TWI786195B - Liquid crystal alignment agent, method for manufacturing liquid crystal element, liquid crystal alignment film, and liquid crystal element - Google Patents

Abstract

Provided is a liquid crystal alignment agent which has good applicability and continuous printability to a fine concave-convex structure, is less susceptible to temperature unevenness during film formation, and can obtain a liquid crystal display element with good afterimage characteristics. The liquid crystal alignment agent contains a polymer component and a solvent component. The solvent component includes a solvent [A], the solvent [A] is at least one selected from the group consisting of 5-membered cyclic lactone, 6-membered cyclic lactone, and 7-membered cyclic lactone, and has a carbon Alkyl with 2 to 10 carbons, alkoxy with 2 to 10 carbons, alkoxyalkyl with 2 to 10 carbons, alkoxyalkoxyalkyl with 2 to 10 carbons, alkoxyalkoxyalkyl with 2 to 10 carbons At least one moiety in the group consisting of alkoxyalkoxy, group [-COR ¹² ] (wherein R ¹² is an alkyl group with 1 to 3 carbons), and a carbon-carbon double bond forming part of the ring structure.

Description

Liquid crystal alignment agent, manufacturing method of liquid crystal element, liquid crystal alignment Film and liquid crystal element

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

Liquid crystal elements are used in various applications represented by display devices such as televisions, personal computers, and smartphones. These liquid crystal elements include a liquid crystal alignment film having a function of aligning liquid crystal molecules in a certain direction. Usually, the liquid crystal alignment film is formed on the substrate by applying a liquid crystal alignment agent obtained by dissolving polymer components in an organic solvent on the substrate, preferably by heating. As a polymer component of a liquid crystal alignment agent, polyamic acid or soluble polyimide is widely used from the point which is excellent in mechanical strength, liquid crystal alignment, and affinity with a liquid crystal. In addition, as the solvent component of the liquid crystal alignment agent, a solvent with high solubility to polymers such as polyamic acid or soluble polyimide (such as N-methyl-2-pyrrolidone or γ-butyrolactone) is generally used. good solvents such as butylcellosolve), and mixed solvents with high wetting and spreading properties on the substrate (for example, poor solvents such as butyl cellosolve) (for example, refer to Patent Document 1 and Patent Document 2).

[Prior art literature]

[Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2017-198975

[Patent Document 2] Japanese Patent Laid-Open No. 2016-206645

With regard to LCD TVs, in order to obtain the sense of presence brought by the further improvement of display quality in recent years, 4K (such as 3840 pixels × 2160 pixels) or 8K (such as 7680 pixels × 4320 pixels) have been produced. The specification of the display device with the number of pixels. As the number of pixels of the display device increases and the pixel size decreases, the pixel electrode becomes a finer structure, and the unevenness density per unit area of the formation surface of the pixel electrode becomes higher. Therefore, when the liquid crystal alignment agent is coated on the formation surface of the pixel electrode to form an alignment film, the liquid crystal alignment agent is not easy to wet and spread to the fine concave-convex structure of the pixel electrode, and there is a concern that the coating on the substrate cannot be sufficiently ensured. sex. In order to obtain good applicability even when the liquid crystal alignment agent is applied to the fine uneven structure, as a solvent component of the liquid crystal alignment agent, it is necessary to suppress a decrease in the solubility of the polymer and to improve the wetting spread to the substrate. sex.

In addition, from the viewpoint of industrial production, it is required that when the liquid crystal alignment agent is printed on the substrate, the volatilization of the solvent from the printing machine can be suppressed, and the polymer is not easily precipitated on the printing machine in the case of continuous printing. Printability was good.

In addition, in recent years, the popularization of large-screen liquid crystal panels has been promoted, and larger-scale production lines have been operated to increase the size of substrates. As an advantage of increasing the size of the substrate, it is possible to obtain a plurality of panels from one substrate, which can reduce the process time and cost, and that it can cope with the increase in the size of the liquid crystal panel itself. Wait. On the other hand, in the case of forming a liquid crystal alignment film on a large substrate, compared with before, it is easy to generate temperature unevenness during post-baking, and it is worried that the pretilt angle of the liquid crystal alignment film will be deviated due to the temperature unevenness, resulting in Shows a reduction in quality.

Regarding liquid crystal display devices, if the residual charge (residual direct current (DC)) in the liquid crystal alignment film is large, it will cause so-called afterimage (also called DC afterimage), that is, after switching the image, the image displayed before remains. image effects. In addition, when the liquid crystal display device is operated for a long time, if the direction of initial alignment deviates from the initial direction at the time of manufacture of the liquid crystal display device, burn-in called AC afterimage may occur. In order to ensure display quality, there is a demand for a liquid crystal display device in which the above-mentioned DC afterimage and AC afterimage are reduced as much as possible.

The present invention was made in view of the above-mentioned problems, and one of the objects is to provide a film that has good coating properties and continuous printing properties on the fine uneven structure, is less affected by temperature unevenness during film formation, and can obtain afterimages. Liquid crystal alignment agent for liquid crystal display elements with good properties.

The present invention employs the following means to solve the above-mentioned problems.

<1>A liquid crystal alignment agent, which contains a polymer component and a solvent component, and the solvent component includes a solvent [A], and the solvent [A] is selected from a 5-membered cyclic lactone, a 6-membered cyclic lactone, and a 7-membered cyclic lactone. At least one of the group consisting of cyclic lactamides, and has an alkyl group selected from 2 to 10 carbons, an alkoxy group with 2 to 10 carbons, an alkoxyalkyl group with 2 to 10 carbons, carbon Alkoxyalkoxyalkyl with 2 to 10, alkoxyalkoxy with 2 to 10 carbons, [-COR ¹² ] (wherein R ¹² is an alkyl with 1 to 3 carbons), and the formation At least one partial structure of the group consisting of carbon-carbon double bonds in a part of the ring.

<2> A method for producing a liquid crystal element, comprising forming a liquid crystal alignment film using the liquid crystal alignment agent as described in <1>.

<3> A liquid crystal alignment film formed using the liquid crystal alignment agent as described in <1>.

<4> A liquid crystal element provided with the liquid crystal alignment film as described in said <2>.

When the liquid crystal alignment agent of the present invention is applied to a substrate surface having a fine uneven structure, it has good wettability and spreadability, and can form a liquid crystal alignment film uniformly on the substrate surface. In addition, in the case of continuous printing in the manufacturing process, it is also possible to make it difficult for the polymer to precipitate on the printing machine. Moreover, the liquid crystal alignment agent of the present invention is less susceptible to the influence of temperature unevenness during film formation heating, thereby obtaining a liquid crystal alignment film that suppresses characteristic deviations caused by temperature unevenness, and can obtain liquid crystals with excellent afterimage characteristics. Display components.

10: ITO electrode substrate for evaluation

11: Glass substrate

12: ITO electrode

A: electrode width

B: Distance between electrodes

C: electrode height

1( a ) to FIG. 1( b ) are diagrams showing a schematic configuration of an ITO electrode substrate for evaluation. FIG. 1( a ) is a plan view, and FIG. 1( b ) is a partially enlarged cross-sectional view.

Hereinafter, each component contained in the liquid crystal alignment agent of this disclosure, and other components arbitrarily blended as needed are demonstrated. Liquid crystal alignment agent contains polymer composition A component and a solvent component, and the polymer component is a liquid polymer composition dissolved in the solvent component.

"Polymer Composition"

Regarding the polymer component contained in the liquid crystal alignment agent, its main skeleton is not particularly limited, for example, polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyamide Amide, polyamide imide, polybenzoxazole precursor, polybenzoxazole, cellulose derivative, polyacetal, styrene-maleimide copolymer, poly(methyl) Acrylic and other main skeleton. In addition, (meth)acrylate means to include acrylate and methacrylate.

From the viewpoint of sufficiently ensuring the performance of the liquid crystal element, as the polymer component, it is preferable to include at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide. Polymer (hereinafter also referred to as "polymer [P]").

<Polyamide>

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

(tetracarboxylic dianhydride)

As a tetracarboxylic dianhydride used for the synthesis|combination of polyamic acid, aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride etc. are mentioned, for example. As these specific examples, aliphatic tetracarboxylic dianhydrides, for example, include 1,2,3,4-butane tetracarboxylic dianhydrides, etc.; alicyclic tetracarboxylic dianhydrides, for example, include: 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, 3- Oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 2,4,6,8-tetracarboxybicyclo [3.3.0]octane-2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraone , cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, etc.; examples of aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene) Diphthalic anhydride, ethylene glycol bis-trimellitic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 4,4'-carboxy diphthalic anhydride, etc., In addition, the tetracarboxylic dianhydride described in Unexamined-Japanese-Patent No. 2010-97188 can also be used. In addition, the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

(diamine compound)

Examples of the diamine compound used in the synthesis of polyamic acid include aliphatic diamine, alicyclic diamine, aromatic diamine, and diaminoorganosiloxane. Specific examples of these diamines include, for example, m-xylylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and hexamethylenediamine. Amines, etc.; examples of alicyclic diamines include: 1,4-diaminocyclohexane, 4,4'-methylene bis(cyclohexylamine), etc.; examples of aromatic diamines: dodecane Oxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2, 4-Diaminobenzene, Pentadecyloxy-2,5-diaminobenzene, Octadecyloxy-2,5-diaminobenzene, Cholesteryloxy-3,5-diaminobenzene Benzene, Cholesteryloxy-3,5-diaminobenzene, Cholesteryloxy-2,4-diaminobenzene, Cholesteryloxy-2,4-diaminobenzene, 3,5 -Cholesteryl diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostyl 3,5-diaminobenzoate, 3,6-bis(4- Aminobenzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 2,4-diamino-N,N-diallylaniline, 4 -(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)benzene base)-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- (wherein "*" represents a bond with X ^I ), R ^I is an alkanediyl group with 1 to 3 carbons, R ^II is a single bond or an alkanediyl group with 1 to 3 carbons, a is 0 or 1, b is an integer of 0 to 2, and c is an integer of 1 to 20, d is 0 or 1. Among them, a and b will not be 0 at the same time)

Side-chain diamines such as the compounds shown, diamines having a cinnamic acid structure in the side chain: p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Thioether, 4-aminophenyl-4-aminobenzoate, 4,4'-diaminoazobenzene, 3,5-diaminobenzoic acid, 1,2-bis(4-amine phenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-amine 1,6-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,10-bis(4- Aminophenoxy)decane, 1,2-bis(4-aminophenyl)ethane, 1,5-bis(4-aminophenyl)pentane, 1,6-bis(4-amine phenyl) hexane, 1,4-bis(4-aminophenylsulfonyl)butane, bis [2-(4-aminophenyl)ethyl]adipic acid, N,N-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(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenyl oxy)phenyl]propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(phenylenediisopropylidene)bisaniline, 1,4-bis(4 -aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-[4,4'-propane-1,3-diylbis(piperidine -1,4-diyl)]diphenylamine, 4,4'-diaminobenzamide aniline, 4,4'-diaminostilbene, 4,4'-diaminodiphenylamine, 1,3-bis(4-aminophenethyl)urea, 1,3-bis(4-aminobenzyl)urea, 1,4-bis(4-aminophenyl)-piperazine, N- Main chain diamines such as (4-aminophenylethyl)-N-methylamine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, etc.; Diaminoorganosiloxanes include, for example, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, etc. In addition, Japanese Patent Application Laid-Open No. 2010-97188 can also be used. recorded diamines.

