KR101798904B1 - Copolymer and Pressure-sensitive adhesive composion - Google Patents
Copolymer and Pressure-sensitive adhesive composion Download PDFInfo
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- KR101798904B1 KR101798904B1 KR1020110102649A KR20110102649A KR101798904B1 KR 101798904 B1 KR101798904 B1 KR 101798904B1 KR 1020110102649 A KR1020110102649 A KR 1020110102649A KR 20110102649 A KR20110102649 A KR 20110102649A KR 101798904 B1 KR101798904 B1 KR 101798904B1
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Abstract
본 발명은 공중합체 및 이를 포함하는 점착제 조성물에 관한 것으로서, 보다 상세하게는 화학식 1로 표시되는 단량체로 형성되는 반복단위를 포함함으로써, 점착제 조성물에 사용되면 양생 시간이 짧고 조액 안정성, 경시 안정성을 우수하게 유지할 수 있으며, 편광판에 적용될 경우 빛샘효과 및 내구성이 개선된다.The present invention relates to a copolymer and a pressure-sensitive adhesive composition containing the same, and more particularly, to a pressure-sensitive adhesive composition comprising a repeating unit formed of a monomer represented by the formula (1) , And when applied to a polarizing plate, the light leakage effect and durability are improved.
Description
본 발명은 가교 촉진제를 따로 첨가하지 않고도 양생 기간을 단축시킬 수 있고, 조액 안정성, 빛샘개선, 내구성, 리워크성 등도 만족시킬 수 있는 점착제 조성물을 제공할 수 있는 공중합체 및 이를 포함하는 점착제 조성물에 관한 것이다.
The present invention relates to a copolymer capable of providing a pressure-sensitive adhesive composition capable of shortening a curing period without addition of a crosslinking accelerator and satisfying liquid stability, light leakage improvement, durability and reworkability, and a pressure- .
액정표시장치(Liquid crystal display device, LCD)는 액정셀과 상기 액정셀의 양면에 점착제층을 매개로 접합된 편광판을 포함하는 액정패널을 구비한다.2. Description of the Related Art A liquid crystal display device (LCD) includes a liquid crystal cell and a liquid crystal panel including a polarizing plate bonded to both sides of the liquid crystal cell via an adhesive layer.
액정셀과 편광판의 접합을 위한 점착제는 기재와의 밀착성, 빛샘 방지성, 내열 및 내습열 내구성뿐만 아니라 리워크성과 같은 물성을 동시에 만족시켜야 한다. 또한, 상기 언급된 물성과 함께 점착제는 양생 기간을 단축시켜 생산성도 향상시킬 것이 요구된다.The adhesive for the bonding of the liquid crystal cell and the polarizing plate should simultaneously satisfy the properties such as adhesiveness to the substrate, light resistance prevention property, heat resistance and anti-wet heat resistance as well as reworkability. In addition, in addition to the above-mentioned physical properties, the pressure-sensitive adhesive is required to shorten the curing period to improve the productivity.
이와 같이 종래 점착제로서 요구되는 물성을 유지하면서도 양생 기간을 단축시키기 위한 방법으로 가교반응을 촉진시키는 가교촉진제를 이용하는 방법이 제안되었다.As described above, a method using a crosslinking accelerator that promotes a crosslinking reaction has been proposed as a method for shortening the curing period while maintaining physical properties required as a conventional pressure-sensitive adhesive.
한국공개특허 제2009-0132116호에는 특정 구조의 루이스 염기를 포함하는 점착제 조성물이 개시되어 있고, 한국공개특허 제2008-0047030호에는 루이스 산을 포함하는 점착제 조성물이 개시되어 있다. 상기 문헌들에 기재된 점착제 조성물은 양생 단축의 효과는 있으나, 가교촉진제의 첨가로 인해 점착제 조성물의 점도가 급격하게 변화되어 저장 안정성을 저하시키고 점착제의 포트-라이프를 단축시키는 단점이 있으며, 이로 인해 공정 안정성에 문제를 일으킬 수 있다.
Korean Patent Laid-Open No. 2009-0132116 discloses a pressure-sensitive adhesive composition comprising a Lewis base having a specific structure, and Korean Published Patent Application No. 2008-0047030 discloses a pressure-sensitive adhesive composition comprising Lewis acid. Although the pressure-sensitive adhesive composition described in the above documents has an effect of shortening the curing time, there is a disadvantage that the viscosity of the pressure-sensitive adhesive composition is rapidly changed due to the addition of the crosslinking accelerator, thereby lowering the storage stability and shortening the pot- It may cause problems in stability.
본 발명은 별도의 가교촉진제를 첨가하지 않고도 양생 기간을 단축시킬 수 있고, 점착제로서 요구되는 물성도 만족시킬 수 있는 점착제 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a pressure-sensitive adhesive composition which can shorten a curing period without adding a crosslinking accelerator and can satisfy physical properties required as a pressure-sensitive adhesive.
또한, 본 발명은 상기 점착제 조성물로 이루어진 점착제층이 적층된 편광판을 제공하는 것을 다른 목적으로 한다.Another object of the present invention is to provide a polarizing plate in which a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition is laminated.
또한, 본 발명은 액정셀의 적어도 한 면에 상기 편광판이 구비된 액정표시장치를 제공하는 것을 또 다른 목적으로 한다.
It is another object of the present invention to provide a liquid crystal display device having the polarizing plate on at least one surface of a liquid crystal cell.
1. 하기 화학식 1로 표시되는 단량체로 형성되는 반복단위를 포함하는 아크릴계 공중합체:1. An acrylic copolymer comprising a repeating unit formed from a monomer represented by the following formula (1): < EMI ID =
(식 중, R1은 수소 또는 메틸기이며; X는 -NH-, -O- 또는 -S-이며; R2는 탄소수 0 내지 3의 알킬렌기이며; R3는 수소, 탄소수 1 내지 3의 알킬기 또는 페닐기임).Wherein R 1 is hydrogen or a methyl group, X is -NH-, -O- or -S-, R 2 is an alkylene group having 0 to 3 carbon atoms, R 3 is hydrogen, an alkyl group having 1 to 3 carbon atoms Or a phenyl group).
2. 위 1에 있어서, 위 공중합체는 탄소수 1 내지 12인 알킬기를 포함하는 (메타)아크릴레이트계 단량체와 상기 화학식 1로 표시되는 단량체가 공중합되어 형성되는 공중합체.2. The copolymer of claim 1, wherein the copolymer is formed by copolymerization of a (meth) acrylate monomer containing an alkyl group having 1 to 12 carbon atoms and a monomer represented by the formula (1).
