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KR19990015101A - Manufacturing method of diffuse reflection sheet - Google Patents

Manufacturing method of diffuse reflection sheet Download PDF

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Publication number
KR19990015101A
KR19990015101A KR1019970037001A KR19970037001A KR19990015101A KR 19990015101 A KR19990015101 A KR 19990015101A KR 1019970037001 A KR1019970037001 A KR 1019970037001A KR 19970037001 A KR19970037001 A KR 19970037001A KR 19990015101 A KR19990015101 A KR 19990015101A
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diffuse reflection
reflection sheet
particles
acrylic urethane
silica particles
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KR100469308B1 (en
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문종건
임대우
김순식
조재은
여운길
정성구
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한형수
주식회사 새한
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    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133502Antiglare, refractive index matching layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12Chemical modification
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3083Birefringent or phase retarding elements
    • G02B5/3091Birefringent or phase retarding elements for use in the UV

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)

Abstract

본 발명은 액정표시장치에 사용되는 것으로 외부로부터 반사되는 빛에 의한 눈부심 방지를 위한 난반사 효과가 특히 우수하고 내스크랫치성, 콘트래스트 등의 물성이 전반적으로 우수한 난반사 시트를 제공하는 것을 그 목적으로 한 것이다.An object of the present invention is to provide a diffuse reflection sheet, which is used in a liquid crystal display device, which has particularly excellent diffuse reflection effect for preventing glare caused by light reflected from the outside and excellent physical properties such as scratch resistance and contrast. I did it.

본 발명은 상기와 같은 목적을 달성하기 위한 일 방법으로 자외선 경화형 아크릴 우레탄계 수지와 실리카 입자 및 용제를 함유한 코팅 조성물을 기재시트위에 코팅하여 건조후 자외선 경화에 의해 제조되는 공지의 난반사시트 제조시, 사용되는 실리카 입자는 밀링처리된 입자로서 평균입자크기가 400㎚-10㎛범위에 있고 표면에 드러나는 입자의 평균개수를 특정한 범위로 조절하여 사용하는 것을 특징으로 한 난반사 시트 제조방법을 제공하는데, 이와 같이 제조된 난반사 시트는 액정표시 장치 등에 사용되는 경우 우수한 물성을 나타낸다.The present invention is a method for achieving the above object by coating a coating composition containing an ultraviolet curable acrylic urethane-based resin, silica particles and a solvent on a base sheet to produce a known diffuse reflection sheet manufactured by ultraviolet curing after drying, The silica particles used are milled particles, which have an average particle size in the range of 400 nm-10 μm, and provide a method for producing a diffuse reflection sheet, characterized in that the average number of particles exposed on the surface is adjusted to a specific range. The diffuse reflection sheet manufactured as described above exhibits excellent physical properties when used in a liquid crystal display.

Description

난반사 시트의 제조방법Manufacturing method of diffuse reflection sheet

본 발명은 액정표시장치에서 사용되는 것으로 외부로부터 반사되는 빛에 의한 눈부심 방지를 위한 난반사효과가 특7히 우수하고 내스크랫치성, 콘트래스트등의 물성이 전반적으로 우수한 난반사 시트의 제조방법에 관한 것이다.The present invention is to be used in the liquid crystal display device in the manufacturing method of the diffuse reflection sheet is particularly excellent in the anti-reflective effect for preventing glare by light reflected from the outside and excellent overall properties such as scratch resistance, contrast, etc. It is about.

기존의 눈부심방지(방현) 가공물로서는 표면에 요철이 있는 롤을 연속적으로 필름에 눌러줌으로써 필름에 요철을 부여하여 난반사효과를 내는 매트상 가공물(1), 수지의 상용성이나 결정화도의 차이를 이용한 확산형 가공물(2) 및 무기화합물의 박층 코팅을 한 가공물(3) 등이 알려져 있다.Existing anti-glare (anti-glare) workpiece is a mat-like workpiece (1) which gives irregular reflection to the film by applying unevenness to the film by continuously pressing a roll having irregularities on the surface, and diffusion using a difference in compatibility or crystallinity of the resin. Molded workpieces 2 and workpieces 3 having a thin layer coating of inorganic compounds are known.

