JPS6412368B2 - - Google Patents
Info
- Publication number
- JPS6412368B2 JPS6412368B2 JP11091980A JP11091980A JPS6412368B2 JP S6412368 B2 JPS6412368 B2 JP S6412368B2 JP 11091980 A JP11091980 A JP 11091980A JP 11091980 A JP11091980 A JP 11091980A JP S6412368 B2 JPS6412368 B2 JP S6412368B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- anhydride
- film
- diamine
- substrate
- 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
Links
- 239000004973 liquid crystal related substance Substances 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 18
- KSFBTBXTZDJOHO-UHFFFAOYSA-N diaminosilicon Chemical compound N[Si]N KSFBTBXTZDJOHO-UHFFFAOYSA-N 0.000 claims description 13
- 150000004985 diamines Chemical class 0.000 claims description 10
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 8
- 229920006254 polymer film Polymers 0.000 claims description 8
- 239000004642 Polyimide Substances 0.000 claims description 7
- 229920005575 poly(amic acid) Polymers 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 description 11
- -1 2,3,6,7-naphthalenetetracarboxylic anhydride Chemical class 0.000 description 10
- 238000000576 coating method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- UOGZBWHPCKPLRL-UHFFFAOYSA-N C1(=CC=CC=C1)[Si](OCCN)(OCCN)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)[Si](OCCN)(OCCN)C1=CC=CC=C1 UOGZBWHPCKPLRL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001354 dialkyl silanes Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CZIZXBQHAXSBAN-UHFFFAOYSA-N 2-[(2-aminophenoxy)-diethylsilyl]oxyaniline Chemical compound C=1C=CC=C(N)C=1O[Si](CC)(CC)OC1=CC=CC=C1N CZIZXBQHAXSBAN-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- WDJZBVROFUQDTE-UHFFFAOYSA-N 3-[3-aminopropoxy(dimethyl)silyl]oxypropan-1-amine Chemical compound NCCCO[Si](C)(C)OCCCN WDJZBVROFUQDTE-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 description 1
- WXAIEIRYBSKHDP-UHFFFAOYSA-N 4-phenyl-n-(4-phenylphenyl)-n-[4-[4-(4-phenyl-n-(4-phenylphenyl)anilino)phenyl]phenyl]aniline Chemical compound C1=CC=CC=C1C1=CC=C(N(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 WXAIEIRYBSKHDP-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【発明の詳細な説明】
本発明は液晶分子を初期状態（未励起状態）で
ホモジニアス配向状態にしておくことが必要な液
晶表示装置に使用可能な、初期のホモジニアス配
向を良質にする手段を施した液晶挾持基板に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides means for improving the quality of initial homogeneous alignment, which can be used in liquid crystal display devices that require liquid crystal molecules to be homogeneously aligned in an initial state (unexcited state). This invention relates to a liquid crystal holding substrate.
従来このような液晶分子の初期状態におけるホ
モジニアス配向を良好にする手段として、基板上
に酸化珪素等の斜方蒸着膜を形成する方法や、各
種表面処理剤、有機高分子等の膜を形成し、その
膜をラビング処理する方法等が知られている。し
かしこれら公知の方法にはそれぞれ以下に述べる
ような欠点があつた。 Conventionally, methods for improving the homogeneous alignment of liquid crystal molecules in the initial state include forming an obliquely evaporated film of silicon oxide or the like on a substrate, or forming a film of various surface treatment agents, organic polymers, etc. , a method of rubbing the film is known. However, each of these known methods has drawbacks as described below.
すなわち、酸化珪素等の斜方蒸着膜は液晶物質
の種類によつて配向能に差があり全く配向しない
ような液晶物質も存在する。これは液晶の温度特
性あるいは電気光学特性を改善するために各種の
液晶を混合して使用する場合に非常に大きな障害
となる。また、各種表面処理剤、有機高分子等の
膜を形成してその膜をラビング処理する方法で
は、膜の耐熱性が低いために、素子組立時の加熱
によつて膜が劣化し、配向性が低下する等の欠点
をもつものがほとんどで、配向規制力の耐熱性が
よいのはポリイミド等の耐熱性有機高分子膜に限
られていた。 That is, the orientation ability of an obliquely vapor deposited film such as silicon oxide differs depending on the type of liquid crystal material, and there are some liquid crystal materials that do not provide orientation at all. This is a very serious problem when using a mixture of various liquid crystals to improve the temperature characteristics or electro-optical characteristics of the liquid crystal. In addition, in the method of forming a film of various surface treatment agents, organic polymers, etc. and then rubbing the film, the heat resistance of the film is low, so the film deteriorates due to heating during device assembly, resulting in poor orientation. Most of them have drawbacks such as a decrease in the heat resistance, and only heat-resistant organic polymer films such as polyimide have good heat resistance of alignment regulating force.