3. 위 2에 있어서, 위 공중합체는 탄소수 1 내지 12인 알킬기를 포함하는 (메타)아크릴레이트계 단량체 100 중량부 및 하기 화학식 1로 표시되는 단량체 0.01 내지 10 중량부가 중합되어 형성되는 공중합체.3. The copolymer of claim 2, wherein the copolymer is formed by polymerizing 100 parts by weight of a (meth) acrylate monomer containing an alkyl group having 1 to 12 carbon atoms and 0.01 to 10 parts by weight of a monomer represented by the following formula (1).
4. 위 2에 있어서, 위 (메타)아크릴레이트계 단량체는 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 공중합체.(Meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (Meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl Lt; RTI ID = 0.0 > of: < / RTI >
5. 위 1에 있어서, 가교성 관능기를 갖는 단량체를 더 포함하여 중합되는 공중합체.5. The copolymer according to 1 above, which further comprises a monomer having a crosslinkable functional group.
6. 위 5에 있어서, 위 가교성 관능기는 히드록시기, 카르복시기, 아미드기 또는 3차 아민기인 공중합체.6. The copolymer according to item 5, wherein the stoichiometric crosslinkable functional group is a hydroxyl group, a carboxyl group, an amide group or a tertiary amine group.
7. 위 5에 있어서, 위 가교성 관능기를 갖는 단량체는 전체 단량체 총 중량에 대하여 0.1 내지 15중량%로 포함되는 공중합체.7. The copolymer according to 5 above, wherein the monomer having a stoichiometric cross-linkable functional group is contained in an amount of 0.1 to 15% by weight based on the total weight of the total monomers.
8. 위 1에 있어서, 중량평균 분자량이 20만 내지 150만인 공중합체.8. The copolymer according to 1 above, which has a weight average molecular weight of 200,000 to 1,500,000.
9. 위 1 내지 8 중 어느 하나의 공중합체 및 가교제를 포함하는 점착제 조성물.9. A pressure-sensitive adhesive composition comprising a copolymer of any one of claims 1 to 8 and a crosslinking agent.
10. 위 9에 있어서, 위 가교제는 위 공중합체 고형분 100 중량부에 대하여 0.1 내지 15 중량부로 포함되는 점착제 조성물.10. The pressure-sensitive adhesive composition according to the above 9, wherein the styrene crosslinking agent is contained in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the styrene copolymer.
11. 위 9의 점착제 조성물로 형성된 점착제층이 구비된 편광판.11. A polarizing plate provided with a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the above 9.
12. 위 11의 편광판이 구비된 액정표시장치.
12. A liquid crystal display device comprising the polarizer of the eleventh aspect.
본 발명에 따른 공중합체는 친핵성 첨가반응의 활성도가 큰 벤질알콜 구조를 포함하므로써, 점착제 조성물에 사용되는 경우 양생 시간을 단축할 수 있으며 조액 안정성도 만족시킬 수 있다.Since the copolymer according to the present invention contains a benzyl alcohol structure having a high nucleophilic addition reaction activity, it can shorten the curing time when used in a pressure-sensitive adhesive composition and can also satisfy the liquid stability.
또한, 본 발명에 따른 공중합체는 벤질알콜의 히드록시기는 페닐의 전자효과에 의해 반응성이 상승될 뿐만 아니라 페놀에 비해 입체장애가 적어, 점착제 조성물에 사용되는 경우에 가교제와의 반응성을 극대화할 수 있다.In addition, the hydroxyl group of the benzyl alcohol according to the present invention is not only increased in reactivity due to the electron effect of phenyl but also less steric hindered than phenol, and can maximize reactivity with the crosslinking agent when used in a pressure-sensitive adhesive composition.
또한, 본 발명에 따른 공중합체는 페닐 구조를 포함함으로써 편광판의 점착층에 적용될 경우에 빛탄성계수가 향상되어 빛샘 효과가 개선되고, 응집력이 상승되어 내구성이 향상된다.In addition, when the copolymer according to the present invention includes a phenyl structure, it is improved in light elastic modulus when applied to an adhesive layer of a polarizing plate, thereby improving the light-shielding effect and improving cohesion and durability.
또한, 본 발명의 점착제 조성물은 가교촉진제와 같은 별도의 첨가제를 첨가하지 않고도 양생 기간을 단축시켜 생산성을 향상시킬 수 있다.In addition, the pressure-sensitive adhesive composition of the present invention can improve the productivity by shortening the curing period without adding any additives such as a crosslinking accelerator.
또한, 본 발명의 점착제 조성물은 초기 점착력이 양호하며 고온 또는 고온·다습한 환경 하에서 경시 변화가 적고 점착력도 과도하게 증가하지 않아 내구성 및 리워크성과 같은 물성을 동시에 만족시킬 수 있다.
In addition, the pressure-sensitive adhesive composition of the present invention has good initial tack and has little change with time under high temperature, high temperature and high humidity environment, and does not excessively increase the adhesive force, thereby satisfying the properties such as durability and reworkability.
본 발명은, 화학식 1로 표시되는 단량체로 형성되는 반복단위를 포함함으로써, 점착제 조성물에 사용되면 양생 시간이 짧고 조액 안정성, 경시 안정성을 우수하게 유지할 수 있으며, 편광판에 적용될 경우 빛샘효과 및 내구성이 개선되는 공중합체 및 이를 포함하는 점착제 조성물에 관한 것이다.The present invention, when used in a pressure-sensitive adhesive composition, includes a repeating unit formed of a monomer represented by the general formula (1), thereby shortening the curing time and maintaining the stability of the liquid bath and the stability over time. When applied to a polarizing plate, And a pressure-sensitive adhesive composition comprising the same.
이하, 본 발명을 상세히 설명하기로 한다. Hereinafter, the present invention will be described in detail.
