KR20210097710A - Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element - Google Patents

Abstract

(식 (1) 중, R₁ ∼ R₄ 는, 수소 원자, 할로겐 원자, 탄소수 1 ∼ 6 의 알킬기 등이고, R₁ ∼ R₄ 의 적어도 1 개는 상기 정의 중의 수소 원자 이외의 기이다. Y₁ 은 하기 식 (H) 로 나타내는 부분 구조를 갖는 2 가의 유기기이다. 식 (3) 중, X₃ 은 방향족 산 2 무수물에서 유래하는 4 가의 유기기, Y₃ 은 식 (m) 으로 나타내는 부분 구조를 갖는 2 가의 유기기이다. R₃₀ 은 수소 원자, 또는 탄소수 1 ∼ 4 의 알킬기이다. Z₃₁, Z₃₂ 는 수소 원자 등이다.)

(Q³ 은 -(CH₂)_n-이고 (n 은 2 ∼ 20 이다), 임의의 -CH₂- 는 -O- 로 치환되어도 된다. 단, 산소 원자끼리가 직접 결합되는 경우는 없다. 벤젠 고리 상의 임의의 수소 원자는 1 가의 유기기로 치환되어도 된다. * 는 결합손을 나타낸다.)The liquid crystal display element excellent in the contrast characteristic which expresses favorable tolerance with respect to an AC afterimage or the residual image derived from residual DC, and suppresses the dispersion|variation in brightness in the liquid crystal aligning film with favorable adhesiveness with sealing compound and in-plane black display The liquid crystal from which An aligning agent is provided.
The following (A) component and (B) component are contained, The liquid crystal aligning agent characterized by the above-mentioned.
(A) Component: The polymer (A) which has a repeating unit represented by following formula (1).
(B) Component: The polymer (B) which has a repeating unit represented by following formula (3).

(In formula (1), R ₁ to R ₄ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, etc., _{and at least one of R 1} to R ₄ is a group other than a hydrogen atom in the above definition. Y ₁ is a divalent organic group having a partial structure represented by the following formula (H): In formula (3), X ₃ is a tetravalent organic group derived from an aromatic acid dianhydride, Y ₃ is a partial structure represented by a formula (m) is a divalent organic _{group having R 30} is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z ₃₁ , Z ₃₂ is a hydrogen atom, etc.)

(Q ³ is -(CH ₂ ) _n - (n is 2 to 20), and any -CH ₂ - may be substituted with -O-. However, oxygen atoms are not directly bonded to each other. Benzene Any hydrogen atom on the ring may be substituted with a monovalent organic group. * represents a bond.)

Description

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

TECHNICAL FIELD This invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and the liquid crystal display element using the same.

DESCRIPTION OF RELATED ART Conventionally, liquid crystal devices are widely used as display parts, such as a personal computer, a smart phone, a mobile phone, and a television. Liquid crystal devices include, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode for applying an electric field to the liquid crystal layer, an alignment film for controlling alignment of liquid crystal molecules in the liquid crystal layer, and supply to the pixel electrode It is equipped with a thin film transistor (TFT) etc. which switch the electrical signal used. As a driving method of liquid crystal molecules, a vertical electric field system such as a TN system and a VA system, and a transverse electric field system such as an IPS system and a fringe field switching (hereinafter referred to as FFS) system are known.

Currently, the liquid crystal aligning film, which is industrially most prevalent, rubs the surface of a film formed on an electrode substrate made of polyamic acid and/or imidized polyimide with a cloth such as cotton, nylon, or polyester in one direction. , is produced by performing a so-called rubbing treatment. The rubbing treatment is an industrially useful method that is simple and excellent in productivity. However, with the increase in performance, high definition, and size of the liquid crystal display element, scratches on the surface of the alignment film generated by the rubbing treatment, dust generation, effects due to mechanical force or static electricity, and further, various problems such as non-uniformity in the alignment treatment surface The branch problem is becoming clearer. As a liquid-crystal orientation treatment method instead of a rubbing process, the photo-alignment method which provides liquid-crystal orientation ability by irradiating the polarized radiation is known. As for the liquid-crystal orientation treatment by a photo-alignment method, the thing using photoisomerization reaction, the thing using photocrosslinking reaction, the thing using photolysis reaction, etc. are proposed (refer nonpatent literature 1, patent document 1).

Although the liquid crystal aligning film which is a structural member of a liquid crystal display element is a film|membrane for aligning liquid crystals uniformly, not only the orientation uniformity of a liquid crystal but various characteristics are needed. For example, an electric charge accumulates in a liquid crystal aligning film by the voltage which drives a liquid crystal, and it affects a display as an afterimage or ghosting (it is called residual image derived from residual DC hereafter), and the display quality of a liquid crystal display element is remarkably improved. Since there exists a problem of reducing, the liquid crystal aligning agent which overcomes these subjects is proposed (refer patent document 2).

Moreover, in an IPS system and an FFS drive system, stability of a liquid-crystal orientation also becomes important. When stability of orientation is small, when a liquid crystal is driven for a long time, a liquid crystal will not return to an initial state, and it will become a cause of the fall of contrast and ghosting (it is hereafter called an AC afterimage). As a method of solving said subject, the specific liquid crystal aligning agent is disclosed by patent document 3.

Further, with the spread of tablets and smart phones, development of a liquid crystal display element having a narrow frame in which a display area is secured as wide as possible is progressing. Since it was necessary to apply|coat a sealing compound on a liquid crystal aligning film by this frame narrowing, the liquid crystal aligning agent with favorable adhesiveness with a sealing compound is disclosed by patent document 4, maintaining liquid-crystal orientation.

Japanese Patent Laid-Open No. 9-297313 International Publication No. 2005/083504 Pamphlet International Publication No. 2015/050135 pamphlet International Publication No. 2015/060360 Pamphlet

"Liquid crystal photo-alignment film" Kidowaki, Ichimura, Functional Materials, November 1997, Vol. 17, No.11 pages 13 to 22

However, in an actual liquid crystal display element, the twist angle will be slightly disturbed in the liquid crystal display element surface due to manufacturing dispersion|variation etc. Then, due to such in-plane variation, in the liquid crystal display element, the brightness at the time of black display is disturbed in-plane. Moreover, the request|requirement of the high definition with respect to a liquid crystal display element is still increasing, and it has become more important than before to show favorable display quality.

This invention was made in view of the said circumstances, and it expresses favorable tolerance with respect to an AC afterimage or residual image derived from residual DC, and suppresses the dispersion|variation in brightness in the surface at the time of the liquid crystal aligning film with good adhesiveness with a sealing compound and black display. One objective is to provide the liquid crystal aligning agent which can obtain the liquid crystal display element excellent in the contrast characteristic.

MEANS TO SOLVE THE PROBLEM This inventor discovered that the said subject was solvable by using the liquid crystal aligning agent containing a specific component, as a result of earnestly researching, and came to complete this invention. Specifically, it makes the following as a summary.

The following (A) component and (B) component are contained, The liquid crystal aligning agent characterized by the above-mentioned.

(A) Component: The polymer (A) which has a repeating unit represented by following formula (1).

(B) component: The polymer (B) containing the repeating unit represented by following formula (3).

[Formula 1]

(R ₁ to R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or a fluorine atom containing 1 to 6 carbon atoms. is a monovalent organic group or a phenyl group, and _{at least one of R 1} to R ₄ represents a group other than a hydrogen atom in the above definition, Y ₁ represents a divalent organic group having a partial structure represented by the following formula (H). )

[Formula 2]

(Q ³ is a structure represented by -(CH ₂ ) _n - (provided that n is an integer of 2 to 20, and any -CH ₂ - may be substituted with -O-. However, oxygen atoms are directly bonded to each other) Any hydrogen atom on the two benzene rings may be substituted with a monovalent organic group. * indicates a bond.)

[Formula 3]

(X ₃ is a tetravalent organic group derived from aromatic acid dianhydride, Y ₃ is a divalent organic group having a partial structure represented by the following formula (m), * is a bond. R ₃₀ is a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms; Z ₃₁ and Z ₃₂ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, or a substituent which may have a substituent an alkynyl group having 2 to 10 carbon atoms, a tert-butoxycarbonyl group, or a 9-fluorenylmethoxycarbonyl group.)

