JP5061709B2 - Composition for liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

  The present invention relates to a liquid crystal alignment film composition, a liquid crystal alignment film obtained from the composition, and a liquid crystal display element having the liquid crystal alignment film.

As compositions for alignment films used for liquid crystal display elements, soluble polyimide solutions and polyamic acid solutions have been put to practical use. After these solutions are applied and dried or baked, the characteristics as alignment films are obtained by rubbing treatment. Is expressed.
However, when the alignment characteristics are expressed by rubbing, there is a problem that dust and static electricity are easily generated due to the alignment film being scraped. For example, when static electricity is generated, dust adheres to the surface of the alignment film and causes display defects. When the alignment film is used for a TFT element, circuit damage of the TFT element may occur due to dust and static electricity. Will drop.

JP 2003-55456 A JP 2005-105264 A

  There has been a demand for an alignment film in which the film is difficult to be removed by rubbing treatment. There has been a demand for a composition for an alignment film and an alignment film capable of uniformly expressing alignment characteristics by rubbing treatment. In addition, an alignment film and a liquid crystal display element that can be manufactured with a high yield have been demanded.

[1] The following formulas (1) and (2-1)
(In the formula, a broken line indicates a bond, and R ¹¹ , R ¹² , R ²¹ and R ²² are each independently an organic group having 2 to 100 carbon atoms.)
Polyester-polyamic acid (A1) having a structural unit represented by the following formulas (3) and (2-1)
(In the formula, broken lines indicate bonds, and R ²¹ , R ²² , R ³¹ , R ³² and R ³³ are each independently an organic group having 2 to 100 carbon atoms.)
The composition for liquid crystal aligning films which has the polymer A containing 1 or more chosen from the group which consists of polyester-polyimide (A2) which has a structural unit represented by these.
[2] Structural unit represented by the following formula (1)
(In the formula, a broken line indicates a bond, and R ¹¹ and R ¹² are each independently an organic group having 2 to 100 carbon atoms.)
And a structural unit represented by the following formula (2-21) and a structural unit represented by the following formula (2-22)
(In the formula, a broken line indicates a bond, and R ²¹ , R ^23, and R ²⁴ are each independently an organic group having 2 to 100 carbon atoms.)
A polyester-polyamic acid (A1) having one or more structural units selected from the group consisting of:
The structural unit represented by the following formula (3)
(In the formula, a broken line indicates a bond, and R ³¹ , R ³² and R ³³ are each independently an organic group having 2 to 100 carbon atoms.)
And a structural unit represented by the following formula (2-21) and a structural unit represented by the following formula (2-22)
(In the formula, a broken line indicates a bond, and R ²¹ , R ^23, and R ²⁴ are each independently an organic group having 2 to 100 carbon atoms.)
The composition for liquid crystal aligning films which has the polymer A containing 1 or more chosen from the group which consists of polyester-polyimide (A2) which has 1 or more structural units chosen from the group which consists of.
[3] Structural unit represented by the following formula (1)
(In the formula, a broken line indicates a bond, and R ¹¹ and R ¹² are each independently an organic group having 2 to 100 carbon atoms.)
And a structural unit represented by the following formula (2-31), a structural unit represented by the following formula (2-32), and a structural unit represented by the following formula (2-33).
(In the formula, a broken line indicates a bond, and R ²¹ , R ²⁵ , R ²⁶ and R ²⁷ are each independently an organic group having 2 to 100 carbon atoms.)
A polyester-polyamic acid (A1) having one or more structural units selected from the group consisting of:
The structural unit represented by the following formula (3)
(In the formula, a broken line indicates a bond, and R ³¹ , R ³² and R ³³ are each independently an organic group having 2 to 100 carbon atoms.)
And a structural unit represented by the following formula (2-31), a structural unit represented by the following formula (2-32), and a structural unit represented by the following formula (2-33).
(In the formula, a broken line indicates a bond, and R ²¹ , R ²⁵ , R ²⁶ and R ²⁷ are each independently an organic group having 2 to 100 carbon atoms.)
The composition for liquid crystal aligning films which has the polymer A containing 1 or more chosen from the group which consists of polyester-polyimide (A2) which has 1 or more structural units chosen from the group which consists of.

[4] Polyester-polyamic acid (A1) obtained using at least the polyvalent hydroxy compound (a1), diamine (a2), and compound (a3) having two or more acid anhydride groups, and polyester-polyamide The composition for liquid crystal aligning films which has the polymer A containing 1 or more chosen from the group which consists of polyester-polyimide (A2) obtained by imidating an acid (A1).
[5] The polyvalent hydroxy compound (a1) is represented by the following formula (5-1):
HO-R ⁵¹ -OH (5-1)
(In the formula, R ⁵¹ is an organic group having 2 to 100 carbon atoms.)
The composition for liquid crystal aligning film as described in [4] which is diol represented by these.
[6] The polyester-polyamic acid (A1) has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2-1),
(In the formula, a broken line indicates a bond, and R ¹¹ , R ¹² , R ²¹ and R ²² are each independently an organic group having 2 to 100 carbon atoms.)
Polyester-polyimide (A2) is a structural unit represented by the following formula (3) and a structural unit represented by the following formula (2-1)
(In the formula, broken lines indicate bonds, and R ²¹ , R ²² , R ³¹ , R ³² and R ³³ are each independently an organic group having 2 to 100 carbon atoms.)
The composition for a liquid crystal alignment film according to [5], comprising:
[7] The polyvalent hydroxy compound (a1) is represented by the following formula (5-2):
(In the formula, R ⁵² is an organic group having 2 to 100 carbon atoms.)
The composition for liquid crystal aligning film as described in [4] which is triol represented by these.
[8] Structural unit in which the polyester-polyamic acid (A1) is represented by the following formula (1)
(In the formula, a broken line indicates a bond, and R ¹¹ and R ¹² are each independently an organic group having 2 to 100 carbon atoms.)
And a structural unit represented by the following formula (2-21) and a structural unit represented by the following formula (2-22)
(In the formula, a broken line indicates a bond, and R ²¹ , R ^23, and R ²⁴ are each independently an organic group having 2 to 100 carbon atoms.)
Having one or more structural units selected from the group consisting of:
The structural unit in which the polyester-polyimide (A2) is represented by the following formula (3)
(In the formula, a broken line indicates a bond, and R ³¹ , R ³² and R ³³ are each independently an organic group having 2 to 100 carbon atoms.)
And a structural unit represented by the following formula (2-21) and a structural unit represented by the following formula (2-22)
(In the formula, a broken line indicates a bond, and R ²¹ , R ^23, and R ²⁴ are each independently an organic group having 2 to 100 carbon atoms.)
The composition for liquid crystal alignment film according to [7], having one or more structural units selected from the group consisting of:
[9] The polyvalent hydroxy compound (a1) is represented by the following formula (5-3):
(In the formula, R ⁵³ is an organic group having 2 to 100 carbon atoms.)
The composition for liquid crystal aligning film as described in [4] which is tetraol represented by these.

[10] Structural unit in which the polyester-polyamic acid (A1) is represented by the following formula (1)
(In the formula, a broken line indicates a bond, and R ¹¹ and R ¹² are each independently an organic group having 2 to 100 carbon atoms.)
And a structural unit represented by the following formula (2-31), a structural unit represented by the following formula (2-32), and a structural unit represented by the following formula (2-33).
(In the formula, a broken line indicates a bond, and R ²¹ , R ²⁵ , R ²⁶ and R ²⁷ are each independently an organic group having 2 to 100 carbon atoms.)
Having one or more structural units selected from the group consisting of:
The structural unit in which the polyester-polyimide (A2) is represented by the following formula (3)
(In the formula, a broken line indicates a bond, and R ³¹ , R ³² and R ³³ are each independently an organic group having 2 to 100 carbon atoms.)
And a structural unit represented by the following formula (2-31), a structural unit represented by the following formula (2-32), and a structural unit represented by the following formula (2-33).
(In the formula, a broken line indicates a bond, and R ²¹ , R ²⁵ , R ²⁶ and R ²⁷ are each independently an organic group having 2 to 100 carbon atoms.)
The composition for a liquid crystal alignment film according to [9], having one or more structural units selected from the group consisting of:
[11] The polyvalent hydroxy compound (a1) is
1 or more selected from the group consisting of
Diamine (a2)
1 or more selected from the group consisting of
Compound (a3) having two or more acid anhydride groups
The composition for liquid crystal aligning film in any one of [4]-[10] which is 1 or more chosen from the group which consists of.
[12] Polyester-polyamic acid (A1) or polyester-polyimide (A2) is 0.5 to 19 moles of amino of diamine (a2) with respect to 1 mole of hydroxy of polyvalent hydroxy compound (a1), acid anhydride The composition for liquid crystal aligning film in any one of [1]-[11] obtained by making 1.5-20 mol of anhydrides of the compound (a3) which has two or more physical groups react.

[13] The composition unit for a liquid crystal alignment film is further represented by the following formula (1):
(In the formula, a broken line indicates a bond, and R ¹¹ and R ¹² are each independently an organic group having 2 to 100 carbon atoms.)
And a structural unit represented by the following formula (4):
(In the formula, a broken line indicates a bond, and R ⁴¹ and R ⁴² are each independently an organic group having 2 to 100 carbon atoms.)
The composition for liquid crystal alignment film in any one of [1]-[12] which has the polymer B containing 1 or more chosen from the group which consists of a polyimide (B2) which has.
[14] A polyamic acid (B1) obtained by using a composition for a liquid crystal alignment film further using at least a diamine (a2) and a compound (a3) having two or more acid anhydride groups, and a polyamic acid ( The composition for liquid crystal aligning film in any one of [1]-[12] which has the polymer B containing 1 or more chosen from the group which consists of the polyimide (B2) obtained by imidating B1).

