JPH02103019A - Liquid crystal oriented film - Google Patents

Abstract

PURPOSE:To obtain a liquid crystal oriented film having superior orientational property and large pretilt angle and being suitable for an SBE display element by using a film comprising a polymer having a structure expressed by the specified formula in a recurrent unit and subjecting the film to orientation treatment. CONSTITUTION:A liquid crystal oriented film prepd. by orienting a polymer film consisting of a polymer having a structure expressed by the general formula I in a recurrent unit is used, wherein R<1> is a tetravalent alicyclic group; R<2> is a divalent org. group; each R<3>-R<7> is an H atom, alkyl, alkenyl, or phenyl group which may be substituted by halogen atom or an OH group, and being same or different to each other; A is a divalent alicyclic or aromatic group which may be substituted by a halogen atom; (n) is zero or 1; R<8> is an H atom or a group expressed by the formula II. The oriented film has high orientational property and a large pretilt angle, providing a liquid crystal oriented film particularly suitable for an SBE element. When the liquid crystal is selected suitably, a liquid crystal display element utilizing the liquid crystal display element can be useable suitably for both TN type liquid crystal and ferroelectric liquid crystal, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a liquid crystal alignment film, and particularly to a liquid crystal alignment film having a large pretilt angle.

(Prior art) Conventionally, a nematic liquid crystal with positive dielectric anisotropy is sandwiched between transparent electrodes coated with a liquid crystal alignment film, so that the long sleeve of the liquid crystal molecules is continuously twisted 90 degrees between the substrates. A liquid crystal display element (TN type display element) having a TN type array cell is known.

The liquid crystal in this liquid crystal display element is aligned by rubbing a liquid crystal alignment film made of polyimide or the like coated on the electrodes.

Since this TN type display element has poor contrast and viewing angle dependence, 5BE (Super twist) has recently been developed as a liquid crystal display element with excellent contrast and viewing angle dependence.
ted Birefringency Effect)
Display devices have become known. This SBE display element uses a blend of nematic liquid crystal and a chiral agent, which is an optically active substance, as the liquid crystal, and uses the birefringence effect produced by continuously twisting the long sleeve of the liquid crystal molecules by more than 180 degrees between the substrates. It is something to be used.

(Problems to be Solved by the Invention) However, the above-mentioned SBE display element conventionally uses a substrate on which silicon dioxide is obliquely vapor-deposited in order to orient the liquid crystal, so the display reproducibility is poor and the manufacturing process is slow. There are problems such as being complicated.

In addition, when an SBE display element is manufactured using a liquid crystal alignment film made of polyimide or the like of the conventional TN display element, the pretilt angle between the long sleeve of the aligned liquid crystal molecules and the liquid crystal alignment film is small, so that the liquid crystal is There is a problem in that the substrates cannot be twisted by more than 180 degrees, making it difficult to obtain the desired display function.

Therefore, an object of the present invention is to provide a liquid crystal alignment film with good liquid crystal alignment and a large pretilt angle.

[Means for Solving the Problems] The present invention solves the above problems by using the general formula (1
): [Here, R1 is a tetravalent alicyclic group, R2 is a divalent organic group, R3, R4, R5, R&, and R7 may be the same or different, and are substituted with a hydrogen atom, a halogen atom, or a hydroxyl group. A is a divalent alicyclic group or an aromatic group which may be substituted with a halogen atom, n is O or 1, and R8 is a hydrogen atom or Formula: %Formula% Examples include a group derived by removing four hydrogen atoms from an alicyclic compound having a telo atom, and R2 is a divalent organic group, for example, t (where R3, R4, R5, R6 R', A and n are the same as above) A liquid crystal alignment film obtained by aligning a film made of a polymer having the structure represented by in the repeating unit. This is what we provide.

The polymer used in the present invention is a polymer having a structure represented by the above general formula (1) in its repeating unit. In general formula (1), R1 is a tetravalent alicyclic group, such as cyclobutane, cyclobencune, cyclohexane,
A group derived by removing 4 hydrogen atoms from a saturated alicyclic hydrocarbon having 4 or more carbon atoms such as bicyclooctane; may be -H, -CH, or -OCH
:I, YO is -CHz Cz Ha-O--S
--(CH2), a divalent aromatic group represented by --C-.

(In the formula, n' represents an integer from 2 to 20.), (CHz)
j (J2 is an integer from 1 to 50), CH.