이러한 가공물 중에서 (1)은 제조공정이 복잡하고 장시간을 요하여 제조단가가 높고, 또한 사용하는 금형의 내구성이나 금형수지를 분리할 때의 난점이 있으며, (2)는 가공물 자체의 내구성에 문제가 있고, (3)의 가공물은 기재 표면에 박층의 단층 또는 다층의 코팅층을 광선의 파장 레벨(Level)에 맞추어 형성한 것으로, 사용한 기재가 제한되어 제조공정이 복잡하고 장치가 복잡해지는 단점이 있다.Among these workpieces, (1) has a complicated manufacturing process and requires a long time, resulting in high manufacturing cost, and difficulty in separating the durability or mold resin of the mold used, and (2) has problems in durability of the workpiece itself. The workpiece of (3) is formed by forming a single layer or a multilayer coating layer on the surface of the substrate in accordance with the wavelength level of the light beam. The substrate used is limited, and thus, the manufacturing process is complicated and the apparatus is complicated.

본 발명은 상기와 같은 문제점을 해결하기 위해 안출된 것으로서, 제조공정이 단순하고 양산화가 가능하며 성능면에서도 우수한 난반사 효과를 가진 시트를 제조하는 방법을 제공하는 것을 그 목적으로 한 것이다.The present invention has been made to solve the above problems, it is an object of the present invention to provide a method for producing a sheet having a simple diffuse reflection effect in terms of performance and the production process is simple and mass production.

본 발명은 상기 목적을 달성하기 위하여 자외선 경화형 아크릴 우레탄계 수지와 실리카 입자 및 용제를 함유한 코팅 조성물을 기재 시트위에 코팅하여 건조 후 자외선 경화방식으로 제조하는 공지의 난반사 시트 제조공정에서 실리카 입자로서 입자의 평균크기가 400㎚∼10㎛인 것을 사용하고 표면에 드러난 입자의 평균개수가 103-108개/㎠의 범위에 있도록 사용하는 것을 특징으로 한 난반사 시트의 제조법을 제공한다.In order to achieve the above object, the present invention provides a coating composition containing an ultraviolet curable acrylic urethane-based resin, silica particles, and a solvent on a base sheet to dry the particles as silica particles in a known diffuse reflection sheet manufacturing process. Provided is a method for producing a diffuse reflection sheet, which uses an average size of 400 nm to 10 μm and uses the particles in the range of 10 3 -10 8 / cm 2.

이하에서 본 발명을 구체적으로 설명한다.Hereinafter, the present invention will be described in detail.

본 발명에 있어서 사용된 자외선 경화형 아크릴 우레탄계 수지는 일반적으로 폴리에스테르 폴리올에 이소시아네이트 모노마를 반응시켜 얻어지는 것이며, 분자 골격중에 우레탄 결합을 가지는 동시에 분자내의 임의위치(가장 좋기로는 분자말단)에 아크릴레이트(메타크릴레이트) 또는 유도된 아크릴레이트(메타크릴레이트)를 가지는 것을 사용하는 것이 좋다. 또한, 아크릴우레탄계 수지는 대부분 모노마와 분자량 5,000미만의 올리고머와의 혼합제를 사용하는데, 올리고머의 분자량이 5,000이상이 되면 고형분의 양을 일정하게 유지하더라도 코팅액의 점도가 올라가고 코팅 후 필름의 표면조도가 작아져 난반사효과가 줄어들고 이 때문에 입자의 함량을 늘리는 경우에는 필름의 선명도가 떨어지는 문제점이 발생한다. 그리고, 이러한 아크릴우레탄계 수지는 굴절율이 1.52 이상인 것을 사용하는데, 이는 굴절율이 대략 1.46 정도인 실리카와의 굴절율 차이를 크게하여 정반사되는 광을 줄이기 위함으로, 즉 코팅층의 표면에서 반사되는 빛은 표면에 드러난 입자에 의해 결정되지만 표면을 통과한 빛의 경우는 입자와 수지를 동시에 통과하게 되므로 이때 수지와 입자의 굴절율 차이를 이용해 빛의 난반사 효과를 극대화 할 수 있는 것이며, 이와같이 제조된 난반사 필름은 내부광의 투과율은 최대로 유지하면서 반사광은 줄일 수 있어 콘트래스트를 향상시킬 수 있는 것이다.UV curable acrylic urethane resins used in the present invention are generally obtained by reacting an isocyanate monoma with a polyester polyol, and having an urethane bond in the molecular backbone, and at the same time in the molecule (most preferably, the end of the molecule). Methacrylates) or derived acrylates (methacrylates). In addition, most of the acrylic urethane-based resin using a mixture of monomer and oligomer of less than 5,000 molecular weight, when the molecular weight of the oligomer is 5,000 or more, even if the amount of solid content is kept constant, the viscosity of the coating liquid rises and the surface roughness of the film after coating is small. The diffuse reflection effect is reduced, and thus, when the content of the particles is increased, the sharpness of the film is deteriorated. In addition, the acrylic urethane resin has a refractive index of 1.52 or more, which is to reduce the specularly reflected light by increasing the refractive index difference with silica having a refractive index of about 1.46, that is, the light reflected from the surface of the coating layer is exposed to the surface Although it is determined by the particles, the light passing through the surface passes through the particles and the resin at the same time, so that the diffuse reflection effect of the light can be maximized by using the difference between the refractive index of the resin and the particles. Can keep the maximum light while reducing the reflected light, thereby improving contrast.