[15] Diamine (a2) is
1 or more selected from the group consisting of
Compound (a3) having two or more acid anhydride groups
The composition for liquid crystal alignment film according to [14], which is 1 or more selected from the group consisting of:

[16] The structural unit in which the polyamic acid (B1) is represented by the following formula (1)
(In the formula, a broken line indicates a bond, and R ¹¹ and R ¹² are each independently an organic group having 2 to 100 carbon atoms.)
Have
The structural unit in which polyimide (B2) is represented by the following formula (4)
(In the formula, a broken line indicates a bond, and R ⁴¹ and R ⁴² are each independently an organic group having 2 to 100 carbon atoms.)
The composition for a liquid crystal alignment film according to [14] or [15], having:
[17] The composition for liquid crystal alignment film according to any one of [13] to [16], wherein the polyamic acid (B1) and the polyimide (B2) are contained in an amount of 1 to 50% by weight based on the composition for liquid crystal alignment film. object.

[18] The composition for liquid crystal alignment film according to [12], wherein the composition for liquid crystal alignment film further contains an epoxy compound (C).
[19] The epoxy compound (C) is represented by the following formulas (C1) to (C5)
The composition for a liquid crystal alignment film according to [18], which is one or more selected from the group consisting of compounds represented by:
[20] The composition for liquid crystal alignment film according to [18] or [19], wherein the epoxy compound (C) is contained in an amount of 0.1 to 40% by weight based on the composition for liquid crystal alignment film.
[21] A liquid crystal alignment film obtained from the composition for liquid crystal alignment film described in any one of [1] to [20].
[22] A liquid crystal display device having the liquid crystal alignment film described in [21].

  In the present specification, the “polyimide” is not particularly limited as long as it is a compound having an imide structure. In the present specification, “polyamic acid” is a polyimide precursor, and is not particularly limited as long as it is a compound having both amide and carboxylic acid configurations. In the present specification, the “polyester-polyimide” is not particularly limited as long as it is a compound having both an ester structure and an imide structure. In the present specification, the “polyester-polyamic acid” is not particularly limited as long as it is a compound having a structure of both an ester and a polyamic acid.

Even if the film obtained from the composition for alignment film according to the preferred embodiment of the present invention is rubbed, the film is hardly scraped, the alignment characteristics are uniformly expressed, and an alignment film having excellent alignment characteristics can be obtained.
An alignment film obtained from the alignment film composition according to a preferred embodiment of the present invention and a liquid crystal display device using the alignment film can be produced with a high yield.
Moreover, the liquid crystal display element which concerns on the preferable aspect of this invention has high contrast.

1st aspect of this invention is a composition for liquid crystal aligning films which has the polymer A containing 1 or more chosen from the group which consists of polyester-polyamic acid (A1) and polyester-polyimide (A2).
In the second aspect of the present invention, the liquid crystal alignment film composition of the first aspect further comprises a polymer B containing one or more selected from the group consisting of polyamic acid (B1) and polyimide (B2). It is a thing.
The third aspect of the present invention is a liquid crystal alignment film obtained from the composition for liquid crystal alignment film of the present invention and a liquid crystal display device having the alignment film.

I Polymer A
The composition for liquid crystal aligning film of the 1st aspect of this invention is a composition which has the polymer A containing 1 or more chosen from the group which consists of polyester-polyamic acid (A1) and polyester-polyimide (A2).
1 Polyester-polyamic acid (A1)
1.1 Constitution of polyester-polyamic acid (A1) The polyester-polyamic acid (A1) is not particularly limited as long as it is a compound having both ester and amide constitutions, but the following three compounds are preferred.
[1] Polyester-polyamic acid (A1-1)
Compound [2] Polyester-polyamic acid (A1-2) having structural unit represented by formula (1) and structural unit represented by formula (2-1)
A structural unit represented by the formula (1), and at least one structural unit selected from the group consisting of the structural unit represented by the formula (2-21) and the structural unit represented by the formula (2-22) Compound [3] Polyester-polyamic acid (A1-3)
The structural unit represented by Formula (1), the structural unit represented by Formula (2-31), the structural unit represented by Formula (2-32), and the structure represented by Formula (2-33). Compound having one or more structural units selected from the group consisting of units

  At the terminal of the polyester-polyamic acid (A1), for example, an acid anhydride group, amino, hydroxy, or the like is configured.

R ^{11 in} Formula (1), Formula (2-1), Formula (2-21), Formula (2-22), Formula (2-31), Formula (2-32), and Formula (2-33) And R ²¹ are each independently a tetravalent organic group having 2 to 100 carbon atoms, R ²² is a divalent organic group having 2 to 100 carbon atoms, and R ²³ and R ²⁴ are each independently a trivalent carbon number. The organic group having 2 to 100 and R ²⁵ , R ²⁶ and R ²⁷ are not particularly limited as long as they are each independently a tetravalent organic group having 2 to 100 carbon atoms.

  In the present specification, the “organic group” is not particularly limited, and examples thereof include a hydrocarbon having 2 to 100 carbon atoms which may have a substituent.

Further, as the monovalent organic group, specifically, an alkoxy having 2 to 20 carbon atoms which may have a substituent, an aryloxy having 6 to 20 carbon atoms which may have a substituent, An optionally substituted amino, an optionally substituted silyl, an optionally substituted alkylthio (—SY ¹ , wherein Y ¹ has a substituent; May represent an alkyl having 2 to 20 carbon atoms.), An arylthio optionally having a substituent (-SY ² , wherein Y ² is an optionally substituted substituent having 6 to 18 carbon atoms. Aryl represents an aryl group), and optionally substituted alkylsulfonyl (—SO ₂ Y ³ , wherein Y ³ represents an optionally substituted alkyl group having 2 to 20 carbon atoms). , an arylsulfonyl optionally having substituent (-SO ₂ Y ^4,: in the formula, Y ⁴ is substituted Also represents an aryl having 6 to 18 carbon atoms.) Can be mentioned.

  In the present specification, the “C2-C20 hydrocarbon” hydrocarbon may be a saturated or unsaturated acyclic group or a saturated or unsaturated cyclic group. When the hydrocarbon having 2 to 20 carbon atoms is acyclic, it may be linear or branched. “C2-C20 hydrocarbon” includes C2-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C4-C20 alkyldienyl, C6-C6. -18 aryl, C7-20 alkylaryl, C7-20 arylalkyl, C4-20 cycloalkyl, C4-20 cycloalkenyl and the like are included.

  In the present specification, the “C 2-20 alkyl” is preferably C 2-10 alkyl, and more preferably C 2-6 alkyl. Examples of alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, dodecanyl and the like.

  In the present specification, “alkenyl having 2 to 20 carbon atoms” is preferably alkenyl having 2 to 10 carbon atoms, and more preferably alkenyl having 2 to 6 carbon atoms. Examples of alkenyl include, but are not limited to, vinyl, allyl, propenyl, isopropenyl, 2-methyl-1-propenyl, 2-methylallyl, 2-butenyl and the like.

  In the present specification, the “alkynyl having 2 to 20 carbon atoms” is preferably alkynyl having 2 to 10 carbon atoms, more preferably alkynyl having 2 to 6 carbon atoms. Examples of alkynyl include, but are not limited to, ethynyl, propynyl, butynyl and the like.

  In the present specification, “alkyl dienyl having 4 to 20 carbon atoms” is preferably alkyl dienyl having 4 to 10 carbon atoms, and more preferably alkyl dienyl having 4 to 6 carbon atoms. Examples of alkyldienyl include, but are not limited to, 1,3-butadienyl and the like.

  In the present specification, “aryl having 6 to 18 carbon atoms” is preferably aryl having 6 to 10 carbon atoms. Examples of aryl include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, phenanthryl and the like.

  In the present specification, the “alkyl aryl having 7 to 20 carbon atoms” is preferably alkyl aryl having 7 to 12 carbon atoms. Examples of alkylaryl include, but are not limited to, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, o-cumenyl, m- Examples thereof include cumenyl, p-cumenyl, mesityl and the like.

  In the present specification, the “arylalkyl having 7 to 20 carbon atoms” is preferably arylalkyl having 7 to 12 carbon atoms. Examples of arylalkyl include, but are not limited to, benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenyl Examples include butyl and 5-phenylpentyl.

  In the present specification, the “cycloalkyl having 4 to 20 carbon atoms” is preferably cycloalkyl having 4 to 10 carbon atoms. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

  In the present specification, “cycloalkenyl having 4 to 20 carbon atoms” is preferably cycloalkenyl having 4 to 10 carbon atoms. Examples of cycloalkenyl include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl and the like.

  In the present specification, “C2-C20 alkoxy” is preferably C2-C10 alkoxy, and more preferably C2-C6 alkoxy. Examples of alkoxy include, but are not limited to, ethoxy, propoxy, butoxy, pentyloxy, and the like.

  In the present specification, “aryloxy having 6 to 20 carbon atoms” is preferably aryloxy having 6 to 10 carbon atoms. Examples of aryloxy include, but are not limited to, phenyloxy, naphthyloxy, biphenyloxy, and the like.

In the present specification, “alkylthio (—SY ¹ , wherein Y ¹ represents an optionally substituted alkyl having 2 to 20 carbon atoms)” and “alkylsulfonyl (—SO ₂ Y ³ , wherein , Y ³ represents an optionally substituted alkyl having 1 to 20 carbon atoms.)] ”, Y ¹ and Y ³ are preferably alkyl having 2 to 10 carbon atoms, and 2 to 6 carbon atoms. More preferably, it is alkyl. Examples of alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, dodecanyl and the like.

In the present specification, “arylthio (—SY ² , wherein Y ² represents optionally substituted aryl having 6 to 18 carbon atoms)” and “arylsulfonyl (—SO ₂ Y ⁴ , wherein , Y ⁴ represents an optionally substituted aryl having 6 to 18 carbon atoms.)] ”, Y ² and Y ⁴ are preferably aryl having 6 to 10 carbon atoms. Examples of aryl include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, phenanthryl and the like.

