TW201518411A - Liquid crystal alignment agent, liquid crystal alignment film, method for producing liquid crystal alignment film, liquid crystal display element and method for producing liquid crystal display element - Google Patents

Abstract

The invention provides a liquid crystal alignment agent, which may obtain a liquid crystal alignment film good at a liquid crystal alignment property and an alignment stability. The liquid crystal alignment agent of the invention contains a polymer constituent, and a compound (D) represented by Formula (1) below. (In the formula, A1 is a group including a polymerizable unsaturated bond, A2 is a functional group which may react with an epoxy group, R1 is a (m+n) valent organic group, m is an integer ranging from 2 to 18, and n is an integer ranging from 1 to 18, wherein, (m+n) ≤ 20 is satisfied.).

Description

Liquid crystal alignment agent, liquid crystal alignment film, method for producing liquid crystal alignment film, liquid crystal display element, and method for producing liquid crystal display element

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

Conventionally, liquid crystal display devices have developed various driving methods in which the electrode structure or the physical properties of liquid crystal molecules used are different. For example, a twisted nematic (TN) type or a super twisted nematic (Super-Twisted Nematic) is known. , STN), Vertical Alignment (VA), Multidomain Vertical Alignment (MVA), In-Plane Switching (IPS), Fringe Field Switching (FFS) Various types of liquid crystal display elements. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. In terms of various properties such as heat resistance, mechanical strength, and affinity with liquid crystal, the material of the liquid crystal alignment film is usually polyamine. Acid or polyimine. In addition, a polymer component in which a polyorganosiloxane having a group which exhibits a desired function is introduced into a side chain is used as a liquid crystal alignment agent has been proposed (for example, see Patent Document 1). Patent Document 1 discloses that a hydrolyzable decane compound containing a decane compound having a chain alkyl group is reacted in the presence of oxalic acid and an alcohol, and a polyorganosiloxane obtained by the reaction is used as a liquid crystal alignment. The polymer component of the agent.

In addition, in recent years, as a new technology for exhibiting pretilt characteristics, Polymer Sustained Alignment (PSA) technology was proposed. The PSA technology is a liquid crystal cell in which a photopolymerizable compound is mixed in a liquid crystal layer, and a liquid crystal cell is formed, and a voltage is applied to the liquid crystal layer, and light is irradiated while the liquid crystal molecules are obliquely aligned. The compound is polymerized to control the molecular alignment of the liquid crystal (for example, see Patent Document 2). According to the PSA technology, there is an advantage that an expansion of the viewing angle or high-speed response can be achieved.

Further, the present applicant has proposed a technique of forming a coating film on a pair of substrates using a liquid crystal alignment agent containing a polyorganosiloxane having a (meth)acryl fluorenyl group, and constructing the same In the liquid crystal cell of the pair of substrates, the liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films in the pair of substrates (see, for example, Patent Document 3).

As a method of imparting a liquid crystal alignment ability to a formed polymer film by using a liquid crystal alignment agent, in recent years, a technique of using a photo-alignment method such as photo-isomerization, photodimerization, or photodecomposition to replace the rubbing method has been proposed. The photo-alignment method is a method of irradiating a polarized light by irradiating a radiation-sensitive organic thin film formed on a substrate or The non-polarized radiation imparts anisotropy to the film, thereby controlling the alignment of the liquid crystal molecules. According to this method, generation of dust or static electricity in the step can be suppressed as compared with the conventional rubbing method, and thus occurrence of display failure or degradation in yield due to dust or the like can be suppressed. In addition, there is an advantage that the coating film formed on the substrate can be uniformly imparted with liquid crystal alignment ability.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 9-281502

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-149647

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2011-118358

In the case of the photo-alignment method in which the chemical change is caused by the irradiation of the ultraviolet ray or the like, the alignment control force of the liquid crystal tends to be inferior to that of the liquid crystal alignment film by the conventional rubbing treatment. In view of the above, in the case of using the photo-alignment method, PSA processing may be performed for the purpose of improving the alignment regulating force of the liquid crystal. However, even if the PSA treatment is performed, the alignment restriction force of the liquid crystal molecules cannot be sufficiently improved, and in particular, in the liquid crystal display device of the transverse electric field type, there is a problem that the display quality is deteriorated or an afterimage is generated after continuous driving for a long period of time. Further, in the production of the vertical alignment type liquid crystal display element, light irradiation processing may be performed on the constructed liquid crystal cell to improve the alignment control force of the liquid crystal. However, in the case where the processing is performed, there is a voltage easily generated due to continuous driving for a long time. The retention rate decreases and the reliability tends to be poor.

The present invention has been made in view of the above problems, and a main object thereof is to provide a A liquid crystal alignment agent which can obtain a liquid crystal alignment film having good liquid crystal alignment properties and alignment stability. Further, another object is to provide a liquid crystal display element having various characteristics such as a voltage holding ratio or an afterimage characteristic.

In order to achieve the above-described problems of the prior art, the inventors of the present invention have found that the above problems can be solved by including a specific compound in the liquid crystal alignment agent, and completed the present invention. Specifically, the present invention provides the following liquid crystal alignment agent, liquid crystal alignment film, method for producing a liquid crystal alignment film, liquid crystal display element, and method for producing a liquid crystal display element.

An aspect of the invention provides a liquid crystal alignment agent comprising a polymer component and a compound (D) represented by the following formula (1).

(In the formula (1), A ¹ is a group containing a polymerizable unsaturated bond, A ² is a functional group reactive with an epoxy group, and R ¹ is an (m+n) valent organic group; m is 2~ An integer of 18, n is an integer from 1 to 18; where (m+n)≦20 is satisfied.)

An aspect of the present invention provides a method for producing a liquid crystal alignment film, comprising: a step of applying the liquid crystal alignment agent onto a substrate to form a coating film, and a step of irradiating the coating film with light. In addition, a system for providing a liquid crystal display element is provided The method comprising the steps of: coating the liquid crystal alignment agent on each surface of a pair of substrates, and then heating the same to form a coating film; and forming a pair of the coating film in a manner opposite to the coating film a step of arranging the liquid crystal cells in a direction in which the substrates are opposed to each other via a layer of liquid crystal molecules, and a step of irradiating light from the outside of the liquid crystal cells.

According to the liquid crystal alignment agent of the present invention, a liquid crystal alignment film having good liquid crystal alignment property and alignment stability can be obtained. In addition, various characteristics such as a voltage holding ratio or afterimage characteristics of a liquid crystal display element including a liquid crystal alignment film produced using the liquid crystal alignment agent are good.

11, 12‧‧‧ electrodes

A, B‧‧‧ substrate

FIG. 1 is a view showing a pattern of a transparent electrode patterned into a comb shape.

2 is a view showing a pattern of a transparent electrode patterned into a slit shape.

The liquid crystal alignment agent of the present invention contains a polymer component and a polyfunctional specific compound (D). Hereinafter, each component contained in the liquid crystal alignment agent of the present invention and other components arbitrarily formulated as needed will be described.

Polymer composition

The polymer component of the present invention is not particularly limited, and examples thereof include polyglycine, polyphthalate, polyimine, polyorganosiloxane, poly(meth)acrylate, polyester, and polyfluorene. An amine, a cellulose derivative, a polyacetal, a polystyrene derivative, a poly(styrene-phenylmethylene iodide) derivative, or the like. Among these polymers, the liquid crystal of the present invention The agent preferably contains at least one polymer (hereinafter also referred to as "specific polymer") selected from the group consisting of polylysine, polyphthalate, polyimine, and polyorganosiloxane. As a polymer component.

<polylysine>

The polyproline of the present invention can be synthesized, for example, by reacting a tetracarboxylic dianhydride with a diamine.

[tetracarboxylic dianhydride]

Examples of the tetracarboxylic dianhydride used for the synthesis of the polyglycolic acid of the present invention include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of the tetracarboxylic dianhydride include aliphatic monocarboxylic dianhydride: 1,2,3,4-butanetetracarboxylic dianhydride; and alicyclic tetracarboxylic dianhydride. : 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro 8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[ 3.2.1] Octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3- Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6- Anhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ] Monoalkane-3,5,8,10-tetraketone, cyclohexanetetracarboxylic dianhydride, etc., and aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, etc. A tetracarboxylic dianhydride or the like described in Japanese Laid-Open Patent Publication No. 2010-97188. Further, the tetracarboxylic dianhydride may be used alone or in combination of two or more.

[diamine]

Examples of the diamine for synthesizing the poly-proline of the present invention include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, a diamine organic decane, and the like. Specific examples of the diamine include aliphatic m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. And the alicyclic diamine may, for example, be 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane Examples of the aromatic diamine include dodecyloxydiaminobenzene, tetradecyloxydiaminobenzene, pentadecyloxydiaminobenzene, and cetyloxydiaminobenzene. , octadecyloxydiaminobenzene, cholesteryloxydiaminobenzene, cholestyloxydiaminobenzene, cholesteryl diaminobenzoate, diamine benzoate Decenyl ester, lanosteryl diaminobenzoate, 3,6-bis(4-aminobenzylideneoxy)cholesterane, 3,6-bis(4-aminophenoxy) Cholestane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1-bis(4-((aminophenyl)) Phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-double (4-((Aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, N-(2,4-di Isotropic liquid crystal alignment containing a diamine group-yl) -4- (4-heptyl cyclohexyl) benzoyl amine compound represented by the following formula (a-1): [Chemical Formula 2]

(In the 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 an alkane having 1 to 3 carbon atoms. Base, a is 0 or 1, b is an integer from 0 to 2, c is an integer from 1 to 20, and d is 0 or 1; where a and b are not 0)

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'-diamine linkage Benzene, 2,7-diaminoguanidine, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9- Bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoro Propane, 4,4'-(p-phenylenediphenylene)diphenylamine, 4,4'-(meta-phenyldiisopropylidene)diphenylamine, 1,4-bis(4-amino Phenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine , 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole , N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N , other diamines such as N'-dimethylbenzidine, 1,4-bis-(4-aminophenyl)-piperazine, 3,5-diaminobenzoic acid, etc.; diamino-based organodecane For example, 1,3-bis (3-amino-propyl) - tetramethyl siloxane silicon and the like; in addition, may also be used Laid-Open Japanese Patent Application Publication No. 2010-97188 diamine described. The diamine may be used alone or in combination of two of the diamines. Used in combination.

The divalent group represented by "-X ^I -(R ^I -X ^II ) _n -" in the formula (D-1) is preferably an alkanediyl group having a carbon number of 1 to 3, *-O-, * -COO- or *-OC ₂ H ₄ -O- (wherein the bond labeled "*" is bonded to the diaminophenyl group). Specific examples of the group "-C _c H _2c+1 " include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and n-decyl group. , n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nine Alkyl, n-icosyl, and the like. The two amine groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position relative to other groups.

Specific examples of the compound represented by the formula (a-1) include a compound represented by the following formula (a-1-1) to the formula (a-1-3), and the like.

<Synthesis of polylysine>

Polylysine can be obtained by reacting a tetracarboxylic dianhydride and a diamine as described above, optionally with a blocking agent. The ratio of the tetracarboxylic dianhydride to the diamine to be used in the synthesis reaction of the poly-proline is preferably 1 equivalent to the amine group of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents. More preferably, it becomes 0.3 The ratio of equivalents to 1.2 equivalents.

Examples of the terminal blocking agent include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, and phenyl isocyanate. A monoisocyanate compound such as an isocyanate isocyanate. The use ratio of the blocking agent is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine to be used.

The synthesis reaction of polylysine is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, and more preferably 0 ° C to 100 ° C. Further, 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 an aprotic polar solvent, a phenol solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenol solvent (the organic solvent of the first group) or an organic solvent selected from the first group is preferably used. One or more kinds of a mixture of one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (organic solvents of the second group). In the latter case, the use ratio of the organic solvent of the second group is preferably 50% by weight or less, more preferably 40% by weight, based on the total amount of the organic solvent of the first group and the organic solvent of the second group. Hereinafter, it is especially preferably 30% by weight or less.

