KR102404080B1 - A liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal element, and the manufacturing method of a liquid crystal element - Google Patents

Abstract

A liquid crystal aligning agent is made to contain the heterocyclic-containing compound which has 2 or more of polymer components and the partial structure which removed n (n is an integer greater than or equal to 1) hydrogen atom in 1 molecule from the structure represented by Formula (1). In formula (1), X ¹ is -CR ¹ =CR ² - or the like. A ¹ is a divalent organic group, and may be bonded to another ring structure to form a condensed ring together with the other ring structure. A plurality of A ¹ and X ¹ in one molecule each independently have the above definition.

Description

A liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal element, and the manufacturing method of a liquid crystal element

(Cross-reference to related applications)

This application is based on the Japanese Patent Application No. 2018-73138 for which it applied on April 5, 2018, The description is used here.

This indication relates to a liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal element, and the manufacturing method of a liquid crystal element.

A liquid crystal element is equipped with the liquid crystal aligning film which has a function to orientate a liquid crystal molecule in a fixed direction. Generally, a liquid crystal aligning film apply|coats the liquid crystal aligning agent in which a polymer component melt|dissolves in an organic solvent to the board|substrate surface, Preferably it is formed on a board|substrate by heating. Moreover, about the organic film formed on the board|substrate using the liquid crystal aligning agent, a rubbing process and a photo-alignment process are performed as needed, and liquid-crystal orientation ability is provided by this.

In recent years, large-screen and high-definition liquid crystal TVs are the main components, and small display terminals such as smart phones and tablet PCs have been popularized, and the demand for higher quality of liquid crystal elements has increased compared to the past. From this background, various liquid crystal aligning agents have been proposed in order to improve the performance of the liquid crystal aligning film and to make various characteristics of the liquid crystal element (for example, liquid crystal alignment, voltage retention, residual image characteristics, etc.) more excellent (for example, For example, refer to Patent Documents 1 to 3).

In Patent Document 1, together with polyimide, an epoxy compound having a nitrogen atom (eg, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 1,3 A liquid crystal aligning agent containing -bis(N,N'-diglycidylaminomethyl)cyclohexane etc.) is disclosed. According to the liquid crystal aligning agent of this patent document 1, the display defect resulting from a rubbing flaw can be suppressed and it is possible to obtain the liquid crystal aligning film which has the outstanding liquid-crystal orientation. Moreover, in patent document 2, the compound (for example, monoallyl diglycidyl isocyanuric acid, triglycidyl isocyanuric acid) containing an imide bond and two or more epoxy groups together with polyamic acid or polyimide etc.) in a liquid crystal aligning agent is disclosed. It is disclosed by patent document 3 that a liquid crystal aligning agent contains the polyfunctional epoxy compound which has two or more 3, 4- epoxycyclohexane rings with a polyamic acid or a polyimide. When forming a liquid crystal aligning film using the liquid crystal aligning agent containing a crosslinking agent, bridge|crosslinking advances by the heating (postbaking) at the time of film formation normally, and hardening of a film|membrane is accelerated|stimulated.

Japanese Laid-Open Patent Publication No. 10-333153 Japanese Laid-Open Patent Publication No. 2007-139949 Japanese Laid-Open Patent Publication No. 2016-170409

In order to sufficiently advance the curing of the film by the addition of the crosslinking agent and to increase the film hardness, it is preferable to heat the film at a high temperature (for example, at 200°C or higher). However, when heating at high temperature is required when forming a liquid crystal aligning film, problems, such as restrict|limiting the material of a board|substrate may arise, and application of a film base material as a board|substrate of a liquid crystal element may be restrict|limited. Moreover, in a color liquid crystal display element, the dye used as a colorant for color filters is comparatively weak to heat, and when it is necessary to heat at the time of film formation at high temperature, there is a concern that the use of the dye is restricted. On the other hand, when hardening of a film|membrane is not enough, film|membrane hardness is not enough, and we are anxious about the liquid-crystal orientation and voltage retention falling.

Moreover, when the solubility of a polymer component falls by addition of a crosslinking agent or a crosslinking agent precipitates in an aligning agent, the applicability|paintability with respect to the board|substrate of a liquid crystal aligning agent becomes inferior. Moreover, we are concerned that the liquid-crystal orientation and voltage retention of the liquid crystal element obtained fall, or a product yield falls.

The present disclosure has been made in view of the above circumstances, and one object thereof is a liquid crystal element having good applicability to a substrate, high film hardness even when film formation is performed at a low temperature, and excellent liquid crystal orientation and voltage retention. It is to provide the liquid crystal aligning agent which can obtain.

According to the present disclosure, the following means are provided.

[1] Liquid crystal alignment comprising a polymer component and a heterocyclic-containing compound having two or more in one molecule a partial structure in which n hydrogen atoms are removed from the structure represented by the following formula (1) (n is an integer greater than or equal to 1) My.

(In formula (1), X ¹ is any of groups represented by each of the following formulas (2-1) to (2-5). A ¹ is a divalent organic group and is bonded to another ring structure. A condensed ring may be formed together with other ring structures. A plurality of A ¹ and X ¹ in one molecule each independently have the above definition.)

(In Formulas (2-1) to (2-5), R ¹ to R ⁷ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms. Formulas (2-3) and Formulas (2-3) and "*" in (2-5) shows that it is a bond with the oxygen atom in Formula (1).)

[2] A liquid crystal aligning film formed using the liquid crystal aligning agent of [1] above.

[3] A liquid crystal element provided with the liquid crystal aligning film of the above [2].

[4] The step of applying the liquid crystal aligning agent of the above [1] to each substrate surface in a pair of substrates, and providing a liquid crystal alignment ability by irradiating the applied substrate surface with light to form a liquid crystal aligning film; A method of manufacturing a liquid crystal element, comprising the step of arranging a pair of substrates on which a liquid crystal aligning film is formed so that the coated surfaces of the substrates face each other through a liquid crystal layer to construct a liquid crystal cell.

[5] The process of applying the liquid crystal aligning agent of said [1] on each said conductive film of a pair of board|substrates which have a conductive film, A pair of board|substrates to which the said liquid crystal aligning agent was apply|coated via a liquid crystal layer A method of manufacturing a liquid crystal device, comprising: constructing a liquid crystal cell by arranging the substrate to face each other so as to face each other; and irradiating light to the liquid crystal cell in a state where a voltage is applied between the conductive films.

According to the liquid crystal aligning agent of this indication, even when heating at the time of film formation is performed at low temperature (for example, the temperature of 170 degrees C or less), the liquid crystal element excellent in the liquid-crystal orientation and voltage retention can be obtained. Moreover, the liquid crystal aligning agent of this indication is excellent in the applicability|paintability with respect to a board|substrate, Therefore, it can suppress the fall of a product yield.

(Form for implementing the invention)

≪Liquid crystal aligning agent≫

The liquid crystal aligning agent of this indication contains a polymer component and an additive component. In addition, as an additive component, a heterocyclic-containing compound having two or more partial structures in one molecule in which n (n is an integer greater than or equal to 1) hydrogen atoms removed from the structure represented by the formula (1) (hereinafter referred to as "compound [W ]"). Below, each component contained in the liquid crystal aligning agent of this indication, and the other component mix|blended arbitrarily as needed are demonstrated.

In addition, in this specification, a "hydrocarbon group" is a meaning including a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" means a straight-chain hydrocarbon group and a branched hydrocarbon group composed of only a chain structure without a cyclic structure in the main chain. However, saturated or unsaturated may be sufficient. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only the structure of an alicyclic hydrocarbon as a ring structure and not containing an aromatic ring structure. However, it is not necessary to be constituted only by the structure of an alicyclic hydrocarbon, and those having a chain structure in a part thereof are also included. An "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be constituted by only the aromatic ring structure, and a chain structure or a structure of an alicyclic hydrocarbon may be included in a part thereof.

<Polymer component>

As long as the polymer component contained in a liquid crystal aligning agent is bridge|crosslinked with a compound [W], the main frame|skeleton is not specifically limited. Specific examples of the polymer component include polyamic acid, polyamic acid ester, polyimide, polyamine, polyenamine, polyorganosiloxane, polyester, polyamide, polyamideimide, polystyrene, polybenzoxazole precursor, polybenzoxa A polymer having a sol, a cellulose derivative, polyacetal, polymaleimide, a styrene-maleimide-based copolymer, or poly(meth)acrylate as the main skeleton and having a functional group that reacts (crosslinking reaction) with compound [W] can be heard In addition, (meth)acrylate means an acrylate and a methacrylate. A polyenamine is a polymer which has a carbon-carbon double bond at the position adjacent to the amino group of polyamine, For example, polyenamino ketone, polyenamino ester, polyenaminonitrile, polyenaminosulfonyl, etc. are mentioned.

Polyamic acid, polyamic acid ester, polyimide, polyamine, polyamic acid, polyamic acid ester, polyamic acid, polyamic acid ester, from the point which can make sufficiently high the performance (for example, liquid-crystal orientation, electrical property, mechanical strength, weather resistance, etc.) of the liquid crystal element obtained among these as a polymer component; It is preferable that it is at least 1 sort(s) selected from the group which consists of polyenamine, polyamide, polystyrene, poly(meth)acrylate, polymaleimide, a styrene-maleimide type copolymer, and polyorganosiloxane. Since the above-mentioned improvement effect by compounding the compound [W] is higher, it is preferable to include a polymer having a structural unit derived from diamine, and specifically, polyamic acid, polyamic acid ester, polyimide, polyamine, It is more preferable to include at least 1 sort(s) chosen from the group which consists of polyenamine and polyamide.

It is preferable that a polymer component contains the polymer which has a primary amino group at the terminal. In this case, bridge|crosslinking by compound [W] is accelerated|stimulated more and it is preferable at the point which can make higher the voltage retention of the liquid crystal element obtained. The polymer having a primary amino group at the terminal is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyamine, polyenamine, and polyamide, and the crosslinking reaction with compound [W] The polymer component is at least one selected from the group consisting of polyamic acids, polyamic acid esters, and polyimides, at least a part of which can further enhance the effect of improving the liquid crystal alignment and voltage retention rate and that it is easy to synthesize. It is particularly preferred to be a species.

(polyamic acid)

Polyamic acid can be obtained by making tetracarboxylic dianhydride and a diamine compound react.

