KR0173312B1 - Manufacturing method of liquid crystal polymer composite for light control - Google Patents
Manufacturing method of liquid crystal polymer composite for light control Download PDFInfo
- Publication number
- KR0173312B1 KR0173312B1 KR1019910021431A KR910021431A KR0173312B1 KR 0173312 B1 KR0173312 B1 KR 0173312B1 KR 1019910021431 A KR1019910021431 A KR 1019910021431A KR 910021431 A KR910021431 A KR 910021431A KR 0173312 B1 KR0173312 B1 KR 0173312B1
- Authority
- KR
- South Korea
- Prior art keywords
- liquid crystal
- pmma
- glass plate
- prepolymer
- transparent conductive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 11
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims abstract description 11
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 42
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 42
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 31
- 239000011521 glass Substances 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 8
- 238000013007 heat curing Methods 0.000 claims abstract 2
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 abstract description 17
- 239000011347 resin Substances 0.000 abstract description 17
- 239000000203 mixture Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 238000001723 curing Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000002952 polymeric resin Substances 0.000 description 7
- 229920003002 synthetic resin Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 101001126084 Homo sapiens Piwi-like protein 2 Proteins 0.000 description 5
- 102100029365 Piwi-like protein 2 Human genes 0.000 description 5
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 description 5
- GYMWQLRSSDFGEQ-ADRAWKNSSA-N [(3e,8r,9s,10r,13s,14s,17r)-13-ethyl-17-ethynyl-3-hydroxyimino-1,2,6,7,8,9,10,11,12,14,15,16-dodecahydrocyclopenta[a]phenanthren-17-yl] acetate;(8r,9s,13s,14s,17r)-17-ethynyl-13-methyl-7,8,9,11,12,14,15,16-octahydro-6h-cyclopenta[a]phenanthrene-3,17-diol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1.O/N=C/1CC[C@@H]2[C@H]3CC[C@](CC)([C@](CC4)(OC(C)=O)C#C)[C@@H]4[C@@H]3CCC2=C\1 GYMWQLRSSDFGEQ-ADRAWKNSSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940102838 methylmethacrylate Drugs 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
Abstract
본 발명은 PMMA 프리폴리머와 액정 모노머의 균일한 혼합용액을 ITO가 코팅된 투명 도전성 유리판에 코팅한 뒤 다시 그 필름위에 동일한 투명 도전성 유리판을 덮어 열경화하여 광조절용 액정 고분자 복합체를 제조하는 방법에 있어, 0.1 내지 0.1 중량%의 벤조일퍼옥사이드의 존재하에 MMA에 20 내지 60 중량%의 PMMA를 용해시켜 원하는 점도로 상기 PMMA 프리폴리머를 준비하는 방법으로 점도조절이 쉽고 양호한 프리폴리머를 제조할 수 있기 때문에 필름제조가 간단하며 PMMA 수지의 우수한 투명성으로 콘트라스트가 우수한 광조절용 셔터의 제작이 가능하다.The present invention is a method for producing a liquid crystal polymer composite for light control by coating a uniform mixture of PMMA prepolymer and liquid crystal monomer on a transparent conductive glass plate coated with ITO and then heat-curing the same transparent conductive glass plate on the film. In the presence of 0.1 to 0.1% by weight of benzoyl peroxide, 20 to 60% by weight of PMMA is dissolved in MMA to prepare the PMMA prepolymer at a desired viscosity. Simple and excellent transparency of PMMA resin makes it possible to manufacture a light control shutter with excellent contrast.
Description
제1도는 고분자 물질내에 액정이 분산된 상태에서의 액정 고분자 복합체의 구조도.1 is a structural diagram of a liquid crystal polymer composite in a state where liquid crystal is dispersed in a polymer material.
제2도는 액정이 배향되어 있는 상태에서의 액정고분자 복합체의 구조도.2 is a structural diagram of a liquid crystal polymer composite in a state where liquid crystal is aligned.
제3도는 본 발명에서 PMMA 조성비 및 분자량에 따른 점도 그라프도.3 is a viscosity graph according to the PMMA composition ratio and molecular weight in the present invention.
제4도는 본 발명에서 PMMA 조성비 및 분자량에 따른 용해시간 그라프도이다.4 is a dissolution time graph according to the PMMA composition ratio and molecular weight in the present invention.
본 발명은 광조절용 액정고분자 복합체의 제조방법에 관한 것으로, 보다 상세하게는 투명한 수지(Matrix resin)내에 균일한 용액으로 분산되어 있는 액정모노머의 전기적, 광학적인 성질을 이용하여 광조절이 가능한 물질을 제조하는 방법에 있어 투명성이 매우 우수한 열가소성 수지인 PMMA(Poly methylme-thacrylate)프리폴리머의 점도를 자유롭게 조절하여 액정고분자 복합체 제조 코팅시 원하는 사용점도로 쉽게 만들 수 있는 방법에 관한 것이다.The present invention relates to a method for manufacturing a liquid crystal polymer composite for light control, and more particularly, to a material capable of light control using the electrical and optical properties of a liquid crystal monomer dispersed in a uniform solution in a transparent resin. The present invention relates to a method of freely controlling the viscosity of PMMA (Poly methylme-thacrylate) prepolymer, which is a thermoplastic resin having excellent transparency, so that it can be easily made into a desired use point when coating a liquid crystal polymer composite.