It is particularly preferred to use a group selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl hydrazine, γ-butyrolactone, four One or more of a group consisting of methyl urea, hexamethylphosphonium triamine, m-cresol, xylenol, and halogenated phenol is used as a solvent, or preferably used within the range of the above ratio A mixture of one or more solvents and other organic solvents.

The amount (a) of the organic solvent used is preferably set to be relative to the reaction solution. The total amount (a+b), the total amount (b) of the tetracarboxylic dianhydride and the diamine is 0.1% by weight to 50% by weight.

As described above, a reaction solution obtained by dissolving polylysine was obtained. The The reaction solution may be directly supplied to the preparation of the liquid crystal alignment agent, or the poly-proline acid contained in the reaction solution may be isolated and then supplied to the preparation of the liquid crystal alignment agent, or the isolated polylysine may be further purified. Further provided for the preparation of the liquid crystal alignment agent. The isolation and purification of polylysine can be carried out according to a known method.

<Polyurethane>

The polyphthalate of the present invention can be obtained, for example, by the following method: [I] by carrying out the polyamine acid obtained by the synthesis reaction, a hydroxyl group-containing compound, a halide, an epoxy group-containing compound, or the like. a method of synthesizing by reaction; [II] a method of reacting a tetracarboxylic acid diester with a diamine; [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine, and the like.

Here, examples of the hydroxyl group-containing compound used in the method [I] include alcohols such as methanol, ethanol, and propanol; and phenols such as phenol and cresol. Further, examples of the halide include bromomethane, bromoethane, octadecadecane, methyl chloride, chlorooctadecane, 1,1,1-trifluoro-2-iodoethane, and the like. Examples of the epoxy group-containing compound include propylene oxide and the like.

The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by subjecting the tetracarboxylic dianhydride exemplified in the synthesis of the polyamic acid to ring opening using the alcohol. Got it. The reaction of the 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-methylmorpholine cation halide, carbonylimidazole, and phosphorus condensing agent. Wait. The tetracarboxylic acid diester dihalide used in the method [III] can be obtained by, for example, reacting a tetracarboxylic acid diester obtained in the above manner with a suitable chlorinating agent such as sulfinium chloride.

The diamine used in the method [II] and the method [III] may be exemplified by a combination of poly-proline The diamine exemplified in the middle. Further, the polyperurate may have only a phthalate structure, or may be a partial ester compound in which a valeric acid structure and a phthalate structure coexist.

<polyimine]

The polyimine contained in the liquid crystal alignment agent of the present invention can be obtained by subjecting, for example, polylysine synthesized in the above manner to dehydration ring closure to ruthenium iodide.

The polyimine may be a fully ruthenium imide formed by dehydration ring closure of all of the proline structures of the polyglycolic acid as its precursor, or only a part of the structure of the proline may be carried out. The dehydration ring closure is a partial ruthenium imide compound which has a structure of proline and coexistence of a quinone ring structure. The polyamidene of the present invention preferably has a ruthenium iodide ratio of 30% or more, more preferably 50% to 99%, and particularly preferably 65% to 99%, from the viewpoint of electrical properties. The ruthenium imidation ratio is a total of the number of the guanidine structure of the polyimine and the number of the quinone ring structure, and the ratio of the number of the quinone ring structure is expressed as a percentage. Here, a part of the quinone ring may be an isoindole ring.

The dehydration ring closure of polylysine is preferably carried out by a method of heating polylysine or dissolving polylysine in an organic solvent. A dehydrating agent and a dehydration ring-closing catalyst are added to the solution, and heating is carried out as needed. Among them, it is preferred to use the latter method.

Adding a dehydrating agent to the solution of the polyproline and dehydrating ring In the method of the chemical agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably from 0.01 mol to 20 mol based on 1 mol of the proline structure of the polyglycolic acid. As the dehydration ring-closing catalyst, for example, a tertiary amine such as pyridine, trimethylpyridine, dimethylpyridine or triethylamine can be used. The amount of the dehydration ring-closure catalyst to be used is preferably 0.01 mol to 10 mol with respect to 1 mol of the dehydrating agent to be used. The organic solvent used in the dehydration ring closure reaction may, for example, be an organic solvent for synthesizing polyglycolic acid. The reaction temperature of the dehydration ring closure reaction is preferably from 0 ° C to 180 ° C, more preferably from 10 ° C to 150 ° C. The reaction time is preferably from 1.0 to 120 hours, more preferably from 2.0 to 30 hours.

A reaction solution containing polyienimine was obtained in the manner described. Reaction solution It can be directly supplied to the preparation of the liquid crystal alignment agent, or can be prepared by removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and then providing the liquid crystal alignment agent, and can also provide the liquid crystal alignment agent after separation of the polyimine. Alternatively, the isolated polyimine may be purified and then supplied to the preparation of the liquid crystal alignment agent. These purification operations can be carried out in accordance with a known method.

Polylysine, polyamidomate, and polyimine obtained in the manner described Preferably, when it is made into a solution having a concentration of 10% by weight, it has 10 mPa. s~800mPa. The solution viscosity of s is more preferably 15 mPa. s~500mPa. s solution viscosity. Furthermore, the solution viscosity (mPa.s) of the polymer is for the use of the polymer a 10% by weight polymer solution prepared by using a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.), and measuring at 25 ° C using an E-type rotational viscometer . The polystyrene-reduced weight average molecular weight measured by gel permeation chromatography is preferably 1,000 to 500,000, more preferably 2,000 to 300,000.

<polyorganooxane>

The polyorganosiloxane which is contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is a polyorganosiloxane having a siloxane skeleton. From the viewpoint of reacting with the group "A2" of the compound (D) to improve the liquid crystal alignment property and the liquid crystal stability, it is preferable to contain a polyorganosiloxane having an epoxy group (hereinafter also referred to as "including Epoxy-based polyorganosiloxanes"). Specific examples of the epoxy group-containing polyorganosiloxane are, for example, a polyorganosiloxane having a repeating unit represented by the following formula (S-1), a hydrolyzate thereof, or a condensate of a hydrolyzate.

(In the formula (S-1), X ¹ is a monovalent organic group having an epoxy group, Y ¹ is a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a carbon number of 6~ An aryl group of 20; X ¹ and Y ^{1 in the} molecule may be the same or different.)

X ¹ in the formula (S-1) is not particularly limited as long as it has an epoxy group, and examples thereof include an epoxy group bonded to a chain hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group. A group of groups, etc. Preferable specific examples of X ¹ include a group represented by the following formula (X1-1) to formula (X1-3), and the like.

(In the formula, "*" indicates a bond with a ruthenium atom.)

In addition, the "chain hydrocarbon group" in the present specification means a linear hydrocarbon group and a branched hydrocarbon group which are not composed of a chain structure and do not include a cyclic structure in the main chain. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not including an aromatic ring structure. Among them, it is not necessary to be composed only of the structure of the alicyclic hydrocarbon, and also includes a hydrocarbon group having a chain structure in a part thereof. The "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. Among them, it is not necessary to be composed only of an aromatic ring structure, and a structure of a chain structure or an alicyclic hydrocarbon may be contained in a part thereof.

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 decyl group, and an anthracene group. These hydrocarbon groups may be linear or branched. The alkoxy group having 1 to 10 carbon atoms of Y ^{1 is} , for example, a group in which the alkyl group is bonded to an oxygen atom, and specific examples thereof include a methoxy group and an ethoxy group. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a benzyl group, a tolyl group and the like.

The epoxy group-containing polyorganosiloxane has an epoxy equivalent of preferably from 100 g/mol to 10,000 g/mol, more preferably from 150 g/mol to 1,000 g/mol.

The polyoxymethylene-containing polyorganosiloxane having a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography is preferably 500 to 100,000, more preferably 1,000 to 10,000, particularly preferably 1,000 to 5,000.

<Synthesis of polyorganosiloxanes>

The epoxy group-containing polyorganosiloxane may be, for example, a hydrolyzable decane compound having an epoxy group (epoxy group-containing decane compound) or the epoxy group-containing decane compound and other decane. The mixture of the compounds is preferably obtained by hydrolysis and condensation in the presence of a suitable organic solvent, water and a catalyst.

Examples of the epoxy group-containing decane compound include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-glycidoxypropylmethyl group. Dimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyldimethylmethoxydecane, 3-glycidoxypropyldimethylethyl Oxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, and the like. The epoxy group-containing decane compound may be used alone or in combination of two or more.

The other decane compound is not particularly limited as long as it is hydrolyzable, and examples thereof include methyltrichlorodecane, methyltrimethoxydecane, methyltriethoxydecane, phenyltrichlorodecane, and phenyl. Trimethoxy decane, methyl dichloro decane, methyl dimethoxy decane, dimethyl dichloro decane, dimethyl dimethoxy decane, two Methyl diethoxy decane, diphenyl dichloro decane, diphenyl dimethoxy decane, methoxy dimethyl decane, ethoxy dimethyl decane, chlorotrimethyl decane, bromotrimethyl Decane, iodine trimethyl decane, methoxy trimethyl decane, ethoxy trimethyl decane, tetramethoxy decane, tetraethoxy decane, octadecyl trichloro decane, octadecyl trimethoxy Base decane, vinyl trichloro decane, vinyl trimethoxy decane, vinyl triethoxy decane, allyl trimethoxy decane, allyl triethoxy decane; 3- (meth) propylene oxime Propyltrichloromethane, 3-(methyl)propenyloxypropyltrimethoxydecane, 3-(methyl)propenyloxypropyltriethoxydecane, 2-(methyl)propene oxime Oxyethyltrichlorodecane, 2-(methyl)propenyloxyethyltrimethoxydecane, 2-(methyl)propenyloxyethyltriethoxydecane, 4-(methyl)propene Nonyloxytrichloromethane, 4-(methyl)propenyloxybutyltrimethoxydecane, 4-(methyl)propenyloxybutyltriethoxydecane, 3-(methyl) Propylene methoxy butyl trimethoxy decane, 3-(methyl)propenyloxypentyltrimethoxydecane, 3-(methyl)propenyloxyhexyltrimethoxydecane, 3-(methyl)propenyloxyheptyltrimethoxydecane, 3-(Methyl)propenyloxyoctyltrimethoxydecane, 3-(methyl)propenyloxydecyltrimethoxydecane, 3-(methyl)propenyloxydecyltrimethoxydecane And 3-(methyl)propenyloxyundecyltrimethoxydecane, 3-(meth)acryloxydecyldodecyltrimethoxydecane, and the like. The other decane compounds may be used alone or in combination of two or more. Further, "(meth)acryloxy" is a meaning including "acryloxy" and "methacryloxy".

In the synthesis of the epoxy group-containing polyorganosiloxane, it is preferred to adjust the epoxy equivalent of the obtained polyorganosiloxane to the above preferred range. The ratio of use of the epoxy group-containing decane compound to other decane compounds.

Organic solvents which can be used in the synthesis of polyorganosiloxanes, for example, can be listed Take: hydrocarbons, ketones, esters, ethers, alcohols, etc. Here, examples of the hydrocarbon include toluene, xylene, and the like; and examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, diethyl ketone, and cyclohexanone. And the ester may, for example, be ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate or the like; For example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc. are mentioned, for example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol single Methyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Among these organic solvents, it is preferred to use a water-insoluble organic solvent. In addition, these organic solvents may be used alone or in combination of two or more.

Synthetic with respect to 100 parts by weight of all decane compounds used in the synthesis The amount of the organic solvent used in the case of the polyorganosiloxane is preferably from 10 parts by weight to 10,000 parts by weight, more preferably from 50 parts by weight to 1,000 parts by weight. Further, the amount of water used in synthesizing the polyorganosiloxane is preferably from 0.5 to 100 moles, more preferably from 1 to 20 moles per mole of the total decane compound used in the synthesis. .

