KR100429470B1 - Preparation of polymer-liquid crystal microcapsules using swelling/phase separation (SPS) method - Google Patents
Preparation of polymer-liquid crystal microcapsules using swelling/phase separation (SPS) method Download PDFInfo
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- KR100429470B1 KR100429470B1 KR10-2000-0064479A KR20000064479A KR100429470B1 KR 100429470 B1 KR100429470 B1 KR 100429470B1 KR 20000064479 A KR20000064479 A KR 20000064479A KR 100429470 B1 KR100429470 B1 KR 100429470B1
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- polymer
- liquid crystal
- swelling
- particles
- phase separation
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000008961 swelling Effects 0.000 title claims abstract description 21
- 238000005191 phase separation Methods 0.000 title claims abstract description 19
- 239000003094 microcapsule Substances 0.000 title claims abstract description 17
- 239000005264 High molar mass liquid crystal Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title description 3
- 239000002245 particle Substances 0.000 claims abstract description 44
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000000839 emulsion Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000004094 surface-active agent Substances 0.000 claims abstract description 4
- 230000000379 polymerizing effect Effects 0.000 claims abstract 2
- 239000006185 dispersion Substances 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011246 composite particle Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000012674 dispersion polymerization Methods 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 2
- 239000004990 Smectic liquid crystal Substances 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims 1
- 229940048053 acrylate Drugs 0.000 claims 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims 1
- 230000003098 cholesteric effect Effects 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 239000000975 dye Substances 0.000 claims 1
- 229920001519 homopolymer Polymers 0.000 claims 1
- 239000002563 ionic surfactant Substances 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 150000003384 small molecules Chemical class 0.000 claims 1
- 229940047670 sodium acrylate Drugs 0.000 claims 1
- 239000002775 capsule Substances 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 239000003995 emulsifying agent Substances 0.000 abstract description 5
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 abstract 1
- 238000004945 emulsification Methods 0.000 abstract 1
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 15
- 239000004926 polymethyl methacrylate Substances 0.000 description 15
- 239000012071 phase Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- -1 tetramethylene ammonium bromide Chemical compound 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
Abstract
본 발명은 팽윤/상분리법을 이용하여 미크론크기의 구형 고분자-액정 캡슐을 제조하는 신기술에 관한 것으로, 좀 더 상세하게는 0.1∼0.3%의 계면활성제가 녹아있는 수용액에 고분자 입자를 분산시키는 1단계, 액정을 포함하는 반응성 단량체를 0.1∼0.3%의 유화제를 함유하는 수용액에서 미세하게 유화시키고, 25∼30℃의 온도에서 서서히 교반시키며 팽윤시키는 2단계, 팽윤이 완전히 종결된 후, 고분자/액정/반응성 단량체 액적에서 단량체를 중합시켜 상분리를 유도하는 3단계로 이루어져 있다. 이때, 사용되는 고분자 입자는 선형 혹은 가교 구조에 상관없이 단량체와 친화성이 있는 모든 고분자 종을 포함한다. 본 방법에서는 액정을 포함하는 단량체의 에멀젼 유화, 팽윤 과정 및 안정한 중합과정이 마지막의 마이크로캡슐의 형태를 결정하는 중요한 인자가 된다.The present invention relates to a new technology for producing micron-sized spherical polymer-liquid crystal capsules using swelling / phase separation, and more specifically, one step of dispersing polymer particles in an aqueous solution in which 0.1 to 0.3% of a surfactant is dissolved. , 2 steps of finely emulsifying the reactive monomer including the liquid crystal in an aqueous solution containing 0.1 to 0.3% of an emulsifier, slowly swelling and swelling at a temperature of 25 to 30 ° C., after the swelling is completely finished, the polymer / liquid crystal / It consists of three steps that induce phase separation by polymerizing monomers in reactive monomer droplets. In this case, the polymer particles used include all polymer species having affinity with monomers regardless of linear or crosslinked structure. In this method, the emulsion emulsification, swelling process and stable polymerization process of the monomer including the liquid crystal are important factors for determining the final microcapsule form.
