KR20130141967A - Anti-glare coating composition and anti-glare film using the same - Google Patents
Anti-glare coating composition and anti-glare film using the same Download PDFInfo
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- KR20130141967A KR20130141967A KR1020120065136A KR20120065136A KR20130141967A KR 20130141967 A KR20130141967 A KR 20130141967A KR 1020120065136 A KR1020120065136 A KR 1020120065136A KR 20120065136 A KR20120065136 A KR 20120065136A KR 20130141967 A KR20130141967 A KR 20130141967A
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- KR
- South Korea
- Prior art keywords
- glare
- particles
- meth
- acrylate
- composition
- Prior art date
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- 239000011248 coating agent Substances 0.000 claims abstract description 19
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- 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
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Abstract
본 발명은 방현성 코팅용 조성물 및 이를 이용한 방현성 필름에 관한 것으로서, 보다 상세하게는 폴리 메틸(메타)아크릴레이트계 고분자 입자로 형성된 코어부 및 상기 코어부 외면에 다수의 실리콘 고분자 입자가 부착되어 형성된 돌기부를 구비하는 광산란 입자를 포함함으로써, 종래보다 소량의 광산란 입자를 사용하여도 종래와 동일하거나 우수한 방현성 및 반사방지 효과를 낼 수 있는 방현성 코팅용 조성물 및 이를 이용한 방현성 필름에 관한 것이다.The present invention relates to a composition for anti-glare coating and an anti-glare film using the same, and more particularly, a plurality of silicon polymer particles are attached to a core part formed of polymethyl (meth) acrylate-based polymer particles and an outer surface of the core part. By including the light-scattering particles having the formed projections, relates to an anti-glare coating composition and an anti-glare film using the same that can produce the same or better anti-glare and anti-reflection effect than conventional, even when using a small amount of light scattering particles .
Description
본 발명은 방현성 코팅용 조성물 및 이를 이용한 방현성 필름에 관한 것으로서, 보다 상세하게는 방현성이 우수한 광산란 입자를 포함하는 방현성 코팅용 조성물 및 이를 이용한 방현성 필름에 관한 것이다.
The present invention relates to a composition for anti-glare coating and an anti-glare film using the same, and more particularly, to an anti-glare coating composition comprising a light-scattering particle excellent in anti-glare properties and an anti-glare film using the same.
방현성 필름은 표면 요철에 의한 광산란성을 이용하여 광 반사를 감소시키는 기능을 갖는 광학 필름으로서, 각종 표시장치 패널, 예컨대 액정표시장치(LCD), 플라즈마표시장치(PDP), 음극선관(CRT), 유기발광다이오드(EL) 등에 배치되어 외부광의 반사로 인한 콘트라스트의 감소를 방지하거나 이미지 반사에 의한 표시장치의 시인성 저하를 방지하는 등의 목적으로 이용되고 있다.An anti-glare film is an optical film having a function of reducing light reflection by using light scattering due to surface irregularities. Various anti-glare films such as liquid crystal display (LCD), plasma display (PDP), and cathode ray tube (CRT) The organic light emitting diode EL is used for the purpose of preventing a decrease in contrast due to reflection of external light or a decrease in visibility of the display device due to image reflection.
방현성 필름은 통상적으로 투명 기재 상에 실리카 또는 고분자 비드와 같은 유기 미립자를 함유하는 방현성 코팅 조성물로 형성된 방현층을 포함하여 구성된다. 이러한 투광성 미립자는 그 표면에서 광을 산란시킴으로써 방현성을 발휘하게 된다. 이와 관련하여, 한국공개특허 제2011-97636호는 구형의 유기 미립자를 함유하는 방현성 하드 코트층을 제안하고 있다. The anti-glare film usually comprises an anti-glare layer formed of an anti-glare coating composition containing organic fine particles such as silica or polymer beads on a transparent substrate. Such translucent microparticles | fine-particles exhibit anti-glare property by scattering light on the surface. In this regard, Korean Patent Laid-Open No. 2011-97636 proposes an anti-glare hard coat layer containing spherical organic fine particles.
하지만, 현재까지 다양한 광산란 입자를 포함하는 방현성 필름이 소개되었으나 이러헌 광확산성 미립자로서는 방현성을 개선하는 데에 한계가 있다.
However, to date, an anti-glare film including various light scattering particles has been introduced, but there are limitations in improving anti-glare properties of such light-diffusing fine particles.
본 발명은 방현성 및 반사방지 효과가 우수한 방현성 코팅용 조성물 및 이를 이용한 방현성 필름을 제공하는 것을 목적으로 한다.An object of the present invention is to provide an anti-glare coating composition excellent in anti-glare and anti-reflection effect and an anti-glare film using the same.
또한, 본 발명은 종래보다 소량의 광산란 입자를 사용해도 종래와 동일하거나 보다 우수한 효과를 나타내는 방현성 코팅용 조성물 및 이를 이용한 방현성 필름을 제공하는 것을 목적으로 한다.
In addition, an object of the present invention is to provide an anti-glare coating composition and an anti-glare film using the same, even if using a smaller amount of light scattering particles than the prior art.
1. 폴리 메틸(메타)아크릴레이트계 고분자 입자로 형성된 코어부 및 상기 코어부 외면에 다수의 실리콘 고분자 입자가 부착되어 형성된 돌기부를 구비하는 광산란 입자를 포함하는 방현성 코팅용 조성물.1. Composition for anti-glare coating comprising a light scattering particles having a core portion formed of polymethyl (meth) acrylate-based polymer particles and a protrusion formed by attaching a plurality of silicon polymer particles to the outer surface of the core portion.
2. 위 1에 있어서, 코어부 입자와 돌기부 입자는 굴절률이 서로 다른 것인 방현성 코팅용 조성물.2. In the above 1, the core particles and the projection particles are anti-glare coating composition is different from the refractive index.
3. 위 2에 있어서, 코어부 입자와 돌기부 입자의 굴절률 차이는 0.03 이상인 방현성 코팅용 조성물.3. In the above 2, the refractive index difference between the core particles and the protrusion particles is 0.03 or more composition for anti-glare coating.
4. 위 1에 있어서, 광산란 입자의 평균 입경은 1 내지 10 ㎛인 방현성 방현성 코팅용 조성물.4. In the above 1, the light-scattering particles have an average particle diameter of 1 to 10 ㎛ anti-glare anti-glare coating composition.
5. 위 1에 있어서, 돌기부 입자의 평균 입경은 0.1 내지 1 ㎛인 방현성 코팅용 조성물.5. In the above 1, the average particle diameter of the protrusion particles is 0.1 to 1 ㎛ anti-glare coating composition.
6. 위 1에 있어서, 실리콘 고분자는 폴리실세스퀴옥산인 방현성 코팅용 조성물.6. In the above 1, the silicone polymer is a polysilsesquioxane anti-glare coating composition.
7. 위 1에 있어서, 광산란 입자는 조성물 총 중량에 대하여 0.1 내지 30 중량%로 포함되는 방현성 코팅용 조성물.7. In the above 1, wherein the light scattering particles, the composition for anti-glare coating containing 0.1 to 30% by weight based on the total weight of the composition.
