KR20190095405A - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element - Google Patents

Abstract

Tetra containing at least 1 sort (s) chosen from tetracarboxylic dianhydride represented by following formula (1), and its derivative (s), and at least 1 sort (s) chosen from tetracarboxylic dianhydride represented by following formula (2), and its derivative (s). At least one polymer selected from a polyimide precursor obtained from a carboxylic acid derivative component and a diamine component containing at least one diamine selected from the following formulas (3) and (4) and an imide: Liquid crystal aligning agent containing.

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element

This invention relates to the liquid crystal aligning agent used for manufacture of a liquid crystal display element, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and the liquid crystal display element using this liquid crystal aligning film.

In the liquid crystal display element used for a liquid crystal television, a liquid crystal display, etc., the liquid crystal aligning film for controlling the arrangement state of a liquid crystal is formed in an element normally. Currently, the most widely used liquid crystal aligning film is a so-called rubbing of the surface of a film made of a polyamic acid formed on an electrode substrate and / or a polyimide imidized thereof in one direction with a cloth such as cotton, nylon, or polyester. It is manufactured by performing a rubbing process.

The rubbing process of the film surface in the alignment process of a liquid crystal aligning film is the industrially useful method which is simple and was excellent in productivity. However, the demand for higher performance, higher definition, and larger size of the liquid crystal display device becomes higher, and scratches, oscillations, influences of mechanical forces and static electricity on the surface of the alignment film generated by the rubbing treatment, and further, within the alignment treatment surface Various problems, such as nonuniformity, become clear. As a liquid-crystal aligning method which replaces a rubbing process, the photo-alignment method which gives a liquid crystal aligning ability by irradiating polarized radiation is known. As a liquid crystal aligning process by the photo-alignment method, the thing using the photoisomerization reaction, the thing using the photocrosslinking reaction, the thing using the photolysis reaction, etc. are proposed (refer nonpatent literature 1).

Moreover, in patent document 1, using the polyimide membrane which has alicyclic structures, such as a cyclobutane ring, in a principal chain for the photo-alignment method is proposed. Such a photo-alignment method can provide liquid crystal aligning ability by the industrially easy manufacturing process. In addition, in the liquid crystal display element of the IPS driving method or the fringe field switching (hereinafter referred to as FFS) driving method, the liquid crystal alignment film to which the liquid crystal alignment ability is imparted by the photo alignment method is provided with the liquid crystal alignment film to which the liquid crystal alignment ability is imparted by the rubbing treatment. In comparison with this, improvement in contrast and viewing angle characteristics of the liquid crystal display device can be expected. As described above, the optical alignment method as described above is attracting attention as a promising liquid crystal alignment treatment method because it is possible to improve the performance of the liquid crystal display element. As a liquid crystal aligning film used for the liquid crystal display element of an IPS drive system or an FFS drive system, in addition to basic characteristics, such as excellent liquid crystal orientation and electrical characteristics, long-term alternating current drive which arises in the liquid crystal display element of an IPS drive system or an FFS drive system It is necessary to suppress the afterimage caused by.

Japanese Patent Laid-Open No. 9-297313

 "Liquid Crystal Light Alignment Film" Kidowaki, Ichimura Functional Materials November 1997 Vol.17, No.11 Pages 13 to 22

The liquid crystal which has a liquid crystal aligning agent which can suppress the afterimage by long-term alternating current drive which arises in the liquid crystal display element of an IPS drive system or a FFS drive system, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and this liquid crystal aligning film. It is an object to provide a display element.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to achieve the said objective, As a result, the polyimide obtained from the tetracarboxylic-acid derivative component which has a tetracarboxylic-acid derivative which has a specific structure, and the diamine component which has a specific structure, or polyimide It discovered that the said objective can be achieved by using the liquid crystal aligning agent containing a precursor. In this way, this invention makes the following a summary.

1. It contains at least 1 sort (s) chosen from tetracarboxylic dianhydride represented by following formula (1), and its derivative (s), and at least 1 sort (s) chosen from tetracarboxylic dianhydride and its derivative (s) represented by following formula (2). At least 1 sort (s) chosen from the polyimide which is a polyimide precursor obtained from the tetracarboxylic-acid derivative component mentioned above, and the diamine component containing at least 1 sort (s) of diamine chosen from following formula (3) and (4) and its imide. The liquid crystal aligning agent containing the polymer of.

[Formula 1]

In the formula, X ₁ is a structure selected from the following formulas (X1-1) to (X1-4), and X ₂ is a structure selected from the following formulas (X2-1) to (X2-2).

[Formula 2]

In the formula, each of R ₃ to R ₆ independently represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, or a fluorine atom. Although it may be the same or different, it is a monovalent organic group of 6, or a phenyl group, At least one is other than a hydrogen atom. R ₇ to R ₂₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, and a 1 to 6 carbon atoms containing fluorine atom. It may be an organic group or a phenyl group, and may be same or different.

[Formula 3]

[Formula 4]

In formula, A <_1> is a single bond, an ester bond, an amide bond, a thioester bond, or a C2-C20 divalent organic group, A <_2> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a thiol group, a nitro group, phosphoric acid group, or a monovalent organic group having a carbon number of 1 ~ 20, a is an integer (整數) of 1 to 4, when a is 2 or more, a structure of a is ₁ may be the same or different. b and c are the integers of 1-2 each independently.

2. The liquid crystal aligning agent of 1. whose ratio of the tetracarboxylic dianhydride represented by said Formula (2) or its derivative is 1-30 mol% with respect to 1 mol of all the tetracarbon derivative components.

3. Liquid crystal aligning agent as described in 1. or 2. whose structure of X < ₁ > is at least 1 sort (s) chosen from following formula (X1-12)-(X1-16).

[Formula 5]

4. Liquid crystal aligning agent in any one of _1-3 whose structure of X <_1> is said formula (X1-12).

5. The structure of X ₂ represented by the formula (X2-1), 1. to 4. The liquid crystal alignment according to any one of the.

6. Liquid crystal aligning agent in any one of 1.-5. Which diamine component contains at least 1 sort (s) chosen from following formula (DA-1)-(DA-20).

[Formula 6]

[Formula 7]

[Formula 8]

The liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of 7. 1.-6.

The liquid crystal display element which comprises the liquid crystal aligning film of 8. 7.

9. Liquid crystal display element as described in 8. whose said liquid crystal display element drives a liquid crystal by a transverse electric field.

According to the liquid crystal aligning agent of this invention, in addition to being excellent in basic characteristics, such as liquid crystal aligning property and an electrical property, afterimage by the long-term alternating current drive which arises in the liquid crystal display element of an IPS drive system or a FFS drive system can be suppressed. A liquid crystal aligning film can be obtained.

Moreover, according to the liquid crystal aligning film and liquid crystal display element of this invention, in addition to being excellent in basic characteristics, such as liquid crystal orientation and an electrical characteristic, afterimage by the long-term alternating current drive which generate | occur | produces in the liquid crystal display element of an IPS drive system or a FFS drive system. Can be suppressed.

 The liquid crystal aligning agent of this invention contains the at least 1 sort (s) of polymer (henceforth a specific polymer) chosen from the polyimide precursor mentioned above and the polyimide which is the imide. Hereinafter, each component used as a raw material which comprises a specific polymer is explained in full detail.