본 발명에서 제안하는 팽윤/상분리법은 미크론크기의 고분자 캡슐을 제조할 수 있는 신기술로서 입자내의 액정의 크기를 팽윤도에 따라 임의로 조절할 수 있을 뿐만 아니라, 다양한 입자를 통한 팽윤의 조절로 단분산의 액정도메인을 형성할 수 있다는 장점을 가지고 있어, 고분자 분산형 액정에 매우 유용하게 이용될 수 있는 기술이라고 기대된다.The swelling / phase separation method proposed by the present invention is a new technology for preparing a micron-sized polymer capsule, which can arbitrarily control the size of the liquid crystal in the particles according to the degree of swelling, and also controls the swelling through various particles. It has the advantage of being able to form a domain, and is expected to be a very useful technique for polymer dispersed liquid crystals.
Description
본 발명은 미크론 크기의 구형 고분자 캡슐을 제조할 수 있는 신기술에 대한 것으로, 좀 더 자세하게는 본 발명자가 제안하는 방법에 의해 고분자-액정 마이크로캡슐을 보다 효과적이고 간단하게 제조하는 방법에 관한 것이다.The present invention relates to a new technology capable of producing micron-sized spherical polymer capsules, and more particularly, to a method for producing polymer-liquid crystal microcapsules more effectively and simply by the method proposed by the present inventors.
일반적으로 고분자-액정 복합체는 폴리비닐알코올등의 수용성 고분자에 액정을 분산시키는 캡슐화 방법, 중합 및 열에 의한 상분리를 이용하는 상분리 방법에 의해 제조된다. 특히, 캡슐화 방법은 제조법이 간단해 널리 이용되고 상업화되기도 했지만, 물을 제거해야하고, 액정의 크기의 분포가 매우 넓어 구동전압의 불안정등의 단점을 가지고 있다. 이에 비해 상분리법은 상분리조건에 따라 액정크기 및 크기분포를 조절할 수 있으나, 상분리법의 어려움등으로 대형의 균일한 복합체의 제조는 어려운 형편이다. 본 연구에서는 위에서 언급한 기존의 방법의 단점을 향상시킬 수 있는 팽윤/상분리법을 제안한다. 제안된 방법은 고분자-액정의 마이크로캡슐을 제조하여 대형의 고분자 분산형 액정의 제조를 가능하게 하였고, 단분산 미크론 크기의 고분자 입자를 사용하여 액정을 캡슐화함으로써 액정의 크기를 단분산화할 수 있는 방법이다.Generally, the polymer-liquid crystal complex is prepared by an encapsulation method of dispersing liquid crystal in a water-soluble polymer such as polyvinyl alcohol, a phase separation method using polymerization and phase separation by heat. In particular, although the encapsulation method is widely used and commercialized due to its simple manufacturing method, water has to be removed, and the size of the liquid crystal is very wide, which has disadvantages such as instability of the driving voltage. On the other hand, the phase separation method can control the liquid crystal size and size distribution according to the phase separation conditions, but it is difficult to prepare a large uniform complex due to the difficulty of the phase separation method. In this study, we propose a swelling / phase separation method that can improve the shortcomings of the conventional methods mentioned above. The proposed method enables the preparation of large-capacity dispersed liquid crystals by preparing polymer-liquid crystal microcapsules and the method of monodispersing the size of liquid crystals by encapsulating liquid crystals using monodisperse micron-sized polymer particles. to be.