[Formula 4]

ADVANTAGE OF THE INVENTION According to the liquid crystal aligning agent of this invention, the liquid crystal aligning film with favorable adhesiveness with a sealing compound can be obtained. Moreover, it is hard to generate|occur|produce the residual image derived from residual DC and AC afterimage, and the liquid crystal display element excellent in the contrast which suppressed the dispersion|variation in the in-plane brightness at the time of black display is obtained.

<Polymer (A)>

The liquid crystal aligning agent of this invention contains the polymer (A) which has a repeating unit represented by said Formula (1). By setting it as such a structure, the liquid crystal aligning film with little generation|occurrence|production of an AC afterimage can be obtained, and the liquid crystal display element excellent in contrast can be obtained. In the formula (1), X ₂ , Y ₁ , Y ₂ , R ₁ , R ₂ , R ₃ , and R ₄ are as defined above.

_{As a tetravalent organic group of X<2>} of Formula (1), it is preferable that it is a tetravalent organic group which has a 5- to 8-membered ring alicyclic structure, It is more preferable that it is a tetravalent organic group which has an alicyclic structure of a 5- to 7-membered ring. . In addition, when the alicyclic structure to which an imide group is bonded is a polycyclic structure, the 5-membered ring or more alicyclic structure WHEREIN: In each ring included in the polycyclic structure, all the atoms which comprise a ring represent 5 or more. Moreover, the said alicyclic structure should just couple|bond with at least 1 of two imide groups, and may have a chain hydrocarbon structure or an aromatic ring structure together with an alicyclic structure.

Specific examples of the alkyl group having 1 to 6 carbon atoms in R ₁ to R ₄ include a methyl group, an ethyl group, a propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t- A butyl group, n-pentyl group, etc. are mentioned. Specific examples of the alkenyl group having 2 to 6 carbon atoms in R ₁ to R ₄ include, for example, a vinyl group, a propenyl group, a butynyl group, and the like, and these may be linear or branched. . Specific examples of the alkynyl group having 2 to 6 carbon atoms in R ₁ to R ₄ include an ethynyl group, 1-propynyl group, 2-propynyl group and the like. The halogen atom in the R ₁ ~ R _4, there may be mentioned a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. A fluoromethyl group, a trifluoromethyl group, etc. are mentioned as a C1-C6 monovalent organic group containing a fluorine atom. From the viewpoint of high photoreactivity, R ₁ to R ₄ are a hydrogen atom or a methyl group, and _{at least one of R 1} to R ₄ is preferably a methyl group, more preferably at least 2 of _{R 1} to R _{4 is a methyl group} it is preferable More preferably, R ₁ and R ₃ are methyl groups and R ₂ and R ₄ are hydrogen atoms.

Specific examples of the monovalent organic group in the formula (H) include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, and a fluorine atom. there may be mentioned divalent organic groups of 1-61, it may be mentioned a structure illustrated in the R ₁ ~ R _4. As a partial structure represented by said formula (H), the partial structure represented by any of following formula (H-1) - (H-6) from a viewpoint with little generation|occurrence|production of an AC residual image is mentioned.

[Formula 5]

_{As a preferable specific example of Y<1>} in said Formula (1), the divalent organic group represented by any of following formula (h-1) - (h-7) from a viewpoint with little generation|occurrence|production of an AC residual image is mentioned. .

[Formula 6]

It is preferable that the polymer (A) further has a repeating unit represented by the following formula (2) from the viewpoint of improving heat resistance.

[Formula 7]

(Wherein, X ₂ is a tetravalent organic group having an alicyclic structure having a 5-membered ring or more. Y ₂ represents a divalent organic group having a partial structure represented by the formula (H).)

_{The tetravalent organic group of X 2 in} the formula (2) is preferably a tetravalent organic group having a 5- to 8-membered ring alicyclic structure, and more preferably a tetravalent organic group having a 5- to 7-membered ring alicyclic structure. . In addition, when the alicyclic structure to which an imide group is bonded is a polycyclic structure, the 5-membered ring or more alicyclic structure WHEREIN: In each ring included in the polycyclic structure, all the atoms which comprise a ring represent 5 or more. Moreover, the said alicyclic structure should just couple|bond with at least 1 of two imide groups, and may have a chain hydrocarbon structure or an aromatic ring structure together with an alicyclic structure.

As _{a preferred specific example of X 2} , a tetravalent organic group represented by any of the following formulas (X2-1) to (X2-12) is exemplified.

[Formula 8]

There is little generation|occurrence|production of an AC residual image, and (X2-1) - (X2-4) are more preferable from a viewpoint of raising the contrast of a liquid crystal display element.

Preferred embodiments of Y ₂ in the formula (2) is the same as the preferred embodiments of Y ₁ in the formula (1).

The polymer (A), from the viewpoint of increasing the contrast of the liquid crystal display element, at least one type of repeating unit selected from the group consisting of a repeating unit represented by the following formula (4) and a repeating unit represented by the following formula (5) is added. can be taken as

[Formula 9]

_{R 41} to R ₄₄ in the formulas (4) and (5) have the same definitions _{as R 1} to R _{4 in} the formula (1), including preferred specific examples, respectively. _{X 5} in Formula (5) is synonymous with _{X 2 in} Formula (2). Y ₄ , Y ₅ represents a divalent organic group represented by the following formula (I).

[Formula 10]

In said formula (I), Q represents a single bond or an oxygen atom, and n represents 0-2. Any hydrogen atom on the benzene ring may be substituted with a monovalent organic group, and as such a monovalent organic group, the structure illustrated by the specific example of the monovalent organic group in the said Formula (H) is mentioned.

Y ₅ of Y _4, and the formula (5) in the formula (4) is, in view to increase the contrast of the liquid crystal display element, the following formula (I-1) ~ (I -3) 2 -valent organic group represented by any one of it is preferable In the following formula, * represents a bond.

[Formula 11]

The said polymer (A) adds at least 1 type of repeating unit selected from the group which consists of a repeating unit represented by a repeating unit represented by following formula (6), and a repeating unit represented by following formula (7) from a viewpoint of improving adhesiveness with a sealing compound can be taken as

[Formula 12]

(Wherein, R ₆₁ to R _{64 have the same definitions as R 1} to R ₄ of the formula (1), including preferred embodiments _{, respectively, and Y 6} , Y ₇ are each independently a moiety represented by the following formula (J-1) having the structure divalent represents a divalent organic group represented by the organic group, or the formula (J-2) expression X ₇ is X ₂ and consent of the formula (2)) in 7

[Formula 13]

In the formulas (J-1) and (J-2), Q ₅ is a single bond, -(CH ₂ ) _n - (n is an integer from 1 to 20), or any of _{-(CH 2} ) _{n -} -CH ₂ - is not adjacent to each other -O-, -COO-, -OCO-, -NQ ₉ -, -NQ ₉ CO-, -CONQ ₉ -, -NQ ₉ CONQ ₁₀ -, -NQ ₉ a group substituted with COO-, -OCOO-, Q ₉ and Q ₁₀ each independently represents a hydrogen atom or a monovalent organic group;

Q ₆ and Q ₇ each independently represent a group having -H, -NHD, -N(D) ₂ , -NHD , or a group having -N(D) ₂ . Q ₈ represents a group having -NHD, -N(D) ₂ , -NHD or a group having -N(D) ₂ . D represents a carbamate protecting group, and examples of the carbamate protecting group include a tert-butoxycarbonyl group and a 9-fluorenylmethoxycarbonyl group. However, _{at least one of Q 5} , Q ₆ and Q ₇ has a carbamate protecting group in the group. *1 represents a bond. Preferred embodiments of Y _6, Y ₇ are, AC afterimages divalent indicating that any of the in low point of view, the following formula (J-1-a) ~ (J-1-d), (J-2-1) and organic groups. "Boc" represents a tert-butoxycarbonyl group.

