KR101023181B1 - Optical film, protection film for polarizer film, polarizer plate fabricated therefrom, and display device employing thereof - Google Patents
Optical film, protection film for polarizer film, polarizer plate fabricated therefrom, and display device employing thereof Download PDFInfo
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- KR101023181B1 KR101023181B1 KR1020070050754A KR20070050754A KR101023181B1 KR 101023181 B1 KR101023181 B1 KR 101023181B1 KR 1020070050754 A KR1020070050754 A KR 1020070050754A KR 20070050754 A KR20070050754 A KR 20070050754A KR 101023181 B1 KR101023181 B1 KR 101023181B1
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- South Korea
- Prior art keywords
- film
- alkene
- copolymer
- polarizer
- monomer
- Prior art date
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Images
Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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Abstract
본 발명은 알켄 단량체 0.1~30몰%, 아크릴레이트계 단량체 30~99몰% 및 이중결합을 하나 이상 가지는 불포화 유기산 단량체 0.1~50몰%를 포함하는 공중합체를 포함하는 광학필름 및 편광자 보호필름과, 이를 이용한 편광판 및 화상표시장치를 제공한다. The present invention provides an optical film and a polarizer protective film comprising a copolymer comprising an alken monomer 0.1-30 mol%, an acrylate monomer 30-99 mol% and 0.1-50 mol% unsaturated organic acid monomer having one or more double bonds; It provides a polarizing plate and an image display device using the same.
광학필름, 편광자 보호필름, 편광판 Optical film, polarizer protective film, polarizer
Description
도 1 은 비교예 1 에서 얻어진 에틸렌-메틸 메타크릴레이트 공중합체의 수소 핵자기 공명 스펙트럼(1H-NMR spectrum) 이다.1 is a hydrogen nuclear magnetic resonance spectrum ( 1 H-NMR spectrum) of the ethylene-methyl methacrylate copolymer obtained in Comparative Example 1. FIG.
도 2 은 실시예 2 에서 얻어진 에틸렌-메틸 메타크릴레이트-메타크릴산 3원 공중합체의 IR 이다.2 is IR of the ethylene-methyl methacrylate-methacrylic acid terpolymer obtained in Example 2. FIG.
도 3 는 실시예 3 에서 얻어진 에틸렌-메틸 메타크릴레이트-메타크릴산 3원 공중합체에 대한 TGA 결과이다3 is a TGA result for the ethylene-methyl methacrylate-methacrylic acid terpolymer obtained in Example 3;
도 4 는 실시예 4 에서 얻어진 에틸렌-메틸 메타크릴레이트-메타크릴산 3원 공중합체에 대한 주사 열량(DSC) 그래프이다.4 is a scanning calorimetry (DSC) graph of the ethylene-methyl methacrylate-methacrylic acid terpolymer obtained in Example 4. FIG.
도 5 는 실시예 4 에서 얻어진 에틸렌-메틸 메타크릴레이트-메타크릴산 3원 공중합체에 대한 겔투과 크로마토그래피(GPC) 분석결과이다.5 is a gel permeation chromatography (GPC) analysis of the ethylene-methyl methacrylate-methacrylic acid terpolymer obtained in Example 4. FIG.
도 6 은 비교예 1 에서 얻어진 에틸렌-메틸 메타크릴레이트 공중합체의 IR 그래프이다.6 is an IR graph of the ethylene-methyl methacrylate copolymer obtained in Comparative Example 1. FIG.
본 발명은 광학필름, 편광자 보호필름, 이를 이용한 편광판 및 이를 이용한 화상표시장치에 관한 것이다. The present invention relates to an optical film, a polarizer protective film, a polarizing plate using the same, and an image display device using the same.
편광판은 일반적으로 폴리비닐알코올(PVA)계 분자사슬이 일정한 방향으로 배향되고 요오드계 화합물 또는 이색성 편광물질을 포함하는 구조를 갖거나, 폴리비닐알코올 필름의 탈수 반응 또는 폴리비닐클로라이드(PVC) 필름의 탈염산 반응에 의하여 형성된 폴리엔(polyene) 구조를 갖는 편광자에, 보호필름으로서 트리아세틸 셀룰로오스 필름(triacetyl cellulose 필름, 이하 TAC 필름)을 폴리비닐알코올계 수용액으로 이루어진 수계 접착제로 적층시킨 구조를 갖는다.A polarizing plate generally has a structure in which a polyvinyl alcohol (PVA) -based molecular chain is oriented in a predetermined direction and includes an iodine compound or a dichroic polarizing material, or a dehydration reaction of a polyvinyl alcohol film or a polyvinyl chloride (PVC) film A polarizer having a polyene structure formed by the dehydrochlorination reaction of the present invention has a structure in which a triacetyl cellulose film (hereinafter referred to as a TAC film) is laminated with an aqueous adhesive composed of a polyvinyl alcohol-based aqueous solution as a protective film. .
편광자로서 사용된 폴리비닐알코올 필름과 편광자용 보호 필름으로서 사용된 TAC 필름은 모두 내열성과 내습성이 충분하지 않다. 따라서, 상기 필름들로 이루어지는 편광판을 고온 혹은 고습의 분위기하에서 장시간 사용하면, 편광도가 저하되고, 편광자와 보호필름이 분리되거나 광특성이 저하되기 때문에 용도면으로 여러 가지 제약을 받고 있다. 이와 같이 지금까지 실용화되고 있는 편광판은 내열성과 내습성의 신뢰성이 부족하다. 또한, TAC 필름은 주변 온도/습도 환경변화에 따라 기존에 가지고 있는 면내 위상차 (Rin)와 두께 방향 위상차 (Rth)의 변화가 심하며, 특히 경사방향에서의 입사광에 대한 위상차의 변화가 크다. 이와 같은 특성을 갖는 TAC필름을 보호필름으로서 포함하는 편광판을 액정표시장치에 적용하면, 주변 온도/습도 환경의 변화에 따라 시야각 특성이 변화하여 화상품질이 저하되는 문제점이 있다. 또한, TAC 필름은 주변 온도/습도 환경 변화에 따른 치수변화율이 클 뿐만 아니라 광탄성계수 값도 상대적으로 커서, 내열, 내습열 환경에서의 내구성 평가 후 국부적으로 위상차 특성의 변화가 발생하여 화상품질이 저하되기 쉽다. The polyvinyl alcohol film used as a polarizer and the TAC film used as a protective film for polarizers do not have sufficient heat resistance and moisture resistance. Therefore, when the polarizing plate made of the above films is used for a long time in an atmosphere of high temperature or high humidity, the polarization degree is lowered, the polarizer and the protective film are separated, or the optical properties are deteriorated. As described above, the polarizing plates that have been put to practical use thus far lack reliability of heat resistance and moisture resistance. In addition, the TAC film has a great change in the in-plane retardation (Rin) and the thickness direction retardation (Rth) in the existing in accordance with the ambient temperature / humidity environment changes, especially the change in the phase difference with respect to the incident light in the oblique direction. When a polarizing plate including a TAC film having such characteristics as a protective film is applied to a liquid crystal display device, there is a problem in that the viewing angle characteristic changes according to a change in the ambient temperature / humidity environment, thereby degrading image quality. In addition, the TAC film has a large dimensional change rate according to the change of the ambient temperature / humidity environment, and the photoelastic coefficient value is also relatively large, and the image quality is degraded due to the change of the phase difference locally after the durability evaluation in the heat and moisture resistant environment. Easy to be
이러한 TAC 필름의 여러 단점들을 보완하기 위한 소재로서 메타크릴(methacryl)계 수지가 잘 알려져 있다. 하지만 메타크릴(methacryl)계 수지는 부서지거나 갈라지기 쉬워 편광판 생산시 반송성에 문제가 되기 쉽고 생산성이 부족하다고 알려져 있다. Methacrylic (methacryl) resin is well known as a material for compensating for the various disadvantages of the TAC film. However, it is known that methacryl-based resins are brittle or cracked, which is a problem in the carrier property in the production of polarizers and is insufficient in productivity.
이러한 문제를 해결하기 위하여, 아크릴계 수지에 다른 수지나 강인성 개량제 등을 블렌딩하는 방법(일본 특개2006-284881, 일본 특개2006-284882)이나 다른 수지를 공압출하여 적층하는 방법(일본 특개2006-243681, 일본 특개2006-215463, 일본 특개2006-215465, 일본 특개2007-017555)들이 제안되고 있다. 그러나 이런 방법들은 아크릴계 수지가 가지고 있는 본래의 고내열성, 고투명성이 충분히 반영되지 못하거나 복잡한 적층체 구조를 가지고 있는 문제가 있다.In order to solve this problem, a method of blending other resins or toughness modifiers with acrylic resins (Japanese Patent Laid-Open No. 2006-284881, Japanese Patent Laid-Open No. 2006-284882) or a method of co-extrusion and laminating other resins (Japanese Patent Laid-Open No. 2006-243681, Japanese Patent Laid-Open No. 2006-215463, Japanese Patent Laid-Open 2006-215465, and Japanese Patent Laid-Open No. 2007-017555) have been proposed. However, these methods do not sufficiently reflect the inherent high heat resistance and high transparency of the acrylic resin or have a complicated laminate structure.
본 발명은 광학적 투명성 및 광학 특성이 우수할 뿐만 아니라, 부서지기 쉬운 특성(brittleness)이 개선되고, 주변 온도와 습도의 환경 변화에 따른 치수 변화율과 광특성 변화가 적으며, 내구성이 우수한 광학필름 및 이를 이용한 고품질의 편광자 보호필름, 편광판, 화상표시장치를 제공하는 것을 목적으로 한다. The present invention is not only excellent in optical transparency and optical properties, but also in brittleness (brittleness) is improved, the change in the dimensional change rate and optical properties according to the environmental changes of the ambient temperature and humidity, the optical film excellent in durability and An object of the present invention to provide a high quality polarizer protective film, a polarizing plate, an image display device using the same.
상기 목적을 달성하기 위하여, 본 발명은 알켄 단량체 0.1~30몰%, 아크릴레 이트계 단량체 30~99몰% 및 이중결합을 하나 이상 가지는 불포화 유기산 단량체 0.1~50몰%를 포함하는 공중합체를 포함하는 광학필름을 제공한다. In order to achieve the above object, the present invention includes a copolymer comprising 0.1 to 30 mol% of alkene monomers, 30 to 99 mol% of acrylate monomers and 0.1 to 50 mol% of unsaturated organic acid monomers having at least one double bond. It provides an optical film.
또한, 본 발명은 알켄 단량체 0.1~30몰%, 아크릴레이트계 단량체 30~99몰% 및 이중결합을 하나 이상 가지는 불포화 유기산 단량체 0.1~50몰%를 포함하는 공중합체를 포함하는 편광자 보호필름을 제공한다. The present invention also provides a polarizer protective film comprising a copolymer comprising an alken monomer 0.1-30 mol%, an acrylate monomer 30-99 mol% and an unsaturated organic acid monomer 0.1-50 mol% having one or more double bonds. do.
또한, 본 발명은 편광자 및 상기 편광자의 적어도 일면에 구비된 보호필름을 포함하고, 상기 보호필름은 알켄 단량체 0.1~30몰%, 아크릴레이트계 단량체 30~99몰% 및 이중결합을 하나 이상 가지는 불포화 유기산 단량체 0.1~50몰%를 포함하는 공중합체를 포함하는 것을 특징으로 하는 편광판을 제공한다. In addition, the present invention includes a polarizer and a protective film provided on at least one side of the polarizer, the protective film is unsaturated unsaturated having at least one alken monomer 0.1-30 mol%, acrylate monomer 30-99 mol% and a double bond It provides a polarizing plate comprising a copolymer comprising 0.1 to 50 mol% of an organic acid monomer.
또한, 본 발명은 상기 편광판을 포함하는 화상표시장치를 제공한다. In addition, the present invention provides an image display device including the polarizing plate.
이하에서 본 발명에 대하여 상세히 설명한다. Hereinafter, the present invention will be described in detail.
본 발명에 따른 광학필름은 알켄 단량체 0.1~30몰%, 아크릴레이트계 단량체 30~99몰% 및 이중결합을 하나 이상 가지는 불포화 유기산 단량체 0.1~50몰%를 포함하는 공중합체를 포함하는 것을 특징으로 한다. The optical film according to the present invention is characterized in that it comprises a copolymer comprising 0.1-30 mol% of alkene monomers, 30-99 mol% of acrylate monomers and 0.1-50 mol% of unsaturated organic acid monomers having at least one double bond. do.
본 발명에 있어서, 상기 공중합체는 알켄 단량체, 아크릴레이트계 단량체 및 불포화 유기산 단량체가 중합되어 형성되는 공중합체를 일컫는 것으로서, 편의상 단량체들의 용어로 그 구조를 표현한 것이며, 실제로 공중합체의 주쇄 사슬에 단량체들의 이중결합이 그대로 존재하는 것이 아님은 본 발명의 기술분야에서 통상의 지식을 가진 자라면 쉽게 이해할 수 있을 것이다. In the present invention, the copolymer refers to a copolymer formed by polymerization of an alkene monomer, an acrylate monomer and an unsaturated organic acid monomer, and for convenience, expresses its structure in terms of monomers, and actually monomers in the main chain of the copolymer. Of these, the double bond does not exist as it will be readily understood by those of ordinary skill in the art.
