JP5853728B2 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

  The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element.

  Currently, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, VA (Vertical Alignment) type, IPS (In-Plane Switching) type, OCB (Optical Compensated Bend) type liquid crystal display type. Are known. In any of these display modes, 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.

  As a material for such a liquid crystal aligning agent, resin materials such as polyamic acid, polyimide, polyamide, and polyester are known. In particular, a liquid crystal aligning film formed from a liquid crystal aligning agent containing polyamic acid or polyimide is heat resistant, mechanical Excellent in mechanical strength, affinity with liquid crystal, etc., and used in many liquid crystal display elements (see Patent Documents 1 to 6).

  In recent years, studies on improving display quality such as higher definition of liquid crystal display elements and lowering power consumption have been advanced, and the range of use of liquid crystal display elements has been expanded. In particular, liquid crystal television applications that are assumed to be used under conditions in which the usage environment such as luminance and driving time is more severe than conventional liquid crystal display elements are expanding with the momentum to expel conventional CRT televisions.

  However, a liquid crystal display element including a liquid crystal alignment film formed from a liquid crystal aligning agent containing a conventional polyamic acid or polyimide, when continuously driven for a long time in a harsh environment such as light stress, heat, moisture, The liquid crystal alignment film is deteriorated, and the display quality may be remarkably lowered due to the deterioration of the electrical characteristics of the liquid crystal cell.

  On the other hand, a substrate on which defects such as pinholes and uneven coating are generated in the manufacturing process of the liquid crystal alignment film may be reused by peeling the coating film (rework). However, when a liquid crystal aligning agent having a conventional epoxy group is used, the reworkability (peelability) of the liquid crystal alignment film may be lowered due to the crosslinking reaction of the epoxy group during baking.

  Under these circumstances, development of a liquid crystal aligning agent that can form a liquid crystal alignment film that maintains good electrical characteristics even when continuous driving is performed for a long time and that has excellent reworkability when defects occur. Is desired.

JP-A-4-153622 JP 60-107020 A JP 56-91277 A U.S. Pat. No. 5,928,733 Japanese Patent Laid-Open No. 62-165628 Japanese Patent Laid-Open No. 11-258605

  The present invention has been made on the basis of the above circumstances, and its purpose is good electrical performance even in the case of continuous driving for a long time under a harsh environment such as light stress, heat, and humidity. An object of the present invention is to provide a liquid crystal aligning agent capable of forming a liquid crystal aligning film that maintains its characteristics and has excellent reworkability when defects occur.

The invention made to solve the above problems is
[A] at least one polymer selected from the group consisting of a polyamic acid and a polyimide formed by dehydrating and ring-closing the polyamic acid (hereinafter also referred to as “[A] polymer”),
[B] Antioxidant and [C] Compound having epoxy group (hereinafter also referred to as “[C] compound”)
It is a liquid crystal aligning agent containing.

  When the liquid crystal aligning agent contains [A] polymer, [B] antioxidant, and [C] compound, and is continuously driven for a long time in a harsh environment such as light stress, heat, and humidity. Even so, good electrical characteristics can be maintained and excellent reworkability can be expressed.

（式（１）中、
Ｒ^１は、水素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜１３のアラルキル基、１，３−ジオキソブチル基又は１，４−ジオキソブチル基である。また、式（１）で表される基は、Ｒ^１で示されるアルキル基、アリール基、アラルキル基、１，３−ジオキソブチル基及び１，４−ジオキソブチル基から１個の水素原子が除かれ２価の基となって、分子鎖の一部を形成していてもよい。
Ｒ^２〜Ｒ^５は、それぞれ独立して炭素数１〜６のアルキル基、炭素数６〜１２のアリール基又は炭素数７〜１３のアラルキル基である。
Ｘ^１は、単結合、カルボニル基、＊−（ＣＨ_２）_ｎ−Ｏ−、＊−Ｏ−、又は＊−ＣＯＮＨ−である。但し、＊で表される結合手は、ピペリジン環と結合する部位を示す。また、ｎは、１〜４の整数である。
Ｘ^２〜Ｘ^５は、それぞれ独立して単結合、カルボニル基、＊＊−ＣＨ_２−ＣＯ−又は＊＊−ＣＨ_２−ＣＨ（ＯＨ）−である。但し、＊＊で表される結合手は、ピペリジン環と結合する部位を示す。）

（式（２）中、Ｒ^６は、炭素数４〜１６の炭化水素基である。但し、上記炭化水素基は炭素骨格鎖中に酸素原子又は硫黄原子を有していてもよい。ａは、０〜３の整数である。Ｒ^７は、水素原子又は炭素数１〜１６の炭化水素基である。但し、Ｒ^７が複数の場合、複数のＲ^７は同一であっても異なっていてもよい。） [B] The antioxidant preferably has a group represented by the following formula (1) or formula (2).

(In the formula (1),
R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, a 1,3-dioxobutyl group, or a 1,4-dioxobutyl group. Further, the group represented by the formula (1) is an alkyl group represented by ^{R 1,} an aryl group, an aralkyl group, of one hydrogen atom from a 1,3-dioxobutyl group and 1,4-dioxobutyl group removed 2 A part of the molecular chain may be formed as a valent group.
R ^{2 to} R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms.
X ¹ is a single bond, a carbonyl group, * — (CH ₂ ) _n —O—, * —O—, or * —CONH—. However, the bond represented by * indicates a site that binds to the piperidine ring. Moreover, n is an integer of 1-4.
X ^{2 to} X ⁵ are each independently a single bond, a carbonyl group, ** — CH ₂ —CO— or ** — CH ₂ —CH (OH) —. However, the bond represented by ** indicates a site that binds to the piperidine ring. )

(In the formula (2), R ⁶ is a hydrocarbon group having 4 to 16 carbon atoms, provided that the hydrocarbon group may have an oxygen atom or a sulfur atom in the carbon skeleton chain. , is .R ⁷ is an integer of 0 to 3, is a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms. However, when R ⁷ is plural, a plurality of R ⁷ is optionally substituted by one or more identical May be good.)

  [B] When the antioxidant has a group having the above specific structure, light resistance and high temperature and high humidity resistance can be further improved.

  [C] The compound is preferably an epoxy group-containing polyorganosiloxane or a monofunctional epoxy compound.

  Even if it is a composition which has an epoxy group by making an epoxy group containing polyorganosiloxane or a monofunctional epoxy compound into a [C] compound, the liquid crystal aligning film which is more excellent in rework property can be formed.

  [A] The polymer is 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 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- (tetrahydro-2,5-dioxo-3-furanyl) -Consisting of naphtho [1,2-c] furan-1,3-dione and 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2,4,6,8-dianhydride A polymer obtained by reacting a tetracarboxylic dianhydride containing at least one selected from the group and a diamine is preferred. By using the specific compound as the acid dianhydride, light resistance and high temperature and high humidity resistance can be further improved.

  The diamines are 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine and 1- (4-aminophenyl) -2,3-dihydro- It is preferable to include at least one selected from the group consisting of 1,3,3-trimethyl-1H-indene-6-amine. By using the specific compound as a diamine, light resistance and high temperature and high humidity resistance can be further improved.

  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, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, personal digital assistants, digital cameras, mobile phones, various monitors, liquid crystal televisions, etc. Used in display devices.