(Synthesis of polyamide acid)

The polyamic acid can be obtained by reacting the above-mentioned tetracarboxylic dianhydride and a diamine compound together with a molecular weight modifier as needed. The use ratio of the tetracarboxylic dianhydride and the diamine compound used in the synthesis reaction of polyamic acid is preferably 0.2 to 2 equivalents of the anhydride group of the tetracarboxylic dianhydride relative to 1 equivalent of the amine group of the diamine compound. Equivalent ratio. Examples of molecular weight regulators include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; phenyl isocyanate, isocyanate Monoisocyanate compounds such as naphthyl ester, etc. The usage ratio of the molecular weight modifier is 100% based on the total of the tetracarboxylic dianhydride and the diamine compound used It is preferable to set it as 20 mass parts or less as mass parts.

The synthesis reaction of polyamic acid is preferably carried out 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 hour to 24 hours.

Examples of the organic solvent used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. A particularly good organic solvent is preferably selected from N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, One or more of the group consisting of γ-butyrolactone, tetramethylurea, hexamethylphosphoryltriamine, m-cresol, xylenol, and halogenated phenol is used as a solvent, or one or more of these are used together with Mixtures of other organic solvents (for example, butylcellosulfate, diethylene glycol diethyl ether, etc.). The amount (a) of the organic solvent used is preferably such that the total amount (b) of tetracarboxylic dianhydride and diamine becomes 0.1% by mass to 50% by mass with respect to the total amount of the reaction solution (a+b). quantity.

In this manner, a reaction solution obtained by dissolving polyamic acid can be obtained. The reaction solution may be directly used for the preparation of the liquid crystal alignment agent, or may be used for the preparation of the liquid crystal alignment agent after separating the polyamic acid contained in the reaction solution.

<Polyuric acid ester>

In the case where the polymer [P] is a polyamic acid ester, the polyamic acid ester can be obtained, for example, by the following method: [I] combining the polyamic acid and the ester obtained by the above synthesis reaction A method of reacting a tetracarboxylic acid diester with a diamine compound; [II] a method of reacting a tetracarboxylic acid diester with a diamine compound; [III] a method of reacting a tetracarboxylic diester dihalide with a diamine compound. The polyamic acid ester contained in the liquid crystal alignment agent may only have the uric acid ester structure, or It can be a partial esterification product in which the amide acid structure and amide ester structure coexist. Furthermore, the reaction solution obtained by dissolving the polyamic acid ester may be directly used for the preparation of the liquid crystal alignment agent, or may be used for the preparation of the liquid crystal alignment agent after separating the polyamic acid ester contained in the reaction solution.

<Polyimide>

When the polymer [P] is a polyimide, the polyimide can be obtained, for example, by dehydrating and ring-closing polyamic acid synthesized as described above and imidizing it. The polyimide may be a complete imide obtained by dehydrating and ring-closing the entire amide acid structure of the polyamic acid as its precursor, or may be a dehydration-ring-closed part of the amide acid structure. And a partial amide imide compound in which the amide acid structure and the amide imide ring structure coexist. The polyimide used in the reaction preferably has an imidization rate of 20%-99%, more preferably 30%-90%. The imidization ratio represents the ratio of the number of imide ring structures to the sum of the number of amide acid structures and the number of imide ring structures of polyimide in percentage. Here, a part of the imide ring may be an isoimide ring.

The dehydration and ring closure of polyamic acid is preferably carried out by the following method: dissolving polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating if necessary. In this method, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as a dehydrating agent, for example. The amount of the dehydrating agent used is preferably 0.01 mol to 20 mol with respect to 1 mol of the amide acid structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. The usage amount of dehydration closed-loop catalyst is preferably relative to the used dehydrating agent 1 mole The ear is set at 0.01 mole to 10 mole. Examples of the organic solvent used in the dehydration ring-closure reaction include the organic solvents exemplified as used in the synthesis of polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0°C to 180°C. The reaction time is preferably from 1.0 hour to 120 hours.

In the manner described, a reaction solution containing polyimide was obtained. The reaction solution can be directly used for the preparation of the liquid crystal alignment agent, and can also be used for the preparation of the liquid crystal alignment agent after separating the polyimide. Polyimides can also be obtained by imidization of polyamide esters.

The polyamic acid, polyamic acid ester and polyimide obtained in the described manner are preferably 10mPa. s ~ 800mPa. s solution viscosity, more preferably with 15mPa. s~500mPa. The solution viscosity of s. Furthermore, the solution viscosity (mPa.s) of polyamic acid, polyamic acid ester, and polyimide is a good solvent for the use of these polymers (eg, γ-butyrolactone, N-methyl- 2-pyrrolidone, etc.), the value measured at 25°C using an E-type rotational viscometer for a polymer solution with a concentration of 10% by mass.

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (Gel Penetration Chromatography, GPC) of polyamic acid, polyamic acid ester, and polyimide is preferably 1,000~ 500,000, more preferably 2,000~300,000. Also, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. By being in such a molecular weight range, the favorable orientation and stability of a liquid crystal display element can be ensured.

From the viewpoint of making the quality of the obtained liquid crystal element better, relatively The total amount of polymer components contained in the liquid crystal alignment agent, the content ratio of the polymer [P] (the total amount when two or more types are contained) is preferably 20% by mass or more, more preferably 30% by mass % or more, and more preferably more than 50% by mass.

"Solvent Composition"

The liquid crystal alignment agent disclosed herein comprises solvent [A] as at least a part of the solvent component, and said solvent [A] is selected from the group consisting of 5-membered cyclic lactone, 6-membered cyclic lactone and 7-membered cyclic lactone At least one of the above, and has an alkyl group selected from 2 to 10 carbons, an alkoxy group with 2 to 10 carbons, an alkoxyalkyl group with 2 to 10 carbons, and an alkoxyalkane with 2 to 10 carbons Oxyalkyl, alkoxyalkoxy with 2 to 10 carbons, group [-COR ¹² ] (wherein R ¹² is an alkyl with 1 to 3 carbons), and a carbon-carbon double bond forming part of the ring At least one partial structure in the formed group (hereinafter also referred to as "specific partial structure").

<Solvent [A]>

The solvent [A] has a structure in which one hydrogen atom bonded to a ring of a specific cyclic ester (γ-butyrolactone, δ-valerolactone, or ε-caprolactam) is substituted with a specific partial structure. By using a compound having such a structure for at least a part of the solvent component, the solubility of the polymer component in the solvent and the wettability of the liquid crystal alignment agent can be expressed in a balanced manner. Thereby, the applicability (printability) of a liquid crystal alignment agent to the surface of the substrate which has the electrode structure of a fine uneven|corrugated shape can be improved. In addition, the boiling point of the solvent component of the liquid crystal alignment agent can be adjusted to an appropriate height, and it is less likely to be affected by temperature unevenness during heating during film formation.

The solvent [A] preferably has an alkyl group having 2 to 10 carbons, an alkoxy group having 2 to 10 carbons, or an alkoxy group having 2 to 10 carbons in the ring portion of γ-butyrolactone or δ-valerolactone. Alkylalkyl, alkoxyalkoxyalkyl with 2 to 10 carbons, compound (a-1) of alkoxyalkoxy with 2 to 10 carbons, substituted or unsubstituted γ-butyl A compound (a-2) in which one vinyl group of the lactone ring is replaced by a carbon-carbon double bond, and a compound in which "-COR ¹² " is bonded to the nitrogen atom in the ring of ε-caprolactam (a -3). Specifically, it is preferably at least one selected from the group consisting of compounds represented by the following formula (1), compounds represented by the following formula (2), and compounds represented by the following formula (3) .

(In formula ( ¹ ), R1 is an alkyl group with 2 to 10 carbons, an alkoxy group with 2 to 10 carbons, an alkoxyalkyl group with 2 to 10 carbons, an alkoxy group with 2 to 10 carbons Alkoxyalkyl, alkoxyalkoxy with carbon number 2~10. n is 1 or 2)

(In formula (2), R ² is a divalent group represented by the following formula (4-1) or formula (4-2))

(In formula (4-1) and formula (4-2), R ⁴ to R ¹¹ are each independently a hydrogen atom or an alkyl group with 1 to 5 carbons. "*1" represents a bond with an oxygen atom )

[chemical 5]

(In formula (3), R ³ is an alkyl group with 1 to 3 carbon atoms).

(compound represented by formula (1))

In the formula (1), R ¹ may be linear or branched. Specific examples of R1 include ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-pentyl, isopentyl, second Pentyl, 3-pentyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc.; alkoxy groups include, for example, each of the above-mentioned alkyl groups bonded to oxygen Atom groups, etc.; alkoxyalkyl groups include, for example, methoxymethyl, methoxyethyl, ethoxymethyl, propoxymethyl, propoxyethyl, butoxyethyl, etc.; Examples of alkoxyalkoxyalkyl groups having 2 to 10 carbon atoms include methoxymethoxymethyl, ethoxymethoxymethyl, ethoxyethoxyethyl, propoxyethoxy Ethyl and the like; alkoxyalkoxy include, for example, methoxyethoxy, ethoxyethoxy, ethoxypropoxy, propoxypropoxy and the like.

