JP2015232109A - Polymer composition, liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, and method for manufacturing liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer composition that gives a liquid crystal display device having excellent response speed characteristics and contrast characteristics and excellent afterimage characteristics, even with a small irradiation quantity of light on the polymer composition.SOLUTION: The polymer composition comprises (A) a polymer and (B) an organic solvent. The (A) polymer has a group represented by formula (1) below. In the formula (1), Rrepresents a specific photo-reactive group; Rrepresents a single bond or a divalent organic group; Yrepresents a cyclic group having a valence of (u+1) or a nitrogen atom; u represents an integer of 2 to 4, however, when Yis a nitrogen atom, u is 2; and * represents a bond.

Description

  The present invention relates to a polymer composition, a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element, and a method for producing a liquid crystal display element.

  Among the liquid crystal display elements, an MVA (Multi-Domain Vertical Alignment) type panel conventionally known as a vertical alignment mode forms protrusions in the liquid crystal panel, thereby restricting the tilting direction of liquid crystal molecules, thereby reducing the field of view. The corner is enlarged. However, according to this method, the lack of transmittance and contrast derived from the protrusions is unavoidable, and the response speed of the liquid crystal molecules is slow.

  In recent years, a PSA (Polymer Sustained Alignment) mode has been proposed in order to solve the problems of the MVA type panel as described above (see, for example, Patent Document 1). In this PSA technology, a polymerizable component that is polymerized by light irradiation is mixed in the liquid crystal layer of the liquid crystal cell, and the liquid crystal cell is tilted by application of voltage, and the liquid crystal cell is irradiated with light, thereby the polymerizable component. Is a technique for controlling the molecular orientation of liquid crystal molecules by polymerizing the polymer. According to this technique, it is said that the viewing angle can be enlarged and the high-speed response of the liquid crystal molecules can be improved.

  Apart from this, Non-Patent Document 1 proposes a method using a liquid crystal alignment film formed from a polyimide liquid crystal aligning agent containing a reactive mesogen. According to Non-Patent Document 1, a liquid crystal display element including a liquid crystal alignment film formed by this method has a high response speed of liquid crystal molecules.

  In addition, the present applicant can provide a desired pretilt angle characteristic to a coating film formed using a liquid crystal aligning agent with as little light dose as possible, and the liquid crystal display has a sufficiently fast response speed of liquid crystal molecules to voltage changes. A technique for obtaining an element has been proposed (see, for example, Patent Document 2). In Patent Document 2, a liquid crystal alignment film is formed on a substrate using a liquid crystal alignment agent containing a polyorganosiloxane having a (meth) acryloyl group in the side chain as a polymer component, and a liquid crystal is formed using the substrate. It is disclosed that a liquid crystal display element is manufactured by forming a cell and irradiating the liquid crystal cell with light while a voltage is applied between the substrates.

JP 2003-149647 A JP 2011-118358 A

Y.-J.Leeet. Al. SID 09 DIGEST, p. 666 (2009)

  However, the liquid crystal display element using the above technique has room for improvement in terms of suppressing the occurrence of afterimages during long-time driving. One possible cause of such afterimages is that the pretilt angle changes as the liquid crystal display element is driven for a long time. When the pretilt angle is changed in the liquid crystal display element, the response speed characteristics and optical characteristics of the liquid crystal molecules are greatly changed, and the display quality tends to be lowered. Another cause of the afterimage generation is considered to be that impurity ions are generated due to the decomposition of the liquid crystal molecules and the liquid crystal alignment film due to ultraviolet irradiation, and these are distributed in the liquid crystal display element. Generation of impurity ions is thought to be suppressed by reducing the amount of ultraviolet irradiation, but if the amount of ultraviolet irradiation is reduced, a liquid crystal alignment film having a sufficiently high pretilt angle cannot be obtained, and the liquid crystal molecules There is a concern that the response speed characteristic and the contrast characteristic may be deteriorated. In particular, in recent years, the demand for higher performance of liquid crystal display elements has further increased, and there has been a demand for better display quality of liquid crystal display elements than before.

  The present invention has been made in view of the above problems, and provides a polymer composition that can exhibit a liquid crystal display device exhibiting excellent response speed characteristics and contrast characteristics even with a small amount of light irradiation and having excellent afterimage characteristics. One purpose.

  As a result of intensive studies to solve the problems of the prior art as described above, the present inventors have found that the above problems can be solved by a polymer composition containing a polymer having a specific structure, The present invention has been completed. Specifically, the present invention provides the following polymer composition, liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element and liquid crystal display element manufacturing method.

  In one aspect, the present invention provides a polymer composition containing (A) a polymer and (B) an organic solvent, wherein the polymer (A) is a polymer having a group represented by the following formula (1). A polymer composition is provided that is a coalescence.

（式（１）中、Ｒ^１は下記式（ｒ１−１）〜式（ｒ１−６）

（式（ｒ１−１）〜式（ｒ１−６）中、Ｒ^５は水素原子又はメチル基であり、Ｘ^５は酸素原子又は−ＮＲ^３０−（ただし、Ｒ^３０は水素原子又はメチル基）である。Ｒ^６は炭素数１〜２０の１価の炭化水素基もしくは当該炭化水素基における少なくとも１個の水素原子をフッ素原子で置換した基、又は複素環を有する１価の基である。Ｒ^７及びＲ^９は水素原子又は炭素数１〜２０のアルキル基である。２個のＲ^８は、それぞれ独立に水素原子若しくは炭素数１〜２０のアルキル基であるか、又は２個のＲ^８が互いに結合することでＲ^８が結合する２個の炭素原子とともに炭素数４〜２０の炭化水素環構造を形成する。Ｒ^１０は水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のフルオロアルキル基である。ただし、複数のＲ^１０は同じでも異なっていてもよい。Ａｒ^１は２価の芳香環基であり、Ａｒ^２及びＡｒ^３は単結合又は２価の芳香環基である。）
のそれぞれで表される基よりなる群から選ばれる１価の基である。Ｒ^２は単結合又は２価の有機基である。Ｙ^１は（ｕ＋１）価の環状基又は窒素原子である。ｕは２〜４の整数である。ただし、Ｙ^１が窒素原子の場合、ｕ＝２である。「＊」は結合手を示す。）

(In the formula (1), R ¹ represents the following formula (r1-1) to formula (r1-6)

(In Formula (r1-1) to Formula (r1-6), R ⁵ is a hydrogen atom or a methyl group, X ⁵ is an oxygen atom or —NR ³⁰ — (wherein R ³⁰ is a hydrogen atom or a methyl group). R ⁶ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, a group in which at least one hydrogen atom in the hydrocarbon group is substituted with a fluorine atom, or a monovalent group having a heterocyclic ring. ⁷ and R ⁹ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and two R ^{8 s} are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, or two R ^{8 s.} Are bonded to each other to form a hydrocarbon ring structure having 4 to 20 carbon atoms with two carbon atoms to which R ⁸ is bonded, and R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 fluoroalkyl groups, provided that a plurality of R ^{1 0} may be the same or different, Ar ¹ is a divalent aromatic ring group, and Ar ² and Ar ³ are a single bond or a divalent aromatic ring group.)
These are monovalent groups selected from the group consisting of groups represented by R ² is a single bond or a divalent organic group. Y ¹ is a (u + 1) -valent cyclic group or a nitrogen atom. u is an integer of 2-4. However, when Y ¹ is a nitrogen atom, u = 2. “*” Indicates a bond. )

  In one aspect, the present invention provides a liquid crystal alignment film formed using a liquid crystal aligning agent as the polymer composition. Moreover, a liquid crystal display element provided with the said liquid crystal aligning film is provided. Furthermore, a step of applying the polymer composition on the conductive film of a pair of substrates having a conductive film to form a coating film, and a pair of substrates on which the coating film has been formed are interposed through the liquid crystal layer. A method of manufacturing a liquid crystal display element, comprising: a step of constructing a liquid crystal cell by facing each other so that the coating films face each other; and a step of irradiating the liquid crystal cell with light while applying a voltage between the conductive films of the pair of substrates. I will provide a. Moreover, this invention provides the polymer which has group represented by the said Formula (1) in another one side surface.

  According to the polymer composition of the present invention, it is possible to obtain a liquid crystal display device which has a high response speed of liquid crystal molecules and a good contrast, and which has a good display property even when continuously driven for a long time. In addition, since the amount of light irradiation for imparting liquid crystal alignment ability is small, decomposition of liquid crystal molecules due to light can be suppressed, and the manufacturing cost of the liquid crystal display element can be reduced. That is, the liquid crystal display element obtained by the present invention is excellent in both performance and cost.

  Below, each component contained in the polymer composition of this invention and the other component arbitrarily mix | blended as needed are demonstrated.

<(A) Polymer>
The polymer composition of this invention contains the polymer (henceforth "(A) polymer") which has group represented by the said Formula (1) as a polymer component.

  Here, the “hydrocarbon group” in the present specification means a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Further, the “chain hydrocarbon group” means a linear hydrocarbon group and a branched hydrocarbon group which are composed only of a chain structure without including a cyclic structure in the main chain. However, it may be saturated or unsaturated. The “alicyclic hydrocarbon group” means a hydrocarbon group that includes only an alicyclic hydrocarbon structure as a ring structure and does not include an aromatic ring structure. However, it is not necessary to be comprised only by the structure of an alicyclic hydrocarbon, The thing which has a chain structure in the part is also included. “Aromatic hydrocarbon group” means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic hydrocarbon structure.

R ^{1 in the} above formula (1) is a monovalent group selected from the group consisting of groups represented by each of the above formulas (r1-1) to (r1-6). In the formula (r1-1), X ⁵ is an oxygen atom or —NR ³⁰ — (R ³⁰ is a hydrogen atom or a methyl group), and preferably an oxygen atom or —NH— from the viewpoint of photoreactivity.

In the above formula (r1-2), examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of R ⁶ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Group, nonyl group, decyl group, dodecyl group, pentadecyl group, octadecyl group, icosyl group and other alkyl groups; substituted or unsubstituted cycloalkyl groups such as cyclohexyl group and methylcyclohexyl group; phenyl group, tolyl group, naphthyl group, etc. Aryl groups such as benzyl group and the like. When R ⁶ is a group obtained by substituting at least one hydrogen atom of a monovalent hydrocarbon group with a fluorine atom, specific examples thereof include at least one hydrogen atom of the above exemplified hydrocarbon group as a fluorine atom. And the like, and examples thereof include a trifluoromethyl group and a 3,3,3-trifluoropropyl group.

When R ⁶ is a monovalent group having a heterocyclic ring, examples of the heterocyclic ring include a nitrogen-containing heterocyclic ring, an oxygen-containing heterocyclic ring, and a sulfur-containing heterocyclic ring. Among these, a nitrogen-containing heterocyclic ring is preferable, and specific examples thereof include, for example, pyrrolidine, piperidine, piperazine, hexamethyleneimine, imidazoline, morpholine, pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, Indole, benzimidazole, purine, quinoline, isoquinoline, naphthyridine, quinoxaline, phthalazine, triazine, azepine, diazepine, acridine, phenazine, phenanthroline, oxazole, thiazole, carbazole, thiadiazole, benzothiazole, phenothiazine, oxadiazole and the like. Moreover, these heterocyclic rings may have a substituent. Specific examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl groups such as methyl group, ethyl group and propyl group; alkoxy such as methoxy group, ethoxy group and propoxy group Group; and the like.
The monovalent group having a heterocyclic ring has a structure formed by removing one or more hydrogen atoms from these heterocyclic rings. The heterocyclic ring in R ⁶ may be directly bonded to the ester bond in formula (r1-2) or may be bonded via a divalent linking group.

In the above formula (r1-2), the divalent aromatic ring group of Ar ¹ is a group formed by removing two hydrogen atoms from atoms constituting the ring skeleton of the aromatic ring. Examples of the aromatic ring include aromatic hydrocarbon rings such as a benzene ring and a naphthalene ring, and heterocyclic rings having aromaticity among the heterocyclic rings exemplified in the description of R ⁶ (for example, pyrrole, imidazole, pyrazole, triazole). Pyridine, pyrimidine, pyridazine, etc.).

The description of the alkyl group of R ⁶ can be applied to the description of the alkyl group having 1 to 20 carbon atoms in R ⁷ of the above formula (r1-3) and R ⁹ of the above formula (r1-5). The alkyl group for R ⁷ and R ⁹ may be linear or branched, but is preferably linear.
The description of Ar ¹ can be applied to specific examples of the divalent aromatic ring group in Ar ^{2 in the} above formula (r1-3) and Ar ³ in the above formula (r1-5).

（式中、＊は結合手を示す。） R ^{8 in the} above formula (r1-4) is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, or together with two carbon atoms to which R ⁸ is bonded by bonding two R ⁸ to each other. A hydrocarbon ring structure having 4 to 20 carbon atoms is formed. When R ⁸ is an alkyl group having 1 to 20 carbon atoms, specific examples thereof include the groups exemplified as the alkyl group for R ⁶ above. Two R ⁸ may be the same or different from each other.
Examples of the hydrocarbon ring structure formed by bonding two R ⁸ to each other include an aliphatic hydrocarbon ring such as a cyclopentane ring and a cyclohexane ring; an aromatic hydrocarbon ring such as a benzene ring; Of these, the hydrocarbon ring structure is preferably an aliphatic hydrocarbon ring, and more preferably a cyclohexane ring. The hydrocarbon ring structure may have a substituent in the ring portion. Specific examples of the substituent include a methyl group and an ethyl group.
R ⁸ is 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 4 carbon atoms, from the viewpoint of photoreactivity.
Specific examples of the formula (r1-4) include groups represented by the following formulas (r1-4-1) to (r1-4-5).

(In the formula, * indicates a bond.)

