JP5556396B2 - Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, compound and method for producing the compound - Google Patents

Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, compound and method for producing the compound Download PDF

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JP5556396B2
JP5556396B2 JP2010130557A JP2010130557A JP5556396B2 JP 5556396 B2 JP5556396 B2 JP 5556396B2 JP 2010130557 A JP2010130557 A JP 2010130557A JP 2010130557 A JP2010130557 A JP 2010130557A JP 5556396 B2 JP5556396 B2 JP 5556396B2
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JP2011070161A (en
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克博 内山
利之 秋池
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Jsr株式会社
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Description

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

  Liquid crystal display elements are widely used in liquid crystal display devices such as mobile phones and liquid crystal televisions because they have advantages such as low power consumption and easy miniaturization and flattening. As a display mode of such a liquid crystal display device, for example, Patent Documents 1 to 4 disclose Twisted Nematic type (TN type), Super Twisted Nematic type (STN type), In-Plane Switching type (in accordance with changes in the alignment state of liquid crystal molecules. A liquid crystal display device having a liquid crystal cell such as an IPS type or a vertical alignment type (VA type) is disclosed. In any display mode, since the alignment state of the liquid crystal molecules is controlled by the liquid crystal alignment film, the characteristics of the liquid crystal alignment film and the liquid crystal alignment agent used as the material of the liquid crystal alignment film are the characteristics of the liquid crystal display element. Affects the expression of.

  It is known that the ability to vertically align liquid crystal molecules of a liquid crystal alignment film (vertical alignment) is manifested by using a liquid crystal aligning agent containing a polymer having a bulky substituent in the side chain. For example, Patent Document 5 uses a large amount of a monomer such as 1-octadecyloxy-2,4-diaminobenzene having a bulky substituent (hereinafter sometimes referred to as “pretilt angle-expressing monomer”), A liquid crystal aligning agent capable of forming a liquid crystal alignment film exhibiting stable vertical alignment by synthesizing a polymer is disclosed. However, such a liquid crystal aligning agent may deteriorate printability, and it is considered difficult to achieve both good vertical alignment and printability.

  In addition, for the purpose of realizing a liquid crystal display element excellent in high voltage holding ratio and weather resistance (resistance to deterioration in electrical characteristics and display quality due to heat and light stress due to long-time driving), together with polyamic acid or polyimide, Liquid crystal aligning agents containing polyfunctional epoxy compounds are disclosed (see Patent Documents 6 and 7).

  On the other hand, substrates with defects such as coating pinholes and coating unevenness that occur in the manufacturing process of the liquid crystal alignment film may peel off the coating for reuse (rework). The peelability of the liquid crystal alignment film is required. However, when a liquid crystal aligning agent containing a large amount of the above-mentioned polyfunctional epoxy compound is used, the releasability of the liquid crystal alignment film at the time of rework may be reduced due to the crosslinking reaction of the epoxy group during baking.

  Under such circumstances, a liquid crystal aligning agent that can form a liquid crystal alignment film that has both good vertical alignment and printability, is excellent in voltage holding ratio and weather resistance, and can be easily peeled off during rework when defects occur. Development is desired.

JP-A-4-153622 JP 60-107020 A JP 56-91277 A US Pat. No. 5,928,733 JP-A-6-136122 Japanese Patent No. 3799700 JP 2008-299318 A

  The present invention has been made based on the above circumstances, and its purpose is to sufficiently satisfy the characteristics such as vertical alignment, voltage holding ratio, and weather resistance required for practical use as a liquid crystal display element. , And a liquid crystal alignment film that can be easily peeled off during rework when a defect occurs, a liquid crystal aligning agent excellent in printability suitable as a material for forming the liquid crystal alignment film, a liquid crystal display element including the liquid crystal alignment film, a compound, and production of the compound The provision of a method.

The invention made to solve the above problems is
[A] At least one polymer selected from the group consisting of polyamic acid and polyimide, and [B] a liquid crystal aligning agent containing a compound represented by the following formula (1).
(In the formula (1), R is each independently a hydrogen atom, a methylol group, group .Q an alkoxymethyl group, or -CH 2 OQ having 2 to 7 carbon atoms represented by the following formula (2 a) Provided that at least one of R is —CH 2 OQ.)
(In the formula (2 a ),
R I is an alkyl group having 4 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton.
R II is a cyclohexylene group or a phenylene group.
Z I is a single bond, —O—, * —COO— or * —OCO—. However, bond marked with * is R I side.
Z II is —O—, * —COO— or * —OCO—. However, bond marked with * is R I side.
n1 is an integer of 1 to 3. n2 is 0 or 1. n3 is an integer of 0-2. n4 is 0 or 1. Provided that when n1 is 2 or more, each independently plurality of R II satisfy the above definition. When n2 and n4 are 0, R I is an alkyl group having 7 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton. )

  When the liquid crystal aligning agent contains the [A] polymer and the [B] compound, the liquid crystal display element sufficiently satisfies characteristics such as vertical alignment, voltage holding ratio, and weather resistance required for practical use as a liquid crystal display element. In addition, it is possible to form a liquid crystal alignment film that can be easily peeled off during rework when defects occur. In addition, the liquid crystal aligning agent is excellent in printability, hardly causes printing unevenness when printed on a substrate, and can contribute to imparting uniform and good vertical alignment.

The [B] compound contained in the liquid crystal aligning agent includes (b1) a compound represented by the following formula (1x) (hereinafter sometimes referred to as “(b1) compound”) and (b2) the following formula (2 ) (Hereinafter, sometimes referred to as “(b2) compound”).
(In Formula (1x), each R x is independently a hydrogen atom, a methylol group, or an alkoxymethyl group having 2 to 7 carbon atoms, provided that at least one of R x is a methylol group or 2 to 7 carbon atoms. Of the alkoxymethyl group.)
(In formula (2), Q is a group represented by the above formula (2 a ).)

  The [B] compound can be easily obtained by reacting the compound (b1) with the compound (b2).

N4 is preferably 0. Q is more preferably at least one selected from the group consisting of groups represented by the following formulas ( 2a- 1) to ( 2a- 5).
(In the formulas (2 a -1) to (2 a -5), R z is an alkyl group having 7 to 40 carbon atoms or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton, and R y is the number of carbon atoms. 4 to 40 alkyl groups.)

  When the compound [B] has the specific group, the liquid crystal alignment film has increased rigidity and is more excellent in weather resistance.

  It is preferable that the usage-amount of a [B] compound is 0.1 to 100 mass parts with respect to 100 mass parts of [A] polymers. By including a specific amount of the non-polar [B] compound as described above with respect to the polar [A] polymer, it is possible to further improve the re-workability in rework when a pretilt angle appears and a defect occurs. .

  A liquid crystal alignment film formed from the liquid crystal alignment agent and a liquid crystal display device including the liquid crystal alignment film are also suitably included in the present invention. The liquid crystal display element can be suitably applied to various devices, and is used for display devices such as a desk calculator, a wristwatch, a table clock, a counting display board, a word processor, a personal computer, and a liquid crystal television.