본 발명에 있어서, 상기 알켄 단량체로는 특별히 한정되지 않으며, 탄소사슬 의 말단에 이중결합을 가지는 1-알켄, 탄소사슬의 중간에 이중결합을 가지는 2-알켄, 3-알켄 등과 같은 알켄을 포함할 수 있다. In the present invention, the alkene monomer is not particularly limited and may include alkenes such as 1-alkene having a double bond at the end of the carbon chain, 2-alkene having a double bond in the middle of the carbon chain, 3-alkene and the like. Can be.
1-알켄의 예로는, 에틸렌, 프로필렌, 1-부텐, 1-펜텐, 1-헥센, 1-헵텐, 1-옥텐, 1-노넨, 1-데센 등을 들 수 있다. 탄소사슬의 중간에 이중결합을 가지는 알켄의 예로는, 2-부텐, 2-펜텐, 2-헥센, 3-헥센, 2-헵텐, 2-옥텐, 2-노넨 등을 들 수 있다.Examples of 1-alkenes include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like. Examples of the alkenes having a double bond in the middle of the carbon chain include 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 2-octene, 2-nonene and the like.
상기 공중합체 중 상기 알켄 단량체의 함량은 0.1~30몰%, 바람직하기로는 10~30몰%이다. 알켄 단량체 없이 극성기를 포함하는 단량체만으로 중합체가 이루어지는 경우에는 필름을 형성하였을 때 부서지기 쉬운 문제가 있다. 특히 상기 공중합체 중 알켄 단량체의 함량이 10몰% 이상인 것이 광학소재의 적층필름에의 적용시 부서지기 쉬운 문제점이 적다. The content of the alkene monomer in the copolymer is 0.1 to 30 mol%, preferably 10 to 30 mol%. If the polymer is composed of only monomers including polar groups without alken monomers, there is a problem of brittleness when the film is formed. In particular, the content of the alkene monomer in the copolymer of 10 mol% or more is less prone to breakage when applied to the laminated film of the optical material.
본 발명에 있어서, 상기 아크릴레이트계 단량체는 에스테르기의 카보닐기와 공액화된(conjugated) 탄소들 간의 이중결합을 가지는 화합물이면 족하고 그것의 치환기는 특별히 한정되지 않는다. 본 명세서에 기재되는 아크릴레이트계 단량체는 아크릴레이트 뿐만 아니라 아크릴레이트계 유도체를 포함하는 것을 의미하는 것으로서 알킬아크릴레이트, 알킬 메타크릴레이트, 알킬 부타크릴레이트 등을 포함하는 개념으로 이해되어야 한다. In the present invention, the acrylate monomer is sufficient as long as it has a compound having a double bond between the carbonyl group of the ester group and the conjugated (conjugated) carbon and its substituent is not particularly limited. The acrylate-based monomers described herein are to be understood to include not only acrylates but also acrylate-based derivatives, and include concepts such as alkyl acrylates, alkyl methacrylates, alkyl butacrylates, and the like.
구체적으로, 상기 아크릴레이트계 단량체의 예로는 하기 화학식 1로 표시되는 화합물이 포함된다: Specifically, examples of the acrylate-based monomer include a compound represented by the following formula (1):
상기 화학식 1에 있어서,In Formula 1,
R1, R2 및 R3은 서로 같거나 상이하며, 각각 독립적으로 수소원자, 헤테로 원자를 포함할 수 있는 탄소수 1 내지 30의 1가 탄화수소기를 나타내고; R4는 수소원자 또는 탄소수 1 내지 6의 알킬기를 나타낸다.R 1 , R 2 and R 3 are the same as or different from each other, and each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 30 carbon atoms which may include a hetero atom; R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
또 다른 예로서, 아크릴레이트계 단량체는 알킬의 탄소수가 1 내지 12인 직쇄 또는 분지형 알킬기를 포함하는 알킬 아크릴레이트, 알킬의 탄소수가 1 내지 12인 직쇄 또는 분지형 알킬기를 포함하는 알킬 메타크릴레이트, 또는 알킬의 탄소수가 1 내지 12인 직쇄 또는 분지형 알킬기를 포함하는 알킬 부타크릴레이트일 수 있다. As another example, the acrylate monomer may be an alkyl acrylate including a straight or branched alkyl group having 1 to 12 carbon atoms of alkyl, or an alkyl methacrylate including a straight or branched alkyl group having 1 to 12 carbon atoms of alkyl. Or alkyl butyacrylate containing a straight or branched alkyl group having 1 to 12 carbon atoms of alkyl.
상기 공중합체 중 상기 아크릴레이트계 단량체의 함량은 30~99몰%, 바람직하게는 35~99몰% 또는 40~99몰%, 더욱 바람직하게는 50~99몰% 또는 50~95몰%, 가장 바람직하게는 50~90몰%이다. The content of the acrylate monomer in the copolymer is 30 to 99 mol%, preferably 35 to 99 mol% or 40 to 99 mol%, more preferably 50 to 99 mol% or 50 to 95 mol%, most Preferably it is 50-90 mol%.
상기 극성 단량체인 아크릴레이트계 공단량체의 함량이 증가할 경우 알켄, 특히 에틸렌 등의 1-알켄의 고유 물성인 결정성을 방지할 수 있어 무결정성 공중합 체의 제조가 가능하다. 이러한 무결정성의 1-알켄-아크릴레이트계 공중합체는 종래 기술로는 제조하기가 곤란하였다. 상기 무결정성 공중합체는 높은 투명성을 가지며 접착성 등도 우수하기 때문에 광학 소재로서 사용이 가능하며, 특히 극성 작용기를 많이 포함하고 있어 금속 등과의 접착력이 우수하여 전기 소자에의 적용에 유리하다. When the content of the acrylate-based comonomer, which is the polar monomer, increases, it is possible to prevent crystallinity, which is inherent in 1-alkenes such as alkenes, in particular ethylene, to prepare an amorphous copolymer. Such amorphous 1-alkene-acrylate-based copolymers were difficult to manufacture by the prior art. The amorphous copolymer can be used as an optical material because of its high transparency and excellent adhesiveness. In particular, the amorphous copolymer has many polar functional groups, and thus has excellent adhesion to metals, and thus is advantageous for application to electrical devices.
상기 반응에서 아크릴레이트계 공단량체의 양이 단량체 총량을 기준으로 30몰% 미만인 경우에는 접합성과 투명성에 문제가 있고 99몰%를 초과하는 경우에는 부서지기 쉬운 문제가 있다. 또한 상기 공중합체를 광학소재용 적층필름에 적용하기 위해서는 필름 형성시 부서지는 성질을 완화하기 위하여 아크릴레이트계 단량체의 양은 95몰% 이하, 더욱 바람직하게는 90몰% 이하로 조절하는 것이 바람직하다.In the reaction, when the amount of the acrylate-based comonomer is less than 30 mol% based on the total amount of monomers, there is a problem in bonding and transparency, and when it exceeds 99 mol%, there is a problem of brittleness. In addition, in order to apply the copolymer to the laminated film for an optical material, the amount of the acrylate-based monomer is preferably adjusted to 95 mol% or less, more preferably 90 mol% or less in order to alleviate the fracture property during film formation.
본 발명에 있어서, 상기 불포화 유기산 단량체는 이중결합을 하나 이상 가지고 있어 그 이중결합에 의하여 라디칼 중합이 가능한 것을 지칭하며, 특별히 이중결합을 하나 이상 가진다는 한정이 없더라도 특별히 달리 지정하지 않는 한 이중결합을 하나 이상 가지는 것으로 이해되어야 한다. In the present invention, the unsaturated organic acid monomer has one or more double bonds and refers to radical polymerization possible by the double bonds, and unless specifically specified otherwise having one or more double bonds, unless otherwise specified, a double bond It should be understood to have one or more.
상기 불포화 유기산 단량체는 카르복실산을 하나 이상 갖는 것이 바람직하다. 상기 불포화 유기산 단량체는 카르복실기와 공액화된(conjugated) 탄소들 간의 이중결합을 가지는 불포화 카르복실산 화합물이 더욱 바람직하며, 그것들의 치환기는 특별히 한정되지 않는다. 구체적으로 상기 불포화 유기산 단량체로는 아크릴산과 같은 1가 카르복실산, 말레산과 같은 2가 카르복실산 등과 같은 1가 또는 다가 카르복실산이 바람직하게 사용될 수 있으나, 반드시 이것들에 한정되는 것은 아니 다. It is preferable that the said unsaturated organic acid monomer has one or more carboxylic acid. The unsaturated organic acid monomer is more preferably an unsaturated carboxylic acid compound having a double bond between a carboxyl group and conjugated carbons, and their substituents are not particularly limited. Specifically, as the unsaturated organic acid monomer, monovalent or polyvalent carboxylic acids such as monovalent carboxylic acids such as acrylic acid and divalent carboxylic acids such as maleic acid may be preferably used, but are not necessarily limited thereto.
상기 불포화 유기산 단량체가 아크릴산인 경우에, 그 아크릴산은 아래 화학식 2로 표시되는 아크릴산 화합물인 것이 바람직하지만, 알킬 메타아크릴산과 같은 다른 아크릴산 유도체도 사용될 수 있다:When the unsaturated organic acid monomer is acrylic acid, the acrylic acid is preferably an acrylic acid compound represented by the following formula (2), but other acrylic acid derivatives such as alkyl methacrylic acid may also be used:
상기 화학식 2에 있어서, In Chemical Formula 2,
R6는 수소원자 또는 탄소수 1 내지 6의 알킬기를 나타낸다.R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
상기 2가 카르복실산으로는 말레산, 최소한 하나의 알킬기가 치환된 말레산 유도체 등을 들 수 있다. Examples of the divalent carboxylic acid include maleic acid and maleic acid derivatives substituted with at least one alkyl group.
상기 공중합체 중 상기 불포화 유기산 단량체의 함량은 0.1~50몰%, 바람직하게는 0.1~30몰%이다. 이러한 불포화 유기산 단량체를 공중합체의 성분으로 도입하면, 공중합체가 높은 유리전이온도를 가지게 되고, 친수성 작용기로 인하여 접착성 등도 우수하게 되기 때문에 광학소재로서 사용이 가능하다. The content of the unsaturated organic acid monomer in the copolymer is 0.1 to 50 mol%, preferably 0.1 to 30 mol%. When the unsaturated organic acid monomer is introduced as a component of the copolymer, the copolymer has a high glass transition temperature, and because of its excellent adhesiveness due to hydrophilic functional groups, it can be used as an optical material.
전술한 단량체들의 반복단위들로 구성되는 공중합체는 하기 화학식 3으로 표시되는 반복단위를 포함할 수 있다:The copolymer composed of repeating units of the aforementioned monomers may include repeating units represented by the following Formula 3:
상기 화학식 3에 있어서,In
a, b 및 c 는 몰비로서, a, b 및 c가 모두 0은 아니고, a, b and c are molar ratios, where a, b and c are not all zero,
R1 내지 R4 및 R6은 전술한 바와 같고, R5는 수소원자 또는 탄소수 1 내지 6의 알킬기이다. R 1 to R 4 and R 6 are as described above, and R 5 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
상기 공중합체는 랜덤 공중합체일 수 있으며, 이 경우 상기 화학식 3으로 표시되는 다양한 반복단위를 포함할 수 있다. The copolymer may be a random copolymer, in which case it may include various repeating units represented by the formula (3).
상기 공중합체는 유리 전이 온도가 80~220℃ 범위, 바람직하게는 100~220℃ 범위의 유리전이온도(Tg)를 가진다. 상기 공중합체가 광학소재용으로 효과적으로 사용되기 위해서는 100℃ 이상의 유리전이온도를 가지는 것이 바람직하다. 또한, 상기 공중합체는 5,000 내지 400,000 범위의 수평균 분자량 또는 10,000 내지 800,000 범위의 중량평균 분자량을 가지는 것이 바람직하고, 공중합체의 초기 중량의 50%가 분해되는 온도(Td50)가 350 내지 550℃의 범위를 가지는 것이 바람직하다.The copolymer has a glass transition temperature (Tg) in the range of 80 to 220 ° C, preferably in the range of 100 to 220 ° C. In order for the copolymer to be effectively used for an optical material, the copolymer preferably has a glass transition temperature of 100 ° C. or higher. In addition, the copolymer preferably has a number average molecular weight in the range of 5,000 to 400,000 or a weight average molecular weight in the range of 10,000 to 800,000, and the temperature (Td50) at which 50% of the initial weight of the copolymer is decomposed is 350 to 550 ° C. It is desirable to have a range.
전술한 공중합체는 전술한 단량체들의 공중합체로서 극성기의 함유량이 월등히 높아 에틸렌과 같은 알켄의 결정성이 존재하지 않게 되므로, 고분자 필름 등으로 가공한 후에도 투명하며, 아크릴산과 같은 불포화 유기산을 포함하므로 높은 유리전이온도를 가지며 접착성이 개선되어 편광판을 포함하는 다층구조의 광학필름의 용도에 적합하게 사용될 수 있다. The above-mentioned copolymer is a copolymer of the above-described monomers, so that the content of the polar group is very high so that the crystallinity of alkenes such as ethylene does not exist, and thus it is transparent even after processing into a polymer film or the like, and thus contains an unsaturated organic acid such as acrylic acid. It has a glass transition temperature and improves adhesiveness, and thus may be suitably used for the use of an optical film having a multilayer structure including a polarizing plate.