1←CHzh-C---1,000CHzh-, CH.

or an aromatic group, R# is an aliphatic group having 2 to 20 carbon atoms or an alicyclic C,
1...R2,%..., - (in the formula, n# is an integer of 1 to 20), etc., represents a monovalent aliphatic group, alicyclic group, or aromatic group, and m is 1 to is an integer of 100] Divalent organic groups such as an organosiloxane group can be mentioned. Also, R3, R'R5, R6 and R? may be the same or different, hydrogen atom; halogen atom; hydroxyl group; alkyl group having 1 to 20 carbon atoms,
For example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group: Alkenyl groups having 1 to 20 carbon atoms, such as vinyl group, propenyl group, butenyl group, hexenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, eicosenyl group; A phenyl group, etc., and an alkyl group, an alkenyl group, and a phenyl group may be substituted with a halogen atom such as fluorine, chlorine, or bromine.

Preferably, it is a long-chain alkyl group having 14 to 22 carbon atoms, such as a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, or an eicosyl group, and may be substituted with the above-mentioned halogen atom. Further, A is a divalent alicyclic group or an aromatic group which may be substituted with a halogen atom, such as a divalent alicyclic M such as cyclobutane, cyclobencune, cyclohexane, a phenylene group, a methylphenylene group, Examples include divalent aromatic groups such as dimethylphenylene group, tetramethylphenylene group, dichlorophenylene group, and difluorophenylene group.

The polymer (hereinafter referred to as "polymer (1)") having the structure represented by the above general formula (1) in its repeating unit, which is contained as a main component of the composition used in the present invention, is, for example, (■): [Here, R', R3, R', R',
R6R7, R", A and n are dicarboxylic acids represented by the above general formula % formula % and/or general formula (■):
[Here, R', R'', R', R5, R6R',
R'', A and n are the same as in the general formula ([), and X represents a halogen atom, such as fluorine, chlorine, bromine, etc.] A dicarboxylic acid dihalide represented by the general formula ([)]
: % formula %() [Here, R2 is the same as the general formula (1)] ).

Further, the polymer (1) has the following general formula (■) obtained by reacting a diamine compound of general formula (IV) with a tetracarboxylic dianhydride represented by general formula (V) described below: Same as formula (1)] A polyamic acid or its derivative having a repeating unit represented by the general formula (■): [Here, R3, R4, R5 and R7 are the above general formula (
Same as 1)] It can also be produced by a method of reacting with an epoxy compound represented by the following. (Hereinafter, this method will be referred to as the "second method.") Hereinafter, the first method and the second method will be explained in order.

■) First method (a) Dicarboxylic acid of the following formula (V
): [Here, R1 and R2 are the tetracarboxylic dianhydride represented by the above-mentioned general [Here, R1 is the same as the above-mentioned general formula (1)], and the following general formula (■): (Here, R1, Ra, R5, Rh, RtA and n can be obtained by reacting with an alcohol compound represented by the above general formula (same as [)].

-i) As the carboxylic dianhydride of formula (V),
For example, 1,2,3,4-cyclobutanetetracarphonic acid dianhydride, 1,2,3,4-cyclopenkunetetracarboxylic dianhydride, 2,3,5-)licarboxycyclobentylacetic dianhydride dicarboxy-norbornane-2-acetic dianhydride, 5-(2,5
-dioxotetrahydrofuryl)-3-methyl-cyclohexenedicarboxylic dianhydride, bicyclo(2,2,2
)-octo-7-nin-tetracarboxylic dianhydride, 1
．． 2.3. Alicyclic tetracarboxylic dianhydrides such as 4-furantetracarboxylic dianhydride can be mentioned.

Among these alicyclic tetracarboxylic dianhydrides of general formula (V), particularly preferred are 1.2, 3.4
-cyclopenkune tetracarboxylic dianhydride, 2,3.
Examples include 5-tricarboxycyclopentyl acetic dianhydride.

