KR101951507B1 - Method for manufacturing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

Provided is a method for manufacturing a liquid crystal alignment film capable of enhancing anisotropy and suppressing unevenness caused by processing.
A film obtained by coating and firing a liquid crystal aligning agent containing at least one kind of polymer selected from the group consisting of polyimide and a precursor of the polyimide on a substrate is irradiated with polarized radiation, (A-2), (A-3), (A-4) and .
(Formula 1)

(A ₁ is a hydrogen atom or an acetyl group, A ₂ is an alkyl group having 1 ~ 6, R ₂ is a hydrogen atom or a methyl group, n is 1 or 2. A ₃ is an alkyl group having _{1 ~ 4. R 3, R} 4 is hydrogen atom or a methyl group. a _5, a ₆ is an alkyl group having 1 ~ 4. a ₆ is an alkyl group or a cycloalkyl group having 3 to 6 carbon atoms.)

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a liquid crystal alignment film, a liquid crystal alignment film, and a liquid crystal display device,

The present invention relates to a method for producing a liquid crystal alignment film for a photo alignment method, a liquid crystal alignment film obtained by the method, and a liquid crystal display element comprising the obtained liquid crystal alignment film.

In a liquid crystal display element used for a liquid crystal television, a liquid crystal display, or the like, a liquid crystal alignment film for controlling the alignment state of the liquid crystal is usually formed in the element.

At present, the most widely used liquid crystal alignment film is a liquid crystal alignment film in which the surface of a film made of polyamic acid and / or polyimide imidized on the electrode substrate is rubbed in one direction with a cloth such as cotton, nylon, or polyester, And the like.

The rubbing treatment of the film surface in the alignment process of the liquid crystal alignment film is an industrially useful method which is simple and excellent in productivity. However, the demand for high performance, high definition, and large size of liquid crystal display elements is further increased, so that the surface of the alignment film caused by the rubbing process is damaged by scratches, oscillation, mechanical force or static electricity, Various problems such as nonuniformity in the alignment treatment surface have become clear.

As an alternative to the rubbing treatment, there is known a photo alignment method in which a liquid crystal aligning ability is imparted by irradiating polarized radiation. The liquid crystal alignment treatment by the photo alignment method has been proposed using a photo-isomerization reaction, a photo-crosslinking reaction, and a photo-decomposition reaction (see Non-Patent Document 1).

On the other hand, when polyimide is used for a liquid crystal alignment film for photo-alignment, its usefulness is expected in that it has higher heat resistance than others.

In Patent Document 1, it has been proposed to use a polyimide film having an alicyclic structure such as a cyclobutane ring in the main chain for the photo alignment method.

However, the liquid crystal alignment film obtained by the photo alignment method has a problem that anisotropy with respect to the alignment direction of the polymer liquid crystal alignment film is small, as compared with rubbing. If the anisotropy is small, sufficient liquid crystal alignability can not be obtained. In the case of a liquid crystal display device, a problem such as a residual image occurs. As a method of increasing the anisotropy of the liquid crystal alignment film obtained by the photo alignment method, it has been proposed to remove the low molecular weight component produced by cutting the main chain of the polyimide by light irradiation after irradiation with light (see Patent Document 2) .

Japanese Patent Application Laid-Open No. 9-297313 Japanese Laid-Open Patent Publication No. 2011-107266

 &Quot; Liquid crystal photo alignment layer " Kiyohito, Ichimura Functional Materials Nov. 1997 Vol. 17, No. 11 13 ~ 22 pages

As a result of a study conducted by the inventors of the present invention, it has been found that a polyimide film obtained by applying and firing a polyimide film or a polyimide precursor is irradiated with polarized radiation and then immersed in water or an organic solvent, . However, when these treatments are performed, there arises a problem such as occurrence of unevenness in the obtained liquid crystal alignment film, and it has been found that the properties of the liquid crystal alignment film are largely impaired.

It is an object of the present invention to provide a method of manufacturing a liquid crystal alignment film capable of enhancing anisotropy of a liquid crystal alignment film obtained by a photo alignment method and suppressing unevenness generated during processing, And a liquid crystal alignment film obtained by the process for producing the liquid crystal alignment film.

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive investigations in order to achieve the above object. As a result, they have found that a film obtained by applying and firing a polyimide film or a polyimide precursor is irradiated with polarized radiation, and then a solution containing a specific organic solvent It is possible to remarkably improve the anisotropy of the obtained liquid crystal alignment film and to solve the problem of non-uniformity occurring in the above-mentioned liquid crystal alignment film.

Thus, the present invention has the following points.

1. An imidized film obtained by applying and firing a liquid crystal aligning agent containing at least one kind of polymer selected from the group consisting of polyimide and a precursor of the polyimide and an organic solvent onto a substrate and then firing the film is irradiated with polarized radiation (A-1), at least one kind selected from the group consisting of the following formula (A-1), formula (A-2), formula (A- By weight of a solvent containing an organic solvent.

[Chemical Formula 1]

Wherein A ₁ is a hydrogen atom or an acetyl group, A ₂ is an alkyl group having 1 to 6 carbon atoms, R ₂ is a hydrogen atom or a methyl group, and n is an integer of 1 or 2. In formula (A-1) (A-3), R ₃ and R ₄ are each independently a hydrogen atom or a methyl group. In the formula (A-2), A ₃ is an alkyl group having 1 to 4 carbon atoms. , A ₅ and A ₆ each independently represent an alkyl group having 1 to 4 carbon atoms.) In the formula (A-5), A ₆ is an alkyl group or a cycloalkyl group having 3 to 6 carbon atoms.)

2. The process for producing a liquid crystal alignment film according to 1 above, wherein the organic solvent has a boiling point of 100 to 180 占 폚.

3. The process for producing a liquid crystal alignment film according to 1 or 2 above, wherein the organic solvent is 1-methoxy-2-propanol, ethyl lactate, diacetone alcohol, methyl 3-methoxypropionate or ethyl 3-ethoxypropionate.

4. The polymer according to any one of 1 to 3 above, wherein the polymer contains at least one polymer selected from the group consisting of a polyimide precursor having a structural unit represented by the following formula (3) and an imidized polymer of the polyimide precursor Wherein the liquid crystal alignment layer is formed on the substrate.

(2)

In the (expression (3), X ₁ is the following formula (X1-1) ~ (is at least one selected from the group consisting of structures represented by the X1-9), Y ₁ is a divalent organic group, R ₁ is A hydrogen atom, or an alkyl group having 1 to 4 carbon atoms.

(3)

(Wherein (in the X1-1), R _3, R _4, R _5, and R ₆ is, an alkynyl group each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, Or a phenyl group.)

5. The polyimide precursor according to item 1, wherein the polymer is at least one selected from the group consisting of a polyimide precursor containing 60 mol% or more of the structural unit represented by the formula (3) with respect to 1 mol of the whole polymer and an imidization polymer of the polyimide precursor The method for producing a liquid crystal alignment film according to 4 above.

6. A process for producing a liquid crystal alignment film as described in 4 above, wherein X ₁ in the formula (3) is represented by the formula (X1-1).

7. The process for producing a liquid crystal alignment film as described in 4 above, wherein in the above formula (3), X ₁ is at least one selected from the group consisting of structures represented by the following formulas (X1-10) to (X1-11).

[Chemical Formula 4]

8. A process for producing a liquid crystal alignment film as described in 4 above, wherein Y ₁ in the formula (3) is at least one selected from the group consisting of structures represented by the following formulas (4) and (5).

[Chemical Formula 5]

(In the formula (5), Z ₁ represents a single bond, an ester bond, an amide bond, a thioester bond, or a divalent organic group having 2 to 10 carbon atoms.)

9. A process for producing a liquid crystal alignment film as described in 8 above, wherein Y ₁ in the formula (3) is a structure represented by the formula (4).

10. A method for producing a liquid crystal alignment film, which comprises applying a film of a liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyimide and a precursor of the polyimide to a substrate, (A-1), at least one kind selected from the group consisting of the formulas (A-1), (A-2), (A-3), An organic solvent, and a solution containing an organic solvent.

11. A liquid crystal alignment film obtained by the process for producing a liquid crystal alignment film according to any one of 1 to 9 above.

12. A liquid crystal display element comprising the liquid crystal alignment film according to 11 above.

According to the method for producing a liquid crystal alignment film of the present invention, a liquid crystal alignment film having a high anisotropy obtained by orientation by a photo alignment method can be obtained, and at the same time, a homogeneous film having no film unevenness can be obtained in the obtained liquid crystal alignment film.

Thus, the liquid crystal alignment film according to the production method of the present invention has high anisotropy, high liquid crystal alignment regulating force, excellent after-image characteristics, and can provide a high-quality liquid crystal display device when used for a liquid crystal display device.

The effect of the improvement of the anisotropy achieved by the method for producing a liquid crystal alignment film of the present invention and the effect of suppressing the occurrence of film unevenness at the time of processing can be understood from the results of Table 1 Similarly, there is a big difference depending on the solvent used.

