JP2015094830A - Liquid crystal alignment agent, liquid crystal alignment film, method for manufacturing liquid crystal alignment film, liquid crystal display element, and method for manufacturing liquid crystal display element - Google Patents

Abstract

Disclosed is a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film having good liquid crystal alignment and alignment stability. A liquid crystal aligning agent contains a polymer component and a compound (D) represented by the following formula (1). (In the formula, A1 is a group containing a polymerizable unsaturated bond, A2 is a functional group capable of reacting with an epoxy group, R1 is an (m + n) -valent organic group, m is an integer of 2 to 18). Yes, n is an integer from 1 to 18. However, (m + n) ≰20 is satisfied.

Description

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

  Conventionally, as a liquid crystal display element, various driving methods having different electrode structures and physical properties of liquid crystal molecules to be used have been developed. For example, TN type, STN type, VA type, MVA type, IPS type, FFS type, etc. Various liquid crystal display elements are known. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. As a material for the liquid crystal alignment film, polyamic acid or polyimide is generally used because various properties such as heat resistance, mechanical strength, and affinity with liquid crystal are good. It has also been proposed to use a polyorganosiloxane in which a group capable of expressing a desired function is introduced into a side chain as a polymer component of a liquid crystal aligning agent (see, for example, Patent Document 1). In Patent Document 1, a hydrolyzable silane compound containing a silane compound having a chain alkyl group is reacted in the presence of oxalic acid and an alcohol, and the polyorganosiloxane obtained by the reaction is reacted with a polymer of a liquid crystal aligning agent. It is disclosed for use as an ingredient.

  In recent years, a PSA (Polymer Sustained Alignment) technique has been proposed as a new technique for developing pretilt angle characteristics. The PSA technology builds a liquid crystal cell in which a photopolymerizable compound is mixed in a liquid crystal layer, and after the liquid crystal cell is built, a voltage is applied to the liquid crystal layer to irradiate light in a state where liquid crystal molecules are tilted and aligned. Polymerization of a polymerizable compound controls the molecular orientation of the liquid crystal (see, for example, Patent Document 2). According to this PSA technology, there is an advantage that the viewing angle can be increased and the response speed can be increased.

  In addition, the present applicant forms a coating film on a pair of substrates using a liquid crystal aligning agent including a polyorganosiloxane having a (meth) acryloyl group, and constructs a liquid crystal cell including the pair of substrates. Thereafter, a technique of irradiating light with a voltage applied between conductive films on a pair of substrates is proposed for a liquid crystal cell (see, for example, Patent Document 3).

  In recent years, photoalignment methods using photoisomerization, photodimerization, photolysis, etc. have been proposed as a method to give liquid crystal alignment ability to polymer thin films formed using liquid crystal alignment agents, as an alternative to rubbing methods. ing. This photo-alignment method is a method in which the radiation-sensitive organic thin film formed on the substrate is irradiated with polarized or non-polarized radiation to make the film anisotropic, thereby controlling the alignment of liquid crystal molecules. is there. According to this method, it is possible to suppress the generation of dust and static electricity in the process as compared with the conventional rubbing method, and therefore it is possible to suppress the occurrence of display defects and the decrease in yield due to dust and the like. It is. In addition, there is an advantage that liquid crystal alignment ability can be uniformly imparted to the coating film formed on the substrate.

JP-A-9-281502 JP 2003-149647 A JP 2011-118358 A

  In the case of a photo-alignment method in which a chemical change is caused by irradiation with ultraviolet rays or the like, it tends to be inferior in terms of the alignment regulating power of the liquid crystal as compared with a liquid crystal alignment film by a conventional rubbing treatment. Considering these points, when the photo-alignment method is used, the PSA treatment may be performed for the purpose of increasing the alignment regulating force of the liquid crystal. However, even if the PSA treatment is performed, the alignment regulating force of the liquid crystal molecules cannot be sufficiently increased, and the display quality is deteriorated particularly in a liquid crystal display element of a horizontal electric field type, or image sticking occurs after continuous driving for a long time. Such a problem may occur. Also in the manufacture of a vertical alignment type liquid crystal display element, the liquid crystal cell thus constructed may be subjected to light irradiation treatment to increase the alignment regulating power of the liquid crystal. However, when this process is performed, the voltage holding ratio is likely to decrease due to continuous driving for a long time, and the reliability tends to be poor.

  This invention is made | formed in view of the said subject, and sets it as the main objective to provide the liquid crystal aligning agent which can obtain the liquid crystal aligning film with favorable liquid crystal aligning property and alignment stability. Another object of the present invention is to provide a liquid crystal display element having various characteristics such as voltage holding ratio and image sticking characteristics.

  As a result of intensive studies to achieve the above-described problems of the prior art, the present inventors have found that the above-described problems can be solved by including a specific compound in the liquid crystal aligning agent. It came to be completed. Specifically, the present invention provides the following liquid crystal aligning agent, liquid crystal alignment film, method for manufacturing the liquid crystal alignment film, liquid crystal display element, and method for manufacturing the liquid crystal display element.

  In one aspect, the present invention provides a liquid crystal aligning agent containing a polymer component and a compound (D) represented by the following formula (1).

(In formula (1), A ¹ is a group containing a polymerizable unsaturated bond, A ² is a functional group capable of reacting with an epoxy group, and R ¹ is a (m + n) -valent organic group. M is an integer of 2 to 18, and n is an integer of 1 to 18. However, (m + n) ≦ 20 is satisfied.

  In one aspect, the present invention provides a method for producing a liquid crystal alignment film, comprising: a step of applying the liquid crystal alignment agent on a substrate to form a coating film; and a step of irradiating the coating film with light. In addition, the liquid crystal aligning agent described above is applied to each surface of a pair of substrates, then heated to form a coating film, and the pair of substrates on which the coating film is formed is divided into a liquid crystal molecule layer. There is provided a method for manufacturing a liquid crystal display element, comprising: a step of constructing a liquid crystal cell so as to face each other through a coating film; and a step of irradiating light from the outside of the liquid crystal cell.

  According to the liquid crystal aligning agent of this invention, the liquid crystal aligning film with favorable liquid crystal aligning property and alignment stability can be obtained. Moreover, a liquid crystal display element provided with the liquid crystal aligning film produced using the said liquid crystal aligning agent has favorable various characteristics, such as a voltage holding rate and an image sticking characteristic.

The figure which shows the pattern of the transparent electrode patterned by the comb-tooth shape. The figure which shows the pattern of the transparent electrode patterned by slit shape.

  The liquid crystal aligning agent of this invention contains a polymer component and a specific polyfunctional compound (D). Below, each component contained in the liquid crystal aligning agent of this invention and the other component arbitrarily mix | blended as needed are demonstrated.

≪Polymer component≫
The polymer component in the present invention is not particularly limited. For example, polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, poly (meth) acrylate, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene- Phenyl maleimide) derivatives and the like. Among these, the liquid crystal aligning agent of the present invention is at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, and polyorganosiloxane as a polymer component (hereinafter also referred to as “specific polymer”). .).

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

[Diamine]
Examples of the diamine used in the synthesis of the polyamic acid in the present invention include aliphatic diamine, alicyclic diamine, aromatic diamine, diaminoorganosiloxane and the like. Specific examples thereof include aliphatic diamines such as metaxylylenediamine, 1,3-propanediamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, and the like; alicyclic diamines such as 1,4- Diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

Examples of aromatic diamines include dodecanoxydiaminobenzene, tetradecanoxydiaminobenzene, pentadecanoxydiaminobenzene, hexadecanoxydiaminobenzene, octadecanoxydiaminobenzene, cholestanyloxydiaminobenzene, and cholesteryloxydiaminobenzene. Cholestanyl diaminobenzoate, cholesteryl diaminobenzoate, lanostannyl diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 1,1-bis (4 -((Aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((amino Phenoxy Methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, N- (2,4-diaminophenyl) -4 -(4-Heptylcyclohexyl) benzamide, the following formula (a-1)
(In Formula (a-1), X ^I and X ^II are each independently a single bond, —O—, —COO— or —OCO—, and R ^I and R ^II are each independently a carbon number. 1 to 3 alkanediyl groups, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1, provided that a and b is never 0 at the same time.)
Liquid crystal aligning group-containing diamine such as a compound represented by:
p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 4-aminophenyl-4′-aminobenzoate, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4 '-Diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 2,2-bis [4- (4 -Aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-amino) Phenyl) hexafluoropropane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phen Nylenediisopropylidene) 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-diamino Carbazole, N, N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, N′-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -Piperazine, other diamines such as 3,5-diaminobenzoic acid, etc .;
Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane; and the diamines described in JP 2010-97188 A can be used. Diamine can be used alone or in combination of two or more.

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

Specific examples of the compound represented by the formula (a-1) include compounds represented by the following formulas (a-1-1) to (a-1-3).

<Synthesis of polyamic acid>
The polyamic acid can be obtained by reacting the above tetracarboxylic dianhydride and diamine together with a terminal blocking agent as necessary. The ratio of the tetracarboxylic dianhydride and the diamine used in the polyamic acid synthesis reaction is 0.2 to 2 for the tetracarboxylic dianhydride acid anhydride group to 1 equivalent of the amino group of the diamine. The ratio which becomes an equivalent is preferable, and the ratio which becomes 0.3-1.2 equivalent is more preferable.
Examples of the end-capping agent include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. Etc. The use ratio of the terminal blocking agent is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less with respect to 100 parts by weight of the total of the tetracarboxylic dianhydride and diamine to be used.

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

Examples of the organic solvent used in the reaction include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenolic solvent (first group organic solvent), or one or more selected from the first group of organic solvents And a mixture of at least one selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (second-group organic solvent). In the latter case, the proportion of the second group organic solvent used is preferably 50% by weight or less, more preferably 40% by weight, based on the total amount of the first group organic solvent and the second group organic solvent. Or less, more preferably 30% by weight or less.
Particularly preferred are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol and halogen. It is preferable to use one or more selected from the group consisting of fluorinated phenols as a solvent, or to use a mixture of one or more of these and another organic solvent in the above range.
The amount of organic solvent used (a) is such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1 to 50% by weight based on the total amount (a + b) of the reaction solution. Is preferred.

  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. Isolation and purification of the polyamic acid can be performed according to known methods.

<Polyamic acid ester>
The polyamic acid ester in the present invention is, for example, [I] a method of synthesizing a polyamic acid obtained by the above synthesis reaction with a hydroxyl group-containing compound, a halide, an epoxy group-containing compound, or the like, [II] tetra It can be obtained by reacting a carboxylic acid diester with a diamine, [III] reacting a tetracarboxylic acid diester dihalide with a diamine, or the like.

