JP2018032029A - Liquid crystal aligning agent and production method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal aligning agent with which a liquid crystal alignment film excellent in stability of impedance and a pretilt angle can be formed, and to achieve further excellent display quality when a liquid crystal alignment film formed from the aligning agent is applied to a liquid crystal display element.SOLUTION: The present invention relates to a liquid crystal aligning agent and a production method of the agent, which comprises: a polymer (A) selected from a group consisting of a polyamic polymer, a polyimide polymer, a polyimide block copolymer and any combinations of these polymers; a polysiloxane (B) containing a cinnamic acid group; and a solvent (C). The present invention also provides a liquid crystal alignment film formed from the liquid crystal aligning agent, a production method of a liquid crystal alignment film, and a liquid crystal display element including the alignment film.SELECTED DRAWING: None

Description

  The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element, and in particular, a liquid crystal aligning agent that can form a liquid crystal aligning film having excellent impedance and pretilt angle stability, and the liquid crystal aligning agent. The present invention relates to a formed liquid crystal alignment film and a liquid crystal display element having the liquid crystal alignment film.

  As liquid crystal displays develop into large display specifications, the wide viewing angle technology of liquid crystal display panels needs to advance and develop to overcome the problem of viewing angles of large displays. A multi-domain vertical alignment (MVA) type liquid crystal display panel is a general wide viewing angle technology. The MVA type liquid crystal display panel can achieve a wide viewing angle display effect by forming protrusions on the liquid crystal panel and restricting the tilt direction of the liquid crystal molecules. However, the MVA liquid crystal display panel has insufficient transmittance and contrast due to the protrusions, and further cannot avoid the problem that the response speed of the liquid crystal molecules is slow.

  In recent years, polymer-sustained alignment (PSA) type technology has been developed to solve the above problems. In this technique, a gap between a pair of substrates formed by a substrate having a patterned conductive film and a substrate not having a patterned conductive film, or a pair of substrates formed by two substrates each having a patterned conductive film In this technique, a liquid crystal composition containing a polymerizable compound is sandwiched in a gap between substrates, and the liquid crystal composition is irradiated with ultraviolet rays when a voltage is applied between conductive films to polymerize the polymerizable compound. As a result, a pretilt angle characteristic appears and the direction of liquid crystal alignment is controlled. With this technology, the conductive film forms a specific structure, and the effect of improving the wide viewing angle and the response speed of liquid crystal molecules can be achieved. Therefore, the transmittance and contrast of the MVA liquid crystal display panel are insufficient. The inevitable problem of being can be solved.

However, in order to polymerize the polymerizable compound, it is necessary to irradiate a large amount of ultraviolet rays (for example, 100,000 J / m ² ). For this reason, in addition to the problem of decomposition of liquid crystal molecules, unreacted compounds that are not polymerized by UV irradiation also remain in the liquid crystal layer to form impurity contamination, resulting in a problem of mura defects in the liquid crystal display element. As a result, the electrical characteristics are adversely affected. Further, the type of liquid crystal molecules used in the liquid crystal layer must be compatible with the polymerizable compound to be added, and therefore the type is limited.

  At the same time, Non-Patent Document 1 proposed a method of forming a liquid crystal alignment film with a polyimide liquid crystal aligning agent containing reactive liquid crystals.

  At this stage, with the demand for higher definition of the liquid crystal display element and suppression of contrast reduction or afterimage development reduction of the liquid crystal display element, the voltage holding ratio must be increased when using the liquid crystal alignment film, The characteristics of decreasing the residual charge when a DC voltage is applied and / or relaxing the residual charge accumulated by the DC voltage at an early stage are becoming increasingly important.

  The polyamic acid and / or polyimide, the polyamic acid and the polyimide can be used so that the residual charge accumulated by the DC voltage can be relaxed early even after increasing the voltage holding ratio and after being exposed to a high temperature for a long time. It is known to use a liquid crystal aligning agent containing a diamine compound that can be used as a raw material (see, for example, Patent Document 1).

International Publication No. 2009/093704

Y. -J. Lee et. al. SID 09 DIGEST, p. 666 (2009)

  However, in recent years, large-screen and high-quality liquid crystal televisions have already been widely used, and liquid crystal display elements for these applications are used in harsh environments compared to conventional display applications that mainly display characters or still screens. Must have excellent stability characteristics of impedance and pretilt angle.

  Therefore, the present invention provides a liquid crystal alignment agent that can form a liquid crystal alignment film having excellent impedance and pretilt angle stability, and the liquid crystal alignment film formed thereby is more excellent when applied to a liquid crystal display element. Whether or not display quality can be realized is an issue that engineers in this field should solve immediately.

  Accordingly, the present invention provides a liquid crystal alignment agent that can form a liquid crystal alignment film having excellent impedance and pretilt angle stability, including a special polymer, a liquid crystal alignment film formed using the liquid crystal alignment agent, and the liquid crystal alignment film A liquid crystal display element having a liquid crystal alignment film is provided.

Therefore, the present invention
A polymer (A);
A polysiloxane (B) containing cinnamic acid groups;
Regarding a liquid crystal aligning agent comprising a solvent (C),
The polymer (A) is selected from the group consisting of a polyamic acid polymer, a polyimide polymer, a polyimide block copolymer, and any combination of the above polymers, and the polymer (A) is represented by the formula ( Including the unit represented by Ia).
[In Formula (Ia), Y is a single bond, —COO—, —CONR _d — or —R _j —NR _d —,
R _d is a hydrogen atom or a C _{1 to} C ₁₀ linear or branched alkyl group,
R _j is a single bond or a C _{1 to} C ₁₀ linear or branched alkyl group;
R _a is a single bond, a C ₁ -C ₁₀ linear or branched alkyl group,
Ht is a nitrogen-containing heterocyclic ring,
R _b is a C _{1 to} C ₁₀ linear or branched oxyalkyl group, nitrile group or carbonyl group;
R _c is a C _{1 to} C ₁₀ linear or branched alkyl group, or R _b and R _c may be bonded to each other to form a single ring,
a1 is an integer of 0 to 1,
a2 is an integer of 0 to 2,
When Y is a single bond, a1 is 0;
When Y is —COO—, —CONR _d — or —R _j —NR _d —, a1 is 1 and * is a bonding position. ]

  The present invention further provides a liquid crystal alignment film formed by the liquid crystal aligning agent described above.

  The present invention further provides a liquid crystal display element including the liquid crystal alignment film described above.

  The present invention also provides a method for producing a liquid crystal aligning agent comprising mixing a polymer (A), a polysiloxane (B) containing a cinnamic acid group, and a solvent (C).

  The present invention also provides a method for producing a liquid crystal alignment film comprising forming a liquid crystal alignment film with a liquid crystal aligning agent, and the liquid crystal aligning agent is formed by the method for producing a liquid crystal aligning agent.

  The present invention also provides a method of manufacturing a liquid crystal display element including a liquid crystal alignment film, and the manufacturing method forms the liquid crystal alignment film with the liquid crystal alignment agent formed by the method of manufacturing a liquid crystal alignment agent. Including that.

The present invention
A polymer (A);
A polysiloxane (B) containing cinnamic acid groups;
A liquid crystal aligning agent comprising a solvent (C),
The polymer (A) is selected from the group consisting of a polyamic acid polymer, a polyimide polymer, a polyimide block copolymer, and any combination of the above polymers, and the polymer (A) is represented by the formula ( Including the unit represented by Ia).
[In Formula (Ia), Y is a single bond, —COO—, —CONR _d — or —R _j —NR _d —,
R _d is a hydrogen atom or a C _{1 to} C ₁₀ linear or branched alkyl group,
R _j is a single bond or a C _{1 to} C ₁₀ linear or branched alkyl group;
R _a is a single bond, a C ₁ -C ₁₀ linear or branched alkyl group,
Ht is a nitrogen-containing heterocyclic ring,
R _b is a C _{1 to} C ₁₀ linear or branched oxyalkyl group, nitrile group or carbonyl group;
R _c is a C _{1 to} C ₁₀ linear or branched alkyl group, or R _b and R _c may be bonded to each other to form a single ring,
a1 is an integer of 0 to 1,
a2 is an integer of 0 to 2,
When Y is a single bond, a1 is 0;
When Y is —COO—, —CONR _d — or —R _j —NR _d —, a1 is 1 and * is a bonding position. ]

  The polymer (A) can be obtained by reacting the mixture. The mixture includes a tetracarboxylic dianhydride component (a1) and a diamine component (a2).

  Specifically, the polymer (A) includes polyamic acid, polyimide, polyamic acid-polyimide block copolymer, or a combination of these polymers. In particular, the polyimide block copolymer includes a polyamic acid block copolymer, a polyimide block copolymer, a polyamic acid-polyimide block copolymer, or a combination of these polymers. A polyamic acid polymer, a polyimide polymer, and a polyamic acid-polyimide block copolymer can all be obtained by reacting a mixture of a tetracarboxylic dianhydride component (a1) and a diamine component (a2).

The polymer (A) contains a unit represented by the formula (Ia).
[In Formula (Ia), Y is a single bond, —COO—, —CONR _d — or —R _j —NR _d —,
R _d is a hydrogen atom or a C _{1 to} C ₁₀ linear or branched alkyl group,
R _j is a single bond or a C _{1 to} C ₁₀ linear or branched alkyl group;
R _a is a single bond, a C ₁ -C ₁₀ linear or branched alkyl group,
Ht is a nitrogen-containing heterocyclic ring,
R _b is a C _{1 to} C ₁₀ linear or branched oxyalkyl group, nitrile group or carbonyl group;
R _c is a C _{1 to} C ₁₀ linear or branched alkyl group, or R _b and R _c may be bonded to each other to form a single ring,
a1 is an integer of 0 to 1,
a2 is an integer of 0 to 2,
When Y is a single bond, a1 is 0;
When Y is —COO—, —CONR _d — or —R _j —NR _d —, a1 is 1 and * is a bonding position. ]

Preferably, the polymer (A) includes a unit represented by the formula (Ia-1), the formula (Ia-2) or the formula (Ia-3).
[Y is a single bond, —COO—, —CONR _d — or —R _j —NR _d —,
R _d is a hydrogen atom or a C _{1 to} C ₁₀ linear or branched alkyl group,
R _j is a single bond or a C _{1 to} C ₁₀ linear or branched alkyl group;
R _a is a single bond, a C ₁ -C ₁₀ linear or branched alkyl group,
R _b is a C _{1 to} C ₁₀ linear or branched oxyalkyl group, nitrile group or carbonyl group;
R _c is a C _{1 to} C ₁₀ linear or branched alkyl group, or R _b and R _c may be bonded to each other to form a single ring,
a1 is an integer of 0 to 1,
a2 is an integer of 0 to 2,
When Y is a single bond, a1 is 0;
When Y is —COO—, —CONR _d — or —R _j —NR _d —, a1 is 1 and * is a bonding position. ]

  The tetracarboxylic dianhydride component (a1) is an aliphatic tetracarboxylic dianhydride compound, an alicyclic tetracarboxylic dianhydride compound, an aromatic tetracarboxylic dianhydride compound, a formula (I-1) to It includes at least one of tetracarboxylic dianhydride compounds represented by formula (I-6) or a combination of these compounds.

  Specific examples of the aliphatic tetracarboxylic dianhydride compound, the alicyclic tetracarboxylic dianhydride compound, and the aromatic tetracarboxylic dianhydride compound are as follows. However, the present invention is not limited to these specific examples.

  Specific examples of the aliphatic tetracarboxylic dianhydride compound include ethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, or a combination of these compounds. However, the present invention is not limited to this.