R is preferably ^a straight chain, more preferably a straight chain alkyl having 3 or more carbons, still more preferably a straight chain alkyl having 3 to 8 carbons, particularly preferably a straight chain having 5 to 8 carbons. alkyl.

R ¹ may be bonded to any position of the γ-butyrolactone ring or the δ-valerolactone ring, preferably at the α position relative to the oxygen atom in the ring.

Specific examples of the compound represented by the formula (1) include, for example, compounds (γ-butyrolactones) in which n is 1: γ-caprolactone, γ-enantholactone, γ-octylactone, γ-Nonanolide, γ-Decanolactone, γ-Undecanolactone, γ-Lauryl Lactone, γ-Tridecanolactone, γ-Myristolactone, α-Propyl-γ -butyrolactone, α-butyl-γ-butyrolactone, α-amyl-γ- Butyrolactone, α-hexyl-γ-butyrolactone, α-heptyl-γ-butyrolactone, α-octyl-γ-butyrolactone, α-decyl-γ-butyrolactone, etc.; n is Compounds of 2 (δ-caprolactones) include, for example, δ-enantholactone, δ-octylactone, δ-nonanolide, δ-decalactone, δ-undecanolactone, δ-dodecanolactone, and δ-caprolactone. δ-tridecanolide, δ-myristalactone, δ-pentadecanolactone, etc. In addition, the compound represented by the said formula (1) can be used individually by 1 type or in combination of 2 or more types.

(compound represented by formula (2))

In the formula (2), the alkyl groups of R ⁴ to R ¹¹ in the formula (4-1) and formula (4-2) can be linear or branched, for example: methyl , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, n-pentyl, isopentyl, etc. In the formula (4-1), preferably at least one of R ⁴ to R ⁷ is an alkyl group, more preferably the alkyl group is bonded to the α-position relative to the oxygen atom in the ring. In the formula (4-2), preferably at least one of R ⁸ to R ¹¹ is an alkyl group, more preferably the alkyl group is bonded to the α-position relative to the oxygen atom in the ring. Among these, R ⁴ and R ⁸ are particularly preferably methyl or ethyl, and R ⁵ to R ⁷ and R ⁹ to R ¹¹ are hydrogen atoms.

Specific examples of the compound represented by the formula (2) include α-angelica lactone, β-angelica lactone, and the like. In addition, the compound represented by the said formula (2) can be used individually by 1 type or in combination of 2 or more types.

(compound represented by formula (3))

In the above formula (3), R ³ may be linear or branched, for example, methyl, ethyl, n-propyl, and isopropyl. R ³ is preferably methyl or ethyl, more preferably methyl.

Specific examples of the compound represented by the formula (3) include N-acetyl-ε-caprolactam, N-propionyl-ε-caprolactam, and the like. N-acetyl-ε-caprolactam is preferred. In addition, the compound represented by the said formula (3) can be used individually by 1 type or in combination of 2 or more types.

The solvent [A] is preferably selected from the compounds represented by the formula (1) and At least one of the group consisting of compounds represented by the formula (2). It is especially preferred to be selected from gamma-enantholactone, gamma-octyl lactone, gamma-nonanolide, gamma-decalactone, gamma-undecanolactone, delta-octyl lactone, delta-nonanolactone, delta - At least one selected from the group consisting of decanolactone, δ-undecylactone, δ-laudecylactone, δ-tridecylactone, α-angelicalide, and β-angelicalide.

<Solvent [B]>

In terms of being able to produce a liquid crystal alignment agent with better wettability, the solvent component is preferably contained together with the solvent [A] and is selected from alcohol-based solvents, chain ester-based solvents, and ether-based solvents. and a solvent different from the solvent [A] (hereinafter also referred to as "solvent [B]") in at least one of the group consisting of a ketone-based solvent.

As specific examples of the solvent [B], alcohol-based solvents include, for example, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, diacetone alcohol, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, benzyl alcohol, etc.; chain ester solvents include, for example, ethyl lactate, butyl lactate, methyl acetate, acetic acid Ethyl ester, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, isoamyl propionate, isoamyl isobutyrate, etc. ; Ether-based solvents include, for example, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether (butylcylosol), ethylene glycol Alcohol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol methyl ethyl ether Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol methyl ether acetate , PGMEA), tetrahydrofuran, diisoamyl ether, etc.; ketone solvents include, for example: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cycloheptanone, cyclopentanone, 3-methyl Cyclohexanone, 4-methylcyclohexanone, diisobutyl ketone, etc.

The solvent [B] is preferably at least one selected from the group consisting of alcohol-based solvents, chain ester-based solvents, and ether-based solvents among the above in terms of improving the coatability. One, more preferably selected from ethylene glycol monobutyl ether (butyl cellosu), diacetone alcohol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, One of the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and 3-methoxy-1-butanol. In addition, as solvent [B], it can use individually by 1 type or in combination of 2 or more types.

<Solvent [C]>

For the purpose of ensuring the solubility of the polymer in the solvent component and suppressing the decrease in product yield due to the precipitation of the polymer in the coating step, the solvent component is preferably combined with the solvent [A] and further includes a solvent having a boiling point of 200 at 1 atmosphere. ℃ above and different from solvent [A] (in the form of hereinafter also referred to as "solvent [C]").

The solvent [C] is preferably at least one selected from the group consisting of aprotic polar solvents and phenols, more preferably an aprotic polar solvent. Specifically, it is particularly preferred to be selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidone, γ-butyrolactone , propylene carbonate, and at least one of the group consisting of compounds represented by the following formula (5).

(In formula (5), R ²¹ and R ²² are each independently a hydrogen atom, or a monovalent hydrocarbon group with 1 to 6 carbon atoms that may have an ether bond, and R ²¹ and R ²² may also be bonded to form a ring. R ²³ is an alkyl group with 1 to 4 carbons)

(compound represented by formula (5))

In the formula (5), as the monovalent hydrocarbon group with 1 to 6 carbons of ^R21 and ^R22 , for example, a chain hydrocarbon group with 1 to 6 carbons, an alicyclic hydrocarbon group with 3 to 6 carbons, An aromatic hydrocarbon group having 5 or 6 carbon atoms, etc. Moreover, as a monovalent group which has "-O-" between the carbon-carbon bonds of this hydrocarbon group, the alkoxyalkyl group etc. which have 2-6 carbon atoms are mentioned, for example.

R ²¹ and R ²² may form a ring together with the nitrogen atom to which R ²¹ and R ²² are bonded by being bonded to each other. Examples of the ring formed by R ²¹ and R ²² being bonded to each other include a pyrrolidine ring and a piperidine ring, and a monovalent chain hydrocarbon group such as a methyl group may be bonded to these rings.

R ²¹ and R ²² are preferably a hydrogen atom or an alkyl group having 1 to 6 carbons, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbons, further preferably a hydrogen atom or a methyl group.

The alkyl group having 1 to 4 carbon atoms in R ²³ may be linear or branched. R ²³ is preferably methyl or ethyl.

Specific examples of the compound represented by the formula (5) include, for example, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, Amide, 3-hexyloxy-N,N-dimethylpropionamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide, etc. . In addition, the compound represented by the said formula (5) can be used individually by 1 type or in combination of 2 or more types.

Among the solvent components, the content ratio of the solvent [A] is preferably 10 mass % or more with respect to the total amount of the solvent components contained in the liquid crystal alignment agent. When it is less than 10% by mass, it tends to be difficult to sufficiently obtain the effect of improving the applicability of the liquid crystal alignment agent. From the aspect that the balance between the solubility of the polymer component and the wettability and spreadability of the liquid crystal alignment agent can be improved, the content ratio of the solvent [A] is more preferably 10% by mass to 85% by mass, and more preferably 15% by mass. %~75% by mass, especially preferably 15%~60% by mass.

From the viewpoint of making the wettability of the liquid crystal alignment agent higher, the content ratio of the solvent [B] is preferably 10% by mass to 80% with respect to the total amount of solvent components contained in the liquid crystal alignment agent. % by mass is more preferably 15% by mass to 70% by mass, more preferably 20% by mass to 50% by mass.

The content of the solvent [C] is preferably 70% by mass or less since film formation can be performed at a lower heating temperature. From the viewpoint of securing the solubility of the polymer component to the solvent, the content of the solvent [C] is preferably 1% by mass to 70% by mass relative to the total amount of the solvent component contained in the liquid crystal alignment agent, Even It is more preferable to set it as 5 mass % - 65 mass %, and it is more preferable to set it as 10 mass % - 60 mass %.

The liquid crystal alignment agent may only contain solvent [A] as a solvent component, and particularly preferably, the solvent component contains solvent [A] and solvent [B], or contains solvent [A], solvent [B] and solvent [C]. However, in this specification, the so-called "solvent [A] and solvent [B]" and "solvent component includes solvent [A], solvent [B], and solvent [C]" are allowed to the extent that the effects of the present invention are not hindered. Instead, solvents other than solvent [A], solvent [B], and solvent [C] are included.

As another solvent, a halogenated hydrocarbon solvent, a hydrocarbon solvent, etc. are mentioned, for example. As specific examples of these, halogenated hydrocarbon solvents include, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, etc.; hydrocarbon solvents such as Examples thereof include hexane, heptane, octane, benzene, toluene, and xylene. The proportion of other solvents is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.2% by mass or less, based on the total amount of solvent components contained in the liquid crystal alignment agent.

<<Other ingredients>>

A liquid crystal alignment agent contains a polymer component and a solvent component, and may contain other components as needed. As the other components, for example, epoxy group-containing compounds (such as N,N,N',N'-tetraglycidyl-m-xylylenediamine, N,N,N',N'-tetraglycidyl Glyceryl-4,4'-diaminodiphenylmethane, etc.), functional silane compounds (such as 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-amine propylmethyldimethoxysilane, etc.), antioxidants, metal chelating compounds, hardening catalysts, hardening accelerators, surfactants, fillers, dispersants, photosensitizers, etc. The proportion of other ingredients can be It selects suitably according to each compound in the range which does not impair the effect of this invention.