[Formula 14]

The polymer (A) is a repeating unit represented by the formula (1), a repeating unit represented by the formula (2), a repeating unit represented by the formula (4), a repeating unit represented by the formula (5), a repeating unit represented by the formula ( In addition to the repeating unit represented by 6) and the repeating unit represented by the formula (7), at least one selected from the group consisting of a repeating unit represented by the following formula (PI-A-1) and a repeating unit represented by (PA-1) may have a repeating unit of

[Formula 15]

In formula (PI-A-1), X _I1 represents a tetravalent organic group, and Y _I1 represents a divalent organic group. However, when X _I1 is synonymous with a tetravalent organic group represented by the following formula (g) or X ₂ of the formula (2), Y _I1 is a divalent organic group having a partial structure represented by the formula (H), Structures other than the divalent organic group represented by the said Formula (I), the divalent organic group which have a partial structure represented by the said Formula (J-1), and the said Formula (J-2) are shown. X _{I1 is any of the following formulas (X I1} -1) to (X _I1-13 ) other than the tetravalent organic group represented by the following formula (g) and the tetravalent organic group _{exemplified by X 2 in the formula (2).} The tetravalent organic group represented by the thing, the tetravalent organic group derived from aromatic tetracarboxylic dianhydride, etc. are mentioned.

[Formula 16]

_{(R 1, R 2, R 3} , R 4 , is the following formula (1) _{R 1, R 2, R 3} , R 4 and consent).

[Formula 17]

Here, aromatic tetracarboxylic dianhydride means the acid dianhydride obtained by the carboxyl group couple|bonded with aromatic rings, such as a benzene ring and a naphthalene ring, dehydrating in a molecule|numerator. Specific examples include a tetravalent organic group represented by any of the following formulas (X3-1) to (X3-2), and a tetravalent organic group represented by any of the following formulas (Xr-1) to (Xr-7). there is.

[Formula 18]

(x and y are each independently a single bond, ether (-O-), carbonyl (-CO-), ester (-COO-), alkanediyl group having 1 to 5 carbon atoms, 1,4-phenylene , sulfonyl or amide group. j and k are each independently an integer of 0 or 1. * represents a bond.)

[Formula 19]

In the formula (PI-A-1), _{specific examples of the divalent organic group of Y I1} include a divalent organic group having a partial structure represented by the formula (H), and a divalent organic group represented by the formula (I). , a divalent organic group having a partial structure represented by the formula (J-1), a divalent organic group represented by the formula (J-2), 2 represented by the following formulas (o-1) to (o-23) A valent organic group, the group etc. which are represented by any one of Formula (Y-1) - (Y-167) described in International Publication No. 2018/117239 are mentioned.

[Formula 20]

[Formula 21]

[Formula 22]

In formula (PA-1), X _A1 represents a tetravalent organic group, and Y _A1 represents a divalent organic group. Specific examples of X _A1 include the structures exemplified for _{X I1} in the above formula (PI-A-1), _{and specific examples of Y A1 include Y I1} in the above formula (PI-A-1) The illustrated structure can be mentioned.

In formula (PA-1), R _A1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; Z _A11 and Z _A12 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkenyl group having 2 to 10 carbon atoms, an optionally substituted alkynyl group having 2 to 10 carbon atoms; tert-butoxycarbonyl group, or 9-fluorenylmethoxycarbonyl group.

Specific examples of the alkyl group having 1 to 5 carbon atoms for R _A1 include methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n- A pentyl group etc. are mentioned. From a viewpoint of the easiness of imidation by heating _{, it is preferable that R<1>} is a hydrogen atom or a methyl group.

Specific examples of the carbon number of alkyl group of 1 to 10 of the Z _A11, Z _A12 example, in addition to the specific example of a carbon number of alkyl group of from 1 to 5 exemplified above R _1, hexyl group, heptyl group, octyl group, nonyl group, having and the like. Specific examples of the alkenyl group having 2 to 10 carbon atoms for Z _A11 and Z _A12 include, for example, a vinyl group, a propenyl group, and a butynyl group, and these may be linear or branched. Specific examples of the alkynyl group having 2 to 10 carbon atoms for Z _A11 and Z _A12 include, for example, an ethynyl group, a 1-propynyl group, and a 2-propynyl group.

Z _A11 and Z _A12 may have a substituent, and examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, a cyano group, and an alkoxy group. .

From a viewpoint of few AC residual images, it is preferable that the total amount of the repeating unit represented by the said Formula (1) and the repeating unit represented by the said Formula (2) of a polymer (A) contains 1-95 mol% of all repeating units.

<Polymer (B)>

The liquid crystal aligning agent of this invention contains the polymer (B) which has a repeating unit represented by said Formula (3). Since the heat resistance of the liquid crystal aligning film obtained can be raised by setting it as such a structure, while a liquid crystal aligning film with few AC afterimages is obtained, the dispersion|variation of the twist angle in plane which generate|occur|produces at the time of manufacture is suppressed, and the liquid crystal display excellent in contrast The element is obtained. In the formula (3), X ₃ , Y ₃ , R ₃₀ , Z ₃₁ , and Z ₃₂ are as defined above.

Specific examples of the alkyl group having 1 to 5 carbon atoms for R ₃₀ include structures exemplified by _{R A1 in the formula (PA-1).} From the viewpoint of easiness of imidization by heating, R ₃₀ is each independently preferably a hydrogen atom or a methyl group.

Specific examples of the Z ₃₁ , Z ₃₂ alkyl group having 1 to 10 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, and the alkynyl group having 2 to 10 carbon atoms are exemplified by _{Z A1} and Z _{A2 in the formula (PA-1)} one structure, and the like.

Z ₃₁ , Z ₃₂ may have a substituent, and examples of the substituent include structures exemplified by _{Z A1} and Z _{A2 of the formula (PA-1).}

From a viewpoint of few AC afterimages _{, it is preferable that Z 31} and Z ₃₂ are each independently a hydrogen atom or a methyl group.

As Y ₃ in the formula (3), in a low-AC residual image point of view, it may be used in the formula (Y3-1) ~ a divalent organic group selected from (Y3-2).

[Formula 23]

As a specific example of the aromatic acid dianhydride _{in X<3>} of said Formula (3), the structure illustrated by _{said X I1 is mentioned.} It is preferable that X<_3> is a tetravalent organic group represented by said Formula (X3-1) or (X3-2) from a viewpoint with few AC residual images. As a tetravalent organic group represented by said formula (X3-1) or (X3-2), a more preferable specific example is a structure represented by any of the following formulas (X3-3) - (X3-19).

[Formula 24]

[Formula 25]

The polymer (B) is selected from the group consisting of a repeating unit represented by the following formula (8) and a repeating unit represented by the following formula (9) from the viewpoint of increasing the seal adhesiveness of the liquid crystal aligning film and reducing the residual image derived from residual DC You may have at least 1 type of repeating unit.

[Formula 26]

(Wherein, X ₈ is a tetravalent organic group having a 5-membered ring or more alicyclic structure, _{and is synonymous with X 2 in} the formula (2) including preferred embodiments. X ₉ is 4 having a 5-membered ring or more alicyclic structure. monovalent and tetravalent organic group derived from an organic group or an aromatic acid dianhydride, and agreed to include X ₃ with a preferred embodiment of the formula (2) X ₂ or the formula (3). Y ₈ is the expression (3 ) is the same as Y ₃ of ), and Y ₉ is a divalent organic group having a partial structure represented by the following formula (n-1) or (n-2): Z ₈₁ , Z ₈₂ , Z ₉₁ , and Z ₉₂ are each of the above It has the same definitions as Z ₃₁ and Z _{32 in} Formula (3), R ₈ and R ₉ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Q ₁ and Q ₂ each independently represent a hydrogen atom or a methyl group. .)

[Formula 27]

Specific examples of the divalent organic group having a partial structure represented by the formula (n-1) or (n-2) include the following formulas (ND-1-2) and (ND-2-1) - (ND-2-3), the structure represented by any of (ND-5) is mentioned.

