JP2002088241A - Liquid crystal aligning agent and liquid crystal display element obtained using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal aligning agent excellent in electrical characteristics such as voltage retention, charge accumulation and the like, liquid crystal aligning properties, a liquid crystal tilt alignment angle and the like, and also excellent in printing properties on a substrate and resistance to a rubbing treatment of a coated film when converted to an alignment film for a liquid crystal display element, and to provide a liquid crystal display element obtained using the same. SOLUTION: The liquid crystal aligning agent is composed of a resin component, which comprises a composition comprising (A) a polyimide precursor comprising a diamine component having a side chain and a tetracarboxylic acid component having an alicyclic structure and (B) a polyimide precursor comprising a tetracarboxylic acid component having an alicyclic structure, where the ratio of the solid content of the polyimide precursor (A) to the total solid content is 5-95 wt.%. The liquid crystal display element is obtained using the liquid crystal aligning agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid crystal alignment agent for a liquid crystal display device. More specifically, a liquid crystal alignment agent capable of obtaining a liquid crystal alignment film having excellent coating film uniformity at the time of printing, and having a high liquid crystal tilt alignment angle and good electrical characteristics, and a liquid crystal display device using the liquid crystal alignment agent About.

[0002]

2. Description of the Related Art At present, as an alignment film for a liquid crystal display element,
Apply a solution of polyimide precursor or soluble polyimide,
Performing a rubbing treatment after firing is widely used industrially.

The characteristics required of this liquid crystal alignment film include a good liquid crystal alignment and a stable and appropriate size of the liquid crystal tilt alignment angle, and a voltage holding characteristic in a liquid crystal cell using an active matrix driving method. Also, electrical characteristics such as charge storage characteristics are important. On the other hand, from the viewpoint of manufacturing a liquid crystal cell, printability of a liquid crystal alignment treatment agent on a substrate and resistance of the coating film to rubbing treatment are extremely important characteristics.

Conventionally, it is difficult to obtain an alignment film having satisfactory electrical characteristics with a liquid crystal alignment treatment agent using a polyimide precursor, although it is excellent in printability. Although the electrical properties of the film were excellent, the printability was poor and the rubbing resistance of the coating film was low.

On the other hand, the present applicant has proposed a liquid crystal alignment treating agent in which a soluble polyimide and a polyimide precursor are mixed (Japanese Patent Application Laid-Open No. 8-220541). In this case, a liquid crystal alignment film having excellent liquid crystal alignment characteristics, electrical characteristics, and rubbing resistance was obtained, but the printability of the liquid crystal alignment treatment agent on the substrate was not always sufficient.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an alignment film for a liquid crystal display device which is excellent in electrical characteristics such as voltage holding ratio and charge accumulation, liquid crystal alignment, and liquid crystal tilt alignment angle. In addition, it is an object of the present invention to provide a liquid crystal alignment agent excellent in printability on a substrate and resistance to rubbing of a coating film, and a liquid crystal display device using the same.

[0007]

Means for Solving the Problems The present inventors have made intensive studies on the above problems and completed the present invention. That is, the present invention is represented by a repeating unit of the general formula I and has a reduced viscosity of 0.05 to
It is represented by a polyimide precursor (A) having a concentration of 3.0 dl / g (concentration: 0.5 g / dl in N-methylpyrrolidone at a temperature of 30 ° C.) and a repeating unit represented by the following general formula II.
A polyimide precursor composition in which a polyimide precursor (B) having a concentration of 0.5 to 3.0 dl / g (in N-methylpyrrolidone at a temperature of 30 ° C., a concentration of 0.5 g / dl) is mixed,
The present invention relates to a liquid crystal alignment treatment agent, wherein the solid content ratio of the polyimide precursor (A) to the total solid content is 5 to 95% by weight.

[0008]

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(In the formula I, R ¹ is a tetravalent organic group having an aliphatic cyclic structure, and ¹⁰ to 95 mol% of R ² is a divalent organic group selected from at least one of the following (1): And 5 mol% or more of R ² represents a divalent organic group selected from at least one of the following (2).)

[0010]

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(In the formula (1), X ¹ and X ² each independently represent a single bond or an ether bond, an amide bond or a C 1 -C 1
5 represents a linear alkyl group or an alkyl group having a branched structure having 1 to 5 carbon atoms, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
R ⁸ each independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms; R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 3 carbon atoms or a phenylene group;
a and b are integers of 0 to 3; c, d and e are each 1 to 3
Indicates an integer. )

[0012]

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In the formula (2), R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a substituent having 6 or more carbon atoms, and X ³ , X ⁴ ,
X ⁷ , X ⁸ , X ¹⁰ and X ¹¹ each independently represent a single bond, an ether bond, an ester bond or an amide bond, and X ⁵ represents a single bond or a linear alkyl group having 1 to 5 carbon atoms or 1 carbon atom. An alkyl group having a branched structure of from 5 to 5,
X ⁶ and X ⁹ represent methine or nitrogen, f represents an integer of 0 to 3, and g represents an integer of 1 to 3. )

[0014]

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(In the formula II, R ¹⁷ represents a tetravalent organic group, at least 10 mol% of which is a tetravalent organic group having an aliphatic cyclic structure, and R ¹⁸ represents a divalent organic group. )) The present invention also relates to a liquid crystal display device using the above liquid crystal aligning agent.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The liquid crystal alignment treatment agent in the present invention is applied on a substrate with electrodes, dried and baked to form a polyimide film, and rubbing the film surface to be used as a liquid crystal alignment film.

The resin component constituting the liquid crystal alignment treating agent of the present invention comprises a polyimide precursor (A) having a side chain represented by the above general formula I and a polyimide precursor (B) represented by the above general formula II )).

Here, the method for obtaining the polyimide precursors of the general formulas I and II is not particularly limited.
Generally, it can be obtained by reacting and polymerizing tetracarboxylic dianhydride and its derivative with diamine.

