JP6337595B2 - Manufacturing method of liquid crystal display element, liquid crystal aligning agent, and liquid crystal aligning film - Google Patents

Description

  The present invention relates to a method for manufacturing a liquid crystal display element, a liquid crystal alignment agent, and a liquid crystal alignment film. Specifically, the present invention relates to a technique for manufacturing a liquid crystal display element having a wide viewing angle and a fast response speed.

  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.

  However, when the orientation of liquid crystal molecules is controlled by the PSA technique, it is necessary to perform light irradiation with a relatively high dose. Therefore, in addition to inconvenience that the liquid crystal molecules decompose, unreacted compounds that did not polymerize even when irradiated with ultraviolet rays remain in the liquid crystal layer. Or it becomes clear that a problem arises in the long-term reliability of a panel, and it has not yet reached practical use.

  On the other hand, 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.Lee et. Al. SID 09 DIGEST, p. 666 (2009)

  However, Non-Patent Document 1 does not provide any guidance on what amount of reactive mesogen should be used. In addition, the necessary amount of ultraviolet irradiation is still large, and concerns regarding display characteristics, voltage holding characteristics, and long-term reliability of the panel have not been eliminated. In particular, in recent years, the demand for higher performance of liquid crystal display elements has further increased, and liquid crystal aligning agents are required to be able to improve the display quality and long-term reliability of liquid crystal display elements.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for manufacturing a liquid crystal display element having a wide viewing angle, a high response speed of liquid crystal molecules, and excellent long-term reliability.

  As a result of intensive studies to achieve the above-described problems of the prior art, the present inventors can solve the above problems by incorporating a polymer having a specific structure in the side chain into the liquid crystal aligning agent. As a result, the present invention has been completed. Specifically, the present invention provides the following method for producing a liquid crystal aligning agent, a liquid crystal aligning agent, and a liquid crystal aligning film.

  In one aspect of the present invention, a liquid crystal aligning agent is applied to each of the conductive films of a pair of substrates having a conductive film, and then heated to form a coating film, and the pair of coating films formed thereon The liquid crystal cell in a state in which a voltage is applied between the conductive film of the pair of substrates, and a step of constructing a liquid crystal cell with the substrate facing each other through a layer of liquid crystal molecules facing the coating film And a step of irradiating with light, wherein the liquid crystal aligning agent comprises a polymer (P) having a side chain having a group represented by the following formula (A).

(In Formula (A), R ¹ is a hydrogen atom or a monovalent organic group, and R ² is a divalent organic group. “*” Represents a bond.)

  The liquid crystal alignment film included in the liquid crystal display element is manufactured using the liquid crystal aligning agent containing the polymer (P), so that the liquid crystal has a wide viewing angle, a high response speed of liquid crystal molecules, and excellent long-term reliability. A display element can be obtained. Further, according to the above manufacturing method, since the amount of light necessary for irradiation is small, liquid crystal molecules are hardly decomposed, which contributes to a reduction in manufacturing cost of the liquid crystal display element. Therefore, the liquid crystal display element manufactured by the above manufacturing method is excellent in both performance and cost, and is suitable for various applications.

It is explanatory drawing which shows the pattern of the transparent conductive film in the liquid crystal cell which has the transparent transparent conductive film manufactured in the Example and the comparative example. It is explanatory drawing which shows the pattern of the transparent conductive film in the liquid crystal cell which has the patterned transparent conductive film manufactured in the Example. It is explanatory drawing which shows the pattern of the transparent conductive film in the liquid crystal cell which has the patterned transparent conductive film manufactured in the Example.

  Below, each component contained in the liquid crystal aligning agent of this invention and the other component arbitrarily mix | blended as needed are demonstrated.

<Polymer (P)>
The liquid crystal aligning agent of this invention contains the polymer (P) which has the group (henceforth "acetylene containing side chain") represented by a following formula (A) in a side chain as a polymer component.
(In Formula (A), R ¹ is a hydrogen atom or a monovalent organic group, and R ² is a divalent organic group. “*” Represents a bond.)

Examples of the monovalent organic group for R ¹ include an alkyl group having 1 to 20 carbon atoms and an aryl group having 5 to 20 carbon atoms, and a group having —O— between the carbon-carbon bonds in these hydrocarbon groups. The hydrogen atom bonded to the carbon atom of each group may be substituted with a fluorine atom.
Here, the alkyl group having 1 to 20 carbon atoms is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, Examples include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group. These may be linear or branched, but are preferably linear.
Examples of the aryl group having 5 to 20 carbon atoms include a phenyl group, an alkylphenyl group, and a naphthyl group. Here, the alkyl group in the alkylphenyl group preferably has 1 to 12 carbon atoms, and more preferably 1 to 5 carbon atoms. Further, the position of the alkyl group bonded to the benzene ring is not particularly limited, but is preferably 4-position with respect to the carbon atom of the carbon-carbon triple bond.
R ¹ is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or an alkylphenyl group having an alkyl group having 1 to 12 carbon atoms, and is preferably a hydrogen atom, a phenyl group, or carbon. An alkylphenyl group having an alkyl group of 1 to 5 is more preferable, and a hydrogen atom or a phenyl group is further preferable.

Examples of the divalent organic group for R ² include a divalent hydrocarbon group, a methylene group in a divalent hydrocarbon group, —O—, —C (═O) —O—, —CO—, —S. —, —C (═O) —S—, —C (═S) —O—, —NR ^a — or —NR ^a —CO— (where R ^a is a hydrogen atom or an alkyl group). And a group having a heterocyclic ring, and the hydrogen atom bonded to the carbon atom of each group may be substituted with a fluorine atom.

  Here, the “hydrocarbon group” in the present specification means a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The “chain hydrocarbon group” means a saturated or unsaturated linear hydrocarbon group or branched hydrocarbon group that does not include a cyclic structure in the main chain and is composed only of a chain structure. 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.

  In the present specification, the “side chain” of the polymer refers to a portion branched from the “main chain” of the polymer. The “main chain” of a polymer refers to a “trunk” portion consisting of the longest chain of atoms in the polymer. It is allowed that the “trunk” portion includes a ring structure. In this case, two or more atoms constituting the ring structure are bonded to other atoms constituting the “trunk” portion, whereby the entire ring structure is present in the main chain. However, it is not necessary that all of the side chains of the polymer (P) are groups represented by the above formula (A), and only some side chains are groups represented by the above formula (A). There may be.

R ² preferably has a group represented by the following formula (1).
(In the formula (1), Ar ¹ represents the following formula (Ar-1)
(In the formula (Ar-1), A ¹¹ and A ¹² are each independently a phenylene group or a cyclohexylene group, and X ³ is a single bond, * ² —COO— or * ² —OCO— (where * . the bond marked with ² binds to a ¹¹⁾ is .s is 0 or 1, "* ^1", carbon -. represents a bond that binds to the carbon atom of the carbon triple bond ". * "Indicates a bond.)
A naphthylene group or a pyridylene group, and the ring portion may have a substituent. X ¹ and X ² are each independently a single bond, —O—, * ³ —C (═O) —O—, * ³ —O—C (═O) —, —CO—, —S—, * ^3- C (= O) -S-, * ^3- S-C (= O)-, * ^3- C (= S) -O-, * ^3- O-C (= S)-, -NR ^a −, * ³ —NR ^a —CO— or * ³ —CO—NR ^a — (wherein R ^a is a hydrogen atom or an alkyl group, and a bond marked with * ³ binds to R ³ ). is there. R ³ is a group having —O— between carbon-carbon bonds in an alkanediyl group having 1 to 20 carbon atoms or an alkanediyl group having 1 to 20 carbon atoms, and the hydrogen atom bonded to the carbon atom is a fluorine atom. It may be substituted, and a part of the carbon-carbon bond may be a double bond or a triple bond. a is 0 or 1. “* ¹ ” indicates a bond bonded to a carbon atom constituting a carbon-carbon triple bond. “*” Indicates a bond. )

In Ar ^1, specific examples of the group represented by the formula (Ar-1), such as a phenylene group, biphenylene group, cyclohexylene group, cyclohexylene group bicyclo cycloheteroalkyl, the following formula (Ar-1-1) ~ Formula (Ar-1-6)
(In formula (Ar-1-1) to formula (Ar-1-6), * ¹ is synonymous with formula (Ar-1)).

And groups represented by each of the above.
Ar ¹ is preferably a 1,4-phenylene group or a 4,4′-biphenylene group, and more preferably a 1,4-phenylene group. Examples of the substituent that the ring portion of Ar ¹ has include a methyl group, an ethyl group, and a fluorine atom. However, the ring portion of Ar ¹ is preferably unsubstituted.
Examples of the alkanediyl group having 1 to 20 carbon atoms of R ³ include a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, a heptanediyl group, an octanediyl group, a nonanediyl group, a decandidiyl group, and an undecandiyl group. Group, dodecanediyl group, tetradecanediyl group, hexadecanediyl group, octadecanediyl group, icosanediyl group and the like. These may be linear or branched, but are preferably linear in terms of liquid crystal alignment. R ³ may be a group in which a part of the carbon-carbon bond of the alkanediyl group is a double bond or a triple bond. For example, prop-1-ene-1,3-diyl group, penta- Examples include 1-ene-1,5-diyl group, hexa-1-ene-1,6-diyl group and the like.
a is 0 or 1; From the viewpoint of pretilt angle stability, when a is 0, R ³ preferably has 8 or more carbon atoms, more preferably 10 or more carbon atoms. When a is 1, R ³ preferably has 2 or more carbon atoms, and more preferably 3 or more.