In the above formula (r1-6), specific examples of the alkyl group having 1 to 5 carbon atoms of R ¹⁰ can include those having 1 to 5 carbon atoms among the alkyl groups exemplified for R ^6. It may be chained or branched. The fluoroalkyl group having 1 to 5 carbon atoms is sufficient if at least one hydrogen atom of the alkyl group having 1 to 5 carbon atoms is substituted with a fluorine atom, for example, a trifluoromethyl group, a pentafluoroethyl group, 2 2,2-trifluoroethyl group and the like. A plurality of R ¹⁰ in the formula may be the same as or different from each other.

All the groups represented by the above formulas (r1-1) to (r1-6) are groups having photoreactivity. Among these, R ¹ is preferably a group represented by the above formula (r1-1) because of high photoreactivity.

In the above formula (1), Y ¹ is a (u + 1) -valent cyclic group or a nitrogen atom. Here, the “(u + 1) -valent cyclic group” in the present specification is a (u + 1) -valent group obtained by removing (u + 1) hydrogen atoms from atoms constituting the ring of the cyclic compound. However, the ring part may have a substituent. When Y ¹ is a (u + 1) -valent cyclic group, the cyclic group is preferably a group having a benzene ring, a cyclohexane ring, a cyclopentane ring, or a pyridine ring as a ring skeleton. Of these, a group obtained by removing (u + 1) hydrogen atoms from the benzene ring is preferable in terms of ease of synthesis and cost.
Examples of the substituent that the ring skeleton of Y ¹ may have include, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), an alkyl group having 1 to 6 carbon atoms, and 1 to 1 carbon atoms. 6 alkoxy groups and the like.
u is an integer of 2 to 4, and is preferably 2 or 3 from the viewpoint of appropriately increasing the photosensitivity of the polymer (A). Note that when ^{Y 1} is a nitrogen atom, u in the formula (1) is 2.

（式（ｒ２−１）中、Ｒ^１２は炭素数１〜２０のアルカンジイル基又は下記式（ｒ２−１−１）

（式（ｒ２−１−１）中、Ｒ^２０及びＲ^２１はそれぞれ独立に１価の置換基である。ｍ１及びｍ２はそれぞれ独立に０〜２の整数である。ただし、１≦（ｍ１＋ｍ２）≦２を満たす。ｔ１及びｔ２はそれぞれ独立に０〜４の整数である。複数のＲ^２０は同一でも異なっていてもよく、複数のＲ^２１は同一でも異なっていてもよい。）
で表される基である。Ｒ^１３は炭素数１〜２０のアルカンジイル基であり、Ｒ^１４は単結合又は炭素数１〜２０のアルカンジイル基である。Ｘ^１及びＸ^２は、それぞれ独立に炭素数１〜６のアルカンジイル基、エーテル結合、エステル結合、アミド結合又はウレイド結合である。ｎ１及びｎ２は、それぞれ独立に０〜２の整数であり、ｎ１＋ｎ２≧１を満たす。「＊^１」を付した結合手がＲ^１に結合する。） R ² in the above formula (1) is a single bond or a divalent organic group. Examples of the divalent organic group represented by R ² include divalent hydrocarbon groups such as a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group; At least one methylene group in the hydrocarbon group of -O-, -CO-, -COO-, -NR ^a- , -CONR ^a- (wherein R ^a is a hydrogen atom or ^a C 1-6 carbon atom; And a group formed by replacing with a divalent functional group such as —COS— or —S—.
A preferred specific example when R ² is a divalent organic group includes a group represented by the following formula (r2-1).

(In the formula (r2-1), R ¹² is an alkanediyl group having 1 to 20 carbon atoms or the following formula (r2-1-1)

(In the formula (r2-1-1), R ²⁰ and R ²¹ are each independently a monovalent substituent. M1 and m2 are each independently an integer of 0 to 2. However, 1 ≦ (m1 + m2) ≦ 2 is satisfied, t1 and t2 are each independently an integer of 0 to 4. The plurality of R ²⁰ may be the same or different, and the plurality of R ²¹ may be the same or different.
It is group represented by these. R ¹³ is an alkanediyl group having 1 to 20 carbon atoms, and R ¹⁴ is a single bond or an alkanediyl group having 1 to 20 carbon atoms. X ¹ and X ² are each independently an alkanediyl group having 1 to 6 carbon atoms, an ether bond, an ester bond, an amide bond or a ureido bond. n1 and n2 are each independently an integer of 0 to 2, and satisfy n1 + n2 ≧ 1. A bond marked with “* ¹ ” is bonded to R ¹ . )

In the above formula (r2-1), examples of the alkanediyl group having 1 to 20 carbon atoms of R ¹² , R ¹³ and R ¹⁴ include a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a pentanediyl group, and a hexanediyl group. , Heptanediyl group, octanediyl group, nonanediyl group, decanediyl group, dodecanediyl group, pentadecanediyl group, octadecanediyl group and the like. These may be linear or branched, but are preferably linear from the viewpoint of providing a pretilt angle. The alkanediyl group in R ¹² , R ¹³ and R ¹⁴ preferably has 1 to 10 carbon atoms, and more preferably 1 to 7 carbon atoms. In addition, the alkanediyl group in R < ¹² >, R < ¹³ > and R < ¹⁴ > may mutually be same or different.

（式中、「＊^１」を付した結合手がＲ^１に結合する。） The group represented by the above formula (r2-1-1) is a group having at least one of a 1,4-phenylene group and a 1,4-cyclohexylene group. Specific examples of R ²⁰ and R ²¹ include a halogen atom such as a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a hydroxyl group.
Examples of the group represented by the above formula (r2-1-1) include 1,4-phenylene group, 1,4-cyclohexylene group, 4,4′-biphenylene group, and 4,4′-bicyclohexylene group. And groups represented by each of the following formula (r2-1-1-1) and formula (r2-1-1-2).

(In the formula, a bond marked with “* ¹ ” is bonded to R ^1. )

X ¹ and X ² are an alkanediyl group having 1 to 6 carbon atoms, an ether bond, an ester bond, an amide bond or a ureido bond. Of these, an ether bond, an ester bond or an amide bond is preferable, and an ether bond or an ester bond is more preferable from the viewpoint of the stability of the synthetic intermediate and the synthesis yield. Incidentally, an ester bond, * - COO- and * --OCO - including both (bond marked with * is bonded to ^{R 13.).} Moreover, an amide bond, * - NH-CO- and * -CO-NH - including both (bond marked with * is bonded to ^{R 13.).}

（式中、Ｒは水素原子又はメチル基である。ｎは１〜１８の整数である。） Preferable specific examples of the group represented by the formula (1) include, for example, the following formula (a-1-1) to formula (a-5-3) and formula (b-1-1) to formula (b- And groups represented by 1-3). In addition, the (A) polymer may have only 1 type of group represented by the said Formula (1), and may have 2 or more types.

(In the formula, R is a hydrogen atom or a methyl group. N is an integer of 1 to 18.)

(A) As the main chain of the polymer, for example, polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) A skeleton composed of acrylate or the like can be given. Here, the “main chain” of the polymer in the present specification is a portion formed by repeating bonding of one or more monomers, and the longest “trunk” portion of the polymer Say.
When the polymer composition of the present invention is used as a liquid crystal aligning agent, the polymer (A) is selected from the group consisting of polyamic acid, polyimide, polyamic acid ester, (meth) acrylic polymer, and polyorganosiloxane. It is preferable that it is at least one polymer.

[Polyamic acid]
When the polymer (A) is a polyamic acid (hereinafter also referred to as “(A) polyamic acid”), the (A) polyamic acid is obtained by, for example, reacting a tetracarboxylic dianhydride and a diamine. Can be obtained. Specifically, for example, (i) a method of synthesizing by polymerization containing a tetracarboxylic dianhydride having a group represented by the above formula (1) as a monomer; (ii) a group represented by the above formula (1) (Iii) a tetracarboxylic dianhydride having a group represented by the above formula (1) and the above-mentioned specific diamine. It can obtain by the method of synthesize | combining by superposition | polymerization included in a monomer. Of these, the method (ii) is preferred because of the ease of monomer synthesis and the wide choice of monomers.

（式（ＤＡ）中、Ｒ^３は単結合又は２価の連結基である。Ｒ^１、Ｒ^２、Ｙ^１及びｕは、それぞれ上記式（１）と同義である。） (Specific diamine)
(A) The specific diamine used for the synthesis of the polyamic acid may be any of aliphatic diamine, alicyclic diamine, aromatic diamine and the like. Specific examples of preferred specific diamines include compounds represented by the following formula (DA).

(In the formula (DA), R ³ is a single bond or a divalent linking group. R ¹ , R ² , Y ¹ and u have the same meanings as those in the above formula (1).)

（式（Ｂ−１）及び式（Ｂ−３）中、Ｒ^１及びＲ^２は上記式（１）と同義である。式（Ｂ−１）中、Ｘ^３及びＸ^４は、それぞれ独立に単結合、−Ｏ−、−ＣＯＯ−＊^１又は−ＯＣＯ−＊^１（「＊^１」を付した結合手がベンゼン環と結合する。）である。ｋは２又は３であり、ｉは０又は１であり、ｒは１〜３の整数である。） In the above formula (DA), specific examples of the divalent linking group for R ³ include, for example, —O—, —CO—, —COO—, —NR ^a —, —CONR ^a — (where R ^a is A hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms), a divalent functional group such as —COS— or —S—; a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group And a divalent hydrocarbon group such as a group obtained by replacing at least one methylene group in a divalent hydrocarbon group with the above divalent functional group. When Y ¹ is a nitrogen atom, R ³ is preferably a single bond or a divalent hydrocarbon group, and more preferably a single bond.
The description of the above formula (1) can be applied to the description of R ¹ , R ² , Y ¹ and u, and preferred specific examples. The two primary amino groups in the diaminophenyl group are preferably in the 2,4-position or 3,5-position with respect to other groups, and more preferably in the 2,4-position.
Preferable specific examples of the compound represented by the formula (DA) include, for example, compounds represented by the following formulas (B-1) and (B-3).

(In Formula (B-1) and Formula (B-3), R ¹ and R ² have the same meanings as in Formula (1) above. In Formula (B-1), X ³ and X ⁴ are each independently A single bond, —O—, —COO— * ¹ or —OCO— * ¹ (the bond marked with “* ¹ ” is bonded to the benzene ring), k is 2 or 3, and i is 0 Or 1 and r is an integer of 1 to 3.)

（式（Ｂ−１−１）及び式（Ｂ−１−２）中、Ａ^１は、上記式（ａ−１−１）〜式（ａ−５−３）のそれぞれで表される基である。） As the divalent group represented by “— (X ³ —C _r H _2r ) _i —X ⁴ —” in the above formula (B-1), an alkanediyl group having 1 to 3 carbon atoms, —O—, —COO— * and —COO—C ₂ H ₄ — * (however, a bond marked with “*” is bonded to a diaminophenyl group) are preferred.
Preferable specific examples of the compound represented by the formula (B-1) include, for example, compounds represented by the following formula (B-1-1) and formula (B-1-2).

(In Formula (B-1-1) and Formula (B-1-2), A ¹ is a group represented by each of Formula (a-1-1) to Formula (a-5-3)). is there.)

（式（Ｂ−３−１）〜式（Ｂ−３−３）中、Ｒは水素原子又はメチル基である。ｎは１〜１８の整数である。） Moreover, as a preferable specific example of the compound represented by the said formula (B-3), the compound represented by each of the following formula (B-3-1)-a formula (B-3-3), etc. are mentioned, for example. It is done.

(In formula (B-3-1) to formula (B-3-3), R is a hydrogen atom or a methyl group. N is an integer of 1 to 18.)

The specific diamine can be synthesized by appropriately combining organic chemistry methods. As an example, a dinitro intermediate having two nitro groups in place of the two primary amino groups in the above formula (DA) is synthesized, and then the nitro group of the obtained dinitro intermediate is converted into an appropriate reduction system. The method of amination using is mentioned. The method for synthesizing the ditro intermediate can be appropriately selected depending on the target compound.
As the specific diamine used for the synthesis of the polyamic acid, one kind of these compounds can be used alone or two or more kinds can be appropriately selected and used.

(Other diamines)
In the synthesis of the polyamic acid, only the specific diamine may be used, but other diamines may be used in combination with the specific diamine.
Examples of the other diamines are classified into diamines having a group capable of developing pretilt angle characteristics (hereinafter also referred to as “pretilt angle developing group”) and diamines having no pretilt angle developing group. it can. Here, examples of the pretilt angle-expressing group include an alkyl group having 2 to 20 carbon atoms, a fluoroalkyl group having 2 to 20 carbon atoms, an alkoxy group having 2 to 20 carbon atoms, and a steroid skeleton having 17 to 51 carbon atoms. A group having a structure in which two or more rings are linked, and the like. The alkyl group, alkoxy group and fluoroalkyl group in the pretilt angle-expressing group are preferably linear.

（式（Ｄ−１）中、Ｘ^I及びＸ^IIは、それぞれ独立に、単結合、−Ｏ−、−ＣＯＯ−又は−ＯＣＯ−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。） Specific examples of the diamine having a pretilt angle-expressing group include, for example, dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene. , Octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2, 5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholesteryloxy-2,4-diamino Cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4 -Aminophenoxy) cholestane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptyl Cyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) ) Cyclohexane, N- (2,4-diaminophenyl) -4- (4-heptylcyclohexyl) benz Bromide, the following formula (D-1)

(In Formula (D-1), X ^I and X ^II are each independently a single bond, —O—, —COO— or —OCO—, and 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, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1, provided that a and b are not 0 at the same time.)

