TW201343726A - Liquid crystal aligning film composition, liquid crystal aligning film and liquid crystal display element - Google Patents

Abstract

An aligning film hard to be reduced by rubbing treatment is sought. An aligning film composition and an aligning film making the aligning characterist appear uniformly are sought. An aligning film and a liquid crystal display element fabricated with a high yield rate are sought. Therefore, this present invention provides a liquid crystal aligning film composition including at least one group chosen from groups composed of polyeater-polyamide acid (A1) and its imidization compound ''polyeater-polyimide (A2)''. The polyeater-polyamide acid (A1) is obtained by at least using polyhydroxy compound (a1), diamine (a2) and a compound (a3) having at least two acid anhydride radicals.

Description

Liquid crystal alignment film composition, liquid crystal alignment film, and liquid crystal display element

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

As a composition for an alignment film used in a liquid crystal display element or the like, a soluble polyimine solution or a polyaminic acid solution has been put to practical use, and the solution is applied, dried or sintered, and then subjected to rubbing treatment to exhibit an alignment film. Characteristics.

However, when the alignment characteristics are exhibited by the rubbing treatment, there is a problem that dust or static electricity is easily generated by cutting the alignment film. For example, if static electricity is generated, dust adheres to the surface of the alignment film to cause display failure. In addition, when this alignment film is used for a TFT element, circuit damage and a decrease in yield of the TFT element are caused by dust and static electricity.

Therefore, an alignment film in which the film is less likely to be damaged by the rubbing treatment is obtained. A composition for an alignment film and an alignment film which can uniformly exhibit alignment characteristics by rubbing treatment are sought. An alignment film and a liquid crystal display element which can be produced in high yield are sought.

The present invention provides a composition for a liquid crystal alignment film, a liquid crystal alignment film obtained by the composition, a liquid crystal display element having the liquid crystal alignment film, and the like.

[1] A composition for a liquid crystal alignment film comprising a polymer A comprising a polyester-polyglycine (A1) selected from the group consisting of the constituent units represented by the following formulas (1) and (2-1) and One or more groups of polyester-polyimine (A2) consisting of the constituent units represented by the following formula (3) and the following formula (2-1), wherein a dotted line indicates a linking site, R ¹¹ R ¹² , R ²¹ , R ²² , R ³¹ , R ³² and R ³³ each independently represent an organic group having 2 to 100 carbon atoms.

[2] A composition for a liquid crystal alignment film comprising a polymer A comprising a group selected from the group consisting of polyester-polyglycine (A1) and polyester-polyimine (A2) Or one or more, the polyester-polyaminic acid (A1) includes a constituent unit represented by the following formula (1) and one or more constituent units selected from the following formula (2-21) and the following formula (2-22) The constituent unit of the group consisting of the constituent units represented by the constituent unit, the polyester-polyimine (A2) includes a constituent unit represented by the following formula (3) and one or more constituents selected from the group consisting of the following formula (2-21) a constituent unit of a group consisting of a unit and a constituent unit represented by the following formula (2-22), wherein a broken line indicates a joint portion, R ¹¹ , R ¹² , R ²¹ , R ²³ , R ²⁴ , R ³¹ , R ³² And R ³³ independently represent an organic group having 2 to 100 carbon atoms.

[3] A composition for a liquid crystal alignment film comprising a polymer A comprising a group selected from the group consisting of polyester-polyglycine (A1) and polyester-polyimine (A2) Or one or more, the polyester-polyaminic acid (A1) includes a constituent unit represented by the following formula (1) and one or more constituent units selected from the following formula (2-31), and the following formula (2-32) The constituent unit of the constituent unit represented by the following formula and the constituent unit represented by the following formula (2-33), the polyester-polyimine (A2) includes a constituent unit represented by the following formula (3) and one or more types a constituent unit of a group consisting of a constituent unit represented by the following formula (2-31), a constituent unit represented by the following formula (2-32), and a constituent unit represented by the following formula (2-33), wherein a dotted line The linking moiety is represented, and R ¹¹ , R ¹² , R ²¹ , R ²⁵ , R ²⁶ , R ²⁷ , R ³¹ , R ³² and R ³³ each independently represent an organic group having 2 to 100 carbon atoms.

[4] A composition for a liquid crystal alignment film comprising a polymer A comprising a polymer selected from the group consisting of polyester-polyglycine (A1) and imidization of polyester-polyglycine (A1) One or more of the group consisting of polyester-polyimine (A2), polyester-polyamide (A1) is at least using a polyvalent hydroxy compound (a1), a diamine (a2), and including 2 Or two or more acid anhydride group-containing compounds (a3).

[5] The composition for a liquid crystal alignment film according to [4], wherein the polyvalent hydroxy compound (a1) is a diol represented by the following formula (5-1), wherein R ⁵¹ is a carbon atom of 2~ 100 organic groups. HO-R ⁵¹ -OH (5-1)

[6] The composition for a liquid crystal alignment film according to [5], wherein the polyester-polylysine (A1) comprises a constituent unit represented by the following formula (1) and a constituent unit represented by the following formula (2-1) The polyester-polyimine (A2) includes a constituent unit represented by the following formula (3) and a constituent unit represented by the following formula (2-1), wherein a broken line indicates a linking site, and R ¹¹ , R ¹² , and R ²¹ R ²² , R ³¹ , R ³² and R ³³ each independently represent an organic group having 2 to 100 carbon atoms.

[7] The liquid crystal alignment film composition according to [4], wherein the polyvalent hydroxy compound (a1) is a triol represented by the following formula (5-2), wherein R ⁵² represents a carbon number of 2~ 100 organic groups.

[8] The composition for liquid crystal alignment film according to [7], wherein the polyester-polyaminic acid (A1) comprises a constituent unit represented by the following formula (1) and one or more selected from the group consisting of the following formula (2- 21) a constituent unit of the constituent unit represented by the structural unit represented by the following formula (2-22), and the polyester-polyimine (A2) includes a constituent unit represented by the following formula (3) and one or a constituent unit of a group consisting of a constituent unit represented by the following formula (2-21) and a constituent unit represented by the following formula (2-22), wherein a broken line indicates a linking portion, R ¹¹ , R ¹² , R ²¹ , R ²³ , R ²⁴ , R ³¹ , R ³² and R ³³ each independently represent an organic group having 2 to 100 carbon atoms.

[9] The composition for a liquid crystal alignment film according to [4], wherein the polyvalent hydroxy compound (a1) is a tetrahydric alcohol represented by the following formula (5-3), wherein R ⁵³ represents a carbon number of 2~ 100 organic groups.

[10] The composition for liquid crystal alignment film according to [9], wherein the polyester-polyaminic acid (A1) comprises a constituent unit represented by the following formula (1) and one or more selected from the group consisting of the following formula (2- 31) a structural unit represented by the constituent unit represented by the following formula (2-32) and a constituent unit represented by the following formula (2-33), and the polyester-polyimine (A2) includes The constituent unit represented by the following formula (3) and one or more constituent units selected from the following formula (2-31), the constituent unit represented by the following formula (2-32), and the constitution represented by the following formula (2-33) a constituent unit of a group consisting of units, wherein a broken line indicates a linking site, and R ¹¹ , R ¹² , R ²¹ , R ²⁵ , R ²⁶ , R ²⁷ , R ³¹ , R ^{32 ,} and R ³³ each independently represent a carbon atom number. It is an organic group of 2 to 100.

The composition for a liquid crystal alignment film according to any one of the above [10], wherein the polyvalent hydroxy compound (a1) is one or more selected from the group consisting of the following compounds, The diamine (a2) is one or more selected from the group consisting of the following compounds, The compound (a3) including two or more acid anhydride groups is one or more selected from the group consisting of the following compounds.

[12] The composition for a liquid crystal alignment film according to any one of [1] to [11] wherein the polyester-polyproline (A1) or the polyester-polyimine (A2) is 0.5 to 20 moles of the amine (a2), 1.5 to 20 moles of the anhydrate of the compound (a3) including 2 or more acid anhydride groups, and 1 mole of hydroxyl groups of the polyvalent hydroxy compound (a1) are obtained. .

[13] The composition for liquid crystal alignment film according to any one of [1] to [12], further comprising a polymer (B) comprising a polymer selected from the group consisting of poly (proline) (B1) and poly One or more groups of the group consisting of quinone imine (B2), the polyamine acid (B1) includes a constituent unit represented by the following formula (1), and the polyimine (B2) includes the formula (4) A constituent unit in which a broken line indicates a linking site, and R ¹¹ , R ¹² , R ⁴¹ and R ⁴² each independently represent an organic group having 2 to 100 carbon atoms.

[14] The composition for liquid crystal alignment film according to any one of [1] to [12], further comprising a polymer (B) comprising a polymer selected from the group consisting of poly(proline) (B1) and One or more groups consisting of polyimine (B2) obtained by polyaminic acid (B1) quinone imidization, poly-proline (B1) is at least using diamine (a2) and including 2 One or two or more acid anhydride group-containing compounds (a3).

[15] The composition for liquid crystal alignment film according to [14], wherein the diamine (a2) is one or more selected from the group consisting of the following compounds, The compound (a3) including two or more acid anhydride groups is one or more selected from the group consisting of the following compounds.

[16] The composition for a liquid crystal alignment film according to [14], wherein the polylysine (B1) comprises a constituent unit represented by the following formula (1), and the polyimine (B2) comprises the following formula (4) A structural unit represented by a dotted line indicating a linking site, and R ¹¹ , R ¹² , R ⁴¹ and R ⁴² each independently represent an organic group having 2 to 100 carbon atoms.

The composition for a liquid crystal alignment film according to any one of the aspects of the present invention, wherein the composition for a liquid crystal alignment film contains 1 to 50% by weight of polyglycine (B1) and polyfluorene. Imine (B2).

[18] The composition for a liquid crystal alignment film according to [12], further comprising an epoxy compound (C).