  Specific examples of the alicyclic tetracarboxylic dianhydride compound include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride. Anhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2 , 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexane Tetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl-cycloheptyl-1,5-diene-1,2,5,6 -Tetracarboxylic acid bis Water, 2,3,5-tricarboxycyclopentylacetic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, or these Although the combination of a compound is mentioned, this invention is not limited to this.

  Specific examples of the aromatic tetracarboxylic dianhydride compound include 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3', 3,4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic Acid dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3 4-dicarboxy Enoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride ( 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride), 3,3 ′, 4,4′-perfluoroisopropylidenediphenyl dicarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl Tetracarboxylic dianhydride, bis (phthalic acid) phenylsulfin oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (Triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride Ethylene glycol-bis (anhydro trimellitate), propylene glycol-bis (anhydro trimellitate), 1,4-butanediol-bis (anhydro trimellitate), 1,6-hexanediol-bis (an Hydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), 2,3,4, 5-tetrahydrofurantetracarboxylic 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-5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione) 1,3,3a, 4,5,9b-hexahi Dro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro -5-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro- 7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7 -Ethyl-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-furani ) Naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) Naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl ) Naphtho [1,2-c] furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, or these Although the combination of these compounds is mentioned, this invention is not limited to this.

The tetracarboxylic dianhydride compounds represented by formula (I-1) to formula (I-6) are as follows.

In the formula (I-5), A1 represents a divalent group containing an aromatic ring; r represents an integer of 1 to 2; A ² and A ³ may be the same, or different And each independently represents a hydrogen atom or an alkyl group. The tetracarboxylic dianhydride compound represented by formula (I-5) includes one of the compounds represented by formula (I-5-1) to formula (I-5-3).

In the formula (I-6), A ⁴ represents a divalent group containing an aromatic ring; A ⁵ and A ⁶ may be the same or different, and each independently represents a hydrogen atom. Indicates an atom or an alkyl group. The tetracarboxylic dianhydride compound represented by the formula (I-6) is preferably a compound represented by the formula (I-6-1).

  The tetracarboxylic dianhydride component (a1) may be used alone or in combination.

  The tetracarboxylic dianhydride component (a1) is preferably 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetra Carboxylic dianhydrides and 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydrides, or combinations of these compounds.

  The amount of the tetracarboxylic dianhydride component (a1) used is preferably 80 to 120 moles per 100 moles of the total moles of the diamine component (a2); the tetracarboxylic dianhydride component (a1) The amount of is more preferably 85 to 115 mol.

The diamine component (a2) according to the present invention contains at least one diamine compound (a2-1) represented by the formula (Ib).
[In Formula (Ib),
Y is a single bond, —COO—, —CONR _d — or —R _j —NR _d —,
R _d is a hydrogen atom or a C _{1 to} C ₁₀ linear or branched alkyl group,
R _j is a single bond or a C _{1 to} C ₁₀ linear or branched alkyl group;
R _a is a single bond, a C ₁ -C ₁₀ linear or branched alkyl group,
Ht is a nitrogen-containing heterocyclic ring,
R _b is a C _{1 to} C ₁₀ linear or branched oxyalkyl group, nitrile group or carbonyl group;
R _c is a C _{1 to} C ₁₀ linear or branched alkyl group, or R _b and R _c may be bonded to each other to form a single ring,
a1 is an integer of 0 to 1,
a2 is an integer of 0 to 2,
When Y is a single bond, a1 is 0, and when Y is —COO—, —CONR _d —, or —R _j —NR _d —, a1 is 1. ]

Preferably, the diamine component (a2) includes a diamine compound (a2-1) represented by the formula (Ib-1), the formula (Ib-2) or the formula (Ib-3).
[Where:
Y is a single bond, —COO—, —CONR _d — or —R _j —NR _d —,
R _d is a hydrogen atom or a C _{1 to} C ₁₀ linear or branched alkyl group,
R _j is a single bond or a C _{1 to} C ₁₀ linear or branched alkyl group;
R _a is a single bond, a C ₁ -C ₁₀ linear or branched alkyl group,
R _b is a C _{1 to} C ₁₀ linear or branched oxyalkyl group, nitrile group or carbonyl group;
R _c is a C _{1 to} C ₁₀ linear or branched alkyl group, or R _b and R _c may be bonded to each other to form a single ring,
a1 is an integer of 0 to 1,
a2 is an integer of 0 to 2,
When Y is a single bond, a1 is 0, and when Y is —COO—, —CONR _d —, or —R _j —NR _d —, a1 is 1. ]

Specific examples of the diamine compound (a2-1) are
It is.

  The amount of diamine compound (a2-1) used may be 20 to 60 mol, preferably 25 to 55 mol, more preferably 100 mol relative to the total amount of diamine component (a2) used. Is 30 mol to 50 mol.

  When the diamine compound (a2-1) is not used as the polymer (A), the produced liquid crystal aligning agent has a defect that the stability of impedance and pretilt angle is not good.

  Preferably, the diamine component (a2) of the present invention may further contain another diamine compound (a2-2).

  Other diamine compounds (a2-2) include aliphatic diamine compounds, cycloaliphatic diamine compounds, aromatic diamine compounds, diamine compounds having formulas (III-1) to (III-25), or combinations thereof. .

  Specific examples of the aliphatic diamine compound include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane. 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 4,4′-diaminoheptane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2, 5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5 Methylnonane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis (3-aminopropoxy) ethane, or a combination of these compounds Include combined. However, the present invention is not limited thereto.

  Specific examples of the alicyclic diamine compound include 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, and isophorone. Diamines, tetrahydrodicyclopentadienylenediamine, tricyclo [6.2.1.02,7] -undecylenedimethyldiamine, 4,4′-methylenebis (cyclohexylamine), or combinations of these compounds, The present invention is not limited to this.

  Specific examples of the aromatic diamine compound include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminobenzoylaniline, and 4,4′-diamino. Diphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'- Aminophenyl) -1,3,3-trimethylindane, hexahydro-4,7-methanoindenylene dimethylenediamine, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bi [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1, 4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10 -Hydroanthracene, 9,10-bis (4-aminophenyl) anthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-methylene-bis (2-chloroaniline), 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyle) Isopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-bis [(4-amino-2-trifluoromethyl) Phenoxy] octafluorobiphenyl, 5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diaminobenzene (5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3 -diaminobenzene), 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane (1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane), or a combination of these compounds, but the present invention is not limited thereto.

The diamine compounds having the formula (a2-2-1) to the formula (a2-226) are as follows.
In Formula (a2-2-1), B ¹ is
Indicates;
B ² is a group containing a steroid skeleton, a trifluoromethyl group, a fluorine atom, an alkyl group having 2 to 30 carbon atoms, or a nitrogen atom-containing ring structure derived from pyridine, pyrimidine, triazine, piperidine, piperazine or the like. Represents a monovalent group.

  Specific examples of the diamine compound represented by the formula (a2-2-1) include ethyl 2,4-diaminophenyl ethyl formate, ethyl 3,5-diaminophenyl ethyl formate (3,5- diaminophenyl ethyl formate), 2,4-diaminophenyl propyl formate, 3,5-diaminophenyl propyl formate, 1-dedecoxy-2,4-diamino Benzene (1-dodecoxy-2,4-diaminobenzene), 1-hexadecoxy-2,4-diaminobenzene, 1-octadecoxy-2,4-diaminobenzene (1-octadecoxy- 2,4-diaminobenzene), at least one of the compounds represented by the formula (a2-2-1-1) to the formula (a2-22-1-6), or a combination of these compounds. The present invention is not limited to this. Yes.

The compounds represented by formula (a2-2-1-1) to formula (a2-22-1-6) are as follows.

In formula (a2-2-2), B ¹ has the same meaning as B ¹ of formula (III-1), B ³ and B ⁴ are each independently a divalent aliphatic ring, divalent Represents an aromatic ring or a divalent heterocyclic ring;
B ⁵ is an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, a fluoroalkoxy group having 1 to 5 carbon atoms, a cyano group, or Indicates a halogen atom.

Specific examples of the compound represented by the formula (a2-2-2) include a compound in which at least one of the compounds represented by the formula (a2-2-2-1) to the formula (a2-2-2-13) is Can be mentioned. Specifically, the compounds represented by formula (a2-2-2-1) to formula (a2-2-2-13) are as follows.
In formula (a2-2-2-10) to formula (a2-2-2-13), s represents an integer of 3 to 12.

In formula (a2-2-3), each B ⁶ independently represents a hydrogen atom, an acyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or Represents a halogen atom, and B ⁶ in each repeating unit may be the same or different;
u represents an integer of 1 to 3.

  Specific examples of the diamine compound represented by the formula (a2-2-3) include when u is 1: p-diaminobenzene, m-diaminobenzene, o-diaminobenzene, 2,5-diaminotoluene and the like. And when u is 2: 4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3 ′ -Dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2 ', 5,5' -Tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, or 4,4'-diamino-2,2'-bis (tri Fluoromethyl Biphenyl, and the like; u is when 3: 1,4-bis (4'-aminophenyl) benzene.

  Specific examples of the diamine compound represented by the formula (a2-2-3) are preferably p-diaminobenzene, 2,5-diaminotoluene, 4,4′-diaminobiphenyl, 3,3′-dimethoxy-4. , 4′-diaminobiphenyl, 1,4-bis (4′-aminophenyl) benzene, or a combination of these compounds.

In formula (a2-2-4), v represents an integer of 2 to 12.

In formula (a2-2-5), w represents an integer of 1 to 5.

  The compound represented by the formula (a2-2-5) is more preferably 4,4′-diamino-diphenyl sulfide.

In formula (a2-2-6), B ⁷ and B ⁹ each independently represent a divalent organic group, and B ⁷ and B ⁹ may be the same or different;
B ⁸ represents a divalent group of a nitrogen atom-containing ring structure derived from pyridine, pyrimidine, triazine, piperidine, piperazine or the like.

In formula ^{(a2-2-7), B 10, B} 11, B 12 and B ¹³ are each independently a hydrocarbon group having 1 to 12 carbon atoms, B ^10, B ^11, B ¹² and B ¹³ may be the same or different; x1 independently represents an integer of 1 to 3; x2 represents an integer of 1 to 20.

In the formula (a2-2-8), B ¹⁴ represents an oxygen atom or a cyclohexylene group;
B ¹⁵ represents a methylene group (—CH ₂ —);
B ¹⁶ represents a phenylene group or a cyclohexylene group;
B ¹⁷ represents a hydrogen atom or a heptyl group.

Specific examples of the diamine compound represented by the formula (a2-2-8) include a compound represented by the formula (a2-2-8-1) and a diamine represented by the formula (a2-2-8-2). Or a combination of these compounds.

The compounds represented by formula (a2-2-9) to formula (a2-2-30) are as follows.
In formula (a2-2-17) ~ formula (a2-2-25), B ¹⁸ is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms,; B ¹⁹ is , Preferably, a hydrogen atom, a C1-C10 alkyl group, or a C1-C10 alkoxy group is shown.

[In Formula (a2-226), B ²⁰ and B ²² each independently represent a single bond, —O—, —COO— or —OCO—, and B ²¹ represents a group having 1 to 3 carbon atoms. an alkylene ^{group, B 23} represents a single bond or an alkylene group having 1 to 3 carbon atoms. d and g each independently represent 0 or 1, e represents an integer of 0 to 2, f represents an integer of 1 to 20, provided that d and e are not 0 at the same time. . ]

In the formula (a2-226), the divalent group represented by “—B ²⁰ — (B ²¹ —B ²² ) _g —” is preferably an alkylene group having 1 to 3 carbon atoms, ^* —O ^-, * -COO- or _{^{* -O-C 2 H 4 -O-}} ( where * indicates the bonding position for coupling the diamino phenyl group). The group represented by “—C _f H _{2f + 1} ” is preferably linear. The two amino groups of the diaminophenyl group are preferably in the 2,4 or 3,5 position relative to the position of the other group.

