JPH02171720A - Liquid crystal dispersion type resin film for optical modulating material - Google Patents
Liquid crystal dispersion type resin film for optical modulating materialInfo
- Publication number
- JPH02171720A JPH02171720A JP32627388A JP32627388A JPH02171720A JP H02171720 A JPH02171720 A JP H02171720A JP 32627388 A JP32627388 A JP 32627388A JP 32627388 A JP32627388 A JP 32627388A JP H02171720 A JPH02171720 A JP H02171720A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- resin film
- resin
- epoxy
- compound
- 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.)
- Pending
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 87
- 239000011347 resin Substances 0.000 title claims abstract description 87
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 19
- 239000006185 dispersion Substances 0.000 title abstract description 6
- 230000003287 optical effect Effects 0.000 title abstract description 4
- 239000004593 Epoxy Substances 0.000 claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000004990 Smectic liquid crystal Substances 0.000 claims abstract description 5
- 230000003098 cholesteric effect Effects 0.000 claims abstract description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 18
- -1 thiol compound Chemical class 0.000 claims description 11
- 239000012948 isocyanate Substances 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 3
- 230000001747 exhibiting effect Effects 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 150000001412 amines Chemical class 0.000 abstract description 16
- 239000007788 liquid Substances 0.000 abstract description 14
- 238000004132 cross linking Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000004848 polyfunctional curative Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 27
- 239000003822 epoxy resin Substances 0.000 description 10
- 229920000768 polyamine Polymers 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000000576 coating method Methods 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical class C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- NFVPEIKDMMISQO-UHFFFAOYSA-N 4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C=C1 NFVPEIKDMMISQO-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 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 1
- 239000001273 butane Substances 0.000 description 1
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical class OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は樹脂マトリクス中に液晶の小滴を均一に分散せ
しめ、かつ電気、磁気、熱等に制御された方法によって
光変調を行う光変調材用液晶分散型樹脂膜に関する。よ
り詳細に述べれば電気、磁気、熱等制御された方法によ
って光線の透過率を変化させることを目的としたブライ
ンド、デイスプレィなど、あるいは特定の光のみ偏光さ
せることを目的とした光シヤツター等を作製するような
場合に好適な光変調材用液晶分散型樹脂膜に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention is an optical modulation method in which droplets of liquid crystal are uniformly dispersed in a resin matrix, and the light is modulated by an electrically, magnetically, or thermally controlled method. The present invention relates to a liquid crystal dispersed resin film for materials. More specifically, we create blinds, displays, etc. that aim to change the transmittance of light rays using controlled methods such as electricity, magnetism, heat, etc., or optical shutters that aim to polarize only specific light. The present invention relates to a liquid crystal dispersion type resin film for a light modulating material suitable for such cases.
液晶分散型樹脂膜の詳細な原理は例えば特許出願公表昭
６１−５０２１２８、あるいは同昭６３−５０１５１２
などに記載されている。また該液晶分散型樹脂膜の製造
方法は例えば公開特許公頼昭６３−１３７２１１に記載
されている。以下液晶分散型樹脂膜の他の液晶素子に対
して有利な点、及び液晶分散型樹脂膜の現状の問題点に
ついて述べる。The detailed principle of the liquid crystal dispersed resin film can be found in, for example, patent application publication No. 61-502128 or No. 63-501512.
etc. are listed. A method for manufacturing the liquid crystal dispersed resin film is described in, for example, Japanese Patent Publication No. 137211/1983. The advantages of the liquid crystal dispersed resin film over other liquid crystal elements and the current problems of the liquid crystal dispersed resin film will be described below.
電気、磁気等に制御された方法によって光変調を行う各
種液晶素子は、通常２枚の透明電極の間に液晶を封入す
ることによって得られ、時計、電卓等の表示素子におい
て実用に供されている。しかしながら液晶は粘度を有す
る液状物質であることから、液晶を支持するために平面
電極として剛直なガラス基板を用いなければならない。Various liquid crystal elements that modulate light using methods controlled by electricity, magnetism, etc. are usually obtained by sealing liquid crystal between two transparent electrodes, and are used practically in display elements for watches, calculators, etc. There is. However, since liquid crystal is a liquid substance with viscosity, a rigid glass substrate must be used as a flat electrode to support the liquid crystal.
さらに均一な表示を得るためには電極間の厚みを厳密に
制御しなければならず、大面積の電極においてそれを行
うのは現状では困難とされている。In order to obtain a more uniform display, the thickness between the electrodes must be strictly controlled, and it is currently difficult to do so with large-area electrodes.
上記の問題点に対して液晶分散型樹脂膜は、液晶を樹脂
マトリクスで封じ込めた固体の形状を有するため、支持
電極としてフレシキブルなプラスチックフィルムを採用
することが可能である。また液晶分散型樹脂膜中に分散
した液晶は比較的均一な粒径を形成するので、電極間の
膜厚はそれほど厳密でなくともよい。さらにＴＮ型液晶
素子の製造過程で行われているような電極面の配向処理
もまった（不用であり、工程面でも簡略化できる。In order to solve the above-mentioned problems, the liquid crystal dispersed resin film has a solid shape in which the liquid crystal is sealed in a resin matrix, so that a flexible plastic film can be used as the supporting electrode. Furthermore, since the liquid crystal dispersed in the liquid crystal dispersed resin film forms a relatively uniform particle size, the film thickness between the electrodes does not need to be so strict. Furthermore, the alignment treatment of the electrode surface, which is performed in the manufacturing process of TN type liquid crystal elements, is unnecessary (it is unnecessary, and the process can be simplified.