[19] The composition for a liquid crystal alignment film according to [18], wherein the epoxy compound (C) is one or more selected from the group consisting of compounds represented by the following formulas (C1) to (C5), In the formula, n is an integer from 0 to 10.

[20] The composition for a liquid crystal alignment film according to [19], wherein the composition for a liquid crystal alignment film contains 0.1 to 40% by weight of an epoxy compound (C).

[21] A liquid crystal alignment film, which is the liquid according to any one of [1] to [20] The crystal is obtained by using a composition for a film.

[22] A liquid crystal display element comprising the liquid crystal alignment film according to [21].

In the present specification, the term "polyimine" is not particularly limited as long as it is a compound having a quinone imine composition. In the present specification, the "polylysine" is a precursor of a polyimine, and is not particularly limited as long as it is a compound having a structure of both a guanamine and a carboxylic acid. In the present specification, the "polyester-polyimine" is not particularly limited as long as it is a compound having a structure of both an ester and a quinone. In the present specification, the "polyester-polyglycolic acid" is not particularly limited as long as it is a compound having a structure of both an ester and a poly-proline.

The film obtained by the composition for an alignment film according to the preferred embodiment of the present invention can obtain an alignment film having less distortion, uniform alignment characteristics, and excellent alignment characteristics even if it is subjected to a rubbing treatment.

The alignment film obtained from the composition for an alignment film according to the preferred embodiment of the present invention and the liquid crystal display element using the alignment film can be produced in a high yield.

The liquid crystal display element according to a preferred embodiment of the present invention has high contrast.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

A first aspect of the present invention provides a composition for a liquid crystal alignment film comprising a polymer A, wherein the polymer A comprises a polyester-polyglycine (A1) and a polyester-polyamide. One or more of the groups consisting of amines (A2).

According to a second aspect of the invention, the composition for a liquid crystal alignment film of the first aspect, further comprising a composition of the polymer B, wherein the polymer B comprises a polyphosphonium (B1) and a polyimine (B2). One or more of the group consisting of.

A third aspect of the present invention is a liquid crystal alignment film obtained from the composition for a liquid crystal alignment film of the present invention and a liquid crystal display element having the alignment film.

I. Polymer A

The composition for a liquid crystal alignment film according to the first aspect of the present invention includes the polymer A, and the polymer A includes a group selected from the group consisting of polyester-polyglycine (A1) and polyester-polyimine (A2). One or more of the groups.

1. Polyester-polyproline (A1)

1.1 Composition of polyester-polyaminic acid (A1)

The polyester-polyaminic acid (A1) is not particularly limited as long as it has a constitution of both an ester and a guanamine, and the following three compounds are preferable.

[1]Polyester-polyglycine (A1-1)

a compound having a structural unit represented by the above formula (1) and a structural unit represented by the above formula (2-1);

[2] Polyester-polyglycine (A1-2)

a compound having a constituent unit represented by the above formula (1) and one or more constituent units selected from the group consisting of the constituent unit represented by the above formula (2-21) and the constituent unit represented by the above formula (2-22) ;

[3] Polyester-polyglycine (A1-3)

The constituent unit represented by the above formula (1) and one or more constituent units selected from the above formula (2-31), the constituent unit represented by the above formula (2-32), and the above formula (2-33) A compound constituting a constituent unit of a group consisting of cells.

An acid anhydride group, an amine group, a hydroxyl group or the like is formed at the end of the polyester-polyaminic acid (A1).

In the above formula (1), formula (2-1), formula (2-21), formula (2-22), formula (2-31), formula (2-32), and formula (2-33), R ¹¹ and R ²¹ each independently represent a tetravalent organic group having 2 to 100 carbon atoms; R ²² represents a divalent organic group having 2 to 100 carbon atoms; and R ²³ and R ²⁴ are independently represented. The trivalent organic group having 2 to 100 carbon atoms; R ²⁵ , R ²⁶ and R ²⁷ each independently represent a tetravalent organic group having 2 to 100 carbon atoms, and is not particularly limited.

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.

Specific examples of the monovalent organic group include an alkoxy group having 2 to 20 carbon atoms which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and an amine having a substituent. a fluorenyl group which may have a substituent, an alkylthio group which may have a substituent (-SY ¹ , wherein Y ¹ represents an alkyl group having 2 to 20 carbon atoms which may have a substituent), and may have a substituent An arylthio group (-SY ² wherein Y ² represents an aryl group having 6 to 18 carbon atoms which may have a substituent.), an alkylsulfonyl group which may have a substituent (-SO ₂ Y ³ , Y ³ represents an alkyl group having 2 to 20 carbon atoms which may have a substituent.) an arylsulfonyl group which may have a substituent (-SO ₂ Y ⁴ , wherein Y ⁴ represents a carbon which may have a substituent An aryl group with an atomic number of 6 to 18.).

In the present specification, the hydrocarbon of "hydrocarbon having 2 to 20 carbon atoms" may be a saturated or unsaturated acyclic hydrocarbon or a saturated or unsaturated cyclic hydrocarbon. When the hydrocarbon having 2 to 20 carbon atoms is an acyclic hydrocarbon, it may be a linear hydrocarbon or a branched hydrocarbon. The "hydrocarbon having 2 to 20 carbon atoms" includes an alkyl group having 2 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and a carbon number. It is an alkadienyl group of 4 to 20, an aryl group having 6 to 18 carbon atoms, an alkaryl group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and 4 carbon atoms. a cycloalkyl group of ~20, a cycloalkenyl group having 4 to 20 carbon atoms, and the like.

In the present specification, the "alkyl group having 2 to 20 carbon atoms" is preferably an alkyl group having 2 to 10 carbon atoms, and more preferably an alkyl group having 2 to 6 carbon atoms. The example of the alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second-stage butyl group, a third-order butyl group, a pentyl group, a hexyl group, and a dodecane group. Base.

In the present specification, the "alkenyl group having 2 to 20 carbon atoms" is preferably an alkenyl group having 2 to 10 carbon atoms, and more preferably an alkenyl group having 2 to 6 carbon atoms. The example of the alkenyl group is not particularly limited, and examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 2-methyl-1-propenyl group, a 2-methylallyl group, and a 2-butenyl group. Wait.

In the present specification, the "alkynyl group having 2 to 20 carbon atoms" is preferably an alkynyl group having 2 to 10 carbon atoms, and more preferably an alkynyl group having 2 to 6 carbon atoms. Examples of the alkynyl group are not particularly limited, and examples thereof include an ethynyl group, a propynyl group, and a butynyl group.

In the present specification, the "alkanediyl group having 4 to 20 carbon atoms" is preferably an alkadienyl group having 4 to 10 carbon atoms, and more preferably an alkadienyl group having 4 to 6 carbon atoms. The example of the alkadienyl group is not particularly limited, and examples thereof include a 1,3-butadienyl group. Wait.

In the present specification, the "aryl group having 6 to 18 carbon atoms" is preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group are not particularly limited, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthracenyl group, a biphenyl group, a fluorenyl group, and a phenanthryl group.

In the present specification, the "alkylaryl group having 7 to 20 carbon atoms" is preferably an alkaryl group having 7 to 12 carbon atoms. The example of the alkaryl group is not particularly limited, and examples thereof include o-tolyl, m-tolyl, p-tolyl, 2,3-methylbenzyl, 2,4-methylbenzyl, 2,5-methylbenzyl, O-isopropylphenyl, m-isopropylphenyl, p-cumyl, mesityl, and the like.

In the present specification, the "aralkyl group having 7 to 20 carbon atoms" is preferably an aralkyl group having 7 to 12 carbon atoms. Examples of the aralkyl group are not particularly limited, and examples thereof include a benzyl group, a phenethyl group, a diphenylmethyl group, a trityl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, and a 2,2-diphenylethyl group. Base, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl and the like.

In the present specification, the "cycloalkyl group having 4 to 20 carbon atoms" is preferably a cycloalkyl group having 4 to 10 carbon atoms. The example of the cycloalkyl group is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

In the present specification, the "cycloalkenyl group having 4 to 20 carbon atoms" is preferably a cycloalkenyl group having 4 to 10 carbon atoms. The example of the cycloalkenyl group is not particularly limited, and examples thereof include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.

In the present specification, the "alkoxy group having 2 to 20 carbon atoms" is preferably an alkoxy group having 2 to 10 carbon atoms, and more preferably an alkoxy group having 2 to 6 carbon atoms. Examples of the alkoxy group are not particularly limited, and include: ethoxy, propoxy, butoxy, pentyl Oxyl and the like.

In the present specification, the "aryloxy group having 6 to 20 carbon atoms" is preferably a carbon source. The number of subunits is 6 to 10 aryloxy groups. The example of the aryloxy group is not particularly limited, and examples thereof include a phenoxy group, a naphthyloxy group, and a biphenyloxy group.

In the present specification, "alkylthio (-SY ¹ wherein Y ¹ represents an alkyl group having 2 to 20 carbon atoms which may have a substituent.)" and "alkylsulfonyl (-SO ₂ Y ³ ) In the middle, Y ³ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent. In the above, Y ¹ and Y ^{2 are} preferably an alkyl group having 2 to 10 carbon atoms, and more preferably 2 carbon atoms. ~6 alkyl. The example of the alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second-stage butyl group, a third-order butyl group, a pentyl group, a hexyl group, and a dodecane group. Base.

In the present specification, "arylthio group (-SY ² wherein Y ² represents an aryl group having 6 to 18 carbon atoms which may have a substituent.)" and "arylsulfonyl group (-SO ₂ Y ⁴ , In the middle, Y ⁴ represents an aryl group having 6 to 18 carbon atoms which may have a substituent. Among them, Y ² and Y ^{4 are} preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group are not particularly limited, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthracenyl group, a biphenyl group, a fluorenyl group, and a phenanthryl group.