In addition, in the first method, aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, etc. can also be used in combination with the tetracarboxylic dianhydride of general formula (V). . Examples of the aromatic tetracarboxylic dianhydride include 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride,
．． 4'-bis(3,4-dicarboxyphenoxy)diphenylsulfonic dianhydride, 4,4'-bis(3,4
-Dicarboxyphenoxy)diphenylpropane dianhydride, 3.3', 4.4' -Perfluoroisopropylidenetetracarboxylic dianhydride, 3.3', 4
．． 4'-biphenyl ether tetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dihydride, m-phenylene-bis(triphenylphthalic acid) ) dianhydride, bis(triphenylphthalic acid) -4,4
'-Diphenyl ether dianhydride, bis(triphenylphthalic acid) -4,4'-diphenylmethanidianhydride, pyromellitic dianhydride, 3.3', 4.4'
-Henzophenonetetracarboxylic dianhydride, 3.3'
, 4.4'-biphenylsulfonetetracarboxylic dianhydride, 1,4.5.8-naphthalenetetracarboxylic dianhydride, 2,3.6.7-naphthalenetetracarboxylic dianhydride, 3.3 ', 4.4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3.3', 4
．． Examples include 4'-tetraphenylsilane, tetracarboxylic dianhydride, and the like. In addition, as the aliphatic tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, 3.3
', 4,4'-perfluoroisopropylidene tetracarboxylic dianhydride, and the like. These may be used alone or in combination of two or more.

When these aromatic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides, etc. are mixed with the tetracarboxylic dianhydride of general formula (V), the mixing ratio is ) for tetracarboxylic dianhydride,
Usually, it is 95 mol% or less.

Examples of the alcohol compound of general formula (Vl) include ethanol, propatool, butanol, hexanol,
Aliphatic alcohols such as heptadecanol, octadecanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol; 3-ethylcyclobutanol , 2-isopropylcyclopentanol, 4-t-butylcyclohexanol and other alicyclic alcohols; 4-L-butyl-α-naphthol, 4-1-butylphenol, p-octylphenol, p-decylphenol, p-penta Alcohol compounds with aromatic groups such as decylphenol, p-hexadecylphenol, and p-octadecylphenol; Aliphatic alcohols with double bonds such as ω-undecylenyl alcohol, oleyl alcohol, and lylyl alcohol; 2-fluoro ethanol, 2,2.2-) refluoroethanol,
Examples include alcohol compounds containing a halogen atom such as 1-chloro-2-octatool, pt-lifluoroethylphenol, and m-trifluoroethylphenol.

Among these alcohol compounds of general formula (Vl), particularly preferred are tetradecanol, hexadecanol, octadecanol, nonadecanol, eicosanol, p-hexadecylphenol, p-octadecylphenol, oleyl alcohol, rylyl alcohol, etc. 2.2.2-) alcohol compounds having a long-chain alkyl group or long-chain alkenyl group having 14 to 20 carbon atoms; and 2.2.2-) alcohol compounds containing a halogen atom such as refluoroethanol.

In order to produce the dicarboxylic acid of the general formula CI, the tetracarboxylic dianhydride of the general formula (V) and the alcohol compound of the general formula (Vl) are dissolved in a solvent in which the dicarboxylic acid to be produced is dissolved. and react. This reaction is -3
The reaction can be carried out by simply stirring the reaction mixture at a temperature of 0 to 30°C, but the reaction may be carried out by heating to a temperature of 30 to 150°C, if necessary.

In this reaction, the amount of the alcohol compound of general formula (Vl) to be used is usually 2 to 20 mol, preferably 2 to 10 mol, per 1 mol of tetracarboxylic dianhydride of general formula (V). It is a percentage.

Examples of the reaction solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N.

N-dimethylformamide, dimethyl sulfoxide, T
- Mention may be made of aprotic scratching solvents such as butyrolactone, tetramethylurea, hexamethylphosphoryltriamide and the like.

(b) -[Dicarbonate dihalogen general formula (01)
The dicarboxylic acid dihalide can be produced, for example, by reacting the dicarboxylic acid of general formula (If) with an inorganic halide.

Examples of the inorganic halides that can be used include phosphoryl chloride, thionyl chloride, phosphorus pentachloride, and phosphorus trichloride.

The reaction can be carried out by simply stirring the reaction mixture consisting of the dicarboxylic acid of general formula (II) and the inorganic halide at room temperature after 20°Cri'i, but if necessary, the reaction may be carried out at 60-150°C. The reaction may be carried out by heating.

Examples of the reaction solvent include those used in the production of the dicarboxylic acid of general formula (II) above.