[Formula 28]

(R ₂₁ and R ₂₂ each independently represents a hydrogen atom or a methyl group, Q ²² independently represents a single bond or *1-R ²³ -Ph-*2, R ²³ represents a single bond, -O-, - COO-, -OCO-, -(CH ₂ ) _l -, -O(CH ₂ ) _m represents a divalent organic group selected from O-, -CONH-, and -NHCO- (l, m is 1 to 5 represents an integer), *1 represents a site bonded to the benzene ring in formula (ND-1-2), *2 represents a site bonded to an amino group in formula (ND-1-2), Ph is phenyl Represents a ren group. n represents an integer of 1 to 3.)

[Formula 29]

In the formula, R ²¹ and R ²² each represent a hydrogen atom or a methyl group. R ²⁴ each independently represents a single bond or a structure of the following formula (Ar), and n represents an integer of 1 to 3. * indicates a bond. In addition, arbitrary hydrogen atoms of the benzene ring may be substituted with monovalent organic groups, such as a methyl group and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.).

[Formula 30]

wherein R ²⁵ is a single bond, -O-, -COO-, -OCO-, -(CH ₂ ) _l -, -O(CH ₂ ) _m O-, -CONR-, and -NRCO- The divalent organic group used is shown, and k shows the integer of 1-5. In addition, R represents hydrogen or a monovalent organic group, such as a C1-C3 alkyl group, and l and m represent the integer of 1-5. *1, *2 represents a bond, *1 couple|bonds with the benzene ring in a formula (ND-2-1) - a formula (ND-2-3).

[Formula 31]

(R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a methyl group. A ₅ represents a single bond or a _{divalent organic group such as -O-, -(CH 2} ) _n - (n is an integer of 1 to 4) indicate.)

Preferred specific examples of the formula (ND-1-2) include structures represented by any of the following formulas (n1-9) to (n1-14).

[Formula 32]

As a preferable specific example of the said Formula (ND-2-1) - (ND-2-3), the structure represented by any of the following formulas (n2-1) - (n2-6) is mentioned.

[Formula 33]

[Formula 34]

Preferred specific examples of the formula (ND-5) include structures represented by any of the following formulas (n5-1) to (n5-8).

[Formula 35]

The polymer (B) has, in addition to the repeating unit represented by the formula (3), the repeating unit represented by the formula (8), and the repeating unit represented by the formula (9), a repeating unit represented by the following formula (PA-2) also be

[Formula 36]

In formula (PA-2), X _A2 represents a tetravalent organic group, and Y _A2 represents a divalent organic group. However, when X _A2 is synonymous with _{X 9} of said formula (9) _{, Y A2} is a divalent organic group which has a partial structure represented by said formula (m), or said formula (n-1) or (n-2) ) represents a structure other than a divalent organic group having a partial structure represented by . R _{A2 is synonymous with R 3} of Formula (3) including preferred embodiments, and Z _A21 , Z _{A22 have the same definitions as Z 31} , Z ₃₂ of Formula (3) including preferred embodiments.

As _{a specific example of X A2} , tetravalent organic origin derived from aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride other than aromatic tetracarboxylic dianhydride illustrated by _{X 3} of said formula (3) can be lifted

Specific examples of Y _A2 include a divalent organic group having a partial structure represented by the formula (m) or a divalent organic group having a partial structure represented by the formula (n-1) or (n-2). A divalent organic group having a pyrrole structure described in WO2017/126627, preferably a divalent organic group represented by the following formula (pr), a divalent oil having a thiophene or furan structure described in International Publication No. WO2018/092759 Device, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4- Two amino groups from diamines having a carboxyl group, such as diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid, and diamine compounds represented by the following formulas [3b-1] to [3b-4] Divalent organic groups excluded, divalent organic groups having -NH-CO-NH- in the molecule of formulas (U-1) to (U-9), etc., paragraphs [0013] to [0013] of International Publication No. WO2018-181566 0030], and the like.

[Formula 37]

In the formula (pr), R ⁸¹ represents a hydrogen atom or a methyl group, R ⁸² each independently represents a single bond or a group "*1-R ⁸³ -Ph-*2", R ⁸³ represents a single bond, -O -, -COO-, -OCO-, -(CH ₂ ) _l -, -O(CH ₂ ) _m represents a divalent organic group selected from O-, -CONH-, and -NHCO- (l, m is 1 to 5), *1 represents a site bonded to a benzene ring in the formula (pr), and *2 represents a site bonded to a nitrogen atom in the formula (PA-2). Ph represents a phenylene group. n represents 1-3.

[Formula 38]

In formula [3b-1], A ¹ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, - O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or N(CH ₃ )CO-, m ¹ and m ² each independently represent an integer of 0 to 4, and m ¹ + m ² represents an integer of 1 to 4, formula [3b -2], m ³ and m ⁴ each independently represent an integer of 1 to 5, in formula [3b-3], A ² represents a linear or branched alkylene group having 1 to 5 carbon atoms, m ⁵ represents an integer of 1 to 5, in formula [3b-4], A ³ and A ⁴ are each independently a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ - , -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, - OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or N(CH ₃ )CO- is represented, and m ⁶ represents an integer of 1-4.

[Formula 39]

It is preferable that the polymer (B) of this invention contains 30-100 mol% of the repeating unit represented by said Formula (3) with respect to all the repeating units of a polymer (B) from a viewpoint of raising contrast, or 40-100 It is preferable to contain mol%, or it is preferable to contain 50-100 mol%.

From a viewpoint with few AC afterimages and residual images derived from residual DC WHEREIN: The orientation ratio of the said polymer (A) and the said polymer (B) is 5/95-95/5 in mass ratio of polymer (A)/polymer (B) it is preferable From a viewpoint from which a liquid crystal aligning film with high reproducibility is obtained, the orientation ratio of the said polymer (A) and the said polymer (B) is mass ratio of polymer (A)/polymer (B), 10/90-90/10 are more preferable, , 20/80 to 80/20 are more preferable.

<The manufacturing method of a polyamic acid, polyamic acid ester, and a polyimide>

The polyamic acid ester, polyamic acid, and polyimide which are polyimide precursors used for this invention can be synthesize|combined by the well-known method described in international publication WO2013/157586, for example.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention contains a polymer (A) and a polymer (B). In addition to the polymer (A) and the polymer (B), the liquid crystal aligning agent of this invention may contain the other polymer. Examples of other polymers include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or a derivative thereof, and poly(styrene-phenylmaleimide). ) derivatives, poly(meth)acrylates, and the like.

A liquid crystal aligning agent is used in order to produce a liquid crystal aligning film, and takes the form of a coating liquid from a viewpoint of forming a uniform thin film. Also in the liquid crystal aligning agent of this invention, it is preferable that it is an above-described polymer component and the coating liquid containing an organic solvent. In that case, the density|concentration of the polymer in a liquid crystal aligning agent can be suitably changed according to setting of the thickness of the coating film which you want to form. From the point of forming a uniform and defect-free coating film, 1 mass % or more is preferable, and from the point of storage stability of a solution, 10 mass % or less is preferable. A particularly preferable concentration of the polymer is 2 to 8% by mass.

The organic solvent contained in a liquid crystal aligning agent will not be specifically limited if a polymer component melt|dissolves uniformly. To give specific examples thereof, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, γ-buty Lolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropane amides (these are collectively referred to as “good solvents”) and the like. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide or γ -It is preferable to use butyrolactone. It is preferable that the good solvent in the liquid crystal aligning agent of this invention is 20-99 mass % of the whole solvent contained in a liquid crystal aligning agent, 20-90 mass % is more preferable, It is 30-80 mass % that it is especially preferable am.

Moreover, the organic solvent contained in a liquid crystal aligning agent uses the mixed solvent which used together the solvent (it is mentioned poor solvent) which improves the applicability|paintability at the time of apply|coating a liquid crystal aligning agent, and the surface smoothness of a coating film in addition to the above solvents It is preferable to do Although the specific example of the organic solvent used together is given below, it is not limited to these examples.