  According to the liquid crystal aligning agent of the present invention, even when a long period of continuous driving is performed under a harsh environment such as light stress, heat, moisture, etc., good electrical characteristics are maintained and defects are generated. A liquid crystal alignment film having excellent reworkability can be formed. Therefore, the liquid crystal display element of the present invention having the liquid crystal alignment film has little deterioration in display quality and can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, The present invention is suitably applied to display devices such as portable information terminals, digital cameras, mobile phones, various monitors, and liquid crystal televisions.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of this invention contains a [A] polymer, [B] antioxidant, and a [C] compound. When the liquid crystal aligning agent contains [A] polymer, [B] antioxidant, and [C] compound, and is continuously driven for a long time in a harsh environment such as light stress, heat, and humidity. Even so, good electrical characteristics can be maintained and excellent reworkability can be expressed. Moreover, the said liquid crystal aligning agent may contain another arbitrary component, unless the effect of this invention is impaired. Hereinafter, each component will be described in detail.

<[A] polymer>
[A] The polymer is at least one polymer selected from the group consisting of a polyamic acid and a polyimide obtained by dehydrating and ring-closing this polyamic acid. [A] The polyamic acid as a polymer is obtained by reacting a tetracarboxylic dianhydride and a diamine. Hereinafter, tetracarboxylic dianhydride and diamine will be described in detail.

[Tetracarboxylic dianhydride]
Examples of tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and the like. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

  Examples of the aliphatic tetracarboxylic dianhydride include butanetetracarboxylic dianhydride.

Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4. , 5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b -Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] Octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene -1,2-dicarboxylic acid Water, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane- 2,4,6,8-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone and the like.

  Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride.

  Examples of other tetracarboxylic dianhydrides include tetracarboxylic dianhydrides described in Japanese Patent Application No. 2010-97188.

  As tetracarboxylic dianhydride, what contains an alicyclic tetracarboxylic dianhydride is preferable. 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 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- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, More preferred are those containing 2-c] furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2,4,6,8-dianhydride. Further, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1, 3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 2, Particularly preferred are those containing 4,6,8-tetracarboxybicyclo [3.3.0] octane-2,4,6,8-dianhydride. By using the specific compound as the acid dianhydride, light resistance and high temperature and high humidity resistance can be further improved.

  Particularly preferred 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, , 3,3a, 4,5,9b-Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 2, , 4,6,8-tetracarboxybicyclo [3.3.0] octane-2,4,6,8-dianhydride is used in an amount of 10 mol% based on the total tetracarboxylic dianhydride. The above is preferable, and 20 mol% to 90 mol% is more preferable.

[Diamine]
Examples of the diamine include aliphatic diamine, alicyclic diamine, aromatic diamine, and diaminoorganosiloxane. These diamines can be used alone or in combination of two or more.

  Examples of the aliphatic diamine include 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and the like.

  Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, and the like.

  Examples of the aromatic diamine include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl. 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) Phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoro Propane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-pheny Diisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4 -Diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole N, N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, N′-dimethylbenzidine, 1,4-bis- (4-aminophenyl)- Piperazine, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, -(4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine, 3,5-diaminobenzoic acid, cholestanyloxy-3,5-diaminobenzene, choleste Nyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, Lanostanyl 3,5-diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4′-trifluoromethoxybenzoyloxy) cyclohexyl -3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cycl Rohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl)- 4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4 -Heptylcyclohexyl) cyclohexane, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine and compounds represented by the following formula (3).

In the formula (3), ^{R 8} is an alkyl group having 1 to 3 carbon atoms, * - O -, * - COO- or * -OCO- is. However, * is a site | part couple | bonded with a diaminophenyl group. b is 0 or 1. c is an integer of 0-2. d is an integer of 1-20. The two amino groups in the diaminophenyl group are preferably bonded to the 2,4 position or the 3,5 position. Moreover, it is preferable that a and b are not 0.

  Examples of the compound represented by the above formula (3) include compounds represented by the following formula.

  Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane. Examples of other diamines include diamines described in Japanese Patent Application No. 2010-97188.

  As the diamine, those containing aromatic diamines are preferable, and 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine and 1- (4-amino More preferred are those containing at least one selected from the group consisting of (phenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine. By including the specific compound as a diamine, light resistance and high temperature and high humidity resistance can be further improved. As a commercial item of the said specific compound, TMDA (made by Nippon Pure Chemicals) is mentioned, for example. TMDA is 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine and 1- (4-aminophenyl) -2,3-dihydro-1, It is a mixture of 3,3-trimethyl-1H-indene-6-amine.

  The use ratio of the preferable aromatic diamine is preferably 20 mol% or more, more preferably 50 mol% or more, and particularly preferably 80 mol% or more based on the total diamine. On the other hand, the upper limit of the use ratio of the aromatic diamine is not particularly limited, but 90 mol% is preferable with respect to the total diamine.

  In addition, the diamine used when synthesizing the polyamic acid in the VA-type alignment film includes dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, as a pretilt component, Hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5 -Diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, Lestenyloxy-2,4-diaminobenzene, cholestenyl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4 -Aminophenoxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4- (aminophenylmethyl) phenyl) -4-butylcyclohexane, 1,1-bis (4- (aminophenylmethyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4- (Aminophenoxymethyl) phenyl) -4-heptylcyclohexane, 1,1-bi It is preferable that 5 mol% or more of (4- (aminophenylmethyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, the compound represented by the above formula (3), etc. is contained in an amount of 5 mol% or more with respect to the total diamine. More preferably.

[Method of synthesizing polyamic acid]
The polyamic acid in the liquid crystal aligning agent can be obtained by reacting the tetracarboxylic dianhydride with a diamine. The proportion of tetracarboxylic dianhydride used in the polyamic acid synthesis reaction is 0.2 equivalent to the acid anhydride group of tetracarboxylic dianhydride with respect to 1 equivalent of amino group contained in the diamine. 2 equivalents are preferable, and 0.3 equivalents to 1.2 equivalents are more preferable.

  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 0.1 hour to 24 hours, more preferably 0.5 hour to 12 hours. Examples of the organic solvent include aprotic polar solvents, phenol and derivatives thereof, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like.

  Examples of the aprotic polar solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide and the like. Can be mentioned.

  Examples of the phenol derivative include m-cresol, xylenol, halogenated phenol and the like.

  Examples of the alcohol include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, and the like.

  Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

  Examples of the ester include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, and diethyl malonate.

  Examples of the ether include 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, Examples include 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, and tetrahydrofuran.

  Examples of the halogenated hydrocarbon include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, and the like.

  Examples of the hydrocarbon include hexane, heptane, octane, benzene, toluene, xylene, isoamylpropionate, isoamylisobutyrate, and diisopentyl ether.

  Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent, phenol and derivatives thereof (first group organic solvent) or one or more selected from the first group of organic solvents and alcohol It is preferable to use a mixture with one or more selected from the group consisting of benzene, ketone, ester, ether, halogenated hydrocarbon and hydrocarbon (second group organic solvent). The use ratio of the organic solvent of the second group is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less with respect to the total of the first group and the second group of organic solvents. .

  As the usage-amount of an organic solvent, 0.1 mass%-50 mass% are preferable with respect to the total amount of tetracarboxylic dianhydride and diamine.