A catalyst which can be used in the synthesis of the polyorganosiloxane is, for example, listed Examples: acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds, and the like. Here, examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, and the like; and examples of the alkali metal compound include: Sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, etc.; the organic base is, for example, a first grade such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine or pyrrole. Organic amine ~ secondary organic amine, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, tertiary organic amine, hydrogen A quaternary organic amine such as tetramethylammonium oxide or the like.

The catalyst is particularly preferably an organic base. The amount of organic base used is based on The reaction conditions such as the type of the organic base and the temperature may be appropriately set, and it is preferably set, for example, from 0.01 to 3 moles, more preferably from 0.05 to 2 moles per mole of the decane compound. .

Hydrolysis in the synthesis of the polyorganosiloxane. The condensation reaction is preferably passed One or two or more kinds of hydrolyzable decane compounds are dissolved in an organic solvent, and the obtained solution is mixed with an organic base and water, for example, by an oil bath or the like.

hydrolysis. In the case of a condensation reaction, it is preferred to set the heating temperature to preferably The heating is preferably carried out at 130 ° C or lower, more preferably at 40 ° C to 100 ° C, for preferably 0.5 hours to 12 hours, more preferably 1 hour to 8 hours. The mixture may be stirred during heating or placed under reflux.

After the reaction is completed, it is preferably an organic solvent which is separated from the reaction liquid by using water. The layer is washed. In the washing, it is preferred to use a water containing a small amount of salt, for example, an aqueous ammonium nitrate solution of about 0.2% by weight or the like, to facilitate the washing operation. The washing is carried out until the water layer after washing becomes neutral, and then the organic solvent layer is dried by removing the organic solvent layer with a desiccant such as anhydrous calcium sulfate or molecular sieve as needed. A solvent, thereby obtaining a target polyorganosiloxane. Further, a commercially available product can also be used as the epoxy group-containing polyorganosiloxane. Examples of the commercially available product include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (above, manufactured by Chisso).

The polyorganosiloxane which is contained in the liquid crystal alignment agent of the present invention can be preferably used A compound having a group capable of imparting a liquid crystal alignment ability to a coating film (hereinafter also referred to as "liquid crystal alignment group") is used. The polyorganosiloxane having a liquid crystal alignment group (hereinafter also referred to as "polyorganosiloxane containing an alignment group") may be contained separately from the epoxy group-containing polyorganosiloxane, or may be It is a form which is contained as a polyorganosiloxane which has an epoxy group and a liquid crystal alignment group. The latter is preferred. Preferable specific examples of the polyorganosiloxane containing the alignment group include, for example, a polyorganosiloxane having a repeating unit represented by the following formula (S-2).

(In the formula (S-2), X ² is a monovalent organic group having a liquid crystal alignment group; and Y ¹ has the same meaning as the above formula (S-1).)

X ² in the formula (S-2) is not particularly limited as long as it has a liquid crystal alignment group. Preferable examples of X ² include a group represented by the following formula (X2-1A) to formula (X2-3B), and the like.

(wherein R ³ is a liquid crystal alignment group; "*" represents a bond with a germanium atom.)

The liquid crystal aligning group (R ³ ) is a group which exhibits photo-alignment properties by photoisomerization, photodimerization, photodecomposition or the like (hereinafter also referred to as "photo-alignment group"), and can impart a coating film. A group having a pretilt characteristic (hereinafter also referred to as "pretilt angle imparting group") or the like.

When the treatment for imparting a liquid crystal alignment ability to a coating film is carried out by a photo-alignment method, it is preferable to contain a polyorganosiloxane having a photo-alignment group. The photo-alignment group may be a group derived from various compounds which exhibit an alignment property by photoisomerization, photodimerization, photodecomposition or the like, and examples thereof include those containing azobenzene or a derivative thereof as a basic skeleton. a group having an azobenzene group, 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, and a diphenyl group A ketone-containing group having a ketone or a derivative thereof as a basic skeleton, a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, and the like. Among them, a group having a cinnamic acid structure is preferred in terms of a good optical alignment property and a viewpoint of easy introduction into a polymer.

The polyorganosiloxane having the photo-alignment group of R ³ of the formula (S-2), for example, the obtained epoxy group-containing polyorganosiloxane, and a carboxylic acid having a photo-alignment group (C-1) obtained by carrying out a reaction. Preferable examples of the carboxylic acid (C-1) include a compound represented by the following formula (C1-1) to formula (C1-3), and the like.

(wherein 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; R ⁶ , R ⁷ and R ⁹ are each independently 1,4-cyclohexylene or 1,4-phenylene; R ¹⁰ is an alkanediyl group having 2 to 10 carbon atoms; Z ¹ , Z ² , Z ³ , Z ⁴ and Z ^{5 is} independently a single bond, an ether group, a thioether group, an ester group or a thioester group; 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); and the formula (C1-2) For the specific example, for example, a compound represented by the following formula (c1-2-1), and the like, and a preferred specific example of the formula (C1-3), for example, represented by the following formula (c1-3-1) Compounds, etc.

[Chemistry 9]

(wherein R ⁸ , R ¹⁰ and R ¹¹ have the same meanings as in the formula (C1-1) to formula (C1-3).)

Examples of the pretilt angle-imparting group include an alkyl group having 4 to 40 carbon atoms, a fluoroalkyl group having 4 to 40 carbon atoms, an alkoxy group having 4 to 40 carbon atoms, and a group having a steroid skeleton having 17 to 51 carbon atoms. A group having a polycyclic structure or the like.

The polyorganosiloxane having the pretilt angle imparting group of R ³ of the formula (S-2), for example, can be obtained by subjecting the obtained epoxy group-containing polyorganosiloxane to a carboxylic acid having a pretilt angle imparting group. (C-2) Obtained by carrying out a reaction. Preferable examples of the carboxylic acid (C-2) include a compound represented by the following formula (C2-1) to formula (C2-5), and the like.

(wherein R ²² is an alkyl group having 4 to 20 carbon atoms or a fluoroalkyl group; and R ¹² is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group; and R ¹³ and R ¹⁵ are each independently 1, 4-cyclohexyl or 1,4-phenyl; R ¹⁴ is a hydrogen atom or a methyl group; and R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are each independently a carbon number of 1 to 10; Alkanediyl; Z ⁶ , Z ⁷ , Z ⁸ , Z ⁹ , Z ¹⁰ , Z ¹¹ , Z ¹² , Z ¹³ and Z ¹⁴ are each independently a single bond, an ether group, a thioether group, an ester group or a thioester group ;p is an integer from 0 to 3, q is an integer from 0 to 2, and r is 0 or 1.)

The alkyl group of R ²² and R ¹² may be linear or branched, and 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); and the formula (C2-2) Specific examples of the compound represented by the following formula (c2-2-1) to formula (c2-2-7), and the like, and preferred examples of the formula (C2-3) include, for example, the following formula. (c2-3-1) The compound represented by the formula (C2-4), and a specific example of the formula (C2-4), for example, a compound represented by the following formula (c2-4-1); Preferable specific examples of 5) include, for example, a compound represented by the following formula (c2-5-1).

(wherein R ²² , R ¹² , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ have the same meanings as in the formula (C2-1) to formula (C2-5), respectively).

In the case of producing a vertical alignment type liquid crystal display element, it is preferable to use a polyorganosiloxane having a pretilt angle imparting group as a polymer component. Further, the method for synthesizing the polyorganosiloxane having the pretilt angle imparting group is not limited thereto, and for example, it may be synthesized by polymerization of a hydrolyzable decane compound having a pretilt angle imparting group in the monomer composition.

As the polyorganosiloxane which is contained in the liquid crystal alignment agent of the present invention, a polyorganosiloxane having a polymerizable unsaturated group can also be used. In the case of using the polyorganosiloxane, the alignment control force of the liquid crystal molecules can be improved 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) acryl fluorenyl group, a vinyl group, and a styryl group. However, from the viewpoint of good sensitivity to light, among them, a (meth) acrylonitrile group is preferable. . The polyorganosiloxane can be reacted with at least one of the carboxylic acids represented by the above formula (C2-2) and formula (C2-5), respectively, with an epoxy group-containing polyorganosiloxane. And get.

[Reaction of an epoxy group-containing polyorganosiloxane with a carboxylic acid]

An epoxy group-containing polyorganosiloxane, and a carboxylic acid having a liquid crystal alignment group The reaction also referred to as "carboxylic acid (C)" is preferably carried out in the presence of a catalyst and an organic solvent.

a carboxylic acid which reacts with an epoxy group-containing polyorganosiloxane to form a carboxylic acid (C) Used alone or in combination with other carboxylic acids. For example, for the purpose of crosslinking the epoxy group-containing polyorganosiloxane, the carboxylic acid (F) represented by the following formula (f) which is another carboxylic acid can be used together with the carboxylic acid (C).

(In the formula (f), R ²³ is a tertiary hydrocarbon group having 4 to 20 carbon atoms.)

R ²³ in the formula (f) is preferably a tertiary alkyl group or a group having a cycloalkane skeleton. Specific examples of R ²³ include a group represented by the following formula (t-1) and formula (t-2), and the like.

(In the 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; in the formula (t-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 is an alicyclic hydrocarbon group having 4 to 20 carbon atoms together with a carbon atom bonded to R ⁴⁴ The valence group; "*" indicates the bond that is bonded to the oxygen atom.)

The bonding position of the carboxyl group in the formula (f) is preferably para.

Preferable specific examples of the carboxylic acid (F) include, for example, compounds represented by the following formulas (f-1) and (f-2). The carboxylic acid (F) may be used alone or in combination of two or more.

Epoxy group 1 with respect to epoxy group-containing polyorganosiloxane The ratio of the carboxylic acid (total amount) to be reacted with the epoxy group-containing polyorganosiloxane is preferably from 0.001 mol to 10 mol, more preferably from 0.01 mol to 5 mol. It is particularly preferably set to 0.05 mol to 2 mol, and particularly preferably set to 0.05 mol to 0.8 mol. Further, by using the epoxy group of the epoxy group-containing polyorganosiloxane, the polyorganosiloxane having a liquid crystal alignment group and an epoxy group can be obtained.

In the case of synthesizing polyorganosiloxane having a polymerizable unsaturated group Next, with respect to the epoxy group-containing polyorganosiloxane having an epoxy group of 1 mole, The ratio (total amount) of the carboxylic acid represented by the formula (C2-2) and the formula (C2-5) is preferably 0.001 mol to 5 mol, and more preferably 0.01 mol to 1 mol. The ear is particularly preferably set to 0.03 mol to 0.6 mol.

In the case of using the carboxylic acid (F), its use ratio is relative to the ring The oxy group 1 is set to 0.01 mol to 1 mol. It is more preferably 0.02 mol to 0.3 mol, and particularly preferably 0.04 mol to 0.2 mol.

The catalyst used in the reaction can be used, for example, as an organic base or an epoxy. A known compound such as a hardening accelerator for the reaction of a compound. Here, the organic base may, for example, be a primary organic amine such as ethylamine, piperazine or piperidine, or a secondary organic amine; a tertiary organic amine such as triethylamine or pyridine; or a tetrabasic organic compound such as tetramethylammonium hydroxide. Amines, etc. Among these compounds, the organic base is preferably a tertiary organic amine or a quaternary organic amine.

Further, examples of the hardening accelerator include benzyldimethylamine, 2,4,6- a tertiary amine such as tris(dimethylaminomethyl)phenol; an imidazole compound such as 2-methylimidazole or 2-n-heptyl imidazole; an organic phosphorus compound such as diphenylphosphine; benzyltriphenylphosphonium chloride; a quaternary phosphonium salt; a diazabicycloalkene such as 1,8-diazabicyclo[5.4.0]undecene-7 or an organic acid salt thereof; zinc octoate, tin octylate, aluminum acetylacetone complex, etc. Organometallic compound; tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride, etc.; boron trifluoride, boric acid a boron compound such as phenyl ester; a metal halogen compound such as zinc chloride or tin chloride. Among these compounds, a quaternary ammonium salt is preferred.