Here, examples of the hydroxyl group-containing compound used in the method [I] include alcohols such as methanol, ethanol and propanol; phenols such as phenol and cresol. Examples of the halide include methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane and the like, and as an epoxy group-containing compound, Examples thereof include propylene oxide.
The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by ring-opening the tetracarboxylic dianhydride exemplified in the synthesis of the polyamic acid using the above alcohols. The reaction of Method [II] is preferably carried out in the presence of a suitable dehydration catalyst. Examples of the dehydration catalyst include 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium halide, carbonylimidazole, a phosphorus condensing agent, and the like. The tetracarboxylic acid diester dihalide used in Method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride.
Examples of the diamine used in the method [II] and the method [III] include diamines exemplified in the synthesis of polyamic acid. The polyamic acid ester may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist.

<Polyimide>
The polyimide contained in the liquid crystal aligning agent of the present invention can be obtained, for example, by dehydrating and ring-closing and imidizing the polyamic acid synthesized as described above.

  The polyimide may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure possessed by the polyamic acid that is the precursor, and only a part of the amic acid structure is dehydrated and cyclized, It may be a partially imidized product in which an imide ring structure coexists. From the viewpoint of electrical characteristics, the polyimide in the present invention preferably has an imidization ratio of 30% or more, more preferably 50 to 99%, and still more preferably 65 to 99%. This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of polyimide amic acid structures and the number of imide ring structures in percentage. Here, a part of the imide ring may be an isoimide ring.

  The polyamic acid is preferably dehydrated and closed by heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and heating the mixture as necessary. Is called. Of these, the latter method is preferred.

  In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the amic acid structure of a polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, triethylamine and the like can be used. It is preferable that the usage-amount of a dehydration ring-closing catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents to be used. Examples of the organic solvent used for the dehydration ring-closing reaction include organic solvents used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

  In this way, a reaction solution containing polyimide is obtained. This reaction solution may be used 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 after isolating the polyimide. You may use for preparation of an aligning agent, or you may use for preparation of a liquid crystal aligning agent, after purifying the isolated polyimide. These purification operations can be performed according to known methods.

  The polyamic acid, polyamic acid ester and polyimide obtained as described above preferably have a solution viscosity of 10 to 800 mPa · s, when this is made into a solution having a concentration of 10% by weight, and 15 to 500 mPa · s. More preferably, it has a solution viscosity of s. In addition, the solution viscosity (mPa · s) of the above polymer is based on a polymer solution having a concentration of 10% by weight prepared using a good solvent for the polymer (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). The value measured at 25 ° C. using an E-type rotational viscometer. Regarding the polyamic acid, polyamic acid ester, and polyimide, the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography is preferably 1,000 to 500,000, and preferably 2,000 to 300,000. More preferred.

<Polyorganosiloxane>
The polyorganosiloxane contained in the liquid crystal aligning agent of this invention should just have a siloxane skeleton, and the structure of a side chain part is not specifically limited. A polyorganosiloxane having an epoxy group (hereinafter also referred to as “epoxy group-containing polyorganosiloxane”) is used from the viewpoint of reacting with the group “A ² ” of the compound (D) to improve liquid crystal alignment and liquid crystal stability. It is preferable to include. Specific examples of the epoxy group-containing polyorganosiloxane include, for example, a polyorganosiloxane having a repeating unit represented by the following formula (S-1), a hydrolyzate thereof, or a condensate of the hydrolyzate.
(In Formula (S-1), X ¹ is a monovalent organic group having an epoxy group, and Y ¹ is a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or carbon. (It is an aryl group of formulas 6 to 20. In the molecule, X ¹ and Y ¹ may be the same or different from each other.)

X ¹ in the formula (S-1) is not particularly limited as long as it has an epoxy group. For example, for a chain hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group Group having an epoxy group bonded thereto. Preferable specific examples of X ¹ include groups represented by the following formulas (X1-1) to (X1-3).
(In the formula, “*” indicates a bond with a silicon atom.)

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

Examples of the alkyl group having 1 to 10 carbon atoms of Y ¹ in the formula (S-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, and a decanyl group. These may be linear or branched. Examples of the alkoxyl group having 1 to 10 carbon atoms of Y ¹ include a group formed by bonding the alkyl group and an oxygen atom, specifically, a methoxy group, an ethoxy group, and the like. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a benzyl group, and a tolyl group.

The epoxy equivalent of the epoxy group-containing polyorganosiloxane is preferably 100 to 10,000 g / mol, and more preferably 150 to 1,000 g / mol.
The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of the epoxy group-containing polyorganosiloxane is preferably 500 to 100,000, more preferably 1,000 to 10,000, More preferably, it is 000-5,000.

<Synthesis of polyorganosiloxane>
The epoxy group-containing polyorganosiloxane as described above is preferably a hydrolyzable silane compound having an epoxy group (epoxy group-containing silane compound), or a mixture of the epoxy group-containing silane compound and another silane compound, It can be obtained by hydrolysis and condensation in the presence of a suitable organic solvent, water and catalyst.

  Examples of the epoxy group-containing silane compound 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. An epoxy group containing silane compound can be used individually by 1 type or in mixture of 2 or more types.

The other silane compound is not particularly limited as long as it is hydrolyzable. For example, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, methyldichlorosilane, methyldimethoxysilane , Dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, Tetramethoxysilane, tetraethoxysilane, octadecyltrichlorosilane, octadecyltrimethoxysilane, vinyltrichloro Silane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane;
3- (meth) acryloxypropyltrichlorosilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 2- (meth) acryloxyethyltrichlorosilane, 2- (meth ) Acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 4- (meth) acryloxybutyltrichlorosilane, 4- (meth) acryloxybutyltrimethoxysilane, 4- (meth) acryloxy Butyltriethoxysilane, 3- (meth) acryloxybutyltrimethoxysilane, 3- (meth) acryloxypentyltrimethoxysilane, 3- (meth) acryloxyhexyltrimethoxysilane, 3- (meth) acryloxyheptyltri Methoxysilane, 3- (meta Acryloxyoctyltrimethoxysilane, 3- (meth) acryloxynonyltrimethoxysilane, 3- (meth) acryloxydecyltrimethoxysilane, 3- (meth) acryloxyundecyltrimethoxysilane, 3- (meth) acryl Roxide decyltrimethoxysilane and the like can be mentioned. Another silane compound may be used individually by 1 type, and may be used in combination of 2 or more type. Note that “(meth) acryloxy” means “acryloxy” and “methacryloxy”.
In the synthesis of the epoxy group-containing polyorganosiloxane, the proportion of the epoxy group-containing silane compound and the other silane compound used may be adjusted so that the epoxy equivalent of the resulting polyorganosiloxane is within the preferred range. preferable.

Examples of the organic solvent that can be used in the synthesis of the polyorganosiloxane include hydrocarbons, ketones, esters, ethers, alcohols, and the like. Here, examples of the hydrocarbon include toluene and xylene; examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone; examples of the ester include ethyl acetate and acetic acid. n-butyl, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc .; examples of the ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc .; For example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Recall mono -n- propyl ether, ethylene glycol monobutyl -n- butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono -n- propyl ether, and respectively. Of these, it is preferable to use a water-insoluble organic solvent. In addition, these organic solvents can be used individually by 1 type or in mixture of 2 or more types.
The amount of the organic solvent used when synthesizing the polyorganosiloxane is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight with respect to 100 parts by weight of the total silane compounds used for the synthesis. It is. Moreover, the amount of water used when synthesizing the polyorganosiloxane is preferably 0.5 to 100 times mol, more preferably 1 to 30 times mol, based on all silane compounds used for synthesis.

Examples of the catalyst that can be used in the synthesis of the polyorganosiloxane include acids, alkali metal compounds, organic bases, titanium compounds, and zirconium compounds. Here, examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, formic acid, succinic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and phosphoric acid; examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, Examples of the organic base include sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, and the like. Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole, triethylamine, and tri-n. A tertiary organic amine such as propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, a quaternary organic amine such as tetramethylammonium hydroxide; it can.
As the catalyst, an organic base is particularly preferable. The amount of the organic base used varies depending on the reaction conditions such as the type of organic base and temperature, and should be set as appropriate. More preferably, it is 0.05-1 times mole.

The hydrolysis / condensation reaction when synthesizing the polyorganosiloxane is performed by dissolving one or more hydrolyzable silane compounds in an organic solvent, mixing the resulting solution with an organic base and water, For example, it is preferably carried out by heating in an oil bath or the like.
During the hydrolysis / condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C., and preferably 0.5 to 12 hours, more preferably 1 to 8 hours. During heating, the mixture may be stirred or placed under reflux.
After completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. In this washing, washing with water containing a small amount of salt, for example, an aqueous ammonium nitrate solution of about 0.2% by weight is preferable because the washing operation is facilitated. Washing is performed until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieves as necessary, and then the solvent is removed to achieve the target. A polyorganosiloxane can be obtained. The epoxy group-containing polyorganosiloxane may be a commercially available product. Examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (manufactured by Chisso Corporation).

As the polyorganosiloxane contained in the liquid crystal aligning agent of the present invention, a compound having a group capable of imparting liquid crystal aligning ability to the coating film (hereinafter also referred to as “liquid crystal aligning group”) is preferably used. it can. The polyorganosiloxane having a liquid crystal alignment group (hereinafter also referred to as “alignment group-containing polyorganosiloxane”) may be contained separately from the epoxy group-containing polyorganosiloxane, or may be an epoxy. The aspect contained as polyorganosiloxane which has group and a liquid crystal aligning group may be sufficient. The latter is preferred. Preferable specific examples of the orientation group-containing polyorganosiloxane include, for example, a polyorganosiloxane having a repeating unit represented by the following formula (S-2).
(In Formula (S-2), X ² is a monovalent organic group having a liquid crystal alignment group. Y ¹ has the same meaning as in Formula (S-1) above.)

X ² in the formula (S-2), the remaining structures are not particularly limited as long as it has a liquid crystal alignment group. Preferable specific examples of X ² include groups represented by the following formulas (X2-1A) to (X2-3B), for example.
(In the formula, R ³ is a liquid crystal aligning group. “*” Represents a bond with a silicon atom.)

Examples of the liquid crystal aligning group (R ³ ) include a group that exhibits photo-alignment by photoisomerization, photodimerization, photolysis, etc. (hereinafter, also referred to as “photo-alignment group”), and pretilt angle characteristics with respect to the coating film. (Hereinafter, also referred to as “pretilt angle providing group”).