For example, diisopropyl ether, diisobutyl ether, diisobutylcarbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1 ,2-Butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3- Ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl Ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate , Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono Butyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether, 3-methoxymethylpropionate, 3-ethoxy Ethyl propionate, 3-methoxyethyl propionate, 3-methoxypropyl propionate, 3-methoxybutyl propionate, lactic acid n-butyl ester, lactic acid isoamyl ester, diethylene glycol monoethyl ether, diisobutyl ketone (2, 6-dimethyl-4-heptanone) and the like.

Among them, diisobutylcarbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2 -Pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, or diisobutyl ketone is preferable.

Preferred combinations of the good solvent and the poor solvent include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and ethylene glycol monobutyl ether. , N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ -Butyrolactone, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol diethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monobutyl ether and 2,6 -Dimethyl-4-heptanone, N-methyl-2-pyrrolidone and γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone And propylene glycol monobutyl ether, 2,6-dimethyl-4-heptanol, N-methyl-2-pyrrolidone, γ-butyrolactone, dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone, Propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, etc. are mentioned. 1-80 mass % of the whole solvent contained in a liquid crystal aligning agent is preferable, as for these poor solvents, 10-80 mass % is more preferable, and its 20-70 mass % is especially preferable. The kind and content of such a solvent are suitably selected according to the coating apparatus of a liquid crystal aligning agent, application|coating conditions, application|coating environment, etc.

The liquid crystal aligning agent of this invention may contain components other than a polymer component and an organic solvent further. As such additional components, an adhesion aid for increasing the adhesion between the liquid crystal aligning film and the substrate or the adhesion between the liquid crystal aligning film and the sealing material, a compound for increasing the strength of the liquid crystal aligning film (also referred to as a crosslinking compound), the dielectric constant or electrical resistance of the liquid crystal aligning film A dielectric material for adjustment, an electrically-conductive material, etc. are mentioned.

As the crosslinkable compound, a group comprising an oxiranyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, and an oxazoline ring structure from the viewpoint of less occurrence of AC afterimage and a high effect of improving film strength. , a compound having a group containing a Meldrum acid structure, a cyclocarbonate group, a group represented by the following formula (d), or a compound represented by the following formula (e) (these are collectively referred to as compound (C)) are preferable.

[Formula 40]

In formulas (d) and (e), R ₇₁ , R _{72 ,} and R ₇₃ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or *—CH ₂ —OH. * indicates a bond. A represents an (m+n) valent organic group having an aromatic ring. m represents the integer of 1-6, n represents the integer of 0-4.

Specific examples of the compound having an oxiranyl group include, for example, the compound described in paragraph [0037] of Japanese Patent Application Laid-Open No. 10-338880, and a compound having a triazine ring in its skeleton as described in International Publication No. WO2017/170483. The compound which has 2 or more oxiranyl groups, such as these, is mentioned. Among these, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N ',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-p-phenylenediamine, the following formula (r-1) A compound containing a nitrogen atom, such as a compound represented by any of to (r-3), is particularly preferred.

[Formula 41]

Specific examples of the compound having an oxetanyl group include compounds having two or more oxetanyl groups described in paragraphs [0170] to [0175] of International Publication No. 2011/132751, for example.

Specific examples of the compound having a protective isocyanate group include, for example, a compound having two or more protective isocyanate groups described in paragraphs [0046] to [0047] of Japanese Patent Application Laid-Open No. 2014-224978, paragraph of International Publication No. 2015/141598 The compound etc. which have 3 or more protected isocyanate groups as described in [0119]-[0120] are mentioned. Among these, compounds represented by any of the following formulas (bi-1) to (bi-3) are preferable.

[Formula 42]

As a specific example of the compound which has a protective isothiocyanate group, the compound which has two or more protective isothiocyanate groups described in Unexamined-Japanese-Patent No. 2016-200798 is mentioned, for example.

Specific examples of the compound having a group containing an oxazoline ring structure include compounds containing two or more oxazoline structures described in paragraph [0115] of, for example, Japanese Unexamined Patent Publication No. 2007-286597.

Specific examples of the compound having a group containing a Meldrum acid structure include compounds having two or more Meldrum acid structures described in International Publication WO2012/091088, for example.

As a specific example of the compound which has a cyclocarbonate group, the compound of international publication WO2011/155577 is mentioned, for example.

The alkyl group of the formula (d) in R _71, R _72, R ₇₃ is 1 to 3 carbon atoms may be mentioned, for example, methyl group, ethyl group, propyl group.

Specific examples of the compound having a group represented by the formula (d) include, for example, International Publication Nos. WO2015/072554 and Paragraph [0058] of Japanese Patent Application Laid-Open No. 2016-118753, represented by the formula (d) The compound which has two or more groups, the compound of Unexamined-Japanese-Patent No. 2016-200798, etc. are mentioned. Among these, compounds represented by any of the following formulas (hd-1) to (hd-8) are preferable.

[Formula 43]

Examples of the (m + n) valent organic group having an aromatic ring in A in the formula (e) include a (m + n) valent aromatic hydrocarbon group having 5 to 30 carbon atoms and an aromatic hydrocarbon group having 5 to 30 carbon atoms directly or a linking group. and an (m+n) valent organic group bonded via a (m+n) valent group having an aromatic heterocycle. As said aromatic hydrocarbon group, benzene, naphthalene, etc. are mentioned, for example. Examples of the aromatic heterocyclic ring include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a pyridazine ring, a pyrazine ring, a benzimidazole ring. , a benzimidazole ring, an indole ring, a quinoxaline ring, an acridine ring, and the like. Examples of the linking group include an alkylene group having 1 to 10 carbon atoms, a group in which one hydrogen atom is removed from the alkylene group, and a divalent or trivalent cyclohexane ring. In addition, arbitrary hydrogen atoms of the said alkylene group may be substituted by organic groups, such as a fluorine atom or a trifluoromethyl group. If a specific example is given, the compound etc. of international publication WO2010/074269 are mentioned. As a preferable specific example, any of following formula (e-1) - (e-9) is mentioned.

[Formula 44]

Examples of the crosslinkable compound are not limited thereto. For example, components other than the above disclosed by [0105] - [0116] of International Publication No. 2015/060357 are mentioned. Moreover, you may use a crosslinkable compound in combination of 2 or more types.

It is preferable that content of the crosslinkable compound in the liquid crystal aligning agent of this invention is 0.5-20 mass parts with respect to 100 mass parts of polymer components contained in a liquid crystal aligning agent, expresses the objective effect, and AC residual image From a viewpoint with little generation|occurrence|production of, More preferably, it is 1-15 mass parts.

As the adhesion aid, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyl Triethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane , 3-Ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyl Triethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane , 9-trimethoxysilyl-3,6-diazanonylacetate, 9-triethoxysilyl-3,6-diazanonylacetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl- 3-Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxy Silane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane , 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyl Silanes such as trimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane A coupling agent is mentioned. When using these silane coupling agents, it is preferable that the usage-amount is 0.1-30 mass parts with respect to 100 mass parts of polymer components contained in a liquid crystal aligning agent from a viewpoint with little generation|occurrence|production of an AC residual image, More preferably, 0.1- 20 parts by mass.

<Method for Producing Liquid Crystal Alignment Film>

The manufacturing method of the liquid crystal aligning film using the liquid crystal aligning agent of this invention heats the coating film of the liquid crystal aligning agent obtained at the process (process (A)) of apply|coating said liquid crystal aligning agent, the process (A), and the process (process) of obtaining a film (B)), the step of irradiating the film obtained in the step (B) with polarized ultraviolet rays (step (C)), more preferably, the film obtained in the step (C) at 100° C. or more, further, the step (B) ) of calcining at a higher temperature (step (D)).

<Step (A)>

It will not specifically limit as a board|substrate which apply|coats the liquid crystal aligning agent used for this invention, if it is a board|substrate with high transparency, You can also use plastic substrates, such as an acryl board|substrate and a polycarbonate board|substrate, together with a glass substrate and a silicon nitride board|substrate. In that case, it is preferable from the point of simplification of a process to use the board|substrate with which the ITO electrode etc. for driving a liquid crystal were formed. In the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used only on one side of the substrate, and a material that reflects light such as aluminum can also be used for the electrode in this case.