It is possible to "hydrocarbons having 1 to 20 carbon atoms", "alkoxy groups having 2 to 20 carbon atoms", "aryloxy groups having 6 to 20 carbon atoms", "amine groups", and "decyl groups". Substituents are introduced into "alkylthio", "arylthio", "alkylsulfonyl" and "arylsulfonyl". Examples of the above substituents include an ester group, a carboxyl group, a decylamino group, an alkyne group, a trimethyldecyl group, an amine group, a phosphonium group, a thio group, a carbonyl group, a nitro group, a sulfo group, an imido group, and a halogen. Alkyl or alkoxy group. In this case, one or more substituents up to the substitutable number may be introduced into the substitutable position, and one to four substituents may be preferably introduced. When the number of substituents is two or more, each substituent may be the same or different.

In the present specification, the example of "an amine group which may have a substituent" is not For example, an amine group, a dimethylamino group, a methylamino group, a methylphenylamino group, a phenylamino group, or the like is defined.

In the present specification, the example of "an alkylene group which may have a substituent" is not There are limitations, such as dimethyl decyl, diethyl decyl, trimethyl decyl, triethyl decyl, trimethoxy decyl, triethoxy decyl, diphenyl methyl decyl, three Phenyl decyl, triphenyloxydecyl, dimethylmethoxydecyl, dimethylphenoxyalkyl, methylmethoxyphenyl, and the like.

Specific examples of the monovalent organic group are listed above, but in the present specification 2 Specific examples of the valent organic group may be a group in which a valence number is further added to the monovalent organic group described in the present specification. Also in the present specification, specific examples of the trivalent organic group include a group in which two valences are further added to the monovalent organic group described in the specification, and specific examples of the tetravalent organic group can be exemplified in the present specification. An additional 3 valence groups are added to the monovalent organic group.

R ¹¹ and R ²¹ in the present specification include hydrocarbons having 2 to 100 carbon atoms. Among them, a hydrocarbon having 4 to 18 carbon atoms is preferable, and it may be an aromatic hydrocarbon or a saturated or unsaturated cyclic hydrocarbon or a saturated or unsaturated acyclic hydrocarbon. Specifically, a skeleton selected from the group consisting of skeletons represented by the following structural formulas, in which a broken line indicates a linking site, is preferred.

R ²² in the present specification includes a hydrocarbon having 2 to 100 carbon atoms. Among them, a hydrocarbon having 2 to 20 carbon atoms is preferable, and it may be an aromatic hydrocarbon or a saturated or unsaturated cyclic hydrocarbon or a saturated or unsaturated acyclic hydrocarbon. When it is an acyclic hydrocarbon, it may be a linear hydrocarbon or a branched hydrocarbon. A hetero atom such as oxygen, nitrogen or sulfur may be included in the molecular skeleton. Specifically, a skeleton selected from the group consisting of skeletons represented by the following structural formulas, in which a broken line indicates a linking site, is preferred.

R ²³ in the present specification includes a hydrocarbon having 2 to 100 carbon atoms. Among them, a hydrocarbon having 3 to 20 carbon atoms is preferable, and it may be an aromatic hydrocarbon or a saturated or unsaturated cyclic hydrocarbon or a saturated or unsaturated acyclic hydrocarbon. When it is an acyclic hydrocarbon, it may be a linear hydrocarbon or a branched hydrocarbon. A hetero atom such as oxygen, nitrogen or sulfur may be included in the molecular skeleton. Specifically, a skeleton selected from the group consisting of skeletons represented by the following structural formulas, in which a broken line indicates a linking site, is preferred.

R ²⁴ in the present specification includes a hydrocarbon having 2 to 100 carbon atoms. Among them, a hydrocarbon having 3 to 20 carbon atoms is preferable, and it may be an aromatic hydrocarbon or a saturated or unsaturated cyclic hydrocarbon or a saturated or unsaturated acyclic hydrocarbon. When it is an acyclic hydrocarbon, it may be a linear hydrocarbon or a branched hydrocarbon. A hetero atom such as oxygen, nitrogen or sulfur may be included in the molecular skeleton. Specifically, a skeleton selected from the group consisting of skeletons represented by the following structural formulas, in which a broken line indicates a linking site, is preferred. Among them, in order to clarify the binding position to OH in the formula (2-22), the OH bonded to R ²⁴ is also included.

R ²⁵ in the present specification includes a hydrocarbon having 2 to 100 carbon atoms. Among them, a hydrocarbon having 3 to 20 carbon atoms is preferable, and it may be an aromatic hydrocarbon or a saturated or unsaturated cyclic hydrocarbon or a saturated or unsaturated acyclic hydrocarbon. When it is an acyclic hydrocarbon, it may be a linear hydrocarbon or a branched hydrocarbon. A hetero atom such as oxygen, nitrogen or sulfur may be included in the molecular skeleton. Specifically, a skeleton selected from the group consisting of skeletons represented by the following structural formulas, in which a broken line indicates a linking site, is preferred.

R ²⁶ in the present specification includes a hydrocarbon having 2 to 100 carbon atoms. Among them, a hydrocarbon having 3 to 20 carbon atoms is preferable, and it may be an aromatic hydrocarbon or a saturated or unsaturated cyclic hydrocarbon or a saturated or unsaturated acyclic hydrocarbon. When it is an acyclic hydrocarbon, it may be a linear hydrocarbon or a branched hydrocarbon. A hetero atom such as oxygen, nitrogen or sulfur may be included in the molecular skeleton. Specifically, a skeleton selected from the group consisting of skeletons represented by the following structural formulas, in which a broken line indicates a linking site, is preferred. Among them, in order to clarify the binding position to OH in the formula (2-32), the OH bonded to R ²⁶ is also included.

R ²⁷ in the present specification includes a hydrocarbon having 2 to 100 carbon atoms. Among them, a hydrocarbon having 3 to 20 carbon atoms is preferable, and it may be an aromatic hydrocarbon or a saturated or unsaturated cyclic hydrocarbon or a saturated or unsaturated acyclic hydrocarbon. When it is an acyclic hydrocarbon, it may be a linear hydrocarbon or a branched hydrocarbon. A hetero atom such as oxygen, nitrogen or sulfur may be included in the molecular skeleton. Specifically, a skeleton selected from the group consisting of skeletons represented by the following structural formulas, in which a broken line indicates a linking site, is preferred. Among them, in order to clarify the binding position to OH in the formula (2-33), the OH bonded to R ²⁷ is also included. .

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

When the composition for a liquid crystal alignment film of the present invention is applied to a substrate, it is necessary to dilute the polymer component contained in the solvent in advance in order to adjust the film thickness. Therefore, the polyester-polyamide in the composition for a liquid crystal alignment film is used. The concentration of the acid (A1) is not particularly limited, and when the solid content is 40% by weight or less, the viscosity of the liquid crystal alignment film composition is most suitable, and it is necessary to easily align the liquid crystal alignment film composition when the liquid crystal alignment film composition is diluted in order to adjust the film thickness. The solvent composition is preferably mixed in the film composition. When coating is carried out by a spin coating method or a printing method, in order to maintain the film thickness favorably, the concentration of the polyester-polyglycine (A1) is preferably 20% by weight or less. In other coating methods, such as dip coating or ink jet method, the concentration of the polyester-polyaminic acid (A1) can be further reduced. On the other hand, when the concentration of the polyester-polyaminic acid (A1) is 1% by weight or more, the film thickness of the resulting alignment film tends to be uniform.

Therefore, the concentration of the polyester-polyglycine (A1) in the composition for a liquid crystal alignment film is preferably from 1 to 50% by weight. When the composition is applied by a usual spin coating method, a printing method, or the like, the concentration of the polyester-polyglycine (A1) in the composition for a liquid crystal alignment film is preferably 1 to 40. % by weight, more preferably 1 to 15% by weight. However, when an inkjet method or the like is used in the coating method of the varnish, a more dilute concentration (for example, 0.1 to 5% by weight) can be used.

1.2 Preparation method of polyester-polyproline (A1)

The polyester-polyglycine (A1) can be produced, for example, by using at least a polyvalent hydroxy compound (a1), a diamine (a2), and a compound (a3) having two or more acid anhydride groups, but is not limited thereto. Preparation.

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

Also, when the polyester-polyglycine (A1-2) is prepared by 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) contained in the poly-proline (A1-2) a residue of the compound (a3) having two or more acid anhydride groups; 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) are a polyvalent hydroxy compound The residue of (a1); R ¹² in the structural unit represented by the formula (1) is a residue of the diamine (a2).

Also, when the polyester-polyglycine (A1-3) is prepared by 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 a constituent unit represented by the formula (2-31), the formula (2-32) or the formula (2-33) R ²¹ 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), and a constituent unit represented by the formula (2-32) R ²⁶ constituting unit represented by formula (2-33) R ²⁷ is the residue of a polyhydric hydroxy compound (a1); a constituent unit represented by the formula (1) R ¹² is a diamine (a2) residue.

Hereinafter, the polyhydroxylation which can be used to obtain polyester-polyglycine (A1) The compound (a1), the diamine (a2), and the compound (a3) having two or more acid anhydride groups will be described.

1.2.1 Polyols (a1)

In the present invention, a polyhydroxyl group for synthesizing polyester-polyglycine (A1) The material (a1) is not particularly limited as long as it has two or more hydroxyl groups, and examples thereof include a diol represented by the formula (5-1) and a triol represented by the formula (5-2). The tetrahydric alcohol represented by (5-3).

In the diol represented by the formula (5-1), R ⁵¹ is not particularly limited as long as it is a divalent organic group having 2 to 100 carbon atoms.

In the triol represented by the formula (5-2), R ⁵² is not particularly limited as long as it is a trivalent organic group having 2 to 100 carbon atoms.

In the tetrahydric alcohol represented by the formula (5-3), R ⁵³ is not particularly limited as long as it is a tetravalent organic group having 2 to 100 carbon atoms.