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. When polyamic acid is dehydrated and cyclized into a polyimide, the above reaction solution may be directly subjected to dehydration and cyclization reaction, or may be subjected to dehydration and cyclization reaction after isolating the polyamic acid contained in the reaction solution. Alternatively, the isolated polyamic acid may be purified and then subjected to a dehydration ring closure reaction. Isolation and purification of the polyamic acid can be performed according to a known method.

[Polyimide synthesis method]
The polyimide that can be contained in the liquid crystal aligning agent can be obtained by dehydrating and ring-closing the polyamic acid to imidize it.

  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. The types and usage ratios of preferred tetracarboxylic dianhydrides and diamines are also the same as in the case of polyamic acid synthesis.

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 30% or more, more preferably 35% to 99%, and particularly preferably 40% to 99%. 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 (3).
Imidation ratio (%) = {1- (A ¹ / A ² ) × α} × 100 (3)

In the above formula (3), A ¹ is a peak area derived from protons of NH groups appearing in the vicinity of 10 ppm of chemical shift, 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 the polyamic acid for synthesizing the polyimide is performed by heating the polyamic acid or by dissolving the polyamic acid in an organic solvent and adding a dehydrating agent and a dehydration ring closure catalyst to the solution. It is done by the method to do. The latter method is preferred.

  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 structural 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 1.0 hour to 120 hours, more preferably 2.0 hours to 30 hours.

  The reaction solution may be used for the preparation of the liquid crystal aligning agent as it is, may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, and the liquid crystal alignment after isolating the polyimide. You may use for preparation of an agent, or you may use for 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. Isolation and purification of the polyimide can be performed according to known methods.

  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-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n- Examples include hexadecyl succinic anhydride.

  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.

  The proportion of the molecular weight regulator used is preferably 20 parts by mass or less and more preferably 10 parts by mass or less with respect to 100 parts by mass in total of the tetracarboxylic dianhydride and diamine used when the polyamic acid is synthesized.

  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 this specification is a value measured at 25 ° C. using an E-type rotational viscometer for a polymer solution having a concentration of 10% by mass prepared using a predetermined solvent. It is.

<[B] Antioxidant>
[B] Antioxidants are compounds that can capture and decompose peroxy radicals and hydroperoxides generated by energy such as ultraviolet rays and heat to suppress oxidative degradation of substances. When radicals are generated in the [A] polymer by ultraviolet rays, heat, etc., new radicals and peroxides are generated based on these radicals (peroxides generate new radicals), and the function of the polymer material deteriorates. May cause. [B] The antioxidant functions as a radical scavenger that invalidates the radicals generated in this way, and as a result, it can prevent oxidation of the polymer material and suppress its deterioration.

  [B] The antioxidant preferably has a group represented by the above formula (1) or (2). [B] When the antioxidant has a group having the above specific structure, light resistance and high temperature and high humidity resistance can be further improved.

In the above formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, a 1,3-dioxobutyl group, or 1, 4-dioxobutyl group. Further, the group represented by the formula (1) is an alkyl group represented by ^{R 1,} an aryl group, an aralkyl group, of one hydrogen atom from a 1,3-dioxobutyl group and 1,4-dioxobutyl group removed 2 A part of the molecular chain may be formed as a valent group. R ^{2 to} R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. X ¹ is a single bond, a carbonyl group, * — (CH ₂ ) _n —O—, * —O—, or * —CONH—. However, the bond represented by * indicates a site that binds to the piperidine ring. Moreover, n is an integer of 1-4. X ^{2 to} X ⁵ are each independently a single bond, a carbonyl group, ** — CH ₂ —CO— or ** — CH ₂ —CH (OH) —. However, the bond represented by ** indicates a site that binds to the piperidine ring. In the above formula (2), ^{R 6} is a hydrocarbon group having 4 to 16 carbon atoms. However, the hydrocarbon group may have an oxygen atom or a sulfur atom in the carbon skeleton chain. a is an integer of 0-3. R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms. However, when R ⁷ is plural, a plurality of R ⁷ may be be the same or different.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, Examples include dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, and nonadecyl group. Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹ include a phenyl group, a 3-fluorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 4-i-propylphenyl group, and 4-n-butylphenyl. Group, 3-chloro-4-methylphenyl group, 4-pyridinyl group, 2-phenyl-4-quinolinyl group, 2- (4'-t-butylphenyl) -4-quinolinyl group, 2- (2'-thiophenyl) ) -4-quinolinyl group and the like. Examples of the alkyl group having 1 to 6 carbon atoms represented by R ^{2 to} R ⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the aralkyl group having 7 to 13 carbon atoms represented by R ^{1 to} R ⁵ include a benzyl group and a phenethyl group. Examples of the aryl group having 6 to 12 carbon atoms represented by R ^{2 to} R ⁵ include a phenyl group. Examples of the hydrocarbon group having 4 to 16 carbon atoms that may have an oxygen atom or a sulfur atom in the carbon skeleton chain represented by R ⁶ include a tert-butyl group, a 1-methylpentadecyl group, and an octylthiomethyl group. Group, dodecylthiomethyl group and the like. Examples of the hydrocarbon group having 1 to 16 carbon atoms represented by R ⁷ include a methyl group, a tert-butyl group, a 1-methylpentadecyl group, and an octylthiomethyl group.

  Examples of the [B] antioxidant represented by the above formula (1) include amine-based antioxidants. Examples of the [B] antioxidant represented by the above formula (2) include phenol-based antioxidants. An antioxidant etc. are mentioned. These [B] antioxidants can be used alone or in combination of two or more.

  Examples of the amine antioxidant include a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, bis (1,2,2,6,6-pentamethyl). -4-piperidyl) sebacate, bis (2,2,6,6, -tetramethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 1,2, 2,6,6-pentamethyl-4-piperidinyl, 2,2,6,6-tetramethyl-4-piperidinyl, carbonic acid = bis (2,2,6,6-tetramethyl-1-undecyloxypiperidine-4 -Yl), pentamethylpiperidyl methacrylate, tetramethylpiperidyl methacrylate, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N Methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N , N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine Condensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl- 4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3 , 5-bis (1,1-dimethyl ether ) -4- hydroxyphenyl] methyl] butyl malonate, and the like.

  Examples of phenolic antioxidants include tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, tris- (2-methyl-4-hydroxy-5-tert-butylphenyl)- Butane, 4,4′-butylidenebis (6-tert-butyl-m-cresol), stearyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4,6-tris ( 3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) mesitylene, thiodiethylenebis [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropion) Amido], isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,6-bis (dodecylthiomethyl) -o-cresol, 4,6-bis (octylthiomethyl) O-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) Methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1, 3,5-triazin-2-ylamino) phenol and the like.

  In addition, a commercial item can be used as these [B] antioxidant.

  Commercially available amine antioxidants include, for example, ADK STAB LA-52, LA-57, LA-63, LA-68, LA-72, LA-77, LA-81, LA-82, LA-87, LA -402, LA-502 (above, manufactured by ADEKA), CHIMASSORB119, CHIMASSORB2020, CHIMASSORB944, TINUVIN622, TINUVIN123, TINUVIN144, TINUVIN765, TINUVIN770, TINUVIN111, TINUVIN783, TINBASIN791, etc.