しかしながら、これらの耐熱性を有するポリイ
ミド系高分子においてもラビング後400℃〜450℃
でガラスフリツトシールを行なうと液晶を封入し
た際に配向不良が生じやすくなる。特に誘起ドメ
インが発生し、表示特性の安定な液晶表示装置を
得ることは困難である。これは従来のポリイミド
系高分子の熱重量分析において400℃付近で重量
減少開始が観測されることから加熱によつて高分
子膜の表面状態に変化がおこりラビング効果がそ
こなわれ、液晶の配向状態を変えてしまうものと
考えられる。上記のような400℃以上の熱処理で
膜に変化がおこらず安定な配向をもつ高分子膜と
して、特開昭53−24850号公報記載のポリイミド
イソインドロキナゾリンジオン系高分子膜が知ら
れているが、これら公知のポリイミドイソインド
ロキナゾリンジオン系高分子膜は、その基板面と
の接着性がわるいためにラビング処理の際に塗膜
に部分的に膜はがれが生じ、そのためにドメイン
が発生する等の配向不良がおこる欠点があつた。 However, even with these heat-resistant polyimide polymers, temperatures of 400°C to 450°C after rubbing
If glass frit sealing is performed in this manner, alignment defects are likely to occur when the liquid crystal is sealed. In particular, induced domains occur, making it difficult to obtain a liquid crystal display device with stable display characteristics. This is because in conventional thermogravimetric analysis of polyimide polymers, weight loss is observed to begin around 400°C, so heating causes a change in the surface condition of the polymer film, damaging the rubbing effect and causing the alignment of the liquid crystal to change. It is thought that the situation will change. A polyimide isoindoquinazolinedione polymer film described in JP-A No. 53-24850 is known as a polymer film that does not undergo any change in the film and has a stable orientation when subjected to heat treatment at 400°C or higher as described above. However, these known polyimide isoindoquinazoline dione polymer films have poor adhesion to the substrate surface, resulting in partial peeling of the coating film during rubbing treatment, resulting in the formation of domains. There was a drawback that poor alignment occurred.
本発明者らは従来技術の上記の欠点をなくすべ
く検討した結果本発明に至つた。すなわち本発明
は、どの様な液晶物質であつても液晶の分子軸を
基板面に対し平行にかつ基板面の特性方向に配向
させ、かつこの液晶配向規制力がきわめて耐熱性
に優れ、なおかつ対ラビング性を向上させた液晶
挾持基板を提供するもので、これによつて液晶表
示素子組立に制限を与えず経時的に安定で長寿命
かつ高性能の液晶表示装置が得られる。 The present inventors conducted studies to eliminate the above-mentioned drawbacks of the prior art, and as a result, they arrived at the present invention. In other words, the present invention allows the molecular axis of liquid crystal to be aligned parallel to the substrate surface and in the characteristic direction of the substrate surface, regardless of the liquid crystal substance, and this liquid crystal alignment regulating force has extremely excellent heat resistance and The present invention provides a liquid crystal holding substrate with improved rubbing properties, thereby making it possible to obtain a liquid crystal display device that is stable over time, has a long life, and has high performance without imposing restrictions on the assembly of liquid crystal display elements.
本発明は、液晶挾持基板上の液晶に面する側に
電極を設け、該基板及び電極上に、カルボン酸無
水物、ジアミン、ジアミノモノアミド、ジアミノ
シランを反応させて得られるポリアミド酸を、脱
水閉環して得られるポリイミドシランイソインド
ロキナゾリンジオン系高分子被膜を形成してなる
液晶挾持基板に関する。 In the present invention, an electrode is provided on the side facing the liquid crystal on a liquid crystal holding substrate, and a polyamic acid obtained by reacting a carboxylic acid anhydride, a diamine, a diamino monoamide, and a diamino silane is dehydrated and ring-closed on the substrate and the electrode. The present invention relates to a liquid crystal holding substrate formed with a polyimidosilane isoindoquinazolinedione polymer coating obtained by the above process.