The catalysis relative to 100 parts by weight of the epoxy group-containing polyorganosiloxane The agent is preferably 100 parts by weight or less, more preferably 0.01 parts by weight to 100 parts by weight, It is especially preferably used in a ratio of 0.1 part by weight to 20 parts by weight.

The epoxy group-containing polyorganosiloxane can be used in the reaction with a carboxylic acid. Examples of the organic solvent include a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, a guanamine compound, and an alcohol compound. Among these compounds, an ether compound, an ester compound, and a ketone compound are preferable from the viewpoints of the solubility of the raw material and the product and the ease of purification of the product, and specific examples of the solvent are particularly preferably 2-butanone, 2 -hexanone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and butyl acetate. In addition, the organic solvent is preferably used in a ratio of a solid content concentration (a ratio of a total weight of components other than the solvent in the reaction solution to the total weight of the solution) of 0.1% by weight or more, and more preferably 5 parts by weight. The ratio of %~50% by weight is used. The reaction temperature is preferably 0 ° C to 200 ° C, and more preferably 50 ° C to 150 ° C. The reaction time is preferably from 0.1 to 50 hours, more preferably from 0.5 to 20 hours.

In addition, the synthesis method of the polyorganosiloxane containing the alignment group is A method of introducing a liquid crystal alignment group by ring-opening addition of an epoxy group which is contained in an epoxy group-containing polyorganosiloxane. This synthesis method is simple and is preferable in terms of improving the introduction rate of the liquid crystal alignment group.

Polyorganosiloxane containing an alignment group by gel permeation chromatography The measured polystyrene-equivalent weight average molecular weight is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000, still more preferably from 3,000 to 20,000.

Bismuth compound (D)≫

The compound (D) is represented by the following formula (1).

[化15]

(In the formula (1), A ¹ is a group containing a polymerizable unsaturated bond, A ² is a functional group reactive with an epoxy group, and R ¹ is an (m+n) valent organic group; m is 2~ An integer of 18, n is an integer from 1 to 18; where (m+n)≦20 is satisfied.)

In the formula (1), in terms of high reactivity to light, A ¹ is preferably at least selected from the group consisting of (meth) acryl methoxy, vinyl and styryl groups. One is more preferably a (meth) acrylonitrileoxy group. Further, the (meth)acrylenyloxy group is intended to include an acryloyloxy group and a methacryloxy group.

The functional group (A ² ) which can react with the epoxy group may, for example, be a carboxyl group, a thiol group, a primary amino group or an epoxy group. Among them, a carboxyl group is preferred in terms of high reactivity with an epoxy group.

The (m+n)-valent organic group of R ¹ may, for example, be a hydrocarbon group such as a chain hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and the methylene group in the hydrocarbon group may be an ether group, a thioether group, an ester group or a thioester. A group substituted with a base or the like. The carbon number of R ¹ is preferably from 1 to 30, and more preferably from 3 to 20.

m is preferably 2 to 10, more preferably 2 to 8. n is preferably 2 to 18, more preferably 2 to 10, and particularly preferably 2 to 8. (m+n) is preferably 4 to 12, and more preferably 4 to 10.

The compound represented by the 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 the formula (1-1), R ² is a hydrogen atom or a methyl group; and R ¹ , m and n have the same meanings as the above formula (1).)

Specific examples of the carboxylic acid-containing poly (meth) acrylate include compounds represented by the following formulas (1-1-1) to (1-1-3), and the like.

(In the formula (1-1-1) to the formula (1-1-3), R ⁴ is a group represented by the following formula (p-1), formula (p-2) or formula (p-3); a plurality of R ^{4 in the} molecule may be the same as or different from each other; wherein, at least one of the plurality of R ⁴ is a group represented by the formula (p-1), and at least one is a formula (p-2) And at least one of the group represented by the formula and the group represented by the formula (p-3); j is an integer of 1 to 10.

(In the formula (p-1) to the formula (p-3), R ² is a hydrogen atom or a methyl group, and R ³⁰ is an alkanediyl group having a carbon number of 1 to 6 or a phenyl group.)

In the formula (1-1-1) to the formula (1-1-3), the number (x) of the groups represented by the formula (p-1) and the formula (p-2) The ratio of the group to be represented and the number of the groups represented by the formula (p-3) (the total number of counts y) can be appropriately adjusted depending on the type of the polymer or the additive to be used, the blending amount, and the like. In the case of a liquid crystal display device of a transverse electric field type, in terms of reducing the afterimage, in the case of a vertically aligned liquid crystal display element, it is preferable to accelerate the response speed of the liquid crystal molecules. More than y.

A commercially available product can be used as the compound (D), or a compound obtained by synthesis can also be used. As a commercial item of the compound (D), for example, the trade names "TO-2349" and "TO-1382" manufactured by East Asia Synthetic Co., Ltd. may be mentioned.

Further, in the case of synthesizing the compound (D), the synthesis method is not particularly limited, and a conventional method of organic chemistry can be appropriately combined. If enumerated The carboxylic acid-containing polyvalent (meth) acrylate represented by the above formula (1-1) is exemplified as an example, and can be synthesized, for example, by the following method: [1] A polyfunctional (meth)acrylic acid having a hydroxyl group is used. An ester compound, a method of reacting with an acid anhydride such as succinic anhydride (corresponding to the following scheme (I)); [2] reacting a polyfunctional (meth) acrylate compound with a carboxylic acid having a thiol group (Michael The method of addition (Michael addition) (corresponding to the following scheme (II)) and the like.

(wherein R ¹ , R ² , m and n have the same meanings as in the formula (1-1); and R ³⁰ is an alkanediyl group having a carbon number of 1 to 6 or a phenyl group.)

The compounding ratio of the compound (D) is preferably from 1 part by weight to 30 parts by weight based on 100 parts by weight of the total of the polymer component in the liquid crystal alignment agent. When it is 1 part by weight or more, the effect of improving the liquid crystal alignment property or the alignment stability can be sufficiently obtained. In addition, when it is 30 parts by weight or less, it is possible to suppress liquid crystal alignment failure. It is more preferably in the range of 3 parts by weight to 25 parts by weight, and particularly preferably in the range of 5 parts by weight to 20 parts by weight. Further, the compound (D) may be used alone. Alternatively, two or more types may be used in combination.

≪Other ingredients≫

The liquid crystal alignment agent of the present invention may contain other components as needed. Preferable specific examples of the other components include, for example, a compound having two or more epoxy groups in the molecule and not corresponding to the compound (D) (hereinafter also referred to as "epoxy group-containing compound"). A compound having two or more carboxyl groups in the molecule does not correspond to the compound (hereinafter referred to as "polycarboxylic acid") of the compound (D).

<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 surface of the substrate. Specific examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and glycerin II. Glycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol 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-xylylenediamine, 1,3-double (N, N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl Base-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-double (N,N-diglycidylaminomethyl)cyclohexane, 1,4-bis(N,N-diglycidylaminomethyl)benzene, 1,3,5-tris(N,N - diglycidylaminomethyl)cyclohexane, the following formula (e-1) to formula (e-3)

Compounds and the like indicated respectively. In addition to the above, an epoxy group-containing polyorganosiloxane such as described in International Publication No. 2009/096598 can also be used.

In the case where an epoxy group-containing compound is added to a liquid crystal alignment agent The compounding ratio of the epoxy group-containing compound is preferably 40 parts by weight or less, and more preferably 0.1 parts by weight to 30 parts by weight, based on 100 parts by weight of the total of the polymers contained in the liquid crystal alignment agent.

<Polycarboxylic acid>

The polyvalent carboxylic acid can be used for the purpose of improving the liquid crystal alignment of the liquid crystal alignment film. Specific examples of the polyvalent carboxylic acid include, for example, fumaric acid, malonic acid, adipic acid, terephthalic acid, isophthalic acid, sebacic acid, and diphenyl ether-4,4'-dicarboxylate. Dicarboxylic acid such as acid, pyridine-2,6-dicarboxylic acid; 1,2,4-butanetricarboxylic acid, 1,2,3-cyclohexanetricarboxylic acid, trimellitic acid, 1,2, a tricarboxylic acid such as 4-naphthalenetricarboxylic acid; 1,2,3,4-cyclobutanetetracarboxylic acid, 2,3,5-tricarboxycyclopentyl acetic acid, cyclopentanetetracarboxylic acid, cyclohexane tetra A tetracarboxylic acid such as a carboxylic acid or pyromellitic acid.

In the case where a polycarboxylic acid is added to a liquid crystal alignment agent, relative to a liquid The compounding ratio of the polyvalent carboxylic acid is preferably 40 parts by weight or less, and more preferably 0.1 parts by weight to 30 parts by weight, based on 100 parts by weight of the total of the polymers contained in the crystal alignment agent.

The other components may be, for example, functional decane, in addition to the above. A compound, a compound having one epoxy group in the molecule, a compound having at least one oxetanyl group in the molecule, a bis-xenylenediamine compound, an antioxidant, a photosensitizer, and the like. The blending amount of these other components can be appropriately adjusted within the range not impairing the effects of the present invention.

In a preferred embodiment of the liquid crystal alignment agent of the present invention, (I) a form comprising only one selected from the group consisting of polyproline, polyphthalate, and polyimine as a polymer component; II) comprising a form selected from the group consisting of polylysine, polyphthalate, and polyimine, and a polyorganosiloxane as a polymer component; (III) comprising only polyorganoindene Oxysilane is used as a form of a polymer component.

Among these forms, the form of the above (II) is preferable, and among the forms of the above (II), the polyorganosiloxane is preferably an epoxy group-containing polyorganosiloxane. The compounding ratio of the polyorganosiloxane in the form of the (II) is preferably from 1 part by weight to 30% by weight based on 100 parts by weight of the total of the polyamic acid, the polyamidomate, and the polyimine. It is more preferably 5 parts by weight to 20 parts by weight.

In addition, when a liquid crystal display element is produced by introducing a polymerizable component into an alignment film and forming a liquid crystal cell and then irradiating the liquid crystal cell with light, it is preferable to blend a polymer having a polymerizable unsaturated group on the side chain. At least a part of the polymer component of the liquid crystal alignment agent. Polymeric unsaturated groups on the side chain The polymer is preferably at least one selected from the group consisting of polyproline, polyphthalate, polyimine, and polyorganooxane, and more preferably polyorganosiloxane. In particular, in the form of the above (II), it is preferable that the polyorganosiloxane is a polymer having a polymerizable unsaturated group, and the effect of improving the liquid crystal alignment property can be obtained with a small amount of light irradiation.

≪Solvent ≫

The liquid crystal alignment agent of the present invention is preferably prepared by dissolving a polymer component, a compound (D), and other components optionally arbitrarily dissolved in an organic solvent.

Here, the solvent used to prepare the liquid crystal alignment agent of the present invention can be listed, for example. For example: 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 Ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl 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, diisoamyl ether, ethyl carbonate, propyl carbonate, and the like. These solvents may be used singly or in combination of two or more.

Solid component concentration in the liquid crystal alignment agent of the present invention (liquid crystal alignment agent The ratio of the total weight of the components other than the solvent to the total weight of the liquid crystal alignment agent is appropriately selected in consideration of viscosity, volatility, and the like, but is preferably in the range of 1% by weight to 10% by weight. That is, the liquid crystal alignment agent of the present invention is applied to a method described later. It is preferable that the surface of the substrate is heated to form a coating film as a liquid crystal alignment film or a coating film which becomes a liquid crystal alignment film. In this case, when the solid content concentration is less than 1% by weight, the film thickness of the coating film becomes too small. A good liquid crystal alignment film cannot be obtained. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large, and a favorable liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal alignment agent increases, and the coating property deteriorates.