The present invention includes a compound represented by the following formula (1).
(In the formula (1), R is each independently a hydrogen atom, a methylol group, group .Q an alkoxymethyl group, or -CH 2 OQ having 2 to 7 carbon atoms represented by the following formula (2 a) Provided that at least one of R is —CH 2 OQ.)
(In the formula (2 a ),
R I is an alkyl group having 4 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton.
R II is a cyclohexylene group or a phenylene group.
Z I is a single bond, —O—, * —COO— or * —OCO—. However, bond marked with * is R I side.
Z II is —O—, * —COO— or * —OCO—. However, bond marked with * is R I side.
n1 is an integer of 1 to 3. n2 is 0 or 1. n3 is an integer of 0-2. n4 is 0 or 1. Provided that when n1 is 2 or more, each independently plurality of R II satisfy the above definition. When n2 and n4 are 0, R I is an alkyl group having 7 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton. )

  The said compound can be conveniently used as components, such as a liquid crystal aligning agent for forming a liquid crystal aligning film.

This invention includes the manufacturing method of the said compound which has a process with which the compound represented by a following formula (1x) and the compound represented by a following formula (2) are made to react.
(In Formula (1x), each R x is independently a hydrogen atom, a methylol group, or an alkoxymethyl group having 2 to 7 carbon atoms, provided that at least one of R x is a methylol group or 2 to 7 carbon atoms. Of the alkoxymethyl group.)
(In formula (2), Q is a group represented by the above formula (2 a ).)

  According to the present invention, liquid crystal alignment that sufficiently satisfies the characteristics required for practical use as a liquid crystal display element, such as vertical alignment, voltage holding ratio, and weather resistance, and is easy to peel off in rework when a defect occurs. A film, a liquid crystal aligning agent excellent in printability suitable as a material for forming the liquid crystal alignment film, a liquid crystal display element including the liquid crystal alignment film, a compound, and a method for producing the compound can be provided. Therefore, the liquid crystal display element of the present invention can be effectively applied to various devices, and is used for display devices such as desk calculators, watches, table clocks, counting display boards, word processors, personal computers, and liquid crystal televisions.

  Hereinafter, embodiments of the present invention will be described in detail.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention includes [A] at least one polymer selected from the group consisting of polyamic acid and polyimide (hereinafter sometimes referred to as “[A] polymer”), and [B] the above formula. The compound represented by (1) (hereinafter sometimes referred to as [B] compound) is contained. Moreover, the said liquid crystal aligning agent may contain arbitrary components, unless the effect of this invention is impaired. Hereinafter, the [A] polymer, the [B] compound and optional components will be described in detail.

<[A] polymer>
[A] The polyamic acid as a polymer is obtained by reacting a tetracarboxylic dianhydride and a diamine, and the polyimide is obtained by dehydrating and ring-closing the polyamic acid. Hereinafter, tetracarboxylic dianhydride and diamine will be described in detail.

[Tetracarboxylic dianhydride]
Examples of the tetracarboxylic dianhydride include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetra. Carboxylic dianhydride, 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-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 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-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-furanyl) -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, bicyclo [ 2.2.2] -Oct-7-ene-2,3,5,6-teto Carboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5 -Dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6- Dianhydride, 4,9-dioxatricyclo [5.3.1.0 2,6 ] undecane-3,5,8,10-tetraone, the following formula (T-1), formula (T-2) A compound represented by: pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Water, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenyl Silane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) ) Diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′ , 3,3'-Bife Nyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine 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 (anhydrotrimellitate), propylene glycol -Bis (anhydro trimellitate), 1,4-butanediol-bis (anhydro trimellitate), 1,6-hexanediol-bis (anhydro trimellitate), 1,8-octanediol-bis (Anhydro trimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis ( Emissions hydro trimellitate), and compounds represented by the following formula (T-3) ~ formula (T-6) are mentioned. These can be used alone or in combination of two or more.

In the above formula, R 1 and R 3 are each independently a divalent organic group having an aromatic ring. R 2 and R 4 are each independently a hydrogen atom or an alkyl group.

  Examples of the compounds represented by the above formulas (T-1) and (T-2) include compounds represented by the following formulas (T-1-1) to (T-2-1).

Among these tetracarboxylic dianhydrides, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro -5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8 -Dimethyl-5- (te Lahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2.2.2] -oct-7-ene-2,3,5 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- ( 2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5 : 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 2,6 ] undecane-3,5,8,10-tetraone, pyromellitic dianhydride, 3,3 ′ , 4,4'-benzophenonetetracarboxylic dianhydride, 3 3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride , At least one selected from the group consisting of the compounds represented by the above formulas (T-1-1) to (T-1-3) and formula (T-2-1) It is preferable to use “anhydride”) in that good liquid crystal orientation can be expressed.

Specific tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5, 9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro- 8-Methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2 , 4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, 5,6 tricarboxy-2-carboxymethyl norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 2, 6] undecane -3, At least one selected from the group consisting of a compound represented by 5,8,10-tetraone, pyromellitic dianhydride and the above formula (T-1-1) is preferable.

  The use ratio of the specific tetracarboxylic dianhydride is preferably 10 mol% or more, more preferably 20 mol% or more, particularly preferably 40 mol% or more, based on the total tetracarboxylic dianhydride. Most preferably, only acid dianhydride is used.

[Diamine]
Examples of the diamine include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenylsulfone, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4 ′ -Diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-ditrifluoromethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) ) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3,3-trimethylin Dan, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] Propane, 2,2-bis [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, 4,4′-bis (4-aminophenoxy) biphenyl, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminophen Orene, 9,9-dimethyl-2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5 5′-tetrachloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoromethylphenoxy) Phenyl] hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-bis [(4-amino-2-trifluoromethyl) phenoxy ] -Octafluorobiphenyl, 3,5-diaminobenzoic acid, 1,4-bis- (4-aminophenyl) -piperazine, compounds represented by the following formulas (D-1) to (D-5), and the like Aromatic diamines of

(In Formula (D-4), y is an integer of 2 to 12. In Formula (D-5), z is an integer of 1 to 5 repetitions.)

1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, Tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylene methylenediamine, tricyclo [6.2.1.0 2,7 ] -undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine) Aliphatic and alicyclic diamines such as 1,3-bis (aminomethyl) cyclohexane and 1,4-bis (aminomethyl) cyclohexane;
2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4 -Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3 , 5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl -S-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6- Aminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6 Phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl -3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N Two primary compounds in the molecule such as' -dimethyl-benzidine, a compound represented by the following formula (D-6), and a compound represented by the following formula (D-7) Amino group and a diamine having a nitrogen atom other than the primary amino group;

(In the formula (D-6), R 5 is a monovalent organic group having a ring structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine, piperidine and piperazine. X 1 is divalent. R 6 is an alkyl group having 1 to 4 carbon atoms, and a1 is an integer of 0 to 3.)

(In the formula (D-7), R 7 is a pyridine, pyrimidine, triazine, a divalent organic group having a ring structure containing a nitrogen atom selected from the group consisting of piperidine and piperazine .X 2 is independently R 8 is independently an alkyl group having 1 to 4 carbon atoms, and a 2 is independently an integer of 0 to 4.)

  A substituted phenylenediamine such as a compound represented by the following formula (D-8);

(In the formula (D-8), R 9 is —O—, —COO— * , —OCO— * , —NHCO— * , —CONH— * or CO— provided that the bond marked with * is R 10 is bonded to R 10. R 10 is a monovalent organic group having a skeleton or a group selected from the group consisting of a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group and a fluorophenyl group, or a carbon number of 6 to 30. R 11 is an alkyl group having 1 to 4 carbon atoms, and a3 is an integer of 0 to 3.)

  And diaminoorganosiloxanes such as compounds represented by the following formula (D-9). These can be used alone or in combination of two or more.

(In Formula (D-9), R 12 is each independently a hydrocarbon group having 1 to 12 carbon atoms, p is each independently an integer of 1 to 3. q is 1 to 20) (It is an integer.)