・Tetracarboxylic acid dianhydride

As tetracarboxylic dianhydride used for the synthesis|combination of polyamic acid, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. Specific examples of these include aliphatic tetracarboxylic dianhydride, such as 1,2,3,4-butanetetracarboxylic dianhydride;

As the alicyclic tetracarboxylic dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride; 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c ] furan-1,3-dione, 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] Furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-2anhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarbon acid dianhydride and the like;

As aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, ethylene glycol bisanhydrotrimate, 4,4'-(hexafluoro loisopropylidene) diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, and the like; In addition to those mentioned respectively, the tetracarboxylic dianhydride of Unexamined-Japanese-Patent No. 2010-97188 can be used. In addition, as tetracarboxylic dianhydride, 1 type can be used individually or in combination of 2 or more types.

・Diamine compound

As a diamine compound used for the synthesis|combination of polyamic acid, a well-known diamine compound can be used, For example, aliphatic diamine, alicyclic diamine, aromatic diamine, diaminoorganosiloxane, etc. are mentioned. The following formulas (7-1) to (7-3) have high reactivity with compound [W] when heated, and can further promote crosslinking and improve the solubility of polymers in solvents. A diamine compound (hereinafter, also referred to as "protecting group-containing diamine") having a partial structure represented by each of can be preferably used.

(In formula (7-1), A ²¹ is a single bond or a divalent organic group having 1 or more carbon atoms, Y ¹ is a protecting group, and R ²¹ to R ²³ are each independently a hydrogen atom or a monovalent group having 1 or more carbon atoms. and m is an integer of 0 to 6. In formula (7-2), Y ² is a protecting group. In formula (7-3), R ²⁴ and R ²⁵ are each independently a divalent hydrocarbon group; Y ³ is a protecting group. "*" indicates a bond.)

In the formulas (7-1) to (7-3), the protecting group of Y ¹ to Y ³ is preferably a group that is released by heat, for example, a carbamate protecting group, an amide protecting group, or an imide protecting group , a sulfonamide-based protecting group, and the like. As the protecting group, a carbamate protecting group is particularly preferable, and specific examples thereof include a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group, and a 1,1-dimethyl-2 group. -Cyanoethyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, 2-(trimethylsilyl)ethoxycarbonyl group, etc. are mentioned. Of these, a tert-butoxycarbonyl group is particularly preferable from the viewpoints of high thermal release properties and the ability to reduce the amount of the deprotected portion remaining in the film.

It is preferable that it is a C1-C10 monovalent hydrocarbon group, and, as for the monovalent organic group of R<^21> and R< ²² >, it is more preferable that it is a C1-C10 alkyl group or a cycloalkyl group.

It is preferable that the monovalent organic group of R< ²³ > is a C1-C10 monovalent|monohydric alkyl group or a protecting group. The protecting group is preferably a carbamate protecting group, and a tert-butoxycarbonyl group is particularly preferred.

It is preferable that it is a C1-C10 divalent chain hydrocarbon group, and, as for the divalent hydrocarbon group of R<^24> and R< ²⁵ >, it is more preferable that it is a C1-C10 alkanediyl group.

Examples of the divalent organic group for A ²¹ include a divalent hydrocarbon group and a group having -O-, -CO-, -COO-, and -NH- between the carbon-carbon bonds of the hydrocarbon group. It is preferable to couple|bond with the aromatic ring, and, as for A ²¹ , it is especially preferable to couple|bond with the benzene ring.

Specific examples of the protective group-containing diamine include compounds represented by the following formulas (d-7-1) to (d-7-14).

(Wherein, TMS represents a trimethylsilyl group.)

When using a protecting group containing diamine, it is preferable to set it as 2 mol% or more with respect to the total amount of the diamine compound used for the synthesis|combination of a polymer, and, as for the usage ratio, it is more preferable to set it as 3-80 mol%, and 5 to It is more preferable to set it as 70 mol%. In addition, protective group containing diamine may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the diamine used for the synthesis of polyamic acid include metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc.; Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine) and the like;

As the aromatic diamine, for example, dodecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecanoxy-2, 4-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3, 5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid Cholestanyl, 3,5-diaminobenzoic acid Cholesteryl, 3,5-diaminobenzoic acid Lanostanil, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 2,4-dia Mino-N,N-diallylaniline, 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl) Phenyl)-4-butylcyclohexane, 3,5-diaminobenzoic acid = 5ξ-cholestan-3-yl, the following formula (E-1)

(In formula (E-1), X ^I and X ^II are each independently a single bond, -O-, *-COO-, or *-OCO- (where "*" represents a bond with X ^I ), R ^I is an alkanediyl group having 1 to 3 carbon atoms, R ^II is a single bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, and b is an integer of 0 to 2; c is an integer from 1 to 20, and d is 0 or 1. However, a and b do not become 0 at the same time.)

A compound represented by , a diamine having a cinnamic acid structure in a side chain, and a side chain diamine such as a compound represented by each of the following formulas (d-8-1) to (d-8-7):

p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4-aminophenyl-4-aminobenzoate, 4,4'-diaminoazobenzene, 3,5-diaminobenzoic acid, 4,4'- Diaminobiphenyl-3,3'-dicarboxylic acid, 1,5-bis(4-aminophenoxy)pentane, 1,2-bis(4-aminophenoxy)ethane, 1,6-bis(4-amino) Phenoxy)hexane, bis[2-(4-aminophenyl)ethyl]hexane diacid, N,N'-bis(4-aminophenyl)-1,4-benzenediamine, N,N'-bis(4- Aminophenyl)-N,N'-dimethyl-1,4-benzenediamine, bis(4-aminophenyl)amine, bis(4-aminophenyl)methylamine, 2,6-diaminopyridine, 1,4-bis (4-Aminophenyl)-piperazine, N,N'-bis(4-aminophenyl)-benzidine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(tri Fluoromethyl) -4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis (4-aminophenyl)hexafluoropropane, 4,4'-(phenylenediisopropylidene)bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-amino Phenoxy) biphenyl, 4,4'-[4,4'-propane-1,3-diylbis(piperizine-1,4-diyl)]dianiline, 4,4'-diaminobenzanilide, 4 ,4'-diaminostylbenzene, 4,4'-diaminodiphenylamine, 1,3-bis(4-aminophenethyl)urea, 1,3-bis(4-aminobenzyl)urea, 1,4 -bis(4-aminophenyl)-piperazine, N-(4-aminophenylethyl)-N-methylamine, a compound represented by each of the following formulas (d-8-8) - a formula (d-8-16) main chain diamines such as; As the diaminoorganosiloxane, for example, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane and the like; In addition to those mentioned respectively, the diamine of Unexamined-Japanese-Patent No. 2010-97188 can be used.

Synthesis of polyamic acid

A polyamic acid can be obtained by making the above tetracarboxylic dianhydride and a diamine compound react with a molecular weight modifier as needed. The ratio of using the tetracarboxylic dianhydride and the diamine compound used in the synthesis reaction of polyamic acid is preferably 0.2 to 2 equivalents of the acid anhydride groups of the tetracarboxylic dianhydride with respect to 1 equivalent of the amino group of the diamine compound. . Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate, etc. can be heard It is preferable that the usage-rate of a molecular weight modifier shall be 20 mass parts or less with respect to a total of 100 mass parts of the tetracarboxylic dianhydride and diamine compound to be used.

In addition, in order to obtain polyamic acid as a polymer having a primary amino group at the terminal, (1) in the reaction of tetracarboxylic dianhydride and diamine compound, the amount of diamine compound to be used is higher than that of tetracarboxylic dianhydride (for example, For example, 1.1-1.5 molar equivalent of the usage-amount of tetracarboxylic dianhydride) method, (2) the method of making the said monoamine compound react as a molecular weight modifier, etc. are mentioned.

The synthesis reaction of polyamic acid is preferably performed in an organic solvent. The reaction temperature at this time is preferably -20°C to 150°C, and the reaction time is preferably 0.1 to 24 hours.

Examples of the organic solvent used for the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphor. At least one selected from the group consisting of triamide, m-cresol, xylenol and halogenated phenol is used as a solvent, or at least one of these and another organic solvent (eg, butyl cellosolve, diethylene glycol) It is preferable to use a mixture with diethyl ether, etc.). It is preferable that the usage-amount (a) of an organic solvent sets it as the quantity from which the total amount (b) of tetracarboxylic dianhydride and diamine will be 0.1-50 mass % with respect to the total amount (a+b) of a reaction solution.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used for preparation of a liquid crystal aligning agent as it is, and after isolating the polyamic acid contained in a reaction solution, you may provide for preparation of a liquid crystal aligning agent.

(polyamic acid ester)

The polyamic acid ester is, for example, [I] a method of reacting the polyamic acid obtained by the above synthesis reaction with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine compound, [III] tetracarboxylic acid It can be obtained by the method of making a diester dihalide and a diamine compound react, etc. The polyamic acid ester made to contain in a liquid crystal aligning agent may have only a amic-acid ester structure, and the partial esterified thing in which a amic-acid structure and a amic-ester structure coexist may be sufficient as it. In addition, the reaction solution formed by dissolving polyamic acid ester may be used for preparation of a liquid crystal aligning agent as it is, and after isolating the polyamic acid ester contained in a reaction solution, you may provide for preparation of a liquid crystal aligning agent.

(Polyimide)

The polyimide can be obtained, for example, by imidizing the polyamic acid synthesized as described above by dehydration and ring closure. The polyimide may be a complete imidized product in which all of the amic acid structures of the polyamic acid, which is its precursor, have been cyclized by dehydration, or may be a partial imidized product in which only a part of the amic acid structure is dehydrated and cyclized to coexist with a amic acid structure and an imide ring structure. good night. It is preferable that the imidation ratio is 20 to 99 %, and, as for the polyimide used for reaction, it is more preferable that it is 30 to 90 %. This imidation ratio represents the ratio of the number of imide ring structures with respect to the sum total of the number of the male acid structures of a polyimide, and the number of imide ring structures in percentage. Here, an isoimide ring may be sufficient as a part of an imide ring.