  “C1-C20 hydrocarbon”, “C2-C20 alkoxy”, “C6-C20 aryloxy”, “amino”, “silyl”, “alkylthio”, “arylthio”, “alkyl” Substituents may be introduced into “sulfonyl” and “arylsulfonyl”. Examples of this substitution include ester, carboxyl, amide, alkyne, trimethylsilyl, amino, phosphonyl, thio, carbonyl, nitro, sulfo, imino, halogeno, and alkoxy. In this case, one or more substituents may be introduced at the substitutable position up to the maximum number that can be substituted, and preferably 1 to 4 substituents may be introduced. When the number of substituents is 2 or more, each substituent may be the same or different.

  In the present specification, examples of “amino optionally having a substituent” include, but are not limited to, amino, dimethylamino, methylamino, methylphenylamino, phenylamino and the like.

  In the present specification, examples of “optionally substituted silyl” include, but are not limited to, dimethylsilyl, diethylsilyl, trimethylsilyl, triethylsilyl, trimethoxysilyl, triethoxysilyl, diphenylmethyl. There are silyl, triphenylsilyl, triphenoxysilyl, dimethylmethoxysilyl, dimethylphenoxysilyl, methylmethoxyphenyl and the like.

  Specific examples of the monovalent organic group have been described above. In the present specification, specific examples of the divalent organic group include a valence of 1 in the monovalent organic group described in the present specification. The group which added one is mentioned. Similarly, in the present specification, specific examples of the trivalent organic group include groups obtained by further increasing the valence by two in the monovalent organic group described in the present specification. Specific examples of the group include groups in which the valence is further increased by three in the monovalent organic group described in the present specification.

In the present specification, R ¹¹ and R ²¹ include hydrocarbons having 2 to 100 carbon atoms. Among them, hydrocarbons having 4 to 18 carbon atoms are preferable, and may be aromatic, saturated or unsaturated cyclic or saturated or unsaturated acyclic hydrocarbon. In particular,
(In the formula, a broken line indicates a bond.)
A skeleton selected from the group consisting of skeletons represented by

In the present specification, R ²² includes a hydrocarbon having 2 to 100 carbon atoms. Among these, C2-C20 is preferable and aromatic, a saturated or unsaturated cyclic, and a saturated or unsaturated acyclic hydrocarbon may be sufficient. In the case of an acyclic hydrocarbon, it may be linear or branched. Further, the molecular skeleton may contain heteroatoms such as oxygen, nitrogen and sulfur. In particular,
(In the formula, a broken line indicates a bond.)
A skeleton selected from the group consisting of skeletons represented by

In the present specification, R ²³ includes hydrocarbons having 2 to 100 carbon atoms. Among these, C3-C20 is preferable and aromatic, a saturated or unsaturated cyclic, and a saturated or unsaturated acyclic hydrocarbon may be sufficient. In the case of an acyclic hydrocarbon, it may be linear or branched. Further, the molecular skeleton may contain heteroatoms such as oxygen, nitrogen and sulfur. In particular,
(In the formula, a broken line indicates a bond.)
A skeleton selected from the group consisting of skeletons represented by

In the present specification, R ²⁴ includes a hydrocarbon having 2 to 100 carbon atoms. Among them, 3 to 20 are preferable, and may be aromatic, saturated or unsaturated cyclic or saturated or unsaturated acyclic hydrocarbon. In the case of an acyclic hydrocarbon, it may be linear or branched. Further, the molecular skeleton may contain heteroatoms such as oxygen, nitrogen and sulfur. In particular,
(In the formula, a broken line indicates a bond. Here, in order to clarify the bonding position with OH in the formula (2-22), it is drawn including OH bonded with R ^24. )
A skeleton selected from the group consisting of skeletons represented by

In the present specification, R ²⁵ includes hydrocarbons having 2 to 100 carbon atoms. Among them, the number of carbon atoms is preferably 3 to 20, and may be aromatic, saturated or unsaturated cyclic or saturated or unsaturated acyclic hydrocarbon. In the case of an acyclic hydrocarbon, it may be linear or branched. Further, the molecular skeleton may contain heteroatoms such as oxygen, nitrogen and sulfur. In particular,
(In the formula, a broken line indicates a bond.)
A skeleton selected from the group consisting of skeletons represented by

In the present specification, R ²⁶ includes hydrocarbons having 2 to 100 carbon atoms. Among them, the number of carbon atoms is preferably 3 to 20, and may be aromatic, saturated or unsaturated cyclic or saturated or unsaturated acyclic hydrocarbon. In the case of an acyclic hydrocarbon, it may be linear or branched. Further, the molecular skeleton may contain heteroatoms such as oxygen, nitrogen and sulfur. In particular,
(In the formula, a broken line indicates a bond. Here, in order to clarify the bonding position with OH in the formula (2-32), it is drawn including OH bonded to R ^26. )
A skeleton selected from the group consisting of skeletons represented by

In the present specification, R ²⁷ includes a hydrocarbon having 2 to 100 carbon atoms. Among them, the number of carbon atoms is preferably 3 to 20, and may be aromatic, saturated or unsaturated cyclic or saturated or unsaturated acyclic hydrocarbon. In the case of an acyclic hydrocarbon, it may be linear or branched. Further, the molecular skeleton may contain heteroatoms such as oxygen, nitrogen and sulfur. In particular,
(In the formula, a broken line indicates a bond. Here, in order to clarify the bonding position with OH in formula (2-33), it is drawn including OH bonded to R ^27. )
A skeleton selected from the group consisting of skeletons represented by

  The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) in the polyester-polyamic acid (A1) contained in the composition for liquid crystal alignment film of the present invention is preferably 5,000 to 500, 000, more preferably 10,000 to 200,000.

When applying the composition for a liquid crystal alignment film of the present invention to a substrate, an operation of previously diluting the polymer component contained for film thickness adjustment with a solvent may be required. The concentration of the polyester-polyamic acid (A1) in the product is not particularly limited, but when the solid content is 40% by weight or less, the viscosity of the composition for liquid crystal alignment film is optimized, and the liquid crystal is adjusted for film thickness adjustment. When it is necessary to dilute the alignment film composition, it is preferable because a solvent can be easily mixed with the liquid crystal alignment film composition. In the spinner method or the printing method, in order to keep the film thickness good, it is often preferable to make it 20% by weight or less. In other coating methods such as dipping method and ink jet method, the polyester-polyamic acid (A1) may be further reduced in concentration. On the other hand, when the concentration of the polyester-polyamic acid (A1) is 1% by weight or more, the thickness of the resulting alignment film tends to be uniform.
Therefore, the concentration of the polyester-polyamic acid (A1) in the liquid crystal alignment film composition is preferably 1 to 50% by weight. When the composition is applied by a normal spinner method, printing method, or the like, the concentration of the polyester-polyamic acid (A1) in the liquid crystal alignment film composition is preferably 1 to 40% by weight, and preferably 1 to 15% by weight. % Is more preferable. However, when ink jet or the like is used for the varnish coating method, it may be used at a more dilute concentration (for example, 0.1 to 5% by weight).

1.2 Production Method of Polyester-Polyamide Acid (A1) The polyester-polyamide acid (A1) is, for example, a compound (a3) having at least two polyhydric hydroxy compounds (a1), diamines (a2), and acid anhydride groups. However, it is not limited to the said manufacturing method.

When the polyester-polyamic acid (A1-1) is produced using at least the polyvalent hydroxy compound (a1), the diamine (a2) and the compound (a3) having two or more acid anhydride groups, the polyester-polyamic acid ( A1-1) contained in the compound having the formula (1 R ¹¹ in the structural unit represented by) and formula (2-1) R ²¹ in the structural unit represented by the two or more anhydride groups (a3 R ²² in the structural unit represented by formula (2-1) is a residue of the polyvalent hydroxy compound (a1), and R ¹² in the structural unit represented by formula (1) is It is a residue of diamine (a2).

Similarly, when the polyester-polyamic acid (A1-2) is produced using at least the polyvalent hydroxy compound (a1), the diamine (a2), and the compound (a3) having two or more acid anhydride groups, the polyester- R ¹¹ in the structural unit represented by the formula (1) and R ²¹ in the structural unit represented by the formula (2-21) or the formula (2-22) included in the polyamic acid (A1-2) are: R ²³ in the structural unit represented by the formula (2-21) and R ²⁴ in the structural unit represented by the formula (2-22), which is a residue of the compound (a3) having two or more acid anhydride groups. Is a residue of the polyvalent hydroxy compound (a1), and R ¹² in the structural unit represented by the formula (1) is a residue of the diamine (a2).

Similarly, when the polyester-polyamic acid (A1-3) is produced using at least the polyvalent hydroxy compound (a1), the diamine (a2), and the compound (a3) having two or more acid anhydride groups, the polyester- R ¹¹ in the structural unit represented by the formula (1) contained in the polyamic acid (A1-3), and the formula (2-31), the formula (2-32) or the formula (2-33). R ²¹ in the structural unit is a residue of the compound (a3) having two or more acid anhydride groups, and R ²⁵ in the structural unit represented by the formula (2-31) is represented by the formula (2-32). R ^{26 in the} structural unit and R ²⁷ in the structural unit represented by the formula (2-33) are residues of the polyvalent hydroxy compound (a1), and R ¹² in the structural unit represented by the formula (1). Is the residue of diamine (a2).

  Hereinafter, the polyvalent hydroxy compound (a1), the diamine (a2), and the compound (a3) having two or more acid anhydride groups that can be used to obtain the polyester-polyamic acid (A1) will be described.

1.2.1 Polyvalent hydroxy compound (a1)

    The polyvalent hydroxy compound (a1) used in the synthesis of the polyester-polyamic acid (A1) in the present invention is not particularly limited as long as it has two or more hydroxy groups. For example, it is represented by the formula (5-1). A diol, a triol represented by the formula (5-2), and a tetraol represented by the formula (5-3) are exemplified.

R ^{51 in the} diol represented by the formula (5-1) is not particularly limited as long as it is a divalent organic group having 2 to 100 carbon atoms.
R ^{52 in the} triol represented by the formula (5-2) is not particularly limited as long as it is a trivalent organic group having 2 to 100 carbon atoms.
R ⁵³ in the tetraol represented by the formula (5-3) is not particularly limited as long as it is a tetravalent organic group having 2 to 100 carbon atoms.