본 발명의 아크릴계 공중합체는 하기 화학식 1로 표시되는 단량체로 형성되는 반복단위를 포함하는 것을 특징으로 한다:The acrylic copolymer of the present invention is characterized by comprising a repeating unit formed from a monomer represented by the following formula (1)
[화학식 1][Chemical Formula 1]
(식 중, R1은 수소 또는 메틸기이며; X는 -NH-, -O- 또는 -S-이며; R2는 탄소수 0 내지 3의 알킬렌기이며; R3는 수소, 탄소수 1 내지 3의 알킬기 또는 페닐기임).Wherein R 1 is hydrogen or a methyl group, X is -NH-, -O- or -S-, R 2 is an alkylene group having 0 to 3 carbon atoms, R 3 is hydrogen, an alkyl group having 1 to 3 carbon atoms Or a phenyl group).
본 발명에 따른 공중합체는 위 화학식 1로 표시되는 단량체가 중합되어 형성되는 반복단위를 포함함으로써, 친핵성 첨가반응의 활성도가 큰 벤질알콜 구조를 포함하게 되어, 점착제 조성물에 사용되는 경우 양생 시간을 단축할 수 있으며 조액 안정성도 만족시킬 수 있다. 또한, 벤질알콜의 히드록시기는 페닐의 전자효과에 의해 반응성이 상승될 뿐만 아니라 페놀에 비해 입체장애가 적어, 점착제 조성물에 사용되는 경우에 가교제와의 반응성을 극대화할 수 있다. 또한, 페닐 구조는 편광판의 점착층에 적용될 경우에 빛탄성계수가 향상되어 빛샘 효과를 개선하고, 응집력을 상승시켜 내구성을 향상시킬 수 있다.The copolymer according to the present invention contains a repeating unit formed by polymerization of the monomer represented by the above formula (1), thereby containing a benzyl alcohol structure having a high activity of the nucleophilic addition reaction. Thus, the curing time when used in the pressure- Can be shortened and the solution stability can be satisfied. In addition, the hydroxyl group of benzyl alcohol not only increases the reactivity due to the electron effect of phenyl but also has less steric hindrance as compared with phenol, so that the reactivity with the crosslinking agent can be maximized when it is used in a pressure-sensitive adhesive composition. In addition, when a phenyl structure is applied to an adhesive layer of a polarizing plate, the light elastic modulus is improved to improve the light-shielding effect, and the durability can be improved by increasing the cohesive force.
본 발명의 아크릴계 공중합체는 위 화학식 1의 단량체와 (메타)아크릴레이트계 단량체를 공중합하여 형성될 수 있는데, (메타)아크릴레이트 단량체는 공중합체의 주된 구조를 형성하고 점착성을 발휘한다. (메타)아크릴레이트계 단량체는 탄소수 1 내지 12인 알킬기를 포함하는 (메타)아크릴레이트계 단량체가 바람직하다. The acrylic copolymer of the present invention can be formed by copolymerizing the monomer of Formula 1 with (meth) acrylate monomer, wherein the (meth) acrylate monomer forms the main structure of the copolymer and exhibits stickiness. (Meth) acrylate monomer is preferably a (meth) acrylate monomer containing an alkyl group having 1 to 12 carbon atoms.
본 발명의 화학식 1의 단량체가 탄소수 1 내지 12인 알킬기를 포함하는 (메타)아크릴레이트계 단량체와 공중합하는 경우, 위 화학식 1로 표시되는 단량체는 (메타)아크릴레이트계 단량체 100 중량부 대비 0.01 내지 10 중량부, 바람직하게는 0.1 내지 8중량부로 포함되어 공중합체를 형성한다. 그 함량이 0.01 중량부 미만이면 점착제 조성물에 사용될 경우 양생 시간 단축 효과가 미미하고, 10 중량부 초과이면 점착제 조성물의 내구성이 저하된다.When the monomer of the formula (1) of the present invention is copolymerized with a (meth) acrylate monomer containing an alkyl group having 1 to 12 carbon atoms, the monomer represented by the formula (1) 10 parts by weight, preferably 0.1 to 8 parts by weight, of the copolymer. When the content is less than 0.01 part by weight, the effect of shortening the curing time is insignificant when used in the pressure-sensitive adhesive composition, while when it is more than 10 parts by weight, the durability of the pressure-
탄소수 1 내지 12인 알킬기를 포함하는 (메타)아크릴레이트 단량체의 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 각각 단독으로 또는 2종 이상 혼합하여 사용할 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, (meth) acrylate, 2-ethylbutyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (Meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl ) Acrylate may be used alone or in combination of two or more.
선택적으로, 본 발명의 공중합체는 가교성 관능기를 갖는 단량체를 더 포함할 수 있다. 가교성 관능기를 갖는 단량체는 화학 결합에 의해 점착제 조성물의 응집력 또는 점착 강도를 보강하여 내구성과 절단성을 부여하기 위한 성분으로서, 예컨대 히드록시기를 갖는 단량체, 카르복시기를 갖는 단량체, 아미드기를 갖는 단량체, 3차 아민기를 갖는 단량체 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있고, 바람직하게는 히드록시기를 갖는 단량체를 사용할 수 있다.Alternatively, the copolymer of the present invention may further comprise a monomer having a crosslinkable functional group. The monomer having a crosslinkable functional group is a component for imparting durability and cutability by reinforcing the cohesive strength or adhesive strength of the pressure-sensitive adhesive composition by chemical bonding, and examples thereof include monomers having a hydroxy group, monomers having a carboxyl group, monomers having an amide group, And amine group-containing monomers. These monomers may be used alone or in admixture of two or more, preferably monomers having a hydroxy group.
히드록시기를 갖는 단량체로는 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.Examples of the monomer having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl Hydroxypropyleneglycol (meth) acrylate, hydroxyalkylene glycol having 2 to 4 carbon atoms in the alkylene group (e.g., methoxyethyl (meth) acrylate, Hydroxybutyl vinyl ether, 8-hydroxyoctyl vinyl ether, 9-hydroxynonyl (meth) acrylate, 4-hydroxybutyl vinyl ether, Vinyl ether, and 10-hydroxydecyl vinyl ether. Of these, 4-hydroxybutyl vinyl ether is preferable.
카르복시기를 갖는 단량체로는 (메타)아크릴산, 크로톤산 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 carboxyl group include monovalent acids such as (meth) acrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, itaconic acid, and fumaric acid, and monoalkyl esters thereof; 3- (meth) acryloylpropionic acid; A succinic anhydride ring-opening addition adduct of 2-hydroxyalkyl (meth) acrylate in which the alkyl group has 2 to 4 carbon atoms, anhydrous succinic ring opening adduct of a hydroxyalkylene glycol (meth) acrylate having 2 to 4 carbon atoms in the alkylene group , Compounds obtained by ring-opening addition of succinic anhydride to caprolactone adducts of 2-hydroxyalkyl (meth) acrylates whose alkyl groups have 2-3 carbon atoms, and among these, (meth) acrylic acid is preferable.