The dehydration ring closure of polyamic acid is preferably performed by dissolving polyamic acid in an organic solvent, adding a dehydrating agent and dehydration ring closure catalyst to this solution, and heating as necessary. In this method, as a dehydrating agent, acid anhydrides, such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride, can be used, for example. The amount of the dehydrating agent to be used is preferably 0.01 to 20 moles with respect to 1 mole of the amic acid structure of the polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. The amount of the dehydration ring closure catalyst to be used is preferably 0.01 to 10 moles with respect to 1 mole of the dehydrating agent to be used. Examples of the organic solvent used for the dehydration ring closure reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180°C. The reaction time is preferably 1.0 to 120 hours. The reaction solution containing the polyimide obtained in this way may be used for preparation of a liquid crystal aligning agent as it is, and after isolating a polyimide, you may provide for preparation of a liquid crystal aligning agent. A polyimide can also be obtained by imidation of polyamic acid ester.

When providing liquid-crystal orientation ability using the photo-alignment method with respect to the organic film formed using the liquid crystal aligning agent, it is preferable to make at least one part of a polymer component into the polymer which has a photo-alignment group. A photoalignable group means the functional group which can provide anisotropy to a film|membrane by photoreactions, such as a photoisomerization reaction by light irradiation, a photodimerization reaction, an optical Fries potential reaction, or a photolysis reaction.

Specific examples of the photo-aligning group include, for example, an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, a cinnamic acid structure-containing group containing cinnamic acid or a derivative thereof (cinnamic acid structure) as a basic skeleton, chalcone or its A chalcone-containing group containing a derivative as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, cyclobutane or a derivative thereof as a basic skeleton cyclobutane-containing structure, a stilbene-containing group having stilbene or a derivative thereof as a basic skeleton, and a phenylbenzoate-containing group containing phenylbenzoate or a derivative thereof as a basic skeleton thereof. Among these, the photo-aligning group is preferably at least one selected from the group consisting of an azobenzene-containing group, a cinnamic acid structure-containing group, a chalcone-containing group, a stilbene-containing group, a cyclobutane-containing structure, and a phenylbenzoate-containing group, It is preferable that it is a cinnamic-acid structure containing group or a cyclobutane containing structure from the point with high sensitivity with respect to and the point which it is easy to introduce|transduce into a polymer.

A polymer having a photo-aligning group is, for example, (1) a method obtained by polymerization using a monomer having a photo-aligning group, (2) synthesizing a polymer having an epoxy group in a side chain, and the epoxy group-containing polymer and a photo-aligning group It can be obtained by the method of making carbonic acid react, etc. Although the content rate of the photo-alignment group in a polymer is suitably set according to the kind of photo-alignment group so that desired liquid-crystal orientation ability with respect to a coating film may be provided, For example, in the case of a cinnamic acid structure containing group, the polymer which has a photo-alignment group. It is preferable to make the content rate of a photo-alignment group into 5 mol% or more with respect to all structural units of , and it is more preferable to set it as 10-60 mol%. When a photo-aligning group is a cyclobutane containing structure, it is preferable to make the content rate of a photo-aligning group into 50 mol% or more with respect to all the structural units of the polymer which has a photo-alignment group, and it is more preferable to set it as 80 mol% or more. In addition, the polymer which has a photo-alignment group may be used individually by 1 type, and may be used in combination of 2 or more type.

Although single 1 type may be sufficient as the polymer component made to contain in a liquid crystal aligning agent, it is good also as 2 or more types of blend systems. For example, a 1st polymer and a 2nd polymer with higher polarity than a 1st polymer are made to contain in a liquid crystal aligning agent. In this case, it is preferable at the point which can cause phase separation by the 2nd polymer with high polarity being unevenly distributed in the lower layer, and the 1st polymer being unevenly distributed in the upper layer. As a preferable aspect of the polymer component of a liquid crystal aligning agent, the following (I) - (III) are mentioned.

(I) An aspect in which the first polymer and the second polymer are polymers selected from the group consisting of polyamic acids, polyamic acid esters and polyimides.

(II) An aspect in which one of the first polymer and the second polymer is one type of polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and the other is polyorganosiloxane.

(III) one of the first polymer and the second polymer is at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and the other one is derived from a monomer having a polymerizable unsaturated bond The aspect which is a polymer (henceforth "polymer (Q)") which has a structural unit.

(Polyorganosiloxane)

The polyorganosiloxane contained in a liquid crystal aligning agent can be obtained by hydrolyzing and condensing a hydrolysable silane compound, for example. As a hydrolysable silane compound, For example, Alkoxysilane compounds, such as tetramethoxysilane, methyltriethoxysilane, phenyl trimethoxysilane, phenyltriethoxysilane, dimethyldiethoxysilane; Alkoxysilane compounds containing nitrogen and sulfur, such as 3-mercaptopropyltriethoxysilane, mercaptomethyltriethoxysilane, 3-aminopropyltrimethoxysilane, and N-(3-cyclohexylamino)propyltrimethoxysilane ; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, etc. of epoxy group-containing silane compounds; 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, vinyltriethoxysilane, p-styryltri unsaturated bond-containing alkoxysilane compounds such as methoxysilane; Trimethoxysilylpropyl succinic anhydride etc. are mentioned. The hydrolyzable silane compound can be used individually by 1 type among these or in combination of 2 or more type. In addition, "(meth)acryloxy" is a meaning including "acryloxy" and "methacryloxy."

The hydrolysis/condensation reaction is performed by reacting one or two or more of the above silane compounds with water, preferably in the presence of a suitable catalyst and organic solvent. At the time of reaction, Preferably the usage-rate of water is 1-30 mol with respect to 1 mol of silane compounds (total amount). As a catalyst to be used, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, etc. are mentioned, for example. The amount of the catalyst to be used varies depending on the type of catalyst, reaction conditions such as temperature, etc., and should be appropriately set. For example, it is preferably 0.01 to 3 moles relative to the total amount of the silane compound. Examples of the organic solvent to be used include hydrocarbons, ketones, esters, ethers, and alcohols, and among these, it is preferable to use a water-insoluble or poorly water-soluble organic solvent. To [ the usage ratio of an organic solvent / 100 mass parts in total of the silane compound used for reaction ], Preferably it is 10-10,000 mass parts.

The hydrolysis/condensation reaction described above is preferably performed by heating, for example, in an oil bath or the like. In that case, the heating temperature is preferably 130°C or less, and the heating time is preferably 0.5 to 12 hours. After completion of the reaction, the target polyorganosiloxane is obtained by removing the solvent after drying the organic solvent layer separated from the reaction solution with a desiccant if necessary. In addition, the synthesis method of polyorganosiloxane is not limited to the said hydrolysis/condensation reaction, For example, you may carry out by the method of making a hydrolysable silane compound react in presence of oxalic acid and alcohol, etc.

When the polyorganosiloxane is a polymer having a photo-aligning group, the synthesis method thereof is not particularly limited, but a polyorganosiloxane having an epoxy group in a side chain (hereinafter, “ A method of synthesizing an epoxy group-containing polyorganosiloxane” and then reacting the epoxy group-containing polyorganosiloxane with a carboxylic acid having a photo-aligning group, and the like. This method is convenient, and moreover, it is preferable at the point which can make high the introduction rate of a photosensitive group and a liquid crystalline structure. In addition, you may synthesize|combine the polyorganosiloxane which has a photo-alignment group in a side chain by reaction containing the hydrolysable silane compound which has a photo-alignment group in a monomer. With respect to polyorganosiloxane, it is preferable to exist in the range of 100-50,000, and, as for the weight average molecular weight (Mw) of polystyrene conversion measured by GPC, it is more preferable to exist in the range of 200-10,000.

(Polymer (Q))

As a monomer which has a polymerizable unsaturated bond used for the synthesis|combination of a polymer (Q), the compound which has a (meth)acryloyl group, a vinyl group, a styryl group, a maleimide group, etc. is mentioned, for example. Specific examples of such compounds include, for example, unsaturated carboxylic acids such as (meth)acrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, and vinylbenzoic acid: alkyl (meth)acrylate, cycloalkyl (meth)acrylic acid, benzyl (meth)acrylate , (meth)acrylic acid-2-ethylhexyl, (meth)acrylic acid trimethoxysilylpropyl, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid glycidyl, (meth)acrylic acid 3,4-epoxycyclohexyl Unsaturated carbonic acid esters, such as methyl, (meth)acrylic acid 3,4-epoxybutyl, and acrylic acid 4-hydroxybutylglycidyl ether: Unsaturated polyhydric carboxylic acid anhydrides, such as maleic anhydride: (meth)acrylic-type compounds, such as; styrene; aromatic vinyl compounds such as methylstyrene and divinylbenzene; conjugated diene compounds such as 1,3-butadiene and 2-methyl-1,3-butadiene; maleimide group-containing compounds such as N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide; and the like. Moreover, when making a polymer (Q) into a polymer which has a photo-alignment group, the compound which has a photo-alignment group can also be used as a monomer which has a polymerizable unsaturated bond. In addition, the monomer which has a polymerizable unsaturated bond can be used individually by 1 type or in combination of 2 or more type.

The polymer (Q) can be obtained, for example, by polymerizing a monomer having a polymerizable unsaturated bond in the presence of a polymerization initiator. As the polymerization initiator to be used, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy Azo compounds such as -2,4-dimethylvaleronitrile) are preferred. It is preferable that the usage ratio of a polymerization initiator shall be 0.01-30 mass parts with respect to 100 mass parts of all monomers used for reaction. The polymerization reaction is preferably carried out in an organic solvent. Examples of the organic solvent used for the reaction include alcohols, ethers, ketones, amides, esters and hydrocarbon compounds, and diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate are preferable. The reaction temperature is preferably 30°C to 120°C, and the reaction time is preferably 1 to 36 hours. The amount of the organic solvent used (a) is preferably such that the total amount (b) of the monomers used for the reaction is 0.1 to 60 mass% with respect to the total amount (a+b) of the reaction solution. It is preferable that it is 250-500,000, and, as for the weight average molecular weight (Mw) of polystyrene conversion measured by GPC about a polymer (Q), it is more preferable that it is 500-100,000.