<Tetracarboxylic acid derivative component>

The tetracarboxylic acid derivative component used for the polymerization of a specific polymer contained in the liquid crystal aligning agent of the present invention is not only tetracarboxylic dianhydride but also tetracarboxylic acid and tetracarboxylic acid which are the tetracarboxylic acid derivatives. A halide compound, a tetracarboxylic-acid dialkyl ester compound, or a tetracarboxylic-acid dialkyl ester dihalide compound can be used. The tetracarboxylic dianhydride or its derivative used for superposition | polymerization of a specific polymer is at least 1 sort (s) chosen from tetracarboxylic dianhydride or its derivative represented by following formula (1), and tetra represented by following formula (2) At least 1 sort (s) chosen from carboxylic acid or its derivative (s) is contained.

[Formula 9]

In formula, X <_1> is a structure chosen from following formula (X1-1) (X1-4).

[Formula 10]

In the formula, each of R ₃ to R ₆ independently represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, or a fluorine atom. Although it may be the same or different, it is a monovalent organic group of 6, or a phenyl group, At least one is other than a hydrogen atom. R ₇ to R ₂₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, and a 1 to 6 carbon atoms containing fluorine atom. It may be an organic group or a phenyl group, and may be same or different.

The viewpoint of suppression of the residual image by the long-term driving with the alternate current, the structure X ₁ is the formula (X1-12) ~ preferably at least one member selected from the structure shown in (X1-16) and of formula (X1-12) Is particularly preferred.

[Formula 11]

50 mol% or more is preferable with respect to all tetracarboxylic dianhydride or 1 mol of its derivatives, and, as for the ratio of the tetracarboxylic dianhydride represented by said Formula (1), 70 mol% or more is more preferable , 80 mol% or more is more preferable.

X ₂ is a structure selected from the following formulas (X2-1) to (X2-2).

[Formula 12]

In the formula (2), the viewpoint of suppression of the residual image by the long-term driving with the alternate current, X ₂ is preferably a structure represented by the following formula (X2-1). The ratio of tetracarboxylic dianhydride or its derivative represented by said Formula (2) is 1-30 mol% with respect to 1 mol of all tetracarboxylic dianhydride or its derivative (all tetracarboxylic-acid derivative component). It is preferable, 10 to 30% is more preferable, and 10 to 20% is further more preferable.

As the tetracarboxylic dianhydride and derivatives thereof used for the polymerization of a specific polymer, tetracarboxylic dianhydride and derivatives thereof represented by the following formula (6) may be used in addition to the formulas (1) and (2).

[Formula 13]

In formula, X <_3> is a tetravalent organic group, The structure is not specifically limited. If a specific example is given, the structure of following formula (X-9)-(X-47) will be mentioned. From the viewpoint of the availability of the compound, the structure of X ₃ is X-17, X-25, X-26, X-27, X-28, X-32, X-35, X-37, X-39 , X-43, X-44, X-45, X-46, and X-47 are preferred. Moreover, it is preferable to use tetracarboxylic dianhydride which has an aromatic ring structure from a viewpoint that the liquid crystal aligning film with which the residual electric charge which accumulate | stored by DC voltage is quick can be obtained, and as a structure of X <_3> , it is X-26. , X-27, X-28, X-32, X-35, and X-37 are more preferable.

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

<Diamine component>

The diamine component used for superposition | polymerization of a specific polymer contained in the liquid crystal aligning agent of this invention contains at least 1 sort (s) chosen from following formula (3) and following formula (4).

[Formula 20]

In formula, A <_1> is a single bond, an ester bond, an amide bond, a thioester bond, or a C2-C20 divalent organic group, A <_2> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a thiol group, a nitro group, phosphoric acid group, or a monovalent organic group having a carbon number of 1 ~ 20, a is an integer from 1 to 4, when a is 2 or more, a structure of a is ₁ may be the same or different. b and c are the integers of 1-2 each independently.

From the standpoints of suppression of residual images due to long-term alternating current drive, and the like, the structures of the following formulas (DA-1) to (DA-20) are preferable as the specific structures of the formula (3) and the formula (4). Especially, DA-1, DA-2, DA-4, DA-5, DA-7 are more preferable.

[Formula 21]

[Formula 22]

[Formula 23]

50-100 mol% is preferable with respect to 1 mol of all diamine components, and, as for content of the diamine represented by the said Formula (3) and said Formula (4), it is more preferable that it is 70 mol%-100 mol%. The diamine used for superposition | polymerization of a specific polymer may contain the diamine represented by following formula (7) other than said Formula (3) and (4).

[Formula 24]

In formula, A <_3> is a hydrogen atom or a C1-C5 alkyl group, a C2-C5 alkenyl group, and a C2-C5 alkynyl group each independently, and may be same or different. From the viewpoint of liquid crystal alignment, A ₃ is preferably a hydrogen atom or a methyl group. Y ₁ is a divalent organic group, and specific examples thereof include the following formulas (Y-1) to (Y-49) and (Y-57) to (Y-168).

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

[Formula 43]

It is preferable to include the structure represented by following formula (8) in the structure of Y <_1> from the viewpoint of the solubility of a polymer improving.

[Formula 44]

In the formula, D is a t-butoxycarbonyl group.

Y-158, Y-159, Y-160, Y-161, Y-162, Y-163 can be mentioned as a specific example of Y <_1> containing the structure of said Formula (8).

<Method for producing polyamic acid ester>

The polyamic acid ester which is a polyimide precursor used for this invention can be synthesize | combined by any of the following (1)-(3).

(1) When synthesized from polyamic acid

Polyamic acid ester can be synthesize | combined by esterifying the polyamic acid obtained from tetracarboxylic dianhydride and diamine. Specifically, the polyamic acid and the esterifying agent can be synthesized by reacting in the presence of an organic solvent at -20 to 150 ° C, preferably at 0 to 50 ° C for 30 minutes to 24 hours, preferably 1 to 4 hours. .

As an esterification agent, what can be easily removed by refinement | purification is preferable, N, N- dimethylformamide dimethyl acetal, N, N- dimethylformamide diethyl acetal, N, N- dimethylformamide dipropyl acetal, N, N-dimethylformamide dineopentylbutyl acetal, N, N-dimethylformamide di-t-butylacetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene , 1-propyl-3-p-tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride, and the like. As for the addition amount of an esterification agent, 2-6 mol equivalent is preferable with respect to 1 mol of repeating units of a polyamic acid, and 2-4 mol equivalent is more preferable.

As for the organic solvent used for said reaction, N, N- dimethylformamide, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, etc. are preferable at the solubility of a polymer, These are 1 type, or 2 or more types. You may mix and use. 1-30 mass% is preferable, and, as for the density | concentration of the polymer in the organic solvent at the time of synthesis | combination, and a high molecular weight is easy to be obtained, a 5-20 mass% is more preferable.

(2) When synthesized by reaction of tetracarboxylic acid diester dichloride and diamine

Polyamic acid ester can be synthesize | combined from tetracarboxylic-acid diester dichloride and diamine. Specifically, tetracarboxylic-acid diester dichloride and diamine are -20-150 degreeC in presence of a base and an organic solvent, Preferably it is 0-50 degreeC, 30 minutes-24 hours, Preferably 1-4 It can synthesize | combine by making time react.

Pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used as the additive base, but pyridine is preferable in order to allow the reaction to proceed mildly. It is preferable that it is 2-4 times mole with respect to tetracarboxylic-acid diester dichloride from a viewpoint that the addition amount of a base is the quantity which is easy to remove, and a high molecular weight is easy to obtain, and 2-3 times mole is more preferable. As for the organic solvent used for said reaction, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, etc. are preferable at the solubility of a monomer and a polymer, These may be used 1 type or in mixture of 2 or more types.