The tetracarboxylic dianhydride and its derivative used for obtaining the polyimide precursor (A) of the general formula I must necessarily have an aliphatic cyclic structure, but preferably have a tetracarboxylic acid The tetravalent organic group constituting the following is (3)

[0020]

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(In the formula (3), R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently hydrogen or an organic group having 1 to 4 carbon atoms;
R ²³ represents hydrogen, fluorine, or an organic group having 1 to 2 carbon atoms, and R ²⁴ represents hydrogen, fluorine, or an organic group having 1 to 4 carbon atoms. And the like, tetracarboxylic acids and dianhydrides thereof, dicarboxylic diacid halides thereof, and the like, more preferably 1, 2, 3,
4-cyclobutanetetracarboxylic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, bicyclo [3,3,0] -octane-2,
4,6,8-tetracarboxylic acid, dianhydrides thereof, dicarboxylic acid diacid halides and the like.
These may be used alone or in combination of two or more.

10 to 95 mol% of the diamine used to obtain the polyimide precursor of the general formula I has the following structure:

[0023]

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(Wherein X ¹ and X ² each independently represent a single bond, an ether bond, an amide bond, a linear alkyl group having 1 to 5 carbon atoms or an alkyl group having a branched structure having 1 to 5 carbon atoms) R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² each independently represent Represents an alkyl group having 1 to 3 carbon atoms or a phenylene group;
Represents an integer of 0 to 3, and c, d, and e each represent an integer of 1 to 3. And at least one of paraphenylenediamine, metaphenylenediamine, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and 3,4'-
Diaminodiphenyl ether 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzanilide,
1,3-bis (3-aminopropyl) -1,1,3
3, -tetramethyldisiloxane. These may be used alone or in combination of two or more. The use ratio of these diamines is 10 to 95 mol%, preferably 50 to 95 mol%, more preferably 7 to 95 mol%.
0 to 90 mol%.

Further, in order to increase the tilt angle of the liquid crystal,
The following structure,

[0026]

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(Wherein, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a substituent having 6 or more carbon atoms, and X ³ , X ⁴ ,
X ⁷ , X ⁸ , X ¹⁰ and X ¹¹ each independently represent a single bond, an ether bond, an ester bond or an amide bond, and X ⁵ represents a single bond or a linear alkyl group having 1 to 5 carbon atoms or 1 carbon atom. An alkyl group having a branched structure of from 5 to 5,
X ⁶ and X ⁹ represent methine or nitrogen, f represents an integer of 0 to 3, and g represents an integer of 1 to 3. ) Is required to be used in an amount of at least 5 mol%, preferably at least 10 mol%, more preferably at least 10 mol%, of the diamine used to obtain the polyimide precursor of the general formula I. Diamine having a cyclohexyl group, a bicyclohexyl group, a phenylcyclohexyl group, or a linear alkyl group having 12 or more carbon atoms as a side chain is 10 mol% or more.

The magnitude of the tilt angle of the liquid crystal varies depending on the size and amount of the side chain of the diamine having a side chain. If the number of carbon atoms in the side chain is less than 6, the effect of introducing the diamine cannot be expected. Is 6 or more, the introduction effect is small when the amount of the diamine used is less than 5 mol%.

The diamine used to obtain the polyimide precursor of the general formula I may be mixed with other diamines as long as the properties of the present invention are not impaired.

The tetracarboxylic dianhydride and its derivative used to obtain the polyimide precursor of the general formula II must have at least 10 mol% of an aliphatic cyclic structure. The tetravalent organic group constituting the carboxylic acid has the following (3)

[0031]

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[0032] ^{(wherein, R 19, R 20, R} 21, R 22 are each independently hydrogen or an organic group having 1 to 4 carbon atoms, R ²³
Represents hydrogen or fluorine or an organic group having 1 to 2 carbon atoms, and R ²⁴ represents hydrogen, fluorine or an organic group having 1 to 4 carbon atoms. And the like, tetracarboxylic acids and dianhydrides thereof, dicarboxylic diacid halides thereof, and the like, more preferably 1, 2, 3, 4
-Cyclobutanetetracarboxylic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, bicyclo [3,3,0] -octane-2,4,
6,8-tetracarboxylic acid, dianhydrides thereof, dicarboxylic acid diacid halides and the like. These may be used alone or in combination of two or more.

Further, among all the tetracarboxylic dianhydrides and derivatives thereof used for obtaining the polyimide precursor of the general formula II in improving the liquid crystal alignment film properties by the liquid crystal alignment treatment agent in the present invention, 1 to 90 mol% is the following (5)

[0034]

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It is preferable to use a tetracarboxylic acid composed of a tetravalent organic group selected from the group consisting of tetracarboxylic acids and dianhydrides thereof and dicarboxylic acid diacid halides thereof.
These may be used alone or in combination of two or more. More preferably, the tetracarboxylic dianhydride and its derivative are pyromellitic acid, their dianhydrides, and their dicarboxylic diacids. Halides and the like.

The diamine that can be used to obtain the polyimide precursor of the general formula II is not particularly limited,
Specific examples thereof include p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene,
6-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, diaminodiphenylmethane, diaminodiphenyl ether, , 2'-diaminodiphenylpropane, bis (3,5-diethyl-4-aminophenyl) methane,
Diaminodiphenyl sulfone, diaminobenzophenone, diaminonaphthalene, 1,4-bis (4-aminophenoxy) benzene, 1,4, -bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 1,3-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) diphenylsulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Bis (4-aminophenyl) hexafluoropropane, 2,
Aromatic diamines such as 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane;
-Aminocyclohexyl) methane, bis (4-amino-
Alicyclic diamines such as 3-methylcyclohexyl) methane and aliphatic diamines such as 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; Silicon diamines such as bis (3-aminopropyl) -1,1,3,3, -tetramethyldisiloxane are exemplified.