ポリイミドシランイソインドロキナゾリンジオ
ン系高分子の前駆体であるポリアミド酸はカルボ
ン酸無水物、ジアミン、ジアミノモノアミド及び
ジアミノシランの反応により合成される。これら
の反応は無水条件下、好ましくは50℃またはそれ
以下の温度で行なわれる。カルボン酸無水物、ジ
アミン、ジアミノモノアミドおよびジアミノシラ
ンの反応割合は、カルボン酸無水物のモル数と、
ジアミン、ジアミノモノアミドおよびジアミノシ
ランのモル数とを等モルとすることが好ましい。
この反応はジメチルフオルムアミド、ジメチルア
セトアミド、ジメチルスルフオキシド、Ｎ−メチ
ルピロリドン等の溶剤の存在下で行なわれる。 Polyamic acid, which is a precursor of polyimidosilane isoindoquinazolinedione-based polymers, is synthesized by the reaction of carboxylic acid anhydride, diamine, diaminomonoamide, and diaminosilane. These reactions are carried out under anhydrous conditions, preferably at temperatures of 50°C or lower. The reaction ratio of carboxylic anhydride, diamine, diaminomonoamide, and diaminosilane is determined by the number of moles of carboxylic anhydride,
It is preferable that the number of moles of diamine, diaminomonoamide and diaminosilane be equimolar.
This reaction is carried out in the presence of a solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide or N-methylpyrrolidone.
カルボン酸無水物としては、たとえばピロメリ
ツト酸無水物、２，３，６，７−ナフタレンテト
ラカルボン酸無水物、３，3′，４，4′−ジフエニ
ルテトラカルボン酸無水物、１，２，５，６−ナ
フタレンテトラカルボン酸無水物、２，2′，３，
3′−ジフエニルテトラカルボン酸無水物、チオフ
エン−２，３，４，５−テトラカルボン酸無水
物、２，２−ビス（３，４−ビスカルボキシフエ
ニル）プロパン無水物、３，４−ジカルボキシフ
エニルスルホン無水物、ベリレン−３，４，９，
10−テトラカルボン酸無水物、ビス（３，４−ジ
カルボキシフエニル）エーテル無水物、３，3′，
４，4′−ベンゾフエノンテトラカルボン酸無水物
などが用いられる。 Examples of the carboxylic anhydride include pyromellitic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 3,3',4,4'-diphenyltetracarboxylic anhydride, 1,2, 5,6-naphthalenetetracarboxylic anhydride, 2,2',3,
3'-diphenyltetracarboxylic anhydride, thiophene-2,3,4,5-tetracarboxylic anhydride, 2,2-bis(3,4-biscarboxyphenyl)propane anhydride, 3,4- Dicarboxyphenylsulfone anhydride, berylene-3,4,9,
10-tetracarboxylic anhydride, bis(3,4-dicarboxyphenyl)ether anhydride, 3,3',
4,4'-benzophenonetetracarboxylic anhydride and the like are used.
ジアミンとしては、たとえばｍ−フエニレンジ
アミン、ｐ−フエニレンジアミン、ｍ−キシレン
ジアミン、ｐ−キシレンジアミン、４，4′−ジア
ミノジフエニルエーテル、４，4′−ジアミノジフ
エニルメタン、３，3′−ジメチル−４，4′−ジア
ミノジフエニルメタン、３，3′，５，5′−テトラ
メチル−４，4′−ジアミノジフエニルメタン、
２，2′−ビス（４−アミノフエニル）プロパン−
４，4′−メチレンジアニリン、ベンジジン、４，
4′−ジアミノジフエニルスルフイド、４，4′−ジ
アミノジフエニルスルホン、１，５−ジアミノナ
フタレン、３，3′−ジメチルベンジジン、３，
3′−ジメトキシベンジジン、ジアミノモノアミド
としてはたとえば、１，４−ジアミノベンゼン−
２−カルボンアミド、４，4′−ジアミノジフエニ
ルエーテル−３−カルボンアミドなどが用いられ
る。 Examples of the diamine include m-phenylenediamine, p-phenylenediamine, m-xylenediamine, p-xylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3 '-Dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane,
2,2'-bis(4-aminophenyl)propane-
4,4'-methylene dianiline, benzidine, 4,
4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 1,5-diaminonaphthalene, 3,3'-dimethylbenzidine, 3,
Examples of 3'-dimethoxybenzidine and diaminomonoamide include 1,4-diaminobenzene-
2-carbonamide, 4,4'-diaminodiphenyl ether-3-carbonamide, etc. are used.