본 발명에서 사용되는 실리카 입자는 이산화규소(SiO2)로 이루어져 있으며, 이와같은 실리카 입자의 밀링 후 입자의 크기는 400㎚-10㎛(보다 바람직하게는 1∼3㎛)정도가 바람직한데, 입자 크기가 400㎚미만인 경우에는 가시광선 영역의 파장을 산란 시키지 못하게 되고, 입자크기가 10㎛보다 클 경우에는 광투과율이 떨어지며 표면 상태가 거칠어지는 단점이 있다.The silica particles used in the present invention are composed of silicon dioxide (SiO 2 ), and the size of the particles after milling of such silica particles is preferably about 400 nm-10 μm (more preferably 1 to 3 μm). If the size is less than 400 nm, the wavelength of the visible light region is not scattered, and if the particle size is larger than 10 μm, the light transmittance is decreased and the surface state is rough.

한편, 본 발명에서는 코팅 후 표면에 드러나는 실리카 입자의 평균 개수는 103개/㎠∼108개/㎠ 범위에 있도록 하는 것을 또다른 특징부로 하는데, 입자의 평균개수가 103개/㎠ 미만 일때는 입자개수가 너무적어 정반사되는 빛의 양이 많아지기 때문에 화상의 콘트레스트가 떨어지고, 108개/㎠ 초과시에는 빛의 산란으로 인해 광투과율이 저하되며 입자의 돌출로 인해 표면경도가 떨어지는 문제점이 있다.On the other hand, the mean number of silica particles revealed on the surface after the coating in the present invention is 10 3/8 ㎠~10 number / ㎠ to another part characterized in that to the range, when the average number of particles 10 3 / under ㎠ Since the number of particles is too small, the amount of reflected light increases, so the contrast of the image falls, and when it exceeds 10 8 / cm 2, the light transmittance decreases due to light scattering, and the surface hardness decreases due to the protrusion of particles. have.

본 발명에서의 코팅 조성물은 아크릴우레탄 수지, 아크릴 수지, 실리카 입자를 용제와 함께 균일하게 혼합하여 만든다. 이때 사용되는 용제로서는 기재에 대하여 불활성인 것이 사용되며, 그 사용량은 고형분 농도가 20∼80중량% 정도가 되도록 사용하는 것이 좋다.The coating composition in the present invention is made by uniformly mixing an acrylic urethane resin, an acrylic resin, and silica particles with a solvent. The solvent used at this time is an inert thing with respect to a base material, It is good to use that the usage-amount so that solid content concentration may be about 20 to 80 weight%.

또한, 상기의 코팅 조성물에는 발명의 목적을 손상시키지 않는 한 각종의 첨가제, 예를들면, 안료, 염료, 대전방지제 등을 첨가할 수 있으며, 특히 자외선 경화를 위해 개시제가 사용되는데, 사용 가능한 개시제로는 아세톤페논류, 벤조페논류, 벤질류, 벤조인류 등이 있다.In addition, various additives such as pigments, dyes, antistatic agents, and the like can be added to the coating composition as long as the object of the invention is not impaired. In particular, an initiator is used for ultraviolet curing, Acetone phenones, benzophenones, benzyl, benzoin, etc. are mentioned.

본 발명에 따라 조제된 코팅 조성물은 기재 시트위에 스프레이법, 그라비에법 등의 일반적인 코팅방법에 의해 통상 두께가 3-10㎛정도로 코팅되며 가열건조 후 자외선을 조사하여 경화시킨다.The coating composition prepared according to the present invention is usually coated in a thickness of about 3-10㎛ by a general coating method such as spray method, gravure method on the substrate sheet and cured by irradiation with ultraviolet rays after heat drying.

기재 시트로서는 통상 TAC(TriAcetate Cellulose)이 사용되며, 그외에 투명한 폴리에스테르 수지, 폴리카보네이트 수지, 폴리아크릴 수지, 염화비닐 수지 등의 플라스틱 시트가 사용될 수 있다.TAC (TriAcetate Cellulose) is usually used as the base sheet, and other plastic sheets such as transparent polyester resins, polycarbonate resins, polyacrylic resins, and vinyl chloride resins may be used.