아미드기를 갖는 단량체로는 (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-isopropyl acrylamide, N-tertiary butyl acrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (Meth) acrylamide, 8-hydroxyoctyl (meth) acrylamide and 2-hydroxyethylhexyl (meth) acrylamide. Of these, (meth) acrylamide is preferable.
3차 아민기를 갖는 단량체로는 N,N-(디메틸아미노)에틸(메타)아크릴레이트, N,N-(디에틸아미노)에틸(메타)아크릴레이트, N,N-(디메틸아미노)프로필(메타)아크릴레이트 등을 들 수 있다.Examples of the monomer having a tertiary amine group include N, N- (dimethylamino) ethyl (meth) acrylate, N, N- (diethylamino) ethyl (meth) ) Acrylate, and the like.
가교성 관능기를 갖는 단량체는 전체 단량체 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 contained in an amount of 0.1 to 15% by weight, more preferably 1 to 10% by weight based on the total weight of the total monomers. When the content is less than 0.1% by weight, the cohesive force of the pressure-sensitive adhesive becomes small and durability may be deteriorated. When the content is more than 10% by weight, a high gel fraction may deteriorate the adhesive strength and cause durability problems.
또한, 상기 단량체들 이외에 다른 중합성 단량체가 점착력을 저하시키지 않는 범위, 예컨대 10중량% 이하로 더 포함될 수 있다.In addition, other polymerizable monomers other than the above-mentioned monomers may be further added in such a range as not to lower the adhesive force, for example, 10% by weight or less.
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 method for producing the copolymer is not particularly limited and can be produced by methods 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 polymerization can be used.
공중합체는 겔투과크로마토그래피(Gel permeation chromatography, GPC)에 의해 측정된 중량평균 분자량(폴리스티렌 환산, Mw)이 20만 내지 150만, 바람직하게 40만 내지 100만일 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 conversion, Mw) of 200,000 to 150,000, preferably 400,000 to 100, as measured by gel permeation chromatography (GPC). If the molecular weight is less than 200,000, the cohesive force between the copolymers is insufficient, which may cause problems in adhesion durability. If the molecular weight is more than 1.5 million, a large amount of diluting solvent is required in order to secure the fairness in the coating.
본 발명의 공중합체는 가교제와 함께 혼합되어 점착제 조성물로 사용될 수 있다.The copolymer of the present invention can be mixed with a crosslinking agent and used as a pressure-sensitive adhesive composition.
가교제는 공중합체를 적절히 가교함으로써 점착제의 응집력을 강화하기 위한 성분으로서, 그 종류는 특별히 한정되지 않는다. 예컨대, 이소시아네이트계 화합물, 에폭시계 화합물 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The crosslinking agent is a component for reinforcing the cohesive force of the pressure-sensitive adhesive by properly crosslinking the copolymer, and the kind thereof is not particularly limited. Examples thereof include isocyanate compounds and epoxy compounds, which may be used alone or in combination of two or more.
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 3몰 중 2몰로부터 얻어지는 디이소시아네이트 우레아에 나머지 1몰의 디이소시아네이트가 축합된 뷰렛체, 트리페닐메탄트리이소시아네이트, 메틸렌비스트리이소시아네이트 등의 3개의 관능기를 함유하는 다관능 이소시아네이트 화합물 등을 들 수 있다.Examples of the isocyanate compound include tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate , Diisocyanate compounds such as 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 compound in which 3 moles of a diisocyanate compound is self-condensed, a diisocyanate obtained from 2 moles of 3 moles of a diisocyanate compound And multifunctional isocyanate compounds containing three functional groups such as burette, triphenylmethane triisocyanate and methylene bistriisocyanate in which the remaining one mole of diisocyanate is condensed in urea.
에폭시계 화합물로는 에틸렌글리콜디글리시딜에테르, 디에틸렌글리콜디글리시딜에테르, 폴리에틸렌글리콜디글리시딜에테르, 프로필렌글리콜디글리시딜에테르, 트리프로필렌글리콜디글리시딜에테르, 폴리프로필렌글리콜디글리시딜에테르, 네오펜틸글리콜디글리시딜에테르, 1,6-헥산디올디글리시딜에테르, 폴리테트라메틸렌글리콜디글리시딜에테르, 글리세롤디글리시딜에테르, 글리세롤트리글리시딜에테르, 디글리세롤폴리글리시딜에테르, 폴리글리세롤폴리글리시딜에테르, 레졸신디글리시딜에테르, 2,2-디브로모네오펜틸글리콜디글리시딜에테르, 트리메틸올프로판트리글리시딜에테르, 펜타에리트리톨폴리글리시딜에테르, 소르비톨폴리글리시딜에테르, 아디핀산디글리시딜에스테르, 프탈산디글리시딜에스테르, 트리스(글리시딜)이소시아누레이트, 트리스(글리시독시에틸)이소시아누레이트, 1,3-비스(N,N-글리시딜아미노메틸)시클로헥산, N,N,N',N'-테트라글리시딜-m-자일릴렌디아민 등을 들 수 있다.Examples of the epoxy compound include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol Hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, glycerol diglycidyl ether, glycerol diglycidyl ether, Diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcinol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol Polyglycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris (glycidyl) isocyanurate N, N ', N'-tetraglycidyl-m-glycidoxyethyl isocyanurate, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, Xylylenediamine, and the like.
또한, 이소시아네이트계 화합물, 에폭시계 화합물과 함께 멜라민계 화합물을 단독 또는 2종 이상 혼합하여 추가로 사용할 수 있다.In addition, an isocyanate compound, an epoxy compound, and a melamine compound may be used alone or in admixture of two or more.
멜리민계 화합물로는 헥사메틸올멜라민, 헥사메톡시메틸멜라민, 헥사부톡시메틸멜라민 등을 들 수 있다.Examples of the melamine-based compound include hexamethylol melamine, hexamethoxymethyl melamine, and hexabutoxymethyl melamine.