  When performing the process which provides liquid crystal aligning ability with respect to a coating film by a photo-alignment method, it is preferable that the polyorganosiloxane which has a photo-alignment group is included. As the photoalignable group, groups derived from various compounds exhibiting orientation by photoisomerization, photodimerization, photolysis, etc. can be employed. For example, an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, A group having a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton, a chalcone-containing group containing chalcone or a derivative thereof as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, coumarin or a derivative thereof And a coumarin-containing group containing as a basic skeleton. Among these, a group having a cinnamic acid structure is preferable from the viewpoint of good photoalignment and easy introduction into a polymer.

The polyorganosiloxane in which R ^{3 in the} formula (S-2) is a photoalignable group includes, for example, the epoxy group-containing polyorganosiloxane obtained above, a carboxylic acid (C-1) having a photoalignment group, and Can be obtained by reacting. Preferable examples of the carboxylic acid (C-1) include compounds represented by the following formulas (C1-1) to (C1-3).
(In the formula, R ⁸ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group in which at least one hydrogen atom in the alkyl group is substituted with a fluorine atom or a cyano group. ^.Z 1 ^{R 6,} R ⁷ and ^{R 9} are each independently 1,4-cyclohexylene group or a 1,4-phenylene group ^{.R 10} is alkanediyl group having 2 to 10 carbon atoms, Z ² , Z ³ , Z ⁴ and Z ⁵ are each independently a single bond, an ether group, a thioether group, an ester group or a thioester group, and s, t and u are each independently 0 or 1. )

The alkyl group having 1 to 20 carbon atoms of R ⁸ and R ¹¹ may be linear or branched, but is preferably linear. Preferable specific examples of the formula (C1-1) include, for example, compounds represented by the following formulas (c1-1-1) to (c1-1-10); Preferable specific examples include, for example, compounds represented by the following formula (c1-2-1); preferred specific examples of the above formula (C1-3) include, for example, the following formula (c1-3-1) And the like.
(In formula, R < ⁸ >, R < ¹⁰ >, R < ¹¹ > is synonymous with said formula (C1-1)-(C1-3).)

  Examples of the pretilt angle-providing group include alkyl groups having 4 to 40 carbon atoms, fluoroalkyl groups having 4 to 40 carbon atoms, alkoxy groups having 4 to 40 carbon atoms, groups having a steroid skeleton having 17 to 51 carbon atoms, and polycyclic rings. Examples thereof include a group having a structure.

The polyorganosiloxane in which R ^{3 in the} above formula (S-2) is a pretilt angle imparting group is, for example, the epoxy group-containing polyorganosiloxane obtained above, a carboxylic acid (C-2) having a pretilt angle imparting group, and Can be obtained by reacting. Preferable examples of the carboxylic acid (C-2) include compounds represented by the following formulas (C2-1) to (C2-5).
(In the formula, R ²² represents an alkyl group or fluoroalkyl group having 4 to 20 carbon atoms. R ¹² represents a hydrogen atom or an alkyl group or fluoroalkyl group having 1 to 20 carbon atoms. R ¹³ and R ^15. Each independently represents a 1,4-cyclohexylene group or a 1,4-phenylene group, R ¹⁴ represents a hydrogen atom or a methyl group, R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ is each independently an alkanediyl group having 1 to 10 carbon atoms, Z ⁶ , Z ⁷ , Z ⁸ , Z ⁹ , Z ¹⁰ , Z ¹¹ , Z ¹² , Z ¹³ and Z ¹⁴ are each independently And a single bond, an ether group, a thioether group, an ester group or a thioester group, p is an integer of 0 to 3, q is an integer of 0 to 2, and r is 0 or 1.)

The alkyl group for R ²² and R ¹² may be linear or branched, but is preferably linear. Preferable specific examples of the formula (C2-1) include, for example, compounds represented by the following formulas (c2-1-1) to (c2-1-9); Preferable specific examples include, for example, compounds represented by the following formulas (c2-2-1) to (c2-2-7); preferred specific examples of the above formula (C2-3) include, for example, Preferred examples of the compound represented by the formula (c2-3-1); and the preferred formula (C2-4) include, for example, a compound represented by the following formula (c2-4-1); Preferable specific examples of (C2-5) include, for example, compounds represented by the following formula (c2-5-1).
^{(Wherein, R 22, R 12, R} 16, R 17, R 18, R 19, R 20, R 21 are each the above formula and (C2-1) ~ (C2-5) synonymous.)

  In the case of producing a vertical alignment type liquid crystal display element, it is preferable that a polyorganosiloxane having a pretilt angle imparting group is included as a polymer component. The method for synthesizing the polyorganosiloxane having a pretilt angle imparting group is not limited to the above. For example, the polyorganosiloxane may be synthesized by polymerization containing a hydrolyzable silane compound having a pretilt angle imparting group in the monomer composition.

  As the polyorganosiloxane contained in the liquid crystal aligning agent of the present invention, a polyorganosiloxane having a polymerizable unsaturated group can also be used. When such a polyorganosiloxane is used, it becomes possible to increase the alignment regulating force of the liquid crystal molecules by the light irradiation treatment after the construction of the liquid crystal cell. Examples of the polymerizable unsaturated group include a group having a (meth) acryloyl group, a vinyl group, and a styryl group. Among them, a (meth) acryloyl group is preferable from the viewpoint of good sensitivity to light. Such polyorganosiloxane can be obtained, for example, by reacting at least one carboxylic acid represented by each of the above formulas (C2-2) and (C2-5) with an epoxy group-containing polyorganosiloxane. it can.

[Reaction of epoxy group-containing polyorganosiloxane and carboxylic acid]
The reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid having a liquid crystal alignment group (hereinafter also referred to as “carboxylic acid (C)”) can be preferably carried out in the presence of a catalyst and an organic solvent.

As the carboxylic acid to be reacted with the epoxy group-containing polyorganosiloxane, carboxylic acid (C) can be used alone or in combination with other carboxylic acids. As another carboxylic acid, for example, a carboxylic acid (F) represented by the following formula (f) can be used simultaneously with the carboxylic acid (C) for the purpose of crosslinking the epoxy group-containing polyorganosiloxane.
(In the formula (f), R ²³ is a tertiary hydrocarbon group having 4 to 20 carbon atoms.)

R ²³ in formula (f) is preferably a tertiary alkyl group or a group having a cycloalkane skeleton. Specific examples of R ²³ include groups represented by the following formulas (t-1) and (t-2).
(In formula (t-1), R ⁴¹ , R ⁴² and R ⁴³ are each independently an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 4 to 20 carbon atoms. Formula (t- In 2), R ⁴⁴ is an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and M ¹ has 4 carbon atoms together with the carbon atom to which R ⁴⁴ is bonded. (It is a divalent group forming an alicyclic hydrocarbon group of ˜20. “*” Represents a bond bonded to an oxygen atom.)

In the above formula (f), the carboxyl group is preferably bonded to the para position.
Preferable specific examples of the carboxylic acid (F) include compounds represented by the following formulas (f-1) and (f-2), for example. Carboxylic acid (F) can be used individually by 1 type or in combination of 2 or more types.

The ratio of the carboxylic acid (total amount) to be reacted with the epoxy group-containing polyorganosiloxane is preferably 0.001 to 10 mol with respect to 1 mol of the epoxy group contained in the epoxy group-containing polyorganosiloxane. It is more preferable to set it as 01-5 mol, It is still more preferable to set it as 0.05-2 mol, 0.05-0.8 mol is especially preferable. In addition, the polyorganosiloxane which has a liquid crystal aligning group and an epoxy group can be obtained by making the usage-amount of carboxylic acid less than the epoxy group which an epoxy-group-containing polyorganosiloxane has.
When synthesizing a polyorganosiloxane having a polymerizable unsaturated group, the use ratio (total amount) of the carboxylic acid represented by each of the above formulas (C2-2) and (C2-5) is the epoxy group-containing poly It is preferable to set it as 0.001-5 mol with respect to 1 mol of epoxy groups which organosiloxane has, It is more preferable to set it as 0.01-1 mol, It is further preferable to set it as 0.03-0.6 mol. preferable.
When using the said carboxylic acid (F), it is preferable that the use ratio shall be 0.01-1 mol with respect to 1 mol of epoxy groups. More preferably, it is 0.02-0.3 mol, More preferably, it is 0.04-0.2 mol.

As the catalyst used in the reaction, for example, a compound known as a so-called curing accelerator that accelerates the reaction of an organic base or an epoxy compound can be used. Examples of the organic base include primary and secondary organic amines such as ethylamine, piperazine and piperidine; tertiary organic amines such as triethylamine and pyridine; quaternary organic amines such as tetramethylammonium hydroxide; Can do. Of these, tertiary organic amines or quaternary organic amines are preferred as the organic base.
Examples of the curing accelerator include tertiary amines such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol; imidazole compounds such as 2-methylimidazole and 2-n-heptylimidazole; Organic phosphorus compounds such as phosphine; quaternary phosphonium salts such as benzyltriphenylphosphonium chloride; diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof Organic metal compounds such as zinc octylate, tin octylate, aluminum acetylacetone complex; tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride Grade ammonium salts; boron trifluoride, such as boron compounds triphenyl borate; and the like; zinc chloride, such as metal halide compound of stannic chloride. Of these, quaternary ammonium salts are preferred.
The catalyst is used in an amount of preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy group-containing polyorganosiloxane. The

Examples of the organic solvent that can be used in the reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, and alcohol compounds. Of these, ether compounds, ester compounds, and ketone compounds are preferred from the viewpoints of solubility of raw materials and products, and ease of purification of the products, and specific examples of particularly preferred solvents include 2-butanone and 2-hexanone. , Methyl isobutyl ketone, cyclopentanone, cyclohexanone, butyl acetate and the like. The organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more. More preferably, it is used in a proportion of 50% by weight. The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.
In addition, the synthesis method of the said orientation group containing polyorganosiloxane is a method of introduce | transducing a liquid crystal aligning group by the ring-opening addition of the epoxy which epoxy group containing polyorganosiloxane has. This synthesis method is convenient because it is simple and can increase the introduction ratio of the liquid crystal orientation group.

  The polystyrene-reduced weight average molecular weight measured by gel permeation chromatography of the orientation group-containing polyorganosiloxane is preferably 1,000 to 200,000, more preferably 2,000 to 50,000. More preferably, it is 3,000 to 20,000.

<< Compound (D) >>
The compound (D) is represented by the following formula (1).
(In formula (1), A ¹ is a group containing a polymerizable unsaturated bond, A ² is a functional group capable of reacting with an epoxy group, and R ¹ is a (m + n) -valent organic group. M is an integer of 2 to 18, and n is an integer of 1 to 18. However, (m + n) ≦ 20 is satisfied.