(C) -IV diamine The diamine compound of general formula (IV) includes, for example, phenylenediamine, metaphenylenediamine, 4.4
'-Diamino diphenylmethane, 4゜4'-diaminodiphenyl ethane, benzidine, 4.4'-diaminodiphenyl sulfide, 4゜4'-diaminodiphenyl sulfone, 4,4' diaminodiphenyl ether, 1,5-
Diaminonaphthalene, 3,3'-dimethyl-44'-diaminobiphenyl, 3,4'-diaminobenzanilide, 3,4'-diaminodiphenyl ether, 3,3'
-Diaminobenzophenone, 3.4'-diaminobenzophenone, 4.4'-diaminobenzophenone, 2,2-
Bis(4-(4-aminophenoxy)phenyl)propane, bis[4(4-aminophenoxy)phenyl]sulfone, 1゜4-bis(4-aminophenoxy)benzene, 1゜3-bis(4-aminophenoxy) ) Benzene, 1
゜3-bis(3-aminophenoxy)benzene, 9゜9
-bis(4-aminophenyl)-10-hydroanthracene, 9.9-bis(4-aminophenyl)fluorene, 4.4'-methylene-bis(2chloroaniline), 2
．． 2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 22'-dichloro-4,4-diamino-5
, 5'-dimethoxybiphenyl, 3,3'-dimethoxy-
Aromatic diamines such as 4,4'-diaminobiphenyl, ■
, 1'-methaxylylene diamine, 1.3 propane diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, 4
,4'-dimethylhbutamethylenediamine,! , 4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7-methanoindanilene shimethylene diamine, tricyclo(6,2,1,O”・7]undecylendimethyldiamine, etc.) or an alicyclic diamine, and the following formula: [Here, R9 is an alkyl group having 1 to 12 carbon atoms such as a methyl group, ethyl group, or propyl group, an alicyclic group such as a cyclohexyl group, or an aromatic group such as a phenyl group. group, p is 1 to
an integer of 20, and q is an integer of 1 to 3].

(d) Person ■ 1' Report The production of polymer (1) by the first method is based on the general formula (II
) and/or the dicarboxylic acid dihalide of general formula (III) and the diamine compound of general formula (IV).

(i) The reaction between the dicarboxylic acid of general formula (■) and the diamine compound of general formula (IV) is carried out in the presence of an acidic or basic catalyst at a high temperature of 100 to 250° C. while dehydrating.

Examples of the reaction catalyst used in this reaction include acidic compounds such as p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid, and organic amines such as pyridine, lutidine, and collidine.

Further, as the reaction solvent, those illustrated in connection with the production of the dicarboxylic acid of general formula (n) can be mentioned, and if necessary, hydrocarbon solvents such as toluene, xylene, and L-butylbenzene can also be used in combination.

(ii) The reaction between the dicarboxylic acid dihalide of general formula (I [
It is carried out at a temperature of 80°C. Examples of the basic catalyst include organic amines such as triethylamine, pyridine, lutidine, and collidine.

Further, examples of the reaction solvent include those exemplified in connection with the production of the dicarboxylic acid of general formula (Il).

In addition, the usage ratio of the dicarboxylic acid or the dicarboxylic acid dihalide and the diamine compound is usually
The amount of the diamine compound is 0.5 to 2 mol, preferably 0.8 to 1.2 mol, per 1 mol of dicarboxylic acid or dicarboxylic acid dihalide.

If the amount of the diamine compound used is outside the entire range, a high molecular weight polymer cannot be obtained, and it is difficult to form a good coating film as a liquid crystal aligning film, which is the object of the present invention.

(iii) dicarboxylic acid of general formula (II) and general formula (
The polymer (1) of the present invention can also be produced by using the dicarboxylic acid dihalide of III) in combination and reacting these with a diamine compound.

In this case, the proportion of the diamine compound to be used may be 0.8 to 1.5 moles relative to the total ff11 moles of the dicarboxylic acid dihalide and the dicarboxylic acid.

Examples of the reaction solvent used include those exemplified in connection with the production of the dicarboxylic acid of general formula (II).

The reaction temperature is usually -30 to 150°C, preferably 0 to 80°C.

In the second method, the polyamic acid or its derivative for producing the polymer (1) has the general formula (IV
) A polyamic acid obtained by reacting a diamine compound of formula (V) with a tetracarboxylic dianhydride of general formula (V), or a derivative in which 90 mol% or less of the amide bonds of the polyamic acid are partially imidized. be. When the imidized amide bond in this derivative exceeds 90 mol %, it becomes difficult to form a liquid crystal alignment film with a large pretilt angle.