8. 위 1에 있어서, 중합성 화합물, 광중합 개시제 및 유기용매를 더 포함하는 방현성 코팅용 조성물.8. according to the above 1, the composition for anti-glare coating further comprising a polymerizable compound, a photopolymerization initiator and an organic solvent.
9. 기재; 및 상기 기재 상에 형성되고, 폴리 메틸(메타)아크릴레이트계 고분자 입자로 형성된 코어부 및 상기 코어부 외면에 다수의 실리콘 고분자 입자가 부착되어 형성된 돌기부를 구비하는 광산란 입자에 의한 표면 요철이 형성된 방현성 코팅층을 포함하는 방현성 필름.9. Base material; And surface irregularities formed by light scattering particles formed on the substrate, and having a core part formed of polymethyl (meth) acrylate-based polymer particles and a protrusion formed by attaching a plurality of silicon polymer particles to an outer surface of the core part. Anti-glare film comprising a glazing coating layer.
10. 위 9에 있어서, 방현성 코팅층은 위 1 내지 8 중 어느 한 항의 방현성 코팅용 조성물로 형성된 것인 방현성 필름.10. In the above 9, the anti-glare coating layer is an anti-glare film formed of the composition for anti-glare coating of any one of the above 1 to 8.
11. 위 9의 방현성 필름을 구비한 편광판.11. Polarizing plate with anti-glare film of the above 9.
12. 위 11의 편광판을 구비한 화상 표시 장치.
12. Image display device provided with the polarizing plate of 11 above.
본 발명의 방현성 코팅용 조성물은 돌기형의 광산란 입자를 포함함으로써 종래보다 소량의 광산란 입자를 사용하여도 종래와 동일하거나 우수한 방현성 및 반사방지 효과를 나타낼 수 있다.The anti-glare coating composition of the present invention may exhibit the same or better anti-glare and anti-reflection effects as in the prior art by using a light-scattering particle of the projection type than a conventional light scattering particles.
본 발명에 따른 광산란 입자는 코어부와 돌기부를 형성하는 물질이 서로 다르고, 그에 따라 굴절률 차이가 발생하므로 광산란 효과를 더욱 상승시킬 수 있다.The light scattering particles according to the present invention are different from each other to form a core portion and a protrusion, and accordingly a difference in refractive index may occur, thereby further increasing the light scattering effect.
본 발명의 방현성 필름은 폴리메틸(메타)아크릴레이트계 고분자 코어부와 실리콘 고분자 돌기부를 갖는 광산란 입자를 사용함으로써 방현성 코팅층의 방오성을 현저하게 향상시킬 수 있다.
The anti-glare film of this invention can remarkably improve the antifouling property of an anti-glare coating layer by using the light-scattering particle which has a polymethyl (meth) acrylate type polymer core part and a silicone polymer protrusion.
도 1은 본 발명에 따른 광산란 입자의 개략적인 수직 단면도이다.
도 2는 종래의 단순 구형입자(a)와 본 발명에 따른 돌기형 입자(b)의 광 산란의 개략적인 모식도이다.
도 3은 본 발명의 방현성 필름의 개략적인 수직 단면도이다.1 is a schematic vertical cross-sectional view of light scattering particles according to the present invention.
Figure 2 is a schematic diagram of the light scattering of the conventional simple spherical particles (a) and the projections (b) according to the present invention.
3 is a schematic vertical cross-sectional view of the anti-glare film of the present invention.
본 발명은 폴리 메틸(메타)아크릴레이트계 고분자 입자로 형성된 코어부 및 상기 코어부 외면에 다수의 실리콘 고분자 입자가 부착되어 형성된 돌기부를 구비하는 광산란 입자를 포함함으로써, 종래보다 소량의 광산란 입자를 사용하여도 종래와 동일하거나 우수한 방현성 및 반사방지 효과를 낼 수 있는 방현성 코팅용 조성물 및 이를 이용한 방현성 필름에 관한 것이다.
The present invention includes a light scattering particle having a core portion formed of polymethyl (meth) acrylate-based polymer particles and a projection portion formed by attaching a plurality of silicon polymer particles to the outer surface of the core portion, thereby using a smaller amount of light scattering particles. Even if it relates to the anti-glare coating composition and the anti-glare film using the same that can produce the same or excellent anti-glare and anti-reflection effect as conventional.
이하 본 발명을 상세하게 설명하도록 한다.Hereinafter, the present invention will be described in detail.
본 발명의 방현성 코팅용 조성물은 폴리 메틸(메타)아크릴레이트계 고분자 입자로 형성된 코어부 및 상기 코어부 외면에 다수의 실리콘 고분자 입자가 부착되어 형성된 돌기부를 구비하는 광산란 입자를 포함하는 것을 특징으로 한다.The anti-glare coating composition of the present invention is characterized in that it comprises a light scattering particles having a core portion formed of polymethyl (meth) acrylate-based polymer particles and a protrusion formed by attaching a plurality of silicon polymer particles to the outer surface of the core portion do.
도 1에는 본 발명에 따른 광산란 입자(110)의 개략적인 수직 단면도가 도시되어 있다.1 is a schematic vertical cross-sectional view of
본 발명에 따른 광산란 입자(110)는 코어부(111)와 돌기부(112)를 구비한다.The
코어부(111)는 투명한 입자로서 폴리메틸(메타)아크릴레이트계 고분자로 제조될 수 있으며, 바람직하게는 구형 입자일 수 있다. 돌기부(112)는 투명한 실리콘 수지로 형성된 돌기부 입자가 상기 코어부(111)의 외면에 부착되어 형성된다. 돌기부(112)에 의해 본 발명의 광산란 입자(110)의 표면적이 현저하게 확장됨으로써, 광산란 입자에 입사하는 광량을 증가시킬 수 있다.The
또한, 돌기부(112)는 입사된 광이 다양한 각도로 산란되도록 함으로써, 광산란 효과를 극대화할 수 있다. 도 2에는 종래의 구형입자(a)와 본 발명에 따라 돌기부를 구비한 광산란 입자(b)의 입사광과 반사광 양태가 개략적으로 도시되어 있다. 도 2를 참고하면, 종래의 구형입자보다 돌기부를 갖는 본 발명에 따른 광산란 입자가 광의 산란 정도가 더욱 광범위하고 다양한 것을 알 수 있다. In addition, the
본 발명에 따른 돌기부를 갖는 광산란 입자(110)의 광산란성을 보다 높이기 위해서, 코어부(111)와 돌기부(112)는 굴절률이 서로 다른 것이 바람직하다. 이러한 굴절률 차이는 코어부(111)와 돌기부(112)의 계면에서도 광의 반사 및 굴절을 발생시키므로 광의 산란을 더욱 효과적으로 유도할 수 있다. 이러한 측면에서, 상기 굴절률 차이는 0.03 이상인 것이 바람직하다.In order to further enhance the light scattering properties of the
본 발명의 광산란 입자(110)는 구체적인 용도에 따라 다양한 입경으로 제조될 수 있다. 통상적으로는 1 내지 10 ㎛의 평균입경을 가질 수 있으나, 이에 한정되는 것은 아니다. 평균 입경이 1㎛ 미만이면 충분한 산란특성이 발현되기 어렵고 방현성 코팅층 표면에 백화현상이 발생하여 해상도 및 투명성이 저하될 수 있고 10㎛ 초과이면 창이나 실내 조명기구 등의 빛에 의한 화면의 눈부심을 방지하는 것이 우수하지만, 필름 표면에 면 반짝임이라고 불리는 신틸레이션(scintillation)이 발생하여, 화상정보의 시각성이 저하하는 문제가 발생할 수 있다. 이 경우, 돌기부 입자는 그 평균입경이 0.1 내지 1 ㎛일 수 있으나, 역시 이에 한정되는 것은 아니다.The
광산란 입자(110)는 방현성 코팅용 조성물 총 중량에 대하여 0.1 내지 30중량%로 포함될 수 있고, 바람직하게 0.1 내지 10중량%인 것이 좋다. 함량이 0.1중량% 미만인 경우 방현성이 충분히 나타나지 않을 수 있으며, 방현성 코팅층의 충분한 표면 경도를 확보하기 어려울 수 있고, 30중량% 초과인 경우 입자에 의한 산란정도가 과도하여 투명성 및 콘트라스트 등의 광학적인 물성저하의 문제점이 존재할 수 있다.