In the aspect of said (II) and (III) WHEREIN: The content rate of the total of polyamic acid, polyamic acid ester, and polyimide sufficiently raises the film hardness of the liquid crystal aligning film obtained, and the liquid-crystal orientation and voltage retention of a liquid crystal element are sufficiently high. It is preferable to set it as 20 mass % or more with respect to the total amount of the polymer component contained in a liquid crystal aligning agent from doing it, It is more preferable to set it as 30 % mass or more, It is still more preferable to set it as 50-90 mass %. When liquid crystal alignment ability is provided by a photo-alignment method to an organic film formed using a liquid crystal aligning agent, polyorganosiloxane, poly (meth) acrylate, or a styrene-maleimide-based copolymer is a polymer having a photo-aligning group It is preferable at the point from which the orientation film which has a more favorable liquid-crystal orientation is obtained by setting it as.

<Compound [W]>

Next, the compound [W] is demonstrated. Compound [W] is an intracyclic enol ester, an extracyclic enol ester, an intracyclic acylamide ester, an extracyclic acylamide ester or an oxime ester, and as a crosslinkable group, from the structure represented by the formula (1) A plurality of groups having a partial structure (hereinafter also referred to as "partial structure A") in which n arbitrary hydrogen atoms have been removed (n is preferably 1 or 2) are included in one molecule.

In said Formula (1), as a divalent organic group of A< ¹ >, a C2-C20 hydrocarbon group, the group etc. which have -O- between the carbon-carbon bond of the said hydrocarbon group are mentioned. A ¹ is preferably a hydrocarbon group having 2 to 20 carbon atoms, more preferably a hydrocarbon group having 2 to 15 carbon atoms, still more preferably a hydrocarbon group having 2 to 10 carbon atoms.

As the monovalent organic group of R ¹ to R ⁷ in the formulas (2-1) to (2-5), a monovalent hydrocarbon group having 1 to 10 carbon atoms and -O between the carbon-carbon bonds of the hydrocarbon group and groups having -. The monovalent organic group of R ¹ to R ⁷ is preferably a monovalent hydrocarbon group, more preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 10 carbon atoms or 6 to 12 carbon atoms. of a monovalent aromatic hydrocarbon group, particularly preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.

The compound [W] is preferably a compound in which a plurality of partial structures A are bonded directly or via a linking group. The linking group is preferably a hydrocarbon group having 1 to 30 carbon atoms, or a group having -O-, -S-, -NH-, or -CO- between the carbon-carbon bonds of the hydrocarbon group. n is preferably 1 or 2. It is preferable that X< ¹ > is group represented by each of the said Formula (2-3) - Formula (2-5) from a viewpoint of the high degree of freedom in setting a compound, and reactivity with a polymer component.

As a preferable specific example of partial structure A, the partial structure represented by each of following formula (3-1) - Formula (3-9) is mentioned. In addition, the following formulas (3-1) and (3-2) correspond to the case where X ¹ in the above formula (1) is the above formula (2-1), and the following formula (3-3) is Corresponds to the case where X ¹ in formula (1) is the formula (2-2), and the following formulas (3-4), (3-5) and (3-6) are represented in the formula (1). Corresponds to the case where X ¹ is the above formula (2-3). In addition, the following formulas (3-7) and (3-8) correspond to the case where X ¹ in the above formula (1) is the above formula (2-4), and the following formula (3-9) is It corresponds to the case of Formula (2-5).

(In Formulas (3-1) to (3-9), R ⁵¹ to R ⁷¹ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 24 carbon atoms, with the proviso that R ⁵¹ to R any one of ⁵⁴ , any one of R ⁵⁵ to R ⁵⁷ , any one of R ⁶⁰ to R ⁶² , any one of R ⁶³ and R ⁶⁴ , any one of R ⁶⁶ to R ⁶⁸ , and R ⁶⁹ and Any one of R ⁷⁰ is a bond. A plurality of R ⁵¹ to R ⁷¹ in one molecule each independently have the above definition. "*" indicates a bond.)

In the formulas (3-1) to (3-9), the monovalent organic group of R ⁵¹ to R ⁷¹ is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent chain hydrocarbon group having 1 to 10 carbon atoms. It is more preferably a group or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, still more preferably an alkyl group or phenyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group or phenyl group having 1 to 5 carbon atoms.

Specific examples of the compound [W] include compounds represented by each of the following formulas (b-1) to (b-11).

(Wherein, "Ph" is a phenyl group.)

The content rate of compound [W] is 0.001 mass part or more with respect to 100 mass parts of total amounts of the polymer component contained in a liquid crystal aligning agent from a viewpoint of fully obtaining the improvement effect of the liquid crystal orientation of the liquid crystal element obtained, and voltage retention Preferably, it is more preferable to set it as 0.003 mass part or more, and it is still more preferable to set it as 0.005 mass part or more. In addition, the content rate of compound [W] is from a viewpoint of suppressing the fall of the electrical property by the compound [W] which remain|survives in the film|membrane after post-baking with respect to 100 mass parts of total amounts of the polymer component contained in a liquid crystal aligning agent, It is preferable to set it as 10 mass parts or less, It is more preferable to set it as 5 mass parts or less, It is still more preferable to set it as 1 mass part or less. In addition, as a compound [W], you may use individually by 1 type, and may use it in combination of 2 or more type.

<Other additive ingredients>

The liquid crystal aligning agent of this indication may contain other additive components other than a compound [W] as needed. Other additive components are not specifically limited, unless the effect of this indication is impaired. Specific examples of other additive components include a compound different from compound [W] and having a crosslinkable group (hereinafter also referred to as a "crosslinkable group-containing compound"), a functional silane compound, an antioxidant, a metal chelate compound, a curing accelerator, an interface an activator, a filler, a dispersing agent, a photosensitizer, a solvent, etc. are mentioned. The blending ratio of other additive components can be appropriately selected according to each compound within a range that does not impair the effects of the present disclosure.

(Compound containing a crosslinkable group)

A crosslinkable group containing compound may be used in order to improve the adhesiveness with the board|substrate of a liquid crystal aligning film, and the reliability of a liquid crystal element further. Examples of the crosslinkable group-containing compound include at least one crosslinkable group selected from the group consisting of a cyclocarbonate group, an epoxy group, an isocyanate group, a block isocyanate group, an oxetanyl group, a trialkoxysilyl group, and a polymerizable unsaturated bond group. The compound etc. which have are mentioned. Examples of the polymerizable unsaturated bond group include a (meth)acryloyl group, an ethylenic carbon-carbon double bond, a vinylphenyl group, a vinyloxy group (CH ₂ =CH-O-), a vinylidene group, and a maleimide group, A cyclocarbonate group, an epoxy group, or (meth)acryl group is preferable at the point with high reactivity by light or heat.

Specific examples of the crosslinkable group-containing compound include 1,6-hexanediol diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl- Aminomethylcyclohexane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri( The compound etc. which are represented by each of meth)acrylate and following formula (11-1) - Formula (11-10) are mentioned. In addition, a crosslinkable group containing compound can be used individually by 1 type or in combination of 2 or more type.

When the crosslinkable group-containing compound is blended with the liquid crystal aligning agent, the blending ratio is the effect of compound [W], that is, even when the post-baking temperature is set to a low temperature (for example, 170 ° C. or less), the crosslinking reaction is It is preferable to set it as 150 mass parts or less with respect to 100 mass parts of compound [W] contained in a liquid crystal aligning agent from a viewpoint of acquiring the effect of making it fully advance and making the liquid crystal element with high enough liquid-crystal orientation and voltage retention, and it is 120 mass It is more preferable to set it as a part or less, and it is still more preferable to set it as 100 mass parts or less. When using compound [W] and a crosslinkable group containing compound together, as for the compounding ratio of a crosslinkable group containing compound, the total amount of compound [W] and a crosslinkable group containing compound is a total of 100 mass parts of the polymer contained in a liquid crystal aligning agent. With respect to it, it is preferable to set it as 10 mass parts or less, It is more preferable to set it as 0.001-5 mass parts, It is further more preferable to set it as 0.001-1 mass part.

<Solvent component>

As for the liquid crystal aligning agent of this indication, a polymer component, compound [W], and the component mix|blended arbitrarily as needed, Preferably, it is prepared as a polymer composition of the solution form melt|dissolved in the organic solvent. Examples of the organic solvent include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons. The number of solvent components may be sufficient as these 1 type, and 2 or more types of mixed solvent may be sufficient as them.

As a solvent component of the liquid crystal aligning agent of this indication, the solvent with high polymer solubility and leveling property (henceforth "1st solvent"), a solvent with good wetness and spreading property (hereinafter also referred to as "second solvent") and , and mixed solvents thereof.

Specific examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, and N,N-dimethylacetamide as the first solvent. , 4-hydroxy-4-methyl-2-pentanone, diisobutyl ketone, ethylene carbonate, propylene carbonate, N-ethyl-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-(t-Butyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-butoxy-N,N-dimethylpropane amide, 3-methoxy-N,N-dimethylpropanamide, and the like;

As the second solvent, for example, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diacetone alcohol, diethylene glycol dimethyl ether, diethylene Glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol, cyclopentanone, butyl lactate, butyl acetate, methyl methoxypropionate and ethyl ethoxypropionate, isoamyl propionate, isoamyl isobutylate, propylene glycol diacetate, dipropylene glycol monomethyl ether, propylene glycol monobutyl ether, diisopentyl ether, and the like. In addition, a solvent may be used individually by these 1 type, and may mix and use 2 or more types.

Although the solid content concentration (ratio which the total mass of components other than the solvent of a liquid crystal aligning agent occupies to the total mass of a liquid crystal aligning agent) in a liquid crystal aligning agent considers a viscosity, volatility, etc., and is suitably selected, Preferably it is 1-10 It is the range of mass %. When solid content concentration is less than 1 mass %, the film thickness of a coating film decreases and it becomes difficult to obtain a favorable liquid crystal aligning film. On the other hand, when solid content concentration exceeds 10 mass %, the film thickness of a coating film becomes excessive and it is hard to obtain a favorable liquid crystal aligning film, and the viscosity of a liquid crystal aligning agent increases, and there exists a tendency for applicability|paintability to fall.