以上のような利点を有する液晶分散型樹脂膜は従来の液
晶素子に比して安価で容易に大面積軽量化が可能である
。A liquid crystal dispersed resin film having the above-mentioned advantages is cheaper than a conventional liquid crystal element and can easily be made large in area and lightweight.
液晶分散型樹脂膜用樹脂マ） ＩＪクスとして熱硬化性
樹脂を用いた例としては、特許出願公表昭６１−５０２
１２８、あるいは同昭６３−５０１５１２などに記載さ
れている。しかしながらこれらに記載されたマトリクス
樹脂は充分硬化しなかったり、脆弱な硬化物しか得られ
ない樹脂組成物であるため、たとえばプラスチックフィ
ルムを電極基板とした実用に供される軽量大面積素子を
構成する配合としては強靭性、耐久性に欠ける。Resin matrix for liquid crystal dispersion type resin film) An example of using a thermosetting resin as an IJ box is the patent application published in 1986-502.
128, or Sho 63-501512. However, the matrix resins described in these are resin compositions that do not cure sufficiently or only yield brittle cured products, so they cannot be used to construct lightweight, large-area devices that can be put to practical use, for example, using plastic films as electrode substrates. As a compound, it lacks toughness and durability.
本発明は上記問題点を鑑みてなされたもので、その目的
は大面積で軽量であり、また安価で耐久性に冨む、実用
に供されるべき光変調材用液晶分散型樹脂膜を提供する
ものである。The present invention was made in view of the above-mentioned problems, and its purpose is to provide a liquid crystal dispersed resin film for a light modulating material that is large in area, lightweight, inexpensive, and highly durable, and which should be put to practical use. It is something to do.
液晶分散型樹脂膜用途を目指した熱硬化性樹脂（以下樹
脂と略す）は、その選択にあたりいくつかの原理的な制
約を受ける。第一に樹脂は使用する液晶の屈折率が一致
していなくてはならない。Thermosetting resins (hereinafter abbreviated as resins) intended for use in liquid crystal dispersed resin films are subject to several theoretical constraints in their selection. First, the refractive index of the resin must match that of the liquid crystal used.
樹脂の屈折率は一般的にその樹脂が有する分子の原子団
の種類に依存する。樹脂中の屈折率を大きくする傾向に
ある原子団は芳香族、或は、窒素原子、硫黄原子、など
のへテロ原子が挙げられ、また屈折率を小さくする原子
団はフッ素原子、珪素原子などが考えられる。従って上
記の原子団を適当に選択し液晶の屈折率に一致するよう
に樹脂を選択しなければならない。The refractive index of a resin generally depends on the type of molecular atomic groups that the resin has. Atom groups that tend to increase the refractive index in the resin include aromatics or heteroatoms such as nitrogen atoms and sulfur atoms, and atomic groups that tend to decrease the refractive index include fluorine atoms and silicon atoms. is possible. Therefore, the above atomic groups must be selected appropriately and the resin must be selected so as to match the refractive index of the liquid crystal.
第二に液晶分散型樹脂膜が形成されるためには、使用す
る樹脂が適当な重合速度を持つものでなければならない
。通常液晶分散型樹脂膜の製造は液晶及び樹脂モノマー
を混合した塗料を調製し、塗膜を硬化されることにより
得られる。樹脂が重合するにつれて液晶が樹脂に対して
不溶化し、液晶層との相分離が生じ、液晶層が形成され
る。この過程における重合速度が特に重要であり、得ら
れた液晶分散型樹脂膜の特性に影響を与える。通常液晶
層が形成されるのは樹脂がゲル化する直前であり、この
時間が速いと形成される液晶層は小さなり、逆にゲル時
間が遅いと液晶層は大きくなる傾向にある。Second, in order to form a liquid crystal dispersed resin film, the resin used must have an appropriate polymerization rate. Usually, a liquid crystal dispersed resin film is produced by preparing a paint mixture of liquid crystal and resin monomer, and curing the paint film. As the resin polymerizes, the liquid crystal becomes insoluble in the resin, phase separation from the liquid crystal layer occurs, and a liquid crystal layer is formed. The polymerization rate in this process is particularly important and influences the properties of the obtained liquid crystal dispersed resin film. Usually, the liquid crystal layer is formed just before the resin gels, and if this time is fast, the formed liquid crystal layer tends to be small, whereas if the gel time is slow, the liquid crystal layer tends to be large.
またこれらの制約に加えて実用に耐えられる液晶分散型
樹脂膜用樹脂として樹脂そのものの耐熱性、耐光性、及
び耐湿性などの緒特性が要求されるのは云うまでもない
。In addition to these constraints, it goes without saying that the resin itself is required to have other properties such as heat resistance, light resistance, and moisture resistance for a resin for a liquid crystal dispersed resin film to withstand practical use.
以上樹脂に課せられた諸条件を満足させるため鋭意検討
を行った結果、本発明の光変調材用液晶分散型樹脂膜を
完成させたものである。As a result of intensive studies to satisfy the various conditions imposed on the resin described above, the liquid crystal dispersed resin film for a light modulating material of the present invention was completed.
本発明は少くとも （ａｌ エポキシ化合物。The present invention provides at least (al epoxy compound.
ｆｂｌ 分子中に少くともチオール基が１個存在して
いる化合物。fbl A compound containing at least one thiol group in the molecule.