Specific examples of the compound represented by the formula (a2-226) include compounds represented by the following formula (a2-226-1) to formula (a2-226-4). .

  Other diamine compounds (a2-2) may be used alone or in combination.

  Specific examples of the other diamine compound (a2-2) are preferably 1,2-diaminoethane, 4,4′-diaminodicyclohexylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 5 -[4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diaminobenzene, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane , Ethyl 2,4-diaminophenylformate, a compound represented by formula (III-1-1), a compound represented by formula (III-1-2), represented by formula (III-1-5) Compound, compound represented by formula (III-2-1), compound represented by formula (III-2-11), p-diaminobenzene, m-diaminobenzene, - diaminobenzene compound represented by formula (III-8-1), or combinations of these compounds, the present invention is not limited thereto.

The amount of the other diamine compound (a2-2) used may be 40 to 80 mol, preferably 45 to 75 mol, based on 100 mol of the diamine component (a2). Preferably, it is 50 mol-70 mol.
Method for producing polymer (A)

The polymer (A) can contain at least one of polyamic acid and polyimide. The polymer (A) may further contain a polyimide block copolymer. Hereinafter, the production method of each polymer described above will be described in more detail.
Method for producing polyamic acid

  In the method for producing a polyamic acid, first, a mixture containing a tetracarboxylic dianhydride component (a1) and a diamine component (a2) is dissolved in a solvent. And polycondensation reaction is performed at the temperature of 0 to 100 degreeC. After reacting for 1 to 24 hours, the reaction solution is distilled under reduced pressure in an evaporator to obtain polyamic acid. Or after pouring a reaction liquid into a lot of poor solvents (poor solvent) and obtaining a precipitate, a polyamic acid is obtained by drying a precipitate by the method of drying under reduced pressure.

  The solvent used in the polycondensation reaction may be the same as or different from the solvent in the liquid crystal aligning agent described below, and the solvent used in the polycondensation reaction is a solvent that can dissolve the reaction product and the product. If there is, it will not be specifically limited. The solvent is preferably (1), for example, N-methyl-2-pyrrolidinone (NMP), N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone Or aprotic polar solvents such as tetramethylurea or hexamethylphosphoramide; or (2) for example, a phenol solvent such as m-cresol, xylenol, phenol, or halogenated phenol. It is not limited to. The amount of the solvent used in the polycondensation reaction is preferably 200 parts by weight to 2000 parts by weight, and more preferably 300 parts by weight to 1800 parts by weight with respect to 100 parts by weight of the total amount of the mixture used.

It should be mentioned that in the polycondensation reaction, the solvent can be used in combination with an appropriate amount of anti-solvent that does not precipitate the polyamic acid. The poor solvent may be used alone or in combination. (1) Methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triglycol, etc. (2) Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone; (3) Esters such as methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, or ethylene glycol monoethyl ether acetate (4) diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether Ethers such as ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, or diethylene glycol dimethyl ether; (5) halogenation such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, or o-dichlorobenzene Or (6) hydrocarbons such as tetrahydrofuran, hexane, heptane, octane, benzene, toluene, or xylene, or any combination of these solvents, but the invention is not limited thereto. The amount of the poor solvent used is preferably 0 to 60 parts by weight and more preferably 0 to 50 parts by weight with respect to 100 parts by weight of the diamine component (a2).
Preparation method of polyimide

  The polyimide production method includes heating the polyamic acid obtained by the above-described polyamic acid production method in the presence of a dehydrating agent and a catalyst. In the heating process, the amic acid functional group in the polyamic acid can be converted (that is, imidized) into an imide functional group by a dehydration cyclization reaction.

  Since the solvent used in the dehydration cyclization reaction may be the same as the solvent (D) in the liquid crystal aligning agent, the description is not repeated here. The amount of the solvent used in the dehydration cyclization reaction is preferably 200 parts by weight to 2000 parts by weight, and more preferably 300 parts by weight to 1800 parts by weight with respect to 100 parts by weight of the polyamic acid. .

  In order to obtain a preferable degree of imidization of the polyamic acid, the operation temperature of the dehydration cyclization reaction is preferably 40 ° C to 200 ° C, more preferably 40 ° C to 150 ° C. When the operation temperature of the dehydration cyclization reaction is lower than 40 ° C., the imidization reaction becomes incomplete, so that the degree of imidization of the polyamic acid decreases. However, when the operating temperature of the dehydration cyclization reaction is higher than 200 ° C., the resulting polyimide has a relatively low weight average molecular weight.

  The dehydrating agent used in the dehydration cyclization reaction can be selected from acid anhydride compounds, and specific examples thereof include acetic anhydride, propionic anhydride, trifluoroacetic anhydride, and the like. The usage-amount of a dehydrating agent is 0.01 mol-20 mol with respect to 1 mol of polyamic acids. The catalyst used in the dehydration cyclization reaction can be selected from (1) pyridine compounds such as pyridine, trimethylpyridine, or dimethylpyridine; and (2) tertiary amine compounds such as triethylamine. The amount of the catalyst used may be 0.5 mol to 10 mol with respect to 1 mol of the dehydrating agent.

The imidation ratio of the polymer (A) may be 0% to 50%, preferably 0% to 45%, more preferably 0% to 40%.
Method for producing polyimide block copolymer

  The polyimide block copolymer is selected from a polyamic acid block copolymer, a polyimide block copolymer, a polyamic acid-polyimide block copolymer, or any combination of these polymers.

  The method for producing the polyimide block copolymer preferably includes firstly dissolving the starting material in a solvent and then performing a polycondensation reaction. The starting material includes at least one polyamic acid and / or at least one polyimide, and may further include a tetracarboxylic dianhydride component and a diamine component.

  The carboxylic anhydride component and the diamine component in the starting material may be the same as the tetracarboxylic dianhydride component (a1) and the diamine component (a2) used in the method for producing the polyamic acid. In addition, the solvent used in the polycondensation reaction may be the same as the solvent (C) in the following liquid crystal aligning agent, and therefore will not be described repeatedly here.

  The amount of the solvent used in the polycondensation reaction is preferably 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight with respect to 100 parts by weight of the starting material. The operating temperature of the polycondensation reaction is preferably 0 ° C to 200 ° C, more preferably 0 ° C to 100 ° C.

  The starting material is preferably (1) two polyamic acids with different end groups and different structures; (2) two polyimides with different end groups and different structures; (3) different end groups and structures Polyamic acid and polyimide having different valences; (4) polyamic acid and carboxylic acid anhydride in which at least one of carboxylic acid anhydride component and diamine component is different from the structure of the carboxylic acid anhydride component and diamine component used for forming polyamic acid A component, and a diamine component; (5) a polyimide, a carboxylic acid anhydride component, wherein at least one of the carboxylic acid anhydride component and the diamine component is different from the structure of the carboxylic acid anhydride component and the diamine component used for forming the polyimide, and Diamine component; (6) Carboxylic anhydride component and diamine component A polyamic acid, a polyimide, a carboxylic anhydride component, and a diamine component, at least one of which is different from the structures of the carboxylic anhydride component and the diamine component used to form the polyamic acid or polyimide; (7) two polyamic acids having different structures Carboxylic acid anhydride component and diamine component; (8) two polyimides having different structures, carboxylic acid anhydride component, and diamine component; (9) having acid anhydride groups as terminal groups and different structures 2 Two polyamic acids and a diamine component; (10) two polyamic acids having an amine group as a terminal group and different structures and a carboxylic acid anhydride component; and (11) an acid anhydride group as a terminal group, And two polyimides having different structures and a diamine component; or (12) Have a down group, and two polyimide structure is different, and carboxylic acid but anhydride component and the like, and the present invention is not limited thereto.

  Unless the effects of the present invention are affected, the polyamic acid, the polyimide and the polyimide block copolymer are preferably terminal-modified polymers whose molecular weights have been adjusted in advance. By using a terminal-modified polymer, the coating film performance of the liquid crystal aligning agent can be improved. The method for producing the terminal-modified polymer includes adding a monofunctional compound simultaneously with the polycondensation reaction of the polyamic acid.

  Specific examples of monofunctional compounds are (1) maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride Or acid monoanhydrides such as n-hexadecyl succinic anhydride; (2) aniline, cyclohexylamine, n-butylamine, n-amylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n A monoamine compound such as octadecylamine or n-eicosylamine; or (3) phenylamine Cyanate or monoisocyanate compounds of naphthyl isocyanate, and the like, but the present invention is not limited thereto.

  The polysiloxane (B) containing a cinnamic acid group according to the present invention comprises an epoxy group-containing polysiloxane (b1) and cinnamic acid obtained by reacting an epoxy group-containing polysiloxane (b1) with a cinnamic acid derivative (b2). Specific examples and synthesis of the derivative (b2) are as follows.

Preferably, the polysiloxane (B) containing a cinnamic acid group includes a unit represented by the formula (IIa).
(R is a fluorine atom or a cyano group;
a is an integer of 0 to 4, and * is a bonding position. )

More preferably, the polysiloxane (B) containing a cinnamic acid group includes a unit represented by the formula (IIa-1) or the formula (IIa-2).
[In Formula (IIa-1) and Formula (IIa-2),
R is a fluorine atom or a cyano group,
a is an integer from 0 to 4 and * is the bond position;
In Formula (IIa-1), R ¹ is a hydrogen atom, a C ₃ -C ₄₀ monovalent organic group having an alicyclic group, or a C ₁ -C ₄₀ alkyl group, provided that the alkyl group Some or all of the hydrogen atoms may be substituted with fluorine atoms,
X ¹ is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-, wherein + indicates the position at which R ¹ is bonded;
R ² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group,
X ² is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-, wherein + indicates a position bonded to R ² , and b is an integer of 0 to 3;
In the formula (IIa-2), R ³ is a hydrogen atom, a C ₃ -C ₄₀ monovalent organic group having an alicyclic group, or a C ₁ -C ₄₀ alkyl group, provided that the alkyl group Some or all of the hydrogen atoms may be substituted with fluorine atoms,
X ³ is an oxygen atom or a divalent aromatic group,
R ⁴ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group,
X ⁴ is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-, wherein + indicates the position bonded to R ⁴ , and c is an integer of 0 to 3. ]

  The epoxy group-containing group contained in the polysiloxane (b1) containing an epoxy group is, for example, a glycidyl group, a glycidyloxy group, an epoxycyclohexyl group, or an oxetanyl group. It is.

  Specifically, the polysiloxane (b1) containing an epoxy group is represented by the group represented by the formula (2-1), the group represented by the formula (2-2), and the formula (2-3). At least one of the groups to be prepared.

Specifically, the groups represented by the formula (2-1) are as follows.
In formula (2-1), B represents a hydrogen atom or a single bond;
m represents an integer of 1 to 3;
n represents an integer of 0 to 6, and when d represents 0, B is a single bond.

Furthermore, the group represented by Formula (2-2) is as follows.
In Formula (2-2), p represents an integer of 0 to 6.

The groups represented by formula (2-3) are as follows.
In formula (2-3), D represents an alkylene group having 2 to 6 carbon atoms; E represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The epoxy group-containing group is preferably represented by a group represented by the formula (2-1-1), a group represented by the formula (2-2-1), and a formula (2-3-1). Contains at least one of the groups.