본 발명에 따른 광산란 입자는 다음과 같은 제조방법의 일 구현예에 따라 제조될 수 있다. Light scattering particles according to the present invention can be prepared according to one embodiment of the production method as follows.
본 발명의 광산란 입자는 폴리 메틸(메타)아크릴레이트계 고분자를 코어부 입자로 하고, 상기 코어부 입자 표면에 실리콘 고분자 미립자를 흡착시켜 그 표면에 돌기부를 형성함으로써 제조될 수 있다.The light scattering particles of the present invention may be prepared by using polymethyl (meth) acrylate-based polymer as core part particles, adsorbing silicon polymer fine particles on the surface of the core part particles, and forming protrusions on the surface thereof.
실리콘 고분자는 고분자 소재의 가공성, 강인성, 가격 등의 장점과 무기물의 내열성, 산화안정성 등의 장점을 모두 가지고 있으므로, 본 발명의 돌기부 입자로서 바람직하다. 이러한 측면에서, 폴리실세스퀴옥산 고분자를 사용하는 것이 보다 바람직하다.Silicone polymers are preferred as the protruding particles of the present invention because they have all the advantages of processability, toughness, price, etc. of polymer materials, heat resistance of inorganic materials, oxidation stability, and the like. In this respect, it is more preferable to use a polysilsesquioxane polymer.
폴리실세스퀴옥산 고분자의 미립자를 제조하는 일 구현예로는 알콕시실란을 가수분해시킨 후 축중합하는 졸-겔법을 사용할 수 있다. 졸-겔 반응 후에는 암모니아 등으로 산 촉매를 중화시켜 폴리실세스퀴옥산 고분자의 미립자가 분산된 현탁액을 얻을 수 있다.As one embodiment of preparing the fine particles of the polysilsesquioxane polymer, a sol-gel method may be used in which an alkoxysilane is hydrolyzed and then polycondensed. After the sol-gel reaction, the acid catalyst may be neutralized with ammonia or the like to obtain a suspension in which fine particles of the polysilsesquioxane polymer are dispersed.
상기 분산액에 코어부 입자인 폴리 메틸(메타)아크릴레이트계 고분자 입자를 투입하면, 코어부 입자 표면에 폴리실세스퀴옥산 미립자가 흡착하여 본 발명의 돌기형 광산란 입자를 얻을 수 있다.When the polymethyl (meth) acrylate polymer particles which are the core particle | grains are thrown into the said dispersion liquid, polysilsesquioxane microparticles | fine-particles adsorb | suck to a core particle | grain surface, and the projection light-scattering particle of this invention can be obtained.
본 발명의 방현성 코팅용 조성물은 전술한 광산란 입자 외에 당분야에서 통상적으로 사용되는 방현성 필름의 제조에 사용되는 성분들을 포함할 수 있다. 예를 들면, 중합성 화합물, 광중합 개시제 및 유기용매를 더 포함할 수 있다.The anti-glare coating composition of the present invention may include components used in the production of anti-glare film commonly used in the art, in addition to the light scattering particles described above. For example, it may further include a polymerizable compound, a photopolymerization initiator and an organic solvent.
중합성 화합물은 방현성 코팅층의 바인더 수지를 형성하고 및 표면 경도를 향상시키기 위한 성분으로서, 당분야에 공지된, 광중합이 가능한 (메타)아크릴레이트 올리고머, (메타)아크릴레이트 단량체 또는 이들의 혼합물들을 사용할 수 있다. The polymerizable compound is a component for forming the binder resin of the anti-glare coating layer and improving the surface hardness. The polymerizable compound may be a photopolymerizable (meth) acrylate oligomer, (meth) acrylate monomer or mixtures thereof known in the art. Can be used.
(메타)아크릴레이트 올리고머로는 예를 들면, 다가 알코올과 다가 카르복실산 및/또는 그 무수물과 아크릴산을 에스테르화함으로써 얻을 수 있는 폴리에스테르(메트)아크릴레이트; 다가 알코올, 다가 이소시아네이트 및 수산기 함유 (메트)아크릴레이트를 반응시킴으로써 얻어지는 우레탄(메트)아크릴레이트; 폴리실록산폴리(메트)아크릴레이트; 등을 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있다.As a (meth) acrylate oligomer, For example, Polyester (meth) acrylate obtained by esterifying polyhydric alcohol, polyhydric carboxylic acid, and / or its anhydride, and acrylic acid; Urethane (meth) acrylates obtained by reacting polyhydric alcohols, polyvalent isocyanates and hydroxyl group-containing (meth) acrylates; Polysiloxane poly (meth) acrylates; Etc. can be used individually or in mixture of 2 or more types, respectively.