（ｃ１分子中に［ａ）と付加反応可能な活性水素を有す
るアミノ基を少くとも１個有するアミン化合物。(c) An amine compound having at least one amino group having an active hydrogen capable of an addition reaction with [a] in the molecule.
及び
（ｄｌ ネマチック相、コレステリンク相又はスメク
チック相を示す液晶を含む組成物中の（ｄｌが少くとも
（ａ）、 （ｂ）及び（ｃ）の硬化反応により得られる
樹脂マトリクス中に微小な液滴で存在することを特徴と
する光変調材用液晶分散型樹脂膜である。and (dl) In a composition containing a liquid crystal exhibiting a nematic phase, a cholesteric phase, or a smectic phase, (dl is at least a minute liquid in the resin matrix obtained by the curing reaction of (a), (b), and (c)). This is a liquid crystal-dispersed resin film for a light modulating material, which is characterized in that it exists in the form of droplets.
本発明に用いられる（ａ）はエポキシ化合物であり、通
常エポキシ樹脂として用いられているもの、例えば多価
フェノール類（例えばビスフェノールΔ類）や多価アル
コール類（例えばグリセリン、ペンタエリスリトール等
）とエピクロルヒドリンとの反応によって得られるポリ
グリシジルエーテル類や、カルボン酸やその無水物（例
えばフタル酸）とエピクロルヒドリンとの反応により得
られるポリグリシジルエステル類、ポリアミン類とエピ
クロルヒドリンとの反応によって得られるポリグリシジ
ルアミン類、或は不飽和化合物（例えばシクロヘキセン
誘導体など）を酸化して得られるエポキシ化合物などが
用いられる。本発明において上記に述べたように樹脂マ
トリクスの屈折率が問題となるので、これらのエポキシ
化合物の内、屈折率が比較的低い脂肪族エポキシ化合物
を用いることが望ましいが樹脂マトリクスに耐久性を賦
与するために、屈折率を変えない程度に芳香族系エポキ
シ化合物を添加することが可能である。また場合によっ
ては樹脂マトリクスに可撓性を与えたり、塗料作製時の
粘度上昇を避けるために、モノエポキシ化合物を始めと
する希釈剤を加えることも可能である。(a) used in the present invention is an epoxy compound, which is usually used as an epoxy resin, such as polyhydric phenols (e.g. bisphenol Δ), polyhydric alcohols (e.g. glycerin, pentaerythritol, etc.) and epichlorohydrin. polyglycidyl ethers obtained by reacting with epichlorohydrin, polyglycidyl esters obtained by reacting carboxylic acid or its anhydride (e.g. phthalic acid) with epichlorohydrin, and polyglycidyl amines obtained by reacting polyamines with epichlorohydrin. , or an epoxy compound obtained by oxidizing an unsaturated compound (for example, a cyclohexene derivative). In the present invention, as mentioned above, the refractive index of the resin matrix is a problem, so among these epoxy compounds, it is desirable to use an aliphatic epoxy compound that has a relatively low refractive index, but it is desirable to use an aliphatic epoxy compound that imparts durability to the resin matrix. Therefore, it is possible to add an aromatic epoxy compound to the extent that the refractive index is not changed. In some cases, it is also possible to add a diluent such as a monoepoxy compound in order to impart flexibility to the resin matrix or to avoid an increase in viscosity during paint preparation.
ｆｂ） 例えば多価フェノール類または多価アルコー
ル類とメルカプトカルボン酸とのエステル化反応による
か、或はエポキシ化合物と硫化水素との反応によって得
られるボリメリカブタン化合物が用いられるが、場合に
よって樹脂マトリクスの架橋密度を小さくしたい場合に
はモノメルカプタン化合物も添加し得る。fb) Polymeric butane compounds obtained, for example, by the esterification reaction of polyhydric phenols or polyhydric alcohols with mercaptocarboxylic acids or by the reaction of epoxy compounds with hydrogen sulfide are used; optionally crosslinking of the resin matrix A monomercaptan compound may also be added if it is desired to reduce the density.
（ｅ）は通常エポキシ樹脂の硬化剤と呼ばれるポリアミ
ン類、例えばエチレンジアミン類、ジエチルアミンプロ
ピルアミン、メンセンジアミン、インフォロンジアミン
、Ｎ−アミノエチルピペラジン、３．９ビス（３アミノ
プロピル） ２，４，８．１０テトラオキサスピロ（
５，５）ウンデカン（商品名ΔＴＵ）、ポリエーテルジ
アミン類（例えば商品名ジエチアミン）等の脂肪族ポリ
アミン類、メタフェニレンジアミン、ジアミノジフェニ
ルメタンなどの芳香族ポリアミン類、およびダイマー酸
を始めとするポリカルボン酸とポリアミン類との縮合に
より得られるポリアミノアミド系硬化剤などが挙げられ
るが、液晶分散型樹脂膜の物性に応じてモノアミン類も
添加し得る。本発明においては屈折率及び硬化速度の関
係から脂肪族ポリアミン類の使用が望ましいが、耐久性
を賦与するために屈折率または硬化速度を変えない程度
に芳香族系アミン等の使用が可能である。(e) is polyamines usually called curing agents for epoxy resins, such as ethylenediamines, diethylaminepropylamine, menthenediamine, infrondiamine, N-aminoethylpiperazine, 3.9bis(3aminopropyl) 2,4, 8.10 Tetraoxaspiro (
5,5) Aliphatic polyamines such as undecane (trade name ΔTU), polyether diamines (e.g. trade name diethiamine), aromatic polyamines such as metaphenylene diamine, diaminodiphenylmethane, and polycarboxylic acids such as dimer acid. Examples include polyaminoamide curing agents obtained by condensation of acids and polyamines, but monoamines may also be added depending on the physical properties of the liquid crystal dispersed resin film. In the present invention, it is desirable to use aliphatic polyamines due to the relationship between refractive index and curing speed, but in order to impart durability, it is possible to use aromatic amines to the extent that the refractive index or curing speed is not changed. .