A particularly preferred range of solid content concentration is based on the coating liquid on the substrate The method used in the case of the crystal matching agent differs. For example, in the case of using the rotator method, the solid content concentration is particularly preferably in the range of 1.5% by weight to 4.5% by weight. In the case of using the printing method, it is particularly preferable to set the solid content concentration to a range of 3% by weight to 9% by weight, thereby setting the solution viscosity to 12 mPa. s~50mPa. The scope of s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration to a range of 1% by weight to 5% by weight, thereby setting the solution viscosity to 3 mPa. s~15mPa. The scope of s. The temperature at which the liquid crystal alignment agent is prepared is preferably from 10 ° C to 50 ° C, more preferably from 20 ° C to 30 ° C.

≪Liquid alignment film and liquid crystal display device≫

The liquid crystal alignment film of the present invention is formed using a liquid crystal alignment agent prepared in the manner described. Further, the liquid crystal display element of the present invention comprises a liquid crystal alignment film formed using the liquid crystal alignment agent. The operation mode of the liquid crystal display element to which 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 by, for example, a method including the following steps (1) to (3).

[Step (1): Formation of coating film]

First, a liquid crystal alignment agent is applied to each surface of a pair of substrates, and then heated to form a coating film.

(1-1) When manufacturing a liquid crystal display device of a TN type, an STN type, a VA type or an MVA type, the two substrates provided with the patterned transparent conductive film are used as a pair, and transparency in each substrate On the surface on which the conductive film is formed, the liquid crystal alignment agent of the present invention is preferably applied by an offset printing method, a spin coating method, a roll coater method or an inkjet printing method. Here, as the substrate, for example, glass such as float glass or soda glass may be used; and polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, poly(alicyclic olefin) may be used. ) A transparent substrate such as plastic. The transparent conductive film provided on one side of the substrate is a Neisser (NESA) film containing tin oxide (SnO ₂ ) (registered trademark of PPG, USA), and indium oxide containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ). Indium tin oxide (ITO) film. In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photolithography 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, and the like may be employed. . When the liquid crystal alignment agent is applied, in order to improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, the surface on which the coating film is formed on the surface of the substrate may be coated with a functional decane compound or a functional titanium compound. Pre-processing.

(1-2) In the case of manufacturing an IPS type or FFS type liquid crystal display element, by forming an electrode on a substrate provided with an electrode including a transparent conductive film or a metal film patterned into a comb-tooth type, and not being provided One side of the opposite substrate of the electrode The liquid crystal alignment agent of the present invention is applied separately, and then each coated surface is heated to form a coating film. The material of the substrate used at this time, the material of the transparent conductive film, the coating method, the heating conditions after coating, the patterning method of the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film of the formed coating film Thick, the same as (1-1). As the metal film, for example, a film containing a metal such as chromium can be used.

In any of the cases (1-1) and (1-2), After coating the liquid crystal alignment agent on the board, the organic solvent is removed to form a coating film as a liquid crystal alignment film or a coating film which becomes a liquid crystal alignment film. It is preferred to remove the solvent by heat treatment. Specifically, after the liquid crystal alignment agent is applied, preheating (prebaking) is preferably performed for the purpose of preventing sag of the applied alignment agent. The prebaking temperature is preferably from 30 ° C to 200 ° C, more preferably from 40 ° C to 150 ° C, and particularly preferably from 40 ° C to 100 ° C. The prebaking time is preferably from 0.25 minutes to 10 minutes, more preferably from 0.5 minutes to 5 minutes. Then, for the purpose of completely removing the solvent, in addition, a calcination (post-baking) step is carried out for the purpose of thermally imidating the proline structure which is present in the polymer as needed. The calcination temperature (post-baking temperature) at this time is preferably 80 ° C to 300 ° C, and more preferably 120 ° C to 250 ° C. The post-baking time is preferably from 5 minutes to 200 minutes, more preferably from 10 minutes to 100 minutes. The film thickness of the film formed in the above manner is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

Further, the polymer contained in the liquid crystal alignment agent of the present invention is a polyfluorene In the case of an amine acid, or a polyamidomate, or a ruthenium-imided polymer having a quinone ring structure and a phthalic acid structure, it is also possible to perform a dehydration ring closure by further heating after the coating film is formed. The reaction was carried out to prepare a coating film which was further imidized.

[Orientation ability processing]

In the case of manufacturing a liquid crystal display element of a TN type, an STN type, an IPS type or an FFS type, a process of imparting a liquid crystal alignment ability to the coating film formed in the above step (1) is usually performed. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. The treatment for imparting the alignment ability includes a rubbing treatment or a treatment using a photo-alignment method in which a coating film is rubbed in a predetermined direction by a roll wound with a cloth containing fibers such as nylon, rayon, or cotton. Among them, it is preferable to use a photo-alignment method in that it is possible to suppress the occurrence of display failure or a decrease in yield due to dust or static electricity, and to impart a liquid crystal alignment ability to the coating film uniformly. On the other hand, in the case of producing a VA liquid crystal display device, the coating film formed in the step (1) can be directly used as the liquid crystal alignment film, but the coating film may be subjected to the above treatment.

In addition, the liquid crystal alignment film after the rubbing treatment may be further subjected to Lower treatment: a treatment for changing a pretilt angle of a partial region of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet rays; or forming a resist film on a part of the surface of the liquid crystal alignment film, and then different from the previous rubbing treatment The treatment of rubbing the direction and then removing the resist film; thereby making the liquid crystal alignment film have different liquid crystal alignment capabilities in each region. In this case, the visual field characteristics of the obtained liquid crystal display element can be improved.

In the photo-alignment method, by applying a polarizing film to a coating film formed on a substrate or Non-polarized radiation to impart liquid crystal alignment capability to the coating film. For the radiation, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 nm to 800 nm can be used. Putting When the ray is polarized, it may be linearly polarized or partially polarized. Further, when the radiation to be used is linearly polarized or partially polarized, the substrate surface may be irradiated from a vertical direction, or may be irradiated from an oblique direction, or these irradiations may be combined. When the non-polarized radiation is irradiated, the direction of the irradiation is an oblique direction.

The light source used can be, for example, a low pressure mercury lamp, a high pressure mercury lamp, Xenon lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, and the like. The ultraviolet light in a preferred wavelength region can be obtained by a method in which a light source is used in combination with, for example, a filter, a diffraction grating, or the like.

The light irradiation can be performed by a method of irradiating the coating film after the post-baking step, a method of irradiating the coating film before the pre-baking step and before the post-baking step, and after the pre-baking step and thereafter. In at least one of the baking steps, a method of irradiating the coating film during heating of the coating film or the like. Light irradiation amount is preferably ^{100J / m 2 ~ 50,000J / m} 2, and more preferably ^{300J / m 2 ~ 20,000J / m} 2. Further, in order to improve the reactivity, the coating film may be irradiated with light while heating the coating film. The temperature at the time of heating is usually from 30 ° C to 250 ° C, preferably from 40 ° C to 200 ° C, more preferably from 50 ° C to 150 ° C. A liquid crystal alignment film is formed on the substrate by such light irradiation treatment.

[Step (2): Construction of the unit]

(2-1) By preparing two (a pair of) substrates in which the liquid crystal alignment film is formed as described above, a liquid crystal cell in which the pair of substrates are disposed via the liquid crystal so as to face the liquid crystal alignment film is manufactured. When manufacturing a liquid crystal cell, the following two methods are mentioned, for example. First, the first method is a previously known method. In this method, first, each liquid crystal is matched In the manner of facing the film, the two substrates are opposed to each other via a gap (cell gap), and the peripheral portions of the two substrates are bonded together using a sealant, and the filled liquid crystal is injected into the cell gap defined by the surface of the substrate and the sealant. Thereafter, the injection hole is sealed, thereby manufacturing a liquid crystal cell. In addition, the second method is a method called a One Drop Fill (ODF) method. In this method, a predetermined portion on one of the two substrates on which the liquid crystal alignment film is formed is coated with, for example, an ultraviolet curable sealing material, and liquid crystal is dropped on a predetermined portion of the liquid crystal alignment film surface. Thereafter, another substrate is bonded in such a manner that the liquid crystal alignment film faces each other. Further, the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant, thereby manufacturing a liquid crystal cell. In the case of using any of the methods, it is preferable to heat the liquid crystal cell produced in the above manner to a temperature at which the liquid crystal to be used becomes an isotropic phase, and then gradually cool to room temperature to remove the liquid crystal. Flow alignment when filling. As the sealant, for example, an epoxy resin containing a hardener and an alumina ball as a spacer can be used. The thickness of the liquid crystal layer is preferably set to 1 μm to 5 μm.

(2-2) In the case of manufacturing a PSA type liquid crystal display element, The liquid crystal cell was constructed in the same manner as in the above (2-1) except that the photopolymerizable compound was injected or dropped together with the liquid crystal.

[Step (3): Light irradiation to the liquid crystal cell]

After the construction of the liquid crystal cell, light is irradiated from the outside of the liquid crystal cell. By the light irradiation, the tilting direction of the liquid crystal molecules is memorized, whereby the alignment of the liquid crystal alignment can be achieved. In the liquid crystal display device of the vertical electric field type, the liquid crystal cell is irradiated with light in a state in which a voltage is applied between the conductive films of the pair of substrates, and in the liquid crystal display device of the transverse electric field type, no voltage is applied between the conductive films. The state is to illuminate the liquid crystal cell. The voltage applied here can be, for example, a direct current of 5V to 50V or an alternating current. Further, as the light to be irradiated, for example, ultraviolet light and visible light including light having a wavelength of 150 nm to 800 nm can be used, but ultraviolet light containing light having a wavelength of 300 nm to 400 nm is preferable. As the light source for illuminating light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. Further, the ultraviolet light in the preferred wavelength region can be obtained by a means for combining a light source with, for example, a filter, a diffraction grating, or the like. The irradiation amount of light is preferably 1,000 J/m ² or more and less than 200,000 J/m ² , and more preferably 1,000 J/m ² to 100,000 J/m ² .

Then, it can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell. A liquid crystal display element of the present invention. The polarizing plate which is bonded to the outer surface of the liquid crystal cell is a polarizing plate in which a polarizing film called "H film" is sandwiched by a cellulose acetate protective film, and the "H film" is made to extend polyvinyl alcohol. A film obtained by absorbing iodine to one side; or a polarizing plate containing the H film itself. Further, in the case where the coating film is subjected to the rubbing treatment, the two substrates are formed to face each other at a predetermined angle in the rubbing direction of each of the coating films, for example, orthogonally or anti-parallel.

The liquid crystal display element of the present invention can be effectively applied to various devices, for example, can be used for: watches, portable game machines, word processors, notebook personal computers, car navigation systems, camcorders, personal digital assistants (Personal Digital Assistant, Various display display devices such as PDAs, digital cameras, mobile phones, smart phones, various monitors, LCD TVs, information displays, and the like.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples.

The solution viscosity of each polymer solution in the synthesis example, the oxime imidization ratio of the polyimine, the weight average molecular weight of the polymer, and the epoxy equivalent were measured by the following methods.

[Solid viscosity of polymer solution]

For a solution having a polymer concentration of 10% by weight using a predetermined solvent, the solution viscosity of the polymer solution was measured at 25 ° C using an E-type rotational viscometer [mPa. s].

[醯Iminization rate of polyimine]

The solution of the polyimine was put into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl hydrazine, and tetramethyl decane was used as a reference material, and it was measured at room temperature. ¹ H- NMR ^{(1 H-Nuclear magnetic resonance,} 1 H-NMR). The oxime imidization ratio [%] was determined from the obtained ¹ H-NMR spectrum using the formula represented by the following formula (1).

醯imination rate [%]=(1-A ¹ /A ² ×α)×100...(1)

(In the formula (1), ^A 1 is the peak area of the proton derived from the NH group appearing near the chemical shift of 10 ppm, A ² is the peak area derived from other protons, and α is the precursor of other protons relative to the polymer The ratio of the number of protons of the NH group in (polyglycine).)

[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.

Pipe column: manufactured by Tosoh (stock), TSKgelGRCXLII

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf/cm ²

[epoxy equivalent]

The epoxy equivalent is a value measured by the "hydrochloric acid-methyl ethyl ketone method" according to Japanese Industrial Standards (JIS) C2105.