가교제는 고형분 함량을 기준으로 공중합체 100중량부에 대하여 0.1 내지 15중량부로 포함되는 것이 바람직하고, 보다 바람직하게는 0.1 내지 5중량부인 것이 좋다. 함량이 0.1중량부 미만인 경우 부족한 가교도로 인해 응집력이 작아지게 되어 들뜸과 같은 내구성 저하가 유발되고 절단성을 해칠 수 있으며, 15중량부 초과인 경우 과다 가교반응에 의해 잔류응력 완화에 문제가 발생할 수 있다.The crosslinking agent is preferably contained in an amount of 0.1 to 15 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the copolymer based on the solid content. When the content is less than 0.1 parts by weight, the cohesive force becomes small due to insufficient crosslinking, resulting in deterioration of durability such as peeling and deterioration of cutability. If the content is more than 15 parts by weight, excessive crosslinking reaction may cause a problem of relaxation of residual stress have.
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 above-mentioned components, the pressure-sensitive adhesive composition according to the present invention may further contain various additives such as a tackifier resin, an antioxidant, a corrosion inhibitor, a leveling agent, and the like for controlling the tackiness, cohesion, viscosity, elastic modulus, glass transition temperature, A lubricant, a surface lubricant, a dye, a pigment, a defoaming agent, a filler, a light stabilizer, an antistatic agent, and the like.
이와 같이 구성된 점착제 조성물은 특히 화학식 1로 표시되는 단량체가 중합된 공중합체를 포함함으로써 양생 기간을 단축시킴과 동시에 우수한 경시안정성을 갖는다. 또한, 점착력, 내열/내습열성 및 리워크성과 같은 물성도 만족시킬 수 있다.The pressure-sensitive adhesive composition thus constituted comprises a copolymer in which the monomer represented by the formula (1) is polymerized, thereby shortening the curing period and having an excellent stability over time. In addition, it can satisfy physical properties such as adhesion, heat / moisture resistance and reworkability.
본 발명의 점착제 조성물은 액정셀과의 접합을 위한 편광판용 점착제뿐만 아니라 표면보호필름용 점착제로서도 모두 사용할 수 있다. 또한, 보호필름, 반사시트, 구조용 점착시트, 사진용 점착시트, 차선표시용 점착시트, 광학용 점착제품, 전자부품용 점착제뿐만 아니라 일반 상업용 점착시트제품, 의료용 패치로도 사용 가능하다.The pressure-sensitive adhesive composition of the present invention can be used not only as a pressure-sensitive adhesive for a polarizing plate for bonding with a liquid crystal cell but also as a pressure-sensitive adhesive for a surface protective film. In addition, it can be used not only as a protective film, a reflective sheet, a structural adhesive sheet, a photographic adhesive sheet, a lane marking adhesive sheet, an optical adhesive product, an electronic component adhesive, but also a general commercial adhesive sheet product or a medical patch.
본 발명의 편광판은 점착제 조성물로 이루어진 점착제층이 적층된 것을 특징으로 한다.The polarizing plate of the present invention is characterized in that a pressure-sensitive adhesive layer composed of a pressure-sensitive adhesive composition is laminated.
점착제층의 두께는 그 점착력에 따라 조절될 수 있으며, 통상 3 내지 100㎛인 것이 바람직하며, 보다 바람직하게는 10 내지 100㎛인 것이 좋다.The thickness of the pressure-sensitive adhesive layer can be adjusted in accordance with the adhesive strength, and is preferably 3 to 100 탆, more preferably 10 to 100 탆.
이러한 편광판은 통상의 액정표시장치에 모두 적용 가능하며, 구체적으로 점착제층이 적층된 편광판을 액정셀의 적어도 한 면에 접합한 액정패널을 포함하는 액정표시장치를 구성할 수 있다.Such a polarizing plate can be applied to all conventional liquid crystal display devices, and specifically a liquid crystal display device including a liquid crystal panel in which a polarizing plate in which a pressure-sensitive adhesive layer is laminated is bonded to at least one surface of a liquid crystal cell can be constituted.
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.It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.
합성예Synthetic example 1 One
1000mL 용량의 둥근플라스크를 0℃ 항온조에 담그고, 4-아미노벤질알코올 100g과 디클로로메탄 용매 300g을 첨가한 후, 30분 동안 교반하여 용해시킨 다음, 아크릴로일클로라이드 50g을 10분간 천천히 적가하였다. 100 g of 4-aminobenzyl alcohol and 300 g of a dichloromethane solvent were added to the flask, and the mixture was stirred for 30 minutes to dissolve. Then, 50 g of acryloyl chloride was slowly added dropwise for 10 minutes.
이어서 트리에틸아민 100g을 30분간 적가한 뒤, 상온에서 30분 추가 교반하고, 증류수 500mL를 추가하고 10분간 교반 후, 분별깔대기로 디클로로메탄층을 분리하고, 감압증류법으로 용매를 제거하여 4-아크릴아미노 벤질알코올을 얻었다.Then, 100 g of triethylamine was added dropwise for 30 minutes, further stirred at room temperature for 30 minutes, and 500 mL of distilled water was added. After stirring for 10 minutes, the dichloromethane layer was separated with a separating funnel and the solvent was removed by vacuum distillation to obtain 4-acryl Aminobenzyl alcohol was obtained.
합성예Synthetic example 2 2
4-아미노벤질알코올 대신 4-티오벤질알코올을 사용한 것을 제외하고는 합성예 1과 동일한 방법을 사용하여 4-아크릴티오 벤질알코올을 얻었다.
4-Acrylthiobenzyl alcohol was obtained in the same manner as in Synthesis Example 1, except that 4-thiobenzyl alcohol was used instead of 4-aminobenzyl alcohol.
실시예Example 1-7 및 1-7 and 비교예Comparative Example 1-4 1-4
하기 표 1에 기재된 성분과 조성비로 공중합체 및 점착제 조성물을 제조하였다(단위: 중량%).Copolymers and pressure-sensitive adhesive compositions were prepared with the components and composition ratios shown in Table 1 below (unit: wt%).