The benzene ring of the aromatic diamine may be substituted with one or two or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group). As R < 6 >, R < 8 > and R < 11 > in the said Formula (D-6), (D-7), and (D-8), a methyl group is respectively preferable. Each of a1, a2 and a3 is preferably 0 or 1, more preferably 0.

The monovalent organic group having a steroid skeleton of R 10 in the above formula (D-8) is preferably those having 17 to 51 carbon atoms, and more preferably those having 17 to 30 carbon atoms. Examples of R 10 having such a steroid skeleton include cholestane-3-yl group, cholesta-5-en-3-yl group, cholesta-24-en-3-yl group, and cholesta-5,24-diene-3- Yl group, lanostane-3-yl group and the like.

  Examples of the compound represented by the above formula (D-6) and formula (D-7) include compounds represented by the following formulas (D-6-1) and (D-7-1).

  Examples of the compound represented by the formula (D-8) include dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, and octadecanoxy-2,5-diamino. Benzene, dodecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene and the following formulas (D-8-1) to formula ( And a compound represented by D-8-9).

  Among these diamines, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4, , 4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropyl Pyridene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1 , 3-bis (aminomethyl) cyclohexane, 3,5-diaminobenzoic acid, 1,4-bis- (4-aminophenyl) -piperazine, represented by each of the above formulas (D-1) to (D-5) 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N′-bis (4-a Nophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, N′-dimethylbenzidine, a compound represented by the above formula (D-6-1), and the above formula (D-7-1). And at least one selected from the group consisting of 1,3-bis (3-aminopropyl) -tetramethyldisiloxane (hereinafter sometimes referred to as “specific diamine (1)”), What contains at least 1 type (henceforth a "specific diamine (2)") selected from the group which consists of a compound represented by a formula (D-8) is preferable.

  Specific diamine (1) includes p-phenylenediamine, 4,4′-diaminodiphenylmethane, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-ditrifluoromethyl-4,4′-. Diaminobiphenyl, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis (4-aminophenyl) hexafluoropropane 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3- Bis (aminomethyl) cyclohexane, compounds represented by the above formulas (D-1) to (D-3), 2,6-diamy Pyridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N, N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, Selected from the group consisting of N'-dimethylbenzidine, 3,5-diaminobenzoic acid, 1,4-bis- (4-aminophenyl) -piperazine and 1,3-bis (3-aminopropyl) -tetramethyldisiloxane At least one of the above is preferred.

  As specific diamine (2), said Formula (D-8-1), Formula (D-8-3), Formula (D-8-4), Formula (D-8-7), and Formula (D-8) At least one selected from the group consisting of compounds represented by -8) is preferred.

  As the usage-amount of the said specific diamine (1) used when synthesize | combining the polyamic acid in the said liquid crystal aligning agent, 10 mol% or more is preferable with respect to all the diamines, 20 mol% or more is more preferable, 40 mol%. The above is particularly preferable. Moreover, as the usage-amount of the said specific diamine (2), 1 mol%-60 mol% are preferable with respect to all the diamines, 5 mol%-50 mol% are more preferable, 8 mol%-40 mol% are especially. preferable.

[Synthesis of polyamic acid]
The polyamic acid in the liquid crystal aligning agent can be obtained by reacting the tetracarboxylic dianhydride with a diamine. The ratio of the tetracarboxylic dianhydride and diamine used in the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.5 per 1 equivalent of the amino group contained in the diamine. Equivalent to 2 equivalents are preferred, and 0.7 equivalents to 1.2 equivalents are more preferred.

  The synthetic reaction of polyamic acid is preferably carried out in an organic solvent, and the reaction temperature is preferably −20 ° C. to 150 ° C., more preferably 0 ° C. to 100 ° C. The reaction time is preferably 0.2 hours to 120 hours, more preferably 0.5 hours to 72 hours. The organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ- Examples include aprotic polar solvents such as butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. As the amount of the organic solvent used (a is the total amount of the organic solvent and the poor solvent described later when used in combination), the total amount b of tetracarboxylic dianhydride and diamine is the amount of the reaction solution. The amount is preferably 0.1% by mass to 30% by mass with respect to the total amount (a + b).

  As the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are considered to be poor solvents for polyamic acid, can be used in combination as long as the polyamic acid to be produced does not precipitate. Examples of the poor solvent include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and methyl acetate. , Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl Ether, ethylene glycol mono-i-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether Ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, Examples include trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutylketone, isoamylpropionate, isoamylisobutyrate, diisopentyl ether and the like.

  When the organic solvent and the poor solvent as described above are used in combination when synthesizing the polyamic acid, the use ratio of the poor solvent is preferably 25% by mass or less, and preferably 10% by mass with respect to the total of the organic solvent and the poor solvent. The following is more preferable.

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. When polyamic acid is dehydrated and cyclized into a polyimide, the above reaction solution may be directly subjected to dehydration and cyclization reaction, or may be subjected to dehydration and cyclization reaction after isolating the polyamic acid contained in the reaction solution. Alternatively, the isolated polyamic acid may be purified and then subjected to a dehydration ring closure reaction. The polyamic acid is isolated by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by distilling the organic solvent in the reaction solution under reduced pressure using an evaporator. Done. The polyamic acid can be purified by a method in which the polyamic acid is dissolved again in an organic solvent and then precipitated with a poor solvent, or a method in which the step of distilling off under reduced pressure with an evaporator is performed once or several times.

[Synthesis of polyimide]
The polyimide that can be contained in the liquid crystal aligning agent can be obtained by dehydrating and ring-closing imidizing polyamic acid obtained by reacting tetracarboxylic dianhydride and diamine.

  Examples of the tetracarboxylic dianhydride and diamine used for the synthesis of polyimide include the same compounds as the tetracarboxylic dianhydride and diamine used for the synthesis of polyamic acid. As the diamine, those containing the specific diamine (1) are preferable, and p-phenylenediamine, 4,4′-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 1,4-bis- (4-aminophenyl)- Selected from the group consisting of piperazine, 2,2′-dimethyl-4,4′-diaminobiphenyl, 1,3-bis (aminomethyl) cyclohexane and 1,3-bis (3-aminopropyl) -tetramethyldisiloxane And a compound represented by the above formula (D-8) (hereinafter referred to as “specific diamine (2 ′)”). ) Is more preferable.

  The amount of the specific diamine (1 ') used is preferably 10 mol% or more, more preferably 20 mol%, particularly preferably 40 mol% or more based on the total diamine. Moreover, as the usage-amount of the said specific diamine (2 '), 1 mol%-60 mol% are preferable with respect to all the diamines, 5 mol%-50 mol% are more preferable, 8 mol%-40 mol% are Particularly preferred.

The polyimide may be a completely imidized product obtained by dehydrating and ring-closing all of the amic acid structure that the polyamic acid as a raw material had, and only a part of the amic acid structure is dehydrated and ring-closed. It may be a partially imidized product having a structure. The imidation ratio of polyimide in the liquid crystal aligning agent is preferably 20% or more, more preferably 35% to 99%, and particularly preferably 45% to 95%. The said imidation rate represents the ratio which the number of the imide ring structure accounts with respect to the sum total of the number of the amic acid structures of polyimide, and the number of imide ring structures in percentage. At this time, a part of the imide ring may be an isoimide ring. The imidization rate can be known by 1 H-NMR of polyimide. The imidation rate in the present specification is calculated from the following formula based on 1 H-NMR measured at room temperature using tetramethylsilane as a reference substance after polyimide was sufficiently dried at room temperature under reduced pressure and then dissolved in deuterated dimethyl sulfoxide. Obtained by (1).
Imidation ratio (%) = {1- (A 1 / A 2 ) × α} × 100 (1)

In the above formula (1), A 1 is a peak area derived from protons of NH groups appearing near a chemical shift of 10 ppm, A 2 is a peak area derived from other protons, and α is a polyimide precursor (polyamic acid). Is the number ratio of other protons to one proton in the NH group.