The following synthesis examples are repeated as needed, and the required amounts of products used in the following synthesis examples, examples, and comparative examples are ensured by repeating the following synthesis scales.

<Synthesis of Compound (D)> [Synthesis Example 1: Synthesis of Compound (1-2-1)]

Compound (1-2-1) was synthesized according to the following Scheme 1.

[Chem. 21]

In a 100 mL three-necked flask equipped with a thermometer, a reflux tube, and a dropping funnel, 6.24 g of a compound (1-2A), 8.64 g of acetonitrile, 6 mg of 2,6-di-t-butyl-4-methoxyphenol, and a mercapto group were added. 2.40 g of propionic acid was heated to 50 °C. Then, 6.07 g of triethylamine was added dropwise thereto over 1 hour, and then the reaction was directly carried out at 50 ° C for 1 hour. After completion of the reaction, 100 mL of ethyl acetate was added thereto, and the mixture was washed once with 100 mL of 1 M aqueous oxalic acid, and then washed with water for 5 times, and then subjected to solvent replacement twice with butyl cellosolve to obtain a solid concentration of 20%. 40 g of a butyl cellosolve solution of the compound (1-2-1).

[Synthesis Example 2: Synthesis of Compound (1-3-1)]

Compound (1-3-1) was synthesized according to the following Scheme 2.

[化22]

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

<Synthesis of polyorganosiloxanes>

[Synthesis Example 3: Synthesis of epoxy group-containing polyorganosiloxane (EPS-1)]

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, 100.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 500 g of methyl isobutyl ketone, and three were charged. 10.0 g of ethylamine was mixed at room temperature. Then, 100 g of deionized water was added dropwise from the dropping funnel for 30 minutes, and then the reaction was carried out at 80 ° C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight aqueous solution of ammonium nitrate until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure, thereby obtaining as a viscous transparent liquid. Polyorganosiloxane (EPS-1).

¹ H-NMR analysis of the polyorganosiloxane (EPS-1) showed that the peak of the oxiranyl group was obtained as the theoretical intensity in the vicinity of the chemical shift (δ) = 3.2 ppm, and it was confirmed that no reaction occurred in the reaction. A side reaction of an epoxy group. The polyorganosiloxane (EPS-1) had an Mw of 2,200 and an epoxy equivalent of 186 g/mole.

[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 cooling tube, 458.7 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane and 3-methylpropenyloxypropane were charged. 162.8 g of methoxymethoxy decane, 3108 g of methyl isobutyl ketone, and 62.2 g of triethylamine were mixed at room temperature. Then, 621.5 g of deionized water was added dropwise from the dropping funnel for 30 minutes, and then the reaction was carried out at 80 ° C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight aqueous solution of ammonium nitrate until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure, thereby obtaining as a viscous transparent liquid. Polyorganosiloxane (EPS-2). Weight average molecular weight of the polyorganosiloxane (EPS-2) Mw is 2,900.

[Synthesis Example 5: Synthesis of a carboxylic acid (3-6-1) containing a liquid crystal alignment group]

The carboxylic acid (3-6-1) was synthesized according to the following Scheme 3.

. Synthesis of Compound (3-6-1A)

In a 2L eggplant type flask equipped with a nitrogen gas 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 600 mL of acetone (MS dry) were added, and then 4-bromobutyl group was added. 32.6 g (0.22 mol) of nitrile was refluxed for 3 hours. After completion of the reaction, 1 L of ethyl acetate was added, and the mixture was washed with 1 L of water, and then washed twice with a saturated aqueous solution of sodium carbonate (200 mL), and then washed three times with 300 mL of water. Then, the organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to obtain 35.5 g of a yellow transparent liquid of compound (3-6-1A).

. Synthesis of Compound (3-6-1)

In a 1000 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen gas introduction tube, 35.52 g (0.188 mol) of compound (3-6-1), 224 mL of pyridine, and 39.13 g (0.376 mol) of malonic acid were dissolved. Next, piperidine 16.0 g (0.188 mol) was added. The reflux was carried out for 3 hours. After completion of the reaction, 800 mL of ethyl acetate and 800 mL of tetrahydrofuran (THF) were added, and the mixture was washed once with 1 N hydrochloric acid water 1 L, twice with 1N aqueous hydrochloric acid, and then 1.5 L of saturated sodium carbonate water was added to ethyl acetate 400 mL. Wash twice. Then, 400 mL of ethyl acetate and 800 mL of THF were added, and the mixture was acidified with 500 mL of 8N hydrochloric acid water, and then washed three times with 400 mL of water, dried with magnesium sulfate, concentrated, and crystallized to obtain a carboxylic acid ( The white crystal of 3-6-1) was 25.2 g.

[Synthesis Example 6: Synthesis of a carboxylic acid (3-9-1) containing a liquid crystal alignment group]

20 g of 4-bromodiphenyl ether, 0.18 g of palladium acetate, 0.98 g of tris(2-methylphenyl)phosphine, 32.4 g of triethylamine, and 135 mL of dimethylacetamide were placed in a 500 mL three-necked flask equipped with a cooling tube. , mixing to make a solution. Next, 7 g of acrylic acid was added to the solution using a syringe, and the mixture was stirred, and then reacted at 120 ° C for 3 hours while stirring. After confirming the completion of the reaction by Thin Layer Chromatography (TLC), the reaction solution was cooled to room temperature. After the insoluble matter was separated by filtration, the filtrate was poured into 300 mL of 1N hydrochloric acid, and the precipitate was collected. The precipitate was recrystallized in a mixed solvent containing ethyl acetate and hexane (ethyl acetate:hexane = 1:1 (volume ratio)), whereby the following formula (3-9-1) was obtained. The compound (carboxylic acid (3-9-1)) represented by 8.4 g.

[Synthesis Example 6-1: Synthesis of carboxylic acid (F-2)]

The carboxylic acid (F-2) was synthesized according to the following procedure.

. Synthesis of Compound (F-2D)

In a 200 mL eggplant type flask equipped with a reflux tube and a nitrogen introduction tube, 21.6 g of monomethyl terephthalate, 88 mL of sulfoxide, and 5 drops of N,N-dimethylformamide were added, and the mixture was carried out at 80 ° C. 1 hour reflux. After the completion of the reaction, the sulfoxide was distilled off under reduced pressure by a suction machine to obtain a pale yellow solid of the compound (F-2B). To the solid, 50 mL of tetrahydrofuran was added to prepare a solution A. 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 gas introduction tube, and a dropping funnel, and the mixture was cooled in an ice bath. Then, 90 mL of a 1.6 M n-butyllithium hexane solution was added dropwise over 30 minutes. Next, after adding A liquid for 30 minutes, stirring was carried out directly under cooling in an ice bath, and after 2 hours, 100 mL of water was added to stop the reaction. then, 400 mL of ethyl acetate was added, and the mixture was washed four times with 400 mL of water, and concentrated and dehydrated to obtain 32.8 g of an orange liquid of the compound (F-2D).

. Synthesis of Compound (F-2)

In a 1 L eggplant type flask, 32.8 g of a compound (F-2D), 150 mL of methanol, 50 mL of water, and 9.95 g of lithium hydroxide monohydrate were charged, and the reaction was carried out for 1 hour at room temperature. After completion of the reaction, 250 mL of tetrahydrofuran and 300 mL of ethyl acetate were added, and the mixture was washed once with 400 mL of diluted hydrochloric acid and washed three times with 300 mL of water. After drying with magnesium sulfate, the mixture was concentrated, and the crystals precipitated by adding hexane were filtered and dried to obtain 14.1 g of yellow needle crystal of compound (F-2).

[Synthesis Example 7: Synthesis of polyorganosiloxane (S-2-1) containing an alignment group]

In a 100 mL three-necked flask, 3.5 g of polyorganosiloxane (EPS-1) synthesized in Synthesis Example 3, 24 g of methyl isobutyl ketone, and 2.42 g of carboxylic acid (3-6-1) were charged. It is produced by polyorganosiloxane (EPS-1), which is equivalent to 50% by mole, and is manufactured under the trade name "UCAT 18X" (San-Apro). 0.35 g of the agent was refluxed for 5 hours. After completion of the reaction, methanol was added to the reaction mixture to form a precipitate, and the solution obtained by dissolving the precipitate in ethyl acetate was washed with water three times, and then the solvent was distilled off to obtain a polyorganosiloxane (S- 2-1) white powder 5g. The polyorganosiloxane (S-2-1) had a weight average molecular weight of 9,200.

[Synthesis Example 8 to Synthesis Example 10, Synthesis Example 10A: Synthesis of polyorganosiloxane containing an alignment group]

The polyorganosiloxane (S-2-2) containing an alignment group was synthesized by the same method as the synthesis example 7 except that the kind and amount of the compound to be used were as described in the following Table 1. Polyorganosiloxane (S-2-4), polyorganosiloxane (S-2-10).

In Table 1, the numerical value of the compounding amount of the carboxylic acid indicates the amount of input [mol%] with respect to the ruthenium atom which the epoxy group-containing polyorganosiloxane has.

[Synthesis Example 11: Synthesis of polyaminic acid (PA-1)]

5.55 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 9.45 g of the diamine compound represented by the following formula (3-7DA) were dissolved in N-methyl-2-pyrrolidone (N-methyl- In 85 g of 2-pyrrolidone, NMP), the reaction was carried out for 6 hours at room temperature. The reaction mixture was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to obtain 10 g of polyamine acid (PA-1).

[Synthesis Example 12: Synthesis of poly-proline (PA-2)]

Cyclobutane tetracarboxylic dianhydride 19.61g (0.1 mole), and 4,4'-diamino-2,2'- 21.23 g (0.1 mol) of dimethylbiphenyl was dissolved in 367.6 g of N-methyl-2-pyrrolidone, and the reaction was carried out for 6 hours at room temperature. The reaction mixture was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to obtain 35 g of polyamine (PA-2).

[Example 1] (1) Preparation of liquid crystal alignment agent

100 parts by weight of an organic group-containing polyorganosiloxane (S-2-1) as a polymer component and 1,000 parts by weight of polyglycolic acid (PA-2), as an East Asian synthesis of the compound (D) 100 parts by weight of "TO-1382" produced and 200 parts by weight of trimellitic acid as another component were mixed, and N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (Butyl Cellosolve) as a solvent were added thereto. BC), a solution having a solvent composition of NMP: BC = 50: 50 (weight ratio) and a solid concentration of 3.0% by weight was prepared. This solution was filtered with a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent (A-1).

(2) Manufacturing of a liquid crystal display element in a transverse electric field mode

A glass substrate having a two-system metal electrode including chromium which is patterned into a comb shape on one side and a counter glass substrate not provided with an electrode are provided as a pair on the surface of the glass substrate having the electrode and the opposite glass substrate On one side, the prepared liquid crystal alignment agent (A-1) was applied by a spinner, and prebaked for 1 minute using a hot plate at 80 ° C, and then in an oven in which the inside of the chamber was replaced with nitrogen, 200 The coating film having a film thickness of 0.1 μm was formed by heating (post-baking) at ° C for 1 hour. A schematic view showing the configuration of the electrode pattern on the glass substrate is shown in Fig. 1 . Hereinafter, the lateral electric field method liquid The two-system metal electrodes (conductive film patterns) of the crystal display element are referred to as an electrode 11 and an electrode 12, respectively.

Then, a Hg-Xe lamp and a Glan-Taylor prism were used to irradiate the surface of the coating film with a polarized ultraviolet ray of 300 J/m ² including a bright line of 313 nm from the normal direction of the substrate to obtain a liquid crystal alignment film. a pair of substrates. A bead spacer was spread on a surface of one of the substrates having a liquid crystal alignment film, and further, an epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm was applied to the periphery by screen printing. Then, the liquid crystal alignment film in each of the substrates of the pair of substrates faces each other, and the orientation of each of the substrates when the polarized ultraviolet rays are irradiated is superposed and pressed, and the adhesive is heated at 150 ° C for 1 hour to heat the adhesive. hardening.

