JP7136187B2 - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal element - Google Patents

Description

Cross-reference to related applications

This application is based on Japanese Application No. 2018-50104 filed on March 16, 2018, and the description thereof is incorporated herein.

TECHNICAL FIELD The present disclosure relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal element.

In recent years, liquid crystal elements are used not only in display devices such as personal computers, liquid crystal televisions, car navigation systems, mobile phones, smartphones, and information displays, but also in various applications such as optical compensation films and light control films. It is Along with such diversification, further improvement in the quality of liquid crystal elements is required, and along with improvements in driving methods and element structures, improvements in liquid crystal alignment films, which are one of the constituent members of liquid crystal elements, have been promoted. ing. A liquid crystal aligning film is generally formed on a substrate by applying a liquid crystal aligning agent obtained by dissolving a polymer component in an organic solvent onto a substrate, and preferably by heating. As the polymer component of the liquid crystal aligning agent, polyamic acid and soluble polyimide are widely used because they are excellent in mechanical strength, liquid crystal alignment, and affinity with liquid crystal (for example, Patent Document 1 and Patent Document 2).

JP 2017-198975 A JP 2016-206645 A

In order to realize a high-quality display with low power consumption, it is important that the light utilization efficiency of the liquid crystal element is high, and therefore the liquid crystal alignment film is required to exhibit high transmittance. In recent years, with the expansion of the applications of liquid crystal elements, they are sometimes used in harsh environments such as high-temperature and high-humidity environments that have not been assumed in the past. Therefore, it is desired to develop a liquid crystal element that is highly reliable even when used in a high-temperature and high-humidity environment (that is, has good high-temperature and high-humidity resistance).

An object of the present disclosure is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal aligning film having high transmittance and good high temperature and high humidity resistance.

The present disclosure employs the following means to solve the above problems.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子又は炭素数１～１０の１価の炭化水素基であり、Ｘ^１は、式中の「－ＮＨＲ^１」及び「－ＮＨＲ^２」のそれぞれに鎖状炭化水素基又は脂環式炭化水素基で結合する２価の有機基である。）
＜２＞ 上記＜１＞の液晶配向剤を用いて形成された液晶配向膜。
＜３＞ 上記＜２＞の液晶配向膜を具備する液晶素子。<1> At least one selected from the group consisting of polyamic acids, polyamic acid esters and polyimides, and containing a polymer (A) having a partial structure derived from a compound represented by the following formula (1), At least one of the molecule of the polymer (A) and the molecule different from the polymer (A) comprises a radically polymerizable group, a photoinitiator group, a photoalignment group and a β-hydroxyester group. A liquid crystal aligning agent having at least one group (R) selected from the group.

(In formula (1), R ¹ and R ² are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and X ¹ is “—NHR ¹ ” and It is a divalent organic group bonded to each of “-NHR ² ” via a chain hydrocarbon group or an alicyclic hydrocarbon group.)
<2> A liquid crystal alignment film formed using the liquid crystal alignment agent of <1> above.
<3> A liquid crystal device comprising the liquid crystal alignment film of <2> above.

According to the liquid crystal aligning agent of the present disclosure, it is possible to obtain a liquid crystal alignment film having high transparency and good high-temperature and high-humidity resistance.

Below, each component contained in the liquid crystal aligning agent of this indication, and the other component arbitrarily mix|blended as needed are demonstrated. The liquid crystal aligning agent contains a polymer component, preferably a liquid polymer composition in which the polymer component is dissolved in a solvent component.

≪Polymer component≫
The liquid crystal aligning agent contains at least one polymer selected from the group consisting of polyamic acids, polyamic acid esters and polyimides. Polyamic acids, polyamic acid esters and polyimides have a structural unit derived from a tetracarboxylic acid derivative and a structural unit derived from a diamine compound. In this specification, the term "tetracarboxylic acid derivative" includes tetracarboxylic dianhydrides, tetracarboxylic diesters and tetracarboxylic diester dihalides. The liquid crystal aligning agent of the present disclosure is a polymer having a partial structure derived from the compound represented by the above formula (1) as at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide (hereinafter , also referred to as “polymer (A)”).

<Polymer (A)>
(polyamic acid)
When the polymer (A) is a polyamic acid, the polyamic acid (hereinafter also referred to as "polyamic acid (A)") can be obtained by reacting a tetracarboxylic dianhydride and a diamine compound.
(tetracarboxylic dianhydride)
Examples of the tetracarboxylic dianhydrides used in the synthesis of the polyamic acid (A) include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides. be able to. Specific examples thereof include aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and ethylenediaminetetraacetic dianhydride;
Alicyclic tetracarboxylic dianhydrides such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1 ,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3′-(tetrahydrofuran-2′,5′-dione), 2,4,6,8-tetracarboxybicyclo[ 3.3.0]octane-2:4,6:8-dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, etc.; pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, ethylene glycol bisanhydrotrimate, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4 '-Carbonyldiphthalic anhydride, and the like; and tetracarboxylic dianhydrides described in JP-A-2010-97188 can be used. A tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

As the tetracarboxylic dianhydride used for synthesizing the polyamic acid (A), aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic acid can be used in that a liquid crystal alignment film having a higher transmittance can be obtained. Tetracarboxylic acid dianhydride preferably containing at least one compound selected from the group consisting of dianhydrides (hereinafter also referred to as "specific acid dianhydride") and having a cyclobutane ring, cyclopentane ring or cyclohexane ring More preferably, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5 It is particularly preferable to contain at least one selected from the group consisting of -tricarboxycyclopentylacetic dianhydride, cyclopentanetetracarboxylic dianhydride and cyclohexanetetracarboxylic dianhydride. The ratio of the specific acid dianhydride used is preferably 20 mol% or more, and 40 mol% or more, relative to the total amount of the tetracarboxylic dianhydride used in the synthesis of the polyamic acid (A). is more preferable, and 70 mol % or more is even more preferable.

(Diamine compound)
The diamine compound used in synthesizing the polyamic acid (A) includes at least the compound represented by the above formula (1) (hereinafter also referred to as "specific diamine D1").
(Specific diamine D1)
In the above formula (1), the monovalent hydrocarbon groups for R ¹ and R ² include chain hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups. As used herein, the term "chain hydrocarbon group" means a linear hydrocarbon group or a branched hydrocarbon group having a main chain that does not contain a cyclic structure and is composed only of a chain structure. However, it may be saturated or unsaturated. The “alicyclic hydrocarbon group” means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not containing an aromatic ring structure. However, it does not have to be composed only of an alicyclic hydrocarbon structure, and includes those having a chain structure in part thereof. An "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it does not have to be composed only of an aromatic ring structure, and may partially contain a chain structure or an alicyclic hydrocarbon structure.

Specific examples of monovalent hydrocarbon groups for R ¹ and R ² include alkyl groups such as methyl group, ethyl group, propyl group and isopropyl group; alkenyl groups such as vinyl group and allyl group; cyclohexyl group and methylcyclohexyl group. substituted or unsubstituted cycloalkyl groups such as; phenyl group, substituted or unsubstituted aryl groups such as methylphenyl groups; . From the viewpoint of reactivity with tetracarboxylic dianhydride, R ¹ and R ² are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, It is more preferably a hydrogen atom.

X ¹ is a divalent organic group bonded to each of "-NHR ¹ " and "-NHR ² " in formula (1) via a divalent chain hydrocarbon group or an alicyclic hydrocarbon group; is. Preferred specific examples of X ¹ include a divalent group represented by the following formula (10).
*-R ⁶¹ -R ⁶² -R ⁶³ -* (10)
(In formula (10), R ⁶¹ is a divalent chain hydrocarbon group having 1 to 10 carbon atoms or a divalent alicyclic hydrocarbon group having 4 to 10 carbon atoms, and R ⁶³ is a single bond, carbon a divalent chain hydrocarbon group of 1 to 10 or a divalent alicyclic hydrocarbon group of 4 to 10 carbon atoms, and R ⁶² is a single bond or a divalent organic group of 1 to 20 carbon atoms; However, when R ⁶³ is a single bond, R ⁶² is a single bond.)

（式（１０－１）及び式（１０－２）中、Ｒ^６６は炭素数１～５のアルキル基であり、ｒは１～１０の整数であり、ｔは０～２の整数である。「＊」はＲ^６２との結合手であることを示す。）In the above formula (10), the divalent chain hydrocarbon groups represented by R ⁶¹ and R ⁶³ may be linear or branched, such as methylene group, ethylene group, propylene group, 1,4-butanediyl group, 2-methyl-1,3-propanediyl group, 1,5-pentanediyl group, 1,6-hexanediyl group and the like.
Examples of divalent alicyclic hydrocarbon groups for R ⁶¹ and R ⁶³ include *-R ⁶⁴ -R ⁶⁵ -, *-R ⁶⁵ -R ⁶⁴ - (provided that R ⁶⁴ is a substituted or unsubstituted cycloalkylene group or a polycyclic saturated hydrocarbon group, R ⁶⁵ is a single bond or an alkanediyl group, and "*" represents a bond with R ^62. ). Specific examples of these include, for example, a 1,3-cyclopentylene group, a 1,4-cyclohexylene group, a bicyclo[4.4.0]decanediyl group, the following formula (10-1) or formula (10-2 ) and the like.

(In formulas (10-1) and (10-2), R ⁶⁶ is an alkyl group having 1 to 5 carbon atoms, r is an integer of 1 to 10, and t is an integer of 0 to 2. "*" indicates a bond with ^R62 .)

^{At least one of R 61 and} R ⁶³ is ^preferably a divalent alicyclic hydrocarbon group in that the transparency of the resulting liquid crystal alignment film can be made higher. R ⁶¹ and R ⁶³ are bound to at least one of “-NHR ¹ ” and “-NHR ² ” in formula (1) via an aliphatic ring (preferably a cyclohexane ring). More preferably, each of "--NHR ¹ " and "--NHR ² " in formula (1) is particularly preferably bonded to an aliphatic ring (preferably a cyclohexane ring). When "-NHR ¹ " and "-NHR ² " in formula (1) are bonded to an aliphatic ring, "-NHR ¹ " and "-NHR" can increase the transparency of the liquid crystal alignment film. ² '' are preferably attached to different aliphatic rings.