일반적으로 투명한 수지에 액정을 혼합하여 만든 액정고분자 복합체(PDLC:Polymer Dispersed Liquid Crystal)는 수지와 액정을 균일하게 혼합한 후 원심분리기나 진공장치를 이용하여 탈포한 뒤 기포가 제거된 용액을 전도성 물질인 ITO(Indium Tin Oxide)가 코팅되어 있는 유리판이나 폴리에스터 필름 사이에서 UV나 열에 의해 경화시켜 필름이나 시트 형태로 제조한다.Generally, PDLC (Polymer Dispersed Liquid Crystal) made by mixing liquid crystal with transparent resin is mixed with resin and liquid crystal uniformly, and then degassed using centrifuge or vacuum device to remove the bubble-free solution. Between the glass plate or polyester film coated with phosphorus ITO (Indium Tin Oxide) is cured by UV or heat to prepare a film or sheet form.
이때 사용되는 고분자 수지로는 열에 의해 경화 가능한 비스페놀A타잎의 투명에폭시, 우레탄등의 열경화성 수지와 투명성이 매우 우수한 PMMA(Poly methyl methacrylate), 폴리비닐포르말, 폴리비닐부티랄, 폴리카보네이트, 폴리이소프렌, 폴리아세탈등의 열가소성 고분자들이 사용된다.The polymer resin used at this time is a thermoepoxy resin such as bisphenol A type which can be cured by heat, thermosetting resins such as urethane and PMMA (Poly methyl methacrylate), polyvinyl formal, polyvinyl butyral, polycarbonate, and polyisoprene having excellent transparency. And thermoplastic polymers such as polyacetal.
이러한 수지들은 대부분이 칩(chip)상태로 존재하거나 경화되기 이전의 프리폴리머상태로 존재한다.Most of these resins exist in a chip state or in a prepolymer state before curing.
광조절용 필름이나 시트 제조시 칩상태로 존재하는 수지는 수지가 녹을 수 있는 아세톤이나 메틸렌 클로라이드, 클로로포름등의 적정용매를 선정하여 수지를 완전히 녹인후, 액정모노머와 균일하게 혼합하여 ITO코팅된 유리판에 코팅한 뒤 용매를 증발시키고 그 위에 또 다른 ITO코팅 유리판을 덮고 경화시켜 제조한다. 프리폴리머 상태로 존재하는 수지는 용매의 증발이 필요없이 고분자 수지와 액정을 균일하게 섞은 후 경화시켜 제조할 수 있다.The resin present in the chip state when manufacturing the light control film or sheet is selected from a suitable solvent such as acetone, methylene chloride, chloroform, etc., in which the resin can be dissolved, and then completely dissolved in the resin, and then uniformly mixed with the liquid crystal monomer and coated on the ITO coated glass plate. After coating, the solvent is evaporated and prepared by covering and curing another ITO coated glass plate thereon. The resin present in the prepolymer state may be prepared by uniformly mixing the polymer resin and the liquid crystal after curing without evaporation of the solvent.
이렇게 하여 경화된 필름내에서의 액정 마이크로드롭플렛(microdroplets)는, 그 마이크로드롭플렛내의 각각의 분자들이 제1도와 같이 대개 동일한 배향을 하고 있으나 드롭플렛 각각의 배향은 다양하다. 그러나 제2도와 같이 ITO코팅된 두 투명전극사이에 전원을 가하면 액정들은 전극면에 수직한 방향으로 정렬하게 된다. 고분자 수지의 굴절률을 ns, 액정분자 배열 장축 방향의 굴절률을 ne라 하면, 제1도에서는 ns와 ne가 달라 입사광이 산란되므로 필름은 불투명하게 나타나나, 제2도와 같이 액정 마이크로드롭플렛이 정렬된 상태에서는 ns와 ne가 일치하게 되어 투명하게 나타난다.Liquid crystal microdroplets in the cured film in this way have the same orientation as those of FIG. 1, although the molecules in the microdroplet are usually in the same orientation as in FIG. However, when power is applied between two ITO-coated transparent electrodes as shown in FIG. 2, the liquid crystals are aligned in a direction perpendicular to the electrode plane. If the refractive index of the polymer resin is n s and the refractive index in the major axis direction of the liquid crystal molecules is n e , the film appears opaque because the incident light is different from n s and n e in FIG. 1. With the flats aligned, n s and n e coincide and appear transparent.