特に低分子量ポリアミン類を硬化剤とした場合該ポリア
ミン類を、通常内在アダクトと呼ばれる方法で、エポキ
シ樹脂、イソシアネート類、アクリル酸エステル類、ま
たはカルボン酸類で高分子量化することが必要となる場
合がある。さらに詳細に述べれば、アミン類の高分子化
に使用される化合物とは、液晶分散型樹脂膜の構成要素
として上述したような（ａ）で代表されるエポキシ化合
物の他にトルエンジイソシアネート、ジフェニルメタン
ジイソシアネート、ヘキサメチレンジイソシアネート、
イソフォロンジイソシアネートなどのイソシアネート類
、ペンタエリスリトールテトラアクリレート、トリメチ
ロールプロパントリアクリレート等のアクリル酸エステ
ル類、あるいはアジピン酸、セバシン酸等の二塩基酸、
末端カルボン酸の液状ゴム等が挙げられる。In particular, when low-molecular-weight polyamines are used as curing agents, it may be necessary to increase the molecular weight of the polyamines with epoxy resins, isocyanates, acrylic esters, or carboxylic acids, usually by a method called endogenous adducting. be. More specifically, the compounds used to polymerize amines include toluene diisocyanate, diphenylmethane diisocyanate, in addition to the epoxy compound represented by (a) mentioned above as a component of the liquid crystal dispersed resin film. , hexamethylene diisocyanate,
Isocyanates such as isophorone diisocyanate, acrylic esters such as pentaerythritol tetraacrylate and trimethylolpropane triacrylate, or dibasic acids such as adipic acid and sebacic acid,
Examples include liquid rubbers with terminal carboxylic acids.
このように高分子量化されたポリアミンは高沸点化され
るために、低分子量ポリアミンを用いて塗膜を形成させ
る場合みられるようなアミンブラッシング現象を硬化速
度を遅らせることなく避けることを可能にする。Since polyamines with high molecular weights have high boiling points, it is possible to avoid the amine brushing phenomenon that occurs when forming coatings using low molecular weight polyamines without slowing down the curing speed. .
ｆｄ）は液晶性化合物からなる組成物であり、その組成
物の示し得る液晶相がネマチック相、スメクチック相、
コレステリック相であれば使用し得る。fd) is a composition consisting of a liquid crystal compound, and the liquid crystal phases that can be exhibited by the composition are nematic phase, smectic phase,
Any cholesteric phase can be used.
本発明の光変調材用液晶分散型樹脂は上記（ａ）〜（ｄ
）からなる組成物に対し重合速度を制御せしめるために
、さらに触媒を添加することが可能である。The liquid crystal dispersed resin for light modulating material of the present invention is as described above (a) to (d).
In order to control the rate of polymerization, it is possible to add further catalysts to the composition.
本発明に於ける触媒とは、主に（ａ）とｆｂ）との反応
、（ａｌと（ｃ）との反応、或は（ａ）と（ｂｌ及び（
ｃ）との混合物との反応における触媒として添加し得る
成分であり、主剤と硬化剤との重合速度により添加量が
定められ、場合によっては無添加でもよい。ここではエ
ポキシ樹脂の反応で通常用いられる三級アミン類、へ、
ンジルジメチルアミン、２−ジメチルアミノメチル）フ
ェノール、２，４．６４リス（ジメチルアミノメチル）
フェノール、Ｎ、Ｎ’ ジメチルピペラジン、ＤＢＵ（
１，８−ジアザビシクロ（５，４，０）ウンデセン−１
）等が挙げられる。The catalyst used in the present invention mainly refers to the reaction between (a) and fb), the reaction between (al and (c)), or the reaction between (a) and (bl and (c)).
It is a component that can be added as a catalyst in the reaction with the mixture with c), and the amount added is determined depending on the polymerization rate of the main ingredient and the curing agent, and it may not be added depending on the case. Here, we will discuss the tertiary amines commonly used in the reaction of epoxy resins.
dimethylamine, 2-dimethylaminomethyl)phenol, 2,4.64lis(dimethylaminomethyl)
Phenol, N, N' dimethylpiperazine, DBU (
1,8-diazabicyclo(5,4,0)undecene-1
) etc.
一般的には液晶分散型樹脂膜が製造される場合の構成要
素としては、主剤成分、硬化剤成分、触媒成分、及び液
晶からなり、触媒成分はあってもなくてもよい。本発明
に於いても、上記組成物の成分（ａｌ〜（ｄ）のうちエ
ポキシ主剤成分（ａ）、硬化剤成分（ｂ）および（ｃ１
、液晶成分（ｄ）に大別することができ、さらに触媒成
分が場合によっては添加されうる。In general, the components for manufacturing a liquid crystal dispersed resin film include a main component, a curing agent component, a catalyst component, and a liquid crystal, and the catalyst component may or may not be present. Also in the present invention, among the components (al to (d)) of the above composition, epoxy base component (a), curing agent component (b) and (c1
, a liquid crystal component (d), and a catalyst component may be added depending on the case.