In the above formula (1), A ¹ is preferably at least one selected from the group consisting of a (meth) acryloyloxy group, a vinyl group, and a styryl group in terms of high reactivity to light, and (meth) acryloyl. More preferred is an oxy group. The (meth) acryloyloxy group includes an acryloyloxy group and a methacryloyloxy group.
Examples of the functional group (A ² ) capable of reacting with the epoxy group include a carboxyl group, a thiol group, a primary amino group, and an epoxy group. Among them, a carboxyl group is preferable in terms of high reactivity with an epoxy group.
Examples of the (m + n) -valent organic group represented by R ¹ include a hydrocarbon group such as a chain hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, and a methylene group in the hydrocarbon group is an ether group or a thioether. And a group substituted by a group, an ester group or a thioester group. R ¹ preferably has 1 to 30 carbon atoms, more preferably 3 to 20 carbon atoms.
m is preferably 2 to 10, and more preferably 2 to 8. n is preferably from 2 to 18, more preferably from 2 to 10, and even more preferably from 2 to 8. (M + n) is preferably from 4 to 12, and more preferably from 4 to 10.
The compound represented by the above formula (1) is preferably a compound represented by the following formula (1-1) (hereinafter also referred to as “carboxylic acid-containing polyvalent (meth) acrylate”).
(In Formula (1-1), R ² is a hydrogen atom or a methyl group. R ¹ , m, and n have the same meanings as those in Formula (1)).

Specific examples of the carboxylic acid-containing polyvalent (meth) acrylate include compounds represented by the following formulas (1-1-1) to (1-1-3).
(In formulas (1-1-1) to (1-1-3), R ⁴ is a group represented by the following formula (p-1), formula (p-2) or formula (p-3). The plurality of R ⁴ in the molecule may be the same or different from each other, provided that at least one of the plurality of R ⁴ is a group represented by the formula (p-1) and at least 1 Each is at least one of a group represented by the formula (p-2) and a group represented by the formula (p-3), j is an integer of 1 to 10.)
(In formulas (p-1) to (p-3), R ² is a hydrogen atom or a methyl group, and R ³⁰ is an alkanediyl group or a phenylene group having 1 to 6 carbon atoms.)

  In the above formulas (1-1-1) to (1-1-3), the number (x) of groups represented by the above formula (p-1) and the group represented by the above formula (p-2). And the ratio with the number (total number y) of groups represented by the said Formula (p-3) can be suitably adjusted according to the kind of polymer to be used, an additive, compounding quantity, etc. In the case of a horizontal electric field type liquid crystal display element, x is preferably larger than y in terms of reducing burn-in, and in the case of a vertical alignment type liquid crystal display element, the response speed of liquid crystal molecules is increased.

As the compound (D), a commercially available product may be used, or a compound obtained by synthesis may be used. As a commercial item of a compound (D), the Toagosei Co., Ltd. brand name "TO-2349", "TO-1382" etc. are mentioned, for example.
Moreover, when synthesizing the compound (D), the synthesis method is not particularly limited, and organic chemical chemistry methods can be combined appropriately. The carboxylic acid-containing polyvalent (meth) acrylate represented by the above formula (1-1) will be described as an example. For example, [1] a polyfunctional (meth) acrylate compound having a hydroxyl group and succinic anhydride A method of reacting with an acid anhydride (corresponding to the following scheme (I)); [2] a method of reacting a polyfunctional (meth) acrylate compound and a carboxylic acid having a thiol group (Michael addition) (the following scheme ( II)), etc.
(In the formula, R ¹ , R ² , m and n have the same meanings as in the above formula (1-1). R ³⁰ is an alkanediyl group or phenylene group having 1 to 6 carbon atoms.)

  The compounding ratio of the compound (D) is preferably 1 to 30 parts by weight with respect to 100 parts by weight as a whole of the polymer components in the liquid crystal aligning agent. By setting it to 1 part by weight or more, the effect of improving the liquid crystal alignment property and alignment stability can be sufficiently obtained. Moreover, it becomes possible to suppress a liquid crystal orientation defect by setting it as 30 weight part or less. More preferably, it is the range of 3-25 weight part, More preferably, it is the range of 5-20 weight part. In addition, the said compound (D) can be used individually by 1 type or in combination of 2 or more types.

≪Other ingredients≫
The liquid crystal aligning agent of this invention may contain the other component as needed. Preferable specific examples of such other components include compounds having two or more epoxy groups in the molecule and not corresponding to the above compound (D) (hereinafter also referred to as “epoxy group-containing compounds”), Examples thereof include compounds having two or more carboxyl groups in the molecule and not corresponding to the above compound (D) (hereinafter also referred to as “polyvalent carboxylic acid”).

<Epoxy group-containing compound>
The epoxy group-containing compound can be used for the purpose of improving the adhesion of the liquid crystal alignment film to the substrate surface. Specific examples of the epoxy group-containing compound include, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether. 2,2-dibromoneopentylglycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N′-tetraglycidyl-p-phenylenediamine, N , N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenyl ether, N, N, N ′, N ′ -Tetraglycidyl-2,2'-dimethyl -4,4'-diaminobiphenyl, trimethylolpropane triglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine, N, N, N ′, N′-tetraglycidyl-1,4-diaminocyclohexane, bis (N, N-diglycidyl-4-aminocyclohexyl) methane, 1,4-bis (N, N-diglycidylaminomethyl) Cyclohexane, 1,4-bis (N, N-diglycidylaminomethyl) benzene, 1,3,5-to Scan (N, N-diglycidyl aminomethyl) cyclohexane, the following formulas (e-1) ~ (e-3)
And the like, and the like. In addition, an epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598 can also be used.
When the epoxy group-containing compound is added to the liquid crystal aligning agent, the blending ratio is preferably 40 parts by weight or less, and 0.1 to 30 parts by weight with respect to a total of 100 parts by weight of the polymer contained in the liquid crystal aligning agent. Is more preferable.

<Polyvalent carboxylic acid>
The polyvalent carboxylic acid can be used for the purpose of improving the liquid crystal alignment property of the liquid crystal alignment film. Specific examples of the polyvalent carboxylic acid include dicarboxylic acids such as fumaric acid, malonic acid, adipic acid, terephthalic acid, isophthalic acid, sebacic acid, diphenyl ether-4,4′-dicarboxylic acid, and pyridine-2,6-dicarboxylic acid. Acid; tricarboxylic acid such as 1,2,4-butanetricarboxylic acid, 1,2,3-cyclohexanetricarboxylic acid, trimellitic acid, 1,2,4-naphthalenetricarboxylic acid; 1,2,3,4-cyclobutanetetra Examples thereof include carboxylic acids, 2,3,5-tricarboxycyclopentylacetic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, and tetracarboxylic acids such as pyromellitic acid.
When polyvalent carboxylic acid is added to the liquid crystal aligning agent, the blending ratio is preferably 40 parts by weight or less, and 0.1 to 30 parts by weight with respect to a total of 100 parts by weight of the polymer contained in the liquid crystal aligning agent. Is more preferable.

  In addition to the above, the other components include, for example, a functional silane compound, a compound having one epoxy group in the molecule, a compound having at least one oxetanyl group in the molecule, a bismaleimide compound, an antioxidant, A photosensitizer etc. are mentioned. The blending amount of these other components can be appropriately adjusted within a range not impairing the effects of the present invention.

As a preferable form of the liquid crystal aligning agent of the present invention, as a polymer component,
(I) A mode consisting of only one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide;
(II) an embodiment comprising a polyorganosiloxane and a kind selected from the group consisting of polyamic acid, polyamic acid ester and polyimide;
(III) an embodiment consisting only of polyorganosiloxane;
And so on.
Of these, the embodiment (II) is preferable, and in the embodiment (II), the polyorganosiloxane is more preferably an epoxy group-containing polyorganosiloxane. The blending ratio of the polyorganosiloxane in the embodiment (II) is preferably 1 to 30 parts by weight, and preferably 5 to 20 parts by weight with respect to 100 parts by weight of the total of polyamic acid, polyamic acid ester and polyimide. It is more preferable.
In the case of producing a liquid crystal display element using a technique in which a polymerizable component is introduced into an alignment film and the liquid crystal cell is irradiated with light after the liquid crystal cell is constructed, at least one of the polymer components of the liquid crystal aligning agent is used. As a part, it is preferable to blend a polymer having a polymerizable unsaturated group in the side chain. The polymer having a polymerizable unsaturated group in the side chain is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyorganosiloxane, more preferably polyorganosiloxane. . In particular, in the embodiment (II), it is preferable that the polyorganosiloxane has a polymerizable unsaturated group, so that the effect of improving liquid crystal alignment can be obtained with a small amount of light irradiation.

≪Solvent≫
The liquid crystal aligning agent of the present invention is preferably constituted by dissolving the polymer component, the compound (D) and other components optionally blended as necessary, in an organic solvent.
Here, examples of the solvent used for preparing the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate Etc. These can be used alone or in admixture of two or more.

  The solid content concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, and the like. The range is preferably 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface as described later, and preferably heated to form a coating film that is a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes excessive and a good liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal aligning agent increases and the coating characteristics are increased. Is inferior.

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

≪Liquid crystal alignment film and liquid crystal display element≫
The liquid crystal alignment film of the present invention is formed by the liquid crystal aligning agent prepared as described above. Moreover, the liquid crystal display element of this invention comprises the liquid crystal aligning film formed using the said liquid crystal aligning agent. The operation mode to which the liquid crystal display element of the present invention is applied is not particularly limited, and can be applied to various operation modes such as TN type, STN type, IPS type, FFS type, VA type, and MVA type. The liquid crystal display element of the present invention can be produced, for example, by a method including the following steps (1) to (3).

[Step (1): Formation of coating film]
First, a liquid crystal aligning agent is apply | coated to each surface of a pair of board | substrate, Then, this is heated and a coating film is formed.
(1-1) When manufacturing a TN-type, STN-type, VA-type, or MVA-type liquid crystal display element, a pair of two substrates each provided with a patterned transparent conductive film is used as a transparent conductive material in each substrate. On the film forming surface, the liquid crystal aligning agent of the present invention is preferably applied by an offset printing method, a spin coating method, a roll coater method or an ink jet printing method, respectively. Here, as the substrate, for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly (cycloaliphatic olefin) can be used. As a transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. Can be used. In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo-etching after forming a transparent conductive film without a pattern, a method of using a mask having a desired pattern when forming a transparent conductive film, etc. be able to. In applying the liquid crystal aligning 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 or a functional titanium compound is formed on the surface of the substrate surface on which the coating film is formed. It is also possible to perform a pretreatment to apply the above in advance.