(메타)아크릴레이트 단량체로는 당 분야에서 공지된 1 내지 6관능성 (메타)아크릴레이트 단량체를 들 수 있다. (메타)아크릴레이트 단량체의 구체적인 예로는, 메틸(메타)아크릴레이트, 알릴(메타)아크릴레이트, 2-에톡시에틸(메타)아크릴레이트, 이소데실(메타)아크릴레이트, 2-도데실티오에틸(메타)아크릴레이트, 옥틸(메타)아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 히드록시에틸(메타)아크릴레이트, 히드록시프로필(메타)아크릴레이트, 히드록시부틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 스테아릴(메타)아크릴레이트, 테트라퍼푸릴(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트, 페녹시프로필(메타)아크릴레이트, 페녹시벤질(메타)아크릴레이트 등의 1관능성 단량체; 1,3-부탄디올디(메타)아크릴레이트, 1,4-부탄디올디(메타)아크릴레이트, 1,6-헥산디올디(메타)아크릴레이트, 에틸렌글리콜디(메타)아크릴레이트, 비스페놀A-에틸렌글리콜디(메타)아크릴레이트, 디에틸렌글리콜디(메타)아크릴레이트, 트리에틸렌글리콜디(메타)아크릴레이트, 폴리에틸렌글리콜디(메타)아크릴레이트, 프로필렌글리콜디(메타)아크릴레이트, 디프로필렌글리콜디(메타)아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트, 디시클로펜타닐디(메타)아크릴레이트, 카프로락톤 변성 디시클로펜테닐디(메타)아크릴레이트, 에틸렌옥사이드 변성 인산디(메타)아크릴레이트, 비스(2-히드록시에틸)이소시아누레이트디(메타)아크릴레이트, 디(아크릴옥시에틸)이소시아누레이트, 알릴화 시클로헥실디(메타)아크릴레이트, 디메틸올디시클로펜탄디(메타)아크릴레이트, 에틸렌옥사이드 변성 헥사히드로프탈산디(메타)아크릴레이트, 트리시클로데칸디메탄올(메타)아크릴레이트, 네오펜틸글리콜 변성 트리메틸올프로판디(메타)아크릴레이트, 아다만탄디(메타)아크릴레이트 등의 2관능성 단량체; 트리메틸올프로판트리(메타)아크릴레이트, 디펜타에리트리톨트리(메타)아크릴레이트, 프로피온산 변성 디펜타에리트리톨트리(메타)아크릴레이트, 펜타에리트리톨트리(메타)아크릴레이트, 프로필렌옥사이드 변성 트리메틸올프로판트리(메타)아크릴레이트, 트리스(2-히드록시에틸)이소시아누레이트트리(메타)아크릴레이트, 트리스(아크릴옥시에틸)이소시아누레이트, 글리세롤트리(메타)아크릴레이트 등의 3관능성 단량체; 디글리세린테트라(메타)아크릴레이트, 펜타에리트리톨테트라(메타)아크릴레이트, 디트리메틸올프로판테트라(메타)아크릴레이트 등의 4관능성 단량체; 디펜타에리트리톨펜타(메타)아크릴레이트, 프로피온산 변성 디펜타에리트리톨펜타(메타)아크릴레이트 등의 5관능성 단량체; 디펜타에리트리톨헥사(메타)아크릴레이트, 카프로락톤 변성 디펜타에리트리톨헥사(메타)아크릴레이트 등의 6관능성 단량체 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다. 본 발명에 있어서 (메타)아크릴레이트는 아크릴레이트, 메타아크릴레이트 또는 이 둘을 동시에 지칭하는 용어이다.Examples of the (meth) acrylate monomers include 1 to 6 functional (meth) acrylate monomers known in the art. Specific examples of the (meth) acrylate monomers include methyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, isodecyl (meth) acrylate, and 2-dodecylthioethyl. (Meth) acrylate, octyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate , Isooctyl (meth) acrylate, stearyl (meth) acrylate, tetraperfuryl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acryl Monofunctional monomers such as acrylate and phenoxybenzyl (meth) acrylate; 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, ethylene glycoldi (meth) acrylate, bisphenol A-ethylene Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, caprolactone modified dicyclopentenyldi (meth) acrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, Bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, di (acryloxyethyl) isocyanurate, allylated cyclohexyldi (meth) acrylate, dimethyloldicyclopentanedi (meth) Methacrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, neopentyl glycol modified trimethylolpropanedi (meth) acrylate, adamantanedi (meth) acrylate, etc. Difunctional monomers of; (Meth) acrylate such as trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri Trifunctional monomers such as tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, glycerol tri ; Tetrafunctional monomers such as diglycerin tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylol propane tetra (meth) acrylate; Pentafunctional monomers such as dipentaerythritol penta (meth) acrylate and propionic acid-modified dipentaerythritol penta (meth) acrylate; Hexafunctional monomers, such as dipentaerythritol hexa (meth) acrylate and caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. are mentioned. These can be used individually or in mixture of 2 or more types. In the present invention, (meth) acrylate is a term that refers to acrylate, methacrylate or both at the same time.
(메타)아크릴레이트 단량체는 방현성 코팅용 조성물 총 중량에 대하여 10 내지 90중량%로 포함될 수 있고, 바람직하게 20 내지 80중량%인 것이 좋다. 함량이 10중량% 미만인 경우 원하는 두께로 코팅이 어려우며, 방현성 코팅층의 충분한 표면 경도를 확보하기 어려울 수 있고, 90중량% 초과인 경우 코팅 조성물의 점도가 상승되어 코팅성이 저하되고 균일한 표면 요철의 형성이 어려울 수 있다.The (meth) acrylate monomer may be included in 10 to 90% by weight based on the total weight of the anti-glare coating composition, preferably 20 to 80% by weight. If the content is less than 10% by weight it is difficult to coat to the desired thickness, it may be difficult to secure sufficient surface hardness of the anti-glare coating layer, if it is more than 90% by weight the viscosity of the coating composition is increased to reduce the coating property and uniform surface irregularities Can be difficult to form.
광중합 개시제는 경화 효율을 향상시키기 위한 성분으로서, 당분야에서 사용되는 것이라면 특별히 제한되지 않고 사용될 수 있다. 예컨대, 벤조인, 벤조인메틸에테르, 벤조인에틸에테르, 벤조인이소프로필에테르, 벤조인-n-부틸에테르, 벤조인이소부틸에테르, 아세토페논, 히드록시디메틸아세토페논, 디메틸아미노아세토페논, 3-메틸아세토페논, 2,2-디메톡시-2-페닐아세토페논, 2,2-디에톡시-2-페닐아세토페논, 4-크로놀로아세토페논, 4,4-디메톡시아세토페논, 2-히드록시-2-메틸-1-페닐프로판-1-온, 2-히드록시-2-메틸-1-페닐-1-온, 1-히드록시시클로헥실페닐케톤, 4-히드록시시클로페닐케톤, 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노-프로판-1-온, 4-(2-히드록시에톡시)페닐-2-(히드록시-2-프로필)케톤, 벤조페논, p-페닐벤조페논, 4,4-디아미노벤조페논, 4,4'-디에틸아미노벤조페논, 디클로로벤조페논, 안트라퀴논, 2-메틸안트라퀴논, 2-에틸안트라퀴논, 2-t-부틸안트라퀴논, 2-아미노안트라퀴논, 2-메틸티옥산톤, 2-에틸티옥산톤, 2-클로로티옥산톤, 2,4-디메틸티옥산톤, 2,4-디에틸티옥산톤, 벤질디메틸케탈, 디페닐케톤벤질디메틸케탈, 아세토페논디메틸케탈, p-디메틸아미노벤조산에스테르, 올리고[2-히드록시-2-메틸-1-(4-(1-메틸비닐)페닐)프로판온], 2,4,6-트리메틸벤조일디페닐포스핀옥사이드, 플루오렌, 트리페닐아민, 카바졸 등을 들 수 있다. 또한, 시판되고 있는 제품으로 상품명 Darocur 1173, Igacure 184, Igacure 907, Igacure 1700(Ciba사) 등도 사용할 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The photopolymerization initiator is a component for improving the curing efficiency, and may be used without particular limitation as long as it is used in the art. For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, hydroxydimethylacetophenone, dimethylaminoacetophenone, 3 -Methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 4-chronoacetophenone, 4,4-dimethoxyacetophenone, 2-hydride Hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-phenyl-1-one, 1-hydroxycyclohexylphenylketone, 4-hydroxycyclophenylketone, 2 -Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone , Benzophenone, p-phenylbenzophenone, 4,4-diaminobenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2 -t-butylanthraquinone, 2-aminoanthraquinone, 2-meth Thioxanthone, 2-ethyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, benzyl dimethyl ketal, diphenyl ketone benzyl dimethyl ketal, acetophenone Dimethyl ketal, p-dimethylaminobenzoic acid ester, oligo [2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone], 2,4,6-trimethylbenzoyldiphenylphosphine Oxide, fluorene, triphenylamine, carbazole and the like. Moreover, as a commercially available product, brand names Darocur 1173, Igacure 184, Igacure 907, Igacure 1700 (Ciba company), etc. can also be used. These can be used individually or in mixture of 2 or more types.