In addition, a diamine having a pretilt angle-developing group described in JP 2010-97188 A can be used.
Examples of the divalent group represented by “—X ^I — (R ^I —X ^II ) _d —” in the above formula (D-1) include alkanediyl groups having 1 to 3 carbon atoms, —O—, * — COO— or —O—C ₂ H ₄ —O— (however, a bond marked with “*” is bonded to a diaminophenyl group) is preferred. Specific examples of the group “—C _c H _{2c + 1} ” include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group. N-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group , N-eicosyl group and the like. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or 3,5-position with respect to other groups.

Specific examples of the compound represented by the formula (D-1) include compounds represented by the following formulas (D-1-1) to (D-1-4). .

Examples of the diamine having no pretilt angle developing group include aliphatic diamine, alicyclic diamine, aromatic diamine, and diaminoorganosiloxane. Specific examples thereof include aliphatic diamines such as metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane; Examples of alicyclic diamines include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine) and the like;
Examples of aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, and 2,2′-. Dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2- Bis (4-aminophenyl) hexafluoropropane, 4,4 ′-(p-phenylenediisopropylidene) Suaniline, 4,4 ′-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole N-phenyl-3,6-diaminocarbazole, N, N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, N′-dimethylbenzidine, 1, 4-bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, 4- (4′-trifluoromethoxybenzoyloxy) ) Cyclohexyl-3,5-diaminobenzoate, 4- (4′-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine , 3-aminobenzylamine, 1- (2,4-diaminophenyl) piperazine-4-carboxylic acid, 4- (morpholin-4-yl) benzene-1,3-diamine, 1,3-bis (N- ( 4-aminophenyl) piperidinyl) propane, α-amino-ω-aminophenylalkylene, 4- (2-aminoethyl) aniline and the like;
Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane; and the like, and each of them has a pretilt angle developing group described in JP 2010-97188 A. No diamine can be used.

When applying the polymer composition to a liquid crystal aligning agent, in order to develop a stable pretilt angle characteristic in the liquid crystal aligning film, the use ratio of the specific diamine is set to (A) the total diamine used for the synthesis of the polyamic acid. Thus, the range is preferably 5 to 95 mol%, and more preferably 30 to 95 mol%.
From the viewpoint of further improving the stability of the pretilt angle expression in the liquid crystal alignment film, it is effective to use a diamine having a pretilt angle developing group in combination. The proportion of the diamine having a pretilt angle-expressing group may be in the range of 2 to 50 mol% with respect to the total diamine used for the synthesis of (A) polyamic acid, from the viewpoint of suppressing the deterioration of orientation failure. Preferably, the range is 5 to 40 mol%.

(Tetracarboxylic dianhydride)
(A) Examples of tetracarboxylic dianhydrides used for the synthesis of polyamic acid include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and the like. Can do. Specific examples thereof include aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4, 5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane -2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- No 1,2-dicarboxylic acid 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2 : 4,6: 8-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, 1,2,4,5 -Cyclohexanetetracarboxylic dianhydride, p-phenylenebis (trimellitic acid monoester anhydride), etc .;
Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride;
In addition to the above, tetracarboxylic dianhydrides described in JP 2010-97188 A can be used. In addition, tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

(Synthesis of polyamic acid)
(A) The polyamic acid can be obtained by reacting the above tetracarboxylic dianhydride and diamine together with a molecular weight regulator as necessary. The ratio of the tetracarboxylic dianhydride and diamine used in the synthesis reaction of the polyamic acid (P) is such that the acid anhydride group of the tetracarboxylic dianhydride is 0. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.
Examples of the molecular weight regulator include acid 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 use ratio of the molecular weight regulator is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less with respect to 100 parts by weight of the total of the tetracarboxylic dianhydride and diamine used.

  (A) The polyamic acid synthesis reaction is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

Examples of the organic solvent used in the reaction include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenolic solvent (first group organic solvent), or one or more selected from the first group of organic solvents And a mixture of at least one selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (second-group organic solvent). In the latter case, the proportion of the second group organic solvent used is preferably 50% by weight or less, more preferably 40% by weight, based on the total amount of the first group organic solvent and the second group organic solvent. Or less, more preferably 30% by weight or less.
Particularly preferred are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol and halogen. It is preferable to use one or more selected from the group consisting of fluorinated phenols as a solvent, or to use a mixture of one or more of these and another organic solvent in the above range.
The amount (a) of the organic solvent used is such that the total amount (b) of the tetracarboxylic dianhydride and diamine and the molecular weight regulator used as required is 0. The amount is preferably 1 to 50% by weight.

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. When preparing a polymer composition as a liquid crystal aligning agent, this reaction solution may be used for the preparation of the liquid crystal aligning agent as it is, and after preparing the polyamic acid contained in the reaction solution, the liquid crystal aligning agent is prepared. You may use, or you may use for preparation of a liquid crystal aligning agent, after refine | purifying the isolated polyamic acid. Isolation and purification of the polyamic acid can be performed according to known methods.

[Polyamic acid ester]
The polyamic acid ester as the polymer (A) is, for example, [I] a method of reacting the polyamic acid (A) obtained by the above synthesis reaction with an esterifying agent, or [II] a tetracarboxylic acid diester and a diamine. And [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine.

  Here, examples of the esterifying agent used in the method [I] include a hydroxyl group-containing compound, an acetal compound, a halide, and an epoxy group-containing compound. Specific examples thereof include hydroxyl group-containing compounds such as alcohols such as methanol, ethanol and propanol; phenols such as phenol and cresol; and acetal compounds such as N, N-dimethylformamide diethyl acetal, N, N-diethylformamide diethyl acetal and the like; halides such as methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane and the like; epoxy group-containing Examples of the compound include propylene oxide.

  The tetracarboxylic acid diester used in Method [II] can be obtained by ring-opening tetracarboxylic dianhydride using the above alcohols. The tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride. The diamine used in the methods [II] and [III] preferably contains the above-mentioned specific diamine, and other diamines may be used as necessary. The polyamic acid ester 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.

[Polyimide]
The polyimide as the polymer (A) can be obtained, for example, by dehydrating and ring-closing the polyamic acid synthesized as described above to imidize.

  The polyimide may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure possessed by the polyamic acid that is the precursor, and only a part of the amic acid structure is dehydrated and cyclized, It may be a partially imidized product in which an imide ring structure coexists. When manufacturing a liquid crystal aligning film using the said polymer composition, it is preferable to set it as 30% or more from a viewpoint of an electrical property, and it is preferable to set it as 50% or more, and 65% or more as for polyimide. More preferably. On the other hand, from the viewpoint of ensuring the solubility of the polymer and improving the coating property, the imidation ratio is preferably 65% or less, and more preferably 30% or less. This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of polyimide amic acid structures and the number of imide ring structures in percentage. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably performed by (i) a method of heating the polyamic acid or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to this solution, and if necessary It is performed by the method of heating.
The reaction temperature in the method (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C., the dehydration ring-closure reaction does not proceed easily, and when the reaction temperature exceeds 200 ° C., the molecular weight of the resulting polymer may decrease. The reaction time is preferably 1.0 to 24 hours, more preferably 1.0 to 12 hours.
In the method (ii), as the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. Although the usage-amount of a dehydrating agent is based on the desired imidation rate, it is preferable to set it as 0.01-20 mol with respect to 1 mol of the amic acid structure of a polyamic acid. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, collidine, lutidine, a triethylamine, can be used, for example. It is preferable that the usage-amount of a dehydration ring-closing catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents to be used.
Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

  In this way, a reaction solution containing polyimide is obtained. When preparing a polymer composition as a liquid crystal aligning agent, this reaction solution may be directly used for the preparation of the liquid crystal aligning agent, and after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, The polyimide may be isolated and then used for the preparation of the liquid crystal aligning agent, or the isolated polyimide may be purified and then used for the preparation of the liquid crystal aligning agent. These purification operations can be performed according to known methods.

The polyamic acid, polyamic acid ester and polyimide obtained as described above preferably have a solution viscosity of 10 to 800 mPa · s, when this is made into a solution having a concentration of 10% by weight, and 15 to 500 mPa · s. More preferably, it has a solution viscosity of s. In addition, the solution viscosity (mPa · s) of the above polymer is based on a polymer solution having a concentration of 10% by weight prepared using a good solvent for the polymer (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). The value measured at 25 ° C. using an E-type rotational viscometer.
Regarding the polyamic acid, polyamic acid ester, and polyimide, the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography is preferably 1,000 to 500,000, and preferably 2,000 to 300,000. More preferred. Moreover, the molecular weight distribution (Mw / Mn) represented by the ratio between Mw and the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. By being in such a molecular weight range, it is possible to ensure good orientation and stability of the liquid crystal display element.

[(Meth) acrylic polymer]
(A) The (meth) acrylic polymer (hereinafter also referred to as “specific (meth) acrylic polymer”) as the polymer can be synthesized by appropriately combining organic chemistry methods. As an example, a (meth) acrylic polymer having a group (Z1) and a group (Z2) using, for example, the reaction of two types of functional groups (Z1, Z2) capable of forming a [1] bonding group ) And a compound having a group represented by the above formula (1) are reacted; [2] a (meth) acrylic compound having a group represented by the above formula (1) in the monomer composition And the like. Among these, the method of the above [1] is preferable because the synthesis of the polymer is easy. In the present specification, “(meth) acryl” means “acryl” and “methacryl”.

In the case of the method [1], examples of one group (Z1) of the two types of functional groups that can form a bonding group include an epoxy group, an isocyanato group, a carboxyl group, and a hydroxyl group. The other group (Z2) is, for example, a carboxyl group when the group (Z1) is an epoxy group; a hydroxyl group when the group (Z1) is an isocyanato group; and a group (Z1) is a carboxyl group. An epoxy group; when the group (Z1) is a hydroxyl group, an acid anhydride group or an epoxy group is preferred. Among these, the group (Z1) is an epoxy group and the group (Z2) is a carboxyl group in that the group represented by the formula (1) can be easily added to the side chain of the polymer. It is preferable.
A (meth) acrylic polymer having an epoxy group (hereinafter also referred to as “epoxy group-containing (meth) acrylic polymer”) and a carboxylic acid having a group represented by the above formula (1) (hereinafter, “ A method of obtaining a (meth) acrylic polymer as a polymer (A) by reaction with a specific carboxylic acid (C-1) ”will be described below as an example.

  The epoxy group-containing (meth) acrylic polymer is, for example, a (meth) acrylic monomer (mc-1) having an epoxy group, or the (meth) acrylic monomer (mc-1) and other It can be obtained by polymerizing a mixture with a (meth) acrylic monomer (mc-2) in the presence of a polymerization initiator. Here, examples of the “(meth) acrylic monomer” include unsaturated carboxylic acid, unsaturated carboxylic acid ester, and unsaturated polyvalent carboxylic acid anhydride.

  Examples of the (meth) acrylic monomer (mc-1) include an unsaturated carboxylic acid ester having an epoxy group. Specific examples thereof include, for example, glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl (meth) acrylate. Α-ethyl acrylate 3,4-epoxybutyl, (meth) acrylate 3,4-epoxycyclohexylmethyl, (meth) acrylate 6,7-epoxyheptyl, α-ethyl acrylate 6,7-epoxyheptyl, Examples include 4-hydroxybutyl glycidyl ether of acrylic acid, (meth) acrylic acid (3-ethyloxetane-3-yl) methyl, and the like. Among these, from the group consisting of glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-methyl-3-oxetanylmethyl (meth) acrylate and 4-hydroxybutyl glycidyl ether acrylate At least one selected is preferable. In addition, as a (meth) acrylic-type monomer (mc-1), the said thing can be used individually by 1 type or in combination of 2 or more types.

The (meth) acrylic monomer (mc-2) is an unsaturated compound having no epoxy group. Specific examples thereof include unsaturated carboxylic acids such as (meth) acrylic acid, (meth) acrylic acid ω-carboxypolycaprolactone, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, α-n. -Butylacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, vinyl benzoic acid and the like;
Examples of unsaturated carboxylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, (n-propyl) (meth) acrylate, isopropyl (meth) acrylate, allyl (meth) acrylate, and (meth) acrylic. Acid-n-butyl, (meth) acrylic acid-isobutyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid benzyl, (meth) acrylic acid-2-ethylhexyl, (meta ) Lauryl acrylate, (meth) acrylic acid trimethoxysilylpropyl, (meth) acrylic acid methoxyethyl, (meth) acrylic acid-N, N-dimethylaminoethyl, (meth) acrylic acid-N, N-diethylaminoethyl, (Meth) acrylic acid methoxypolyethylene glycol, (meth) acrylic acid octoxy (Meth) acrylic acid esters such as reethylene glycol and tetrahydrofurfuryl (meth) acrylate: α-alkoxyacrylic acid esters such as methyl α-methoxyacrylate and methyl α-ethoxyacrylate: methyl crotonate, ethyl crotonate, etc. Crotonic acid esters, etc .;
Examples of unsaturated polycarboxylic anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrahydrophthalic anhydride and the like;
Other examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. As the (meth) acrylic monomer (mc-2), the above can be used singly or in combination of two or more.

In the epoxy group-containing (meth) acrylic polymer, the total amount (number of moles) of epoxy groups per 1 g is preferably 5.0 × 10 ⁻⁵ mol / g or more, and 1.0 × 10 ^−4. It is more preferable that it is -1.0 * 10 ^<-2 > mol / g, and it is still more preferable that it is 5.0 * 10 < ^-4 > -5.0 * 10 < ^-3 > mol / g. Therefore, the use ratio of the (meth) acrylic monomer (mc-1) should be adjusted so that the total number of moles of epoxy groups per gram of the (meth) acrylic polymer falls within the above numerical range. Is preferred.
In addition, as a monomer used for synthesis, for example, 1,3-butadiene or the like can be used in addition to the (meth) acrylic monomers (mc-1) and (mc-2) within the scope of the effects of the present invention. Vinyl monomers such as isoprene, styrene monomers such as styrene and hydroxystyrene, unsaturated carboxylic acid amide compounds such as N-isopropylacrylamide and N, N-dimethylmethacrylamide, and unsaturated ketones such as methyl vinyl ketone It may contain other monomers such as compounds. Moreover, you may use a molecular weight modifier with a (meth) acrylic-type monomer as needed.