In the present invention, specific examples of the polyvalent hydroxy compound (a1) for synthesizing the polyester-polyglycine (A1) include:

Polyethylene glycol having a molecular weight of 1000 or less;

Tetrapropylene glycol, polypropylene glycol having a molecular weight of 1000 or less;

1,2-decanediol, 1,12-nonanediol;

Second and fourth grade pentaerythritol, bisphenol A (trade name), bisphenol S (trade name), bisphenol F (trade name), diethanolamine and triethanolamine, trade name "SEO-2" (Japan Chemical ( Company), the product name "SKYCHDM" (manufactured by Shin-Nippon Chemical and Chemical Co., Ltd.), the trade name "Ricabinol HB" (manufactured by Shin-Nippon Chemical and Chemical Co., Ltd.), and the compound of the following formula (A), R ^A1 and R ^A3 each independently represent -(CH ₂ )xO-(CH ₂ )y-; x and y each independently represent an integer of 1 to 15; R ^A2 represents an alkylene group having 1 to 5 carbon atoms; It is an integer from 2 to 50.

From the viewpoint of reducing the chipping of the liquid crystal alignment film formed of the composition for liquid crystal alignment film obtained in the rubbing treatment, when the polyvalent hydroxy compound (a1) is a diol, it is preferred to:

More preferably:

When the polyvalent hydroxy compound (a1) uses a triol, it is preferred to:

More preferably:

When the polyvalent hydroxy compound (a1) uses a tetrahydric alcohol, it is preferred to:

More preferably:

The polyester-polyglycine (A1) used in the present invention is preferably a trihydric or tetrahydric alcohol, and most preferably three, in comparison with a diol, in terms of viscosity and molecular weight adjustment. Alcohol.

Further, the polyvalent hydroxy compound (a1) may be used singly or in combination of two or more kinds.

1.2.2 Diamine (a2)

In the present invention, the diamine (a2) used in the synthesis of the polyester-polyglycine (A1) is not particularly limited, and specific examples thereof are: bis[4-(4-aminophenoxy)phenyl]fluorene, Bis[4-(3-aminophenoxy)phenyl]indole, bis[3-(4-aminophenoxy)phenyl]indole, [4-(4-aminophenoxy)phenyl [3-(4-Aminophenoxy)phenyl]anthracene, [4-(3-aminophenoxy)phenyl][3-(4-aminophenoxy)phenyl]anthracene, a compound represented by the formula (b): wherein R ₃ and R ₄ independently represent an alkyl group having 1 to 3 carbon atoms or a phenyl group; and R ₅ independently represents a methylene group, a phenylene group or an alkyl group-substituted phenylene group; Base; x independently represents an integer from 1 to 6; y is an integer from 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-phenylene di Amine, p-phenylenediamine, m-xylylenediamine, p-xylenediamine, 2,2'-diaminodiphenylpropane, benzidine, 1,1-bis[4-(4- Aminophenoxy)phenyl]cyclohexane, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-methylcyclohexane, bis[4-(4-amine Benzyl)phenyl]methane, 1,1-bis[4-(4-aminobenzyl)phenyl]cyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl ]-4-methylcyclohexane and a compound represented by the following formula.

In the above specific examples, from the viewpoint of liquid crystal alignment, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, and 3,3'-dimethyl-4 are preferable. , 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, Aniline, 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-methyl Cyclohexane, bis[4-(4-aminobenzyl)phenyl]methane, 1,1-bis[4-(4-aminobenzyl)phenyl]cyclohexane, 1,1-double [4-(4-Aminobenzyl)phenyl]-4-methylcyclohexane and a compound represented by the following formula.

Further particularly preferred: 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenyl Methane, 2,2'-diaminodiphenylpropane and the following compounds.

The diamine (a2) may be used alone or in combination of two or more. It is not limited to the above diamine as long as it is a diamine which achieves the purpose.

1.2.3 Compounds having 2 or more acid anhydride groups (a3)

In the present invention, the compound (a3) having two or more acid anhydride groups used in the synthesis of the polyester-polyglycine (A1) is not particularly limited, and tetracarboxylic dianhydride is preferred. Specific examples of the compound (a3) having an acid anhydride group include styrene-maleic anhydride copolymer, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetra Hydronaphthalene-1,2-dicarboxylic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, a compound represented by the following formula, etc. .

In the above specific examples, from the viewpoint of liquid crystal alignment, it is preferred that:

Further particularly preferred:

The compound (a3) having 2 or more acid anhydride groups may be used singly or in combination of two or more kinds.

1.2.4 Additives added to polyester-polyglycine (A1)

When the polyester-polyglycine (A1) used in the present invention has an acid anhydride group at the molecular terminal, a monohydric alcohol may be added as needed to cause it to react. The polyester-polyaminic acid (A1) to which a monohydric alcohol is added is preferable because, for example, flatness is improved.

The monohydric alcohol to be added may, for example, be methanol, ethanol, 1-propanol or the like. Propyl 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, phenol, decyl alcohol, maltitol, linalool, terpineol, dimethylbenzyl methine methanol, ethyl lactate, glycidol, 3-ethyl-3-hydroxymethyl propylene oxide Wait.

For example, from the aspect of improving the flatness of the composition for the obtained liquid crystal alignment film Specific examples of the above monohydric alcohol are preferably: isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, 3-ethyl-3-hydroxymethyl propylene oxide; more preferably Benzyl alcohol.

In addition, if 3-aminopropyltrimethoxydecane, 3-aminopropyltriethyl Oxydecane, 3-aminopropylmethyldimethoxydecane, 3-aminopropylmethyldiethoxydecane, 4-aminobutyltrimethoxydecane, 4-aminobutyl three Ethoxy decane, 4-aminobutyl dimethyl diethoxy decane, p-aminophenyl trimethoxy decane, p-aminophenyl triethoxy decane, p-aminophenyl methyl dimethoxy decane a monoamine containing decane such as aminophenylmethyldiethoxy decane, m-aminophenyltrimethoxydecane, and m-aminophenyl dimethyldimethoxy decane, and a polyhydric group having an acid anhydride group at a molecular terminal When the ester-polyproline (A1) is reacted, for example, the chemical resistance of the obtained coating film is improved, which is preferable.

In addition, it is also possible to simultaneously add a monohydric alcohol and a monoamine containing decane to the poly The ester-polyaminic acid (A1) is allowed to react.

1.2.5 Reaction conditions

The polyester-polyaminic acid (A1) preferably has 0.5 to 19 moles of the diamine (a2) A 1.5 to 20 mol anhydrate of the compound (a3) having two or more acid anhydride groups is reacted with a 1 mol hydroxyl group of the polyvalent hydroxy compound (a1). The polyester-polyglycine (A1) is more preferably a 2 to 20 mol anhydrate of the compound (a3) having 1 to 9 mol amine groups of the diamine (a2) and 2 or more acid anhydride groups. The monohydroxy compound (a1) is obtained by reacting a 1 molar hydroxyl group.

The solvent used to obtain the polyester-polyglycine (A1) is only capable of The compound is not particularly limited, and examples thereof include diglyme, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, and 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 and the like. Among them, preferred are methyl 3-methoxypropionate, diethylene glycol methyl ethyl ether, ethylene glycol monobutyl ether, γ-butyrolactone, and N-methyl-2-pyrrolidone.

The above solvents may be used singly or in combination of two or more kinds. Use with a solvent. Other solvents may be used in addition to the above solvents, but other solvents are preferably used in a ratio of 30% by weight or less.

When compared to the polyhydric hydroxy compound (a1), the diamine (a2) and have 2 or 2 When 100 parts by weight or more of a solvent of 100 parts by weight or more of the compound (a3) of the acid anhydride group is used, the reaction proceeds smoothly, which is preferable. The reaction is preferably carried out at 10 ° C to 200 ° C for 0.2 to 20 hours.

When a monoamine containing decane is added to the polyester-polyglycine (A1), In the reaction, after the reaction of the polyvalent hydroxy compound (a1), the diamine (a2), and the compound (a3) having two or more acid anhydride groups is completed, the reaction liquid is preferably cooled to 40 ° C or lower, followed by cooling. A monoamine containing decane is added and allowed to react at 10 to 40 ° C for 0.1 to 6 hours.

It should be noted that a monohydric alcohol can be added to the polyester-polyglycine (A1). Make it react.

The order in which the reaction raw materials are added to the reaction system is not particularly limited. which is, The polyvalent hydroxy compound (a1), the diamine (a2), and the compound (a3) having two or more acid anhydride groups are simultaneously added to the solvent; the diamine (a2) and the polyvalent hydroxy compound (a1) are dissolved in the reaction. a compound (a3) having two or more acid anhydride groups is added to the solvent; the polyvalent hydroxy compound (a1) and the compound (a3) having two or more acid anhydride groups are reacted in advance to synthesize a copolymer, and then a diamine (a2) is added to the copolymer; a diamine (a2) and a compound (a3) having two or more acid anhydride groups are reacted in advance to synthesize a copolymer, and then a polyvalent hydroxy compound (a1) is added to the copolymer. Any one of the methods can be used.

2. Polyester-polyimine (A2)

2.1 Composition of polyester-polyimine (A2)

The polyester-polyimine (A2) is not particularly limited as long as it has a constitution of both an ester and a quinone, and the following three compounds are preferable.

[1] Polyester-polyimine (A2-1)

a compound having a structural unit represented by the formula (3) and a constituent unit represented by the formula (2-1);

[2] Polyester-polyimine (A2-2)

a compound having a constituent unit represented by the formula (3) and one or more constituent units selected from the group consisting of the constituent unit represented by the formula (2-21) and the constituent unit represented by the formula (2-22);

[3] Polyester-polyimine (A2-3)

The constituent unit represented by the formula (3) and one or more constituent units selected from the formula (2-31), the constituent unit represented by the formula (2-32), and the constituent unit represented by the formula (2-33) The group of compounds that make up the unit.

The terminal of the polyester-polyimine (A2), for example, constitutes an acid anhydride group, an amine group, a hydroxyl group or the like.

In the formula (3), R ³¹ and R ³³ each independently represent a tetravalent organic group having 2 to 100 carbon atoms, and R ³² is preferably a divalent organic group having 2 to 100 carbon atoms. Yes, there is no particular limitation.