  Examples of commercially available phenolic antioxidants include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 (above, ADEKA). IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1098, IRGANOX 1135, IRGANOX 1330, IRGANOX 1726, IRGANOX 1425, IRGANOX 1520, IRGANOX 245, IRGANOX 259, IRGANOX 3114, IRNOX 3570, IRGANOX 3590, IRGANOX 3570

  Examples of commercially available sulfur-based antioxidants include ADK STAB AO-412, AO-503 (manufactured by ADEKA), IRGANOX PS 800, IRGANOX PS 802 (manufactured by BASF Japan), and the like.

  Moreover, as [B] antioxidant other than [B] antioxidant represented by the said Formula (1) and Formula (2), for example, phosphorus antioxidant, sulfur type antioxidant, and these A blend type compound etc. are mentioned.

  Examples of phosphorus antioxidants include 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (octadecyl). Oxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4 , 8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 2,4,8,10-tetrakis (1,1-dimethylethyl) -6-[(2-ethylhexyl) oxy] -12H- Dibenzo [d, g] [1,3,2] dioxaphosphocin, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butyl-5-methylphen L) [1,1-biphenyl] -4,4′-diylbisphosphonite, tris [2-[[2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3, 2] Dioxaphosphine-6-yl] oxy] ethyl] amine, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis [2,4-bis (1,1 dimethylethyl) ) -6-methylphenyl] ethyl ester phosphorous acid and the like.

  Examples of the sulfur-based antioxidant include didodecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, and the like.

  Examples of commercially available phosphorous antioxidants include ADK STAB PEP-4C, PEP-8, PEP-36, HP-10, 2112 (above, manufactured by ADEKA), GSY-P101 (above, manufactured by Sakai Chemical Industry). IRGAFOS168, IRGAFOS12, IRGAFOS126, IRGAFOS38, IRGAFOS P-EPQ (above, manufactured by BASF Japan) and the like.

  Examples of commercially available sulfur-based antioxidants include IRGANOX PS 800FL, IRGANOX PS 802FL (manufactured by BASF Japan).

  Examples of commercially available blended antioxidants include ADK STAB A-611, A-612, A-613, AO-37, AO-15, AO-18, 328 (above, manufactured by ADEKA), TINUVIN111, TINUVIN783, TINUVIN791 (above, BASF Japan make) etc. are mentioned.

  Of these [B] antioxidants, phenol-based antioxidants and amine-based antioxidants are preferred. [B] The content ratio of the antioxidant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the polymer (A). Or less.

<[C] Compound>
[C] A compound is a compound which has an epoxy group. In the present specification, an epoxy group refers to a group containing an oxiranyl group and an oxetanyl group. [C] The compound is not particularly limited as long as it has one or more epoxy groups in the molecule. For example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol di- Glycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, '-Tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine, glycidoxymethyltrimethoxysilane, glycine Sidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3,3 '-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, , 3-Bis [(3-ethyl-3-oxetanylmethoxy Methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3-ethyl-3-oxetanylmethyl) ether Tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipenta Erythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylol Propanetetrakis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [2- (3-oxetanyl) butyl] ether, 1 , 4-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,2-bis [(3-ethyloxetane -3-yl) methoxy] benzene, 4,4′-bis [(3-ethyl Oxetane-3-yl) methoxy] biphenyl, 2,2′-bis [(3-ethyl-3-oxetanyl) methoxy] biphenyl, 3,3 ′, 5,5′-tetramethyl [4,4′-bis ( 3-ethyloxetane-3-yl) methoxy] biphenyl, 2,7-bis [(3-ethyloxetane-3-yl) methoxy] naphthalene, 1,6-bis [(3-ethyloxetane-3-yl) methoxy ] -2,2,3,3,4,4,5,5-octafluorohexane, 3 (4), 8 (9) -bis [(1-ethyl-3-oxetanyl) methoxymethyl] -tricyclo [5 .2.1.0 ^2,6 ] decane, 4,4′-bis [(1-ethyl-3-oxetanyl) methyl] thiodibenzene thioether, 2,3-bis [(3-ethyloxetane-3-yl) ) Methoxymethyl] Lubornane, 2-ethyl-2-[(3-ethyloxetane-3-yl) methoxymethyl] -1,3-O-bis [(1-ethyl-3-oxetanyl) methyl] -propane-1,3-diol 2,2-dimethyl-1,3-O-bis [(3-ethyloxetane-3-yl) methyl] -propane-1,3-diol, 2-butyl-2-ethyl-1,3-O- Bis [(3-ethyloxetane-3-yl) methyl] -propane-1,3-diol, 1,4-O-bis [(3-ethyloxetane-3-yl) methyl] -butane-1,4- Diol, 2,4,6-O-tris [(3-ethyloxetane-3-yl) methyl] cyanuric acid, etherified product of bisphenol A and 3-ethyl-3-chloromethyloxetane, bisphenol F and 3-ethyl -3- Etherified product of loromethyl oxetane, etherified product of phenol novolak and 3-ethyl-3-chloromethyl oxetane, etherified product of cresol novolak and 3-ethyl-3-chloromethyl oxetane, oxetanylsilsesquioxane, 3- Examples thereof include silicon alkoxide of ethyl-3-hydroxymethyl oxetane.

  Moreover, as a commercial item of [C] compound, for example, Denacol EX611, EX612, EX614, EX622, EX512, EX621, EX621, EX411, EX421, EX313, EX321, EX201, EX211, EX212, EX252, EX911, EX941, EX941, EX920, EX931, EX111, EX121, EX141, EX142, EX146, EX192, EX721, EX203, EX711, EX147, EX221, EX221 EX150, Denalex R45EPT, EX810, EX811, EX811, EX850, EX851, EX821, EX830, EX830, EX831, EX841, EX861, EX145, EX147 (and above, Nagase Chem) Manufactured by Ax), Aron Oxetane OXT-121 (XDO), 221 (DOX), HQOX, RSOX, CTOX, 4,4′-BPOX, 2,2′-BPOX, TM-BPOX, 2,7-NpDOX, OFH -DOX, NDMOX, TMPTOX, NPGOX, BisAOX, BisFOX, PNOX, CNOX, OX-SQ, OX-SC (above, manufactured by Toagosei Co., Ltd.), ETARNACOLL OXBP (above, manufactured by Ube Industries), and the like.

  As the other [C] compound, an epoxy group-containing polyorganosiloxane described in WO2009 / 096598 can also be used.

  Of these, the compound [C] is preferably an epoxy group-containing polyorganosiloxane or a monofunctional epoxy compound. Even if it is a composition which has an epoxy group by making an epoxy group containing polyorganosiloxane or a monofunctional epoxy compound into a [C] compound, the liquid crystal aligning film which is more excellent in rework property can be formed.

  As a method for synthesizing an epoxy group-containing polyorganosiloxane, a polyorganosiloxane having an epoxy group is first synthesized by using a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group and another silane compound. And then this and a carboxylic acid (for example, 4-octyloxybenzoic acid, 4′-pentyl-1,1′-bicyclohexyl-4-carboxylic acid, etc.), preferably in the presence of a suitable organic solvent, water and catalyst. Can be synthesized by hydrolysis or hydrolysis / condensation.