The divalent organic group for R ⁶² includes, for example, a divalent group in which the methylene group of a chain hydrocarbon group is substituted with —O— or —NH—, a divalent aromatic ring group, and a divalent heterocyclic group. etc. Examples of divalent aromatic ring groups include groups obtained by removing two hydrogen atoms from a ring portion of an aromatic hydrocarbon ring such as a benzene ring, naphthalene ring and anthracene ring. Examples of divalent heterocyclic groups include aromatic heterocyclic rings such as pyridine ring, groups obtained by removing two hydrogen atoms from the ring portion of aliphatic heterocyclic rings such as piperazine ring and pyrimidine ring, and the like.

X ¹ preferably does not have an aromatic ring in that the transmittance of the resulting liquid crystal alignment film can be made higher. In this case, R ⁶² in the above formula (10) is preferably a single bond or a divalent aliphatic heterocyclic group, more preferably a single bond or a divalent nitrogen-containing aliphatic heterocyclic group. . In particular, in formula (1) above, X ¹ has a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, or a nitrogen-containing aliphatic heterocycle, and "- NHR ¹ ” and “—NHR ² ” are divalent groups that bind to each of them with a divalent chain hydrocarbon group or an alicyclic hydrocarbon group. X ¹ has a divalent alicyclic hydrocarbon group or a nitrogen-containing aliphatic heterocyclic ring, and “—NHR ¹ ” and “—NHR ² ” in formula (1) are preferably It is more preferable to be a divalent group bonded to each by a divalent chain hydrocarbon group or an alicyclic hydrocarbon group. When X ¹ is a divalent chain hydrocarbon group, it preferably has 2 or more carbon atoms, more preferably 2 to 10 carbon atoms, from the viewpoint of the transmittance of the resulting liquid crystal alignment film.

Specific examples of the specific diamine D1 include compounds represented by the following formulas (1-1) to (1-17).

When synthesizing the polyamic acid (A), the ratio of the specific diamine D1 used is the total amount of the diamine compound used for synthesis in that the effect of improving the transmittance and high temperature and humidity resistance of the liquid crystal alignment film can be sufficiently obtained. On the other hand, it is preferably 10 mol % or more, more preferably 20 mol % or more, and even more preferably 30 mol % or more. In addition, the usage ratio of the specific diamine D1 is preferably 90 mol % or less, more preferably 80 mol % or less, in order to sufficiently obtain the effect of improving performance by using other diamines in combination as shown below. , 70 mol % or less. Specific diamine D1 can be used individually by 1 type or in combination of 2 or more types.

(other diamines)
The diamine compound used in synthesizing the polyamic acid (A) may be only the specific diamine D1, but together with the specific diamine D1, diamines other than the specific diamine D1 (hereinafter also referred to as "other diamines") are used. You may

Alignment group-containing diamine Other preferred examples of diamines include diamine compounds ( Hereinafter, it is also referred to as "orienting group-containing diamine".). The orienting group-containing diamine preferably has a partial structure represented by the following formula (2).
*-L ¹ -R ¹¹ -R ¹² -R ¹³ -R ¹⁴ (2)
(In formula (2), L ¹ is a single bond, -O-, -CO-, -COO-* ¹ , -OCO-* ¹ , -NR ¹⁵ -, -NR ¹⁵ -CO-* ¹ , -CO —NR ¹⁵ —* ¹ , an alkanediyl group having 1 to 6 carbon atoms, —OR ¹⁶ —* ¹ , or —R ¹⁶ —O-* ¹ (provided that R ¹⁵ is a hydrogen atom or a is a monovalent hydrocarbon group, R ¹⁶ is an alkanediyl group having 1 to 3 carbon atoms, and "* ¹ " indicates a bond with R ^{11. R 11 and} R ¹³ are each independently a single bond, a phenylene group or a cycloalkylene group, and R ¹² is a single bond, a phenylene group, a cycloalkylene group, -R ¹⁷ -B ¹ -* ² or -B ¹ -R ¹⁷ -* ² (where R ¹⁷ is a phenylene group or a cycloalkylene group, and B ¹ is -COO-* ³ , -OCO-* ³ , or an alkanediyl group having 1 to 3 carbon atoms. "* ² " indicates a bond with R ¹³ , and “* ³ ” indicates a bond with R ^17. ) R ¹⁴ is a hydrogen atom, a fluorine atom, a cyano group, a carbon 1 to 18 alkyl group, 1 to 18 carbon atom fluoroalkyl group, 1 to 18 carbon atom alkoxy group, 1 to 18 carbon atom fluoroalkoxy group, 17 to 51 carbon atom hydrocarbon group having a steroid skeleton , or a monovalent organic group having a radically polymerizable group, a photoinitiator group, or a cyano group, provided that when all of R ¹¹ , R ¹² and R ¹³ are single bonds, R ¹⁴ has 4 carbon atoms -18 alkyl group, C4-18 fluoroalkyl group, C4-18 alkoxy group, C4-18 fluoroalkoxy group, or C17-51 hydrocarbon group having a steroid skeleton "*" indicates a bond.)

（式中、「＊」は結合手であることを表す。）In formula (2) above, the alkanediyl groups of L ¹ and B ¹ and the alkyl, fluoroalkyl, alkoxy and fluoroalkoxy groups of R ¹⁴ are preferably linear. Examples of the group having a steroid skeleton for R ¹⁴ include cholestanyl group, cholesteryl group, lanostanyl group and the like. At least two of R ¹¹ , R ¹² and R ¹³ preferably have a phenylene group or a cycloalkylene group.
Specific examples of the partial structure represented by the above formula (2) include, for example, partial structures represented by the following formulas (2-1) to (2-11), cholestanyloxy group, cholestanyloxycarbonyl group, cholesteryloxy group, lanostanyloxy group, and the like. However, the orienting group is not limited to these specific examples.

(In the formula, "*" represents a bond.)

（式（Ｅ－１）中、Ｘ^I及びＸ^IIは、それぞれ独立して、単結合、－Ｏ－、＊－ＣＯＯ－又は＊－ＯＣＯ－（ただし、「＊」はＸ^Ｉとの結合手を示す。）であり、Ｒ^Ｉは炭素数１～３のアルカンジイル基であり、Ｒ^ＩＩは単結合又は炭素数１～３のアルカンジイル基であり、ａは０又は１であり、ｂは０～２の整数であり、ｃは１～２０の整数であり、ｄは０又は１である。但し、ａ及びｂが同時に０になることはない。）
で表される化合物等が挙げられる。上記式（Ｅ－１）で表される化合物としては、例えば下記式（Ｅ－１－１）～式（Ｅ－１－４）のそれぞれで表される化合物等が挙げられる。

Specific examples of orienting group-containing diamines include dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, pentadecanoxy- 2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholesterol Nyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate, 3,6-bis(4-aminobenzoyloxy)cholestane , 3,6-bis(4-aminophenoxy)cholestane, 4-(4′-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl ) Phenyl)-4-butylcyclohexane, 3,5-diaminobenzoic acid = 5ξ-cholestan-3-yl, the following formula (E-1)

(In formula (E-1), X ^I and X ^II are each independently a single bond, -O-, *-COO- or *-OCO- (wherein "*" is a bond with X ^I ), R ^I is an alkanediyl group having 1 to 3 carbon atoms, R ^II is a single bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, and b is is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1. However, a and b are not 0 at the same time.)
Compounds represented by and the like. Examples of the compound represented by the formula (E-1) include compounds represented by the following formulas (E-1-1) to (E-1-4).

When synthesizing the polyamic acid (A), the proportion of the alignment group-containing diamine used may be 1 mol% or more with respect to the total amount of the diamine compounds used in the synthesis in order to improve the liquid crystal alignment. It is preferably 5 to 50 mol %, more preferably 10 to 40 mol %. The orienting group-containing diamines can be used singly or in combination of two or more.

Nitrogen-containing diamine Other preferred examples of other diamines are from the group consisting of a nitrogen-containing heterocycle, an amino group, a protected amino group, an amide group, a protected amide group, a urea group, and a protected urea group. An aromatic diamine compound (hereinafter also referred to as "nitrogen-containing diamine") having at least one selected partial structure can be mentioned. When the polymer (A) has a partial structure derived from a nitrogen-containing diamine, the effect of improving the resistance to high temperature and high humidity of the liquid crystal alignment film can be enhanced, which is preferable.

（式（Ｎ－１）中、Ｒ^２０は水素原子、炭素数１～１０の１価の炭化水素基又は保護基である。「＊」は結合手であることを表す。）Nitrogen-containing heterocycles possessed by nitrogen-containing diamines include, for example, pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzimidazole, purine, quinoline, isoquinoline, naphthyridine, quinoxaline, phthalazine, triazine, carbazole, acridine, piperidine, piperazine, pyrrolidine, hexamethyleneimine and the like. Among them, it is preferable to have at least one selected from the group consisting of pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole and acridine.
The amino group, protected amino group, amido group, protected amido group, urea group and protected urea group preferably have a structure represented by the following formula (N-1).

(In formula (N-1), R ²⁰ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms or a protecting group. "*" represents a bond.)

In the above formula (N-1), examples of monovalent hydrocarbon groups for R ²⁰ include alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclohexyl group; phenyl group and methylphenyl group; and the like.
The protecting group is preferably a group that is released by heat, and examples thereof include carbamate-based protecting groups, amide-based protecting groups, imide-based protecting groups, and sulfonamide-based protecting groups. Among these, the tert-butoxycarbonyl group is preferable because it has high detachability by heat and the amount of the deprotected portion remaining in the film can be reduced. R ²⁰ is preferably a hydrogen atom, a methyl group or a t-butoxycarbonyl group.