Then, 0.3% by weight of the polymerizable liquid crystal represented by the following formula (L-1) is added to the liquid crystal "MLC-7028" manufactured by Merck Co., Ltd. from the liquid crystal injection port to the gap between the substrates. The resulting liquid crystal mixture is then sealed with an epoxy-based adhesive. Then, in order to remove the flow alignment at the time of liquid crystal injection, it was heated at 150 ° C, and then slowly cooled to room temperature, and further subjected to UV light irradiation from the outside of the liquid crystal cell (irradiation amount: 2,000 mJ/cm ² (λ = 365nm)). Then, the polarizing plate is bonded to the outer surface of the substrate so that the polarizing directions of the polarizing plates are orthogonal to each other, and the polarizing plate is bonded to the optical axis of the polarized ultraviolet light of the liquid crystal alignment film. Liquid crystal display element.

[化27]

(3) Evaluation of liquid crystal alignment

For the manufactured liquid crystal display element, an optical microscope is used to observe when turned on. Turns off (ON.OFF) (applies.releases) the presence or absence of an abnormal area in the change in brightness and darkness at a voltage of 5V. In this case, the case where the abnormal region was not observed at all was evaluated as "excellent liquid crystal alignment", and when a small amount of abnormal region was observed, the liquid crystal alignment property was evaluated as "good", and the case where a plurality of abnormal regions were observed was evaluated as liquid crystal. Orientation is "bad". As a result, in the first embodiment, the liquid crystal alignment property was "good".

(4) Evaluation of afterimage characteristics

The produced transverse electric field type liquid crystal display element was placed in an environment of 25 ° C and 1 atmosphere, no voltage was applied to the electrode 12, and a combined voltage of an alternating voltage of 3.5 V and a direct current voltage of 5 V was applied to the electrode 11 for 2 hours. Immediately thereafter, a voltage of 4 V was applied to both the electrode 11 and the electrode 12. The time from when the voltage of the alternating current of 4 V was applied to the two electrodes was reached until the difference in light transmittance between the electrodes 11 and 12 was not visually recognized. When the time is 20 seconds or more and less than 60 seconds, the afterimage characteristics are evaluated as "excellent", and when the time is 60 seconds or more and less than 100 seconds, the afterimage characteristics are "good", and 100 seconds or more and less than 150 are evaluated. In the case of a second, it was evaluated as an afterimage characteristic "may", and when it was more than 150 seconds, it was evaluated as an afterimage characteristic "poor". As a result, in the first embodiment, the afterimage characteristics were "good".

[Example 2 to Example 20, Comparative Example 1, Comparative Example 2]

The liquid crystal alignment agent (A-2) was prepared by the same operation as in Example 1 except that the type and amount of the polymer, the compound (D), and other components to be used were changed as described in Table 2 below. Liquid crystal alignment agent (A-20), liquid crystal alignment agent (R-1), and liquid crystal alignment agent (R-2). Further, the obtained liquid crystal alignment agent (A-2) to liquid crystal alignment agent (A-20), liquid crystal alignment agent (R-1), and liquid crystal alignment agent (R-2) were produced in the same manner as in Example 1. The liquid crystal display element was evaluated for liquid crystal alignment and afterimage characteristics. The results are shown in Table 3 below.

In Table 2, the numerical values in parentheses indicate the compounding ratio (parts by weight) of each compound. The carboxylic acid-containing polyacrylate of the compound (D) (trade names "TO-1382" and "TO-2349") is obtained from East Asia Synthetic Co., Ltd. The abbreviations of the compound (D) and other components in Table 2 are as follows.

(Compound (D))

D-1: the compound represented by the formula (1-2-1)

D-2: the compound represented by the formula (1-3-1)

(other additives)

EP-1: N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

As shown in Table 3, in the liquid crystal display elements of Examples 1 to 20, the liquid crystal alignment properties and the afterimage characteristics were evaluated as "excellent" or "good". On the other hand, in Comparative Example 1 and Comparative Example 2 in which the liquid crystal alignment agent contained no compound (D), liquid crystal alignment The evaluation of "bad" is the evaluation of the afterimage characteristics.

[Synthesis Example 13: Synthesis of a carboxylic acid (7-3-1) containing a liquid crystal alignment group]

The carboxylic acid (7-3-1) was synthesized according to the following Scheme 4.

. Synthesis of Compound (7-3-1A)

5.00 g (36.22 mmol) of hydroxybenzoic acid, 150 mL of tetrahydrofuran, 100 mL of third butanol, and 0.177 g of N,N-dimethylaminopyridine were added to a 1-L three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen gas introduction tube. (1.45 mmol). Next, 8.22 g (39.84 mmol) of dicyclohexylcarbodiimide was dissolved in 50 mL of tetrahydrofuran in a dropping funnel, and the mixture was added dropwise for 30 minutes, and the reaction was carried out for 15 hours. After completion of the reaction, the mixture was filtered through celite, and the obtained filtrate was concentrated, and ethyl acetate (300 mL) was added thereto, and the mixture was washed twice with a sodium hydrogencarbonate aqueous solution, and washed with water three times, and then concentrated and vacuum dried. Thereby obtaining an orange viscous liquid. The viscous liquid was purified by a cerium oxide column (developing solvent: hexane/ethyl acetate) = 80/20), thereby obtaining 3.6 g of white crystals of Compound (7-3-1A).

. Synthesis of Compound (7-3-1B)

To a 500 mL three-necked flask equipped with a thermometer and a nitrogen gas introduction tube, 12.25 g (63.1 mmol) of compound (7-3-1A), 16.64 g (66.2 mmol) of 11-bromoundecyl alcohol, and N,N-dimethyl group were added. 180 mL of acetamide, 9.58 g (69.4 mmol) of potassium carbonate, and 2.09 g (12.6 mmol) of potassium iodide were reacted at 100 ° C for 2 hours. After completion of the reaction, 500 mL of ethyl acetate was added, and the mixture was washed with dilute hydrochloric acid for one time, and washed with water three times, and then dried over magnesium sulfate, concentrated and dehydrated to obtain a compound (7-3- 1B) 21.3 g of a white solid.

. Synthesis of Compound (7-3-1D)

Into a 1-L three-necked flask equipped with a thermometer and a nitrogen gas introduction tube, 16.48 g (58.4 mmol) of the compound (7-3-1C), 21.3 g (58.4 mmol) of the compound (7-3-1B), and 440 mL of dichloromethane were added. It was suspended and cooled in an ice bath. Next, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride 13.47 g (70.3 mmol) and N,N-dimethylaminopyridine 1.43 g (11.7) were added. After stirring for 2 hours under ice-cooling, the mixture was returned to room temperature and reacted for 16 hours. After completion of the reaction, 2 L of ethyl acetate was added, and the mixture was washed three times with water, and then dried over magnesium sulfate. Then, the white precipitate obtained 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)

In a 500 mL eggplant type flask, 26.0 g (41.3 mmol) of the compound (7-3-1D), 55 mL of trifluoroacetic acid, and 110 mL of dichloromethane were added, and the mixture was carried out at room temperature. Hour response. After completion of the reaction, the solvent was removed by a suction machine, and then 2 L of ethyl acetate and 2 L of tetrahydrofuran were added, and the mixture was washed with water three times, and then dried over magnesium sulfate. Then, the precipitate obtained by concentration was filtered and dried to obtain 20.64 g of a white crystal of carboxylic acid (7-3-1).

[Synthesis Example 14: Synthesis of a carboxylic acid (8-1-1) containing a liquid crystal alignment group]

The 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 gas introduction tube, 15.0 g of the compound (6-6-1), 16.6 g of the compound (7-3-1B), and 270 mL of dichloromethane were added, and the mixture was cooled in an ice bath at 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 at 5 ° C. The reaction was carried out 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 with dilute hydrochloric acid for one time, washed with water three times, dried over magnesium sulfate, and then concentrated to crystallize. The white crystal of the compound (8-1-1A) was 18.4 g (purity: 100%).

. Synthesis of Carboxylic Acid (8-1-1)

In a 500 mL eggplant type flask equipped with a nitrogen gas introduction tube, 18.4 g of a compound (8-1-1A), 90 mL of dichloromethane, and 45 mL of trifluoroacetic acid were added, and the reaction was carried out for 4 hours at room temperature. After completion of the reaction, trifluoroacetic acid was removed by a suction machine, and the mixture was dissolved in 600 mL of ethyl acetate and 300 mL of THF, and washed three times with water. Then, the mixture was dried over magnesium sulfate, and concentrated to crystallize to obtain 12.8 g (purity: 99.9%) of white crystals of carboxylic acid (8-1-1).

[Synthesis Example 15: Synthesis of carboxylic acid (9-1-1) containing a liquid crystal alignment group]

The carboxylic acid (9-1-1) was synthesized according to the following Scheme 6.

. Synthesis of Compound (9-1-1A)

The compound (9-1-1A) was synthesized by the same method as the compound (8-1-1).

. Synthesis of Compound (9-1-1B)

The compound (9-1-1B) was synthesized by the same method as the compound (7-3-1B).

. Synthesis of Compound (9-1-1C)

In a 100 mL three-necked flask equipped with a thermometer and a nitrogen gas introduction tube, 3.4 g of the compound (9-1-1A), 2.2 g of the compound (9-1-1B), and 30 mL of dichloromethane were added, and the mixture was cooled in an ice bath at 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 the mixture was carried out at 5 ° C or lower. 24 hours reaction. After the completion of the reaction, 300 mL of ethyl acetate was added, and the mixture was washed with water three times, and dried over magnesium sulfate, and then concentrated and crystallized to obtain white crystals of the compound (9-1-1C). .

. Synthesis of Carboxylic Acid (9-1-1)

In a 100 mL eggplant type flask, 2.4 g of the compound (9-1-1C), 4 mL of trifluoroacetic acid, and 8 mL of dichloromethane were added, and the mixture was reacted at room temperature for 2 hours. After completion of the reaction, the solvent was removed by a suction machine, and then 50 mL of ethyl acetate and 50 mL of tetrahydrofuran were added, and the mixture was washed with water three times, and then dried over magnesium sulfate. Then, the precipitate obtained by concentration was filtered and dried to obtain 1.7 g of a white crystal of a carboxylic acid (9-1-1).

[Synthesis Example 16: Synthesis of a carboxylic acid (10-1-1) containing a liquid crystal alignment group]

The carboxylic acid (10-1-1) was synthesized according to the following Scheme 7.

. Synthesis of Compound (10-1-1A)

The compound (10-1-1A) was synthesized by the same method as the compound (7-3-1).

. Synthesis of Compound (10-1-1B)

The compound (10-1-1B) was synthesized by the same method as the compound (7-3-1C).

. Synthesis of Compound (10-1-1C)

Into a 300 mL three-necked flask equipped with a thermometer and a nitrogen gas introduction tube, 9.21 g (20 mmol) of the compound (10-1-1A), 5.89 g (20 mmol) of the compound (9-1-1B), and 80 mL of dichloromethane were added to perform ice. The bath is cooled. Next, add 1-ethyl -3-(3-Dimethylaminopropyl)carbodiimide hydrochloride 4.60 g (24 mmol), N,N-dimethylaminopyridine 0.489 g (4.0 mmol), cooled in ice bath After stirring for 4 hours, it was returned to room temperature, and the reaction was carried out overnight. After completion of the reaction, 1000 mL of ethyl acetate was added, and the mixture was washed four times with 300 mL of water, and then dried over magnesium sulfate. Then, the white precipitate which was concentrated to about 100 mL was filtered and dried to obtain a white crystal of 7.93 g (purity: 94.4%, yield: 53.8%) of the compound (10-1-1C).