1-30 mass% is preferable, and, as for the polymer density | concentration in the organic solvent at the time of synthesis | combination from a viewpoint that precipitation of a polymer does not occur easily and a high molecular weight is easy to be obtained, 5-20 mass% is more preferable. Moreover, in order to prevent the hydrolysis of tetracarboxylic-acid diester dichloride, it is preferable that the organic solvent used for the synthesis | combination of a polyamic acid ester is dehydrated as much as possible, reaction is performed in nitrogen atmosphere, and mixing of external air is carried out. It is desirable to prevent.

(3) When synthesized polyamic acid from tetracarboxylic acid diester and diamine

Polyamic acid ester can be synthesize | combined by polycondensing tetracarboxylic-acid diester and diamine. Specifically, tetracarboxylic acid diester and diamine are in the presence of a condensing agent, a base, and an organic solvent at 0 to 150 ° C, preferably 0 to 100 ° C for 30 minutes to 24 hours, preferably 3 to 15 hours. It can synthesize | combine by making time react.

Examples of the condensing agent include triphenyl phosphite, dicyclohexyl carbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, and dimethoxy-1 , 3,5-triazinylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazole- 1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphite, (2,3-dihydro-2-thioxo-3-benzooxazolyl) phosphonic acid diphenyl and the like Can be used. It is preferable that it is 2-3 times mole with respect to tetracarboxylic-acid diester, and, as for the addition amount of a condensing agent, 2-2.5 times mole is more preferable.

As the base, tertiary amines such as pyridine and triethylamine can be used. The addition amount of base is an amount which is easy to remove, and from a viewpoint of obtaining a high molecular weight body easily, 2-4 times mole is preferable with respect to a diamine component, and 2-3 times mole is more preferable. N-methyl-2-pyrrolidone, (gamma) -butyrolactone, N, N- dimethylformamide, etc. are mentioned as said organic solvent. In the above reaction, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. 0-1.0 times mole is preferable with respect to a diamine component, and, as for the addition amount of a Lewis acid, 2.0-3.0 times mole is more preferable.

Since the high molecular weight polyamic acid ester is obtained among the synthesis | combining method of said three polyamic acid ester, the synthesis method of said (1) or said (2) is especially preferable. The solution of the polyamic acid ester obtained as mentioned above can deposit a polymer by inject | pouring into a poor solvent, stirring well. Precipitation is carried out several times, followed by washing with a poor solvent, followed by normal temperature or heat drying to obtain a powder of purified polyamic acid ester. The poor solvent is not particularly limited, but water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, toluene and the like can be given, and water, methanol, ethanol, 2-propanol and the like are preferable.

<Method for producing polyamic acid>

The polyamic acid which is a polyimide precursor used for this invention can be synthesize | combined by the following method. Specifically, the compound is synthesized by reacting tetracarboxylic dianhydride and diamine in the presence of an organic solvent at -20 to 150 ° C, preferably 0 to 50 ° C for 30 minutes to 24 hours, preferably 1 to 12 hours. can do.

As for the organic solvent used for said reaction, N, N- dimethylformamide, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, etc. are preferable at the solubility of a monomer and a polymer, These are 1 type or 2 types You may mix and use the above. The concentration of the polymer is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoint that the precipitation of the polymer does not occur easily and a high molecular weight is easily obtained.

The polyamic acid obtained as described above can be recovered by depositing a polymer by injecting the reaction solution into a poor solvent while stirring the reaction solution well. Further, the precipitate is subjected to several times, and after washing with a poor solvent, the powder of purified polyamic acid can be obtained by normal temperature or heat drying. The poor solvent is not particularly limited, but water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, toluene and the like can be given, and water, methanol, ethanol, 2-propanol and the like are preferable.

<Method for producing polyimide>

The polyimide used for this invention can be manufactured by imidating the said polyamic acid ester or polyamic acid. When manufacturing a polyimide from polyamic acid ester, chemical imidation which adds a basic catalyst to the polyamic acid solution obtained by melt | dissolving the said polyamic acid ester solution or polyamic acid ester resin powder in an organic solvent is easy. Chemical imidation is preferable since the imidation reaction advances at a comparatively low temperature, and molecular weight fall of a polymer does not occur easily in the process of imidation.

Chemical imidation can be performed by stirring the polyamic acid ester to make it imidate in basic catalyst presence in an organic solvent. As an organic solvent, the solvent used at the time of the polymerization reaction mentioned above can be used. Pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned as a basic catalyst. Especially, triethylamine is preferable because it has sufficient basicity to advance reaction.

The temperature at the time of performing an imidation reaction is -20-140 degreeC, Preferably it is 0-100 degreeC, and reaction time can be implemented for 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 times mole, preferably 2 to 20 times mole of the amic acid ester group. The imidation ratio of the polymer obtained can be controlled by adjusting catalyst amount, temperature, and reaction time.

When producing a polyimide from a polyamic acid, chemical imidation which adds a catalyst to the solution of the said polyamic acid obtained by reaction of a diamine component and tetracarboxylic dianhydride is easy. Chemical imidation is preferable since the imidation reaction advances at a comparatively low temperature, and molecular weight fall of a polymer does not occur easily in the process of imidation.

Chemical imidation can be performed by stirring the polymer to make it imidate in presence of a basic catalyst and an acid anhydride in an organic solvent. As an organic solvent, the solvent used at the time of the polymerization reaction mentioned above can be used. Pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned as a basic catalyst. Especially, pyridine is preferable because it has a basicity suitable for advancing reaction. Moreover, acetic anhydride, trimellitic anhydride, a pyromellitic dianhydride, etc. are mentioned as acid anhydride, Especially, since acetic anhydride is used, since refinement | purification after completion | finish of reaction becomes easy, it is preferable.

The temperature at the time of performing an imidation reaction is -20-140 degreeC, Preferably it is 0-100 degreeC, and reaction time can be implemented for 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 times mole, preferably 2 to 20 times mole of the polyamic acid group, and the amount of the acid anhydride is 1 to 50 times mole, preferably 3 to 30 times mole of the polyamic acid group. The imidation ratio of the polymer obtained can be controlled by adjusting catalyst amount, temperature, and reaction time. Since the added catalyst etc. remain | survived in the solution after the imidation reaction of polyamic acid ester or polyamic acid, the imidated polymer obtained is collect | recovered by the means described below, it is redissolved with an organic solvent, and the liquid crystal of this invention It is preferable to set it as an aligning agent.

The polymer of the polyimide obtained as mentioned above can be precipitated by inject | pouring into a poor solvent, stirring well. Precipitation is carried out several times, and after washing with a poor solvent, it is possible to obtain a powder of a purified polymer by normal temperature or heat drying. Although the said poor solvent is not specifically limited, Methanol, 2-propanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, etc. are mentioned, methanol, ethanol, etc. are mentioned. , 2-propanol, acetone and the like are preferable.

<Liquid crystal aligning agent>

The liquid crystal aligning agent used for this invention has the form of the solution which the polymer component melt | dissolved in the organic solvent. As for the molecular weight of a polymer, 2,000-500,000 are preferable at a weight average molecular weight, More preferably, it is 5,000-300,000, More preferably, it is 10,000-100,000. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.