In a preferred embodiment of the present invention, the polysiloxane (a-1) containing an epoxy group according to the present invention includes a copolymer obtained by subjecting the first mixture to hydrolysis and partial condensation, and the first mixture comprises: A silane monomer (b1-1) having a structure represented by the formula (1-1) is included.
Si (R _e ) _w1 (OR _f ) _4-w1 formula (1-1)
(Where:
R _e represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkyl group containing an epoxy group, or an alkoxy group containing an epoxy group. And at least one R _a is an alkyl group containing an epoxy group or an alkoxy group containing an epoxy group, and when R _e is plural, each is the same or different,
R _f represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms, and when R _f is plural, each is the same or different; And w1 shows the integer of 1-3. )

When R _e in Formula (1-1) represents an alkyl group having 1 to 10 carbon atoms, specifically, R _e is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or n-butyl. Group, tert-butyl group, n-hexyl group or n-decyl group. R _e may be an alkyl group having another substituent on the alkyl group. Specifically, R _e is, for example, a trifluoromethyl group, a 3,3,3-trifluoropropyl group, It may be a 3-aminopropyl group, a 3-mercaptopropyl group, or a 3-isocyanatopropyl group.

When R _e in Formula (1-1) represents an alkenyl group having 2 to 10 carbon atoms, specifically, R _e is, for example, a vinyl group. In addition, R _e may be an alkenyl group having another substituent on the alkenyl group. Specifically, R _e is, for example, a 3-acryloxypropyl group or a 3-methylacryloxypropyl group. May be.

When R _e in Formula (1-1) represents an aromatic group having 6 to 15 carbon atoms, specifically, R _e is, for example, a phenyl group, a tolyl group (tolyl), or a naphthyl group (naphthyl). In addition, R _e may be an aromatic group having another substituent on the aromatic group. Specifically, R _e is, for example, a p-hydroxyphenyl group (p-hydroxyphenyl), 1- (p- Hydroxyphenyl) ethyl group (1- (p-hydroxyphenyl) ethyl), 2- (p-hydroxyphenyl) ethyl group (2- (p-hydroxyphenyl) ethyl) or 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) ) Pentyl group (4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl).

In addition, when R _e in Formula (1-1) represents an alkyl group containing an epoxy group or an alkoxy group containing an epoxy group, a specific example of R _e is contained in the polysiloxane (b1) containing the epoxy group. Epoxy group, which will not be further described here.

In the definition of R _f , the alkyl group having 1 to 6 carbon atoms includes, but is not limited to, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and the like. The acyl group having 1 to 6 carbon atoms includes, but is not limited to, an acetyl group. The aromatic group having 6 to 15 carbon atoms includes a phenyl group, but is not limited thereto.

  Specific examples of the silane monomer (b1-1) include 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 3- (N-allyl-N-diglycidyl) aminopropyltrimethoxysilane, and 3-glycidoxypropyl. Trimethoxysilane (3-glycidyloxypropyltrimethoxysilane), 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxy Propyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxy Ethyl methyl diet Silane, 2-glycidoxyethyldimethylmethoxysilane, 2-glycidoxyethyldimethylethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, 4-glycidoxybutylmethyldimethoxy Silane, 4-glycidoxybutylmethyldiethoxysilane, 4-glycidoxybutyldimethylmethoxysilane, 4-glycidoxybutyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, ((3-ethyl-3 -Oxetanyl) Xyl) propyltrimethoxysilane, ((3-ethyl-3-oxetanyl) methoxy) propyltriethoxysilane, ((3-methyl-3-oxetanyl) methoxy) propylmethyldimethoxysilane, ((3-methyl-3-oxetanyl) )) Methoxy) propyldimethylmethoxysilane, DMS-E01, DMS-E12, DMS-E21, DMS-32 and other commercial products (manufactured by JNC), or combinations of these compounds.

  Specific examples of the silane monomer (b1-1) represented by the formula (1-1) are preferably 3-glycidoxypropyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 4-glycidoxy Butyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, ((3-ethyl-3-oxetanyl) methoxy) propyltrimethoxy Silane, ((3-ethyl-3-oxetanyl) methoxy) propyltriethoxysilane, DMS-E01, DMS-E12, or a combination of these compounds.

  The amount of the silane monomer (b1-1) used is 0.5 to 1.0 mol, preferably 0.6 to 1.0 mol, more preferably 1 mol of the total amount of monomers in the mixture. Is 0.7-1.0 mol.

The mixture for reacting to produce the polysiloxane (b1) containing an epoxy group according to the present invention further contains another silane monomer (b1-2) having a structure represented by the formula (1-2).
Si (R _g ) w2 (OR _h ) _4-w2 formula (1-2)
(Where:
R _g represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms or an acid anhydride group, and a plurality of R _g Each is the same or different,
R _h represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and when R _h is plural, each is the same or different, And w2 represents an integer of 0 to 3. )

In the definition of R _g, the alkyl group of carbon number 1-10, an aryl group an alkenyl group or 6 to 15 carbon atoms from 2 to 10 carbon atoms, wherein _{R e} defined alkyl group having 1 to 10 carbon atoms , The same as an alkenyl group having 2 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and will not be further described here.

When R _e in Formula (1-2) represents an alkyl group containing an acid anhydride group, the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. Specifically, the alkyl group containing the acid anhydride group is, for example, an ethyl succinic anhydride represented by the formula (1-2-1) or a propyl succinate represented by the formula (1-2-2). An acid anhydride or a propylglutaric acid anhydride represented by the formula (1-2-3). Of particular interest is that an acid anhydride group is a group formed by intramolecular dehydration of a dicarboxylic acid, provided that the dicarboxylic acid is, for example, succinic acid or It is glutaric acid.

When R _h in Formula (1-2) represents an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, specific examples and preferred examples thereof are the above R _f And will not be described further here.

  The other silane monomer (b1-2) represented by the formula (1-2) may be used alone or in combination. The other silane monomer (b1-2) represented by the formula (1-2) is, for example, a compound having one silicon atom. The compound having one silicon atom is a silane compound having four hydrolyzable groups, a silane compound having three hydrolyzable groups, a silane compound having two hydrolyzable groups, a silane compound having one hydrolyzable group, or Including the combination.

  Specific examples of the silane compound having four hydrolyzable groups include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, Or the combination of these compounds is mentioned.

  Specific examples of the silane monomer having three hydrolyzable groups are methyltrimethoxysilane (abbreviated as MTMS), methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane. (Methyltri-n-butoxysilane), ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyl Trimethoxysilane (n-propyltrimethoxysilane), n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyl Limethoxysilane (n-hexyltrimethoxysilane), n-hexyltriethoxysilane (n-hexyltriethoxysilane), decyltrimethoxysilane (decyltrimethoxysilane), vinyltrimethoxysilane (vinyltrimethoxysilane), vinyltriethoxysilane (vinyltriethoxysilane), 3-acryloxypropyl Trimethoxysilane (3-acryoyloxypropyltrimethoxysilane), 3-methylacryloyloxypropyltrimethoxysilane (MPTMS), 3-methylacryloyloxypropyltriethoxysilane, phenyltrimethoxysilane (PTMS) , Phenyltriethoxysilane (PTES), p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ethyltrime Toxisilane (1- (p-hydroxyphenyl) ethyltrimethoxysilane), 2- (p-hydroxyphenyl) ethyltrimethoxysilane (2- (p-hydroxyphenyl) ethyltrimethoxysilane), 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl Trimethoxysilane (4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane), trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane (3,3,3-trifluoropropyltrimethoxysilane), 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane (3-mercaptopropyltrimethoxysilane) , 3- (triphenoxysilyl) propyl succinic anhydride, a commercial product manufactured by Shin-Etsu Chemical: 3- (trimethoxysilyl) propyl succinic anhydride (3-trimethoxysilyl propyl succinic anhydride) ) (Trade name: X-12-967), commercial product manufactured by WACKER: 3- (triethoxysilyl) propyl succinic anhydride (trade name: GF-20) ), 3- (trimethoxysilyl) propyl glutaric anhydride (3- (trimethoxysilyl) propyl glutaric anhydride, TMSG), 3- (triethoxysilyl) propyl glutaric anhydride (3- (triethoxysilyl) propyl glutaric anhydride), 3- (triphenoxysilyl) propylglutaric anhydride (3- (triphenoxysilyl) propyl glutaric anhydride) or a compound thereof Combinations thereof.

  Specific examples of the silane compound having two hydrolyzable groups are methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, 3 -Mercaptopropylmethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, or combinations of these compounds.

  Specific examples of the silane compound having one hydrolyzable group include methoxydimethylsilane, methoxytrimethylsilane, methoxymethyldiphenylsilane, tri-n-butyldiethoxysilane, or a combination of these compounds.

  The other silane monomer (b1-2) represented by the formula (1-2) is preferably tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxy. Examples include silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, or combinations of these compounds.

  The amount of the silane monomer (b1-2) used is 0 to 0.5 mol, preferably 0 to 0.4 mol, more preferably 0 to 0 mol with respect to 1 mol of the total amount of monomers in the mixture. 0.3 mole.

  The mixture can further comprise a commercially available silane monomer. Specific examples of commercially available silane monomers include, for example, KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5844, X-21-5844, X-21-5845, X-21-5847, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X- 22-170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40- 2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40 9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (manufactured by Shin-Etsu Chemical); glass resin (manufactured by Showa Denko KK); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2402 , SR2410, SR2411, SR2416, SR2420 (manufactured by Dow Corning Toray); FZ3711, FZ3722 (manufactured by Nihon Unicar); DMS-S12, DMS- 15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (manufactured by Chisso Corp.); MS51, MS56 (manufactured by Mitsubishi Chemical Corp.);

  The polycondensation reaction to form a polysiloxane containing an epoxy group can be carried out by adding an organic solvent or water to the silane compound or a mixture thereof, or optionally further adding a catalyst, and then, for example, an oil bath at 50 ° C. to 150 ° C. ( A general method such as heating by an oil bath) can be included, and the heating time is preferably 30 minutes to 120 hours. During heating, the mixture may be stirred or placed under reflux.

  The organic solvent is not particularly limited, and may be the same as or different from the solvent (C) contained in the liquid crystal aligning agent of the present invention.

  Specific examples of the organic solvent include hydrocarbon compounds such as toluene or xylene; ketone compounds such as methyl ethyl ketone, methyl isobutyl ketone, methyl-n-pentyl ketone, diethyl ketone, cyclohexanone, 2-butanone, or 2-hexanone; ethyl acetate, Ester compounds such as n-butyl acetate, isopentyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, or ethyl lactate; ether compounds such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, or dioxane; 1 -Hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono- alcohol compounds such as n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, or propylene glycol mono-n-propyl ether; N-methyl-2-pyrrolidone, N, N- Examples include amide solvents such as dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, or 1,3-dimethyl-2-imidazolidinone, or combinations of these organic solvents.

  An organic solvent may be used individually or may be used in combination of multiple.

  The amount of the organic solvent used is preferably 10 parts by weight to 1200 parts by weight, and more preferably 30 parts by weight to 1000 parts by weight with respect to 100 parts by weight of all the silane compounds.

  The amount of water used is preferably 0.5 to 20 moles per mole of hydrolyzable groups of all silane compounds.

  The catalyst is not particularly limited, and the catalyst is preferably selected from acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds, or combinations thereof.

  Specific examples of the acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, succinic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acid, polybasic acid anhydride, or combinations thereof.

  Specific examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, or a combination thereof.

  Specific examples of organic bases include primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, or pyrrole; triethylamine, tri-n-propylamine , Tertiary organic amines such as tri-n-butylamine, pyridine, 4-dimethylaminopyridine, or diazabicycloundecene; quaternary organic amines such as tetramethylammonium hydroxide, or the like The combination of these compounds is mentioned.