. Synthesis of Carboxylic Acid (10-1-1)

To a 100 mL eggplant type flask, 4.72 g (6.41 mmol) of the compound (10-1-1 C), 7 mL of trifluoroacetic acid, and 14 mL of dichloromethane were added, and the mixture was reacted at room temperature for 1 hour. After completion of the reaction, the solvent was removed by a suction machine, and then 100 mL of ethyl acetate and 100 mL of THF (supplemented with a stabilizer) were added thereto, and the mixture was washed three times with 100 mL of water, and then dried over magnesium sulfate. Next, a few mg of the polymerization inhibitor was added, and the precipitate which was concentrated to about 80 mL was filtered and dried to obtain 2.59 g of a white crystal of a carboxylic acid (10-1-1) (purity: 97.2%, yield It is 59.4%).

[Synthesis Example 17: Synthesis of polyorganosiloxane (S-2-5) containing an alignment group]

In a 100 mL three-necked flask, 8.7 g of polyorganosiloxane (EPS-1) synthesized in Synthesis Example 3, 114 g of methyl isobutyl ketone, and 2.7 g of compound (6-6-1) were added (relative to Polyorganosiloxane (EPS-1) has a ruthenium atom equivalent to 20 mol%) and compound (7-3-1) 8.5 g (relative to polyorganosiloxane (EPS-1)) Helium atom, equivalent to 30 mol%) and tetrabutylammonium bromide 0.89 g, The reaction was carried out at 90 ° C for 30 hours. After completion of the reaction, methanol was added to the reaction mixture to form a precipitate, and the solution obtained by dissolving the precipitate in ethyl acetate was washed with water three times, and then the solvent was distilled off to obtain a polyorganosiloxane (S-2). -5) 15 g of white powder. The polyorganosiloxane (S-2-5) had a weight average molecular weight of 9,500.

[Synthesis Example 18 to Synthesis Example 21, Synthesis Example 21A: Synthesis of polyorganosiloxane containing an alignment group]

The polyorganosiloxane (S-2-6) containing an alignment group was synthesized by the same method as the synthesis example 17 except that the kind and amount of the compound to be used were as described in the following Table 4. Polyorganosiloxane (S-2-9) containing an alignment group, polyorganosiloxane (S-2-11) containing an alignment group.

In Table 4, the numerical value of the compounding amount of the carboxylic acid indicates the amount of input [mol%] with respect to the ruthenium atom of the epoxy group-containing polyorganosiloxane.

[Synthesis Example 22: Synthesis of Polyimine (P1-1)]

19.1 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride And 8.49 g of cholestyloxy-2,4-diaminobenzene (a compound represented by the following formula (DA-1)) and 7.42 g of p-phenylenediamine as a diamine are dissolved in NMP 140 g, The reaction was carried out for 4 hours at 60 °C. The obtained polyaminic acid solution was divided into small amounts, NMP was added, and the viscosity was measured by a solution having a solid concentration of 10%. As a result, the solution viscosity was 100 mPa. s. To the obtained polyaminic 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 carried out at 110 ° C for 4 hours. After the imidization reaction, the solvent in the system is subjected to solvent replacement using a new NMP (by this operation, the pyridine and acetic anhydride used in the oxime imidization reaction are removed to the outside of the system), and about 15% by weight is obtained. A solution of polyamidiamine (PI-1) having a ruthenium iodization rate of about 50%.

[Example 21] (1) Preparation of liquid crystal alignment agent

200 parts by weight of an organic group-containing polyorganosiloxane (S-2-5) as a polymer component, 1,000 parts by weight of polyimine (PI-1), and a compound (1) as a compound (D) -2-1) 10 parts by weight, and added thereto as a solvent NMP and butyl cellosolve (BC) were prepared into a solution having a solvent composition of NMP: BC = 50:50 (weight ratio) and a solid concentration of 3.0% by weight. This solution was filtered using a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent (A-21).

(2) Fabrication of a liquid crystal display element having a transparent electrode without a pattern

A liquid crystal display element having a transparent electrode without a pattern was produced using the prepared liquid crystal alignment agent (A-21). First, a liquid crystal alignment agent (A-21) was applied onto a transparent electrode surface of a glass substrate having a transparent electrode (without pattern) including an ITO film using a liquid crystal alignment film printer (manufactured by Nippon Photoprint Co., Ltd.). Then, the solvent was removed by heating (prebaking) on a hot plate at 80 ° C for 1 minute, and then heated (post-baking) on a hot plate at 150 ° C for 10 minutes to form a coating film having an average film thickness of 600 Å.

The coating film was subjected to a rubbing treatment using a rubbing machine having a roller wound with a rayon cloth at a roll rotation speed of 400 rpm, a table moving speed of 3 cm/sec, and a hair press-in length of 0.1 mm. Then, ultrasonic cleaning was performed for 1 minute in ultrapure water, followed by drying in a 100 ° C clean oven for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of (two pieces) substrates having a liquid crystal alignment film.

Next, an epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm is applied to the outer edges of the pair of substrates having the liquid crystal alignment film, and then the liquid crystal alignment film faces are opposed to each other. Connect to harden the adhesive. Then, 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 photocurable adhesive to produce a liquid crystal display element.

Repeat the operation to make 3 transparent electrodes with no pattern Liquid crystal display element. One of them is directly supplied to the evaluation of the orientation described later. Each of the other two liquid crystal display elements was subjected to light irradiation in a state where a voltage was applied between the conductive films by the following method (light irradiation step), and then the alignment and the voltage holding ratio were evaluated.

(light irradiation step)

For two of the three liquid crystal display elements obtained, an alternating current 10 V having a frequency of 60 Hz was applied between the electrodes, and in the liquid crystal driven state, an ultraviolet gland irradiation device using a metal halide lamp as a light source was used. The irradiation amount of 100,000 J/m ² was irradiated with ultraviolet rays from the outside of the liquid crystal display element. Further, the irradiation amount is a value measured using a light amount meter measured with a wavelength of 365 nm as a reference.

(3) Evaluation of the orientation

For the three liquid crystal display elements manufactured, light leakage in a state where no voltage is applied is observed by visual observation under backlight illumination. Whether there is confusion or not. The evaluation is carried out as follows: there will be no light leakage. The situation of coordination disorder is evaluated as an "good" alignment, and there will be light leakage. The situation of disorderedness was evaluated as an "defective" alignment. As a result, all of the three liquid crystal display elements of Example 21 were "good" in alignment.

(4) Evaluation of voltage retention rate

In the three liquid crystal display elements manufactured, the liquid crystal display element having a light irradiation amount of 100,000 J/m ² was applied at 23 ° C with an application time of 60 μsec and a span of 167 msec, and then measured. The voltage holding ratio [%] after 167 milliseconds since the application was released. VHR-1 manufactured by Toyo Technica Co., Ltd. was used as a measuring device. As a result, the voltage holding ratio was 98%.

(5) Fabrication of a liquid crystal display element having a patterned transparent electrode

A liquid crystal display element having a patterned transparent electrode was produced using the prepared liquid crystal alignment agent (A-21). First, liquid crystal alignment is used on each electrode surface of a pair of glass substrates (substrate A, substrate B) each having an ITO electrode which is patterned into a slit shape and divided into a plurality of regions as shown in FIG. 2 . A film printing machine (manufactured by Japan Photo Printing Co., Ltd.) was used to coat the liquid crystal alignment agent (A-21). Then, the solvent was removed by heating (prebaking) on a hot plate at 80 ° C for 1 minute, and then heated (post-baking) on a hot plate at 150 ° C for 10 minutes to form a coating film having an average film thickness of 600 Å. The coating film was subjected to ultrasonic cleaning in ultrapure water for 1 minute, and then dried in a 100 ° C clean oven for 10 minutes, thereby obtaining a pair of (two pieces) substrates having a liquid crystal alignment film.

Then, an epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm is applied to each outer edge of the pair of substrates having the liquid crystal alignment film, and then the liquid crystal alignment film faces are overlapped and crimped. , harden the adhesive. Then, 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 photocurable adhesive to produce a liquid crystal display element.

The above operation was repeated to fabricate three liquid crystal display elements having patterned transparent electrodes. With respect to these three liquid crystal display elements, in the same manner as in the case of manufacturing the liquid crystal cell having the transparent electrode having no pattern, ultraviolet rays are irradiated at an irradiation dose of 100,000 J/m ² in a state where a voltage is applied between the conductive films. Then, the evaluation of the response speed is performed. Further, the pattern of the electrode used here is the same type of pattern as the electrode pattern of the PSA mode.

(6) Evaluation of response speed

For each of the three liquid crystal display elements manufactured as described above, the visible light lamp was first irradiated without applying a voltage, and the brightness of the light transmitted through the liquid crystal display element was measured by a photo multimeter. The measured value at this time was taken as a relative transmittance of 0%. Next, in the same manner as described above, the transmittance (light transmittance of light transmitted through the liquid crystal display element) when AC 60 V was applied for 5 seconds between the electrodes of the liquid crystal display element was measured, and this value was regarded as 100% relative transmittance. Then, the time until the relative transmittance was changed from 10% to 90% when 60 V of alternating current was applied to each liquid crystal display element was measured, and this time was defined as the response speed [msec]. In addition, the response speed was evaluated by the average of three units. As a result, the response speed of the liquid crystal display element of Example 21 was 10 msec.

[Example 22 to Example 26, Comparative Example 3]

The liquid crystal alignment agent (A-22) was prepared by the same operation as in Example 21 except that the type and amount of the polymer (P) and the compound (D) to be used were changed as described in the following Table 5. Liquid crystal alignment agent (A-26), liquid crystal alignment agent (R-3). Further, using the obtained liquid crystal alignment agent (A-22) to liquid crystal alignment agent (A-26) and liquid crystal alignment agent (R-3), a transparent electrode having no pattern was produced in the same manner as in Example 21. A liquid crystal display element and a liquid crystal display element having a patterned transparent electrode, and the various evaluations were performed. The results are shown in Table 6 below.

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

As shown in Table 6, the liquid crystal display elements of Examples 21 to 26 all had an evaluation that the liquid crystal alignment property was "good". In addition, the voltage holding rate is as high as 98% or more, and the response speed is also fast. On the other hand, in Comparative Example 3, the liquid crystal alignment property and the response speed were the same as those in the examples, but the voltage holding ratio was as low as 95%.

11, 12‧‧‧ electrodes

Claims (9)

A liquid crystal alignment agent comprising: a polymer component; and a compound (D) represented by the following formula (1), (In the formula (1), A ¹ is a group containing a polymerizable unsaturated bond, A ² is a functional group reactive with an epoxy group, and R ¹ is an (m+n) valent organic group; m is 2~ An integer of 18, n is an integer from 1 to 18; wherein (m + n) ≦ 20) is satisfied. The liquid crystal alignment agent according to claim 1, wherein the n is an integer of 2 to 18. The liquid crystal alignment agent according to claim 1 or 2, wherein the A ¹ is at least selected from the group consisting of (meth) acryl methoxy, vinyl and styryl groups. One. The liquid crystal alignment agent according to claim 1 or 2, which comprises a group selected from the group consisting of polyproline, polyphthalate, polyimine and polyorganosiloxane. At least one is used as the polymer component. The liquid crystal alignment agent according to claim 1 or 2, which contains an epoxy group-containing polyorganosiloxane as the polymer component. A liquid crystal alignment film which is formed using the liquid crystal alignment agent according to any one of the above-mentioned items of the first aspect of the invention. A method for producing a liquid crystal alignment film, comprising: coating a liquid crystal alignment agent according to any one of claims 1 to 5 on a substrate to form a coating film; and performing the coating film on the coating film The step of light irradiation. A liquid crystal display element comprising the liquid crystal alignment film according to claim 6 or the liquid crystal alignment film obtained by the method for producing a liquid crystal alignment film according to claim 7 of the patent application. A method for producing a liquid crystal display device, comprising: coating a liquid crystal alignment agent according to any one of claims 1 to 5 on each surface of a pair of substrates, followed by heating to form a step of coating a film; a step of arranging a pair of substrates on which the coating film is formed with a layer of liquid crystal molecules facing each other to form a liquid crystal cell; and a step of constructing a liquid crystal cell from the liquid crystal cell The step of performing light irradiation on the outside.