또한, 본 명세서에서 기재되는 알켄-아크릴레이트-불포화 유기산 공중합체는 그 단량체 성분으로서 1종의 알켄, 1종의 아크릴레이트 및 1종의 불포화 유기산으로 조성될 수 있을 뿐만 아니라, 상기 알켄, 아크릴레이트 및 불포화 유기산 중 적어도 하나가 2종 이상으로 조성될 수 있다. 또한, 상기 중합체의 물성의 범위 및 본 발명의 목적을 벗어나지 않는다면, 공단량체를 추가적으로 포함할 수 있다. 공단량체의 예로는 말레이미드, 메틸말레이미드, 에틸말레이미드, 부타디엔, 스틸렌 등을 들 수 있다.In addition, the alkene-acrylate-unsaturated organic acid copolymer described herein may be composed of one alkene, one acrylate and one unsaturated organic acid as its monomer component, as well as the alkene, acrylate And at least one of unsaturated organic acids may be composed of two or more kinds. In addition, without departing from the scope of the physical properties of the polymer and the object of the present invention, it may further comprise a comonomer. Examples of the comonomers include maleimide, methyl maleimide, ethyl maleimide, butadiene, styrene and the like.
상기 공중합체는 알켄 단량체, 아크릴레이트계 단량체 및 이중결합을 하나 이상 가지는 불포화 유기산 단량체를 루이스산 또는 금속산화물 존재하에서 라디칼 중합개시제에 의하여 중합시키는 단계를 포함하는 방법에 의하여 제조될 수 있다. The copolymer may be prepared by a method comprising polymerizing an alkene monomer, an acrylate monomer, and an unsaturated organic acid monomer having at least one double bond with a radical polymerization initiator in the presence of a Lewis acid or a metal oxide.
상기 금속산화물은 중합반응에서 실질적으로 산점(acid site)를 제공하는 루이스산과 같은 역할을 하므로 개념상 루이스산에 포함되는 것이다. 그러나, 일반적인 다른 루이스산과 비교하여 중합반응 후에도 실질적으로 그 구조나 조성의 변화가 없어, 간단하게 분리가 가능할 뿐만 아니라 재사용이 가능하다는 추가적 이점이 있기 때문에, 본 명세서에서는 편의상 일반적인 다른 루이스산과 구별하여 금속산 화물 또는 복합금속산화물이라고 명명하기로 한다. The metal oxide is conceptually included in the Lewis acid because it serves as a Lewis acid which provides an acid site in the polymerization reaction. However, compared to other Lewis acids in general, there is no change in structure or composition substantially after the polymerization reaction, and thus, there is an additional advantage that not only can be easily separated but also reused. It is called an oxide or a complex metal oxide.
상기 금속산화물은 하기 화학식 4로 표시되는 화합물인 것이 바람직하다:The metal oxide is preferably a compound represented by the following formula (4):
상기 화학식 4에 있어서,In Chemical Formula 4,
M은 알칼리 토금속, 전이금속, 13족, 및 14족 금속으로 이루어진 그룹 중에서 선택된 하나 이상을 나타내고;M represents at least one selected from the group consisting of alkaline earth metals, transition metals, group 13, and group 14 metals;
N은 5족 또는 6족 원자를 나타내며;N represents a Group 5 or 6 atom;
O는 산소원자를 나타내고;O represents an oxygen atom;
x, y 및 z는 M 및 N의 산화 상태에 의하여 결정되는 값으로,x, y and z are values determined by the oxidation state of M and N,
x > 0이고, y ≥ 0이며, z > 0이다.x> 0, y> 0, and z> 0.
더욱 구체적으로, 상기 금속산화물은 산화 알루미늄(Al2O3), 산화 이트륨(Y2O3), 산화 아연(ZrO2), 산화 하프뮴(HfO2), 산화 규소(SiO2), 산화보론(B2O3), 산화 세슘(CeO2), 산화 디스프로슘(Dy2O3), 산화 에르븀(Er2O3), 산화 유로퓸(Eu2O3), 산화 가돌리늄(Gd2O3), 산화홀뮴(Ho2O3), 산화란탄(La2O3), 산화 루테튬(Lu2O3), 산화 네오디뮴(Nd2O3), 산화 프라세오디뮴(Pr6O11), 산화 사마륨(Sm2O3), 산화 테르븀(Tb2O3), 산화 토륨(Th4O7), 산화 툴륨(Tm2O3), 산화 이테르븀(Yb2O3), 산화 주석(SnO), 및 산화 티타늄(TiO2)과 같은 금속산화물과, 디스프로슘 알루미네이 트(Dy3Al5O12), 이트늄 알루미네이트(Y3Al5O12), 알루미늄 티타네이트(Al2O3·TiO2), 알루미늄 실리케이트 (3Al2O3·2SiO2), 칼슘 티타네이트(CaTiO3), 칼슘 지르코네이트(CaZrO3), 철 티타네이트(FeTiO3), 마그네슘 알루미네이트(MgO·Al2O3), 세슘 알루미네이트(CeAl11O18), Al2(SO4)3, 및 AlPO4와 같은 복합금속산화물로 이루어진 군에서 선택된 하나 이상인 것이 바람직하다.More specifically, the metal oxide is aluminum oxide (Al 2 O 3 ), yttrium oxide (Y 2 O 3 ), zinc oxide (ZrO 2 ), hafnium oxide (HfO 2 ), silicon oxide (SiO 2 ), boron oxide (B 2 O 3 ), cesium oxide (CeO 2 ), dysprosium oxide (Dy 2 O 3 ), erbium oxide (Er 2 O 3 ), europium oxide (Eu 2 O 3 ), gadolinium oxide (Gd 2 O 3 ), Holmium oxide (Ho 2 O 3 ), lanthanum oxide (La 2 O 3 ), ruthetium oxide (Lu 2 O 3 ), neodymium oxide (Nd 2 O 3 ), praseodymium oxide (Pr 6 O 11 ), samarium oxide (Sm 2 O 3 ), terbium oxide (Tb 2 O 3 ), thorium oxide (Th 4 O 7 ), thorium oxide (Tm 2 O 3 ), ytterbium oxide (Yb 2 O 3 ), tin oxide (SnO), and titanium oxide ( Metal oxides such as TiO 2 ), dysprosium aluminate (Dy 3 Al 5 O 12 ), yttnium aluminate (Y 3 Al 5 O 12 ), aluminum titanate (Al 2 O 3 · TiO 2 ), aluminum silicate (3Al 2 O 3 · 2SiO 2 ), calcium titanate (CaTiO 3 ), calcium zirconate (CaZrO 3 ), iron Selected from the group consisting of complex metal oxides such as titanate (FeTiO 3 ), magnesium aluminate (MgOAl 2 O 3 ), cesium aluminate (CeAl 11 O 18 ), Al 2 (SO 4 ) 3 , and AlPO 4 It is preferred that there is at least one.
상기 금속산화물은 여과 장치만을 사용하는 물리적인 방법으로도 100 % 가까이 회수할 수 있고, 회수된 금속 산화물을 다시 중합에 사용할 수 있기 때문에, 경제적일 뿐만 아니라, 생성되는 공중합체를 고순도로 얻을 수 있다는 장점이 있다. 회수된 금속산화물은 통상적으로 20회 정도는 재사용할 수 있다. The metal oxide can be recovered to near 100% even by a physical method using only a filtration device, and since the recovered metal oxide can be used for polymerization again, it is not only economical but also high-purity copolymer can be obtained. There is an advantage. The recovered metal oxide can generally be reused about 20 times.
상기 루이스산으로는, 스칸듐, 티타늄, 바나듐, 크롬, 망간, 철, 코발트, 구리, 아연, 붕소, 알루미늄, 이트륨, 지르코늄, 니오븀, 몰리브덴, 카드늄, 레늄 및 주석으로 이루어진 군에서 선택된 하나 이상의 금속 양이온을 포함하여 형성되는 루이스산인 것이 바람직하고, 할라이드, 트리플레이트(triflate), HPO3 2-, H3PO2-, CF3COO-, C7H15OSO2- 및 SO4 2-로 이루어진 군에서 선택된 하나 이상의 음이온을 포함하는 것이 바람직하다. 더욱 구체적으로, 알루미늄 트리클로라이드, 스칸듐 트리플레이트, 아연 트리플레이트, 구리 트리플레이트, 트리플루오르보론, 이들의 2 이상의 혼합물 등인 것이 바람직하다.The Lewis acid includes at least one metal cation selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium, rhenium, and tin. a Lewis acid is preferable to be formed, including, and halide, triflate (triflate), HPO 3 2-, H 3 PO 2 -, CF 3 COO -, C 7 H 15 OSO 2 - and the group consisting of SO 4 2- It is preferable to include at least one anion selected from. More specifically, it is preferable that they are aluminum trichloride, scandium triflate, zinc triflate, copper triflate, trifluoroboron, a mixture of two or more thereof.
상기 공중합체의 제조방법에서, 상기 금속산화물 또는 상기 루이스산은 아크릴레이트계 공단량체를 기준으로 0.01~ 200몰% 사용되는 것이 바람직하다.In the method of preparing the copolymer, the metal oxide or the Lewis acid is preferably used in an amount of 0.01 to 200 mol% based on the acrylate comonomer.
상기 금속산화물 또는 루이스산을 사용함으로써, 제조되는 상기 공중합체에 반복단위로 포함되는 단량체들의 함량을 요구되는 물성에 따라 적절하게 조절 및 제어할 수 있다. 특히 에틸렌 또는 프로필렌과 같이 반응조건에서 기체상으로 존재하는 알켄 단량체가 용매에 일부 용해되어 중합반응에 참여하는 경우, 금속산화물 또는 루이스산은 제조되는 공중합체의 요구되는 물성에 필요한 적정량의 알켄 단량체가 중합되도록 조절하는 역할을 할 수 있고, 또한 종래기술에 비하여 저온저압에서 중합반응이 이루어지게 하는 역할을 한다. By using the metal oxide or Lewis acid, it is possible to appropriately control and control the content of the monomers contained in the repeating unit in the copolymer produced according to the required physical properties. Particularly when the alkene monomer present in the gas phase under the reaction conditions such as ethylene or propylene is partially dissolved in the solvent to participate in the polymerization reaction, the metal oxide or Lewis acid is polymerized in an appropriate amount of the alkene monomer necessary for the required physical properties of the copolymer prepared. It may serve to control as possible, and also serves to make the polymerization reaction at a low temperature low pressure compared to the prior art.
상기 라디칼 중합개시제로는 과산화물, 아조 화합물 등인 것이 바람직하다. 더욱 구체적으로, 과산화물 화합물의 예로 과산화수소, 데카노닐 퍼옥시드, t-부틸 퍼옥시 네오데카노에이트, t-부틸 퍼옥시 피발레이트, 3,5,5-트리메틸 헥사노일 퍼옥시드, 디에틸 퍼옥시드, t-부틸 퍼옥시-2-에틸 헥사노에이트, t-부틸 퍼옥시 이소부티레이트, 벤조일 퍼옥시드, t-부틸 퍼옥시 아세테이트, t-부틸 퍼옥시 벤조에이트, 디-t-부틸 퍼옥시드, t-아밀 퍼옥시 네오데카노에이트, t-아밀 퍼옥시 피발레이트, t-아밀 퍼옥시-2-에틸 헥사노에이트, 1,1,3,3-테트라메틸 부틸 히드로퍼옥시드, 알칼리 금속 퍼설페이트, 퍼보레이트 및 퍼카르보네이트를 들 수 있고, 아조 화합물의 예로 2,2'-아조-비스(이소부티로니트릴)(AIBN)(2,2'-azo-bis(isobutyronitrile))과 같은 아조 화합물을 들 수 있다. 바람직한 개시제는 아조 화합물이다. 이러한 개시제들의 혼합물을 사용할 수도 있다. It is preferable that it is a peroxide, an azo compound, etc. as said radical polymerization initiator. More specifically, examples of the peroxide compound include hydrogen peroxide, decanonyl peroxide, t-butyl peroxy neodecanoate, t-butyl peroxy pivalate, 3,5,5-trimethyl hexanoyl peroxide, diethyl peroxide t-butyl peroxy-2-ethyl hexanoate, t-butyl peroxy isobutyrate, benzoyl peroxide, t-butyl peroxy acetate, t-butyl peroxy benzoate, di-t-butyl peroxide, t Amyl peroxy neodecanoate, t-amyl peroxy pivalate, t-amyl peroxy-2-ethyl hexanoate, 1,1,3,3-tetramethyl butyl hydroperoxide, alkali metal persulfate, Perborate and percarbonate, and examples of azo compounds include azo compounds such as 2,2'-azo-bis (isobutyronitrile) (AIBN) (2,2'-azo-bis (isobutyronitrile)). Can be mentioned. Preferred initiators are azo compounds. Mixtures of such initiators may also be used.