Although the density | concentration of the polymer of the liquid crystal aligning agent used for this invention can be suitably changed with the setting of the thickness of the coating film to form, it is preferable that it is 1 mass% or more from the point which forms a uniform, defect-free coating film, and a solution It is preferable to set it as 10 mass% or less from the point of the storage stability of this. The density | concentration of especially preferable polymer is 2-8 mass%.

The organic solvent contained in the liquid crystal aligning agent of this invention will not be specifically limited if a polymer component melt | dissolves uniformly. Specific examples include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone , N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, 3-meth And oxy-N, N-dimethylpropanamide. You may use these 1 type or in mixture of 2 or more types. Moreover, if individual, even if it is a solvent which cannot melt | dissolve a polymer component uniformly, as long as it is a range in which a polymer does not precipitate, you may mix with said organic solvent.

The liquid crystal aligning agent of this invention may contain the solvent for improving the coating film uniformity at the time of apply | coating a liquid crystal aligning agent to a board | substrate besides the organic solvent for dissolving a polymer component. In general, a solvent having a lower surface tension than that of the organic solvent is used. Specifically, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1 Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2 Acetate, butyl cellosolve acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester Etc. can be mentioned. These solvent may use 2 or more types together.

In addition to the above, in the liquid crystal aligning agent of this invention, the silane coupler for the purpose of improving the adhesiveness of the dielectric or electrically conductive material, the liquid crystal aligning film, and the board | substrate for the purpose of changing the electrical properties, such as polymers other than a specific polymer, and the dielectric constant and electroconductivity of a liquid crystal aligning film, is mentioned. You may add the crosslinking | crosslinked compound for the purpose of raising the hardness and the density of a film at the time of using a ring agent and a liquid crystal aligning film, and also the imidation promoter for the purpose of advancing the imidation of a polyamic acid efficiently when baking a coating film.

<Liquid crystal aligning film, liquid crystal display element>

A liquid crystal aligning film is a film | membrane obtained by apply | coating said liquid crystal aligning agent to a board | substrate, and drying and baking. It will not specifically limit, if it is a board | substrate with high transparency as a board | substrate which apply | coats the liquid crystal aligning agent of this invention, A plastic substrate, such as an acryl substrate and a polycarbonate board | substrate, etc. can also be used with a glass substrate and a silicon nitride substrate. In that case, when the board | substrate with which the ITO electrode etc. for driving a liquid crystal were formed is used, it is preferable at the point of the process simplification. Moreover, in a reflective liquid crystal display element, as long as it is a board | substrate of one side, it can also be used as opaque things, such as a silicon wafer, and the material which reflects light, such as aluminum, can also be used for the electrode in this case.

Although the coating method of a liquid crystal aligning agent is not specifically limited, Industrially, the method of performing by screen printing, offset printing, flexographic printing, the inkjet method, etc. is common. Other coating methods include a dip method, a roll coater method, a slit coat method, a spinner method, a spray method, and the like, and may be used according to the purpose.

After apply | coating a liquid crystal aligning agent on a board | substrate, a solvent can be evaporated and it can be set as a liquid crystal aligning film by heating means, such as a hotplate, a thermocyclic oven, or an IR (infrared rays) oven. The drying after apply | coating the liquid crystal aligning agent of this invention, and the baking process can select arbitrary temperature and time. Usually, in order to remove the solvent contained enough, baking is carried out at 50-120 degreeC for 1 to 10 minutes, Then, the conditions baked at 150-300 degreeC for 5 to 120 minutes are mentioned. Since the reliability of a liquid crystal display element may fall when the thickness of the liquid crystal aligning film after baking is too thin, 5-300 nm is preferable and 10-200 nm is more preferable.

As for the method of orientation-processing the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention, the photo-alignment method is preferable. As a preferable example of the photo-alignment method, the radiation which deflected to the surface of the said liquid crystal aligning film in the fixed direction is irradiated, and if necessary, heat-processes at the temperature of 150-250 degreeC preferably, and liquid-crystal orientation (liquid crystal orientation) (Also referred to as "ability."). As the radiation, ultraviolet rays or visible rays having a wavelength of 100 to 800 nm can be used. Especially, it is the ultraviolet-ray which has a wavelength of preferably 100-400 nm, More preferably, 200-400 nm.

Moreover, in order to improve liquid crystal alignability, you may irradiate a radiation, heating the board | substrate with which the liquid crystal aligning film was coated at 50-250 degreeC. Moreover, as for the irradiation amount of the said radiation, 1-10,000mJ / cm <2> is preferable. Especially, 100-5,000 mJ / cm <2> is preferable. The liquid crystal aligning film thus produced can stably align the liquid crystal molecules in a constant direction. The higher the extinction ratio of the polarized ultraviolet rays is, since higher anisotropy can be imparted, it is preferable. Specifically, 10: 1 or more is preferable and, as for the extinction ratio of the ultraviolet-ray polarized linearly, 20: 1 or more is more preferable.

Moreover, a contact process can also be given to the liquid crystal aligning film which irradiated the polarized radiation by the said method using water or a solvent. As a solvent used for the said contact processing, if it is a solvent which melt | dissolves the decomposition product produced | generated from the liquid crystal aligning film by irradiation of radiation, it will not specifically limit. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate And diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate or cyclohexyl acetate. Especially, water, 2-propanol, 1-methoxy-2-propanol, or ethyl lactate are preferable at the point of versatility and the safety of a solvent. More preferred is water, 1-methoxy-2-propanol or ethyl lactate. One type of solvent may be sufficient and it may combine it 2 or more types.

An immersion process and a spray process (also called a spray process) are mentioned as said contact process, ie, the process which makes water and a solvent contact the liquid crystal aligning film which irradiated the polarized radiation. It is preferable that the processing time in these processes is 10 second-1 hour from the point which melt | dissolves the decomposition product produced | generated from the liquid crystal aligning film by radiation efficiently. Especially, it is preferable to immerse for 1 to 30 minutes. Moreover, although the solvent at the time of the said contact process may be normal temperature, and you may heat, Preferably it is 10-80 degreeC. Especially, 20-50 degreeC is preferable. Moreover, you may perform an ultrasonication etc. as needed from the point of solubility of a decomposer.

After the above-mentioned contact treatment, it is preferable to perform rinsing (also referred to as rinse) with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone or methyl ethyl ketone, or firing the liquid crystal alignment film. In that case, either one of rinsing and baking may be performed, or both may be performed. It is preferable that the temperature of baking is 150-300 degreeC. Especially, 180-250 degreeC is preferable. More preferably, it is 200-230 degreeC. Moreover, as for the time of baking, 10 second-30 minutes are preferable. Especially, 1 to 10 minutes are preferable.

The liquid crystal aligning film of this invention is preferable as a liquid crystal aligning film of the liquid crystal display element of transverse electric field systems, such as an IPS system and a FFS system, and is especially useful as a liquid crystal aligning film of the liquid crystal display element of a FFS system. After obtaining the board | substrate with a liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention, a liquid crystal display element manufactures a liquid crystal cell by a known method, and is obtained using this liquid crystal cell. As an example of the manufacturing method of a liquid crystal cell, it demonstrates taking the liquid crystal display element of a passive matrix structure as an example. Moreover, the liquid crystal display element of an active matrix structure in which switching elements, such as TFT (Thin Film Transistor), was formed in each pixel part which comprises an image display may be sufficient.