R ³¹ and R ³³ in the present specification may independently list a tetravalent hydrocarbon having 2 to 100 carbon atoms, and among them, a hydrocarbon having 3 to 20 carbon atoms may be used, which may be an aromatic hydrocarbon or a saturated or unsaturated hydrocarbon. A cyclic hydrocarbon or a saturated or unsaturated acyclic hydrocarbon. A hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom may be included in the molecular skeleton.

R ³² in the present specification includes a divalent hydrocarbon having 2 to 100 carbon atoms, and among them, a hydrocarbon having 3 to 20 carbon atoms is preferable, and it may be an aromatic hydrocarbon or a saturated or unsaturated cyclic hydrocarbon or saturated or Unsaturated acyclic hydrocarbons. A hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom may be included in the molecular skeleton.

It should be noted that R ¹¹ in the formula (2-1), the formula (2-21), the formula (2-22), the formula (2-31), the formula (2-32), and the formula (2-33) And R ²¹ to R ^{27 are} as described above.

Chemical resistance of the film obtained from the composition for liquid crystal alignment film of the present invention The degree of preference is generally that the higher the molecular weight of the polyester-polyimine (A2), and the solubility with respect to the solvent is generally preferably as the molecular weight of the polyester-polyimine (A2) is lower. Therefore, the weight average molecular weight of the polyester-polyimine (A2) contained in the composition for liquid crystal alignment films of the present invention is preferably 5,000 to 500,000, more preferably 10,000 to 200,000.

In the present invention, the polyester-polyimine (A2) in the composition for liquid crystal alignment film The content (when the polyester-polyaminic acid (A1) is also included, the total content of the polyester-polyamide acid (A1) and the polyester-polyimine (A2)) is not particularly limited, and The total amount of the composition for the liquid crystal alignment film is preferably 1 to 50% by weight, more preferably 1 to 40% by weight, particularly preferably 2 to 30% by weight. When it is in the above-mentioned concentration range, the viscosity of the composition for a liquid crystal alignment film is most suitable, and it is preferable to form a coating film of a uniform film thickness by coating by various coating methods.

2.2 Preparation method of polyester-polyimine (A2)

The polyester-polyimine (A2) used in the present invention can be, for example, The polyester-polyimine (A1) oxime prepared by using the polyvalent hydroxy compound (a1), the diamine (a2), and the compound (a3) having two or more acid anhydride groups is used for imidization.

a mixture of polyester-polyglycine (A1) and polyester-polyimine (A2) The preparation is carried out by mixing the separately synthesized polyester-polyproline (A1) and polyester-polyimine (A2), and a part of the polyester-polyglycine (A1) is imidized. .

When the above production method is employed, R ³¹ and R ³³ in the constituent unit represented by the formula (3) contained in the polyester-polyimine (A2-1) and the constituent unit represented by the formula (2-1) R ²¹ is a residue of the compound (a3) having two or more acid anhydride groups; 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 is a residue of the diamine (a2).

Also, when the polyhydric hydroxy compound (a1), the diamine (a2), and the compound (a3) having two or more acid anhydride groups are used, the polyester-polyglycine (A1-2) quinone imine is used. When the polyester-polyimine (A2-2) is produced, R ³¹ and R ³³ and the formula in the constituent unit represented by the formula (3) contained in the polyester-polyimine (A2-2) compound (a3) is a constituent unit represented by (2-21) or (2-22) is R ²¹ having two or more acid anhydride groups or two residues; constituent unit represented by the formula (2-21) in constituent units represented by R ²³ and the formula (2-22) is R ²⁴ is a polyhydric hydroxy compound (a1) residues; constituent unit represented by the formula (3) R ³² in the diamine (a2) residues .

Also, when the polyhydric hydroxy compound (a1), the diamine (a2), and the compound (a3) having two or more acid anhydride groups are used, the polyester-polyglycine (A1-3) quinone imine is used. When the polyester-polyimine (A2-3) is produced, R ³¹ and R ³³ and the formula in the constituent unit represented by the formula (3) contained in the polyester-polyimine (A2-3) R ²¹ in the structural unit represented by the formula (2-31) or the formula (2-32) or the formula (2-33) is a residue of the compound (a3) having two or more acid anhydride groups; R ²⁵ in the structural unit represented by R ²⁵ , R ²⁶ in the structural unit represented by formula (2-32), and R ²⁷ in the structural unit represented by formula (2-33) are residues of polyvalent hydroxy compound (a1) R ³² in the structural unit represented by the formula (3) is a residue of the diamine (a2).

II. Polymer B

The composition for a liquid crystal alignment film according to the second aspect of the present invention includes the polymer A. And polymer B, the above polymer A comprises one or more selected from the group consisting of polyester-polyglycine (A1) and polyester-polyimine (A2); the above polymer B includes One or more groups consisting of polylysine (B1) and polyimine (B2).

Polylysine (B1)

1.1 Composition of polyaminic acid (B1)

The polyaminic acid (B1) is not particularly limited as long as it is a compound having a constituent of decylamine, and a compound having a structural unit represented by the formula (1) is preferred.

The constituent unit represented by the formula (1) constituting the poly-proline (B1) is the same as the formula (1) showing the constituent unit constituting the polyester-polyglycolic acid (A1).

1.2 Preparation method of polyproline (B1)

The polyamic acid (B1) can be produced, for example, using at least a diamine (a2) and a compound (a3) having 2 or more acid anhydride groups, but is not limited to this production method.

When the polyamine (B1) is prepared using at least the diamine (a2) and the compound (a3) having two or more acid anhydride groups, the formula (1) contained in the polyproline (B1) is represented by R ¹¹ in the constituent 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).

A diamine (a2) which can be used for obtaining polyglycine (B1), a compound (a3) having two or more acid anhydride groups, and a polyester (polyamide) (A1) which can be used for obtaining a polyester-polyamide acid (A1) The diamine (a2) is the same as the compound (a3) having two or more acid anhydride groups.

2. Polyimine (B2)

2.1 Composition of polyimine (B2)

The polyimine (B2) is not particularly limited as long as it is a compound having a quinone imine composition, and is preferably a compound having a structural unit represented by the formula (4).

In the formula (4) constituting the polyimine (B2), R ^{41 may} be a tetravalent organic group having 2 to 100 carbon atoms, and R ^{42 may have} a divalent carbon number of 2 to 100. The organic group is not particularly limited.

R ⁴¹ in the present specification includes a tetravalent hydrocarbon having 2 to 100 carbon atoms, and among them, a hydrocarbon having 3 to 20 carbon atoms is preferable, and it may be an aromatic hydrocarbon or a saturated or unsaturated cyclic hydrocarbon or saturated or Unsaturated acyclic hydrocarbons. A hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom may be included in the molecular skeleton.

R ⁴² in the present specification includes a divalent hydrocarbon having 2 to 100 carbon atoms, and among them, a hydrocarbon having 3 to 20 carbon atoms is preferable, and it may be an aromatic hydrocarbon or a saturated or unsaturated cyclic hydrocarbon or saturated or Unsaturated acyclic hydrocarbons. A hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom may be included in the molecular skeleton.

2.2 Preparation method of polyimine (B2)

The polyimine (B2) used in the present invention can be, for example, a polylysine (B1) prepared by using at least a diamine (a2) and a compound (a3) having two or more acid anhydride groups. Amination is carried out for the preparation.

When the above production method is employed, R ⁴¹ in the structural unit represented by the formula (4) contained in the polyimine (B2) is a residue of the compound (a3) having two or more acid anhydride groups; ⁴² is the residue of the diamine (a2).

a mixture of polyaminic acid (B1) and polyimine (B2) can be separated by The synthesized polyglycine (B1) and polyimine (B2) are mixed, and a part of the polyglycine (B1) is imidized or the like to prepare.

III. Mixture of Polymer A and Polymer B

The composition for liquid crystal alignment film according to the second aspect of the present invention includes polylysine At least any one of (B1) and polyimine (B2). The content of polyproline (B1) and polyimine (B2) (when both polyamines (B1) and polyimine (B2) are included) is not particularly limited, as opposed to The total amount of the composition for the liquid crystal alignment film is preferably 1 to 50% by weight, more preferably 2 to 30% by weight. This is because if it is in the above concentration range, the effect can be maintained for the frictional cut and the alignment can be improved.

IV. Epoxy compound (C)

The composition for a liquid crystal alignment film of the present invention may include an epoxy as needed. Compound (C).

The epoxy compound (C) used in the present invention may have an epoxy group as long as it has an epoxy group. It is not particularly limited, and a compound having two or more ethylene oxides is preferred.

In the present invention, the content of the epoxy resin in the composition for the liquid crystal alignment film is not It is particularly limited, and is preferably 0.1 to 40% by weight, more preferably 0.2 to 30% by weight. When the content of the epoxy resin is in the above-mentioned concentration range, the coating film formed of the composition for liquid crystal alignment film is not easily scratched by the rubbing treatment, and the durability is good. When the content of the epoxy resin is in the above concentration range, the heat resistance and chemical resistance of the coating film are excellent, which is preferable.

Specific examples of the epoxy compound (C) include bisphenol A type epoxy Resin, glycidyl ester epoxy resin, alicyclic epoxy resin, with ethylene oxide A polymer of a monomer and a copolymer of a monomer having ethylene oxide and another monomer, and the like.