상기 라디칼 중합개시제는 임의의 적절한 방식으로, 예컨대 순수한 형태, 적절한 용매에 용해된 형태 및/또는 단량체 또는 공단량체 공급물 스트림과 혼합된 형태로 반응 스트림에 첨가할 수 있다. 상기 공중합체를 제조함에 있어서 사용되는 라디칼 중합개시제는 상기 아크릴레이트계 단량체를 기준으로 0.01~10몰% 범위로 첨가되는 것이 바람직하나, 반드시 이에 한정되는 것은 아니며 필요에 따라 적절히 사용할 수 있다.The radical polymerization initiator can be added to the reaction stream in any suitable manner, such as in pure form, in dissolved form in a suitable solvent and / or in admixture with a monomer or comonomer feed stream. The radical polymerization initiator used in preparing the copolymer is preferably added in the range of 0.01 to 10 mol% based on the acrylate monomer, but is not necessarily limited thereto, and may be appropriately used if necessary.
상기 공중합체의 중합반응은 용매, 특히 유기용매에서 수행되는 것이 바람직하다. 그러한 용매의 예는 톨루엔, 클로로벤젠, n-헥산, 헵탄, 테트라하이드로퓨란, 에테르, 메탄올, 에탄올, 클로로포름, 및 메틸렌클로라이드로 이루어진 군에서 선택된 하나 이상의 용매인 것이 바람직하지만, 반드시 이에 한정되는 것은 아니다. 즉, 본 발명의 기술분야에서 사용 가능한 용매라면 특별히 한정되는 것은 아니다.The polymerization of the copolymer is preferably carried out in a solvent, in particular an organic solvent. Examples of such solvents are preferably, but not necessarily limited to, one or more solvents selected from the group consisting of toluene, chlorobenzene, n-hexane, heptane, tetrahydrofuran, ether, methanol, ethanol, chloroform, and methylene chloride. . That is, the solvent that can be used in the technical field of the present invention is not particularly limited.
상기 중합반응에 있어서, 아크릴레이트계 단량체 및 불포화 유기산 단량체는 반응조건 하에서 일반적으로 액상으로 존재하기 때문에 용매에 용해되어 중합반응에 참여한다. 따라서, 전술한 공중합체에 포함되는 단량체들이 반응조건에서 액상으로 존재할 수 있는 것이라면 반응압력은 특별히 한정되지 않는다. In the polymerization reaction, the acrylate monomer and the unsaturated organic acid monomer are generally present in the liquid phase under the reaction conditions, so that they are dissolved in a solvent and participate in the polymerization reaction. Therefore, the reaction pressure is not particularly limited as long as the monomers included in the aforementioned copolymer may exist in the liquid phase under the reaction conditions.
한편, 알켄 단량체는 특히 에틸렌과 프로필렌의 경우에는 반응조건에서 일반적으로 기체 상태로 존재하기 때문에, 알켄 단량체를 본 발명의 공중합체의 반복단위에 적정량으로 함유시키기 위해서는 가압의 반응조건이 요구되지만, 상기 알켄 단량체가 반응조건에서 액상으로 존재하는 경우라면 반응압력은 특별히 한정되지 않는다.On the other hand, since the alkene monomer is generally present in the gaseous state under the reaction conditions, especially in the case of ethylene and propylene, in order to contain the alkene monomer in an appropriate amount in the repeating unit of the copolymer of the present invention, the reaction conditions under pressure are required. If the alkene monomer is present in the liquid phase under the reaction conditions, the reaction pressure is not particularly limited.
상기 중합반응은, 1000기압 이상 및 100℃ 이상 고온고압의 가혹한 반응조건을 요하는 종래기술과는 달리, 200기압 이하 및 150℃ 이하, 바람직하게는 50기압 이하 및 100℃ 이하의 온화한 조건에서도 수행될 수 있어, 공정이 단순하고, 제조되는 공중합체의 물성 제어가 용이하다. 또한, 상기 금속 산화물은 특히 수분 안전성이 뛰어나 효율적이며 재활용이 가능하다.The polymerization reaction is carried out under mild conditions of 200 atm and 150 ° C or less, preferably 50 atm or less and 100 ° C or less, unlike the prior art which requires harsh reaction conditions of at least 1000 atm and at least 100 ° C and high temperature and high pressure. The process can be simple, and the physical properties of the copolymer produced can be easily controlled. In addition, the metal oxide is particularly excellent in water safety, efficient and recyclable.
구체적으로, 상기 공중합체의 중합을 위한 반응 조건은, 알켄 단량체가 반응조건에서 기체상인 경우, 중합반응이 5 내지 200 기압의 압력 및 30 내지 150℃의 온도 조건에서 이루어지는 것이 바람직하고, 특히 바람직하게는 상기 반응이 20 내지 50 기압의 압력 및 50 내지 80℃의 온도 조건에서 수행된다. Specifically, the reaction conditions for the polymerization of the copolymer, when the alkene monomer is gaseous in the reaction conditions, the polymerization reaction is preferably made at a pressure of 5 to 200 atm and temperature conditions of 30 to 150 ℃, particularly preferably The reaction is carried out at a pressure of 20 to 50 atm and a temperature of 50 to 80 ℃.
본 발명의 한 구체적인 구현예는 알켄 단량체로서 에틸렌 또는 프로필렌, 아크릴레이트계 단량체로서 메틸 메타크릴레이트 또는 메틸아크릴레이트, 불포화 유기산 단량체로서 메타크릴산 또는 아크릴산, 금속산화물로서 산화알루미늄을 사용하여 5 내지 50기압의 압력과 50 내지 80℃의 온도에서 AIBN을 중합개시제로 하여 중합하는 것이다. One specific embodiment of the invention is 5 to 50 using ethylene or propylene as an alkene monomer, methyl methacrylate or methylacrylate as an acrylate monomer, methacrylic acid or acrylic acid as unsaturated organic acid monomer, and aluminum oxide as metal oxide. The polymerization is carried out using AIBN as a polymerization initiator at a pressure of atmospheric pressure and a temperature of 50 to 80 ° C.
상기 공중합체 중에서 알켄-아크릴레이트-아크릴산 3원 공중합체는 알켄-아크릴레이트 2원 공중합체를 부분적으로 가수분해하여 제조될 수도 있다. 부분적 가수분해는 가수분해를 위한 산 또는 염기 촉매의 종류 및 반응매질의 종류를 적절하게 선택하여 통상적인 가수분해를 위한 반응조건 하에서 수행될 수 있다. 이 경우, 원료로서 사용되는 알켄-아크릴레이트 2원 공중합체에서 아크릴레이트의 함량은 생 성되는 3원 공중합체의 아크릴레이트와 아크릴산의 함량의 합이어야 하며, 또한 최종적인 3원 공중합체에서 요구되는 단량체 함량비가 성립할 수 있도록 적절하게 가수분해 조건이 설정되어야 한다. 이러한 가수분해 조건은 가수분해를 위한 산 또는 염기 촉매의 종류, 반응매질의 종류, 반응온도, 반응압력, 반응시간 등을 포함할 수 있으며, 당기술분야에서 통상의 지식을 가지는 자라면 실험적 방법에 의하여 얻을 수 있는 가수분해율을 참고하여 적절하게 선택할 수 있을 것이다.The alkene-acrylate-acrylic acid terpolymer in the copolymer may be prepared by partially hydrolyzing the alkene-acrylate binary copolymer. Partial hydrolysis can be carried out under reaction conditions for conventional hydrolysis by appropriately selecting the type of acid or base catalyst and the reaction medium for hydrolysis. In this case, the content of acrylate in the alkene-acrylate binary copolymer used as raw material should be the sum of the content of acrylate and acrylic acid of the tertiary copolymer to be produced and is also required in the final terpolymer. Proper hydrolysis conditions must be set so that the monomer content ratio can be established. Such hydrolysis conditions may include the type of acid or base catalyst for hydrolysis, the type of reaction medium, the reaction temperature, the reaction pressure, the reaction time, and the like. By selecting the hydrolysis rate can be appropriately selected.
전술한 공중합체를 이용하여 본 발명에 따른 광학필름을 제작하는 방법은 특별히 한정되어 있는 것은 아니며, 예컨대 용융 압출법, 캘린더 제막법, 용액 캐스트 제막법 등을 이용할 수 있다. 상기 용융 압출법은 공중합체를 실린더 중에서 가열 용융하고, 스크류로 가압한 후, T 다이 등의 다이로부터 밖으로 배출하는 방법이다. 용융 압출 온도에 대해서 설명하면, 압출기 내부 온도는 압출기 주입구에서부터 230℃, 240℃, 240℃, 245℃이며, 다이(Die) 온도는 250℃로 하는 것이 바람직하다. 상기 용액 캐스트 제막법은 유기용매로 공중합체 수지 용액을 제조한 후, 제막하고, 용매를 건조시키고, 권취하는 방법이다.The method for producing the optical film according to the present invention using the copolymer described above is not particularly limited, and for example, a melt extrusion method, a calender film forming method, a solution cast film forming method, or the like can be used. The melt extrusion method is a method in which a copolymer is heated and melted in a cylinder, pressurized with a screw, and then discharged out from a die such as a T die. Referring to the melt extrusion temperature, the extruder internal temperature is 230 ° C, 240 ° C, 240 ° C, 245 ° C from the extruder inlet, and the die temperature is preferably 250 ° C. The said solution cast film forming method is a method of manufacturing a copolymer resin solution with an organic solvent, then forming into a film, drying a solvent, and winding up.
상기 광학필름을 제조하기 위해서 공중합체 수지에 일반적인 첨가제, 예를 들면 가소제, 윤활제, 충격완화제, 안정제, 자외선흡수제 등을 첨가될 수 있다. 특히, 본 발명에 따른 광학필름이 편광자의 보호필름으로 사용되는 경우, 편광자 및 액정패널을 외부 자외선으로부터 보호하기 위하여, 상기 공중합체 수지에 자외선흡수제를 첨가할 수 있다. 자외선 흡수제의 종류는 특별히 한정되어 있지 않지만, 벤조트리아졸계 자외선흡수제, 트리아진계 자외선 흡수제의 사용이 바람직하다. 바람 직하게로는 Tinuvin P 및 Tinuvin 360이 사용될 수 있다. 열안정제로는 Iganox 259, Iganox 1010 등이 첨가될 수 있다. In order to manufacture the optical film, general additives such as plasticizers, lubricants, impact modifiers, stabilizers, ultraviolet absorbers, and the like may be added to the copolymer resin. In particular, when the optical film according to the present invention is used as a protective film of the polarizer, in order to protect the polarizer and the liquid crystal panel from external ultraviolet rays, an ultraviolet absorber may be added to the copolymer resin. Although the kind of ultraviolet absorber is not specifically limited, The use of a benzotriazole type ultraviolet absorber and a triazine type ultraviolet absorber is preferable. Preferably Tinuvin P and Tinuvin 360 can be used. As the heat stabilizer, Iganox 259, Iganox 1010, or the like may be added.
전술한 바와 같은 공중합체를 포함하는 광학필름은 광투과도, 유리 전이 온도 및 인성이 높은 공중합체 수지를 사용하여 제조되므로, 높은 광학적 투명성을 가지며, 극성 작용기를 가지는 단량체의 함량이 높아 접착성이 우수하므로 편광판 등과 같은 적층 필름으로 사용하기에 적합하다. 또한, 본 발명에 따른 광학필름은 우수한 광학 특성을 가질 뿐만 아니라, 온도 및 습도에 따른 치수 변화율과 광특성 변화가 적어 다양한 광학용 필름으로 사용이 가능하다. Since the optical film including the copolymer as described above is manufactured using a copolymer resin having high light transmittance, glass transition temperature and toughness, the optical film has high optical transparency and excellent adhesion due to the high content of monomer having polar functional groups. Therefore, it is suitable for use as a laminated film such as a polarizing plate. In addition, the optical film according to the present invention not only has excellent optical properties, but also changes in dimensional change rate and optical properties according to temperature and humidity, and thus can be used as various optical films.
또한, 본 발명은 알켄 단량체 0.1~30몰%, 아크릴레이트계 단량체 30~99몰% 및 이중결합을 하나 이상 가지는 불포화 유기산 단량체 0.1~50몰%를 포함하는 공중합체를 포함하는 편광자 보호필름을 제공한다. The present invention also provides a polarizer protective film comprising a copolymer comprising an alken monomer 0.1-30 mol%, an acrylate monomer 30-99 mol% and an unsaturated organic acid monomer 0.1-50 mol% having one or more double bonds. do.
본 발명에 따른 편광자 보호필름의 두께는 20 내지 200μm인 것이 바람직하다.The thickness of the polarizer protective film according to the present invention is preferably 20 to 200μm.