Specific examples of nitrogen-containing diamines include 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 1 ,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis( 4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, each of the following formulas (N-1-1) to (N-1-13) and the like compounds represented.

In the synthesis of the polyamic acid (A), the ratio of the nitrogen-containing diamine used is 5 to 70 mol with respect to the total amount of the diamine compounds used in the synthesis, in order to sufficiently obtain the effect of improving the resistance to high temperature and high humidity of the liquid crystal element. %, more preferably 10 to 60 mol %, even more preferably 15 to 50 mol %. A nitrogen-containing diamine can be used individually by 1 type or in combination of 2 or more types.

Other diamines used in the synthesis of polyamic acid (A) include, in addition to the above, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4-aminophenyl-4-aminobenzoate, 4,4'-diamino azobenzene, 3,5-diaminobenzoic acid, 1,5-bis(4-aminophenoxy)pentane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1 ,6-bis(4-aminophenoxy)hexane, 1,2-bis(4-aminophenyl)ethane, 1,5-bis(4-aminophenyl)pentane, bis[2-(4-aminophenyl)ethyl] Hexanedioic acid, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2,2 -bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(phenylenediisopropylidene)bisaniline, 1,4-bis(4 -aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diaminodiphenylamine and other aromatic diamines, and specific diamine D2 described later. Other diamines can be used singly or in combination of two or more.

(Synthesis of polyamic acid)
Polyamic acid (A) can be obtained by reacting the above tetracarboxylic dianhydride and diamine compound together with a molecular weight modifier, if necessary. In the synthesis reaction of the polyamic acid (A), the ratio of the tetracarboxylic dianhydride and the diamine compound used is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.00 to 1 equivalent of the amino group of the diamine compound. A ratio of 2 to 2 equivalents is preferred. Examples of molecular weight modifiers include monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. can be mentioned. The proportion of the molecular weight modifier used is preferably 20 parts by mass or less with respect to a total of 100 parts by mass of the tetracarboxylic dianhydride and the diamine compound used.

The synthesis reaction of polyamic acid (A) is preferably carried out in an organic solvent. At this time, the reaction temperature is preferably −20° C. to 150° C., and the reaction time is preferably 0.1 to 24 hours. Organic solvents used in the reaction include, for example, aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Specific examples include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol and One or more selected from the group consisting of halogenated phenols can be used as a reaction solvent, or a mixture of one or more of these and other organic solvents (e.g., butyl cellosolve, diethylene glycol diethyl ether, etc.) can be used. preferable. The amount (a) of the organic solvent used is such that the total amount (b) of the tetracarboxylic dianhydride and the diamine is 0.1 to 50% by mass with respect to the total amount (a+b) of the reaction solution. is preferred.
As described above, a polymer solution in which the polyamic acid (A) is dissolved is obtained. This polymer solution may be used for the preparation of the liquid crystal aligning agent as it is, or may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid (A) contained in the polymer solution.

(polyamic acid ester)
When the polymer (A) is a polyamic acid ester, the polyamic acid ester (hereinafter also referred to as "polyamic acid ester (A)") is, for example, [I] polyamic acid (A) and an esterifying agent [II] a method of reacting a tetracarboxylic acid diester with a diamine compound; [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine compound; The polyamic acid ester (A) may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist. In the above [II] and [III], the tetracarboxylic acid derivative and the diamine compound containing the specific diamine D1 are reacted. In addition, the reaction solution obtained by dissolving the polyamic acid ester (A) may be directly subjected to the preparation of the liquid crystal aligning agent, and after isolating the polyamic acid ester (A) contained in the reaction solution, may be used for the preparation of

(polyimide)
When the polymer (A) is a polyimide, the polyimide (hereinafter also referred to as "polyimide (A)") is imidized by dehydration ring closure of the polyamic acid (A) synthesized as described above, for example. can be obtained by The polyimide (A) may be a complete imidized product obtained by dehydrating and ring-closing all the amic acid structures of the precursor polyamic acid (A), and only a part of the amic acid structure is dehydrated and ring-closed. , a partially imidized product in which an amic acid structure and an imide ring structure coexist. The polyimide (A) preferably has an imidization rate of 20 to 99%, more preferably 30 to 90%. The imidization rate is expressed as a percentage of the ratio of the number of imide ring structures to the sum of the number of amic acid structures and the number of imide ring structures of the polyimide. Here, part of the imide ring may be an isoimide ring.

The dehydration and ring closure of the polyamic acid (A) is preferably carried out by dissolving the polyamic acid (A) in an organic solvent, adding a dehydrating agent and a dehydration and ring closure catalyst to the solution, and heating if necessary. In this method, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as a dehydrating agent. The dehydrating agent is preferably used in an amount of 0.01 to 20 mol per 1 mol of the amic acid structure of the polyamic acid (A). Tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used as dehydration ring-closing catalysts. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol per 1 mol of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closure reaction include the organic solvents exemplified as those used in the synthesis of the polyamic acid (A). The reaction temperature for the dehydration ring closure reaction is preferably 0 to 180°C. The reaction time is preferably 1.0 to 120 hours. In addition, the reaction solution containing a polyimide (A) may be used for preparation of a liquid crystal aligning agent as it is, and after isolating a polyimide (A), it may be used for preparation of a liquid crystal aligning agent.

The solution viscosity of the polymer (A) used for the preparation of the liquid crystal aligning agent preferably has a solution viscosity of 10 to 800 mPa s when the solution has a concentration of 10% by mass, and preferably 15 to 500 mPa s. It is more preferable to have a solution viscosity of The solution viscosity (mPa s) is E It is a value measured at 25° C. using a type rotational viscometer.

The polystyrene equivalent weight average molecular weight (Mw) of the polymer (A) measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. is. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene equivalent number average molecular weight (Mn) measured by GPC is preferably 7 or less, more preferably 5 or less. In preparing the liquid crystal aligning agent, the polymer (A) may be used singly or in combination of two or more.

<Component having a group (R)>
The liquid crystal aligning agent contains a component having at least one group (R) selected from the group consisting of a radically polymerizable group, a photoinitiator group, a photoaligning group and a β-hydroxyester group. The component may be the polymer (A) or a compound different from the polymer (A). Moreover, the liquid crystal aligning agent may contain these both. It is preferable that the liquid crystal aligning agent contains a compound different from the polymer (A) as a compound having a group (R) in that the transmittance of the obtained liquid crystal alignment film can be further increased. It is preferable that the polymer (A) having the group (R) is contained in the liquid crystal aligning agent in order to improve the high temperature and high humidity resistance of the liquid crystal aligning agent.

(Radical polymerizable group)
Among the groups (R), the radically polymerizable group is not particularly limited as long as it is a functional group that can be polymerized by irradiation with radiation or the action of radicals. Specific examples of radically polymerizable groups include (meth)acryloyloxy, vinyl, allyl, vinylphenyl, maleimide, vinyloxy, and ethynyl groups. Among these, a (meth)acryloyloxy group, a vinyl group, an allyl group, an ethynyl group, or a vinylphenyl group is preferred because of its high thermal reactivity.

(photoinitiator group)
The photoinitiator group is a site that produces the ability to initiate polymerization by light or a site that has a photosensitizing action. It is a group having a structure derived from an initiable compound (photoinitiator). The photoinitiator group is preferably a group having a structure derived from a radical polymerization initiator capable of generating radicals upon irradiation with light. Specifically, it preferably has an acetophenone structure, an oxime ester structure, a dibenzoyl structure, a benzoin structure, a benzophenone structure, an alkylphenone structure, or an acylphosphine oxide structure. Among these, the photoinitiator group is preferably a group having an alkylphenone structure or an acetophenone structure.

Further specific examples of structures having a photoinitiator group include, for example, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2- methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, phenyl 2-(meth)acryloyl Oxy-2-propylketone, 4-isopropylphenyl 2-(meth)acryloyloxy-2-propylketone, 4-(2-(meth)acryloyloxyethoxy)-benzoin, 4-(meth)acryloyloxyphenyl 2-( Examples include structures derived from meth)acryloyloxy-2-propylketone, 4-(meth)acryloyloxybenzophenone, and the like.

（式（５）中、Ｒは、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、少なくとも１個の水素原子がフッ素原子で置換された炭素数１～１０のフッ素含有アルキル基、少なくとも１個の水素原子がフッ素原子で置換された炭素数１～１０のフッ素含有アルコキシ基、又はフッ素原子である。ａは０～４の整数である。ａが２以上の場合、複数のＲは同一でも異なっていてもよい。「＊」は結合手を示す。）(Photo-orientation group)
The photo-orientation group is a functional group that imparts anisotropy to the film by photoisomerization reaction, photodimerization reaction, photodecomposition reaction, and photofries rearrangement reaction caused by light irradiation. Specific examples of photo-orientation groups include azobenzene-containing groups containing azobenzene or a derivative thereof as a basic skeleton, cinnamic acid structure-containing groups containing cinnamic acid or a derivative thereof as a basic skeleton, and chalcone containing chalcone or a derivative thereof as a basic skeleton. containing group, benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, cyclobutane-containing structure containing cyclobutane or a derivative thereof as a basic skeleton, phenylbenzoate or a derivative thereof as a basic skeleton and phenylbenzoate-containing structures containing as. Among these, the cinnamic acid structure-containing group is preferable because of its high sensitivity to light, and examples thereof include groups having a partial structure represented by the following formula (5).

(In formula (5), R is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a fluorine-containing alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. a fluorine-containing alkoxy group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, or a fluorine atom, a is an integer of 0 to 4. When a is 2 or more, plural may be the same or different."*" indicates a bond.)