«Liquid crystal alignment film and liquid crystal element»

The liquid crystal aligning film of this indication is formed with the liquid crystal aligning agent prepared as mentioned above. Moreover, the liquid crystal element of this indication is equipped with the liquid crystal aligning film formed using the liquid crystal aligning agent demonstrated above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited, and for example, TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS (In-Plane Switching) type , FFS (Fringe Field Switching) type, OCB (Optically Compensated Bend) type, PSA (Polymer Sustained Alignment) type, etc. can be applied to various modes. The liquid crystal element can be manufactured, for example, by a method including the following steps 1 to 3. In step 1, the substrate used differs depending on the desired operation mode. Steps 2 and 3 are common to each operation mode.

<Step 1: Formation of a coating film>

First, a liquid crystal aligning agent is apply|coated on a board|substrate, Preferably a coating film is formed on a board|substrate by heating an application surface. As a board|substrate, For example, glass, such as float glass and soda glass; A transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate or poly(alicyclic olefin) can be used. As the transparent conductive film formed on one surface of the substrate, an NESA film (registered trademark of PPG Corporation in the United States) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), etc. are used. can When manufacturing a TN-type, STN-type, or VA-type liquid crystal element, two substrates on which the patterned transparent conductive film is formed are used. On the other hand, when manufacturing an IPS-type or FFS-type liquid crystal element, the board|substrate on which the electrode patterned in the comb-tooth shape is formed, and the counter board|substrate on which the electrode is not formed are used. On the electrode formation surface, application|coating of the liquid crystal aligning agent to a board|substrate becomes like this. Preferably the offset printing method, the flexographic printing method, the spin coating method, the roll coater method, or the inkjet printing method perform.

After apply|coating a liquid crystal aligning agent, for purposes, such as liquid flow prevention of the apply|coated liquid crystal aligning agent, Preferably, preliminary heating (prebaking) is performed. Pre-baking temperature becomes like this. Preferably it is 30-200 degreeC, and pre-baking time becomes like this. Preferably it is 0.25 to 10 minutes. Then, the solvent is completely removed, and a baking (post-baking) process is implemented for the purpose of thermal imidation of the amic-acid structure in a polymer component as needed. The firing temperature (post-baking temperature) at this time is preferably 80 to 250°C, more preferably 80 to 200°C. Moreover, the liquid crystal aligning agent using compound [W] as a crosslinking agent is preferable at the point which can obtain the liquid crystal element which shows favorable liquid-crystal orientation and voltage retention, even when it post-baking at the comparatively low temperature of 170 degrees C or less. Post-baking time becomes like this. Preferably it is 5 to 200 minutes. Thus, the film thickness of the film|membrane formed becomes like this. Preferably it is 0.001-1 micrometer.

<Step 2: Orientation treatment>

When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal element, the process (orientation process) which provides liquid-crystal orientation ability to the coating film formed in the said process 1 is performed. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. As the alignment treatment, a rubbing treatment in which the coating film formed on the substrate is rubbed in a certain direction with a roll wound with a cloth made of, for example, nylon, rayon, cotton, or the like fiber, or the coating film formed on the substrate is irradiated with light to align the liquid crystal on the coating film A photo-alignment treatment or the like that imparts the ability can be used. On the other hand, in the case of manufacturing a vertical alignment (VA) type liquid crystal element, the coating film formed in step 1 can be used as it is as a liquid crystal aligning film. good night. The liquid crystal aligning film suitable for the liquid crystal element of a vertical alignment type can be used suitably also for a PSA type liquid crystal element.

Light irradiation for photo-alignment is a method of irradiating the coating film after the post-baking process, a method of irradiating the coating film after the pre-baking process and before the post-baking process, heating the coating film in at least any of the pre-baking process and the post-baking process It can carry out by the method of irradiating with respect to a coating film, etc. in the middle. As radiation irradiated to the coating film, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used. Preferably, it is an ultraviolet-ray containing light of a wavelength of 200-400 nm. When the radiation is polarized light, linearly polarized light or partially polarized light may be sufficient. When the radiation to be used is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination thereof. In the case of non-polarized radiation, the irradiation direction is set to an oblique direction.

As a light source to be used, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser etc. are mentioned, for example. The radiation dose to the substrate surface is preferably 400 to 50,000 J/m 2 , more preferably 1,000 to 20,000 J/m 2 . After light irradiation for imparting orientation ability, the substrate surface is treated with, for example, water or an organic solvent (eg, methanol, isopropyl alcohol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, etc.) Alternatively, a process for washing using a mixture thereof or a process for heating the substrate may be performed.

<Step 3: Construction of a liquid crystal cell>

A liquid crystal cell is manufactured by preparing two board|substrates with a liquid crystal aligning film as mentioned above, and arrange|positioning a liquid crystal between the board|substrates of 2 sheets opposingly arranged. In order to manufacture a liquid crystal cell, for example, two board|substrates are opposingly arrange|positioned through a gap|interval so that a liquid crystal aligning film may oppose, the periphery of two board|substrates is joined using a sealing compound, The cell enclosed by the board|substrate surface and a sealing compound. A method of sealing an injection hole by injecting and filling a liquid crystal into a gap, a method using an ODF method, etc. are mentioned. As a sealing agent, the epoxy resin etc. containing the aluminum oxide sphere as a hardening|curing agent and a spacer can be used, for example. As a liquid crystal, a nematic liquid crystal and a smectic liquid crystal are mentioned, Among these, a nematic liquid crystal is preferable. In the PSA mode, after the construction of the liquid crystal cell, a process of irradiating the liquid crystal cell with light in a state where a voltage is applied between the conductive films included in the pair of substrates is performed.

When manufacturing a PSA type liquid crystal element, it carries out similarly to the above except that a photopolymerizable compound is inject|poured or dripped with a liquid crystal between a pair of board|substrates which have an electrically conductive film, and a liquid crystal cell is constructed. Thereafter, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The voltage to be applied here can be, for example, 5 to 50 V of direct current or alternating current. As the light to be irradiated, for example, although ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. As a light source of irradiation light, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser etc. can be used, for example. The amount of light irradiated is preferably 1,000 to 200,000 J/m 2 , more preferably 1,000 to 100,000 J/m 2 .

Then, a polarizing plate is bonded to the outer surface of a liquid crystal cell as needed, and it is set as a liquid crystal element. As a polarizing plate, the polarizing plate which sandwiched the polarizing film called "H film" which absorbed iodine while extending|stretching orienting polyvinyl alcohol, with a cellulose acetate protective film, or the polarizing plate which consists of H film itself is mentioned.

The liquid crystal element of the present disclosure can be effectively applied to various uses, for example, a watch, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, a smart phone, It is applicable to various display devices, such as various monitors, a liquid crystal TV, and an information display, a dimming film, retardation film, etc. Moreover, the liquid crystal element of this indication is used suitably also about the liquid crystal element which used dye as the coloring agent of a color filter layer. Here, as the dye, a known dye that can be used in a liquid crystal element can be used.

Example

Hereinafter, although an Example demonstrates specifically, the content of this indication is not limited to the following Example.

In the following examples, the weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the polymer, and the solution viscosity of the polymer were measured by the following methods.

<Weight average molecular weight, number average molecular weight and molecular weight distribution>

By gel permeation chromatography (GPC), Mw and Mn were measured under the following conditions. In addition, molecular weight distribution (Mw/Mn) was computed from the obtained Mw and Mn.

GPC column: TSKgelGRCXLII manufactured by Tosoh Corporation

Mobile phase: N,N-dimethylformamide solution containing lithium bromide and phosphoric acid

Column temperature: 40°C

Flow rate: 1.0 mL/min

Pressure: 68kgf/cm2

<Solution Viscosity of Polymer>

The solution viscosity (mPa·s) of the polymer solution was measured at 25°C using an E-type rotational viscometer.

The abbreviation of the compound used in the following example is shown below. In addition, in the following, for convenience, "the compound represented by Formula (X)" may be simply represented as "Compound (X)".

(Tetracarboxylic acid dianhydride)

(diamine compound)

(Compound [W])

(Other crosslinking agents)

<Synthesis of compound [W]>

[Synthesis Examples 1-1 to 1-8]

Compounds (BL-1) to (BL-8) were respectively synthesized according to the methods described in the following literature.

• Compound (BL-1): Endo-enol ester; M. Ueda, M. Yabuuchi, Y. Imai, J. Polym. Sci., Polym. Chem. Ed,, 15, 323 (1977)

• Compound (BL-2): Endo-acyl imidate; M. Ueda, Y. Imai, J. Polym. Sci., Polym. Chem. Ed,, 17, 1163 (1979)

• Compound (BL-3): Endo-acyl imidate; M. Ueda, K. Kino, Y. Imai, J. Polym. Sci., Polym. Chem. Ed., 13, 659 (1975)

·Compound (BL-4): Endo-enol ester; M. Ueda, T. Takahashi, Y. Imai, J. Polym. Sci., Polym. Chem. Ed,, 15, 2641 (1977)

Compound (BL-5): Exo-enol ester; M. Ueda, T. Takahashi, Y. Imai, J. Polym. Sci., Polym. Chem. Ed,, 14 591 (1976)

• Compound (BL-6): Endo-acyl imidate; M. Ueda, K. Kino, K. Yamaki, Y. Imai, J. Polym. Sci., Polym. Chem. Ed,, 16, 155 (1978)

·Compound (BL-7): Oxime ester; M. Ueda, H. Hazome, Y. Imai, J. Polym. Sci., Polym. Chem. Ed., 14, 1127 (1976)

Compound (BL-8): Exo-acyl omidate; M. Ueda, S. Kanno, Y. Imai, J. Polym. Sci., Polvm.

<Synthesis of polymer>

[Synthesis Example 2-1: Synthesis of polyamic acid]

In a 100 mL two-necked flask under nitrogen, 50 mol parts of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 50 mol parts of 1,2,3,4-cyclobutanetetracarboxylic dianhydride were N-methyl-2-p It melt|dissolves in rollidone (NMP), then, 10 mol part of compound (DA-1) and 90 mol part of compound (DA-2) are added, reaction is performed at 60 degreeC for 4 hours, and polymer (P-1) is 20 mass % containing solution was obtained. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution with a polyamic acid concentration of 10 mass % was 1020 mPa*s.

[Synthesis Examples 2-2 to 2-14]

The same operation as in Synthesis Example 2-1 was performed except that the type and amount of the monomer to be used was changed as shown in Table 1 below, and polyamic acid (referred to as polymers (P-2) to (P-14), respectively) A solution containing In addition, "-" in Table 1 means that the compound of the corresponding column was not used.