The reaction for producing polyamic acid from the diamine compound and the tetracarboxylic dianhydride is carried out in a solvent at -3
It can be carried out at 0-150°C, preferably 0-80°C.

Examples of the solvent used include those exemplified in connection with the production of the dicarboxylic acid of general formula (n).

As a method for partially imidizing polyamic acid,
Similar to the above in which the polyamic acid was dissolved? A dehydrating agent in an amount equivalent to the amide bond to be imidized in the polyamic acid and a basic catalyst in an amount of 50 to 300 equivalents, preferably 100 to 200 equivalents of the dehydrating agent are mixed in a container.
A method of carrying out the dehydration and ring-closing reaction at 0°C, preferably 0-150°C, can be mentioned.

Examples of the dehydrating agent used include anhydrides of organic acids such as acetic anhydride, trifluoroacetic anhydride, and propionic anhydride.

Examples of the basic catalyst include the aforementioned organic amines.

Epoxy compounds of the general formula (■) include, for example, propylene oxide, 1,2-epoxybutane, 1,2-epoxypenkune, l,2-epoxyhexane, 1,2- Epoxyhebutane, L2-epoxyoctane, 1.2-epoxynonane, 1.2-epoxydecane, 1.2-epoxyundecane, 1.2-epoxydodecane, 1.2-
Epoxytridecane, 12epoxytetradecane, 1.
Aliphatic epoxy compounds such as 2-epoxypentadecane, 1.2-epoxyhexadecane, 1,2-epoxyheptadecane, 1.2-epoxyoctadecane, 1.2-epoxynonadecane: 3,4-epoxy 1-butene, 1
12-epoxy-5-hexene, 2-epoxy-7
- Aliphatic epoxy compounds having double bonds such as octene; styrene oxide, glycidyl phenyl ether, glycidyl-4-methoxyphenyl ether, N-(2,
Aromatic epoxy compounds such as 3-epoxypropyl) phthalimide and glycidyl biphenyl ether; and halogenated epoxy compounds such as shrimp fluorohydrin, shrimp chlorohydrin, and shrimp bromohydrin. Among these, preferred are (1), 2-epoxytetradecane, 1.2-epoxypentadecane, 1.2-epoxyhexadecane, 1.2-epoxyheptadecane, and 1.2-epoxyheptadecane.
These are aliphatic epoxy compounds having a long chain alkyl group having 12 to 20 carbon atoms, such as epoxy octadecane and 1,2-epoxy nonadecane, and halogenated epoxy compounds, such as shrimp fluorohydrin.

(C) −°1′ of Δ■ The production of the polymer (1) by the second method is carried out by reacting a polyamic acid or a derivative thereof with an epoxy compound of the general formula (■). This reaction is carried out in a solvent, usually from 0 to
It is carried out at 200°C, preferably 20 to 250°C.

The amount of the epoxy compound used in the reaction is usually 0.005 to 1.0 mol, preferably 0.01 to 0.0 mol, per mol of the polyamic acid structural unit in the polyamic acid or its derivative. The ratio is .5 mol.

As the solvent used in the reaction, the solvents exemplified for the production of the dicarboxylic acid of general formula (n) can be used.

The above reaction can be carried out without the need for a catalyst, but in order to accelerate the reaction, if necessary, for example, a tertiary amine such as triethylamine, pyridine, lutidine, collidine, etc. may be added to the epoxy compound. O, O, 1~1
It is recommended to use 50 mol%, preferably 0.5 to 100 mol%.

The reaction mixtures obtained by the above first and second methods are:
Pour into a large amount of methanol to precipitate the polymer (1),
Further purification is performed by washing with methanol.

The intrinsic viscosity of this polymer ([) is usually 0.05 to 10
d1/g (in 30'C,,N,N-dimethylacetamide), preferably about 0.05 to 5a/g.

The content of the structural unit represented by the general formula (1) in the polymer (1) is usually about 0.1 to 90 mol%, preferably about 0.5 to 50 mol%.

The polymer (1) obtained as described above is dissolved in a solvent and has a solid content of 0.1 to 30% by weight, preferably 0.5% by weight.
It is used after preparing a solution of ~20% by weight.