본 발명은 공정이 보다 간단하고 미크론 단위의 단분산의 액정을 함유한 미크론 크기의 구형 고분자 캡슐을 제조하는 신기술을 제공하는데 있다. 상기 목적을 달성하기 위하여 본 발명은 도 1에서 모식화되어 있는 팽윤/상분리법을 제안한다. 이 팽윤/상분리법은 다음과 같은 점에서 그 우수성을 지닌다. 첫째, 사용 가능한 고분자의 제한이 적다. 단지 분산중합, 유화중합 및 현탁중합으로 입자를 제조할 수 있기만 하면 된다. 둘째, 중합 속도를 자유롭게 조절 가능하기 때문에 액정의 상분리를 기존의 방법에 비해 간단하게 제어 할 수 있다. 또, 액정의 도입량을 초기 고분자 입자에 대해 1-2배정도의 범위에서 쉽게 조절 가능하므로, 액정 입자의 미크론 단위의 크기에서 쉽게 조절 가능하다. 본 계에서는 고분자 입자와 에멀젼 사이의 입자 크기 차이가 액정과 단량체의 팽윤을 결정하는 중요한 인자가 된다. 따라서, 이 과정에서 액정/단량체 에멀젼을 가능한 한 작게 제조하는 것이 바람직하다. 넷째, 이상의 결과로부터 본 발명에서 제안하는 팽윤/상분리법은 적용하고자 하는 분야의 요구조건에 따라, 다양한 고분자 캡슐의 제조가 가능하다. 특히, 공정이 매우 단순하고 쉽기 때문에, 최종 고분자 캡슐의 제조를 위한 시간절약과 생산성의 면에서 매우 우수하다고 판단된다.The present invention seeks to provide a novel technique for producing micron-sized spherical polymer capsules with simpler processes and containing monodisperse liquid crystals in microns. In order to achieve the above object, the present invention proposes a swelling / phase separation method, which is illustrated in FIG. 1. This swelling / phase separation method is superior in the following points. First, there are few restrictions on the polymer that can be used. It is only necessary that the particles be prepared by dispersion polymerization, emulsion polymerization and suspension polymerization. Second, since the polymerization rate can be freely adjusted, phase separation of the liquid crystal can be easily controlled as compared to the conventional method. In addition, since the amount of liquid crystal introduced can be easily adjusted in a range of about 1-2 times with respect to the initial polymer particles, it can be easily adjusted in the size of the micron unit of the liquid crystal particles. In this system, the particle size difference between the polymer particles and the emulsion is an important factor in determining the swelling of the liquid crystal and the monomer. Therefore, it is desirable to make the liquid crystal / monomer emulsion as small as possible in this process. Fourth, the swelling / phase separation method proposed in the present invention from the above results, it is possible to manufacture a variety of polymer capsules according to the requirements of the field to be applied. In particular, since the process is very simple and easy, it is judged to be very excellent in terms of time saving and productivity for the production of the final polymer capsule.
도 1은 본 발명에서 제안하는 팽윤/상분리법에 대한 모식도1 is a schematic diagram of the swelling / phase separation method proposed in the present invention
도 2는 PMMA-액정 마이크로캡슐에 대한 현미경사진2 is a micrograph for PMMA-liquid crystal microcapsules
이하 본 발명을 좀 더 구체적으로 살펴보면 다음과 같다.Looking at the present invention in more detail as follows.
먼저, 고분자 입자를 분산안정제가 0.1∼0.3% 녹아있는 수용액에서 서서히 교반시키면서 완전히 재분산시킨다. 본 발명에 적용되는 고분자 입자는 사용하고자 하는 액정의 정상 굴절률과 비슷한 굴절률을 가지는 모든 고분자 구형체를 포함한다. 구체적으로는 라디칼 개시에 의하여 중합된 아크릴 혹은 비닐 고분자 입자, 용매 침적에 의하여 제조된 올레핀 고분자 입자 및 엔지니어링 고분자 입자, 금속/고분자 복합입자 혹은 무기/고분자 복합입자 등을 들 수 있는데, 전체 함량에 대해 10% 정도가 적절하다. 한편, 본 발명에서 사용되는 분산 안정제로는 수용성 고분자 또는 계면활성제로, 구체적으로는 젤라틴, 스타치, 소듐 폴리아크릴레이트, 히드록시에틸셀룰로오즈, 카복시메틸셀룰로오즈, 폴리비닐피롤리돈, 폴리비닐 알콜등의 고분자와 소듐 도데실 술페이트 등의 음이온성 계면활성제, 테트라메칠렌 암모늄 브로마이드와 같은 양이온성 계면활성제 또는 트윈, 스판계통의 비이온성 계면활성제를 포함한다.First, the polymer particles are completely redispersed with gentle stirring in an aqueous solution in which the dispersion stabilizer is dissolved 0.1 to 0.3%. The polymer particles applied to the present invention include all polymer spheres having a refractive index similar to the normal refractive index of the liquid crystal to be used. Specific examples include acrylic or vinyl polymer particles polymerized by radical initiation, olefin polymer particles and engineering polymer particles produced by solvent deposition, metal / polymer composite particles or inorganic / polymer composite particles. 10% is appropriate. On the other hand, the dispersion stabilizer used in the present invention is a water-soluble polymer or surfactant, specifically gelatin, starch, sodium polyacrylate, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, etc. And anionic surfactants such as sodium dodecyl sulphate, cationic surfactants such as tetramethylene ammonium bromide, or twin and span type nonionic surfactants.