Specific examples of the polyvalent hydroxy compound (a1) used in the synthesis of the polyester-polyamic acid (A1) in the present invention include:
Polyethylene glycol with a molecular weight of 1000 or less

Tetrapropylene glycol, polypropylene glycol with a molecular weight of 1000 or less
1,2-dodecanediol, 1,12-dodecanediol

Dipentaerythritol, bisphenol A (trade name), bisphenol S (trade name), bisphenol F (trade name), diethanolamine, and triethanolamine, trade name “SEO-2” (manufactured by Nikka Chemical Co., Ltd.), trade name “SKYCHDM” (manufactured by Shin Nippon Rika Co., Ltd.), trade name “Rikabinol HB” (manufactured by Shin Nippon Rika Co., Ltd.), and compounds of the following formula (A) can be mentioned.
(A)
(Wherein, R ^A1, R ^A3 are each independently - (CH2) x-O- ( CH2) a y-, x, y are each independently an integer of 1 to 15, R ^A2 is 1 carbon atoms -5 alkylene, m is an integer of 2-50.)

In the case of using a diol as the polyvalent hydroxy compound (a1) from the viewpoint of reducing scraping in the rubbing treatment of the liquid crystal alignment film comprising the composition for liquid crystal alignment film obtained

Is preferred,
Is more preferable.

When triol is used as the polyvalent hydroxy compound (a1)
Is preferred,
Is more preferable.

When tetraol is used as the polyvalent hydroxy compound (a1)
Is preferred,
Is more preferable.

  The polyester-polyamic acid (A1) used in the present invention is preferably triol or tetraol, and most preferably triol, rather than diol, from the viewpoint of adjusting the viscosity and molecular weight.

  The polyvalent hydroxy compound (a1) can be used alone or in combination of two or more.

1.2.2 Diamine (a2)
In the present invention, the diamine (a2) used for the synthesis of the polyester-polyamic acid (A1) is not particularly limited, but specific examples include bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, [4- (4-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone, a compound represented by the formula (b)
(B)
Wherein R ₃ and R ₄ are independently alkyl or phenyl having 1 to 3 carbon atoms, R ₅ is independently methylene, phenylene or alkyl-substituted phenylene. X is independently 1 to 1 6 is an integer, and y is an integer of 1 to 10.),
4,4'-diaminodiphenylmethane, 4,3'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2 , 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 2,2'-diaminodiphenylpropane, Benzidine, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-methylcyclohexane, bis [4- (4-amino Benzyl) phenyl] methane, 1,1-bis [4- (4-aminobenzyl) phenyl] cyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] -4-methylcyclohexane and the following formula And the like.

  Among these specific examples, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2-bis, in terms of liquid crystal orientation. [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexa Fluoropropane, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 2,2'-diaminodiphenylpropane, benzidine, 1,1-bis [4- (4-aminophenoxy) Phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-methylcyclohexane, bis [4- (4-aminobenzyl) phenyl] methane, 1,1-bis [4- (4 -Aminobenzyl) phenyl] cyclohexane, 1,1-bis [4- (4-a Minobenzyl) phenyl] -4-methylcyclohexane and the compounds represented below are preferred.

Furthermore, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane 2,2′-diaminodiphenylpropane and the following compounds are particularly preferred.

  The diamine (a2) can be used alone or in combination of two or more. Moreover, as long as this objective is achieved, it is not limited to these diamines.

1.2.3 Compound (a3) having two or more acid anhydride groups
In the present invention, the compound (a3) having two or more acid anhydride groups used for the synthesis of the polyester-polyamic acid (A1) is not particularly limited, but tetracarboxylic dianhydride is preferable. Specific examples of the compound (a3) having an acid anhydride group include a styrene-maleic anhydride copolymer, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydro. Naphthalene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, a compound represented by the following formula, and the like: Can be mentioned.

Among these specific examples, from the aspect of liquid crystal alignment
Is preferred, and
Is particularly preferred.

  Moreover, the compound (a3) which has two or more acid anhydride groups can be used individually or in combination of 2 or more types.

1.2.4 Additives to be added to polyester-polyamic acid (A1) If the polyester-polyamic acid (A1) used in the present invention has an acid anhydride group at the molecular end, it may be necessary. A monohydric alcohol can be added and reacted. The polyester-polyamic acid (A1) to which a monohydric alcohol is added is preferable because, for example, the flatness is good.

  The monohydric alcohol added is methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene. Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, phenol, borneol, maltol, linalool, terpineol, dimethylbenzyl carbinol, ethyl lactate, glycidol, 3-ethyl-3 -Hydroxymethyloxetane etc. Can.

  For example, among the specific examples of the monohydric alcohol, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, 3 from the viewpoint of improving the flatness of the obtained composition for liquid crystal alignment film. -Ethyl-3-hydroxymethyloxetane is preferred, and among these, benzyl alcohol is more preferred.

In addition, polyester-polyamic acid (A1) having an acid anhydride group at the molecular end is added to 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldisilane. Ethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxy Reaction of silicon-containing monoamines such as silane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane improves the chemical resistance of the resulting coating film, for example. The Preferable than that.
In addition, the monohydric alcohol and the silicon-containing monoamine can be simultaneously added to the polyester-polyamic acid (A1) for reaction.

1.2.5 Reaction Conditions The polyester-polyamic acid (A1) has 0.5 to 19 moles of amino of the diamine (a2) and an acid anhydride group based on 1 mole of hydroxy of the polyvalent hydroxy compound (a1). It is preferably obtained by reacting an anhydride of compound (a3) having two or more in an amount of 1.5 to 20 mol. The polyester-polyamic acid (A1) is a compound (a3) having 1 to 9 moles of amino of the diamine (a2) and two or more acid anhydride groups with respect to 1 mole of hydroxy of the polyvalent hydroxy compound (a1). It is more preferable to obtain 2 to 20 moles of the anhydride of

The solvent used for obtaining the polyester-polyamic acid (A1) is not particularly limited as long as the compound can be synthesized. For example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, Ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, γ-butyrolactone, N-methyl-2-pyrrolidone, and N, N -Dimethylacetamide, etc. Of these, methyl 3-methoxypropionate, diethylene glycol methyl ethyl ether, ethylene glycol monobutyl ether, γ-butyrolactone and N-methyl-2-pyrrolidone are preferably used.
These solvents can be used alone or as a mixed solvent of two or more. In addition to the above solvents, other solvents can be mixed and used, but the other solvents are preferably used in a proportion of 30% by weight or less.

When the solvent is used in an amount of 100 parts by weight or more based on 100 parts by weight in total of the polyvalent hydroxy compound (a1), the diamine (a2), and the compound (a3) having two or more acid anhydride groups, the reaction proceeds smoothly. Therefore, it is preferable. The reaction is preferably carried out at 10 to 200 ° C. for 0.2 to 20 hours.
When a silicon-containing monoamine is added to the polyester-polyamic acid (A1) for reaction, the reaction between the polyvalent hydroxy compound (a1), the diamine (a2), and the compound (a3) having two or more acid anhydride groups After the reaction is completed, the reaction solution is cooled to 40 ° C. or lower, and then a silicon-containing monoamine is added and reacted at 10 to 40 ° C. for 0.1 to 6 hours.
In addition, you may make it react by adding monohydric alcohol to polyester-polyamic acid (A1).

  Moreover, it does not specifically limit to the addition order to the reaction system of a reaction raw material. That is, the polyhydric hydroxy compound (a1), the diamine (a2), and the compound (a3) having two or more acid anhydride groups are simultaneously added to the solvent, and the diamine (a2) and the polyvalent hydroxy compound (a1) are reacted with each other. The compound (a3) having two or more acid anhydride groups is added after being dissolved in the polyhydric hydroxy compound (a1) and the compound (a3) having two or more acid anhydride groups. After synthesizing the polymer, after adding the diamine (a2) to the copolymer, reacting the diamine (a2) and the compound (c1) having two or more acid anhydride groups in advance to synthesize the copolymer Any method such as adding a polyvalent hydroxy compound (a1) to the copolymer can be used.

2 Polyester-Polyimide (A2)
2.1 Constitution of polyester-polyimide (A2) The polyester-polyimide (A2) is not particularly limited as long as it is a compound having both ester and imide constitutions, but the following three compounds are preferred.
[1] Polyester-polyimide (A2-1)
Compound [2] polyester-polyimide (A2-2) having a structural unit represented by formula (3) and a structural unit represented by formula (2-1)
A structural unit represented by the formula (3), and at least one structural unit selected from the group consisting of the structural unit represented by the formula (2-21) and the structural unit represented by the formula (2-22) Compound [3] Polyester-Polyimide (A2-3)
The structural unit represented by Formula (3), the structural unit represented by Formula (2-31), the structural unit represented by Formula (2-32), and the structure represented by Formula (2-33). Compound having one or more structural units selected from the group consisting of units

  At the terminal of the polyester-polyimide (A2), for example, an acid anhydride group, amino, hydroxy, or the like is configured.

In formula (3), R ³¹ and R ³³ are each independently a tetravalent organic group having 2 to 100 carbon atoms, and R ³² is particularly limited if it is a divalent organic group having 2 to 100 carbon atoms. is not.

In the present specification, R ³¹ and R ³³ are each independently a tetravalent hydrocarbon having 2 to 100 carbon atoms. Among them, 3 to 20 carbon atoms are preferable, and aromatic, saturated or unsaturated cyclic groups are used. Or a saturated or unsaturated acyclic hydrocarbon. Further, the molecular skeleton may contain a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.

R ³² in the present specification includes divalent hydrocarbons having 2 to 100 carbon atoms. Among them, 3 to 20 carbon atoms are preferable, and aromatic, saturated or unsaturated cyclic or saturated or unsaturated non-carbon. It may be a cyclic hydrocarbon. Further, the molecular skeleton may contain a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.