공중합체는 질소가스가 환류되고 온도조절이 용이하도록 냉각장치를 설치한 1 L의 반응기에 하기 표 1의 성분 및 조성비로 이루어진 단량체 혼합물을 투입한 후, 용제로 에틸아세테이트(EAc)를 단량체 혼합물과 동일한 중량으로 투입하였다. 그 다음 산소를 제거하기 위하여 질소가스를 1 시간 동안 퍼징한 후, 62 ℃로 유지하였다. 상기 혼합물을 균일하게 한 후, 반응개시제로 아조비 스이소부티로니트릴(AIBN)을 단량체 혼합물 100 중량부 대비 0.07 중량부로 투입하고, 8 시간 동안 반응시켜 제조하였다.The copolymer was prepared by charging a monomer mixture composed of the components and composition ratios shown in Table 1 below into a 1 L reactor equipped with a cooling device so that nitrogen gas was refluxed and temperature was easily controlled, ethyl acetate (EAc) The same weight was added. Nitrogen gas was then purged for 1 hour to remove oxygen and then maintained at 62 ° C. After homogenizing the mixture, azobisisobutyronitrile (AIBN) was added as a reaction initiator to 0.07 part by weight of 100 parts by weight of the monomer mixture and reacted for 8 hours.
4AABA : 4-아크릴아미노 벤질알코올
4ATBA : 4-아크릴티오 벤질알코올
2HEA : 2-하이드록시에틸아크릴레이트
AA : 아크릴산
Cor-L : 코로네이트-L(트리메틸올프로판의 톨릴렌디이소시아네이트 부가물 , 니혼폴리우레탄코교주식회사 제품)
Cor-HXR : 코로네이트-HXR(헥사메틸렌디이소시아네이트계, 니혼폴리우레탄코교주식회사 제품)
실시예 1-7의 공중합체의 중량평균 분자량은 다음과 같음:
실시예1: 80만, 실시예2: 80만, 실시예3: 80만,
실시예4: 80만, 실시예5: 80만, 실시예6: 80만, 실시예7: 80만BA: butyl acrylate
4AABA: 4-acrylamylbenzyl alcohol
4ATBA: 4-Acrylthiobenzyl alcohol
2HEA: 2-hydroxyethyl acrylate
AA: Acrylic acid
Cor-L: Coronate-L (tolylene diisocyanate adduct of trimethylol propane, manufactured by Nippon Polyurethane Kogyo Co., Ltd.)
Cor-HXR: Coronate-HXR (hexamethylene diisocyanate type, manufactured by Nippon Polyurethane Kogyo Co., Ltd.)
The weight average molecular weight of the copolymer of Example 1-7 is as follows:
Example 1: 800,000, Example 2: 800,000, Example 3: 800,000,
Example 4: 800,000, Example 5: 800,000, Example 6: 800,000, Example 7: 800,000
실험예Experimental Example
삭제delete
상기 표 1에 따라 제조된 실시예 1-7과 비교예 1-4의 점착제 조성물 용액을 박리필름에 코팅하여 건조한 후 25 ㎛가 되도록 도포하고, 100℃ 1분간 건조시켜, 점착제 조성물로 이루어진 점착층을 형성하였다. The pressure-sensitive adhesive composition solutions of Examples 1-7 and Comparative Example 1-4 prepared according to Table 1 were coated on a release film, dried and coated at 25 占 퐉 and dried at 100 占 폚 for 1 minute to obtain an adhesive layer .
상기 제조된 점착층을 185 ㎛ 두께의 요오드계 편광판에 점착가공한 후, 충분한 숙성과정을 위하여 23 ℃의 온도와 60%의 습도조건에서 양생일 동안 보관하여 실시예 1-7과 비교예 1-4에 해당하는 편광판을 얻었다. The adhesive layer thus prepared was adhered to an iodine polarizing plate having a thickness of 185 μm and stored for two days at a temperature of 23 ° C. and a humidity of 60% for a sufficient aging process, 4 was obtained.
얻어진 편광판은 적절한 크기로 절단하여 하기 평가에 사용하였으며, 그 결과를 하기 표 2에 기재하였다.The resulting polarizer was cut to an appropriate size and used in the following evaluation. The results are shown in Table 2 below.
1. 내열/1. Heat resistance / 내습열Wet heat 신뢰성 responsibility
시험예 1에서 제조한 점착제 시트로부터 이형필름을 박리한 후, 두께 185㎛의 요오드계 편광판에 점착 가공하였다. 상기의 편광판을 90mmX170mm로 절단하고 유리기판 (110mm X 190mm X 0.7mm)에 양면으로 광학 흡수축이 크로스된 상태로 부착시켰다. 이때 가해진 압력은 5kg/cm2으로 기포나 이물이 생기지 않도록 크린룸 작업을 하였다. 이 시편들을 내열특성은 80℃의 온도에서 1000시간 동안 방치한 후에 기포나 박리의 발생 여부를 관찰하였다. 시편의 상태를 평가하기 직전에 상온에서 24시간 방치한 후 실시하였다. 내습열 특성을 파악하기 위하여 60℃의 온도 및 90%의 상대습도 조건하에서 1000시간 방치한 후에 기포나 박리의 발생 여부를 관찰하였다. 또한, 상기에서 제조된 점착 편광판을 5개월 이상 방치 후 상기의 방법으로 신뢰성을 평가하였다. 신뢰성에 대한 평가기준은 다음과 같다. The release film was peeled from the pressure-sensitive adhesive sheet prepared in Test Example 1, and then subjected to pressure-sensitive adhesive processing on an iodine-based polarizer having a thickness of 185 μm. The polarizing plate was cut to 90 mm x 170 mm, and adhered on both sides of a glass substrate (110 mm x 190 mm x 0.7 mm) with the optical absorption axes crossed. At this time, the applied pressure was 5 kg / cm 2 , and the clean room operation was performed so that bubbles or foreign matter would not be generated. The heat resistance of these specimens was measured at a temperature of 80 ℃ for 1000 hours before bubble or peeling was observed. The specimens were allowed to stand at room temperature for 24 hours immediately before evaluating the state of the specimens. In order to understand the wet heat resistance characteristics, the samples were allowed to stand at a temperature of 60 ° C and a relative humidity of 90% for 1000 hours, and then the occurrence of bubbles or peeling was observed. In addition, the adhesive polarizer prepared above was allowed to stand for 5 months or more, and the reliability was evaluated by the above method. The evaluation criteria for reliability are as follows.