  Dehydration and ring closure of polyamic acid for synthesizing the polyimide can be performed by (i) heating the polyamic acid or (ii) dissolving the polyamic acid in an organic solvent, and adding a dehydrating agent and a dehydrating ring closure catalyst to this solution. And it is performed by the method of heating as needed.

  As reaction temperature in the method of (i), 50 to 200 degreeC is preferable and 60 to 170 degreeC is more preferable. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the resulting polyimide may decrease. The reaction time is preferably 0.5 hours to 168 hours, more preferably 0.5 hours to 72 hours.

  In the method (ii), examples of the dehydrating agent include acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. As a usage-amount of a dehydrating agent, 0.01-20 mol is preferable with respect to 1 mol of repeating units of a polyamic acid.

  Examples of the dehydration ring closure catalyst include tertiary amines such as pyridine, collidine, lutidine, and triethylamine. The amount of the dehydration ring closure catalyst used is preferably 0.01 mol to 10 mol with respect to 1 mol of the dehydrating agent used. Examples of the organic solvent used for the dehydration ring closure reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature for the dehydration ring closure reaction is preferably 0 ° C to 180 ° C, more preferably 10 ° C to 150 ° C. The reaction time is preferably 0.5 hours to 168 hours, more preferably 0.5 hours to 72 hours.

  The polyimide obtained in the method (i) may be used for the preparation of the liquid crystal aligning agent as it is, or may be used for the preparation of the liquid crystal aligning agent after purifying the obtained polyimide. On the other hand, in the above method (ii), a reaction solution containing polyimide is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution. May be used for the preparation of a liquid crystal aligning agent, or may be used for the preparation of a liquid crystal aligning agent after purifying the isolated polyimide. In order to remove the dehydrating agent and the dehydration ring closure catalyst from the reaction solution, for example, a method such as solvent substitution can be applied. The polyimide is isolated and purified by the same operations as described above as the method for isolating and purifying the polyamic acid.

  The polyamic acid or polyimide that can be contained in the liquid crystal aligning agent may be a terminal-modified polymer having a controlled molecular weight. By using the terminal-modified polymer, the coating properties of the liquid crystal aligning agent can be further improved without impairing the effects of the present invention. Such a terminal-modified polymer is obtained by adding a molecular weight regulator to a polymerization reaction system when synthesizing a polyamic acid. Examples of molecular weight regulators include acid monoanhydrides, monoamine compounds, monoisocyanate compounds, and the like.

  Examples of the acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n -Hexadecyl succinic acid anhydride etc. are mentioned.

  Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, Examples include n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-eicosylamine.

  Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

  As a usage-amount of a molecular weight modifier, 10 mass parts or less are preferable with respect to a total of 100 mass parts of tetracarboxylic dianhydride and diamine used when synthesize | combining a polyamic acid, and 6 mass parts or less are more preferable.

  The polyamic acid or polyimide obtained as described above preferably has a solution viscosity of 20 mPa · s to 800 mPa · s, and a solution viscosity of 30 mPa · s to 500 mPa · s, when a 10% by mass solution is obtained. It is more preferable that In addition, the solution viscosity (mPa · s) of the polymer in the present specification is a weight of 10% by mass prepared using a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) of the polymer. The combined solution is a value measured at 25 ° C. using an E-type rotational viscometer.

<[B] Compound>
The [B] compound in the liquid crystal aligning agent is a compound represented by the above formula (1). [B] The compound reacts (b1) 1 mole part of the compound with (b2) compounds 1 to (n-1) mole parts (where n is the number of —CH 2 OQ contained in the (b1) compound). It is preferable to obtain it. Hereinafter, the (b1) compound and the (b2) compound will be described in detail.

[(B1) Compound]
R x in the above formula (1x) is preferably an alkoxymethyl group having 2 to 5 carbon atoms, more preferably a methoxymethyl group, an ethoxymethyl group, or a butoxymethyl group, and particularly preferably a methoxymethyl group.

  Examples of the compound (b1) include alkoxymethylated melamine such as N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine. As commercial products, Cymel 300, Cymel 301, Cymel 303, Cymel 350, Cymel 370, Cymel 325, Cymel 327, Cymel 703, Cymel 712, My Coat 715, Cymel 701, Cymel 285, Cymel 232, Cymel 235, Cymel 236 Cymel 238, Cymel 211, Cymel 254, My Coat 212, Cymel 202, My Coat 508 (MITSU-CYTEC, LTD), and the like.

[(B2) Compound]
The alkyl group having 4 to 40 carbon atoms represented by R I in Q in the above formula (2) is preferably an alkyl group having 5 to 24 carbon atoms, such as a pentyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, stearyl group and the like (where the alkyl group of 7 to 40 carbon atoms indicated R I when n2 and n4 is 0, preferably an alkyl group having 8 to 24 carbon atoms, such as octyl group, decyl Group, dodecyl group, hexadecyl group, stearyl group and the like);
The fluoroalkyl group having 1 to 40 carbon atoms is preferably a fluoroalkyl group having 4 to 20 carbon atoms. For example, trifluoromethylpropyl group, trifluoromethylbutyl group, trifluoromethylhexyl group, trifluoromethyldecyl group, pentafluoro And ethylpropyl group, pentafluoroethylbutyl group, pentafluoroethyloctyl group and the like;
Examples of the hydrocarbon group of 17 to 51 having a steroid skeleton include groups represented by the following formulas (R I- 1) to (R I -3).

In the above formula (R I- 1) to formula (R I -3), the bond marked with * is on the Z I side.

As the cyclohexylene group and phenylene group represented by R II in Q in the above formula (2), a 1,4-cyclohexylene group and a 1,4-phenylene group are preferable. In the above formula (2), as the divalent group represented by- (R II ) n1- , when n1 is 1, 1,4-phenylene group, 1,2-cyclohexylene group and the like are preferable. . When n1 is 2, 4,4′-biphenylene group, 4,4′-bicyclohexylene group, and a group represented by the following formula are preferable.

(Wherein a bond is R I side marked with *.)

  When n1 is 3, a group represented by the following formula is preferred.

(Wherein a bond is R I side marked with *.)

N3 in the above formula (2 a ) is preferably 2. Examples of (b2) compounds include 1-pentanol, 1-hexanol, 1-octanol, 1-dodecanol, stearyl alcohol, 4-dodecylphenol, 4-hexyloxyphenol, 4-octyloxyphenol, 4-decyloxyphenol. 4-dodecyloxyphenol, 4-octadecyloxyphenol, 4-trifluoromethylphenol, 4-trifluoromethoxyphenol, 4-trifluoromethylpropyloxyphenol, 4-trifluoromethylbutyloxyphenol, 4-hexafluoropropyl Examples thereof include oxyphenol and compounds represented by the following formulas (b2-1) to (b2-6).

(In the formulas (b2-2) and (b2-4) to (b2-6), RI has the same meaning as the formula (2 a ).)