광중합 개시제는 방현성 코팅용 조성물 총 중량에 대하여 0.05 내지 10중량%로 포함될 수 있다. 함량이 0.05중량% 미만인 경우 경화 속도가 늦어질 수 있으며, 10중량% 초과인 경우 과경화로 방현성 코팅층에 크랙이 발생할 수 있다.The photopolymerization initiator may be included in an amount of 0.05 to 10 wt% based on the total weight of the antiglare coating composition. When the content is less than 0.05% by weight, the curing speed may be slow, and when the content is more than 10% by weight, cracks may occur in the anti-glare coating layer due to overcuring.
유기용매는 조성물의 다른 성분들을 균일하게 분산/용해시키고 적절한 점도를 유지시키는 성분으로서, 당분야에 공지된 것이라면 특별한 제한 없이 사용될 수 있다. 예를 들면, 알코올계 용매, 케톤계 용매, 헥산계 용매, 벤젠계 용매 등이 각각 단독으로 또는 2종 이상 혼합되어 사용될 수 있다.The organic solvent is a component which uniformly disperses / dissolves other components of the composition and maintains an appropriate viscosity, and may be used without particular limitation as long as it is known in the art. For example, an alcohol solvent, a ketone solvent, a hexane solvent, a benzene solvent, or the like may be used alone or in combination of two or more thereof.
알코올계 용매는 예를 들면, 메탄올, 에탄올, 이소프로필알코올, 부탄올, 헥산올, 시클로헥산올, 에틸렌글리콜, 2-메톡시에탄올, 2-에톡시에탄올, 메틸셀로솔브, 에틸셀로솔브, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르아세테이트 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Alcohol solvents include, for example, methanol, ethanol, isopropyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, 2-methoxyethanol, 2-ethoxyethanol, methyl cellosolve, ethyl cellosolve, Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc. are mentioned, These can be used individually or in mixture of 2 or more types.
케톤계 용매는 예를 들면, 메틸에틸케톤, 메틸부틸케톤, 메틸이소부틸케톤, 메틸아밀케톤, 디에틸케톤, 디프로필케톤, 아세톤, 시클로헥사논 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the ketone solvents include methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl amyl ketone, diethyl ketone, dipropyl ketone, acetone, cyclohexanone, and the like. It can be mixed and used.
헥산계 용매는 예를 들면, 헥산, 헵탄, 옥탄 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the hexane solvents include hexane, heptane and octane, and these may be used alone or in combination of two or more thereof.
벤젠계 용매는 예를 들면, 벤젠, 톨루엔, 자일렌 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Benzene solvents include, for example, benzene, toluene, xylene, and the like, and these may be used alone or in combination of two or more thereof.
유기 용매는 방현성 코팅용 조성물 총 중량에 대하여 10 내지 90중량%로 포함될 수 있다. 함량이 10중량% 미만인 경우 점도가 높아 작업성이 저하될 수 있으며, 90중량% 초과인 경우 건조 및 경화 과정에서 시간이 많이 소요되어 경제성이 저하될 수 있다.The organic solvent may be included in 10 to 90% by weight based on the total weight of the composition for anti-glare coating. If the content is less than 10% by weight, the viscosity may be high and workability may be lowered. If the content is more than 90% by weight, it may take a long time in the drying and curing process, thereby reducing economic efficiency.
본 발명의 방현성 코팅용 조성물은 상기 성분과 함께 필요에 따라 항산화제, 자외선 흡수제, 광안정제, 계면활성제, 레벨링제, 윤활제, 방오제 등의 첨가제를 1종 이상 더 포함할 수 있다.The anti-glare coating composition of the present invention may further include one or more additives such as antioxidants, ultraviolet absorbers, light stabilizers, surfactants, leveling agents, lubricants, antifouling agents and the like, as necessary with the above components.
본 발명은 상기 방현성 코팅용 조성물을 이용한 방현성 필름을 제공한다.The present invention provides an anti-glare film using the composition for anti-glare coating.
본 발명의 방현성 필름의 일 구현예가 도 3에 도시되어 있다.One embodiment of the anti-glare film of the present invention is shown in FIG. 3.
본 발명의 방현성 필름(10)은 기재(200); 및 상기 기재(200) 상에 형성되고, 폴리 메틸(메타)아크릴레이트계 고분자 입자로 형성된 코어부 및 상기 코어부 외면에 다수의 실리콘 고분자 입자가 부착되어 형성된 돌기부를 구비하는 광산란 입자(110)에 의한 표면 요철이 형성된 방현성 코팅층(100)을 포함하는 것을 특징으로 한다.
기재(200)는 투명성이 우수한 필름이라면 특별히 한정되지 않는다. 구체적으로, 폴리에틸렌테레프탈레이트, 폴리에틸렌이소프탈레이트, 폴리에틸렌나프탈레이트, 폴리부틸렌테레프탈레이트 등의 폴리에스테르계 수지; 디아세틸셀룰로오스, 트리아세틸셀룰로오스, 아세틸셀룰로오스부틸레이트, 이소부틸에스테르셀룰로오스, 프로피오닐셀룰로오스, 부티릴셀룰로오스, 아세틸프로피오닐셀룰로오스 등의 셀룰로오스계 수지; 폴리카보네이트계 수지; 폴리메틸(메타)아크릴레이트, 폴리에틸(메타)아크릴레이트 등의 아크릴계 수지; 폴리스티렌, 아크릴로니트릴-스티렌 공중합체 등의 스티렌계 수지; 폴리에틸렌, 폴리프로필렌, 시클로 또는 노보넨 구조를 갖는 폴리올레핀, 에틸렌-프로필렌 공중합체 등의 폴리올레핀계 수지; 염화비닐계 수지; 나일론, 방향족 폴리아미드 등의 아미드계 수지; 폴리에테르이미드, 폴리이미드 등의 이미드계 수지; 폴리에테르술폰계 수지; 술폰계 수지; 폴리에테르케톤계 수지; 폴리에테르에테르케톤계 수지; 황화 폴리페닐렌계 수지; 에틸렌-비닐아세테이트 수지; 폴리비닐아세탈 수지; 폴리비닐알코올계 수지; 염화비닐리덴계 수지; 비닐부티랄계 수지; 알릴레이트계 수지; 폴리옥시메틸렌계 수지; 에폭시계 수지 등과 같은 열가소성 수지로 구성된 필름을 들 수 있다. 이들은 미연신, 1축 또는 2축 연신된 필름일 수 있다. 이들 중에서 투명성과 내열성이 우수한, 1축 또는 2축 연신된 폴리에스테르계 필름, 투명성이 좋고 광학 이방성이 없는 트리아세틸셀룰로오스 필름이 바람직하다.The
기재(200)의 두께는 특별히 한정되지 않으며, 예컨대 8 내지 1,000㎛일 수 있으며, 바람직하게는 40 내지 100㎛인 것이 좋다.The thickness of the
방현성 코팅층(100)은 방현성을 갖는 층으로서, 기재와 접합되지 않는 면에 광산란 입자에 의한 표면 요철이 형성된 층이다. The
방현성 코팅층(100)의 형성방법은 특별히 한정되지 않는다. 구체적으로, 기재 상에 방현성 코팅용 조성물을 도포한 후 건조 및 경화하는 공정을 통하여 형성할 수 있다. 도포는 공지된 방법, 예컨대 다이 코터, 에어 나이프, 마이어 바, 리버스 롤, 스프레이, 블레이드, 캐스팅, 그라비아, 스핀 코팅 등의 방법을 이용할 수 있다. 도포 두께는 건조 후 1 초과 내지 50㎛ 이하가 되도록 할 수 있다. 건조는 30 내지 150℃의 온도로 1초 내지 2시간, 바람직하게 5초 내지 1시간 동안 휘발 성분을 휘발시키는 방식으로 수행할 수 있다. The formation method of the
건조가 완료되면 자외선을 조사하여 경화시킨다. 경화에는 고압수은 램프, 무전극 램프, 크세논(xenon) 램프, 메탈할라이드 계열의 램프 등을 이용할 수 있으며, 조사량은 약 0.01 내지 10J/㎠, 바람직하게 0.1 내지 2J/㎠인 것이 좋다.When drying is complete, ultraviolet rays are cured by irradiation. For curing, a high pressure mercury lamp, an electrodeless lamp, a xenon lamp, a metal halide lamp, or the like may be used, and the irradiation amount may be about 0.01 to 10 J / cm 2, preferably 0.1 to 2 J / cm 2.
