional feeling is recognized visually.
X: D값이 60%이상일 때 입체감의 저하가 확실히 시인됨X: When the D value is 60% or more, the deterioration of the three-dimensional effect is clearly recognized.
(5) 패턴화된 위상차층의 단위 패턴 간격 변화율 측정(5) Measurement of unit pattern interval variation rate of patterned retardation layer
실험예 (2)와 동일한 방법으로 복합편광판을 제조하고, 32인치 소다글라스에 접합하고 오토클레이브 처리 하였다. 초기 단위패턴의 간격을 측정하고, 60℃에서 250시간 방치한 후 다시 단위패턴의 간격을 측정하여 단위 패턴 간격 변화율을 평가하였다.In the same manner as in Experimental Example (2), a composite polarizing plate was manufactured, bonded to 32-inch soda glass, and subjected to autoclave treatment. The interval of the initial unit pattern was measured, and the unit pattern interval change rate was evaluated by measuring the interval of the unit pattern again after leaving it at 60 ° C. for 250 hours.
표 3
Figure PCTKR2014006577-appb-T000003
 TABLE 3
Figure PCTKR2014006577-appb-T000003
표 3을 참고하면, 실시예 1 내지 8의 점착제 조성물은 박리력이 매우 우수하였다. 또한, 이를 이용하여 접합된 복합 편광판의 내열성 및 내습열성도 매우 우수하고, 위치별 차이 없이 매우 우수한 입체감을 나타냈다. 또한, 패턴화된 위상차층의 단위 패턴 간격 변화율(%)이 (0.13% 이하로 매우 적어 입체감의 전면 균일성 확보가 용이하다. Referring to Table 3, the pressure-sensitive adhesive composition of Examples 1 to 8 was very excellent. In addition, the heat resistance and the heat-and-moisture resistance of the composite polarizing plate bonded using this were also very good, and showed a very good three-dimensional feeling without difference between positions. In addition, the unit pattern interval change rate (%) of the patterned retardation layer is very small (0.13% or less), so that it is easy to secure the front uniformity of the stereoscopic effect.
그러나, 비교예 1 내지 3의 점착제 조성물은 박리력이 떨어지고, 내열성 및 내습열성이 불량하였다. 또한, 단위 패턴 간격 변화율(%)이 0.13% 초과로써 실시예보다 저하된 결과를 보였으며, 특히 비교예 2는 박리력과 내열성 및 내습열성 평가에서, 비교예 3은 입체감 평가에서 현저히 저하된 결과를 나타내었다.However, the adhesive compositions of Comparative Examples 1 to 3 were inferior in peeling force, and were poor in heat resistance and heat and moisture resistance. In addition, the percentage change in the unit pattern interval (%) was more than 0.13%, the results were lower than in the examples, in particular Comparative Example 2 in the peel force and heat resistance and moisture and heat resistance evaluation, Comparative Example 3 was significantly reduced in the three-dimensional evaluation Indicated.

Claims (13)