R ² is preferably a group represented by the above formula (1) or a group represented by the following formula (1-1).
(In Formula (1-1), R ⁴ is an alkanediyl group having 1 to 10 carbon atoms, and R ⁷ is a monovalent organic group having a carbon-carbon triple bond. Ar ¹ , X ¹ , R ³ , X ² and a have the same meaning as in the above formula (1), provided that a plurality of Ar ¹ , X ¹ , R ³ , X ² , R ⁴ and a each independently have the above definition. ¹ "represents a bond bonded to the carbon atom constituting the carbon-carbon triple bond." * "Represents a bond.)

R ⁴ preferably has 1 to 5 carbon atoms, and more preferably 1 or 2 carbon atoms. R ⁷ can be exemplified by the same structure as “R ¹ —C≡C—” in the above formula (A).

Preferable specific examples of the group represented by the formula (A) include groups represented by the following formulas (1-1-1) to (1-13-3). However, in the following formulas (1-1-1) to (1-13-1-5), m and n are each independently an integer of 1 to 20. “*” Indicates a bond bonded to the main chain.

One of the polymers (P) in the present invention is at least one selected from the group consisting of a structural unit represented by the following formula (2-1) and a structural unit represented by the following formula (2-2). The polymer which has is mentioned.
(In Formula (2-1) and Formula (2-2), P ¹ is a tetravalent organic group and Q ¹ is a divalent organic group. R ²¹ and R ²² are each independently a hydrogen atom. Or it is a monovalent organic group.)
Such a polymer (P) is, for example, the following [I] to [III]:
[I] A method of reacting a tetracarboxylic dianhydride having a group represented by the above formula (A) with a diamine;
[II] A method of reacting tetracarboxylic dianhydride with a diamine having a group represented by the above formula (A);
[III] A compound having a group represented by the above formula (A) (hereinafter referred to as “polymer (p-1)”) (hereinafter referred to as “polymer (p-1)”) in at least a part of the structural unit. , Also referred to as “compound (c)”).
Etc. can be obtained. In the above formula (2), P ¹ is a tetravalent organic group derived from tetracarboxylic acid, and Q ¹ is a divalent organic group derived from diamine. Among these, it is preferable to use the method [II] or the method [III] in terms of easy production. Hereinafter, a method for synthesizing the polymer (P) by the method [II] or the method [III] will be described.

-Regarding method [II] [polyamic acid (P)]
One of the polymers (P) obtained by the above method [II] is a polyamic acid having a group represented by the above formula (A) in the side chain (hereinafter also referred to as “polyamic acid (P)”). Is mentioned. In the synthesis of polyamic acid (P), examples of the tetracarboxylic dianhydride used in the reaction include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Things can be mentioned. Specific examples of these are:
Examples of the aliphatic tetracarboxylic dianhydride include 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, cyclohexanetetracarboxylic dianhydride 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, the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

The tetracarboxylic dianhydride used for the synthesis of the polyamic acid (P) preferably contains an alicyclic tetracarboxylic dianhydride in terms of good solubility in a solvent and transparency. Among them, 2,3,5-tricarboxycyclopentyl acetic 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, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride and 1,2,3 More preferably, it contains at least one selected from the group consisting of 4-cyclobutanetetracarboxylic dianhydride (hereinafter also referred to as “specific tetracarboxylic dianhydride”), and 2,3,5-tricarboxycyclopentyl. Acetic dianhydride Group consisting of 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride More preferably, at least one selected from the group consisting of:
The tetracarboxylic dianhydride used for the synthesis of polyamic acid contains the above-mentioned specific tetracarboxylic dianhydride in an amount of 20 mol% or more based on the total amount of the tetracarboxylic dianhydride used for the synthesis. Is preferable, more preferably 50 mol% or more, and even more preferably 80 mol% or more.

The diamine used when the polyamic acid (P) is synthesized by the method [II] includes a diamine having a group represented by the formula (A) (hereinafter also referred to as “specific diamine”). The specific diamine may have a group represented by the above formula (A) and two primary amino groups, and examples thereof include a compound represented by the following formula (D-1).
(In formula (D-1), R ¹ and R ² have the same meanings as the above formula (A).)

In the above formula (D-1), specific examples of the group represented by R ¹ and R ² and “R ¹ —C≡C—R ² —” include those of the group represented by the above formula (A). The explanation can be applied. As “R ¹ —C≡C—R ² —”, among the specific examples of the group represented by the above formula (A), the above formula (1-1-2), the formula (1-1-7), Formula (1-3-2), Formula (1-3-5), Formula (1-6-2), Formula (1-7-2), Formula (1-7-5), Formula (1-9) -2), Formula (1-9-7), Formula (1-10-2), Formula (1-10-7), Formula (1-11-2), Formula (1-11-1), Formula It is preferably a group represented by each of (1-12-2), formula (1-12-5), formula (1-13-2), and formula (1-13-1-5). In addition, it is preferable that m and n are integers of 2-12.
Two amino groups in di aminophenyl group of the formula (D-1), it is preferred for ^{R 2} is a 2,4-position or 3,5-position.

Preferred specific examples of the specific diamine include any of the groups exemplified as preferred specific examples of “R ¹ —C≡C—R ² —” and diaminophenyl represented by the following formula (4A) or formula (4B): Examples thereof include a compound formed by bonding with a group.
(In Formula (4A) and Formula (4B), “*” is a bond bonded to the group represented by Formula (A)).

  The diamine used for the synthesis of the polyamic acid (P) by the above method [II] may be only the specific diamine, but other diamines may be used in combination with the specific diamine.

Examples of other diamines that can be used here include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes. Specific examples of these include aliphatic diamines such as metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and the like;
Examples of alicyclic diamines include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

Examples of aromatic diamines include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 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) bisaniline, 4,4 ′-(m-phenylenediisopropylene Riden) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diamino Pyrimidine, 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, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, 1- (4-aminophen 2) -2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine, 3,5-diaminobenzoic acid, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3, 5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, 3,5-diamino Ranostanyl benzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, octadecanoxy -2,4-diaminobenzene, 4- (4'-trifluoromethoxyben Iroxy) cyclohexyl-3,5-diaminobenzoate, 4- (4′-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptyl Cyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3 -Aminobenzylamine and the following formula (a-1)
(In formula (a-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.)

A compound represented by:
Examples of diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane;
In addition to these, diamines described in JP 2010-97188 A can be used. As other diamine, these can be used individually by 1 type or in combination of 2 or more types.

Examples of the divalent group represented by “—X ^I — (R ^I —X ^II ) _d —” in the formula (a-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 the groups exemplified as the alkyl group having 1 to 20 carbon atoms in the description of the above formula (A), and are preferably linear. 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 (a-1) include compounds represented by the following formulas (a-1-1) to (a-1-3). .

  The content ratio of the specific diamine is preferably 1 mol% or more, more preferably 10 mol% or more, and more preferably 50 mol% or more based on the total amount of diamine used for the synthesis of the polyamic acid. Further preferred. By setting the content ratio of the specific diamine to 1 mol% or more, it is possible to increase the pretilt angle when the ultraviolet ray is irradiated with a voltage applied, and to increase the response speed of the liquid crystal display element. There is no restriction | limiting in particular in the upper limit of the content rate of specific diamine, It can set arbitrarily in the range of 100 mol% or less. When using other diamine together, it is preferable that the content rate of specific diamine shall be 99 mol% or less, and it is more preferable to set it as 97 mol% or less. In addition, specific diamine can be used individually by 1 type or in combination of 2 or more types.

[Molecular weight regulator]
In synthesizing the polyamic acid, a terminal-modified polymer may be synthesized using an appropriate molecular weight regulator together with the tetracarboxylic dianhydride and diamine as described above. By using such a terminal-modified polymer, the coating property (printability) of the liquid crystal aligning agent can be further improved without impairing the effects of the present invention.

Examples of molecular weight regulators include acid monoanhydrides, monoamine compounds, monoisocyanate compounds, and the like. Specific examples of these acid monoanhydrides include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic acid. Nic acid anhydride, n-hexadecyl succinic acid anhydride, etc .;
Examples of monoamine compounds include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine; examples of monoisocyanate compounds include phenyl isocyanate and naphthyl isocyanate; Each 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.

<Synthesis of polyamic acid>
The ratio of the tetracarboxylic dianhydride and the diamine used for the synthesis reaction of the polyamic acid (P) is such that the acid anhydride group of the tetracarboxylic dianhydride is 0 with respect to 1 equivalent of the amino group of the diamine. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.
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 0.1 to 24 hours, more preferably 0.5 to 12 hours.

Examples of the organic solvent include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Specific examples of these organic solvents include aprotic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, Hexamethylphosphortriamide and the like; phenolic solvents such as phenol, m-cresol, xylenol, halogenated phenol and the like;
Examples of the alcohol include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, and the like. Examples of the ketone include acetone, methyl ethyl ketone, and methyl isobutyl. Ketone, cyclohexanone, etc .; as the above ester, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, isoamyl Propionate, isoamyl isobutyrate and the like; ethers such as diethyl ether, diisopentyl ether, ethylene glycol methyl Ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, tetrahydrofuran and the like; Examples of the hydrocarbon include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like. Examples of the hydrocarbon include hexane, heptane, octane, benzene, toluene, Xylene and the like; respectively.

  Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenolic solvent (first group of organic solvents), or one or more selected from the first group of organic solvents, It is preferable to use a mixture with one or more 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. The amount (α) of the organic solvent used is such that the total amount (β) of tetracarboxylic dianhydride and amine compound (B) is 0.1 to 50% by weight based on the total amount (α + β) of the reaction solution. It is preferable to make it an amount.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. When polyamic acid is dehydrated and cyclized into a polyimide, the above reaction solution may be directly subjected to dehydration and cyclization reaction, or may be subjected to dehydration and cyclization reaction after isolating the polyamic acid contained in the reaction solution. Alternatively, the isolated polyamic acid may be purified and then subjected to a dehydration ring closure reaction. Isolation and purification of the polyamic acid can be performed according to known methods. Incidentally, by the above method [II], it is possible to obtain a polymer containing a structural unit having a group represented by the formula (A) in the to Q ¹ in the formula (2-1).

[Polyimide (P)]
One example of the polymer (P) obtained by the method [II] is a polyimide having a group represented by the above formula (A) in the side chain (hereinafter also referred to as “polyimide (P)”). It is done. Polyimide (P) can be obtained by dehydrating and ring-closing imidized polyamic acid (P) synthesized as described above.

  The polyimide (P) may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure of the polyamic acid that is the precursor, or by dehydrating and cyclizing only a part of the amic acid structure. A partially imidized product in which an acid structure and an imide ring structure coexist may be used. The polyimide in the present invention preferably has an imidation ratio of 30% or more, more preferably 50 to 99%, and still more preferably 60 to 99%. 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 polyamic acid is preferably dehydrated and closed by heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and heating the solution as necessary. . Of these, the latter method is preferred.

  In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the amic acid structure of a polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine, triethylamine, N-methylpiperidine and the like can be used. 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. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, or after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, it may be used for the preparation of the liquid crystal aligning agent. You may use for preparation of an aligning agent, or you may use for preparation of a liquid crystal aligning agent, after purifying the isolated polyimide. These purification operations can be performed according to known methods. Incidentally, by the above method [II], it is possible to obtain a polymer containing a structural unit having a group represented by the formula (A) in the to Q ¹ in the formula (2-2).

The polyamic acid (P) and the polyimide (P) 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. More preferably, it has a solution viscosity of ˜500 mPa · 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.
The polyamic acid (P) and the polyimide (P) preferably have a polystyrene-equivalent weight average molecular weight of 500 to 300,000 as measured by gel permeation chromatography (GPC), and 1,000 to 200,000. It is more preferable that

-About method [III] The polymer (p-1) used by the said method [III] has the following formula (PA-1) in at least one part of a structural unit.
(In formula (PA-1), P ¹ is a tetravalent organic group derived from tetracarboxylic acid, and Q ¹ is a divalent organic group derived from diamine.)

And a polyamic acid and a polyimide obtained by dehydrating and ring-closing only a part of the amic acid structure.

  When the polymer (p-1) is a polyamic acid, the polyamic acid may be the polyamic acid (P), may be a polyamic acid having no acetylene-containing side chain, or they It may be a mixture of The polyamic acid as the polymer (p-1) can be synthesized using the same tetracarboxylic dianhydride, specific diamine and other diamine as in the above method [II].

It is preferable that the other diamine used for the synthesis | combination of the polyamic acid which is the said polymer (p-1) contains the diamine which has a carboxyl group. Specific examples of the carboxyl group-containing diamine include, for example, 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 4,4′-diaminobiphenyl-2,2′-dicarboxylic acid. 4,4′-diaminodiphenylmethane-3,3′-dicarboxylic acid, 4,4′-diaminodiphenyl ether-3,3′-dicarboxylic acid, and the like.
The proportion of the carboxyl group-containing diamine used is preferably 1 mol% or more, more preferably 10 to 99 mol%, based on the total amount of diamine used for the synthesis of the polymer (p-1). 50 to 97 mol% is more preferable.

  When the polymer (p-1) includes a polyimide obtained by dehydrating and ring-closing only a part of the amic acid structure, the polyimide may be the polyimide (P) and does not have the acetylene-containing side chain. It may be polyimide or a mixture thereof. The polyimide as the polymer (p-1) can be obtained by dehydrating and ring-closing a part of the amic acid structure in the polyamic acid as the polymer (p-1).

The polymer (p-1) preferably has a solution viscosity of 10 to 800 mPa · s, and preferably has a solution viscosity of 15 to 500 mPa · s, when this is a 10% by weight solution. More preferably. In addition, the solution viscosity (mPa · s) of the above-mentioned polymer is determined using an E-type rotational viscometer for a polymer solution having a concentration of 10% by weight prepared using a good solvent for the polymer (for example, N-methylpyrrolidone). It is the value measured at 25 ° C.
The polymer (p-1) preferably has a polystyrene-equivalent weight average molecular weight measured by GPC of 500 to 300,000, and more preferably 1,000 to 200,000.

The compound (c) to be reacted with the polymer (p-1) is a compound having a group represented by the above formula (A), and a preferred specific example is represented by the following formula (3). Compound etc. are mentioned.
(In Formula (3), Y ¹ is a monovalent group having an epoxy group, a halogen atom, or * -SO ₃ -R ⁴ (where R ⁴ is a methyl group, a trifluoromethyl group, or a substituted or unsubstituted phenyl group). is a group.) .R ¹ and ^{R 2} are the same meaning as ^{R 1} and ^{R 2} in formula (a).)

In the above formula (3), the monovalent group having an epoxy group of Y ¹ is preferably a group represented by the following formula (5). t is preferably 1.
(In formula (5), t is an integer of 1 to 5. “*” represents a bond.)

Examples of the halogen atom for Y ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a bromine atom or an iodine atom is preferable. R ⁴ is preferably a methyl group, a trifluoromethyl group or a tolyl group.

The group represented by “R ¹ —C≡C—R ² —” in the above formula (3) is a specific example of the group represented by (A) above when Y ¹ is an epoxy group-containing group. Among them, the above formula (1-1-2), formula (1-1-7), formula (1-3-2), formula (1-3-5), formula (1-6-2), formula (1-7-2), Formula (1-7-5), Formula (1-9-2), Formula (1-9-7), Formula (1-10-2), Formula (1-10- 7), Formula (1-11-2), Formula (1-11-1), Formula (1-12-2), Formula (1-12-5), Formula (1-13-2) and Formula ( It is preferable that it is group represented by each of 1-13-5). In this case, m and n are preferably integers of 2 to 12.
On the other hand, when Y ¹ is a halogen atom or “* -SO ₃ -R ⁴ ”, the above formula (1-1-1), formula (1-3-1), formula (1-4-1), formula (1-5-1), Formula (1-6-1), Formula (1-7-1), Formula (1-8-1), Formula (1-9-1), Formula (1-10- 1), a group represented by each of formula (1-11-1), formula (1-12-1) and formula (1-13-1). In this case, m and n are preferably integers of 2 to 12.
A compound (c) in which the group represented by “R ¹ —C≡C—R ² —” is a hydrocarbon group and Y ¹ is a halogen atom or “* —SO ₃ —R ⁴ ” is used. By this, the polyamic acid ester which has group represented by the said Formula (A) in a side chain can be obtained by superposition | polymerization which contains specific diamine in a monomer composition.

The reaction of the polymer (p-1) and the compound (c) can be performed by appropriately combining organic chemistry methods. For example, when a compound (hereinafter also referred to as “compound (c-1)”) in which Y ^{1 in the} above formula (3) is an epoxy group-containing group is used as the compound (c), the polymer (p-1) And the compound (c-1) can be subjected to an addition reaction to obtain the polymer (P).

  The reaction between the polymer (p-1) and the compound (c-1) is preferably carried out in an organic solvent using a catalyst as necessary. As an organic solvent, the thing similar to the organic solvent used for the synthesis | combination of the said polyamic acid (P) can be used. The amount (α1) of the organic solvent used is such that the total amount (β1) of the polymer (p-1) and the compound (c-1) is 1 to 50% by weight with respect to the total amount (α1 + β1) of the reaction solution. It is preferable to make it an amount. Preferably it is 5 to 40 weight%.

As the catalyst used in 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, piperazine and piperidine; tertiary organic amines such as triethylamine and pyridine; quaternary organic amines such as tetramethylammonium hydroxide; Can do. 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 and 2,4,6-tris (dimethylaminomethyl) phenol; imidazole compounds such as 2-methylimidazole and 2-n-heptylimidazole; Organic phosphorus compounds such as phosphine; quaternary phosphonium salts such as benzyltriphenylphosphonium chloride; diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof Organic metal compounds such as zinc octylate, tin octylate and aluminum acetylacetone complex; such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride Grade ammonium salts; boron trifluoride, such as boron compounds triphenyl borate; and the like; zinc chloride, such as metal halide compound of stannic chloride. Of these, quaternary ammonium salts are preferred.
The usage-amount of a catalyst is 0.1-100 weight part with respect to 100 weight part of polymers (p-1), Preferably it is 1-30 weight part.

  The ratio of the polymer (p-1) and the compound (c-1) used in the synthesis reaction of the polymer (P) is a compound with respect to 1 mol of the amic acid structure of the polymer (p-1). The ratio that (c-1) is 0.01 to 10 mol is preferable, the ratio that is 0.1 to 5 mol is more preferable, and the ratio that is 0.5 to 3 mol is more preferable. The reaction temperature can be in the range of 10 ° C to 250 ° C, preferably 50 to 150 ° C, and more preferably 70 to 120 ° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

In the case of using a compound (hereinafter also referred to as “compound (c-2)”) in which Y ^{1 in the} above formula (3) is a halogen atom or “* —SO ₃ —R ⁴ ” as the compound (c), The reaction with the polymer (p-1) is preferably carried out in an organic solvent using a catalyst as necessary. As an organic solvent, the thing similar to the organic solvent used for the synthesis | combination of the said polyamic acid (P) can be used. The amount (α2) of the organic solvent used is such that the total amount (β2) of the polymer (p-1) and the compound (c-2) is 1 to 50% by weight with respect to the total amount (α2 + β2) of the reaction solution. It is preferable to make it an amount. Preferably it is 5 to 40 weight%.