In the partial structure represented by the above formula (5), one of the two bonds "*" is an alkyl group having 3 to 20 carbon atoms, an alkyl group having 3 to 20 carbon atoms, and a 20 fluoroalkyl group, alkoxy group having 3 to 20 carbon atoms, fluoroalkoxy group having 3 to 20 carbon atoms, substituted or unsubstituted phenylene group, substituted or unsubstituted cyclohexyl group, or —R ³¹ —R ³² —* ² (provided that R ³¹ is a phenylene group or a cyclohexylene group, and R ³² is a single bond, an oxygen atom, —COO—, —OCO when bonded to the benzene ring in formula (5) - or an alkanediyl group having 1 to 3 carbon atoms, which is an oxygen atom when bonded to a carbonyl group in formula (5)."* ² " is a benzene ring or is a bond with a carbonyl group).

Specific examples of the group having a partial structure represented by the above formula (5) include a monovalent group obtained by removing the hydrogen atom of the carboxyl group of cinnamic acid, and the benzene ring of the monovalent group. A group into which a substituent is introduced, a monovalent group in which the carboxyl group of cinnamic acid is esterified and a divalent organic group is bonded to the benzene ring, a substituent on the benzene ring of the monovalent group is introduced, and the like.

（式（６）中、Ｒ^５０は芳香族基である。「＊」は結合手であることを示す。）(β-hydroxyester group)
A β-hydroxyester group is a group in which a hydroxyl group is bonded to the carbonyl group of an ester group (-COO-) at the β-position. The β-hydroxyester group preferably has a structure represented by the following formula (6).

(In formula (6), R ⁵⁰ is an aromatic group. "*" indicates a bond.)

In the above formula (6), the aromatic ring group of R ⁵⁰ is a group obtained by removing two hydrogen atoms from the ring portion of the aromatic ring. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring; aromatic heterocycles such as pyridine ring, pyrimidine ring and pyrazine ring. In addition, these aromatic rings may have a substituent (for example, an alkyl group, an alkoxy group, etc.) on the ring portion. Among these, the aromatic ring group for R ⁵⁰ is particularly preferably a phenylene group.

（式（６－１）～式（６－４）中、Ｒ^５１は、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、少なくとも１個の水素原子がフッ素原子で置換された炭素数１～２０のフッ素含有アルキル基、少なくとも１個の水素原子がフッ素原子で置換された炭素数１～２０のフッ素含有アルコキシ基、又はフッ素原子である。「＊」は結合手であることを示す。）Specific examples of the partial structure having a β-hydroxyester group include structures represented by the following formulas (6-1) to (6-4).

(In formulas (6-1) to (6-4), R ⁵¹ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and at least one hydrogen atom is substituted with a fluorine atom. is a fluorine-containing alkyl group having 1 to 20 carbon atoms, a fluorine-containing alkoxy group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, or a fluorine atom. indicates that.)

The content ratio of the group (R) in the liquid crystal aligning agent can be selected according to the type of the group (R). Specifically, the content of the radically polymerizable group is preferably 5 to 90 mol%, preferably 10 to 80 mol%, with respect to the total monomer unit amount of the polymer component contained in the liquid crystal aligning agent. is more preferable.
The content of the photoinitiator group is preferably 0.1 to 90 mol%, more preferably 1 to 80 mol%, with respect to the total monomer unit amount of the polymer component contained in the liquid crystal aligning agent. preferable.
The content of the photo-aligning group is preferably 5 to 90 mol %, more preferably 10 to 80 mol %, relative to the total amount of monomer units of the polymer component contained in the liquid crystal aligning agent.
The content of the β-hydroxyester group is preferably 5 to 90 mol%, more preferably 10 to 80 mol%, relative to the total amount of monomer units of the polymer component contained in the liquid crystal aligning agent. .

When the polymer (A) has a group (R), the diamine compound having the group (R) introduces the group (R) into the side chain of the polymer (A) because of the high degree of freedom of monomer selection. preferably. In this case, among the monomers used to synthesize the polymer (A), the specific diamine D1 may have the group (R), or a diamine compound different from the specific diamine D1 may have the group (R). may be Among these, in the synthesis of the polymer (A), a specific diamine D1 and a diamine compound having a group (R) ( However, it is a compound different from the specific diamine D1.) is preferably used.

When the liquid crystal aligning agent contains a compound different from the polymer (A) as a component having a group (R), the compound may be a low-molecular-weight compound having no repeating unit, but liquid crystal alignment In that it can improve the transmittance of the film and the resistance to high temperature and high humidity of the liquid crystal element in a well-balanced manner, it is derived from the compound represented by the above formula (1) having the group (R) together with the polymer (A). It is particularly preferable to contain a polymer having no partial structure (hereinafter also referred to as "polymer (B)").

<Polymer (B)>
Although the main skeleton of the polymer (B) is not particularly limited, it can be polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, and polymerizable unsaturated polymer in that the permeability and high-temperature and high-humidity resistance of the liquid crystal alignment film can be increased. It is preferably at least one selected from the group consisting of polymers having structural units derived from monomers having bonds. Examples of the monomer having a polymerizable unsaturated bond include (meth)acrylic compounds, conjugated diene compounds, aromatic vinyl compounds, maleimide compounds, and the like. Among the above, the polymer (B) is more preferably at least one selected from the group consisting of polyamic acids, polyamic acid esters, polyimides and polyorganosiloxanes, and particularly preferably polyorganosiloxanes.

（式中、Ｒ^５１は、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、少なくとも１個の水素原子がフッ素原子で置換された炭素数１～２０のフッ素含有アルキル基、少なくとも１個の水素原子がフッ素原子で置換された炭素数１～２０のフッ素含有アルコキシ基、又はフッ素原子である。Ｌ^２は２価の連結基である。）When the polymer (B) is at least one selected from the group consisting of polyamic acids, polyamic acid esters and polyimides, the polymer (B) is a compound different from the specific diamine D1 as a monomer, and It can be obtained by using a diamine compound having a group (R) (hereinafter also referred to as “specific diamine D2”). Specific examples of the specific diamine D2 include, but are not particularly limited to, compounds represented by the following formulas (r-1) to (r-11).

(Wherein, R ⁵¹ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a fluorine-containing alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, A fluorine-containing alkoxy group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, or a fluorine atom.L2 is a ^divalent linking group.)

The content of structural units derived from the specific diamine D2 in the polymer (B) is preferably 5 to 50 mol% of the total amount of structural units derived from the diamine compound in the polymer (B). It is more preferably 10 to 45 mol %, and even more preferably 20 to 40 mol %. Specific diamine D2 can be used individually by 1 type or in combination of 2 or more types. In addition, when the polymer (A) has a structural unit derived from the specific diamine D2, the content ratio of the structural unit is 5 to 5 with respect to the total amount of structural units derived from the diamine compound possessed by the polymer (A). It is preferably 50 mol %, more preferably 10 to 40 mol %.

<Polyorganosiloxane (B)>
When the polymer (B) is a polyorganosiloxane, the polyorganosiloxane (hereinafter also referred to as "polyorganosiloxane (B)") is composed of (1) a hydrolyzable silane compound having an epoxy group (S1) alone, or by hydrolytic condensation of a mixture of the silane compound (S1) and other hydrolyzable silane compounds, polyorganosiloxane having epoxy groups in side chains (hereinafter also referred to as "polyorganosiloxane E" ), then reacting polyorganosiloxane E with a carboxylic acid having a group (R), (2) hydrolytic condensation of a monomer containing a hydrolyzable silane compound having a group (R) and the like. Among these methods, the method (1) is preferred because it is simple and the efficiency of introduction of the group (R) into the side chain of the polymer is high.

Examples of the silane compound (S1) include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, and 3-glycid. Xypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, (3-ethyl (meth)acrylate) oxetan-3-yl)methyl, (3-methyloxetan-3-yl)methyl (meth)acrylate and the like. The silane compound (S1) may be used alone or in combination of two or more.

Other silane compounds include, for example, tetraalkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane; Silane compounds; sulfur-containing alkoxysilane compounds such as 3-mercaptopropyltriethoxysilane and mercaptomethyltriethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 Nitrogen-containing alkoxysilane compounds such as -aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane; 3-(meth)acryloxypropyltrimethoxysilane, 3-( Unsaturated bond-containing alkoxysilane compounds such as meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane and vinyltriethoxysilane; acid anhydride groups such as trimethoxysilylpropylsuccinic anhydride containing alkoxysilane compound, and the like. As other silane compounds, one of these may be used alone, or two or more thereof may be used in combination.

The hydrolysis/condensation reaction using a hydrolyzable silane compound is carried out by reacting one or more of the above silane compounds with water, preferably in the presence of a suitable catalyst and organic solvent. In the reaction, the ratio of water used is preferably 1 to 30 mol per 1 mol of the silane compound (total amount). Examples of catalysts to be used include acids, alkali metal compounds, organic bases (eg, triethylamine, tetramethylammonium hydroxide, etc.), titanium compounds, zirconium compounds, and the like. The amount of the catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, etc., and should be set as appropriate. . The organic solvent to be used includes, for example, hydrocarbons, ketones, esters, ethers, alcohols, etc. Among these, it is preferable to use a water-insoluble or sparingly water-soluble organic solvent. The ratio of the organic solvent to be used is preferably 50 to 1,000 parts by mass with respect to 100 parts by mass of the silane compounds used in the reaction.

The above hydrolysis/condensation reaction is preferably carried out by heating, for example, in an oil bath. At that time, the heating temperature is preferably 130° C. or lower, and the heating time is preferably 0.5 to 12 hours. After completion of the reaction, polyorganosiloxane E can be obtained by removing the solvent from the organic solvent layer separated from the reaction solution. After obtaining the polyorganosiloxane E, the polyorganosiloxane E is reacted with a carboxylic acid having a group (R). The reaction of polyorganosiloxane E and carboxylic acid is preferably carried out in an organic solvent in the presence of a catalyst. Examples of organic solvents include ketones, ethers, esters, amides and alcohols. A quaternary organic amine salt or a quaternary ammonium halide can be preferably used as the catalyst. After completion of the reaction, the desired polyorganosiloxane can be obtained by drying the organic solvent layer separated from the reaction solution with a desiccant, if necessary, and then removing the solvent.