特に本発明に用いられる硬化剤成分（ｂ）及び（ｃ１の
内から、特に成分（ｃ）のみを用いた樹脂組成分（以下
エポキシ−アミン系成分と略す）は特徴として硬化剤が
アミン系なので硬化物の架橋密度を上げることが可能で
あり、それゆえ樹脂の耐水性、耐薬品性が期待できる。In particular, the resin composition (hereinafter abbreviated as epoxy-amine component) using only the curing agent component (b) and (c1) (hereinafter abbreviated as epoxy-amine component) used in the present invention is characterized by the fact that the curing agent is amine-based. It is possible to increase the crosslinking density of the cured product, and therefore the water resistance and chemical resistance of the resin can be expected.
が一般的に樹脂中に窒素原子を含んでしまうために耐光
性に劣るとされ、架橋密度が密なゆえ硬化物は硬くなり
、電気特性、特に駆動電圧（電圧印加により液晶が充分
に応答する電圧）が高くなる傾向にある。Generally, resins contain nitrogen atoms, which is considered to have poor light resistance, and the high crosslinking density makes the cured product hard. voltage) tends to increase.
一方、本発明に用いられる硬化剤成分（ｂｌ及び（ｃ）
の中から、特に成分（ｂ）のみを用いた樹脂組成分（以
下エポキシ−メルカプタン系成分と略す）はエポキシ−
アミン系に較べて架橋密度が疎であり、柔らかい硬化物
が得られる。しかも硬化はエポキシ−アミン系に較べて
速く、得られた塗膜もむらが少ない。電気特性において
も樹脂の柔らかさ故、駆動電圧を低く抑えることが可能
である。反面架橋密度が低いので樹脂の耐水性、耐薬品
性はエポキシ−アミン系に劣る。On the other hand, the curing agent components (bl and (c) used in the present invention)
Among them, resin compositions using only component (b) (hereinafter abbreviated as epoxy-mercaptan components) are epoxy-mercaptan-based components.
The crosslinking density is lower than that of amine-based products, and soft cured products can be obtained. Furthermore, curing is faster than with epoxy-amine systems, and the resulting coating film is less uneven. In terms of electrical properties, due to the softness of the resin, it is possible to keep the driving voltage low. On the other hand, since the crosslinking density is low, the water resistance and chemical resistance of the resin are inferior to those of epoxy-amine type.
本発明はこれらエポキシ−アミン系成分、エボギシーメ
ル力ブタン系成分の両者の欠点を補うために（ｂ）及び
（ｃ１の両者を混合して使用することを特徴とする。即
ちエポキシ−メルカプタン系硬化物の特徴である硬化樹
脂の柔らかさを保ちつつ、アミン系硬化剤を添加するこ
とにより樹脂の架橋密度を密にし、耐水性、耐熱性をエ
ボキーメル力ブタン系硬化物を賦与することを目的とす
る。両者を混合することにより、エポキシ−メルカプタ
ン系由来の駆動電圧の低さに加えて、エポキシ−メルカ
プタン系成分由来の耐久性を有する、実用の液晶分散型
樹脂膜を得ることが出来る。The present invention is characterized in that both (b) and (c1) are used as a mixture in order to compensate for the drawbacks of both the epoxy-amine component and the epoxy-mercaptan-based component. That is, the epoxy-mercaptan-based cured product The aim is to maintain the softness of the cured resin, which is a characteristic of the cured resin, and increase the crosslinking density of the resin by adding an amine curing agent, thereby imparting water resistance and heat resistance to the evoxymel-butane cured product. By mixing both, it is possible to obtain a practical liquid crystal-dispersed resin film that has not only the low driving voltage derived from the epoxy-mercaptan component but also the durability derived from the epoxy-mercaptan component.
本発明における組成物の配合量は光変調材用液晶分散型
樹脂膜の物性により厳密に定められる。The amount of the composition in the present invention is strictly determined depending on the physical properties of the liquid crystal dispersed resin film for the light modulator.
本発明に用いられる組成物の配合比はエポキシ成分（ａ
ｌと硬化剤成分（ｂｌ及び（ｃ）との比率、硬化剤成分
（ｂ）と（ｃ１の比率、及び液晶成分（ｄ）の添加比率
の４っの成分比によって決定される。さらにこれらの比
率は組成物の硬化における温度に依存する。同一成分比
の樹脂組成物において、硬化温度により光変調材用液晶
分散型樹脂膜の物性は影響を受ける。The blending ratio of the composition used in the present invention is the epoxy component (a
It is determined by the four component ratios: the ratio of curing agent components (bl and (c)), the ratio of curing agent components (b) and (c1), and the addition ratio of liquid crystal component (d). The ratio depends on the temperature at which the composition is cured.In resin compositions having the same component ratio, the physical properties of the liquid crystal-dispersed resin film for a light modulator are affected by the curing temperature.
つまり硬化温度が高くなるにつれて析出する液晶粒の粒
径が小さくなり、得られる光変調材用液晶分散型樹脂膜
は赤味を帯びる。逆に硬化温度が低いと析出する液晶粒
は大きくなり、光変調材用液晶分散型樹脂膜は青味を帯
びる。In other words, as the curing temperature increases, the particle size of the precipitated liquid crystal grains becomes smaller, and the resulting liquid crystal dispersed resin film for a light modulator becomes reddish. On the other hand, if the curing temperature is low, the precipitated liquid crystal grains become large, and the liquid crystal dispersed resin film for the light modulator becomes bluish.