[Synthesis Example 2-15]

In a 100 mL two-necked flask under nitrogen, 100 mol parts of 2,3,5-tricarboxycyclopentylacetic acid dianhydride (compound (AH-2)) was dissolved in N-methyl-2-pyrrolidone (NMP), and continued Thus, (E)-4-(3-(2,4-diaminophenethoxy)-3-oxopropa-1-en-1-yl)phenyl4-(4,4,4-trifluorobu 100 mol parts of oxy)benzoate was added, it reacted at 60 degreeC for 24 hours, and the solution containing 30 mass % of polymers (P-15) was obtained. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution with a polyamic acid concentration of 10 mass % was 640 mPa*s.

[Synthesis Example 3-1: Synthesis of polyorganosiloxane]

A polymer (ES-1) was synthesized according to Scheme 1 below.

90.0 g of 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane, 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine were thrown into a 1000 ml 3-neck flask, and it mixed at room temperature. Next, 100 g of deionized water was dripped from the dropping funnel over 30 minutes, and then, the reaction was performed 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 mass aqueous ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure. Methyl isobutyl ketone was added in an appropriate amount, and the 50 mass % solution of the polyorganosiloxane (E-1) which has an epoxy group was obtained.

In a 500 ml three-necked flask, 26.69 g (0.3 mol equivalent) of side chain carboxylic acid (ca-1) shown below, 2.00 g of tetrabutylammonium bromide, 80 g of a solution containing polyorganosiloxane (E-1), and methyl isobutyl ketone 239 g was added, and it stirred at 110 degreeC for 4 hours. After cooling to room temperature, the liquid separation washing operation was repeated 10 times with distilled water. Then, the organic layer was collect|recovered, concentration and NMP dilution were repeated twice with the rotary evaporator, and the 15 mass % NMP solution of the polymer (ES-1) intermediate body was obtained. After adding 0.45 g (0.1 mol equivalent) of trimellitic anhydride to 50 g of this intermediate solution, it was prepared so that the solid content concentration was 10 mass % using NMP, and then stirred at room temperature for 4 hours to obtain a polymer (ES-1) An NMP solution was obtained.

[Synthesis Example 3-2]

In Synthesis Example 3-1, the polymer ( An NMP solution containing ES-2) was obtained.

[Synthesis Example 4-1: Synthesis of styrene-maleimide-based copolymer]

1. Synthesis of compound (MI-1)

Compound (MI-1) was synthesized according to Scheme 2 below.

(E)-3-(4-((4-(4,4,4-trifluorobutoxy)benzoyl)oxy)phenyl)acrylic acid 11.8g, thionyl chloride 20g, N 0.01 g of N-dimethylformamide was added, and it stirred at 80 degreeC for 1 hour. Then, excess thionyl chloride was removed with a diaphragm pump, 100 g of tetrahydrofuran was added, and it was set as the solution A. Newly, 5.67 g of 4-hydroxyphenyl maleimide, 200 g of tetrahydrofuran, and 12.1 g of triethylamine were added to a 500 mL three-neck flask containing a stirrer, and an ice bath was carried out. The solution A was dripped there, and it stirred at room temperature for 3 hours. The reaction liquid was reprecipitated with 800 mL of water, and 13.3 g of compound (MI-1) was obtained by vacuum-drying the obtained white solid.

2. Synthesis of polymers

In a 100 mL two-necked flask under nitrogen, 5.00 g (8.6 mmol) of the compound (MI-1) obtained above as a polymerization monomer, 0.64 g (4.3 mmol) of 4-vinylbenzoic acid, and 4-(2,5-dioxo-) 3-pyrrolin-1-yl) benzoic acid 2.82 g (13.0 mmol) and 4-(glycidyloxymethyl) styrene 3.29 g (17.2 mmol), 2,2'-azobis (2,4) as a radical polymerization initiator -Dimethylvaleronitrile) 0.31g (1.3mmol), 2,4-diphenyl-4-methyl-1-pentene 0.52g (2.2mmol) as a chain transfer agent, and 25ml of tetrahydrofuran as a solvent were added, and at 70°C Polymerization was carried out for 5 hours. After reprecipitation in n-hexane, the precipitate was filtered and vacuum dried at room temperature for 8 hours to obtain the target polymer (StMI-1). The weight average molecular weight Mw measured in polystyrene conversion by GPC was 30000, and molecular weight distribution Mw/Mn was 2.

[Synthesis Example 4-2]

In Synthesis Example 4-1, the polymer (StMI-2) was performed in the same manner as in Synthesis Example 4-1 except that the maleimide compound (MI-2) shown below was used instead of the compound (MI-1). ) was obtained. The weight average molecular weight Mw measured in polystyrene conversion by GPC was 35000, and molecular weight distribution Mw/Mn was 2.

<Manufacturing and evaluation of rubbing FFS type liquid crystal display element>

[Example 1]

1. Preparation of liquid crystal aligning agent (AL-1)

To a solution containing 100 parts by mass of the polymer (P-1) obtained in Synthesis Example 2-1, 200 parts by mass of the polymer (P-11) obtained in Synthesis Example 2-11, 5 parts by mass of the compound (BL-1); And NMP and butyl cellosolve (BC) were added as a solvent, and a solvent composition set it as the solution whose NMP/BC=50/50 (mass ratio) and solid content concentration are 4.0 mass %. A liquid crystal aligning agent (AL-1) was prepared by filtering this solution with the filter with a hole diameter of 1 micrometer.

2. Evaluation of applicability

After applying the liquid crystal aligning agent (AL-1) prepared above on a glass substrate using a spinner and prebaking for 1 minute on an 80 degreeC hotplate, it was 30 in 230 degreeC oven which replaced the inside of the furnace with nitrogen. By heating for minutes (post-baking), a coating film having an average film thickness of 0.1 µm was formed. This coating film was observed with the microscope with a magnification of 100 times and 10 times, and the presence or absence of film thickness nonuniformity and a pinhole was investigated. Evaluation was "good (A)" when neither film thickness unevenness nor pinholes were observed even when observed with a microscope at 100 magnifications. "Possible (B)" when both the film thickness unevenness and pinhole were not observed under the microscope, and "bad (C)" when at least any of the film thickness unevenness and pinhole was clearly observed under a 10-fold microscope. . In this Example, neither a film thickness nonuniformity nor a pinhole was observed even with the microscope of 100 times, but applicability|paintability was evaluation of "good|favorableness (A)".

3. Evaluation of Membrane Hardness

On the glass substrate, the liquid crystal aligning agent (AL-1) prepared above was apply|coated using the spinner, and prebaking was performed for 1 minute on an 80 degreeC hotplate. Then, it heated at 150 degreeC for 1 hour in the oven which replaced the inside of the furnace with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. About the obtained coating film, based on JIS-K5400, pencil hardness (surface hardness) was evaluated. As a result of evaluating the case where the pencil hardness was 4H or more as "A", the case where it was 2H or 3H as "B", the case where it was H as "C", and the case where it was less than H as "D", the pencil hardness of this liquid crystal aligning film was It was an evaluation of "A".

4. Manufacturing of rubbing horizontal liquid crystal display device (1)

On the transparent electrode surface of the transparent electrode glass substrate which consists of an ITO film, the liquid crystal aligning agent (AL-1) prepared above was apply|coated using the spinner, and prebaking was performed for 1 minute on an 80 degreeC hotplate. Then, it heated at 230 degreeC for 1 hour in the oven which substituted the inside of the furnace with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. This coating film was rubbed with a rubbing machine having a roll wound with rayon cloth at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm/sec, and a bushy foot press-in length of 0.1 mm. Then, the board|substrate which has a liquid crystal aligning film was obtained by performing ultrasonic cleaning for 1 minute in ultrapure water and drying for 10 minutes in 100 degreeC clean oven then. A pair (two sheets) of the board|substrate which has a liquid crystal aligning film was created by repeating this series of operation.

After applying an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 3.5 µm to the outer periphery of the surface having one liquid crystal aligning film of the substrate by screen printing, the liquid crystal aligning film surfaces are overlapped and pressed together so that the surfaces face each other, and the adhesive is applied hardened Then, after filling the nematic liquid crystal (MLC-6221, manufactured by Merck) between a pair of substrates from the liquid crystal injection port, sealing the liquid crystal injection port with an acrylic light-curing adhesive, and bonding the polarizing plate to both sides of the outer side of the substrate, Liquid crystal display element A of a rubbing horizontal type was manufactured.

5. Manufacturing of rubbing horizontal liquid crystal display device (2)

The liquid crystal display element B of the rubbing horizontal type was manufactured by performing operation similar to said 4. except the point which changed post-baking temperature from 230 degreeC to 150 degreeC.

6. Evaluation of liquid crystal orientation

For each of the rubbing horizontal liquid crystal display elements A and B manufactured above, the presence or absence of an anomalous domain in the change of the contrast when the voltage of 5 V is turned ON/OFF (applied/released) was examined under an optical microscope. The liquid-crystal orientation was evaluated by making the case where "A" and an abnormal domain exist in "B", and the case where there is an abnormal domain entirely as "C" in the case where there was an abnormal domain in "A" and a part. As a result, in this Example, the liquid-crystal orientation was "A" also about the element A which made post-baking temperature 230 degreeC, and the element B which set it as 150 degreeC.

7. Evaluation of Voltage Conservation Rate (VHR)

For each of the rubbing horizontal liquid crystal display elements A and B manufactured above, a voltage of 5 V was applied with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage retention rate 167 milliseconds after application release was measured. As the measuring device, VHR-1 manufactured by Toyo Technica Corporation was used. At this time, "S" when the voltage retention ratio is 98% or more, "A" when it is 95% or more and less than 98%, "B" when it is 80% or more and less than 95%, and "C" when it is 50% or more and less than 80%. , was set to "D" in the case of less than 50%. As a result, in this Example, the voltage retention rate was evaluation of "A" also about the element A which set the post-baking temperature to 230 degreeC, and the element B which made the post-baking temperature 150 degreeC.