이와 같은 액정 고분자 복합체는 여러 가지 방법으로 제조 가능하나 대표적인 제조방법은 다음과 같은 것들이 있다. 첫때, PVA등의 수용성 폴리머를 물에 녹인 후 물에 녹지 않는 액정 모노머와 섞어 에멀젼을 만든 다음 ITO코팅된 유리판과 같은 기판에 코팅하고 열을 가하여 물을 제거한 후 그 위에 다시 투명 도전성 기판을 덮어 만드는 에멀젼 방법, 둘째, 액정모노머를 녹일 수 있는 고분자 수지의 프리폴리머와 액정을 균일하게 혼합한 혼합물을 만든 후 이 프리폴리머가 경화됨에 따라 액정의 용해도가 감소하여 액정 드롭리트를 형성하는 뉴크리에이션(Nucleation)법, 셋째, 자외선에 의해 경화 가능한 모노머 또는 프리폴리머를 투명 도전성 전극 사이에 넣고 UV경화시키는 방법, 넷째, 고분자 수지와 액정을 모두 녹일 수 있는 용매를 선택하여 투명 도전성 전극 위에 코팅한 뒤 용매를 제거하고 그 위에 다시 투명 도전성 전극을 덮어 제조하는 방법, 다섯째, 열에 의해 중합됨으로써 경화 가능한 액상의 모노머나 프리폴리머를 두장의 투명 도전성 전극사이에서 경화시켜 만드는 방법등이 있다.Such a liquid crystal polymer composite can be manufactured by various methods, but typical manufacturing methods are as follows. At first, water-soluble polymer such as PVA is dissolved in water and mixed with liquid monomer which is not soluble in water to make an emulsion. Then, it is coated on a substrate such as ITO coated glass plate and heated to remove water and then cover the transparent conductive substrate on it. Emulsion method, and second, a nucleation method in which a prepolymer of a polymer resin capable of dissolving a liquid crystal monomer and a mixture of a liquid crystal are uniformly mixed, and then the solubility of the liquid crystal decreases as the prepolymer is cured to form a liquid crystal droplet. Third, UV curing the monomer or prepolymer curable by UV light between the transparent conductive electrode, and UV curing method. Fourth, a solvent capable of dissolving both the polymer resin and the liquid crystal is selected and coated on the transparent conductive electrode to remove the solvent. Method of manufacturing by covering the transparent conductive electrode on top again, fifth, by heat Sum being and a method of making a cured liquid monomer or prepolymer capable to cure between two sheets of transparent conductive electrodes.
위와 같은 방법들은 모두 일정점도를 가지는 액상 혼합물을 코팅하는 공정을 수반하거나, 고분자 수지나 액정 모노머를 녹이는데 사용된 용매나 물을 제거해야 하는 문제점이 있다.All of the above methods involve a process of coating a liquid mixture having a certain viscosity or a problem in that the solvent or water used to dissolve the polymer resin or the liquid crystal monomer is removed.
다섯 번째 방법과 같이 프리폴리머를 열에 의해 경화시키는 방법은 용매를 제거할 필요는 없으나 코팅에 적합한 원하는 점도로 얻기가 어렵다. 특히 고분자 수지중 가장 투명성이 뛰어난 것으로 알려진 PMMA는 그 투명성으로 인해 PDLC 제조시의 매트릭스 수지로 사용이 바람직하나, 아세톤이나 클로로포름과 같은 용매에 녹여 사용해야 하거나 MMA(Methyl methacrylate)모노머 상태에서 중합시켜 사용해야 한다.The method of curing the prepolymer by heat, like the fifth method, does not need to remove the solvent but is difficult to obtain at the desired viscosity suitable for coating. In particular, PMMA, which is known to have the highest transparency among polymer resins, is preferable to be used as a matrix resin for PDLC manufacturing due to its transparency. However, PMMA should be dissolved in a solvent such as acetone or chloroform or polymerized in MMA (Methyl methacrylate) monomer. .
용매를 제거하여 사용하는 경우에 있어서는 필름의 중앙부위까지의 균일한 용매의 제거가 매우 어려우며, MMA를 중합하여 PMMA 프리폴리머를 제조할 경우에는 일정수준의 전도단계에서 급격한 겔화(Gelation)현상으로 일정점도의 프리폴리머를 안정적으로 얻는 것이 거의 불가능하다.In the case of removing the solvent, it is very difficult to remove the uniform solvent to the center of the film, and in the case of producing PMMA prepolymer by polymerizing MMA, it has a certain viscosity due to rapid gelation phenomenon at a certain level of conduction. It is almost impossible to stably obtain a prepolymer of.
따라서 본 발명은 이 같은 종래의 결점을 해소하기 위해서 안출된 것으로, 기본적으로 투명성이 뛰어난 PMMA수지를 사용하되 액정고분자복합체의 제조에 적합한 사용점도를 손쉽게 조절확보할 수 있게 되므로써 본 발명을 완성하게 되었다.Therefore, the present invention was devised to solve such a conventional drawback, and basically, PMMA resin having excellent transparency can be used, but it is possible to easily adjust and secure a suitable viscosity suitable for the production of liquid crystal polymer composites, thereby completing the present invention. .