More specifically, the epoxy resin can be exemplified by the trade name "Epycoat". 807", "Epycoat 815", "Epycoat 825", "Epycoat 827", and the compound "Epycoat 828", "Epycoat 190P", and "Epycoat 191P" represented by the above formula (C4) (above, oiled SHELLEPOXY) ), the product name "Epycoat 1004", "Epycoat 1256" (above, manufactured by Nippon Epoxy Co., Ltd.), the trade name "Araldite CY177", and the compound "Araldite CY184" represented by the above formula (C1) (Japan CIBAGEIGY (share) )), the product name "Celoxide 2021P", "EHPE-3150" (manufactured by DICEL Chemical Co., Ltd.), and the product name "TECMORE VG3101L" (Mitsui) of the compound represented by the above formula (C3). Chemical compound (manufactured by ALDORICH Co., Ltd.), a compound represented by the above formula (C5), "4,4'-methylenebis(N,N-diglycidylaniline)". In addition, the liquid crystal composition of the present invention includes a mixture of compounds of n=0 to 4 represented by the above formula (C4), "Epycoat 828", and a compound of the above formula (C1), "Araldite CY184" (manufactured by CIBAGEIGY, Japan) The product name "Celoxide 2021P" (manufactured by DICEL Chemical Industry Co., Ltd.) and the product name "TECMORE VG3101L" (manufactured by Mitsui Chemicals Co., Ltd.) expressed by the above formula (C3), and the above formula The compound "4,4'-methylenebis(N,N-diglycidylaniline)" (manufactured by ALDORICH Co., Ltd.) represented by (C5) is preferable because it has good transparency and flatness.

Specific examples of the monomer having ethylene oxide include (meth) propyl Glycidyl acrylate, 3,4-epoxycyclohexyl (meth) acrylate and (meth)acrylic acid Methyl glycidyl ester.

Specific examples of other monomers copolymerized with a monomer having ethylene oxide Examples thereof include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate Propyl ester, styrene, methyl styrene, chloromethyl styrene, (3-ethyl-3-epoxypropenyl) methyl (meth) acrylate, N-cyclohexyl maleimide and N - phenyl maleimine and the like.

Preferred specific examples of the polymer of the monomer having ethylene oxide can be listed. For example: polyglycidyl methacrylate and the like. Preferable specific examples of the copolymer of the monomer having ethylene oxide and other monomers 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-epoxypropane) A (meth) acrylate-glycidyl methacrylate copolymer and a styrene-glycidyl methacrylate copolymer.

V. Additive 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 one or more selected from the group consisting of polyester-polyglycine (A1) and its ruthenium polyester-polyimine (A2), but According to the required characteristics, it may also include: a surfactant, an antistatic agent, a coupling agent, an epoxy hardener such as trimellitic acid, an amino decane compound, a solvent, and other additives. Additives such as the above surfactants, for example, added to the liquid crystal alignment film The composition is uniformly mixed and dissolved for use.

(1) Surfactant

For example, when it is desired to improve the coatability, a surface may be added according to this purpose. Active agent. Specific examples of the surfactant to be added to the composition for a liquid crystal alignment film of the present invention include the trade names "Byk-300", "Byk-306", "Byk-335", "Byk-310", and "矽-based surfactants such as Byk-341, "Byk-344", "Byk-370", (BYK CHEMIE), trade names "Byk-354", "ByK-358", "Byk-361" (Acrylic surfactants such as BYK CHEMIE); fluorine-based surfactants such as "DFX-18", "FTERGENT 250", and "FTERGENT 251" (manufactured by NEOS).

The above surfactants may be used singly or in combination of two or two. Mix on top.

Surfactants are used to improve the wettability, flatness or The coating additive is preferably used by adding 0.01 to 1% by weight to the liquid crystal alignment film composition.

(2) Antistatic agent

The antistatic agent added to the composition for liquid crystal alignment film of the present invention is not There is a particular limitation, and a usual antistatic agent can be used. Specific examples thereof include a metal oxide such as tin oxide, tin oxide, and cerium oxide composite oxide, tin oxide, and indium oxide composite oxide, or a fourth-order ammonium salt.

The above antistatic agent may be used alone or in combination of two or two. Mix on top.

The antistatic agent is an additive for preventing charging, and is preferably used by adding 0.01 to 1% by weight to the liquid crystal alignment film composition.

(3) Coupling agent

The coupling agent to be added to the composition for a liquid crystal alignment film of the present invention is not particularly limited, and a usual coupling agent can be used. The couplant to be added is preferably a decane coupling agent, and specific examples thereof include a trialkoxy decane compound or a dialkoxy decane compound. Preferable are, for example, γ-vinylpropyltrimethoxydecane, γ-vinylpropyltriethoxydecane, γ-acrylenylpropylmethyldimethoxydecane, γ-propylene decylpropyl Trimethoxy decane, γ-propylene decyl propyl methyl diethoxy decane, γ-propylene decyl propyl triethoxy decane, γ-methyl propyl decyl propyl methyl dimethoxy decane, γ-Methyl propylene decyl propyl trimethoxy decane, γ-methyl propylene propyl propyl methyl diethoxy decane, γ-methyl propylene propyl propyl triethoxy decane, γ-glycidol Oxypropyl propyl dimethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-glycidoxy propyl methyl diethoxy decane, γ-glycidoxy propyl three Ethoxy decane, γ-aminopropylmethyldimethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropylmethyldimethoxydecane, γ-aminopropyl Triethoxy decane, N-aminoethyl-γ-iminopropylmethyldimethoxydecane, N-aminoethyl-γ-aminopropyltrimethoxydecane, N-amino group Ethyl-γ-aminopropyl diethoxy Alkane, N-phenyl-γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltriethoxydecane, N-phenyl-γ-aminopropylmethyldimethyl Oxydecane, N-phenyl-γ-aminopropylmethyldiethoxydecane, γ-mercaptopropylmethyldimethoxydecane, γ-aminopropyltrimethoxydecane, γ-mercapto Propylmethyldiethoxydecane, γ-mercaptopropyltriethoxydecane, γ-isocyanide Acid ester propyl methyl diethoxy decane, γ-isocyanate propyl triethoxy decane, and the like. Among them, preferred are: γ-vinylpropyltrimethoxydecane, γ-acrylonitrilepropyltrimethoxydecane, γ-methylpropenylpropyltrimethoxydecane, and γ-isocyanatepropyltriethoxydecane. Wait.

The above coupling agent may be used alone or in combination of two or more. Used together.

The coupling agent preferably adds 0.01 to 3 weight to the composition for the liquid crystal alignment film. % to use.

(4) Epoxy hardener

An epoxy hardener added to the composition for a liquid crystal alignment film of the present invention It is not particularly limited, and a usual epoxy curing agent can be used. Specific examples thereof include an organic acid diterpene compound, imidazole and a derivative thereof, dicyandiamide, an aromatic amine, a polyvalent carboxylic acid, and a polycarboxylic acid anhydride. More specifically, examples thereof include dicyandiamides such as dicyandiamide; organic acids such as diammonium adipate and 1,3-bis(decylcarboxyethyl)-5-isopropylhydantoin; Dioxane; 2,4-diamino-6-[2'-ethylimidazolyl-(1')]ethyltriazine, 2-phenylimidazole, 2-phenyl-4-methylimidazole, An imidazole derivative such as 2-phenyl-4-methyl-5-hydroxymethylimidazole; an anhydride such as phthalic anhydride, trimellitic anhydride or 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride; . Among them, trimellitic acid and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride having good transparency are preferred.

The above epoxy hardener may be used singly or in two or two Mix on top.

The epoxy hardener is preferably added to the composition for the liquid crystal alignment film by 0.05 to 5 Use % by weight.

(5) Aminodecane compounds

The composition for liquid crystal alignment film of the present invention may be added with an alkyl decylation. Compound. The amino decane compound may, for example, be p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, m-aminophenyltrimethoxydecane or m-aminophenyltriethoxydecane. Aminopropyltrimethoxydecane, aminopropyltriethoxydecane, and the like.

The above aminodecane compounds may be used singly or in two or two. More than one kind of mixture is used.

The amino decane compound is added for good adhesion to the substrate. The agent is preferably used by adding 0.05 to 2% by weight to the liquid crystal alignment film composition.

(6) Solvent

The solvent which can be contained in the composition for liquid crystal alignment film of the present invention is only required The polymer A or the polymer B to be contained can be dissolved, and is not particularly limited. The solvent widely includes a solvent which is usually used in the preparation process or use of a polymer component such as polyaminic acid or soluble polyimine, and can be appropriately selected depending on the purpose of use.

The above solvents are exemplified below. Relative to polyaminic acid or soluble polyimine Examples of aprotic polar organic solvents which are solvophilic are: N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N, N - dimethylacetamide, dimethyl hydrazine, N,N-dimethylformamide, N,N-diethylformamide, diethylacetamide, γ-butyrolactone, and the like. Examples of other solvents for the purpose of improving coatability and the like include alkyl lactate, 3-methyl-3-methoxybutanol, and tetralin. Ethylene glycol monoalkyl ether such as isophorone or ethylene glycol monobutyl ether, diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol a monoalkyl ether, a propylene glycol monoalkyl ether such as propylene glycol monobutyl ether, a dialkyl malonate such as diethyl malonate, a dipropylene glycol monoalkyl ether such as dipropylene glycol monomethyl ether, or the like, and the like. Ester compound. Among the above solvents, N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol can be particularly preferably used. Monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, methyl 3-methoxypropionate, and the like.

The above solvents may be used singly or in combination of two or more kinds. use. The solvent is preferably added so that the solid content in the liquid crystal alignment film composition is from 1 to 60% by weight.

(7) Other additives

The composition for a liquid crystal alignment film of the present invention can also not detract from the present invention The range of characteristics (preferably within 20% by weight of the composition for a liquid crystal alignment film) is used in combination with a polymer component such as a polyester, an acrylic polymer or an acrylate polymer.

The composition for a liquid crystal alignment film of the present invention can be used without impairing the object of the present invention. a reaction product of a dicarboxylic acid or a derivative thereof and a diamine, a polyamine or a tetracarboxylic dianhydride, a reaction product of a dicarboxylic acid or a derivative thereof and a diamine, and a polyamidoximine, etc. Composition.

VI. Manufacturing of liquid crystal alignment film and substrate for liquid crystal display element

The composition of the liquid crystal alignment film of the present invention is applied to the surface of a substrate such as glass or a substrate such as an electrode such as an ITO (indium tin oxide) electrode or a glass such as a color filter. The composition may be formed into a liquid crystal alignment film by heating or drying necessary for dehydration or ring closure reaction.