  (1-2) When manufacturing an IPS type or FFS type liquid crystal display element, an electrode forming surface of a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape, and an electrode are provided. The liquid crystal aligning agent of this invention is each apply | coated to one surface of the counter substrate which is not, and then a coating film is formed by heating each application surface. About the preferable film thickness of the material of the board | substrate used at this time, the material of a transparent conductive film, the coating method, the heating conditions after application | coating, the patterning method of a transparent conductive film or a metal film, the pre-processing of a board | substrate, and the coating film formed Is the same as (1-1) above. As the metal film, for example, a film made of a metal such as chromium can be used.

  In both cases (1-1) and (1-2), after applying a liquid crystal aligning agent on the substrate, the organic solvent is removed to form a coating film or a liquid crystal aligning film as a liquid crystal aligning film. A coating film is formed. It is preferable to remove the solvent by heat treatment. Specifically, after application of the liquid crystal aligning agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied aligning agent. The pre-baking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-bake time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, a firing (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, for thermal imidization of the amic acid structure present in the polymer. The firing temperature (post-bake temperature) at this time is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. Thus, the film thickness of the formed film is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

  In addition, when the polymer contained in the liquid crystal aligning agent of the present invention is a polyamic acid, a polyamic acid ester, or an imidized polymer having an imide ring structure and an amic acid structure, a coating is applied. It is good also as a coating film made more imidized by advancing dehydration ring-closing reaction by further heating after film formation.

[Orientation ability imparting treatment]
When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal display element, a treatment for imparting liquid crystal alignment ability to the coating film formed in the step (1) is usually performed. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. Examples of the treatment for imparting alignment ability include rubbing treatment in which a coating film is rubbed in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton, and treatment by a photo-alignment method. Among these, use of the photo-alignment method is possible in that it is possible to suppress the occurrence of display defects due to dust and static electricity and the reduction in yield, and the liquid crystal alignment ability can be uniformly imparted to the coating film. Is preferred. On the other hand, when manufacturing a VA type liquid crystal display element, the coating film formed in the step (1) can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to the above-described treatment.
In addition, the liquid crystal alignment film after the rubbing treatment is further subjected to a process for changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet rays or a surface of the liquid crystal alignment film. A resist film is formed on the part, and a rubbing process is performed in a direction different from the previous rubbing process, followed by a process of removing the resist film, so that the liquid crystal alignment film has different liquid crystal alignment capabilities for each region. . In this case, it is possible to improve the visibility characteristics of the obtained liquid crystal display element.

In the photo-alignment method, liquid crystal alignment ability is imparted to the coating film by irradiating the coating film formed on the substrate with polarized or non-polarized radiation. As the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. When the radiation used is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, may be performed from an oblique direction, or a combination thereof. When non-polarized radiation is irradiated, the irradiation direction is an oblique direction.
As a light source to be used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. Ultraviolet rays in a preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter or a diffraction grating.
Light irradiation is applied in at least one of the method of irradiating the coating film after the post-baking process, the method of irradiating the coating film after the pre-baking process and before the post-baking process, the pre-baking process, and the post-baking process. It can be performed by a method of irradiating the coating film while heating the film. The amount of light irradiation is preferably 100 to 50,000 J / m ² , more preferably 300 to 20,000 J / m ² . Moreover, you may perform light irradiation with respect to a coating film, heating a coating film, in order to improve the reactivity. The temperature at the time of heating is 30-250 degreeC normally, Preferably it is 40-200 degreeC, More preferably, it is 50-150 degreeC. By such light irradiation treatment, a liquid crystal alignment film is formed on the substrate.

[Step (2): Cell construction]
(2-1) A liquid crystal cell in which two substrates (a pair) having the liquid crystal alignment film formed thereon as described above are prepared, and the pair of substrates are arranged so that the liquid crystal alignment film faces each other with the liquid crystal interposed therebetween. Manufacturing. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. First, the first method is a conventionally known method. In this method, first, two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the substrate surface And after injecting and filling a liquid crystal in the cell gap divided by the sealing agent, a liquid crystal cell is manufactured by sealing the injection hole. The second method is a method called an ODF (One Drop Fill) method. In this method, for example, an ultraviolet light curable sealing material is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and a predetermined number of places on the liquid crystal alignment film surface are applied. After the liquid crystal is dropped on the other substrate, the other substrate is bonded so that the liquid crystal alignment film faces. A liquid crystal cell is manufactured by spreading the liquid crystal over the entire surface of the substrate and then 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 at the time of filling the liquid crystal. It is desirable to do. As the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used. The thickness of the liquid crystal layer is preferably 1 to 5 μm.
(2-2) When manufacturing a PSA type liquid crystal display element, a liquid crystal cell is constructed in the same manner as in the above (2-1) except that a photopolymerizable compound is injected or dropped together with a liquid crystal.

[Step (3): Light irradiation on liquid crystal cell]
After the liquid crystal cell is constructed, the liquid crystal cell is irradiated with light from the outside. By storing the direction in which the liquid crystal molecules are tilted by this light irradiation, it becomes possible to stabilize the liquid crystal alignment. Light irradiation to the liquid crystal cell is performed in a state where a voltage is applied between the conductive films of a pair of substrates in a vertical electric field type liquid crystal display element, and in a state where no voltage is applied between the conductive films in a horizontal electric field type liquid crystal display element. . The voltage applied here can be, for example, 5 to 50 V direct current or alternating current. Moreover, as light to irradiate, the ultraviolet-ray and visible light which contain light with a wavelength of 150-800 nm can be used, for example, However, The ultraviolet-ray containing light with a wavelength of 300-400 nm is preferable. As a light source of irradiation light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. In addition, the ultraviolet rays in the above preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter diffraction grating. The irradiation dose of light, preferably less than 1,000 J / ^{m 2} or more 200,000 J / ^{m 2,} more preferably from 1,000~100,000J / ^{m 2.}

  And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell. As a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film itself in which a polarizing film called an “H film” in which iodine is absorbed while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films The polarizing plate which consists of can be mentioned. When the rubbing treatment is performed on the coating film, the two substrates are arranged to face each other so that the rubbing directions in each coating film are at a predetermined angle, for example, orthogonal or antiparallel.

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

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

The solution viscosity of each polymer solution in the synthesis example, the imidization ratio of polyimide, the weight average molecular weight of the polymer, and the epoxy equivalent were measured by the following methods.
[Solution viscosity of polymer solution]
The solution viscosity [mPa · s] of the polymer solution was measured at 25 ° C. using an E-type rotational viscometer for a solution prepared to a polymer concentration of 10% by weight using a predetermined solvent.
[Imidation rate of polyimide]
The polyimide solution was poured into pure water, and the resulting precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. From the obtained ¹ H-NMR spectrum, the imidation ratio [%] was determined by the formula represented by the following formula (1).
Imidation ratio [%] = (1-A ¹ / A ² × α) × 100 (1)
(In Formula (1), A ¹ is a peak area derived from protons of NH groups appearing near a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a precursor of a polymer (polyamic acid). The number ratio of other protons to one proton of NH group in)
[Weight average molecular weight of polymer]
The weight average molecular weight Mw of the polymer is a polystyrene equivalent value measured by gel permeation chromatography under the following conditions.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²
[Epoxy equivalent]
The epoxy equivalent is a value measured according to the “hydrochloric acid-methyl ethyl ketone method” of JIS C2105.
The following synthesis examples were repeated at the following synthesis scale as necessary to secure the necessary amount of product to be used in the following synthesis examples, examples and comparative examples.

<Synthesis of Compound (D)>
[Synthesis Example 1: Synthesis of Compound (1-2-1)]
Compound (1-2-1) was synthesized according to Scheme 1 below.

  In a 100 mL three-necked flask equipped with a thermometer, a reflux tube and a dropping funnel, 6.24 g of compound (1-2A), 8.64 g of acetonitrile, 6 mg of 2,6-di-t-butyl-4-methoxyphenol and mercaptopropionic acid 2.40 g was added and heated to 50 ° C. Subsequently, 6.07 g of triethylamine was added dropwise over 1 hour, and then reacted at 50 ° C. for 1 hour. After completion of the reaction, 100 mL of ethyl acetate was added, and the mixture was washed once with 100 mL of 1M aqueous oxalic acid and 5 times with water, and then subjected to solvent replacement twice with butyl cellosolve, whereby the compound (1-2) 40 g of a butyl cellosolve solution of -1) was obtained.

[Synthesis Example 2: Synthesis of Compound (1-3-1)]
Compound (1-3-1) was synthesized according to Scheme 2 below.

  In a 100 mL three-necked flask equipped with a thermometer, a reflux tube and a dropping funnel, 12.2 g of compound (1-3A), 15.8 g of acetonitrile, 12 mg of 2,6-di-t-butyl-4-methoxyphenol and mercaptopropionic acid 3.61 g was added and heated to 50 ° C. Subsequently, 6.07 g of triethylamine was added dropwise over 1 hour, and then reacted at 50 ° C. for 1 hour. After completion of the reaction, 100 mL of ethyl acetate was added, and the mixture was washed once with 100 mL of 1M oxalic acid water and 5 times with water, and then solvent replacement twice with butyl cellosolve to obtain a compound having a solid content concentration of 20% (1-3). 70 g of a butyl cellosolve solution of -1) was obtained.

<Synthesis of polyorganosiloxane>
[Synthesis Example 3: Synthesis of Epoxy Group-Containing Polyorganosiloxane (EPS-1)]
A reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine, and room temperature. Mixed. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain polyorganosiloxane (EPS- 1) was obtained as a viscous transparent liquid.
When this polyorganosiloxane (EPS-1) was subjected to ¹ H-NMR analysis, a peak based on the oxiranyl group was obtained in the vicinity of chemical shift (δ) = 3.2 ppm according to the theoretical intensity. It was confirmed that no side reaction occurred. Mw of the polyorganosiloxane (EPS-1) was 2,200, and the epoxy equivalent was 186 g / mol.

[Synthesis Example 4: Synthesis of epoxy group-containing polyorganosiloxane (EPS-2)]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 458.7 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 162.8 3-methacryloxypropyltrimethoxysilane, methyl 3108 g of isobutyl ketone and 62.2 g of triethylamine were charged and mixed at room temperature. Next, 621.5 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain polyorganosiloxane (EPS- 2) was obtained as a viscous transparent liquid. The weight average molecular weight Mw of this polyorganosiloxane (EPS-2) was 2,900.

[Synthesis Example 5: Synthesis of liquid crystal aligning group-containing carboxylic acid (3-6-1)]
Carboxylic acid (3-6-1) was synthesized according to Scheme 3 below.