  The amount of the catalyst used varies depending on the reaction conditions such as the type and temperature, and can be set as appropriate. For example, with respect to 1 mol of all silane compounds, the addition amount of the catalyst is 0.01 mol to 5 mol, preferably 0.03 mol to 3 mol, and more preferably 0.05 to 1 mol. It is.

  In consideration of stability, it is preferable to wash the organic solvent layer separated from the reaction solution with water after the polycondensation reaction is completed. When washing is performed, water containing a small amount of salt is preferably used. For example, washing is performed with an aqueous ammonium nitrate solution of about 0.2% by weight. Washing is performed until the washed aqueous layer is neutral, and if necessary, the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieves, and then the solvent is removed. By removing, polysiloxane (b1) containing an epoxy group can be obtained.

  When the polysiloxane (b1) containing an epoxy group is not used as the polysiloxane (B) containing a cinnamic acid group, the produced liquid crystal aligning agent has a defect that impedance and pretilt angle are not stable.

The cinnamic acid derivative (b2) is at least one selected from the group consisting of compounds represented by formulas (3-1) to (3-2).

[In Formula (3-1) and Formula (3-2),
R is a fluorine atom or a cyano group, and * is a bonding position;

In Formula (3-1), R ¹ is a hydrogen atom, a C ₃ -C ₄₀ monovalent organic group having an alicyclic group, or a C ₁ -C ₄₀ alkyl group, provided that the alkyl group Some or all of the hydrogen atoms may be substituted with fluorine atoms,
X ¹ is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-, wherein + indicates the position at which R ¹ is bonded;
R ² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group,
X ² is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-, wherein + indicates a position bonded to R ² , and b is an integer of 0 to 3;
X ⁵ is a single bond, an oxygen atom, a sulfur atom, a methylene group, a C _{2 to} C ₁₀ alkylene group, a C _{2 to} C ₁₀ alkenylene group or a divalent aromatic group,
When X ⁵ is a single bond, h is 1 and R ⁵ is a hydrogen atom;
When X ⁵ is a methylene group, an alkylene group, an alkenylene group or a divalent aromatic group, h is 0 or 1, and R ⁵ is a carboxyl group, a hydroxyl group, —SH, —NCO, —NHR ′, —CH = CH ₂ or _-SO 2 Cl, provided that, R 'is hydrogen atom or an alkyl group of _C 1 -C _6,
In the formula (3-2), R ³ is a hydrogen atom, a C _{3 to} C ₄₀ monovalent organic group having a cycloaliphatic group or a C _{1 to} C ₄₀ alkyl group, provided that the alkyl group Some or all of the hydrogen atoms may be substituted with fluorine atoms,
X ³ is an oxygen atom or a divalent aromatic group,
R ⁴ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group,
X ⁴ is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-, wherein + indicates the position to bond with R ⁴ , and c is an integer of 0 to 3;
R ⁶ is a divalent aromatic group, a divalent heterocyclic group or a divalent condensed cyclic group,
X ⁶ is an oxygen atom, —COO— ⁺ or —OCO— ⁺ , wherein + represents a position bonded to R ⁶ ;
k is an integer of 0 to 3 and R ⁷ is a carboxyl group, a hydroxyl group, —SH, —NCO, —NHR ′, —CH═CH ₂ or —SO ₂ Cl, where R ′ is , A hydrogen atom or a C _{1 to} C ₆ alkyl group, and X ⁷ is a single bond, —OCO— (CH ₂ ) _i − ⁺ or —O— (CH ₂ ) _j − ⁺ , provided that i And j each represents an integer of 0 to 10, and + represents a position where R ⁷ is bonded.
In the compound represented by the formula (3-1), preferably, X ⁵ is a compound having a single bond and R ⁵ has a carboxyl group, or X ⁵ is a methylene group, an alkylene group or a divalent aromatic. And R ⁵ is a compound having a carboxyl group. In the compound represented by the formula (3-2), preferably R ⁷ is a compound having a carboxyl group. ]

Preferably, specific examples of the compound represented by the formula (3-1) are as follows.

R ¹ is the same as defined above, and is not described separately here. D is an integer of 0 to 10.

Specific examples of the compound represented by the formula (3-2) are as follows.

R ³ is the same as defined above and will not be described separately here.

  In a specific example of the present invention, the amount of the cinnamic acid derivative (b2) used is 0.15 to 0.5 mol, preferably 0.15 to 0.45, relative to 1 mol of the total amount of monomers in the mixture. Mol, more preferably 0.2 to 0.45 mol.

  When the cinnamic acid derivative (b2) is not used as the polysiloxane (B) containing cinnamic acid groups, the produced liquid crystal aligning agent has a defect that impedance and pretilt angle are not stable.

  When the cinnamic acid derivative (b2) is used within the above range, the stability of the pretilt angle is good.

Furthermore, a part of the cinnamic acid derivative may be substituted with a compound represented by the following formula (4) as long as the effect of the present invention is not inhibited.
W ¹⁵ -W ¹⁶ -W ¹⁷ formula (3-3)

In Formula (3-3), W ¹⁵ represents a C 4-20 alkyl group or alkoxy group, or a C 3-40 monovalent organic group containing an alicyclic group, and a hydrogen atom of the alkyl group some or all of the atoms of may be replaced by fluorine atom; W ¹⁶ is a single bond or a phenylene group, and when W ¹⁵ is an alkoxy group, W ¹⁶ is an phenylene group; W ¹⁷ is , A carboxylic acid group, a hydroxyl group, —SH, —NCO, or —NHW, wherein W is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, —CH═CH ₂ , and —SO ₂ Cl. One is shown.

  The polysiloxane (B) containing a cinnamic acid group of the present invention can be synthesized by reacting a polysiloxane (b1) containing an epoxy group with a cinnamic acid derivative (b2) in the presence of a catalyst.

  The catalyst can contain a well-known compound such as an organic salt or a curing accelerator capable of facilitating the reaction between the epoxy compound and the acid anhydride.

  Organic salts include, for example, primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, or pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylamino Tertiary organic amines such as pyridine or diazabicycloundecene; or quaternary organic amines such as tetramethylammonium hydroxide can be included. Among these organic amines, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, or 4-dimethylaminopyridine, or quaternary organic amines such as tetramethylammonium hydroxide. Is preferred.

  Specific examples of the curing accelerator include, for example, tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, or triethanolamine; 2-methylimidazole 2-n-heptylimidazole, 2-n-alkaliimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2 -Dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-5-n-undecylimidazole, 1- (2-cyanoethyl) ) -2-Phenylimidazole, 1- (2-cyanoethyl) -2- Til-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis (hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-phenyl-4, 5-bis [(2′-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate Tate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-S-triazine, 2 , 4-Diamino-6- (2'-n-undecylimidazolyl) ethyl-S-triazine, 2,4-diamino-6- [2 -Ethyl-4'-methylimidazolyl- (1 ')] ethyl-S-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, or 2,4-diamino-6- [ 2'-methylimidazolyl- (1 ')] imidazole compounds such as isocyanuric acid adducts of ethyl-S-triazine; organophosphorus compounds such as diphenylphosphine, triphenylphosphine, or triphenyl phosphite; benzyltriphenylphosphonium Chloride (benzyl triphenyl phosphonium chloride), tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, Rutriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium-O, O-diethyl phosphorodithionate, tetra-n-butylphosphonium Quaternary phosphonium salts such as tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate or tetraphenylphosphonium tetraphenylborate; 1,8 Diazabicycloalkenes such as diazabicyclo [5.4.0] undecene-7 or organic acid salts thereof; organometallic compounds such as zinc octylate, tin actylate, or aluminum acetylacetone complex Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, or tetra-n-butylammonium chloride; boron compounds such as boron trifluoride or triphenylborate Metal halide compounds such as zinc chloride or stannic chloride; high melting point dispersion type latent curing accelerators such as amine addition accelerators such as dicyandiamide or adducts of amine and epoxy resin; imidazole compounds, organic A microcapsule type latent curing accelerator in which the surface of a phosphorus compound or a quaternary phosphonium salt curing accelerator is coated with a polymer; an amine salt type latent curing accelerator; Lewis acid or High temperature solution such as Bronsted acid salt Examples include latent curing accelerators such as releasing thermal cationic polymerization type latent curing accelerators.

  Specific examples of the curing accelerator preferably include quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.

  The amount of the catalyst used is 100 parts by weight or less, preferably 0.01 parts by weight to 100 parts by weight, more preferably 100 parts by weight of the polysiloxane (B) containing cinnamic acid groups. 0.1 parts by weight to 20 parts by weight.

  The reaction temperature is preferably 0 ° C to 200 ° C, more preferably 50 ° C to 150 ° C. The reaction time is preferably 0.1 hour to 50 hours, more preferably 0.5 hour to 20 hours.

  The synthesis reaction of the polysiloxane (B) containing a cinnamic acid group may be performed in the presence of an organic solvent if necessary. The organic solvent is not particularly limited, and may be the same as or different from the organic solvent used for preparing the polysiloxane (b1) containing an epoxy group and the solvent (C) contained in the liquid crystal aligning agent of the present invention. Good. Specific examples of the organic solvent preferably include 2-butanone, 2-hexanone, methyl isobutyl ketone, n-butyl acetate, or a combination thereof.

  The amount of polysiloxane (B) containing a cinnamic acid group is 5 to 30 parts by weight, preferably 5 to 28 parts by weight, based on 100 parts by weight of the total amount of polymer (A). More preferably, it is 8 to 28 parts by weight.

  The solvent used in the liquid crystal aligning agent of the present invention is not particularly limited as long as it does not react with the polymer (A), the polysiloxane (B) containing a cinnamic acid group, and any other compound. The solvent is preferably the same as the solvent used in the synthesis of the polyamic acid, and at the same time, the poor solvent used in the synthesis of the polyamic acid can be used together.

  Specific examples of the solvent (C) include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy Propionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene Glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether Examples include, but are not limited to, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, N, N-dimethylformamide, or N, N-dimethyl acetamide. . A solvent (C) may be used individually or may be used in combination of multiple.

  The amount of the solvent (D) used is 1500 to 4000 parts by weight, preferably 1800 to 3800 parts by weight, more preferably 100 parts by weight of the polymer (A). 2000 parts by weight to 3500 parts by weight.

  If the effect of the present invention is not affected, an additive (D) may be selectively added to the liquid crystal aligning agent. The additive (D) includes a compound containing at least two epoxy groups, a silane compound having a functional group, or a combination thereof.

  Specific examples of the compound containing at least two epoxy groups are 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, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglyce Examples include dil-4,4′-diaminodiphenylmethane, N, N-glycidyl-p-glycidyloxyaniline, 3- (N, N-glycidyl) aminopropyltrimethoxysilane, or combinations of these compounds. Is not limited to this.

  A compound containing at least two epoxy groups may be used alone or in combination.

  The amount of the compound containing at least two epoxy groups may be 0 to 40 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the polymer (A). Parts by weight.

  Specific examples of the silane compound having a functional group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl). ) -3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, N- Ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-to Methoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6- Diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltri Examples include methoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, or a combination of these compounds. It is not limited to.

  An additive (D) may be used individually or may be used in combination of multiple.

  The amount of the silane compound having a functional group may be 0 to 10 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer (A). It is.

The amount of additive (D) used is preferably 0.5 to 50 parts by weight, more preferably 1 to 45 parts by weight, based on 100 parts by weight of the total amount of polymer (A) used. Part.
<Method for producing liquid crystal aligning agent>

  The manufacturing method of the liquid crystal aligning agent of this invention is not specifically limited, It can manufacture using a general mixing method. For example, the polymer (A) formed by the above-described method and the polysiloxane (B) containing cinnamic acid groups are uniformly mixed to obtain a mixture. And a solvent (C) is added on the temperature conditions of 0 to 200 degreeC. Next, additive (D) is added selectively and finally stirring is continued with a stirrer until the mixture is dissolved. Furthermore, it is preferable to add a solvent (C) at the temperature of 20 to 60 degreeC.

