JPS59148028A - Electrooptic electrode substrate - Google Patents

Abstract

PURPOSE:To obtain an electrode substrate having superior durability, moisture resistance, heat resistance and orienting power by forming a film of a resin composition consisting of a resin contg. bismaleimide and a triazine resin monomer as principal components and of epoxy resin and by orienting the surface of the film. CONSTITUTION:A transparent electrode film is formed on the surface of a substrate, and a film of a resin composition consisting of a resin contg. bismaleimide and a triazine resin monomer as principal components and of epoxy resin is formed on a part or whole of the surface of the substrate including the electrode film. The surface of the resin composition film is then oriented. The former resin contains essentially bismaleimide represented by the formula, dicyanate represented by a formula NidenticalC-O-Ar2-CidenticalN and triazine resin having triazine rings each formed by cyclopolymerizing three or more said dicyanate molecules in the molecule and cyanate groups at the terminals of the molecule. In the formulae, each of Ar1 and Ar2 is a bivalent aromatic group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an electro-optical electrode substrate having excellent durability, moisture resistance, heat resistance, and orientation.

[Technical Disadvantages and Problems of the Invention] Recently, the application of optical anisotropy of liquid crystals to display devices has been progressing in various fields. The most commonly used display method is one that utilizes the dynamic scattering phenomenon in which a nematic liquid crystal compound with angular dielectric anisotropy scatters light when an electric field is applied (hereinafter referred to as DS type device). (hereinafter referred to as the FE type vise), which is used for display by avoiding changes in optical rotation by orienting a nematic liquid crystal compound with positive anisotropy.

In the DS type device, uniformity of the initial alignment of the liquid crystal is not necessarily required for the operating principle, but in the FE type device, the operating principle is to control or rearrange the initial alignment of the liquid crystal using an electric field, and the optical principle at that time is used. The uniformity of the initial alignment of the liquid crystal is particularly important because changes in the liquid crystal are utilized. Conventionally, a method of rubbing the electrode substrate in one direction with cloth or the like has been known as a means of obtaining uniformity of the initial alignment of liquid crystal, but with this method, the alignment of liquid crystal molecules is partially different, and the alignment Although the uniformity of the film is sufficient, it has the disadvantage that the orientation is lost within a short period of time.

In order to overcome the above drawbacks, a method has been used in which the electric TFI substrate is rubbed in one direction using a certain type of surfactant, but this method improves the uniformity of orientation to some extent. Another problem is that the surfactant has no heat resistance, and the surfactant causes deterioration of the liquid crystal.Furthermore, if an electric field is continued to be applied, the surfactant will decompose and change in quality due to the electric field, and the orientation will be destroyed. It has the disadvantage of being Furthermore, a method is used in which an electrode substrate coated with a conventional integrated polyimide resin is rubbed in one direction, but this method has excellent alignment effects and heat resistance for liquid crystals, but the curing and condensation temperature of the polyimide resin is Due to its high cost, it has the disadvantage that it cannot be coated on flexible electrode substrates (for example, films made of polyester stellate, etc.).

[Purpose of the Invention J The present invention has been made in order to improve the various drawbacks as described above, and provides an electro-optic electrode substrate with excellent durability, heat resistance, moisture resistance, and good orientation. The purpose is to provide.

[Summary of the Invention] As a result of intensive research to achieve the above object, the present invention has discovered an electro-optic electrode substrate with excellent characteristics.
=It is something.

That is, a resin whose main components are (a) hismaleimide and a heliazine resin, etc. is applied to a part or the entire surface of the substrate surface having a transparent electrode film, including the electrode film.
The present invention is an electro-optical electrode substrate characterized in that it has a resin composition film made of an L/4C resin, and the resin composition film is subjected to an orientation treatment.

Examples of the electrode substrate used in the present invention include a glass plate or a plastic plate such as polyester having a thin film of tin oxide or indium oxide provided as a transparent electrode on a part or the entire surface of one surface by means such as vapor deposition. is used (1 is used)

(a) Resin whose main component is bismaleimidodine resin monomer used in the present invention (bismaleimide represented by the general formula 0, and represented by the general formula N=C-0-Ar 2-O-C=N dicyanate, and in the molecule (where dicyanate is 3
A triazine resin having a triazine ring cyclopolymerized with more than one molecule and a cyanane 1-group [N=C-0-] at the end of the molecule, for example, the following structural formula (j) (However, △r1.△ 1 and 2 represent the same or different divalent aromatic groups). An example of such a resin is B1 (trade name) manufactured by Mitsubishi Gas Kagaku Ne4.

Examples of the epoxy resin (b) used in the present invention include the following bisla-1-nor dieboxides. Shell chemistry 1! ! (EpikoLe
)827,828,834.1001.