방현성 필름은 산술평균 표면 거칠기(Ra)가 0.05㎛ ≤ Ra ≤ 0.3㎛이고, 또한, 표면 요철의 평균간격(Sm)이 30㎛ ≤ Sm ≤ 100㎛이고, 표면 요철의 평균 경사각(θa)이 0.5° ≤ θa ≤ 5°일 수 있다. 상기 범위에서 우수한 방현성을 나타낼 수 있다.The anti-glare film had an arithmetic mean surface roughness Ra of 0.05 µm ≤ Ra ≤ 0.3 µm, an average spacing Sm of surface irregularities of 30 µm ≤ Sm ≤ 100 µm, and an average inclination angle θa of surface irregularities. 0.5 ° ≦ θa ≦ 5 °. It can exhibit excellent anti-glare property in the above range.
전술한 바와 같은 구성의 본 발명의 방현성 필름은 돌기형의 광산란 입자를 포함함으로써 종래보다 소량의 광산란 입자를 사용하여도 종래와 동일하거나 우수한 방현성 및 반사방지 효과를 나타낼 수 있으며, 특히 광산란 입자는 코어부와 돌기부를 형성하는 물질이 서로 다르고, 그에 따라 굴절률 차이가 발생하므로 광산란 효과를 더욱 상승시킬 수 있다. 아울러, 폴리메틸(메타)아크릴레이트계 고분자 코어부와 실리콘 고분자 돌기부를 갖는 광산란 입자를 사용함으로써 방현성 코팅층의 방오성을 현저하게 향상시킬 수 있다.The anti-glare film of the present invention having the configuration as described above may have the same or better anti-glare property and anti-reflection effect as in the prior art even when a small amount of light-scattering particles are included than the conventional ones, in particular, light-scattering particles Since the materials forming the core and the protrusions are different from each other, and thus a refractive index difference occurs, the light scattering effect may be further increased. In addition, the antifouling property of the anti-glare coating layer can be remarkably improved by using light scattering particles having a polymethyl (meth) acrylate polymer core portion and a silicon polymer protrusion.
본 발명은 상기 방현성 필름이 구비된 편광판과 화상표시장치를 제공한다.The present invention provides a polarizing plate and an image display device provided with the anti-glare film.
평관판은 편광자의 적어도 일면에 편광자 보호필름이 적층된 통상의구조의 것일 수 있으며, 이러한 구조의 편광판의 적어도 일면, 즉 편광자 또는 편광자 보호필름의 적어도 일면에 상기 방현성 필름이 구비된 것을 특징으로 한다.The flat plate may have a conventional structure in which a polarizer protective film is laminated on at least one surface of the polarizer, and the anti-glare film is provided on at least one surface of the polarizing plate of this structure, that is, the polarizer or the polarizer protective film. do.
방현성 필름이 구비된 편광판은 화상표시장치에 내장되거나 또는 윈도우 표면에 부착되는 방식으로 구비될 수 있다.The polarizing plate provided with the anti-glare film may be provided in a manner embedded in the image display device or attached to the window surface.
방현성 필름이 구비된 편광판은 화상표시장치, 예컨대 반사형, 투과형 및 반투과형 액정표시장치(LCD)와 TN형, STN형, OCB형, HAN형, VA형, IPS형 등의 각종 구동 방식의 액정표시장치(LCD)에 바람직하게 이용될 수 있다. 뿐만 아니라, 플라즈마표시장치(PDP), 전계방출소자(FED), 유기발광다이오드소자, 무기발광다이오드소자, 전자 페이퍼 등의 화상표시장치에도 바람직하게 이용될 수 있다.
Polarizing plate equipped with anti-glare film is an image display device such as reflective, transmissive and transflective liquid crystal display (LCD) and various driving methods such as TN type, STN type, OCB type, HAN type, VA type and IPS type. It can be preferably used for a liquid crystal display (LCD). In addition, the present invention can be preferably used for an image display device such as a plasma display device (PDP), a field emission device (FED), an organic light emitting diode device, an inorganic light emitting diode device, and an electronic paper.
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.
실시예Example
실시예Example 1 One
(1) 돌기형 (1) projection type 광산란Light scattering 입자 제조 Particle manufacturing
온도계, 환류 장치 및 교반기를 구비한 반응 용기에 물 450중량부, 5중량% 농도의 염산 15중량부를 첨가해서 균일용액으로 했다. 이것을 실온에서 교반하면서 메틸트리메톡시실란 770중량부를 첨가하여, 신속하게 가수분해반응이 진행시켰다. 5분 후에 반응 온도가 70℃까지 상승하고, 투명한 반응액을 얻을 수 있었다. 얻어진 반응액을 충분히 교반 후, 교반을 정지하고, 24시간 정치했다. 450 weight part of water and 15 weight part of hydrochloric acid of 5 weight% concentration were added to the reaction container provided with the thermometer, the reflux apparatus, and the stirrer to make a homogeneous solution. 770 weight part of methyl trimethoxysilane was added stirring this at room temperature, and the hydrolysis reaction advanced rapidly. After 5 minutes, the reaction temperature was raised to 70 ° C., whereby a clear reaction solution was obtained. After stirring the obtained reaction liquid sufficiently, stirring was stopped and it was left to stand for 24 hours.