At 25 ° C., the viscosity of the liquid crystal aligning agent of the present invention is usually 15 cps to 35 cps, preferably 17 cps to 33 cps, and more preferably 20 cps to 30 cps.
<Method for forming liquid crystal alignment film>

  After applying the liquid crystal aligning agent of the present invention to the substrate, if necessary, a coating film obtained by heat treatment such as pre-bake and post-bake is directly used as the liquid crystal aligning film. . Further, the coating film may be subjected to treatment such as rubbing, irradiation with polarized light or light of a specific wavelength, or ion beam. Further, when a voltage is applied to the liquid crystal display element after filling the liquid crystal, ultraviolet rays are irradiated to form an SCVA film.

  At this time, the substrate to be used is not particularly limited as long as it is a highly transparent substrate. The substrate is, for example, a glass substrate, polycarbonate, poly (meth) acrylate, polyethersulfone, polyacrylate, polyurethane, polysulfone, polyether, polyetherketone, polymethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile. Cellulose triacetate, cellulose diacetate, or cellulose acetate butyrate. From the viewpoint of simplifying the process, the substrate is preferably a substrate on which an indium tin oxide (ITO) electrode for driving the liquid crystal is formed. Further, when the reflective liquid crystal display element is a single-sided substrate, an opaque object such as a silicon wafer may be used. Further, the electrode in this case can include a light reflecting material such as aluminum.

  The method for applying the liquid crystal aligning agent is not particularly limited. For example, a printing method such as screen printing, offset printing, or flexo printing, an inkjet method, a spray coating method, or a roll coating. Method, dipping, slit coating, or spin coating. From the viewpoint of productivity, transfer printing widely used industrially is also suitable for the present invention.

  After applying the liquid crystal aligning agent by the method described above, a coating film is formed by pre-baking and post-baking. The pre-baking process after applying the liquid crystal alignment agent is not necessary, but when the time between application and post-baking is not fixed to each substrate, or when post-baking is not performed immediately after application, pre-baking It is preferred to carry out the process further. The condition of the pre-bake process is only to volatilize the organic solvent without changing the shape of the coating film by transporting the substrate or the like. The conditions for the prebaking treatment are not particularly limited, and the temperature at which the prebaking treatment is performed is, for example, 40 ° C to 150 ° C, preferably 50 ° C to 120 ° C, more preferably 60 ° C to 100 ° C. . The prebaking time is 0.1 to 30 minutes, preferably 0.5 to 15 minutes, and more preferably 1 to 5 minutes.

  The conditions for the post-bake treatment are not particularly limited, and the temperature at which the post-bake treatment is performed is, for example, 100 ° C. to 350 ° C., preferably 120 ° C. to 300 ° C., more preferably 150 ° C. to 250 ° C. It is. The time for performing post-baking is 5 minutes to 240 minutes, preferably 10 minutes to 100 minutes, and more preferably 20 minutes to 90 minutes. Heating can be performed by a well-known method, for example, it can be performed by a hot plate, a hot air circulating furnace, or an infrared furnace.

The thickness of the liquid crystal alignment film obtained after post-baking is not particularly limited, and may be, for example, 1 nm to 1000 nm, preferably 5 nm to 500 nm, and more preferably 10 nm to 300 nm.
<Liquid crystal display element and manufacturing method thereof>

  The liquid crystal display element of this invention contains the liquid crystal aligning film formed of the liquid crystal aligning agent of this invention. The liquid crystal display element of this invention can be manufactured based on the following method.

  Specifically, the liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above-described method and then manufacturing a liquid crystal cell by a well-known method. Specific examples of the liquid crystal display element include, for example, a vertical alignment type liquid crystal display element including a liquid crystal cell. The liquid crystal cell includes two substrates disposed opposite to each other, a liquid crystal layer disposed between the substrates, and a book. It has a liquid crystal alignment film formed by the liquid crystal aligning agent of the invention and disposed between the substrate and the liquid crystal layer.

  More specifically, in a vertical alignment type liquid crystal display device having a liquid crystal cell, the liquid crystal cell is manufactured by the following method: After applying the liquid crystal aligning agent of the present invention to two substrates, prebaking and post A liquid crystal alignment film is formed by baking. Then, the two substrates are arranged so that the liquid crystal alignment films face each other. A liquid crystal layer formed of liquid crystal is sandwiched between two substrates, and the liquid crystal layer is disposed in contact with the liquid crystal alignment film. Finally, a voltage is applied to the liquid crystal alignment film and the liquid crystal layer, and at the same time, ultraviolet rays are irradiated.

  The polymerizable compound is polymerized by applying a voltage while irradiating the liquid crystal alignment film and the liquid crystal layer formed of the liquid crystal alignment agent of the present invention with ultraviolet rays. At the same time, the alignment of the liquid crystal is more effectively fixed by reacting the polymerizable unsaturated groups of the polysiloxane with each other or by reacting the polymerizable unsaturated group with the polymerizable compound. As a result, a liquid crystal display element that is excellent in UV resistance and free from uneven defects is formed.

Methods for sandwiching the liquid crystal layer between two substrates include, for example, the following two well-known methods:
(Method 1)

A pair of substrates each having a liquid crystal alignment film formed thereon is prepared, and spacers such as beads are scattered on the liquid crystal alignment film of one substrate. Then, after the other substrate is bonded so that the liquid crystal alignment films face each other, liquid crystal is injected under reduced pressure and sealed.
(Method 2)

  Prepare a pair of substrates each formed with a liquid crystal alignment film, spray spacers such as beads on the liquid crystal alignment film on one substrate, drop the liquid crystal, and then place the other so that the liquid crystal alignment film faces each other The substrates are bonded and sealed.

  In these two methods, the thickness of the spacer is preferably 1 μm to 30 μm, and more preferably 2 μm to 10 μm.

  The step of manufacturing a liquid crystal cell by applying a voltage while irradiating the liquid crystal alignment film and the liquid crystal layer with ultraviolet rays is performed, for example, by applying a voltage between the electrodes arranged on the substrate and applying an electric field to the liquid crystal alignment film and the liquid crystal layer. Applying, and irradiating ultraviolet rays while maintaining the electric field. In particular, the voltage applied between the electrodes is, for example, 5 Vp-p to 30 Vp-p, and preferably 5 Vp-p to 20 Vp-p. The irradiation amount of ultraviolet rays is, for example, 1J to 60J, preferably less than 40J, more preferably less than 10J. The smaller the amount of UV irradiation, the lower the reliability that can be reduced due to the destruction of the liquid crystal or material forming the liquid crystal display element. Further, the production efficiency can be increased by reducing the time of ultraviolet irradiation. Since the present invention can increase the response speed even when the amount of ultraviolet irradiation is small, a liquid crystal display element having a sufficiently high response speed can be formed even with a low irradiation amount such as 5J.

  Thus, when ultraviolet rays are applied while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, a polymerizable compound can be reacted to produce a polymer, and in addition, a polymerizable unsaturated group possessed by polysiloxane can be produced. Can react with each other when irradiated with ultraviolet light, or can react with a polymerizable compound. By the above reaction, the liquid crystal alignment film can obtain a more excellent cured structure, and the obtained liquid crystal display element can have the properties of being excellent in ultraviolet resistance and having no hue unevenness.

  Furthermore, the liquid crystal aligning agent can be used not only for the production of a vertical alignment type liquid crystal display element such as an SCVA type liquid crystal display, but also suitable for the application of a liquid crystal alignment film manufactured by a rubbing process or a photo-alignment process. Yes.

  The liquid crystal includes, for example, nematic liquid crystal or smectic liquid crystal. Specific examples of the liquid crystal include nematic liquid crystal having a positive dielectric anisotropy. Examples thereof include biphenyl-based liquid crystal and phenyl cyclohexane-based liquid crystal. , Ester liquid crystals, terphenyl liquid crystals, biphenyl cyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, Bicyclooctane-based liquid crystal, cubane-based liquid crystal, or a combination of these liquid crystals may be used, but the present invention is not limited thereto. In addition, in the liquid crystal described above, cholesteric liquid crystal such as cholesteryl chloride, cholesteryl nonabenzoate, cholesteryl carbonate; trade name “C-15” or “CB-15” (Chiral agent sold by Merck); or p-decyloxybenzylidene-p-amino-2-p-decyloxybenzylidene-p-amino-2- A ferroelectric liquid crystal such as methyl butyl cinnamate may be further added.

  Specific examples of the liquid crystal include a liquid crystal having negative dielectric anisotropy, and examples thereof include a dicyanobenzene-based liquid crystal and a pyridazine-based liquid crystal. , Schiff base-based liquid crystal, azoxy-based liquid crystal, biphenyl-based liquid crystal, phenyl cyclohexane-based liquid crystal, or these The combination of the liquid crystal is mentioned.

The invention is further illustrated by the following examples. It should be understood, however, that these examples are merely examples and are not intended to limit the practice of the invention.
Synthetic synthesis example A-1-1 of polymer (A)

A nitrogen injection port, a stirrer, a condenser tube, and a thermometer are installed in a 500 ml four-necked flask to introduce nitrogen gas. In a four-necked flask, 0.01 mol of a2-1-1, 0.0375 mol of p-diaminobenzene (hereinafter referred to as a2-2-1), 0.0025 mol of a2-2. -6, and 80 g N-methyl-2-pyrrolidone (NMP) are added and stirred at room temperature until the ingredients are dissolved. Next, 0.05 mol of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (hereinafter referred to as a1-1) and 20 g of NMP are added, and the mixture is allowed to react at room temperature for 2 hours. After the reaction is completed, the reaction solution is poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer is filtered, and washing with methanol and filtration are repeated three times. Then, the polymer is placed in a vacuum oven and dried at a temperature of 60 ° C. to obtain a polymer (A-1-1).
Synthesis Example A-1-2 to Synthesis Example A-1-10 and Comparative Synthesis Example A-4-1 to Comparative Synthesis Example A-4-3

The polymers of Synthetic Example A-1-2 to Synthetic Example A-1-10 and Comparative Synthetic Example A-4-1 to Comparative Synthetic Example A-4-3 were prepared in the same steps as Synthetic Example A-1-1. The difference is that the type and amount of the tetracarboxylic dianhydride component and the type and amount of the diamine component are changed (shown in Tables 1 and 2).
Synthesis Example A-2-1

A nitrogen injection port, a stirrer, a condenser tube, and a thermometer are installed in a 500 ml four-necked flask to introduce nitrogen gas. In a four-necked flask, 0.01 mol of a2-1-1, 0.0375 mol of p-diaminobenzene (hereinafter referred to as a2-2-1), 0.0025 mol of a2-2. -6, and 80 g N-methyl-2-pyrrolidone (NMP) are added and stirred at room temperature until the ingredients are dissolved. Next, 0.05 mol of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (hereinafter referred to as a1-1) and 20 g of NMP are added. After the mixture is reacted at room temperature for 6 hours, 97 g NMP, 2.55 g acetic anhydride, and 19.75 g pyridine are added. And temperature is raised to 60 degreeC and a mixture is stirred continuously for 2 hours, and imidation reaction is performed. After the reaction is completed, the reaction solution is poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer is filtered, and washing with methanol and filtration are repeated three times. Then, the polymer is placed in a vacuum oven and dried at a temperature of 60 ° C. to obtain a polymer (A-2-1).
Synthesis Example A-2-2 to Synthesis Example A-2-5

The polymer of Synthesis Example A-2-2 to Synthesis Example A-2-5 was prepared in the same steps as Synthesis Example A-2-1, and the difference was the type and amount of tetracarboxylic dianhydride component And the type and amount of the diamine component were changed (shown in Table 1).
Synthesis Example A-3-1

  A nitrogen injection port, a stirrer, a condenser tube, and a thermometer are installed in a 500 ml four-necked flask to introduce nitrogen gas. Then, in a four-necked flask, 0.025 mol of p-diaminobenzene (hereinafter referred to as a2-2-1) and 40 g of N-methyl-2-pyrrolidone (NMP) were added, and the ingredients were mixed. Stir at room temperature until dissolved. Next, 0.025 mol of pyromellitic dianhydride (hereinafter referred to as a1-3) and 10 g of NMP are added. After the mixture is reacted at room temperature for 6 hours, 50 g NMP, 1.3 g acetic anhydride, and 10 g pyridine are added. And temperature is raised to 60 degreeC and a mixture is stirred continuously for 2 hours, and imidation reaction is performed. After the reaction is completed, the reaction solution is poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer is filtered, and washing with methanol and filtration are repeated three times. Then, the polymer is placed in a vacuum oven and dried at a temperature of 60 ° C. to obtain a polymer (A-3-1-1).