1002.100/1.1007, 1009, manufactured by Dow Chemi Cuff 1 Company l] HiR330, 331, 332° 334.
335,336,337,660゜661.662,6
67.668,669, Araltai 1 manufactured by Ciba Geigy
~ (Araldite) G'T250.2'6
0,280.6071,6084°6097.6099
, Jones 1Dabney Epi-Re5
510, 5101, Ebikuron sio, 1ooo, 1oio manufactured by Iriichi Hoinki Chemical Industry Co., Ltd.

3010 (all above are product names).

Furthermore, (b) as a clay resin (with a boxy base number of 3 on average)
For example, by using the above-mentioned novolac 1-boxy resin, it is possible to further improve mechanical properties and heat resistance. As the novolak epoxy resin to be used, one having a min-r rating of 500 or more is suitable. For example, Ciba Geigy's 7'Y Lutile T-(Ara
ldite) E PN 1138°1139, F=
CN1273.1280.1299, EFN431,438 manufactured by Tau Chemical, ERR-0 manufactured by Shell Chemical 71
100,E[yo['3-Q 4 /I 7.

Examples include ERI B-04-48. The following components may be used alone or in combination of two or more.

The blending ratio of the resin mainly composed of bismaleimide and triazine resin monomer <a> and the 1-boxy resin (b) is preferably in the range of 10:90 to 90:10 (weight pressure), Above all < 30: 70~
70:30 (preferably in the amm run range).

If the blending ratio of component (a) is less than 10 parts by weight, the resulting resin will have poor heat resistance, and conversely, if the blending ratio of component (11) is less than 10 parts by weight, the viscosity of the resin will increase, resulting in poor workability. Things get worse.

(a) Bismaleimide and heliazine resin tops
When blending the resin whose main component is and the epoxy resin (b), these resins may be added and dissolved at the same time in a common solvent, but it is preferable to dissolve the latter in the common solvent first. It is desirable to dissolve the former.

Common solvents mentioned above include acelin, methyl ethyl ketone, dioxane, dioxane, bempine,
Examples include toluene, turben 1-naf(), industrial kalin, cellosolve acetate, ethylce(solzo), dimethylformamide, ?methylat?1-amide, N-methylpyrrolidone, etc. These solvents may be used alone or in combination of two or more. used in combination.

Note that the resins in (a) and (b) above are dissolved in a solvent.
l? After that, by avoiding heating reaction in the temperature range of 80 to 120°C for several hours, cyanate single phase'! :i, cyane~1
～M epoxy group, cyanate group and bismaleimide [
It is also possible to conduct a bipartite reaction to control the molecular weight of the C resin silk composition.

In addition, in addition to the resin composition (a) containing bismaleimide and 1 to lyazine resin 7-mer as main components, and the epoxy resin (b), other resins such as polyester are added to this resin composition. resin, polyimide (polyamide) resin,
Modification can also be achieved by incorporating Shodong such as poly-1 stellimide resin.

The mixing ratio of resin and solvent (resin content: 1 degree) can be changed arbitrarily depending on the coating method, and if necessary, the resin content can be made to a high concentration and heated during painting to reduce the viscosity. It may also be used by

To form a film on a substrate using the above resin composition,
Usually, it is dissolved in a solvent and applied to the substrate using a solution of about 40% o, oi -, by brush coating, dipping, A-lu1~, printing methods such as stamping, spin coating, spraying, etc. After that, 1oo~200'C1 preferably 15
After heat treatment at 0 to 180°C and drying with solvent, (a) a resin mainly composed of bismaleimide and 1-lyazine resin and <b> an epoxy resin are combined to form an imide-triazine-epoxy resin by avoiding a crosslinking reaction. Apply a film.

1- After providing the film, the surface of the film is rubbed in a certain direction with a tool such as a b for orientation treatment, thereby obtaining the electro-optic electrode substrate of the present invention.

The electro-optical electrode substrate according to the present invention has extremely excellent uniformity in the initial alignment of liquid crystal, and the heating temperature during film formation is low, so it can be used not only on glass substrates but also on heat-sensitive films such as polyester (25 g), It is also applicable to 7. Another advantage is that even if the temperature of the electrode substrate increases, the alignment effect of liquid crystal molecules is not affected, and the liquid crystal molecules in the cell remain stable for a long period of time.

By sealing a nemagic liquid crystal exhibiting positive dielectric anisotropy by a known method between the alignment-treated surfaces of the pair of electrode substrates according to the present invention, electro-optic Display devices can be created (-). Such electrode substrates can be effectively used in various electro-optical devices, such as electronic CJ-1-1 camphors, wristwatches, table clocks, etc. It can be used for a display Mbff such as a counting display board.

[Embodiments of the invention] Next, the present invention will be specifically explained using examples.

Example 1 The io and ozB moieties of 1 Piquat 1007 were converted to diethlene glycol monobutyl conyteracetate 7-1 to 1188iI
After melting at a temperature of 90℃ in the im part, add B King 2170.
(Mitsubishi Gas Chemical Co., Ltd.!! IBT Resin trade name) was added to prepare a 1% solution in which 2.0 weight and 15 parts were uniformly dissolved.