  Examples of the catalyst used in the reaction include a base. For example, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate and the like can be used. Of these, potassium carbonate is particularly preferred. The usage-amount of a base is 10-300 weight part with respect to 100 weight part of polymers (p-1), Preferably it is 20-100 weight part.

  The ratio of the polymer (p-1) and the compound (c-2) used for the synthesis reaction of the polymer (P) is a compound with respect to 1 mol of the amic acid structure of the polymer (p-1). The ratio that (c-2) is 0.01 to 10 mol is preferable, the ratio that is 0.1 to 5 mol is more preferable, and the ratio that is 0.5 to 3 mol is more preferable. The reaction temperature can be in the range of 10 ° C to 250 ° C, preferably 50 to 150 ° C, and more preferably 70 to 120 ° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

In this way, a reaction solution containing the polymer (P) is obtained. This reaction solution may be used for the preparation of the liquid crystal aligning agent as it is, or may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, and the polymer (P) is isolated. In addition, it may be used for preparing a liquid crystal aligning agent, or may be used for preparing a liquid crystal aligning agent after purifying the isolated polymer (P). These purification operations can be performed according to known methods. In addition, a polymer containing a structural unit having a group represented by the above formula (A) in at least one of R ²¹ and R ^{22 in} the above formula (2-1) by the above method [III], and the above formula A polymer containing a structural unit having a group represented by the above formula (A) in at least one of R ²¹ and R ²² in (2-1) and Q ¹ can be obtained.

[Polyorganosiloxane]
One of the polymers (P) in the present invention includes a polymer having polyorganosiloxane as the main chain. Such a polymer (P) is obtained by, for example, hydrolyzing and condensing a silane compound containing an epoxy group and, if necessary, another silane compound in an appropriate organic solvent in the presence of water and a catalyst. Further, it can be synthesized by a method of reacting a carboxylic acid compound having a group represented by the above formula (A).

  Examples of the silane compound containing an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. In addition, the silane compound containing an epoxy group can use these 1 type individually or in combination of 2 or more types. Of these, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is preferred.

  Other silane compounds include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetra Chlorosilane, etc .; methyltrimethoxysilane, methyltriethoxysilane, octadecyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert- Butoxysilane, methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-i o-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, hexamethylenebis (trimethoxy Silane), 1,2-bis (trimethoxysilyl) ethane, 1,2bis (triethoxysilyl) ethane, etc .; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane, etc .; trimethylmethoxysilane, trimethylethoxysilane, trimethyl And chlorosilane. Other silane compounds can be used alone or in combination of two or more.

Examples of the carboxylic acid compound having a group represented by the above formula (A) include a compound represented by the following formula (4).
(In the formula (4), ^{Y 2} is, .R ¹ and ^{R 2} is a monovalent group having a carboxyl group has the same meaning as ^{R 1} and ^{R 2} in formula (A).)

Examples of Y ^{2 in the} above formula (4) include a carboxyl group and —R ³¹ —COOH (R ³¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms). Preferable specific examples of R ³¹ include, for example, an alkanediyl group or “—R ³² —R ³³ — *” (wherein R ³² is an alkanediyl group and R ³³ is an aromatic ring. * Is a bond bonded to a carboxyl group. Show hand.) Etc. Specific examples of the group represented by “R ¹ —C≡C—R ² —” in the above formula (4) are the formula (1-1-1) to the formula (1-13-3). And the group represented.
Examples of the organic solvent used in the reaction include alcohol solvents, ketone solvents, amide solvents, ester solvents, and other aprotic organic solvents. You may use this organic solvent individually by 1 type or in combination of 2 or more types.

The water added in the synthesis of the polyorganosiloxane can be added intermittently or continuously in the raw material silane compound or in a solution obtained by dissolving the silane compound in an organic solvent. The catalyst may be added in advance to a raw material silane compound or a solution in which the silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in the added water.
The reaction temperature for the synthesis of the polyorganosiloxane is preferably 0 to 100 ° C, more preferably 15 to 80 ° C. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.
Thus, a polyorganosiloxane having an epoxy group in the side chain (hereinafter also referred to as “epoxy group-containing polyorganosiloxane”) can be obtained. For the epoxy group-containing polyorganosiloxane, the polystyrene-reduced weight average molecular weight measured by gel permeation chromatography (GPC) is preferably 500 to 1,000,000, and preferably 1,000 to 100,000. Is more preferable, and it is more preferable that it is 1,000-50,000.

  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. The use ratio of the carboxylic acid to be reacted with the epoxy group-containing polyorganosiloxane is as follows. It is preferable to set it as 0.001-1.5 mol with respect to 1 mol of epoxy groups which siloxane has, It is more preferable to set it as 0.01-0.9 mol, It is set as 0.05-0.8 mol. More preferably.

As the catalyst used in the above reaction, for example, a known compound can be used as a so-called curing accelerator that accelerates the reaction of an organic base or an epoxy compound. Specifically, examples of the organic base include pyridine, 4-dimethylaminopyridine, tetramethylammonium hydroxide, and the like. Examples of the curing accelerator include benzyldimethylamine, 2-methylimidazole, diphenylphosphine, benzyltriphenylphosphonium chloride, zinc octylate, tin octylate, tetraethylammonium bromide, boron trifluoride, zinc chloride. In addition to stannic chloride, known latent curing accelerators can be used.
The catalyst is preferably 100 parts by weight or less, more preferably 0.01 to 80 parts by weight, still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy group-containing polyorganosiloxane to be reacted with carboxylic acid. Can be used at a rate of

  Examples of the organic solvent that can be used in the reaction of the epoxy group-containing polyorganosiloxane and the carboxylic acid include hydrocarbons, ethers, esters, ketones, amides, alcohols, and the like. Of these, ethers, esters, and ketones are preferable 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, methyl isobutyl ketone 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 between the epoxy group-containing polyorganosiloxane and the carboxylic acid 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 a suitable desiccant as required, and then the solvent is removed, whereby a polyorganosiloxane having an acetylene group can be obtained as the polymer (P).

[Polymer of compound having polymerizable carbon-carbon double bond]
As one of the polymers (P) in the present invention, a polymer having a polymer of a compound having a polymerizable carbon-carbon double bond as a main chain can be mentioned. Such a polymer (P) is obtained by polymerizing, for example, a compound having an epoxy group and a polymerizable carbon-carbon double bond and, if necessary, another polymerizable unsaturated compound in a suitable organic solvent. In the presence of an initiator, for example, a polymer is synthesized by radical polymerization, and then this polymer is reacted with a carboxylic acid compound having a group represented by the above formula (A) in a suitable organic solvent. Etc. can be synthesized.

  Examples of the carboxylic acid compound having a group represented by the above formula (A) include a compound represented by the above formula (4).

  Examples of the polymerizable unsaturated compound containing an epoxy group include glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5 -Dimethyl-4-glycidyl) benzylacrylamide, 4-hydroxybutyl (meth) acrylate glycidyl ether, p-vinylbenzyl glycidyl ether, 2- (2,3-epoxycyclopentyl) ethyl (meth) acrylate, 2- (3,4 -Epoxycyclohexyl) ethyl (meth) acrylate, 2- (7,8-epoxy [tricyclo [5.2.1.0] dec-2-yl]) ethyl (meth) acrylate, and the like. The polymerizable unsaturated compound containing an epoxy group can be used alone or in combination of two or more. In the present specification, “(meth) acrylate” indicates that acrylate and methacrylate are included.

  Other polymerizable unsaturated compounds include cholestanyl acrylate, 4- (4′-n-propylbicyclohexyl-4-yl) phenyl methacrylate, 4- (4′-n-butylbicyclohexyl-4-yl) phenyl Methacrylate, 4- (4′-n-pentylbicyclohexyl-4-yl) phenyl methacrylate, 4- (4′-n-hexylbicyclohexyl-4-yl) phenyl methacrylate, 4- (4′-n-heptylbi) Cyclohexyl-4-yl) phenyl methacrylate, 4- (4′-n-propylbicyclohexyl-4-yl) phenyl acrylate, 4- (4′-n-butylbicyclohexyl-4-yl) phenyl acrylate, 4- ( 4′-n-pentylbicyclohexyl-4-yl) phenyl acrylate, 4- ( '-N-hexylbicyclohexyl-4-yl) phenyl acrylate, 4- (4'-n-heptylbicyclohexyl-4-yl) phenyl acrylate, 4- (4-n-heptylcyclohexyl) phenyl methacrylate, 4- ( 4-n-heptylcyclohexyl) phenyl acrylate, 4- (4-n-propylcyclohexyl) phenyl methacrylate, 4- (4-n-propylcyclohexyl) phenyl acrylate, 4- (4-n-butylcyclohexyl) phenyl methacrylate, 4 -(4-n-butylcyclohexyl) phenyl acrylate, 4- (4-n-pentylcyclohexyl) phenyl methacrylate, 4- (4-n-pentylcyclohexyl) phenstyrene, α-methylstyrene, acenaphthylene, methyl (meta ) Acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.02 , 6] decan-8-yl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, 4-hydroxybutyl (meth) acrylate, 2 -Hydroxyalkyl (meth) acrylate such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, N-methylolacrylamide Such as allyl alcohol and the like. Other polymerizable unsaturated compounds can be used alone or in combination of two or more.