<평가기준><Evaluation Criteria>
ⓞ: 기포나 박리 없음Ⓞ: No bubble or peeling
○: 기포나 박리 5개미만○: Only bubbles or peeling 5 ants
△: 기포나 박리 5개이상 10개미만△: Bubbles or peeling 5 or more and 10 or less
×: 기포나 박리 10개이상X: 10 or more bubbles or peeling
2. 점착력 측정2. Adhesion measurement
점착제 시트를 폭 25mm, 길이 100mm의 크기로 잘라내고, 이형필름을 박리한 후, 트리아세틸셀룰로오스(보호필름)와 폴리비닐알코올(편광자)로 구성된 편광판에 0.25 MPa의 압력으로 라미네이션하고 오토클레이브를 처리하여 평가 샘플을 제조하였다.The pressure-sensitive adhesive sheet was cut to a size of 25 mm in width and 100 mm in length, and the release film was peeled off. The polarizing plate composed of triacetylcellulose (protective film) and polyvinyl alcohol (polarizer) was laminated at a pressure of 0.25 MPa and autoclaved To prepare an evaluation sample.
제조한 샘플을 23℃ X 50% RH의 환경하에서 24시간 방치한 샘플과, 50℃ X 50% RH의 환경하에서 48시간 방치한 샘플을 UTM (만능인장시험기, Instron)을 사용하여 박리 속도 10 m/min, 박리각도 180o로 박리할 때의 점착력을 측정하였다. 측정은 23℃ X 50% RH의 환경하에서 실시하였다.The sample thus prepared was allowed to stand under the environment of 23 占 폚 X 50% RH for 24 hours and the sample left in the environment of 50 占 폚 and 50% RH for 48 hours was peeled off at a peeling speed of 10 m / min, and the peel angle was 180 DEG. The measurement was carried out in an environment of 23 캜 X 50% RH.
3. 3. 리워크성Re-workability 측정 Measure
편광판을 폭 25mm, 길이 100mm의 크기로 잘라내고, 이형필름을 박리한 후, 코닝사 #1737 유리에 0.25 MPa의 압력으로 라미네이션하고 5기압, 50℃의 조건으로 20분 동안 오토클레이브를 처리하여 평가 샘플을 제조하였다. 내열조건인 80℃ 오븐에 넣은 후 10시간 뒤 꺼내어 120시간 상온 방치 후 1.3cm/s의 속도로 박리하고, 내습조건인 60℃, 90RH% 오븐에 넣은 후 12시간 뒤 꺼내어 120시간 상온 방치 후 1.3cm/s 의 속도로 박리하였다.The polarizing plate was cut to a size of 25 mm in width and 100 mm in length, and the release film was peeled off. The glass plate was laminated to Corning # 1737 glass at a pressure of 0.25 MPa and autoclaved for 20 minutes under conditions of 5 atm and 50 캜. . After putting it in an oven at 80 ℃ which is a heat-resistant condition, it was taken out after 10 hours, left for 120 hours at room temperature, peeled at a rate of 1.3 cm / s, put in an oven at 60 ° C and 90% RH for 12 hours, cm / s.
○: 양쪽 조건 모두에서 유리 기판에 점착제의 남음이 없고 편광판의 찢어짐 없이 깨끗이 박리?: No peeling of the pressure-sensitive adhesive on the glass substrate in both the conditions, and the glass substrate was cleanly peeled off without tearing the polarizing plate
×: 어느 한쪽 조건 이상에서 패널에 점착제가 남아있거나 박리과정에서 편광판이 찢어짐X: Pressure-sensitive adhesive remains on the panel under either condition or the polarizer tears in the peeling process
4. 4. 양생시간Curing time 단축 평가 ( Short evaluation ( 3일차Day 3 겔분율Gel fraction ))
제조된 점착제 부착 편광판을 23℃ 65%RH에서 3일 동안 양생하였다. 정칭(精秤)한 250메쉬의 철망(100㎜×100㎜)에 양생된 점착제 부착 편광판의 점착제층을 약 0.25g 첩부하고, 겔분이 새어나가지 않도록 감싼다. 정밀 천칭으로 중량을 정확하게 측정한 후, 철망을 에틸아세테이트 용액에 3일간 침지한다. 침지된 철망을 꺼내어 소량의 에틸아세테이트 용액으로 세정하고, 120℃에서 4시간 건조한 후 중량을 측정한다. 측정된 중량을 이용하여 하기 수학식 1로 겔분율을 계산하였다.The prepared polarizer with a pressure-sensitive adhesive was cured at 23 DEG C and 65% RH for 3 days. Approximately 0.25 g of the pressure-sensitive adhesive layer of the polarizing plate with pressure-sensitive adhesive cured on a wire mesh (100 mm x 100 mm) of a 250 mesh precisely weighed is attached, and the gel is wrapped so as not to leak. After accurately weighing the weight with a precision balance, the wire net is immersed in the ethyl acetate solution for 3 days. The immersed wire mesh is taken out, washed with a small amount of ethyl acetate solution, dried at 120 ° C for 4 hours and then weighed. Using the measured weight, the gel fraction was calculated by the following equation (1).
[식 중, A는 철망의 중량(g), B는 점착제층을 첩부한 철망의 중량(점착제 중량, g), C는 침지 후 건조한 철망의 중량(겔화된 수지의 중량, g)임)].(Weight of glued resin, g), C is the weight of glued resin (weight of gelled resin, dried) after immersion, and A is weight of wire net (g) .
○: 70% ≤ 3일차 겔분율 ?: 70%? 3 The initial gel fraction
△: 60% ≤ 3일차 겔분율 < 70%?: 60%? 3 Primary gel fraction <70%
X: 60% > 3일차 겔분율 X: 60% > 3 < tb >
5. 5. 빛샘Light beam 현상 평가( Evaluation of phenomena 광누출시험Light leakage test ))
편광판 점착시트(200㎜ × 200㎜)를 유리기판(210 ㎜ × 210 ㎜ × 0.7 ㎜)에 광학 흡수축이 90˚로 교차하여 양면에 부착하여 시편을 제조하였다. 제조된 시편을 오토클레이브에서 5기압, 50℃의 조건으로 20분 동안 처리한 후 60℃, 상대습도 90%의 오븐에서 300시간 동안 방치하였다. 암실에서 방치된 시편으로부터 빛이 새어 나오는 부분이 있는지 육안으로 관찰하고, 하기 기준에 의거하여 평가하였다.The polarizing plate adhesive sheet (200 mm x 200 mm) was attached to both surfaces of the glass substrate (210 mm x 210 mm x 0.7 mm) with the optical absorption axis crossed at 90 deg. The prepared specimens were treated in an autoclave at 5 atm and 50 ° C for 20 minutes and then placed in an oven at 60 ° C and 90% relative humidity for 300 hours. The sample was visually observed for light leakage from specimens left in the dark room, and evaluated according to the following criteria.