  Examples of the silane compound having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-glycidyloxypropylmethyldiethoxysilane. 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane Etc. These can be used alone or in combination of two or more.

  Examples of other silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, trichlorosilane, trichlorosilane, Methoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluoro Tri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyl Reethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, 2- (trifluoromethyl) ethyltrichlorosisilane, 2- (trifluoromethyl ) Ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyltri-i-propoxysilane, 2- (tri Fluoromethyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-hexyl) ethyltrichlorosilane, 2- (perfluoro-n-hexyl) ethyltri Methoxysila 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, 2- (Perfluoro-n-octyl) ethyltrimethoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro -N-octyl) ethyltri-i-propoxysilane, 2- (perfluoro -N-octyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-octyl) ethyltri-sec-butoxysilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, hydroxymethyltri- n-propoxysilane, hydroxymethyltri-i-propoxysilane, hydroxymethyltri-n-butoxysilane, hydroxymethyltri-sec-butoxysilane, 3- (meth) acryloxypropyltrichlorosilane, 3- (meth) acryloxy Propyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltri-i-propoxy Lan, 3- (meth) acryloxypropyltri-n-butoxysilane, 3- (meth) acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercapto Propyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltri-n-butoxysilane, 3-mercaptopropyltri-sec-butoxysilane, mercapto Methyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane Vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri-n-butoxysilane, allyltri -Sec-butoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxy Silane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi-i-propoxysilane, methyldi-n-butoxysila Methyldi-sec-butoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-i-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, (Methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n- Octyl) ethyl] diethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-i -Propoxysilane, (methyl) [2- (perfluoro-n-octyl ) Ethyl] di-n-butoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-sec-butoxysilane, (methyl) (3-mercaptopropyl) dichlorosilane, (methyl) (3 -Mercaptopropyl) dimethoxysilane, (methyl) (3-mercaptopropyl) diethoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (3-mercaptopropyl) di-i-propoxy Silane, (methyl) (3-mercaptopropyl) di-n-butoxysilane, (methyl) (3-mercaptopropyl) di-sec-butoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxy Silane, (methyl) (vinyl) diethoxysilane, (methyl) (vinyl) di-n- Roxy silane, (methyl) (vinyl) di-i-propoxy silane, (methyl) (vinyl) di-n-butoxy silane, (methyl) (vinyl) di-sec-butoxy silane, divinyl dichlorosilane, divinyl dimethoxy silane, divinyl Diethoxysilane, divinyldi-n-propoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n- Propoxysilane, diphenyldi-i-propoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, black Rotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxytrimethylsilane, i-propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (Chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane, (ethoxy) (methyl ) Silane compounds having one silicon atom such as diphenylsilane. These can be used alone or in combination of two or more.

  The epoxy equivalent of the polyorganosiloxane having an epoxy group is preferably 50 g / mol to 10,000 g / mol, more preferably 100 g / mol to 10,000 g / mol, and particularly preferably 100 g / mol to 1,000 g / mol. . Therefore, when synthesizing a polyorganosiloxane having an epoxy group, the usage ratio of the silane compound having an epoxy group and another silane compound may be set so that the epoxy equivalent of the resulting polyorganosiloxane is within the above range. preferable. The epoxy equivalent in this specification refers to a value measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

  Examples of the organic solvent that can be used in the synthesis of the polyorganosiloxane having an epoxy group include hydrocarbon compounds, ketone compounds, ester compounds, ether compounds, and alcohol compounds. These can be used alone or in combination of two or more.

  Examples of the hydrocarbon compound include toluene and xylene. Examples of the ketone compound include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone. Examples of the ester compound include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethyl lactate. Examples of the ether compound include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like. Examples of the alcohol compound include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl. Examples include ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like.

  As the usage-amount of an organic solvent, 10 mass parts-10,000 mass parts are preferable with respect to 100 mass parts of all the silane compounds, and 50 mass parts-1,000 mass parts are more preferable.

  As the usage-amount of water at the time of synthesize | combining the polyorganosiloxane which has an epoxy group, 0.5 times mole-100 times mole are preferable with respect to all the silane compounds, and 1 time mole-30 times mole are more preferable.

  When synthesizing a polyorganosiloxane having an epoxy group, the hydrolysis or hydrolysis / condensation reaction involves dissolving an epoxy group-containing silane compound and, if necessary, another silane compound in an organic solvent, and dissolving the solution in an organic base. And it is preferable to carry out by mixing with water and heating with, for example, an oil bath.

  The heating temperature during the hydrolysis / condensation reaction is preferably 130 ° C. or lower, and more preferably 40 ° C. to 100 ° C. The heating time is preferably 0.5 hours to 12 hours, and more preferably 1 hour to 8 hours. During the heating, the mixed solution may be stirred or placed under reflux.

  After completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. In washing, it is preferable to wash with water containing a small amount of salt, for example, an aqueous ammonium nitrate solution of about 0.2% by mass because the washing operation is easy. Washing is performed until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieves as necessary, and then the target is removed by removing the solvent. A polyorganosiloxane having an epoxy group is obtained.

  A commercially available product may be used as the polyorganosiloxane having an epoxy group. Examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21, EMS-32 (manufactured by Chisso).

The polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography of the polyorganosiloxane having an epoxy group is preferably 500 to 100,000, and more preferably 1,000 to 10,000. In the present specification, Mw is a polystyrene equivalent value measured by gel permeation chromatography having the following specifications.
Column: Tosoh, TSK-GEL
Solvent: Tetrahydrofuran Column temperature: 40 ° C
Pressure: 80 kgf / cm ²

  [C] The content ratio of the compound is preferably 40 parts by mass or less, more preferably 1 part by mass to 30 parts by mass or less with respect to 100 parts by mass of the [A] polymer.

<Optional component>
The liquid crystal aligning agent includes, in addition to the [A] polymer, [B] antioxidant and [C] compound, other polymers and functionalities other than the [A] polymer as long as the effects of the present invention are not impaired. Arbitrary components, such as a silane compound, can be contained. Each of these optional components may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.

[Other polymers]
Other polymers can be used to improve solution and electrical properties. Examples of other polymers include polyamic acid esters, polyesters, polyamides, polysiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like. Further, the content of the other polymer can be appropriately determined according to the purpose.

[Functional silane compounds]
The functional silane compound can be contained from the viewpoint of further improving the printability of the liquid crystal aligning agent. Examples of the functional silane compound 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-aminopropyltri Methoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-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-aminopropyltriethoxysilane, N-bis (oxyethylene ) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, and the like. As a usage-amount of a functional silane compound, 2 mass parts or less are preferable with respect to 100 mass parts of [A] polymers, and 0.1 mass part-1 mass part are more preferable.

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

  Examples of the organic solvent 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, Examples include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, and propylene carbonate. These can be used alone or in combination of two or more.

  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 On the other hand, it may be difficult to obtain a good liquid crystal alignment film because the thickness is too small. 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 can be obtained. It may be difficult to obtain, 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, 10 to 50 degreeC is preferable and 20 to 30 degreeC is more preferable.

<Method for Forming Liquid Crystal Alignment Film and Method for Manufacturing Liquid Crystal Display Element>
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, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, personal digital assistants, digital cameras, mobile phones, various monitors, liquid crystal televisions, etc. Used in display devices.