  Examples of the organic solvent include alcohol solvents, ether solvents, ketone organic solvents, amide solvents, ester organic solvents, hydrocarbon solvents, and the like. These organic solvents may be used alone or in combination of two or more.

  Examples of the polymerization initiator include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (4-methoxy-2). , 4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis (t-butylperoxy) cyclohexane; hydrogen peroxide; And redox type initiators comprising a peroxide and a reducing agent. Of these, azo compounds are preferred, and 22,2'-azobis (2,4-dimethylvaleronitrile) is more preferred. These polymerization initiators may be used alone or in combination of two or more.

  As reaction temperature, 0 degreeC-200 degreeC are preferable, and 50 degreeC-150 degreeC is more preferable. As reaction time, 0.1 hour-50 hours are preferable, and 0.5 hour-20 hours are more preferable.

  When the polymer constituting the polymer component is a (meth) acrylic polymer, the weight average molecular weight (Mw) in terms of polystyrene by GPC is preferably 250 to 500,000, more preferably 500 to 100,000, More preferably, it is 1,000 to 50,000.

  The reaction between the (meth) acrylic polymer having an epoxy group (hereinafter also referred to as “epoxy group-containing (meth) acrylic polymer”) and the carboxylic acid compound is preferably performed in the presence of a catalyst and an organic solvent. it can. Here, it is preferable that the usage-amount of a carboxylic acid compound shall be 0.001-1.5 mol with respect to 1 mol of epoxy groups which an epoxy-group-containing (meth) acryl polymer has, 0.01-0. It is more preferable to set it as 9 mol, and it is still more preferable to set it as 0.05-0.8 mol.

As the catalyst used in the above reaction, for example, a known compound can be used as a so-called curing accelerator that accelerates the reaction of an organic base or an epoxy compound. Specifically, examples of the organic base include pyridine, 4-dimethylaminopyridine, tetramethylammonium hydroxide, and the like. Examples of the curing accelerator include benzyldimethylamine, 2-methylimidazole, diphenylphosphine, benzyltriphenylphosphonium chloride, zinc octylate, tin octylate, tetraethylammonium bromide, boron trifluoride, zinc chloride. In addition to stannic chloride, known latent curing accelerators can be used.
The catalyst is preferably 100 parts by weight or less, more preferably 0.01 to 80 parts by weight, and still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy group-containing (meth) acrylic polymer. Can be used in

  Examples of the organic solvent that can be used in the reaction between the (meth) acrylic polymer and the carboxylic acid include hydrocarbons, ethers, esters, ketones, amides, alcohols, and the like. Of these, ethers, esters, and ketones are preferable 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, methyl isobutyl ketone 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 of the epoxy group-containing (meth) acrylic polymer and the carboxylic acid 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 (meth) acrylic polymer having an acetylene group as the polymer (P).

<Solvent>
The liquid crystal aligning agent of the present invention is preferably constituted by dissolving the polymer (P) in an organic solvent. Examples of the solvent used for preparing the liquid crystal aligning agent of the present invention 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 diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether (DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diiso Examples include pentyl ether, ethylene carbonate, propylene carbonate, and the like. These can be used alone or in admixture of two or more.

<Other ingredients>
The liquid crystal aligning agent of this invention may contain the other component as needed. Examples of such other components include other polymers other than the polymer (P), compounds having at least one epoxy group in the molecule (hereinafter referred to as “epoxy group-containing compound”), functional silane compounds, and the like. Can be mentioned.

[Other polymers]
The above other polymers can be used for improving solution properties and electrical properties. Examples of such other polymers include polymers selected from the group consisting of polyamic acid, polyimide, and polyamic acid ester, and polymers having no acetylene-containing side chain, polyester, polyamide, polysiloxane, cellulose derivatives, Examples include polyacetal, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like.
When other polymers are added to the liquid crystal aligning agent, the blending ratio is preferably 50% by weight or less, more preferably 0.1 to 40% by weight, more preferably 0.1% by weight to the total amount of the polymer in the composition. 1 to 30% by weight is more preferable.

[Epoxy group-containing compound]
The epoxy group-containing compound can be used to improve the adhesion and electrical properties with the substrate surface in the liquid crystal alignment film. Here, examples of the epoxy group-containing compound 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-xylenediamine 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodi Enirumetan, 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 also be used.
When these epoxy compounds are added to the liquid crystal aligning agent, the blending ratio is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the total of the polymers contained in the liquid crystal aligning agent. preferable.

[Functional silane compounds]
The functional silane compound can be used for the purpose of improving the printability of the liquid crystal aligning agent. 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 added to the liquid crystal aligning agent, the blending ratio is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight, based on 100 parts by weight of the total polymer.

  As other components, in addition to the above, a compound having at least one oxetanyl group in the molecule, an antioxidant, or the like can be used.

  The solid content concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, and the like. The range is preferably 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface as described later, and preferably heated to form a coating film that is a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small 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, resulting in poor coating characteristics. Become.

  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 the spinner method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. 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 liquid crystal aligning agent of this invention becomes like this. Preferably it is 10-50 degreeC, More preferably, it is 20-30 degreeC.

<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal alignment film of the present invention is formed by the liquid crystal aligning agent prepared as described above. Moreover, the liquid crystal display element of this invention comprises the liquid crystal aligning film formed using the said liquid crystal aligning agent. The operation mode of the liquid crystal display element is not particularly limited, and various operation modes such as TN type, STN type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB type, etc. Applicable to. Among these, it is preferable to apply to the vertical alignment type.

  The liquid crystal display element of the present invention comprises (1) a step of applying a liquid crystal aligning agent on each of the conductive films of a pair of substrates having a conductive film, and then heating this to form a coating film, (2) a coating film A step of constructing a liquid crystal cell by arranging a pair of substrates formed with a liquid crystal molecule facing each other through a layer of liquid crystal molecules, and (3) applying a voltage between conductive films of the pair of substrates In this state, the liquid crystal cell can be manufactured by a method including light irradiation.

[Step (1): Formation of coating film]
As a substrate used for manufacturing a liquid crystal display element, for example, a glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used. As the conductive film, a transparent conductive film is preferably used. For example, a NESA (registered trademark) film made of SnO _{2 or} an ITO film made of In ₂ O ₃ —SnO ₂ can be used. Each of the conductive films is preferably a patterned conductive film partitioned into a plurality of regions. By using such a conductive film, the direction of the pretilt angle of the liquid crystal molecules is changed for each region by applying a different voltage for each region when a voltage is applied between the conductive films in the following step (3). be able to. This makes it possible to further widen the viewing angle characteristics.

  In order to apply the liquid crystal aligning agent on the conductive film of the substrate, for example, an appropriate application method such as a roll coater method, a spinner method, a printing method, or an ink jet method can be used. After coating, the coated surface is preheated (prebaked) and then baked (postbaked) to form a coating film. The pre-bake conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C., and the post-bake conditions are preferably 120 to 300 ° C., more preferably 150 to 250 ° C., preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.

  The coating film thus formed may be used as it is for the production of a liquid crystal cell in the next step, or may be subjected to a rubbing treatment on the coating surface as necessary prior to the production of the liquid crystal cell. The rubbing treatment can be performed by rubbing the coating film surface in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton. Note that a resist film may be formed on a part of the coating film surface after the rubbing process is performed, and then the resist film may be removed after the rubbing process is performed in a direction different from the previous rubbing process. At this time, it is possible to further improve the field-of-view characteristics of the obtained liquid crystal display element by using different rubbing directions for each region.

[Step (2): Construction of liquid crystal cell]
Next, the pair of substrates on which the coating film has been formed are arranged to face each other with the coating film facing each other through the liquid crystal layer to form a liquid crystal cell. The liquid crystal molecules used here are preferably nematic liquid crystals having negative dielectric anisotropy, such as dicyanobenzene liquid crystals, pyridazine liquid crystals, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, and phenylcyclohexane liquid crystals. Can be used. The thickness of the liquid crystal molecule layer is preferably 1 to 5 μm.

  In order to produce a liquid crystal cell using such a liquid crystal, for example, the following two methods can be mentioned. As a first method, two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealant, A liquid crystal cell is manufactured by injecting and filling liquid crystal into the cell gap defined by the substrate surface and the sealing agent, and then sealing the injection hole. As a second 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 further formed on the liquid crystal alignment film surface. Then, 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 agent. To manufacture.

Thereafter, 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. As light to irradiate, for example, ultraviolet light and visible light including light having a wavelength of 150 to 800 nm can be used, but ultraviolet light including light having a wavelength of 300 to 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. Ultraviolet rays in the above preferred wavelength region can be obtained by means of using a light source in combination with, for example, a filter or a diffraction grating. The amount of light irradiation is preferably 1,000 J / m ² or more and less than 100,000 J / m ² , more preferably 1,000 to 50,000 J / m ² .

In the manufacture of a conventionally known PSA mode liquid crystal display element, it was necessary to irradiate light of about 100,000 J / m ^{2. In} this manufacturing method, the amount of light irradiation is 50, 000J / ^{m 2} or less, even if further was 10,000 J / ^{m 2} or less can be obtained a desired liquid crystal display device. Therefore, in addition to reducing the manufacturing cost of the liquid crystal display element, it is possible to avoid deterioration in electrical characteristics and long-term reliability due to intense light irradiation.

  And a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell after performing the above-mentioned treatment. As a polarizing plate used here, a polarizing plate formed by sandwiching a polarizing film called “H film” in which polyvinyl alcohol is stretched and oriented while absorbing iodine while being covered with a cellulose acetate protective film, or a polarizing film made of the H film itself, etc. 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.