The polymerization reaction using the (meth) acrylic monomer is preferably performed by radical polymerization. Examples of the polymerization initiator used in the polymerization reaction include initiators usually used in radical polymerization. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4 -Dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds; benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis ( Examples thereof include organic peroxides such as t-butylperoxy) cyclohexane; hydrogen peroxide; redox initiators composed of these peroxides and reducing agents. Of these, azo compounds are preferable, and 2,2′-azobis (isobutyronitrile) is more preferable. As a polymerization initiator, these can be used individually by 1 type or in combination of 2 or more types.
The use ratio of the polymerization initiator is preferably 0.01 to 50 parts by weight, and more preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of all monomers used in the reaction.

  The polymerization reaction of the (meth) acrylic monomer is preferably performed in an organic solvent. Examples of the organic solvent used in the reaction include alcohols, ethers, ketones, amides, esters, hydrocarbon compounds, and the like. Among these, it is preferable to use at least one selected from the group consisting of alcohols and ethers, and it is more preferable to use partial ethers of polyhydric alcohols. Preferred examples thereof include diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate. In addition, as an organic solvent, these can be used individually by 1 type or in combination of 2 or more types.

  In the polymerization reaction of the (meth) acrylic monomer, the reaction temperature is preferably 30 ° C to 120 ° C, and more preferably 60 ° C to 110 ° C. The reaction time is preferably 1 to 36 hours, and more preferably 2 to 24 hours. The amount of organic solvent used (a) is such that the total amount (b) of monomers used in the reaction is 0.1 to 50% by weight with respect to the total amount of reaction solution (a + b). It is preferable to do.

  In this way, a solution containing an epoxy group-containing (meth) acrylic polymer can be obtained. This reaction solution may be used for the reaction with the specific carboxylic acid (C-1) as it is, or after the reaction solution is concentrated or diluted as necessary, it is used for the reaction with the specific carboxylic acid (C-1). Also good. Moreover, after isolating the epoxy group-containing (meth) acrylic polymer contained in the reaction solution, it may be subjected to a reaction with the specific carboxylic acid (C-1). From the viewpoint of reducing the number of steps, it is preferable that the reaction is carried out with the specific carboxylic acid (C-1) while the epoxy group-containing (meth) acrylic polymer is contained in the reaction solution.

（上記式（Ａ−１−１）〜式（Ａ−５−３）中、Ｒは水素原子又はメチル基である。ｎは１〜１８の整数である。） Next, specific carboxylic acid (C-1) is made to react with the obtained epoxy-group-containing (meth) acrylic polymer. As the specific carboxylic acid (C-1), for example, a compound in which a carboxyl group is bonded to the bond portion in the group represented by each of the above formulas (a-1-1) to (a-5-3), etc. Specific examples include compounds represented by the following formulas (A-1-1) to (A-5-3). Specific carboxylic acid (C-1) can be used individually by 1 type or in combination of 2 or more types.

(In the above formula (A-1-1) to formula (A-5-3), R is a hydrogen atom or a methyl group. N is an integer of 1 to 18.)

In addition, the synthesis method of specific carboxylic acid (C-1) is not specifically limited, It can synthesize | combine combining a conventionally well-known method. As an example of the synthesis method, for example, a carboxylic acid having the group R ¹ in the above formula (1) and a carboxylic acid having two or more hydroxyl groups such as dihydroxybenzoic acid are preferably reacted in the presence of a dehydrating agent. And the like.

The carboxylic acid used for the reaction with the epoxy group-containing (meth) acrylic polymer may be the specific carboxylic acid (C-1) alone, but together with the specific carboxylic acid (C-1), the specific carboxylic acid (C-1) Other carboxylic acids (C-2) other than C-1) may be used in combination.
Other carboxylic acid (C-2) should just be carboxylic acid which does not have group represented by the said Formula (1), As an example, acrylic acid, methacrylic acid, omega-carboxy-poly Examples include caprolactone monoacrylate and monohydroxyethyl acrylate phthalate.
Moreover, as other carboxylic acid (C-2), the carboxylic acid which has a pretilt angle expression group is mentioned. Here, as the pretilt angle-expressing group that other carboxylic acid (C-2) may have, groups exemplified by the diamine having the pretilt angle-expressing group, cyclohexyl group, hydroxycyclohexyl group, phenyl group And a hydroxyphenyl group.

（式中、ｊは０〜１２の整数であり、ｈは１〜２０の整数である。）
なお、その他のカルボン酸（Ｃ−２）としては、これらのうちから選択される１種を単独で又は２種以上を組み合わせて使用することができる。 Specific examples of the carboxylic acid having a pretilt angle-expressing group in other carboxylic acid (C-2) include, for example, caproic acid, lauric acid, pentadecylic acid, palmitic acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, C6-C20 fatty acids such as linolenic acid and arachidic acid, compounds represented by the following formulas (2-1-1) to (2-1-4), and the following formula (2-2-1) To a compound represented by each of formulas (2-2-5).

(In the formula, j is an integer of 0 to 12, and h is an integer of 1 to 20.)
In addition, as other carboxylic acid (C-2), 1 type selected from these can be used individually or in combination of 2 or more types.

The use ratio of the carboxylic acid to be reacted with the epoxy group-containing (meth) acrylic polymer is 0.001 to 1.5 mol with respect to a total of 1 mol of the epoxy groups of the (meth) acrylic polymer. Is preferable, and 0.01 to 1.0 mol is more preferable.
Moreover, it is preferable that the usage-amount of specific carboxylic acid (C-1) shall be 0.01-0.8 mol with respect to a total of 1 mol of the epoxy group which a (meth) acrylic-type polymer has. When the use ratio is less than 0.01 mol, the sensitivity of the (A) polymer to light is inferior, and sufficient liquid crystal alignment ability may not be imparted to the coating film formed from the polymer composition. Moreover, when it exceeds 0.8 mol, the sensitivity of the (A) polymer to light becomes too high, and it may be difficult to control the pretilt angle of the coating film formed from the polymer composition to a suitable angle. Preferably it is 0.03-0.6 mol, More preferably, it is 0.05-0.4 mol.
From the viewpoint of sufficiently obtaining the effects of the present invention, the use ratio of the other carboxylic acid (C-2) is 80 mol% with respect to the total amount of carboxylic acid used for the synthesis of the specific (meth) acrylic polymer. It is preferable to set it as follows, and it is more preferable to set it as 50 mol% or less.

The reaction between the epoxy group-containing (meth) acrylic polymer and the carboxylic acid can be preferably performed in the presence of a catalyst and an organic solvent. Here, as the catalyst used for the reaction, for example, a compound known as a so-called curing accelerator that accelerates the reaction of an organic base or an epoxy compound can be used.
Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine and piperidine; tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine and pyridine; tetramethylammonium hydroxy And quaternary organic amines such as Of these, tertiary organic amines or quaternary organic amines are preferred as the organic base.
Examples of the curing accelerator include tertiary amines such as benzyldimethylamine; imidazole compounds such as 2-methylimidazole; organic phosphorus compounds such as diphenylphosphine; quaternary phosphonium salts such as benzyltriphenylphosphonium chloride. Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7; organometallic compounds such as zinc octylate and tin octylate; quaternary ammonium salts such as tetraethylammonium bromide and tetrabutylammonium bromide In addition to boron compounds such as boron trifluoride; metal halogen compounds such as zinc chloride and stannic chloride; and well-known latent curing accelerators can be used. Of these, quaternary ammonium salts are preferred.
The amount of the catalyst used is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight or less, and still more preferably 0.1 to 100 parts by weight of the (meth) acrylic polymer to be reacted with the carboxylic acid. ~ 20 parts by weight.

As an organic solvent used for reaction, the illustration of the organic solvent which can be used for the synthesis | combination of an epoxy group containing (meth) acrylic-type polymer can be applied, and it is preferable that it is ester especially. The organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more, It is more preferable to use it at a ratio of 5 to 50% by weight.
In the reaction between the epoxy group-containing (meth) acrylic polymer and the carboxylic acid, the reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

  Thus, a solution containing the specific (meth) acrylic polymer as the polymer (A) can be obtained. When the polymer composition is applied to a liquid crystal aligning agent, this reaction solution may be used for the preparation of the liquid crystal aligning agent as it is, and after isolating the (meth) acrylic polymer contained in the reaction solution. You may use for preparation of a liquid crystal aligning agent, or you may use for preparation of a liquid crystal aligning agent, after refine | purifying the isolated photo-alignment (meth) acrylic-type polymer. Isolation and purification of the (meth) acrylic polymer can be performed according to a known method.

The specific (meth) acrylic polymer obtained as described above preferably has a solution viscosity of 1 to 500 mPa · s when it is made into a solution having a concentration of 10% by weight, and preferably 3 to 200 mPa · s. More preferably, it has a solution viscosity of s. In addition, the solution viscosity (mPa · s) of the above polymer is an E-type rotation with respect to a polymer solution having a concentration of 10% by weight prepared using a good solvent (for example, N-methyl-2-pyrrolidone) of the polymer. It is a value measured at 25 ° C. using a viscometer.
For the specific (meth) acrylic polymer, the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography improves the liquid crystal alignment of the liquid crystal alignment film to be formed, and the liquid crystal alignment From the viewpoint of ensuring stability over time, it is preferably 250 to 500,000, more preferably 500 to 300,000, and still more preferably 1,000 to 200,000.

[Polyorganosiloxane]
(A) Polyorganosiloxane as a polymer (hereinafter also referred to as “specific polyorganosiloxane”) is, for example,
[1] Hydrolyzable silane compound having an epoxy group (ms-1) or a polymer obtained by hydrolytic condensation of a mixture of the silane compound (ms-1) and another silane compound (hereinafter referred to as “ An epoxy group-containing polyorganosiloxane ”) and a carboxylic acid having a group represented by the above formula (1) (specific carboxylic acid (C-1)),
[2] A method of hydrolyzing and condensing a hydrolyzable silane compound having a group represented by the above formula (1), or a mixture of the silane compound and another silane compound,
And so on. In view of easy reaction, the method [1] is preferable.
In addition, the epoxy group-containing polyorganosiloxane corresponds to “a polymer having a functional group (Z1)”, and the specific carboxylic acid (C-1) has “the group represented by the above formula (1) and It corresponds to “a compound having a group (Z2) capable of reacting with the functional group (Z1) to form a bonding group”.

  The silane compound (ms-1) is a hydrolyzable silane compound having an epoxy group. Specific examples thereof include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropyldimethylmethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethyldimethylmethoxysilane, 2-glycidoxyethyldimethylethoxysilane, 4- Glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, 4-glycidoxybutylmethyldimethoxysilane, 4-glycidoxybutylmethyldiethoxysilane, 4-glycidoxybutyldimethylmethoxysilane, 4 - Sidoxybutyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxy Examples include silane. As the silane compound (ms-1), one of these can be used alone, or two or more can be used in combination.

Other silane compounds are not particularly limited as long as they are hydrolyzable silane compounds, and can be appropriately selected according to the purpose of use of the polymer composition. Specific examples of other silane compounds include, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trimethoxysilylpropyl succinic anhydride, dimethyldimethoxy Alkoxysilanes containing hydrocarbon side chains such as silane and dimethyldiethoxysilane;
3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-aminopropyltrimethoxy Alkoxysilanes containing nitrogen and sulfur atoms such as silane, 3-aminopropyltriethoxysilane, N- (3-cyclohexylamino) propyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane;
3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 8- (meth) acryloyloxyoctyltrimethoxysilane, 3- An unsaturated hydrocarbon-containing alkoxysilane such as (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane;
And so on. In addition, the said other silane compound can use said thing individually by 1 type or in combination of 2 or more types. In the present specification, “(meth) acryloyl” means acryloyl and methacryloyl.

From the viewpoint of suppressing side reactions caused by an excessive amount of epoxy groups while allowing a sufficient amount of photoreactive groups (R ¹ ) to be introduced into the side chain of the polymer, The epoxy equivalent of the organosiloxane is preferably 80 to 10,000 g / mol, and more preferably 100 to 1,000 g / mol. Therefore, when synthesizing an epoxy group-containing polyorganosiloxane, the use ratio of the silane compound (ms-1) and other silane compounds should be adjusted so that the epoxy equivalent of the resulting polyorganosiloxane is within the above range. Is preferred.

The hydrolysis / condensation reaction of the silane compound is carried out by reacting one or more of the above silane compounds with water, preferably in the presence of an appropriate catalyst and an organic solvent.
In the hydrolysis / condensation reaction, the proportion of water used is preferably 0.5 to 100 mol, more preferably 1 to 30 mol, per 1 mol of the silane compound (total amount).

Examples of the catalyst used in the hydrolysis / condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds and the like.
Specific examples of the catalyst include acids such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, succinic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resins, various Lewis acids, etc .; alkali metal compounds As, for example, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like;
Examples of organic bases include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole: triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diaza And tertiary organic amines such as bicycloundecene: quaternary organic amines such as tetramethylammonium hydroxide; Of these, tertiary organic amines or quaternary organic amines are preferred as the organic base.
Examples of the catalyst include alkali metal compounds or organic bases, in that side reactions such as ring opening of epoxy groups can be suppressed, hydrolysis condensation rate can be increased, and storage stability is excellent. An organic base is particularly preferable.
The amount of the organic base used varies depending on the reaction conditions such as the type of organic base and temperature, and should be set as appropriate. More preferably, it is 0.05-1 times mole.