The substrate is not only glass such as fluoride glass having good smoothness, but also Examples thereof include polyesters such as polyethylene terephthalate and polybutylene terephthalate; epoxy resins, phenol resins, polyimines, polycarbonates, polyfluorenes, and polyethers. , heat resistant resin such as polyether phthalimide, acetaminophen, polyamino acid ester, aromatic polyamine; polystyrene, polyacrylate, polymethacrylate, polypropylene decylamine, polyethylene, polypropylene A vinyl polymer such as a vinyl polymer; a fluorine-containing resin such as polyvinylidene fluoride; and a conversion product thereof.

The composition for coating the liquid crystal alignment film on the surface of the substrate can be spin-coated The method, the printing method, the dip coating method, the dropping method, the inkjet method, and the like are carried out. The process of performing the heat treatment or the drying treatment necessary for the dehydration and ring closure reaction of the composition for liquid crystal alignment film of the present invention coated on the surface of the substrate can be carried out by heating in a hot plate or in an infrared oven, for example, by heating in an oven or an infrared oven. Method, etc. The drying process is preferably carried out at a relatively low temperature in the range in which the solvent can evaporate, and the heat treatment process is generally preferably carried out at a temperature of about 150 to 300 °C.

The electrode provided on the substrate may be a transparent substrate such as glass by sputtering or the like. After depositing a metal such as chrome on the board, it is formed by etching a mask pattern having a predetermined shape as a mask.

In this way, rubbing method and optical alignment are performed on the resin film hardened on the substrate. By alignment treatment such as a method or a transfer method, the characteristics of the liquid crystal alignment film are exhibited in the above resin film, and a liquid crystal alignment film is prepared. Thereby, a liquid crystal is formed on the substrate. A substrate for a liquid crystal display element of a film.

It is preferable to use a rubbing method in the above alignment treatment, and the conditions of the rubbing treatment are not In particular, it is preferably obtained from the composition for a liquid crystal alignment film of the present invention under the conditions that the amount of the hair foot is 0.2 to 0.8 mm, the moving speed of the stage is 5 to 250 mm/sec, and the rotation speed of the roll is 500 to 2,000 rpm. The resin film is subjected to a rubbing treatment.

Composition for liquid crystal alignment film of the present invention comprising epoxy compound (C) The obtained liquid crystal alignment film is more tough than the liquid crystal alignment film obtained from the liquid crystal alignment film composition containing no epoxy compound (C), and has transparency, heat resistance, chemical resistance, and flatness. It is preferable because it is more excellent in adhesion and splash resistance.

VII. Manufacture of liquid crystal display elements

The liquid crystal display element of the present invention is provided by a plurality of liquid crystal displays of the present invention A spacer control material is disposed between the substrate for the element or between the substrate for liquid crystal display element of the present invention and the second transparent substrate, and the liquid crystal composition is filled between the substrates. According to circumstances, the liquid crystal display element can be further attached with a polarizing plate.

The liquid crystal display element of the present invention can also be washed before and after the alignment treatment The liquid is washed and manufactured. The washing method may, for example, be brushing, spray washing, steam washing or ultrasonic washing. The above methods may be used singly or in combination. As the washing liquid, various alcohols such as pure water or methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene, toluene, and xylene; halogen solvents such as dichloromethane; and ketones such as acetone and methyl ethyl ketone may be used. Not limited to this. Of course, the above washing liquid uses a washing liquid which is sufficiently purified and has less impurities.

The liquid crystal composition used in the liquid crystal display element of the present invention is not particularly For definition, various liquid crystal compositions having a positive dielectric anisotropy can be used. Examples of the preferred liquid crystal composition are disclosed in Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Publication No. Hei 5-501735, Japanese Patent Application Laid-Open No. Hei No. 8-157826, and Japanese Patent Application No. Hei 8-231960 Japanese Laid-Open Patent Publication No. Hei 9-241644 (JP-A-A No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 9-255956, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. 2000-087040, Japanese Laid-Open Patent Publication No. 2001-48822, and the like.

Various liquid crystal compositions having a negative dielectric anisotropy can also be used. Optimal Examples of the liquid crystal composition are disclosed in Japanese Laid-Open Patent Publication No. Sho 57-114532, Japanese Laid-Open Patent Publication No. Hei No. 2-4725, Japanese Patent Laid-Open No. Hei-4-224885, Japanese Patent Application Laid-Open No. Hei. Japanese Laid-Open Patent Publication No. Hei 10-- No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei 10-236993, Japanese Laid-Open Patent Publication No. Hei 10-236994, Japanese Laid-Open Patent Publication No. Hei No. Hei 10-237000, Japanese Patent Publication No. Hei 10-237004, Japanese Patent Application Laid-Open No. Hei 10-237024 Japanese Laid-Open Patent Publication No. Hei 10-237075, Japanese Laid-Open Patent Publication No. Hei 10-237076, No. Hei 10-237448 (EP967261A1) Japanese Laid-Open Patent Publication No. H10-287874, Japanese Laid-Open Patent Publication No. Hei No. H10-287875, Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. JP-A-2000-256307, JP-A-2001-019965, JP-A-2001-072626, JP-A-2001-192657, and the like.

The above liquid crystal composition having positive or negative dielectric anisotropy may also be added. One or more optically active compounds are added for reuse.

Further, the composition for a liquid crystal alignment film of the present invention can also be used without damage Further, a polymer component having a polylysine having another composition, a soluble polyimine, a polyester, an acrylic polymer, or an acrylate polymer is used in combination with the range of the characteristics of the present invention (preferably within 20 mol%). Further, in the composition for a liquid crystal alignment film of the present invention, a dicarboxylic acid or a derivative thereof and a diamine which are polymer components used in the composition for a liquid crystal alignment film can be added in a range which does not impair the object of the present invention. The reaction product polyamine or tetracarboxylic dianhydride, a reaction product of a dicarboxylic acid or a derivative thereof and a diamine, a polymer component such as polyamidoximine.

Example

Hereinafter, the present invention will be described by way of examples and comparative examples, but the present invention It is not limited to these embodiments.

Compound (a3) having two or more acid anhydride groups (tetracarboxylic dianhydride)

1,2,3,4-cyclobutane tetracarboxylic 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-Heptadecylphenyl)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

Polyhydroxy 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 Composition (1A) for Liquid Crystal Alignment Film

Into a 200 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, 1.96 g of CBDA (10 mmol), 2.18 g of PMDA (10 mmol), 0.36 g of 1,4-butanediol (4 mmol), and 84.7 g were placed. The NMP was dehydrated and stirred at 120 ° C for 1 hour under a stream of dry nitrogen. After cooling to 25 ° C, 3.20 g of APE (16 mmol) was added. While maintaining the temperature of the reaction system at 25 ° C for 30 hours, after adding 38.5 g BC, 23.1 g GBL, the temperature was raised to 50 ° C and stirring was continued, when the viscosity of the composition reached 30 ~ 35 mPa. The reaction was terminated when s (using an E-type viscometer at 25 ° C) to obtain a composition (1A) for a liquid crystal alignment film of a polyester-polyglycolic acid having a solid content of 5% by weight. The weight average molecular weight of the obtained composition was 23,000. In addition, the weight average molecular weight was measured at a column temperature of 50 ° C using a GPC measuring apparatus manufactured by Shimadzu Corporation. The molar ratios of PMDA, CBDA, APE, and BOH used were PMDA/CBDA/APE/BOH=25/25/40/10.

[Example 1] Preparation of liquid crystal alignment film, liquid crystal display element substrate, and liquid crystal display element

The liquid crystal alignment film composition 1A obtained in Synthesis Example 1 was diluted with a mixed solvent of NMP/BC/GBL (=60/25/15, weight ratio) to adjust the solid content to 3% by weight, which was used as a liquid crystal alignment for coating. Film composition (varnish (1A)).

The varnish (1A) was coated on a glass substrate with electrodes using a spinner. The coating conditions were: 2200 rpm, 15 seconds. After the film coating, pre-sintering was performed at 80 ° C for about 5 minutes, and then heat treatment was performed at 210 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of about 75 nm. Using a friction processing device manufactured by GAUGE Co., Ltd., the frictional cloth (hair length 1.8 mm: rayon) has a gross footing amount of 0.40 mm, a stage moving speed of 60 mm/sec, and a roller rotation speed of The obtained liquid crystal alignment film was subjected to a rubbing treatment at 1,500 rpm.

The surface of the liquid crystal alignment film after the rubbing treatment was observed with an optical microscope of 100 times and 400 times, and no cutting marks and cutting residues due to the rubbing treatment were observed.

The obtained substrate for a liquid crystal display element was ultrasonically washed in ultrapure water for 5 minutes, and then dried in an oven at 120 ° C for 30 minutes. On the substrate for liquid crystal display element with an electrode, a spacer of 7 μm was spread, and the surface on which the alignment film was formed was bonded to the inside, and sealed with an epoxy curing agent to form an antiparallel cell having an interval of 7 μm. . The liquid crystal composition shown below was injected into the above-mentioned cell, and the injection port was sealed with a light hardener, and heat-treated at 110 ° C for 30 minutes, and then returned to room temperature to prepare a liquid crystal display element.

Liquid crystal composition

The alignment of the liquid crystal alignment film in the liquid crystal display element was confirmed by observation with a polarizing microscope. It should be noted that the composition of the liquid crystal composition used as the liquid crystal material is as follows. This composition had an NI point of 100.0 ° C and a birefringence of 0.093.

Using a polarizing microscope, the alignment state of the liquid crystal display element was confirmed in a state where no voltage was applied at room temperature. Light and dark were observed when the box was rotated, and no light leakage due to poor alignment was observed in the dark state.

[Synthesis Example 2~16]

The tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound used in the preparation of the liquid crystal alignment film composition and their molars are shown in Table 1 and Table 2. The liquid crystal alignment film compositions (2A) to (16A) were prepared under the same conditions as in Synthesis Example 1 except for the change.