The weight average molecular weight of each polymer in the synthesis example, the imidization ratio of polyimide, the solution viscosity of each polymer solution, and the epoxy equivalent were measured by the following methods.
[Weight average molecular weight of polymer]
The weight average molecular weight Mw of the polymer is a polystyrene equivalent value measured by gel permeation chromatography under the following conditions.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran or N, N-dimethylformamide solution containing lithium bromide and phosphoric acid Temperature: 40 ° C
Pressure: 68 kgf / cm ²
[Imidation rate of polyimide]
The polyimide solution was poured into pure water, and the resulting precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. From the obtained ¹ H-NMR spectrum, the imidation ratio [%] was determined by the formula represented by the following 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.
[Epoxy equivalent]
The epoxy equivalent was measured according to the “hydrochloric acid-methyl ethyl ketone method” of JIS C2105.

<Synthesis of compounds>
[Synthesis Example 1]
Compound (1-1-2-1) was synthesized according to the following scheme 1.

Synthesis of compound (1-1-2-1A) In a 200 mL three-necked flask equipped with a nitrogen introduction tube and a thermometer, 7.4 g of 2,4-dinitrofluorobenzene, 50 mL of tetrahydrofuran, 8.1 g of triethylamine and 10-undecyne- 6.7 g of 1-ol was charged and reacted at 60 ° C. for 12 hours. After completion of the reaction, 100 mL of ethyl acetate was added, and the mixture was washed once with dilute hydrochloric acid and three times with water, dried over magnesium sulfate, concentrated under reduced pressure, and dried to give a yellow solid of compound (1-1-2-1A) 9.4g was obtained.
Synthesis of compound (1-1-2-1) In a 200 mL three-necked flask equipped with a nitrogen inlet tube and a thermometer, 9.4 g of compound (1-1-2-1A), 36 g of zinc, 6.0 g of ammonium chloride After adding 50 mL of tetrahydrofuran and 50 mL of ethanol and cooling with ice, 11 mL of water was slowly added and allowed to react 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, and after separating and washing three times with water, the filtrate was concentrated under reduced pressure, hexane was added and the precipitated crystals were filtered and dried. 5.0-g brown powder of 1-1-2-1) was obtained.

[Synthesis Example 2]
Compound (1-3C) was synthesized according to the following scheme 2.

Synthesis of Compound (1-3A) In a 300 mL three-necked flask equipped with a nitrogen inlet tube and a thermometer, 19.8 g of ethyl 4-bromobutyrate, 21.3 g of 4-iodophenol, 100 mL of N, N-dimethylformamide and carbonic acid 26.8 g of potassium was charged and reacted at 80 ° C. for 2 hours. After completion of the reaction, 250 mL of ethyl acetate was added, followed by separation and washing four times with water, followed by concentration under reduced pressure and drying to obtain 32.2 g of a deep red liquid of compound (1-3A).
Synthesis of compound (1-3B) In a 200 mL three-necked flask equipped with a vacuum line, a nitrogen inlet tube and a dropping funnel, 20.0 g of compound (1-3A), 1.1 g of palladium chloride ditriphenylphosphine and copper iodide 0 .57 g was charged, and vacuum / nitrogen substitution in the system was repeated three times. Next, after adding 60 mL of triethylamine, 10.4 g of 1-butyl-4-ethynylbenzene was slowly added dropwise and reacted at room temperature for 3 hours. After completion of the reaction, 250 mL of ethyl acetate was added, washed 4 times with water, concentrated under reduced pressure, and dried under vacuum to obtain 25.2 g of a crude purified product of black compound (1-3B).
-Synthesis | combination of compound (1-3C) 25.2g of compounds (1-3B), tetrahydrofuran 200mL, and 1N sodium hydroxide aqueous solution 100mL were added to a 1L eggplant flask, and it was made to react at 50 degreeC for 6 hours. After completion of the reaction, ethyl acetate was added, and the mixture was washed with dilute hydrochloric acid twice and with water three times, then concentrated under reduced pressure, hexane was added and the precipitated crystals were filtered and dried to give a black powder of compound (1-3C) Of 17.1 g.

[Synthesis Example 3]
Compound (P) was synthesized according to the following scheme 3.

  To a 200 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 10.1 g of 2,4-dinitrochlorobenzene, 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, 300 mL of ethyl acetate was added, followed by separation and washing four times with water, and then dried with magnesium sulfate. Then, 10.5 g of yellow crystals of compound (P) were obtained by adding hexane and concentrating under reduced pressure.

[Synthesis Example 4]
Compound (1-3-5-1) was synthesized according to the following scheme 4.

Synthesis of compound (1-3-5-1A) In a 300 mL three-necked flask equipped with a nitrogen introduction tube and a thermometer, 10.1 g of compound (1-3C), 4.1 g of compound (P) and 100 mL of methylene chloride were added. After cooling with ice, 3.5 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.18 g of N, N-dimethylaminopyridine were added, and the mixture was ice-cooled for 2 hours and at room temperature all day and night. Reacted. After completion of the reaction, 200 mL of ethyl acetate and 200 mL of tetrahydrofuran were added and the mixture was washed three times with water, then dried over magnesium sulfate, ethanol was added, and the mixture was concentrated under reduced pressure to give the compound (1-3-5-1A). 9.5 g of black crystals were obtained.
Synthesis of compound (1-3-5-1) In a 300 mL three-necked flask equipped with a nitrogen inlet tube and a thermometer, 9.5 g of compound (1-3-5-1A), 14 g of zinc, 2.2 g of ammonium chloride After adding 100 mL of tetrahydrofuran and 20 mL of ethanol and cooling with ice, 10 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 100 mL of ethyl acetate was added to the obtained filtrate, followed by separation and washing with water three times. Ethanol was added and the filtrate was concentrated under reduced pressure, and the precipitated crystals were filtered and dried. 7.1 g of black crystals of 1-3-5-1) were obtained.

[Synthesis Example 5]
Compound (1-1-1-1) was synthesized according to the following scheme 5.

  A 300 mL three-necked flask equipped with a dropping funnel and a nitrogen introduction tube was charged with 16.8 g of 10-undecin-1-ol, 50 mL of tetrahydrofuran and 12.1 g of triethylamine and cooled on ice. Next, a solution obtained by dissolving 16.8 g of trifluoromethanesulfonic acid chloride in 100 mL of tetrahydrofuran was dropped with a dropping funnel over 1 hour, and then reacted at room temperature all day and night. After completion of the reaction, 200 mL of ethyl acetate was added, and the mixture was washed three times with water, dried over magnesium sulfate, and concentrated under reduced pressure to obtain an oily liquid. Next, the oily liquid is purified with a silica column (developing solvent is hexane: ethyl acetate = 8: 2 (weight ratio)), concentrated under reduced pressure, and dried under vacuum to obtain the compound (1-1-1-1). 24.0 g of a colorless transparent oil was obtained.

<Synthesis of polyamic acid>
[Synthesis Example 6]
6.5 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride (50 mol% with respect to the total amount of tetracarboxylic dianhydride and diamine used for polymerization), and compound as diamine (1-1-2-1) 7.3 g (45 mol%) and octadecanoxy-2,4-diaminobenzene (compound represented by the following formula (DA-1)) 1.1 g (5 mol%) were N -It melt | dissolved in 85 g of methyl-2-pyrrolidone (NMP), and it reacted at 60 degreeC for 6 hours, and obtained the solution containing polyamic acid (it is set as polymer (PA-1)). 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.

[Synthesis Examples 7, 8, and 9]
Polymerization was carried out in the same manner as in Synthesis Example 6 except that the composition shown in Table 1 was used.

In Table 1, the amount of tetracarboxylic dianhydride and diamine charged (mol%) is the ratio of each compound used relative to the total amount of tetracarboxylic dianhydride and diamine used in the polymerization. Abbreviations of the compounds are as follows.
(T-1): 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (DA-2): 3,5-diaminobenzoic acid (compound represented by the following formula (DA-2))
(DA-3): 2- (methacryloyloxy) ethyl-3,5-diaminobenzoate (compound represented by the following formula (DA-3))

<Synthesis of polyimide>
[Synthesis Example 10]
6.1 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride (50 mol% based on the total amount of tetracarboxylic dianhydride and diamine used for polymerization), and compound as diamine (1-1-2-1) 6.9 g (45 mol%) and compound (DA-1) 1.1 g (5 mol%) were dissolved in N-methyl-2-pyrrolidone (NMP) 79.3 g, Reaction was performed at 60 degreeC for 6 hours, and the solution containing a polyamic acid was obtained. 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. Subsequently, 106.7 g of NMP, 2.15 g of pyridine and 2.78 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new NMP (by this operation, pyridine and acetic anhydride used in the imidization reaction were removed from the system), and a polyimide having an imidation ratio of about 50% ( A solution containing a polymer (PI-1)) was obtained.

<Synthesis of polyamic acid ester>
[Synthesis Example 11]
To a 300 mL three-necked flask equipped with a nitrogen inlet tube and a thermometer, 100 g of the polymer (PA-3), 66 g of the compound (1-1-1-1) and 15.2 g of potassium carbonate were added, and The reaction was allowed for 5 hours. After completion of the reaction, the reaction solution was poured into 2 L of ethanol, and the deposited precipitate was filtered and vacuum-dried to obtain 45 g of a white solid. In addition, the obtained white solid was made into the polymer (PAE-1). ^When confirmed by ¹ H-NMR, it was confirmed that 240 mol% of acetylene was introduced per 100 mol% of the structural unit of the polymer (PAE-1).