24시간 정치 뒤, 반응액은 상층의 액체 및 하층의 점착성이 있는 부분 축합물의 2층이 되었다. 용기를 천천히 기울여 상층액을 제거하고, 계속해서 피펫을 이용해서 될 수 있는 한 상층액을 제거하고, 하층의 부분 축합물 510중량부를 얻었다. 이 부분 축합물을 400중량부 취득하여, 메탄올 2200중량부와 잘 혼합하여, 부분 축합물/메탄올 혼합액을 얻었다.After standing for 24 hours, the reaction solution became two layers of the liquid of the upper layer and the cohesive partial condensate of the lower layer. The container was tilted slowly to remove the supernatant, and then the supernatant was removed as much as possible using a pipette to obtain 510 parts by weight of the partial condensate of the lower layer. 400 parts by weight of this partial condensate was obtained and mixed well with 2200 parts by weight of methanol to obtain a partial condensate / methanol mixture.
온도계, 환류 장치 및 교반기를 구비한 반응 용기에 공정에서 얻은 부분 축합물/메탄올 혼합액 2600중량부를 200rpm으로 교반하면서, 25℃의 항온으로 한 후, 1중량% 농도의 암모니아 수용액 3000중량부를 신속하게 첨가했다. 첨가 직후에 폴리오르가노실세스퀴옥산 미립자가 생성되었고, 백색의 현탁액을 얻었다. The reaction vessel equipped with a thermometer, a reflux device and a stirrer was brought to a constant temperature of 25 ° C. while stirring 2600 parts by weight of the partial condensate / methanol mixture obtained at the process at 200 rpm, and then 3000 parts by weight of an aqueous 1% by weight aqueous ammonia solution was added quickly. did. Immediately after addition, polyorganosilsesquioxane fine particles were produced, yielding a white suspension.
이후 평균입경 3㎛의 폴리메틸메타크릴레이트(PMMA) 입자를 투입하여 실온에서 PMMA입자 표면에 상기 0.5㎛으로 성장한 실리콘 미립자를 흡착시킨 후 여과, 건조해서 표면에 돌기가 형성된 광산란 입자의 분말을 얻었다.Thereafter, polymethyl methacrylate (PMMA) particles having an average particle diameter of 3 μm were added to adsorb the silicon fine particles grown at 0.5 μm on the surface of the PMMA particles at room temperature, followed by filtration and drying to obtain powder of light scattering particles having protrusions on the surface. .
(2) 코팅 조성물 제조(2) coating composition preparation
우레탄 아크릴레이트(MU9800, 미원상사) 16.5중량%, 펜타에리트리톨트리아크릴레이트와 펜타에리트리톨테트라아크릴레이트의 혼합 단량체(M340, 미원상사) 12.2중량%, 앞서 제조된 광산란 입자(코어부 입자: 평균입경 3.0㎛, 굴절률 1.495; 돌기부 입자: 평균 입경 0.5㎛, 굴절률 1.43) 4중량%, 메틸에틸케톤 40중량%, 에틸아세테이트 25중량% 광중합개시제 1-히드록시시클로헥실페닐케톤(I-184, 시바사) 2중량% 및 첨가제로서 실리콘 변성 오일(BYK-378, BYK사) 를 1시간 동안 혼합하여 방현성 반사방지 코팅 조성물을 제조하였다.Urethane acrylate (MU9800, Miwon Corporation) 16.5% by weight, mixed monomer (M340, Miwon Corporation) of pentaerythritol triacrylate and pentaerythritol tetraacrylate (12.2% by weight), previously prepared light scattering particles (core part particles: average Particle size 3.0 mu m, refractive index 1.495; protrusion particles: average particle diameter 0.5 mu m, refractive index 1.43) 4 wt%, methyl ethyl ketone 40 wt%, ethyl acetate 25 wt% photoinitiator 1-hydroxycyclohexylphenyl ketone (I-184, Ciba G) 2 wt% and silicone modified oil (BYK-378, BYK Co., Ltd.) as an additive was mixed for 1 hour to prepare an anti-glare antireflective coating composition.
(3) 필름 제조(3) film manufacturing
두께가 80㎛인 트리아세틸셀룰로오스(TAC) 필름의 일면에 위 (1)에서 제조된 코팅 조성물을 마이어 바를 이용하여 건조 후 두께가 3.5㎛가 되도록 도포한 후 80℃에서 1분 동안 건조하였다. 그 다음, 500mJ/㎠의 조사량으로 자외선을 조사하여 경화시켜 방현성 반사방지층을 형성함으로써 방현성 반사방지 필름을 제조하였다.After coating the coating composition prepared in (1) on one side of the triacetyl cellulose (TAC) film having a thickness of 80㎛ using a Meyer bar to apply a thickness of 3.5㎛ and dried at 80 ℃ for 1 minute. Subsequently, an anti-glare antireflection film was prepared by irradiating ultraviolet rays with an irradiation dose of 500 mJ / cm 2 to form an anti-glare antireflection layer.
실시예Example 2-4, 2-4, 비교예Comparative Example 1-4 1-4
상기 실시예 1과 동일하게 실시하되, 하기 표 1의 성분 및 함량을 사용하였다. 이때, 함량은 중량%이다.The same procedure as in Example 1, except that the ingredients and contents of Table 1 were used. At this time, the content is% by weight.
시험예Test Example
상기 실시예 및 비교예에서 제조된 방현성 반사방지 필름의 물성을 하기 방법으로 측정하고, 그 결과를 하기 표 2에 나타내었다.Physical properties of the anti-glare antireflection film prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 2 below.
1. 투과율(%), 1.transmittance (%), 헤이즈Hayes
분광광도계(HZ-1, 일본 스가사)를 이용하여 TAC 면을 광원(D65)으로 향하도록 하여 전광선 투과율(total transmittance) 및 전체 헤이즈값(Ha)을 측정하였다.The total transmittance and total haze value Ha were measured by using a spectrophotometer (HZ-1, Suga, Japan) with the TAC plane facing the light source D65.
2. 연필 경도2. pencil hardness
제조된 방현성 필름 표면, 즉 방현성 반사방지층에 연필 경도 시험기(PHT, 한국 석보과학사)를 이용하여 500g 하중을 걸고 연필 경도를 측정하였다. 연필은 미쯔비시사 제품을 사용하고, 한 연필 경도당 5회 측정하였다. 스크래치가 2개 이상이면 불량으로 판정하였으며, 불량이 발생하기 이전의 연필로 연필 경도를 표시하였다.The pencil hardness was measured by applying a 500g load to the prepared anti-glare film surface, that is, the anti-glare anti-reflective layer using a pencil hardness tester (PHT, Seokbo Science Co., Ltd.). The pencil used Mitsubishi Corporation, and measured five times per pencil hardness. If there were two or more scratches, it was determined to be defective, and pencil hardness was indicated by a pencil before the failure occurred.