  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. The liquid crystal display element of the present invention includes the liquid crystal alignment film. Hereinafter, a method for forming the liquid crystal alignment film and a method for manufacturing the liquid crystal display element will be described in detail.

(1-1)
When manufacturing a TN type, STN type, or VA type liquid crystal display element, a pair of two substrates provided with a patterned transparent conductive film is used as a pair, and the liquid crystal alignment of the present invention is formed on each transparent conductive film forming surface. The agent is preferably applied by an offset printing method, a spin coating method, or an ink jet printing method, respectively, and then each coated surface is heated to form a coating film. As the substrate, for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, alicyclic olefin, or the like can be used. As a transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark, manufactured by PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), etc. Can be used.

  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 0.25 to 10 minutes, more preferably 0.5 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-bake time is preferably 5 minutes to 200 minutes, more preferably 10 minutes to 100 minutes. 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.

(1-2)
When manufacturing an IPS type liquid crystal display element, the conductive film formation surface of the substrate provided with the transparent conductive film patterned in a comb-tooth shape and the one surface of the counter substrate provided with no conductive film are provided on the surface of the present invention. The liquid crystal aligning agent is preferably applied by an offset printing method, a spin coating method, or an ink jet printing method, and then each coated surface is heated to form a coating film. The material used for the substrate and transparent conductive film, the patterning method for the transparent conductive film, the pretreatment of the substrate, and the heating method after applying the liquid crystal aligning agent are the same as in (1-1) above. The preferable film thickness of the coating film to be formed is the same as (1-1) above.

(2) When the liquid crystal display element manufactured by the method of the present invention is a VA liquid crystal display element, the coating film formed as described above can be used as a liquid crystal alignment film as it is. If desired, it may be used after the following rubbing treatment. On the other hand, when manufacturing a liquid crystal display element other than the VA type, a rubbing treatment is performed on the coating film formed as described above to obtain a liquid crystal alignment film.

  The rubbing treatment can be performed by rubbing the coating film surface formed as described above with a roll around which a cloth made of fibers such as nylon, rayon, and cotton is wound in a certain direction. Thereby, the orientation ability of liquid crystal molecules is imparted to the coating film to form a liquid crystal orientation film. Further, the liquid crystal alignment film formed as described above is irradiated with ultraviolet rays on a part of the liquid crystal alignment film as disclosed in, for example, Japanese Patent Application Laid-Open Nos. 6-222366 and 6-281937. By changing the pretilt angle of a partial region of the liquid crystal alignment film or by forming a resist film on a part of the surface of the liquid crystal alignment film as disclosed in JP-A-5-107544, The rubbing treatment is performed in a different direction from the rubbing treatment, and then the resist film is removed to improve the visual field characteristics of the liquid crystal display device obtained by having the liquid crystal alignment film have different liquid crystal alignment ability for each region. It is possible.

(3) A liquid crystal cell is manufactured by preparing two substrates on which the liquid crystal alignment film is formed and disposing liquid crystals between the two substrates disposed to face 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 the sealing material and dropping the liquid crystal at predetermined locations on the liquid crystal alignment film surface, the other substrate is bonded so that the liquid crystal alignment film faces and the liquid crystal is spread over the entire surface of the substrate. A liquid crystal cell can be manufactured by irradiating the entire surface of the substrate with ultraviolet light to cure the sealant.

  Regardless of which method is used, the liquid crystal cell manufactured as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase, and then slowly cooled to room temperature, thereby removing the flow alignment during liquid crystal injection. It is desirable to do. 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 commercially available as cholesteric liquid crystals (manufactured by Merck, C-15, CB-15) such as cholesteryl chloride, cholesteryl nonate, cholesteryl carbonate, etc .; p-decyloxybenzylidene-p-amino A ferroelectric liquid crystal such as -2-methylbutyl cinnamate 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.

  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]
2,2.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as tetracarboxylic dianhydride and 2.6 g (0.02) of p-phenylenediamine (PDA) as diamine Mol), 10.4 g (0.02 mol) of cholestanyl 3,5-diaminobenzoate (HCDA) and 9.1 g (0.06 mol) of 3,5-diaminobenzoic acid (DAB) were added to N-methyl-2- It melt | dissolved in 176 g of pyrrolidone (NMP), and it reacted at 60 degreeC for 6 hours, and obtained the solution containing 10 mass% of polyamic acids. The solution viscosity of the obtained polyamic acid solution was 102 mPa · s. Next, 410 g of NMP was added to the obtained polyamic acid solution, 7.9 g of pyridine and 10.2 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After dehydration ring closure reaction, the solvent in the system is replaced with new NMP (removing pyridine and acetic anhydride used in the dehydration ring closure reaction out of the system), so that a polyimide (A-1) having an imidation ratio of about 47% Was obtained. A small amount of the obtained polyimide solution was collected, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 56 mPa · s.

[Synthesis Example 2]
22.3 g (0.1 mol) of TCA as tetracarboxylic dianhydride, and 3.9 g (0.02 mol) of 4,4′-diaminodiphenylmethane (DDM) as a diamine, 5.2 g (0.01 mol) of HCDA, Cholestanyloxy-2,4-diaminobenzene (HCODA) (4.9 g, 0.01 mol) and DAB (9.1 g, 0.06 mol) were dissolved in NMP (182 g) and reacted at 60 ° C. for 6 hours to obtain polyamic acid. A solution containing 10% by mass was obtained. The solution viscosity of the obtained polyamic acid solution was 117 mPa · s. Next, 423 g of NMP was added to the obtained polyamic acid solution, 10.2 g of pyridine and 13.2 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new NMP to obtain a solution containing 15% by mass of polyimide (A-2) having an imidization ratio of about 67%. A small amount of the obtained polyimide solution was collected, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 70 mPa · s.

[Synthesis Example 3]
TCA 17.9 g (0.08 mol) and 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1 as tetracarboxylic dianhydride , 2-c] furan-1,3-dione (TDA) 6.0 g (0.02 mol), and PDA 2.2 g (0.02 mol), HCDA 10.4 g (0.02 mol) and DAB 9. 1 g (0.06 mol) was dissolved in 182 g of NMP and reacted at 60 ° C. for 6 hours to obtain a solution containing 10% by mass of polyamic acid. The solution viscosity of the obtained polyamic acid solution was 99 mPa · s. Next, 423 g of NMP was added to the obtained polyamic acid solution, 7.9 g of pyridine and 10.2 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with new NMP to obtain a solution containing 15% by mass of polyimide (A-3) having an imidation ratio of about 51%. A small amount of the obtained polyimide solution was collected, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 55 mPa · s.

[Synthesis Example 4]
TCA 18.0 g (0.08 mol) and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) as tetracarboxylic dianhydride -Naphtho [1,2-c] furan-1,3-dione (MTDA) 6.3 g (0.02 mol), and diamine PDA 2.2 g (0.02 mol), HCDA 10.5 g (0.02 mol) ) And 9.2 g (0.06 mol) of DAB were dissolved in 185 g of NMP and reacted at 60 ° C. for 6 hours to obtain a solution containing 10% by mass of polyamic acid. The solution viscosity of the obtained polyamic acid solution was 92 mPa · s. Next, 429 g of NMP was added to the obtained polyamic acid solution, 8.0 g of pyridine and 10.3 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with new NMP to obtain a solution containing 15% by mass of polyimide (A-4) having an imidization ratio of about 48%. A small amount of the obtained polyimide solution was collected, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 50 mPa · s.