The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, etc., preferably 1 mass %~10% by mass. When the solid content concentration is less than 1% by mass, the film thickness of the coating film is too small, making it difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, the film thickness of the coating film is too large, making it difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent tends to increase, resulting in poor applicability.

"Liquid Crystal Alignment Film and Liquid Crystal Components"

The liquid crystal element disclosed herein includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above. Liquid crystal components can be effectively used in various purposes, such as clocks, portable game consoles, word processors, notebook personal computers, car navigation systems, camcorders, personal digital assistants (Personal Digital Assistant, PDA), digital Various display devices such as cameras, mobile phones, smart phones, various monitors, LCD TVs, and information displays, or light-adjustable films, retardation films, etc. In the case of being used as a liquid crystal display device, the operation mode of the liquid crystal is not particularly limited, for example, it can be applied to twisted nematic (Twisted Nematic, TN) type, super twisted nematic (Super Twisted Nematic, STN) type, vertical alignment type (including vertical alignment-multi-domain vertical alignment (Vertical Alignment-Multi-domain Vertical Alignment, VA-MVA) type, vertical alignment-pattern vertical alignment (Vertical Alignment-Patterned Vertical Alignment, VA-PVA) type, etc.), coplanar switching (In-Plane Switching, IPS) type, fringe field switching (Fringe Field Switching, FFS) type, Optically Compensated Bend (Optically Compensated Bend, OCB) type and other action modes.

A liquid crystal display element is taken as an example, and the manufacturing method of a liquid crystal element is demonstrated. The liquid crystal display element can be manufactured by the method including the following steps 1 to 3, for example. In step 1, the board used differs depending on the desired operation mode. Step 2 and Step 3 are common in all operation modes.

(Step 1: Formation of coating film)

Firstly, the liquid crystal alignment agent is coated on the substrate, and the coated surface is preferably heated to form a coating film on the substrate. As the substrate, for example, glass such as float glass and soda glass can be used; polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly(alicyclic olefin) and other plastic transparent substrates. As the transparent conductive film provided on one side of the substrate, a Nesser (NESA) film (registered trademark of PPG Corporation of the United States) containing tin oxide (SnO ₂ ), a film containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) Indium tin oxide (Indium tin oxide, ITO) film, etc. In the case of manufacturing a TN-type, STN-type or VA-type liquid crystal element, two substrates provided with patterned transparent conductive films are used. On the other hand, when manufacturing an IPS or FFS liquid crystal element, a substrate provided with electrodes including a comb-shaped transparent conductive film or metal film and a counter substrate provided with no electrodes are used. As the metal film, for example, a film containing metal such as chromium can be used. The coating of the liquid crystal alignment agent on the substrate is preferably carried out on the electrode formation surface by lithography, spin coating, roll coater, flexo printing or inkjet printing.

After coating the liquid crystal alignment agent, in order to prevent the dripping of the coated liquid crystal alignment agent For purposes such as liquid, it is preferable to perform preheating (prebaking). The pre-baking temperature is preferably 30° C. to 200° C., and the pre-baking time is preferably 0.25 minutes to 10 minutes. Thereafter, a calcination (post-baking) step is implemented for the purpose of completely removing the solvent and optionally thermally imidizing the amide acid structure present in the polymer. The calcination temperature (post-baking temperature) at this time is preferably 80° C. to 300° C., and the post-baking time is preferably 5 minutes to 200 minutes. The film thickness of the film thus formed is preferably 0.001 μm to 1 μm. After coating the liquid crystal alignment agent on the substrate, the organic solvent is removed to form a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film.

(Step 2: Alignment Processing)

When manufacturing a TN type, STN type, IPS type or FFS type liquid crystal display element, the process (alignment process) which provides liquid crystal alignment capability to the coating film formed in the said process 1 is implemented. Thereby, the alignment ability of a liquid crystal molecule is given to a coating film, and it becomes a liquid crystal alignment film. As alignment treatment, can enumerate: Utilize the roller that wraps the cloth that comprises fiber such as nylon (nylon), rayon (rayon), cotton (cotton) for example to rub the rubbing treatment of coating film towards certain direction; A photo-alignment treatment in which a coating film formed on a substrate is irradiated with light to impart liquid crystal alignment capability to the coating film. On the other hand, in the case of producing a vertical alignment type liquid crystal element, the coating film formed in the above step 1 can be directly used as a liquid crystal alignment film, but the coating film can also be subjected to an alignment treatment. The liquid crystal alignment agent suitable for vertical alignment type liquid crystal display elements may also be suitable for use in polymer stabilized alignment (Polymer sustained alignment, PSA) type liquid crystal display elements.

(Step 3: Construction of the Liquid Crystal Cell)

A liquid crystal cell is manufactured by preparing two substrates on which the liquid crystal alignment film is formed in the above manner, and disposing liquid crystal between the two substrates facing each other. To manufacture a liquid crystal cell, for example, include: (1) arrange two substrates facing each other through a gap (spacer) so that the liquid crystal alignment films face each other, and bond the peripheral parts of the two substrates together using a sealant. The liquid crystal is injected and filled in the cell gap divided by the surface of the substrate and the sealant, and then the injection hole is sealed; (2) the sealant is applied to a predetermined position on one of the substrates on which the liquid crystal alignment film is formed, and then After dropping the liquid crystal at several places on the surface of the liquid crystal alignment film, attach another substrate in such a way that the liquid crystal alignment film faces each other, and press and expand the liquid crystal to the entire surface of the substrate (one drop filling, ODF) mode), etc. It is desirable to further heat the manufactured liquid crystal cell up to the temperature at which the liquid crystal used becomes an isotropic phase, and then gradually cool it to room temperature to remove the flow alignment at the time of liquid crystal filling.

As the sealing agent, for example, an epoxy resin containing a curing agent and alumina balls as spacers can be used. As the spacer, a photo spacer, a bead spacer, or the like can be used. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred. In addition, nematic liquid crystals or smectic liquid crystals may be used by adding, for example, cholesteric liquid crystals, chiral reagents, ferroelectric liquid crystals, and the like.

Next, if necessary, a polarizing plate is bonded to the outer surface of the liquid crystal cell. As the polarizing plate, a polarizing plate obtained by sandwiching a polarizing film called "H film" that stretches and aligns polyvinyl alcohol while absorbing iodine between cellulose acetate protective films, or a polarizing plate including an H film Polarizer itself. Obtaining liquid crystal display elements in the described manner pieces.

[Example]

Hereinafter, the present invention will be further described in detail by means of examples, but the present invention is not limited by these examples.

In the following examples, the weight average molecular weight Mw of the polymer, the imidization rate of polyimide in the polymer liquid, the solution viscosity and the epoxy equivalent of the polymer solution were measured by the following methods. The necessary amounts of raw material compounds and polymers used in the following examples were ensured by repeating the synthesis on the synthesis scale shown in the following synthesis examples as needed.

[The weight average molecular weight Mw of the polymer]

The weight average molecular weight Mw is a polystyrene conversion value measured by GPC under the following conditions.

Pipe string: manufactured by Tosoh Co., Ltd., TSKgelGRCXLII

Solvent: THF

Temperature: 40°C

Pressure: 68kgf/ ^cm2

[Imidation rate of polyimide]

Put the solution of polyimide into pure water, and after fully drying the obtained precipitate under reduced pressure at room temperature, dissolve it in deuterated dimethyl sulfide, and use tetramethylsilane as the reference substance, at room temperature ¹ H-NMR (Nuclear Magnetic Resonance, NMR) was measured. From the obtained ¹ H-NMR spectrum, the imidization rate [%] was calculated by the following formula (1).

Imidization rate[%]=(1-(A ¹ /(A ² ×α)))×100…(1)

(In formula (1), A ¹ is the peak area of the proton derived from the NH group that appears near the chemical shift of 10 ppm, A ² is the peak area derived from other protons, and α is the precursor of the polymer (polyamide The ratio of the number of other protons to one proton of the NH group in the acid)

[Solution viscosity of polymer solution]

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

[epoxy equivalent]

The epoxy equivalent is measured by the hydrochloric acid-methyl ethyl ketone method described in Japanese Industrial Standards (JIS) C 2105.

The abbreviations of the compounds are as follows. In addition, the compound (wherein X is an integer of 1-6) represented by formula (DA-X) may be simply shown as "compound (DA-X)" below.

(diamine compound)

[chemical 7]

(solvent)

<Synthesis of Polymer>

[Synthesis Example 1: Synthesis of Polyimide (PI-1)]

22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride (TCA) as tetracarboxylic dianhydride, 8.6 g (0.08 mol) of p-phenylenediamine (PDA) as diamine ) and 10.5 g (0.02 mol) of cholestanyl 3,5-diaminobenzoate (HCDA) were dissolved in 166 g of N-methyl-2-pyrrolidone (NMP), and carried out at 60°C for 6 The reaction was carried out for 1 hour to obtain a solution containing 20% by mass of polyamic acid. A small amount of the obtained polyamic acid solution was fractionated, and NMP was added to prepare a solution having a polyamic acid concentration of 10% by mass. solution, and the measured solution viscosity was 90 mPa. s.

Next, NMP was added to the obtained polyamic acid solution to prepare a solution having a polyamic acid concentration of 7% by mass, 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and a dehydration ring-closure reaction was performed at 110° C. for 4 hours. . After the dehydration ring-closure reaction, the solvent in the system is replaced with new NMP (by this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed from the system. The same below), thereby obtaining the imide-containing A solution of 26% by mass of polyimide (PI-1) with a conversion rate of about 68%. A small amount of the obtained polyimide solution was divided, and NMP was added to prepare a solution having a polyimide concentration of 10% by mass. The measured solution viscosity was 45 mPa. s. Next, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. This precipitate was washed with methanol, and dried at 40° C. for 15 hours under reduced pressure to obtain polyimide (PI-1).