[Examples 5, 8 and 9]

Except having changed the compounding composition as shown in following Table 2, it prepared by the same solid content concentration as Example 1, and obtained the liquid crystal aligning agent, respectively. In addition, while carrying out similarly to Example 1 using each liquid crystal aligning agent and performing evaluation of the applicability|paintability and film hardness of a liquid crystal aligning agent, it carried out similarly to Example 1, and manufactured rubbing horizontal type liquid crystal display elements A and B, Various evaluations were performed. Their results are shown in Table 3 below.

<Production and evaluation of optical FFS type liquid crystal display element>

[Example 2]

1. Preparation of liquid crystal aligning agent (AL-2)

A liquid crystal aligning agent (AL-2) was prepared in the same solvent composition and solid content concentration as in Example 1, except that the type and amount of the polymer to be used and the crosslinking agent were changed as shown in Table 2 below.

2. Evaluation of applicability

Except using (AL-2) instead of (AL-1) for the liquid crystal aligning agent, it carried out similarly to the said Example 1, and evaluated applicability|paintability. As a result, it was "A" in this Example.

3. Evaluation of Membrane Hardness

Film hardness was evaluated like the said Example 1 except having used (AL-2) instead of (AL-1) for a liquid crystal aligning agent. As a result, it was "A" in this Example.

4. Manufacture of optical FFS type liquid crystal display element (1)

The liquid crystal aligning agent (AL-2) prepared above on each surface of the glass substrate in which the flat electrode, the insulating layer, and the comb-tooth electrode were laminated|stacked on one side in this order, and the opposing glass substrate on which an electrode is not formed , was applied using a spinner, and heated (prebaked) for 1 minute on a hot plate at 80°C. Then, drying (post-baking) was performed for 30 minutes in 230 degreeC oven which substituted the inside of the furnace with nitrogen, and the coating film with an average film thickness of 0.1 micrometer was formed. The surface of the coating film was subjected to photo-alignment treatment by irradiating 1,000 J/m 2 of ultraviolet rays containing a linearly polarized 254 nm bright line from the normal direction to the substrate using an Hg-Xe lamp to form a liquid crystal aligning film on the substrate.

Next, with respect to a pair of substrates having a liquid crystal aligning film, a liquid crystal injection port is left on the edge of the surface on which the liquid crystal aligning film is formed, and an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 µm is applied by screen printing, and then the polarization axis at the time of light irradiation The substrates were superimposed on each other so that the projection direction to the substrate surface was antiparallel to each other and pressed, and the adhesive was thermosetted at 150°C for 1 hour. Next, a nematic liquid crystal (MLC-7028, manufactured by Merck Corporation) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow orientation at the time of liquid crystal injection, after heating this at 120 degreeC, it cooled slowly to room temperature, and the liquid crystal cell was manufactured. Next, the optical FFS type liquid crystal display element by bonding a polarizing plate to the outer both surfaces of a board|substrate so that the polarization direction of the polarization direction may mutually be orthogonal, and make an angle of 90 degrees with the projection direction of the optical axis of the optical axis of a liquid crystal aligning film to the board|substrate surface. A was prepared.

5. Manufacture of optical FFS type liquid crystal display element (2)

The liquid crystal display element B of optical FFS type was manufactured by performing operation similar to said 4. except the point which changed post-baking temperature from 230 degreeC to 150 degreeC.

6. Evaluation of liquid crystal orientation

About the optical FFS type liquid crystal display elements A and B manufactured above, it carried out similarly to the said Example 1, and evaluated the liquid-crystal orientation. As a result, in this Example, both optical FFS-type liquid crystal display elements A and B had liquid-crystal orientation "A".

7. Evaluation of Voltage Conservation Rate (VHR)

About the optical FFS type liquid crystal display elements A and B manufactured above, it carried out similarly to the said Example 1, and evaluated the voltage retention. As a result, in this Example, both the optical FFS type|mold liquid crystal display elements A and B were evaluation of "A" in the voltage retention ratio.

[Examples 10 to 12]

Except having changed the compounding composition as shown in following Table 2, it prepared by the same solid content concentration as Example 1, and obtained the liquid crystal aligning agent, respectively. Moreover, while carrying out similarly to Example 1 using each liquid crystal aligning agent, and performing evaluation of the applicability|paintability and film hardness of a liquid crystal aligning agent, it carried out similarly to Example 2, and manufactured optical FFS type liquid crystal display elements A and B, Various evaluations were performed. Their results are shown in Table 3 below.

<Manufacture and evaluation of VA type liquid crystal display element>

[Example 3]

1. Preparation of liquid crystal aligning agent (AL-3)

A liquid crystal aligning agent (AL-3) was prepared in the same solvent composition and solid content concentration as in Example 1, except that the type and amount of the polymer and crosslinking agent to be used were changed as shown in Table 2 below.

2. Evaluation of applicability

Except using (AL-3) instead of (AL-1) for the liquid crystal aligning agent, it carried out similarly to the said Example 1, and evaluated applicability|paintability. As a result, it was "A" in this Example.

3. Evaluation of Membrane Hardness

Film hardness was evaluated like the said Example 1 except having used (AL-3) instead of (AL-1) for a liquid crystal aligning agent. As a result, it was "A" in this Example.

4. Manufacture of VA-type liquid crystal display device (1)

On the transparent electrode surface of the transparent electrode glass substrate which consists of an ITO film, the liquid crystal aligning agent (AL-3) prepared above was apply|coated using the spinner, and prebaking was performed for 1 minute on an 80 degreeC hotplate. Then, it heated at 230 degreeC for 1 hour in the oven which substituted the inside of the furnace with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. By repeating this operation, a pair (two sheets) of the board|substrate which has a liquid crystal aligning film was created.

After applying an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 3.5 µm to the outer periphery of the surface having one liquid crystal aligning film of the substrate by screen printing, the liquid crystal aligning film surfaces are overlapped and pressed together so that the surfaces face each other, and the adhesive is applied hardened Next, after filling the negative liquid crystal (MLC-6608, manufactured by Merck) between a pair of substrates from the liquid crystal injection port, sealing the liquid crystal injection port with an acrylic light-curing adhesive, and bonding a polarizing plate to both surfaces of the outer side of the substrate, VA The type liquid crystal display element A was manufactured.

5. Manufacture of VA type liquid crystal display device (2)

VA-type liquid crystal display element B was manufactured by performing operation similar to said 4. except the point which changed post-baking temperature from 230 degreeC to 150 degreeC.

6. Evaluation of liquid crystal orientation

About the VA type liquid crystal display elements A and B manufactured above, it carried out similarly to the said Example 1, and evaluated the liquid-crystal orientation. As a result, in this Example, both VA-type liquid crystal display elements A and B had liquid-crystal orientation "A".

7. Evaluation of Voltage Conservation Rate (VHR)

About the VA-type liquid crystal display elements A and B manufactured above, it carried out similarly to the said Example 1, and evaluated the voltage retention. As a result, in this Example, both VA-type liquid crystal display elements A and B were evaluation of "A" in voltage retention.

[Example 4]

Except having changed the compounding composition as shown in following Table 2, it prepared by the same solid content concentration as Example 1, and obtained the liquid crystal aligning agent. Moreover, while carrying out similarly to Example 1 using the obtained liquid crystal aligning agent, and evaluating the applicability|paintability and film hardness of a liquid crystal aligning agent, it carried out similarly to Example 3, manufacturing VA type liquid crystal display elements A, B, and various evaluation did The results are shown in Table 3 below.

<Production and evaluation of PSA type liquid crystal display element>

[Example 6]

1. Preparation of liquid crystal aligning agent (AL-6)

A liquid crystal aligning agent (AL-6) was prepared in the same solvent composition and solid content concentration as in Example 1, except that the type and amount of the polymer to be used and the crosslinking agent were changed as shown in Table 2 below.

2. Evaluation of applicability

Except using (AL-6) instead of (AL-1) for the liquid crystal aligning agent, it carried out similarly to the said Example 1, and evaluated applicability|paintability. As a result, it was "A" in this Example.

3. Evaluation of Membrane Hardness

Film hardness was evaluated like the said Example 1 except having used (AL-6) instead of (AL-1) for a liquid crystal aligning agent. As a result, it was "A" in this Example.

4. Preparation of liquid crystal composition

With respect to 10 g of nematic liquid crystal (the Merck company make, MLC-6608), 0.3 mass of the photopolymerizable compound represented by 5 mass % of a liquid crystalline compound represented by a following formula (L1-1) and a following formula (L2-1) with respect to 10 g % was added and mixed to obtain liquid crystal composition LC1.

5. Manufacture of PSA type liquid crystal display device (1)

The liquid crystal aligning agent (AL-6) prepared above is applied using a liquid crystal aligning film printer (manufactured by Nippon Shashin Insatsu Co., Ltd.) on each electrode surface of two glass substrates each having a conductive film made of an ITO electrode, , after heating (pre-baking) for 2 minutes on a hot plate at 80° C. to remove the solvent, and then heating (post-baking) for 10 minutes on a hot plate at 230° C. to form a coating film having an average film thickness of 0.06 μm. About these coating films, after performing ultrasonic cleaning for 1 minute in ultrapure water, a pair (two sheets) of board|substrates which have a liquid crystal aligning film were obtained by drying in 100 degreeC clean oven for 10 minutes. In addition, the pattern of the electrode used is a pattern similar to the electrode pattern in PSA mode.

Next, an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 µm is applied to the outer edge of the surface having a liquid crystal aligning film of one of the pair of substrates, and then the liquid crystal aligning film surfaces are overlapped and pressed together so that the liquid crystal aligning film faces are facing each other, and the adhesive is applied hardened Next, between a pair of board|substrates from a liquid crystal injection port, after filling liquid crystal composition LC1 prepared above, the liquid crystal cell was manufactured by sealing the liquid crystal injection port with an acrylic photocuring adhesive agent. After that, an alternating current of 10 V with a frequency of 60 Hz is applied between the conductive films of the liquid crystal cell, and in a state where the liquid crystal is driven, using an ultraviolet irradiation device using a metal halide lamp as a light source, ultraviolet rays at an irradiation amount of 100,000 J/m2 investigated. In addition, this irradiation amount is the value measured using the photometer measured with wavelength 365nm reference|standard. Then, PSA type liquid crystal display element A by bonding a polarizing plate to the outer both surfaces of a board|substrate so that the polarization direction may mutually be orthogonal and the projection direction of the optical axis of the ultraviolet-ray of a liquid crystal aligning film to the board|substrate surface may make an angle of 45 degrees. was manufactured

6. Manufacture of PSA type liquid crystal display device (2)

PSA type liquid crystal display element B was manufactured by performing operation similar to said 5. except the point which changed post-baking temperature from 230 degreeC to 150 degreeC.