As a method for reacting tetracarboxylic dianhydride and its derivative with diamine to obtain a polyimide precursor, tetracarboxylic dianhydride and diamine are reacted with N-
The reaction is generally performed in an organic polar solvent such as methylpyrrolidone. At this time, the molar ratio of the tetracarboxylic dianhydride to the diamine is preferably 0.8 to 1.2. As in the ordinary polycondensation reaction, the degree of polymerization of the produced polymer increases as the molar ratio approaches 1.

If the degree of polymerization is too low, the strength of the coating film is insufficient, and if the degree of polymerization is too high, the workability in forming the coating film may be poor. Therefore, the degree of polymerization of the product in this reaction is 0.05 to 3.0 dl / g (concentration: 0.5 g / dl in N-methylpyrrolidone at a temperature of 30 ° C.) in terms of reduced viscosity of the polyimide precursor solution. Is preferred.

The temperature at which the tetracarboxylic dianhydride is reacted with the diamine is not particularly limited.
Any temperature from 0 C to 150 C, preferably from -5 C to 100 C can be selected.

Organic polar solvents usable for reacting tetracarboxylic dianhydride with diamine include N, N
-Dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ
-Butyrolactone and the like. These may be used alone or as a mixture. Furthermore, a solvent that does not dissolve the polyimide precursor may be used by mixing with the above solvent as long as the polyimide precursor generated by the polymerization reaction does not precipitate.

The polyimide precursor thus obtained can be used as it is. Alternatively, it can be used by precipitating and isolating it in a poor solvent such as methanol or ethanol, recovering it, and then re-dissolving it in a suitable solvent. Good. The solvent to be redissolved
There is no particular limitation as long as it can dissolve the obtained polyimide precursor, and N, N-dimethylformamide, N, N
N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, γ-butyrolactone and the like can be mentioned.

In order to obtain the liquid crystal alignment treating agent of the present invention from the polyimide precursors represented by the general formulas I and II obtained by the above methods, the polyimide precursor of the general formula I and the general formula The solid content ratio of the polyimide precursor of II is 5: 9
This can be achieved by mixing to a ratio of 5 to 95: 5.

The mixing ratio of the polyimide precursor of the general formula II with respect to the polyimide precursor of the general formula I can be arbitrarily set within the above range in adjusting the properties such as the tilt orientation angle of the liquid crystal, the voltage holding ratio and the charge storage characteristics. Can be selected.

The liquid crystal alignment treatment agent in the present invention may be any one as long as two kinds of polyimide precursors are uniformly mixed, and the mixing means is not particularly limited, but from the viewpoint of sufficiently mixing resins having different structures. It is preferable to dissolve each resin in an organic solvent in advance, adjust to a desired solid content concentration and a solvent composition, and then mix and stir.
The stirring time at the time of mixing varies depending on the viscosity and solid content of the solution, but is usually 0.5 to 50 hours. If the stirring time is short and mixing is insufficient, the properties may be changed during storage or use of the liquid crystal alignment treatment agent, and if the stirring time is longer than necessary, the production efficiency of the liquid crystal alignment treatment agent is deteriorated. .

The solvent used in the liquid crystal alignment treatment agent of the present invention is not particularly limited as long as it can dissolve the polyimide precursor, and examples thereof include 2-pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, Examples thereof include N-vinylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and γ-butyrolactone. Particularly, it is preferable that N-methylpyrrolidone contains at least 20% of the total polymer solution weight, and 30%. More preferably, it is contained.

Further, even a solvent which does not dissolve the polyimide precursor by itself can be used in addition to the above solvent as long as the solubility is not impaired. Examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, -Phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, dipropylene glycol monomethyl Ether, 2- (2-ethoxypropoxy)
Examples include propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and isoamyl lactate.

The content of the polyimide precursor in the liquid crystal alignment treating agent of the present invention thus obtained is not particularly limited as long as it is a homogeneous solution, but is usually 1 to 15% by weight as solid content, preferably 2 to 15% by weight. 8% by weight.

For the purpose of further improving the adhesion between the polyimide resin film and the substrate, an additive such as a coupling agent can be added to the obtained resin solution. Examples of the coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane,
Aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N
Examples thereof include functional silane-containing compounds such as-(2-aminoethyl) -3-aminopropylmethyldimethoxysilane. In addition, epoxy group-containing compounds can also be used. Not
Further, if necessary, several kinds of coupling agents may be mixed and used. The addition ratio of these coupling agents is usually 40 parts by weight or less, preferably 0.01 to 20 parts by weight, based on 100 parts by weight of the resin solids.

In the liquid crystal display device of the present invention, the liquid crystal aligning agent is applied to a substrate with electrodes, and dried, baked, rubbed, and the like to obtain a liquid crystal alignment film. Thus, a liquid crystal display element was obtained.

As a base material of the substrate with electrodes, a transparent material such as glass or plastic can be used. In a reflection type liquid crystal display device, an opaque material such as a silicon wafer can be used as long as only one substrate is used. Similarly, the electrode may be made of a material that reflects light, such as aluminum, in addition to a transparent material such as ITO, and may be used for the reflective liquid crystal display device.

The method for applying the liquid crystal alignment treatment agent in the present invention is not particularly limited, and examples thereof include a roll coater method, a spinner method, a printing method, and the like. Is widely used. The liquid crystal alignment treatment agent of the present invention has excellent coatability on a substrate, and has a feature that, for example, a uniform coating film can be obtained even when a small amount of foreign matter adheres to the substrate, and is particularly useful for a transfer printing method. It is.

Drying after the application of the alignment treatment agent is not particularly limited as long as the solvent is evaporated to such an extent that the shape of the coating film is not deformed before firing.