본 발명에 따른 편광자 보호필름은 접착력 향상을 위해 보호필름의 표면을 개질할 수 있다. 개질 방법으로는 코로나 처리, 플라즈마 처리, UV 처리 등으로 보호필름의 표면을 처리하는 방법과 보호필름의 표면에 프라이머층을 형성하는 방법 등이 있고, 상기 두 방법을 동시에 사용할 수도 있다. 프라이머의 종류는 특별히 한정되지 않지만 실란커플링제와 같이 반응성 관능기를 가지는 화합물을 사용하는 것이 바람직하다.The polarizer protective film according to the present invention can modify the surface of the protective film to improve the adhesion. Modification methods include a method of treating the surface of the protective film by corona treatment, plasma treatment, UV treatment, and the like to form a primer layer on the surface of the protective film, and the above two methods may be used at the same time. Although the kind of primer is not specifically limited, It is preferable to use the compound which has a reactive functional group like a silane coupling agent.
또한, 본 발명은 편광자 및 상기 편광자의 적어도 일면에 구비된 보호필름을 포함하고, 상기 보호필름은 알켄 단량체 0.1~30몰%, 아크릴레이트계 단량체 30~99몰% 및 이중결합을 하나 이상 가지는 불포화 유기산 단량체 0.1~50몰%를 포함하는 공중합체를 포함하는 것을 특징으로 하는 편광판을 제공한다. In addition, the present invention includes a polarizer and a protective film provided on at least one side of the polarizer, the protective film is unsaturated unsaturated having at least one alken monomer 0.1-30 mol%, acrylate monomer 30-99 mol% and a double bond It provides a polarizing plate comprising a copolymer comprising 0.1 to 50 mol% of an organic acid monomer.
본 발명에 있어서, 상기 편광자로는 당기술분야에 알려져 있는 것을 제한되지 않고 사용할 수 있으며, 예컨대 요오드 또는 이색성 염료를 포함하는 폴리비닐알콜(PVA)로 이루어진 필름을 사용할 수 있다. 상기 편광자는 PVA 필름에 요오드 또는 이색성 염료를 염착시켜서 제조될 수 있으나, 이의 제조방법은 특별히 한정되지 않는다. 본 명세서에 있어서, 편광자는 보호 필름을 포함하지 않는 상태를 의미하며, 편광판은 편광자와 보호 필름을 포함하는 상태를 의미한다. In the present invention, as the polarizer can be used without limitation what is known in the art, for example, a film made of polyvinyl alcohol (PVA) containing iodine or dichroic dye can be used. The polarizer may be prepared by dyeing iodine or dichroic dye on the PVA film, but a method of manufacturing the same is not particularly limited. In the present specification, the polarizer means a state not including a protective film, and the polarizing plate means a state including a polarizer and a protective film.
상기 편광자와 보호필름의 접착은 접착제층을 이용하여 수행할 수 있다. 상기 보호 필름과 편광판의 합지시 사용가능한 접착제로는 당기술분야에 알려져 있는 것이면 특별히 제한되지 않는다. 예컨대 일액형 또는 이액형의 폴리비닐알콜(PVA)계 접착제, 폴리우레탄계 접착제, 에폭시계 접착제, 스티렌 부타디엔 고무계(SBR계) 접착제, 또는 핫멜트형 접착제 등이 있으나, 이들 예에만 한정되지 않는다. Adhesion of the polarizer and the protective film may be performed using an adhesive layer. The adhesive usable in lamination of the protective film and the polarizing plate is not particularly limited as long as it is known in the art. For example, there are one- or two-component polyvinyl alcohol (PVA) adhesives, polyurethane adhesives, epoxy adhesives, styrene butadiene rubber (SBR) adhesives, and hot melt adhesives, but are not limited to these examples.
상기 접착제 중 폴리비닐알콜계 접착제가 바람직하며, 특히 아세트아세틸기를 함유하는 폴리비닐알코올계 수지 및 아민계 금속화합물 가교제를 포함하는 접착제를 사용하는 것이 바람직하다. 상기 편광판용 접착제는 상기 아세트아세틸기를 함유하는 폴리비닐알코올계 수지 100 중량부 및 상기 아민계 금속화합물 가교제 1 내지 50 중량부를 포함할 수 있다. Among the adhesives, a polyvinyl alcohol adhesive is preferable, and in particular, it is preferable to use an adhesive containing a polyvinyl alcohol resin containing an acetacetyl group and an amine metal compound crosslinking agent. The adhesive for the polarizing plate may include 100 parts by weight of the polyvinyl alcohol-based resin containing the acetacetyl group and 1 to 50 parts by weight of the amine-based metal compound crosslinking agent.
상기 폴리비닐알코올계 수지는 상기 편광자와 투명보호필름을 충분히 접착할 수 있고, 광학적 투시도가 우수하며, 경시적인 황변 등의 변화가 없는 것이면 특별히 한정되지 않으나, 특히 가교제와의 원활한 가교반응을 고려하면 아세트아세틸기가 함유된 폴리비닐알코올계 수지를 이용하는 것이 바람직하다.The polyvinyl alcohol-based resin is not particularly limited as long as it can sufficiently adhere the polarizer and the transparent protective film, have excellent optical transparency, and there is no change in yellowing over time, but in particular, considering a smooth crosslinking reaction with a crosslinking agent, It is preferable to use polyvinyl alcohol-type resin containing an acetacetyl group.
여기서, 상기 폴리비닐알코올계 수지의 중합도 및 검화도는 아세트아세틸기를 함유하기만 하면 특별히 한정되지 않으나, 바람직하게는 중합도가 200 내지 4,000의 범위내이고, 검화도가 70몰% 내지 99.9몰%의 범위내인 것이 좋다. 분자 움직임의 자유로움에 따른 함유 물질과의 유연한 혼합을 고려하면, 중합도는 1,500 내지 2,500의 범위내이고, 검화도는 90몰% 내지 99.9몰%의 범위내인 것이 더욱 바람직하다. 이때, 상기 폴리비닐알코올계 수지는 상기 아세트아세틸기를 0.1 내지 30몰%로 포함하는 것이 바람직하다. 상기 아세트아세틸기의 범위에서 가교제와의 반응이 원활할 수 있으며, 목적하는 접착제의 내수성 및 접착력에 충분히 유의하기 때문이다.Here, the polymerization degree and saponification degree of the polyvinyl alcohol-based resin is not particularly limited as long as it contains an acetacetyl group. Preferably, the polymerization degree is in the range of 200 to 4,000, and the saponification degree is 70 mol% to 99.9 mol%. It is good to be in range. Considering the flexible mixing with the containing material according to the freedom of molecular movement, the degree of polymerization is in the range of 1,500 to 2,500, and the degree of saponification is more preferably in the range of 90 mol% to 99.9 mol%. In this case, the polyvinyl alcohol-based resin preferably comprises 0.1 to 30 mol% of the acetacetyl group. This is because the reaction with the crosslinking agent may be smooth in the range of the acetacetyl group, and sufficiently pays attention to the water resistance and adhesion of the desired adhesive.
상기 아민계 금속화합물 가교제는 상기 폴리비닐알코올계 수지와의 반응성을 갖는 관능기를 가지는 수용성 가교제로서, 아민계 리간드를 함유하는 금속 착물 형태인 것이 바람직하다. 가능한 금속으로는 지르콘늄(Zr), 타이타늄(Ti), 하프늄(Hf), 텅스텐(W), 철(Fe), 코발트(Co), 니켈(Ni), 루테늄(Ru), 오스뮴(Os), 로듐(Rh), 이리듐(Ir), 팔라듐(Pd), 백금(Pt) 등의 전이 금속이 가능하며, 중심 금속에 결합된 리간드로는 일차아민, 이차아민(다이아민), 삼차아민이나 암모늄하이드록사이드 등의 적어도 하나 이상의 아민기를 포함한 것이 모두 가능하다. 그 사용량은 상기 폴리비닐알콜계 수지 100 중량부에 대하여 1 중량부 내지 50 중량부의 범위로 조절되는 것이 바람직하다. 상기한 범위에서 목적하는 접착제에 충분히 유의적인 접착력을 부여할 수 있으며, 접착제의 저장 안정성(pot life)을 향상시킬 수 있기 때문이다.The amine-based metal compound crosslinking agent is a water-soluble crosslinking agent having a functional group having reactivity with the polyvinyl alcohol-based resin, preferably in the form of a metal complex containing an amine ligand. Possible metals include zirconium (Zr), titanium (Ti), hafnium (Hf), tungsten (W), iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), osmium (Os), Transition metals such as rhodium (Rh), iridium (Ir), palladium (Pd), and platinum (Pt) are possible, and ligands bound to the central metal are primary amines, secondary amines (diamines), tertiary amines and ammonium hydrides. It is possible to include at least one or more amine groups, such as locksides. Its amount is preferably adjusted in the range of 1 part by weight to 50 parts by weight based on 100 parts by weight of the polyvinyl alcohol-based resin. This is because it is possible to impart sufficiently significant adhesive strength to the desired adhesive within the above range, and to improve the pot life of the adhesive.
상기 편광판용 접착제로서 상기 아세트아세틸기를 함유하는 폴리비닐알코올계 수지 및 상기 아민계 금속화합물 가교제를 포함하는 수용액의 pH는 9 이하일 수 있다.PH of the aqueous solution containing the polyvinyl alcohol-based resin containing the acetacetyl group and the amine-based metal compound crosslinking agent as the adhesive for the polarizing plate may be 9 or less.
여기서, 상기 아세트아세틸기를 함유하는 폴리비닐알코올계 수지와 상기 아민계 금속화합물 가교제를 함유하는 접착제 수용액은 pH 조절제를 사용하여 그 pH를 9이하로 조절하는 것이 바람직하다. 보다 바람직하게는 pH를 2초과 9이하의 범위로 조절할 수 있고, 더욱 바람직하게는 pH를 4 내지 8.5 범위로 조절할 수 있다.Here, it is preferable that the pH of the adhesive aqueous solution containing the polyvinyl alcohol-based resin containing the acetacetyl group and the amine-based metal compound crosslinking agent is adjusted to 9 or less using a pH adjusting agent. More preferably, the pH can be adjusted in the range of 2 seconds and 9 or less, and more preferably in the range of 4 to 8.5.
상기 편광자와 보호필름의 접착은 편광막의 보호 필름 또는 편광막인 PVA 필름의 표면 상에 롤 코터, 그라비어 코터, 바 코터, 나이프 코터, 또는 캐필러리 코터 등을 사용하여 접착제를 먼저 코팅하고, 접착제가 완전히 건조되기 전에 보호 필름과 편광막을 합지 롤로 가열압착하거나 상온압착하여 합지하는 방법에 의하여 수행될 수 있다. 핫멜트형 접착제를 이용하는 경우에는 가열 압착롤을 사용하여야 한다. The adhesion of the polarizer and the protective film is first coated with an adhesive using a roll coater, a gravure coater, a bar coater, a knife coater, or a capillary coater on the surface of a polarizing film or a PVA film that is a polarizing film. It may be carried out by a method of laminating the protective film and the polarizing film by heating or pressing at room temperature before it is completely dried. In the case of using a hot melt adhesive, a heat press roll should be used.
폴리우레탄계 접착제를 사용하는 경우 광에 의해 황변되지 않는 지방족 이소시아네이트계 화합물을 이용하여 제조된 폴리우레탄계 접착제를 이용하는 것이 바람직하다. 일액형 또는 이액형의 드라이 라미네이트용 접착제 또는 이소시아네이트와 하이드록시기와의 반응성이 비교적 낮은 접착제를 사용하는 경우에는 아세테이 트계 용제, 케톤계 용제, 에테르계 용제, 또는 방향족계 용제 등으로 희석된 용액형 접착제를 사용할 수도 있다. 이때 접착제 점도는 5000 cps 이하의 저점도형인 것이 바람직하다. 상기 접착제들은 저장안정성이 우수하면서도 400 ~ 800nm에서의 광투과도가 90% 이상인 것이 바람직하다.When using a polyurethane adhesive, it is preferable to use the polyurethane adhesive manufactured using the aliphatic isocyanate compound which is not yellowed by light. When using one-component or two-component dry laminate adhesives or adhesives with relatively low reactivity between isocyanates and hydroxyl groups, a solution type diluted with an acetate solvent, a ketone solvent, an ether solvent, or an aromatic solvent, etc. Adhesives can also be used. At this time, the adhesive viscosity is preferably low viscosity of 5000 cps or less. The adhesives are excellent in storage stability and preferably have a light transmittance of 90% or more at 400 to 800 nm.
충분한 점착력을 발휘할 수 있으면 점착제도 사용될 수 있다. 점착제는 합지 후 열 또는 자외선에 의하여 충분히 경화가 일어나 기계적 강도가 접착제 수준으로 향상되는 것이 바람직하며, 계면접착력도 커서 점착제가 부착된 양쪽 필름 중 어느 한 쪽의 파괴없이는 박리되지 않는 정도의 점착력을 갖는 것이 바람직하다.A tackifier can also be used if it can exert sufficient adhesive force. The adhesive is preferably cured by heat or ultraviolet rays after lamination, and thus the mechanical strength is improved to the level of the adhesive. The adhesive strength is also large, and thus the adhesive strength is such that the adhesive cannot be peeled off without breaking of either film to which the adhesive is attached. It is preferable.