エポキシ成分（ａ）と硬化剤成分（ｂ）及び（ｃ）との
比率はエポキシ成分におけるエポキシ当量と硬化剤成分
の活性水素当量の比によって決定される。通常エポキシ
当量ｌに対し硬化剤成分の活性水素当量が０．２〜１．
８になる量を添加すればよいが、この配合比により得ら
れる光変調材用液晶分散型樹脂膜の耐久性、及び電気特
性、特に駆動電圧に影響を与える。The ratio of epoxy component (a) to hardener components (b) and (c) is determined by the ratio of the epoxy equivalent in the epoxy component to the active hydrogen equivalent of the hardener component. Usually, the active hydrogen equivalent of the curing agent component is 0.2 to 1.
However, this mixing ratio affects the durability and electrical properties of the liquid crystal dispersed resin film for light modulating material, especially the driving voltage.
本発明においては、硬化剤成分に於けるアミン系硬化剤
（ｃ１とメルカプタン系硬化剤（ｂｌの比率が重要であ
り、この比によって本発明の光変調材用液品分散型樹脂
膜の物性、例えば駆動電圧、耐久性に変化を与える。ア
ミン系硬化剤の比率を増やすと、耐水性、耐熱性を与え
るが、駆動電圧が上界する。逆にメルカプタン系硬化剤
の比率を増やすと、駆動電圧は下がるが、逆に耐水性は
劣る。また低沸点のアミン系硬化剤の添加比率を増やす
とアミン系硬化剤由来のアミンブラッシング現象が現れ
、塗膜にむらが生じる。特にアミン系硬化剤を高い比率
で配合した場合、使用するアミン系硬化物を予めエポキ
シ樹脂と反応させ、高分子量化しておくか、あるいはア
ミン系硬化剤とエポキシ樹脂、イソシアネート、アクリ
ル酸エステル類等との付加反応によりアミン系硬化剤を
高沸点化することにより、塗１漠のむらを解消すること
が可能である。In the present invention, the ratio of the amine curing agent (c1) and the mercaptan curing agent (bl) in the curing agent components is important, and this ratio determines the physical properties of the liquid dispersion type resin film for light modulating material of the present invention. For example, it changes the driving voltage and durability.Increasing the ratio of amine-based curing agent provides water resistance and heat resistance, but increases the driving voltage.On the contrary, increasing the ratio of mercaptan-based curing agent The voltage decreases, but on the other hand, the water resistance is inferior.Also, when the addition ratio of low boiling point amine hardeners is increased, the amine brushing phenomenon derived from the amine hardeners appears, causing unevenness in the coating.Especially with amine hardeners. When compounding in a high ratio, the amine-based cured product used must be reacted with an epoxy resin in advance to increase its molecular weight, or the amine-based curing agent may be added through an addition reaction with an epoxy resin, isocyanate, acrylic ester, etc. By increasing the boiling point of the amine curing agent, it is possible to eliminate uneven coating.
組成物における触媒成分量は、基本的には組成物の重合
速度に関与するが、得られる光変調材用液晶分散型樹脂
膜の物性においては液晶量の粒径の大きさに影響を与え
る。つまり触媒成分の添加量を増やすことにより、光変
調材用液晶分散型樹脂膜中の液晶量は小さくなり光変調
材用液晶分散型樹脂膜は赤味を帯び、逆に添加量を減ら
せば粒径は大きくなり青味を帯びる。また触媒量は樹脂
膜塗料のボットライフにも影響を与える。 組成物への
液晶の添加量は、得られる光変調材用液晶分散型樹脂膜
の０度（ヘーズ）、駆動電圧に影響を与える。最適液晶
量近傍で液晶量を増やしていくと光変調材用液晶分散型
樹脂膜は青味を帯び、駆動電圧は下がるが、逆に光変調
材用液晶分散型樹脂膜の０度は低下する。次に液晶量を
減らしていくと光変調材用液晶分散型樹脂膜は赤味を帯
び、駆動電圧が上昇すると共に０度も低下する。The amount of the catalyst component in the composition is basically related to the polymerization rate of the composition, but it also affects the particle size of the amount of liquid crystals in the physical properties of the resulting liquid crystal-dispersed resin film for a light modulator. In other words, by increasing the amount of the catalyst component added, the amount of liquid crystal in the liquid crystal-dispersed resin film for light modulating material becomes smaller and the liquid crystal-dispersing resin film for light modulating material becomes reddish; The diameter increases and becomes bluish. The amount of catalyst also affects the bot life of the resin film paint. The amount of liquid crystal added to the composition influences the 0 degrees (haze) and driving voltage of the resulting liquid crystal-dispersed resin film for light modulating material. When the amount of liquid crystal is increased near the optimum amount of liquid crystal, the liquid crystal dispersed resin film for light modulating material becomes bluish and the driving voltage decreases, but conversely, the 0 degree of the liquid crystal dispersed resin film for light modulating material decreases. . Next, when the amount of liquid crystal is decreased, the liquid crystal dispersed resin film for the light modulating material becomes reddish, and as the driving voltage increases, the temperature decreases to 0 degrees.
以下に本発明の詳細を実施例により述べるが本発明はこ
れらの実施例に縛られるものではない。The details of the present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.