Synthesis of Compound (3-6-1A) In a 2 L eggplant flask equipped with a nitrogen introduction tube and a reflux tube, 24.4 g (0.2 mol) of p-hydroxybenzaldehyde, 138.2 g (1.0 mol) of potassium carbonate, and After adding 600 mL of acetone (MS dried), 32.6 g (0.22 mol) of 4-bromobutyronitrile was added and refluxed for 3 hours. After completion of the reaction, 1 L of ethyl acetate was added and washed with 1 L of water, then washed twice with 200 mL of a saturated aqueous sodium carbonate solution, and further washed with 300 mL of water three times. Next, after drying an organic layer with magnesium sulfate, 35.5g of yellow transparent liquid of a compound (3-6-1A) was obtained by distilling a solvent off under reduced pressure.
-Synthesis | combination of a compound (3-6-1) 35.52g (0.188 mol) of compounds (3-6-1), 224 mL of pyridines, and malon were added to a 1000 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube. 39.13 g (0.376 mol) of acid was dissolved. Next, 16.0 g (0.188 mol) of piperidine was added and refluxed for 3 hours. After completion of the reaction, 800 mL of ethyl acetate and 800 mL of THF were added, washed once with 1 L of 2N aqueous hydrochloric acid and twice with 1N aqueous hydrochloric acid, then added with 1.5 L of saturated aqueous sodium carbonate, and washed twice with 400 mL of ethyl acetate. . Next, after adding 400 mL of ethyl acetate and 800 mL of THF, the solution was acidified with 500 mL of 8N hydrochloric acid, washed with 400 mL of water three times, dried over magnesium sulfate, concentrated, and crystallized to give carboxylic acid (3-6 25.2 g of white crystals of 1) were obtained.

[Synthesis Example 6: Synthesis of liquid crystal aligning group-containing carboxylic acid (3-9-1)]
A 500 mL three-necked flask equipped with a condenser is charged with 20 g of 4-bromodiphenyl ether, 0.18 g of palladium acetate, 0.98 g of tris (2-tolyl) phosphine, 32.4 g of triethylamine, and 135 mL of dimethylacetamide and mixed with the solution. did. Next, 7 g of acrylic acid was added to the above solution using a syringe and stirred, and then reacted at 120 ° C. for 3 hours with stirring. After confirming the completion of the reaction by thin layer chromatography (TLC), the reaction solution was cooled to room temperature. The insoluble material was filtered off, and the filtrate was poured into 300 mL of 1N hydrochloric acid to collect the precipitate. The precipitate was recrystallized from a mixed solvent consisting of ethyl acetate and hexane (ethyl acetate: hexane = 1: 1 (volume ratio)) to give a compound represented by the following formula (3-9-1) (carboxylic acid 8.4 g of (3-9-1)) was obtained.

[Synthesis Example 6-1: Synthesis of carboxylic acid (F-2)]
Carboxylic acid (F-2) was synthesized according to the following scheme.

Synthesis of compound (F-2D) To a 200 mL eggplant flask equipped with a reflux tube and a nitrogen introduction tube, 21.6 g of monomethyl terephthalate, 88 mL of thionyl chloride and 5 drops of N, N-dimethylformamide were added at 80 ° C. for 1 hour. Refluxed. After completion of the reaction, thionyl chloride was distilled off under reduced pressure with an aspirator to obtain a pale yellow solid of compound (F-2B). Tetrahydrofuran 50mL was added to this solid, and it was set as A liquid. On the other hand, 13.7 g of 1-ethylcyclopentanol was added to a 500 mL three-necked flask equipped with a thermometer, a nitrogen inlet tube and a dropping funnel, and the mixture was ice-cooled. Subsequently, 90 mL of 1.6M n-butyllithium hexane solution was added dropwise over 30 minutes. Next, after dripping A liquid over 30 minutes, it stirred under ice-cooling as it was, and after 2 hours, 100 mL of water was added and reaction was stopped. Next, 400 mL of ethyl acetate was added, washed 4 times with 400 mL of water, and concentrated to dryness to obtain 32.8 g of an orange liquid of the compound (F-2D).
Synthesis of Compound (F-2) A 1 L eggplant flask was charged with 32.8 g of Compound (F-2D), 150 mL of methanol, 50 mL of water, and 9.95 g of lithium hydroxide monohydrate, and reacted at room temperature for 1 hour. . After completion of the reaction, 250 mL of tetrahydrofuran and 300 mL of ethyl acetate were added and washed once with 400 mL of diluted hydrochloric acid and three times with 300 mL of water. After drying with magnesium sulfate, the mixture was concentrated, hexane was added, and the precipitated crystals were filtered and dried to obtain 14.1 g of yellow needle crystals of the compound (F-2).

[Synthesis Example 7: Synthesis of orientation group-containing polyorganosiloxane (S-2-1)]
In a 100 mL three-necked flask, 3.5 g of the polyorganosiloxane (EPS-1) synthesized in Synthesis Example 3 above, 24 g of methyl isobutyl ketone, 2.42 g of carboxylic acid (3-6-1) (polyorganosiloxane (EPS- 1) (corresponding to 50 mol% with respect to silicon atoms) and 0.35 g of a trade name “UCAT 18X” (manufactured by San Apro Co., Ltd., epoxy compound curing accelerator) were charged and refluxed for 5 hours. After completion of the reaction, methanol was added to the reaction mixture to form a precipitate. A solution obtained by dissolving the precipitate in ethyl acetate was washed with water three times, and then the solvent was distilled off to remove polyorganosiloxane (S- 2 g of white powder of 2-1) was obtained. The weight average molecular weight of the polyorganosiloxane (S-2-1) was 9,200.

[Synthesis Examples 8 to 10 and 10A: Synthesis of orientation group-containing polyorganosiloxane]
The orientation group-containing polyorganosiloxanes (S-2-2) to (S-2-4) are prepared in the same manner as in Synthesis Example 7 except that the types and amounts of the compounds used are as shown in Table 1 below. , (S-2-10) was synthesized.

  In Table 1, the numerical value of the blending amount of carboxylic acid indicates the charged amount [mol%] with respect to silicon atoms of the epoxy group-containing polyorganosiloxane.

[Synthesis Example 11: Synthesis of polyamic acid (PA-1)]
Dissolve 5.55 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 9.45 g of a diamine compound represented by the following formula (3-7DA) in 85 g of N-methyl-2-pyrrolidone (NMP). The reaction was performed at room temperature for 6 hours. The reaction mixture was poured into a large excess of methanol to precipitate the reaction product. This precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 10 g of polyamic acid (PA-1).

[Synthesis Example 12: Synthesis of polyamic acid (PA-2)]
19.61 g (0.1 mol) of cyclobutanetetracarboxylic dianhydride and 21.23 g (0.1 mol) of 4,4′-diamino-2,2′-dimethylbiphenyl were mixed with N-methyl-2-pyrrolidone. It melt | dissolved in 367.6g and reacted for 6 hours at room temperature. The reaction mixture was poured into a large excess of methanol to precipitate the reaction product. This precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 35 g of polyamic acid (PA-2).

[Example 1]
(1) Preparation of liquid crystal aligning agent As polymer components, 100 parts by weight of orientation group-containing polyorganosiloxane (S-2-1) and 1,000 parts by weight of polyamic acid (PA-2), compound (D) 100 parts by weight of “TO-1382” manufactured by Toa Gosei Co., Ltd. and 200 parts by weight of trimellitic acid as other components were mixed, and N-methyl-2-pyrrolidone (NMP) and butyl cellosolve ( BC) was added to obtain a solution having a solvent composition of NMP: BC = 50: 50 (weight ratio) and a solid content concentration of 3.0% by weight. The liquid crystal aligning agent (A-1) was prepared by filtering this solution through a filter having a pore diameter of 0.2 μm.

(2) Manufacture of a transverse electric field type liquid crystal display element A glass substrate having a pair of metal electrodes made of chromium patterned in a comb shape on one side and a counter glass substrate on which no electrode is provided is a pair of glass substrates. After applying the liquid crystal aligning agent (A-1) prepared above on the surface having the electrode and the one surface of the counter glass substrate using a spinner and pre-baking with an 80 ° C. hot plate for 1 minute, Was heated (post-baked) at 200 ° C. for 1 hour in an oven substituted with nitrogen to form a coating film having a thickness of 0.1 μm. A schematic diagram showing the electrode pattern configuration on the glass substrate is shown in FIG. The two metal electrodes (conductive film pattern) of the horizontal electric field mode liquid crystal display element are hereinafter referred to as an electrode 11 and an electrode 12, respectively.
Next, a pair of substrates having a liquid crystal alignment film by irradiating polarized ultraviolet rays 300 J / m ² including a 313 nm emission line from the normal direction of the substrate using a Hg-Xe lamp and a Grand Taylor prism on the surfaces of the coating films, respectively. Obtained. A bead spacer was dispersed on the surface of the substrate having one liquid crystal alignment film, and an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm was applied to the outer periphery by screen printing. Thereafter, the liquid crystal alignment film surfaces of each of the pair of substrates are made to face each other, and the substrates are stacked and pressure-bonded so that the directions of the respective substrates are reversed when irradiated with polarized ultraviolet rays. Heat cured.
Next, after filling a liquid crystal mixture in which 0.3 wt% of a polymerizable liquid crystal represented by the following formula (L-1) is added to a liquid crystal “MLC-7028” manufactured by Merck in the gap between the substrates from the liquid crystal injection port, The liquid crystal inlet was sealed with an epoxy adhesive. Then, in order to remove the flow alignment at the time of liquid crystal injection, this is heated at 150 ° C. and then slowly cooled to room temperature, and further irradiated with UV light from the outside of the liquid crystal cell (irradiation amount: 2,000 mJ / cm ² (λ = 365 nm)). Next, a polarizing plate is bonded to both outer surfaces of the substrate so that the polarization directions thereof are orthogonal to each other and the optical axis of the polarized ultraviolet light of the liquid crystal alignment film is orthogonal to the direction of projection onto the substrate surface. Manufactured.

(3) Evaluation of liquid crystal orientation The presence or absence of an abnormal domain in the change in brightness when the voltage of 5 V was turned ON / OFF (applied / released) was observed with an optical microscope for the liquid crystal display element manufactured above. At this time, the liquid crystal orientation was “excellent” when no abnormal domains were observed, the liquid crystal orientation was “good” when a few abnormal domains were observed, and the liquid crystal orientation was observed when multiple abnormal domains were observed. Rated as “bad”. As a result, in Example 1, the liquid crystal alignment was “good”.

(4) Evaluation of image sticking characteristics The horizontal electric field type liquid crystal display device manufactured as described above is placed in an environment of 25 ° C. and 1 atm, no voltage is applied to the electrode 12, and an AC voltage of 3.5V and a DC voltage are applied to the electrode 11. A composite voltage of 5V was applied for 2 hours. Immediately thereafter, an AC voltage of 4 V was applied to both the electrode 11 and the electrode 12. The time from when the voltage of 4V AC was started to be applied to both electrodes until the difference in light transmittance between the electrode 11 and the electrode 12 could not be visually confirmed was measured. The seizure property “excellent” when this time is 20 seconds or more and less than 60 seconds, the seizure property “good” when it is 60 seconds or more and less than 100 seconds, and the seizure property when it is 100 seconds or more and less than 150 seconds. The characteristic “OK” was evaluated as a “bad” burn-in characteristic when 150 seconds were exceeded. As a result, in Example 1, the image sticking characteristic was “good”.