사용가능한 점착제의 구체적인 예로서는 광학투명성이 우수한 천연고무, 합성고무 또는 엘라스토머, 염화비닐/초산비닐 공중합체, 폴리비닐알킬에테르, 폴리아크릴레이트, 변성 폴리올레핀계 점착제 등과 여기에 이소시아네이트 등의 경화제를 첨가한 경화형 점착제를 들 수 있다.Specific examples of the pressure-sensitive adhesives that can be used include natural rubber, synthetic rubber or elastomer having excellent optical transparency, a vinyl chloride / vinyl acetate copolymer, polyvinyl alkyl ether, polyacrylate, modified polyolefin-based pressure-sensitive adhesive, and a curing type in which a curing agent such as isocyanate is added thereto. An adhesive is mentioned.
상기와 같이 제조되는 본 발명의 편광판은 각종 용도에 이용될 수 있다. 구체적으로, 액정표시장치(LCD)용 편광판, 유기 EL 표시장치의 반사 방지용 편광판 등을 포함하는 화상표시장치에 바람직하게 사용될 수 있다. 또한, 본 발명에 따른 편광판은 각종 기능성 막, 예를 들면 λ/4판, λ/2판 등의 위상차판, 광확산판, 시야각 확대판, 휘도 향상판, 반사판 등의 여러 가지 광학층을 조합한 복합 편광판에 적용될 수 있다.The polarizing plate of the present invention manufactured as described above can be used in various applications. Specifically, it can be preferably used for an image display device including a polarizing plate for liquid crystal display (LCD), an anti-reflective polarizing plate of an organic EL display device, and the like. In addition, the polarizing plate according to the present invention combines various optical layers such as retardation plates, light diffusing plates, viewing angle expanding plates, brightness enhancing plates, reflecting plates such as various functional films, for example, λ / 4 plates, λ / 2 plates, and the like. It can be applied to one composite polarizer.
본 발명에 따른 편광판은 이후 화상표시장치 등에의 적용이 용이하도록 적어도 일면에 점착제층을 구비할 수 있다. 또한, 상기 편광판이 화상표시장치 등에 적 용될 때까지 점착제층을 보호하기 위하여 상기 점착제층 상에 이형필름을 추가로 구비할 수 있다. The polarizing plate according to the present invention may be provided with a pressure-sensitive adhesive layer on at least one surface so as to be easily applied to an image display device. In addition, a release film may be further provided on the pressure-sensitive adhesive layer to protect the pressure-sensitive adhesive layer until the polarizing plate is applied to an image display device or the like.
또한, 본 발명은 상기 편광판을 포함하는 화상표시장치를 제공한다. In addition, the present invention provides an image display device including the polarizing plate.
예컨대, 본원 발명은 광원, 제1 편광판, 액정셀, 제2 편광판을 순차적으로 적층된 상태로 포함하고, 상기 제1 편광판 및 제2 편광판 중 적어도 하나는 편광자 및 상기 편광자의 적어도 일면에 구비된 보호필름을 포함하고, 상기 보호필름은 알켄 단량체 0.1~30몰%, 아크릴레이트계 단량체 30~99몰% 및 이중결합을 하나 이상 가지는 불포화 유기산 단량체 0.1~50몰%를 포함하는 공중합체를 포함하는 것을 특징으로 하는 편광판인 것을 특징으로 하는 액정표시장치를 제공한다. 상기 액정셀은 액정층; 이를 지지할 수 있는 기판; 및 상기 액정에 전압을 인가하기 위한 전극층을 포함한다. 이때, 본 발명에 따른 편광판은 횡전계방식(In-Plane Switching mode; IPS mode), 수직배향방식(Vertically Aligned mode; VA mode), OCB 방식(Optically Compensated Birefringence mode), 비틀린 네마틱(Twisted Nematic mode; TN mode), FFS(Fringe Field Switching mode; FFS mode) 방식 등의 모든 액정 모드에 적용될 수 있다.For example, the present invention includes a light source, a first polarizing plate, a liquid crystal cell, and a second polarizing plate sequentially stacked, and at least one of the first and second polarizing plates is provided on at least one surface of the polarizer and the polarizer. It includes a film, wherein the protective film comprises a copolymer comprising 0.1 to 30 mol% of alkene monomers, 30 to 99 mol% of acrylate monomers and 0.1 to 50 mol% of unsaturated organic acid monomers having at least one double bond. A liquid crystal display device characterized in that it is a polarizing plate characterized by. The liquid crystal cell is a liquid crystal layer; A substrate capable of supporting this; And an electrode layer for applying a voltage to the liquid crystal. At this time, the polarizing plate according to the present invention is an in-plane switching mode (IPS mode), vertically aligned (VA mode), OCB (Optically Compensated Birefringence mode), twisted nematic mode (Twisted Nematic mode) TN mode) and FFS (Fringe Field Switching mode; FFS mode).
본 발명에 따른 화상표시장치에 있어서, 본 발명에 따른 편광자 보호필름은 편광판의 액정셀측에 내부 보호 필름으로서 배치될 수도 있고, 동시에/또는 편광판의 액정셀의 반대측에 외부 보호 필름으로서 배치될 수도 있다. In the image display apparatus according to the present invention, the polarizer protective film according to the present invention may be arranged as an inner protective film on the liquid crystal cell side of the polarizing plate and / or at the same time as an outer protective film on the opposite side of the liquid crystal cell of the polarizing plate. .
이하에서는 실시예를 통하여 본 발명을 보다 상세히 설명한다. 다만, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐 본 발명의 범위가 하기 실시예의 내용 으로 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only for illustrating the present invention and the scope of the present invention is not limited to the contents of the following examples.
중합에 필요한 유기 시약과 용매는 알드리치(Aldrich)사 제품으로 표준 방법에 의해 정제하였으며, 에틸렌은 어플라이드 가스 테크놀로지(Applied Gas Technology)사의 고순도 제품을 수분 및 산소 여과 장치를 통과시킨 후 중합을 진행하였다.The organic reagents and solvents required for the polymerization were purified by a standard method by Aldrich, and ethylene was polymerized after passing a high purity product of Applied Gas Technology through a water and oxygen filtration device.
공중합체 내 단량체 함량비를 구하기 위하여 베리안(Varian)사에서 제조한 500 MHz NMR을 이용하여 스펙트럼을 얻었다. 수득된 중합체의 열적 특성인 유리전이온도(Tg)는 TA 인스트루먼트(TA Instrument)사에서 나온 DSC Q100에서 측정하였으며, Td_50(50% 열분해 온도)은 동일사의 TGA를 이용하였다.In order to obtain a monomer content ratio in the copolymer, spectra were obtained using 500 MHz NMR manufactured by Varian. The glass transition temperature (Tg), which is a thermal property of the obtained polymer, was measured by DSC Q100 from TA Instrument, and Td_50 (50% pyrolysis temperature) was used as TGA of the same company.
분자량 및 분자량 분포는 워터스(Waters)사에서 GPC(gel permeation chromatography) 분석을 통해 얻었다. 분석 온도는 25℃ 이었고 테트라하이드로퓨란(THF)을 용매로 사용하였고, 폴리스티렌으로 표준화하여 수평균분자량(Mn) 및 중량평균분자량(Mw)을 구했다.Molecular weight and molecular weight distribution were obtained by gel permeation chromatography (GPC) analysis from Waters. The analytical temperature was 25 ° C., tetrahydrofuran (THF) was used as the solvent, and standardized with polystyrene to obtain the number average molecular weight (Mn) and the weight average molecular weight (Mw).
에틸렌-아크릴레이트 공중합체Ethylene-acrylate Copolymer
비교예 1Comparative Example 1
125mL 고압 반응 장치를 진공으로 만든 후, 아르곤을 충진시켰다. 상기 아르곤 분위기의 반응기에 메틸 메타크릴레이트 28mmol과 알루미나 28mmol을 투입하였다. 그리고, 톨루엔에 녹인 개시제 AIBN을 0.084mmol 투입하였다. 이어서, 35bar의 에틸렌 충진시킨 후 반응기 온도를 75℃까지 상승시키고 18시간 동안 중합을 실시하였다. The 125 mL high pressure reactor was evacuated and filled with argon. 28 mmol of methyl methacrylate and 28 mmol of alumina were added to an argon atmosphere reactor. And 0.084 mmol of initiator AIBN dissolved in toluene was added. Subsequently, after charging 35 bar of ethylene, the reactor temperature was raised to 75 ° C. and polymerization was performed for 18 hours.
비교예 2Comparative Example 2
알루미나를 미투입한 것을 제외하고는 상기 비교예 1와 동일한 방법으로 중합하였다.Polymerization was carried out in the same manner as in Comparative Example 1 except that alumina was not added.
상기 비교예 1 및 비교예 2의 중합 조건 및 결과를 표 1 및 표 2에 나타내었다. 상기 비교예 1의 중합 분석 결과인 NMR 스펙트럼(1H-NMR spectrum)을 도 1에 나타내었고, 비교예 1의 중합분석 결과인 IR 스펙트럼은 도 6에 나타내었다.The polymerization conditions and results of Comparative Example 1 and Comparative Example 2 are shown in Table 1 and Table 2. An NMR spectrum ( 1 H-NMR spectrum) as a result of polymerization analysis of Comparative Example 1 is shown in FIG. 1, and an IR spectrum as a result of polymerization analysis of Comparative Example 1 is shown in FIG. 6.
/[단량체]
(부피비)[menstruum]
/ [Monomer]
(Volume ratio)
/[MMA]
(mole비)[Mountain Lewis]
/ [MMA]
(mole rain)
/[단량체]
(mole비)[Initiator]
/ [Monomer]
(mole rain)
압력
(bar)Ethylene
pressure
(bar)
(℃)Temperature
(℃)
(h)time
(h)
표 1에서 [단량체]는 MMA 의 부피 또는 몰수를 의미한다.In Table 1, [monomer] means the volume or number of moles of MMA.
(℃)Td_50
(℃)
(mole%)Ethylene Content
(mole%)
비교예 1의 실험 결과 에틸렌 함량 14mole%를 갖는 에틸렌-메틸 메타크릴레이트 랜덤 공중합체가 중합되었다. 비교예 2는 비교예1의 중합 조건과 비교하여 알루미나를 투입하지 않은 상태에서 자유 라디칼 중합한 결과로서, 비교예 1에 비해 에틸렌 함량이 줄어든 9.7mol% 함유한 랜덤 공중합체가 중합되었다. 에틸렌 함량이 줄었으므로 유리전이온도는 비교예 1보다 높게 얻어졌다.As a result of the experiment of Comparative Example 1, an ethylene-methyl methacrylate random copolymer having an ethylene content of 14 mole% was polymerized. Comparative Example 2 is a result of free radical polymerization in the state in which alumina is not added as compared with the polymerization conditions of Comparative Example 1, and a random copolymer containing 9.7 mol% having reduced ethylene content compared to Comparative Example 1 was polymerized. Since the ethylene content was reduced, the glass transition temperature was obtained higher than that of Comparative Example 1.
이 결과를 통해 알루미나 투입여부는 공중합체 내 에틸렌 함량 증대 효과를 가져오며, 에틸렌 함량이 증대되면 유리전이온도가 낮아진다는 것을 알 수 있다. 이 두 중합체는 에틸렌 함량이 10mole% 이상이므로 성형성이 좋은 고투명 광학 필름으로 제조 가능하나, 유리전이온도가 100도 이하이므로 광학필름에 적용하기에 내열성이 부족한 단점이 있다. 즉, 에틸렌의 함유량을 높임으로서 아크릴레이트의 부서지기 쉬운 특성을 보완하여 필름형성이 좋으나, 낮은 유리 전이 온도로 인해 응용범위가 제한된다.This result shows that the addition of alumina has an effect of increasing the ethylene content in the copolymer, and the glass transition temperature is lowered when the ethylene content is increased. These two polymers can be produced as a highly transparent optical film having good moldability because the ethylene content is more than 10mole%, but the glass transition temperature is less than 100 degrees has a disadvantage of lacking heat resistance to apply to the optical film. That is, the film formation is good by supplementing the fragile property of the acrylate by increasing the content of ethylene, but the application range is limited due to the low glass transition temperature.
1-알켄-아크릴레이트-아크릴산 공중합체1-alkene-acrylate-acrylic acid copolymer
실시예 1Example 1
125ml Parr 고압 반응 장치를 진공으로 만든 후, 아르곤을 충진시켰다. 아르곤 분위기의 반응기에 메틸 메타크릴레이트(MMA) 28mmol, 메타크릴산 (MAA) 5.6mmol, 그리고 루이스산으로는 알루미나 28mmol을 투입하였다. 그리고, 톨루엔에 녹인 개시제 AIBN을 0.056mmol 투입하였다. 이어서, 35bar의 에틸렌을 충진시킨 후 반응기 온도를 65℃까지 상승시키고 18시간 동안 중합을 실시하였다. The 125 ml Parr high pressure reactor was evacuated and filled with argon. 28 mmol of methyl methacrylate (MMA), 5.6 mmol of methacrylic acid (MAA), and 28 mmol of alumina were added to Lewis acid in an argon atmosphere reactor. And 0.056 mmol of initiator AIBN dissolved in toluene was added. Subsequently, after charging 35 bar of ethylene, the reactor temperature was raised to 65 ° C. and polymerization was performed for 18 hours.