That is, when water, isopropyl alcohol or the like is used as a solvent as shown in the following Table 1, improvement of the anisotropy of the obtained liquid crystal alignment film is hardly observed, and when these solvents are used, As shown in Fig.

However, in the case of contact treatment with a solution containing at least one organic solvent selected from the group consisting of the compounds represented by the above formulas (A-1) to (A-5) in the present invention, the anisotropy of the liquid crystal alignment layer And at the same time, the occurrence of unevenness in the obtained liquid crystal alignment film can be remarkably suppressed.

≪ Polyimide and its polyimide precursor >

In the present invention, at least one kind of polymer selected from the group consisting of a polyimide having anisotropy and a precursor of the polyimide (hereinafter simply referred to as a polymer) is irradiated with polarized radiation. The structure of the polyimide precursor or the polyimide precursor satisfying this condition is not particularly limited.

For example, as the polymer to be used in the present invention, a polyimide precursor having a structural unit represented by the following formula (3) and an imidized polymer of the polyimide precursor are preferable because of the high anisotropy of the resulting liquid crystal alignment film . From the viewpoint of solubility in an organic solvent, a polyimide precursor having a structural unit represented by the following formula (3) is particularly preferable.

[Chemical Formula 6]

In the formula (3), R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of easiness of imidization by heating, a hydrogen atom or a methyl group is particularly preferable.

X ₁ is at least one member selected from the group consisting of the structures represented by the following formulas (X1-1) to (X1-9).

(7)

In the formula (X1-1), R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, And may be the same or different. R ₃ , R ₄ , R ₅ , and R ₆ are each independently preferably a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group from the viewpoint of liquid crystal alignability. X ₁ is more preferably at least one selected from the group consisting of the structures represented by the following formulas (X1-10) and (X1-11).

[Chemical Formula 8]

Y ₁ is a divalent organic group, and its structure is not particularly limited. It is preferable that at least one kind selected from the group consisting of the structures represented by the following formulas (Y1-1) and (Y1-2) is preferable because the resultant liquid crystal alignment film has high anisotropy.

[Chemical Formula 9]

In the formula (5), Z ₁ is a single bond, an ester bond, an amide bond, a thioester bond or a divalent organic group having 2 to 10 carbon atoms.

In the Z ₁ , the ester bond is represented by -C (O) O- or -OC (O) -. The amide bond may represent a structure represented by -C (O) NH-, -C (O) NR-, -NHC (O) - or -NRC (O) -. R is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof having 1 to 10 carbon atoms.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group and a bicyclohexyl group. Examples of the alkenyl group include those obtained by substituting one or more CH ₂ -CH ₂ structures present in the alkyl group with a CH = CH structure, and more specifically, a vinyl group, allyl group, 1-propenyl group, A phenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, a 2-hexenyl group, a cyclopropenyl group, a cyclopentenyl group and a cyclohexenyl group. Examples of the alkynyl group include those wherein at least one CH ₂ -CH ₂ structure present in the alkyl group is substituted with a C≡C structure. More specifically, an ethynyl group, 1-propynyl group, 2-propynyl group, . The aryl group includes, for example, a phenyl group.

The thioester bond may represent a structure represented by -C (O) S- or -SC (O) -.

When Z ₁ is an organic group having 2 to 10 carbon atoms, it can be represented by the following formula (6).

[Chemical formula 10]

In formula (6), Z ₄ , Z ₅ and Z ₆ each independently represent a single bond, -O-, -S-, -NR ₁₁ -, an ester bond, an amide bond, a thioester bond, a urea bond , Carbonate bond, or carbamate bond. R ₁₁ is a hydrogen atom, a methyl group, or a t-butoxycarbonyl group.

The ester bond, amide bond, and thioester bond in Z ₄ , Z ₅ , and Z ₆ may have the same structure as the above ester bond, amide bond, and thioester bond.

The urea bond may represent a structure represented by -NH-C (O) NH- or -NR-C (O) NR-. R is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof having 1 to 10 carbon atoms, and these groups may be the same as the above-mentioned alkyl group, alkenyl group, alkynyl group and aryl group.

The carbonate bond may represent a structure represented by -O-C (O) -O-.

The carbamate bond includes a structure represented by -NH-C (O) -O-, -OC (O) -NH-, -NR-C (O) -O-, or -OC Lt; / RTI > R is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof having 1 to 10 carbon atoms, and these groups may be the same as the above-mentioned alkyl group, alkenyl group, alkynyl group and aryl group.

R ₉ and R ₁₀ in formula (6) each independently represent a structure selected from the group consisting of a single bond, an alkylene group having 1 to 10 carbon atoms, an alkenylene group, an alkynylene group, an arylene group, or a combination thereof. R ₉ and R ₁₀ of the case which is a single bond, R ₉ or R one of the ₁₀ not, having 2 to 10 carbon atoms, alkylene group, alkenylene group, alkynylene group, arylene group, or is selected from the combined group thereof Structure.

Examples of the alkylene group include a structure in which one hydrogen atom is removed from the alkyl group. Specific examples thereof include a methylene group, a 1,1-ethylene group, a 1,2-ethylene group, a 1,2-propylene group, a 1,3-propylene group, Propylene group, a 1,2-cyclopentylene group, a 1,2-cyclobutylene group, a 1,3-cyclohexylene group, a 1,2- Butylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group and the like.

Examples of the alkenylene group include a structure in which one hydrogen atom is removed from the alkenyl group. More specifically, examples thereof include a 1,1-ethenylene group, a 1,2-ethenylene group, a 1,2-ethenylene methylene group, a 1-methyl-1,2-ethenylene group, 1-ethylene group, 1,2-ethenylene-1,2-ethylene group, 1,2-ethenylene-1,2-propylene group, 1,2- Butylene group, 2-ethenylene-1,4-butylene group and 1,2-ethenylene-1,2-butylene group.

Examples of the alkynylene group include a structure in which one hydrogen atom is removed from the alkynyl group. Specific examples thereof include an ethynylene group, an ethynylene-1,2-ethylene group, an ethynylene-1,2-propylene group, an ethynylene- -Propylene group, ethynylene-1,4-butylene group, ethynylene-1,2-butylene group and the like.

Examples of the arylene group include a structure in which one hydrogen atom is removed from the aryl group. More specifically, examples thereof include a 1,2-phenylene group, a 1,3-phenylene group and a 1,4-phenylene group.

When a structure having a high linearity or a rigid structure is contained in Y ₁ , a liquid crystal alignment film having good liquid crystal alignability can be obtained. Therefore, as the structure of Z ₁ , a single bond or a structure represented by the following formulas (A1-1) to -25) is more preferable.

(11)

[Chemical Formula 12]

The structure represented by the formula (4) is particularly preferable for the structure of Y ₁ because a liquid crystal orientation film having excellent liquid crystal alignability can be obtained as the structure of Y ₁ is rigid.

In the imidized polymer of the polyimide precursor and the polyimide precursor containing the structural unit represented by the formula (3), the proportion of the structural unit represented by the formula (3) 60 to 100 mol% is preferable. The higher the ratio of the structural unit represented by the above formula (3) is, the more preferable it is 80 to 100 mol%, and the more preferable it is 90 to 100 mol%, because a liquid crystal alignment film having a good liquid crystal alignability can be obtained.

The polymer component of the present invention may be a polyimide precursor containing a structural unit represented by the following formula (7) and a polyimide precursor thereof in addition to the structural unit represented by the above formula (3).

[Chemical Formula 13]

In the formula (7), R ₁ has the same definition as R ₁ in the formula (3).

X ₃ is a tetravalent organic group, and its structure is not particularly limited. Specific examples include structures of the following formulas (X-9) to (X-42). From the viewpoint of availability of the compound, the structure of X ₃ is preferably X-17, X-25, X-26, X-27, X-28, X-32 or X-39. It is preferable to use tetracarboxylic acid dianhydride having an aromatic ring structure from the viewpoint of obtaining a liquid crystal alignment film which can alleviate the residual charge accumulated by the DC voltage. The X ₃ structure includes X-26 , X-27, X-28, X-32, X-35, or X-37 are more preferable.

[Chemical Formula 14]

[Chemical Formula 15]

In the formula (7), Y ₄ is a divalent organic group and its structure is not particularly limited. Specific examples of Y _{4 include structures} of the following formulas (Y-1) to (Y-74).

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

Because of its excellent solubility in organic solvents of the polymer component, it roneun Y ₄ in the formula (7), Y-8, Y-20, Y-21, Y-22, Y-28, Y-29, Y- 30, Y-72, Y-73, or Y-74.

When the proportion of the structural unit represented by the formula (7) in the polymer component is high, the liquid crystal alignability of the liquid crystal alignment film is lowered. Therefore, the proportion of the structural unit represented by the formula (7) Is preferably 0 to 40 mol%, more preferably 0 to 20 mol%.