<Synthesis of polyorganosiloxane>
[Synthesis Example 12-1]
While charging 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as a hydrolyzable silane compound into a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 500 g of methyl isobutyl ketone And 10.0 g of triethylamine were charged and mixed at room temperature. 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the reaction was carried out at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer is taken out and washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to have an epoxy group. Polyorganosiloxane was obtained as a viscous transparent liquid. When ¹ H-NMR analysis was performed on the polyorganosiloxane having an epoxy group, 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 side reaction occurred. When the epoxy equivalent of this polyorganosiloxane having an epoxy group was measured, it was 186 g / equivalent.
Next, in a 200 mL three-necked flask, 10.0 g of the polyorganosiloxane having an epoxy group obtained above, 30.28 g of methyl isobutyl ketone as a solvent, and compound 5 represented by the above formula (1-3C) as a carboxylic acid compound .69 g and 3.09 g of a compound represented by the following formula (C-1) (corresponding to 30 mol% and 20 mol% respectively with respect to the epoxy group of the polyorganosiloxane), and UCAT18X (trade name) as a catalyst , Sun Apro Co., Ltd.) 0.10 g was charged and reacted at 100 ° C. with stirring for 48 hours. After completion of the reaction, a solution obtained by adding ethyl acetate to the reaction mixture was washed with water three times, and the solvent was distilled off to obtain 10.0 g of polyorganosiloxane (Si-1) having an acetylene structure. The weight average molecular weight Mw of the obtained polymer was 6,300.

[Synthesis Example 12-2]
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and methacryloxypropyltrimethoxysilane (1: 1 in molar ratio) as hydrolyzable silane compounds, and represented by the above formula (C-1) as carboxylic acid The synthesis of the polyorganosiloxane having an epoxy group and the reaction between the polyorganosiloxane and the carboxylic acid compound were carried out in the same manner as in Synthesis Example 12-1, except that the compound (25 mol% with respect to the epoxy group of the polyorganosiloxane) was used. And polyorganosiloxane (Si-2) was obtained. The weight average molecular weight Mw of the obtained polymer was 5,700.

<Synthesis of Polymer of Compound Having Polymerizable Carbon-Carbon Double Bond>
[Synthesis Example 13-1]
To a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 3,4-epoxycyclohexylmethyl methacrylate (ECMMA, 60 mol parts), 2-hydroxyethyl methacrylate (HEMA, 15 mol parts), N- Cyclohexylmaleimide (CMI, 10 mol parts) and styrene (ST, 15 mol parts) were charged, and diethylene glycol ethyl methyl ether was added and dissolved so that the total amount of the polymerizable unsaturated compounds was 50% by weight. Here, 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator is 3 mol% based on the total number of moles of the polymerizable unsaturated compound, and α-methylstyrene dimer is used as a chain transfer agent. Only 0.5 times the weight of the polymerization initiator was added. Subsequently, after bubbling with a nitrogen stream for 10 minutes to perform nitrogen substitution in the system, a polymerization reaction was performed at 70 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol and then dried under reduced pressure at 40 ° C. for 15 hours to obtain a methacrylic acid ester copolymer having an epoxy group.
Next, 10.0 g of the above-obtained methacrylic acid ester copolymer having an epoxy group, 30.28 g of methyl isobutyl ketone as a solvent, and the above formula (1-3C) as a carboxylic acid compound are added to a 200 mL three-necked flask. 5.90 g of the compound, and 3.21 g of the compound represented by the above formula (C-1) (corresponding to 30 mol% and 20 mol% respectively with respect to the polymethacrylic acid ester), and UCAT 18X as the catalyst 0.10 g (trade name, manufactured by San Apro Co., Ltd.) was charged and reacted at 90 ° C. with stirring for 12 hours. After completion of the reaction, a solution obtained by adding ethyl acetate to the reaction mixture was washed with water three times. The organic layer after washing with water is poured into a large excess of methanol to precipitate a polymer, and the recovered precipitate is dried at 40 ° C. for 12 hours, whereby a methacrylic acid ester copolymer (Ac-1) having an acetylene structure is obtained. 10.5 g) was obtained. The weight average molecular weight Mw of the obtained polymer was 16,800.

[Synthesis Example 13-2]
As a carboxylic acid compound, succinic acid 1- [2- (methacryloyloxy) ethyl] and a compound represented by the above formula (C-1) (30 mol% and 20 mol% respectively with respect to the polymethacrylic acid ester) and In the same manner as in Synthesis Example 13-1, the synthesis of a methacrylic ester copolymer having an epoxy group and the reaction of the methacrylic ester copolymer having an epoxy group with a carboxylic acid compound were carried out to obtain a methacrylic ester. A copolymer (Ac-2) was obtained. The weight average molecular weight Mw of the obtained polymer was 14,500.

[Example 1]
(1) Preparation of polymer composition To the solution containing the polymer (PA-1) obtained in Synthesis Example 6, N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added as organic solvents, and BC It was set as the solution whose density | concentration is 40 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.

(2) Manufacture and Evaluation of Liquid Crystal Cell Using the polymer composition prepared above, a total of 6 liquid crystal display elements are manufactured by changing the pattern (2 types) and ultraviolet irradiation amount (3 levels) of the transparent electrode. And evaluated as follows.

(2-1) Manufacture of a liquid crystal cell having a transparent electrode without a pattern The polymer composition prepared above has a transparent electrode made of an ITO film using a liquid crystal alignment film printer (Nissha Printing Co., Ltd.). After coating on the transparent electrode surface of the glass substrate and heating (pre-baking) on a hot plate at 80 ° C. for 1 minute to remove the solvent, heating (post-baking) on a hot plate at 150 ° C. for 10 minutes. A coating film having a thickness of 600 mm was formed. 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. Thereafter, 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 5.5 μm to the outer edge of the surface having the liquid crystal alignment film for one of the pair of substrates, the liquid crystal alignment film surface is placed on the pair of substrates. The adhesives were cured by overlapping and pressing so as to face each other. Next, after filling nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) between a pair of substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an acrylic photocuring adhesive to produce a liquid crystal cell.
The above operation was repeated to produce three liquid crystal cells having unpatterned transparent electrodes. One of them was directly used for the evaluation of the pretilt angle and the evaluation of the pretilt angle stability described later. The remaining two liquid crystal cells were each subjected to pretilt angle evaluation and pretilt angle stability evaluation after light irradiation with a voltage applied between the conductive films by the following method.

For two of the liquid crystal cells obtained above, an alternating current of 10 Hz is applied between the electrodes, and the liquid crystal is driven, using an ultraviolet gland irradiation device using a metal halide lamp as the light source, UV was irradiated at dose of 10,000 J / ^{m 2} or 100,000J / ^{m 2.} In addition, this irradiation amount is the value measured using the light meter measured on the basis of wavelength 365nm.

(2-2) Evaluation of Pretilt Angle The liquid crystal cell produced as described above is described in Non-Patent Document 3 (TJ Scheffer et. Al. J. Appl. Phys. Vo. 19, p. 2013 (1980)). In accordance with the above method, the value of the tilt angle from the substrate surface of the liquid crystal molecules measured by the crystal rotation method using He—Ne laser light was defined as the pretilt angle. As a result, the pretilt angle of the liquid crystal cell of this example was 88 °.

(2-3) Production of Liquid Crystal Cell Having Patterned Transparent Electrode The polymer composition prepared above was patterned into slits as shown in FIG. It apply | coated using the liquid crystal aligning film printer (made by Nissha Printing Co., Ltd.) on each electrode surface of 2 glass substrates to have, and the solvent was removed by heating (prebaking) for 1 minute on an 80 degreeC hotplate. Then, it heated for 10 minutes on a 150 degreeC hotplate (post-baking), and formed the coating film with an average film thickness of 600 mm. The coating film was subjected to ultrasonic cleaning for 1 minute in ultrapure water and then dried in a clean oven at 100 ° C. 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.
Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer edge of the surface having the liquid crystal alignment film for one of the pair of substrates. The adhesives were cured by overlapping and pressing them so that they face each other. Next, after filling nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) between a pair of substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an acrylic photocuring adhesive to produce a liquid crystal cell.
The above operation was repeated to produce three liquid crystal cells having patterned transparent electrodes. One of them was used for evaluation of response speed as described later. For the remaining two liquid crystal cells, light upon the (2-1) and the irradiation amount of 10,000 J / ^{m 2} or 100,000J / ^{m 2} while applying a voltage between the conductive film in a similar manner Irradiated and then subjected to evaluation of response speed. The electrode pattern used here is the same type as the electrode pattern in the PSA mode.

(2-4) Evaluation of response speed First, the liquid crystal cell manufactured above was irradiated with a visible light lamp without applying a voltage, and the luminance of light transmitted through the liquid crystal cell was measured with a photomultimeter. The value was 0% relative transmittance. Next, the transmittance when 60 V AC was applied between the electrodes of the liquid crystal cell for 5 seconds was measured in the same manner as described above, and this value was defined as a relative transmittance of 100%. When 60 V AC was applied to each liquid crystal cell, the time until the relative transmittance shifted from 10% to 90% was measured, and this time was defined as the response speed and evaluated. As a result, in this example, the response speed of the liquid crystal cell was 28 ms.

(2-5) Evaluation of Pretilt Angle Stability The pretilt angle after applying the liquid crystal cell having the non-patterned transparent electrode prepared in (2-1) above at 24V AC for 24 hours was measured. A change in the pretilt angle of less than 2 ° was judged as “good” and a change of 2 ° or more was judged as bad. As a result, the liquid crystal display element of this example had “good” pretilt angle stability.