Examples of the organic solvent used in the hydrolysis / condensation reaction include hydrocarbons, ketones, esters, ethers, alcohols and the like. Specific examples thereof include hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone and cyclopentanone; esters such as ethyl acetate. N-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like; alcohols; For example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl Glycol mono -n- propyl ether, ethylene glycol monobutyl -n- butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono -n- propyl ether and the like; may be mentioned, respectively. Of these, it is preferable to use a water-insoluble organic solvent. In addition, these organic solvents can be used individually by 1 type or in mixture of 2 or more types.
The use ratio of the organic solvent in the hydrolytic condensation reaction is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight with respect to 100 parts by weight of the total silane compounds used in the reaction. .

  The hydrolysis / condensation reaction is preferably carried out by dissolving the silane compound as described above in an organic solvent, mixing this solution with an organic base and water, and heating the solution with, for example, an oil bath. During the hydrolysis / condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C. The heating time is preferably 0.5 to 12 hours, and more preferably 1 to 8 hours. During heating, the mixture may be stirred or placed under reflux. After completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. In this washing, washing with water containing a small amount of salt (for example, an aqueous ammonium nitrate solution of about 0.2% by weight) is preferable in that the washing operation is facilitated. Washing is performed until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve as necessary, and then the solvent is removed to remove the solvent. The polyorganosiloxane can be obtained.

  In the method [1], the epoxy group-containing polyorganosiloxane obtained by the above reaction is then reacted with a specific carboxylic acid (C-1). Thereby, the epoxy group which epoxy group-containing polyorganosiloxane has, and carboxylic acid react, and the polyorganosiloxane which has group represented by the said Formula (1) in a side chain can be obtained. The carboxylic acid used in this reaction may be the specific carboxylic acid (C-1) alone, or other carboxylic acid together with the specific carboxylic acid (C-1). About the specific example of specific carboxylic acid (C-1) and other carboxylic acid, the description of the bonic acid to cut used for the synthesis | combination of the said specific (meth) acrylic-type polymer is applicable.

The proportion of the carboxylic acid to be reacted with the epoxy group-containing polyorganosiloxane is preferably 0.001 to 1.5 mol, based on 1 mol of the total epoxy groups of the polyorganosiloxane, 0.01 to 1 More preferably, it is 0.0 mol.
Moreover, it is preferable that the usage-amount of specific carboxylic acid (C-1) shall be 0.01-0.8 mol with respect to 1 mol of total of the epoxy group which polyorganosiloxane has. When the use ratio is less than 0.01 mol, the sensitivity of the (A) polymer to light is too low, and when it exceeds 0.8 mol, the photosensitivity of the (A) polymer tends to be too high. Preferably it is 0.03-0.6 mol, More preferably, it is 0.05-0.4 mol.
The proportion of other carboxylic acid (C-2) used is 80 mol% or less based on the total amount of carboxylic acid used for the synthesis of the specific polyorganosiloxane, from the viewpoint of sufficiently obtaining the effects of the present invention. Is preferable, and it is more preferable to set it as 50 mol% or less.

The reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid can be preferably carried out in the presence of a catalyst and an organic solvent.
Examples of the catalyst used in the reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid include compounds exemplified as the catalyst that can be used in the reaction between the epoxy group-containing (meth) acrylic polymer and the carboxylic acid. . Of these, organic bases are preferred. The ratio of the catalyst used is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyorganosiloxane to be reacted with the carboxylic acid. is there.

  Examples of the organic solvent used in the above reaction include hydrocarbons, ethers, esters, ketones, amides, alcohols and the like. Of these, ethers, esters, and ketones are preferred from the viewpoints of solubility of raw materials and products, and ease of purification of the products. Specific examples of particularly preferred solvents include 2-butanone, 2-hexanone, and methylisobutyl. Examples thereof include ketones and butyl acetate. The organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more, It is more preferable to use it at a ratio of 5 to 50% by weight.

  The reaction temperature in the above reaction is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours. Moreover, after completion | finish of reaction, it is preferable to wash | clean the organic-solvent layer fractionated from the reaction liquid with water. After washing with water, the organic solvent layer is dried with an appropriate desiccant as necessary, and then the solvent is removed to obtain a polyorganosiloxane having a group represented by the above formula (1).

The specific polyorganosiloxane obtained as described above preferably has a solution viscosity of 1 to 500 mPa · s, and a solution of 3 to 200 mPa · s, when this is a 10% by weight solution. More preferably, it has a viscosity. In addition, the solution viscosity (mPa · s) of the above polymer is an E-type rotation with respect to a polymer solution having a concentration of 10% by weight prepared using a good solvent (for example, N-methyl-2-pyrrolidone) of the polymer. It is a value measured at 25 ° C. using a viscometer.
For a specific polyorganosiloxane, the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography improves the liquid crystal alignment of the liquid crystal alignment film to be formed, and the stability over time of the liquid crystal alignment. From the standpoint of ensuring, it is preferably 1,000 to 50,000, more preferably 3,000 to 30,000.

<Other ingredients>
Although the said polymer composition contains the (A) polymer, it may contain the other component as needed. Other components that may be added to the polymer composition include, for example, (A) other polymers other than the polymer, compounds having at least one epoxy group in the molecule (hereinafter referred to as “epoxy group-containing compound”). ), A functional silane compound, a compound having at least two photopolymerizable groups in the molecule (hereinafter also referred to as “photopolymerizable compound”), and the like.

[Other polymers]
The above other polymers can be used for improving solution properties and electrical properties. Such other polymer is a polymer not having the group represented by the above formula (1), and the main skeleton thereof is not particularly limited. Specifically, for example, polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate and the like as the main skeleton Can be mentioned. Among these, at least one polymer selected from the group consisting of polyamic acid, polyimide, polyamic acid ester, (meth) acrylic polymer, and polyorganosiloxane is preferable. Other polymers can be synthesized by a conventionally known method.
When other polymers are blended in the polymer composition, the blending ratio is preferably 50 parts by weight or less with respect to 100 parts by weight in total of the polymers contained in the polymer composition. It is more preferable to set it as 1-40 weight part, and it is still more preferable to set it as 0.1-30 weight part or less.

[Epoxy group-containing compound]
The epoxy group-containing compound can be used in order to improve adhesion and electrical properties with the substrate surface in the coating film when a coating film is formed on the substrate using the polymer composition. Examples of such epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylylene diene Amine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diamy Diphenylmethane, N, N-diglycidyl - benzylamine, N, N-diglycidyl - aminomethyl cyclohexane, N, N-diglycidyl - may be mentioned as being preferred and cyclohexylamine. In addition, as an example of the epoxy group-containing compound, an epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598 can be used.
When these epoxy compounds are blended into the polymer composition, the blending ratio is preferably 40 parts by weight or less with respect to a total of 100 parts by weight of the polymer contained in the polymer composition. More preferably, the content is ˜30 parts by weight.

[Functional silane compounds]
The functional silane compound can be used for the purpose of improving the printability of the polymer composition when a coating film is formed on the substrate using the polymer composition. Examples of such functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl). ) -3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3- Aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl -3,6- Methyl azananoate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycid And xylpropyltrimethoxysilane.
When these functional silane compounds are blended in the polymer composition, the blending ratio is preferably 2 parts by weight or less with respect to a total of 100 parts by weight of the polymer contained in the polymer composition. More preferably, the content is 0.02 to 0.2 parts by weight.

（式（Ｂ−ＩＩ）中、Ｒは水素原子又はメチル基であり、Ｙ^２及びＹ^３は、それぞれ独立に酸素原子又は硫黄原子である。）
で表される１価の基の少なくとも２個とを有する化合物（以下「化合物（Ｗ）」ともいう。）などが挙げられる。 [Photopolymerizable compound]
The photopolymerizable compound can be used for the purpose of improving response speed, display characteristics, long-term reliability, etc. of liquid crystal molecules in a liquid crystal display element. As such a photopolymerizable compound, for example, the following formula (BI) in the molecule
^{-X 11 -Y 11 -X 12 - (} B-I)
(In formula (BI), X ¹¹ and X ¹² are each independently a 1,4-phenylene group or a 1,4-cyclohexylene group, and Y ¹¹ is a single bond having 1 to 4 carbon atoms. A divalent hydrocarbon group, —COO—C _n H _2n —OCO— (n is an integer of 1 to 10), an oxygen atom, a sulfur atom or —COO—, wherein X ¹¹ and X ¹² are one or (It may be substituted with a plurality of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, fluorine atoms or cyano groups.)
At least one of the divalent groups represented by the following formula (B-II):

(In Formula (B-II), R is a hydrogen atom or a methyl group, and Y ² and Y ³ are each independently an oxygen atom or a sulfur atom.)
And a compound having at least two of the monovalent groups represented by (hereinafter also referred to as “compound (W)”).

Examples of the divalent group represented by the above formula (BI) include a 4,4′-biphenylene group, and each of the following formulas (BI-2) to (BI-6): A group in which at least one hydrogen atom of a benzene ring and a cyclohexane ring in the group is substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluorine atom, or a cyano group, etc. Is mentioned.

Y ² in the above formula (B-II) is preferably an oxygen atom.
Specific examples of the compound (W) include di (meth) acrylate having a biphenyl structure, di (meth) acrylate having a phenyl-cyclohexyl structure, di (meth) acrylate having a 2,2-diphenylpropane structure, and diphenylmethane. Examples thereof include di (meth) acrylate having a structure and di-thio (meth) acrylate having a diphenylthioether structure.
Specific examples of the compound (W) include di (meth) acrylates having a biphenyl structure, such as 4 '-(meth) acryloyloxy-biphenyl-4-yl- (meth) acrylate, 2- [4'-(2- (Meth) acryloyloxy-ethoxy) -biphenyl-4-yloxy] -ethyl (meth) acrylate, [1,1′-biphenyl] -4,4′-diyl bis (2- (meth) acrylate, 4-((2 -(Meth) acryloyloxy) ethoxy) carbonyl) phenyl 4 '-((meth) acryloyloxy)-[1,1'-biphenyl] -4-carboxylate, 4-((meth) acryloyloxy) phenyl 4'- ((4-((Meth) acryloyloxy) benzoyl) oxy)-[1,1′-biphenyl] -4-carboxylate, bishydroxyl Ethoxybiphenyl di (meth) acrylate, 2- (2- {4 ′-[2- (2- (meth) acryloyloxy-ethoxy) -ethoxy] -biphenyl-4-yloxy} -ethoxy) -ethyl (meth) acrylate, Di (meth) acrylate of biphenyl ethylene oxide adduct, di (meth) acrylate of biphenyl propylene oxide adduct, 2- (4 ′-(meth) acryloyloxy-biphenyl-4-iroxy) -ethyl (meth) acrylate, etc. ;
Examples of the di (meth) acrylate having a phenyl-cyclohexyl structure include 4- (4- (meth) acryloyloxy-phenyl) -cyclohexyl (meth) acrylate, 2- (4- (4-((meth) acryloyloxy) cyclohexyl) Phenoxy) ethyl (meth) acrylate, 2- {4- [4- (2- (meth) acryloyloxy-ethoxy) -phenyl] -cyclohexyloxy} -ethyl (meth) acrylate, 2- [2- (4- {4 -[2- (2- (meth) acryloyloxy-ethoxy) -ethoxy] -phenyl} -cyclohexyloxy) -ethoxy] -ethyl (meth) acrylate and the like;

Examples of the di (meth) acrylate having a 2,2-diphenylpropane structure include 4- [1- (4- (meth) acryloyloxy-phenyl) -1-methyl-ethyl] -phenyl (meth) acrylate, 2- (4 -{1- [4- (2- (meth) acryloyloxy-ethoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -ethyl (meth) acrylate, bishydroxyethoxy-bisphenol A di (meth) acrylate, 2 -{2- [4- (1- {4- [2- (2- (meth) acryloyloxy-ethoxy) -ethoxy] -phenyl} -1-methyl-ethyl) -phenoxy] -ethoxy} -ethyl (meth) Acrylate, di (meth) acrylate of bisphenol A ethylene oxide adduct, propylene oxide of bisphenol A Additive di (meth) acrylate, 2- (4- {1- [4- (2- (meth) acryloyloxy-propoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -1-methyl-ethyl ( Such as meth) acrylate;

Examples of the di (meth) acrylate having a diphenylmethane structure include 4- (4- (meth) acryloyloxy-benzyl) -phenyl (meth) acrylate, 2- {4- [4- (2- (meth) acryloyloxy-ethoxy)- Benzyl] -phenyl} -ethyl (meth) acrylate, di (meth) acrylate of ethylene oxide adduct of bisphenol F, di (meth) acrylate of propylene oxide adduct of bisphenol F, 2- [2- (4- {4- [2- (2- (meth) acryloyloxy-ethoxy) -ethoxy] -benzyl} -phenoxy) -ethoxy] -ethyl (meth) acrylate, 2- {4- [4- (2- (meth) acryloyloxy-propoxy) -Benzyl-phenoxy} -1-methyl-ethyl (meth) acrylate, 2 [2- (4- {4- [2- (2- (meth) acryloyloxy-propoxy) -propoxy] -benzyl} -phenoxy) -1-methyl-ethoxy] -1-methyl-ethylethyl (meth) acrylate, etc. ;
Examples of the di-thio (meth) acrylate having a diphenylthioether structure include 4- (4-thio (meth) acryloylsulfanyl-phenylsulfanyl) -phenyldithio (meth) acrylate, bis (4-methacryloylthiophenyl) sulfide Etc .;
As other compounds (W), for example, pentane-1,5-diyl bis (4-((meth) acryloyloxy) benzoate, 2,5-bis {4- (3-acryloyloxy-propoxy) -benzoic acid} toluene, etc. Can be mentioned respectively.