Although the application method of a liquid crystal aligning agent is not specifically limited, Industrially, the method of performing by screen printing, an offset printing, a flexographic printing, the inkjet method, etc. is common. As another coating method, there exist a dip method, the roll coater method, the slit coater method, the spinner method, the spray method, etc., You may use these according to the objective.

<Step (B)>

A process (B) is a process of baking the liquid crystal aligning agent apply|coated on the board|substrate, and forming a film|membrane. After apply|coating a liquid crystal aligning agent on a board|substrate, a solvent is evaporated by heating means, such as a hot plate, heat circulation type oven, or IR (infrared) type oven, or the heat of the amic acid or amic acid ester in a polymer Midization can be performed or carried out. The drying after apply|coating the liquid crystal aligning agent of this invention, and a baking process can select arbitrary temperature and time, and may perform it in multiple times. As temperature which removes the organic solvent of a liquid crystal aligning agent, it can implement in the temperature range of 40-150 degreeC, for example. You may implement at 40-120 degreeC from a viewpoint of shortening a process. Although it does not specifically limit as a baking time, The baking time of 1 to 10 minutes or 1 to 5 minutes is mentioned. When performing thermal imidation of the amic acid in a polymer or amic acid ester, the process of baking at the temperature range of 190-250 degreeC or 200-240 degreeC after the process of removing the said organic solvent, for example. can do. Although it does not specifically limit as a baking time, The baking time of 5-40 minutes or 5-30 minutes is mentioned.

<Step (C)>

A process (C) is a process of irradiating the ultraviolet-ray which polarized to the film|membrane obtained by the process (B). As an ultraviolet-ray, it is preferable to use the ultraviolet-ray which has a wavelength of 200-400 nm, Especially, Preferably the ultraviolet-ray which has a wavelength of 200-300 nm is more preferable. In order to improve liquid-crystal orientation, you may irradiate an ultraviolet-ray, heating the board|substrate with which the liquid crystal aligning film was coated at 50-250 degreeC. Moreover, as for the irradiation amount of the said radiation, 1-10,000 mJ/cm<2> is preferable. Especially, 100-5,000 mJ/cm<2> is preferable. The liquid crystal aligning film produced in this way can orientate a liquid crystal molecule stably in a fixed direction.

Since higher anisotropy can be provided so that the extinction ratio of the polarized ultraviolet-ray is high, it is preferable. Specifically, 10:1 or more is preferable and, as for the extinction ratio of the ultraviolet-ray polarized on a straight line, 20:1 or more is more preferable.

<Step (D)>

The process (D) is a process of baking the film|membrane obtained by the process (C) at 100 degreeC or more and the temperature higher than the process (B). Although it will not specifically limit as long as the calcination temperature is 100 degreeC or more and is higher than the calcination temperature in the process (B), 150-300 degreeC is preferable, 150-250 degreeC is more preferable, 200-250 degreeC is still more preferable. do. The calcination time is preferably 5 to 120 minutes, more preferably 5 to 60 minutes, still more preferably 5 to 30 minutes.

When the thickness of the liquid crystal aligning film after baking is too thin, since the reliability of a liquid crystal display element may fall, 5-300 nm is preferable and 10-200 nm is more preferable.

Moreover, after performing any process in the said process (C) or (D), the obtained liquid crystal aligning film can also be contact-processed using water and a solvent.

It will not specifically limit, if it is a solvent which melt|dissolves the decomposition|disassembly product produced|generated from the liquid crystal aligning film by irradiation of an ultraviolet-ray as a solvent used for the said contact process. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate. , diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, or cyclohexyl acetate. Among them, water, 2-propanol, 1-methoxy-2-propanol, or ethyl lactate is preferable from the viewpoint of versatility and solvent safety. More preferred are water, 1-methoxy-2-propanol or ethyl lactate. You may use a solvent in combination of 2 or more types.

As said contact process, ie, a process which makes water and a solvent contact the liquid crystal aligning film which irradiated the polarized ultraviolet-ray, an immersion process and a spray process (it is also mentioned a spray process) are mentioned. It is preferable that the processing time in these processes dissolves efficiently the decomposition|disassembly product produced|generated from the liquid crystal aligning film with an ultraviolet-ray, that they are 10 second - 1 hour. Especially, it is preferable to perform an immersion process for 1 minute - 30 minutes. Moreover, although the solvent at the time of the said contact treatment may be heated also at normal temperature, Preferably it is 10-80 degreeC. Especially, 20-50 degreeC is preferable. In addition to this, you may perform ultrasonic treatment etc. as needed from the point of the solubility of a decomposition product.

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

The liquid crystal aligning film of this invention is preferable as a liquid crystal aligning film of the liquid crystal display element of transverse electric field systems, such as an IPS system and an FFS system, Especially useful as a liquid crystal aligning film of the liquid crystal display element of an FFS system. After obtaining the board|substrate with a liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention, a liquid crystal display element produces a liquid crystal cell by a known method, and is obtained using the liquid crystal cell.

As an example of the manufacturing method of a liquid crystal cell, the liquid crystal display element of a passive matrix structure is taken as an example and demonstrated. Moreover, the liquid crystal display element of the active matrix structure in which switching elements, such as TFT (Thin Film Transistor), were formed in each pixel part which comprises an image display may be sufficient.

Specifically, 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 that a desired image display can be performed. 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 SiO ₂ -TiO ₂ film formed by a sol-gel method.

Next, a liquid crystal aligning film is formed on each board|substrate, the other board|substrate is superimposed on one board|substrate so that a mutual liquid crystal aligning film surface may oppose, and the periphery is adhere|attached with a sealing compound. In order to control a board|substrate clearance gap in a sealing compound, it is preferable to mix the spacer normally, and to disperse|distribute the spacer for board|substrate clearance gap control also to the in-plane part which does not form a sealing compound. In a part of a sealing compound, the opening part which can be filled with a liquid crystal from the outside is provided. Next, a liquid crystal material is inject|poured in the space surrounded by the board|substrate of 2 sheets and sealing agent through the opening part formed in the sealing compound, and this opening part is sealed with an adhesive agent after that. A vacuum injection method may be used for injection|pouring, and the method which utilized capillary phenomenon in air|atmosphere may be used. As the liquid crystal material, either a positive liquid crystal material or a negative liquid crystal material may be used. Next, a polarizing plate is installed. A pair of polarizing plates are affixed to the surface on the opposite side to the liquid-crystal layer of two board|substrates specifically,.

As mentioned above, by using the manufacturing method of this invention, the afterimage by the long-term alternating current drive which generate|occur|produces in the liquid crystal display element of an IPS drive system or an FFS drive system can be suppressed. Moreover, in a process (B), after removing an organic solvent in the temperature range of 40-150 degreeC, by implementing a process (C), a liquid crystal aligning film can be obtained with fewer processes than before. After the liquid crystal aligning agent of this invention removes an organic solvent in the temperature range of 40-150 degreeC in a process (B), in the manufacturing method of a liquid crystal aligning film including the process of implementing a process (C), especially preferably Can be used.

By using the liquid crystal aligning agent of this invention as mentioned above, there are few generation|occurrence|production of the residual image and AC residual image derived from residual DC, and the liquid crystal aligning film with high sealing adhesiveness can be obtained. Moreover, the liquid crystal display element excellent in the contrast which suppressed the dispersion|variation in the in-plane brightness at the time of black display can be obtained, and the liquid crystal display element which has favorable display quality is obtained.

Example

The present invention will be more specifically described below by way of examples, but the present invention is not limited thereto. The abbreviation of the compound in the following and the measuring method of each characteristic are as follows.