The polyorganosiloxane (B) preferably has a polystyrene equivalent weight average molecular weight (Mw) measured by GPC in the range of 500 to 100,000, more preferably in the range of 1,000 to 30,000. , 1,000 to 20,000.

The content of the polymer (A) is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass, based on the total amount of the polymer components contained in the liquid crystal aligning agent. It is more preferable to set it as above. Further, when the polymer (A) and the polymer (B) are contained in the liquid crystal aligning agent, the content ratio of the polymer (B) is 1 with respect to the total amount of the polymer components contained in the liquid crystal aligning agent. It is preferably at least 1% by mass, more preferably 1 to 30% by mass, even more preferably 2 to 20% by mass.

（式（３）中、Ｒ^８１は、炭素数２～５の１価の炭化水素基、又は当該炭化水素基における炭素－炭素結合間に「－Ｏ－」を有する１価の基である。）

（式（４）中、Ｒ^８２及びＲ^８３は、それぞれ独立に、水素原子、炭素数１～６の１価の炭化水素基、若しくは当該炭化水素基の炭素－炭素結合間に「－Ｏ－」を有する１価の基であるか、又は、Ｒ^８２及びＲ^８３が互いに合わせられてＲ^８２及びＲ^８３が結合する窒素原子と共に構成される環構造を表す。Ｒ^８４は、炭素数１～６のアルキル基である。）≪Solvent component≫
As the solvent component of the liquid crystal aligning agent, the solubility of the solvent in the polymer (A) and the wetting and spreading property of the liquid crystal aligning agent can be improved, and the heating temperature during film formation can be lowered. It is preferable to include at least one solvent (hereinafter also referred to as "specific solvent") selected from the group of solvents shown below (group consisting of [X] solvent and [Y] solvent).
Solvent group:
[X] Solvent: a compound represented by the following formula (3), a compound represented by the following formula (4), and 1,3-dimethyl-2-imidazolidinone.
[Y] Solvents: dipropylene glycol monomethyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, diisopentyl ether, diacetone alcohol, and propylene glycol monobutyl ether.

(In formula (3), R ⁸¹ is a monovalent hydrocarbon group having 2 to 5 carbon atoms, or a monovalent group having “—O—” between carbon-carbon bonds in the hydrocarbon group. )

(In formula (4), R ⁸² and R ⁸³ each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or “—O— ", or represents a ring structure in which R ⁸² and R ⁸³ are combined with each other and composed together with the nitrogen atom to which R ⁸² and R ⁸³ are attached. R ⁸⁴ has 1 to is the alkyl group of 6.)

・ [X] About the solvent (compound represented by formula (3))
In the compound represented by the above formula (3), the monovalent hydrocarbon group having 2 to 5 carbon atoms of R ⁸¹ is preferably a chain hydrocarbon group, such as an alkyl group having 2 to 5 carbon atoms, alkenyl and alkynyl groups. Examples of the monovalent group having "-O-" between carbon-carbon bonds in the hydrocarbon group include alkoxyalkyl groups having 2 to 5 carbon atoms.
Specific examples thereof include alkyl groups having 2 to 5 carbon atoms such as ethyl group, propyl group, butyl group and pentyl group; and alkenyl groups having 2 to 5 carbon atoms such as vinyl group and 1-propenyl group. , 2-propenyl group, 3-butenyl group, etc.; as alkynyl groups having 2 to 5 carbon atoms, such as ethynyl group, 2-propynyl group, 2-butynyl group, etc.; For example, methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, ethoxymethyl group, ethoxyethyl group, etc.; For example, an ethoxymethyl group, an ethoxyethyl group, etc. can be mentioned, respectively, and these may be linear or branched. R ⁸¹ is preferably an alkyl group having 2 to 5 carbon atoms or an alkoxyalkyl group among the above.

Specific examples of the compound represented by the formula (3) include N-ethyl-2-pyrrolidone, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n- Butyl)-2-pyrrolidone, N-(t-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N -Methoxybutyl-2-pyrrolidone and the like. Among these, N-ethyl-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-(t-butyl)-2-pyrrolidone, and N-methoxypropyl-2-pyrrolidone are particularly preferably used. can be done. As the compound represented by the above formula (3), these exemplified compounds can be used singly or in combination of two or more.

(Compound represented by formula (4))
In the compound represented by the above formula (4), the monovalent hydrocarbon group having 1 to 6 carbon atoms for R ⁸² and R ⁸³ includes, for example, a chain hydrocarbon group having 1 to 6 carbon atoms, a chain hydrocarbon group having 3 to 6 carbon atoms, 6 alicyclic hydrocarbon groups, and aromatic hydrocarbon groups having 5 or 6 carbon atoms. Examples of the monovalent group having "--O--" between the carbon-carbon bonds of the hydrocarbon group include alkoxyalkyl groups having 2 to 6 carbon atoms.
Specific examples thereof include chain hydrocarbon groups having 1 to 6 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group. or branched. Examples of alicyclic hydrocarbon groups having 3 to 6 carbon atoms include cyclopentyl and cyclohexyl groups; examples of aromatic hydrocarbon groups include phenyl groups; and alkoxyalkyl groups having 2 to 6 carbon atoms. can include, for example, the groups mentioned in the description of R ⁸¹ in the above formula (3); R ⁸² and R ⁸³ in formula (4) may be the same or different. Also, R ⁸² and R ⁸³ may combine with each other to form a ring together with the nitrogen atom to which R ⁸² and R ⁸³ are bonded. Examples of the ring formed by bonding R ⁸² and R ⁸³ together include a pyrrolidine ring and a piperidine ring, and these rings are bonded with a monovalent chain hydrocarbon group such as a methyl group. may be
R ⁸² and R ⁸³ are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, still more preferably a hydrogen atom or a methyl group. be.
Examples of the alkyl group having 1 to 6 carbon atoms for R ⁸⁴ include the groups exemplified in the explanation of the alkyl group having 1 to 6 carbon atoms for R ⁸² and R ⁸³ above. An alkyl group having 1 to 4 carbon atoms is preferred.

Specific examples of the compound represented by the formula (4) include 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-hexyloxy-N,N- dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide, and the like. In addition, the compound represented by the said Formula (4) can be used individually by 1 type or in combination of 2 or more types.

The [X] solvent is preferably at least one selected from the group consisting of the compound represented by the above formula (3) and 1,3-dimethyl-2-imidazolidinone. It is more preferable that the represented compound is at least one selected from the group consisting of a compound in which R ⁸¹ is an alkyl group having 2 to 5 carbon atoms or an alkoxyalkyl group and 1,3-dimethyl-2-imidazolidinone.
When preparing the liquid crystal aligning agent, only one of the [X] solvent and [Y] solvent may be used as the specific solvent, but it is possible to achieve both good coating uniformity and transparency. In that respect, it is preferable that only the [X] solvent is used among the [X] solvent and the [Y] solvent, or at least one [X] solvent and at least one [Y] solvent are contained , [X] solvent and at least one [Y] solvent are particularly preferably contained.

[X] The proportion of the solvent used (the total amount when two or more types are used) is sufficient to obtain the effect of suppressing the precipitation of the polymer component while making it possible to lower the baking temperature during film formation. It is preferable to set it as 1 mass % or more with respect to the total amount of solvents contained in a liquid crystal aligning agent, and it is more preferable to set it as 10 mass % or more. In addition, the use ratio is preferably 90% by mass or less with respect to the total amount of solvent contained in the liquid crystal aligning agent in order to sufficiently obtain the effect of improving coating properties by using the [Y] solvent in combination, and 70% by mass. It is more preferable to make it mass % or less. As the [X] solvent, one type may be used alone, or two or more types may be used in combination.

[Y] The proportion of the solvent used (the total amount when two or more types are used) is sufficient to achieve the effect of improving the coating properties of the liquid crystal aligning agent while making it possible to lower the baking temperature during film formation. 1% by mass or more, and more preferably 10% by mass or more, relative to the total amount of the solvent contained in the liquid crystal aligning agent. Moreover, it is preferable to set it as 80 mass % or less with respect to the total amount of the solvent contained in a liquid crystal aligning agent, and, as for the usage ratio, it is more preferable to set it as 70 mass % or less. As the [Y] solvent, one type may be used alone, or two or more types may be used in combination.

The solvent component in the liquid crystal aligning agent may be only the specific solvent, may be used in combination with a solvent other than the specific solvent (hereinafter also referred to as "[Z] solvent"), or may be only the [Z] solvent. The [Z] solvent includes a solvent having high polymer solubility and leveling property (hereinafter also referred to as “first solvent”) and a solvent having good wet spreadability (hereinafter also referred to as “second solvent”. ). Specifically, examples of the first solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2 - pentanone, diisobutyl ketone, ethylene carbonate, propylene carbonate, etc.;
Examples of the second solvent include ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, and ethylene. glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol diethyl ether acetate, isoamyl propionate, isoamyl isobutyrate and the like can be mentioned, respectively. In addition, as a [Z] solvent, you may use individually by 1 type, and may mix and use 2 or more types.

When using [X] solvent, [Y] solvent and [Z] solvent as solvents, the proportion of [Z] solvent used (the total amount when using two or more types) is included in the liquid crystal aligning agent It is preferably 50% by mass or less, more preferably 30% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less, relative to the total amount of the solvent. It is particularly preferable that the solvent component of the liquid crystal aligning agent consists of [X] solvent and [Y] solvent.

≪Other ingredients≫
The liquid crystal aligning agent may contain other components other than a polymer component and a solvent component as needed. The liquid crystal aligning agent, as other components, is selected from the group consisting of a cyclic ether group, a cyclic carbonate group, an isocyanate group, a blocked isocyanate group, an oxazoline group, a β-hydroxyalkylamide group, a Meldrum acid group, a methylol group and an alkylmethylol group. It is preferable to further contain a compound (C) having in its molecule at least one functional group (hereinafter also referred to as “functional group D”) capable of By containing the compound (C) in the liquid crystal aligning agent, the high temperature and high humidity resistance of the obtained liquid crystal alignment film (and thus the high temperature and high humidity resistance of the liquid crystal element) can be further improved, which is preferable.