  Compound (W) can be synthesized by combining organic chemistry methods as appropriate, or can be obtained as a commercial product. Examples of commercially available compounds (W) include bishydroxyethoxy BP diacrylate, bishydroxyethoxy Bis-A diacrylate (manufactured by Honshu Chemical Industry Co., Ltd.); Aronix M-208, M-210 (Toagosei Co., Ltd.) SR-349, SR-601, SR-602 (manufactured by Sartomer); KAYARAD R-712, R-551 (manufactured by Nippon Kayaku Co., Ltd.); NK ester BPE-100, NK ester BPE-200, NK ester BPE-500, NK ester BPE-1300, NK ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.); Actilane 420 (manufactured by Nippon Shibel Hegner Co., Ltd.); light ester BP-2EM, light acrylate BP- 4EA, light acrylate BP-4PA, epoxy ester 3000 , Epoxy ester 3000A (manufactured by Kyoeisha Chemical Co., Ltd.); V # 540, V # 700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.); FA-321M (manufactured by Hitachi Chemical Co., Ltd.); MPSMA (Sumitomo Seika Co., Ltd.) Lipoxy VR-77 (manufactured by Showa Polymer Co., Ltd.) and the like.

  When the photopolymerizable compound is blended in the polymer composition, the blending ratio is preferably 1 to 100 parts by weight with respect to a total of 100 parts by weight of the polymer contained in the polymer composition. More preferably, it is made into 50 weight part. A compound (W) can be used individually by 1 type or in combination of 2 or more types.

  In addition to the above, examples of other components include compounds having at least one oxetanyl group in the molecule, antioxidants, surfactants, metal chelating agents, photosensitizers, antistatic agents, and the like. .

<(B) Organic solvent>
The polymer composition of the present invention is prepared as a liquid composition in which the above-mentioned polymer (A) and other components used as necessary are dispersed or dissolved in an appropriate solvent.

  Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, Ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, 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 Recall diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, etc. be able to. These can be used alone or in admixture of two or more.

  The solid content concentration in the polymer composition of the present invention (the ratio of the total weight of components other than the solvent of the polymer composition to the total weight of the polymer composition) is appropriately determined in consideration of viscosity, volatility, and the like. Although selected, it is preferably in the range of 1 to 10% by weight. When the polymer composition of the present invention is used as a liquid crystal aligning agent, it is applied to a substrate surface as described later, and preferably a film that is a liquid crystal alignment film or a liquid crystal alignment film when heated. Is formed. At this time, when the solid content concentration is less than 1% by weight, the film thickness of the coating film becomes too small, and it becomes difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film because the film thickness is excessive, and the viscosity of the liquid crystal aligning agent increases and the applicability decreases. There is a tendency.

  The particularly preferable range of the solid content concentration varies depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, when applied to a substrate by the spinner method, the solid content concentration (the ratio of the total weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is 1.5 to 4.5% by weight. It is particularly preferable that the range is In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s. The temperature at the time of preparing the polymer composition is preferably 10 to 50 ° C, more preferably 20 to 30 ° C.

  The polymer composition of the present invention can be used for various applications such as a retardation film, a polarizer, an antireflection film, a selective reflection film, a color compensation film, a viewing angle compensation film, a liquid crystal alignment film, and a color filter. it can. Especially, it is suitable as a resin composition (liquid crystal aligning agent) for liquid crystal aligning film formation of a liquid crystal display element.

<Liquid crystal display element>
The liquid crystal display element of this invention comprises the liquid crystal aligning film formed using the said polymer composition as a liquid crystal aligning agent. The operation mode of the liquid crystal display element of the present invention is not particularly limited. For example, TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB type, etc. It can be applied to the operation mode.

The liquid crystal display element includes, for example, the following steps (1) to (3).
(1) A step of forming a coating film by applying the polymer composition on the conductive film of a pair of substrates having a conductive film;
(2) A step of constructing a liquid crystal cell by arranging a pair of substrates on which a coating film is formed so as to face each other with the coating film facing each other through a liquid crystal layer,
(3) A step of irradiating the liquid crystal cell with light while applying a voltage between the conductive films on the pair of substrates.
It can manufacture by the method containing. In the step (1), a substrate to be used differs depending on a desired operation mode. Step (2) and step (3) are common to each operation mode.

[Step (1): Formation of coating film]
First, the polymer composition of the present invention is applied on a substrate, and then the coated surface is heated to form a coating film on the substrate.
(1-1) For example, when manufacturing a TN type, STN type, or VA type liquid crystal display element, first, a pair of two substrates on which a patterned transparent conductive film is provided, and each transparent conductive film is formed. On the surface, the polymer composition is preferably applied by an offset printing method, a spin coating method, a roll coater method or an ink jet printing method, respectively. As the substrate, for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly (cycloaliphatic olefin) can be used. As a transparent conductive film provided on one surface of the substrate, 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 ), etc. Can be used. In order to obtain a patterned transparent conductive film, for example, after forming a transparent conductive film without a pattern, a method of forming a pattern by photo-etching; a method of using a mask having a desired pattern when forming a transparent conductive film; And so on. In applying the polymer composition, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound or functional titanium is formed on the surface of the substrate surface on which the coating film is formed. You may give the pretreatment which apply | coats a compound etc. previously.

  After applying the polymer composition, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied polymer composition. The pre-baking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-bake time is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 minutes. Then, a baking (post-baking) process is implemented for the purpose of removing a solvent completely and heat imidating the amic acid structure which exists in a polymer as needed. The firing temperature (post-bake temperature) at this time is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The thickness of the film thus formed is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

  (1-2) In the case of manufacturing an IPS type or FFS type liquid crystal display element, an electrode forming surface of a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape, and an electrode are provided. The polymer composition is applied to one surface of the counter substrate that is not coated, and then the coated surface is formed by heating each coated surface. Regarding the material used for the substrate and the transparent conductive film, the coating method, the heating conditions after coating, the patterning method for the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film thickness of the coating film to be formed The same as (1-1). As the metal film, for example, a film made of a metal such as chromium can be used.

  In both cases (1-1) and (1-2), after applying the polymer composition on the substrate, the organic solvent is removed to form a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film. Is done. At this time, by further heating after the coating film is formed, a dehydration ring-closing reaction of the polyamic acid, polyamic acid ester and polyimide compounded in the polymer composition may be advanced to obtain a more imidized coating film.

  When manufacturing a TN type, STN type, IPS type, or FFS type liquid crystal display element, the process which provides liquid crystal aligning ability to the coating film formed at the said process (1) is implemented. Thereby, the orientation ability of liquid crystal molecules is imparted to the coating film to form a liquid crystal orientation film. On the other hand, when manufacturing a VA type liquid crystal display element, the coating film formed in the above step (1) can be used as it is as a liquid crystal alignment film, but even if the coating film is subjected to alignment ability imparting treatment. Good. Examples of the orientation ability imparting treatment include rubbing treatment in which the coating film is rubbed in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton.

  In addition, the liquid crystal alignment film after the rubbing treatment is further subjected to a process for changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet rays or a surface of the liquid crystal alignment film. A resist film is formed on the part, and a rubbing process is performed in a direction different from the previous rubbing process, followed by a process of removing the resist film, so that the liquid crystal alignment film has different liquid crystal alignment capabilities for each region. . In this case, it is possible to improve the visibility characteristics of the obtained liquid crystal display element. A liquid crystal alignment film suitable for a VA liquid crystal display element can also be suitably used for a PSA (Polymer sustained alignment) type liquid crystal display element.

[Step (2): Construction of liquid crystal cell]
Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal cell is manufactured by disposing a liquid crystal between the two substrates disposed to face each other. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a conventionally known method. First, two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded together using a sealing material. A liquid crystal cell can be manufactured by injecting and filling liquid crystal into the cell gap partitioned by the step, and then sealing the injection hole. The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealant is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped at predetermined locations on the liquid crystal alignment film surface. After that, the other substrate is bonded so that the liquid crystal alignment film faces, and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealing material, thereby manufacturing a liquid crystal cell. can do. Regardless of which method is used, the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase and then gradually cooled to room temperature. It is desirable to remove.

As a sealing material, what is normally used as an adhesive agent for liquid crystals can be used, for example, an epoxy resin containing a curing agent can be used. Moreover, as the sealing material, a material further containing aluminum oxide spheres as a spacer may be used.
Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable. For example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl. Cyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used. Further, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, and cholesteryl carbonate; chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck & Co., Inc.). A ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be added and used.

[Step (3): Light irradiation step]
After the construction of the liquid crystal cell, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The voltage applied here can be, for example, 5 to 50 V direct current or alternating current. Moreover, as light to irradiate, the ultraviolet-ray and visible light which contain light with a wavelength of 150-800 nm can be used, for example, However, The ultraviolet-ray containing light with a wavelength of 300-400 nm is preferable. As a light source of irradiation light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. In addition, the ultraviolet rays in the above preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter diffraction grating. The irradiation dose of light, preferably 1,000~200,000J / ^{m 2,} more preferably from 1,000~100,000J / ^{m 2.}

  And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell. As a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film itself in which a polarizing film called an “H film” in which iodine is absorbed while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films The polarizing plate which consists of can be mentioned.

  The liquid crystal display element of the present invention can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, The present invention can be used for various display devices such as various monitors, liquid crystal televisions, and information displays.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

In the following Examples and Synthesis Examples, the weight average molecular weight Mw of the polymer, the imidization rate, and the solution viscosity of the polymer solution were measured by the following methods. Hereinafter, the compound represented by Formula X may be simply referred to as “Compound X”.
[Weight average molecular weight Mw of polymer]
Mw is a polystyrene equivalent value measured by GPC under the following conditions.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²
[Imidation rate of polymer]
A solution containing polyimide is poured into pure water, and the resulting precipitate is sufficiently dried at room temperature under reduced pressure, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR is measured at room temperature using tetramethylsilane as a reference substance. did. From the obtained ¹ H-NMR spectrum, the imidation ratio was determined using the following mathematical formula (1).
Imidation ratio (%) = (1-A ¹ / A ² × α) × 100 (1)
(In Formula (1), A ¹ is a peak area derived from protons of NH groups appearing near a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a precursor of a polymer (polyamic acid). The number ratio of other protons to one proton of NH group in)
[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 for a solution prepared to a polymer concentration of 10% by weight using a predetermined solvent.

<Synthesis example of carboxylic acid>
[Synthesis Example 1]
Compound (X-1) was synthesized as in Scheme 1.

Synthesis of Compound (X-1a) 195 g of 6-bromohexanoic acid and 2 L of methylene chloride were placed in a 5 L three-necked flask equipped with a septum and stirred. 1 kg of isobutene gas was introduced into the system while bubbling and allowed to react. The flow rate of isobutene gas was 1 kg / 2h. Then, after stirring for 1 hour, it was left still for 12 hours. After nitrogen substitution, the reaction solution was poured into 2.5 L of an ion exchange resin (Amberlite IRA-67, manufactured by Organo Corporation) and stirred for 3 hours. After removing the ion exchange resin by filtration, the filtrate was concentrated to obtain 126 g of a colorless liquid of compound (X-1a).
Synthesis of compound (X-1b) In a 5 L three-necked flask equipped with a reflux tube and a thermometer, 126 g of compound (X-1a), 82.9 g of potassium carbonate, 1.3 g of 2,6-di-t-butylcresol , 2 L of N, N-dimethylacetamide and 258 g of methacrylic acid were added and reacted at 100 ° C. for 2 hours. After completion of the reaction, 2 L of cyclohexane was added, and the mixture was washed once with water, twice with saturated aqueous sodium carbonate, and twice with water, then dried over magnesium sulfate and concentrated under reduced pressure to 300 mL. Next, after purification with a silica column (developing solvent: hexane: ethyl acetate (weight ratio) = 9: 1), 64 g of a colorless liquid of compound (X-1b) was obtained by concentration under reduced pressure.
-Synthesis | combination of compound (X-1) 64 g of compounds (X-1b), 300 mL of methylene chloride, and 150 g of trifluoroacetic acid were added to the 1 L eggplant flask, and it was made to react at room temperature for 2 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, added with 300 mL of cyclohexane, washed with water 10 times, dried over magnesium sulfate, concentrated, and dried under vacuum to obtain 45 g of a colorless liquid of compound (X-1).

[Synthesis Example 2]
Compound (A-1-1-1) was synthesized as in Scheme 2.

  To a 500 mL eggplant flask equipped with a reflux tube, 20 g of compound (X-1), 200 mL of thionyl chloride and 0.1 g of N, N-dimethylformamide were added and refluxed for 1 hour. After completion of the reaction, thionyl chloride was distilled off by concentration under reduced pressure, and 100 mL of methylene chloride was added (this solution is referred to as “A1 solution”). Meanwhile, in a 300 mL three-necked flask equipped with a dropping funnel and a thermometer, 6.0 g of sodium hydroxide, 7.7 g of 3,4-dihydroxybenzoic acid, 0.02 g of 2,6-di-t-butylcresol and 60 mL of water were added. In addition, it was ice-cooled. Next, the previously prepared A1 solution was added dropwise over 3 hours under ice cooling, and the mixture was further reacted at room temperature for 1 hour. After completion of the reaction, a white precipitate was collected by filtration, added with 300 mL of ethyl acetate and 300 mL of 1M hydrochloric acid, washed with water three times, dried over magnesium sulfate, added with ethanol, and concentrated under reduced pressure to yield white crystals 15.5g of compounds (A-1-1-1) were obtained by filtering and drying.

[Synthesis Example 3]
Compound (A-1-3-1) was synthesized as in Scheme 3.