<Production method of polyamic acid ester>

The polyamic acid ester used as the polyimide precursor used in the present invention can be synthesized by the following methods (1) to (3).

(1) Synthesis from polyamic acid

The polyamic acid ester can be synthesized by esterifying a polyamic acid obtained from a tetracarboxylic acid dianhydride and a diamine.

Specifically, it can be synthesized by reacting the polyamic acid and the esterifying agent 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 4 hours .

The esterification agent is preferably one which can be easily removed by purification. Examples of the esterification agent include N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide dineopentylbutyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazine, , 1-propyl-3-p-tolyltriazine, and 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride. The amount of the esterifying agent to be added is preferably 2 to 6 molar equivalents, more preferably 2 to 4 molar equivalents relative to 1 mol of the repeating unit of the polyamic acid.

The organic solvent to be used in the reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the solubility of the polymer, May be used.

The concentration of the polymer in the organic solvent at the time of the synthesis is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass%, from the viewpoint that the precipitation of the polymer does not occur well and the high molecular weight product is easily obtained .

(2) Synthesis by reaction of tetracarboxylic acid diester dichloride with diamine

Polyamic acid esters can be synthesized from tetracarboxylic acid diester dichloride and diamines.

Specifically, the tetracarboxylic acid diester dichloride and the diamine are reacted in the presence of a base and an organic solvent at -20 to 150 ° C, preferably 0 to 50 ° C for 30 minutes to 24 hours, preferably 1 to 4 hours Can be synthesized by reacting for a time.

As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable for the reaction to proceed mildly. The amount of the base to be added is preferably 2 to 4 times by mole, more preferably 2 to 3 times by mole, based on the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high toughness.

The organic solvent to be used in the reaction is preferably N-methyl-2-pyrrolidone or? -Butyrolactone from the viewpoint of the solubility of the monomer and the polymer, and they may be used alone or in combination of two or more.

The concentration of the polymer in the organic solvent at the time of the synthesis is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint that the precipitation of the polymer does not occur well and a high molecular weight product is easily obtained. In order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the organic solvent used for the synthesis of the polyamic acid ester is desirably dehydrated as much as possible, and the reaction is carried out in a nitrogen atmosphere, .

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

The polyamic acid ester can be synthesized by polycondensation of a tetracarboxylic acid diester and a diamine.

Specifically, the tetracarboxylic acid diester and diamine are reacted 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 Can be synthesized by reacting for a time.

Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy- N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) 1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate and (2,3-dihydro-2-thioxo-3-benzoxazolyl) . The amount of the condensing agent to be added is preferably 2 to 3 times by mole, more preferably 2 to 2.5 times by mole, based on the tetracarboxylic acid diester.

As the base, tertiary amines such as pyridine and triethylamine can be used. The amount of the base to be added is an amount that is easy to remove and is preferably 2 to 4 times, more preferably 2 to 3 times, the amount of the diamine component from the viewpoint of easily obtaining a high molecular weight product.

Examples of the organic solvent include N-methyl-2-pyrrolidone,? -Butyrolactone, and N, N-dimethylformamide.

In addition, 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. The amount of the Lewis acid to be added is preferably 0.1 to 5 times, more preferably 2 to 3 times, the amount of the diamine component.

Among the methods for synthesizing the above three polyamic acid esters, the synthesis method of the above (1) or (2) is particularly preferable because a polyamic acid ester having a high molecular weight can be obtained.

The solution of the polyamic acid ester thus obtained can be precipitated by pouring into a poor solvent while stirring well. After several times of precipitation and washing with a poor solvent, the purified polyamic acid ester powder can be obtained at room temperature or by heating and drying. Examples of the poor solvent include, but are not limited to, water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone and toluene. Water, methanol, ethanol and 2-propanol are preferred.

<Production method of polyamic acid>

Polyamic acid, which is a polyimide precursor used in the present invention, can be synthesized by the following method.

Specifically, the tetracarboxylic acid dianhydride and the diamine are reacted 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.

The organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or gamma -butyrolactone from the solubility of the monomer and the polymer, May be mixed and used.

The concentration of the polymer is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass, from the viewpoint that the precipitation of the polymer does not occur well and a high molecular weight product is easily obtained.

The polyamic acid thus obtained can be recovered by precipitating the polymer by injecting the reaction solution into a poor solvent while stirring well. It is also possible to obtain a purified polyamic acid powder by conducting precipitation several times, washing with a poor solvent, and then drying at room temperature or by heating. Examples of the poor solvent include, but are not limited to, water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone and toluene. Water, methanol, ethanol and 2-propanol are preferred.

<Production method of polyimide>

The polyimide used in the present invention can be prepared by imidizing the polyamic acid ester or polyamic acid.

In the case of producing a polyimide from a polyamic acid ester, chemical imidization by adding a basic catalyst to the polyamic acid solution obtained by dissolving the polyamic acid ester solution or the polyamic acid ester resin powder in an organic solvent is simple. The chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer does not decrease during the imidization process.

The chemical imidization can be carried out by stirring the polyamic acid ester to be imidized in an organic solvent in the presence of a basic catalyst. As the organic solvent, a solvent used in the polymerization reaction described above may be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, triethylamine is preferred because it has sufficient basicity to proceed the reaction.

The temperature at which the imidization reaction is carried out is -20 to 140 占 폚, preferably 0 to 100 占 폚, and the reaction time is 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 times by mole, preferably 2 to 20 times by mole, of the amic acid ester group. The imidization rate of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time.

In the case of producing a polyimide from polyamic acid, chemical imidization by adding a catalyst to the solution of the polyamic acid obtained in the reaction of the diamine component and the tetracarboxylic acid dianhydride is simple. The chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is not lowered in the process of imidization.

The chemical imidization can be carried out by stirring the polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As the organic solvent, a solvent used in the polymerization reaction described above may be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferred since it has a basicity suitable for proceeding the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride, and the use of acetic anhydride in the presence of acetic anhydride is preferable because purification after completion of the reaction is facilitated.

The temperature at which the imidization reaction is carried out is -20 to 140 ° C, preferably 0 to 100 ° C, and the reaction time is 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 times by mole, preferably 2 to 20 times by mole, of the polyamic acid group, and the amount of the acid anhydride is 1 to 50 times by mole, preferably 3 to 30 times by mole of the polyamic acid group. The imidization rate of the resulting polymer can be controlled by controlling the amount of catalyst, the temperature, and the reaction time.

Since the added catalyst remains in the solution after the imidization reaction of the polyamic acid ester or polyamic acid, the imidized polymer thus obtained is recovered and redissolved in an organic solvent, It is preferable to use an orientation agent.

The solution of the polyimide obtained as described above can be precipitated by pouring into a poor solvent while stirring well. After the precipitation is carried out several times, it is washed with a poor solvent and then heated or dried at room temperature to obtain a purified polymer powder.

Examples of the poor solvent include, but are not limited to, methanol, 2-propanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, , 2-propanol, acetone, and the like.

<Liquid Crystal Aligner>

The liquid crystal aligning agent used in the present invention has a form of a solution in which a polymer component is dissolved in an organic solvent. The molecular weight of the polymer is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100,000 in terms of weight average molecular weight. 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.

The concentration of the polymer of the liquid crystal aligning agent used in the present invention can be appropriately changed according to the setting of the thickness of the coating film to be formed. It is preferably 1% by mass or more from the viewpoint of forming a uniform and defect-free coating film, From the viewpoint of storage stability, it is preferable that the content is 10% by mass or less. A particularly preferable concentration of the polymer is 2 to 8 mass%.

The organic solvent contained in the liquid crystal aligning agent used in the present invention is not particularly limited as long as the polymer component is uniformly dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl- , N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethylsulfoxide, dimethylsulfone,? -Butyrolactone, 1,3-dimethyl-imidazolidinone, N, N-dimethylpropanamide, and the like. These may be used alone or in combination of two or more. Even if the solvent can not dissolve the polymer component uniformly, it may be mixed with the organic solvent as long as the solvent does not precipitate the polymer.

The liquid crystal aligning agent used in the present invention may contain, in addition to the organic solvent for dissolving the polymer component, a solvent for improving the film uniformity when the liquid crystal aligning agent is applied to the substrate. Such a solvent generally uses a solvent having a lower surface tension than the organic solvent. Specific examples thereof include ethylcellosolve, butylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy- 2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether- Propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid, isoamyl acetate, Esters and the like. These solvents may be used in combination of two or more.

As the liquid crystal aligning agent of the present invention, a polymer other than the polymer, a dielectric substance or a conductive substance for changing electric characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film, a liquid crystal alignment film A silane coupling agent for improving the adhesion of the substrate, a crosslinkable compound for increasing the hardness and density of the film when the film is used as a liquid crystal alignment film, and further, for the purpose of efficiently advancing the imidization of the polyamic acid An imidization accelerator may be added.

&Lt; Production method of liquid crystal alignment film &

The method for producing a liquid crystal alignment film of the present invention comprises a step of applying a liquid crystal aligning agent to a substrate and baking, a step of irradiating the obtained film with polarized radiation, and a step of contacting the film irradiated with the radiation with a specific organic solvent.