[Examples 2 to 20, Comparative Examples 1 and 2]
Liquid crystal aligning agents (A-2) to (A-) are obtained by performing the same operations as in Example 1 except that the types and amounts of the polymer, compound (D) and other components used are changed as shown in Table 2 below. 20), (R-1) and (R-2) were prepared. Moreover, while using the obtained liquid crystal aligning agent (A-2)-(A-20), (R-1), (R-2), a liquid crystal display element was manufactured similarly to Example 1, and liquid crystal was manufactured. The orientation and image sticking characteristics were evaluated. The results are shown in Table 3 below.

In Table 2, the numbers in parentheses indicate the blending ratio (parts by weight) of each compound. The carboxylic acid-containing polyvalent acrylate (trade names “TO-1382” and “TO-2349”) of the compound (D) was obtained from Toagosei Co., Ltd. Abbreviations of the compound (D) and other components in Table 2 have the following meanings.
(Compound (D))
D-1: Compound represented by the above formula (1-2-1) D-2: Compound represented by the above formula (1-3-1) (other additives)
EP-1: N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane

  As shown in Table 3, all of the liquid crystal display elements of Examples 1 to 20 were evaluated as “excellent” or “good” in terms of liquid crystal orientation and image sticking characteristics. On the other hand, in Comparative Examples 1 and 2 in which the liquid crystal aligning agent did not contain the compound (D), the liquid crystal alignment was evaluated as “bad”, and the image sticking property was evaluated as “good”.

[Synthesis Example 13: Synthesis of liquid crystal aligning group-containing carboxylic acid (7-3-1)]
Carboxylic acid (7-3-1) was synthesized according to Scheme 4 below.

Synthesis of compound (7-3-1A) In a 1 L three-necked flask equipped with a dropping funnel, a thermometer and a nitrogen introduction tube, 5.00 g (36.22 mmol) of hydroxybenzoic acid, 150 mL of tetrahydrofuran, 100 mL of t-butanol and N , N-dimethylaminopyridine 0.177 g (1.45 mmol) was added. Next, 8.22 g (39.84 mmol) of dicyclohexylcarbodiimide was dissolved in 50 mL of tetrahydrofuran in a dropping funnel and dropped over 30 minutes, and the reaction was allowed to proceed for 15 hours. After completion of the reaction, the filtrate obtained by filtration through celite was concentrated, 300 mL of ethyl acetate was added, and the mixture was washed with an aqueous solution of sodium bicarbonate twice and with water three times, and then concentrated and vacuum dried. An orange viscous liquid was obtained. This viscous liquid was subjected to silica column purification (developing solvent: hexane / ethyl acetate = 80/20) to obtain 3.6 g of white crystals of compound (7-3-1A).
-Synthesis | combination of compound (7-3-1B) Compound (7-3-1A) 12.25g (63.1mmol), 11-bromoundecanol 16 were added to a 500 mL three necked flask equipped with the thermometer and the nitrogen inlet tube. .64 g (66.2 mmol), N, N-dimethylacetamide 180 mL, potassium carbonate 9.58 g (69.4 mmol) and potassium iodide 2.09 g (12.6 mmol) were added and reacted at 100 ° C. for 2 hours. After completion of the reaction, 500 mL of ethyl acetate was added and the mixture was washed once with dilute hydrochloric acid and three times with water, then dried over magnesium sulfate, concentrated and dried to give a white solid of compound (7-3-1B) 21. 3 g was obtained.

-Synthesis | combination of compound (7-3-1D) 16.48 g (58.4 mmol) of compound (7-3-1C) and compound (7-3-1B) were added to a 1 L three neck flask provided with the thermometer and the nitrogen inlet tube. 21.3 g (58.4 mmol) and 440 mL of methylene chloride were added and suspended, and the mixture was ice-cooled. Next, 13.47 g (70.3 mmol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1.43 g (11.7 mmol) of N, N-dimethylaminopyridine were added under ice cooling. After stirring for 2 hours, the mixture was returned to room temperature and reacted for 16 hours. After completion of the reaction, 2 L of ethyl acetate was added, followed by separation / washing with water three times, and then drying with magnesium sulfate. Next, the white precipitate produced by concentration was filtered and dried to obtain 26.0 g of a white crystal of the compound (7-3-1D).
Synthesis of carboxylic acid (7-3-1) 26.0 g (41.3 mmol) of compound (7-3-1D), 55 mL of trifluoroacetic acid and 110 mL of methylene chloride were added to a 500 mL eggplant flask and reacted at room temperature for 5 hours. I let you. After completion of the reaction, the solvent was removed by an aspirator, 2 L of ethyl acetate and 2 L of tetrahydrofuran were added, washed 3 times with water, and dried over magnesium sulfate. Next, 20.64 g of white crystals of carboxylic acid (7-3-1) were obtained by filtering and drying the precipitate produced by concentration.

[Synthesis Example 14: Synthesis of liquid crystal aligning group-containing carboxylic acid (8-1-1)]
Carboxylic acid (8-1-1) was synthesized according to the following scheme 5.

Synthesis of Compound (8-1-1A) In a 1 L three-necked flask equipped with a thermometer and a nitrogen introduction tube, 15.0 g of Compound (6-6-1), 16.6 g of Compound (7-3-1B) and 270 mL of methylene chloride was added and ice-cooled to 5 ° C or lower. Next, 10.47 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 1.11 g of N, N-dimethylaminopyridine were added and reacted at 5 ° C. or lower for 24 hours. After completion of the reaction, 500 mL of ethyl acetate and 250 mL of THF were added, and the mixture was washed once with dilute hydrochloric acid and three times with water, dried over magnesium sulfate, concentrated and crystallized to give white crystals of compound (8-1-1A). 18.4 g (100% purity) was obtained.
Synthesis of carboxylic acid (8-1-1) 18.4 g of compound (8-1-1A), 90 mL of methylene chloride and 45 mL of trifluoroacetic acid were added to a 500 mL eggplant flask equipped with a nitrogen inlet tube for 4 hours at room temperature. Reacted. After completion of the reaction, trifluoroacetic acid was removed with an aspirator, and then dissolved in 600 mL of ethyl acetate and 300 mL of THF and washed with water three times. Next, after drying with magnesium sulfate, concentration and crystallization yielded 12.8 g of white crystals of carboxylic acid (8-1-1) (purity 99.9%).

[Synthesis Example 15: Synthesis of liquid crystal aligning group-containing carboxylic acid (9-1-1)]
Carboxylic acid (9-1-1) was synthesized according to Scheme 6 below.

-Synthesis | combination of compound (9-1-1A) The compound (9-1-1A) was synthesize | combined by the method similar to the said compound (8-1-1).
-Synthesis | combination of compound (9-1-1B) The compound (9-1-1B) was synthesize | combined by the method similar to the said compound (7-3-1B).
Synthesis of compound (9-1-1C) In a 100 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 3.4 g of compound (9-1-1A), 2.2 g of compound (9-1-1B) and 30 mL of methylene chloride was added, and the mixture was ice-cooled to 5 ° C. or lower. Next, 1.7 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.18 g of N, N-dimethylaminopyridine were added and reacted at 5 ° C. or lower for 24 hours. After completion of the reaction, 300 mL of ethyl acetate was added, and the mixture was washed three times with water, dried over magnesium sulfate, concentrated, and crystallized to obtain 2.4 g of white crystals of the compound (9-1-1C).
Synthesis of carboxylic acid (9-1-1) 2.4 g of compound (9-1-1C), 4 mL of trifluoroacetic acid and 8 mL of methylene chloride were added to a 100 mL eggplant flask and allowed to react at room temperature for 2 hours. After completion of the reaction, the solvent was removed by an aspirator, 50 mL of ethyl acetate and 50 mL of tetrahydrofuran were added, washed 3 times with water, and dried over magnesium sulfate. Next, 1.7 g of white crystals of carboxylic acid (9-1-1) were obtained by filtering and drying the precipitate produced by concentration.

[Synthesis Example 16: Synthesis of liquid crystal aligning group-containing carboxylic acid (10-1-1)]
Carboxylic acid (10-1-1) was synthesized according to Scheme 7 below.

-Synthesis | combination of compound (10-1-1A) Compound (10-1-1A) was synthesize | combined by the method similar to the said compound (7-3-1).
-Synthesis | combination of compound (10-1-1B) Compound (10-1-1B) was synthesize | combined by the method similar to compound (7-3-1C).
-Synthesis | combination of a compound (10-1-1C) Compound (10-1-1A) 9.21g (20 mmol) and a compound (9-1-1B) 5 to a 300 mL three necked flask provided with the thermometer and the nitrogen inlet tube. .89 g (20 mmol) and 80 mL of methylene chloride were added, and the mixture was ice-cooled. Next, 4.60 (24 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.489 g (4.0 mmol) of N, N-dimethylaminopyridine were added, and the mixture was cooled with ice for 4 hours. After stirring, the mixture was returned to room temperature and reacted for a whole day and night. After completion of the reaction, 1000 mL of ethyl acetate was added, and liquid separation washing was performed 4 times with 300 mL of water, followed by drying with magnesium sulfate. Next, the white precipitate produced by concentration to about 100 mL was filtered and dried to obtain 7.93 g of a white crystal of the compound (10-1-1C) (purity 94.4%, yield 53.8). %).
Synthesis of carboxylic acid (10-1-1) To a 100 mL eggplant flask, 4.72 g (6.41 mmol) of compound (10-1-1C), 7 mL of trifluoroacetic acid and 14 mL of methylene chloride were added and reacted at room temperature for 1 hour. I let you. After completion of the reaction, the solvent was removed by an aspirator, 100 mL of ethyl acetate and 100 mL of THF (with a stabilizer) were added, washed 3 times with 100 mL of water, and dried over magnesium sulfate. Next, several mg of a polymerization inhibitor was added and concentrated to about 80 mL, and the resulting precipitate was filtered and dried to obtain 2.59 g (purity 97.2%) of white crystals of carboxylic acid (10-1-1). Yield 59.4%).