  To a 200 mL eggplant flask equipped with a reflux tube, 6 g of compound (X-1), 60 mL of thionyl chloride and 0.03 g of N, N-dimethylformamide were added and refluxed for 1 hour. After completion of the reaction, thionyl chloride was removed by concentration under reduced pressure, and 30 mL of methylene chloride was added (this solution is referred to as “A2 solution”). Meanwhile, in a 100 mL three-necked flask equipped with a dropping funnel and a thermometer, 1.6 g of sodium hydroxide, 1.7 g of 3,4,5-trihydroxybenzoic acid, 0.01 g of 2,6-di-t-butylcresol and 20 mL of water was added and cooled with ice. Next, the previously prepared A2 solution was added dropwise over 3 hours under ice cooling, and the mixture was further reacted at room temperature for 1 hour. After completion of the reaction, a white precipitate was collected by filtration, 300 mL of ethyl acetate and 300 mL of 1M aqueous hydrochloric acid were added, and the mixture was washed three times with water, dried over magnesium sulfate, and concentrated under reduced pressure to 10 mL. Next, it is purified with a silica column (developing solvent is hexane: ethyl acetate (weight ratio) = 8: 2), ethanol is added and concentrated under reduced pressure, and the resulting white crystals are filtered and dried to give compound (A-1 2.9 g of 3-1) was obtained.

[Synthesis Example 4]
Compound (A-3-1-1) was synthesized as in Scheme 4.

  To a 200 mL eggplant flask equipped with a reflux tube, 6 g of compound (X-2), 60 mL of thionyl chloride and 0.03 g of N, N-dimethylformamide were added and refluxed for 1 hour. After completion of the reaction, thionyl chloride was distilled off by concentration under reduced pressure, and 30 mL of methylene chloride was added (this solution is referred to as “A3 solution”). On the other hand, 1.6 g of sodium hydroxide, 2.5 g of 3,4-dihydroxybenzoic acid, 0.01 g of 2,6-di-t-butylcresol and 20 mL of water were added to a 100 mL three-necked flask equipped with a dropping funnel and a thermometer. And ice-cooled. Next, the previously prepared A3 solution was added dropwise over 3 hours under ice cooling, and the mixture was further reacted at room temperature for 1 hour. After completion of the reaction, a white precipitate was collected by filtration, 300 mL of ethyl acetate and 300 mL of 1M aqueous hydrochloric acid were added, and the mixture was washed three times with water, dried over magnesium sulfate, and concentrated under reduced pressure to 10 mL. Next, it is purified with a silica column (developing solvent is hexane: ethyl acetate (weight ratio) = 8: 2), ethanol is added and concentrated under reduced pressure, and the resulting white crystals are filtered and dried to give compound (A-3 As a result, 2.9 g of (1-1) was obtained.

[Synthesis Example 5]
Compound (A-5-1-1) was synthesized as in Scheme 5.

  To a 500 mL three-necked flask equipped with a dropping funnel and a thermometer, 9.6 g of sodium hydroxide, 12.4 g of 3,4-dihydroxybenzoic acid, 0.02 g of 2,6-di-t-butylcresol and 120 mL of water were added and iced. Chilled. Next, a solution of 16.8 g of methacryloyl chloride dissolved in 160 mL of methylene chloride was added dropwise over 3 hours under ice-cooling, and the mixture was further reacted at room temperature for 1 hour. After completion of the reaction, a white precipitate was recovered by filtration, and 200 mL of tetrahydrofuran, 400 mL of ethyl acetate and 500 mL of 1M hydrochloric acid water were added, and the mixture was washed three times with water, then dried over magnesium sulfate, and ethanol was added to concentrate under reduced pressure. The white crystals were filtered and dried to obtain 11.6 g of compound (A-5-1-1).

<Synthesis example of specific diamine>

[Synthesis Example 6]
Compound (B-1-1-1) was synthesized as shown in Scheme 6 below.

Synthesis of Compound (B-1-1a) In a 300 mL three-necked flask equipped with a thermometer, 5.8 g of Compound (A-5-1-1), 4.2 g of 2,4-dinitrophenethyl alcohol, and methylene chloride 100 mL was added and ice-cooled. Next, 4.6 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.24 g of N, N-dimethylaminopyridine were added, and the mixture was allowed to react for 2 hours under ice-cooling and overnight at room temperature. . After completion of the reaction, 200 mL of ethyl acetate and 200 mL of THF were added, washed once with dilute hydrochloric acid and three times with water, and then dried over magnesium sulfate. Next, ethanol was added and concentrated under reduced pressure, and the pale yellow crystals deposited were filtered and dried to obtain 7.8 g of Compound (B-1-1a).
Synthesis of compound (B-1-1-1) In a 300 mL three-necked flask equipped with a nitrogen inlet tube and a thermometer, 7.8 g of compound (B-1-1a), 21 g of zinc, 3.4 g of ammonium chloride, tetrahydrofuran After adding 80 mL and 20 mL of ethanol and cooling with ice, 8 mL of water was slowly added and reacted at room temperature for 3 hours. After completion of the reaction, zinc was removed by filtration, 80 mL of ethyl acetate was added to the obtained filtrate, and the mixture was washed three times with water, ethanol was added, and the mixture was concentrated under reduced pressure to give the compound (B-1-1-1). 5.4 g of light brown crystals were obtained.

[Synthesis Example 7]
-Synthesis | combination of compound (Y-1) Compound (Y-1) was synthesize | combined like the scheme 7.

  To a 200 mL three-necked flask equipped with a thermometer and a nitrogen introducing tube, 10.1 g of 2,4-dinitrofluorobenzene, 50 mL of ethanol, 7.9 g of diethanolamine and 6.3 g of sodium hydrogen carbonate were added and reacted at 60 ° C. for 8 hours. . After completion of the reaction, the mixture was washed four times with water added with 300 mL of ethyl acetate, dried over magnesium sulfate, and hexane was added to concentrate under reduced pressure to obtain 10.5 g of yellow crystals of compound (Y-1). .

-Synthesis | combination of compound (B-3-1-1) The compound (B-3-1-1) was synthesize | combined like the scheme 8.

Synthesis of Compound (B-3-1-1a) To a 300 mL three-necked flask equipped with a thermometer, 8.0 g of Compound (X-1), 5.4 g of Compound (Y-1) and 100 mL of methylene chloride were added and iced. Chilled. Next, 9.2 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.24 g of N, N-dimethylaminopyridine were added and reacted for 2 hours under ice-cooling and overnight at room temperature. . After completion of the reaction, 200 mL of ethyl acetate and 100 mL of tetrahydrofuran were added, and the mixture was washed once with dilute hydrochloric acid and three times with water, then dried over magnesium sulfate, and ethanol was added and dried under reduced pressure to filter the precipitated yellow crystals. By drying, 10.2 g of the compound (B-3-1-1a) was obtained.
Synthesis of Compound (B-3-1-1) In a 300 mL three-necked flask equipped with a nitrogen introduction tube and a thermometer, 10.2 g of Compound (B-3-1-1a), 21 g of zinc, 3.4 g of ammonium chloride After adding 80 mL of tetrahydrofuran and 20 mL of ethanol and cooling with ice, 8 mL of water was slowly added and reacted at room temperature for 3 hours. After completion of the reaction, zinc was removed by filtration, and 80 mL of ethyl acetate was added to the obtained filtrate, followed by separation and washing with water three times, addition of ethanol and concentration under reduced pressure to thereby add the compound (B-3-1-1). 7.4 g of light brown crystals were obtained.

<Synthesis of polyamic acid>
[Synthesis Example PA-1]
170.4 g (0.760 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 291.8 g (0.688) of compound (B-1-1-1) as a diamine compound Mol) and 37.8 g (0.076 mol) of (3,5-diaminobenzoyloxy) cholestane were dissolved in 2000 g of NMP and reacted at 60 ° C. for 6 hours to obtain a polyamic acid solution. It was 150,000 when the weight average molecular weight of the obtained polyamic acid (it is set as "polymer PA-1") was measured. A small amount of the obtained polymer PA-1 was collected, NMP was added, and the viscosity was measured with a solution having a solid content concentration of 10%. The result was 57 mPa · s.

[Synthesis Example PA-2]
153.0 g (0.705 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 285.4 g (0.496) of compound (B-3-1-1) as a diamine compound Mol), 21.6 g (0.142 mol) of 3,5-diaminobenzoic acid and 35.0 g (0.071 mol) of (3,5-diaminobenzoyloxy) cholestane were dissolved in 2000 g of NMP, It was made to react for time, and the polyamic acid solution was obtained. It was 150,000 when the weight average molecular weight of the obtained polyamic acid (it is set as "polymer PA-2") was measured. Further, a small amount of the obtained polymer PA-2 was fractionated, NMP was added, and the viscosity was measured with a solution having a solid content concentration of 10%, and it was 57 mPa · s.

[Comparative Synthesis Example PA-3]
170.4 g (0.760 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 291.8 g (0.688 mol) of p-phenylenediamine and (3,3) as diamine compounds 57.8 g (0.076 mol) of 5-diaminobenzoyloxy) cholestane was dissolved in 2000 g of NMP and reacted at 60 ° C. for 6 hours to obtain a polyamic acid solution. It was 150,000 when the weight average molecular weight of the obtained polyamic acid (it is set as "polymer PA-3") was measured. In addition, a small amount of the obtained polymer PA-3 was collected, NMP was added, and the viscosity was measured with a solution having a solid content concentration of 10%. As a result, it was 57 mPa · s.

[Comparative Synthesis Example PA-4]
170.4 g (0.760 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 291.8 g (0.688 mol) of p-phenylenediamine and (3,3) as diamine compounds 37.8 g (0.076 mol) of 5-diaminobenzoyloxy) cholestane was dissolved in 2000 g of NMP and reacted at 60 ° C. for 6 hours to obtain a polyamic acid. It was 150,000 when the weight average molecular weight of the obtained polyamic acid (it is set as "polymer PA-4") was measured. A small amount of the obtained polymer PA-4 was fractionated, NMP was added, and the viscosity was measured with a solution having a solid content concentration of 10%. As a result, it was 57 mPa · s.

<Synthesis of polyimide>
[Comparative Synthesis Example PI-1]
110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 43 g (0.40 mol) of p-phenylenediamine as diamine and 3 (3,5-diaminobenzoyl) 52 g (0.10 mol) of oxy) cholestane was dissolved in 830 g of NMP and reacted at 60 ° C. for 6 hours. A small amount of the obtained polyamic acid solution was collected, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 60 mPa · s.
Next, 1,900 g of NMP was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with new NMP (by this operation, pyridine and acetic anhydride used for the dehydration cyclization reaction were removed from the system), and the imidation rate was about 50%. A solution containing about 15% by weight of polyimide (referred to as “polymer (PI-1)”) was obtained. A small amount of the obtained polyimide solution was collected, NMP was added, and the solution viscosity measured as a solution having a solid content concentration of 10% by weight was 47 mPa · s.

<Synthesis of (meth) acrylic polymer>
[Synthesis Example AC-1]
A four-necked flask equipped with a stir bar, three-way cock and thermometer was charged with 30.0 g (0.211 mol) of glycidyl methacrylate as a monomer, 60 g of diethylene glycol ethyl methyl ether as a solvent, and 2,2 ′ as a polymerization initiator. -1.2 g of azobis (2,4-dimethylvaleronitrile) and 0.6 g of α-methylstyrene dimer as a molecular weight modifier were added. This was bubbled in a nitrogen stream for about 10 minutes to perform nitrogen substitution in the system, and then reacted at 70 ° C. for 5 hours in a nitrogen atmosphere to contain 33% by weight of an epoxy group-containing (meth) acrylic polymer. A solution was obtained.
Next, in a 1000 mL three-necked flask, 91.0 g of the epoxy group-containing (meth) acrylic polymer obtained above, 54.3 g (0.105 mol) of the compound (A-1-1-1), diethylene glycol ethylmethyl 212.3 g of ether and 2.0 g of UCAT 18X (a quaternary amine salt of Sun Apro) were charged and stirred at 80 ° C. for 36 hours. After completion of the reaction, reprecipitation was performed with water, and the precipitate was dissolved in ethyl acetate to obtain a solution. This solution was washed with water three times, and then the solvent was distilled off to obtain 21.6 g of a (meth) acrylic polymer (referred to as “polymer AC-1”) as a white powder. It was 30,000 when the weight average molecular weight of obtained polymer AC-1 was measured. Further, a small amount of the obtained polymer AC-1 was sampled, and NMP was added thereto, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight was 17 mPa · s.

[Synthesis Example AC-2]
In Synthesis Example AC-1, by performing the same operation as in Synthesis Example AC-1, except that 75.1 g (0.105 mol) of the compound (A-1-3-1) was used as the carboxylic acid, 21.6 g of a (meth) acrylic polymer (referred to as “polymer AC-2”) was obtained as a white powder. It was 33,000 when the weight average molecular weight of obtained polymer AC-2 was measured. Further, a small amount of the obtained polymer AC-2 was collected, NMP was added, and the solution viscosity measured as a solution having a (meth) acrylic polymer concentration of 10% by weight was 15 mPa · s.

[Comparative Synthesis Example AC-3]
In Synthesis Example AC-1, the same operation as in Synthesis Example AC-1 was performed, except that 75.1 g (0.105 mol) of Compound (X-1) was used as the carboxylic acid. 21.6 g of a combined product (referred to as “polymer AC-3”) was obtained as a white powder. It was 33,000 when the weight average molecular weight of obtained polymer AC-3 was measured. Further, a small amount of the obtained polymer AC-3 was fractionated, and NMP was added thereto, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight was 15 mPa · s.