In a separate 500 ml four-necked flask, a nitrogen inlet, stirrer, condenser, and thermometer are installed to introduce nitrogen gas. Then, in the four-necked flask, the above polymer (A-3-1-1), 0.025 mol of a2-1-4, and 100 g of NMP are added, and room temperature until the components are dissolved. Stir with. Next, 0.025 mol of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (hereinafter referred to as a1-1) and 10 g of NMP are added. After the mixture is reacted at room temperature for 6 hours, 50 g of NMP, 1.3 g of acetic anhydride, and 10 g of pyridine are added and the mixture is reacted at room temperature for 2 hours. After the reaction is completed, the reaction solution is poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer is filtered, and washing with methanol and filtration are repeated three times. Then, the polymer is placed in a vacuum oven and dried at a temperature of 60 ° C. to obtain a polymer (A-3-1).
In Tables 1 and 2, a1-1 2,3,5-tricarboxycyclopentyl acetic acid dianhydride a1-2 1,2,3,4-cyclobutanetetracarboxylic dianhydride a1-3 pyromellitic dianhydride
a2-2-1 p-phenylenediamine a2-2-2 4,4′-diaminodiphenylmethane a2-2-3 4,4′-diaminodiphenyl ether
Synthesis Example of Polysiloxane (B) Containing Cinnamic Acid Group Synthesis Example B-1

A stirrer, a condenser, and a thermometer are installed in a 500 ml three-necked flask. In a three-necked flask, 0.5 mol of 2-glycidoxyethyltrimethoxysilane (hereinafter, GETMS), 0.4 mol of methyltrimethoxysilane (hereinafter, MTMS), 0.1 mol of Dimethyldimethoxysilane (hereinafter, DDMMS) and 600 g of propylene glycol monomethyl ether (hereinafter, PGME) were added, and the mixture was stirred at room temperature while adding an aqueous solution of triethylamine (hereinafter, TEA) (20 g of TEA / 200 g of TEA). H ₂ O) is added within 30 minutes. Then, the three-necked flask is immersed in a 30 ° C. oil bath and stirred for 30 minutes, and then the temperature of the oil bath is raised to 90 ° C. within 30 minutes. When the internal temperature of the solution reaches 75 ° C., the mixture is continuously heated and stirred and polycondensation is carried out for 6 hours. After the reaction is completed, the organic layer is separated and washed with a 0.2 mass% aqueous ammonium nitrate solution to obtain a solution containing a polysiloxane compound.

Then, 0.15 mol of cinnamic acid derivative 5HBPA, 0.05 mol of OCTBA, and 0.2 g of curing accelerator UCAT18X (manufactured by SAN-APRO) are added to the solution containing the polysiloxane compound. Thereafter, the three-necked flask is immersed in an oil bath at 30 ° C. and stirred for 10 minutes, and then the temperature of the oil bath is increased to 115 ° C. within 30 minutes. When the internal temperature of the solution reaches 100 ° C., the mixture is continuously heated and stirred for 24 hours. After the reaction is complete, the organic layer is removed and washed with water. Then, it dries with magnesium sulfate and removes the solvent to obtain a polysiloxane (B-1) containing cinnamic acid groups.
Synthesis Example B-2 to Synthesis Example B-7 and Comparative Synthesis Example B′-1 to Comparative Synthesis Example B′-3

The polymers of Synthetic Example B-2 to Synthetic Example B-7 and Comparative Synthetic Example B′-1 to Comparative Synthetic Example B′-3 are produced in the same steps as Synthetic Example B-1, and are different. The point is that the types and amounts of silane compounds containing epoxy groups, other silane compounds, cinnamic acid derivatives, solvents, catalysts, and curing accelerator solvents were changed, and the reaction temperature and polycondensation time were changed. Yes (shown in Table 3).
The compounds corresponding to the abbreviations in Table 3 are as follows.
GETMS 2-glycidoxyethyltrimethoxysilane
(2-glycidoxyethyltrimethoxy silane)
GBTMS 4-Glycidoxybutyltrimethoxysilane
(4-glycidoxybutyltrimethoxysilane)
ECETS 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
(2- (3,4-epoxycyclohexyl) ethyltrimethoxy silane)
ECEES 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane
(2- (3,4-epoxycyclohexyl) ethyltriethoxysilane)
OXTMS ((3-Ethyl-3-oxetanyl) methoxy) propyltrimethoxysilane
(((3-ethyl-3-oxetanyl) methoxy) propyltrimethoxysilane)
OXTES ((3-Ethyl-3-oxetanyl) methoxy) propyltriethoxysilane
((3-ethyl-3-oxetanyl) methoxy) propyltriethoxysilane)
MTMS methyltrimethoxy silane
DMDMS dimethyldimethoxy silane
PTMS phenyltrimethoxysilane
PTES phenyltriethoxy silane
PGME Propylene glycol monomethyl ether
(Propylene glycol monomethyl ether)
MIBK methylisobutylketone
TEA triethylamine
Examples of Liquid Crystal Alignment Agent, Liquid Crystal Alignment Film, and Liquid Crystal Display Element and Comparative Example Example 1

  100 parts by weight of polymer (A-1-1), 5 parts by weight of polysiloxane (B-1) containing cinnamic acid groups, and 3000 parts by weight of N-methyl-2-pyrrolidone (hereinafter C-1) Weigh. And it stirs continuously at room temperature until it melt | dissolves with a stirring apparatus, The liquid crystal aligning agent of Example 1 is formed.

The liquid crystal display element of Example 1 was evaluated by the following evaluation method, and the results are shown in Table 4.
Examples 2 to 16 and Comparative Examples 1 to 8

The liquid crystal aligning agents of Examples 2 to 16 and Comparative Examples 1 to 8 were respectively prepared in the same steps as in Example 1, and the differences were as shown in Tables 4 and 5, as shown in Table 4 and Table 5. The amount used was changed. The liquid crystal aligning agents obtained in Examples 2 to 16 and Comparative Examples 1 to 8 were evaluated by the following evaluation methods, and the results are shown in Tables 4 and 5.
The compounds corresponding to the abbreviations in Table 4 and Table 5 are as follows.
D-1 N-methyl-2-pyrrolidone (NMP)
D-2 ethylene glycol n-butyl ether
D-3 N, N-dimethylacetamide
E-1 N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane (N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenyl methane)
E-2 N, N-glycidyl-p-glycidyloxyaniline
<Evaluation method>
a. Imidization rate

  The imidation ratio indicates a percentage of the number of imide rings to the total amount of the number of amide acid functional groups and the number of imide rings in the polymer.

The detection method includes dissolving each polymer of the synthesis example in a suitable deuteration solvent (for example, deuterated dimethyl sulfoxide) after drying under reduced pressure. Then, at room temperature (e.g., 25 ° C.) to detect the ¹ H- nuclear magnetic resonance ^{(1 H-nuclear magnetic resonance,} 1 H-NMR) , the use of tetramethylsilane as a reference substance, imide by Equation (1) Determine the conversion rate (%).
Δ1: Peak area generated by chemical shift of NH group protons near 10 ppm Δ2: Peak area derived from other protons α: NH group proton in polymer precursor (polyamic acid) 1 Number of other protons per unit <Impedance>

The prepared liquid crystal aligning agent is dropped on an aluminum dish having a diameter of 32 mm and baked with a heating plate, and then a thin film having a thickness of about 0.01 mm is obtained. Subsequently, the resistance value of the thin film was measured with an AGILENT 4339b High resistance meter, the positive and negative electrodes of the resistance meter were sandwiched between both ends of the aluminum pan containing the thin film, and the measured resistance value was recorded at a voltage of 50 V. The evaluation standards are as follows.
○: Resistance value ≧ 1.0 × 10 ⁻¹⁵ ;
×: Resistance value <1.0 × 10 ⁻¹⁵ .
<Stability of pretilt angle>

  The prepared liquid crystal aligning agent is applied to the transparent electrode surface of the glass substrate containing the ITO film (the liquid crystal aligning film printer is manufactured by Nissha Printing Co., Ltd.) and heated on a heating plate at 80 ° C. for 1 minute (pre-baking) ) After removing the solvent and further heating for 10 minutes on a heating plate at 150 ° C. (post-baking), a coating film having an average film thickness of 600 mm can be obtained. The coating film is placed on a friction machine wound with an artificial fiber cloth and subjected to a friction treatment at a rotational speed of 400 rpm, a lateral movement speed of 3 cm / second, and a fiber length of 0.1 mm. Thereafter, ultrasonic cleaning is performed in ultrapure water for 1 minute, and then drying is performed in an oven at 100 ° C. for 10 minutes to obtain a substrate having a liquid crystal alignment film. The above process is repeated to obtain a pair (two sheets) of substrates having a liquid crystal alignment film.

  Next, an epoxy resin adhesive filled with an alumina sphere having a diameter of 5.5 μm is applied to the outer edge of the substrate having the liquid crystal alignment film, and then the surface of the liquid crystal alignment film is folded face to face to wait for the adhesive to cure. . Then, after filling a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) from a liquid crystal injection port between a pair of substrates, the liquid crystal injection port is sealed with an acrylic photocuring agent. A display element can be obtained.

The initial pretilt angle of the liquid crystal unit produced as described above was measured with a pretilt angle measuring device (manufactured by Optipro, Shintech), and the liquid crystal display element on which the initial pretilt angle was measured was irradiated at a dose of 10,000 J / m ² at 60 ° C. A fluorescent lamp is irradiated and an AC voltage of 20 Vp-p is applied for 20 hours, and the pretilt angle is evaluated by the amount of change before and after, and the evaluation standard is as follows.
A: Change amount of pretilt angle ≦ 1 °;
○: 1 ° <change in pretilt angle ≦ 2 °;
X: Pretilt angle change> 2 °.

  As described above, the present invention has been disclosed by the embodiments. However, the present invention is not intended to limit the present invention, and is within the scope of the technical idea of the present invention so that those skilled in the art can easily understand. Therefore, the scope of patent protection must be determined based on the scope of claims and the equivalent area.