表１は本発明の実施例１〜４、比較例１．２の組成物、
電圧印加時の０度、および耐熱、耐湿性結果を示す。尚
表中
１９１Ｐ ：油化シェルエポキシ０＠製商品名“エピ
コート３
Ｎ−ＡＥＰ ： Ｎ−アミノエチルピペラジンＲＯ，
ＴＮ４０３： 日本ロソシュ社製液晶組成物Ｅ４３
：ＢＤＨ社製液晶組成物
ＤＭＰ３０ ： ）リス（ジメチルアミノエチレン
）フェノールを示す。Table 1 shows the compositions of Examples 1 to 4 of the present invention, Comparative Example 1.2,
The results are shown at 0 degrees when voltage is applied, as well as heat resistance and humidity resistance. In addition, 191P in the table: Product name "Epicoat 3" manufactured by Yuka Shell Epoxy 0@ N-AEP: N-aminoethylpiperazine RO,
TN403: Liquid crystal composition E43 manufactured by Nippon Rososh Co., Ltd.
:Liquid crystal composition DMP30 manufactured by BDH Co., Ltd. :) Indicates lith(dimethylaminoethylene)phenol.
比較例１，２、実施例１〜６
表１に示すように比較例１，２、実施例１〜４の配合に
於いて得られた樹脂組成物に日本合成ゴム製ポリスチレ
ンビーズ（粒径２０μｍ）を０．５重量パーセント添加
し、撹拌し、真空ポンプにより脱気した。この樹脂組成
物を３０ｃｍ角の大きさの２枚の透明導電性フィルム（
ダイセイ化学工業（株製、商品名“セレノク”Ｋ、ＬＣ
，，１２５μｍ）の間に流し込み、ＲＫ Ｐｒ１ｎｔ
Ｃｏａｔ Ｉｎｓｔｒｕｍｅｎｔｓ Ｌｔｄ。Comparative Examples 1 and 2, Examples 1 to 6 As shown in Table 1, polystyrene beads manufactured by Nippon Synthetic Rubber (particle size 20 μm ) was added at 0.5 weight percent, stirred, and degassed using a vacuum pump. This resin composition was applied to two 30 cm square transparent conductive films (
Daisei Chemical Industry (Co., Ltd., product name “Serenoku” K, LC)
,,125μm), RK Pr1nt
Coat Instruments Ltd.
製グラビア・ブルーファーにより導電性フィルムによっ
て挟まれた２０μ厚の樹脂塗膜を得た。さらに７０℃恒
温槽で１時間加熱し樹脂を硬化させた。得られたシート
の塗膜のむらは目視によった。A resin coating film with a thickness of 20 μm sandwiched between conductive films by Gravure Blue Fur was obtained. Furthermore, the resin was cured by heating in a constant temperature bath at 70° C. for 1 hour. The unevenness of the coating film of the obtained sheet was visually observed.
シートの０度は東洋精機（ｌ製ヘーズメーターにより測
定した。耐熱性試験は８０℃恒温槽により、耐湿性試験
はプレーンシャー・クツカー・テスターにより、８０℃
、９５％ＲＨの条件で行い、シート電極面間にＯＶ、４
０Ｖの電圧を印加した状態での０度を測定し、初期値の
０度に対して０度が２倍になった時点を劣化時間とした
。以下表１に示された、主剤Ａ、Ｂ、硬化剤Ａ、Ｂの合
成例を示す。The 0 degrees of the sheet was measured using a haze meter made by Toyo Seiki (L).The heat resistance test was conducted using an 80℃ constant temperature bath, and the moisture resistance test was conducted using a Plainscher Kutzker tester at 80℃.
, 95% RH condition, OV between the sheet electrode surfaces, 4
0 degree was measured with a voltage of 0 V applied, and the time point when 0 degree became twice the initial value of 0 degree was defined as the deterioration time. Synthesis examples of main ingredients A and B and curing agents A and B shown in Table 1 are shown below.
合成例１
エポキシ樹脂として東部化成（株製、商品名“エポトー
ト”ＹＨ−３００１４ｇ、）リエチレンイトフ
←す９ミン０．１５ ｇを加え撹拌混合した後、７０℃
１時間加熱した。こうして得られたエポキシ樹脂を主剤
Ａとする。Synthesis Example 1 After adding 0.15 g of lyethylene nitrate (manufactured by Tobu Kasei Co., Ltd., trade name "Epotote" YH-30014 g) as an epoxy resin and stirring and mixing, the mixture was heated to 70°C.
Heated for 1 hour. The epoxy resin thus obtained is used as the main resin A.
合成例２
エポキシ樹脂としてＹＨ−３００ｍｌ １４ ｇ、味の
素（■製ＡＴＩＪ０．４１ ｇを加え撹拌混合した後、
７０℃１時間加熱した。こうして得られたエポキシ樹脂
を主剤Ｂとする。Synthesis Example 2 After adding 14 g of YH-300ml as an epoxy resin and 0.41 g of Ajinomoto (ATIJ manufactured by ■) and stirring and mixing,
It was heated at 70°C for 1 hour. The epoxy resin obtained in this way is used as the main resin B.
合成例３
滴下ロート及び撹拌機を備えた２００ｍ１３つロフラス
コに淀化学■製ＴＭＴＰＩ ０６ ｇに、トリエチレン
トリアミン５ｇを加え撹拌混合した後、常温下日本化薬
■製アクリレートモノマー（商品名に八ＹＡＲＡＤ）
ＴＭＰＴＡを１部注意深く滴下した。ＴＭＰＴ八滴下へ
同時に発熱が始まり約 ４０°Ｃまで温度が上昇した。Synthesis Example 3 5 g of triethylenetriamine was added to 06 g of TMTPI manufactured by Yodo Kagaku ■ in a 200 m 13-loaf flask equipped with a dropping funnel and a stirrer, and the mixture was stirred and mixed. )
One portion of TMPTA was carefully added dropwise. When eight drops of TMPT were added, heat generation started and the temperature rose to approximately 40°C.