The firing of the liquid crystal alignment treatment agent in the present invention is performed by
It can be performed at any temperature between 100 and 350 ° C.,
Preferably it is 150-300 degreeC, More preferably, it is 200-250 degreeC. Although the conversion from the polyimide precursor to the polyimide changes depending on the firing temperature, the liquid crystal alignment treatment agent in the present invention does not necessarily need to be imidized at 100%. However, the heat treatment temperature required for the post-rubbing process, such as curing of the sealant, is 10
It is preferable to bake at a temperature higher than or equal to ° C.

[0054]

EXAMPLES Synthesis Example 1 13.88 g (0.07 mol) of 4,4'-diaminodiphenylmethane (hereinafter abbreviated as DDM) and 8.77 g (0.03 m) of 1-dodecanoxy-2,4-diaminobenzene
ol) with N-methylpyrrolidone (hereinafter abbreviated as NMP) 2
34 g, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter abbreviated as CBDA) 1
8.63 g (0.095 mol) was added and reacted at room temperature for 3 hours to prepare a polyimide precursor solution. The reduced viscosity ηsp / c of the obtained resin is 0.7 dl / g (0.5% by weight).
NMP solution, 30 ° C.). This is solid content concentration 6
%, Butyl cellosolve (hereinafter abbreviated as BCS) concentration 20%
Was diluted with NMP and BCS to obtain a polyimide precursor solution A-1.

Synthesis Example 2 19.83 g (0.1 mol) of DDM was added to 222 g of NMP
CBDA 9.81 g (0.05 mol)
l) and pyromellitic dianhydride (hereinafter abbreviated as PMDA)
9.60 g (0.044 mol) was added and reacted at room temperature for 4 hours to prepare a polyimide precursor solution. The reduced viscosity ηsp / c of the obtained resin is 0.7 dl / g (0.5% by weight).
NMP solution, 30 ° C.). This is solid content concentration 6
%, And diluted with NMP and BCS to a BCS concentration of 20% to obtain a polyimide precursor solution A-2.

Synthesis Example 3 14.87 g (0.075 mol) of DDM and 7.31 g (0.07 g) of 1-dodecanoxy-2,4-diaminobenzene
25 mol) was dissolved in 231 g of NMP, and CBD was added thereto.
A18.63 g (0.095 mol) was added, and
The mixture was reacted for a time to prepare a polyimide precursor solution. The reduced viscosity ηsp / c of the obtained resin was 0.7 dl / g (0.5% by weight NMP solution, 30 ° C.). This was diluted with NMP and BCS so that the solid content concentration was 6% and the BCS concentration was 20%, to obtain a polyimide precursor solution A-3.

Synthesis Example 4 15.86 g (0.08 mol) of DDM and 5.85 g (0.02 mol) of 1-dodecanoxy-2,4-diaminobenzene
mol) was dissolved in 229 g of NMP, and CBDA1 was added thereto.
8.63 g (0.095 mol) was added and reacted at room temperature for 3 hours to prepare a polyimide precursor solution. The reduced viscosity ηsp / c of the obtained resin was 0.7 dl / g. The NM was adjusted to a solid content of 6% and a BCS concentration of 20%.
The mixture was diluted with P and BCS to obtain a polyimide precursor solution A-4.

Synthesis Example 5 11.9 g (0.06 mol) of DDM, 8.77 g (0.03 m) of 1-dodecanoxy-2,4-diaminobenzene
ol) and 2.49 g (0.01 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane in NM
Dissolved in 229 g of P, and 18.63 g of CBDA
(0.095 mol) and reacted at room temperature for 3 hours to prepare a polyimide precursor solution. The reduced viscosity ηsp / c of the obtained resin was 0.7 dl / g (0.5% by weight NMP solution, 30 ° C.). This is solid concentration 6%, BCS
The mixture was diluted with NMP and BCS to a concentration of 20% to obtain a polyimide precursor solution A-5.

Synthesis Example 6 19.83 g (0.1 mol) of DDM was added to 255 g of NMP.
And CBDA 18.43 g (0.094 m
ol) and reacted at room temperature for 4 hours to prepare a polyimide precursor solution. The reduced viscosity ηsp / c of the obtained resin was 0.7 dl / g (0.5% by weight NMP solution, 30 ° C.). This was diluted with NMP and BCS so as to have a solid content concentration of 6% and a BCS concentration of 20% to obtain a polyimide precursor solution A-6.

Synthesis Example 7 15.86 g (0.08 mol) of DDM and 6.97 g (0.1%) of 1-hexadecanoxy-2,4-diaminobenzene
02mol) was dissolved in 235 g of NMP, and CBD was added thereto.
A18.63 g (0.095 mol) was added, and
The mixture was reacted for a time to prepare a polyimide precursor solution. The reduced viscosity ηsp / c of the obtained resin was 0.7 dl / g (0.5% by weight NMP solution, 30 ° C.). This was diluted with NMP and BCS so as to have a solid content concentration of 6% and a BCS concentration of 20% to obtain a polyimide precursor solution A-7.

Synthesis Example 8 17.84 g (0.09 mol) of DDM and 3.49 g (0.1%) of 1-hexadecanoxy-2,4-diaminobenzene
01 mol) was dissolved in 226 g of NMP, and CBD was added thereto.
A18.63 g (0.095 mol) was added, and
The mixture was reacted for a time to prepare a polyimide precursor solution. The reduced viscosity ηsp / c of the obtained resin was 0.7 dl / g (0.5% by weight NMP solution, 30 ° C.). This was diluted with NMP and BCS so as to have a solid content concentration of 6% and a BCS concentration of 20% to obtain a polyimide precursor solution A-8.