7. Evaluation of liquid crystal orientation

About the PSA type liquid crystal display elements A and B manufactured above, it carried out similarly to Example 1, and evaluated the liquid-crystal orientation. As a result, in this Example, the liquid-crystal orientation of both PSA type liquid crystal display elements A and B was "A".

8. Evaluation of Voltage Conservation Rate (VHR)

About the PSA type liquid crystal display elements A and B manufactured above, it carried out similarly to Example 1, and evaluated the voltage retention. As a result, in this Example, both PSA type liquid crystal display elements A and B were evaluation of "A" in voltage retention.

[Examples 7, 13, and 14]

Except having changed the compounding composition as shown in following Table 2, it prepared by the same solid content concentration as Example 1, and obtained the liquid crystal aligning agent, respectively. Moreover, while carrying out similarly to Example 1 using the obtained liquid crystal aligning agent, and evaluating the applicability|paintability and film hardness of a liquid crystal aligning agent, it carried out similarly to Example 6, and manufactured PSA type liquid crystal display elements A and B, It carried out similarly to Example 1, and performed various evaluation. The evaluation results are shown in Table 3 below.

<Production and evaluation of optical vertical liquid crystal display device>

[Example 15]

1. Preparation of liquid crystal aligning agent (AL-15)

A liquid crystal aligning agent (AL-15) was prepared in the same solvent composition and solid content concentration as in Example 1, except that the type and amount of the polymer and crosslinking agent to be used were changed as shown in Table 2 below.

2. Evaluation of applicability

Except having used (AL-15) instead of (AL-1) for a liquid crystal aligning agent, it carried out similarly to the said Example 1, and evaluated applicability|paintability. As a result, it was "A" in this Example.

3. Evaluation of Membrane Hardness

Film hardness was evaluated like the said Example 1 except having used (AL-15) instead of (AL-1) for a liquid crystal aligning agent. As a result, it was "A" in this Example.

4. Manufacture of optical vertical liquid crystal display device (1)

On the transparent electrode surface of the transparent electrode glass substrate which consists of an ITO film, the liquid crystal aligning agent (AL-15) prepared above was apply|coated using the spinner, and prebaking was performed for 1 minute on an 80 degreeC hotplate. Then, it heated at 230 degreeC for 1 hour in the oven which substituted the inside of the furnace with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. Next, the surface of this coating film was irradiated with 1,000 J/m of polarized ultraviolet light including a bright line of 313 nm using an Hg-Xe lamp and a Glan Taylor prism from a direction inclined by 40° from the substrate normal to impart liquid crystal alignment ability. . The same operation was repeated and a pair (two sheets) of board|substrates which have a liquid crystal aligning film were created.

After applying an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 3.5 µm to the outer periphery of the surface having a liquid crystal aligning film of one of the substrates by screen printing, the liquid crystal aligning film surfaces of a pair of substrates are opposed to each other, It pressed so that the projection direction of the optical axis of an ultraviolet-ray to the board|substrate surface was antiparallel, and the adhesive agent was thermosetted at 150 degreeC over 1 hour. Next, after filling the gap between the substrates from the liquid crystal injection port with negative liquid crystal (Merck Corporation, MLC-6608), the liquid crystal injection port was sealed with an epoxy adhesive. Moreover, in order to remove the flow orientation at the time of liquid crystal injection, after heating this at 130 degreeC, it cooled slowly to room temperature. Next, an optical vertical liquid crystal display element by bonding a polarizing plate to both outer surfaces of the substrate so that the polarization direction thereof is orthogonal to each other and forms an angle of 45° with the projection direction of the optical axis of the ultraviolet ray of the liquid crystal aligning film to the substrate surface. A was prepared.

5. Manufacturing of optical vertical liquid crystal display device (2)

The optical vertical type liquid crystal display element B was manufactured by performing operation similar to said 4. except the point which changed the post-baking temperature from 230 degreeC to 150 degreeC.

6. Evaluation of liquid crystal orientation

About the optical vertical type liquid crystal display elements A and B manufactured above, it carried out similarly to the said Example 1, and evaluated the liquid-crystal orientation. As a result, in this Example, the liquid-crystal orientation was "A" for both optical vertical type liquid crystal display elements A and B.

7. Evaluation of Voltage Conservation Rate (VHR)

About the optical vertical type liquid crystal display element manufactured above, it carried out similarly to the said Example 1, and evaluated the voltage retention. As a result, in this Example, both of the optical vertical liquid crystal display elements A and B, the voltage retention rate was evaluation of "A".

[Examples 16 to 25 and Comparative Examples 1 to 6]

Except having changed the compounding composition as shown in following Table 2, it prepared by the same solid content concentration as Example 1, and obtained the liquid crystal aligning agent, respectively. Moreover, while carrying out similarly to Example 1 using each liquid crystal aligning agent, and performing evaluation of the applicability|paintability and film hardness of a liquid crystal aligning agent, it carried out similarly to Example 15, and manufactured optical vertical type liquid crystal display elements A and B, Various evaluations were performed. Their results are shown in Table 3 below. In addition, in Table 2, "-" means that the compound of the corresponding column was not used.

As shown in Table 3, among Examples 1-25 using the liquid crystal aligning agent containing compound [W] as a crosslinking agent, except Example 14, all applicability|paintability is evaluation of "A", Example 14 is "B ' was the evaluation. Moreover, Examples 1-25 were favorable also about the liquid-crystal orientation and voltage retention of the obtained liquid crystal display element, and was evaluation of "S", "A", or "B". In particular, Example 17 using the polymer (P-12) rich in diamine was especially excellent in the liquid-crystal orientation as evaluation of "S" when the post-baking temperature was 150 degreeC. On the other hand, when Example 22 using the polymer (P-13) rich in acid anhydride made post-baking temperature 150 degreeC, liquid-crystal orientation was evaluation of "B".

On the other hand, Comparative Example 1 which does not contain a crosslinking agent, and Comparative Examples 2-6 containing only a crosslinking agent different from compound [W], when the post-baking temperature is 230 degreeC, liquid-crystal orientation and voltage retention are "A" Or it was evaluation of "B", but when post-baking temperature was 150 degreeC, it was evaluation of "C" or "B", and it was a result inferior to an Example.

From these results, it turned out that the liquid crystal aligning film and liquid crystal element formed using the liquid crystal aligning agent containing compound [W] are excellent in applicability|paintability, film hardness, liquid-crystal orientation, and voltage retention.

Claims (9)

It contains a polymer component and a heterocyclic-containing compound having two or more partial structures in one molecule in which n (n is an integer of 1 or more) hydrogen atoms from the structure represented by the following formula (1) are removed,
The liquid crystal aligning agent in which the said polymer component contains the polymer which has a partial structure represented by each of following formula (7-1) - Formula (7-3).

(In formula (1), X ¹ is any of groups represented by each of the following formulas (2-1) to (2-5); A ¹ is a divalent organic group, bonded to another ring structure, A condensed ring may be formed together with other ring structures; a plurality of A ¹ and X ¹ in one molecule each independently have the above definition)

(In Formulas (2-1) to (2-5), R ¹ to R ⁷ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms; Formulas (2-3) and Formulas (2-3) and "*" in (2-5) shows that it is a bond with the oxygen atom in Formula (1))

(In formula (7-1), A ²¹ is a single bond or a divalent organic group having 1 or more carbon atoms, Y ¹ is a protecting group, and R ²¹ to R ²³ are each independently a hydrogen atom or a monovalent group having 1 or more carbon atoms. a group; m is an integer of 0 to 6; in formula (7-2), Y ² is a protecting group; in formula (7-3), R ²⁴ and R ²⁵ are each independently a divalent hydrocarbon group; Y ³ is a protecting group; “*” indicates a bond) The method of claim 1,
The liquid crystal aligning agent whose said heterocyclic-containing compound is a compound which has any of the partial structures represented by each of following formula (3-1) - formula (3-9) 2 or more in 1 molecule.

(In formulas (3-1) to (3-9), R ⁵¹ to R ⁷¹ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 24 carbon atoms; provided that R ⁵¹ to R any one of ⁵⁴ , any one of R ⁵⁵ to R ⁵⁷ , any one of R ⁶⁰ to R ⁶² , any one of R ⁶³ and R ⁶⁴ , any one of R ⁶⁶ to R ⁶⁸ , and R ⁶⁹ and any one of R ⁷⁰ is a bond; a plurality of R ⁵¹ to R ⁷¹ in one molecule each independently have the above definition; "*" indicates a bond) delete The method of claim 1,
The said polymer component contains the polymer which has a primary amino group at the terminal, The liquid crystal aligning agent. The method of claim 1,
The said polymer component contains at least 1 sort(s) chosen from the group which consists of a polyamic acid, polyamic acid ester, and a polyimide, liquid crystal aligning agent. The liquid crystal aligning film formed using the liquid crystal aligning agent in any one of Claims 1, 2, 4, and 5. A liquid crystal element provided with the liquid crystal aligning film of Claim 6. Liquid crystal by apply|coating the liquid crystal aligning agent in any one of Claims 1, 2, 4, and 5 to each board|substrate surface in a pair of board|substrate, and irradiating light to the said apply|coated board|substrate surface, A process of forming a liquid crystal aligning film by imparting alignment ability;
A step of constructing a liquid crystal cell by arranging a pair of substrates on which the liquid crystal aligning film is formed so that the coated surfaces of the substrates face each other through a liquid crystal layer
A method of manufacturing a liquid crystal device comprising a. The process of apply|coating the liquid crystal aligning agent in any one of Claims 1, 2, 4, and 5 on each said electrically conductive film of a pair of board|substrates which have an electrically conductive film;
A step of constructing a liquid crystal cell by arranging a pair of substrates to which the liquid crystal aligning agent is applied so that the coated surfaces of the substrates face each other through a liquid crystal layer;
Step of irradiating light to the liquid crystal cell in a state where a voltage is applied between the conductive films
A method of manufacturing a liquid crystal device comprising a.