Specific examples of the compound (C) include compounds having a cyclic ether group such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, N, N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4' -diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine, etc.; compounds having a cyclic carbonate group such as N,N,N', N'-tetra[(2-oxo-1,3-dioxolan-4-yl)ethyl]-4,4'-diaminodiphenylmethane and the like;
Examples of compounds having isocyanate groups or blocked isocyanate groups include tolylene diisocyanate, xylylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, etc.; Compounds such as 2,2'-bis(4-propyl-2-oxazoline), 2,2'-bis(4-phenyl-2-oxazoline), 1,2-bis(2-oxazoline-2-yl) Ethane, 1,4-bis(2-oxazolin-2-yl)cyclohexane, 1,3-bis(2-oxazolin-2-yl)benzene, 1,3-bis(4,5-dihydro-2-oxazolyl) Benzene, 1,3-bis(4-methyl-2-oxazolin-2-yl)benzene, etc.; compounds having a β-hydroxyalkylamide group, such as trade name "Primid XL-552" (manufactured by Em Chemie), etc. a compound having a Meldrum's acid group, such as a compound having 2 to 4 Meldrum's acid structures; a compound having a methylol group or an alkylmethylol group, such as trimethylolpropane, bis[2-ethyl-2,2- bis(hydroxymethyl)ethyl] ether, 2,2′-[oxybis(methylene)]bis[2-ethyl-1,3-propanediol], 2,2-bis(4-hydroxymethylphenyl)propane, 2, 2-bis(2,3,4-trihydroxymethylphenyl)propane, 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine and the like can be mentioned, respectively.

The content ratio of the compound (C) is 1 to 50 parts by mass with respect to 100 parts by mass of the total amount of the polymer components contained in the liquid crystal aligning agent, from the viewpoint of sufficiently obtaining the effect of improving the high temperature and high humidity resistance. is preferred, and 3 to 30 parts by mass is more preferred. As the compound (C), one type may be used alone, or two or more types may be used in combination. In addition, you may make it a polymer (A) have the functional group D instead of making a liquid crystal aligning agent contain the functional group D as an additive. In this case, the polymer (A) having the functional group (D) can be obtained by using the diamine compound having the functional group D as a monomer.

Other components contained in the liquid crystal aligning agent include, in addition to the compound (C), for example, a polymer different from the polymer (A) and the polymer (B), an antioxidant, a metal chelate compound, a curing accelerator, Surfactants, fillers, dispersants, photosensitizers and the like are included. The blending ratio of other components can be appropriately selected according to each compound within a range that does not impair the effects of the present invention.

The solid content concentration in the liquid crystal aligning agent (ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., but preferably It is in the range of 1 to 10% by mass. If the solid content concentration is less than 1% by mass, the film thickness of the coating film becomes too small, making it difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, the film thickness of the coating film becomes excessively large, making it difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases, resulting in poor coating properties. tend to

<<Liquid crystal alignment film and liquid crystal element>>
The liquid crystal alignment film of the present disclosure is formed from the liquid crystal alignment agent prepared as described above. Moreover, the liquid crystal element of this indication comprises the liquid crystal aligning film formed using the liquid crystal aligning agent demonstrated above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited. Field Switching) type, OCB (Optically Compensated Bend) type, and PSA type (Polymer Sustained Alignment) type. Among these, the liquid crystal aligning agent of the present disclosure can be particularly preferably applied for the production of a PSA type liquid crystal element and a vertical alignment type (light vertical type) liquid crystal element using a photo-alignment method.

A liquid crystal element can be manufactured, for example, by a method including steps 1 to 3 below. Step 1 uses different substrates depending on the desired mode of operation. Steps 2 and 3 are common to each operation mode.
<Step 1: Formation of coating film>
First, a liquid crystal aligning agent is applied onto a substrate, and preferably the coated surface is heated to form a coating film on the substrate. Examples of the substrate include glass such as float glass and soda glass; and transparent substrates made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and poly(alicyclic olefin). Examples of the transparent conductive film provided on one surface of the substrate include an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), and the like. can be used.
When manufacturing a TN-type, STN-type or VA-type liquid crystal element, two substrates provided with patterned transparent conductive films are used. On the other hand, when manufacturing an IPS-type or FFS-type liquid crystal element, a substrate provided with electrodes patterned in a comb shape and a counter substrate provided with no electrodes are used.

The method of applying the liquid crystal aligning agent to the substrate is not particularly limited. method, direct gravure coater method, chamber doctor coater method, offset gravure coater method, impregnation coater method, MB coater method, and the like.

After applying the liquid crystal aligning agent, preheating (pre-baking) is preferably carried out for the purpose of preventing dripping of the applied liquid crystal aligning agent. The pre-baking temperature is preferably 30-200° C., and the pre-baking time is preferably 0.25-10 minutes. Thereafter, the solvent is completely removed and, if necessary, a baking (post-baking) step is carried out for the purpose of thermal imidization of the amic acid structures present in the polymer. The baking temperature (post-baking temperature) at this time is preferably 80 to 280.degree. C., more preferably 80 to 250.degree. The post-bake time is preferably 5-200 minutes. The film thickness of the formed film is preferably 0.001 to 1 μm.

<Step 2: Alignment treatment>
When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal element, the coating film formed in the above step 1 is subjected to a treatment (orientation treatment) for imparting liquid crystal orientation ability. As a result, the coating film is provided with the ability to align liquid crystal molecules to form a liquid crystal alignment film. As the alignment treatment, it is preferable to use a rubbing treatment in which the surface of the coating film formed on the substrate is rubbed with cotton or the like, or a photo-alignment treatment in which the coating film is irradiated with light to impart liquid crystal alignment ability. On the other hand, in the case of manufacturing a vertical alignment type liquid crystal element, the coating film formed in the above step 1 may be used as a liquid crystal alignment film as it is, and the coating film is subjected to an alignment treatment in order to further increase the liquid crystal alignment ability. may be applied.

Light irradiation for photo-alignment is a method of irradiating the coating film after the post-baking process, a method of irradiating the coating film after the pre-baking process and before the post-baking process, pre-baking process and post-baking process. In at least one of the methods, the coating film is irradiated while the coating film is being heated, or the like. As the radiation to irradiate the coating film, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. Ultraviolet rays including light with a wavelength of 200 to 400 nm are preferred. When the radiation is polarized, it may be linearly polarized or partially polarized. When the radiation used is linearly polarized or partially polarized, irradiation may be performed in a direction perpendicular to the substrate surface, obliquely, or a combination thereof. In the case of non-polarized radiation, the irradiation direction is oblique.

Examples of light sources to be used include low pressure mercury lamps, high pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps and excimer lasers. The dose of radiation is preferably 400 to 50,000 J/m ² , more preferably 1,000 to 20,000 J/m ² . After light irradiation for imparting alignment ability, the substrate surface is washed with, for example, water, an organic solvent (eg, methanol, isopropyl alcohol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, etc.), or a mixture thereof. A treatment to heat the substrate may be performed.

<Step 3: Construction of liquid crystal cell>
A liquid crystal cell is manufactured by preparing two substrates on which a liquid crystal alignment film is formed as described above and arranging a liquid crystal between the two substrates facing each other. In order to manufacture a liquid crystal cell, for example, two substrates are arranged facing each other with a gap therebetween so that the liquid crystal alignment films face each other, the peripheral portions of the two substrates are bonded together with a sealing agent, and the surfaces of the substrates and the sealing agent are bonded together. A method of injecting liquid crystal into a cell gap surrounded by and sealing the injection hole, a method of ODF method, and the like. As the sealant, for example, an epoxy resin or the like containing a curing agent and aluminum oxide spheres as spacers can be used. Liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred.

In the PSA mode, a polymerizable compound (for example, a polyfunctional (meth)acrylate compound) is filled in the cell gap together with the liquid crystal, and after the liquid crystal cell is constructed, a voltage is applied between the conductive films of the pair of substrates. A process of irradiating the liquid crystal cell with light is performed. In producing a PSA mode liquid crystal device, the proportion of the polymerizable compound used is 0.01 to 3 parts by weight, preferably 0.1 to 1 part by weight, per 100 parts by weight of liquid crystal in total. The applied voltage can be, for example, 5 to 50 V DC or AC. As the light for irradiation, for example, ultraviolet light containing light with a wavelength of 150 to 800 nm and visible light can be used, but ultraviolet light containing light with a wavelength of 300 to 400 nm is preferable. The irradiation amount of light is preferably 1,000 to 200,000 J/m ² , more preferably 1,000 to 100,000 J/m ² .

When the liquid crystal element is used as a display device, a polarizing plate is attached to the outer surface of the liquid crystal cell as necessary to form a liquid crystal element. Examples of the polarizing plate include a polarizing plate in which a polarizing film called "H film" in which iodine is absorbed while stretching orientation of polyvinyl alcohol is sandwiched between cellulose acetate protective films, or a polarizing plate composed of the H film itself.

The liquid crystal device of the present invention described in detail above can be effectively applied to various uses. Specifically, for example, various display devices such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions, information displays, It can be used as a light modulating element, a retardation film, and the like.

Hereinafter, the embodiments will be described in more detail based on examples, but the present invention is not limitedly interpreted by the following examples.