R ¹¹ and R ²¹ in Formula (2-1), Formula (2-21), Formula (2-22), Formula (2-31), Formula (2-32), and Formula (2-33) to R ²⁷ is as described above.

  The chemical resistance of the film obtained from the composition for liquid crystal alignment film of the present invention is generally preferably higher as the polyester-polyimide (A2) has a higher molecular weight, and the solubility in the solvent is generally higher than the polyester-polyimide (A2). ) Is preferably as low as possible. Therefore, the weight average molecular weight of the polyester-polyimide (A2) contained in the composition for liquid crystal alignment film of the present invention is preferably 5,000 to 500,000, and more preferably 10,000 to 200,000. preferable.

  In the present invention, the content of polyester-polyimide (A2) in the composition for liquid crystal alignment film (when polyester-polyamic acid (A1) is also included, polyester-polyamic acid (A1) and polyester-polyimide (A2) Is not particularly limited, but is preferably 1 to 50% by weight, more preferably 1 to 40% by weight, and particularly preferably 2 to 30% by weight based on the total amount of the liquid crystal alignment film composition. Within these concentration ranges, the viscosity of the liquid crystal alignment film composition is optimal, and a coating film having a uniform thickness can be formed by various coating methods.

2.2 Production Method of Polyester-Polyimide (A2) The polyester-polyimide (A2) used in the present invention has, for example, at least two polyhydric hydroxy compounds (a1), diamines (a2) and two or more acid anhydride groups. It can manufacture by imidizing the polyester-polyamic acid (A1) manufactured using the compound (a3).
Moreover, the mixture of the polyester-polyamic acid (A1) and the polyester-polyimide (A2) is obtained by mixing the polyester-polyamic acid (A1) and the polyester-polyimide (A2), respectively, It can be produced by imidizing a part of A1).

When such a production method is used, R ³¹ and R ³³ in the structural unit represented by the formula (3) contained in the polyester-polyimide (A2-1) and the configuration represented by the formula (2-1) R ^{21 in the} unit is a residue of the compound (a3) having two or more acid anhydride groups, and R ²² in the structural unit represented by the formula (2-1) is a residue of the polyvalent hydroxy compound (a1). R ³² in the structural unit represented by the formula (3) is a residue of the diamine (a2).

Similarly, the polyester-polyamic acid (A1-2) produced using at least the polyvalent hydroxy compound (a1), the diamine (a2), and the compound (a3) having two or more acid anhydride groups is imidized. When the polyester-polyimide (A2-2) is produced, R ³¹ and R ³³ in the structural unit represented by the formula (3) contained in the polyester-polyimide (A2-2), and the formula (2-21) Alternatively, R ²¹ in the structural unit represented by the formula (2-22) is a residue of the compound (a3) having two or more acid anhydride groups, and R in the structural unit represented by the formula (2-21). ²³ and R ²⁴ in the structural unit represented by the formula (2-22) are residues of the polyvalent hydroxy compound (a1), and R ³² in the structural unit represented by the formula (3) is the diamine (a2). Residue.

Similarly, the polyester-polyamic acid (A1-3) produced using at least the polyvalent hydroxy compound (a1), the diamine (a2), and the compound (a3) having two or more acid anhydride groups is imidized. When the polyester-polyimide (A2-3) is produced, R ³¹ and R ³³ in the structural unit represented by the formula (3) contained in the polyester-polyimide (A2-3), and the formula (2-31) , R ²¹ in the structural unit represented by the formula (2-32) or the formula (2-33) is a residue of the compound (a3) having two or more acid anhydride groups, and in the formula (2-31) R ²⁵ in the structural unit represented, R ²⁶ in the structural unit represented by the formula (2-32), and R ²⁷ in the structural unit represented by the formula (2-33) are residues of the polyvalent hydroxy compound (a1). A group of formula (3) R ³² in the structural unit represented by is a residue of a diamine (a2).

II Polymer B
The composition for liquid crystal aligning film of the 2nd aspect of this invention is the polymer A containing 1 or more chosen from the group which consists of polyester-polyamic acid (A1) and polyester-polyimide (A2), and polyamic acid (B1). And a polymer B containing one or more selected from the group consisting of polyimide (B2).
1 Polyamic acid (B1)
1.1 Constitution of Polyamic Acid (B1) The polyamic acid (B1) is not particularly limited as long as it is a compound having an amide structure, but a compound having a structural unit represented by the formula (1) is preferable.
The structural unit represented by the formula (1) constituting the polyamic acid (B1) is the same as the formula (1) representing the structural unit constituting the polyester-polyamic acid (A1).

1.2 Production method of polyamic acid (B1) Polyamic acid (B1) can be produced using , for example, at least diamine (a2) and compound (a3) having two or more acid anhydride groups. It is not limited.

When the polyamic acid (B1) is produced using at least the diamine (a2) and the compound (a3) having two or more acid anhydride groups, the structure represented by the formula (1) contained in the polyamic acid (B1) R ^{11 in the} unit is a residue of the compound (a3) having two or more acid anhydride groups, and R ¹² is a residue of the diamine (a2).
The diamine (a2) and the compound (a3) having two or more acid anhydride groups that can be used to obtain the polyamic acid (B1) are diamines that can be used to obtain the polyester-polyamic acid (A1). The same as (a2) and the compound (a3) having two or more acid anhydride groups.

2 Polyimide (B2)
2.1 Constitution of polyimide (B2) The polyimide (B2) is not particularly limited as long as it is a compound having an imide constitution, but a compound having a constitutional unit represented by the formula (4) is preferable.
In formula (4) constituting the polyimide (B2), R ⁴¹ is a tetravalent organic group having 2 to 100 carbon atoms, and R ⁴² is particularly limited if it is a divalent organic group having 2 to 100 carbon atoms. is not.

R ⁴¹ in the present specification includes tetravalent hydrocarbons having 2 to 100 carbon atoms. Among them, 3 to 20 carbon atoms are preferable, and aromatic, saturated or unsaturated cyclic or saturated or unsaturated non-carbon. It may be a cyclic hydrocarbon. Further, the molecular skeleton may contain a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.

In the present specification, R ⁴² is a divalent hydrocarbon having 2 to 100 carbon atoms, and among them, 3 to 20 carbon atoms are preferable, and aromatic, saturated or unsaturated cyclic or saturated or unsaturated non-carbon. It may be a cyclic hydrocarbon. Further, the molecular skeleton may contain a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.

2.2 Production Method of Polyimide (B2) The polyimide (B2) used in the present invention is, for example, a polyamide produced using at least a diamine (a2) and a compound (a3) having two or more acid anhydride groups. It can be produced by imidizing the acid (B1).
When such a production method is used, R ⁴¹ in the structural unit represented by the formula (4) contained in the polyimide (B2) is a residue of the compound (a3) having two or more acid anhydride groups, R ⁴² is a residue of a diamine (a2).

  Moreover, the mixture of the polyamic acid (B1) and the polyimide (B2) is to mix the synthesized polyamic acid (B1) and the polyimide (B2), respectively, and imidize a part of the polyamic acid (B1). Can be manufactured by etc.

III. Mixture of Polymer A and Polymer B The liquid crystal alignment film composition of the second aspect of the present invention has at least one of polyamic acid (B1) and polyimide (B2). The content of the polyamic acid (B1) and the polyimide (B2) (when both the polyamic acid (B1) and the polyimide (B2) are included, the total of both) is not particularly limited, but the composition for liquid crystal alignment film The amount is preferably 1 to 50% by weight, more preferably 2 to 30% by weight based on the total amount. This is because these concentration ranges can maintain the effect against rubbing scraping and can further improve the orientation.

IV Epoxy compound (C)
The liquid crystal alignment film composition of the present invention may contain an epoxy compound (C) as necessary.
The epoxy compound (C) used in the present invention is not particularly limited as long as it has an epoxy, but a compound having two or more oxiranes is preferable.
In the present invention, the content of the epoxy resin in the liquid crystal alignment film composition is not particularly limited, but is preferably 0.1 to 40% by weight, and more preferably 0.2 to 30% by weight. When the concentration is within these ranges, the coating film formed from the composition for liquid crystal alignment film has good durability such that the film is hardly scraped by rubbing treatment. Further, the above concentration range is preferable because the heat resistance and chemical resistance of the coating film are improved.

Specific examples of the epoxy compound (C) include a bisphenol A type epoxy resin, a glycidyl ester type epoxy resin, an alicyclic epoxy resin, a polymer of a monomer having an oxirane, and a copolymer weight of the monomer having an oxirane and another monomer. Coalescence, etc.
More specifically, as the epoxy resin, trade names “Epicoat 807”, “Epicoat 815”, “Epicoat 825”, “Epicoat 827”, “Epicoat 828” which is a compound represented by the above formula (C4), “Epicoat 190P”, “Epicoat 191P” (manufactured by Yuka Shell Epoxy Co., Ltd.), trade names “Epicoat 1004”, “Epicoat 1256” (manufactured by Japan Epoxy Resin Co., Ltd.), trade names “Araldite CY177” ”,“ Araldite CY184 ”(manufactured by Ciba Geigy Japan), which is a compound represented by the above formula (C1), and trade names“ Celoxide 2021P ”,“ EHPE-3150 ”, which are compounds represented by the above formula (C2). ”(Manufactured by Daicel Chemical Industries, Ltd.), a trade name“ Tech ” AVG3101L "(manufactured by Mitsui Chemicals, Inc.), the compound"4,4'-methylenebis (N, N-diglycidylaniline) "(manufactured by Aldrich) represented by the above formula (C5), and the like. . Among these, the liquid crystal composition of the present invention is “Epicoat 828” which is a mixture of compounds represented by the above formula (C4) and n = 0 to 4, and “Araldite” which is a compound represented by the above formula (C1). CY184 ”(manufactured by Ciba Geigy Japan), trade name“ Celoxide 2021P ”(manufactured by Daicel Chemical Industries), which is a compound represented by the above formula (C2), and a compound represented by the above formula (C3). Including certain trade name “Techmore VG3101L” (Mitsui Chemicals), compound “4,4′-methylenebis (N, N-diglycidylaniline)” (manufactured by Aldrich) represented by the above formula (C5) Is preferable because of good transparency and flatness.