중합이 끝나면 중합액은 필터를 통해 알루미나를 제거하고, 에틸렌 또는 헥산에 침전시켰다. 얻어진 고분자는 24시간 동안 감압 하 Tg 이하의 온도에서 건조하였다.After the polymerization, the polymerization solution was removed alumina through a filter, and precipitated in ethylene or hexane. The obtained polymer was dried at a temperature below Tg under reduced pressure for 24 hours.
실시예 2Example 2
용매량 및 MAA 투입량을 조절한 것을 제외하고는 실시예 1과 동일한 방법으로 중합을 실시하였다. 얻어진 공중합체의 IR 결과를 도 2에 나타내었다. The polymerization was carried out in the same manner as in Example 1 except that the solvent amount and the MAA amount were adjusted. IR result of the obtained copolymer is shown in FIG.
실시예 3Example 3
MAA 투입량을 조절한 것을 제외하고는 실시예 1과 동일한 방법으로 중합을 실시하였다. 얻어진 공중합체에 대한 TGA 결과를 도 3에 나타내었다. The polymerization was carried out in the same manner as in Example 1 except that the amount of MAA charged was adjusted. The TGA results for the obtained copolymer are shown in FIG. 3.
실시예 4Example 4
알루미나를 미투입하고, MAA의 투입량을 조절한 것을 제외하고는 실시예 1과 동일한 방법으로 중합을 실시하였다. 얻어진 공중합체에 대한 주사 열량(DSC) 그래프 및 겔투과 크로마토그래피(GPC) 분석 결과를 각각 도 4 및 5에 나타내었다. Polymerization was carried out in the same manner as in Example 1 except that the alumina was not added and the amount of MAA was adjusted. Scanning calorimetry (DSC) graph and gel permeation chromatography (GPC) analysis of the obtained copolymer are shown in FIGS. 4 and 5, respectively.
실시예1 내지 4의 결과 유리전이온도가 140℃ 이상인 에틸렌-MMA-MAA 삼원 공중합체가 합성되었다. 비교예에서 합성된 공중합체의 단점인 낮은 유리전이온도 문제를 해결하였으며, TGA로 측정된 50% 열분해온도도 450도 이상으로 높게 얻어졌다. 에틸렌 함량이 높아질수록 유리전이온도는 낮아지고 아크릴산 함량이 높아질수록 유리전이온도는 높아지므로 중합조건 변화에 따라 원하는 내열성 및 물성에 맞는 고분자를 합성할 수 있다.As a result of Examples 1 to 4, an ethylene-MMA-MAA terpolymer having a glass transition temperature of 140 ° C. or more was synthesized. The low glass transition temperature problem, which is a disadvantage of the copolymer synthesized in the comparative example, was solved, and the 50% pyrolysis temperature measured by TGA was obtained as high as 450 degrees or more. The higher the ethylene content, the lower the glass transition temperature, and the higher the acrylic acid content, the higher the glass transition temperature, so that polymers suitable for the desired heat resistance and physical properties can be synthesized according to the polymerization conditions.
실시예 5Example 5
MAA 투입량를 MMA 대비 0.1 mole 비로 줄이고, 반응용매인 톨루엔의 양을 늘렸다. 중합온도는 70도, 개시제의 농도는 단량체 대비 0.001 mole 비로 줄여서 6시간 반응하였다. 루이스산으로는 알루미나를 사용하였다.The amount of MAA input was reduced to 0.1 mole ratio compared to MMA, and the amount of toluene, a reaction solvent, was increased. The polymerization temperature was 70 degrees, the concentration of the initiator was reduced to 0.001 mole ratio relative to the monomer and reacted for 6 hours. Alumina was used as the Lewis acid.
실시예 5의 결과와 실시예 1 내지 4의 결과를 비교하였을 때, 에틸렌 함량이 높아 필름 제조시 brittleness가 보다 개선되어 광학 필름으로 더 바람직하다. 비교예 1과 비교하였을 때, 에틸렌 함량이 더 높음에도 불구하고 Tg가 높은 것은 MAA 가 포함된 3원 공중합체이기 때문이며 Tg가 121도이므로 LCD 필름 가공 공정에 적용 가능한 내열성을 확보하였다.When the results of Example 5 and the results of Examples 1 to 4 are compared, the brittleness of the film is improved due to the high ethylene content, which is more preferable as the optical film. Compared with Comparative Example 1, despite the higher ethylene content, the higher Tg is due to the ternary copolymer containing MAA and Tg is 121 degrees, thereby securing heat resistance applicable to the LCD film processing process.
실시예 6Example 6
루이스산으로서 알루미나 대신 산화 티타늄(Ti2O3)을 투입하고, 용매 투입량을 줄인 것을 제외하고는 실시예 5과 동일한 방법으로 중합을 실시하였다.As the Lewis acid, titanium oxide (Ti 2 O 3 ) was added instead of alumina, and polymerization was carried out in the same manner as in Example 5 except that the amount of the solvent added was reduced.
실시예 6의 결과 산화티타늄을 사용해도 알루미나를 사용했을 때와 유사한 결과를 얻었으며, 다양한 금속 산화물이 루이스 산으로 적용 가능하다.As a result of Example 6, the use of titanium oxide gave similar results as with alumina, and various metal oxides could be applied as Lewis acids.
실시예 7Example 7
아크릴산으로서 1가 산인 MAA 대신 2가 산인 말레산(Maleic acid)을 투입하고, 용매 투입량을 줄인 것을 제외하고는 실시예 6과 동일한 방법으로 중합을 실시하였다.The polymerization was carried out in the same manner as in Example 6 except that maleic acid, which is a divalent acid, was added instead of the monovalent acid, MAA, as acrylic acid, and the amount of the solvent added was reduced.
실시예 7의 결과에서와 같이 2가 산도 적용 가능하며, 투입량 조절로 원하는 물성의 고분자를 생성할 수 있다.As in the result of Example 7, divalent acid is also applicable, and the dosage can be adjusted to produce a polymer of the desired physical properties.
실시예 8Example 8
말레산 대신 말레산 무수물(Maleic anhydride)을 투입한 것을 제외하고는 실시예 7과 동일한 방법으로 중합을 실시하였다. 얻어진 에틸렌-메틸 메타크릴레이트-말레산 무수물 3원 랜덤 공중합체는 테트라하이드로퓨란에 녹여서 염화수소 수용액을 넣고, 50도에서 24시간 교반하는 후반응을 실시하였다. The polymerization was carried out in the same manner as in Example 7, except that maleic anhydride was added instead of maleic acid. The obtained ethylene-methyl methacrylate-maleic anhydride ternary random copolymer was dissolved in tetrahydrofuran, poured into an aqueous hydrogen chloride solution, and then stirred at 50 ° C. for 24 hours to carry out a post reaction.
실시예 8의 결과, 산 존재 하에서 가수분해 반응을 통해 말레산 무수물이 2가의 산인 말레산(Maleic acid) 형태로 변화되었음을 IR로 확인하였다. 말레산 무수물로 공중합한 뒤 후반응을 통해서 실시예 7과 유사한 3원 공중합체 중합이 가능함을 확인하였다. 가수분해 반응의 정도를 조절함에 따라 에틸렌-메틸 메타 크릴레이트-말레산 무수물- 말레산4원 랜덤 공중합체로도 변화시킬 수 있다.As a result of Example 8, it was confirmed by IR that maleic anhydride was changed to maleic acid (maleic acid) form through a hydrolysis reaction in the presence of an acid. After copolymerizing with maleic anhydride, it was confirmed that similar terpolymer copolymerization as in Example 7 was possible through post-reaction. By controlling the degree of hydrolysis reaction, it can also be changed to ethylene-methyl methacrylate-maleic anhydride-maleic acid quaternary random copolymer.
실시예 9Example 9
비교예 1에서 중합한 에틸렌-메틸 메타크릴레이트 공중합체를 실시예 8과 같이 가수분해 반응을 실시하였다. 산 존재 하에서 가수분해 반응을 통해 메틸 메타크릴레이트의 일부를 메타크릴 산으로 바꾸었으며, 산의 수산화기가 생성됐음을 IR로 확인하였다. The ethylene-methyl methacrylate copolymer polymerized in Comparative Example 1 was subjected to a hydrolysis reaction as in Example 8. A portion of methyl methacrylate was converted to methacrylic acid through a hydrolysis reaction in the presence of an acid, and IR was confirmed to form a hydroxyl group of the acid.
실시예 9의 결과, 에틸렌-메틸 메타크릴레이트-메타크릴 산 3원 공중합체로 전환되면서 Tg 및 열변형온도(Td)가 상승하였으며 분자량에는 큰 변화가 없었다. 이와 같이 가수분해 반응을 통해서도 3원 공중합체를 합성할 수 있다.As a result of Example 9, Tg and heat distortion temperature (Td) were increased while being converted to ethylene-methyl methacrylate-methacrylic acid terpolymer, and there was no significant change in molecular weight. In this manner, the ternary copolymer can be synthesized through the hydrolysis reaction.
상기 실시예 1 내지 9 의 중합 조건 및 결과를 표 3 및 표 4에 나타내었다. 한편, 실시예 2의 중합분석 결과인 IR 스펙트럼은 도 2에 나타내었고, 실시예 3의 중합분석 결과인 TGA 스펙트럼은 도 3에 나타내었으며, 실시예 4의 중합분석 결과인 DSC 스펙트럼은 도 4에, 그리고 실시예 4의 중합분석 결과인 GPC 스펙트럼은 도 5에 각각 나타내었다.The polymerization conditions and results of Examples 1 to 9 are shown in Tables 3 and 4. Meanwhile, the IR spectrum of the polymerization analysis of Example 2 is shown in FIG. 2, the TGA spectrum of the polymerization analysis of Example 3 is shown in FIG. 3, and the DSC spectrum of the polymerization analysis of Example 4 is shown in FIG. 4. And GPC spectra, which are the results of polymerization analysis of Example 4, are shown in FIG. 5.
/[단량체]
(부피비)[menstruum]
/ [Monomer]
(Volume ratio)
/[MMA]
(mole비)[Alumina]
/ [MMA]
(mole rain)
/[MMA]
(mole비)[Titanium oxide]
/ [MMA]
(mole rain)
/[MMA]
(mole비)[MAA]
/ [MMA]
(mole rain)
/[MMA]
(mole비)[Maleic acid]
/ [MMA]
(mole rain)
/[MMA]
(mole비)[Maleic anhydride]
/ [MMA]
(mole rain)
압력
(bar)Ethylene
pressure
(bar)
/[단량체]
(mole비)[AIBN]
/ [Monomer]
(mole rain)
(℃)Temperature
(℃)
(h)time
(h)
표 3에서 [단량체]는 MMA + MAA 의 부피 또는 몰수를 의미한다.In Table 3, [monomer] means the volume or number of moles of MMA + MAA.
(℃)Td_50
(℃)
1Example
One
2Example
2
3Example
3
4Example
4
5Example
5
6Example
6
7Example
7
8Example
8
9Example
9
실시예 10~13Examples 10-13
반응기에 메틸 메타크릴레이트(MMA) 28mmol, 메타크릴산(MAA) 5.6mmol, 그리고 루이스산으로는 알루미나 28mmol을 투입하였다. 그리고, 톨루엔에 녹인 개시제 AIBN을 0.056mmol 투입하였다. 이어서, 하기 표5에 기재된 1-알켄 단량체를 반응기에 투입한 후 반응기 온도를 65℃까지 상승시키고 18시간 동안 중합을 실시하였다.28 mmol of methyl methacrylate (MMA), 5.6 mmol of methacrylic acid (MAA), and 28 mmol of alumina were added to Lewis acid. And 0.056 mmol of initiator AIBN dissolved in toluene was added. Subsequently, the 1-alkene monomer shown in Table 5 was added to the reactor, and then the reactor temperature was raised to 65 ° C. and polymerization was performed for 18 hours.
중합이 끝나면 중합액은 필터를 통해 알루미나를 제거하고, 에틸렌 또는 헥산에 침전시켰다. 얻어진 고분자는 24시간 동안 감압 하 Tg 이하의 온도에서 건조하였다. 제조된 공중합체의 물성 측정 결과를 하기 표 6에 나타내었다. After the polymerization, the polymerization solution was removed alumina through a filter, and precipitated in ethylene or hexane. The obtained polymer was dried at a temperature below Tg under reduced pressure for 24 hours. The physical property measurement results of the prepared copolymer are shown in Table 6 below.
/[단량
체]
(부피
비)[menstruum]
/ [Quantity
sieve]
(volume
ratio)
미나]
/[MMA]
(mole
비)[Alu
Mina]
/ [MMA]
(mole
ratio)
지르코늄]
/[MMA]
(mole
비)[Oxidation
zirconium]
/ [MMA]
(mole
ratio)
/[MMA]
(mole
비)[MAA]
/ [MMA]
(mole
ratio)
/[MMA]
(mole
비)[1-butene]
/ [MMA]
(mole
ratio)
/[MMA]
(mole
비)[1-hexene]
/ [MMA]
(mole
ratio)
decen
e]
/[MMA]
(mole
비)[One-
decen
e]
/ [MMA]
(mole
ratio)
/단량체]
(mole
비)[AIBN]
/ Monomer]
(mole
ratio)
(℃)Temperature
(℃)
(h)time
(h)
표 5에서 [단량체]는 MMA + MAA 의 부피 또는 몰수를 의미한다.In Table 5, [monomer] means the volume or number of moles of MMA + MAA.