스크래치 0-1개: OK0-1 scratches: OK
스크래치 2개 이상: NG2 or more scratches: NG
3. 표면 거칠기3. Surface Roughness
제조된 방현성 반사방지 필름을 투명한 광학용 점착제를 사용하여 TAC 필름이 유리와 접합되도록 하여 접합체를 제조하였다. 표면 거칠기 측정기(SE4000, 코사카연구소 제작)를 이용하여 측정범위 1.5㎜, 측정속도 0.1㎜/초로 JIS B 0601-1994의 규정에 의거하여 산술평균 표면 거칠기(Ra, ㎛), 요철의 평균 간격 Sm(㎛) 및 평균 경사각(θa, °)을 측정하였다.The prepared anti-glare antireflection film was bonded to glass using a transparent optical pressure-sensitive adhesive to prepare a bonded body. Using a surface roughness measuring instrument (SE4000, manufactured by Kosaka Research Institute) with a measuring range of 1.5 mm and a measuring speed of 0.1 mm / sec, the arithmetic mean surface roughness (Ra, μm) and the average spacing Sm of the unevenness in accordance with JIS B 0601-1994 Μm) and average tilt angles (θa, °) were measured.
4. 형광등 4. fluorescent tube 반사방현성Reflection
제조된 방현성 반사방지 필름을 흑색 아크릴판에 접합한 후 형광등의 반사 시인성을 통해 방현성 유무를 확인하였다.After the prepared anti-glare antireflection film was bonded to a black acrylic plate, the presence or absence of anti-glare was confirmed through reflection visibility of fluorescent lamps.
5. 방오성5. Antifouling property
(1) 수-접촉각(1) male contact angle
상온(25℃)에서 필름표면에 물방울을 적하한 후, 1분 후에 접촉각 측정기(CAM100, KSV사)를 사용하여 물방울에 대한 접촉각을 측정하였다. 접촉각은 물방울의 좌우 접촉각을 같은 시료로 5번을 측정하여 그 평균치를 사용하였다.After dropping water droplets onto the film surface at room temperature (25 ° C.), a contact angle measuring device (CAM100, KSV) was used one minute later to measure the contact angle to the water droplets. The contact angle was measured 5 times with the same sample to the left and right contact angle of the water droplets and used the average value.
(2)올레익산-접촉각(2) oleic acid-contact angle
상온(25℃)에서 필름표면에 올레익산을 적하한 후, 1분 후에 접촉각 측정기(CAM100, KSV사)를 사용하여 올레익산에 대한 접촉각을 측정하였다. 접촉각은 올레익산의 좌우 접촉각을 같은 시료로 5번을 측정하여 그 평균치를 사용하였다.After dropping oleic acid on the film surface at room temperature (25 ° C.), the contact angle with respect to oleic acid was measured after 1 minute using a contact angle measuring device (CAM100, KSV). The contact angle was measured 5 times with the same sample of the left and right contact angle of the oleic acid and used the average value.
상기 표 2를 참고하면, 실시예들은 모두 형광등 반사방현성이 우수한 것을 확인할 수 있다.Referring to Table 2, it can be seen that the embodiments are all excellent in the fluorescent light reflectivity.
구체적으로, 광확산 입자가 동일한 함량으로 포함된 실시예와 비교예를 각각 비교해보면, 전체 헤이즈 값이 비교예보다 실시예가 높은 것을 알 수 있으며, 표면 거칠기(Ra) 및 경사각(θa)도 비교예보다 실시예가 높은 것을 알 수 있는 바, 본 발명의 방현성 필름의 방현성 및 반사방지효과가 우수한 것을 알 수 있다.Specifically, when comparing the Examples and Comparative Examples each containing the light diffusing particles in the same content, it can be seen that the overall haze value is higher than the Comparative Example, the surface roughness (Ra) and the inclination angle (θa) is also Comparative Example As it turns out that an Example is higher, it turns out that the anti-glare property and anti-reflective effect of the anti-glare film of this invention are excellent.
또한, 본 발명의 실시예의 수-접촉각 및 올레익산-접촉각이 비교예에 비해 현저하게 큰 것을 확인할 수 있는 바, 이로부터 실시예들의 방현성 필름이 방오성이 우수한 것을 알 수 있다.
In addition, it can be seen that the water-contact angle and the oleic acid-contact angle of the embodiment of the present invention are significantly larger than those of the comparative example, from which it can be seen that the anti-glare film of the examples has excellent antifouling properties.
10: 방현성 필름
100: 방현성 코팅 200: 기재 필름
110: 광산란 입자
111: 코어부 112: 돌기부10: anti-glare film
100: anti-glare coating 200: base film
110: light scattering particles
111: core portion 112: protrusion
Claims (12)
A composition for anti-glare coating comprising a light scattering particles having a core portion formed of polymethyl (meth) acrylate-based polymer particles and a protrusion formed by attaching a plurality of silicon polymer particles to an outer surface of the core portion.
The anti-glare coating composition according to claim 1, wherein the core particles and the projection particles have different refractive indices.
The anti-glare coating composition according to claim 2, wherein a difference in refractive index between the core particles and the protrusion particles is 0.03 or more.
The composition for anti-glare anti-glare coating according to claim 1, wherein the average particle diameter of the light scattering particles is 1 to 10 µm.
The composition for anti-glare coating according to claim 1, wherein the average particle diameter of the protrusion particles is 0.1 to 1 µm.
The composition for anti-glare coating of claim 1, wherein the silicone polymer is polysilsesquioxane.
The composition of claim 1, wherein the light scattering particles are present in an amount of 0.1 to 30 wt% based on the total weight of the composition.
The anti-glare coating composition according to claim 1, further comprising a polymerizable compound, a photopolymerization initiator, and an organic solvent.
상기 기재 상에 형성되고, 폴리 메틸(메타)아크릴레이트계 고분자 입자로 형성된 코어부 및 상기 코어부 외면에 다수의 실리콘 고분자 입자가 부착되어 형성된 돌기부를 구비하는 광산란 입자에 의한 표면 요철이 형성된 방현성 코팅층을 포함하는 방현성 필름.
materials; And
Anti-glare with surface irregularities formed by light scattering particles formed on the substrate and having a core portion formed of polymethyl (meth) acrylate-based polymer particles and a protrusion formed by attaching a plurality of silicon polymer particles to an outer surface of the core portion. Anti-glare film comprising a coating layer.
The anti-glare film of claim 9, wherein the anti-glare coating layer is formed of the composition for anti-glare coating of any one of claims 1 to 8.
The polarizing plate provided with the anti-glare film of Claim 9.
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| KR1020120065136A KR20130141967A (en) | 2012-06-18 | 2012-06-18 | Anti-glare coating composition and anti-glare film using the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170037386A (en) * | 2015-09-25 | 2017-04-04 | 주식회사 엘지화학 | Coating composition and plastic film prepared therefrom |
| JP2018155811A (en) * | 2017-03-15 | 2018-10-04 | 日東電工株式会社 | Polarizing plate and image display device |
| WO2019151686A1 (en) * | 2018-02-05 | 2019-08-08 | 삼성전자주식회사 | Display device |
-
2012
- 2012-06-18 KR KR1020120065136A patent/KR20130141967A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170037386A (en) * | 2015-09-25 | 2017-04-04 | 주식회사 엘지화학 | Coating composition and plastic film prepared therefrom |
| JP2018155811A (en) * | 2017-03-15 | 2018-10-04 | 日東電工株式会社 | Polarizing plate and image display device |
| CN108627899A (en) * | 2017-03-15 | 2018-10-09 | 日东电工株式会社 | Polarizing film and image display device |
| WO2019151686A1 (en) * | 2018-02-05 | 2019-08-08 | 삼성전자주식회사 | Display device |
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