  Specific examples of the monomer having oxirane include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

  Specific examples of the oxirane-containing monomer and other monomers copolymerized include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, iso -Butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, Mention may be made of chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide and N-phenylmaleimide.

  Preferable specific examples of the monomer polymer having oxirane include polyglycidyl methacrylate. Preferred examples of the copolymer of the monomer having oxirane and another monomer include methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2 -Hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer and styrene-glycidyl methacrylate copolymer.

V Additives Added to the Composition for Liquid Crystal Alignment Film of the Present Invention The composition for liquid crystal alignment film of the present invention comprises a polyester-polyamic acid (A1) and a polyester-polyimide (A2) which is an imidized product thereof. 1 or more selected from, but depending on the required properties, surfactants, antistatic agents, coupling agents, epoxy hardeners such as trimellitic acid, aminosilicon compounds, solvents, and other additives You may have. These additives such as surfactants are used, for example, by adding them to the liquid crystal alignment film composition and mixing and dissolving them uniformly.

(1) Surfactant For example, when it is desired to improve the coatability, a surfactant that meets this purpose can be added. Specific examples of the surfactant added to the liquid crystal alignment film composition of the present invention include trade names “Byk-300”, “Byk-306”, “Byk-335”, “Byk-310”, “Byk”. -341 "," Byk-344 "," Byk-370 "(manufactured by BYK-Chemie Co., Ltd.) and other silicon surfactants, trade names" Byk-354 "," ByK-358 "," Byk-361 " Fluorine-based surfactants such as “DFX-18”, “Furgent 250”, “Furgent 251” (manufactured by Neos), etc. An agent can be mentioned.
These antistatic agents may be used alone or in admixture of two or more.
The surfactant is used to improve wettability, flatness, or coatability to the base substrate, and is used by adding 0.01 to 1% by weight in the liquid crystal alignment film composition. preferable.

(2) Antistatic agent The antistatic agent added to the composition for liquid crystal aligning films of this invention is not specifically limited, A normal antistatic agent can be used. Specific examples include metal oxides such as tin oxide, tin oxide / antimony oxide composite oxide, and tin oxide / indium oxide composite oxide, and quaternary ammonium salts.
These antistatic agents may be used alone or in admixture of two or more.
An antistatic agent is used in order to prevent electrification, and it is preferable to add and use 0.01 to 1 weight% in the composition for liquid crystal aligning films.

(3) Coupling agent The coupling agent added to the composition for liquid crystal aligning films of this invention is not specifically limited, A normal coupling agent can be used. The coupling agent to be added is preferably a silane coupling agent, and specific examples thereof include trialkoxysilane compounds and dialkoxysilane compounds. Preferably, for example, γ-vinylpropyltrimethoxysilane, γ-vinylpropyltriethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, γ-acryloylpropyl Triethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycyl Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropylmethyl Rudimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-aminoethyl-γ-iminopropylmethyldimethoxysilane, N-aminoethyl-γ-aminopropyl Trimethoxysilane, N-aminoethyl-γ-aminopropyltodiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropylmethyl Dimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercapto B pills triethoxysilane, .gamma. isocyanate propyl methyl diethoxy silane, .gamma. isocyanate propyl triethoxysilane and the like. Among these, γ-vinylpropyltrimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and the like can be given.

These coupling agents may be used alone or in combination of two or more.
The coupling agent is preferably used by adding 0.01 to 3% by weight in the liquid crystal alignment film composition.

(4) Epoxy hardener The epoxy hardener added to the composition for liquid crystal aligning films of this invention is not specifically limited, A normal epoxy hardener can be used. Specific examples include organic acid dihydrazide compounds, imidazole and derivatives thereof, dicyandiamide, aromatic amines, polyvalent carboxylic acids, and polyvalent carboxylic acid anhydrides. More specifically, dicyandiamides such as dicyandiamide, adipic acid dihydrazide, organic acid dihydrazides such as 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 2,4-diamino-6- [2′- Ethylimidazolyl- (1 ′)]-ethyltriazine, 2-phenylimidazole, 2-phenyl-4-methylimidazole, imidazole derivatives such as 2-phenyl-4-methyl-5-hydroxymethylimidazole, phthalic anhydride, Examples include merit acid and acid anhydrides such as 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride. Among these, trimellitic acid and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride having good transparency are preferable.

These epoxy curing agents may be used alone or in combination of two or more.
The epoxy curing agent is preferably used by adding 0.05 to 5% by weight in the liquid crystal alignment film composition.

(5) Aminosilicon compound An aminosilicon compound can be added to the composition for liquid crystal alignment films of the present invention. Examples of the aminosilicon compound include paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, and the like.
These aminosilicon compounds may be used alone or in combination of two or more.
The aminosilicon compound is used for improving the adhesion to the substrate, and is preferably used by adding 0.05 to 2% by weight in the composition for liquid crystal alignment film.

(6) Solvent The solvent that can be contained in the composition for liquid crystal alignment film of the present invention is not particularly limited as long as it is a solvent that can dissolve the polymer A and polymer B contained therein. The solvent widely includes solvents usually used in the production process and application of polymer components such as polyamic acid and soluble polyimide, and can be appropriately selected depending on the purpose of use.

  Examples of these solvents are as follows. Examples of aprotic polar organic solvents which are the parent solvents for polyamic acid and soluble polyimide are N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N, N-dimethyl. Acetamide, dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide, γ-butyrolactone and the like. Examples of other solvents for the purpose of improving coatability include ethylene glycol monoalkyl ethers such as alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether, and diethylene glycol monoethyl ether. Such as diethylene glycol monoalkyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether such as propylene glycol monobutyl ether, dialkyl malonate such as diethyl malonate, dipropylene glycol monomethyl ether, etc. Examples include dipropylene glycol monoalkyl ether and ester compounds such as these acetates. Among these solvents, N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Diethylene glycol methyl ethyl ether, methyl 3-methoxypropionate and the like can be particularly preferably used.

  These solvents may be used alone or in combination of two or more. Moreover, it is preferable to add and use a solvent so that solid content concentration in the composition for liquid crystal aligning films may be 1 to 60 weight%.

(7) Other additives The composition for a liquid crystal alignment film of the present invention is a polyester, an acrylic acid polymer, an acrylate within a range that does not impair the characteristics of the present invention (preferably within 20% by weight of the composition for a liquid crystal alignment film). It can also be used by mixing with a polymer component such as a polymer.
The composition for liquid crystal alignment film of the present invention includes a reaction product of polyamide or tetracarboxylic dianhydride, dicarboxylic acid or its derivative and diamine, which is a reaction product of dicarboxylic acid or its derivative and diamine. A polymer component such as a certain polyamideimide can be added within a range not to impair the object of the present invention.

VI Manufacture of Liquid Crystal Alignment Film / Liquid Crystal Display Element Substrate The composition for a liquid crystal alignment film of the present invention is formed on the surface of a substrate such as glass, or glass provided with an electrode such as an ITO (Indium Tin Oxide) electrode, a color filter, or the like. A liquid crystal alignment film can be formed by applying to the substrate surface and heating or drying the composition necessary for dehydration and ring closure reaction.

  As the substrate, for example, glass such as fluorinate glass with good smoothness, polyester such as polyethylene terephthalate and polybutylene terephthalate, epoxy resin, phenol resin, polyimide, polycarbonate, polysulfone, polyethersulfone, polyetherimide, Heat-resistant resins such as acetyl cellulose, polyamino acid ester, and aromatic polyamide, polystyrene, polyacrylic acid ester, polymethacrylic acid ester, vinyl polymers such as polyacrylamide, polyethylene, and polypropylene, fluorine-containing resins such as polyvinylidene fluoride, and the like Examples thereof include a plastic film formed from a modified product of

The liquid crystal alignment film composition can be applied to the substrate surface by a spinner method, a printing method, a dipping method, a dropping method, an ink jet method, or the like. As a process in which the composition for a liquid crystal alignment film of the present invention applied to the substrate surface is subjected to heat treatment or drying treatment necessary for dehydration / ring-closure reaction, for example, a method of heating in an oven or an infrared furnace A method of heating on a hot plate is used. The drying step is preferably performed at a relatively low temperature within a range where the solvent can be evaporated, and the heat treatment step is generally preferably performed at a temperature of about 150 to 300 ° C.
The electrode provided on the substrate may be formed by depositing a metal such as chromium on a transparent substrate such as glass using a sputtering method and then performing etching using a resist pattern of a predetermined shape as a mask. it can.

  The resin film thus cured on the substrate is subjected to an alignment treatment such as a rubbing method, a photo-alignment method, or a transfer method, whereby the resin film exhibits characteristics as a liquid crystal alignment film, and a liquid crystal alignment film is manufactured. This also manufactures a substrate for a liquid crystal display element in which a liquid crystal alignment film is formed on the substrate.

  Among these alignment treatments, it is preferable to use a rubbing method, but the conditions for the rubbing treatment are not particularly limited. In the resin film obtained from the composition for liquid crystal alignment film of the present invention, The rubbing treatment is preferably performed under the conditions of an indentation amount of 0.2 to 0.8 mm, a stage moving speed of 5 to 250 mm / sec, and a roller rotation speed of 500 to 2,000 rpm.

  The liquid crystal alignment film obtained from the composition for liquid crystal alignment film of the present invention containing the epoxy compound (C) is further tougher than the liquid crystal alignment film obtained from the composition for liquid crystal alignment film not containing the epoxy compound (C). In some cases, transparency, heat resistance, chemical resistance, flatness, adhesion, and sputtering resistance may be excellent.

VII Manufacture of Liquid Crystal Display Element The liquid crystal display element of the present invention has a spacer disposed between a plurality of liquid crystal display element substrates of the present invention or between the liquid crystal display element substrate of the present invention and a second transparent substrate. And the liquid crystal composition is sealed between the substrates. In some cases, the liquid crystal display element may further have a polarizing film attached thereto.