10Example
10
11Example
11
12Example
12
13Example
13
아크릴레이트계 비닐 단량체 중에서 유리전이온도가 가장 높은 메틸 메타크릴레이트의 경우 일반적으로 단독 중합시 유리전이온도가 110℃로 얻어진다. 필름 형성시 부서지는 단점을 극복하기 위해 아크릴레이트계 고분자에 에틸렌을 공단량체로 첨가하는데 이 때 내열성이 저하되는 문제점이 발생한다. 그러나 가공상의 열을 견디기 위해 유리전이온도가 100℃ 이상은 되어야 하므로 이 문제를 아크릴산 첨가로 해결할 수 있다. 또한 아크릴산은 극성기인 카르복실기를 함유하고 있어 광학필름으로 적용시 접착성이 증대된다.In the case of methyl methacrylate having the highest glass transition temperature among the acrylate-based vinyl monomers, the glass transition temperature is generally 110 ° C. upon homopolymerization. When ethylene is added to the acrylate-based polymer as a comonomer in order to overcome the disadvantages of film formation, a problem arises in that the heat resistance is lowered. However, the glass transition temperature must be 100 ° C or higher to withstand the heat of processing, so this problem can be solved by the addition of acrylic acid. In addition, acrylic acid contains a carboxyl group, which is a polar group, and thus increases adhesion when applied to an optical film.
보호필름 제막Protective film production
상기 공중합체들 중 일부 조성에 대해서 제막을 실시하여 보호필름을 제조하여 평가하였다. 비교예 및 실시예를 통해 얻은 공중합체를 테트라하이드로퓨란(THF)에 30 중량%로 용해한 후 용액 내 가스를 제거하기 위하여 하루 동안 방치하였다. 얻어진 고분자 용액을 유리판에 도포 후 400 μm의 간격으로 유지되어 있는 필름 규제기를 이용하여 일정한 속도로 제막한 후 하루 동안 50℃ 오븐에서 건조하였다. 건조 후 필름의 두께가 80 μm 임을 확인하였다.Some compositions of the copolymers were coated to form a protective film and evaluated. The copolymers obtained through the Comparative Examples and Examples were dissolved in tetrahydrofuran (THF) at 30% by weight and then left for one day to remove gas from the solution. After the obtained polymer solution was applied to a glass plate, a film was formed at a constant rate using a film regulator maintained at an interval of 400 μm, and then dried in a 50 ° C. oven for one day. After drying, the thickness of the film was confirmed to be 80 μm.
(열팽창계수 측정) (Coefficient of Thermal Expansion)
제조된 광학필름 시편을 TMA(Mettler Toledo사제)를 이용하여 분당 10℃의 속도로 가온하면서 치수변화를 측정하고, 40℃에서 80℃ 구간의 기울기로 열팽창계수를 계산하였다.Using the TMA (Mettler Toledo Co., Ltd.) TMA (manufactured by Mettler Toledo) was heated at a rate of 10 ℃ per minute dimensional change was measured, the coefficient of thermal expansion was calculated by the slope of 40 ℃ to 80 ℃ section.
(투습도 측정)(Moisture permeability measurement)
투습도 측정장치(PERMATRAN-W Model 398, Mocon 사제)로 40℃/100%RH 조건하에서의 투습도를 측정하였다.The moisture permeability was measured on 40 degreeC / 100% RH conditions with the moisture permeability measuring apparatus (PERMATRAN-W Model 398, a product made by Mocon).
(Retardation 측정)(Retardation measurement)
Axometrics사의 폴라리미터(Polarimeter)(Axoscan)을 이용하여, 제조된 광학필름의 평면방향 리타데이션(retardation) (Rin), 두께방향 리타데이션(Rth)을 측정하였다. 각각의 리타데이션은 다음 식에 의해 정의된다.Using Axometrics' Polarimeter (Axoscan), the planar retardation (Rin) and thickness retardation (Rth) of the prepared optical film were measured. Each retardation is defined by the following equation.
Rin = (nx-ny) x d, Rth = (nz-ny) x d Rin = (nx-ny) x d, Rth = (nz-ny) x d
여기에서, nx, ny, nz 는 각 방향별 굴절율을, d는 필름의 두께를 의미한다.Here, nx, ny, nz means refractive index in each direction, and d means the thickness of a film.
(광탄성계수 측정)(Photoelastic coefficient measurement)
Axoscan에 스프링형 인장기를 장착하여 보호필름에 인장력을 가하면서 평면방향 리타데이션을 측정하여 광탄성계수를 측정하였다.A spring type tensioner was mounted on the Axoscan and the photoelastic coefficient was measured by measuring the retardation in the planar direction while applying a tensile force to the protective film.
제조된 광학필름의 물성 측정 결과를 하기 표 7에 나타내었다. 비교예로 TAC 필름(후지필름사)의 물성을 비교하였다(비교예3).The physical property measurement results of the prepared optical film are shown in Table 7 below. As a comparative example, the physical properties of the TAC film (FUJIFILM Corporation) were compared (Comparative Example 3).
(g/(m2 day))Breathable
(g / (m 2 day))
실시예들의 경우 평면방향 리타데이션(Rin)과 두께방향 리타데이션(Rth)이 비교예3에 비해서 월등히 작았고, 광탄성계수도 작았으며, 투습도 역시 낮은 결과를 보였다. 비교예1과 2는 열팽창계수가 다른 실시예나 TAC 필름(비교예 3)에 비해서 상대적으로 높은 값을 보였다.In the case of Examples, the planar retardation (Rin) and the thickness retardation (Rth) were significantly smaller than those of Comparative Example 3, the photoelastic coefficient was small, and the moisture permeability was also low. Comparative Examples 1 and 2 showed relatively high values as compared with Examples or TAC films (Comparative Example 3) having different thermal expansion coefficients.
편광판 제조Polarizer manufacturers
(편광자 제조)(Polarizer manufacturing)
두께 75㎛의 폴리비닐 알코올(PVA) 필름(중합도: 2400)을 요오드 (I2)와 요오드화칼륨(KI)을 포함하는 수용액에서 침지시킨 후, 5배 연신하였다. 이어서, 상기 필름을 붕산과 요오드화칼륨 수용액 조 안으로 투입하여 가교 처리를 하고, 80 ℃에서 5분간 건조하여 편광자를 제조하였다. A polyvinyl alcohol (PVA) film (polymerization degree: 2400) having a thickness of 75 μm was immersed in an aqueous solution containing iodine (I 2 ) and potassium iodide (KI), and then stretched five times. Subsequently, the film was introduced into a boric acid and potassium iodide aqueous bath to undergo crosslinking treatment, and dried at 80 ° C. for 5 minutes to prepare a polarizer.
(편광자 보호필름 표면처리)(Polarizer Protective Film Surface Treatment)
편광자와의 접착력 향상을 위하여 편광자 보호필름 표면에 코로나 처리를 하고 실란계 프라이머를 도포하였다. 실란계 프라이머로서 3-아미노트리메톡시 실란 (3-aminotrimethoxy silane, Fluka사)을 이소프로필알콜(isopropylalcohol)과 물의 공용매(95/5중량비)에 2%의 농도로 용해시키고 24시간 동안 교반시킨 후 코로나 처리된 보호필름 표면에 와이어 바 (wire bar, #5)를 이용하여 코팅하고, 60℃ 오븐에서 10분 동안 건조하였다. 비교예 3의 TAC 필름의 경우에는 15중량 %의 수산화나트륨 수용액에 5분 동안 침지하고 60도 오븐에서 10분동안 건조하여 표면 처리를 하였다. In order to improve adhesion with the polarizer, the surface of the polarizer protective film was subjected to corona treatment and a silane primer was applied. As a silane-based primer, 3-aminotrimethoxy silane (3-aminotrimethoxy silane, Fluka) was dissolved in isopropyl alcohol (isopropylalcohol) and water in a solvent (95/5 weight ratio) at a concentration of 2% and stirred for 24 hours. After the corona treated protective film surface was coated using a wire bar (wire bar, # 5), and dried in an oven at 60 ℃ for 10 minutes. In the case of the TAC film of Comparative Example 3, it was immersed in 15% by weight aqueous sodium hydroxide solution for 5 minutes and dried in a 60 degree oven for 10 minutes to be surface treated.
(접착제, 편광판 제조) (Adhesive, polarizing plate production)
순수에 아세트아세틸기(5%)를 함유하는 폴리비닐알코올(평균중합도 2000, 감화도 94%)를 녹여 3.8%의 수용액을 제조하였다. Polyvinyl alcohol (average degree of polymerization 2000, degree of 94%) containing acetacetyl group (5%) was dissolved in pure water to prepare an aqueous solution of 3.8%.
순수에 지르코늄 아민 화합물 (AC-7, Daichi Kigenso Kagaku Kogyo 사제)를 녹여 3.8%의 수용액을 제조하였다. 이 지르코늄 아민 화합물 수용액을 상기에서 제조한 폴리비닐알코올 수용액에 폴리비닐알코올 100 중량부당 20 중량부의 비로 첨가하여 교반하면서 혼합하였다. 이 혼합 용액에 1M의 염산 수용액을 첨가하여 pH를 8.5로 조절하여 접착제를 제조하였다. A zirconium amine compound (AC-7, manufactured by Daichi Kigenso Kagaku Kogyo) was dissolved in pure water to prepare an aqueous solution of 3.8%. This zirconium amine compound aqueous solution was added to the polyvinyl alcohol aqueous solution prepared above at the ratio of 20 weight part per 100 weight part of polyvinyl alcohol, and it mixed, stirring. 1 M hydrochloric acid aqueous solution was added to this mixed solution to adjust pH to 8.5 to prepare an adhesive.
상기에서 제조한 접착제를 이용하여, 폴리비닐알코올계 편광자의 양면에 보호필름으로서 비교예와 실시예의 공중합체를 이용하여 제조된 필름을 라미네이트(laminate)한 후 80℃오븐에서 10분 동안 건조, 접착시켜 편광판을 제조하였다.Using the adhesive prepared above, after laminating the film prepared using the copolymer of Comparative Example and Example as a protective film on both sides of the polyvinyl alcohol-based polarizer, dried and bonded for 10 minutes at 80 ℃ oven To obtain a polarizing plate.
(광학물성 평가)(Optical evaluation)
분광광도계(n&k spectrometer, n&k Technology사제)를 이용하여 제조된 편광판의 단체 투과도와 직교 투과도를 측정하였다.The single transmittance and orthogonal transmittance of the polarizing plate manufactured using the spectrophotometer (n & k spectrometer, n & k Technology Co., Ltd.) were measured.
제조된 편광판의 물성 측정 결과를 하기 표 8에 나타내었다. The physical property measurement results of the prepared polarizing plate are shown in Table 8 below.
보호필름use
Protective film
(%)Orthogonal Transparency
(%)
편광판을 제조한 후의 편광특성에는 TAC 필름을 적용한 비교예와 큰 차이가 없었다.The polarization characteristic after manufacturing a polarizing plate did not have a big difference with the comparative example which applied the TAC film.
본 발명에 따른 광학필름은 광학적 투명성 및 광학 특성이 우수하고, 부서지기 쉬운 특성(brittleness)이 개선되었으며, 주변 온도와 습도의 환경 변화에 따른 치수 변화율과 광특성 변화가 적고, 내구성이 우수하므로 다양한 용도에서 유용하게 사용될 수 있다. 특히, 상기 광학필름은 고품질의 편광자 보호필름으로 사용될 수 있고, 이에 따라 내열성, 내습성 등 내구성이 우수한 고품질의 편광판 및 화상표시장치를 제공할 수 있다. The optical film according to the present invention has excellent optical transparency and optical properties, improved brittleness, less change in dimensional change and optical properties due to environmental changes in ambient temperature and humidity, and excellent durability. It can be usefully used in the application. In particular, the optical film may be used as a high quality polarizer protective film, thereby providing a high quality polarizing plate and an image display device having excellent durability such as heat resistance and moisture resistance.
Claims (17)
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KR1020070050754A KR101023181B1 (en) | 2007-05-25 | 2007-05-25 | Optical film, protection film for polarizer film, polarizer plate fabricated therefrom, and display device employing thereof |
CN200880017555XA CN101720337B (en) | 2007-05-25 | 2008-05-23 | Optical film, protection film for polarizer film, polarizer plate fabricated therefrom, and display device employing thereof |
PCT/KR2008/002911 WO2008147081A1 (en) | 2007-05-25 | 2008-05-23 | Optical film, protection film for polarizer film, polarizer plate fabricated therefrom, and display device employing thereof |
US12/451,674 US8242225B2 (en) | 2007-05-25 | 2008-05-23 | Optical film, protection film polarizer film, polarizer plate fabricated thereform, and display device employing therof |
JP2010509280A JP2010528336A (en) | 2007-05-25 | 2008-05-23 | Optical film, polarizer protective film, polarizing plate using the same, and image display device using the same |
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