In this solution, an electrode substrate, which had been patterned with nether glass having a conductive film of indium oxide and then washed in a conventional manner, was immersed.

After dipping, heat treatment was performed at 200°C for 60 minutes to cause a crosslinking reaction, and a 100OX thick resin composition film was formed on the electrode substrate.
Dan tno lko.

Next, the pair of electrode substrates provided with the resin composition films were rubbed in one direction with a cloth to undergo orientation treatment. After that, the cells were assembled in such a way that the friction directions were perpendicular to each other, 44 nemagic liquid crystals with positive dielectric anisotropy were placed, and a polarizing film was placed on both sides of the outside of the hill to adjust the polarization position of the polarizing film. A display device was created by laminating the substrates so that they were parallel to the friction direction of the adjacent substrates. The display device has excellent durability and is moisture resistant (60℃ x 95% RHX 500 hours filJ
) No destruction of orientation was observed in the heat resistance (80"CX 500 hours) test, and the uniformity of orientation was also good Qf.

Example 2 8.0 parts of Epicoat 828, B King 217° (trade name of B Luzine, manufactured by Mitsubishi Gas Chemical Co., Ltd.) io, o heavy products, and Toji 1 were dissolved in 1 part of 20.0 width u of dilene glycol diethyl ether. After reacting in the solution at 120° C. for 1 hour, the mixture was further diluted with 1762.0 parts by weight of diethyl glycol diethyl ether to prepare a 1% solution in which the mixture was uniformly dissolved. This solution was offset printed on a Borini L stell film having a conductive film of indium oxide,
A heat treatment was performed at 150°C for 1 hour to cause a crosslinking reaction, and a 100OX thick resin composition film was provided on the electrode substrate. Next, a pair of polygon pull film electrode substrates provided with the resin composition coating were rubbed in one direction with a cloth for orientation treatment.

After that, a nematic liquid crystal with positive dielectric anisotropy was assembled into a sea urchin-C cell in which the friction direction was perpendicular to the direction of friction.
Then, a display device was created by pasting polarizing films on both sides of the outside of the cell so that the polarization direction of each polarizing film was parallel to the friction direction of the adjacent substrate. (Go back, moisture resistant (60℃ x 95%R)
HX 50 (between 111,'i), heat resistance (80℃ x 50
0 hour) test, no destruction of the orientation was observed, and the uniformity of the orientation was also good.

Comparative Example 1 After cleaning Neriglass for electrodes on which indium oxide was vapor-deposited,
After dipping in a 0.5% aqueous solution of polyA xychetylene nonilf''-nyl-del as an alignment treatment agent and coating with C, vacuum drying was avoided. Next, the coated surface was rubbed in one direction with a cloth to prepare an oriented glass. A pair of Nesa glasses thus obtained were assembled in parallel so as to be perpendicular to the IT friction direction, a commercially available nematic liquid crystal was encapsulated, and a polarizing film was laminated on both sides of the outside of the cell to create a display device.

This display device had uneven alignment of brightness and darkness in the display area when an electric field was applied, and the alignment was destroyed after 100 hours at 60° C. and 95% RH, resulting in poor durability.

Comparative Example 2 A display device was created in the same manner as in Comparative Example 1 after creating the neri glass in which the orientation treatment was performed by directly rubbing the neriglass surface in one direction with a cloth without using the orientation treatment agent in comparative example 1. This display device had uneven alignment of brightness and darkness in the display area when an electric field was applied, and the alignment began to break down after 3 hours at 50°C, and completely broke down after 2 days, resulting in poor durability and heat resistance. Ta.

As is clear from the above description, the electro-optical electrode substrate of the present invention has excellent durability, moisture resistance, and heat resistance, and has extremely good orientation and optical properties. It has 11 unprecedented abilities that can be applied to substrates such as poor polyester films.

Claims (1)

[Scope of Claims] 1. A resin whose main components are (a) > bismaleimide and triazine resin monomer;
1. An electro-optical electrode substrate comprising a resin composition film made of an epoxy resin, the surface of the resin composition film being subjected to orientation treatment. 2 The blending ratio of (a) and (1) in the resin composition is 1
The electro-optical electrode substrate according to claim 1, characterized in that the weight ratio is in the range of 0:90 to 90:10 (weight ratio). 3 The resin whose main components are bismaleimide and triazine resin monomer is hismaleimide represented by the general formula, dicyanane-1 ~ represented by the general formula N=co-A+' 2-C=N, and 1-riazine resin having l-, l-noazine rings formed by cyclization of three or more molecules of the dicyanate in the molecule and having a cyanide-1-group [N=C-0-] at the molecular end (however, Ar
The electro-optical electrode substrate according to claim 1 or 2, characterized in that the electro-optical electrode substrate has as a main component: +, Ar2 represent the same or different divalent aromatic groups.