Specifically, a transparent glass substrate is prepared, and a common electrode is formed on one board | substrate, and a segment electrode is formed on the other board | substrate. These electrodes can be made into an ITO electrode, for example, and are patterned so that desired image display can be performed. Next, an insulating film is formed on each board | substrate so that a common electrode and a segment electrode may be coat | covered. The insulating film can be, for example, a film of SiO ₂ -TiO ₂ formed by the sol-gel method.

Next, a liquid crystal aligning film is formed on each board | substrate, the other board | substrate is superposed on one board | substrate so that mutual liquid crystal aligning film surfaces may oppose, and the periphery is bonded by a sealing agent. In order to control a board | substrate gap, it is preferable to mix a spacer, and to distribute the spacer for board | substrate gap control also to the in-plane part which does not form a sealant. In a part of the sealing compound, the opening part which can fill a liquid crystal from the exterior is formed. Next, a liquid crystal material is injected into the space surrounded by two substrates and the sealing agent through the opening formed in the sealing agent, and then the opening is sealed with an adhesive agent. For injection, a vacuum injection method may be used, or a method using a capillary phenomenon in the atmosphere may be used. As the liquid crystal material, any of a positive liquid crystal material and a negative liquid crystal material may be used. Next, the polarizing plate is installed. Specifically, a pair of polarizing plate is affixed on the surface on the opposite side to the liquid crystal layer of two board | substrates.

By using the liquid crystal aligning agent of this invention as mentioned above, the liquid crystal aligning film which suppresses the afterimage by alternating current drive, and makes adhesiveness with a sealing compound and a base substrate compatible can be obtained. It is especially useful about the liquid crystal aligning film obtained by irradiating polarized radiation.

Example

Although an Example is given to the following and this invention is demonstrated to it further more concretely, this invention is not limited to these. The symbol of the compound below and the measuring method of each characteristic are as follows.

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

BCS: Butyl Cellosolve

DA-1: 1,2-bis (4-aminophenoxy) ethane

DA-2: bis (4-aminophenoxy) methane

DA-3: N-tert-butoxycarbonyl-N- (2- (4-aminophenyl) ethyl) -N- (4-aminobenzyl) amine

DA-4: p-phenylenediamine

DA-5: Refer to following formula (DA-5).

DA-6: 4,4'-diaminodiphenylamine

DA-7: 4,4'-diaminodiphenylmethane

DA-8: Refer to the following formula (DA-8).

CA-1: See formula (CA-1) below.

CA-2: See formula (CA-2) below.

CA-3: Refer to the following formula (CA-3)

CA-4: See formula (CA-4) below.

AD-1: See following formula (AD-1).

[Formula 45]

[Formula 46]

[Formula 47]

[Viscosity]

The viscosity of the solution was measured at 1.1 mL of sample amount, cone rotor TE-1 (1 ° 34 ', R24), and a temperature of 25 ° C using an E-type viscometer TVE-22H (manufactured by Torquay Industries, Ltd.).

[Molecular Weight]

The molecular weight was measured by a GPC (room temperature gel permeation chromatography) apparatus, and the number average molecular weight (Mn) and the weight average molecular weight (Mw) were computed as a polyethylene glycol and polyethylene oxide conversion value.

GPC apparatus: manufactured by Shodex (GPC-101), column: manufactured by Shodex (KD803, KD805 in series), column temperature: 50 ° C, eluent: N, N-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr H ₂ O) is 30 mmol / l, phosphoric acid and anhydrous crystals (o-phosphate) is 30 mmol / l, tetrahydrofuran (THF) is 10 ml / l), flow rate: 1.0 ml / min.

Standard sample for calibration curve preparation: TSK standard polyethylene oxide (weight average molecular weight (Mw) about 900,000, 150,000, 100,000, 30,000) by Tosoh Corporation, and polyethylene glycol (peak top molecular weight (Mp) about 12,000, 4,000 by Polymer Laboratories , 1,000). The measurement measured separately two samples of the sample which mixed four types, 900,000, 100,000, 12,000, 1,000, and the sample which mixed three types, 150,000, 30,000, and 4,000, in order to avoid that a peak overlaps.

<Measurement of imidation ratio>

20 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard, φ 5 (manufactured by Kusano Scientific Co., Ltd.)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) (0.53 mL) Was added and ultrasonication was added to complete dissolution. The solution was measured for 500 MHz of proton NMR by means of an NMR measuring instrument (JNW-ECA500) (manufactured by Nippon Electron Datum). The imidation ratio sets a proton derived from the structure which does not change before and after imidation as a reference proton, and the peak integration value derived from the peak integration value of this proton and the NH group of the amic acid which appears in the vicinity of 9.5 ppm-10.0 ppm It calculated | required by the following formula using the value.

Imidation ratio (%) = (1-αx / y) × 100

In the above formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is the NH of the amic acid when the polyamic acid (imidization ratio is 0%). The ratio of the number of reference protons to one proton.

[Production of Liquid Crystal Cell]

The liquid crystal cell provided with the structure of a fringe field switching (FFS) mode liquid crystal display element is manufactured. Initially, the board | substrate with an electrode was prepared. The substrate is a glass substrate having a size of 30 mm x 50 mm and a thickness of 0.7 mm. On the board | substrate, the ITO electrode provided with the non-printed pattern which comprises a counter electrode as a 1st layer is formed. On the counter electrode of 1st layer, the SiN (silicon nitride) film | membrane formed into a film by CVD method is formed as 2nd layer. The film thickness of the SiN film of 2nd layer is 500 nm, and functions as an interlayer insulation film. On the SiN film of a 2nd layer, the comb-tooth shaped pixel electrode formed by patterning an ITO film as a 3rd layer is arrange | positioned, and two pixels of a 1st pixel and a 2nd pixel are formed. Each pixel has a length of 10 mm and a width of about 5 mm. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.

The pixel electrode of 3rd layer has the comb-tooth shaped shape comprised by putting in multiple arrangement | array | sequence the "<"-shaped electrode element in which the center part was bent. The width | variety of the short direction of each electrode element is 3 micrometers, and the space | interval between electrode elements is 6 micrometers. Since the pixel electrode which forms each pixel is comprised by putting in multiple arrangement | array | sequence the "<"-shaped electrode element in which the center part was bent, the shape of each pixel is not rectangular but is bent in the center part like the electrode element, It has a shape similar to the letter b in bold. Each pixel is divided up and down on the center of the bent portion, and has a first region above and a second region below.

When the 1st area | region and 2nd area | region of each pixel are compared, the formation direction of the electrode element of the pixel electrode which comprises them differs. That is, based on the rubbing direction of the liquid crystal alignment film described later, the electrode element of the pixel electrode is formed to form an angle of + 10 ° (clockwise) in the first region of the pixel, and the pixel electrode of the pixel electrode in the second region of the pixel. The electrode elements are formed to form an angle of 10 degrees (clockwise). That is, in the first region and the second region of each pixel, the directions of rotational operations (in-plane switching) in the substrate surface of the liquid crystal caused by the application of voltage between the pixel electrode and the counter electrode become opposite directions. Consists of.