Claims (18)

A polymer (A);
A polysiloxane (B) containing cinnamic acid groups;
A liquid crystal aligning agent comprising a solvent (C) and
The polymer (A) is selected from the group consisting of a polyamic acid polymer, a polyimide polymer, a polyimide block copolymer, and any combination of the above polymers, and the polymer (A) is represented by the formula ( Liquid crystal aligning agent containing the unit represented by Ia).
[In Formula (Ia), Y is a single bond, —COO—, —CONR _d — or —R _j —NR _d —,
R _d is a hydrogen atom or a C _{1 to} C ₁₀ linear or branched alkyl group,
R _j is a single bond or a C _{1 to} C ₁₀ linear or branched alkyl group;
R _a is a single bond, a C ₁ -C ₁₀ linear or branched alkyl group,
Ht is a nitrogen-containing heterocyclic ring,
R _b is a C _{1 to} C ₁₀ linear or branched oxyalkyl group, nitrile group or carbonyl group;
R _c is a C _{1 to} C ₁₀ linear or branched alkyl group, or R _b and R _c may be bonded to each other to form a single ring,
a1 is an integer of 0 to 1,
a2 is an integer of 0 to 2,
When Y is a single bond, a1 is 0;
When Y is —COO—, —CONR _d — or —R _j —NR _d —, a1 is 1 and * is a bonding position. ] The liquid crystal aligning agent of Claim 1 in which the said polymer (A) contains the unit represented by Formula (Ia-1), Formula (Ia-2), or Formula (Ia-3).
[Y is a single bond, —COO—, —CONR _d — or —R _j —NR _d —,
R _d is a hydrogen atom or a C _{1 to} C ₁₀ linear or branched alkyl group,
R _j is a single bond or a C _{1 to} C ₁₀ linear or branched alkyl group;
R _a is a single bond, a C ₁ -C ₁₀ linear or branched alkyl group,
R _b is a C _{1 to} C ₁₀ linear or branched oxyalkyl group, nitrile group or carbonyl group;
R _c is a C _{1 to} C ₁₀ linear or branched alkyl group, or R _b and R _c may be bonded to each other to form a single ring,
a1 is an integer of 0 to 1,
a2 is an integer of 0 to 2,
When Y is a single bond, a1 is 0;
When Y is —COO—, —CONR _d — or —R _j —NR _d —, a1 is 1 and * is a bonding position. ] The liquid crystal aligning agent of Claim 1 in which the polysiloxane (B) containing the said cinnamic acid group contains the unit represented by Formula (IIa).
(R is a fluorine atom or a cyano group;
a is an integer of 0 to 4, and * is a bonding position. ) The liquid crystal aligning agent of Claim 1 in which the polysiloxane (B) containing the said cinnamic acid group contains the unit represented by Formula (IIa-1) or Formula (IIa-2).
[In Formula (IIa-1) and Formula (IIa-2),
R is a fluorine atom or a cyano group,
a is an integer from 0 to 4 and * is the bond position;
In Formula (IIa-1), R ¹ is a hydrogen atom, a C ₃ -C ₄₀ monovalent organic group having an alicyclic group, or a C ₁ -C ₄₀ alkyl group, provided that the alkyl group Some or all of the hydrogen atoms may be substituted with fluorine atoms,
X ¹ is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-, wherein + indicates the position at which R ¹ is bonded;
R ² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group,
X ² is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-, wherein + indicates a position bonded to R ² , and b is an integer of 0 to 3;
In the formula (IIa-2), R ³ is a hydrogen atom, a C ₃ -C ₄₀ monovalent organic group having an alicyclic group, or a C ₁ -C ₄₀ alkyl group, provided that the alkyl group Some or all of the hydrogen atoms may be substituted with fluorine atoms,
X ³ is an oxygen atom or a divalent aromatic group,
R ⁴ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group,
X ⁴ is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-, wherein + indicates the position bonded to R ⁴ , and c is an integer of 0 to 3. ]   The liquid crystal aligning film formed with the liquid crystal aligning agent of any one of Claims 1-4.   A liquid crystal display element comprising the liquid crystal alignment film according to claim 5. A method for producing a liquid crystal aligning agent comprising mixing a polymer (A), a polysiloxane (B) containing a cinnamic acid group, and a solvent (C),
The polymer (A) is produced by reacting a mixture containing a tetracarboxylic dianhydride component (a1) and a diamine component (a2),
The manufacturing method of the liquid crystal aligning agent in which this diamine component (a2) contains at least 1 type of diamine compound (a2-1) represented by Formula (Ib).
[In Formula (Ib),
Y is a single bond, —COO—, —CONR _d — or —R _j —NR _d —,
R _d is a hydrogen atom or a C _{1 to} C ₁₀ linear or branched alkyl group,
R _j is a single bond or a C _{1 to} C ₁₀ linear or branched alkyl group;
R _a is a single bond, a C ₁ -C ₁₀ linear or branched alkyl group,
Ht is a nitrogen-containing heterocyclic ring,
R _b is a C _{1 to} C ₁₀ linear or branched oxyalkyl group, nitrile group or carbonyl group;
R _c is a C _{1 to} C ₁₀ linear or branched alkyl group, or R _b and R _c may be bonded to each other to form a single ring,
a1 is an integer of 0 to 1,
a2 is an integer of 0 to 2,
When Y is a single bond, a1 is 0, and when Y is —COO—, —CONR _d —, or —R _j —NR _d —, a1 is 1. ] The liquid crystal alignment of Claim 7 in which the said diamine component (a2) contains the diamine compound (a2-1) represented by a formula (Ib-1), a formula (Ib-2), or a formula (Ib-3). Manufacturing method.
[Where:
Y is a single bond, —COO—, —CONR _d — or —R _j —NR _d —,
R _d is a hydrogen atom or a C _{1 to} C ₁₀ linear or branched alkyl group,
R _j is a single bond or a C _{1 to} C ₁₀ linear or branched alkyl group;
R _a is a single bond, a C ₁ -C ₁₀ linear or branched alkyl group,
R _b is a C _{1 to} C ₁₀ linear or branched oxyalkyl group, nitrile group or carbonyl group;
R _c is a C _{1 to} C ₁₀ linear or branched alkyl group, or R _b and R _c may be bonded to each other to form a single ring,
a1 is an integer of 0 to 1,
a2 is an integer of 0 to 2,
When Y is a single bond, a1 is 0, and when Y is —COO—, —CONR _d —, or —R _j —NR _d —, a1 is 1. ]   The method for producing a liquid crystal aligning agent according to claim 7, wherein the polysiloxane (B) containing a cinnamic acid group is obtained by reacting a polysiloxane (b1) containing an epoxy group with a cinnamic acid derivative (b2). . The polysiloxane (b1) containing the epoxy group is composed of a group represented by the formula (2-1), a group represented by the formula (2-2), and a group represented by the formula (2-3). The method for producing a liquid crystal aligning agent according to claim 9, comprising at least one selected from the group.
[In Formula (2-1), B represents an oxygen atom or a single bond,
m represents an integer of 1 to 3,
n represents an integer of 0 to 6, provided that when n represents 0, B is a single bond. ]
[In Formula (2-2), p shows the integer of 0-6. ]
[In Formula (2-3), D represents an alkylene group having 2 to 6 carbon atoms, and
E represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ] The polysiloxane (b1) containing the epoxy group contains a copolymer formed by hydrolysis and partial condensation of a mixture containing a silane monomer (b1-1) represented by the following structural formula (1-1) The manufacturing method of the liquid crystal aligning agent of Claim 9.
Si (R _e ) _w1 (OR _f ) _4-w1 formula (1-1)
(Where:
R _e represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkyl group containing an epoxy group, or an alkoxy group containing an epoxy group. And at least one R _e is an alkyl group containing an epoxy group or an alkoxy group containing an epoxy group, and when R _e is plural, each may be the same or different,
R _f represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and when R _f is plural, They may be different, and w1 represents an integer of 1 to 3. ) The liquid crystal aligning agent according to claim 9, wherein the cinnamic acid derivative (b2) is at least one selected from the group consisting of compounds represented by formulas (3-1) to (3-2). Method.
[In Formula (3-1) and Formula (3-2),
R is a fluorine atom or a cyano group, and a is an integer of 0 to 4,
In Formula (3-1), R ¹ is a hydrogen atom, a C ₃ -C ₄₀ monovalent organic group having an alicyclic group, or a C ₁ -C ₄₀ alkyl group, provided that the alkyl group Some or all of the hydrogen atoms may be substituted with fluorine atoms,
X ¹ is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-, wherein + indicates the position at which R ¹ is bonded;
R ² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group,
X ² is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-, wherein + indicates a position bonded to R ² , and b is an integer of 0 to 3;
X ⁵ is a single bond, an oxygen atom, a sulfur atom, a methylene group, a C _{2 to} C ₁₀ alkylene group, a C _{2 to} C ₁₀ alkenylene group or a divalent aromatic group,
When X ⁵ is a single bond, h is 1 and R ⁵ is a hydrogen atom;
When X ⁵ is a methylene group, an alkylene group, an alkenylene group or a divalent aromatic group, h is 0 or 1, and R ⁵ is a carboxyl group, a hydroxyl group, —SH, —NCO, —NHR ′, —CH = CH ₂ or _-SO 2 Cl, provided that, R 'is hydrogen atom or an alkyl group of _C 1 -C _6,
In the formula (3-2), R ³ is a hydrogen atom, a C _{3 to} C ₄₀ monovalent organic group having a cycloaliphatic group or a C _{1 to} C ₄₀ alkyl group, provided that the alkyl group Some or all of the hydrogen atoms may be substituted with fluorine atoms,
X ³ is an oxygen atom or a divalent aromatic group,
R ⁴ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group,
X ⁴ is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-, wherein + indicates the position to bond with R ⁴ , and c is an integer of 0 to 3;
R ⁶ is a divalent aromatic group, a divalent heterocyclic group or a divalent condensed cyclic group,
X ⁶ is an oxygen atom, —COO— ⁺ or —OCO— ⁺ , wherein + represents a position bonded to R ⁶ ;
k is an integer of 0 to 3 and R ⁷ is a carboxyl group, a hydroxyl group, —SH, —NCO, —NHR ′, —CH═CH ₂ or —SO ₂ Cl, where R ′ is , A hydrogen atom or a C _{1 to} C ₆ alkyl group, and X ⁷ is a single bond, —OCO— (CH ₂ ) _i − ⁺ or —O— (CH ₂ ) _j − ⁺ , provided that i And j each represents an integer of 0 to 10, and + represents a position where R ⁷ is bonded. ]   The liquid crystal alignment of Claim 7 whose usage-amount of the diamine compound (a2-1) represented by the said Formula (Ib) is 20-60 mol with respect to 100 mol of total moles of the said diamine component (a2). Manufacturing method.   The manufacturing method of the liquid crystal aligning agent of Claim 11 whose usage-amount of the said silane monomer (b1-1) is 0.5-1 mol with respect to 1 mol of monomers whole quantity in the said mixture.   The method for producing a liquid crystal aligning agent according to claim 11, wherein the total amount of monomers in the mixture is 1 mol, and the amount of the cinnamic acid derivative (b2) used is 0.15 to 0.5 mol.   The amount of the polysiloxane (B) containing a cinnamic acid group is 5 to 30 parts by weight and the amount of the solvent (C) is 1500 to 4000 parts by weight with respect to 100 parts by weight of the polymer (A). The manufacturing method of the liquid crystal aligning agent of Claim 7.   It is a manufacturing method of the liquid crystal aligning film including forming a liquid crystal aligning film with a liquid crystal aligning agent, Comprising: This liquid crystal aligning agent is formed with the manufacturing method of the liquid crystal aligning agent of any one of Claims 7-16. A method for producing a liquid crystal alignment film.   It is a manufacturing method of the liquid crystal display element containing a liquid crystal aligning film, Comprising: Forming this liquid crystal aligning film with the liquid crystal aligning agent formed by the manufacturing method of the liquid crystal aligning agent of any one of Claims 7-16 The manufacturing method of a liquid crystal display element containing this.