(1) a step of applying a liquid crystal aligning agent to a substrate and baking

The liquid crystal aligning agent thus obtained is applied to a substrate, followed by drying and firing, thereby obtaining a film in which the polyimide film or the polyimide precursor is imidized.

The substrate to which the liquid crystal aligning agent to be used in the present invention is applied is not particularly limited as long as it is a substrate having high transparency. A glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, It is preferable to use a substrate having an ITO electrode or the like formed thereon for simplification of the process. In a reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used only for a substrate on one side. In this case, a material that reflects light such as aluminum can also be used as the electrode in this case. Examples of the application method of the liquid crystal aligning agent used in the present invention include a spin coating method, a printing method, and an ink jet method.

The drying and firing steps after application of the liquid crystal aligning agent can be carried out at arbitrary temperature and time. Usually, in order to sufficiently remove the contained organic solvent, it is dried at 50 to 120 ° C, preferably 60 to 100 ° C for 1 to 10 minutes, and then dried at 150 to 300 ° C, preferably 200 to 250 ° C, ~ 120 minutes. The thickness of the coated film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may deteriorate. Therefore, it is 5 to 300 nm, preferably 10 to 200 nm.

(2) a step of irradiating the obtained film with polarized radiation

Anisotropy is imparted to the film obtained by the above method (1) in a direction perpendicular to the polarization direction by irradiating polarized radiation (hereinafter also referred to as photo-alignment treatment).

As a specific example of the photo-alignment treatment, the surface of the coating film is irradiated with radiation polarized in a predetermined direction, and if necessary, heat treatment is further carried out at a temperature of 150 to 250 ° C to give a liquid crystal aligning ability Method. As the wavelength of the radiation, ultraviolet rays and visible rays having a wavelength of 100 to 800 nm can be used. Of these, ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and those having a wavelength of 200 to 400 nm are particularly preferable.

The irradiation dose of the radiation is preferably in the range of 1 to 10,000 mJ / cm 2, and particularly preferably in the range of 100 to 5,000 mJ / cm 2.

(3) a step of contacting the film irradiated with the radiation with a solution containing an organic solvent

In the above, the film irradiated with the polarized radiation is then contact-treated with a solution containing a specific organic solvent. The organic solvent used here is selected from the group consisting of the following formula (A-1), formula (A-2), formula (A-3), formula (A- At least one organic solvent or organic solvent.

[Chemical Formula 21]

In the formula (A-1), A ₁ is a hydrogen atom or an acetyl group, A ₂ is an alkyl group having 1 to 6 carbon atoms, R ₂ is a hydrogen atom or a methyl group, and n is an integer of 1 or 2.

In the formula (A-2), A ₃ is an alkyl group having 1 to 4 carbon atoms.

In the formula (A-3), R ₃ and R ₄ are each independently a hydrogen atom or a methyl group.

In the formula (A-4), A ₅ and A ₆ is an alkyl group having from 1 to 4 carbon atoms independently of each other.

In the formula (A-5), A ₆ is an alkyl group or a cycloalkyl group having 3 to 6 carbon atoms.

The organic solvents of the above formulas (A-1) to (A-5) preferably have a boiling point of preferably 100 to 180 ° C, more preferably 110 to 160 ° C. When the boiling point is high, the film remains in the film and adversely affects the characteristics of the liquid crystal alignment film. On the other hand, when the boiling point is low, the film tends to be easily volatilized.

Among the organic solvents of the above formulas (A-1) to (A-5), among them, 1-methoxy-2-propanol, 1-methoxy Propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate. Is preferable. Particularly, at least one species selected from the group consisting of 1-methoxy-2-propanol and ethyl lactate is preferable.

The solution containing the organic solvent used for the contact treatment may contain a solvent or a solvent other than the organic solvent of the above formulas (A-1) to (A-5) within the range not impairing the effect of the present invention . Other solvents include, but are not limited to, water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone and the like. In particular, water is more preferable in view of versatility and safety.

The content of the at least one organic solvent selected from the group consisting of the above-mentioned formulas (A-1) to (A-5) is not particularly limited so long as the total amount of the solution used for the contact treatment Is preferably 10 to 100 mass%, more preferably 30 to 100 mass%, and particularly preferably 50 to 100 mass%.

In the present invention, the contact treatment of a film irradiated with polarized radiation and a solution containing an organic solvent is carried out by a treatment in which the film and the liquid preferably sufficiently come into contact, such as an immersion treatment, a spray (spray) treatment or the like. Among them, a method of immersing the film in a solution containing an organic solvent, preferably for 10 seconds to 1 hour, more preferably for 1 to 30 minutes, is preferable. The contact treatment may be carried out at room temperature, but is preferably carried out at 10 to 80 캜, more preferably at 20 to 50 캜. It is also possible to implement means for increasing the contact of ultrasonic waves or the like as necessary.

After the contact treatment, any one or both of rinsing (rinsing) with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone or the like and drying may be performed for removing the organic solvent in the used solution . The temperature for drying is preferably 80 to 250 ° C, more preferably 80 to 150 ° C.

<Liquid crystal display element>

The liquid crystal display element of the present invention can be obtained by obtaining a substrate having a liquid crystal alignment film obtained by the production method of the present invention and obtained from a liquid crystal aligning agent and then manufacturing a liquid crystal cell by a known method, Device.

As an example of a method for manufacturing a liquid crystal cell, a liquid crystal display element having a passive matrix structure will be described as an example. Further, the liquid crystal display element may have an active matrix structure in which a switching element such as a TFT (Thin Film Transistor) is formed in each pixel portion constituting the image display.

First, a transparent glass substrate is prepared, a common electrode is formed on one substrate, and a segment electrode is formed on the other substrate. These electrodes can be, for example, ITO electrodes and are patterned so as to perform desired image display. Next, an insulating film is formed on each substrate so as to cover the common electrode and the segment electrode. The insulating film can be, for example, a film made of SiO ₂ -TiO ₂ formed by a sol-gel method.

Next, the liquid crystal alignment film of the present invention is formed on each substrate.

Next, the other substrate is superimposed on one substrate so that the orientation film surfaces of the other substrates face each other, and the periphery is bonded to the substrate with a sealing material. In order to control the substrate gap, a spacer is normally mixed in the sealing material. It is also preferable to disperse the spacer for controlling the gap of the substrate to the in-plane portion where the sealing material is not formed. In the part of the sealing material, an opening portion capable of filling the liquid crystal from the outside is formed.

Next, the liquid crystal material is injected into the space surrounded by the two substrates and the sealing material through the opening formed in the sealing material. Thereafter, this opening is sealed with an adhesive. For the injection, a vacuum injection method may be used, or a method using capillary phenomenon in the atmosphere may be used. Next, the polarizing plate is installed. More specifically, a pair of polarizers is attached to a surface of the two substrates opposite to the liquid crystal layer. Through the above steps, the liquid crystal display element of the present invention is obtained. Since this liquid crystal display element uses the liquid crystal alignment film obtained by the production method of the liquid crystal alignment film of the present invention as the liquid crystal alignment film, it has excellent afterimage characteristics and can be preferably used for a liquid crystal television with a large screen and high precision.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

The abbreviations of the compounds used in Examples and Comparative Examples and the measurement methods of the respective properties are as follows.

NMP: N-methyl-2-pyrrolidone

GBL:? -Butyrolactone

BCS: butyl cellosolve

IPA: 2-propanol

PGMEA: 1-methoxy-2-propanol acetate

PG: Propylene glycol

MMP: methyl-3-methoxypropionate

DE-1: The following formula (DE-1)

DA-1: The following formula (DA-1)

DA-2: The following formula (DA-2)

DA-3: The following formula (DA-3)

Additive A: N -? - (9-Fluorenylmethoxycarbonyl) -N-t-butoxycarbonyl-L-histidine

[Chemical Formula 22]

The molecular weight, anisotropy of the alignment film, and evaluation method of film unevenness are shown below.

[Molecular Weight]

The molecular weight of the polyamic acid ester 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 calculated as polyethylene glycol and polyethylene oxide conversion values.

GPC apparatus: manufactured by Shodex Corp. (GPC-101)

Column: manufactured by Shodex Co., Ltd. (serial of KD803, KD805)

Column temperature: 50 ° C

Eluent: N, N- dimethylformamide (as an additive, lithium bromide-hydrate (LiBr · H ₂ O) is 30 m㏖ / ℓ (L), phosphoric acid anhydrous crystal (o- phosphoric acid) is 30 m㏖ / ℓ, 10 ml / l of tetrahydrofuran (THF)

Flow rate: 1.0 ml / min

Standard samples for preparing a calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (polymer peak molecular weight (Mp) 4,000, 1,000). In order to avoid overlapping of peaks, the measurement was carried out separately on two samples of samples mixed with four types of 900,000, 100,000, 12,000 and 1,000, and three samples of 150,000, 30,000 and 4,000.

[Anisotropy of alignment layer]

The measurement of the anisotropy of the alignment film was carried out as follows.

The measurement was carried out using an ultraviolet-visible-near infrared spectrophotometer (UV-3100PC) manufactured by Shimadzu Corporation. The anisotropy was measured from the absorbance (the value of 235 nm) with respect to the alignment direction of the obtained alignment film and the absorbance with respect to the direction perpendicular to the alignment direction.

[Membrane unevenness]

The film unevenness was evaluated by observing the substrate with the film after the immersion treatment with naked eyes and classified as follows.

○: No unevenness

△: Unevenness was seen a little

X: Large unevenness and whitening were observed

&Lt; Synthesis Example 1 &

In a 500 ml four-necked flask equipped with a stirrer, 4.58 g (42.4 mmol) of p-phenylenediamine was placed in a nitrogen atmosphere, 1.79 g (4.71 mmol) of DA-1 was further added, , 254 g of GBL and 8.40 g (106 mmol) of pyridine as a base were added and dissolved by stirring. Next, while stirring the diamine solution, 14.4 g (44.2 mmol) of DE-1 was added and the reaction was allowed to proceed at 15 占 폚 overnight. After stirring overnight, 1.23 g (13.6 mmol) of acryloyl chloride was added, and the mixture was reacted at 15 DEG C for 4 hours. A solution of the obtained polyamic acid ester was added to 1477 g of IPA under stirring. The precipitated white precipitate was collected by filtration, washed with 738 g of IPA five times, and dried to obtain 17.3 g of a white polyamic acid ester resin powder &Lt; / RTI &gt; The yield was 96.9%. The molecular weight of the polyamic acid ester was Mn = 14,288 and Mw = 29,956.

The obtained polyamic acid ester resin powder (3.69 g) was taken in a 100 ml Erlenmeyer flask, and 33.2 g of GBL was added. The mixture was stirred at room temperature for 24 hours and dissolved to obtain a polyamic acid ester solution.

&Lt; Synthesis Example 2 &

5.26 g of the polyamic acid ester solution obtained in Synthesis Example 1, 3.16 g of GBL, 2.11 g of BCS and 0.19 g of Additive A were added to a 20 ml sample tube into which a stirrer was placed, and the mixture was stirred with a magnetic stirrer for 30 minutes , Liquid crystal aligning agent A was obtained.

&Lt; Synthesis Example 3 &

2.50 g (23.1 mmol) of p-phenylenediamine was added, 0.59 g (1.22 mmol) of DA-2 was further added, and the mixture was poured into a 500 mL four-necked flask equipped with a stirrer, , 129 g of GBL, and 4.34 g (54.9 mmol) of pyridine as a base were added and dissolved by stirring. Next, while stirring the diamine solution, 7.44 g (22.9 mmol) of DE-1 was added and the reaction was allowed to proceed at 15 占 폚 overnight. After stirring overnight, 0.63 g (7.01 mmol) of acryloyl chloride was added and the reaction was carried out at 15 ° C for 4 hours. The resulting polyamic acid ester solution was added to 574 g of IPA while stirring. The precipitated white precipitate was collected by filtration, washed with 382 g of IPA five times, and dried to obtain 8.82 g of a white polyamic acid ester resin powder &Lt; / RTI &gt; The yield was 97.8%. The molecular weight of the polyamic acid ester was Mn = 16617 and Mw = 37387.

0.80 g of the obtained polyamic acid ester resin powder was placed in a 100 ml Erlenmeyer flask, 7.20 g of GBL was added, and the mixture was stirred at room temperature for 24 hours and dissolved to obtain a polyamic acid ester solution.

&Lt; Synthesis Example 4 &

8.00 g of the polyamic acid ester solution obtained in Synthesis Example 3, 8.01 g of GBL, 4.00 g of BCS and 0.28 g of Additive A were added to a 20-ml sample tube equipped with a stirrer and stirred with a magnetic stirrer for 30 minutes , Liquid crystal aligning agent B was obtained.

&Lt; Synthesis Example 5 &

A 500 ml four-necked flask equipped with a stirrer was charged with 1.23 g (11.3 mmol) of p-phenylenediamine, and further added with 4,4'-diamino-1,2-diphenylethane Was added 0.80 g (3.77 mmol) of NMP, followed by addition of 27.0 g of NMP, 91.2 g of GBL and 2.69 g (34.0 mmol) of pyridine as a base, followed by dissolving with stirring. Then, while stirring the diamine solution, 4.61 g (14.2 mmol) of DE-1 was added and the reaction was allowed to proceed at 15 占 폚 overnight. After stirring overnight, 0.39 g (4.34 mmol) of acryloyl chloride was added and the reaction was carried out at 15 ° C for 4 hours. The solution of the obtained polyamic acid ester was added to 384 g of IPA under agitation. The precipitated white precipitate was collected by filtration, washed with 256 g of IPA five times, and dried to obtain 5.11 g of white polyamic acid ester resin powder &Lt; / RTI &gt; The yield was 89.6%. The molecular weight of the polyamic acid ester was Mn = 14806 and Mw = 32719.

0.80 g of the obtained polyamic acid ester resin powder was placed in a 100 ml Erlenmeyer flask, 7.20 g of GBL was added, and the mixture was stirred at room temperature for 24 hours and dissolved to obtain a polyamic acid ester solution.

&Lt; Synthesis Example 6 &

8.01 g of the polyamic acid ester solution obtained in Synthesis Example 5, 8.01 g of GBL, 4.00 g of BCS and 0.28 g of Additive A were added to a 20 ml sample tube containing the stirrer, and the mixture was stirred with a magnetic stirrer for 30 minutes , Liquid crystal aligning agent C was obtained.

&Lt; Synthesis Example 7 &

In a 500 ml four-necked flask equipped with a stirrer, 2.80 g (25.9 mmol) of p-phenylenediamine was added, and 1.45 g (6.47 mmol) of DA-3 was further added thereto. , And 6.18 g (78.1 mmol) of pyridine as a base were added and dissolved by stirring. Then, while stirring the diamine solution, 9.89 g (30.4 mmol) of DE-1 was added, and the reaction was allowed to proceed at 15 占 폚 overnight. After stirring overnight, 0.38 g (4.21 mmol) of acryloyl chloride was added and the reaction was carried out at 15 ° C for 4 hours. The resulting polyamic acid ester solution was added to 1230 g of water with stirring. The precipitated white precipitate was collected by filtration, washed with 1230 g of IPA five times, and dried to obtain 10.2 g of a white polyamic acid ester resin powder &Lt; / RTI &gt; The yield was 83.0%. The molecular weight of the polyamic acid ester was Mn = 20,786 and Mw = 40,973.

0.798 g of the obtained polyamic acid ester resin powder was placed in a 100 ml Erlenmeyer flask, 7.18 g of GBL was added, and the mixture was stirred at room temperature for 24 hours and dissolved to obtain a polyamic acid ester solution.

&Lt; Synthesis Example 8 &

8.02 g of GBL, 4.00 g of BCS and 0.28 g of additive A were added to a 20-ml sample tube containing the stirrer, and 7.98 g of the polyamic acid ester solution obtained in Synthesis Example 7 was added, and stirred for 30 minutes with a magnetic stirrer , Liquid crystal aligning agent D was obtained.

&Lt; Synthesis Example 9 &

46.0 g (0.43 mol) of p-phenylenediamine, 17.8 g (0.075 mol) of DA-3 and 1389 g of NMP were placed in a 300 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, . While this solution was stirred, 107 g (0.48 mol) of 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added, and NMP was further added thereto so as to have a solid content concentration of 10 mass% And the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid (PAA-1). The viscosity of this polyamic acid solution at 25 캜 was 215 mPa.. The molecular weight of the polyamic acid was Mn = 12629 and Mw = 29521.

&Lt; Synthesis Example 10 &

11.0 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 9, 5.00 g of NMP, 4.01 g of BCS and 0.15 g of Additive A were placed in a 50 ml sample tube equipped with a stirrer and stirred with a magnetic stirrer for 30 minutes To obtain liquid crystal aligning agent E.

&Lt; Synthesis Example 11 &

4.25 g (20.0 mmol) of 4,4'-diamino-1,2-diphenylethane was placed in a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 70.9 g of NMP was added, Followed by stirring and dissolving. While stirring the diamine solution, 3.82 g (19.5 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added, NMP was further added so that the solid content concentration became 10% by mass, At room temperature for 24 hours to obtain a solution of polyamic acid (PAA-2). The viscosity of the polyamic acid solution at 25 캜 was 156 mPa.. The molecular weight of this polyamic acid was Mn = 13966 and Mw = 33163.

&Lt; Synthesis Example 12 &

12.2 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 11 was taken in a 20 ml sample tube containing the stirrer, 5.12 g of NMP and 2.90 g of BCS were added and stirred for 30 minutes by a magnetic stirrer, To obtain an orientation agent F.

&Lt; Synthesis Example 13 &

5.17 g (20.0 mmol) of 1,3-bis (4-aminophenoxy) propane was placed in a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 72.0 g of NMP was added, And dissolved by stirring. While stirring the diamine solution, 3.79 g (19.3 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added, NMP was further added so that the solid content concentration became 10% by mass, And stirred for 24 hours to obtain a solution of polyamic acid (PAA-3). The viscosity of the polyamic acid solution at 25 캜 was 162 mPa.. The molecular weight of the polyamic acid was Mn = 25902 and Mw = 40413.

&Lt; Synthesis Example 14 &

11.9 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 13 was taken in a 20 ml sample tube containing the stirrer, 3.98 g of NMP and 3.97 g of BCS were added and stirred for 30 minutes by a magnetic stirrer, To obtain an alignment agent G.

&Lt; Example 1 &gt;

The liquid crystal aligning agent A obtained in Synthesis Example 2 was filtered with a filter of 1.0 占 퐉, spin-coated on a glass substrate, dried on a hot plate at 80 占 폚 for 3 minutes and then baked at 230 占 폚 for 10 minutes to give a film thickness of 100 Nm polyimide film was obtained. Ultraviolet rays of 254 nm were irradiated with 1.2 J / cm &lt; 2 &gt; through the polarizing plate on this coating film surface.

Subsequently, the substrate with the film thus obtained was immersed in PGME (boiling point: 120 ° C) for 3 minutes at 25 ° C, rinsed with IPA for 1 minute (rinsed), and dried in an oven at 80 ° C for 10 minutes to obtain a liquid crystal alignment film . The anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was measured. As a result, the size of the anisotropy was 1.84. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 2 &gt;

A substrate having a film obtained by applying UV light to a polyimide film coated, dried, and fired on a substrate using the liquid crystal aligning agent A obtained in Synthesis Example 2 was subjected to the same procedure as in Example 1 to obtain PGMEA (boiling point: 146 占 폚 ) At 25 캜 for 3 minutes, rinsed with IPA for 1 minute, and dried in an oven at 80 캜 for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.51. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 3 &gt;

The substrate on which the film obtained by applying the UV light to the polyimide film coated, dried and fired on the substrate using the liquid crystal aligning agent A obtained in Synthesis Example 2 was subjected to the same procedure as in Example 1, 1 (volume ratio) mixed solvent for 3 minutes, rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.69. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

<Example 4>

The liquid crystal alignment agent A obtained in Synthesis Example 2 was used in the same manner as in Example 1, and the substrate on which the film obtained by applying, drying and firing the polyimide film on the substrate was irradiated with ultraviolet light was dissolved in ethyl lactate (boiling point: 154 占 폚) at 25 占 폚 for 3 minutes, rinsed with IPA for 1 minute, and dried in an oven at 80 占 폚 for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.9. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 5 &gt;

The liquid crystal aligning agent A obtained in Synthesis Example 2 was used in the same manner as in Example 1, and the substrate on which the film obtained by applying, drying and firing the polyimide film on the substrate was irradiated with ultraviolet rays was treated with butyl cellosolve : 169 占 폚) at 25 占 폚 for 10 minutes, rinsed with IPA for 1 minute, and dried in an oven at 80 占 폚 for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.69. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 6 &gt;

A substrate on which a film obtained by applying UV light to a polyimide film coated, dried and fired on a substrate using the liquid crystal aligning agent A obtained in Synthesis Example 2 was subjected to the same procedure as in Example 1, ) At 25 캜 for 3 minutes, rinsed with water for 1 minute, and dried in an oven at 80 캜 for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.82. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 7 &gt;

The liquid crystal alignment agent A obtained in Synthesis Example 2 was used in the same manner as in Example 1, and the substrate on which the film obtained by applying, drying and firing the polyimide film on the substrate was irradiated with ultraviolet light was dissolved in ethyl lactate (boiling point: 154 deg. C) for 3 minutes at 25 deg. C, rinsed with water for 1 minute, and dried in an oven at 80 deg. C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.84. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 8 &gt;

A substrate on which a film obtained by applying ultraviolet light to a polyimide film coated, dried, and baked on a substrate using the liquid crystal aligning agent A obtained in Synthesis Example 2 was treated in the same manner as in Example 1 with diacetone alcohol (boiling point: 169 占 폚) at 25 占 폚 for 3 minutes, rinsed with water for 1 minute, and dried in an oven at 80 占 폚 for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.77. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 9 &gt;

The substrate with the film obtained by applying UV light to the polyimide film coated, dried and fired on the substrate using the liquid crystal aligning agent A obtained in Synthesis Example 2 was subjected to MMP (boiling point: 145 ° C ) At 25 캜 for 3 minutes, rinsed with water for 1 minute, and dried in an oven at 80 캜 for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.77. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 10 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The liquid crystal aligning agent B obtained in Synthesis Example 4 was used, and the substrate with the film obtained by applying UV light to the polyimide film coated, dried and sintered on the substrate was immersed in PGME (boiling point: 120 ° C) for 3 minutes at 25 ° C , Rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.72. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 11 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The liquid crystal aligning agent B obtained in Synthesis Example 4 was used, and the substrate having the film obtained by applying UV light to the polyimide film coated, dried and fired on the substrate was immersed in ethyl lactate (boiling point: 154 캜) at 25 캜 for 3 Minute, rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 2.11. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 12 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The liquid crystal aligning agent C obtained in Synthesis Example 6 was used, and the substrate with the film obtained by applying UV light to the polyimide film coated on the substrate, dried and fired was immersed in PGME (boiling point: 120 ° C) for 3 minutes at 25 ° C , Rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.53. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 13 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The liquid crystal aligning agent C obtained in Synthesis Example 6 was used and the substrate having the film obtained by applying, drying and firing the polyimide film on the substrate and irradiating ultraviolet rays was immersed in ethyl lactate (boiling point: 154 캜) at 25 캜 for 3 Minute, rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.94. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 14 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The liquid crystal aligning agent D obtained in Synthesis Example 8 was used, and the substrate having the film obtained by applying UV light to the polyimide film coated on the substrate, dried and fired was immersed in PGME (boiling point: 120 ° C) for 3 minutes at 25 ° C , Rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The degree of anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.40. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 15 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The liquid crystal aligning agent D obtained in Synthesis Example 8 was used, and the substrate on which the film obtained by applying, drying and firing the polyimide film on the substrate was irradiated with ultraviolet light was immersed in ethyl lactate (boiling point: 154 캜) at 25 캜 for 3 Minute, rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The degree of anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.70. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 16 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The liquid crystal aligning agent A obtained in Synthesis Example 2 was used, and the substrate on which the film obtained by applying, drying and baking the polyimide film on the substrate was irradiated with ultraviolet rays was immersed in PGME (boiling point: 120 ° C) for 3 minutes at 25 ° C , Rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.37. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 17 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The liquid crystal aligning agent A obtained in Synthesis Example 2 was used, and the substrate having the film obtained by applying, drying and baking the polyimide film on the substrate was irradiated with ultraviolet rays at a temperature of 25 DEG C at 25 DEG C in ethyl lactate (boiling point: 154 DEG C) Minute, rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.77. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 18 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The substrate with the film obtained by applying ultraviolet rays to the polyimide film coated, dried and fired on the substrate using the liquid crystal aligning agent E obtained in Synthesis Example 10 was immersed in PGME (boiling point: 120 ° C) for 3 minutes at 25 ° C , Rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.33. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 19 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The liquid crystal aligning agent E obtained in Synthesis Example 10 was used and the substrate with the film obtained by applying UV light to the polyimide film coated, dried and fired on the substrate was immersed in ethyl lactate (boiling point: 154 ° C) at 25 ° C for 3 Minute, rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The size of anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.2. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 20 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 1.0 J / cm 2. The substrate to which the film obtained by applying UV light to the polyimide film coated, dried and fired on the substrate using the liquid crystal aligning agent F obtained in Synthesis Example 12 was immersed in PGME (boiling point: 120 ° C) for 3 minutes at 25 ° C , Rinsed with IPA for 1 minute, and dried in an oven at 80 ° C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.15. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 21 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 1.0 J / cm 2. The liquid crystal aligning agent F obtained in Synthesis Example 12 was used, and the substrate having the film obtained by applying UV light to the polyimide film coated, dried and fired on the substrate was immersed in ethyl lactate (boiling point: 154 캜) at 25 캜 for 3 Minute, rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.12. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 22 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 1.0 J / cm 2. The liquid crystal aligning agent G obtained in Synthesis Example 14 was used, and the substrate with the film obtained by applying UV light to the polyimide film coated on the substrate, dried and fired was immersed in PGME (boiling point: 120 ° C) for 3 minutes at 25 ° C , Rinsed with IPA for 1 minute, and dried in an oven at 80 ° C for 10 minutes to obtain a liquid crystal alignment film.

The degree of anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.11. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Example 23 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 1.0 J / cm 2. The liquid crystal aligning agent G obtained in Synthesis Example 14 was used, and the substrate on which the film obtained by applying, drying and firing the polyimide film on the substrate was irradiated with ultraviolet light was immersed in ethyl lactate (boiling point: 154 캜) at 25 캜 for 3 Minute, rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.10. Further, when the liquid crystal alignment film was observed with naked eyes, no unevenness was observed.

&Lt; Comparative Example 1 &

The substrate on which the film obtained by irradiating ultraviolet rays onto the polyimide film coated, dried and fired on the substrate using the liquid crystal aligning agent A obtained in Synthesis Example 2 was treated in the same manner as in Example 1 with IPA (boiling point: 82.4 DEG C ) At 25 캜 for 3 minutes and then dried in an oven at 80 캜 for 10 minutes to obtain a liquid crystal alignment film.

The size of anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.2. Further, when the alignment film was observed with the naked eye, a slight irregularity was observed.

&Lt; Comparative Example 2 &

The liquid crystal alignment agent A obtained in Synthesis Example 2 was used in the same manner as in Example 1 to irradiate ultraviolet light onto the polyimide film coated on the substrate, dried and fired, and the substrate having the film attached thereto was immersed in water (boiling point: 100 ° C ) For 3 minutes, rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.25. Further, when the liquid crystal alignment film was observed with naked eyes, the unevenness was slightly seen.

&Lt; Comparative Example 3 &

A substrate on which a film obtained by applying UV light to a polyimide film coated, dried, and fired on a substrate using the liquid crystal aligning agent A obtained in Synthesis Example 2 was treated in the same manner as in Example 1 to obtain PG (boiling point: 187 deg. C ) At 25 캜 for 3 minutes, rinsed with IPA for 1 minute, and dried in an oven at 80 캜 for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.45. Further, when the alignment film was observed with the naked eye, large unevenness and whitening were observed.

&Lt; Comparative Example 4 &

A substrate on which a film obtained by irradiating ultraviolet rays onto a polyimide film coated, dried and fired on a substrate using the liquid crystal aligning agent A obtained in Synthesis Example 2 was treated in the same manner as in Example 1 with GBL (boiling point: 204 ° C ) At 25 캜 for 3 minutes, rinsed with IPA for 1 minute, and dried in an oven at 80 캜 for 10 minutes to obtain a liquid crystal alignment film.

In the obtained liquid crystal alignment film, all of the films were dissolved, and measurement of anisotropy and measurement of film thickness were impossible.

&Lt; Comparative Example 5 &

A substrate on which a film obtained by applying ultraviolet rays to a polyimide film coated, dried and fired on a substrate using the liquid crystal aligning agent A obtained in Synthesis Example 2 was subjected to NMP (boiling point: 202 占 폚 ) At 25 캜 for 3 minutes, rinsed with IPA for 1 minute, and dried in an oven at 80 캜 for 10 minutes to obtain a liquid crystal alignment film.

In the obtained liquid crystal alignment film, all of the films were dissolved, and measurement of anisotropy and measurement of film thickness were impossible.

&Lt; Comparative Example 6 &gt;

In the same manner as in Example 1, the liquid crystal aligning agent A obtained in Synthesis Example 2 was used, and the liquid crystal alignment layer on the substrate with the film obtained by irradiating ultraviolet rays onto the polyimide film coated on the substrate, dried, The size of the anisotropy was 1.18. Film unevenness of the liquid crystal alignment film was not observed.

&Lt; Comparative Example 7 &

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The liquid crystal aligning agent B obtained in Synthesis Example 4 was used, and the substrate with the film obtained by applying UV light to the polyimide film coated on the substrate, dried and fired was immersed in IPA (boiling point: 82.4 ° C) for 3 minutes at 25 ° C And dried in an oven at 80 ° C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.19. Further, when the alignment film was observed with the naked eye, a slight irregularity was observed.

&Lt; Comparative Example 8 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The substrate with the film obtained by applying ultraviolet rays to the polyimide film coated, dried and fired on the substrate using the liquid crystal aligning agent B obtained in Synthesis Example 4 was dipped in water (boiling point: 100 ° C) for 3 minutes, Rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.17. Further, when the liquid crystal alignment film was observed with naked eyes, the unevenness was slightly seen.

&Lt; Comparative Example 9 &

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The size of anisotropy with respect to the alignment direction of the liquid crystal alignment film on the substrate on which the film obtained by applying ultraviolet rays to the polyimide film coated, dried and fired on the substrate was obtained using the liquid crystal aligning agent B obtained in Synthesis Example 4 was 1.12. Film unevenness of the liquid crystal alignment film was not observed.

&Lt; Comparative Example 10 &

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The liquid crystal aligning agent C obtained in Synthesis Example 6 was used, and the substrate with the film obtained by applying, drying and firing the polyimide film on the substrate was irradiated with ultraviolet rays and immersed in IPA (boiling point: 82.4 ° C) for 3 minutes at 25 ° C And dried in an oven at 80 ° C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.12. Further, when the alignment film was observed with the naked eye, a slight irregularity was observed.

&Lt; Comparative Example 11 &

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. A substrate having a film obtained by applying ultraviolet rays to a polyimide film coated, dried and fired on a substrate using the liquid crystal aligning agent C obtained in Synthesis Example 6 was dipped in water (boiling point: 100 ° C) for 3 minutes, Rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.16. Further, when the liquid crystal alignment film was observed with naked eyes, the unevenness was slightly seen.

&Lt; Comparative Example 12 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The anisotropy of the alignment direction of the liquid crystal alignment film on the substrate on which the film obtained by irradiating ultraviolet rays to the polyimide film coated, dried and fired on the substrate using the liquid crystal aligning agent C obtained in Synthesis Example 6 was 1.11. Film unevenness of the liquid crystal alignment film was not observed.

&Lt; Comparative Example 13 &

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The liquid crystal aligning agent D obtained in Synthesis Example 8 was used, and the substrate with the film obtained by applying the UV light to the polyimide film coated on the substrate, dried and fired was immersed in IPA (boiling point: 82.4 ° C) for 3 minutes at 25 ° C And dried in an oven at 80 ° C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.19. Further, when the alignment film was observed with the naked eye, a slight irregularity was observed.

&Lt; Comparative Example 14 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The liquid crystal aligning agent D obtained in Synthesis Example 8 was used, and the substrate with the film obtained by applying UV light to the polyimide film coated on the substrate, dried and fired was immersed in water (boiling point: 100 ° C) for 3 minutes, Rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.19. Further, when the liquid crystal alignment film was observed with naked eyes, the unevenness was slightly seen.

&Lt; Comparative Example 15 &

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The anisotropy of the alignment direction of the liquid crystal alignment film on the substrate on which the film obtained by irradiating ultraviolet light to the polyimide film coated, dried, and baked on the substrate using the liquid crystal aligning agent D obtained in Synthesis Example 8 was 1.12. Film unevenness of the liquid crystal alignment film was not observed.

&Lt; Comparative Example 16 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The liquid crystal aligning agent A obtained in Synthesis Example 2 was used, and the substrate having the film obtained by applying, drying and baking the polyimide film on the substrate was exposed to IPA (boiling point: 82.4 DEG C) for 3 minutes at 25 DEG C And dried in an oven at 80 ° C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.17. Further, when the alignment film was observed with the naked eye, a slight irregularity was observed.

&Lt; Comparative Example 17 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The liquid crystal alignment agent A obtained in Synthesis Example 2 was used, and the substrate with the film obtained by applying UV light to the polyimide film coated on the substrate, dried and fired was immersed in water (boiling point: 100 ° C) for 3 minutes, Rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.17. Further, when the liquid crystal alignment film was observed with naked eyes, the unevenness was slightly seen.

&Lt; Comparative Example 18 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The anisotropy of the alignment direction of the liquid crystal alignment film on the substrate on which the film obtained by irradiating ultraviolet rays onto the polyimide film coated, dried and fired on the substrate using the liquid crystal aligning agent A obtained in Synthesis Example 2 was 1.12. Film unevenness of the liquid crystal alignment film was not observed.

&Lt; Comparative Example 19 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The liquid crystal aligning agent E obtained in Synthesis Example 10 was used, and the substrate with the film obtained by applying UV light to the polyimide film coated on the substrate, dried and fired was immersed in IPA (boiling point: 82.4 ° C) for 3 minutes at 25 ° C And dried in an oven at 80 ° C for 10 minutes to obtain a liquid crystal alignment film.

The degree of anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.11. Further, when the alignment film was observed with the naked eye, a slight irregularity was observed.

&Lt; Comparative Example 20 &

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. A substrate having a film obtained by applying ultraviolet rays to a polyimide film coated, dried and fired on a substrate using the liquid crystal aligning agent E obtained in Synthesis Example 10 was immersed in water (boiling point: 100 占 폚) for 3 minutes, Rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The degree of anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.11. Further, when the liquid crystal alignment film was observed with naked eyes, the unevenness was slightly seen.

&Lt; Comparative Example 21 &

Except that ultraviolet rays of 254 nm were irradiated at 0.5 J / cm &lt; 2 &gt;. The liquid crystal aligning agent E obtained in Synthesis Example 10 was used and the anisotropy of the alignment direction of the liquid crystal alignment film on the substrate with the film obtained by applying ultraviolet rays to the polyimide film coated, dried and baked on the substrate was 1.08. Film unevenness of the liquid crystal alignment film was not observed.

&Lt; Comparative Example 22 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 1.0 J / cm 2. The liquid crystal aligning agent F obtained in Synthesis Example 12 was used to immerse the substrate on which the film obtained by applying, drying and firing the polyimide film on the substrate with ultraviolet light was immersed in IPA (boiling point: 82.4 ° C) for 3 minutes at 25 ° C And dried in an oven at 80 ° C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.04. Further, when the alignment film was observed with naked eyes, nonuniformity was observed.

&Lt; Comparative Example 23 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 1.0 J / cm 2. The liquid crystal aligning agent F obtained in Synthesis Example 12 was used to immerse a substrate having a film obtained by applying UV light on a polyimide film coated, dried and fired on a substrate for 3 minutes in water (boiling point: 100 ° C) Rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of the anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.10. Further, when the liquid crystal alignment film was observed with naked eyes, the unevenness was slightly seen.

&Lt; Comparative Example 24 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 1.0 J / cm 2. The anisotropy of the alignment direction of the liquid crystal alignment film on the substrate with the film obtained by irradiating ultraviolet rays onto the polyimide film coated, dried, and baked on the substrate using the liquid crystal aligning agent F obtained in Synthesis Example 12 was 1.06. Film unevenness of the liquid crystal alignment film was not observed.

&Lt; Comparative Example 25 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 1.0 J / cm 2. The liquid crystal aligning agent G obtained in Synthesis Example 14 was used to immerse the substrate on which the film obtained by applying, drying and firing the polyimide film on the substrate with ultraviolet rays was immersed in IPA (boiling point: 82.4 DEG C) for 3 minutes at 25 DEG C And dried in an oven at 80 ° C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.09. Further, when the alignment film was observed with naked eyes, nonuniformity was observed.

&Lt; Comparative Example 26 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 1.0 J / cm 2. The liquid crystal aligning agent G obtained in Synthesis Example 14 was used to immerse the substrate on which the film obtained by applying, drying and firing a polyimide film on a substrate with ultraviolet light was immersed in water (boiling point: 100 ° C) for 3 minutes, Rinsed with IPA for 1 minute, and dried in an oven at 80 DEG C for 10 minutes to obtain a liquid crystal alignment film.

The magnitude of anisotropy with respect to the alignment direction of the obtained liquid crystal alignment film was 1.09. Further, when the liquid crystal alignment film was observed with naked eyes, the unevenness was slightly seen.

&Lt; Comparative Example 27 &gt;

Except that ultraviolet rays of 254 nm were irradiated at 1.0 J / cm 2. Using liquid crystal aligning agent G obtained in Synthesis Example 14, the size of anisotropy with respect to the alignment direction of the liquid crystal alignment film on the substrate on which the film obtained by applying ultraviolet rays to the polyimide film coated on the substrate, dried and fired was 1.07. Film unevenness of the liquid crystal alignment film was not observed.

Table 1 summarizes the type of the solvent used, the size of anisotropy of the obtained liquid crystal alignment film, and film unevenness for Examples 1 to 22 and Comparative Examples 1 to 27 described above.

Industrial availability

The liquid crystal alignment film obtained by the production method of the present invention has high anisotropy and is widely useful for TN devices, STN devices, TFT liquid crystal devices, and vertically aligned liquid crystal display devices. In addition, by giving high anisotropy, it is possible to reduce the afterimage resulting from the liquid crystal aligning property, for example, the afterimage due to the AC drive generated in the IPS drive method or the FFS drive type liquid crystal display device, And is particularly useful as a liquid crystal display element of a driving system or a liquid crystal alignment film of a liquid crystal television.

Further, the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2011-202229 filed on September 15, 2011 are incorporated herein by reference and the disclosure of the specification of the present invention is hereby incorporated by reference.

Claims (12)

A method for manufacturing a semiconductor device, which comprises applying an imidized film obtained by applying and firing a liquid crystal aligning agent containing at least one kind of polymer selected from the group consisting of polyimide and a precursor of the polyimide and an organic solvent onto a substrate, Subsequently, at least one organic solvent selected from the group consisting of the following formula (A-1), formula (A-2), formula (A-3), formula (A- Wherein the liquid crystal alignment layer is a liquid crystal alignment layer,
The content of the at least one organic solvent selected from the group consisting of the above-mentioned formulas (A-1) to (A-5) is 30 to 100% by mass relative to the total amount of the solution used for the contact treatment A method for producing a liquid crystal alignment film.
[Chemical Formula 1]

Wherein A ₁ is a hydrogen atom or an acetyl group, A ₂ is an alkyl group having 1 to 6 carbon atoms, R ₂ is a hydrogen atom or a methyl group, and n is an integer of 1 or 2. In formula (A-1) (A-3), R ₃ and R ₄ are each independently a hydrogen atom or a methyl group. In the formula (A-2), A ₃ is an alkyl group having 1 to 4 carbon atoms. , A ₅ and A ₆ each independently represent an alkyl group having 1 to 4 carbon atoms.) In the formula (A-5), A ₆ is an alkyl group or a cycloalkyl group having 3 to 6 carbon atoms.) The method according to claim 1,
Wherein the organic solvent has a boiling point of 100 to 180 占 폚. The method according to claim 1,
Wherein the organic solvent is 1-methoxy-2-propanol, ethyl lactate, diacetone alcohol, methyl 3-methoxypropionate or ethyl 3-ethoxypropionate. The method according to claim 1,
Wherein the polymer contains at least one polymer selected from the group consisting of a polyimide precursor having a structural unit represented by the following formula (3) and an imidized polymer of the polyimide precursor.
(2)

In the (expression (3), X ₁ is the following formula (X1-1) ~ (is at least one selected from the group consisting of structures represented by the X1-9), Y ₁ is a divalent organic group, R ₁ is A hydrogen atom, or an alkyl group having 1 to 4 carbon atoms.
(3)

(Wherein (in the X1-1), R _3, R _4, R _5, and R ₆ is, an alkynyl group each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, Or a phenyl group.) 5. The method of claim 4,
Wherein the polymer is at least one kind selected from the group consisting of a polyimide precursor containing 60 mol% or more of the structural unit represented by the formula (3) with respect to 1 mol of the whole polymer and an imidization polymer of the polyimide precursor, A method for producing an orientation film. 5. The method of claim 4,
A process for producing a liquid crystal alignment film, wherein X ₁ in the formula (3) is represented by the formula (X1-1). 5. The method of claim 4,
The formula (3) in, X ₁ is the following formula, at least one type method for producing a liquid crystal alignment layer is selected from the group consisting of structures represented by (X1-10) and (X1-11) to.
[Chemical Formula 4]

5. The method of claim 4,
Wherein at least one kind selected from the group consisting of the structures represented by the following formulas (4) and (5) is represented by Y ₁ in the above formula (3).
[Chemical Formula 5]

(In the formula (5), Z ₁ represents a single bond, an ester bond, an amide bond, a thioester bond, or a divalent organic group having 2 to 10 carbon atoms.) 9. The method of claim 8,
Wherein Y ₁ in the formula (3) is a structure represented by the formula (4). A film obtained by applying and firing a liquid crystal aligning agent containing at least one polymer selected from the group consisting of a polyimide and a precursor of the polyimide onto a substrate is subjected to contact treatment treatment of a liquid crystal alignment film And at least one organic solvent selected from the group consisting of the following formula (A-1), formula (A-2), formula (A-3), formula (A- Wherein the liquid is a liquid containing at least one compound selected from the group consisting of
The content of the at least one organic solvent selected from the group consisting of the above-mentioned formulas (A-1) to (A-5) is 30 to 100% by mass relative to the total amount of the contact treatment liquid of the liquid crystal alignment film Contact liquid of liquid crystal alignment film.
[Chemical Formula 6]

Wherein A ₁ is a hydrogen atom or an acetyl group, A ₂ is an alkyl group having 1 to 6 carbon atoms, R ₂ is a hydrogen atom or a methyl group, and n is an integer of 1 or 2. In formula (A-1) (A-3), R ₃ and R ₄ are each independently a hydrogen atom or a methyl group. In the formula (A-2), A ₃ is an alkyl group having 1 to 4 carbon atoms. , A ₅ and A ₆ each independently represent an alkyl group having 1 to 4 carbon atoms.) In the formula (A-5), A ₆ is an alkyl group or a cycloalkyl group having 3 to 6 carbon atoms.) A liquid crystal alignment film obtained by the process for producing a liquid crystal alignment film according to any one of claims 1 to 9. A liquid crystal display element comprising the liquid crystal alignment film according to claim 11.