  Examples of the organic solvent that can be used for the reaction include the organic solvents exemplified as those used for the synthesis of the polyamic acid. Of these, aprotic organic solvents are preferred, for example, N-methyl-2-pyrrolidone, acetonitrile, dimethyl sulfoxide, N, N-dimethylacetamide, N, N-dimethylformamide, N, N′-dimethylimidazolidinone, dimethyl Examples thereof include sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphotriamide, tetrahydrofuran and the like. The proportion of the organic solvent used is preferably such that the proportion of the total mass of the (b1) compound and (b2) compound in the reaction solution is 1% by mass or more, more preferably 5% by mass to 50% by mass. .

  As reaction temperature, 20 to 250 degreeC is preferable and 50 to 180 degreeC is more preferable. The reaction time is preferably 0.1 hour to 72 hours, more preferably 0.5 hour to 48 hours.

  The obtained solution containing the [B] compound may be used as it is for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after isolating and purifying the [B] compound from the reaction solution. May be. Examples of the method for isolating and purifying the [B] compound from the reaction solution include liquid-liquid extraction method, column chromatography, distillation method, recrystallization and the like.

As a preferable [B] compound in the present invention, a part of —CH 2 OQ possessed by (b1) compound reacts with (b2) compound, and (b1) —CH 2 OQ derived from the compound; (b2) having a group R I derived from the compound. By containing the [B] compound in the liquid crystal aligning agent, a liquid crystal aligning film having excellent vertical alignment can be formed without impairing the printability of the liquid crystal aligning agent.

As the compound [B], the Q is more preferably a compound represented by the above formulas (2 a -1) to (2 a -5).

  The proportion of the [B] compound used in the liquid crystal aligning agent is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the [A] polymer. 1 part by mass to 30 parts by mass is particularly preferable.

<Optional component>
The liquid crystal aligning agent contains the above [A] polymer and [B] compound, and optionally has a compound having at least one epoxy group in the [C] molecule (hereinafter referred to as “[C] epoxy compound”). Optional components such as [D] functional silane compounds, [E] polyfunctional (meth) acrylates, and [F] melamine compounds (excluding [B] compounds). Hereinafter, each component will be described in detail.

[[C] Epoxy compound]
The said [C] epoxy compound can be used from a viewpoint of improving the adhesiveness with respect to the substrate surface of the liquid crystal aligning film formed. Preferred [C] epoxy compounds include, for example, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin 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′-tetraglycidyl-4, Examples include 4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, and the like. [C] As a compounding ratio of an epoxy compound, 30 mass parts or less are preferable with respect to 100 mass parts of [A] polymers, and 0.1 mass part-25 mass parts are more preferable.

[[D] Functional silane compound]
The [D] functional silane compound can be used from the viewpoint of further improving the printability of the liquid crystal aligning agent. [D] Examples of functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl). ) -3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3- Aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1, , 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-aminopropyltriethoxysilane, N-bis (Oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, and the like. [D] The use ratio of the functional silane compound is preferably 2 parts by mass or less, and more preferably 1 part by mass or less with respect to 100 parts by mass of the [A] polymer.

[[E] polyfunctional (meth) acrylate]
[E] The polyfunctional (meth) acrylate can be used from the viewpoint of further improving the weather resistance of the liquid crystal aligning agent. [E] Examples of the polyfunctional (meth) acrylate include ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, trimethylolpropane triacrylate, tri Methylolpropane trimethacrylate, pentaerythritol triacrylate, Taerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acryloyloxyethyl) phosphate, And tri (2-methacryloyloxyethyl) phosphate.

  Examples of commercially available products include Aronix M-210, M-240, M-6200, M-309, -400, -402, -405, -450, -1310, and -1600. -1960, -7100, -8030, -8060, -8100, -8100, -8530, -8560, -9050, Aronix TO-1450 (Toa Gosei Co., Ltd.), KAYARAD HDDA, HX -220, R-604, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, MU-2100, MU-4001, KAYARAD TMPTA , DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, MAX- 3510 (Nippon Kayaku Co., Ltd.), Biscote 260, 312, 335HP, 295, 300, 360, GPT, 3PA, 400 (Osaka Organic Chemical Co., Ltd.), New Frontier R- 1150 (above, Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD DPHA-40H (above, Nippon Kayaku Co., Ltd.) and the like.

  [E] The use ratio of the polyfunctional (meth) acrylate is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, with respect to 100 parts by mass of the [A] polymer.

[[F] Melamine Compound]
The [F] melamine compound can be used from the viewpoint of further improving the weather resistance of the liquid crystal aligning agent. [F] Examples of the melamine compound include the compound (b1). [F] As a use rate of a melamine compound, 100 mass parts or less are preferred to 50 mass parts or less to 100 mass parts of [A] polymer.

<Method for preparing liquid crystal aligning agent>
The liquid crystal aligning agent is prepared as a solution-like composition in which the [A] polymer, the [B] compound, and, if necessary, optional components are preferably dissolved in an organic solvent.

  As an organic solvent, the solvent illustrated as what is used for the synthesis reaction of a polyamic acid is mentioned. Moreover, the poor solvent illustrated as what can be used together in the case of the synthesis reaction of polyamic acid can also be selected suitably, and can be used together. Preferred organic solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, butyl lactate Butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-i-propyl ether, ethylene glycol mono -N-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether. These can be used alone or in combination of two or more. A more preferable solvent composition is a composition obtained by combining the above solvents, in which the [A] polymer, [B] compound, and optional components are not precipitated in the liquid crystal aligning agent, and the surface tension of the liquid crystal aligning agent. Is a composition in the range of 25 mN / m to 40 mN / m.

  The solid content concentration of the liquid crystal aligning agent (the ratio of the total mass of components excluding the organic solvent in the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, and the like. However, it is preferably 1% by mass to 10% by mass. When the liquid crystal aligning agent is applied to the substrate surface and a coating film to be a liquid crystal aligning film is formed by removing the organic solvent, if the solid content concentration is less than 1% by mass, the film of this coating film If the thickness is too small, it may be difficult to obtain a good liquid crystal alignment film. On the other hand, if the solid content concentration exceeds 10% by mass, the film thickness of the coating film becomes excessive and a good liquid crystal alignment film is obtained as well. In some cases, it may be difficult, and the viscosity of the liquid crystal aligning agent may increase, resulting in poor coating characteristics.

  A more preferable solid content concentration range varies depending on a method used when a liquid crystal aligning agent is applied to the substrate. For example, when the spinner method is used, the range of 1.5% by mass to 4.5% by mass is preferable. In the case of using the printing method, the range is preferably 3% by mass to 9% by mass, and the solution viscosity is preferably in the range of 12 mPa · s to 50 mPa · s. In the case of the ink jet method, the range is preferably 1% by mass to 5% by mass, and the solution viscosity is preferably in the range of 3 mPa · s to 15 mPa · s.

  As temperature at the time of preparing the said liquid crystal aligning agent, 0 to 100 degreeC is preferable and 20 to 60 degreeC is more preferable. The liquid crystal aligning agent is preferably used for forming a liquid crystal alignment film used particularly for a vertical alignment type liquid crystal display element.

<Liquid crystal alignment film and method for forming the same>
A liquid crystal alignment film formed from the liquid crystal alignment agent is also suitably included in the present invention. Hereinafter, a method for forming a liquid crystal alignment film using the liquid crystal alignment agent will be described in detail.