Next, after filtering a liquid crystal aligning agent with a 1.0 micrometer filter, the spin coating method is carried out to the glass substrate which has the prepared said substrate with an electrode, and the columnar spacer of 4 micrometers in height in which the ITO film | membrane is formed into a film at the back surface. By application. After drying for 5 minutes on an 80 degreeC hotplate, baking was performed for 20 minutes by the 230 degreeC hot air circulation type oven, and the coating film of 100 nm of film thickness was formed. The ultraviolet-ray of wavelength 254nm which linearly polarized extinction ratio 10: 1 or more through this polarizing plate through the polarizing plate was irradiated. This board | substrate was immersed in at least 1 sort (s) of solvent chosen from water and an organic solvent for 3 minutes, and then immersed in pure water for 1 minute, and it heated for 5 minutes on the 150-300 degreeC hotplate, and obtained the board | substrate with a liquid crystal aligning film. After the said two board | substrates are set as one set, the sealing compound is printed on a board | substrate, and the other one board | substrate is bonded so that a liquid crystal aligning film surface may face, and an orientation direction may become 0 degree, after that, a sealing agent is hardened and an empty cell Was prepared. Liquid crystal MLC-3019 (made by Merck) was injected into this empty cell by the pressure reduction injection method, the injection hole was sealed, and the FFS drive liquid crystal cell was obtained. Then, the obtained liquid crystal cell was heated at 110 degreeC for 1 hour, and used for each evaluation after leaving to stand overnight.

[Afterimage evaluation by long-term AC drive]

The liquid crystal cell of the same structure as the liquid crystal cell used for said afterimage evaluation was prepared. Using this liquid crystal cell, an alternating voltage of ± 5 V was applied at a frequency of 60 Hz for 120 hours in a constant temperature environment of 60 ° C. Then, it was made the state between the pixel electrode and the counter electrode of a liquid crystal cell shortened, and it was left to stand at room temperature as it is for one day.

After standing, the liquid crystal cell was provided between two polarizing plates arranged so that the polarization axes were orthogonal, the backlight was turned on in the absence of voltage, and the arrangement angle of the liquid crystal cell was adjusted so that the luminance of transmitted light was the smallest. The rotation angle when the liquid crystal cell was rotated from the darkest angle of the second region of the first pixel to the darkest angle of the first region was calculated as the angle Δ. Similarly, in the second pixel, the same angle Δ was calculated by comparing the second region and the first region.

[Evaluation of Pencil Hardness]

The sample of pencil hardness evaluation was produced as follows. The liquid crystal aligning agent was apply | coated to the 30 mm x 40 mm ITO board | substrate by application | coating by the spin coat method. After drying for 2 minutes on a 80 degreeC hotplate, baking was performed for 14 minutes by 230 degreeC hot air circulation type oven, and the coating film of 100 nm of film thickness was formed. Orientation processing, such as rubbing and polarized ultraviolet irradiation, was performed to this coating film surface, and the board | substrate with a liquid crystal aligning film was obtained. The substrate was immersed in at least one solvent selected from water and an organic solvent for 3 minutes, then immersed in pure water for 1 minute, and heated on a hot plate at 150 ° C to 300 ° C for 14 minutes to obtain a substrate with a liquid crystal alignment film. . This board | substrate was measured by the pencil hardness test method (JIS K5400).

[Evaluation of Adhesiveness]

The sample of adhesive evaluation was produced as follows. The liquid crystal aligning agent was apply | coated to the ITO board | substrate of 30 mm x 40 mm by the spin coat method. After drying for 2 minutes on a 80 degreeC hotplate, baking was performed for 14 minutes by the 230 degreeC hot air circulation type oven, and the coating film of 100 nm of film thickness was formed. Orientation processing, such as rubbing and polarized ultraviolet irradiation, was performed to this coating film surface, and the board | substrate with a liquid crystal aligning film was obtained. The substrate was immersed in at least one solvent selected from water and an organic solvent for 3 minutes, then immersed in pure water for 1 minute, and heated on a hot plate at 150 ° C to 300 ° C for 14 minutes to obtain a substrate with a liquid crystal alignment film. .

Thus, two board | substrates obtained were prepared, after apply | coating a 4 micrometer bead spacer on the liquid crystal aligning film surface of one board | substrate, the sealing compound (Kyoritsu Chemical make XN-1500T) was dripped. Next, the liquid crystal aligning film surface of the other board | substrate was made inside, and it bonded together so that the overlap width of a board | substrate might be 1 cm. At that time, the amount of sealing compound dropping was adjusted so that the diameter of the sealing compound after bonding might be set to 3 mm. After fixing two board | substrates bonded together with a clip, it thermosetted 150 degreeC for 1 hour, and manufactured the sample for adhesive evaluation. Then, after fixing a sample board | substrate with the table-type precision universal testing machine AGS-X500N by Shimadzu Corporation, and the stage part of an upper and lower board | substrate, it press-fits from the upper part of a board | substrate center part, and the pressure (N) at the time of peeling Measured.

Synthesis Example 1

In a 100 ml four-necked flask with a stirrer and a nitrogen introduction tube, 2.78 g (11.4 mmol) for DA-1, 3.50 g (15.2 mmol) for DA-2, and 3.89 g (11.4 m) for DA-3 Mol), 46.3g of NMP (s) were added, and it stirred, sending nitrogen, and melt | dissolved. While stirring this diamine solution, 6.64g (29.6 mmol) and 1.42g (5.70 mmol) CA-1 are added, Furthermore, 36.8g of NMP are added so that solid content concentration may be 18 mass%, and 40 degreeC It stirred for 24 hours and obtained polyamic-acid solution (A) (viscosity: 850 mPa * s). The molecular weight of the polyamic acid was Mn = 15500 and Mw = 36500.

<Synthesis Examples 2-12>

By using the diamine component, tetracarboxylic-acid component, and NMP shown in following Table 1 similarly to reaction temperature, solid content concentration, and synthesis example 1, the polyamic-acid solution (B)-(shown in following Table 1) ( L) was obtained. Moreover, the viscosity and molecular weight of the obtained polyamic acid are shown in following Table 1.

Synthesis Example 13

30g of obtained polyamic-acid solution (A) was obtained to the 100 mL four neck flask with a stirrer and a nitrogen inlet tube, 15.0g of NMP was added, and it stirred for 30 minutes. 3.32 g of acetic anhydride and 0.43 g of pyridine were added to the obtained polyamic acid solution, and it heated at 55 degreeC for 3 hours, and performed chemical imidation. The obtained reaction liquid was thrown into 213 ml of methanol with stirring, and the precipitate deposited was collected by filtration, and then washed three times with 213 ml of methanol. The polyimide resin powder (A) was obtained by drying the obtained resin powder at 60 degreeC for 12 hours. The imidation ratio of this polyimide resin powder was 65%, Mn = 6800 and Mw = 12000.

<Synthesis Examples 14-23>

The polyimide resin powders (B) to (K) shown in Table 2 were obtained by performing the same procedure as in Synthesis Example 13, except that the polyamic acid solution shown in Table 2, NMP, acetic anhydride, pyridine, and methanol were used. .

<Synthesis Examples 24-28>

The polyamic-acid solution shown in following Table 1-2 by carrying out similarly to reaction temperature, solid content concentration, and synthesis example 1 using the diamine component, the tetracarboxylic-acid component, and NMP shown in following Table 1-2 ( M)-(Q) were obtained. Moreover, the viscosity and molecular weight of the obtained polyamic acid are shown in following Table 1-2.

TABLE 1-2

<Synthesis Examples 29-31>

Except having used the polyamic-acid solution shown in Table 2, NMP, acetic anhydride, a pyridine, and methanol, it carries out similarly to the synthesis example 13, and performs the polyimide resin powder (M)-(Q) shown in following Table 2-2. Got it.