Synthesis Example 9 17.84 g (0.09 mol) of DDM and 3.78 g (0.1%) of 1-octadecanoxy-2,4-diaminobenzene
01 mol) was dissolved in 235 g of NMP, and CBD was added thereto.
A18.63 g (0.095 mol) was added, and
The mixture was reacted for a time to prepare a polyimide precursor solution. The reduced viscosity ηsp / c of the obtained resin was 0.7 dl / g (0.5% by weight NMP solution, 30 ° C.). This was diluted with NMP and BCS so that the solid content concentration was 6% and the BCS concentration was 20%, to obtain a polyimide precursor solution A-9.

Synthesis Example 10 10.81 g (0.1 mol) of p-phenylenediamine
Was dissolved in 166 g of NMP, and CBDA 18.43 was added thereto.
g (0.094 mol) was added and reacted at room temperature for 4 hours to prepare a polyimide precursor solution. The reduced viscosity ηsp / c of the obtained resin was 0.7 dl / g (0.5% by weight NMP solution, 30 ° C.). This is solid concentration 6%, BCS
The mixture was diluted with NMP and BCS to a concentration of 20% to obtain a polyimide precursor solution A-10.

Synthesis Example 11 14.2 g of 4,4′-diaminodiphenyl ether
(0.07 mol) and 8.77 g (0.03 mol) of 1-dodecanoxy-2,4-diaminobenzene in NMP2
76 g, and CBDA 18.63 g (0.0
95 mol) and reacted at room temperature for 3 hours to prepare a polyimide precursor solution. Reduced viscosity of the obtained resin ηsp /
c is 0.7 dl / g (0.5% by weight NMP solution, 30
° C). The solid content is 6% and the BCS concentration is 20.
%, And diluted with NMP and BCS to obtain a polyimide precursor solution A-11.

Synthesis Example 12 19.83 g (0.1 mol) of DDM was added to 111 g of NMP.
And γ-butyrolactone in 111 g.
A9.81g (0.05mol) and PMDA 9.60g
(0.044 mol) and reacted at room temperature for 4 hours to prepare a polyimide precursor solution. The reduced viscosity ηsp / c of the obtained resin was 0.7 dl / g (0.5% by weight NMP solution, 30 ° C.). This is solid concentration 6%, BCS
The mixture was diluted with γ-butyrolactone and BCS to a concentration of 20% to obtain a polyimide precursor solution A-12.

Synthesis Example 13 30.03 g of 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride (0.
1 mol), 9.73 g of p-phenylenediamine (0.
09 mol) and 3.77 g (0.01 mol) of 1-octadecanoxy-2,4-diaminobenzene.
In 0 g, the mixture was reacted at 50 ° C. for 20 hours to prepare a polyimide precursor intermediate solution.

50 g of this polyimide precursor intermediate solution was diluted with 100 g of NMP, 17.6 g of acetic anhydride and 8.2 g of pyridine were added as imidization catalysts, and reacted at 40 ° C. for 3 hours to obtain a polyimide resin solution. The reduced viscosity ηsp / c of the obtained resin is 0.8 dl / g (0.5 wt% NMP
Solution, 30 ° C.). This solution was poured into 500 ml of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a white polyimide resin powder. NMR confirmed that the polyimide powder was 90% imidized.

This polyimide powder was treated with a solid content of 6%, B
Γ-butyrolactone and BC so that the CS concentration becomes 20%
The resultant was dissolved with S to obtain a polyimide solution P-1.

Example 1 The polyimide precursor solution A-1 obtained in Synthesis Example 1 and the polyimide precursor solution A-2 obtained in Synthesis Example 2 were mixed at a weight ratio of 2: 8, After stirring at room temperature for 5 hours, the mixture was filtered with a filter having a pore size of 0.5 μm to prepare a liquid crystal alignment treatment agent B-1.

When this liquid crystal alignment treatment agent was printed on a glass substrate provided with a transparent electrode by a printing machine, the printed state of the coating film was uniform, and no unevenness like a scum was observed. When the liquid crystal alignment agent was spin-coated on a chromium-deposited substrate (prepared by dropping and drying a liquid in which a 6 μm spacer was dispersed in an organic solvent) which had been contaminated with foreign substances in advance, the periphery of the spacer and other No repelling of the film was observed also in the portion, and it was confirmed by an optical microscope observation that a uniform coating film was formed.

This liquid crystal alignment treatment agent was spin-coated on a glass substrate with a transparent electrode, and placed on a hot plate at 230 ° C. for 1 hour.
The substrate was baked for 5 minutes to obtain a substrate with a polyimide film having a thickness of 1000 °. After rubbing the polyimide film with a cloth, the surface condition of the film was observed using an optical microscope, and no peeling or scraping of the film was observed. This substrate was assembled with a 50 μm spacer interposed therebetween so that the rubbing direction was reversed, and the periphery was hardened with an epoxy-based adhesive.
LC-2003 (manufactured by Merck) was injected to prepare a liquid crystal cell. The liquid crystal injection port was sealed with an epoxy adhesive.

When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that uniform liquid crystal alignment without defects was obtained. In this cell, the tilt angle of the liquid crystal was measured by the crystal rotation method.
°.

Next, in order to measure the electric characteristics of the liquid crystal cell, a polyimide film was formed and rubbed in the same manner as above, and a 6 μm spacer was sprayed on the film surface, and then combined so that the rubbing directions were orthogonal. After the periphery was solidified with an epoxy-based adhesive, liquid crystal MLC-2003C (manufactured by Merck) was injected to produce a 90 ° twist liquid crystal cell. The liquid crystal injection port was sealed with an epoxy adhesive. When the alignment state of the liquid crystal in this cell was observed with a polarizing microscope, it was confirmed that uniform alignment without defects was obtained.

As a result of measuring the voltage holding ratio of this liquid crystal cell, it was confirmed that the voltage holding ratio was as high as 98% at 23 ° C. and 82% at 90 ° C. In addition, a rectangular wave of 30 Hz / ± 3 V in which 3 V DC was superimposed on the cell was applied at 23 ° C. for 60 minutes, and the residual voltage remaining in the liquid crystal cell immediately after the 3 V DC was cut was measured by an optical flicker elimination method. After that,
The charge accumulation was as small as 05 V.