[Synthesis Example 17: Synthesis of orientation group-containing polyorganosiloxane (S-2-5)]
In a 100 mL three-necked flask, 8.7 g of polyorganosiloxane (EPS-1) synthesized in Synthesis Example 3 above, 114 g of methyl isobutyl ketone, and 2.7 g of compound (6-6-1) (polyorganosiloxane (EPS- 1) (corresponding to 20 mol% with respect to silicon atoms), 8.5 g of compound (7-3-1) (corresponding to 30 mol% with respect to silicon atoms of polyorganosiloxane (EPS-1)), and Tetrabutylammonium bromide 0.89g was charged and reacted at 90 ° C for 30 hours. After completion of the reaction, methanol was added to the reaction mixture to form a precipitate. A solution obtained by dissolving the precipitate in ethyl acetate was washed with water three times, and then the solvent was distilled off to remove polyorganosiloxane (S- 15 g of white powder 2-5) was obtained. The weight average molecular weight of the polyorganosiloxane (S-2-5) was 9,500.

[Synthesis Examples 18 to 21, 21A: Synthesis of orientation group-containing polyorganosiloxane]
The orientation group-containing polyorganosiloxanes (S-2-6) to (S-2-9) were prepared in the same manner as in Synthesis Example 17 except that the types and amounts of the compounds used were as shown in Table 4 below. , (S-2-11) was synthesized.

  In Table 4, the numerical value of the blending amount of carboxylic acid indicates the amount [mol%] charged with respect to silicon atoms of the epoxy group-containing polyorganosiloxane.

[Synthesis Example 22: Synthesis of polyimide (PI-1)]
2,3,5-tricarboxycyclopentylacetic acid dianhydride 19.1 g as tetracarboxylic dianhydride, and cholestanyloxy-2,4-diaminobenzene (represented by the following formula (DA-1) as diamine Compound (8.49 g) and p-phenylenediamine (7.42 g) were dissolved in NMP (140 g) and reacted at 60 ° C. for 4 hours. A small amount of the resulting polyamic acid solution was taken, NMP was added, and the viscosity was measured with a solution having a solid content concentration of 10%. The solution viscosity was 100 mPa · s. To the obtained polyamic acid solution, 325 g of NMP, 6.74 g of pyridine, and 8.69 g of acetic anhydride were added, and dehydration ring closure was performed at 110 ° C. for 4 hours. After the imidization reaction, the solvent in the system was replaced with new NMP (pyridine and acetic anhydride used for the imidization reaction were removed from the system in this operation), and a polyimide (PI) with an imidation ratio of about 50% (PI A solution containing about 15% by weight of -1) was obtained.

[Example 21]
(1) Preparation of liquid crystal aligning agent As polymer components, 200 parts by weight of alignment group-containing polyorganosiloxane (S-2-5), 1,000 parts by weight of polyimide (PI-1), and compound (D) 10 parts by weight of the compound (1-2-1) was mixed, and NMP and butyl cellosolve (BC) were added as a solvent thereto, the solvent composition was NMP: BC = 50: 50 (weight ratio), and the solid content concentration was A 3.0 wt% solution was obtained. A liquid crystal aligning agent (A-21) was prepared by filtering this solution through a filter having a pore diameter of 0.2 μm.

(2) Manufacture of a liquid crystal display element having a transparent electrode without pattern Using the liquid crystal aligning agent (A-21) prepared above, a liquid crystal display element having a transparent electrode without pattern was manufactured. First, the liquid crystal aligning agent (A-21) is apply | coated on the transparent electrode surface of the glass substrate which has a transparent electrode (no pattern) which consists of ITO film | membranes using a liquid crystal aligning film printer (Nissha Printing Co., Ltd. product). did. Next, the solvent was removed by heating (pre-baking) on an 80 ° C. hot plate for 1 minute, and then heating (post-baking) on a 150 ° C. hot plate for 10 minutes to form a coating film having an average film thickness of 600 mm. .
The coating film was rubbed with a rubbing machine having a roll wrapped with a rayon cloth at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair foot indentation length of 0.1 mm. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then drying was performed in a 100 ° C. clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film.
Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edges of the pair of substrates having the liquid crystal alignment film, the liquid crystal alignment film surfaces are overlapped and pressure bonded. The adhesive was cured. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) 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 display element. .

The above operation was repeated to produce three liquid crystal display elements having a transparent electrode without pattern. One of them was used for the evaluation of orientation described later. The remaining two liquid crystal display elements were each irradiated with light in a state where a voltage was applied between the conductive films by the following method (light irradiation step), and then subjected to evaluation of orientation and voltage holding ratio.
(Light irradiation process)
An ultraviolet gland irradiation apparatus using a metal halide lamp as a light source in a state where an alternating current of 10 Hz is applied between the electrodes of two of the three liquid crystal display elements obtained above and the liquid crystal is driven. Was irradiated from the outside of the liquid crystal display element at an irradiation dose of 100,000 J / m ² . In addition, this irradiation amount is the value measured using the light meter measured on the basis of wavelength 365nm.

(3) Evaluation of orientation With respect to the three liquid crystal display elements produced as described above, the presence or absence of light leakage / alignment disorder in a state where no voltage was applied was visually observed under backlight irradiation. In the evaluation, the case where there was no light leakage / alignment disorder was evaluated as “good”, and the case where there was light leakage / alignment disorder was determined as “defective”. As a result, all three liquid crystal display elements of Example 21 had “good” orientation.

(4) Evaluation of voltage holding ratio Among the above manufactured liquid crystal display elements with a light irradiation amount of 100,000 J / m ² , a voltage of 5 V was applied at 23 ° C. with an application time of 60 microseconds and a span of 167 milliseconds. Then, the voltage holding ratio [%] 167 milliseconds after the application release was measured. As a measuring device, VHR-1 manufactured by Toyo Corporation was used. As a result, the voltage holding ratio was 98%.

(5) Manufacture of the liquid crystal display element which has the patterned transparent electrode The liquid crystal display element which has the patterned transparent electrode was manufactured using the liquid crystal aligning agent (A-21) prepared above. First, on each electrode surface of a pair of glass substrates (substrates A and B) each having an ITO electrode that is patterned into a slit shape as shown in FIG. The liquid crystal aligning agent (A-21) was apply | coated using Nissha Printing Co., Ltd. product. Next, the solvent was removed by heating (pre-baking) on an 80 ° C. hot plate for 1 minute, and then heating (post-baking) on a 150 ° C. hot plate for 10 minutes to form a coating film having an average film thickness of 600 mm. . The coating film was subjected to ultrasonic cleaning in ultrapure water for 1 minute and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a pair (two) of substrates having a liquid crystal alignment film.
Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edges of the pair of substrates having the liquid crystal alignment film, the liquid crystal alignment film surfaces are overlapped and pressure-bonded so as to face each other. The adhesive was cured. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled between the pair of substrates from the liquid crystal inlet, and then the liquid crystal inlet was sealed with an acrylic photo-curing adhesive to produce a liquid crystal display element. .

The above operation was repeated to produce three liquid crystal display elements having patterned transparent electrodes. For these three liquid crystal display elements, ultraviolet rays were applied at a dose of 100,000 J / m ² with a voltage applied between the conductive films in the same manner as in the production of the liquid crystal cell having the transparent electrode without pattern. After irradiation, the response speed was evaluated. The electrode pattern used here is the same type as the PSA mode electrode pattern.

(6) Evaluation of response speed For each of the three liquid crystal display elements manufactured above, first, a visible light lamp was irradiated without applying a voltage, and the luminance of the light transmitted through the liquid crystal display element was measured with a photomultimeter. It was measured. The measured value at this time was 0% relative transmittance. Next, the transmittance (luminance of light transmitted through the liquid crystal display element) when AC 60 V was applied between the electrodes of the liquid crystal display element for 5 seconds was measured in the same manner as described above, and this value was set as 100% relative transmittance. did. Then, when AC 60 V was applied to each liquid crystal display element, the time until the relative transmittance shifted from 10% to 90% was measured, and this time was defined as the response speed [msec]. The response speed was evaluated by the average value of three cells. As a result, the response speed of the liquid crystal display element of Example 21 was 10 msec.

[Examples 22 to 26, Comparative Example 3]
Liquid crystal aligning agents (A-22) to (A-26) are prepared in the same manner as in Example 21 except that the types and amounts of the polymer (P) and the compound (D) used are changed as shown in Table 5 below. ) And (R-3) were prepared. Further, using the obtained liquid crystal aligning agents (A-22) to (A-26) and (R-3), a liquid crystal display element having a non-patterned transparent electrode and a patterned transparent electrode in the same manner as in Example 21. While manufacturing the liquid crystal display element which has, said various evaluation was performed. The results are shown in Table 6 below.

  In Table 5, the numerical values in parentheses for each compound indicate the blending ratio (parts by weight) of each compound. The abbreviations for compound (D) are the same as those in Table 2.

  As shown in Table 6, all of the liquid crystal display elements of Examples 21 to 26 were evaluated as “good” in liquid crystal alignment. In addition, the voltage holding ratio was as high as 98% or more, and the response speed was fast. On the other hand, in Comparative Example 3, although the liquid crystal alignment and response speed were the same as those in the example, the voltage holding ratio was as low as 95%.

  11, 12 ... Electrodes

Claims (9)

The liquid crystal aligning agent containing a polymer component and the compound (D) represented by following formula (1).
(In formula (1), A ¹ is a group containing a polymerizable unsaturated bond, A ² is a functional group capable of reacting with an epoxy group, and R ¹ is a (m + n) -valent organic group. M is an integer of 2 to 18, and n is an integer of 1 to 18. However, (m + n) ≦ 20 is satisfied.   The liquid crystal aligning agent of Claim 1 whose said n is an integer of 2-18. The liquid crystal aligning agent according to claim 1 or 2, wherein the A ¹ is at least one selected from the group consisting of a (meth) acryloyloxy group, a vinyl group, and a styryl group.   The liquid crystal aligning agent as described in any one of Claims 1-3 containing at least 1 type chosen from the group which consists of a polyamic acid, a polyamic acid ester, a polyimide, and polyorganosiloxane as said polymer component.   The liquid crystal aligning agent as described in any one of Claims 1-4 containing an epoxy-group-containing polyorganosiloxane as said polymer component.   The liquid crystal aligning film formed using the liquid crystal aligning agent as described in any one of Claims 1-5. A step of applying a liquid crystal aligning agent according to any one of claims 1 to 5 to form a coating film on a substrate;
And a step of irradiating the coating film with light.   The liquid crystal display element which comprises the liquid crystal aligning film of Claim 6 obtained by the liquid crystal aligning film of Claim 6, or the manufacturing method of Claim 7. Applying the liquid crystal aligning agent according to any one of claims 1 to 5 on each surface of a pair of substrates, and then heating this to form a coating film;
A step of constructing a liquid crystal cell by arranging a pair of substrates on which the coating film is formed so that the coating film faces each other through a layer of liquid crystal molecules; and
Irradiating light from the outside of the liquid crystal cell.