[Examples 2-6 and Comparative Examples 1-3]
In Example 1 above, 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 2 below, and various liquid crystal cells were produced using this. evaluated. The evaluation results are shown in Table 2 below.

  As shown in Table 2, in the examples, good results were obtained in all of the pretilt angle, the response speed of liquid crystal molecules, and the pretilt angle stability. On the other hand, in the comparative example, the pretilt angle stability was evaluated as “bad”. From this result, according to the liquid crystal aligning agent containing the polymer (P), the merit of the PSA mode can be realized with a small amount of light irradiation. It was suggested that a liquid crystal display element having a wide viewing angle, a high response speed of liquid crystal molecules, a high transmittance, and a high contrast can be manufactured while suppressing a decrease in holding characteristics and a lack of long-term reliability.

  Furthermore, Example 1 except that each polymer composition used in Examples 1 to 6 was used and the ITO electrode pattern of the glass substrate was changed to the pattern shown in FIG. 2 and the pattern shown in FIG. In the same manner, various liquid crystal cells were produced and evaluated. When any polymer composition was used, the same effects as in Examples 1 to 6 were obtained in both the pattern shown in FIG. 2 and the pattern shown in FIG.

  1: ITO electrode, 2: slit part, 3: light shielding film

Claims (6)

A pair of substrates provided with a conductive film and a coating film formed on the conductive film are arranged to face each other with the coating film facing each other through a liquid crystal layer, thereby constructing a liquid crystal cell, and having the pair of substrates A liquid crystal aligning agent for forming a liquid crystal alignment film on the substrate by irradiating the liquid crystal cell with a voltage applied between conductive films,
Containing a polymer (P) having a side chain having a group represented by the following formula (A) ,
The polymer (P) is a polymer having at least one selected from the group consisting of a structural unit represented by the following formula (2-1) and a structural unit represented by the following formula (2-2), a polyorgano It is at least one selected from the group consisting of siloxane and a polymer of a compound having a polymerizable carbon-carbon double bond,
As the polymer (P), a polymer having at least one selected from the group consisting of a structural unit represented by the following formula (2-1) and a structural unit represented by the following formula (2-2): A polymer obtained by reacting at least a polymer (p-1) having an amic acid structure with a compound represented by the following formula (3);
The polyorganosiloxane as the polymer (P) is obtained by reacting a polymer having polyorganosiloxane as a main chain and having at least one epoxy group in the molecule with a compound represented by the following formula (4). A polymer obtained by
The polymer of a compound having a polymerizable carbon-carbon double bond as the polymer (P) has a polymer of a compound having a polymerizable carbon-carbon double bond as a main chain, and at least one in the molecule. One of the liquid crystal aligning agent to the polymer having an epoxy group, wherein the polymer der Rukoto obtained by reacting a compound represented by the following formula (4).
(In Formula (A), R ¹ is a hydrogen atom or a monovalent organic group, and R ² is a divalent organic group. “*” Represents a bond.)
(In Formula (2-1) and Formula (2-2), P ¹ is a tetravalent organic group and Q ¹ is a divalent organic group. R ²¹ and R ²² are each independently a hydrogen atom. Or it is a monovalent organic group.)
(In Formula (3), Y ¹ is a monovalent group having an epoxy group, a halogen atom, or * -SO ₃ -R ⁴ (where R ⁴ is a methyl group, a trifluoromethyl group, or a substituted or unsubstituted phenyl group). is a group.) .R ¹ and ^{R 2} are the same meaning as ^{R 1} and ^{R 2} in formula (a).)
(In the formula (4), ^{Y 2} is, .R ¹ and ^{R 2} is a monovalent group having a carboxyl group has the same meaning as ^{R 1} and ^{R 2} in formula (A).) Wherein R ² is a group represented by the following formula (1), the liquid crystal aligning agent of claim 1.
(In the formula (1), Ar ¹ represents the following formula (Ar-1)
(In the formula (Ar-1), A ¹¹ and A ¹² are each independently a phenylene group or a cyclohexylene group, and X ³ is a single bond, * ² —COO— or * ² —OCO— (where * . the bond marked with ² binds to a ¹¹⁾ is .s is 0 or 1, "* ^1", carbon -. represents a bond that binds to the carbon atom of the carbon triple bond ". * "Indicates a bond.)
A naphthylene group or a pyridylene group, and the ring portion may have a substituent. X ¹ and X ² are each independently a single bond, —O—, * ³ —C (═O) —O—, * ³ —O—C (═O) —, —CO—, —S—, * ^3- C (= O) -S-, * ^3- S-C (= O)-, * ^3- C (= S) -O-, * ^3- O-C (= S)-, -NR ^a −, * ³ —NR ^a —CO— or * ³ —CO—NR ^a — (wherein R ^a is a hydrogen atom or an alkyl group, and a bond marked with * ³ binds to R ³ ). is there. R ³ is a group having —O— between carbon-carbon bonds in an alkanediyl group having 1 to 20 carbon atoms or an alkanediyl group having 1 to 20 carbon atoms, and the hydrogen atom bonded to the carbon atom is a fluorine atom. It may be substituted, and a part of the carbon-carbon bond may be a double bond or a triple bond. a is 0 or 1. “* ¹ ” indicates a bond bonded to a carbon atom constituting a carbon-carbon triple bond. “*” Indicates a bond. ) The liquid crystal aligning film formed using the liquid crystal aligning agent of Claim 1 or 2 . A method of manufacturing a liquid crystal display element,
Applying a liquid crystal aligning agent on each of the conductive films of the pair of substrates having a conductive film, and then heating the liquid crystal aligning agent 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 of the pair of substrates,
The liquid crystal aligning agent contains a polymer (P) having a group represented by the following formula (A) in the side chain,
The polymer (P) is a polymer having at least one selected from the group consisting of a structural unit represented by the following formula (2-1) and a structural unit represented by the following formula (2-2), a polyorgano It is at least one selected from the group consisting of siloxane and a polymer of a compound having a polymerizable carbon-carbon double bond,
As the polymer (P), a polymer having at least one selected from the group consisting of a structural unit represented by the following formula (2-1) and a structural unit represented by the following formula (2-2): A polymer obtained by reacting at least a polymer (p-1) having an amic acid structure with a compound represented by the following formula (3);
The polyorganosiloxane as the polymer (P) is obtained by reacting a polymer having polyorganosiloxane as a main chain and having at least one epoxy group in the molecule with a compound represented by the following formula (4). A polymer obtained by
The polymer of a compound having a polymerizable carbon-carbon double bond as the polymer (P) has a polymer of a compound having a polymerizable carbon-carbon double bond as a main chain, and at least one in the molecule. a polymer having a One epoxy group, a method of manufacturing a liquid crystal display element characterized polymer der Rukoto obtained by reacting a compound represented by the following formula (4).
(In Formula (A), R ¹ is a hydrogen atom or a monovalent organic group, and R ² is a divalent organic group. “*” Represents a bond.)
(In Formula (2-1) and Formula (2-2), P ¹ is a tetravalent organic group and Q ¹ is a divalent organic group. R ²¹ and R ²² are each independently a hydrogen atom. Or it is a monovalent organic group.)
(In Formula (3), Y ¹ is a monovalent group having an epoxy group, a halogen atom, or * -SO ₃ -R ⁴ (where R ⁴ is a methyl group, a trifluoromethyl group, or a substituted or unsubstituted phenyl group). is a group.) .R ¹ and ^{R 2} are the same meaning as ^{R 1} and ^{R 2} in formula (a).)
(In the formula (4), ^{Y 2} is, .R ¹ and ^{R 2} is a monovalent group having a carboxyl group has the same meaning as ^{R 1} and ^{R 2} in formula (A).) The method for producing a liquid crystal display element according to claim 4 , wherein R ² has a group represented by the following formula (1).
(In the formula (1), Ar ¹ represents the following formula (Ar-1)
(In the formula (Ar-1), A ¹¹ and A ¹² are each independently a phenylene group or a cyclohexylene group, and X ³ is a single bond, * ² —COO— or * ² —OCO— (where * . the bond marked with ² binds to a ¹¹⁾ is .s is 0 or 1, "* ^1", carbon -. represents a bond that binds to the carbon atom of the carbon triple bond ". * "Indicates a bond.)
A naphthylene group or a pyridylene group, and the ring portion may have a substituent. X ¹ and X ² are each independently a single bond, —O—, * ³ —C (═O) —O—, * ³ —O—C (═O) —, —CO—, —S—, * ^3- C (= O) -S-, * ^3- S-C (= O)-, * ^3- C (= S) -O-, * ^3- O-C (= S)-, -NR ^a −, * ³ —NR ^a —CO— or * ³ —CO—NR ^a — (wherein R ^a is a hydrogen atom or an alkyl group, and a bond marked with * ³ binds to R ³ ). is there. R ³ is a group having —O— between carbon-carbon bonds in an alkanediyl group having 1 to 20 carbon atoms or an alkanediyl group having 1 to 20 carbon atoms, and the hydrogen atom bonded to the carbon atom is a fluorine atom. It may be substituted, and a part of the carbon-carbon bond may be a double bond or a triple bond. a is 0 or 1. “* ¹ ” indicates a bond bonded to a carbon atom constituting a carbon-carbon triple bond. “*” Indicates a bond. ) The method for manufacturing a liquid crystal display element according to claim 4 , wherein the conductive film is a patterned conductive film partitioned into a plurality of regions.