Example 2 The polyimide precursor solution A-1 obtained in Synthesis Example 1 and the polyimide precursor solution A-2 obtained in Synthesis Example 2 were mixed at a weight ratio of 1: 9, After stirring at room temperature for 5 hours, the mixture was filtered through a filter having a pore size of 0.5 μm to prepare a liquid crystal alignment treatment agent B-2.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as the orientation of the liquid crystal, and the tilt angle of the liquid crystal was 3.0 °. In addition, the voltage holding ratio of the liquid crystal cell was as high as 98% at 23 ° C. and 80% at 90 ° C., and the residual voltage was 0.1 V, indicating a small charge accumulation.

Example 3 The polyimide precursor solution A-1 obtained in Synthesis Example 1 and the polyimide precursor solution A-2 obtained in Synthesis Example 2 were mixed at a weight ratio of 5: 5. After stirring at room temperature for 5 hours, the mixture was filtered through a filter having a pore size of 0.5 μm to prepare a liquid crystal alignment treatment agent B-3.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as the orientation of the liquid crystal, and the tilt angle of the liquid crystal was 4.8 °. In addition, the voltage holding ratio of the liquid crystal cell was as high as 98% at 23 ° C. and 82% at 90 ° C., and the residual voltage was as small as 0.1 V with little charge accumulation.

Example 4 The polyimide precursor solution A-3 obtained in Synthesis Example 3 and the polyimide precursor solution A-2 obtained in Synthesis Example 2 were mixed at a weight ratio of 2: 8, After stirring at room temperature for 5 hours, the mixture was filtered through a filter having a pore size of 0.5 μm to prepare a liquid crystal alignment treatment agent B-4.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as the orientation of the liquid crystal, and the tilt angle of the liquid crystal was 3.3 °. In addition, the voltage holding ratio of the liquid crystal cell was as high as 98% at 23 ° C. and 81% at 90 ° C., and the residual voltage was as low as 0.05 V and the charge accumulation was small.

Example 5 The polyimide precursor solution A-4 obtained in Synthesis Example 4 and the polyimide precursor solution A-2 obtained in Synthesis Example 2 were mixed at a weight ratio of 2: 8. After stirring at room temperature for 5 hours, the mixture was filtered with a filter having a pore size of 0.5 μm to prepare a liquid crystal alignment treatment agent B-5.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as the orientation of the liquid crystal, and the tilt angle of the liquid crystal was 3.0 °. In addition, the voltage holding ratio of the liquid crystal cell was as high as 98% at 23 ° C. and 82% at 90 ° C., and the residual voltage was as low as 0.05 V and the charge accumulation was small.

Example 6 The polyimide precursor solution A-5 obtained in Synthesis Example 5 and the polyimide precursor solution A-2 obtained in Synthesis Example 2 were mixed at a weight ratio of 2: 8. After stirring at room temperature for 5 hours, the mixture was filtered with a filter having a pore size of 0.5 μm to prepare a liquid crystal alignment treatment agent B-6.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as the orientation of the liquid crystal, and the tilt angle of the liquid crystal was 3.8 °. In addition, the voltage holding ratio of the liquid crystal cell was as high as 98% at 23 ° C. and 82% at 90 ° C., and the residual voltage was 0 V and the charge accumulation was small.

Example 7 The polyimide precursor solution A-1 obtained in Synthesis Example 1 and the polyimide precursor solution A-6 obtained in Synthesis Example 6 were mixed at a weight ratio of 2: 8, After stirring at room temperature for 5 hours, the mixture was filtered through a filter having a pore size of 0.5 μm to prepare a liquid crystal alignment treatment agent B-7.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as the orientation of the liquid crystal, and the tilt angle of the liquid crystal was 4.5 °. Further, the voltage holding ratio of the liquid crystal cell was as high as 98% at 23 ° C. and 83% at 90 ° C., and the residual voltage was as low as 0.05 V with little charge accumulation.

Example 8 The polyimide precursor solution A-7 obtained in Synthesis Example 7 and the polyimide precursor solution A-6 obtained in Synthesis Example 6 were mixed at a weight ratio of 2: 8. After stirring at room temperature for 5 hours, the mixture was filtered with a filter having a pore size of 0.5 μm to prepare a liquid crystal alignment treatment agent B-8.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as the orientation of the liquid crystal, and the tilt angle of the liquid crystal was 12 °. Further, the voltage holding ratio of the liquid crystal cell was as high as 98% at 23 ° C. and 83% at 90 ° C., and the residual voltage was as low as 0.05 V with little charge accumulation.

Example 9 The polyimide precursor solution A-8 obtained in Synthesis Example 8 and the polyimide precursor solution A-6 obtained in Synthesis Example 6 were mixed at a weight ratio of 2: 8. After stirring at room temperature for 5 hours, the mixture was filtered through a filter having a pore size of 0.5 μm to prepare a liquid crystal alignment treatment agent B-9.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as the orientation of the liquid crystal, and the tilt angle of the liquid crystal was 6.4 °. Further, the voltage holding ratio of the liquid crystal cell was as high as 98% at 23 ° C. and 83% at 90 ° C., and the residual voltage was as low as 0.05 V with little charge accumulation.

Example 10 The polyimide precursor solution A-8 obtained in Synthesis Example 8 and the polyimide precursor solution A-6 obtained in Synthesis Example 6 were mixed at a weight ratio of 25:75. After stirring at room temperature for 5 hours, the mixture was filtered with a filter having a pore size of 0.5 μm to prepare a liquid crystal alignment treatment agent B-10.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as liquid crystal orientation, and the liquid crystal tilt orientation angle was 5.8 °. Further, the voltage holding ratio of the liquid crystal cell was as high as 98% at 23 ° C. and 83% at 90 ° C., and the residual voltage was as low as 0.05 V with little charge accumulation.