[Synthesis Example 2: Synthesis of Polyimide (PI-2)]

TCA 110g (0.50 moles) and 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo- 3-furyl)naphtho[1,2-c]furan-1,3-dione 160g (0.50 mol), PDA as diamine 91g (0.85 mol), 1,3-bis(3-amine 25 g (0.10 mol) of propyl) tetramethyldisiloxane and 25 g (0.040 mol) of 3,6-bis(4-aminobenzoyloxy) cholestane, and 1.4 g (0.015 mol) of aniline was dissolved in 960 g of NMP, and reacted at 60° C. for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was divided and NMP was added to prepare a solution having a polyamic acid concentration of 10% by mass, and the measured solution viscosity was 60 mPa. s.

Next, 2,700 g of NMP was added to the obtained polyamic acid solution, 390 g of pyridine and 410 g of acetic anhydride were added, and a dehydration ring-closure reaction was performed at 110° C. for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with new γ-butyrolactone (GBL), thereby obtaining about 2,500 g of polyimide ( PI-2) 15% by mass solution. A small amount of this solution was taken, and NMP was added to prepare a solution having a polyimide concentration of 10% by mass. The measured solution viscosity was 70 mPa. s. Next, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol, and dried at 40° C. for 15 hours under reduced pressure to obtain polyimide (PI-2).

[Synthesis Example 3: Synthesis of Polyimide (PI-3)]

The diamines used were changed to 0.08 moles of 3,5-diaminobenzoic acid (3,5DAB) and 0.02 moles of cholestoxy-2,4-diaminobenzene (HCODA). , by the same method as in Synthesis Example 1 to obtain a polyamic acid solution. A small amount of the obtained polyamic acid solution was divided, and NMP was added to prepare a solution having a polyamic acid concentration of 10% by mass. The measured solution viscosity was 80 mPa. s.

Next, imidization was performed by the same method as in Synthesis Example 1 to obtain a solution containing 26% by mass of polyimide (PI-3) having an imidization rate of about 65%. A small amount of the obtained polyimide solution was divided and NMP was added to prepare a solution having a polyimide concentration of 10% by mass, and the measured solution viscosity was 40 mPa. s. Next, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. This precipitate was washed with methanol, and dried at 40° C. for 15 hours under reduced pressure to obtain polyimide (PI-3).

[Synthesis Example 4: Synthesis of Polyimide (PI-4)]

In addition to changing the diamine used to 0.06 mol of 4,4'-diaminodiphenylmethane, 0.02 mol of compound (DA-1) and 0.02 mol of compound (DA-2), by A polyamide acid solution was obtained in the same manner as in Synthesis Example 1. A small amount of the obtained polyamic acid solution was divided and NMP was added to prepare a solution having a polyamic acid concentration of 10% by mass, and the measured solution viscosity was 60 mPa. s.

Next, imidization was performed by the same method as in Synthesis Example 1 to obtain a solution containing 26% by mass of polyimide (PI-4) having an imidization rate of about 65%. A small amount of the obtained polyimide solution was divided and NMP was added to prepare a solution having a polyimide concentration of 10% by mass. The measured solution viscosity was 33 mPa. s. Next, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. This precipitate was washed with methanol, and dried at 40° C. for 15 hours under reduced pressure to obtain polyimide (PI-4).

[Synthesis Example 5: Synthesis of Polyimide (PI-5)]

The tetracarboxylic dianhydride used was changed to 0.08 mol of 1,2,3,4-cyclobutane tetracarboxylic dianhydride and 0.02 mol of pyromellitic dianhydride, and the diamine used was changed to 4-aminophenyl-4-aminobenzoate (the compound represented by the formula (DA-6)) 0.098 mol, and 3,6-bis(4-aminobenzoyloxy) A polyamic acid solution was obtained in the same manner as in Synthesis Example 1 above except that cholestane was 0.002 mol. A small amount of the obtained polyamic acid solution was divided, and NMP was added to prepare a solution having a polyamic acid concentration of 10% by mass. The measured solution viscosity was 80 mPa. s.

Then, imidization was carried out by the same method as in Synthesis Example 1 to obtain A solution containing 26% by mass of polyimide (PI-5) with an imidization rate of approximately 75%. A small amount of the obtained polyimide solution was divided, and NMP was added to prepare a solution having a polyimide concentration of 10% by mass. The measured solution viscosity was 41 mPa. s. Next, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. This precipitate was washed with methanol, and dried at 40° C. for 15 hours under reduced pressure to obtain polyimide (PI-5).

[Synthesis Example 6: Synthesis of Polyamic Acid (PA-1)]

200 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CB) as tetracarboxylic dianhydride, 2,2'-dimethyl-4,4 210g (1.0 mole) of '-diaminobiphenyl was dissolved in a mixed solvent of 370g of NMP and 3,300g of GBL, and reacted at 40°C for 3 hours to obtain a solution with a solid content concentration of 10% by mass and a solution viscosity of 160mPa ． s polyamide solution. Then, the polyamic acid solution was poured into a large excess of methanol and the reaction product was precipitated. This precipitate was washed with methanol, and dried at 40° C. for 15 hours under reduced pressure to obtain polyamic acid (PA-1).

[Synthesis Example 7: Synthesis of Polyamic Acid (PA-2)]

7.0 g (0.031 moles) of TCA as tetracarboxylic dianhydride and 13 g (corresponding to 1 mole relative to 1 mole of TCA) of compound (DA-5) as diamine were dissolved in 80 g of NMP. The reaction was carried out at 60° C. for 4 hours to obtain a solution containing 20% by mass of polyamic acid (PA-3). The solution viscosity of the polyamide acid solution is 2,000mPa. s. Furthermore, compound (DA-5) was synthesized according to the description in JP-A-2011-100099. Then, the polyamic acid solution was poured into a large excess of methanol and the reaction product was precipitated. The precipitate was washed with methanol, It was dried under reduced pressure at 40°C for 15 hours to obtain polyamic acid (PA-2).

[Synthesis Example 8: Synthesis of Polyamide Acid (PA-3)]

The diamine used was changed to 0.7 moles of 1,3-bis(4-aminophenethyl)urea and 0.3 moles of compound (DA-2). The method obtains the polyamic acid solution. A small amount of the obtained polyamic acid solution was divided and NMP was added to prepare a solution having a polyamic acid concentration of 10% by mass, and the measured solution viscosity was 70 mPa. s. Then, the polyamic acid solution was poured into a large excess of methanol and the reaction product was precipitated. This precipitate was washed with methanol, and dried at 40° C. for 15 hours under reduced pressure to obtain polyamic acid (PA-3).

[Synthesis Example 9: Synthesis of polyamide acid (PA-4)]

The tetracarboxylic dianhydride used was changed to 1.0 mole of 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, and the diamine used was changed to p-phenylene 0.3 moles of diamine, 0.2 moles of compound (DA-3), and 0.5 moles of 1,2-bis(4-aminophenoxy)ethane. The method obtains the polyamic acid solution. A small amount of the obtained polyamic acid solution was divided and NMP was added to prepare a solution having a polyamic acid concentration of 10% by mass, and the measured solution viscosity was 90 mPa. s. Then, the polyamic acid solution was poured into a large excess of methanol and the reaction product was precipitated. This precipitate was washed with methanol, and dried at 40° C. for 15 hours under reduced pressure to obtain polyamic acid (PA-4).

[Synthesis Example 10: Synthesis of Polyamic Acid (PA-5)]

The diamine used was changed to 0.2 mol of 2,4-diamino-N,N-diallylaniline, 0.2 mol of 4,4'-diaminodiphenylamine, and 4,4' -Diaminodiphenylmethane 0.6 Except for this, a polyamic acid solution was obtained by the same method as in Synthesis Example 6 above. A small amount of the obtained polyamic acid solution was divided, and NMP was added to prepare a solution having a polyamic acid concentration of 10% by mass. The measured solution viscosity was 95 mPa. s. Then, the polyamic acid solution was poured into a large excess of methanol and the reaction product was precipitated. This precipitate was washed with methanol, and dried at 40° C. for 15 hours under reduced pressure to obtain polyamic acid (PA-5).

[Synthesis Example 11: Synthesis of Polyamide Ester (PAE-1)]

Add 0.035 moles of 2,4-bis(methoxycarbonyl)-1,3-dimethylcyclobutane-1,3-dicarboxylic acid to 20ml of thionyl chloride, add a catalytic amount of N , N-dimethylformamide, and then stirred at 80° C. for 1 hour. Then, the reaction solution was concentrated, and the residue was dissolved in 113 g of γ-butyrolactone (GBL) (this solution was referred to as reaction solution A). Separately, 0.01 mol of p-phenylenediamine, 0.01 mol of 1,2-bis(4-aminophenoxy)ethane, and 0.014 mol of compound (DA-4) were added to 6.9 g of pyridine, 44.5 g of It was dissolved in NMP and 33.5 g of GBL, and cooled to 0°C. Then, the reaction liquid A was slowly added dropwise to this solution over 1 hour, and after completion of the dropwise addition, it was stirred at room temperature for 4 hours. The obtained polyamic acid ester solution was added dropwise to 800 ml of pure water while stirring, and the deposited precipitate was filtered. Next, 15.5 g of polymer powders were obtained by washing five times with 400 ml of isopropyl alcohol (IPA) and drying. The weight average molecular weight Mw of the obtained polyamide ester (PAE-1) was 34,000.

[Synthesis Example 12: Synthesis of polyorganosiloxane (APS-1))]

Add 100.0 g of 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS) and 500 g of methyl isobutyl ketone to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube and 10.0 g of triethylamine were mixed at room temperature. Then, after adding 100 g of deionized water dropwise from the dropping funnel over 30 minutes, the reaction was performed at 80° C. for 6 hours while stirring under reflux. After the reaction, the organic layer was taken out, washed with 0.2 mass % ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure, thereby obtaining the reaction in the form of a viscous transparent liquid. Non-toxic polyorganosiloxane (EPS-1). As a result of ¹ H-NMR analysis of this reactive polyorganosiloxane (EPS-1), a peak due to the epoxy group was obtained around chemical shift (δ)=3.2ppm, which was consistent with the theoretical intensity, confirming that No side reaction of epoxy group occurred in the reaction. The weight average molecular weight Mw of the obtained reactive polyorganosiloxane was 3,500, and the epoxy equivalent was 180 g/mol.