In the following examples, the weight average molecular weight Mw of the polymer, the imidization rate of the polyimide in the polymer solution, the solution viscosity of the polymer solution, and the epoxy equivalent were measured by the following methods. Necessary amounts of the raw material compounds and polymers used in the following examples were ensured by repeating the synthesis on the synthesis scale shown in the synthesis examples below as necessary.
[Polymer weight average molecular weight Mw]
The weight average molecular weight Mw is a polystyrene conversion value measured by GPC under the following conditions.
Column: TSKgelGRCXLII manufactured by Tosoh Corporation
Solvent: Tetrahydrofuran, or N,N-dimethylformamide solution containing lithium bromide and phosphoric acid Temperature: 40°C
Pressure: 68kgf/ ^cm2
[Imidization rate of polyimide]
The polyimide solution was poured into pure water, and the resulting precipitate was thoroughly dried under reduced pressure at room temperature, dissolved in deuterated dimethylsulfoxide, and subjected to ¹ H-NMR measurement at room temperature using tetramethylsilane as a reference substance. From the obtained ¹ H-NMR spectrum, the imidization rate [%] was determined by the following formula (1).
Imidation rate [%]=(1−(A ¹ /(A ² ×α)))×100 (1)
(In formula (1), A ¹ is the peak area derived from protons of the NH group appearing near the chemical shift of 10 ppm, A ² is the peak area derived from other protons, and α is the precursor of the polymer (polyamic acid ) is the number ratio of other protons to one proton of the NH group.)
[Solution Viscosity of Polymer Solution]
The solution viscosity (mPa·s) of the polymer solution was measured at 25° C. using an E-type rotational viscometer.
[Epoxy equivalent]
The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C2105.

（ジアミン化合物）

The abbreviations of the compounds are as follows. In addition, below, the compound represented by Formula (X) may be simply shown as "compound (X)."
(tetracarboxylic acid derivative)

(Diamine compound)

(Hydrolyzable silane compound and carboxylic acid)

(crosslinking agent)

<Synthesis of polymer>
1. Synthesis of Polyamic Acid [Synthesis Example 1]
100 mol parts of 2,3,5-tricarboxycyclopentylacetic dianhydride as a tetracarboxylic dianhydride, 20 mol parts of cholestanyloxy-2,4-diaminobenzene as a diamine, 30 mol parts of compound (d-4), and 50 mole parts of 4,4'-diaminodiphenyl ether were dissolved in N-methyl-2-pyrrolidone (NMP) and reacted at 60°C for 6 hours to obtain a solution containing 30% by mass of polyamic acid. A small amount of the obtained polyamic acid solution was taken, and NMP was added to prepare a solution having a polyamic acid concentration of 20% by mass. Then, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. This precipitate was washed with methanol and dried at 40° C. under reduced pressure for 15 hours to obtain a polymer (PAA-1).
[Synthesis Examples 2 to 18, 20, 21]
The same operation as in Synthesis Example 1 was performed except that the types and amounts of the tetracarboxylic dianhydride and diamine used were changed as shown in Table 1 below, and polyamic acids (polymers (PAA-2) to (PAA- 18), (PAA-20), (PAA-21)) were obtained.

2. Synthesis of Polyamic Acid Ester [Synthesis Example 19]
100 mol parts of compound (t-4) was added to thionyl chloride, a catalytic amount of N,N-dimethylformamide was added, and the mixture was stirred at 80° C. for 1 hour. Compound (t-4) is a mixture of compounds (t-4-1) to (t-1-4). After that, the reaction solution was concentrated, and the residue was dissolved in γ-butyrolactone (GBL) (this solution was designated as reaction solution A). Separately, 20 mol parts of cholestanyloxy-2,4-diaminobenzene, 30 mol parts of compound (d-4), 30 mol parts of compound (d-9), and 20 mol parts of compound (d-14) were added to pyridine and γ-butyrolactone (GBL) (pyridine:GBL=8.7:91.3 (mass ratio)) was added to dissolve and cooled to 0°C. Next, reaction liquid A was slowly added dropwise to this solution over 1 hour, and after the dropwise addition was completed, the mixture was stirred at room temperature for 4 hours. The resulting polyamic acid ester solution was added dropwise to 800 ml of pure water while stirring, and the deposited precipitate was filtered. Subsequently, it was washed with isopropyl alcohol five times and dried to obtain polymer powder (polyamic acid ester). The weight average molecular weight Mw of the obtained polymer (PAE-1) was 50,000.

3. Synthesis of Polyimide [Synthesis Example 22]
100 mol parts of 2,3,5-tricarboxycyclopentylacetic dianhydride as a tetracarboxylic dianhydride, 20 mol parts of cholestanyloxy-2,4-diaminobenzene as a diamine, 50 mol parts of compound (d-10), And 30 mol parts of compound (d-11) were dissolved in NMP and reacted at 60° C. for 6 hours to obtain a solution containing 30% by mass of polyamic acid. A small amount of the obtained polyamic acid solution was taken, and NMP was added to prepare a solution having a polyamic acid concentration of 20% by mass.
Next, NMP was added to the obtained polyamic acid solution to make a solution with a polyamic acid concentration of 7% by mass, pyridine and acetic anhydride were added, and a dehydration ring-closing reaction was carried out at 110° C. for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was replaced with new NMP to obtain a solution containing 26% by mass of polyimide (polymer (PI-1)) with an imidization rate of about 75%. A small amount of the obtained polyimide solution was taken, and NMP was added to prepare a solution having a polyimide concentration of 15% by mass. Then, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. This precipitate was washed with methanol and dried at 40° C. under reduced pressure for 15 hours to obtain a polymer (PI-1).
[Synthesis Example 23]
A polyimide (polymer (PI-2)) was obtained in the same manner as in Synthesis Example 22 except that the types and amounts of the tetracarboxylic dianhydride and diamine used were changed as shown in Table 1 below.

4. Synthesis of epoxy group-containing polyorganosiloxane [Synthesis Example 24]
A reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with 100.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine, and the temperature was maintained at room temperature. mixed with. Then, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the reaction was carried out at 80° C. for 6 hours while stirring under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by mass aqueous solution of ammonium nitrate until the water after washing became neutral. A siloxane (polymer (ESSQ-1)) was obtained as a viscous transparent liquid. When the polymer (ESSQ-1) was subjected to ¹ H-NMR analysis, a peak due to the epoxy group was obtained at a chemical shift (δ) of around 3.2 ppm, suggesting that a side reaction of the epoxy group occurred during the reaction. Confirmed not. The resulting polymer (ESSQ-1) had a weight average molecular weight Mw of 3,500 and an epoxy equivalent of 180 g/mol.
[Synthesis Examples 25-27]
The same operation as in Synthesis Example 24 was performed except that the type and amount of the hydrolyzable silane compound used was changed as shown in Table 2 below, and epoxy group-containing polyorganosiloxanes (polymers (ESSQ-2) to (ESSQ -4)) was obtained.

5. Synthesis of Polyorganosiloxane (B) [Synthesis Example 28]
In a 200 mL three-necked flask, 10.0 g of the polymer (ESSQ-1), 30.28 g of methyl isobutyl ketone as a solvent, compound (e-2) as a modifying component (carboxylic acid having an orientation group), the polymer ( An amount equivalent to 25 mol% of the total amount of epoxy groups possessed by ESSQ-1) and 0.10 g of UCAT 18X (trade name, manufactured by San-Apro Co., Ltd.) as a catalyst were charged, and stirred at 100°C for 48 hours. reacted. After completion of the reaction, the solution obtained by adding ethyl acetate to the reaction mixture was washed with water three times, and the organic layer was dried using magnesium sulfate. A coalescence (PSQ-1) was obtained. The weight average molecular weight Mw of the obtained polymer was 8,000.
[Synthesis Examples 29-31]
A polymer (PSQ- 2) to (PSQ-4) were obtained respectively. In Table 3, the numbers in parentheses for the modifying components indicate the ratio (mol%) of each modifying component to the total amount of epoxy groups in the epoxy-group-containing polyorganosiloxane used in the synthesis.

[Example 1]
1. Preparation of liquid crystal aligning agent To the polymer (PAA-16) obtained in Synthesis Example 16 above, NMP and butyl cellosolve (BC) are added as solvents, the solid content concentration is 4.0% by mass, and the mixing ratio of the solvent is NMP:BC. = 42:58 (mass ratio). After sufficiently stirring this solution, it was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal aligning agent (S-1).
2. Preparation of liquid crystal composition Per 10 g of nematic liquid crystal (manufactured by Merck & Co., MLC-6608), 5% by mass of a liquid crystalline compound represented by the following formula (L1-1) and A liquid crystal composition LC1 was obtained by adding and mixing 0.3% by mass of a photopolymerizable compound.

3. Manufacture of PSA type liquid crystal display element 1 above. The prepared liquid crystal aligning agent (S-1) is applied using a spinner to a glass substrate with a transparent electrode made of a pair (2 sheets) of ITO film, and pre-baked for 1 minute with a hot plate at 80 ° C., A coating film (liquid crystal alignment film) having a film thickness of 0.08 μm was formed by heating at 200° C. for 1 hour in an oven replaced with nitrogen to remove the solvent. This coating film was subjected to rubbing treatment using a rubbing machine having a roll wrapped with rayon cloth at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm/sec, and a pile pushing length of 0.1 mm. After that, ultrasonic cleaning was performed in ultrapure water for 1 minute, followed by drying in a 100° C. clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two sheets) of substrates having liquid crystal alignment films. This rubbing treatment is a weak rubbing treatment performed for the purpose of controlling tilting of the liquid crystal and performing the alignment division by a simple method.
An epoxy resin adhesive containing aluminum oxide spheres with a diameter of 3.5 μm was applied to the outer periphery of the surface of one of the substrates having the liquid crystal alignment film by screen printing, and then the liquid crystal alignment film surfaces of the pair of substrates were made to face each other. , were pressed together, and heated at 150° C. for 1 hour to thermally cure the adhesive. Next, after filling the gap between the substrates with the liquid crystal composition LC1 through the liquid crystal injection port, the liquid crystal injection port is sealed with an epoxy adhesive. After heating for 1 minute, it was gradually cooled to room temperature.
Next, an AC voltage of 10 V with a frequency of 60 Hz was applied between the electrodes to the liquid crystal cell thus obtained, and while the liquid crystal was being driven, an ultraviolet ray of 50,000 J was applied using an ultraviolet irradiation apparatus using a metal halide lamp as a light source. / ^m2 . Note that this irradiation amount is a value measured using a photometer that measures at a wavelength of 365 nm. Further, a liquid crystal display element was manufactured by bonding polarizing plates to both outer surfaces of the substrate so that the polarizing directions of the two polarizing plates were orthogonal to each other.