  1. 탄소수 1 내지 12의 알킬기를 갖는 (메타)아크릴레이트 모노머 및 가교성 관능기를 갖는 모노머를 포함하여 중합된 공중합체; 및 A copolymer polymerized including a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and a monomer having a crosslinkable functional group; And
    상기 가교성 관능기를 갖는 모노머 100 중량부에 대하여 이소시아네이트 가교제 200 내지 2,000중량부;를 포함하는, 점착제 조성물.An adhesive composition comprising; 200 to 2,000 parts by weight of an isocyanate crosslinking agent based on 100 parts by weight of the monomer having a crosslinkable functional group.
  2. 청구항 1에 있어서, 상기 이소시아네이트 가교제는 3관능 이상인, 점착제 조성물.The pressure-sensitive adhesive composition of claim 1, wherein the isocyanate crosslinking agent is at least trifunctional.
  3. 청구항 1에 있어서, 상기 이소시아네이트 가교제는 톨릴렌디이소시아네이트, 자일렌디이소시아네이트, 2,4-디페닐메탄디이소시아네이트, 4,4-디페닐메탄디이소시아네이트, 헥사메틸렌디이소시아네이트, 이소포론디이소시아네이트, 테트라메틸자일렌디이소시아네이트, 나프탈렌디이소시아네이트, 다가 알콜계 화합물 1몰에 디이소시아네이트 화합물 3몰을 반응시킨 부가체, 디이소시아네이트 화합물 3몰을 자기 축합시킨 이소시아누레이트체, 디이소시아네이트 화합물 3몰과 트리메틸올프로판체와의 어덕트체, 디이소시아네이트 화합물 3몰 중 2몰로부터 얻어지는 디이소시아네이트 우레아에 나머지 1몰의 디이소시아네이트가 축합된 뷰렛체, 트리페닐메탄트리이소시아네이트 및 메틸렌비스트리이소시아네이트로 이루어진 군에서 선택되는 적어도 하나인, 점착제 조성물.The method of claim 1, wherein the isocyanate crosslinking agent is tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxyl Adduct obtained by reacting 3 moles of diisocyanate compound with 1 mole of rendiisocyanate, naphthalene diisocyanate, polyhydric alcohol compound, isocyanurate body self-condensing 3 moles of diisocyanate compound, 3 moles of diisocyanate compound and trimethylolpropane At least one selected from the group consisting of adducts with, biurets obtained by condensation of the remaining 1 mole of diisocyanate to diisocyanate urea obtained from 2 moles of 3 moles of the diisocyanate compound, triphenylmethanetriisocyanate and methylenebistriisocyanate Nine, the pressure-sensitive adhesive composition.
  4. 청구항 1에 있어서, 상기 이소시아네이트 가교제는, 자일렌디이소시아네이트, 헥사메틸렌디이소시아네이트 및 이소포론디이소시아네이트 중 적어도 1종의 3몰을 자기 축합시킨 이소시아누레이트체; 및 자일렌디이소시아네이트, 헥사메틸렌디이소시아네이트 및 이소포론디이소시아네이트 중 적어도 1종의 3몰과 트리메틸올프로판체와의 어덕트체로 이루어진 군에서 선택되는 적어도 1종인, 점착제 조성물.The said isocyanate crosslinking agent is an isocyanurate body which self-condensed at least 1 mol of 3 mol of xylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate; And at least one member selected from the group consisting of at least one of 3 moles of xylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate and an adduct of trimethylolpropane.
  5. 청구항 1에 있어서, 상기 탄소수 1 내지 12의 알킬기를 갖는 (메타)아크릴레이트 모노머는, 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, n-프로필 (메타)아크릴레이트, 이소프로필(메타)아크릴레이트, n-부틸 (메타)아크릴레이트, 2-부틸 (메타)아크릴레이트, t-부틸 (메타)아크릴레이트, 2-에틸헥실 (메타)아크릴레이트, 2-에틸부틸 (메타)아크릴레이트, 펜틸 (메타)아크릴레이트, n-옥틸 (메타)아크릴레이트, 이소옥틸 (메타)아크릴레이트, n-노닐 (메타)아크릴레이트, 이소노닐 (메타)아크릴레이트, 데실 (메타)아크릴레이트 및 라우릴 (메타)아크릴레이트로 이루어진 군에서 선택되는 적어도 1종인, 점착제 조성물.The (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth). Acrylate, n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, Pentyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate and lauryl The pressure-sensitive adhesive composition, which is at least one selected from the group consisting of (meth) acrylates.
  6. 청구항 1에 있어서, 상기 가교성 관능기는 히드록시기, 카르복시기, 아미드기 또는 3차 아민기인, 점착제 조성물.The said crosslinkable functional group is an adhesive composition of Claim 1 which is a hydroxyl group, a carboxy group, an amide group, or a tertiary amine group.
  7. 편광자, 및Polarizer, and
    상기 편광자의 일면에 청구항 1 내지 6 중 어느 한 항의 접착제 조성물을 통해 접합된 패턴화된 위상차층을 포함하는, 복합 편광판.A composite polarizing plate comprising a patterned retardation layer bonded to one surface of the polarizer through the adhesive composition of any one of claims 1 to 6.
  8. 청구항 7에 있어서, 상기 편광자는 패턴화된 위상차층과 접합되는 면의 반대면에 보호필름 또는 위상차필름의 기능을 가진 필름이 더 접합된 것인, 복합 편광판.The composite polarizing plate of claim 7, wherein the polarizer is further bonded with a film having a function of a protective film or a retardation film on a surface opposite to the surface to be bonded to the patterned retardation layer.
  9. 청구항 7에 있어서, 상기 패턴화된 위상차층은 에스테르 결합을 포함하는 반응성 액정 모노머를 함유한 액정 코팅층을 포함하는, 복합 편광판.The composite polarizing plate according to claim 7, wherein the patterned retardation layer comprises a liquid crystal coating layer containing a reactive liquid crystal monomer containing an ester bond.
  10. 청구항 7에 있어서, 편광자와 패턴화된 위상차층 사이의 박리력이 3 N/25mm 이상인, 복합 편광판.The composite polarizing plate according to claim 7, wherein the peeling force between the polarizer and the patterned retardation layer is 3 N / 25 mm or more.
  11. 청구항 7에 있어서, 상기 패턴화된 위상차층은 배향막을 포함하지 않는, 복합 편광판.The composite polarizing plate according to claim 7, wherein the patterned retardation layer does not include an alignment film.
  12. 청구항 7에 있어서, 60℃에 250시간 동안 노출된 경우에 패턴화된 위상차층의 단위 패턴 간격 변화율이 0.13%이하인, 복합 편광판.The composite polarizing plate according to claim 7, wherein the unit pattern interval change rate of the patterned retardation layer is 0.13% or less when exposed to 250 ° C. for 250 hours.
  13. 청구항 7의 복합 편광판을 포함하는 화상표시장치.An image display device comprising the composite polarizing plate of claim 7.
PCT/KR2014/006577 2013-08-08 2014-07-21 Adhesive composition and composite polarizing plate using same WO2015020322A1 (en)

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CN113056531A (en) * 2018-11-20 2021-06-29 乐金华奥斯有限公司 Self-repairable coating composition and sheet using same

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KR20120120078A (en) * 2011-04-22 2012-11-01 후지모리 고교 가부시키가이샤 Adhesive composition and surface protection film
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CN113056531B (en) * 2018-11-20 2022-05-31 乐金华奥斯有限公司 Self-repairable coating composition and sheet using same
CN111171766A (en) * 2020-03-17 2020-05-19 苏州世华新材料科技股份有限公司 Ultralow-water-absorption acrylate pressure-sensitive adhesive and preparation method thereof

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