Table 2-2

<Example 1>

10.00 g of the 18 mass% polyamic acid solution (A) obtained in Synthesis Example 1 was taken in a 100 ml Erlenmeyer flask, 14.00 g of NMP and 6.00 g of BCS were added and mixed at 25 ° C. for 8 hours to form a liquid crystal aligning agent (1) Got. Abnormalities, such as haze and precipitation, were not seen by this liquid crystal aligning agent, and it was confirmed that it is a uniform solution.

<Example 2>

1.80 g of the polyimide resin powder (A) obtained in Synthesis Example 13 was taken in a 100 ml Erlenmeyer flask, 10.2 g of NMP was added so that the solid concentration was 15%, stirred at 70 ° C. for 24 hours to dissolve, and the polyimide solution (K ) 0.09g of AD-1, 2.90g of NMP, 9.00g of GBL, 6.00g of BCS were added to this polyimide solution, and it stirred at room temperature for 3 hours, and obtained the liquid crystal aligning agent (2). Abnormalities, such as haze and precipitation, were not seen by this liquid crystal aligning agent, and it was confirmed that it is a uniform solution.

<Examples 3 to 5>

Liquid crystal aligning agents (3)-(5) were obtained by carrying out similarly to Example 2 except having used polyimide resin powder (B)-(D) instead of the polyimide resin powder (A).

<Example 6>

5.50 g of the 15 mass% polyimide solution (D) and 5.50 g of the 15 mass% polyamic acid solution (E) obtained in Example 5 were taken in a 100 ml Erlenmeyer flask, 0.83 g of AD-1, 4.82 g of NMP, 7.35g of GBL and 6.00g of BCS were added, and it stirred at room temperature for 3 hours, and obtained the liquid crystal aligning agent (6). Abnormalities, such as haze and precipitation, were not seen by this liquid crystal aligning agent, and it was confirmed that it is a uniform solution.

<Examples 7 to 8>

Liquid crystal aligning agents (7)-(8) were obtained by carrying out similarly to Example 2 except having used polyimide resin powder (E)-(F) instead of the polyimide resin powder (A).

Comparative Example 1

The liquid crystal aligning agent (9) was obtained by carrying out similarly to Example 1 except having used polyamic-acid solution (H) instead of the polyamic-acid solution (A).

<Comparative Examples 2 to 6>

Liquid crystal aligning agents (10)-(14) were obtained by carrying out similarly to Example 2 except having used polyimide resin powder (G)-(K) instead of the polyimide resin powder (A).

Example 9

After filtering the liquid crystal aligning agent (1) obtained in Example 1 with a 1.0 micrometer filter, the spin coating method was carried out to the glass substrate which has the prepared said substrate with an electrode, and the columnar spacer of 4 micrometers height in which the ITO film | membrane is formed into the back surface. By application. After drying for 5 minutes on an 80 degreeC hotplate, baking was performed for 20 minutes by the 230 degreeC hot air circulation type oven, and the coating film of 100 nm of film thickness was formed. 0.25 J / cm <2> of ultraviolet-rays of wavelength 254nm which linearly polarized with extinction ratio 26: 1 through this polarizing plate through the polarizing plate were irradiated. This board | substrate was immersed in the mixed solution of pure water: 2-propanol = 1/1 for 3 minutes, and then immersed in pure water for 1 minute, and it dried for 14 minutes on a 230 degreeC hotplate, and obtained the board | substrate with a liquid crystal aligning film.

The said two board | substrates obtained are made into one set, a sealing compound is printed on a board | substrate, and the other one board | substrate is bonded so that a liquid crystal aligning film surface may face, and an orientation direction may be 0 degree, and then the sealing compound is hardened and empty The cell was prepared. Liquid crystal MLC-3019 (made by Merck) was injected into this empty cell by the pressure reduction injection method, the injection hole was sealed, and the FFS drive liquid crystal cell was obtained. Then, the obtained liquid crystal cell was heated at 110 degreeC for 1 hour, it was left overnight, and the afterimage evaluation by long-term alternating current drive was performed. The value of angle (DELTA) of this liquid crystal cell after long-term alternating current drive was 0.20.

<Examples 10-16, Comparative Examples 7-12>

Instead of the liquid crystal aligning agent (1), using the liquid crystal aligning agent shown in Table 3, respectively, FFS drive by the method similar to Example 9 except having made the irradiation amount of an ultraviolet-ray, and immersion solution shown in Table 3, respectively. The liquid crystal cell was produced and residual image evaluation by long-term alternating current drive was performed. Table 3 shows the value of the angle Δ of this liquid crystal cell after the long-term alternating current drive in each.

<Example 17>

After filtering the said liquid crystal aligning agent (1) with the 1.0 micrometer filter, it applied to the glass substrate which has the prepared said substrate with an electrode and columnar spacer of 4 micrometers height in which the ITO film | membrane was formed into the back surface by spin coating method. . After drying for 5 minutes on an 80 degreeC hotplate, baking was performed for 20 minutes by the 230 degreeC hot air circulation type oven, and the coating film of 100 nm of film thickness was formed. After irradiating 0.25 J / cm <2> of ultraviolet-rays of wavelength 254 nm which linearly polarized extinction ratio 26: 1 through this polarizing plate through this polarizing plate, it was immersed in the mixed solution of pure water: 2-propanol = 1/1 for 5 minutes, and then in pure water. It heated on the 230 degreeC hot plate immersed for 1 minute for 14 minutes, and obtained the board | substrate with a liquid crystal aligning film. This board | substrate was measured by the pencil hardness test method (JIS K5400), and it was 3H.

<Examples 18-25, Comparative Examples 13-18>

Instead of the liquid crystal aligning agent (1), the liquid crystal aligning agent shown in Table 4 was used, and also the pencil hardness was carried out similarly to Example 17 except having made the irradiation amount of an ultraviolet-ray, and immersion solution shown in Table 4, respectively. Test samples were each prepared. Table 4 shows the results of the evaluation of each pencil hardness test.

Example 26

After filtering the liquid crystal aligning agent (1) obtained in Example 1 with a 1.0 micrometer filter, it applied to the ITO board | substrate of 30 mm x 40 mm by the spin coat method. After drying for 2 minutes on a 80 degreeC hotplate, baking was performed for 14 minutes by the 230 degreeC hot air circulation type oven, and the coating film of 100 nm of film thickness was formed. Using a rubbing device with a roll diameter of 120 mm on this coating film surface, rubbing treatment was performed with a rayon cloth under conditions of a roll rotation speed of 300 rpm, a roll traveling speed of 20 mm / sec, and an indentation amount of 0.1 mm, and soaked in pure water for 1 minute. It ultrasonically wash | cleaned and dried in 80 degreeC thermocycling oven, and obtained the board | substrate with a liquid crystal aligning film.

Thus, two board | substrates obtained were prepared, after apply | coating a 4 micrometer bead spacer on the liquid crystal aligning film surface of one board | substrate, the sealing compound (Kyoritsu Chemical make XN-1500T) was dripped. Next, the liquid crystal aligning film surface of the other board | substrate was made inside, and it bonded together so that the overlap width of a board | substrate might be 1 cm. At that time, the amount of sealing compound dropping was adjusted so that the diameter of the sealing compound after bonding might be set to 3 mm. After fixing two board | substrates bonded together with a clip, it thermosetted 150 degreeC for 1 hour, and manufactured the sample for adhesive evaluation. As a result of performing adhesive evaluation, the strength at the time of peeling was 20N.