4. Evaluation of transmittance The liquid crystal aligning agent (S-1) prepared above is applied onto a quartz substrate using a spin coater, and heated (pre-baked) for 1 minute on a hot plate at 80 ° C. After removing the solvent. , and heated (post-baked) for 30 minutes in a clean oven at 230° C. under nitrogen to form a coating film having an average film thickness of 0.08 μm. The quartz substrate on which the coating film was formed was measured using an ultraviolet-visible-near-infrared spectrophotometer (manufactured by JASCO Corporation, product name "V-670"), and the same kind of quartz substrate without a coating film was used as a reference. Absorption spectra in the ultraviolet and visible regions were measured. When the transmittance at a wavelength of 400 nm was 98.0% or more, the film transmittance was "very good"; when it was 97.0% or more and less than 98.0%, it was "good"; When it was less than 0%, it was judged as "acceptable", and when it was less than 96.0%, it was judged as "poor". The transmittance of the film formed using the liquid crystal aligning agent (S-1) was 98.0%, which was "very good".

5. Evaluation of high-temperature and high-humidity resistance A voltage of 5 V was applied to the liquid crystal display element immediately after production at a temperature of 60 ° C. for an application time of 60 microseconds for a span of 167 milliseconds. A voltage holding ratio (initial voltage holding ratio VH ₁ ) was measured. As a measuring device, a product name "VHR-1" manufactured by Toyo Technica Co., Ltd. was used. Next, after the liquid crystal display element after measuring the initial voltage holding rate VH ₁ was stored in an oven set at 85° C. and 85% humidity for 300 hours, the voltage holding rate was measured in the same manner as for the initial voltage holding rate VH ₁ . It was measured. This value was taken as the post _- stress voltage holding ratio VH2. The rate of decrease in voltage holding ratio obtained by the following formula (2) was defined as ΔVHR (%), and high temperature and high humidity resistance was evaluated by ΔVHR.
ΔVHR=(VH2/VH1)× ₁₀₀ ( ₂ )
The evaluation was "Very good" when ΔVHR was 80% or more, "Good" when 70% or more and less than 80%, "Fair" when 60% or more and less than 70%, 60% A case of less than that was defined as "poor". As a result, in Example 1, ΔVHR was 80%, and the evaluation was "extremely good".

[Examples 2 to 32 and Comparative Examples 1 to 4]
1. of Example 1 above, except that the composition of the liquid crystal aligning agent was changed as shown in Tables 4 and 5 below. A liquid crystal aligning agent was prepared in the same manner as. Moreover, using the obtained liquid crystal aligning agent, a PSA type liquid crystal display device was produced in the same manner as in Example 1, and transmittance and high temperature and humidity resistance were evaluated. The results are shown in Tables 4 and 5 below. In Examples 2 to 32 and Comparative Examples 1 to 4, a plurality of types of polymers were blended to prepare liquid crystal aligning agents. In Examples 19 to 22, a cross-linking agent was added to the liquid crystal aligning agent.

In Tables 4 and 5, the numbers in parentheses for the polymer and the cross-linking agent indicate the blending ratio (parts by mass) of each compound with respect to the total 100 parts by mass of the polymer components and additives used in the preparation of the liquid crystal aligning agent. . The numerical value of the solvent composition indicates the blending ratio (mass ratio) of each solvent with respect to the total solvent components used in the preparation of the liquid crystal aligning agent. The abbreviations of the compounds are as follows.
<Solvent>
NMP: N-methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone DMI: 1,3-dimethyl-2-imidazolidinone BC: butyl cellosolve DEDG: diethylene glycol diethyl ether

As can be seen from Tables 4 and 5, in all of Examples 1 to 32, the transmittance of the liquid crystal alignment film showed a high value of 97% or more, and the high temperature and high humidity resistance was either "very good" or "good". was an evaluation. In addition, Examples 4 and 5 using the specific diamine D1 having no aromatic ring have higher transmittance of the liquid crystal alignment film than Example 6 using the specific diamine D1 having an aromatic ring. was confirmed.
On the other hand, Comparative Example 1 using a liquid crystal aligning agent that does not contain a component having a structural unit and group (R) derived from the specific diamine D1, the transmittance and high temperature and humidity resistance of the alignment film was lower than the Examples. Further, in Comparative Examples 2 to 4, which do not contain at least one of the structural units derived from the specific diamine D1 and the component having the group (R), either the transmittance of the alignment film or the high-temperature and high-humidity resistance is lower than that of the examples. was also inferior.

Claims (9)

At least one selected from the group consisting of polyamic acids, polyamic acid esters and polyimides, and containing a polymer (A) having a partial structure derived from a compound represented by the following formula (1),
The polymer (A) includes a nitrogen-containing heterocyclic ring (excluding the imide ring of the polyimide), an amino group, a protected amino group, an amide group, a protected amide group, a urea group and a protected urea having at least one partial structure selected from the group consisting of groups,
A radical polymerizable group, a photoinitiator group, a cinnamic acid structure-containing group and a β-hydroxy ester group in at least one of the molecule of the polymer (A) and the molecule different from the polymer (A) The liquid crystal aligning agent which has at least 1 type of group (R) chosen from the group consisting in a side chain.

(In formula (1), R ¹ and R ² are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and X ¹ is “—NHR ¹ ” and It is a divalent organic group bonded to each of “-NHR ² ” via a chain hydrocarbon group or an alicyclic hydrocarbon group.) The liquid crystal aligning agent according to claim ¹ , wherein said X1 is a divalent group having no aromatic ring. The liquid crystal aligning agent according to claim 1 or 2 , further comprising a polymer (B) having the group (R) and having no partial structure derived from the compound represented by the formula (1). . The liquid crystal aligning agent according to any one of claims 1 to 3 , wherein the polymer (A) has a partial structure derived from a tetracarboxylic acid derivative having a cyclobutane ring, cyclopentane ring or cyclohexane ring. The liquid crystal aligning agent according to any one of claims 1 to 4 , wherein the polymer (A) has a partial structure represented by the following formula (2).
*-L ¹ -R ¹¹ -R ¹² -R ¹³ -R ¹⁴ (2)
(In formula (2), L ¹ is a single bond, -O-, -CO-, -COO-* ¹ , -OCO-* ¹ , -NR ¹⁵ -, -NR ¹⁵ -CO-* ¹ , -CO —NR ¹⁵ —* ¹ , an alkanediyl group having 1 to 6 carbon atoms, —OR ¹⁶ —* ¹ , or —R ¹⁶ —O-* ¹ (provided that R ¹⁵ is a hydrogen atom or a is a monovalent hydrocarbon group, R ¹⁶ is an alkanediyl group having 1 to 3 carbon atoms, and "* ¹ " indicates a bond with R ^{11. R 11 and} R ¹³ are each independently a single bond, a phenylene group or a cycloalkylene group, and R ¹² is a single bond, a phenylene group, a cycloalkylene group, -R ¹⁷ -B ¹ -* ² or -B ¹ -R ¹⁷ -* ² (where R ¹⁷ is a phenylene group or a cycloalkylene group, and B ¹ is -COO-* ³ , -OCO-* ³ , or an alkanediyl group having 1 to 3 carbon atoms. "* ² " indicates a bond with R ¹³ , and “* ³ ” indicates a bond with R ^17. ) R ¹⁴ is a hydrogen atom, a fluorine atom, a cyano group, a carbon 1 to 18 alkyl group, 1 to 18 carbon atom fluoroalkyl group, 1 to 18 carbon atom alkoxy group, 1 to 18 carbon atom fluoroalkoxy group, 17 to 51 carbon atom hydrocarbon group having a steroid skeleton , or a monovalent organic group having a radically polymerizable group, a photoinitiator group, or a cyano group, provided that when all of R ¹¹ , R ¹² and R ¹³ are single bonds, R ¹⁴ has 4 carbon atoms -18 alkyl group, C4-18 fluoroalkyl group, C4-18 alkoxy group, C4-18 fluoroalkoxy group, or C17-51 hydrocarbon group having a steroid skeleton "*" indicates a bond.) at least one functional group selected from the group consisting of a cyclic ether group, a cyclic carbonate group, an isocyanate group, a blocked isocyanate group, an oxazoline group, a β-hydroxyalkylamide group, a Meldrum's acid group, a methylol group and an alkylmethylol group in the molecule; The liquid crystal aligning agent according to any one of claims 1 to 5 , further comprising a compound (C) having The liquid crystal aligning agent according to any one of claims 1 to 6 , which contains at least one [X] solvent and at least one [Y] solvent shown below.
Solvent group:
[X] Solvent: a compound represented by the following formula (3), a compound represented by the following formula (4), and 1,3-dimethyl-2-imidazolidinone.
[Y] Solvents: dipropylene glycol monomethyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, diisopentyl ether, diacetone alcohol, and propylene glycol monobutyl ether.

(In formula (3), R ⁸¹ is a monovalent hydrocarbon group having 2 to 5 carbon atoms, or a monovalent group having “—O—” between carbon-carbon bonds in the hydrocarbon group. )

(In formula (4), R ⁸² and R ⁸³ each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or “—O— ", or represents a ring structure in which R ⁸² and R ⁸³ are combined with each other and composed together with the nitrogen atom to which R ⁸² and R ⁸³ are attached. R ⁸⁴ has 1 to is the alkyl group of 6.) A liquid crystal alignment film formed using the liquid crystal alignment agent according to any one of claims 1 to 7 . A liquid crystal device comprising the liquid crystal alignment film according to claim 8 .