[Examples 2 to 16]

A substrate for a liquid crystal display device was produced under the same conditions as in Example 1 except that the compositions for liquid crystal alignment films (2A) to (16A) obtained in Synthesis Examples 2 to 16 were used, and observed with an optical microscope at 100 times and 400 times. Liquid crystal alignment film surface, confirm Cutting marks and cutting debris on the surface of the substrate caused by friction. An antiparallel cassette was produced using this substrate, and the alignment state was confirmed by a polarizing microscope. The results are shown in Table 3.

[Synthesis Example 17] Synthesis of Polylysine (17PA)

Into a 200 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, 3.54 g of 4ChB1B (7.0 mmol) and 55 g of dehydrated NMP were placed and dissolved, and 0.9607 g of CBDA (3.5 mmol) and 0.77 g of PMDA (3.5 mmol) were added. ), while maintaining the temperature of the reaction system at 25 ° C under a dry nitrogen stream for 30 hours, then adding 25 g of BC, 25 g of GBL, heating to 50 ° C and stirring, when the viscosity of the composition reached 30 ~ 35 mPa. The reaction was terminated when s (using an E-type viscometer at 25 ° C) to obtain a composition for liquid crystal alignment film (17PA) containing polyglycine having a solid content of 5% by weight. The weight average molecular weight of the obtained composition was 30,560. In addition, the weight average molecular weight was measured at a column temperature of 50 ° C using a GPC measuring apparatus manufactured by Shimadzu Corporation.

The molar ratios of PMDA, CBDA and 4ChB1B used were PMDA/CBDA/4ChB1B=25/25/50.

[Synthesis Examples 18 to 28]

The same conditions as in Synthesis Example 17 were carried out except that the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound used in the preparation of the liquid crystal alignment film composition and the moir thereof were changed as shown in Tables 4 and 5, respectively. A composition for liquid crystal alignment film (18PA) to (28PA) was prepared.

[Synthesis Example 29]

The composition for liquid crystal alignment film (17PA) containing the polyester-polyglycolic acid-containing liquid crystal alignment film obtained in Synthesis Example 12 and the liquid crystal alignment film composition (17PA) obtained in Synthesis Example 17 were used in a weight ratio of 17 PA/ 12A=20/80 was mixed to prepare a composition for a liquid crystal alignment film containing polyester-polyglycine and polyglycine.

[Synthesis Example 30 to Synthesis Example 40]

The composition for a liquid crystal alignment film containing a polyester-polyglycine and a composition for a liquid crystal alignment film containing a polyglycolic acid are mixed at a weight ratio shown in Table 6 to prepare a polyester-polylysine and A composition for a liquid crystal alignment film of polylysine.

[Example 17]

The liquid crystal alignment film composition 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 to 3% by weight as a liquid crystal alignment film for coating. Composition (varnish (1G)).

Using the above varnish 1G, the surface of the liquid crystal alignment film was observed with an optical microscope of 100 times and 400 times in accordance with the method described in Example 1, and the cutting marks and the cutting residue caused by the friction were confirmed. An antiparallel cassette was produced using this substrate, and the alignment state was confirmed by a polarizing microscope. The results are shown in Table 7.

[Examples 18 to 28]

A composition for a liquid crystal alignment film for coating (varnish (2G) to (12G)) was prepared using the composition for a liquid crystal alignment film obtained in Synthesis Examples 30 to 40.

Then, in the same manner as in Example 17, except that the above varnish was used. The substrate for liquid crystal display elements was produced under the conditions, and the surface of the liquid crystal alignment film was observed with an optical microscope of 100 times and 400 times, and the cutting marks and the cutting residue on the surface of the substrate due to friction were confirmed. An antiparallel cassette was produced using this 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 liquid crystal alignment film composition (1A) obtained in Synthesis Example 1, 0.25 g of a epoxidized epoxy resin of Celoxide (trademark) 2021P manufactured by DICEL Co., Ltd. (1.0 mmol) was used to prepare a composition (1B) for a liquid crystal alignment film.

[Synthesis Examples 42 to 66] Synthesis of Compositions for Liquid Crystal Alignment Films

In addition to the composition for a liquid crystal alignment film including polyester-polyglycolic acid shown in Table 8, a composition for a liquid crystal alignment film including polyglycine, and an epoxy resin (1.0 mmol), and Synthesis Example 41 Compositions (2B) to (14B) and (1G) to (12G) of a liquid crystal alignment film containing an epoxy resin were prepared under the same conditions.

[Example 29]

The liquid crystal alignment film composition (1B) prepared in Synthesis Example 41 was diluted with a mixed solvent of NMP/BC/GBL (=60/25/15, weight ratio) to give a polyester-polylysine and an epoxy resin. The total solid content was adjusted to 3% by weight to prepare a varnish (1B).

Using the above varnish (1B), the surface of the liquid crystal alignment film was observed with an optical microscope of 100 times and 400 times in the same manner as in Example 1, and the cutting marks and the cutting residue due to friction were confirmed. An antiparallel cassette was produced using this 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 prepared under the same conditions as in Example 29 except that the composition for a liquid crystal alignment film prepared in Synthesis Examples 42 to 66 was used.

Using the above varnish, the surface of the liquid crystal alignment film was observed with an optical microscope of 100 times and 400 times as described in Example 1, and the cut marks caused by friction were confirmed. Traces and cutting debris. An antiparallel cassette was produced using this substrate, and the alignment state was confirmed by a polarizing microscope.

[Comparative Example 1]

A 200 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet was charged with 4.00 g of APE (20 mmol) and 84.7 g of dehydrated NMP. The mixture was stirred and dissolved under a stream of dry nitrogen. While maintaining the temperature of the reaction system at 25 ° C, 1.96 g of CBDA (10 mmol) and 2.18 g of PMDA (10 mmol) were slowly added, and the mixture was reacted under a dry nitrogen stream for 30 hours, after which 38.7 g of BC and 23.1 g of GBL were added. Warm up to 50 ° C and continue to stir, when the viscosity of the varnish reaches 30 ~ 35mPa. The reaction was terminated when s (using an E-type viscometer, 25 ° C) to obtain a polyamic acid composition (29PA) having a solid content of 5% by weight. The weight average molecular weight of the obtained composition was 29,000. In addition, the weight average molecular weight was measured at a column temperature of 50 ° C using a GPC measuring apparatus manufactured by Shimadzu Corporation.

The composition (29PA) obtained as above was diluted with a mixed solvent of NMP/BC/GBL (=60/25/15, weight ratio), and the solid content was adjusted to 3% by weight to prepare a varnish as a coating composition. (29PA).

A liquid crystal alignment film, a liquid crystal display element substrate, and a liquid crystal display element were prepared in the same manner as in Example 1 except that varnish (29PA) was used.

The surface of the produced liquid crystal alignment film was observed with an optical microscope of 100 times and 400 times, and the cutting marks and the cutting residue caused by the friction were clearly confirmed.

Using a polarizing microscope, alignment failure of the liquid crystal display element was confirmed in a state where no voltage was applied at room temperature. Light and dark were observed when the cartridge was rotated, and light leakage caused by poor alignment was confirmed in the dark state.

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

While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

Claims (9)

A composition for a liquid crystal alignment film comprising: a polymer A comprising a polyester selected from the group consisting of polyester-polyproline (A1) and imidization of polyester-polyglycine (A1) One or more groups consisting of quinone imine (A2), wherein the polyester-polyaminic acid (A1) is at least a polyvalent hydroxy compound (a1), a diamine (a2), and includes two or two The above acid anhydride-based compound (a3); and the polymer (B) comprising a polyimine (B2) selected from the group consisting of poly-proline (B1) and imidized poly (protonic acid) (B1) One or more of the group consisting of polyproline (B1) obtained by using at least a diamine (a2) and a compound (a3) comprising two or more acid anhydride groups. The liquid crystal alignment film composition according to claim 1, wherein the polyvalent hydroxy compound (a1) is one or more selected from the group consisting of the following compounds, The diamine (a2) is one or more selected from the group consisting of the following compounds, The compound (a3) including two or more acid anhydride groups is one or more selected from the group consisting of the following compounds. The composition for liquid crystal alignment film according to claim 1 or 2, wherein the polyester-polylysine (A1) or the polyester-polyimine (A2) is 0.5 of the diamine (a2). 1.5 to 20 moles of the compound (a3) containing 2 or more acid anhydride groups The anhydrate of the ear is obtained by reacting with 1 mol of a hydroxyl group of the polyvalent hydroxy compound (a1). The liquid crystal alignment film composition according to the above aspect, wherein the polylysine (B1) comprises a constituent unit represented by the following formula (1), and the polyimine (B2) comprises the following formula (4) In the formula, the dotted line indicates a linking moiety, and R ¹¹ , R ¹² , R ⁴¹ and R ⁴² each independently represent an organic group having 2 to 100 carbon atoms. The liquid crystal alignment film composition according to claim 1, wherein the diamine (a2) for synthesizing the polyamic acid (B1) is one or a group selected from the group consisting of the following compounds; the above, The compound (a3) including two or more acid anhydride groups for synthesizing the polyamic acid (B1) is one or more selected from the group consisting of the following compounds. The liquid crystal alignment film composition according to the above aspect of the invention, wherein the polylysine (B1) comprises a constituent unit represented by the following formula (1), and the polyimine (B2) comprises the following formula (4) In the formula, the dotted line indicates a linking moiety, and R ¹¹ , R ¹² , R ⁴¹ and R ⁴² each independently represent an organic group having 2 to 100 carbon atoms. The liquid crystal alignment film composition according to the above aspect of the invention, wherein the composition for the liquid crystal alignment film comprises 1 to 50% by weight of poly-proline (B1) and polyimine (B2). . A liquid crystal alignment film is obtained by any one of items 1 to 7 of the patent application scope The composition for a liquid crystal alignment film is obtained. A liquid crystal display element comprising the liquid crystal alignment film according to item 8 of the patent application.