  The liquid crystal display element of the present invention can also be manufactured by performing a cleaning process with a cleaning liquid before and after the alignment process. Examples of the cleaning method include brushing, jet spray, steam cleaning, and ultrasonic cleaning. These methods may be performed alone or in combination. The cleaning liquid is pure water, various alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, halogen solvents such as methylene chloride, and ketones such as acetone and methyl ethyl ketone. Although it can be used, it is not limited to these. Of course, these cleaning liquids are sufficiently purified and have few impurities.

  The liquid crystal composition used in the liquid crystal display element of the present invention is not particularly limited, and various liquid crystal compositions having positive dielectric anisotropy can be used. Examples of preferred liquid crystal compositions include Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. 5-501735, Japanese Patent Laid-Open No. 8-157826, Japanese Patent Laid-Open No. 8-231960, and Japanese Patent Laid-Open No. 9-241644. (JP885272A1), JP-A-9-302346 (EP806466A1), JP-A-8-199168 (EP722998A1), JP-A-9-235552, JP-A-9-255556, JP-A-9-241463 (EP885271A1), JP-A-10-204016 (EP844229A1), JP-A-10-204436, JP-A-10-231482, JP-A-2000-087040, JP Opened in Gazette 2001-48822 It is.

  Various liquid crystal compositions having negative dielectric anisotropy can also be used. Examples of preferred liquid crystal compositions include JP-A-57-141432, JP-A-2-4725, JP-A-4-224858, JP-A-8-40953, JP-A-8-104869, Japanese Laid-Open Patent Publication No. 10-168076, Japanese Laid-Open Patent Publication No. 10-168453, Japanese Laid-Open Patent Publication No. 10-236989, Japanese Laid-Open Patent Publication No. 10-236990, Japanese Laid-Open Patent Publication No. 10-236992, Japanese Laid-Open Patent Publication No. 10-236993, Japanese Laid-open Patent Publication No. -236994, JP-A-10-237000, JP-A-10-237004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075, JP-A-10-237076 JP, 10-237448, (EP967261A1), JP 10-28. 874, JP-A-10-287875, JP-A-10-291945, JP-A-11-029581, JP-A-11-080049, JP-A-2000-256307, JP-A-2001-019965, JP-A-2001-072626, JP-A-2001-192657, and the like.

One or more optically active compounds may be added to the liquid crystal composition having a positive or negative dielectric anisotropy.
Furthermore, the composition for a liquid crystal alignment film of the present invention includes a polyamic acid, a soluble polyimide, a polyester, an acrylic polymer, and an acrylate having other compositions within a range that does not impair the characteristics of the present invention (preferably within 20 mol%). It is also possible to mix and use polymer components such as polymers. The liquid crystal alignment film composition of the present invention includes a polymer component used in the liquid crystal alignment film composition, a polyamide or a tetracarboxylic dianhydride, which is a reaction product of dicarboxylic acid or a derivative thereof and diamine. In addition, a polymer component such as polyamideimide, which is a reaction product of dicarboxylic acid or a derivative thereof and diamine, can be added within a range that does not impair the object of the present invention.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to these Examples.

Compound (a3) having two or more acid anhydride groups (tetracarboxylic dianhydride)
1,2,3,4-cyclobutanetetracarboxylic dianhydride: CBDA
Pyromellitic dianhydride: PMDA

Diamine (a2)
4,4′-diaminodiphenyl ether: APE
4,4'-diaminodiphenylmethane: DDM
1,3-bis [4- (4-aminobenzyl) phenyl] propane: BZ3
3-Benzyl-1,4-diaminobenzene: P1PDA
1,1-bis [4- (4-aminobenzyl) phenyl] -4-butylcyclohexane: 4ChB1B
3-[(4-Hexadecylphenyl) methyl] -1,4-diaminobenzene: 16P1P
3-[(4-Dodecylphenyl) methyl] -1,4-diaminobenzene
: 12P1P
3-({4- [4- (4-pentylcyclohexyl) cyclohexyl] phenyl} methyl) -1,4-diaminobenzene: 5ChChP1P
3-[(4- {4- [2- (4-Heptylcyclohexyl) ethyl] cyclohexyl} phenyl) methyl] -1,4-diaminobenzene: 7Ch2ChP1P

Polyvalent hydroxy compound (a1)
1,4-butanediol: BOH
1,5-pentanediol: POH
1,2,4-butanetriol: BTOH
2- (Hydroxymethyl) -2-methylpropane-1,3-diol: TMEOH
Tetrakis (hydroxymethyl) methane: PETOH

Epoxy resin (C)
Celoxide 2021P: SE2021P
Araldite CY177: CY177
4,4′-methylenebis (N, N-diglycidylaniline): TGDDM
Solvent N-methyl-2-pyrrolidone: NMP
γ-butyrolactone: GBL
Ethylene glycol monobutyl ether: BC
(Butyl cellosolve)

[Synthesis Example 1] Preparation of liquid crystal alignment film composition (1A) 1.96 g (10 mmol) of CBDA in a 200 ml four-necked flask equipped with a thermometer, stirrer, raw material charging inlet and nitrogen gas inlet, PMDA 2.18 g (10 mmol), 1,4-butanediol 0.36 g (4 mmol), and dehydrated NMP 84.7 g were added, and the mixture was stirred at 120 ° C. for 1 hour in a dry nitrogen stream. After cooling to 25 ° C., 3.20 g (16 mmol) of APE was added. After reacting for 30 hours while maintaining the temperature of the reaction system at 25 ° C., 38.5 g of BC and 23.1 g of GBL were added, the temperature was raised to 50 ° C. and stirring was continued, and the viscosity of the composition was 30 to 35 mPa · s. The reaction was terminated when the temperature reached s (using an E-type viscometer, 25 ° C.), and a polyester-polyamic acid liquid crystal alignment film composition (1A) having a solid content concentration of 5% by weight was obtained. The weight average molecular weight of the obtained composition was 23,000. The weight average molecular weight was measured at a column temperature of 50 ° C. using a Shimadzu GPC measuring device. The molar ratio of PMDA, CBDA, APE and BOH used was PMDA / CBDA / APE / BOH = 25/25/40/10.

[Example 1] Manufacture of liquid crystal alignment film, substrate for liquid crystal display element, and liquid crystal display element The composition 1A for liquid crystal alignment film obtained in Synthesis Example 1 is NMP / BC / GBL (= 60/25/15, weight ratio). ) To obtain a composition for liquid crystal alignment film (varnish (1A)) for coating.

Varnish (1A) was applied onto a glass substrate with an electrode using a spinner. The coating conditions were 2200 rpm and 15 seconds. After coating, the film was pre-baked at 80 ° C. for about 5 minutes, and then heat-treated at 210 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of about 75 nm. Using the rubbing treatment apparatus manufactured by Iinuma Gauge Co., Ltd., the obtained liquid crystal alignment film was 0.40 mm in the amount of pushing the rubbing cloth (hair length 1.8 mm: rayon), the stage moving speed was 60 mm / sec, The rubbing process was performed at a roller rotation speed of 1500 rpm.
When the surface of the liquid crystal alignment film after the rubbing treatment was observed with an optical microscope with a magnification of 100 times and 400 times, no traces of scraping or scraping due to rubbing were observed.

The obtained substrate for a liquid crystal display element was subjected to ultrasonic cleaning in ultrapure water for 5 minutes and then dried in an oven at 120 ° C. for 30 minutes. A 7 μm gap material was sprayed on the substrate for a liquid crystal display element with electrodes, and the surfaces on which the alignment film was formed were bonded together, and sealed with an epoxy curing agent to produce an anti-parallel cell with a gap of 7 μm. A liquid crystal composition shown below was injected into the cell, the injection port was sealed with a photocuring agent, heat treatment was performed at 110 ° C. for 30 minutes, and then the temperature was returned to room temperature to produce a liquid crystal display element.

The orientation of the liquid crystal alignment film in the liquid crystal display element was confirmed by polarization microscope observation. The composition of the liquid crystal composition used as the liquid crystal material is shown below. The NI point of this composition was 100.0 ° C., and the birefringence was 0.093.
Moreover, the orientation state of the liquid crystal display element was confirmed using a polarizing microscope in a state where no voltage was applied at room temperature. When the cell was rotated, brightness and darkness were observed, and light leakage due to alignment failure in the dark state was not observed.

[Synthesis Examples 2 to 16]
Under the same conditions as in Synthesis Example 1, except that the tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound used in the production of the liquid crystal alignment film composition and the molar ratio thereof were changed as shown in Tables 1 and 2. The compositions for liquid crystal alignment films (2A) to (16A) were produced.

[Examples 2 to 16]
A liquid crystal display element substrate was produced under the same conditions as in Example 1 except that the liquid crystal alignment film compositions (2A) to (16A) obtained in Synthesis Examples 2 to 16 were used. Observation was performed with a double and 400 times optical microscope, and the traces of the substrate surface and scraps were confirmed by rubbing. An antiparallel cell was prepared using the substrate, and the alignment state was confirmed by a polarizing microscope. The results are shown in Table 3.

[Synthesis Example 17] Synthesis of polyamic acid (17PA) In a 200 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet and a nitrogen gas inlet, 3.54 g (7.0 mmol) of 4ChB1B was added to 55 g of dehydrated NMP. After dissolution, 0.9607 g (3.5 mmol) of CBDA and 0.77 g (3.5 mmol) of PMDA were added and reacted for 30 hours while maintaining the temperature of the reaction system at 25 ° C. in a dry nitrogen stream. After adding 25 g of BC and 25 g of GBL, the temperature was raised to 50 ° C. and stirring was continued, and the reaction was terminated when the viscosity of the composition reached 30 to 35 mPa · s (using an E-type viscometer. 25 ° C.). A liquid crystal alignment film composition (17PA) containing a polyamic acid having a solid content concentration of 5% by weight was obtained. The weight average molecular weight of the obtained composition was 30,560. The weight average molecular weight was measured at a column temperature of 50 ° C. using a Shimadzu GPC measuring device.
The molar ratio of PMDA, CBDA and 4ChB1B used was PMDA / CBDA / 4ChB1B = 25/25/50.