○ : 빛샘의 불균일 현상을 육안으로 판단하기 어려움○: It is difficult to visually judge the non-uniformity of light gaps
△ : 빛샘의 불균일 현상이 다소 있음△: Light scattering is somewhat uneven
× : 빛샘의 불균일 현상이 있음
X: There is a non-uniformity of light leakage
25℃ 24hrAdhesion at room temperature
25 ° C 24hr
50℃ 48hrThermal adhesion
50 ° C 48hr
상기 표 2에 기재된 바와 같이, 본 발명에 따른 공중합체를 포함한 실시예들의 점착제 조성물에 비하여, 비교예들의 점착제 조성물은 내열성/내습열성이 저하되는 것을 알 수 있다.As shown in Table 2, the pressure-sensitive adhesive compositions of Comparative Examples were found to have lower heat resistance / humidity resistance than the pressure-sensitive adhesive compositions of the examples including the copolymer according to the present invention.
또한, 점착제 조성물의 양생시간 단축효과는 3일차 겔분율로 평가할 수 있는데, 실시예들의 겔분율이 비교예들에 비해 우수한 것을 알 수 있다. 그리고 빛샘효과 역시 실시예들로 제조된 편광판이 비교예들에 비해 개선된 효과를 나타냄을 확인할 수 있다.In addition, the effect of shortening the curing time of the pressure-sensitive adhesive composition can be evaluated by the third-order gel fraction, and it can be seen that the gel fraction of the examples is superior to the comparative examples. Also, it can be confirmed that the polarizing plate prepared in the examples has an improved effect as compared with the comparative examples.
Claims (12)
가교제를 포함하는 점착제 조성물:
[화학식 1]
(식 중, R1은 수소 또는 메틸기이며; X는 -NH-, -O- 또는 -S-이며; R2는 탄소수 0 내지 3의 알킬렌기이며; R3는 수소, 탄소수 1 내지 3의 알킬기 또는 페닐기임).
An acrylic copolymer comprising a repeating unit formed from a monomer represented by the following formula (1); And
A pressure-sensitive adhesive composition comprising a crosslinking agent:
[Chemical Formula 1]
Wherein R 1 is hydrogen or a methyl group, X is -NH-, -O- or -S-, R 2 is an alkylene group having 0 to 3 carbon atoms, R 3 is hydrogen, an alkyl group having 1 to 3 carbon atoms Or a phenyl group).
The pressure-sensitive adhesive composition according to claim 1, wherein the copolymer is formed by copolymerization of a (meth) acrylate-based monomer containing an alkyl group having 1 to 12 carbon atoms and a monomer represented by the formula (1).
The pressure-sensitive adhesive composition according to claim 2, wherein the copolymer is formed by polymerizing 100 parts by weight of a (meth) acrylate monomer containing an alkyl group having 1 to 12 carbon atoms and 0.01 to 10 parts by weight of a monomer represented by the following formula (1).
[3] The method of claim 2, wherein the (meth) acrylate monomer is at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (Meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl And a pressure-sensitive adhesive layer.
The pressure-sensitive adhesive composition according to claim 1, wherein the copolymer further comprises a monomer having a crosslinkable functional group.
The pressure-sensitive adhesive composition according to claim 5, wherein the crosslinkable functional group is a hydroxyl group, a carboxyl group, an amide group or a tertiary amine group.
The pressure-sensitive adhesive composition according to claim 5, wherein the monomer having a crosslinkable functional group is contained in an amount of 0.1 to 15% by weight based on the total weight of the total monomers.
The pressure-sensitive adhesive composition according to claim 1, wherein the copolymer has a weight average molecular weight of 200,000 to 1,500,000.
The pressure-sensitive adhesive composition according to claim 1, wherein the cross-linking agent is contained in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the solid content of the copolymer.
A polarizer comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of claim 1.
A liquid crystal display device comprising the polarizer of claim 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110102649A KR101798904B1 (en) | 2011-10-07 | 2011-10-07 | Copolymer and Pressure-sensitive adhesive composion |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110102649A KR101798904B1 (en) | 2011-10-07 | 2011-10-07 | Copolymer and Pressure-sensitive adhesive composion |
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| Publication Number | Publication Date |
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| KR20130038026A KR20130038026A (en) | 2013-04-17 |
| KR101798904B1 true KR101798904B1 (en) | 2017-11-20 |
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| KR1020110102649A KR101798904B1 (en) | 2011-10-07 | 2011-10-07 | Copolymer and Pressure-sensitive adhesive composion |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102016512B1 (en) * | 2017-08-24 | 2019-08-30 | 건국대학교 산학협력단 | Acrylic adhesive composition having dual curing system, Preparation method thereof, Adhesive film comprising the composition, and display device comprising the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008096734A (en) * | 2006-10-12 | 2008-04-24 | Fujifilm Corp | Protection film for polarizing plate, polarizing plate and liquid crystal display apparatus |
| JP2010078700A (en) | 2008-09-24 | 2010-04-08 | Nitto Denko Corp | Adhesive for polarizing plate, polarizing plate, method for manufacturing the same, optical film and image display device |
| JP2010209229A (en) | 2009-03-11 | 2010-09-24 | Toyo Ink Mfg Co Ltd | Adhesive composition, and adhesive laminate using the same |
| US20110159283A1 (en) | 2009-12-29 | 2011-06-30 | Kyoung Jin Ha | Adhesive binder, adhesive composition including the same, optical member, and associated methods |
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2011
- 2011-10-07 KR KR1020110102649A patent/KR101798904B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008096734A (en) * | 2006-10-12 | 2008-04-24 | Fujifilm Corp | Protection film for polarizing plate, polarizing plate and liquid crystal display apparatus |
| JP2010078700A (en) | 2008-09-24 | 2010-04-08 | Nitto Denko Corp | Adhesive for polarizing plate, polarizing plate, method for manufacturing the same, optical film and image display device |
| JP2010209229A (en) | 2009-03-11 | 2010-09-24 | Toyo Ink Mfg Co Ltd | Adhesive composition, and adhesive laminate using the same |
| US20110159283A1 (en) | 2009-12-29 | 2011-06-30 | Kyoung Jin Ha | Adhesive binder, adhesive composition including the same, optical member, and associated methods |
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|---|---|
| KR20130038026A (en) | 2013-04-17 |
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