本発明で用いられるジアミノシランとしては例
えば一般式
（式中Ｒは２価の炭化水素基、R1、R2は１価の
炭化水素基である。）
で示される化合物が用いられ、その例としては、
ジ（アミノプロポキシ）ジメチルシラン等のジ
（アミノアルコキシ）ジアルキルシラン、ジ（ア
ミノエトキシ）ジフエニルシラン等のジ（アミノ
アルコキシ）ジアリルシラン、ジ（アミノフエノ
キシ）ジエチルシラン等のジ（アミノフエノキ
シ）ジアルキルシラン、ジ（アミノフエノキシ）
ジフエニルシラン等のジ（アミノフエノキシ）ジ
アリルシラン、ジ（アミノプロポキシ）メチルフ
エニルシラン等のジ（アミノアルコキシ）アルキ
ルアリルシランなどの化合物がある。ジアミノシ
ランは、例えばジクロルシランとヒドロキシルア
ミンとをテトライソプロポキシチタン等のチタン
のアルコキサイドを触媒として反応させて得られ
る。 For example, the diaminosilane used in the present invention has the general formula (In the formula, R is a divalent hydrocarbon group, and R 1 and R 2 are monovalent hydrocarbon groups.) Compounds represented by the following are used, and examples thereof include:
Di(aminoalkoxy)dialkylsilane such as di(aminopropoxy)dimethylsilane, di(aminoalkoxy)diallylsilane such as di(aminoethoxy)diphenylsilane, di(aminophenoxy)dialkylsilane such as di(aminophenoxy)diethylsilane, di(aminophenoxy)dialkylsilane such as di(aminophenoxy)diethylsilane, etc. aminophenoxy)
There are compounds such as di(aminophenoxy) diallylsilanes such as diphenylsilane, and di(aminoalkoxy)alkylarylsilanes such as di(aminopropoxy)methylphenylsilane. Diaminosilane is obtained, for example, by reacting dichlorosilane and hydroxylamine using a titanium alkoxide such as tetraisopropoxytitanium as a catalyst.
カルボン酸無水物、ジアミン、ジアミノモノア
ミドおよびジアミノシランは耐熱性の点からいず
れも芳香族系の化合物を用いることが好ましい。 It is preferable to use aromatic compounds for the carboxylic acid anhydride, diamine, diaminomonoamide, and diaminosilane from the viewpoint of heat resistance.
カルボン酸無水物、ジアミン、シアミノモノア
ミド、およびジアミノシランは、それぞれ二種以
上を併用してもよい。 Two or more types of carboxylic acid anhydride, diamine, cyaminomonoamide, and diaminosilane may be used in combination.
ジアミノモノアミドおよびジアミノシランのジ
アミン、ジアミノモノアミドおよびジアミノシラ
ン中に含まれる割合には制限はないが、接着性、
耐熱性および安定性の点からジアミン、ジアミノ
モノアミドおよびジアミノシランの総量に対して
ジアミノモノアミドを0.1〜50モル％、ジアミノ
シランを0.1〜50モル％とすることが好ましい。 There is no limit to the proportion of diaminomonoamide and diaminosilane contained in diamine, diaminomonoamide and diaminosilane, but adhesiveness,
From the viewpoint of heat resistance and stability, it is preferable that the amount of diaminomonoamide is 0.1 to 50 mol% and the amount of diaminosilane is 0.1 to 50 mol% based on the total amount of diamine, diaminomonoamide, and diaminosilane.