As the solvent used here, for example, general formula (II)
The same solvents as those exemplified for the production of the dicarboxylic acid can be mentioned. This solvent also includes alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons such as -a organic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, Ethylene glycol, propylene glycol, 1,4-butanediol,
Triethylene glycol, ethylene glycol methyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, Diethylene glycol dimethyl ether, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, 0-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene isomopolymer (1”) is precipitated. They can be mixed and used to the extent that they do not cause any damage.

A liquid crystal display element using the liquid crystal alignment film of the present invention can be manufactured, for example, by the following method.

First, the polymer is applied to a substrate having a transparent electrode by a roll coater method, a spinner method, a printing method, etc. to form a coating film.
It is preferably dried at about 120 to 200°C.

The thickness of the coating film after drying is usually 0.001 to 1 μm, preferably 0.005 to 0.5 μm.

When forming a liquid crystal alignment film on a substrate, in order to further improve the adhesion between the substrate and the liquid crystal alignment film, if necessary,
It is also possible to apply a silane coupling agent, a titanium coupling agent, etc. on the substrate in advance.

In the present invention, a coating film obtained by applying the polymer to a substrate is subjected to alignment treatment to obtain a liquid crystal alignment film. The method of this orientation treatment is not particularly limited, and for example, nylon,
A rubbing method is used in which the surface of the coating film is rubbed with a roll wrapped in a cloth made of synthetic fibers such as polyester or cotton.

A liquid crystal display element using the liquid crystal alignment film of the present invention has a structure in which, for example, a pair of transparent conductive films are provided on the inner surfaces of upper and lower substrates, and a liquid crystal alignment film is provided on each transparent conductive film. to do. Furthermore, a polarizing plate is integrally provided on the outside of each substrate, a liquid crystal is sandwiched between the substrates, and the peripheral edge of the substrate is sealed with a sealing material to encapsulate the liquid crystal.

To explain more specifically the method for manufacturing a liquid crystal display element using the liquid crystal alignment film of the present invention in accordance with the example shown above, a pair of transparent conductive films having a liquid crystal alignment film formed as described above. Place the two substrates facing each other with a gap between them so that the liquid crystal alignment film is on the inside, seal the periphery with a sealant leaving a liquid crystal filling opening, and fill the gap between the two substrates with liquid crystal from the filling opening. do.

Next, the filling port is sealed with a sealant to form a liquid crystal cell, and a liquid crystal display element can be obtained by pressing, for example, perpendicular polarizing plates to the outside of the two substrates.

Substrates used in the manufacture of liquid crystal display elements using the liquid crystal alignment film of the present invention include, for example, float glass, soda glass, polyethylene terephthalate, polybutylene terephthalate-1~, polyether sulfone, polycarbonate 2-
Examples include transparent substrates made of plastics, plastics, and other materials.

As the transparent conductive film, NESA film made of SnO□, I
An ITOI model consisting of n20l-5n02 can be used. Pattern formation of these transparent conductive films can be performed by a photo-etching method, a method using a mask in advance, or the like.

As the sealant, for example, an epoxy resin containing a hardening agent and aluminum oxide spheres as spacers can be used.

The liquid crystal is not particularly limited as long as it has positive dielectric anisotropy, and liquid crystals that form nematic liquid crystals, such as Schiff-based liquid crystals, azoxy-based 7ffl products, biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals, and ester-based liquid crystals, can be used. Liquid crystal, terphenyl liquid crystal, biphenylcyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal,
Bicyclooctane liquid crystal, cupane liquid crystal, etc. are preferred. These liquid crystals are usually used as a mixture, but
May be used alone.

Furthermore, for these liquid crystals, cholestyl chloride,
Cholesteric liquid crystals such as cholesteryl nonaate and cholesteryl carbonate, and chiral agents such as those sold under the trade names C15 and CB-15 (manufactured by British Druckhouse) can also be used.

As the sealant for the filling port of the liquid crystal, organic sealants are particularly preferable because they can be used at low temperatures.

The polarizing plate used on the outside of the substrate (outside of the liquid crystal cell) is a polarizing plate made by sandwiching a polarizing film called II film, which is made by stretching and aligning polyvinyl alcohol and absorbing iodine, between cellulose acetate protective films, or H film. Examples include polarizing plates made of these.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

In addition, the measurement of the pretilt angle in the examples is (T,
J, 5cheffer, et al.
J, 8pp1. Phys,, 48°17
83 (1977), F. Nakano, et.
al,, JPN, J, Appl.