(menstruum)

NMP: N-methyl-2-pyrrolidone, GBL: γ-butyrolactone,

BCS: Butyl Cellosolve,

(diamine)

DA-1 to DA-8: compounds represented by the following formulas (DA-1) to (DA-8);

(tetracarboxylic dianhydride)

CA-1 to CA-4: compounds represented by the following formulas (CA-1) to (CA-4)

(additive)

C-1: a compound represented by the following formula (C-1)

C-2: 2,2'-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane

S-1: a compound represented by the following formula (S-1);

[Formula 45]

[Formula 46]

[Formula 47]

<Viscosity>

Using an E-type viscometer TVE-22H (manufactured by Toki Industries, Ltd.), it measured at a sample amount of 1.1 ml, a controller TE-1 (1°34', R24), and a temperature of 25°C.

<Measurement of imidization rate>

20 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific Co., Ltd.)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) (0.53 ml) was added, and ultrasonic wave was applied to completely dissolve it. Proton NMR of 500 MHz was measured for this solution with the NMR measuring instrument (JNW-ECA500, the Nippon Electronics Datum company make). The imidation rate is determined by determining a proton derived from a structure that does not change before and after imidization as a reference proton, and the peak integration value of this proton and the proton peak integration value derived from the NH group of the amic acid appearing in the vicinity of 9.5 ppm to 10.0 ppm. Using the value, it calculated|required by the following formula|equation.

Imidization rate (%) = (1 - α·x/y) × 100

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

[Synthesis Example of Polymer]

Hereinafter, the synthesis example of a polyamic acid and a polyimide is shown. In addition, in their naming, A shows that it is (A) component, B represents that it is (B) component, and PI shows that it is a polyimide.

<Synthesis Example 1>

In a 300 mL four-neck flask with a stirring device and a nitrogen inlet tube, 4.89 g (20.0 mmol) of DA-1, 2.59 g (24.0 mmol) of DA-2, 4.61 g (20.0 mmol) of DA-3 and 4.61 g (20.0 mmol) of DA 5.46 g (16.0 mmol) of -5 was weighed, 197 g of NMP was added, and it stirred, sending nitrogen, and it melt|dissolved. 14.2 g (63.2 mmol) of CA-1 and 3.00 g (12.0 mmol) of CA-2 are added, stirring this diamine solution, stirring at 40 degreeC for 24 hours, and polyamic acid solution (A-1) (viscosity: 425 mPa) s) was obtained.

<Synthesis Example 2>

52.6 g (0.264 mol) of DA-7 and 13.1 g (0.066 mol) of DA-8 were weighed in a 1 L separable flask with a stirring device and a nitrogen introduction tube, 481.7 g of NMP was added, and nitrogen was added It was dissolved by stirring while sending. 41.3 g (0.165 mol) and 124.5 g of NMP were added for CA-2, stirring this diamine solution, and it was made to react at 50 degreeC for 4 hours. Then, 45.1 g (0.153 mol) and 255.8 g of NMP were added to CA-4, it stirred at 70 degreeC for 24 hours, and 15 wt% polyamic-acid solution (B-1) (viscosity: 895 mPa*s) was obtained .

<Synthesis Example 3>

3.42 g (0.014 mol) of DA-1 was weighed in a 100 ml four-necked flask with a stirring device and a nitrogen introduction tube, 30.8 g of NMP was added, and it stirred, sending nitrogen, and it was made to melt|dissolve. Stirring this diamine solution, adding 3.62 g (0.012 mol) and 20.0 g of NMP for CA-4, stirring at 50 degreeC for 12 hours, and a 12 wt% polyamic-acid solution (B-2) (viscosity: 129 mPa* s) was obtained.

<Synthesis Example 4>

16.4 g (0.035 mol) of DA-6 and 22.2 g (0.091 mol) of DA-1 were weighed into a 500 ml separable flask with a stirring device and a nitrogen inlet tube, 283.6 g of NMP was added, and nitrogen was added It was dissolved by stirring while sending. 6,51 g (0.026 mol) and 47.7 g of NMP were added for CA-2 while stirring this diamine solution, and it was made to react at 50 degreeC for 2 hours. Then, 28.8 g (0.098 mol) and 87.9 g of NMP were added to CA-4, and it stirred for 12 hours then, and obtained a 15 wt% polyamic-acid solution (B-3) (viscosity: 791 mPa*s).

<Synthesis Example 5>

100 g of the polyamic acid solution (A-1) obtained in the 300 mL four necked flask with a stirring device and with a nitrogen introduction pipe was measured, 50g of NMP was added, and it stirred for 30 minutes. To the obtained polyamic-acid solution, 16.78g and pyridine 5.20g were added to acetic anhydride, and it heated at 50 degreeC for 3 hours, and performed chemical imidation. The polyimide resin powder was obtained by throwing-in stirring the obtained reaction liquid into 600 ml of methanol, filtering the depositing deposit, and washing|cleaning resin powder by performing the same operation twice, by drying at 60 degreeC for 12 hours. . The imidation ratio of this polyimide resin powder was 71 %. The obtained polyimide resin powder 3.60g was taken in a 100 ml Erlenmeyer flask, 26.4g of NMPs were added so that solid content concentration might be 12%, it stirred at 70 degreeC for 24 hours, it was made to melt|dissolve, and the polyimide solution (A-1-PI) was obtained .

The point of the polyamic-acid solution and polyimide solution obtained by the said synthesis examples 1-5 is shown in following Table 1.

The numerical value in parentheses in Table 1 shows the compounding ratio (molar part) of each compound with respect to 100 molar parts of the total amount of the tetracarboxylic acid derivative used for synthesis with respect to a tetracarboxylic-acid component, and for a diamic acid component, it was used for synthesis. The compounding ratio (molar part) of each compound with respect to 100 mol part of total amounts of diamine is shown. About the organic solvent, the compounding ratio (mass part) of each organic solvent with respect to 100 mass parts of total amounts of the organic solvent used for synthesis|combination is shown.

[Preparation of liquid crystal aligning agent]

<Comparative Example 1>

3.00 g of polyimide solution (A-1-PI) and 3.60 g of polyamic-acid solution (B-1) are weighed in the 20 ml sample tube which put the stirrer, and 0.63 g of NMP, 3.60 g of GBL, BCS further 3.0 g, 0.90 g of a GBL solution containing 1% by weight of S-1, and 0.27 g of an NMP solution containing 10% by weight of C-1 were added, stirred with a magnetic stirrer for 30 minutes, and the liquid crystal aligning agent (R1 ) was obtained.

<Example 1>

3.67 g of polyimide solution (A-1-PI) and 5.50 g of polyamic-acid solution (B-2) are weighed to the 20 ml sample tube which put the stirrer, Furthermore, 0.50 g of NMP, 4.90 g of GBL, BCS 4.00 g of a GBL solution containing 1% by weight of S-1, and 0.33 g of an NMP solution containing 10% by weight of C-1 and 1.10 g, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (1 ) was obtained.

<Example 2>

3.00 g of polyimide solution (A-1-PI) and 3.60 g of polyamic acid solution (B-3) are weighed in the 20 ml sample tube which put the stirrer, and 0.63 g of NMP, 3.60 g of GBL, BCS further 3.0 g, 0.90 g of a GBL solution containing 1% by weight of S-1, and 0.27 g of an NMP solution containing 10% by weight of C-1 were added, stirred with a magnetic stirrer for 30 minutes, and the liquid crystal aligning agent (2 ) was obtained.

<Example 3>

3.00 g of polyimide solution (A-1-PI) and 3.60 g of polyamic acid solution (B-3) are weighed in the 20 ml sample tube which put the stirrer, and 0.63 g of NMP, 3.60 g of GBL, BCS further 3.0 g, 0.90 g of a GBL solution containing 1% by weight of S-1, 0.027 g of C-2, and 0.27 g of an NMP solution containing 10% by weight of C-1 were added, and a magnetic stirrer for 30 minutes It stirred and obtained the liquid crystal aligning agent (3).