上記ポリアミド酸の基板及び電極への塗布は、
該ポリアミド酸をジメチルフオルムアミド、ジメ
チルアセトアミド、ジメチルスルフオキシド、Ｎ
−メチルピロリドン等の0.01〜40重量％溶液とし
て、これをデイツプ法、スピンナ法、スプレー
法、印刷法、刷毛塗り法などにより塗布して行な
われる。塗布後100℃〜400℃好ましくは250℃〜
350℃で加熱処理し、脱水閉環してポリイミドシ
ランイソインドロキナゾリンジオン系高分子被膜
が得られる。 The application of the above polyamic acid to the substrate and electrodes is as follows:
The polyamic acid is dimethylformamide, dimethylacetamide, dimethylsulfoxide, N
- A solution of 0.01 to 40% by weight of methylpyrrolidone or the like is applied by dip method, spinner method, spray method, printing method, brush coating method, etc. 100℃~400℃ after coating, preferably 250℃~
A polyimidosilane isoindoquinazolinedione polymer film is obtained by heat treatment at 350°C and dehydration and ring closure.
以下、実施例及び比較例により本発明を具体的
に説明する。 Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples.
実施例 １
Ｎ−メチルピロリドン中でジ（アミンエトキ
シ）ジフエニルシラン0.1モルと４，4′−ジアミ
ンジフエニルエーテル0.8モル、４，4′−ジアミ
ンジフエニルエーテル−３−カルボンアミド0.1
モル及び３，3′，４，4′−ベンゾフエノンテトラ
カルボン酸無水物1.0モルを縮合して得られたポ
リイミドシランイソインドロキナゾリンジオン系
高分子の前駆体であるポリアミド酸の10重量％Ｎ
−メチルピロリドン溶液をスピンナを用いて酸化
インジウムの電極が形成されたガラス基板に塗布
した。塗布後300℃で２時間加熱閉環させポリイ
ミドシランイソインドロキナゾリンジオン系高分
子被膜を800Åの厚さに形成した。その後該被膜
を一定方向にガーゼでラビング処理を行なつた
が、該ポリイミドシランイソインドロキナゾリン
ジオン系高分子被膜にはがれは生じなかつた。ま
た上記のラビング処理した被膜を有する基板の一
対を用い、低融点ガラスフリツトを用いて450℃
で30分加熱圧着して液晶表示セルを作製し、液晶
を封入して配向性を観察したが、配向や良好であ
つた。Example 1 0.1 mol of di(amine ethoxy) diphenylsilane and 0.8 mol of 4,4'-diamine diphenyl ether, 0.1 mol of 4,4'-diamine diphenyl ether-3-carbonamide in N-methylpyrrolidone.
10% by weight of polyamic acid, which is a precursor of polyimidosilane isoindoquinazolinedione polymer, obtained by condensing 1.0 mole of 3,3',4,4'-benzophenonetetracarboxylic acid anhydride. N
- A methylpyrrolidone solution was applied using a spinner to a glass substrate on which an indium oxide electrode was formed. After coating, ring closure was performed by heating at 300° C. for 2 hours to form a polyimidosilane isoindoquinazolinedione polymer film with a thickness of 800 Å. Thereafter, the coating was rubbed in a certain direction with gauze, but no peeling occurred in the polyimidosilane isoindoquinazolinedione polymer coating. In addition, using a pair of substrates with the above-mentioned rubbed coating, the film was heated to 450°C using a low melting point glass frit.
A liquid crystal display cell was prepared by heat-pressing for 30 minutes, and the liquid crystal was sealed and the orientation was observed, and the orientation was good.
上記の実施例において使用したジ（アミノエト
キシ）ジフエニルシランは次の方法により合成し
た。 Di(aminoethoxy)diphenylsilane used in the above examples was synthesized by the following method.
ジメトキシジフエニルシラン（信越化学社製
KBM202）122.2ｇとエタノールアミン61.1ｇを
両者の総量に対して0.1重量％のテトライソプロ
ポキシチタンを触媒として70℃で反応させた。反
応終了後、85℃で生成したメタノールを除去し、
ジ（アミノエトキシ）ジフエニルシランを得た。 Dimethoxydiphenylsilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
122.2g of KBM202) and 61.1g of ethanolamine were reacted at 70°C using 0.1% by weight of tetraisopropoxytitanium based on the total amount of both as a catalyst. After the reaction is complete, remove the methanol produced at 85℃,
Di(aminoethoxy)diphenylsilane was obtained.