Then, 10.0 g of reactive polyorganosiloxane (EPS-1), 30.28 g of methyl isobutyl ketone as a solvent, and 4-dodecyloxybenzene as a reactive compound were added to a 200 mL three-necked flask. 3.98 g of formic acid and 0.10 g of UCAT 18X (trade name, manufactured by San-Apro Co., Ltd.) as a catalyst were reacted at 100° C. for 48 hours while stirring. After the reaction was completed, ethyl acetate was added to the reaction mixture, the obtained solution was washed three times with water, the organic layer was dried with magnesium sulfate, and the solvent was distilled off to obtain liquid crystal alignment polyorganosiloxane (APS- 1) 9.0g. The weight average molecular weight Mw of the obtained polymer was 9,900.

[Example 1]

1. Preparation of liquid crystal alignment agent

γ-enantholactone (γHL), N-methyl-2-pyrrolidone (NMP) and Ding Basecellosu (BC) was prepared as a solution having a solid content concentration of 6.5% by mass and a solvent mixing ratio of γHL:NMP:BC=40:30:30 (mass ratio). After the solution was fully stirred, it was filtered through a filter with a pore diameter of 1 μm, thereby preparing a liquid crystal alignment agent (S-1). Furthermore, the liquid crystal alignment agent (S-1) is mainly used in the manufacture of vertical alignment type liquid crystal display elements.

2. Evaluation of surface roughness (printability)

The liquid crystal alignment agent (S-1) prepared in the above 1. was coated on the glass substrate using a rotator, and after pre-baking for 1 minute using a heating plate at 80°C, the chamber was replaced with nitrogen at 200 The coating film with an average film thickness of 0.1 µm was formed by heating in an oven at °C for 1 hour (post-baking). The surface of the obtained coating film was observed with an atomic force microscope (AFM), and the center average roughness (Ra) was measured. When Ra was 5 nm or less, the printability was evaluated as "good (◯)", when it was greater than 5 nm and less than 10 nm, it was evaluated as "possible (△)", and when it was more than 10 nm, it was evaluated as "poor (×)". As a result, the printability was evaluated as "good" in this Example.

3. Evaluation of continuous printability

About the liquid crystal aligning agent (S-1) prepared above, the printability (continuous printability) when printing to a board|substrate was performed continuously was evaluated. Evaluation was performed as follows. First, using a liquid crystal alignment film printer (manufactured by Nippon Photo Printing Machine Co., Ltd., Angstromer type "S40L-532"), the liquid crystal alignment agent (S-1 ) was printed on the transparent electrode surface of a glass substrate with a transparent electrode including an ITO film under the condition of 20 drops (about 0.2 g) back and forth. The printing on the board|substrate was implemented 20 times using the new board|substrate at intervals of 1 minute.

Next, the liquid crystal alignment agent (S-1) was distributed (single pass) onto the anilox roller at intervals of 1 minute, and each time a total of 10 operations were performed to bring the anilox roller into contact with the printing plate (hereinafter referred to as idling) ( During this period, printing on the glass substrate was not performed). In addition, this idling operation is performed in order to carry out the printing of a liquid crystal alignment agent intentionally under severe conditions.

After 10 idling cycles, the glass substrate is used for formal printing. In the actual printing, after idling, put 5 substrates at intervals of 30 seconds, heat each printed substrate at 80°C for 1 minute (pre-baking) to remove the solvent, and then heat at 200°C for 10 minutes (post-baking) ), forming a coating film with a film thickness of approximately 0.08 μm. Printability (continuous printability) was evaluated by observing this coating film with the microscope of 20 times magnification. In the evaluation, the case where no polymer precipitation was observed in the first main printing after idling was evaluated as "good (○)" for continuous printability, and the case where polymer precipitation was observed in the first main printing after idling was evaluated as "good (○)". Continuous printability was evaluated as "possible (△)" when no polymer precipitation was observed during five main printings, and continuous printability was evaluated when polymer precipitation was observed after repeated five main printings "Bad (×)". As a result, the continuous printability was "good (◯)" in this example. In addition, regarding the liquid crystal alignment agent with good printability, it has been found by experiments that the precipitation of the polymer is improved (disappeared) during the continuous feeding into the substrate. In addition, the number of idle rotations was changed to 15, 20, and 25 times, and the printability of the liquid crystal alignment agent was evaluated in the same manner as described above. As a result, in this example, the idle rotations were set to 15 and 20 times. "Good (○)" at the first time, and "OK (△)" at the 25th time.

4. Coatability evaluation on fine uneven surface

Using the ITO electrode substrate 10 for evaluation shown in FIG. 1( a ) and FIG. 1( b ), the applicability of the liquid crystal alignment agent to the surface of the fine unevenness was evaluated. As the ITO electrode substrate 10 for evaluation, it was used on one surface of a glass substrate 11 in which a plurality of stripe-shaped ITO electrodes 12 were arranged at predetermined intervals (see FIG. 1( a ) and FIG. 1( b )). In addition, the electrode width A was set to 50 μm, the distance B between electrodes was set to 2 μm, and the electrode height C was set to 0.2 μm. Using the wettability evaluation device LSE-A100T (manufactured by NIC), the liquid crystal alignment agent (S-1) prepared in the above 1. was dripped on the electrode formation surface of the ITO electrode substrate 10 for this evaluation, and the evaluation effect was The ease of fusion of the uneven surface of the substrate. At this time, the larger the wetting spread of the droplet (specifically, the larger the wetting spread area S (mm ² /μL) of the droplet relative to the liquid volume), the greater the effect of the liquid crystal alignment agent on the fine uneven surface. The better the applicability is.

In the evaluation, the case where the area S was 15 mm ² /μL or more was rated as “excellent (◎)”, the case where the area S was 10 mm ² /μL or more and less than 15 mm ² /μL was rated as “good (○)”, and the area S was rated as “good (○)”. When S was greater than 5 mm ² /μL and less than 10 mm ² /μL, it was evaluated as “acceptable (Δ)”, and when the area S was 5 mm ² /μL or less, it was evaluated as “poor (×)”. As a result, in this example, the area S was 10 mm ² /µL, and the applicability to the surface of fine unevenness was judged as "good".

5. Fabrication of Vertically Aligned Liquid Crystal Cells

Using a liquid crystal alignment film printer (manufactured by Nippon Photo Printing Co., Ltd.), the liquid crystal alignment agent (S-1) prepared in the above 1. was coated on a transparent film with a fine slit ITO electrode structure. The glass substrate of the electrode, and the transparent electrode surface of the glass substrate with a transparent electrode having a patterned ITO electrode structure. Then, after removing the solvent by heating on a hot plate at 80° C. for 1 minute (pre-baking), proceed on a hot plate at 180° C. Heating (post-baking) was performed for 10 minutes to form a coating film with an average film thickness of 0.8 μm. Each substrate after the coating film was formed was ultrasonically cleaned in ultrapure water for 1 minute, and then dried in a clean oven at 100° C. for 10 minutes. Thereby, a pair (2 pieces) of substrates having a liquid crystal alignment film was obtained.

Secondly, after coating the outer edge of the surface with the liquid crystal alignment film with an epoxy resin adhesive added with alumina balls with a diameter of 5.5 μm, a pair of substrates are overlapped and crimped in such a way that the faces of the liquid crystal alignment film face each other, so that the adhesive Adhesive hardening. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck) was filled between the pair of substrates from the liquid crystal inlet, and the liquid crystal inlet was sealed with an acrylic light-curing adhesive to manufacture a liquid crystal cell.

Moreover, the liquid crystal cell was manufactured by the method similar to the above except having changed post-baking temperature from 180 degreeC to 120 degreeC or 230 degreeC, respectively. The obtained liquid crystal cell was used for the following 6. evaluation.

6. Evaluation of the deviation characteristic (post-baking margin) of the pretilt angle with respect to the post-baking temperature unevenness

The pretilt angles of the liquid crystal cells obtained by fabricating the liquid crystal alignment film at different post-baking temperatures (120° C., 180° C. and 230° C.) were respectively measured. Then, the measured value at 230°C is set as the reference pretilt angle θp, and the deviation of the pretilt angle relative to the temperature variation of the post-baking is evaluated from the difference Δθ (=θp-θa) between the reference pretilt angle θp and the measured value θa. characteristic. In addition, the smaller Δθ is, the smaller the variation of the pretilt angle with respect to temperature unevenness is, and the more excellent it is. In the measurement of the pretilt angle, it will be based on the non-patent literature "T.J. Scheffer et.al. (T.J.Scheffer et.al.) Journal of Applied Physics, Volume 19, Page 2013 (J.Appl.Phys.vo.19, p. 2013)(1980)", the value of the inclination angle of liquid crystal molecules with respect to the substrate surface measured by the crystal rotation method using He-Ne laser light was defined as the pretilt angle [°]. In the evaluation, the case where △θ was 0.2° or less was evaluated as "good (○)", the case of greater than 0.2° and less than 0.5° was evaluated as "acceptable (△)", and the case of 0.5° or more was evaluated as "poor (×)". As a result, in this Example, when the post-baking temperature was 180°C, the post-baking margin was evaluated as "good", and when the post-baking temperature was 120°C, it was evaluated as "possible".

7. Evaluation of AC afterimage characteristics

A liquid crystal cell for evaluation was produced in the same manner as in 5. above, except that the electrode structure was two systems of ITO electrodes (electrode 1 and electrode 2 ) capable of switching application/non-application of voltage. This liquid crystal cell for evaluation was placed at 60° C., no voltage was applied to the electrode 2 , and an AC voltage of 10 V was applied to the electrode 1 for 300 hours. Immediately after 300 hours had elapsed, an AC voltage of 3 V was applied to both the electrode 1 and the electrode 2, and the difference ΔT [%] in light transmittance between both electrodes was measured. At this time, the case where ΔT was less than 2% was rated as "good (○)", the case where 2% or more and less than 3% was rated as "possible (△)", and the case where 3% or more was rated It is "Bad (×)". As a result, it was evaluated as "good" in this Example.