The crystal rotation method using a 1ie-Ne laser beam was carried out in accordance with the method described in Phys., 19 2013 (1980)).

Example I 2.3.5-22.4 g of tricarboxycyclopentyl acetic anhydride and 48.5 g of l-hexadecanol
was dissolved in 1347 g of N,N-dimethylacetamide and reacted at 80"C for 5 hours. The resulting reaction product solution was cooled in a water bath and maintained at 0 to 5 cm while stirring. 23.8 g of thionyl chloride was added dropwise over 1 hour.

After completion of the dropwise addition, the temperature was returned to room temperature and left for one day and night. Next, 38.0 g of triethylamine was added at room temperature and 4.4'-diaminodiphenylmethane 99.0 g was added with stirring.
Add 1g slowly over 30 minutes, and add 2.
3.89.7 g of 5-tricarboxycyclopentyl acetic dianhydride was added. After reacting at room temperature for 200 hours,
The reaction mixture was added dropwise into approximately 10 methanol to precipitate the resulting polymer. The precipitated polymer was filtered out using a glass filter, and then the precipitated polymer was filtered out using a glass filter. After washing with methanol, it was dried under reduced pressure.

The intrinsic viscosity of the polymer obtained as described above is 30
When measured in °C, N, N-dimethylacetamide, it was 0.9M! /g. Further, the content of the structural unit represented by the general formula (1) in the obtained polymer was 20 mol%.

Next, a solution of the obtained polymer in N,N-dimethylacetamide (solid content concentration: 5% by weight) was prepared, and this solution was filtered through a filter with a pore size of 1 μm to remove insoluble matter and obtain a homogeneous solution. Ta.

This solution was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of ITO using a spinner at a rotation speed of 3.00 Or.
, p, m for 3 minutes, and then dried at 180'C for 3 hours to obtain a liquid crystal alignment film with a dry film thickness of 0.1 μm.

Using a rubbing machine equipped with a roll wrapped with nylon cloth, the obtained liquid crystal alignment film was rotated at 5 rolls.
The rubbing process was performed at a stage movement speed of 1 cm/sec.

Next, an epoxy resin adhesive containing aluminum oxide spheres with a diameter of 17 μm was applied by screen printing to the outer edge of each side of the pair of substrates having the rubbed liquid crystal alignment film, and then the pair of substrates were rubbed in the upper and lower directions. They were stacked in opposite directions and pressed together to harden the adhesive, leaving a chamber inside to be filled with liquid crystal.

Next, after injecting a nematic liquid crystal (manufactured by Merck & Co., Ltd., ZLI-1365) from the liquid crystal filling port formed in the adhesive layer, an epoxy adhesive (manufactured by Mitsui Toatsu Chemical Co., Ltd., Structbond A liquid crystal cell was prepared by sealing the liquid crystal filling port with 5A).

The orientation of the obtained liquid crystal cell was good, and the pretilt angle was measured to be 12°.

Example 2 A liquid crystal cell was prepared in the same manner as in Example 1 except that 54.1 g of ■-octadecanol was used instead of 1-hexadecanol, and the pretilt angle was measured to be 8°. .

Example 3 2.3.5-) 22.4 g of lycarboxycyclopentyl acetic dianhydride and 19.8 g of 4.4'-diaminodiphenylmethane were added to 380 g of N-methyl-2-pyrrolidone.
．． Polyamic acid was produced by dissolving the mixture in 2g of the solution and reacting at 60°C with stirring for 6 hours. The intrinsic viscosity of the obtained polyamic acid was measured in N,N-dimethylacetamide at 30°C and was found to be 1.58 ca/g. In addition, the general formula ([) in the obtained polyamic acid
The content of the structural unit represented by was 20 mol%.

Next, the obtained polyamic acid was dissolved in 422.3 g of N-methyl 2-pyrrolidone to a concentration of 5% by weight, and 0.158 g of pyridine and 9.9 g of 1,2-epoxyhexadecane were dissolved.
62 g was added and reacted at 80°C for 6 hours without stirring. The obtained reaction mixture was poured into a large amount of methanol, and the produced polymer was precipitated while cooling. The obtained polymer was filtered, washed with a small amount of methanol, and then dried under reduced pressure.