즉, 본 발명은 원하는 전도의 PMMA 프리폴리머와 액정 모노머의 균일한 혼합용액을 ITO가 코팅되어 있는 투명 도전성 유리판에 코팅한 뒤 다시 필름위에 동일한 투명 도전성 유리판을 덮어 열경화하여, 광조절용 셔터를 제조하거나 LCD로의 응용이 가능한 액정 고분자 복합체(PDLC)를 제조하는 방법에 관한 것으로, 특히 0.1 내지 1.0 중량%의 벤조일퍼옥사이드(BPO)의 존재하에서 MMA에 20 내지 60 중량%의 PMMA를 용해시켜 손쉽고도 정확하게 상기한 원하는 점도의 PMMA 프리폴리머를 준비하는 방법을 제공하는 것이다.That is, the present invention is coated with a transparent conductive glass plate coated with ITO on a homogeneous mixed solution of the PMMA prepolymer and the liquid crystal monomer of the desired conductivity and then heat-cured by covering the same transparent conductive glass plate on the film to prepare a shutter for light control The present invention relates to a method for producing a liquid crystal polymer composite (PDLC) that can be applied to LCD, and in particular in the presence of 0.1 to 1.0% by weight of benzoyl peroxide (BPO) by dissolving 20 to 60% by weight of PMMA in MMA easily and accurately It is to provide a method for preparing a PMMA prepolymer of the desired viscosity as described above.
본 발명에서 원하는 점도의 PMMA 프리폴리머를 준비하는 방법을 설명하면 콘덴사 장치가 구비된 용기에 MMA와 20 내지 60 중량%의 PMMA를 평량하여 투입하고 여기에 0.1 내지 1.0 중량%의 BPO를 넣고 충분한 시간동안 교반시켜 행한다.In the present invention, a method for preparing a PMMA prepolymer having a desired viscosity is described by adding a basis weight of MMA and 20 to 60% by weight of PMMA to a container equipped with a condensate device, and adding 0.1 to 1.0% by weight of BPO to the container. Stirring is carried out.
여기에서 교반시간은 사용하는 PMMA의 분자량과 투입량 및 최종희망 점도수준에 따라 달라질 수 있으나(제4도참조) 균질한 PMMA 프리폴리머용액을 획득하는 선에서, 즉 2 내지 8시간 범위가 좋다.Here, the stirring time may vary depending on the molecular weight and dosage of the PMMA used and the final desired viscosity level (see FIG. 4). However, the stirring time is preferably in the range of 2 to 8 hours in order to obtain a homogeneous PMMA prepolymer solution.
본 발명에서 사용하는 PMMA의 분자량 수준은 최종적으로 원하는 점도수준, 준비시간등을 감안하여 선택되어져야 하나 바람직하게는 25,000 내지 100,000의 것이 사용상 유리하고, PMMA의 사용량은 MMA와의 총량기준 20 내지 60 중량%범위 내에서 사용되는 PMMA의 분자량, 준비시간 및 최종희망점도를 감안하여 선택되어야 한다(제3-4도 참조). 제3-4도에서 보는 바와 같이 동일 분자량의 PMMA에서 그 조성비가 증가할수록 프리폴리머의 점도는 증가하며, 동일조성에서 PMMA의 분자량이 클수록 프리폴리머의 점도는 증가하고 용해시키는 시간도 증가한다.The molecular weight level of PMMA used in the present invention should be selected in consideration of the final desired viscosity level, preparation time, etc. Preferably it is advantageous in use of 25,000 to 100,000, the amount of PMMA is 20 to 60% by weight based on the total amount with MMA It should be selected taking into account the molecular weight, preparation time and final desired viscosity of the PMMA used in the range of% (see Figure 3-4). As shown in FIGS. 3-4, the viscosity of the prepolymer increases as the composition ratio of PMMA having the same molecular weight increases. In the same composition, the viscosity of the prepolymer increases and the dissolution time increases as the molecular weight of PMMA increases.
상기와 같이하여 제조된 본 발명 소정수준의 PMMA 프로폴리머에 30 내지 70 중량%의 액정 모노머 혼합물(E-7:E.Merck 사 제품)을 혼합하여 균일한 혼합용액을 만들고, 이 혼합용액을 탈포하여 투명 도전성 유리판 위에 코팅하고 그 위에 동일한 유리판을 덮은 후 경화시켜 필름을 만든 후 전극에 전원을 연결하면 콘트라스트 및 응답속도가 좋은 광조절제로 사용할 수 있는 것이다.30 to 70% by weight of the liquid crystal monomer mixture (E-7: manufactured by E. Merck) was mixed with the PMMA polymer of the present invention prepared as described above to make a uniform mixed solution, and the mixed solution was defoamed. After coating on a transparent conductive glass plate and covering the same glass plate on it to cure it to make a film and then connect the power to the electrode can be used as a light control agent with good contrast and response speed.