8. Evaluation of DC afterimage characteristics

The liquid crystal cell for evaluation was placed at 60° C., a DC voltage of 0.5 V was applied to the electrode 1 for 24 hours, and the voltage remaining in the electrode 1 after the DC voltage was cut off (residual DC voltage) was obtained by the scintillation removal method. At this time, the case where the residual DC voltage was less than 100mV was evaluated as "good (○)" in the DC afterimage characteristic, and the case where the residual DC voltage was 100mV or more and less than The case of 300 mV was evaluated as "acceptable (Δ)", and the case of 300 mV or more was evaluated as "poor (x)". As a result, it was evaluated as "good" in this Example.

[Example 2～Example 10 and Comparative Example 1～Comparative Example 8]

The type and compounding amount of the polymer, and the solvent composition are respectively set as described in the following Table 1, except that, the liquid crystal alignment agent (S-2 ~ S-10, SR- 1~SR-8). In addition, various evaluations were performed in the same manner as in Example 1 using the prepared liquid crystal alignment agent. The evaluation results are shown in Table 2 below.

[Example 11]

1. Preparation of liquid crystal alignment agent

A liquid crystal alignment agent (S-11) was prepared in the same manner as in Example 1 except that the polymer component and the solvent composition were changed as described in the following Table 1. Furthermore, the liquid crystal alignment agent (S-11) is mainly used in the manufacture of horizontal alignment type liquid crystal display elements.

2. Evaluation of liquid crystal alignment agent

Except having used the liquid crystal alignment agent (S-11), it carried out similarly to Example 1, and evaluated the surface roughness, continuous printing property, and the applicability to the surface of fine roughness. These results are shown in Table 2 below.

3. Fabrication of rubbed FFS type liquid crystal cell

Use a spinner to apply the liquid crystal alignment agent (S-11) prepared in the above 1. on the glass substrate on which a flat plate electrode, an insulating layer and a comb-shaped electrode are sequentially laminated on one side and the opposite glass substrate without an electrode. Each surface was heated for 1 minute on a hot plate at 80° C. (pre-baking). Then, in the 230 that carried out nitrogen replacement in the storehouse Drying (post-baking) was performed in an oven at °C for 30 minutes to form a coating film with an average film thickness of 0.1 μm. The surface of the coating film was subjected to rubbing treatment with a rubbing machine having a roller wound with rayon cloth at a roller rotation speed of 400 rpm, a table moving speed of 3 cm/sec, and a bristle indentation length of 0.1 mm. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a clean oven at 100° C. for 10 minutes, thereby obtaining a substrate with a liquid crystal alignment film.

Then, for a pair of substrates with a liquid crystal alignment film, leave a liquid crystal injection port at the edge of the surface on which the liquid crystal alignment film is formed, and apply epoxy resin adhesive with alumina balls with a diameter of 5.5 μm by screen printing. After laying, the substrates were laminated and bonded by pressure, and the adhesive was thermally cured at 150° C. for 1 hour. Next, after filling nematic liquid crystal (Merck & Co., MLC-7028) between the pair of substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy-based adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, after heating this at 120 degreeC, it was gradually cooled to room temperature, and the liquid crystal cell was manufactured.

4. Evaluation of liquid crystal cell

Except having used the rubbed FFS type liquid crystal cell obtained in said 3., the post-baking margin, AC afterimage characteristic, and DC afterimage characteristic were evaluated similarly to Example 1. These results are shown in Table 2 below.

[Example 12 and Example 13]

A liquid crystal alignment agent (S-12) and a liquid crystal alignment agent (S-13) were prepared in the same manner as in Example 1, except that the polymer component and the solvent composition were changed as described in Table 1 below. In addition, the surface roughness, Various evaluations were performed for continuous printing property and coating property to a fine uneven surface, and a rubbed FFS type liquid crystal cell was manufactured in the same manner as in Example 11. These results are shown in Table 2 below.

[Example 14]

1. Preparation of liquid crystal alignment agent

A liquid crystal alignment agent (S-14) was prepared in the same manner as in Example 1 except that the polymer component and the solvent composition were changed as described in the following Table 1. Furthermore, the liquid crystal alignment agent (S-14) is mainly used in the manufacture of PSA-type liquid crystal display elements.

2. Evaluation of liquid crystal alignment agent

Except having used the liquid crystal alignment agent (S-14), it carried out similarly to Example 1, and evaluated the surface roughness, continuous printing property, and the applicability to the surface of fine roughness. These results are shown in Table 2 below.

3. Preparation of liquid crystal composition

To 10 g of nematic liquid crystals (manufactured by Merck, MLC-6608), 5% by mass of the liquid crystal compound represented by the following formula (L1-1) and 0.3% by mass of the liquid crystal compound represented by the following formula (L2-1) were added. The indicated photopolymerizable compounds were mixed to obtain a liquid crystal composition LC1.

4. Manufacture of PSA type liquid crystal unit

Using a liquid crystal alignment film printer (manufactured by Nippon Photo Printing Co., Ltd.) The prepared liquid crystal alignment agent (S-14) was coated on each electrode surface of two glass substrates with conductive films containing ITO electrodes, heated (pre-baked) on a hot plate at 80°C for 2 minutes and the solvent After the removal, it was heated (post-baked) on a hot plate at 150° C. for 10 minutes to form a coating film with an average film thickness of 0.06 μm. These coating films were cleaned by ultrasonic waves for 1 minute in ultrapure water, and then dried in a clean oven at 100° C. for 10 minutes to obtain a pair (two) of substrates with liquid crystal alignment films. In addition, the pattern of the electrode used is the same kind of pattern as the electrode pattern in PSA mode.

Then, on the outer edge of the surface with the liquid crystal alignment film of one of the pair of substrates, after coating the epoxy resin adhesive with aluminum oxide balls with a diameter of 5.5 μm, the surface of the liquid crystal alignment film is opposite. way overlapping and crimping to harden the adhesive. Then, after filling the prepared liquid crystal composition LC1 between the pair of substrates from the liquid crystal injection port, the liquid crystal injection port is sealed with an acrylic light-curing adhesive, thereby manufacturing a liquid crystal cell. Thereafter, AC 10V at a frequency of 60 Hz was applied between the conductive films of the liquid crystal cell to drive the liquid crystal, and ultraviolet rays were irradiated at an irradiation dose of 100,000 J/m ² using an ultraviolet irradiation device using a metal halide lamp as the light source. In addition, this irradiation amount is the value measured using the light meter which measures based on wavelength 365nm.

5. Evaluation of liquid crystal cell

Except having used the PSA type liquid crystal cell obtained in said 4., the post-baking margin, AC afterimage characteristic, and DC afterimage characteristic were evaluated similarly to Example 1. These results are shown in Table 2 below.

[Example 15~Example 17, Example 27, Example 28]

Liquid crystal alignment agents were prepared in the same manner as in Example 1, except that the polymer component and the solvent composition were changed as described in the following Table 1. In addition, except for using each liquid crystal alignment agent, in the same manner as in Example 1, the surface unevenness, continuous printing property, and coating property to the surface of fine unevenness were evaluated, and in the same manner as in Example 14, a PSA type liquid crystal cell was produced. various evaluations. These results are shown in Table 2 below.

[Example 18]

1. Preparation of liquid crystal alignment agent

A liquid crystal alignment agent (S-18) was prepared in the same manner as in Example 1 except that the polymer component and the solvent composition were changed as described in the following Table 1. Furthermore, the liquid crystal alignment agent (S-18) is mainly used in the manufacture of optical vertical alignment type liquid crystal display elements.

2. Evaluation of liquid crystal alignment agent

Except having used the liquid crystal alignment agent (S-18), it carried out similarly to Example 1, and evaluated the surface roughness, continuous printing property, and the applicability to the surface of fine roughness. These results are shown in Table 2 below.

3. Fabrication of Optical Vertically Aligned Liquid Crystal Cells

The prepared liquid crystal alignment agent (S-18) was coated on the transparent electrode surface of the glass substrate with transparent electrodes including the ITO film using a spinner, and pre-baked for 1 minute by using a heating plate at 80°C. Then, it heated at 230 degreeC for 1 hour in the oven which substituted the inside of a chamber with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. Next, using a Hg-Xe lamp and a Glan-Taylor prism, the surface of the coating film was irradiated with polarized ultraviolet rays of 1,000 J/m ² including a bright line of 313 nm from a direction inclined 40° from the normal line of the substrate. And endow the liquid crystal with alignment ability. Repeat the same operation to make a pair (two) of substrates with liquid crystal alignment films.

On the outer periphery of the surface with the liquid crystal alignment film of one of the substrates, an epoxy resin adhesive containing alumina balls with a diameter of 3.5 μm was applied by screen printing, and the liquid crystals of the pair of substrates were aligned. The film surfaces faced each other, and pressure bonding was performed so that the optical axis of ultraviolet light of each substrate was antiparallel to the projection direction of the substrate surface, and the adhesive was thermally cured at 150° C. for 1 hour. Next, after filling the gap between the substrates from the liquid crystal injection port with a negative type liquid crystal (MLC-6608, manufactured by Merck), the liquid crystal injection port was sealed with an epoxy-based adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, it heated at 130 degreeC, and cooled gradually to room temperature.

4. Evaluation of liquid crystal cell

The post-baking margin, AC afterimage characteristics, and DC afterimage characteristics were evaluated in the same manner as in Example 1 except that the optical vertical alignment type liquid crystal cell obtained in the above 3. was used. These results are shown in Table 2 below.

[Example 19 and Example 20]

Liquid crystal alignment agents were prepared in the same manner as in Example 1, except that the polymer component and the solvent composition were changed as described in the following Table 1. In addition, except for using each liquid crystal alignment agent, in the same manner as in Example 1, the surface unevenness, continuous printability, and coatability to the surface of fine unevenness were evaluated, and in the same manner as in Example 18, an optical vertical alignment type was produced. Various evaluations were performed for liquid crystal cells. These results are shown in Table 2 below.