A solution of the obtained polymer in N-methyl-2-pyrrolidone (
Solid content concentration: 5% by weight) was prepared, and insoluble matter was removed by filtration through a filter with a pore size of 1 μm to obtain a homogeneous solution.

Using this solution, a liquid crystal mole was prepared in the same manner as in Example 1. The alignment of this liquid crystal cell was good, and the pretilt angle was 4.8°.

Example 4 Example 3 except that 10.7 g of 1,2 epoxy octadecane was used instead of 1,2-epoxy hexadecane.
A liquid crystal cell was prepared in the same manner as above. The orientation of the obtained liquid crystal cell was good, and the pretilt angle was 8.2°.

Example 5 22.4 g of 2.3.5-tricarboxycyclopentyl acetic anhydride and 19.8 g of 4.4'-diaminodiphenylmethane were added to 380 g of N-methyl-2-pyrrolidone.
．． Polyamic acid was prepared by dissolving 2g of the solution and reacting for 6 hours while maintaining the temperature at 60°C and stirring. Next, 422.3 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid.
7.91 g of pyridine and 10.2 g of acetic anhydride were added, and the reaction mixture was reacted at 120"C for 3 hours. The resulting reaction mixture was poured into a large amount of methanol. The produced polymer was precipitated. The obtained polymer was filtered off, further washed with methanol, and then dried under reduced pressure.

When the intrinsic viscosity of the obtained polymer was measured, it was found to be 1.6.
3/g (30°C, N,N-dimethylacetamide), and '+1-NMI?' by dissolving the polymer in deuterated dimethyl sulfoxide. As a result of measuring the spectrum, it was found that in this polymer, 55% of the amide bonds existing in the polyamic acid before reaction were imide bonds. Further, the content of the structural unit represented by the general formula (1) in the obtained polymer was 20 mol%.

This polymer was dissolved in N-methyl-2-pyrrolidone solution to a concentration of 5% by weight, and 0.158 g of pyridine and 1.
9.62 g of 2-epoxyhexadecane was added and reacted.

An N-methyl-2-pyrrolidone solution (solid content concentration: 5% by weight) of the obtained reaction product was prepared and filtered through a filter with a pore size of 1 μm to remove insoluble matter to obtain a homogeneous solution.

Using this solution, a night crystal cell was produced in the same manner as in Example 1). The alignment of this liquid crystal cell was good, and the pretilt angle was 6.5°.

Example 6 Example 5 except that 10.7 g of 1.2-epoxyoctadecane was used instead of 1.2-epoxyhexadecane.
A liquid crystal cell was prepared in the same manner as above. The alignment of this liquid crystal cell was good, and the pretilt angle was 10.3°.

Example 7 (1) A liquid crystal cell was produced in the same manner as in Example 5, except that 3.04 g of shrimp fluorohydrin was used instead of 2-epoxyhexadecane. The alignment of this liquid crystal cell was good, and the pretilt angle was 3.5°.

〔Effect of the invention〕

The liquid crystal alignment film of the present invention has good alignment properties and a large pretilt angle, and is particularly suitable for use in SBE display elements.

In addition, the liquid crystal display element using the liquid crystal alignment film of the present invention can be made into an SBE display element, a T
It can be suitably used for any liquid crystal display element such as an N-type display element or a ferroelectric liquid crystal display element.

Furthermore, the liquid crystal display element using the liquid crystal alignment film of the present invention has excellent liquid crystal alignment and reliability, and can be effectively used in various devices by combining the polarization of linearly polarizing plates and circularly polarizing plates. It can be used, for example, in display devices such as calculators, wristwatches, table clocks, coefficient display boards, word processing sensors, personal computers, and late night televisions.

Agent Patent Attorney Shushi Iwamiya

Claims (1)

[Claims] General formula: ▲Mathematical formula, chemical formula, table, etc.▼(I) [Here, R^1 is a tetravalent alicyclic group, R^2 is a divalent organic group, R^ 3, R^4, R^5, R^6 and R^7 may be the same or different, and are an alkyl group, alkenyl group or phenyl group which may be substituted with a hydrogen atom, a halogen atom or a hydroxyl group, A is a divalent alicyclic group or aromatic group that may be substituted with a halogen atom, n is 0 or 1, and R^8 is a hydrogen atom or a formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R^3, R^4, R^5, R^6, R^7,
A and n are the same as above) A liquid crystal aligning film obtained by aligning a film made of a polymer having a structure represented by the following in its repeating unit.