이하에서 실시예 및 비교예를 들어 본 발명을 좀 더 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

(실시예 1∼4, 비교예 1, 2)(Examples 1-4, Comparative Examples 1 and 2)

아래 표 1 에 기재된 바와 같이 구성된 코팅 조성물을 공지의 방법으로 난반사 시트를 제조하였는바, 이때 밀링처리하여 사용하였으며, 실시예1∼실시예4 에서는 코팅 후 표면에 드러나는 입자의 개수가 103개/㎠∼108개/㎠ 범위가 되도록 입자량을 조절하여 코팅하였으며, 비교예 1,2에서는 표면에 드러나는 입자의 개수가 103개/㎠미만, 또는 109개/㎠ 초과되도록 하였다. 이때 난반사 시트는 평균 코팅 두께가 5㎛ 되도록 하였으며, 물성을 조사하여 표 1 에 나타내었다.The coating composition configured as described in Table 1 below was prepared by a known method for the diffuse reflection sheet, which was used by milling, in Examples 1 to 4, the number of particles exposed on the surface after coating is 10 3 / Particles were adjusted to be coated so as to be in the range of cm 2 to 10 8 / cm 2, and in Comparative Examples 1 and 2, the number of particles exposed on the surface was less than 10 3 pieces / cm 2 or more than 10 9 pieces / cm 2. At this time, the diffuse reflection sheet was to have an average coating thickness of 5㎛, it is shown in Table 1 by examining the physical properties.

비교1Comparison 1 실시1Conduct1 실시2Conduct2 실시3Conduct 3 실시4Conduct4 비교2Comparison 2 아크릴우레탄수지(g)Acrylic Urethane Resin (g) 100100 100100 100100 100100 100100 100100 실리카 입자(개/㎠)Silica Particles (pcs / ㎠) 103미만Less than 10 3 103∼104 10 4 3-10 104∼105 10 5 4-10 106∼107 10 6-10 7 107∼108 10 7-10 8 109초과More than 10 9 광중합개시제(g)Photopolymerization Initiator (g) 55 55 55 55 55 55 용제(g) 1)Solvent (g) 1) 170170 170170 170170 170170 170170 170170 실리카입경Silica particle diameter 1.5㎛1.5 μm 1.5㎛1.5 μm 1.5㎛1.5 μm 1.5㎛1.5 μm 1.5㎛1.5 μm 1.5㎛1.5 μm Haze (%)Haze (%) 77 1313 2020 2929 3535 4444 광택도Glossiness 6868 4747 3535 2525 2121 1616 광투과율(%)Light transmittance (%) 9090 9090 8989 8888 8888 8585 콘트래스트Contrast 불량Bad 양호Good 양호Good 양호Good 양호Good 양호Good

(실시예 5∼7, 비교예 3, 4)(Examples 5-7, Comparative Examples 3 and 4)

하기 표 2 는 조성물 중 아크릴 우레탄계 수지의 굴절율에 따른 반사광의 변화를 나타낸 것으로, 실시예5∼실시예7 에서는 굴절율이 1.52 이상인 수지를 사용하였으며, 비교예3, 비교예4에서는 굴절율이 각각 1.48, 1.50인 수지를 사용하였다. 코팅액의 조성 및 코팅방식은 실시예 1과 동일하게 하여 평균 코팅두께 5㎛의 난반사 시트를 얻었으며, 물성을 조사하여 표 2 에 나타내었다.Table 2 shows the change in the reflected light according to the refractive index of the acrylic urethane resin in the composition. In Examples 5 to 7, resins having a refractive index of 1.52 or more were used. In Comparative Examples 3 and 4, the refractive index was 1.48, respectively. A resin of 1.50 was used. The composition and the coating method of the coating solution were the same as in Example 1 to obtain a diffuse reflection sheet having an average coating thickness of 5㎛, it is shown in Table 2 by examining the physical properties.

비교3Comparison 3 비교4Comparison 4 실시5Conduct 5 실시6Conduct6 실시7Conduct7 아크릴우레탄수지굴절율Acrylic Urethane Refractive Index 1.481.48 1.501.50 1.521.52 1.541.54 1.561.56 실리카 입자(g)Silica particles (g) 55 55 55 55 55 광중합개시제(g)Photopolymerization Initiator (g) 55 55 55 55 55 Haze(%)Haze (%) 30.230.2 30.430.4 30.530.5 29.729.7 30.530.5 광택도Glossiness 33.533.5 29.329.3 25.025.0 25.825.8 2626

상기 실시예 및 비교예에서도 확인 되듯이 본 발명에 따라 얻어지는 난반사 시트는 실리카가 함유된 경화피막으로 인해 양호한 방현성을 가지며, 자외선 경화피막의 경도가 높기 때문에 내스크래치성이 우수한 특성을 나타내는 한편 콘트래스트가 우수한 성능을 진닌다.As can be seen from the above examples and comparative examples, the diffused reflection sheet according to the present invention has good anti-glare property due to the cured film containing silica, and exhibits excellent scratch resistance due to the high hardness of the UV cured film. Trast has excellent performance.