Example 11 The polyimide precursor solution A-8 obtained in Synthesis Example 8 and the polyimide precursor solution A-6 obtained in Synthesis Example 6 were mixed at a weight ratio of 1: 9, After stirring at room temperature for 5 hours, the mixture was filtered with a filter having a pore size of 0.5 μm to prepare a liquid crystal alignment treatment agent B-11.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as the orientation of the liquid crystal, and the tilt angle of the liquid crystal was 4.0 °. In addition, the voltage holding ratio of the liquid crystal cell was as high as 98% at 23 ° C. and 81% at 90 ° C., and the residual voltage was as low as 0.05 V and the charge accumulation was small.

Example 12 The polyimide precursor solution A-9 obtained in Synthesis Example 9 and the polyimide precursor solution A-6 obtained in Synthesis Example 6 were mixed at a weight ratio of 2: 8. After stirring at room temperature for 5 hours, the mixture was filtered with a filter having a pore size of 0.5 μm to prepare a liquid crystal alignment treatment agent B-12.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as the orientation of the liquid crystal, and the tilt angle of the liquid crystal was 12 °. Further, the voltage holding ratio of the liquid crystal cell was as high as 98% at 23 ° C. and 83% at 90 ° C., and the residual voltage was as low as 0.05 V with little charge accumulation.

Example 13 The polyimide precursor solution A-9 obtained in Synthesis Example 9 and the polyimide precursor solution A-6 obtained in Synthesis Example 6 were mixed at a weight ratio of 1: 9, After stirring at room temperature for 5 hours, the mixture was filtered with a filter having a pore size of 0.5 μm to prepare a liquid crystal alignment treatment agent B-13.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as the orientation of the liquid crystal, and the tilt angle of the liquid crystal was 11 °. In addition, the voltage holding ratio of the liquid crystal cell was as high as 98% at 23 ° C. and 82% at 90 ° C., and the residual voltage was as low as 0.05 V and the charge accumulation was small.

Example 14 The polyimide precursor solution A-1 obtained in Synthesis Example 1 and the polyimide precursor solution A-10 obtained in Synthesis Example 10 were mixed at a weight ratio of 2: 8. After stirring at room temperature for 5 hours, the mixture was filtered through a filter having a pore size of 0.5 μm to prepare a liquid crystal alignment treatment agent B-14.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as the orientation of the liquid crystal, and the tilt angle of the liquid crystal was 4.3 °. In addition, the voltage holding ratio of the liquid crystal cell was as high as 98% at 23 ° C. and 82% at 90 ° C., and the residual voltage was as low as 0.05 V and the charge accumulation was small.

Example 15 The polyimide precursor solution A-11 obtained in Synthesis Example 11 and the polyimide precursor solution A-6 obtained in Synthesis Example 6 were mixed at a weight ratio of 2: 8. After stirring at room temperature for 5 hours, the mixture was filtered with a filter having a pore size of 0.5 μm to prepare a liquid crystal alignment treatment agent B-15.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as the orientation of the liquid crystal, and the tilt angle of the liquid crystal was 4.5 °. In addition, the voltage holding ratio of the liquid crystal cell was as high as 98% at 23 ° C. and 78% at 90 ° C., and the residual voltage was 0.1 V, and the charge accumulation was small.

Comparative Example 1 The polyimide precursor solution A-1 obtained in Synthesis Example 1 was filtered through a filter having a pore size of 0.5 μm, and the liquid crystal aligning agent C-
1 was prepared.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as the orientation of the liquid crystal, and the tilt angle of the liquid crystal was 7.1 °. Further, the voltage holding ratio of the liquid crystal cell was as high as 98% at 23 ° C. and 83% at 90 ° C. However, the residual voltage was as large as 0.5 V and the charge accumulation was large.

Comparative Example 2 The polyimide precursor solution A-5 obtained in Synthesis Example 5 was filtered through a filter having a pore size of 0.5 μm, and the liquid crystal aligning agent C-
2 was prepared.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as the orientation of the liquid crystal, and the tilt angle of the liquid crystal was 6.4 °. The voltage holding ratio of the liquid crystal cell was as high as 97% at 23 ° C. and 83% at 90 ° C. However, the residual voltage was as high as 0.45 V and the charge accumulation was large.

Comparative Example 3 The polyimide precursor solution A-2 obtained in Synthesis Example 2 was filtered through a filter having a pore size of 0.5 μm, and the liquid crystal aligning agent C-
3 was prepared.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as the orientation of the liquid crystal.
The liquid crystal tilt alignment angle was as low as 1.5 °. The voltage holding ratio of the liquid crystal cell was as low as 95% at 23 ° C. and 55% at 90 ° C. The residual voltage was as small as 0.1 V and the charge accumulation was small.

Comparative Example 4 The polyimide precursor solution A-6 obtained in Synthesis Example 6 was filtered through a filter having a pore size of 0.5 μm, and the liquid crystal aligning agent C-
4 was prepared.

This alignment agent was evaluated in the same manner as in Example 1. As a result, printability, uniformity of coating film, rubbing resistance,
All were good as in Example 1, such as the orientation of the liquid crystal.
The liquid crystal tilt alignment angle was as low as 2.3 °. The voltage holding ratio of the liquid crystal cell was as high as 98% at 23 ° C. and 82% at 90 ° C., and the residual voltage was 0.1 V and the charge accumulation was small.

Comparative Example 5 Polyimide solution P-1 obtained in Synthetic Example 13 and Synthetic Example 1
The polyimide precursor solution A-12 obtained in Step 2 was mixed at a weight ratio of 2: 8, and the mixture was stirred at room temperature for 5 hours, and then filtered through a filter having a pore size of 0.5 μm. -5 was prepared.