이 같은 본 발명에 따라 종래 투명성이 매우 우수한 PMMA를 아세톤이나 클로로포름과 같은 용매에 직접 녹여 액정모노머와 균일하게 섞은 후 용매를 증발시켜 PDLC를 제작하는 방법에서 필름내에서의 용매의 완전한 증발이 어렵고 필름과 유리판이 균일하게 밀착하는 필름제조도 어려웠던 점을 완전히 개선하게 되었고, 또 종래 PMMA를 열을 가하여 녹인 후 액정 모노머와 혼합한 뒤 냉각하여 경화시키는 방법에서 액정 모노머가 수지의 연화점 이상에서 손상될 염려가 있어 콘트라스트와 구동전압에 절대적으로 불리하고 녹은(melted)수지의 점도도 높기 때문에 액정 모노머와의 균일한 혼합도 어려웠던 결점을 또한 개선할 수 있게 되었다.According to the present invention, it is difficult to completely evaporate the solvent in the film in the method of preparing PDLC by directly dissolving PMMA having excellent transparency directly into a solvent such as acetone or chloroform and uniformly mixing it with a liquid crystal monomer and then evaporating the solvent. In addition, it was completely improved that it was difficult to produce a film in which the glass plate and the glass plate were uniformly adhered to each other.In addition, the liquid crystal monomer may be damaged above the softening point of the resin in the method of melting the PMMA by heating it, mixing it with the liquid crystal monomer, and cooling and curing it. Since it is absolutely disadvantageous in contrast and driving voltage, and the melted resin has a high viscosity, it is also possible to improve the defect that it was difficult to uniformly mix with the liquid crystal monomer.
즉, 본 발명에서는 MMA에 PMMA를 용해시킴으로서 점도조절이 쉽고 코팅조건이 양호한 프리폴리머를 제조할 수 있기 때문에 필름제조가 매우 간단하며 PMMA수지의 우수한 투명성으로 콘트라스트가 우수한 광조절용 셔터의 제작이 가능하고, 아크릴 수지의 특성상 유리판과의 접착력도 우수하기 때문에 필름위에 도전성 유리판을 다시 덮어 경화시킬 경우, 수지와 유리판이 쉽게 접착하여 제조하기가 쉬운 이점을 가지게 된다.That is, in the present invention, by dissolving PMMA in MMA, it is possible to prepare a prepolymer that is easy to control viscosity and has good coating conditions. Thus, film production is very simple and excellent transparency of PMMA resin makes it possible to manufacture a light adjusting shutter having excellent contrast. Since the adhesive strength with the glass plate is also excellent due to the characteristics of the acrylic resin, when the conductive glass plate is cured again on the film, the resin and the glass plate easily have an advantage of being easily bonded and manufactured.
이하에 실시예를 들어 설명한다.An example is given and described below.
[실시예 1]Example 1
콘덴서 장치가 달려있는 3구 플라스크에 MMA 100g과 분자량 10만의 PMMA(Poly Science사) 53.8g (35wt%)을 넣고 여기에 BPO 0.46g(0.3wt%)을 투입하여 6시간 동안 교반시켜 25℃에서 Brookfield 회전점도계로 12,000cps의 점도를 가지는 PMMA 프리폴리머용액을 만든다. 이 용액에 40wt%의 액정 혼합물인 E-7을 섞어 2500rpm에서 3분간 교반하고, 1000rpm에서 1분간 교반하여 우유빛의 균일한 에멀젼 용액을 만든다.Into a three-necked flask equipped with a condenser device, 100 g of MMA and 53.8 g (35 wt%) of PMMA (Poly Science) had a molecular weight of 100,000, and 0.46 g (0.3 wt%) of BPO was added thereto, followed by stirring for 6 hours. A PMMA prepolymer solution with a viscosity of 12,000 cps was made with a Brookfield Rotational Viscometer. 40 wt% of liquid crystal mixture E-7 was mixed in the solution and stirred at 2500 rpm for 3 minutes and stirred at 1000 rpm for 1 minute to form a milky uniform emulsion solution.
이 균질 혼합용액을 25℃에서 100rpm으로 교반시키면서 20분 동안 진공 (0.4torr)을 걸어 용액중의 기포를 완전히 탈포시킨 뒤 ITO 코팅된 투명 도전성 유리판에 부어 RDS-50 제막봉을 이용하여 바코터로 1cm/sec의 속도로 코팅한다.The homogeneous mixed solution was vacuumed (0.4torr) for 20 minutes while stirring at 100rpm at 25 ° C to completely deflate the bubbles in the solution, and poured into an ITO-coated transparent conductive glass plate using a RDS-50 film forming rod. Coating at 1 cm / sec.
코팅된 필름 윗면에 동일한 투명 도전성 유리판을 덮은 후 100℃의 오븐에 넣어 1시간 동안 경화시킨다. 경화된 후의 필름의 두께는 20㎛로서 불투명한 우유빛이지만 양쪽의 ITO 전극에 전원을 가하면 마이크로드롭플렛 내의 액정 모노머들이 전극방향에 수직한 방향으로 정렬되어 입사광이 투명하게 나타나므로 광조절용 셔터 등에 사용할 수 있다.The same transparent conductive glass plate was covered on the top of the coated film, and then placed in an oven at 100 ° C. to cure for 1 hour. The film thickness after curing is opaque and milky, but when the power is applied to both ITO electrodes, the liquid crystal monomers in the microdroplet are aligned in the direction perpendicular to the direction of the electrode and the incident light appears transparent. Can be.
이 때 구동전압으로 40V를 가했을 경우 응답속도는 5-7mili second였고 콘트라스트는 15 : 1이었다.At this time, when 40V was applied as the driving voltage, the response speed was 5-7mili second and the contrast was 15: 1.
[실시예 2]Example 2
실시예1과 같은 반응 기구를 이용하여 MMA 100g과 분자량 10만의 PMMA 33.3g (25wt%)을 넣고 여기에 BPO 0.40g(0.3wt%)을 투입하여 4시간 동안 교반시켜 8500cps의 점도를 가지는 PMMA프리폴리머용액을 만든다. 실시예1과 동일한 비율로 액정 혼합물을 섞은 후 탈포하여, 투명도전성 유리판에 실시예1과 동일조건으로 코팅시킨다.Using the same reaction mechanism as in Example 1, 100 g of MMA and 33.3 g (25 wt%) of PMMA having a molecular weight of 100,000 were added thereto, and 0.40 g (0.3 wt%) of BPO was added thereto, followed by stirring for 4 hours. PMMA prepolymer having a viscosity of 8500 cps. Make a solution. The liquid crystal mixture was mixed and degassed in the same ratio as in Example 1, and then coated on the transparent conductive glass plate under the same conditions as in Example 1.
100℃의 오븐에서 1시간 동안 경화시킨 후 필름의 두께는 16㎛였으며 구동전압으로 40V를 가할 경우 응답속도는 4 내지 5 mili second였고 콘트라스트 18 : 1 이였다.After curing for 1 hour in an oven at 100 ℃ the thickness of the film was 16㎛, when applying a driving voltage of 40V was the response speed was 4 to 5 mili second and contrast 18: 1.
[실시예 3]Example 3
실시예1과 같은 반응 기구를 이용하여 MMA 100g과 분자량 25,000의 PMMA(Poly Science사) 75.2g(43wt%)을 넣고 여기에 BPO 0.52(0.3wt%)을 투입하여 7시간 동안 교반시킨다. 이때 PMMA 프리플리머의 점도는 실시예1과 같은 12,000cps였다.Using the same reaction mechanism as in Example 1, 100 g of MMA and 75.2 g (43 wt%) of PMMA (Poly Science) having a molecular weight of 25,000 were added thereto, and BPO 0.52 (0.3 wt%) was added thereto and stirred for 7 hours. At this time, the viscosity of the PMMA prepolymer was 12,000 cps as in Example 1.
실시예1과 같이 액정 모노머를 혼합한 후 코팅하여 경화한 뒤의 필름의 두께는 20㎛였으며, 투명 도전성 유리판 양쪽 전극에 구동전압으로 40V를 가했을 경우 응답속도는 5-7mili second 였고 콘트라스트는 15 : 1 이었다.After mixing and curing the liquid crystal monomers as in Example 1, the thickness of the film was 20 μm. When 40 V was applied to both electrodes of the transparent conductive glass plate as a driving voltage, the response speed was 5-7 mili second and the contrast was 15: 1 was.
[비교예 1]Comparative Example 1
실시예1과 동일한 반응 기구를 이용하여 분자량 10만인 PMMA 10g을 120g의 클로로포름과 4시간 동안 교반하여 완전히 녹인다. 이 용액에 40wt%의 액정 혼합물인 E-7을 섞어 2,5000rpm에서 3분간 교반하고, 1,000rpm에서 1분간 교반하여 우유빛의 균일한 에멀젼 용액을 만든다. 실시예1과 동일 조건으로 코팅한 뒤 70℃ 오븐에서 3시간 동안 방치하여 필름내의 클로로포름을 증발시킨다.Using the same reaction mechanism as in Example 1, 10 g of PMMA having a molecular weight of 100,000 was completely dissolved by stirring with 120 g of chloroform for 4 hours. 40 wt% of liquid crystal mixture E-7 was mixed in the solution and stirred at 2,5000 rpm for 3 minutes and stirred at 1,000 rpm for 1 minute to form a milky uniform emulsion solution. After coating under the same conditions as in Example 1, the mixture was left for 3 hours in an oven at 70 ° C. to evaporate chloroform in the film.
필름위에 투명 도전성 유리판을 투명 도전성 유리판을 밀착시킨 뒤 천천히 냉각시켜 PMMA를 경화시킨다.The transparent conductive glass plate is brought into close contact with the transparent conductive glass plate on the film, and then slowly cooled to cure the PMMA.
이때 필름의 두께는 16㎛로서, 구동전압으로 50V를 가했을 경우 응답속도는 8 mili second 였고 콘드라스트는 10 : 1이었다.At this time, the thickness of the film was 16㎛, when 50V was applied as the driving voltage, the response speed was 8 mili second and the contrast was 10: 1.
[비교예 2]Comparative Example 2
분자량 10만인 PMMA 50g을 180℃까지 가열하여 완전히 용융시킨 후 120℃까지 서냉시킨다. 여기에 액정 모노머인 E-7을 40wt% 섞어 후 1,5000rpm에서 5분간 혼합한다. 실시예1과 동일한 방법으로 코팅한 뒤 상온에서 천천히 냉각시켜 경화시킨다. 이때 필름의 두께는 21㎛였으며 구동전압으로 40V를 가했을 경우 응답속도는 7 내지 9 mili second 였고 콘드라스트는 9 : 1이었다.50 g of PMMA having a molecular weight of 100,000 was heated to 180 ° C to completely melt, and then slowly cooled to 120 ° C. 40 wt% of E-7 which is a liquid crystal monomer is mixed there, and then mixed at 1,5000 rpm for 5 minutes. After coating in the same manner as in Example 1, it is slowly cooled at room temperature and cured. At this time, the thickness of the film was 21㎛, the response speed was 7 to 9 mili second when the driving voltage was applied to 40V and the contrast was 9: 1 :.
[비교예 3]Comparative Example 3
분자량 22,000의 PVA(Poly Vinyl Alcohol)를 증류수에 녹여 20wt%의 PVA용액을 만든다. 이 용액에 40wt%의 액정 혼합물인 E-7을 섞어 2,5000rpm에서 3분간 교반한 뒤 1,000rpm에서 1분간 더 교반하여 균일한 혼합 용액을 만든다.Polyvinyl alcohol (PVA) having a molecular weight of 22,000 is dissolved in distilled water to make a 20 wt% PVA solution. 40 wt% of liquid crystal mixture E-7 was mixed in the solution and stirred at 2,5000 rpm for 3 minutes, followed by further stirring at 1,000 rpm for 1 minute to make a uniform mixed solution.
실시예1과 동일한 방법으로 코팅하여 70℃의 오븐에서 2시간 동안 건조시켜 물을 완전히 증발시킨다. 물이 제거된 필름위에 투명 도전성 유리판을 덮은 후 100℃ 오븐에서 1시간 동안 방치하여 필름의 윗면과 유리판을 밀착시킨다.Coating in the same manner as in Example 1 and dried in an oven at 70 ℃ for 2 hours to completely evaporate the water. The transparent conductive glass plate was covered on the film from which water was removed, and left in an oven at 100 ° C. for 1 hour to closely adhere the upper surface of the film to the glass plate.
유리판의 양쪽 전극에 전원을 걸어 광조절재로 사용하였을때 40V의 구동전압에서 응답속도는 5 내지 6 mili second 였으며 콘드라스트는 8 : 1이었다.When the power was applied to both electrodes of the glass plate and used as the light regulating material, the response speed was 5 to 6 mili second at a driving voltage of 40 V, and the contrast was 8: 1.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019910021431A KR0173312B1 (en) | 1991-11-27 | 1991-11-27 | Manufacturing method of liquid crystal polymer composite for light control |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019910021431A KR0173312B1 (en) | 1991-11-27 | 1991-11-27 | Manufacturing method of liquid crystal polymer composite for light control |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR0173312B1 true KR0173312B1 (en) | 1999-03-20 |
Family
ID=19323650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019910021431A Expired - Lifetime KR0173312B1 (en) | 1991-11-27 | 1991-11-27 | Manufacturing method of liquid crystal polymer composite for light control |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR0173312B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100516029B1 (en) * | 2002-06-07 | 2005-09-26 | (주)싸이텍연구소 | UV curable light-modulating film for light control structure and preparation thereof |
| KR101347940B1 (en) * | 2012-08-29 | 2014-01-08 | 동국대학교 산학협력단 | Method for polymer dispersed liquid crystal by chiller |
| CN112130361A (en) * | 2019-06-25 | 2020-12-25 | 深圳市诚德利科技有限公司 | Ultrathin light adjusting film for vehicle and preparation method |
-
1991
- 1991-11-27 KR KR1019910021431A patent/KR0173312B1/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100516029B1 (en) * | 2002-06-07 | 2005-09-26 | (주)싸이텍연구소 | UV curable light-modulating film for light control structure and preparation thereof |
| KR101347940B1 (en) * | 2012-08-29 | 2014-01-08 | 동국대학교 산학협력단 | Method for polymer dispersed liquid crystal by chiller |
| US9028290B2 (en) | 2012-08-29 | 2015-05-12 | Dongguk University Industry-Academic Cooperation Foundation | Method of producing polymer dispersed liquid crystal device using cooling plate |
| CN112130361A (en) * | 2019-06-25 | 2020-12-25 | 深圳市诚德利科技有限公司 | Ultrathin light adjusting film for vehicle and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| West | Phase separation of liquid crystals in polymers | |
| US4673255A (en) | Method of controlling microdroplet growth in polymeric dispersed liquid crystal | |
| US4994204A (en) | Light modulating materials comprising a liquid crystal phase dispersed in a birefringent polymeric phase | |
| US5240636A (en) | Light modulating materials comprising a liquid crystal microdroplets dispersed in a birefringent polymeric matri method of making light modulating materials | |
| US5301046A (en) | Electro-optical device having a layer comprising an oblate liquid crystal dispersed in a resin and method for forming the same | |
| US5359443A (en) | Process for producing heat-resistant optical element by heating liquid crystal polymer at polymerization temperature during or after orientation treatment | |
| JP2810742B2 (en) | Light modulation material containing liquid crystal microdroplets dispersed in birefringent polymer matrix | |
| WO1994006050A1 (en) | Directly formed polymer dispersed liquid crystal light shutter displays | |
| JPH04220620A (en) | Manufacture of liquid crystal electro-optical device | |
| KR0173312B1 (en) | Manufacturing method of liquid crystal polymer composite for light control | |
| EP0724006A1 (en) | Liquid crystalline epoxy resins in polymer dispersed liquid crystal composites | |
| JP2002214653A (en) | Light controllable material, light controllable film and method of manufacturing light controllable film | |
| JP3137275B2 (en) | Liquid crystal display device and method of manufacturing the same | |
| JPH06222343A (en) | Liquid crystal display element and production of this element | |
| JP2766218B2 (en) | Manufacturing method of liquid crystal optical element | |
| JP2574027B2 (en) | Liquid crystal light control material manufacturing method | |
| EP0787782A2 (en) | Process and materials for highly transparent polymer dispersed liquid crystals | |
| JPS63287820A (en) | Optical modulation substance and application, production thereof | |
| KR101892568B1 (en) | Polymer dispersed liquid crystal lenz | |
| JPH04240613A (en) | liquid crystal electro-optical element | |
| JPH01252689A (en) | Liquid crystal device | |
| CN117801337A (en) | PDLC spacer material with high transmittance and preparation method thereof | |
| JPH01299022A (en) | Light adjusting material sheet, light adjusting material and its manufacture | |
| JPH0228284A (en) | Liquid crystal device | |
| JPH0540254A (en) | Liquid crystal display element and production thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PA0109 | Patent application |
Patent event code: PA01091R01D Comment text: Patent Application Patent event date: 19911127 |
|
| PG1501 | Laying open of application | ||
| A201 | Request for examination | ||
| PA0201 | Request for examination |
Patent event code: PA02012R01D Patent event date: 19960725 Comment text: Request for Examination of Application Patent event code: PA02011R01I Patent event date: 19911127 Comment text: Patent Application |
|
| E701 | Decision to grant or registration of patent right | ||
| PE0701 | Decision of registration |
Patent event code: PE07011S01D Comment text: Decision to Grant Registration Patent event date: 19980930 |
|
| GRNT | Written decision to grant | ||
| PR0701 | Registration of establishment |
Comment text: Registration of Establishment Patent event date: 19981029 Patent event code: PR07011E01D |
|
| PR1002 | Payment of registration fee |
Payment date: 19981029 End annual number: 3 Start annual number: 1 |
|
| PG1601 | Publication of registration | ||
| PR1001 | Payment of annual fee |
Payment date: 20010912 Start annual number: 4 End annual number: 4 |
|
| PR1001 | Payment of annual fee |
Payment date: 20020926 Start annual number: 5 End annual number: 5 |
|
| PR1001 | Payment of annual fee |
Payment date: 20030929 Start annual number: 6 End annual number: 6 |
|
| PR1001 | Payment of annual fee |
Payment date: 20041001 Start annual number: 7 End annual number: 7 |
|
| PR1001 | Payment of annual fee |
Payment date: 20050930 Start annual number: 8 End annual number: 8 |
|
| PR1001 | Payment of annual fee |
Payment date: 20060927 Start annual number: 9 End annual number: 9 |
|
| PR1001 | Payment of annual fee |
Payment date: 20070928 Start annual number: 10 End annual number: 10 |
|
| PR1001 | Payment of annual fee |
Payment date: 20080926 Start annual number: 11 End annual number: 11 |
|
| PR1001 | Payment of annual fee |
Payment date: 20090928 Start annual number: 12 End annual number: 12 |
|
| PR1001 | Payment of annual fee |
Payment date: 20100927 Start annual number: 13 End annual number: 13 |
|
| FPAY | Annual fee payment |
Payment date: 20110926 Year of fee payment: 14 |
|
| PR1001 | Payment of annual fee |
Payment date: 20110926 Start annual number: 14 End annual number: 14 |
|
| EXPY | Expiration of term | ||
| PC1801 | Expiration of term |
Termination date: 20121009 Termination category: Expiration of duration |