比較例 １
Ｎ−メチルピロリドン中で、４，4′−ジアミノ
ジフエニルエーテル0.9モル、４，4′−ジアミノ
ジフエニルエーテル−３−カルボンアミド0.1モ
ル及び３，3′，４，4′−ベンゾフエノンテトラカ
ルボン酸無水物1.0モルを縮合して得られるポリ
イミドイソインドロキナゾリンジオンの前駆体で
あるポリアミド酸の10重量％Ｎ−メチルピロリド
ン溶液を用い、上記実施例１と同様の方法で処理
してポリイミドイソインドロキナゾリンジオンの
被膜を800Åの厚さに形成した。その後上記実施
例１とまつたく同様にしてラビング処理を行なつ
たところ、部分的に基板からはがれが生じた。ま
た上記実施例１と同様にして液晶表示セルを作製
したところ、部分的に配向不良が観測された。Comparative Example 1 In N-methylpyrrolidone, 0.9 mol of 4,4'-diaminodiphenyl ether, 0.1 mol of 4,4'-diaminodiphenyl ether-3-carbonamide and 3,3',4,4'-benzo Treated in the same manner as in Example 1 above using a 10% by weight N-methylpyrrolidone solution of polyamic acid, which is a precursor of polyimidoisoindoquinazolinedione obtained by condensing 1.0 mol of phenotetracarboxylic anhydride. A film of polyimide isoindoquinazolinedione was formed to a thickness of 800 Å. Thereafter, when a rubbing process was performed in the same manner as in Example 1, partial peeling occurred from the substrate. Further, when a liquid crystal display cell was produced in the same manner as in Example 1, poor alignment was observed in some parts.
実施例および比較例に示すとおり、本発明のポ
リイミドシランイソインドロキナゾリンジオン系
高分子被膜は基板に対して非常に優れた接着性を
示し、あらゆるラビング処理条件に耐えることが
できる。また液晶配向規制力の耐熱性が450℃以
上ときわめて優れているため、本発明になる液晶
挾持基板を用いればフリツトシール等の液晶素子
組立に制限を与えず経時的に安定で長寿命かつ、
高特性の液晶表示装置を得ることができる。 As shown in the Examples and Comparative Examples, the polyimidosilane isoindoquinazolinedione polymer film of the present invention exhibits very excellent adhesion to the substrate and can withstand all kinds of rubbing treatment conditions. In addition, the heat resistance of the liquid crystal alignment regulating force is extremely excellent at 450°C or higher, so if the liquid crystal holding substrate of the present invention is used, there will be no restrictions on liquid crystal element assembly such as frit seals, and it will be stable over time and have a long life.
A liquid crystal display device with high characteristics can be obtained.
Claims (1)
け、該基板及び電極上に、カルボン酸無水物、ジ
アミン、ジアミノモノアミド、ジアミノシランを
反応させて得られるポリアミド酸を、脱水閉環し
て得られるポリイミドシランイソインドロキナゾ
リンジオン系高分子被膜を形成してなる液晶挾持
基板。1 An electrode is provided on the side facing the liquid crystal on the liquid crystal holding substrate, and a polyamic acid obtained by reacting a carboxylic acid anhydride, diamine, diamino monoamide, and diamino silane is dehydrated and ring-closed on the substrate and the electrode. A liquid crystal holding substrate formed by forming a polyimide silane isoindoquinazoline dione polymer film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11091980A JPS5734524A (en) | 1980-08-11 | 1980-08-11 | Substrate for sandwiching liquid crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11091980A JPS5734524A (en) | 1980-08-11 | 1980-08-11 | Substrate for sandwiching liquid crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5734524A JPS5734524A (en) | 1982-02-24 |
| JPS6412368B2 true JPS6412368B2 (en) | 1989-02-28 |
Family
ID=14547949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11091980A Granted JPS5734524A (en) | 1980-08-11 | 1980-08-11 | Substrate for sandwiching liquid crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5734524A (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5949562B2 (en) * | 1979-07-06 | 1984-12-04 | 株式会社日立製作所 | liquid crystal display element |
-
1980
- 1980-08-11 JP JP11091980A patent/JPS5734524A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5734524A (en) | 1982-02-24 |
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