[Example 21]

1. Preparation of liquid crystal alignment agent

A liquid crystal alignment agent (S-21) was prepared in the same manner as in Example 1, except that the polymer component and the solvent composition were changed as described in the following Table 1. Furthermore, the liquid crystal alignment agent (S-21) is mainly used in the manufacture of optical horizontal alignment type liquid crystal display elements.

2. Evaluation of liquid crystal alignment agent

Except having used the liquid crystal alignment agent (S-21), it carried out similarly to Example 1, and evaluated the surface roughness, continuous printing property, and the applicability to the surface of fine roughness. These results are shown in Table 2 below.

3. Fabrication of Optical Horizontal Alignment Liquid Crystal Cells

Use a spinner to apply the liquid crystal alignment agent (S-21) prepared above on each of the glass substrates on which a flat electrode, an insulating layer, and a comb-shaped electrode are sequentially laminated on one side and the opposite glass substrate without an electrode. surface and heat (pre-bake) on a hot plate at 80°C for 1 minute. Then, it dried (post-baked) for 30 minutes in the oven of 230 degreeC which substituted nitrogen gas in the chamber, and formed the coating film with an average film thickness of 0.1 micrometer. A Hg-Xe lamp was used to irradiate the surface of the coating film with 1,000 J/m ² of ultraviolet light including a linearly polarized 254 nm bright line from the normal direction of the substrate to perform photo-alignment treatment to form a liquid crystal alignment film on the substrate.

Then, for a pair of substrates with a liquid crystal alignment film, leave a liquid crystal injection port at the edge of the surface on which the liquid crystal alignment film is formed, and apply epoxy resin adhesive with alumina balls with a diameter of 5.5 μm by screen printing. After laying, the substrates were stacked and pressure-bonded so that the projection direction of the polarization axis to the substrate surface during light irradiation was antiparallel, and the adhesive was thermally cured at 150° C. for 1 hour. Then, between a pair of substrates from the liquid crystal injection After filling the port with a nematic liquid crystal (MLC-7028, manufactured by Merck & Co., Ltd.), the liquid crystal injection port was sealed with an epoxy-based adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, after heating this at 120 degreeC, it was gradually cooled to room temperature, and the liquid crystal cell was manufactured.

4. Evaluation of liquid crystal cell

The post-baking margin, AC afterimage characteristics, and DC afterimage characteristics were evaluated in the same manner as in Example 1 except that the optical horizontal alignment type liquid crystal cell obtained in the above 3. was used. These results are shown in Table 2 below.

[Example 22~Example 26]

Liquid crystal alignment agents were prepared in the same manner as in Example 1, except that the polymer component and the solvent composition were changed as described in the following Table 1. In addition, except for using each liquid crystal alignment agent, the surface unevenness, continuous printing property, and coating property to the fine uneven surface were evaluated in the same manner as in Example 1, and an optical horizontal alignment type was produced in the same manner as in Example 21. Various evaluations were performed for liquid crystal cells. These results are shown in Table 2 below.

[Example 29]

1. Preparation of liquid crystal alignment agent

A liquid crystal alignment agent (S-29) was prepared in the same manner as in Example 1 except that the polymer component and the solvent composition were changed as described in the following Table 1. Furthermore, the liquid crystal alignment agent (S-29) is mainly used in the manufacture of TN-mode liquid crystal display elements.

2. Evaluation of liquid crystal alignment agent

Except having used the liquid crystal alignment agent (S-29), it carried out similarly to Example 1, and evaluated the surface roughness, continuous printing property, and the applicability to the surface of fine roughness. Will These results are shown in Table 2 below.

3. Manufacture of TN type liquid crystal cell

Use a spinner to coat the liquid crystal alignment agent (S-29) prepared in the above 1. on the transparent electrode surface of the glass substrate with transparent electrodes containing the ITO film, and use a heating plate at 80°C for 1 minute pre-baking . Then, it heated at 230 degreeC for 1 hour in the oven which replaced the inside of a chamber with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. The coating film was subjected to a rubbing treatment with a rubbing machine having a roller wound with a rayon cloth at a roller rotation speed of 400 rpm, a platen moving speed of 3 cm/sec, and a bristle indentation length of 0.1 mm. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a clean oven at 100° C. for 10 minutes, thereby obtaining a substrate with a liquid crystal alignment film. This series of operations is repeated to prepare a pair (two) of substrates with liquid crystal alignment films.

On the outer periphery of the surface with the liquid crystal alignment film of one of the substrates, use screen printing to coat the epoxy resin adhesive with alumina balls with a diameter of 3.5 μm, and make the respective liquid crystal alignment film surfaces face each other. Overlap and crimp in such a way that the adhesive hardens. Next, after filling nematic liquid crystal (Merck & Co., MLC-6221) between the pair of substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an acrylic light-curable adhesive.

4. Evaluation of liquid crystal cell

Except having used the TN type liquid crystal cell obtained in said 3., the post-baking margin, AC afterimage characteristic, and DC afterimage characteristic were evaluated similarly to Example 1. These results are shown in Table 2 below.

[Table 1]

In Table 1, the numerical value of the polymer composition represents that each polymer is relative to the liquid crystal The compounding ratio (parts by mass) of 100 parts by mass in total of the polymer components used in the preparation of the additive. The numerical value of a solvent composition shows the compounding ratio (mass part) of each solvent with respect to the total 100 mass parts of the solvent components used for preparation of a liquid crystal aligning agent. The abbreviations of the compounds are as follows.

<solvent>

a: γ-enantholactone

b: γ-octylactone

c: γ-nonanolide

d: γ-Undecylactone

e: δ-octyl lactone

f: δ-decalactone

g: δ-Lauryl lactone

h: δ-tridecanolide

i: α-angelicalide

j: β-angelica lactone

k: N-acetyl-ε-caprolactam

L: γ-butyrolactone

m: γ-valerolactone

n: γ,γ-Dimethyl-γ-butyrolactone

o: δ-valerolactone

p: N-methylcaprolactam

q: 1,3-Dimethyl-2-imidazolidinone

r: N-methyl-2-pyrrolidone

s: butyl cellosu

t: diacetone alcohol

u: diethylene glycol diethyl ether

v: N-ethyl-2-pyrrolidone

As can be seen from Table 2, in Examples 1 to 29 containing the solvent [A], the surface unevenness, continuous printing property, and coating property on the finely uneven surface were all "excellent", "good" or "Yes" rating. In addition, the post-baking margin was also small, and the AC afterimage characteristics and DC afterimage characteristics of the obtained liquid crystal display element were evaluated as "good" or "possible".

On the other hand, in Comparative Example 1 to Comparative Example 8 that did not contain the solvent [A], the coatability to the surface of fine unevenness was inferior to that of Examples. In addition, in Comparative Examples 1 to 3, the polymer was easily precipitated, and the continuous printability was also poor.

Claims (10)

A liquid crystal alignment agent, which contains a polymer component and a solvent component, and the solvent component includes a solvent [A], and the solvent [A] is selected from a 5-membered cyclic lactone, a 6-membered cyclic lactone, and a 7-membered cyclic lactone At least one of the group consisting of amines, and has an alkyl group selected from 2 to 10 carbons, an alkoxy group with 2 to 10 carbons, an alkoxyalkyl group with 2 to 10 carbons, and an alkyl group with 2 to 10 carbons. Alkoxyalkoxyalkyl with 10, alkoxyalkoxy with 2 to 10 carbons, group [-COR ¹² ] (wherein R ¹² is an alkyl with 1 to 3 carbons), and a part of the ring At least one partial structure in the group consisting of carbon-carbon double bonds, the content ratio of the solvent [A] is 10% by mass or more relative to the total amount of the solvent component. The liquid crystal alignment agent as described in Item 1 of the scope of the patent application, wherein the solvent [A] is selected from the compound represented by the following formula (1), the compound represented by the following formula (2) and the following formula ( 3) At least one of the group consisting of the represented compounds,

(In formula ( ¹ ), R1 is an alkyl group with 2 to 10 carbons, an alkoxy group with 2 to 10 carbons, an alkoxyalkyl group with 2 to 10 carbons, an alkoxy group with 2 to 10 carbons Alkoxyalkyl or alkoxyalkoxy with 2 to 10 carbons; n is 1 or 2)

(In formula (2), R ² is a divalent group represented by the following formula (4-1) or formula (4-2))

(In formula (4-1) and formula (4-2), R ⁴ ~ R ¹¹ are each independently a hydrogen atom or an alkyl group with 1 to 5 carbons; "*1" represents a bond with an oxygen atom )

(In formula (3), R ³ is an alkyl group with 1 to 3 carbon atoms). The liquid crystal alignment agent as described in item 1 or item 2 of the scope of patent application, wherein the solvent component further includes a solvent [B], and the solvent [B] is selected from alcohol-based solvents, chain ester-based solvents, ethers At least one of the group consisting of solvents and ketone solvents. The liquid crystal alignment agent described in item 3 of the scope of the patent application, wherein relative to the total amount of the solvent component, the content ratio of the solvent [B] is 20% by mass to 90% by mass. The liquid crystal alignment agent as described in claim 3 of the patent application, wherein the solvent component further includes a solvent [C] having a boiling point of 200° C. or higher at 1 atmosphere. The liquid crystal alignment agent described in item 5 of the scope of the patent application, wherein relative to the total amount of the solvent component, the content ratio of the solvent [B] is 20% by mass to 80% by mass, and relative to the solvent component The total amount, the content ratio of the solvent [C] is 10% by mass to 70% by mass. The liquid crystal alignment agent described in item 1 or item 2 of the scope of the patent application, It contains at least one selected from the group consisting of polyamic acid, polyamide ester and polyimide as the polymer component. A method for manufacturing a liquid crystal element, which uses the liquid crystal alignment agent described in any one of the first to seventh items of the patent application to form a liquid crystal alignment film. A liquid crystal alignment film, which is formed by using the liquid crystal alignment agent described in any one of items 1 to 7 of the patent application. A liquid crystal element, which includes the liquid crystal alignment film described in item 9 of the patent application.

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