<Examples 27-33, Comparative Examples 19-24>

Instead of the liquid crystal aligning agent (1), using the liquid crystal aligning agent shown in Table 5, respectively, and also having made the irradiation amount of an ultraviolet-ray, and immersion solution shown in Table 5, adhesive evaluation by the same method as Example 26 Samples of dragons were prepared. Table 5 shows the results of the evaluation of the adhesion.

<Example 34>

1.80 g of the polyimide resin powder (M) obtained in Synthesis Example 29 was taken in a 100 ml Erlenmeyer flask, 10.2 g of NMP was added so that the solid content concentration was 15%, stirred at 70 ° C for 24 hours to dissolve, and the polyimide solution (M ) 0.09g of AD-1, 2.90g of NMP, 9.00g of GBL, 6.00g of BCS were added to this polyimide solution, and it stirred at room temperature for 3 hours, and obtained the liquid crystal aligning agent (15). Abnormalities, such as haze and precipitation, were not seen by this liquid crystal aligning agent, and it was confirmed that it is a uniform solution.

<Example 35>

6.00 g of 15 mass% polyimide solution (M) obtained in the same manner as in Example 34 and 6.00 g of 15 mass% polyamic acid solution (N) obtained in Synthesis Example 25 were taken in a 100 ml Erlenmeyer flask, and AD-1 0.09g, 2.90g of NMP, 9.00g of GBL, 6.00g of BCS were added, and it stirred at room temperature for 3 hours, and obtained the liquid crystal aligning agent (16). Abnormalities, such as haze and precipitation, were not seen by this liquid crystal aligning agent, and it was confirmed that it is a uniform solution.

<Example 36>

1.80 g of polyimide resin powder (O) obtained in Synthesis Example 30 was taken in a 100 ml Erlenmeyer flask, 10.2 g of NMP was added so that the solid content concentration was 15%, stirred at 70 ° C for 24 hours to dissolve, and the polyimide solution (O ) 0.09g of AD-1, 2.90g of NMP, 9.00g of GBL, 6.00g of BCS were added to this polyimide solution, and it stirred at room temperature for 3 hours, and obtained the liquid crystal aligning agent (17). Abnormalities, such as haze and precipitation, were not seen by this liquid crystal aligning agent, and it was confirmed that it is a uniform solution.

<Example 37>

6.00 g of 15 mass% polyimide solution (O) obtained in the same manner as in Example 36 and 6.00 g of 15 mass% polyamic acid solution (E) obtained in Synthesis Example 5 were taken in a 100 mL Erlenmeyer flask, and AD-1 0.09g, 2.90g of NMP, 9.00g of GBL, 6.00g of BCS were added, and it stirred at room temperature for 3 hours, and obtained the liquid crystal aligning agent (18). Abnormalities, such as haze and precipitation, were not seen by this liquid crystal aligning agent, and it was confirmed that it is a uniform solution.

<Examples 38-39>

Liquid crystal aligning agents (19)-(20) were obtained by carrying out similarly to Example 34 except having used polyimide resin powder (Q)-(P) instead of the polyimide resin powder (M).

<Examples 40 to 45>

Instead of the liquid crystal aligning agent (1), the liquid crystal aligning agent shown in Table 3-2 was used, respectively, and also the same method as Example 9 except having shown the irradiation amount of an ultraviolet-ray and an immersion solution in Table 3-2. An FFS drive liquid crystal cell was produced and residual image evaluation by a long-term alternating current drive was performed. The value of the angle (DELTA) of this liquid crystal cell after long-term alternating current drive in each is shown in Table 3-2.

Table 3-2

<Examples 46-51>

Instead of the liquid crystal aligning agent (1), it uses the liquid crystal aligning agent shown in Table 4-2, and is the same as Example 17 except having made the irradiation amount of an ultraviolet-ray, and immersion solution shown in Table 4-2, respectively. Each sample for the pencil hardness test was prepared. The result of having evaluated each pencil hardness test is shown in Table 4-2.

Table 4-2

<Examples 52-57>

Instead of the liquid crystal aligning agent (1), the liquid crystal aligning agent shown in Table 5-2 was used, and also the same as Example 26 except having made the irradiation amount of an ultraviolet-ray, and immersion solution shown in Table 5-2, respectively. The sample for adhesive evaluation was produced by the method. The result of having evaluated adhesiveness is shown in Table 5-2.

Table 5-2

Industrial availability

By the liquid crystal aligning agent of this invention, the liquid crystal aligning film which has high film hardness and seal adhesiveness can be obtained in addition to favorable afterimage characteristic. Therefore, the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention has a high yield in liquid crystal panel manufacture, and can reduce the afterimage by AC drive which arises in the liquid crystal display element of an IPS drive system or a FFS drive system. The liquid crystal display element of the IPS drive system and FFS drive system which are excellent in an afterimage characteristic is obtained. Therefore, the use in the liquid crystal display element which high display quality is calculated | required is possible.

Claims (9)

Tetra containing at least 1 sort (s) chosen from tetracarboxylic dianhydride represented by following formula (1), and its derivative (s), and at least 1 sort (s) chosen from tetracarboxylic dianhydride represented by following formula (2), and its derivative (s). At least one polymer selected from a polyimide precursor obtained from a carboxylic acid derivative component and a diamine component containing at least one diamine selected from the following formulas (3) and (4) and an imide: It contains, The liquid crystal aligning agent characterized by the above-mentioned.

In the formula, X ₁ is a structure selected from the following formulas (X1-1) to (X1-4), and X ₂ is a structure selected from the following formulas (X2-1) to (X2-2).

In the formula, each of R ₃ to R ₆ independently represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, or a fluorine atom. Although it may be the same or different, it is a monovalent organic group of 6, or a phenyl group, At least one is other than a hydrogen atom. R ₇ to R ₂₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, and a 1 to 6 carbon atoms containing fluorine atom. It may be an organic group or a phenyl group, and may be same or different.

In formula, A <_1> is a single bond, an ester bond, an amide bond, a thioester bond, or a C2-C20 divalent organic group, A <_2> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a thiol group, a nitro group, phosphoric acid group, or a monovalent organic group having a carbon number of 1 ~ 20, a is an integer from 1 to 4, when a is 2 or more, a structure of a is ₁ may be the same or different. b and c are the integers of 1-2 each independently. The method of claim 1,
The ratio of the tetracarboxylic dianhydride represented by said formula (2), or its derivative is 1-30 mol% with respect to 1 mol of all the tetracarbon derivative components, The liquid crystal aligning agent characterized by the above-mentioned. The method according to claim 1 or 2,
The structure of X < ₁ > is at least 1 sort (s) chosen from following formula (X1-12)-(X1-16), The liquid crystal aligning agent characterized by the above-mentioned.

The method according to any one of claims 1 to 3,
The structure of X <_1> is said formula (X1-12), The liquid crystal aligning agent characterized by the above-mentioned. The method according to any one of claims 1 to 4,
The structure of X <_2> is represented by said formula (X2-1), The liquid crystal aligning agent characterized by the above-mentioned. The method according to any one of claims 1 to 5,
The diamine component contains at least 1 sort (s) chosen from following formula (DA-1)-(DA-20), The liquid crystal aligning agent characterized by the above-mentioned.

It is obtained from the liquid crystal aligning agent in any one of Claims 1-6, The liquid crystal aligning film characterized by the above-mentioned. The liquid crystal aligning film of Claim 7 is provided, The liquid crystal display element characterized by the above-mentioned. The method of claim 8,
And said liquid crystal display element drives a liquid crystal in a transverse electric field.