<Synthesis of polyorganosiloxane>
[Synthesis Example PS-1]
A reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with 139.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 139.0 g of methyl isobutyl ketone, and 13.9 g of triethylamine. And mixed at room temperature. Next, 111.2 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 60 ° C. for 3 hours while mixing under reflux. After completion of the reaction, the organic layer is taken out and washed with a 0.2% by mass aqueous ammonium nitrate solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to obtain an epoxy group-containing polyorganosiloxane. Was obtained as a viscous transparent liquid. The epoxy group-containing polyorganosiloxane was subjected to ¹ H-NMR analysis, and a peak based on the epoxy group was obtained in the vicinity of the chemical shift (δ) = 3.2 ppm according to the theoretical intensity. It was confirmed that no reaction occurred.
Subsequently, 56.0 g of the epoxy group-containing polyorganosiloxane obtained above, 206.0 g of methyl isobutyl ketone, 54.3 g (0.105 mol) of the compound (A-1-1-1) and a 100 mL three-necked flask were obtained. 0.6 g of UCAT 18X (quaternary amine salt from San Apro) was charged and stirred at 80 ° C. for 36 hours. After completion of the reaction, reprecipitation is performed with water, and the precipitate is dissolved in ethyl acetate to obtain a solution. The solution is washed with water three times, and then the solvent is distilled off to remove polyorganosiloxane (this is a polymer ( PS-2) was obtained as a white powder. It was 30,000 when the weight average molecular weight of the obtained polymer (PS-1) was measured. Further, a small amount of the obtained polymer (PS-1) was collected, NMP was added, and the solution viscosity measured as a solution having a polyorganosiloxane concentration of 10% by weight was 17 mPa · s.

[Synthesis Example PS-2]
In Synthesis Example PS-1, the same procedure as in Synthesis Example PS-1 was carried out except that 75.1 g (0.105 mol) of the compound (A-3-1-1) was used as the carboxylic acid. 21.6 g of organosiloxane (referred to as “polymer (PS-2)”) was obtained as a white powder. It was 33,000 when the weight average molecular weight of the obtained polymer (PS-2) was measured. Further, a small amount of the obtained polymer (PS-2) was collected, NMP was added, and the solution viscosity measured as a solution having a polyorganosiloxane concentration of 10% by weight was 15 mPa · s.

[Comparative Synthesis Example PS-3]
In Synthesis Example PS-1, the same procedure as in Synthesis Example PS-1 was carried out except that 75.1 g (0.105 mol) of Compound (X-1) was used as the carboxylic acid. 21.6 g of “Polymer (PS-3)” as white powder. It was 33,000 when the weight average molecular weight of the obtained polymer (PS-3) was measured. Further, a small amount of the obtained polymer (PS-3) was collected, NMP was added, and the solution viscosity measured as a solution having a polyorganosiloxane concentration of 10% by weight was 15 mPa · s.

[Example 1]
<Preparation of polymer composition>
(A) N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) are added as organic solvents to a solution containing the polymer (PA-1) obtained in Synthesis Example PA-1 as a polymer, and BC It was set as the solution whose density | concentration is 20 weight% with respect to all the organic solvents, and whose solid content concentration is 6.0 weight%. A polymer composition was prepared by filtering this solution using a filter having a pore size of 1 μm.

<Manufacture of liquid crystal cells>
The polymer composition prepared above was applied onto a transparent electrode surface of a glass substrate having a transparent electrode made of an ITO film using a liquid crystal alignment film printer (Nissha Printing Co., Ltd.), and hot at 80 ° C. After removing the solvent by heating (pre-baking) on the plate for 1 minute, heating (post-baking) on a hot plate at 200 ° C. for 10 minutes to form a coating film having an average film thickness of 800 mm.
The coating film was rubbed with a rubbing machine having a roll wrapped with a rayon cloth at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair foot indentation length of 0.1 mm. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then drying was performed 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) of substrates having a liquid crystal alignment film. The rubbing process is a weak rubbing process performed for the purpose of controlling the tilting of the liquid crystal and performing alignment division by a simple method.

Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 μm to the outer edge of the surface having the liquid crystal alignment film for one of the pair of substrates, the pair of substrates is liquid crystal alignment film surface The adhesives were cured by overlapping and pressing so that they face each other. Thereafter, nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled between the pair of substrates from the liquid crystal injection port, and the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to produce a liquid crystal cell.
Next, an alternating current of 15 Vrms with a frequency of 60 Hz is applied between the electrodes of the liquid crystal cell obtained above, and the liquid crystal is driven, using an ultraviolet irradiation device using a metal halide lamp as a light source, from the outside of the liquid crystal cell. Ultraviolet rays were irradiated at a dose of ² J / cm ² . In addition, this irradiation amount is the value measured using the light meter measured on the basis of wavelength 365nm.
In addition to manufacturing two more liquid crystal cells in the same manner as described above, the amount of ultraviolet rays irradiated to the liquid crystal cell was changed to 5 J / cm ² for one liquid crystal cell and 10 J / cm ² for the other liquid crystal cell. In the same manner as described above, ultraviolet irradiation was performed with a voltage applied between the electrodes of the liquid crystal cell.

<Evaluation of pretilt angle>
About each liquid crystal cell manufactured above, according to the method described in Non-Patent Document 2 (TJ Scheffer et.al. J.Appl.Phys. Vo.19, p.2013 (1980)), respectively. The value of the tilt angle of the liquid crystal molecules from the substrate surface measured by the crystal rotation method using He—Ne laser light was defined as the pretilt angle.
Table 1 below shows the respective pretilt angles in the liquid crystal cells with irradiation doses of ² J / cm ² , 5 J / cm ² and 10 J / cm ² . This liquid crystal cell showed a pretilt angle of 88.2 degrees when irradiated with 5 J / cm ² of ultraviolet rays. From the relationship between the response speed and the contrast, it is preferable that the value is 85 degrees or more and 88.5 degrees or less, and thus it was found that the liquid crystal cell has a good pretilt angle characteristic.

<Evaluation of afterimage>
The liquid crystal cell subjected to the above ultraviolet treatment was subjected to measurement of the pretilt angle again by the method described above after applying AC 7 Vrms with a frequency of 60 Hz for 168 hours to each pixel in an oven at a temperature of 40 ° C. Each of the pre-tilt angle of the liquid crystal cell dose ^{2J / cm 2, 5J / cm} 2 and 10J / cm ² at this time are shown together in Table 1.
Table 1 also shows the amount of change in the pretilt angle before and after the stress of 168 hours. It can be evaluated that the smaller the amount of change in the pretilt angle, the better the afterimage characteristics. In Example 1, it was found that the pretilt angle change amount was 0.3 degrees in a liquid crystal cell with an ultraviolet irradiation amount of 5 J / cm ² , and it had good afterimage characteristics.

[Examples 2 to 9 and Comparative Examples 1 to 5]
A polymer composition was prepared in the same manner as in Example 1 except that the amount of each component used was as described in Table 1 below, and a liquid crystal cell was produced and evaluated using the polymer composition. In Example 3, Example 8 and Example 9, (A) the polymer and other polymer were used in combination, and in Comparative Examples 1 to 5, only the other polymer was used as the polymer. The results are shown in Table 1 below. In Table 1, the numerical value of the blending amount of the polymer is the blending ratio (weight ratio) of each polymer with respect to the total amount of the polymers used for preparing the polymer composition.

As shown in Table 1, in Examples 1 to 9, liquid crystal cells showing good pretilt angle characteristics could be obtained even when the ultraviolet irradiation amount was 5 J / cm ² . Further, in the liquid crystal cell of the example, even when the ultraviolet irradiation amount was 5 J / cm ² , the amount of change in the pretilt angle before and after the stress application was small, and the afterimage characteristics were good. On the other hand, in Comparative Examples 1 to 5, the pretilt angle characteristics and the afterimage characteristics of the liquid crystal cell were inferior to those of the Examples.

[Examples 10 to 13]
A polymer composition was prepared in the same manner as in Example 1 except that the amounts of the polymer and additive used were as shown in Table 2 below. Moreover, the liquid crystal cell was manufactured and evaluated using the prepared polymer composition. In Example 11, the (A) polymer and other polymers were used in combination. The results are shown in Table 2 below. In Table 2, the numerical value of the blending amount of the polymer and the additive is the blending ratio (weight ratio) of each compound with respect to the total amount of the polymer used for the preparation of the polymer composition.

In Table 2, the abbreviations of the additives have the following meanings.
w-1, [1,1′-biphenyl] -4,4′-diyl bis (2-methacrylate)
w-2; 4-((2-methacryloyloxy) ethoxy) carbonyl) phenyl 4 ′-(methacryloyloxy)-[1,1′-biphenyl] -4-carboxylate w-3; 4- (methacryloyloxy) phenyl 4 '-((4- (methacryloyloxy) benzoyl) oxy)-[1,1'-biphenyl] -4-carboxylate w-4; 2- (4- (4- (methacryloyloxy) cyclohexyl) phenoxy) ethyl Methacrylate

As shown in Table 2, a liquid crystal cell exhibiting good pretilt angle characteristics was also obtained for the liquid crystal aligning agent blended with the additive. In addition, even when the ultraviolet irradiation amount was as small as 5 J / cm ² , the amount of change in the pretilt angle before and after the application of stress was small and the afterimage characteristics were good.

Claims (11)

(A) a polymer, and (B) an organic solvent,
The polymer composition (A) has a group represented by the following formula (1).

(In the formula (1), R ¹ represents the following formula (r1-1) to formula (r1-6)

(In Formula (r1-1) to Formula (r1-6), R ⁵ is a hydrogen atom or a methyl group, X ⁵ is an oxygen atom or —NR ³⁰ — (wherein R ³⁰ is a hydrogen atom or a methyl group). R ⁶ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, a group in which at least one hydrogen atom in the hydrocarbon group is substituted with a fluorine atom, or a monovalent group having a heterocyclic ring. ⁷ and R ⁹ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and two R ^{8 s} are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, or two R ^{8 s.} Are bonded to each other to form a hydrocarbon ring structure having 4 to 20 carbon atoms with two carbon atoms to which R ⁸ is bonded, and R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 fluoroalkyl groups, provided that a plurality of R ^{1 0} may be the same or different, Ar ¹ is a divalent aromatic ring group, and Ar ² and Ar ³ are a single bond or a divalent aromatic ring group.)
These are monovalent groups selected from the group consisting of groups represented by R ² is a single bond or a divalent organic group. Y ¹ is a (u + 1) -valent cyclic group or a nitrogen atom. u is an integer of 2-4. However, when Y ¹ is a nitrogen atom, u = 2. “*” Indicates a bond. ) The polymer composition according to claim 1, wherein R ² is a group represented by the following formula (r2-1).

(In the formula (r2-1), R ¹² is an alkanediyl group having 1 to 20 carbon atoms or the following formula (r2-1-1)

(In the formula (r2-1-1), R ²⁰ and R ²¹ are each independently a monovalent substituent. M1 and m2 are each independently an integer of 0 to 2. However, 1 ≦ (m1 + m2) ≦ 2 is satisfied, t1 and t2 are each independently an integer of 0 to 4. The plurality of R ²⁰ may be the same or different, and the plurality of R ²¹ may be the same or different.
It is group represented by these. R ¹³ is an alkanediyl group having 1 to 20 carbon atoms, and R ¹⁴ is a single bond or an alkanediyl group having 1 to 20 carbon atoms. X ¹ and X ² are each independently an alkanediyl group having 1 to 6 carbon atoms, an ether bond, an ester bond, an amide bond or a ureido bond. n1 and n2 are each independently an integer of 0 to 2, and satisfy n1 + n2 ≧ 1. A bond marked with “* ¹ ” is bonded to R ¹ . )   The polymer (A) is at least one polymer selected from the group consisting of polyamic acid, polyimide, polyamic acid ester, (meth) acrylic polymer, and polyorganosiloxane. Polymer composition.   The said (A) polymer further has group (however, group except the group applicable to the group represented by said Formula (1)) which can express a pretilt angle characteristic, It is any one of Claims 1-3. The polymer composition according to item.   The polymer according to any one of claims 1 to 4, wherein the polymer (A) is a polymer obtained by polymerization containing a compound having a group represented by the formula (1) in a monomer composition. Composition.   The (A) polymer is a group having a functional group (Z1) and a group having the group represented by the above formula (1) and capable of reacting with the functional group (Z1) to form a bonding group. The polymer composition as described in any one of Claims 1-4 which is a polymer obtained by making the compound which has (Z2) react.   The liquid crystal aligning agent which consists of a polymer composition as described in any one of Claims 1-6.   The liquid crystal aligning film formed using the polymer composition as described in any one of Claims 1-6.   A liquid crystal display element provided with the liquid crystal aligning film of Claim 8. On the conductive film of a pair of substrates having a conductive film, a step of applying the polymer composition according to any one of claims 1 to 6 to form a coating film;
A step of constructing a liquid crystal cell by arranging the pair of substrates on which the coating film is formed so as to face each other with the coating film facing each other through a liquid crystal layer;
Irradiating the liquid crystal cell with light while applying a voltage between the conductive films on the pair of substrates. The polymer which has group represented by following formula (1).

(In the formula (1), R ¹ represents the following formula (r1-1) to formula (r1-6)

(In Formula (r1-1) to Formula (r1-6), R ⁵ is a hydrogen atom or a methyl group, X ⁵ is an oxygen atom or —NR ³⁰ — (wherein R ³⁰ is a hydrogen atom or a methyl group). R ⁶ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, a group in which at least one hydrogen atom in the hydrocarbon group is substituted with a fluorine atom, or a monovalent group having a heterocyclic ring. ⁷ and R ⁹ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and two R ^{8 s} are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, or two R ^{8 s.} Are bonded to each other to form a hydrocarbon ring structure having 4 to 20 carbon atoms with two carbon atoms to which R ⁸ is bonded, and R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 fluoroalkyl groups, provided that a plurality of R ^{1 0} may be the same or different, Ar ¹ is a divalent aromatic ring group, and Ar ² and Ar ³ are a single bond or a divalent aromatic ring group.)
These are monovalent groups selected from the group consisting of groups represented by R ² is a single bond or a divalent organic group. Y ¹ is a (u + 1) -valent cyclic group or a nitrogen atom. u is an integer of 2-4. However, when Y ¹ is a nitrogen atom, u = 2. “*” Indicates a bond. )