  The liquid crystal alignment film of this invention is formed on a board | substrate by apply | coating the said liquid crystal aligning agent on a board | substrate, and heating a coating surface then. Specifically, as a pair of two substrates provided with a patterned transparent conductive film, the liquid crystal aligning agent of the present invention is preferably formed on each transparent conductive film forming surface, preferably a roll coater method, a spinner method, Each of the coated surfaces is coated by a printing method and an inkjet method, and then the coated surface is formed by heating each coated surface. Since the liquid crystal aligning agent is excellent in printability, it is preferable to employ a printing method as a coating method.

  Examples of the substrate include glass substrates such as float glass and soda glass, and transparent substrates including plastic substrates such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and alicyclic olefin.

Examples of the transparent conductive film provided on one surface of the substrate include a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO 2 ), an ITO film made of indium oxide-tin oxide (In 2 O 3 —SnO 2 ), and the like. Can be mentioned.

  As a method for obtaining a patterned transparent conductive film, for example, a method for forming a pattern by photo-etching after forming a transparent conductive film without a pattern, and a method for using a mask having a desired pattern when forming a transparent conductive film Etc. When applying the liquid crystal alignment agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound, a functional titanium compound, etc. A pretreatment for applying in advance may be performed.

  After applying the liquid crystal aligning agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping. As temperature of prebaking, 30 to 200 degreeC is preferable, 40 to 150 degreeC is more preferable, and 40 to 100 degreeC is especially preferable. The prebaking time is preferably from 0.1 minutes to 10 minutes, more preferably from 0.5 minutes to 5 minutes.

  Next, baking (post-baking) is carried out for the purpose of completely removing the solvent and, if necessary, heat imidizing the polyamic acid. As temperature of post-baking, 80 to 300 degreeC is preferable and 120 to 250 degreeC is more preferable. The post-baking time is preferably 1 minute to 300 minutes, and more preferably 2 minutes to 120 minutes. The liquid crystal aligning agent forms a coating film that becomes a liquid crystal aligning film by removing the organic solvent after coating, but the polymer contained in the liquid crystal aligning agent has both a polyamic acid or imide ring structure and an amic acid structure. In the case of a polyimide having a coating film, it may be heated further after the coating film is formed so that the dehydration ring-closing reaction proceeds to form a more imidized coating film.

  As a film thickness of the coating film formed, 0.001 micrometer-1 micrometer are preferable, and 0.005 micrometer-0.5 micrometer are more preferable.

  The coating film thus formed can be used as it is as a liquid crystal alignment film for a vertical alignment type liquid crystal display element, but this coating film surface may optionally be rubbed. The rubbing treatment is performed by rubbing the coating film surface in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton.

<Liquid crystal display element and manufacturing method thereof>
The liquid crystal display element of the present invention includes the liquid crystal alignment film. A preferred operation mode in the liquid crystal display element of the present invention is a vertical alignment type. Hereinafter, a method for producing a vertical alignment type liquid crystal display device including the liquid crystal alignment film of the present invention will be described in detail.

  Two substrates on which the liquid crystal alignment film is formed are prepared, and a liquid crystal cell is manufactured by disposing a liquid crystal between the two substrates opposed to each other. Here, when the rubbing treatment is performed on the coating film, the two substrates are disposed to face each other so that the rubbing directions in the respective coating films are at a predetermined angle, for example, orthogonal or antiparallel. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

  The first method is a conventionally known method. First, two substrates are arranged to face each other through a gap (cell gap) so that the liquid crystal alignment films face each other. A liquid crystal cell can be manufactured by pasting the periphery of the substrate using a sealing agent, injecting and filling the liquid crystal into the cell gap defined by the substrate surface and the sealing agent, and then sealing the injection hole.

  The second method is a technique called an ODF (One Drop Fill) method in which, for example, an ultraviolet light curable material is placed at a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed. After applying a sealing material and dropping liquid crystal on the liquid crystal alignment film surface, the other substrate is bonded so that the liquid crystal alignment film faces, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant. Thus, a liquid crystal cell can be manufactured.

  Regardless of which method is used, the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase, and then gradually cooled to room temperature, so that the flow alignment during liquid crystal injection is achieved. It is desirable to remove. And the said liquid crystal display element is obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell.

  Examples of the sealing agent include an aluminum resin sphere as a spacer and an epoxy resin containing a curing agent.

  Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal. Of these, nematic liquid crystal is preferable. In the case of the VA liquid crystal cell, nematic liquid crystal having negative dielectric anisotropy is preferable. Examples of such liquid crystal include dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, and phenylcyclohexane liquid crystal. In the case of a TN liquid crystal cell or STN liquid crystal cell, a nematic liquid crystal having positive dielectric anisotropy is preferable. Examples of such liquid crystal include biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, and cubane liquid crystal. . Further, chiral agents such as those sold as cholesteric liquid crystals (Merck, “C-15”, “CB-15”) such as cholesteryl chloride, cholesteryl nonate, cholesteryl carbonate, etc. for the above liquid crystal; p-decyloxybenzylidene A ferroelectric liquid crystal such as -p-amino-2-methylbutylcinnamate can be further added and used.

  As a polarizing plate bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film in which a polarizing film called an “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films The polarizing plate which consists of itself is mentioned.

<Compound>
The compound of the present invention is represented by the above formula (1). The said compound can be conveniently used as components, such as a liquid crystal aligning agent for forming a liquid crystal aligning film. The detailed description of the compound and the method for producing the compound is omitted in the description of the [B] compound included in the liquid crystal aligning agent, and is therefore omitted here.

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not interpreted limitedly based on description of this Example.

<[A] Synthesis of polymer>
[Synthesis Example 1 to Synthesis Example 13]
To N-methyl-2-pyrrolidone, diamines and tetracarboxylic dianhydrides of the types and amounts shown in Table 1 below are added in this order to obtain a solution having a monomer concentration of 20% by mass and reacted at 60 ° C. for 4 hours. Thus, a solution containing polyamic acid was obtained. A small amount of each solution was sampled, and N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass is shown in Table 1. Next, after adding pyridine and acetic anhydride to each of the polyamic acid solutions so as to be the number of moles listed in Table 1 with respect to 1 mol of the amic acid unit of the polyamic acid, the solution is heated to 110 ° C. The dehydration ring closure reaction was performed for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone (in this operation, pyridine and acetic anhydride used for the dehydration ring-closing reaction were removed from the system), and polyimide ( A solution containing 16% by mass of PI-1) to (PI-13) was obtained. Table 1 also shows the imidization ratio of each polyimide contained in these polyimide solutions and the solution viscosity measured as an N-methyl-2-pyrrolidone solution having a polyimide concentration of 10% by mass.

[Synthesis Example 14 to Synthesis Example 16]
Except that the types and amounts of diamine and tetracarboxylic dianhydride were changed to the types and amounts shown in Table 1, respectively, the same procedure as in Synthesis Example 1 to Synthesis Example 13 was repeated, and polyamic acid (PA-1) to A solution containing (PA-3) was obtained. A small amount of each solution was sampled, and N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass is also shown in Table 1.

  Abbreviations of diamines and tetracarboxylic anhydrides in Table 1 are as follows.