[Synthesis Example 5]
TCA 18.0 g (0.08 mol) and 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2,4,6,8-dianhydride (BODA) as tetracarboxylic dianhydride ) 5.0 g (0.02 mol), and PDA 2.2 g (0.02 mol), HCDA 10.5 g (0.02 mol) and DAB 9.2 g (0.06 mol) as diamines were dissolved in 179 g of NMP, Reaction was performed at 0 degreeC for 6 hours, and the solution containing 10 mass% of polyamic acids was obtained. The solution viscosity of the obtained polyamic acid solution was 81 mPa · s. Next, 416 g of NMP was added to the obtained polyamic acid solution, 7.9 g of pyridine and 10.2 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new NMP to obtain a solution containing 15% by mass of polyimide (A-5) having an imidization ratio of about 50%. A small amount of the obtained polyimide solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 42 mPa · s.

[Synthesis Example 6]
22.5 g (0.1 mol) of TCA as tetracarboxylic dianhydride and 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine as diamine And 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine (TMDA) 10.7 g (0.04 mol), HCDA 10.5 g ( 0.02 mol) and 6.1 g (0.04 mol) DAB were dissolved in 199 g of NMP and reacted at 60 ° C. for 6 hours to obtain a solution containing 10% by mass of polyamic acid. The solution viscosity of the obtained polyamic acid solution was 80 mPa · s. Next, 462 g of NMP was added to the obtained polyamic acid solution, 7.9 g of pyridine and 10.2 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new NMP to obtain a solution containing 15% by mass of polyimide (A-6) having an imidization ratio of about 44%. A small amount of the obtained polyimide solution was collected, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 66 mPa · s.

[Synthesis Example 7]
TCA 18.0 g (0.08 mol) and TDA 6.0 g (0.02 mol) as tetracarboxylic dianhydrides, and TMDA 5.3 g (0.02 mol), HCDA 10.5 g (0.02 mol) and diamine 9.2 g (0.06 mol) of DAB was dissolved in 196 g of NMP and reacted at 60 ° C. for 6 hours to obtain a solution containing 10% by mass of polyamic acid. The solution viscosity of the obtained polyamic acid solution was 84 mPa · s. Next, 455 g of NMP was added to the obtained polyamic acid solution, 7.9 g of pyridine and 10.2 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new NMP to obtain a solution containing 15% by mass of polyimide (A-7) having an imidization ratio of about 49%. A small amount of the obtained polyimide solution was collected, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 52 mPa · s.

[Synthesis Example 8]
TCA 17.9 g (0.08 mol) and MTDA 6.3 g (0.02 mol) as tetracarboxylic dianhydrides and TMDA 5.3 g (0.02 mol), HCDA 10.4 g (0.02 mol) and diamine as diamines DAB 9.1 g (0.06 mol) was dissolved in NMP 196 g and reacted at 60 ° C. for 6 hours to obtain a solution containing 10% by mass of polyamic acid. The solution viscosity of the obtained polyamic acid solution was 75 mPa · s. Next, 455 g of NMP was added to the obtained polyamic acid solution, 7.9 g of pyridine and 10.2 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new NMP to obtain a solution containing 15% by mass of polyimide (A-8) having an imidization ratio of about 47%. A small amount of the obtained polyimide solution was collected, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 49 mPa · s.

[Synthesis Example 9]
TCA 17.8 g (0.08 mol) and BODA 5.0 g (0.02 mol) as tetracarboxylic dianhydride, and TMDA 5.3 g (0.02 mol), HCDA 10.4 g (0.02 mol) and diamine as diamine DAB 9.1g (0.06mol) was melt | dissolved in NMP190g, reaction was performed at 60 degreeC for 6 hours, and the solution containing 10 mass% of polyamic acids was obtained. The solution viscosity of the obtained polyamic acid solution was 85 mPa · s. Next, 442 g of NMP was added to the obtained polyamic acid solution, 7.9 g of pyridine and 10.2 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new NMP to obtain a solution containing 15% by mass of polyimide (A-9) having an imidization ratio of about 56%. A small amount of the obtained polyimide solution was collected, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 50 mPa · s.

<Synthesis of [C] Compound>
[Synthesis Example 10]
A reactor equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with 34.5 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 34.5 g of methyl isobutyl ketone and 3.45 g of triethylamine, Mixed at room temperature. Next, 27.6 g of deionized water was dropped from the dropping funnel over 30 minutes, and then the reaction was performed at 80 ° C. for 6 hours while stirring under reflux. After completion of the reaction, the organic layer is taken out, washed with 0.2 g mass% ammonium nitrate aqueous solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to give a viscous organopolysiloxane. A solution was obtained. As a result of ¹ H-NMR analysis of this organopolysiloxane, a peak based on the epoxy group was obtained in the vicinity of chemical shift (σ) = 3.2 ppm according to the theoretical intensity, and side reaction of the epoxy group occurred during the reaction. Not confirmed. The Mw of this polyorganosiloxane was 3,000, and the epoxy equivalent was 185 g / mol.

  In a 200 mL three-necked flask, 7.3 g of the polyorganosiloxane obtained, 3.0 g of 4-octyloxybenzoic acid, 41.6 g of methyl isobutyl ketone as a solvent, and 0.7 g of tetrabutylammonium bromide as a catalyst were charged at 100 ° C. The reaction was carried out with stirring for 8 hours. After completion of the reaction, a solution obtained by adding ethyl acetate to the reaction mixture was washed with water three times, and the organic layer was dried using magnesium sulfate, and then the solvent was distilled off, whereby an epoxy group-containing polyorganosiloxane C- 10.1 g of 4 was obtained. The Mw of C-4 was 8,000.

[Synthesis Example 11]
In Synthesis Example 10, 7.7 g of the above polyorganosiloxane, 3.5 g of 4′-pentyl-1,1′-bicyclohexyl-4-carboxylic acid instead of 4-octyloxybenzoic acid, and tetrabutylammonium bromide as a catalyst 10.9 g of an epoxy group-containing polyorganosiloxane C-7 was obtained in the same manner as in Synthesis Example 10 except that the amount was 0.8 g. The Mw of C-7 was 8,500.

<Preparation of liquid crystal aligning agent>
[B] Antioxidant and other [C] compounds used for the preparation of each liquid crystal aligning agent are as follows.

<[B] Antioxidant>
B-1: IRGANOX 1010FF (phenolic antioxidant)
B-2: ADK STAB LA-72 (amine-based antioxidant)
B-3: TINUVIN 622LD (amine antioxidant)
B-4: IRGAFOS12 (phosphorus antioxidant)
B-5: IRGANOX PS 800FL (sulfur antioxidant)
B-6: ADK STAB AO-40 (phenolic antioxidant)

<[C] Compound>
C-1: N, N, N ′, N′-tetraglycidyl-m-xylenediamine C-2: manufactured by Nagase ChemteX, EX-142
C-3: N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane C-5: Aron oxetane OXT-121
C-6: Dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether

[Example 1]
[A] NMP and ethylene glycol-mono-n-butyl ether are added to a solution containing 100 parts by mass of polyimide (A-1) as a polymer, and [B] (B-1) as an antioxidant is added. 3 parts by mass and 2 parts by mass of the above (C-1) as a [C] compound were added and stirred sufficiently. The solvent composition was NMP: ethylene glycol-mono-n-butyl ether = 60: 40 (mass ratio), solid content A solution having a concentration of 3.0% by mass was obtained. A liquid crystal aligning agent was prepared by filtering this solution using a filter having a pore diameter of 1 μm.