This alignment agent was evaluated in the same manner as in Example 1. As a result, although the state of the coating film printed on the glass substrate provided with the transparent electrode by the printing machine was uniform, a slight unevenness in the form of scum was observed. When spin-coated on a chromium-deposited substrate that had been contaminated with foreign matter or the like in advance, repelling of the film was observed, and observation with an optical microscope confirmed that fine film thickness unevenness was present. The rubbing resistance and the orientation of the liquid crystal were good. The liquid crystal tilt alignment angle was 5.6 °. The voltage holding ratio of the liquid crystal cell is 98% at 23 ° C., and 9%.
It shows a high voltage holding ratio of 80% at 0 ° C. and a residual voltage of 0.
The charge accumulation was as small as 1 V.

[0113]

The liquid crystal alignment treating agent according to the present invention is excellent in uniformity of a coating film at the time of printing, and is excellent in electric characteristics such as voltage holding ratio and charge accumulation, liquid crystal alignment, and liquid crystal alignment. A film is obtained. The liquid crystal display device having the liquid crystal alignment film formed by using the liquid crystal alignment treatment agent of the present invention has more excellent characteristics than before and the production yield is increased.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Go Go Ono 722-1, Tsuboi-cho, Funabashi-shi, Chiba Nissan Chemical Industry Co., Ltd. Electronic Materials Research Laboratory (72) Inventor Hideyuki Endo 722-1, Tsuboi-cho, Funabashi-shi, Chiba Nissan Chemical F-term (reference) in the Electronic Materials Research Laboratories of Industrial Co., Ltd. XA19 ZA09 ZA41 ZB23

Claims (9)

[Claims] 1. A compound represented by the following general formula I:
When the reduced viscosity is 0.05 to 3.0 dl / g (N at a temperature of 30 ° C.)
-Methylpyrrolidone, represented by a polyimide precursor (A) having a concentration of 0.5 g / dl) and a repeating unit represented by the following general formula II, and having a reduced viscosity of 0.05 to 3.0 dl / g (temperature of 30 ° C.)
A polyimide precursor (B) having a concentration of 0.5 g / dl in N-methylpyrrolidone, wherein the solid content ratio of the polyimide precursor (A) to the total solid content is 5 Liquid crystal alignment treating agent, characterized in that the amount is from 95 to 95% by weight. Embedded image (In the formula I, R ¹ is a tetravalent organic group having an aliphatic cyclic structure, and ¹⁰ to 95 mol% of R ² is a divalent organic group selected from at least one of the following (1); Further R
At least 5 mol% to 90 mol% of ² below (2)
Shows a divalent organic group selected from the types. ) (In (1), X ¹ and X ² each independently represent a single bond, an ether bond, an amide bond, a linear alkyl group having 1 to 5 carbon atoms or an alkyl group having a branched structure having 1 to 5 carbon atoms.) , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms;
^{9, R 10, R 11,} R 12 is each independently an alkyl group or a phenylene group having 1 to 3 carbon atoms, a, b is 0 to 3
, C, d, and e each represent an integer of 1 to 3. ) (In (2), R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ each independently represent a substituent having 6 or more carbon atoms, and X ³ , X ⁴ , X ⁷ , X ⁸ , X
¹⁰ and X ¹¹ each independently represent a single bond, an ether bond, an ester bond or an amide bond, and X ⁵ has a single bond or a linear alkyl group having 1 to 5 carbon atoms or a branched structure having 1 to 5 carbon atoms. X ⁶ and X ⁹ represent methine or nitrogen, f represents an integer of 0 to 3, and g represents an integer of 1 to 3. ) (In the formula II, R ¹⁷ represents a tetravalent organic group, of which 10 mol%
The above is a tetravalent organic group having an aliphatic cyclic structure,
¹⁸ represents a divalent organic group. ) 2. The liquid crystal alignment treatment agent according to claim 1, wherein R ¹ in the general formula I is a tetravalent organic group selected from at least one of the following (3). Embedded image (In (3), R ¹⁹ , R ²⁰ , R ²¹ , and R ²² are each independently hydrogen or an organic group having 1 to 4 carbon atoms, and R ²³ is hydrogen, fluorine, or an organic group having 1 to 2 carbon atoms. R ²⁴ represents hydrogen, fluorine or an organic group having 1 to 4 carbon atoms.) 3. The liquid crystal alignment treating agent according to claim 1, wherein the aliphatic cyclic structure of R ¹⁷ in the general formula II is a tetravalent organic group selected from at least one of the above (3). 4. The liquid crystal alignment treating agent according to claim 1, wherein R ¹ in the general formula I is a tetravalent organic group selected from at least one of the following (4). Embedded image 5. The liquid crystal according to claim 1, wherein the aliphatic cyclic structure of R ¹⁷ in the general formula II is a tetravalent organic group selected from at least one of the above (4). Alignment agent. 6. 1 to 90 mol% of R ¹⁷ in the general formula II
(However, the total molar ratio of the tetravalent organic group having an aliphatic cyclic structure of R ¹⁷ does not exceed 100 mol%.)
Is a tetravalent organic group selected from at least one of the following (5): The liquid crystal alignment treatment agent according to any one of claims 1 to 5, wherein Embedded image 7. 1 to 90 mol% of R ¹⁷ in the general formula II
(However, it does not exceed 100 mol% in total with the molar ratio of the tetravalent organic group having an aliphatic cyclic structure of R ¹⁷ ), which is the following (6): The liquid crystal alignment treating agent according to the above. Embedded image 8. The method according to claim 1, wherein 10 to 95 mol% of R ² in the general formula I is a divalent organic group selected from at least one of the following (7). Liquid crystal alignment agent. Embedded image 9. A liquid crystal display device using the liquid crystal alignment treatment agent according to claim 1. Description: