KR20130038243A - Liquid crystal alignment agent for use in photo-alignment process, and liquid crystal alignment film using same - Google Patents

Abstract

(식 (1) 중, Y 는 2 가의 유기기이고, R₁ 은 탄소수 1 ～ 5 의 알킬기이고, R₂ ～ R₅ 는 각각 독립적으로 수소 원자, 할로겐 원자, 탄소수 1 ～ 20 의 탄화수소기이고, 동일하거나 상이해도 된다)
(B) 성분：테트라카르복실산 2 무수물과 디아민으로부터 얻어지는 폴리아믹산.It provides the liquid crystal aligning agent for obtaining the liquid crystal aligning film which shows favorable liquid-crystal orientation, irrespective of the irradiation amount of polarized ultraviolet-ray, and performs uniform and favorable photo-alignment alignment process even if there exists a deviation of irradiation amount.
Liquid crystal aligning agent containing following (A) component and (B) component. (A) component: At least 1 sort (s) of polymer chosen from the group which consists of the polyamic acid ester which has a repeating unit represented by following formula (1), and the imidation polymer of this polyamic acid ester.
[Formula 1]

(In Formula (1), Y is a divalent organic group, R <_1> is a C1-C5 alkyl group, R <_2> -R <_5> is a hydrogen atom, a halogen atom, and a C1-C20 hydrocarbon group each independently, May be the same or different)
(B) Component: Polyamic acid obtained from tetracarboxylic dianhydride and diamine.

Description

Liquid crystal aligning agent for photo-alignment processing method, and liquid crystal aligning film using the same {LIQUID CRYSTAL ALIGNMENT AGENT FOR USE IN PHOTO-ALIGNMENT PROCESS, AND LIQUID CRYSTAL ALIGNMENT FILM USING SAME}

This invention relates to the liquid crystal aligning agent for manufacturing a liquid crystal aligning film, and the liquid crystal aligning film obtained from this liquid crystal aligning agent. More specifically, the liquid crystal aligning agent used for formation of the liquid crystal aligning film which can provide a liquid-crystal aligning ability by photo-alignment processing method, ie irradiation of the polarized ultraviolet-ray, instead of a rubbing process, and obtained from such a liquid crystal aligning agent It relates to a liquid crystal aligning film.

In the liquid crystal display element used for a liquid crystal television, a liquid crystal display, etc., the liquid crystal aligning film for controlling the arrangement state of a liquid crystal is formed in an element normally.

At present, according to the method most widely used industrially, this liquid crystal aligning film is made by making the surface of the film which consists of polyamic acid formed on the electrode substrate and / or the polyimide which imidized it into the cloth of cotton, nylon, polyester, etc. It is manufactured by performing what is called a rubbing process to rub in the direction.

The method of rubbing a film surface in the alignment process of a liquid crystal aligning film is an industrially useful method which is simple and is excellent in productivity. However, the demand for higher performance, higher precision, and larger size of the liquid crystal display device is further increased, and scratches, oscillations, effects of mechanical forces or static electricity on the surface of the alignment film generated by the rubbing treatment, and further, within the alignment treatment surface Various problems, such as nonuniformity, become clear.

As a method which replaces a rubbing process, the photo-alignment method which gives a liquid crystal aligning ability by irradiating a polarized ultraviolet-ray is known. As a liquid crystal aligning process by the photo-alignment method, the thing using photoisomerization reaction, the thing using photocrosslinking reaction, the thing using photodecomposition reaction, etc. are proposed (refer nonpatent literature 1).

In patent document 1, using the polyimide membrane which has alicyclic structures, such as a cyclobutane ring, in a principal chain for the photo-alignment method is proposed. When the alignment film for photo-alignment using a polyimide is used, the usefulness is anticipated from the point which has high heat resistance compared with another.

The photo-alignment method described above is a rubbingless alignment treatment method, which has the advantage of being industrially produced by a simple manufacturing process, and attracts attention as a promising liquid crystal alignment treatment method. There exist problems, such as the orientation regulation force of a liquid crystal, the electrical characteristics as a liquid crystal display element, the stability of these characteristics, etc., and are not reaching practical use generally.

Japanese Patent Application Laid-Open No. 9-297313

 "Liquid crystal light alignment film" Otowaki, Ichimura functional material November, 1997 issue Vol.17 No.1113-22 page

In recent years, large screens of liquid crystal display devices have become widespread. When a rubbing treatment is performed on a large screen substrate, nonuniformity of rubbing strength occurs in the substrate surface, and the display becomes uneven when a liquid crystal display device is used. On the other hand, in the photo-alignment method, it is expected because display unevenness can be reduced compared with the rubbing method. However, also in the photo-alignment method, since the liquid-crystal orientation changes with the irradiation amount of polarized ultraviolet-ray, there exists a possibility that the display nonuniformity similar to a rubbing method may arise because a nonuniformity of irradiation intensity arises in a board | substrate surface.

This problem is one of the optical alignment methods that are expected to occur with the large screen, and in order to produce a liquid crystal display device that exhibits the advantages of the optical alignment method to the maximum, the light exhibiting good liquid crystal alignment is irrespective of the irradiation amount. An alignment film is required.

The objective of this invention WHEREIN: When performing an orientation process by the photo-alignment method, irrespective of the irradiation amount of a polarization ultraviolet-ray, it shows favorable liquid-crystal orientation, and the dispersion | variation in the irradiation amount which a liquid crystal aligning ability expresses in the liquid crystal aligning film with a large irradiation area of a big screen. Even if there exists, it is providing the liquid crystal aligning agent for obtaining the liquid crystal aligning film which is performed uniformly and favorable alignment process.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined, and at least 1 sort (s) of polymer chosen from the group which consists of the polyamic acid ester which has a cyclobutane ring in a principal chain, and the imidation polymer of this polyamic acid ester, and tetracarboxylic dianhydride, By using the liquid crystal aligning agent containing the polyamic acid obtained by making it react with diamine, it discovered that the said subject could be solved and came to complete this invention.

That is, this invention makes the following a summary.

1. The liquid crystal aligning agent containing the following (A) component and (B) component.

(A) component: At least 1 sort (s) of polymer chosen from the group which consists of the polyamic acid ester which has a repeating unit represented by following formula (1), and the imidation polymer of this polyamic acid ester.

[Formula 1]

(In formula (1), Y is a divalent organic group, R <_1> is a C1-C5 alkyl group, R <_2> -R <_5> is a hydrogen atom, a halogen atom, or a C1-C30 hydrocarbon group each independently, May be the same or different)

(B) Component: Polyamic acid obtained from tetracarboxylic dianhydride and diamine.

2. The liquid crystal aligning agent of said 1 whose content rate of (A) component and (B) component is 1/9-9/1 by mass ratio (A / B).

3. Said 1 or 2 whose (A) component is at least 1 sort (s) of polymer chosen from the group which consists of the polyamic acid ester which has 40 mol% or more of repeating units represented by said Formula (1), and the imidation polymer of this polyamic acid ester. 2 liquid crystal aligning agent.

4. Liquid crystal aligning agent in any one of said 1-3 whose component (A) is polyamic acid ester which has repeating unit represented by following formula (3).

[Formula 2]

(In Formula (3), Y is a divalent organic group and R <_6> is a C1-C5 alkyl group.)

5. Liquid crystal aligning agent in any one of said 1-3 whose component (A) is polyamic acid ester which has repeating unit represented by following formula (4).

(3)

(In Formula (4), Y is a divalent organic group and R <_6> is a C1-C5 alkyl group.)

6. The liquid crystal aligning agent in any one of said 1-5 whose Y is at least 1 sort (s) chosen from the group which consists of the following structural formulas.

[Formula 4]

7. Polya obtained by using the tetracarboxylic dianhydride containing component (B) containing at least 1 sort (s) chosen from the group which consists of tetracarboxylic dianhydride of following formula (B-1)-(B-9). The liquid crystal aligning agent in any one of said 1-6 which is a mixed acid.

[Chemical Formula 5]

8. Component (B) has 20 mol% or more of all the tetracarboxylic dianhydride at least 1 sort (s) of tetracarboxylic dianhydride selected from the group which consists of said Formula (B-1)-(B-9). The liquid crystal aligning agent of said 7 which is polyamic acid obtained using tetracarboxylic dianhydride.

9. Component (B) is described in any one of said 1-8 which is polyamic acid obtained using diamine containing at least 1 sort (s) chosen from the group which consists of following formula (B-10)-(B-13). Liquid crystal aligning agent.

[Formula 6]

10. Said component (B) is polyamic acid obtained using diamine which has 20 mol% or more of at least 1 sort (s) of diamine chosen from the group which consists of said Formula (B-10)-(B-13) of all diamine. The liquid crystal aligning agent of 9.

11. The liquid crystal aligning film obtained by irradiating polarized ultraviolet-ray to the film obtained by apply | coating and baking the liquid crystal aligning agent in any one of said 1-10.

Since the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention has a large irradiation amount range of the polarized ultraviolet ray from which favorable liquid crystal aligning property is obtained, and favorable liquid crystal alignability is obtained irrespective of the irradiation amount of a polarized ultraviolet ray, the nonuniformity of irradiation intensity will be in a board | substrate surface. Even when it arises, the liquid crystal aligning film with a wide process margin which is uniform and has favorable liquid-crystal orientation is provided.

[(A) component]

The polyamic acid ester in this invention is converted into polyimide by the imidation reaction shown below by the action of a heating or a catalyst. Since polyamic acid ester does not produce molecular weight fall by reverse reaction, the polyimide with many molecular weights is obtained even after baking. Thereby, the liquid crystal display element excellent in more favorable liquid-crystal orientation and reliability is obtained. In addition, the imidation polymer in this invention is a polymer obtained by imidating a polyamic acid ester. Since an imidation polymer may not melt | dissolve in the organic solvent used for a liquid crystal aligning film depending on a structure, as a component (A) of this invention, polyamic acid ester is especially preferable.

[Formula 7]

(A) component contained in the liquid crystal aligning agent of this invention is at least 1 sort (s) of polymer chosen from the group which consists of the polyamic acid ester which has a repeating unit represented by following formula (1), and the imidation polymer of this polyamic acid ester. .

[Formula 8]

In Formula (1), R <_1> is a C1-C5 alkyl group, Preferably, it is a C1-C2 alkyl group. As carbon number in R <_1> increases, the temperature at which imidation advances becomes high. Thus, R ₁ is, in view of the already coded ease due to heat, it is a methyl group is particularly preferred. In Formula (1), R <_2> -R <_5> is respectively independently a hydrogen atom, a halogen atom, or a C1-C30, Preferably they are 1-10 hydrocarbon groups, and may be same or different.

As a specific example of a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. As an example of a C1-C30 hydrocarbon group, it selects from the group which consists of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and these combinations, These may have a substituent. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, t-butyl group, hexyl group, octyl group, decyl group, cyclopentyl group, cyclohexyl group and bicyclohexyl group. The alkenyl groups are, there may be mentioned that by replacing one or more CH ₂ -CH ₂ structures present in the alkyl group with the structure CH = CH, more specifically, vinyl, allyl, 1-propenyl group, isopropenyl A phenyl group, 2-butenyl group, 1, 3- butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentenyl group, cyclohexenyl group, etc. are mentioned.

The alkynyl groups include, may be mentioned that one or more CH ₂ -CH ₂ structures present in the alkyl group was substituted with C≡C structure, more specifically, ethynyl group, 1-propynyl group, 2-propynyl group Etc. can be mentioned. As an aryl group, a phenyl group, (alpha)-naphthyl group, (beta) -naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1- anthryl group, 2- anthryl group, 9, for example -Anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, etc. are mentioned.

The alkyl group, the alkenyl group, the alkynyl group, and the aryl group may have a substituent if the carbon number is 1 to 30, preferably 1 to 10, as a whole, or may form a ring structure depending on the substituent.

Examples of this substituent include a halogen group, hydroxyl group, thiol group, nitro group, organooxy group, organothio group, organosylyl group, acyl group, ester group, thioester group, phosphate ester group, amide group, aryl group, alkyl group And alkenyl groups and alkynyl groups.

As a halogen group which is a substituent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

As an organooxy group which is a substituent, the structure represented by -O-R, such as an alkoxy group, an alkenyloxy group, an aryloxy group, can be shown. As this R, the alkyl group, alkenyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may substitute by these R again. Specific examples of the alkyloxy group include a methoxy group, ethoxy group, propyloxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group and lauryloxy group Etc. can be mentioned.

As an organothio group which is a substituent, the structure represented by -S-R, such as an alkylthio group, an alkenylthio group, an arylthio group, can be shown. As this R, the alkyl group, alkenyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may substitute by these R again. Specific examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, and Uryl thio group etc. are mentioned.

As an organosilyl group which is a substituent, the structure represented by -Si- (R) ₃ can be shown. This R may be same or different and can illustrate an alkyl group, an aryl group, etc. which were mentioned above. The substituent mentioned above may substitute by these R again. Specific examples of the alkylsilyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, tripentylsilyl group, trihexylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group and octyldimethyl Silyl group, decyldimethylsilyl group, and the like.

As an acyl group which is a substituent, the structure represented by -C (O) -R can be shown. As this R, the alkyl group, alkenyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may substitute by these R again. Specific examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group and the like.

As ester group which is a substituent, the structure represented by -C (O) O-R or -OC (O) -R can be shown. As this R, the alkyl group, alkenyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may substitute by these R again.

As a thioester group which is a substituent, the structure represented by -C (S) O-R or -OC (S) -R can be shown. As this R, the alkyl group, alkenyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may substitute by these R again.

As a phosphate ester group which is a substituent, the structure represented by -OP (O)-(OR) ₂ can be shown. This R may be same or different and can illustrate an alkyl group, an aryl group, etc. which were mentioned above. The substituent mentioned above may substitute by these R again.

Substituent of the amide group _{include, -C (O) NH 2,} -C (O) NHR, -NHC (O) R, -C (O) N (R) represented by the structure _2, or -NRC (O) R Can be represented. This R may be same or different and can illustrate an alkyl group, an aryl group, etc. which were mentioned above. The substituent mentioned above may substitute by these R again.

As an aryl group which is a substituent, the thing similar to the aryl group mentioned above is mentioned. The other substituent mentioned above may substitute by this aryl group further.

As an alkyl group which is a substituent, the thing similar to the alkyl group mentioned above is mentioned. The other substituent mentioned above may substitute by this alkyl group again.

As an alkenyl group which is a substituent, the same thing as the alkenyl group mentioned above is mentioned. The other substituent mentioned above may substitute by this alkenyl group again.

As an alkynyl group which is a substituent, the thing similar to the alkynyl group mentioned above is mentioned. The other substituent mentioned above may substitute by this alkynyl group again.

When R <_2> -R <_5> is a structure with high volume, since there exists a possibility of inhibiting liquid crystal alignability, a hydrogen atom, a C1-C6 alkyl group, or a phenyl group is more preferable, and a hydrogen atom or a methyl group is still more preferable.

(A) component of this invention is a following formula (9) with the tetracarboxylic-acid derivative of following formula (6)-(8), or the tetracarboxylic-acid derivative represented by following formula (6)-(8). It can manufacture by condensation-polymerizing these tetracarboxylic-acid derivatives and the diamine represented by following formula (12) using the tetracarboxylic-acid derivative represented by)-(11).

[Chemical Formula 9]

[Formula 10]

[Formula 11]

In formula, R <_2> -R <_5> is the same as that of the definition in said Formula (1), respectively. R ₆ is an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms. The polyamic acid ester has a higher temperature at which imidization proceeds as the number of carbon atoms in the alkyl group increases. For this reason, R ₆ is particularly preferably a methyl group from the viewpoint of ease of heat imidation.

As content of the tetracarboxylic-acid derivative of said Formula (6)-(8), 1 mol%-100 mol% are preferable with respect to all the tetracarboxylic-acid derivative. When the content of the tetracarboxylic acid derivatives of the formulas (6) to (8) is too small, the photo-alignment property becomes insufficient, and since the good liquid crystal orientation is not obtained, 20 mol% to 100 mol based on the total tetracarboxylic acid derivatives % Is more preferable, and 40 mol%-100 mol% are further more preferable.

X in said formula (9)-(11) is a tetravalent organic group, The structure is not specifically limited. If the specific example is given, the structure represented by following X-1 to X-46 will be mentioned. Moreover, you may use two or more types of these tetracarboxylic-acid derivatives.

[Chemical Formula 12]

[Chemical Formula 13]

[Formula 14]

[Formula 15]

In said Formula (12), Y is a divalent organic group, The structure is not specifically limited. If the specific example is given, the structure represented by following formula Y-1-Y-108 will be mentioned. Moreover, two or more types may be sufficient as a diamine compound.

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Formula 22]

(23)

&Lt; EMI ID =

(25)

(26)

(27)

(28)

[Formula 29]

(30)

(31)

(32)

(33)

As Y, in order to acquire favorable liquid crystal alignability, it is preferable to introduce the diamine with a high linearity. As Y, Y-7, Y-10, Y-11, Y-12, Y-13, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-41 , Y-42, Y-43, Y-44, Y-45, Y-46, Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y Diamines of -74, Y-75, Y-98, Y-100, Y-101, Y-102, Y-103, Y-104, Y-105, Y-106, Y-107, or Y-108 More preferred. Good liquid crystal orientation is obtained by adding 30-100 mol% of these diamine and more preferably 50-100 mol% of all diamine.

Moreover, when trying to make a high pretilt angle, it is preferable to introduce in a polyamic acid ester the diamine which has a long chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton, or a combination structure in a side chain. Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y-86, Y-87 , Diamines of Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96, or Y-97 are more preferable. Arbitrary pretilt angle can be expressed by adding 1-50 mol% of these diamines, More preferably, 5-30 mol% of all diamines.

Especially, as Y, it is preferable that it is at least 1 sort (s) chosen from the group which consists of following structural formulas.

[Formula 34]

[Component (B)] [

(B) component of this invention is shown below by heating with the polyamic acid obtained by polycondensation of the tetracarboxylic dianhydride which has a structure of following formula (13), and the diamine which has a structure of following formula (14). It is a polymer which has a site | part which can carry out imidation reaction.

(35)

(36)

[Formula 37]

In formula (13), X <_1> is a tetravalent organic group, The structure is not specifically limited. If a concrete example is given, the structure of said Formula (X-1)-(X-46) will be mentioned. Moreover, two or more types may be sufficient as tetracarboxylic dianhydride.

As (B) component, the polyamic acid which does not produce a photolysis reaction or is slow in reaction rate of photolysis than the said (A) component is preferable. Therefore, as the structure of X ₁ , X-1, X-5, X-6, X-7, X-8, X-16, X-17, X-18, X-19, X-21, X -22, X-23, X-24, X-25, X-26, X-27, X-28, X-29, X-30, X-31, X-32, X-33, X-39 , X-40, X-41, X-42, X-42, or X-46 are preferred.

The preferred amount of the tetracarboxylic acid dianhydride having the structure: X ₁ is, it is preferably 5 to 100 mol% for the total tetracarboxylic acid dianhydride. Since there are many ratios of such tetracarboxylic dianhydride, since the surface free energy of a polymer is high and high solubility polyamic acid is obtained, 20-100 mol% is more preferable, and 40-100 mol% is more preferable.

Especially, as above-mentioned, in order to improve liquid-crystal orientation further by distributing (A) component on a film surface, as polyamic acid of (B) component, the surface free energy is high and the solubility polyamic acid is preferable. . Therefore, as a structure of X <_1> in (B) component, it also includes water availability and X-1, X-5, X-6, X-8, X-16, X-19, X-25, X -26 or X-32 is more preferable, and especially X-25 or X-32 is preferable.

The tetracarboxylic dianhydride which has such a preferable X <_1> structure is represented by the following (B-1)-(B-9), Among these, (B-1) or (B-9) is especially preferable. .

(38)

In formula (14), Y <_1> is a divalent organic group, The structure is not specifically limited. If a concrete example is given, the structure of said formula (Y-1)-(Y-108) will be mentioned. Moreover, two or more types may be sufficient as diamine.

Since the afterimage resulting from the accumulation of direct current voltage can be reduced by lowering the volume resistivity of the polyamic acid, it is preferable to introduce a diamine having a structure having a hetero atom, a polycyclic aromatic structure, or a biphenyl skeleton into the polyamic acid. . Y ₁ for this purpose is Y-19, Y-23, Y-25, Y-26, Y-27, Y-30, Y-31, Y-32, Y-33, Y-34, Y-35, Y-36, Y-40, Y-41, Y-42, Y-44, Y-45, Y-49, Y-50, Y-51, or Y-61 is preferable.

The amount of the diamine compound having the structure wherein Y ₁ is preferred, and for the whole diamine, and 5 mol% to 100 mol% is preferred. Since the polarity of a polymer improves and the film surface ratio of (A) component increases so that this usage amount increases, 20 mol%-100 mol% are more preferable, and 40 mol%-100 mol% are more preferable.

Especially, as above-mentioned, since liquid crystal aligning property can be improved further by distributing (A) component on a film surface, as a polyamic acid of (B) component, it is preferable that surface free energy is high, and a secondary amino group, It is preferable to introduce high polar substituents, such as a hydroxyl group, an amide group, a ureido group, and a carboxyl group, into a polyamic acid. Therefore, as Y ₁ , Y-19, Y-31, Y-40, Y-45, Y-98, or Y-99 is more preferable, and Y-98 or Y-99 containing a carboxyl group is particularly preferable. .

Tetracarboxylic acid dianhydride having a structure of such preferred Y ₁ is represented by (B-10) ~ (B -13) below, of which, (B-10) or (B-11) is particularly preferred .

[Chemical Formula 39]

[Production of (A) component and (B) component]

(Production of Polyamic Acid)

Polyamic acid can be manufactured by polycondensation of tetracarboxylic dianhydride and a diamine compound.

When manufacturing a polyamic acid, tetracarboxylic dianhydride and a diamine compound, Preferably it is -20 degreeC-140 degreeC in presence of an organic solvent, Preferably it is 30 minutes-24 hours, in 0 degreeC-50 degreeC It can be manufactured by making it react for 1 to 12 hours. The solvent used for producing the polyamic acid is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the solubility of the monomer and the polymer, and these are one or two species. You may mix and use the above. When the polymer concentration at the time of manufacture is too high, precipitation of a polymer tends to occur, and when too low, molecular weight does not become high, Therefore, the total amount in the reaction liquid of tetracarboxylic dianhydride and a diamine compound is 1-30 mass%, 5-20 mass% is more preferable.

The polyamic acid obtained as mentioned above can make the reaction solution into the raw material of the (A) component of this invention, or (B) component, However, when it is not want to contain the solvent used for superposition | polymerization in a liquid crystal aligning agent, a polymer It can be used as a polyamic acid in this invention after collect | recovering as a solid as a solid.

By inject | pouring into a poor solvent, stirring a reaction solution well, a polymer can precipitate a polymer and can be collect | recovered. Precipitation is carried out several times, followed by washing with a poor solvent, followed by normal temperature or heat drying to obtain a powder of purified polyamic acid.

Although the said poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, etc. are mentioned.

(Production of Polyamic Acid Ester)

Polyamic acid ester can be manufactured by a well-known manufacturing method, and the following (a)-(c) method is mentioned specifically, It is not limited to this.

(a) When polyamic acid ester is produced from polyamic acid

The polyamic acid ester in this invention can be manufactured by esterifying the polyamic acid in above-mentioned this invention. Specifically, the polyamic acid ester is a polyamic acid and an esterifying agent in the presence of an organic solvent, at -20 ° C to 140 ° C, preferably at 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 to 4 hours. It can manufacture by making time react.

As said esterification agent, what can be easily removed by refinement | purification is preferable, N, N- dimethylformamide dimethyl acetal, N, N- dimethylformamide diethyl acetal, N, N- dimethylformamide dipropyl acetal , N, N-dimethylformamide dineopentylbutyl acetal, N, N-dimethylformamide di-t-butylacetal, 1-methyl-3-p-tolyltriagen, 1-ethyl-3-p-tolyltri Agen, 1-propyl-3-p-tolyltriazene, and the like. As for the addition amount of an esterifying agent, 2-6 molar equivalent is preferable with respect to 1 mol of repeating units of a polyamic acid.

The solvent used for the production of the polyamic acid ester is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the solubility of the monomer and the polymer, and these are either one or two. You may mix and use types or more. When the polymer concentration at the time of manufacture is too high, precipitation of a polymer tends to occur, and when too low, molecular weight does not become high, Therefore, the total amount in the reaction liquid of a polyamic acid and an esterifying agent is 1-30 mass%, Preferably it is 5-20 mass % Is more preferable.

(b) When polyamic acid ester is prepared from acid chloride and diamine compound

Polyamic acid ester can be manufactured by polycondensation of a bis (chlorocarbonyl) compound and a diamine compound.

Specifically, the bis (chlorocarbonyl) compound and the diamine compound are in the presence of a base and an organic solvent at -20 ° C to 140 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 It can manufacture by making it react for 4 hours. As the base, pyridine, triethylamine, or 4-dimethylaminopyridine can be used, but pyridine is preferable in order to proceed the reaction gently. If the amount of base added is too large, it is difficult to remove. If the amount of base added is too small, the molecular weight becomes small. Therefore, the amount of the base is preferably 2 to 4 times molar with respect to the bis (chlorocarbonyl) compound.

As a solvent used for manufacture of a polyamic acid ester, N-methyl- 2-pyrrolidone or (gamma) -butyrolactone is preferable from the solubility of a monomer and a polymer, These may be used 1 type or in mixture of 2 or more types. . When the polymer concentration at the time of manufacture is too high, precipitation of a polymer tends to occur, and when too low, molecular weight will not become high, Therefore, the total amount in the reaction liquid of a bis (chlorocarbonyl) compound and a diamine compound is 1-30 mass%, , 5-20 mass% is more preferable. Moreover, in order to prevent the hydrolysis of a bis (chlorocarbonyl) compound, the solvent used for manufacture of a polyamic acid ester should be dehydrated as much as possible, and it is good to prevent mixing of external air in nitrogen atmosphere.

(c) When polyamic acid ester is produced from dialkyl ester dicarboxylic acid and diamine compound

Polyamic acid ester can be manufactured by polycondensing a tetracarboxylic-acid dialkyl ester and a diamine compound with a condensing agent.

Specifically, the dialkyl ester dicarboxylic acid and the diamine compound are mixed at 0 ° C. to 140 ° C., preferably at 0 ° C. to 100 ° C., for 30 minutes to 24 hours, preferably in the presence of a condensing agent, a base, and an organic solvent. Can be manufactured by making it react for 3 to 15 hours.

Examples of the condensing agent include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole and dimethoxy-1 , 3,5-triadinylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazole -1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphite, (2,3-dihydro-2-thioxo-3-benzooxazolyl) phosphonic acid diphenyl, etc. Can be used. It is preferable that the addition amount of a condensing agent is 2-3 times mole with respect to dialkyl ester dicarboxylic acid.

As the base, tertiary amines such as pyridine and triethylamine can be used. If the amount of base added is too large, it is difficult to remove. If the amount of base added is too small, the molecular weight becomes small. Therefore, the amount of the base is preferably 2 to 4 times molar with respect to the diamine component.

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. It is preferable that the addition amount of Lewis acid is 0-1.0 times mole with respect to a diamine component.

Since the high molecular weight polyamic acid ester is obtained among the manufacturing method of said three polyamic acid ester, the manufacturing method of (a) or (b) is especially preferable.

The solution of the polyamic acid ester obtained as mentioned above can deposit a polymer by inject | pouring into a poor solvent, stirring well. Precipitation is carried out several times, followed by washing with a poor solvent, followed by normal temperature or heat drying to obtain a purified polyamic acid ester powder.

Although the said poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, etc. are mentioned.

The ratio of the diamine component and tetracarboxylic acid derivative (tetracarboxylic dianhydride, tetracarboxylic acid dialkyl derivative) used for the said polycondensation reaction is 1: 0.7-1: 1.2 by molar ratio from a viewpoint of molecular weight control. desirable. The closer this molar ratio is to 1: 1, the larger the molecular weight of the polyamic acid ester obtained. The molecular weight of the polyamic acid ester affects the viscosity of the varnish and the physical strength of the polyimide film. If the molecular weight of the polyamic acid ester is too large, the coating property and coating film uniformity of the varnish may deteriorate, and the molecular weight is too small. If it is, the strength of the polyimide film obtained may become inadequate. Therefore, as for the molecular weight of the polyamic acid ester used for the liquid crystal distribution perfume of this invention, 2,000-500,000 are preferable at a weight average molecular weight, More preferably, it is 5,000-300,000, More preferably, it is 10,000-100,000.

[Production of Polyimide]

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

Chemical imidation can be performed by stirring the polymer to make it imidate in presence of a basic catalyst and an acid anhydride in an organic solvent. As an organic solvent, the solvent used at the time of the polymerization reaction mentioned above can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Especially, pyridine is preferable because it has a basicity suitable for advancing reaction. As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be mentioned. Among them, acetic anhydride is preferable because the purification after completion of the reaction becomes easy.

The temperature at the time of performing an imidation reaction is -20 degreeC-140 degreeC, Preferably it is 0 degreeC-100 degreeC, and reaction time can be implemented for 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times, of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times of the amic acid group. The imidization rate of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. Since the added catalyst etc. remain | survived in the solution after imidation reaction, it is preferable to collect | recover the obtained imidation polymer by means of the below-mentioned, to redissolve | dissolve in an organic solvent, and to make it the liquid crystal aligning agent of this invention.

The polymer of the polyimide obtained as mentioned above can be precipitated by inject | pouring into a poor solvent, stirring well. Precipitation is carried out several times, followed by washing with a poor solvent, followed by normal temperature or heat drying to obtain a purified polyamic acid ester powder.

Although the said poor solvent is not specifically limited, Methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, etc. are mentioned.

[Liquid crystal aligning agent]

The liquid crystal aligning agent of this invention is a solution in which the polyamic acid ester or polyimide ((A) component) and polyamic acid ((B) component) which have the specific structure obtained as mentioned above are melt | dissolved in a solvent uniformly.

As for content ratio of (A) component and (B) component in the liquid crystal aligning agent of this invention, 1 / 9-9 / 1 are preferable, and, as for mass ratio (A / B), 3 / 7-7 / 3 are More preferred. When content of (A) component is extremely small with respect to content of (B) component, since liquid-crystal orientation becomes inadequate and when it is large, since the effect of this invention is not fully exhibited, it is not preferable.

As a solvent used for the liquid crystal aligning agent of this invention, the solvent which can melt | dissolve the said (A) component and (B) component is used.

It will not specifically limit, if it dissolves (A) component and (B) component as such a solvent. By all means, if the specific example is given, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2- Pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 1, 3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, etc. are mentioned. You may use these 1 type or in mixture of 2 or more types. Moreover, even if it is a solvent which does not melt a polymer independently, as long as it is a range in which a polymer does not precipitate, you may mix. Moreover, the solvent which melt | dissolves (A) component and the solvent which dissolves (B) component may be same or different, and two or more types of mixed solvents may be sufficient as it.

Moreover, in this invention, although the solubility to (A) component and (B) component is small, the solvent (henceforth poor solvent) for improving the coating-film uniformity at the time of apply | coating a liquid crystal aligning agent to a board | substrate can also be used. The poor solvent is not particularly limited as long as it improves the coating film uniformity with low surface tension. By the way, if the specific example is given, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2 Propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-mono Ethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, etc. Can be mentioned. These solvents may be used in combination of two or more.

The liquid crystal aligning agent of this invention may contain various additives, such as a silane coupling agent and a crosslinking agent. A silane coupling agent is added in order to improve the adhesiveness of the board | substrate with which a liquid crystal aligning agent is apply | coated, and the liquid crystal aligning film formed there. Although the specific example of a silane coupling agent is given to the following, it is not limited to this.

3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3- Amine silane coupling agents such as phenylaminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine and 3-aminopropyldiethoxymethylsilane; vinyltrimethoxy Silane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, p-styryl tree Vinyl silane coupling agents such as methoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Epoxy, such as methyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane System silane coupling agents; such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. Methacryl silane coupling agents; acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; ureido-based silane coupling agents such as 3-ureidopropyltriethoxysilane; bis (3- (triethoxysilyl) Sulfide silane coupling agents such as propyl) disulfide and bis (3- (triethoxysilyl) propyl) tetrasulfide; 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3 Mercapto-based silane coupling agents such as -octanoylthio-1-propyltriethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane and 3-isocyanatepropyltrimethoxysilane; triethoxysil Butyl aldehyde-based silane coupling agents such as aldehydes; triethoxy silyl propyl methyl carbamate, carbamate-based silane coupling agent such as (3-triethoxysilylpropyl) -t- butyl carbamate.

When the amount of the silane coupling agent added is too large, unreacted may adversely affect liquid crystal alignment, and when too small, the effect on adhesiveness does not appear. Therefore, 0.01 to 5.0% by weight is preferable with respect to the solid content of the polymer, 0.1-1.0 weight% is more preferable.

When adding the said silane coupling agent, in order to prevent precipitation of a polymer, it is preferable to add before adding the solvent for improving said coating-film uniformity. Moreover, when adding a silane coupling agent, before mixing a polyamic acid ester solution and a polyamic acid solution, it can add to both a polyamic acid ester solution, a polyamic acid solution, or a polyamic acid ester solution and a polyamic acid solution. Moreover, it can add to a polyamic-acid ester polyamic-acid mixed solution. Since a silane coupling agent is added for the purpose of improving the adhesiveness of a polymer and a board | substrate, as a addition method of a silane coupling agent, it adds to the polyamic-acid solution which can be localized in a film | membrane and a board | substrate interface, and a polymer and a silane coupling agent are added. After making it fully react, the method of mixing with a polyamic acid ester solution is more preferable.

You may add the imidation promoter, in order to advance imidation of polyamic acid ester efficiently, when baking a coating film. Although the specific example of the imidation promoter of polyamic acid ester is given to the following, it is not limited to this.

[Formula 40]

(41)

D in said Formula (B-1)-(B-17) is a tert-butoxy carbonyl group or 9-fluorenyl methoxycarbonyl group each independently. In addition, although several D exists in (B-14)-(B-17) in one formula, these may mutually be same or different.

Although content of an imidation promoter will not be restrict | limited especially if it is a range in which the effect which promotes the thermal imidation of polyamic acid ester is not restrict | limited, The amic acid ester site | part 1 of following formula (12) contained in the polyamic acid ester in a liquid crystal aligning agent. To moles, the B component is preferably 0.01 mol or more, more preferably 0.05 mol or more, even more preferably 0.1 mol or more. Moreover, the amic acid ester site | part of following formula (12) contained in the polyamic acid ester in a liquid crystal aligning agent in the point that the imidation promoter itself remaining in the film | membrane after baking minimizes the adverse effect on the various characteristics of a liquid crystal aligning film. To 1 mol, Preferably the imidation promoter is 2 mol or less, More preferably, it is 1 mol or less, More preferably, it is 0.5 mol or less.

(42)

When adding an imidation promoter, since imidation may advance by heating, it is preferable to add, after diluting with a good solvent and a poor solvent.

Needless to say, you may use various additives, such as a crosslinking agent, further in the liquid crystal aligning agent of this invention. Moreover, two types may be sufficient as the polymer of (A) component of this invention and the polyamic acid of (B) component, respectively.

Although the polymer density | concentration containing (A) component and (B) component in the liquid crystal aligning agent of this invention can be suitably changed with the setting of the thickness of the liquid crystal aligning film to form, it is preferable to set it as 1-10 mass%. And 2-8 mass% is more preferable. If it is less than 1 mass%, it will become difficult to form a uniform and defect-free coating film, and when more than 10 mass%, the storage stability of a solution may worsen.

[Method for producing liquid crystal aligning agent]

The liquid crystal aligning agent of this invention has at least 1 sort (s) of polymer ((A) component) and polyamic acid ((B) component) chosen from the polyamic acid ester which has a specific structure, and the imidation polymer of this polyamic acid ester.

As a ratio of (A) component with respect to the total amount of (A) component and (B) component, 5 mass%-95 mass% are preferable. When there is little ratio of (A) component, sufficient liquid-crystal orientation may not be obtained, and when there is little ratio of (B) component, the effect made into the objective of this invention may not be acquired. Therefore, as a ratio of (A) component, 20 mass%-80 mass% are more preferable, and 30 mass%-70 mass% are more preferable.

As a method of mixing (A) component and (B) component, the method of mixing the polymer of (A) component and the powder of the polyamic acid of (B) component, dissolving in a solvent, the powder of the polymer of (A) component, Method for mixing polyamic acid solution of component (B), method for mixing polymer solution of component (A) and powder of polyamic acid of component (B), polymer solution of component (A) and polyamic acid of component (B) There is a method of mixing the solution. Even when the good solvent to dissolve the polymer of the component (A) and the polyamic acid of the component (B) is different, the polyamic acid mixed solution of the polymer- (B) component of the component (A) can be obtained. The method of mixing the polymer solution of and the polyamic-acid solution of (B) component is more preferable.

As a method of preparing the polymer solution of (A) component, the powder of the polymer of (A) component is melt | dissolved in the said good solvent, and the polymer solution of (A) component and the reaction solution of the polymer of (A) component are used as it is. There is a way. When (A) component is polyamic acid ester or the imidation polymer of polyamic acid ester, the method of melt | dissolving a polymer powder is more preferable, and when (A) component is polyamic acid, using a polymerization reaction solution as it is The method is more preferred. At this time, 10-30% is preferable and 10-15% of a polymer concentration is especially preferable. Moreover, when melt | dissolving the powder of the polymer of (A) component, you may heat. 20 to 150 degreeC is preferable and 20 to 80 degreeC of heating temperature is especially preferable.

As a method of preparing the polyamic-acid solution of (B) component, there exists a method of melt | dissolving the powder of polyamic acid in the said good solvent, making it a polyamic-acid solution, and using the polymerization reaction solution as it is, and leaving a polymerization reaction solution as it is. The method to use is more preferable. In the case of re-dissolving the polyamic acid powder, the polymer concentration is preferably 10 to 30%, particularly preferably 10 to 15%. Moreover, when melt | dissolving the powder of a polymer, you may heat. 20 to 150 degreeC is preferable and 20 to 80 degreeC of heating temperature is especially preferable.

When adding a silane coupling agent, before mixing the polymer solution of (A) component and the polyamic acid solution of (B) component, the polymer solution of (A) component, the polyamic acid solution of (B) component, or (A It can be added to both the polymer solution of the component) and the polyamic acid solution of the component (B). Moreover, it can add to the polyamic-acid mixed solution of the polymer- (B) component of (A) component. Since a silane coupling agent is added for the purpose of improving the adhesiveness of a polymer and a board | substrate, as a addition method of a silane coupling agent, it adds to the polyamic-acid solution of (B) component which can be localized in a film | membrane and a board | substrate interface, and a polymer After fully reacting with a silane coupling agent, a method of mixing with the polymer solution of the component (A) is more preferable. If the amount of the silane coupling agent added is too large, unreacted may adversely affect the liquid crystal alignment property. If the amount of the silane coupling agent is too large, the effect on the adhesiveness does not appear. Therefore, 0.01 to 5.0% by weight is preferable, and 0.1 is based on the solid content of the polymer. ~ 1.0 weight% is more preferable.

When mixing the polymer solution of (A) component and the polyamic-acid solution of (B) component, 10-30% is preferable and, as for the polymer concentration in these solutions, 10-15% is especially preferable. Moreover, when mixing, you may heat, 20 degreeC-100 degreeC is preferable, and 20 degreeC-60 degreeC is especially preferable.

When adding a silane coupling agent or a crosslinking agent, it is preferable to add before adding a poor solvent in order to prevent precipitation of a polymer. Moreover, when the polymer of (A) component is polyamic acid ester, you may add an imidation promoter, in order to advance imidation of polyamic acid ester efficiently, when baking a coating film. When adding an imidation promoter, since imidation may advance by heating, it is preferable to add, after diluting with a good solvent and a poor solvent.

The liquid crystal aligning agent of this invention is obtained by adding the said good solvent and the said poor solvent to the polymer of the obtained A) component and the polyamic-acid mixed solution of (B) component, and diluting so that it may become a predetermined polymer density | concentration.

[Liquid Crystal Alignment Layer]

The liquid crystal aligning film of this invention can apply | coat to a board | substrate after drying the liquid crystal aligning agent of the said invention preferably, and to make it a coating film. As a board | substrate which apply | coats the liquid crystal aligning agent of this invention, if it is a board | substrate with high transparency, it will not specifically limit, Plastic substrates, such as a glass substrate, a silicon nitride substrate, an acrylic substrate, a polycarbonate substrate, etc. can be used, and ITO for liquid crystal drive It is preferable to use a substrate on which an electrode or the like is formed from the viewpoint of simplification of the process. In the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used only for a substrate on one side, and in this case, a material for reflecting light such as aluminum can be used.

As a coating method of a liquid crystal aligning agent, a spin coat method, the printing method, the inkjet method, etc. are mentioned. After apply | coating the liquid crystal aligning agent of this invention, Preferably, it dries and bakes. In order to fully remove the organic solvent contained in the liquid crystal aligning agent, Preferably it is made to dry at 50-120 degreeC, Preferably it is 1 to 10 minutes. Then, Preferably it is baked at 150-300 degreeC, More preferably, it is baked at 150-250 degreeC. Although baking time changes also with baking temperature, Preferably it is 5-120 minutes, More preferably, it is performed for 5-60 minutes.

Although the thickness of a liquid crystal aligning film is not specifically limited, Since the reliability of a liquid crystal display element may fall when too thin, it is 5-300 nm, Preferably it is 10-200 nm. This coating film surface can be used as a liquid crystal aligning film by performing orientation processing, such as rubbing.

The liquid crystal aligning film of this invention is a liquid crystal aligning film to which liquid crystal aligning ability is provided by irradiating the ultraviolet-ray which polarized. Moreover, the liquid crystal aligning film of this invention is a liquid crystal aligning film which obtains uniform and favorable liquid crystal alignability even when the light irradiation range which expresses liquid crystal aligning property is wide compared with the conventional photo-alignment liquid crystal aligning film, and a substrate surface nonuniformity of irradiation intensity arises. .

As a specific example of the photo-alignment treatment method, the ultraviolet-ray polarized in the fixed direction is irradiated to the said coating film surface, and if necessary, further heat-processes at the temperature of 150-250 degreeC, and provides liquid crystal aligning ability. The method can be mentioned. As an ultraviolet-ray, it is preferable to have a wavelength of 100-400 nm, and it is especially preferable to have a wavelength of 200-400 nm. Moreover, in order to improve liquid crystal alignability, you may irradiate an ultraviolet-ray, heating a coating-film board | substrate at 50-250 degreeC. It is preferable that the irradiation amount of the said ultraviolet-ray is in the range of 1-10,000mJ / cm <2>, and it is especially preferable to exist in the range which is 100-5,000mJ / cm <2>.

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

Example

The symbol and structure of the compound used by the present Example and the comparative example are shown below.

1,3 DMCBDE-Cl: Dimethyl 1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate

BDA ： 1,2,3,4-butanetetracarboxylic dianhydride

CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

PMDA: pyromellitic acid 2 anhydride

1,3 DMCBDA ： 1,3-dimethylcyclobutanetetracarboxylic dianhydride

DA-A ： 4,4′-diaminodiphenylmethane

DA-B ： 4,4′-diaminodiphenylamine

DA-C: 4,4'- diamino diphenyl ether

DA-D: 3,5-diaminobenzoic acid

(Organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cellosolve

γ-BL: γ-butyrolactone

Below, each measuring method of ¹ HNMR, a viscosity, molecular weight, liquid crystal alignability, and an afterimage characteristic evaluation is shown.

[ ¹ HNMR]

Apparatus: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (manufactured by Varian): 400 MHz

Standard substance: Tetramethylsilane (TMS)

Solvent: DMSO-d6

[Viscosity]

In the synthesis example, the viscosity of the polyamic acid ester and the polyamic acid solution was 1.1 ml of sample volume, Contorter TE-1 (1 ° 4 ', R24), using an E-type viscometer TVE-22H (manufactured by Toki Kogyo Co., Ltd.), It measured at the temperature of 25 degreeC.

[Molecular Weight]

In addition, the molecular weight of polyamic acid ester is measured by the GPC (room temperature gel permeation chromatography) apparatus, and it is also called a number average molecular weight (henceforth Mn) and a weight average molecular weight (henceforth Mw) as a polyethylene glycol and polyethylene oxide conversion value. ) Was calculated.

GPC device: manufactured by Shodex (GPC-101)

Column ： Shodex Co. (KD803, KD805 serial)

Column temperature: 50 ° C

Eluent: N, N-dimethylformamide (as additive, lithium bromide-hydrate (LiBr.H ₂ O) is 30 mmol / L, phosphoric acid anhydride (o-phosphate) is 30 mmol / L, tetrahydrofuran (THF) 10 ml / l)

Flow rate: 1.0 ml / min

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

[Liquid crystal orientation]

254 nm ultraviolet-ray which polarized was irradiated to the film obtained by apply | coating and baking a liquid crystal aligning agent, and produced the liquid crystal aligning film of this invention. The light irradiation amount at this time was 100 mJ, 200 mJ, 300 mJ, 400 mJ. After producing a liquid crystal cell using the liquid crystal aligning film which performed the orientation process by each irradiation amount, the liquid crystal orientation was observed with the polarization microscope, and the liquid crystal orientation was evaluated on the following references | standards.

<Evaluation Criteria>

(Double-circle): There is a change of contrast by rotating a cell (the orientation of a liquid crystal can be confirmed). There is also little light leakage under cross nicol.

(Circle): Although light leakage is observed slightly under cross nicol, there exists a change of contrast by rotating a cell (the orientation of a liquid crystal can be confirmed).

(Triangle | delta): Although a flow orientation is observed and light leakage is observed under cross nicol, there is a change of contrast by rotating a cell (the orientation of a liquid crystal can be confirmed).

X: There is no change of contrast by rotating a cell (the orientation of a liquid crystal is not orientated).

Synthesis of dimethyl 1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate (1,3 DMCBDE-Cl)

a-1: Synthesis of tetracarboxylic acid dialkyl ester

(43)

In a 3-liter four-necked flask in a nitrogen stream, 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride (compound of formula (5-1), hereinafter 1,3-DM 220 g (0.981 mol) and 2200 g (6.87 mol, 10 wt times based on 1,3-DM-CBDA) of methanol were charged and heated to reflux at 65 DEG C for 30 minutes. It became a uniform solution. The reaction solution was stirred under heating reflux for 4 hours 30 minutes as it is. This reaction solution was measured by high performance liquid chromatography (hereinafter abbreviated by HPLC). The analysis of this measurement result is mentioned later.

After the solvent was distilled off from this reaction liquid by the evaporator, 1301 g of ethyl acetate was added, it heated to 80 degreeC, and was refluxed for 30 minutes. Then, it cooled until internal temperature became 25 degreeC at a speed | rate of 2-3 degreeC for 10 minutes, and stirred at 25 degreeC in that state for 30 minutes. The precipitated white crystals were taken out by filtration, and the crystals were washed twice with 141 g of ethyl acetate, and then dried under reduced pressure to obtain 103.97 g of white crystals.

This crystal was confirmed to be Compound (1-1) according to the results of 1 H NMR analysis and X-ray crystal structure analysis (HPLC relative area 97.5%) (yield 36.8%).

Synthesis of a-2.1,3-DM-CBDE-C1

(44)

Into a 3-liter four-necked flask in a nitrogen stream, 234.15 g (0.81 mol) of compound (1-1) and 1170.77 g (11.68 mol. 5 wt times) of n-heptane were injected, followed by 0.64 g (0.01 mol) of pyridine. Was added and the mixture was heated and stirred to 75 ° C under magnetic stirrer stirring. Then, 289.93 g (11.68 mol) of thionyl chlorides were dripped over 1 hour. Foaming started immediately after dripping, and 30 minutes after completion | finish of dripping, the reaction solution became uniform and foaming was stopped. Then, after stirring for 1 hour and 30 minutes at 75 degreeC in that state, the solvent was distilled off by the evaporator until the content of 924.42 g became 40 degreeC in water bath. The insolubles were filtered by heating this to 60 degreeC, dissolving the crystal | crystallization which precipitated at the time of solvent distillation, and performing hot filtration at 60 degreeC, and then the filtrate was cooled to 25 degreeC for 10 minutes at the speed of 1 degreeC. . After stirring for 30 minutes at 25 degreeC in that state, the precipitated white crystal | crystallization was taken out by filtration and this crystal was wash | cleaned with 264.21g of n-heptane. By drying under reduced pressure, 226.09 g of white crystals were obtained.

Subsequently, 226.09 g of white crystals obtained above and 452.18 g of n-heptane obtained above were injected into a 3-liter four-necked flask in a nitrogen stream, and then the mixture was heated and stirred at 60 ° C to dissolve the crystals. Thereafter, the mixture was cooled and stirred at a rate of 1 ° C. for 10 minutes to 25 ° C. to precipitate crystals. After stirring for 1 hour at 25 degreeC in that state, the precipitated white crystal | crystallization was taken out by filtration, this crystal was wash | cleaned with 113.04g of n-hexane, and 203.91g of white crystal | crystallization was obtained by drying under reduced pressure. This crystal was analyzed by 1H NMR analysis to obtain Compound (3-1), that is, dimethyl-1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate (1 , 3-DM-CBDE-C1) (HPLC relative area 99.5%) (yield 77.2%).

<Synthesis example 1> polyamic acid ester

A 300 ml (liter) four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, 8.0102 g (40.35 mmol) of DA-A was added, 158.1 g of NMP was added, and 7.20 g (91.03 mmol) of pyridine was added as a base. And stirred to dissolve. Next, 1.34 DM-CBDE-C1 was added 2.3419g (37.93 mmol), stirring this diamine solution, and it was made to react under water cooling for 4 hours.

The obtained solution of polyamic acid ester was added to 1757 g of water while stirring, and the precipitated white precipitate was collected by filtration, then, once with 1757 g of water, once with 1757 g of ethanol, and 3 with 439 g of ethanol. It washed once and dried, and obtained 16.63 g of white polyamic acid ester resin powders. The yield was 94.6%. Moreover, the molecular weight of this polyamic acid ester was Mn = 10,180 and Mw = 21,476.

14.8252 g of the obtained polyamic acid ester resin powder was taken in a 200 ml Erlenmeyer flask, 99.3048 g of NMP was added, stirred at room temperature for 24 hours, and dissolved to obtain a polyamic acid ester solution (PAE-1).

&Lt; Synthesis Example 2 &

3.9687 g (20.017 mmol) of DA-A was taken into a 300 ml four-necked flask equipped with a stirring apparatus and a nitrogen inlet tube, 26.44 g of γ-BL and 30.08 g of NMP were added, and nitrogen was It stirred by sending and dissolved. While stirring this diamine solution, 4,4701g (19.941 mmol) is added to 1,3 DMCBDA, NMP is further added so that solid content concentration may be 10 mass%, and it stirs at room temperature for 24 hours, and makes polyamic acid (PAA A solution of -1) was obtained. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 41.4 mPa * s. Moreover, the molecular weight of this polyamic acid was Mn = 10724 and Mw = 22520.

&Lt; Synthesis Example 3 &

6.0852 g (39.99 mmol) of DA-D was taken to the 100 mL four-necked flask with a stirring apparatus and the nitrogen inlet tube attached, 29.24g of NMP was added, and it stirred and sent out nitrogen and dissolved. 7.8503g (39.62 mmol) BDA was added stirring this diamine solution, Furthermore, NMP was added so that solid content concentration might be 25 mass%, and it stirred at room temperature for 24 hours, and obtained the polyamic-acid solution. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 2676 mPa * s. Moreover, the molecular weight of this polyamic acid was Mn = 9,024 and Mw = 17,757.

27.1035 g of the polyamic acid solution was taken into a 100 mL Erlenmeyer flask, 18.069 g of NMP was added, and stirred at room temperature for 4 hours to obtain a polyamic acid solution (PAA-2).

&Lt; Synthesis Example 4 &

3.0467 g (20.02 mmol) of DA-D were taken to the 100 mL four-necked flask with a stirring apparatus and the nitrogen introduction tube attached, 27.23g of NMP was added, and it stirred and sent out nitrogen and dissolved. 3.8974 g (19.87 mmol) CBDA was added stirring this diamine solution, Furthermore, NMP was added so that solid content concentration might be 15 mass%, and it stirred at room temperature for 24 hours, and obtained the solution of polyamic acid (PAA-3). . The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 448.4 mPa * s. Moreover, the molecular weight of this polyamic acid was Mn = 18,772 and Mw = 48,808.

&Lt; Synthesis Example 5 &

To a 100 ml four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube, 7.9719 g (40.01 mmol) of DA-B, 1.5246 g (10.02 mmol) of DA-D were added, and 40.64 g of NMP was added. It was made to dissolve while stirring while sending nitrogen. 9.8377g (49.65 mmol) added BDA, stirring this diamine solution, NMP was further added so that solid content concentration might be 25 mass%, and it stirred at room temperature for 24 hours, and obtained the solution of polyamic acid. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 14550 mPa * s. Moreover, the molecular weight of this polyamic acid was Mn = 16,230 and Mw = 34,539.

45.1642 g of the obtained polyamic acid solution was taken into a 100 ml Erlenmeyer flask, 33.87 g of NMP was added, and stirred at room temperature for 24 hours to dissolve, thereby obtaining a 15 mass% polyamic acid solution (PAA-4).

&Lt; Synthesis Example 6 &

To a 100 ml four-necked flask equipped with a stirring apparatus and a nitrogen inlet tube, 1.848 g (9.23 mmol) of DA-C and 2.1025 g (13.82 mmol) of DA-D were added, and 39.7 g of NMP was added thereto. It was made to dissolve while stirring while sending nitrogen. 4.8162 g (22.08 mmol) PMDA was added stirring this diamine solution, Furthermore, NMP was added so that solid content concentration might be 15 mass%, and it stirred at room temperature for 24 hours, and obtained the solution of polyamic acid (PAA-5). . The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 257 mPa * s. Moreover, the molecular weight of this polyamic acid was Mn = 13,620 and Mw = 28,299.

&Lt; Example 1 &gt;

To a 20 ml sample tube containing a stirrer, 1.5339 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 1 and 1.3574 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 3 were taken, and NMP was 1.1775 g, 1.0164g of BCS were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained the liquid crystal aligning agent (I).

<Example 2>

1.5160 g of polyamic acid ester solution (PAE-1) obtained in Synthesis Example 1 and 0.9026 g of polyamic acid solution (PAA-3) obtained in Synthesis Example 4 were taken into a 20 ml sample tube containing a stirrer, and NMP was 1.6340 g, 1.0121g of BCS were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained liquid crystal aligning agent (II).

<Example 3>

In a 20 ml sample tube containing a stirrer, 1.5293 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 1 and 0.8973 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 5 were taken, and N160 was 1.6160 g and BCS. 1.0150g was added and stirred for 30 minutes with the magnetic stirrer, and liquid crystal aligning agent (III) was obtained.

<Example 4>

1.5018 g of polyamic acid ester solution (PAE-1) obtained in Synthesis Example 1 and 1.1008 g of polyamic acid solution (PAA-5) obtained in Synthesis Example 6 were taken in a 20 ml sample tube with a stirrer, and NMP was 1.4859. 1.0214g of g and BCS were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained the liquid crystal aligning agent (IV).

&Lt; Comparative Example 1 &

4.253 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 1 was taken into a 20 ml sample tube containing a stirrer, 1.4419 g of NMP and 1.4194 g of BCS were added thereto, followed by stirring for 30 minutes with a magnetic stirrer to give a liquid crystal. An aligning agent (a) was obtained.

<Comparative Example 2>

3.095 g of polyamic acid solution (PAA-1) obtained in Synthesis Example 2 was taken into a 20 ml sample tube containing a stirrer, 1.0163 g of NMP and 1.0322 g of BCS were added thereto, followed by stirring for 30 minutes with a magnetic stirrer to align the liquid crystal. (C) was obtained.

<Example 5> Preparation of Cell

After filtering the liquid crystal aligning agent (I) obtained in Example 1 with a 1.0 micrometer filter, spin-coating on the glass substrate with a transparent electrode, drying for 5 minutes on a hotplate of 80 degreeC, and the temperature at 250 degreeC The polyimide membrane with a film thickness of 100 nm was obtained through baking for 1 hour. 100 mJ / cm <2> of 254 nm ultraviolet-rays were irradiated to this coating film surface through the polarizing plate, and the board | substrate with a liquid crystal aligning film was obtained.

After preparing two board | substrates with such a liquid crystal aligning film, disperse | distributing a 6 micrometers spacer to the liquid crystal aligning film surface of one board | substrate, combining so that the orientation of two board | substrates may be antiparallel, leaving a liquid crystal injection port, and surrounding By sealing, empty cells having a cell gap of 6 μm were prepared. A liquid crystal (MLC-2041, manufactured by Merck Co., Ltd.) was vacuum-injected into the empty cell at room temperature, the injection port was sealed to obtain a liquid crystal cell. When liquid crystal aligning property was confirmed with the polarization microscope about this liquid crystal cell, it was confirmed that it is a favorable liquid crystal aligning state.

It shows in Table 1 mentioned later about the liquid-crystal orientation evaluation result when the irradiation amount of a polarized ultraviolet-ray is 200 mJ / cm <2>, 300 mJ / cm <2> and 400 mJ / cm <2>.

<Example 6>

A liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (II) obtained in Example 2 was used. About this liquid crystal cell, the liquid crystal orientation was confirmed with the polarization microscope about this liquid crystal cell. The results are shown in Table 1 described later.

<Example 7>

A liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (III) obtained in Example 3 was used. About this liquid crystal cell, the liquid crystal orientation was confirmed with the polarization microscope about this liquid crystal cell. The results are shown in Table 1 described later.

&Lt; Example 8 &gt;

A liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (IV) obtained in Example 4 was used. About this liquid crystal cell, the liquid crystal orientation was confirmed with the polarization microscope about this liquid crystal cell. The results are shown in Table 1 described later.

&Lt; Comparative Example 3 &

A liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (a) obtained in Comparative Example 1 was used. About this liquid crystal cell, the liquid crystal orientation was confirmed with the polarization microscope about this liquid crystal cell. The results are shown in Table 1 described later.

&Lt; Comparative Example 4 &

A liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (c) obtained in Comparative Example 2 was used. About this liquid crystal cell, the liquid crystal orientation was confirmed with the polarization microscope about this liquid crystal cell. The results are shown in Table 1 described later.

By contrast with Examples 5-8 and Comparative Examples 3 and 4, it turns out that the liquid crystal aligning agent of this invention widens the range of the light irradiation amount which a liquid-crystal orientation ability expresses.

Industrial availability

In the photo-alignment method, the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention can obtain favorable liquid-crystal orientation, regardless of the irradiation amount of polarized ultraviolet ray. In particular, it is widely useful for a big screen display element, a television, etc.

In addition, all the content of the JP Patent application 2010-058559, a claim, drawing, and the abstract for which it applied on March 15, 2010 is referred here, and it takes in as an indication of the specification of this invention.

Claims (11)

Liquid crystal aligning agent containing following (A) component and (B) component.
(A) component: At least 1 sort (s) of polymer chosen from the group which consists of the polyamic acid ester which has a repeating unit represented by following formula (1), and the imidation polymer of this polyamic acid ester.
[Formula 1]

(In formula (1), Y is a divalent organic group, R <_1> is a C1-C5 alkyl group, R <_2> -R <_5> is a hydrogen atom, a halogen atom, or a C1-C30 hydrocarbon group each independently, May be the same or different)
(B) Component: Polyamic acid obtained from tetracarboxylic dianhydride and diamine. The method of claim 1,
The liquid crystal aligning agent whose content ratio of (A) component and (B) component is 1/9-9/1 by mass ratio (A / B). 3. The method according to claim 1 or 2,
The liquid crystal aligning agent whose (A) component is at least 1 sort (s) of polymer chosen from the group which consists of the polyamic acid ester which has 40 mol% or more of repeating units represented by said Formula (1), and the imidation polymer of this polyamic acid ester. The method according to any one of claims 1 to 3,
Liquid crystal aligning agent whose component (A) is polyamic acid ester which has a repeating unit represented by following formula (3).
(2)

(In Formula (3), Y is a divalent organic group and R <_6> is a C1-C5 alkyl group.) The method according to any one of claims 1 to 3,
The liquid crystal aligning agent whose component (A) is a polyamic acid ester which has a repeating unit represented by following formula (4).
(3)

(In Formula (4), Y is a divalent organic group and R <_6> is a C1-C5 alkyl group.) 6. The method according to any one of claims 1 to 5,
In Formula (1), Y is at least 1 sort (s) chosen from the group which consists of following structural formulas, The liquid crystal aligning agent.
[Chemical Formula 4]

7. The method according to any one of claims 1 to 6,
Component (B) is a polyamic acid obtained using the tetracarboxylic dianhydride containing at least 1 sort (s) chosen from the group which consists of tetracarboxylic dianhydride of following formula (B-1)-(B-9). Liquid crystal aligning agent.
[Chemical Formula 5]

The method of claim 7, wherein
Tetracar which has 20 mol% or more of all the tetracarboxylic dianhydride at least 1 sort (s) of tetracarboxylic dianhydride selected from the group which the said component (B) consists of said formula (B-1)-(B-9). The liquid crystal aligning agent which is a polyamic acid obtained using an acid dianhydride. The method according to any one of claims 1 to 8,
The liquid crystal aligning agent whose (B) component is a polyamic acid obtained using the diamine containing at least 1 sort (s) chosen from the group which consists of following formula (B-10)-(B-13).
[Chemical Formula 6]

The method of claim 9,
The liquid crystal aligning agent whose component (B) is a polyamic acid obtained using the diamine which has 20 mol% or more of at least 1 sort (s) of diamine chosen from the group which consists of said Formula (B-10)-(B-13) of all diamine. . The liquid crystal aligning film obtained by irradiating polarized ultraviolet-ray to the film obtained by apply | coating and baking the liquid crystal aligning agent in any one of Claims 1-10.