[Synthesis Examples 18 to 28]
Under the same conditions as in Synthesis Example 17 except that the tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound used in the production of the liquid crystal alignment film composition and the molar ratio thereof were changed as shown in Tables 4 and 5. Then, liquid crystal alignment film compositions (18PA) to (28PA) were produced.

[Synthesis Example 29]
A composition for liquid crystal alignment film (12A) containing the polyester-polyamic acid obtained in Synthesis Example 12 and a composition for liquid crystal alignment film (17PA) containing the polyamic acid obtained in Synthesis Example 17 were mixed at a weight ratio of 17 PA. / 12A = 20/80 to prepare a liquid crystal alignment film composition containing polyester-polyamic acid and polyamic acid.

[Synthesis Example 30 to Synthesis Example 40]
A liquid crystal alignment film containing polyester-polyamic acid and polyamic acid by mixing a composition for liquid crystal alignment film containing polyester-polyamic acid and a composition for liquid crystal alignment film containing polyamic acid in a weight ratio as shown in Table 6 The composition for preparation was prepared.

[Example 17]
The composition for liquid crystal alignment film prepared in Synthesis Example 29 was diluted with a mixed solvent of NMP / BC / GBL (= 60/25/15, weight ratio) to adjust the solid content concentration to 3% by weight. And a composition for liquid crystal alignment film (varnish (1G)) for coating.
Using this varnish 1G, the surface of the liquid crystal alignment film was observed with an optical microscope of 100 times and 400 times by the method described in Example 1, and the trace of scraping and scraping residue were confirmed by rubbing. An antiparallel cell was prepared using the substrate, and the alignment state was confirmed by a polarizing microscope. The results are shown in Table 7.

[Examples 18 to 28]
Coating liquid crystal alignment film compositions (varnishes (2G) to (12G)) were prepared using the liquid crystal alignment film compositions obtained in Synthesis Examples 30 to 40.
A substrate for a liquid crystal display element was produced under the same conditions as in Example 17 except that these varnishes were used, and the surface of the liquid crystal alignment film was observed with a 100 × and 400 × optical microscope. We confirmed the traces and scraps. An antiparallel cell was prepared using the substrate, and the alignment state was confirmed by a polarizing microscope. The results are shown in Table 7.

[Synthesis Example 41] Synthesis of composition for liquid crystal alignment film (1B)
100.0 g of the composition for liquid crystal alignment film (1A) obtained in Synthesis Example 1 and Daicel, which is an alicyclic epoxy resin, 0.25 g (1.0 mmol) of Celoxide (trademark) 2021P were mixed to obtain a liquid crystal alignment. A film composition (1B) was prepared.

[Synthesis Examples 42 to 66] Synthesis of Composition for Liquid Crystal Alignment Film Composition for Liquid Crystal Alignment Film Containing Polyester-Polyamide Acid, Composition for Liquid Crystal Alignment Film Containing Polyamide Acid and Epoxy Resin (1.0 mmol) The composition for liquid crystal aligning films (2B)-(14B) and (1G)-(12G) containing an epoxy resin was adjusted on the same conditions as the synthesis example 41 except having used this.

[Example 29]
The composition for liquid crystal alignment film (1B) prepared in Synthesis Example 41 was diluted with a mixed solvent of NMP / BC / GBL (= 60/25/15, weight ratio) to obtain polyester-polyamic acid and epoxy resin. The varnish (1B) was manufactured by adjusting so that the total solid content concentration was 3% by weight.
According to the same method as in Example 1, the surface of the liquid crystal alignment film was observed with an optical microscope of 100 times and 400 times for this varnish (1B), and the rubbing traces and scraps were confirmed. An antiparallel cell was prepared using the substrate, and the alignment state was confirmed by a polarizing microscope. The results are shown in Table 9.

[Example 30 to Example 54]
A varnish was produced by diluting under the same conditions as in Example 29 except that the composition for liquid crystal alignment film prepared in Synthesis Examples 42 to 66 was used.
Using these varnishes, the surface of the liquid crystal alignment film was observed with an optical microscope of 100 times and 400 times by the method described in Example 1, and the traces of scrapes and scraps were confirmed by rubbing. An antiparallel cell was prepared using the substrate, and the alignment state was confirmed by a polarizing microscope.

[Comparative Example 1]
4.00 g (20 mmol) of APE and 84.7 g of dehydrated NMP were placed in a 200 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet and a nitrogen gas inlet, and dissolved under stirring in a dry nitrogen stream. While maintaining the temperature of the reaction system at 25 ° C., 1.96 g (10 mmol) of CBDA and 2.18 g (10 mmol) of PMDA were slowly added and reacted in a dry nitrogen stream for 30 hours, and then 38.7 g of BC and GBL were added. 23.1 g was added. When the temperature was raised to 50 ° C. and stirring was continued, the reaction was terminated when the viscosity of the varnish reached 30 to 35 mPa · s (using an E-type viscometer. 25 ° C.), and the solid content was 5% by weight. A polyamic acid composition (29 PA) was obtained. The weight average molecular weight of the obtained composition was 29,000. The weight average molecular weight was measured at a column temperature of 50 ° C. using a Shimadzu GPC measuring device.

  The composition (29PA) obtained as described above was diluted with a mixed solvent of NMP / BC / GBL (= 60/25/15, weight ratio) to adjust the solids concentration to 3% by weight. A varnish (29PA), which is a coating composition, was produced.

A liquid crystal alignment film, a liquid crystal display element substrate and a liquid crystal display element were produced in the same manner as in Example 1 except that varnish (29 PA) was used.
When the surface of the manufactured liquid crystal alignment film was observed with an optical microscope of 100 times and 400 times, the trace of scraping due to rubbing and scraped scraps were clearly confirmed.
Moreover, the alignment defect of the liquid crystal display element was confirmed in the state of no voltage application at room temperature using a polarizing microscope. When the cell was rotated, light and darkness was observed, and light leakage due to poor alignment in the dark state was confirmed.

  Examples of the utilization method of the present invention include a liquid crystal alignment film, a liquid crystal display element substrate, and a liquid crystal display element.

Claims (8)

Polyester-polyamic acid (A1) obtained by using at least a polyvalent hydroxy compound (a1), a diamine (a2), and a compound (a3) having two or more acid anhydride groups, and polyester-polyamic acid (A1) ) a polyester obtained by imidizing - a liquid crystal alignment film composition comprising a polymer a containing at least one selected from the group consisting of polyimide (A2),
The composition for liquid crystal aligning films whose said polyvalent hydroxy compound (a1) is 1 or more chosen from the group which consists of triol and tetraol. The polyester-polyamic acid (A1) is a structural unit represented by the following formula (1)

(In the formula, a broken line indicates a bond, and R ¹¹ and R ¹² are each independently an organic group having 2 to 100 carbon atoms.)
And a structural unit represented by the following formula (2-21) and a structural unit represented by the following formula (2-22)
(In the formula, a broken line indicates a bond, and R ²¹ , R ²³ and R ²⁴ are each independently an organic group having 2 to 100 carbon atoms.)
Possess one or more structural units selected from the group consisting of,
The polyester-polyimide (A2) is a structural unit represented by the following formula (3)
(In the formula, a broken line indicates a bond, and R ³¹ , R ³² and R ³³ are each independently an organic group having 2 to 100 carbon atoms.)
And a structural unit represented by the following formula (2-21) and a structural unit represented by the following formula (2-22)
(In the formula, a broken line indicates a bond, and R ²¹ , R ²³ and R ²⁴ are each independently an organic group having 2 to 100 carbon atoms.)
The composition for liquid crystal aligning film of Claim 1 which has 1 or more structural units chosen from the group which consists of. The polyester-polyamic acid (A1) is a structural unit represented by the following formula (1)

(In the formula, a broken line indicates a bond, and R ¹¹ and R ¹² are each independently an organic group having 2 to 100 carbon atoms.)
And a structural unit represented by the following formula (2-31), a structural unit represented by the following formula (2-32), and a structural unit represented by the following formula (2-33).
(In the formula, a broken line indicates a bond, and R ²¹ , R ²⁵ , R ²⁶ and R ²⁷ are each independently an organic group having 2 to 100 carbon atoms.)
Possess one or more structural units selected from the group consisting of,
The polyester-polyimide (A2) is a structural unit represented by the following formula (3)
(In the formula, a broken line indicates a bond, and R ³¹ , R ³² and R ³³ are each independently an organic group having 2 to 100 carbon atoms.)
And a structural unit represented by the following formula (2-31), a structural unit represented by the following formula (2-32), and a structural unit represented by the following formula (2-33).
(In the formula, a broken line indicates a bond, and R ²¹ , R ²⁵ , R ²⁶ and R ²⁷ are each independently an organic group having 2 to 100 carbon atoms.)
To have a least one structural unit selected from the group consisting of liquid crystal alignment film composition of claim 1. The polyvalent hydroxy compound (a1) is
The composition for liquid crystal aligning film in any one of Claims 1-3 which is 1 or more chosen from the group which consists of. The diamine (a2) is
1 or more selected from the group consisting of
Compound (a3) having two or more acid anhydride groups
The composition for liquid crystal aligning film in any one of Claims 1-4 which is 1 or more chosen from the group which consists of. The polyester-polyamic acid (A1) or the polyester-polyimide (A2) has 0.5-19 moles of amino of the diamine (a2) and an acid anhydride group with respect to 1 mole of hydroxy of the polyvalent hydroxy compound (a1). The composition for liquid crystal aligning film in any one of Claims 1-5 obtained by making 1.5-20 mol of anhydrides of the compound (a3) which has two or more. The liquid crystal aligning film obtained from the composition for liquid crystal aligning films in any one of Claims 1-6 . A liquid crystal display device having the liquid crystal alignment film according to claim 7 .