[Diamine]
d-1: p-phenylenediamine d-2: 4,4′-diaminodiphenylmethane d-3: 2,2′-dimethyl-4,4′-diaminobiphenyl d-4: 1,3-bis (aminomethyl) Cyclohexane d-5: 1,3-bis (3-aminopropyl) tetramethyldisiloxane d-6: diamine d-7 represented by the above formula (D-8-3): above formula (D-8-1) ) [Tetracarboxylic dianhydride]
t-1: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride t-2: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

<Synthesis of [B] Compound>
[Example 1]
After dissolving 320 g of formalin, 8 mL of 1N sodium hydroxide, and 20 g of melamine at 35 ° C., the crystals of hexamethylolmelamine deposited by standing overnight at room temperature are filtered by suction, washed with methanol, and then vacuum dried. 48 g of a purified product of hexamethylolmelamine was obtained. Next, 250 mL of tetrahydrofuran and 130 g of stearyl alcohol were added to this hexamethylolmelamine and heated to 70 ° C., then 1 mL of 0.5N hydrochloric acid was added and reacted for 8 hours, and then neutralized with 0.5N aqueous sodium hydroxide solution. The reaction was terminated. Subsequently, the reaction solution was poured into 2 L of water, and the resulting precipitate was filtered off. The precipitate was purified by a silica column using chloroform / ethanol as a developing solvent, whereby the average number of substitutions of stearyl groups was 1.8. Compound (B-1) was obtained. The average number of substitutions was analyzed by GPC.

[Example 2]
A compound having an average substitution number of a group having a steroid skeleton of 1.0 (B—) except that 93 g of the compound represented by the above formula (b2-3) was used in place of stearyl alcohol, and was operated in the same manner as in Example 1. 2) was obtained.

[Example 3]
A cyclohexylphenyl skeleton was prepared in the same manner as in Example 1 except that 59 g of a compound represented by the above formula (b2-5) (wherein R I is a pentyl group) was used instead of stearyl alcohol. A compound (B-3) having an average number of substitutions of 1.1 was obtained.

[Example 4]
A compound (B-4) having an average octyl group substituent number of 0.4 was obtained in the same manner as in Example 1 except that 10 g of 1-octanol was used instead of stearyl alcohol.

<Preparation of liquid crystal aligning agent>
[Example 5 and Example 5 ']
In a solution containing (PI-1) as an [A] polymer in an amount corresponding to 100 parts by mass in terms of polyimide (PI-1), γ-butyrolactone, N-methyl-2-pyrrolidone and ethylene glycol- A solution containing mono-n-butyl ether and further containing the compound (B-1) as the [B] compound, in an amount corresponding to 5 parts by mass in terms of the [B] compound contained therein, and [C ] As an epoxy compound, 10 parts by mass of N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane was added, and the solvent composition was γ-butyrolactone: N-methyl-2-pyrrolidone: ethylene glycol-mono -N-butyl ether = 40:30:30 (mass ratio) and the solid content concentration obtained the solution of 6.5 mass%. When this solution was visually observed, it was a clear solution without turbidity. A liquid crystal aligning agent for printability evaluation was prepared by filtering this solution using a filter having a pore size of 0.2 μm, and Example 5 was obtained.
Further, in the same manner as described above, the solvent composition was γ-butyrolactone: N-methyl-2-pyrrolidone: ethylene glycol-mono-n-butyl ether = 40: 30: 30 (mass ratio), and the solid content concentration was 4.0% by mass. A liquid crystal aligning agent for evaluating the vertical alignment property and voltage holding ratio was prepared by filtering using a filter having a pore diameter of 0.2 μm, and was designated as Example 5 ′.

[Examples 6 to 19 (6 ′ to 19 ′) and Comparative Examples 1 to 4 (1 ′ to 4 ′)]
The liquid crystal aligning agent was prepared in the same manner as in Example 5 (Example 5 ′) except that the types and amounts used of the compounds to be blended were changed to the types and amounts shown in Table 2, respectively, and the solid content concentration 6.5% by mass of Examples 6 to 19 and Comparative Examples 1 to 4 (solid content of 4.0% by mass of Examples 6 ′ to 19 ′ and Comparative Examples 1 ′ to 4 ′) were used.

<Evaluation of printability>
The transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film using the liquid crystal aligning agent having a solid content concentration of 6.5% by mass prepared above using a liquid crystal alignment film printer (Nissha Printing Co., Ltd., Angstromer). After removing the solvent by heating (pre-baking) on a hot plate at 80 ° C. for 1 minute, heating (post-baking) on a hot plate at 200 ° C. for 10 minutes to form a coating film with an average film thickness of 750 mm Formed. This coating film was visually observed to check the degree of printing unevenness. Here, “++” indicates that no streaky unevenness or surface unevenness is observed on the coating surface, and “+” indicates that a slight amount of streaky unevenness or surface unevenness is visually recognized on the coating surface. The case where streaky unevenness or surface unevenness or both of these were clearly confirmed on the film surface was evaluated as printability “-”. The results are shown in Table 2.

Abbreviations of [C] epoxy compounds and other compounds in Table 2 are as follows.
[[C] Epoxy compound]
C-1: N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane C-2: N, N, N ′, N′-tetraglycidyl-m-xylenediamine [[E] Functional (meth) acrylate]
E-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Aronix M402, Toagosei Co., Ltd.)
[[F] Melamine Compound]
F-1: Hexamethoxymethylolmelamine (Cymel C300, MITSU-CYTEC)
F-2: Melamine having methoxymethylol group, butoxymethylol group and imino group (Cymel C211, MITSU-CYTEC)

<Manufacture of liquid crystal display elements>
The liquid crystal aligning agent having a solid content concentration of 4.0% by mass prepared above was applied onto a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm using a spinner, and then 80 ° C. After heating (pre-baking) on the hot plate for 1 minute to remove the solvent, the film was heated (post-baking) in a clean oven at 200 ° C. for 60 minutes to form a coating film having a thickness of 0.08 μm. The coating film was rubbed with a rubbing machine having a roll wrapped with a rayon cloth under the conditions of a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair foot indentation length of 0.4 mm. The substrate having the rubbed coating film was ultrasonically cleaned in pure water for 1 minute, and further heated and dried in a clean oven at 100 ° C. for 10 minutes to produce a substrate having a rubbed coating film. This series of operations was repeated to produce a pair (two) of substrates having a rubbing-treated coating film. After applying an epoxy resin adhesive containing aluminum oxide spheres with a diameter of 3.5 μm to the outer edges of the coating film forming surfaces of the pair of substrates, both substrates are opposed to the liquid crystal alignment film surface, and each coating film is rubbed. The adhesive was cured by overlapping and pressing so that the directions were antiparallel. Next, a negative type liquid crystal (Merck, MLC-6608) is filled between the substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, and polarizing plates are formed on both sides of the substrate. The liquid crystal display element for vertical alignment evaluation was manufactured by bonding together.

<Vertical alignment evaluation>
About the said liquid crystal display element, the display element was driven, the element was observed visually and vertical alignment property was evaluated. It is known that pre-tilt angle development is reduced by rubbing treatment, but even when rubbing treatment is performed, a liquid crystal alignment film in which good alignment is observed is “+”, and good alignment is observed. The liquid crystal alignment film which did not exist was made into "-". The results are shown in Table 3.

<Evaluation of voltage holding ratio>
In the production of the liquid crystal display element, a liquid crystal display element for voltage holding evaluation was produced in the same manner except that the rubbing treatment and the subsequent ultrapure water cleaning and drying operation were not performed. With respect to this liquid crystal display element, a voltage of 5 V was applied at 60 ° C. with an application time of 60 microseconds and a span of 167 microseconds, and then the voltage holding ratio after 167 milliseconds from release of application was measured. The results are shown in Table 3.