본 발명에서 사용되는 단량체는 고분자 입자에 대해서 상용성을 지니고 액정의 이방성을 파괴할 수 있을 정도의 용해력을 가지고 있어야 한다. 부수적으로, 물에 대하여 소량의 용해도를 가지고 있어야 수상을 통해 입자로 확산이 가능하므로 조금의 친수성을 가지는 소수성의 단량체가 필요하다. 최종의 액정의 마이크로캡슐을 얻기 위해서는 팽윤된 단량체를 중합하여 액정의 상분리를 유도해야 하는데, 중합을 위해서 열중합이나 자외선 광중합이 가능한 아크릴레이트계나 비닐계의 단량체가 필요하다. 위의 조건에 알맞는 단량체로는 메칠메타아크릴레이트, 부칠메타아크릴레이트, 아크릴로니트릴, 스틸렌, 글리시딜메타크릴레이트등이다.The monomer used in the present invention should be compatible with the polymer particles and have a solubility that can destroy the anisotropy of the liquid crystal. Incidentally, it is necessary to have a small amount of solubility in water so that it can be diffused into the particles through the water phase, so that a hydrophilic monomer having some hydrophilicity is required. In order to obtain the final microcapsules of the liquid crystal, it is necessary to polymerize the swollen monomer to induce phase separation of the liquid crystal. An acrylate or vinyl monomer capable of thermal polymerization or ultraviolet photopolymerization is required for the polymerization. Suitable monomers for the above conditions are methyl methacrylate, butyl methacrylate, acrylonitrile, styrene, glycidyl methacrylate and the like.
액정을 포함하는 단량체의 수상 내에서 효과적인 에멀젼 형성을 돕기 위하여 전체 수상에 대해 0.1∼1%의 유화제를 첨가한다. 유화제는 이온성을 지니는 모든 음이성 유화제 및 양이온성 유화제를 포함하고, 친수성 유기 화합물에 의하여 제조된 모든 비이온성 유화제를 포함한다.0.1 to 1% of an emulsifier is added to the entire aqueous phase to aid in the formation of an emulsion in the aqueous phase of the monomer comprising the liquid crystal. Emulsifiers include all negative and cationic emulsifiers with ionicity, and all nonionic emulsifiers prepared by hydrophilic organic compounds.
이하 실시예 및 비교예를 통하여 본 발명의 방법을 좀 더 구체적으로 살펴보기로 한다.Hereinafter, the method of the present invention will be described in more detail with reference to Examples and Comparative Examples.
실시예 1Example 1
3∼4㎛의 고분자 입자는 분산중합에 의하여 제조된다. 반응기에 메틸메타크릴레이트 단량체를 전체 중량 대비 10중량%, 지용성 개시제인 아조비스이소부티로니트릴를 단량체에 대해 1중량%, 폴리비닐피롤리돈 (분자량 40,000g/mol) 분산 안정화제를 전체 중량 대비 4중량%를 메탄올에 완전히 용해시킨다. 이어서 질소 분위기에서 55℃의 온도에서 24시간 동안 40 rpm의 교반속도로 중합을 실시한다. 제조된 폴리메틸메타크릴레이트(PMMA) 입자는 원심분리와 물로 세척을 수회 실시하여 미반응물과 분산 안정제를 제거한 후, 상온에서 건조시켜 분말 형태의 고분자 입자를 얻었다.Polymer particles of 3 to 4 µm are prepared by dispersion polymerization. 10% by weight of the methyl methacrylate monomer in the reactor, 1% by weight of azobisisobutyronitrile, a fat-soluble initiator, to the monomer, polyvinylpyrrolidone (molecular weight 40,000 g / mol) dispersion stabilizer to the total weight 4% by weight is completely dissolved in methanol. Subsequently, the polymerization is carried out at a stirring speed of 40 rpm for 24 hours at a temperature of 55 ° C. in a nitrogen atmosphere. The prepared polymethyl methacrylate (PMMA) particles were centrifuged and washed several times with water to remove unreacted materials and dispersion stabilizers, and then dried at room temperature to obtain polymer particles in powder form.
제조된 PMMA 고분자 입자 0.2-0.5g을 0.25중량%의 소듐 도데실 술페이트수용액 40g에 재분산시킨다. 이어서, 메칠메타크릴레이트 0.4g과 스틸렌 0.3g에 액정E7(머크사) 0.2-0.4g이 녹아있는 용액과 단량체에 대해 0.1중량%의 벤조일퍼옥사이드를 균일하게 혼합한 후, 0.25% 소듐 도데실 술페이트 수용액 15g에 첨가한 후 혼합믹서를 이용하여 15,000 rpm에서 5분간 유화시킨다. 얻어진 에멀젼은 약 수십-수백nm의 액적크기를 지닌다. 유화된 액정/단량체 에멀젼을 PMMA 분산액에 첨가한 후, 상온에서 200 rpm의 교반속도로 3시간 동안 완전히 팽윤시킨다.0.2-0.5 g of the prepared PMMA polymer particles are redispersed in 40 g of 0.25% sodium dodecyl sulfate aqueous solution. Subsequently, after mixing the solution of 0.2-0.4 g of liquid crystal E7 (Merck Co., Ltd.) in 0.4 g of methyl methacrylate and 0.3 g of styrene, 0.1% by weight of benzoyl peroxide was uniformly mixed with 0.25% sodium dodecyl. The solution was added to 15 g of an aqueous solution of sulfate and then emulsified at 15,000 rpm for 5 minutes using a mixing mixer. The resulting emulsion has a droplet size of about tens to hundreds of nm. The emulsified liquid crystal / monomer emulsion is added to the PMMA dispersion, followed by complete swelling for 3 hours at a stirring speed of 200 rpm at room temperature.
팽윤된 PMMA/액정/단량체 액적 내에 존재하는 단량체는 55℃에서 7시간 동안 중합하고, 이어서 분산 안정제와 기타 첨가제를 반복적인 원심분리를 통하여 완전히 제거함으로서 액정이 단일 입자로 상분리된 PMMA 마이크로캡슐을 제조한다.Monomers present in the swollen PMMA / liquid crystal / monomer droplets were polymerized at 55 ° C. for 7 hours, followed by complete removal of the dispersion stabilizer and other additives through repeated centrifugation to prepare PMMA microcapsules in which the liquid crystal phase separated into single particles. do.
실시예 2Example 2
상기 실시예 1과 동일하게 PMMA 마이크로캡슐을 제조하되, 본 발명자가 대한민국 특허 제 0205280 호와 출원 제 10-2000-14905 호에 소개한 아킬렌 옥시드 디아크릴레이트를 메칠메타크릴에이트 단량체 대비 2-3중량% 도입하여 가교 PMMA 입자를 이용한다.Preparation of the PMMA microcapsules in the same manner as in Example 1, but the present invention was introduced in the Republic of Korea Patent No. 0205280 and Patent Application No. 10-2000-14905 2 to the methacrylate oxide diacrylate compared to the methyl methacrylate monomer 3% by weight of crosslinked PMMA particles are used.
실시예 3Example 3
상기 실시예 1과 동일하게 PMMA 마이크로캡슐을 제조하되, 실시예 2에서 제조된 가교 PMMA 입자에 액정을 팽윤시키고, 중합을 통해 상분리를 유도한다.Prepare PMMA microcapsules in the same manner as in Example 1, but swell the liquid crystal to the cross-linked PMMA particles prepared in Example 2, and induces phase separation through polymerization.
비교예 1Comparative Example 1
상기 실시예 1과 2에서 제조되는 PMMA 입자의 입자크기와 분산도는 광학현미경 (Optical Microcsope)과 주사전자현미경 (Scanning Electron Microscope) 사진 결과를 이용하여 측정한다. 시편은 분말 형태의 입자를 유리 위에 단층으로 도포시키고 금으로 코팅하여 제조한다. 약 200개 이상 입자를 측정하고 수평균입경과 중량평균입경을 각각 얻는다. 분산지수는 중량평균입경에 대한 수평균입경의 비율로부터 얻는다. 그 결과는 표 1에 나타내었다.Particle size and dispersion of the PMMA particles prepared in Examples 1 and 2 were measured using optical microcsope and scanning electron micrographs. Specimens are prepared by coating particles in powder form in a single layer on glass and coating with gold. About 200 or more particles are measured and a number average particle diameter and a weight average particle diameter are obtained, respectively. The dispersion index is obtained from the ratio of the number average particle diameter to the weight average particle diameter. The results are shown in Table 1.
얻어진 PMMA 입자는 가교 유무에 관계없이 단분산이었다. 이와 같은 결과는 기존 본 발명자가 대한민국 특허 출원 제 10-2000-14905호 소개한 내용과 동일하다The obtained PMMA particles were monodisperse with or without crosslinking. These results are the same as the contents introduced by the present inventors Korean Patent Application No. 10-2000-14905
비교예 2Comparative Example 2
실시예 1과 3에서 제시하는 액정을 포함한 PMMA 입자는 광학현미경을 이용하여 팽윤되는 과정을 관찰하였다. 에멀젼 도입 후, 수시간내에 모든 에멀젼이 연속상에서 사라지고 육안으로는 관찰이 어려웠다.PMMA particles including the liquid crystals shown in Examples 1 and 3 were observed to swell using an optical microscope. Within a few hours after the introduction of the emulsion, all emulsions disappeared in a continuous phase and were difficult to visually observe.
중합이 다 진행된 후 PMMA-액정 마이크로캡슐의 현미경 사진을 도 2에 나타내었다. 액정이 선형 PMMA 입자 내에 존재함을 편광현미경으로 확인할 수 있었다. 그러나, 시간이 흐름에 따라 마이크로캡슐의 외부로 액정이 빠져나오는 것을 볼 수 있다. 이러한 문제점은 가교 PMMA를 사용할 경우 현저하게 개선되었다. 이는 가교망이 불안정한 액정상의 상안정성을 크게 향상시키기 때문인 것으로 판단된다.After the polymerization was completed, the micrograph of the PMMA-liquid crystal microcapsules is shown in FIG. 2. It was confirmed by the polarizing microscope that the liquid crystal is present in the linear PMMA particles. However, as time passes, it can be seen that the liquid crystal comes out of the microcapsules. This problem is markedly improved when using crosslinked PMMA. This is because the crosslinking network greatly improves the phase stability of the unstable liquid crystal phase.
이상에서 상술한 바와 같이, 본 발명에서 제안하는 팽윤/상분리법은 기존 고분자 마이크로캡슐의 제조 방법과는 상당한 차별성을 지니는 신기술로서 다양한 액정을 함유하는 고분자캡슐을 임의로 제조할 수 있으므로, 현재 다양한 액정 디스플레이산업에 광범위하게 응용할 수 있을 것으로 기대된다.As described above, the swelling / phase separation method proposed by the present invention is a new technology having considerable differentiation from the existing method for preparing polymer microcapsules, and thus it is possible to arbitrarily prepare polymer capsules containing various liquid crystals. It is expected to be widely applicable to the industry.
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| KR880002539A (en) * | 1987-07-20 | 1988-05-09 | 우시구보 도모아끼 | Swinging plate refrigerant compressor |
| KR970002345A (en) * | 1995-06-23 | 1997-01-24 | 양승택 | Measurement of Radiation Emissions in Giga-Hertz Transverse Electromagnetic (GTEM) Cells |
| JPH1081882A (en) * | 1996-09-05 | 1998-03-31 | Toshiba Corp | Liquid crystal microcapsule and liquid crystal display element produced therefrom |
| KR19990029886A (en) * | 1997-09-17 | 1999-04-26 | 니시무로 타이죠 | Liquid Crystal Microcapsules and Liquid Crystal Display Devices |
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| KR880002539A (en) * | 1987-07-20 | 1988-05-09 | 우시구보 도모아끼 | Swinging plate refrigerant compressor |
| KR970002345A (en) * | 1995-06-23 | 1997-01-24 | 양승택 | Measurement of Radiation Emissions in Giga-Hertz Transverse Electromagnetic (GTEM) Cells |
| JPH1081882A (en) * | 1996-09-05 | 1998-03-31 | Toshiba Corp | Liquid crystal microcapsule and liquid crystal display element produced therefrom |
| KR19990029886A (en) * | 1997-09-17 | 1999-04-26 | 니시무로 타이죠 | Liquid Crystal Microcapsules and Liquid Crystal Display Devices |
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