Claims (4)

자외선 경화형 아크릴 우레탄계 수지와 실리카 입자 및 용제를 함유한 코팅 조성물을 기재 시트위에 코팅하여 건조후 자외선 경화방식으로 제조하는 공지의 난반사 시트 제조공정에서, 사용되는 실리카 입자는 밀링처리된 입자로서 평균 입자크기가 400㎚-10㎛이고 표면에 드러난 입자의 평균개수가 103개/㎠∼108개/㎠ 범위에 있는 것을 사용하는 것을 특징으로 하는 난반사 시트의 제조방법In the well known diffused reflection sheet manufacturing process in which a coating composition containing an ultraviolet curable acrylic urethane resin, silica particles and a solvent is coated on a substrate sheet and then dried by UV curing, the silica particles used are milled particles and have an average particle size. Is 400 nm-10 µm and the average number of particles exposed on the surface is in the range of 10 3 particles / cm 2 to 10 8 particles / cm 2. 제 1 항에 있어서, 아크릴 우레탄계 수지는 굴절율을 1.52 이상인 것이 사용되는 것을 특징으로 하는 난반사 시트의 제조방법The method for producing a diffuse reflection sheet according to claim 1, wherein the acrylic urethane resin has a refractive index of 1.52 or more. 제 1 항에 있어서, 아크릴 우레탄계 수지는 폴리에스테르 폴리올에 이소시아네이트모노마를 반응시켜 얻어지는 것임을 특징으로 하는 난반사 시트의 제조방법The method for producing a diffuse reflection sheet according to claim 1, wherein the acrylic urethane resin is obtained by reacting an isocyanate monomer with a polyester polyol. 제 1 항에 있어서, 아크릴우레탄계 수지는 모노마와 분자량 5,000미만의 올리고머와의 혼합체를 사용하는 것을 특징으로 하는 난반사시트의 제조방법The method for producing a diffuse reflection sheet according to claim 1, wherein the acrylic urethane resin is a mixture of monoma and an oligomer having a molecular weight of less than 5,000.
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
KR100824325B1 (en) * 2006-05-26 2008-04-22 요업기술원 Anti-glare coating comprising silica fine hollow spheres, and anti-glare film produced therefrom
KR100959683B1 (en) * 2001-12-28 2010-05-26 엘지디스플레이 주식회사 Reflective Liquid Crystal Display and Manufacturing Method Thereof
US8040456B2 (en) 2003-01-15 2011-10-18 Semiconductor Energy Laboratory Co., Ltd. Liquid crystal display device and manufacturing method of liquid crystal display device

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JPS54158078A (en) * 1978-06-05 1979-12-13 Osaka Gas Co Ltd Waste melting furnace
JPH05341109A (en) * 1992-06-04 1993-12-24 Toyo Alum Kk Light reflecting plate
JPH0727905A (en) * 1993-07-14 1995-01-31 Keiwa Shoko Kk Reflecting sheet material
JP3092035B2 (en) * 1993-10-13 2000-09-25 松下電器産業株式会社 Liquid crystal display device and method of manufacturing reflector thereof
JPH09113707A (en) * 1995-10-19 1997-05-02 Dainippon Printing Co Ltd Light reflector and manufacturing method thereof

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Publication number Priority date Publication date Assignee Title
KR100959683B1 (en) * 2001-12-28 2010-05-26 엘지디스플레이 주식회사 Reflective Liquid Crystal Display and Manufacturing Method Thereof
US8040456B2 (en) 2003-01-15 2011-10-18 Semiconductor Energy Laboratory Co., Ltd. Liquid crystal display device and manufacturing method of liquid crystal display device
US8218105B2 (en) 2003-01-15 2012-07-10 Semiconductor Energy Laboratory Co., Ltd. Liquid crystal display device and manufacturing method of liquid crystal display device
US8634041B2 (en) 2003-01-15 2014-01-21 Semiconductor Energy Laboratory Co., Ltd. Liquid crystal display device and manufacturing method of liquid crystal display device
KR100824325B1 (en) * 2006-05-26 2008-04-22 요업기술원 Anti-glare coating comprising silica fine hollow spheres, and anti-glare film produced therefrom

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