滴下後約１２時間撹拌してトリエチレンＬ皐３ミン変性
硬化剤を得た。この硬化剤を硬化剤Ａとする。After the dropwise addition, the mixture was stirred for about 12 hours to obtain a triethylene L-triamine modified curing agent. This curing agent will be referred to as curing agent A.
合成例４
滴下ロート及び撹拌機を備えた２００ｍ１３つロフラス
コにＴとＰＴＡ １０６ｇに、ＡＴｌｌｏｇを力■え撹
拌混合した後、約６０℃に加熱しながらＴＭＰＴＡ１部
を注意深く滴下した。滴下終了後６０℃で約へ
２時間撹拌、後室温で約１２時間撹拌してＳＴＵ変性硬
化剤を得た。この硬化剤を硬化剤Ｂとする。Synthesis Example 4 After stirring and mixing AT1log with 106 g of T and PTA in a 200 m 13-bottle flask equipped with a dropping funnel and a stirrer, 1 part of TMPTA was carefully added dropwise while heating to about 60°C. After the dropwise addition was completed, the mixture was stirred at 60° C. for about 2 hours, and then stirred at room temperature for about 12 hours to obtain an STU-modified curing agent. This curing agent will be referred to as curing agent B.
本発明の樹脂組成物により耐久性にとみ、かつ
軽量大型化が可能な液晶分散型樹脂膜の製造が可能にな
った。The resin composition of the present invention has made it possible to produce a liquid crystal-dispersed resin film that is durable, lightweight, and large-sized.
Claims (1)
るチオール化合物、 （ｃ）分子中に（ａ）と付加反応可能な活性水素を有す
るアミノ基を少くとも１個有するアミノ化合物及び （ｄ）ネマチック相、コレステリック相又はスメクチッ
ク相を示す液晶。 を含む組成物中の（ｄ）が少くとも（ａ）、（ｂ）及び
（ｃ）の硬化反応により得られる樹脂マトリクス中に微
小な液滴で存在することを特徴とする光変調材用液晶分
散型樹脂膜。 （２）特許請求項１記載の組成中の （ａ）のエポキシ当量 の比が （ｂ）及び（ｃ）の活性水素当量 ０．２〜１．８であり、（ｂ）の活性水素当量と（ｃ）
の活性水素当量との比が０．１〜０．９であり、（ｄ）
の比が組成物の重量に対して０．２〜０．５であること
を特徴とする光変調材用液晶分散型樹脂膜。 （３）特許請求項１記載の（ｃ）がエポキシ化合物、カ
ルボン酸化合物、アクリル化合物、あるいはイソシアネ
ート化合物とアミノ化合物とを付加反応させることによ
り得られる高分子量化アミノ化合物であることを特徴と
する光変調材用液晶分散型樹脂膜。[Scope of Claims] (a) an epoxy compound; (b) a thiol compound in which at least one thiol group is present in the molecule; (c) an amino acid having an active hydrogen in the molecule that can undergo an addition reaction with (a). An amino compound having at least one group and (d) a liquid crystal exhibiting a nematic phase, cholesteric phase or smectic phase. A liquid crystal for a light modulating material, characterized in that (d) in a composition containing the above exists in minute droplets in a resin matrix obtained by the curing reaction of at least (a), (b) and (c). Dispersed resin membrane. (2) In the composition according to claim 1, the ratio of the epoxy equivalents of (a) to the active hydrogen equivalents of (b) and (c) is 0.2 to 1.8, and the active hydrogen equivalents of (b) and (c)
and the active hydrogen equivalent is 0.1 to 0.9, and (d)
A liquid crystal dispersed resin film for a light modulating material, characterized in that the ratio of 0.2 to 0.5 to the weight of the composition. (3) (c) in claim 1 is a high molecular weight amino compound obtained by addition reacting an epoxy compound, a carboxylic acid compound, an acrylic compound, or an isocyanate compound with an amino compound. Liquid crystal dispersed resin film for light modulating material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32627388A JPH02171720A (en) | 1988-12-26 | 1988-12-26 | Liquid crystal dispersion type resin film for optical modulating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32627388A JPH02171720A (en) | 1988-12-26 | 1988-12-26 | Liquid crystal dispersion type resin film for optical modulating material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02171720A true JPH02171720A (en) | 1990-07-03 |
Family
ID=18185924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32627388A Pending JPH02171720A (en) | 1988-12-26 | 1988-12-26 | Liquid crystal dispersion type resin film for optical modulating material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02171720A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5354498A (en) * | 1990-03-16 | 1994-10-11 | Fuji Xerox Co., Ltd. | Phase separation liquid crystal polymer |
| US5558813A (en) * | 1991-03-25 | 1996-09-24 | Fuji Xerox Co., Ltd. | Liquid crystal-polymer composite film |
| US7439000B2 (en) * | 2005-10-25 | 2008-10-21 | 3M Innovative Properties Company | High clarity cholesteric liquid crystal films |
-
1988
- 1988-12-26 JP JP32627388A patent/JPH02171720A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5354498A (en) * | 1990-03-16 | 1994-10-11 | Fuji Xerox Co., Ltd. | Phase separation liquid crystal polymer |
| US5558813A (en) * | 1991-03-25 | 1996-09-24 | Fuji Xerox Co., Ltd. | Liquid crystal-polymer composite film |
| US7439000B2 (en) * | 2005-10-25 | 2008-10-21 | 3M Innovative Properties Company | High clarity cholesteric liquid crystal films |
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