<Evaluation of reworkability of liquid crystal alignment film>
On the transparent conductive film made of ITO provided on one surface of a glass substrate having a thickness of 1 mm, the liquid crystal aligning agent prepared above is applied by a spinner, and prebaked on a hot plate at 100 ° C. for 90 seconds. A coating film of about 0.08 μm was formed. This operation was repeated to prepare two substrates with a coating film. Next, the two obtained substrates were stored in a dark room at 25 ° C. under a nitrogen atmosphere. After 12 hours and 72 hours from the start of storage, they were removed from the dark room and immersed in a beaker containing NMP at 40 ° C. for 2 minutes. After 2 minutes, the substrate was taken out of the beaker and washed several times with ultrapure water, and then water droplets on the surface were removed by air blow, the substrate was observed, and whether a coating film remained was observed with an optical microscope. Remove from the dark room after 72 hours, “++” if the film is not peeled after NMP soaking and has good releasability. The substrate taken out from the dark room after 72 hours could not be removed, but removed from the dark room after 12 hours. Substrates that were peelable were designated as “+” and those that could not be peeled were designated as “−”. The results are shown in Table 3.

<Evaluation of weather resistance>
About the liquid crystal display element manufactured above, after applying a voltage of 5 V at 70 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, a voltage holding ratio after 167 milliseconds after the release of application was measured (Toyo Technica, VHR-1), and the value was defined as the initial voltage holding ratio (VH 1N ). Next, the liquid crystal cell after the initial voltage holding ratio measurement was irradiated with light for 1000 hours using a weather meter using a carbon arc as a light source. For the liquid crystal cell after light irradiation, the voltage holding ratio was measured again by the same method as described above, and the value was defined as the voltage holding ratio after light irradiation (VH AF ). Here, the decrease amount of the voltage holding ratio obtained as VH IN -VH AF was defined as ΔVHR and calculated. When the decrease amount ΔVHR of the voltage holding ratio is less than 2.5%, “++”, when it is 2.5% or more and less than 5%, “+”, when it is 5% or more, “− " The results are shown in Table 3.

  As is clear from the results in Tables 2 and 3, the liquid crystal aligning agent of the present invention was found to be excellent in printability. In addition, the liquid crystal alignment film formed from the liquid crystal alignment agent sufficiently satisfies the characteristics required for practical use as a liquid crystal display element, such as vertical alignment, voltage holding ratio, and weather resistance, and is easy to peel off during rework. I found out

  According to the present invention, liquid crystal alignment that sufficiently satisfies the characteristics required for practical use as a liquid crystal display element, such as vertical alignment, voltage holding ratio, and weather resistance, and is easy to peel off in rework when a defect occurs. A film, a liquid crystal aligning agent excellent in printability suitable as a material for forming the liquid crystal alignment film, a liquid crystal display element including the liquid crystal alignment film, a compound, and a method for producing the compound can be provided. Therefore, the liquid crystal display element of the present invention can be effectively applied to various devices, and is used for display devices such as desk calculators, watches, table clocks, counting display boards, word processors, personal computers, and liquid crystal televisions.

Claims (7)

  1. [A] At least one polymer selected from the group consisting of polyamic acid and polyimide, and [B] a liquid crystal aligning agent containing a compound represented by the following formula (1).
    (In the formula (1), R is each independently a hydrogen atom, a methylol group, group .Q an alkoxymethyl group, or -CH 2 OQ having 2 to 7 carbon atoms represented by the following formula (2 a) Provided that at least one of R is —CH 2 OQ.)
    (In the formula (2 a ),
    R I is an alkyl group having 4 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton.
    R II is a cyclohexylene group or a phenylene group.
    Z I is a single bond, —O—, * —COO— or * —OCO—. However, bond marked with * is R I side.
    Z II is —O—, * —COO— or * —OCO—. However, bond marked with * is R I side.
    n1 is an integer of 1 to 3. n2 is 0 or 1. n3 is an integer of 0-2. n4 is 0 or 1. Provided that when n1 is 2 or more, each independently plurality of R II satisfy the above definition. When n2 and n4 are 0, R I is an alkyl group having 7 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton. )
  2. [B] the compound is
    (B1) a compound represented by the following formula (1x);
    (B2) The liquid crystal aligning agent of Claim 1 which is a reaction product with the compound represented by following formula (2).
    (In Formula (1x), each R x is independently a hydrogen atom, a methylol group, or an alkoxymethyl group having 2 to 7 carbon atoms, provided that at least one of R x is a methylol group or 2 to 7 carbon atoms. Of the alkoxymethyl group.)
    (In formula (2), Q is a group represented by the above formula (2 a ).)
  3.   The liquid crystal aligning agent according to claim 1, wherein the n4 is 0.
  4. The liquid crystal aligning agent according to claim 3, wherein the Q is at least one selected from the group consisting of groups represented by the following formulas ( 2a- 1) to ( 2a- 5).
    (In the formulas (2 a -1) to (2 a -5), R z is an alkyl group having 7 to 40 carbon atoms or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton, and R y is the number of carbon atoms. 4 to 40 alkyl groups.)
  5.   [B] The liquid crystal aligning agent according to any one of claims 1 to 4, wherein a use ratio of the compound is 0.1 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the polymer [A]. .
  6.   The liquid crystal aligning film formed from the liquid crystal aligning agent of any one of Claims 1-5.
  7. A liquid crystal display element provided with the liquid crystal aligning film of Claim 6.
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CN103959151B (en) * 2011-09-30 2016-08-31 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells
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Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3296264A (en) * 1963-09-30 1967-01-03 Colgate Palmolive Co Fiber-reactive fluoroalkyl derivatives of amino-aldehyde compounds and textiles "soil proofed" therewith
JPS5132887A (en) * 1974-09-10 1976-03-19 Mitsubishi Rayon Co Kenronaru senshokubutsuoataeru tenshanasenho
JPS6321907B2 (en) 1979-12-25 1988-05-10 Citizen Watch Co Ltd
US4474913A (en) * 1983-04-14 1984-10-02 Henkel Corporation Polyvinylchloride processing
JP2869511B2 (en) 1990-10-17 1999-03-10 日本航空電子工業株式会社 Tn type liquid crystal display element
JPH06107020A (en) 1992-09-29 1994-04-19 Toyota Motor Corp Oil pressure control device for vehicle with automatic transmission
JP3212162B2 (en) 1992-10-22 2001-09-25 日産化学工業株式会社 Diaminobenzene derivatives and polyimides and liquid crystal alignment film
GB9612167D0 (en) * 1996-06-11 1996-08-14 Sharp Kk Ferroelectric liquid crystal device alignment
JP3738492B2 (en) * 1996-08-06 2006-01-25 Jsr株式会社 Liquid crystal aligning agent and liquid crystal display element
JP3799700B2 (en) 1996-12-12 2006-07-19 Jsr株式会社 Liquid crystal aligning agent and liquid crystal display element
WO2001060882A1 (en) 2000-02-15 2001-08-23 Solutia Inc. Alkoxymethyl melamine crosslinkers
CN1831086A (en) 2001-11-12 2006-09-13 Lg电线有限公司 Triazine ring based polymers for photoinduced liquid crystal alignment
JPWO2006093131A1 (en) * 2005-03-01 2008-08-07 大日本印刷株式会社 Film with alignment film and optical element
KR100949641B1 (en) * 2006-05-16 2010-03-26 샤프 가부시키가이샤 Process for manufacturing display panel, display panel manufacturing apparatus and display panel
JP5120047B2 (en) 2007-05-02 2013-01-16 Jsr株式会社 Vertical alignment type liquid crystal aligning agent and liquid crystal display element
CN101333198A (en) 2008-07-02 2008-12-31 张家港顺昌化工有限公司 Method for preparing HMMM resin

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