[Examples 2-39 and Comparative Examples 1-12]
Each liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the types and contents of the components to be blended were changed to the types and contents shown in Table 1, respectively. In Table 1, “-” indicates that the corresponding component was not used.

<Formation of liquid crystal alignment film>
Each liquid crystal aligning agent is applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film having a thickness of 1 mm by a spinner, pre-baked at 80 ° C. for 1 minute on a hot plate, and then post-baked at 210 ° C. for 30 minutes. By baking, a liquid crystal alignment film having a film thickness of about 80 nm was formed.

<Manufacture of liquid crystal display elements>
The formation of the liquid crystal alignment film was repeated to obtain a pair (two) of substrates having the liquid crystal alignment film. Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to either one of the outer edges of the pair of substrates having the liquid crystal alignment film, and then superposed so that the liquid crystal alignment film surfaces face each other. And then the adhesive was cured. Next, a nematic liquid crystal (MLC, MLC-6608) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to produce a liquid crystal cell. . This was repeated to produce another pair of liquid crystal cells.

<Evaluation>
The following evaluation was performed about the formed liquid crystal aligning film and the manufactured liquid crystal display element. The results are also shown in Table 1.

[Light resistance]
For the manufactured liquid crystal cell pair, after applying a voltage of 5 V at 70 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, the voltage holding ratio after 167 milliseconds from the release of application was determined as VHR- manufactured by Toyo Technica. 1 was measured. This value was defined as the initial voltage holding ratio (VH ₁ ) (%). Next, the liquid crystal cell after the initial voltage holding ratio measurement was irradiated with light for 1,000 hours using a weather meter using a carbon arc as a light source. With respect to the liquid crystal cell after light irradiation, the voltage holding ratio was measured again by the same method as described above. This value was defined as a voltage holding ratio (VH ₂ (%) after light irradiation. A decrease amount ΔVHR (%) of the voltage holding ratio was obtained from the following formula and was regarded as light resistance.
ΔVHR (%) = VH ₁ −VH ₂
When ΔVHR was less than 2.5%, the light resistance was excellent, the case where it was 2.5% or more and less than 5.0% was judged good, and the case where it was 5.0% or more was judged as poor.

[High temperature and high humidity resistance]
For the other pair of liquid crystal cells manufactured as described above, a voltage of 5 V was applied at 70 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio after 167 milliseconds from release of application was manufactured by Toyo Technica. Measured with VHR-1. This value was defined as the initial voltage holding ratio (VH ₃ ) (%). Next, the voltage holding ratio was measured again by the same method as described above for the liquid crystal cell after storing the liquid crystal cell after the initial voltage holding ratio measurement in an oven set at 60 ° C. and 90% humidity for 500 hours. This value was defined as the voltage holding ratio (VH ₄ ) (%) after high temperature and high humidity stress. The decrease amount ΔVHR ′ (%) of the voltage holding ratio was obtained from the following formula and was regarded as high temperature and high humidity resistance.
ΔVHR ′ (%) = VH ₃ −VH ₄
When ΔVHR was less than 3.0%, the high temperature and humidity resistance was excellent, when it was 3.0% or more and less than 5.0%, it was judged good, and when it was 5.0% or more, it was judged as bad. .

[Reworkability]
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 80 nm 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. When the coating film residue was not observed after NMP immersion, the reworkability was judged to be excellent (A). The substrate after 72 hours was observed after 12 hours, but was removed from the dark room after 12 hours. When the coating film residue was not observed, it was judged as good (B). After 12 hours, the substrate was taken out of the dark room, and when the coating film residue was observed, it was judged as defective (C).

  As is clear from the results in Table 1, the liquid crystal aligning agent of the present invention maintains good electrical characteristics even when it is continuously driven for a long time under a severe environment of light stress, heat and humidity. In addition, it was found that a liquid crystal alignment film having excellent reworkability when defects occur can be formed.

  According to the liquid crystal aligning agent of the present invention, even when a long period of continuous driving is performed under a harsh environment such as light stress, heat, moisture, etc., good electrical characteristics are maintained and defects are generated. A liquid crystal alignment film having excellent reworkability can be formed. Therefore, the liquid crystal display element of the present invention having the liquid crystal alignment film has little deterioration in display quality and can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, The present invention is suitably applied to display devices such as portable information terminals, digital cameras, mobile phones, various monitors, and liquid crystal televisions.

Claims (6)

[A] at least one polymer selected from the group consisting of polyamic acid and polyimide formed by dehydrating and ring-closing this polyamic acid,
[B] an antioxidant, and [C] a compound having an epoxy group,
[A] The polymer is 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 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- (tetrahydro-2,5-dioxo-3-furanyl) -Consisting of naphtho [1,2-c] furan-1,3-dione and 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2,4,6,8-dianhydride A liquid crystal aligning agent which is a polymer obtained by reacting a tetracarboxylic dianhydride containing at least one selected from the group and a diamine . The diamine is 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine and 1- (4-aminophenyl) -2,3-dihydro- The liquid crystal aligning agent of Claim 1 containing at least 1 sort (s) selected from the group which consists of 1,3,3-trimethyl-1H-indene-6-amine. [B] The liquid crystal aligning agent according to claim 1 or 2 , wherein the antioxidant has a group represented by the following formula (1) or formula (2).

(In formula (1), R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, a 1,3-dioxobutyl group, or 1, The group represented by the formula (1) is ^one from the alkyl group, aryl group, aralkyl group, 1,3-dioxobutyl group and 1,4-dioxobutyl group represented by R ^1. The hydrogen atom may be removed to form a divalent group to form a part of the molecular chain.
R ^{2 to} R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms.
X ¹ is a single bond, a carbonyl group, * — (CH ₂ ) _n —O—, * —O—, or * —CONH—. However, the bond represented by * indicates a site that binds to the piperidine ring. Moreover, n is an integer of 1-4.
X ^{2 to} X ⁵ are each independently a single bond, a carbonyl group, ** — CH ₂ —CO— or ** — CH ₂ —CH (OH) —. However, the bond represented by ** indicates a site that binds to the piperidine ring. )

(In the formula (2), R ⁶ is a hydrocarbon group having 4 to 16 carbon atoms, provided that the hydrocarbon group may have an oxygen atom or a sulfur atom in the carbon skeleton chain. , is .R ⁷ is an integer of 0 to 3, is a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms. However, when R ⁷ is plural, a plurality of R ⁷ is optionally substituted by one or more identical May be good.) The liquid crystal aligning agent according to claim 1 , wherein the compound [C] is an epoxy group-containing polyorganosiloxane or a monofunctional epoxy compound. The liquid crystal aligning film formed from the liquid crystal aligning agent of any one of Claims 1-4 . A liquid crystal display element provided with the liquid crystal aligning film of Claim 5 .