<Example 4>

3.00 g of polyimide solution (A-1-PI) and 3.60 g of polyamic acid solution (B-3) are weighed in the 20 ml sample tube which put the stirrer, Furthermore, 0.45 g of NMP, 3.60 g of GBL, BCS 3.0 g, 0.90 g of a GBL solution containing 1% by weight of S-1, 0.027 g of C-2, and 0.45 g of an NMP solution containing 10% by weight of C-1 were added, and a magnetic stirrer for 30 minutes It stirred and obtained the liquid crystal aligning agent (4).

The point of the liquid crystal aligning agent obtained by said Examples 1-4 and the comparative example 1 is shown in following Table 2.

The numerical value in parentheses in Table 2 shows the compounding ratio (mass part) of each polymer component or additive with respect to a total of 100 mass parts of the polymer component used for preparation of a liquid crystal aligning agent about a polymer and an additive, respectively. About an organic solvent, the compounding ratio (mass part) of each organic solvent with respect to 100 mass parts of total amounts of the organic solvent used for preparation of a liquid crystal aligning agent is shown.

<Production of liquid crystal display element>

A substrate to which an electrode was attached was prepared. The substrate is a glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. On the board|substrate, the IZO electrode provided with the pattern of the beta phase which comprises a counter electrode as a 1st layer is formed. On the counter electrode of the first layer, as the second layer, a SiN (silicon nitride) film formed by the CVD method is formed. The film thickness of the SiN film of the second layer is 500 nm, and functions as an interlayer insulating film. On the SiN film of the 2nd layer, the comb-tooth-shaped pixel electrode formed by patterning the IZO film as a 3rd layer is arrange|positioned, and two pixels of a 1st pixel and a 2nd pixel are formed. The size of each pixel is 10 mm long and about 5 mm wide. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.

The pixel electrode of the 3rd layer has a comb-tooth-shaped shape comprised by arranging a plurality of "<-letter"-shaped electrode elements in which the central part is bent at an inner angle of 160 degrees. The width in the width direction of each electrode element is 3 mu m, and the interval between the electrode elements is 6 mu m. Since the pixel electrode forming each pixel is constituted by arranging a plurality of "< letter"-shaped electrode elements in which the central part is bent, the shape of each pixel is not a rectangular shape, but is bent at the center part like the electrode element. , it has a shape resembling the bold letter 'K'. And each pixel is divided|segmented up and down with the bent part in the center as a boundary, and has the 1st area|region above and the 2nd area|region below the bending|flexion part.

In addition, a second glass substrate having a columnar spacer having a height of 3.5 µm on the surface and an ITO film for antistatic formation on the rear surface is formed separately from the glass substrate with the electrode (hereinafter also referred to as the first glass substrate). It prepared and produced one set of liquid crystal cells.

The liquid crystal aligning agent filtered with the filter with a hole diameter of 1.0 micrometer was apply|coated to the surface of each said 1 set of glass substrates by spin coat application|coating, and it dried for 2 minutes on an 80 degreeC hotplate. Thereafter, the coating film surface is irradiated with a predetermined amount of ultraviolet rays having a wavelength of 254 nm linearly polarized with an extinction ratio of 26:1 through a polarizing plate, and then baked in a hot air circulation type oven at 230° C. for 30 minutes, and a film thickness of 100 nm A board|substrate with a liquid crystal aligning film was obtained. Moreover, when the liquid crystal aligning film formed in a 1st glass substrate orientates so that the direction which divides the inner angle of a pixel bending part into equal parts and the orientation direction of a liquid crystal may be orthogonal, and the liquid crystal aligning film formed in a 2nd glass substrate produces a liquid crystal cell The alignment treatment was performed so that the alignment direction of the liquid crystal on the first substrate coincided with the alignment direction of the liquid crystal on the second substrate.

Next, a sealing compound was printed on one side of the said 1 set of glass substrates with a liquid crystal aligning film, the other board|substrate was bonded so that a liquid crystal aligning film surface might face, the sealing compound was hardened, and the empty cell was produced. . Liquid crystal MLC-3019 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the FFS drive liquid crystal cell was obtained. Then, after heating the obtained liquid crystal cell at 120 degreeC for 1 hour and leaving it to stand overnight, it was used for evaluation.

[evaluation]

<In-plane uniformity of contrast>

The twist angle of the liquid crystal display element was evaluated using OPTIPRO-micro by Syntech Corporation. The produced liquid crystal display element was installed on the measurement stage, and 20 points|pieces were measured in the 1st pixel plane in the state of no voltage application, and the standard deviation was computed. Evaluation was made into "poor" when the twist angle standard deviation was 0.4 or more, and when it was less than 0.4, it was made into "good|favorableness".

<Stability evaluation of liquid crystal orientation>

Using the liquid crystal display element used for the said evaluation, the alternating voltage of 10VPP was applied in the constant temperature environment of 60 degreeC at the frequency of 30Hz for 168 hours. Then, it was set as the state which short-circuited between the pixel electrode of a liquid crystal display element, and a counter electrode, and it was left to stand at room temperature as it is for one day.

After standing, the liquid crystal display element was installed between two polarizing plates arranged so that the polarization axes were orthogonal to each other, the backlight was turned on in a state where no voltage was applied, and the arrangement angle of the liquid crystal display element was adjusted so that the luminance of the transmitted light was the smallest. And the rotation angle at the time of rotating a liquid crystal display element from the angle at which the 2nd area|region of a 1st pixel becomes the darkest to the angle at which the 1st area|region becomes the darkest was computed as angle (DELTA). Similarly, in the second pixel, the second region and the first region were compared, and the same angle Δ was calculated. And the average value of the angle (DELTA) value of a 1st pixel and a 2nd pixel was computed as angle (DELTA) of a liquid crystal display element. When the value of angle (DELTA) of this liquid crystal display element exceeded 0.1 degree|times, it evaluated as "defect". When the value of angle (DELTA) of this liquid crystal cell did not exceed 0.1 degree|times, it evaluated as "good|favorableness".

<Evaluation of the relaxation characteristics of the accumulated charge>

The residual image was evaluated using the following optical systems. The prepared liquid crystal display element was installed between two polarizing plates arranged so that the polarization axes were perpendicular to each other, the LED backlight was turned on in a state where no voltage was applied, and the arrangement angle of the liquid crystal display element was adjusted so that the luminance of the transmitted light was the smallest.

Next, the V-T curve (voltage-transmittance curve) was measured, applying the alternating voltage of frequency 30Hz to this liquid crystal display element, and the relative transmittance|permeability computed the alternating voltage used as 23 % as a drive voltage.

In residual image evaluation, a DC voltage of 1V was simultaneously applied, and it was made to drive for 40 minutes, applying the alternating voltage of frequency 30Hz from which a relative transmittance|permeability will be 23 %, and driving a liquid crystal display element. After that, the applied DC voltage value was set to 0 V, only the application of the DC voltage was stopped, and the driving was further performed in that state for 15 minutes.

Evaluation was made into "good" when the relative transmittance fell to 27% or less from the time when the application of the DC voltage was started until 45 minutes passed. When 45 minutes or more were required until the relative transmittance|permeability fell to 27 % or less, it evaluated as "poor".

And the residual image evaluation by the method mentioned above was performed on the temperature condition of a 23 degreeC state temperature of a liquid crystal display element.

<Evaluation of seal adhesion>

[Sample production]

The liquid crystal aligning agent produced above was apply|coated to the 30 mm x 40 mm ITO board|substrate by spin coat. After drying for 2 minutes on an 80 degreeC hotplate, 254 nm ultraviolet-ray is irradiated to the coating-film surface through a polarizing plate, and then baking is performed in 230 degreeC hot-air circulation type oven for 20 minutes, and the coating film with a film thickness of 100 nm is irradiated. formed. After preparing the board|substrate of 2 sheets obtained in this way and apply|coating the bead spacer with a diameter of 4 micrometers on the liquid crystal aligning film surface of one board|substrate, the sealing compound (XN-1500T by Kyoritsu Chemical) was dripped. Next, the liquid crystal aligning film surface of the other board|substrate was turned inside, and it bonded so that the overlapping width of a board|substrate might be set to 1 cm. In that case, the sealing compound dripping amount was adjusted so that the diameter of the sealing compound after bonding might be set to 3 mm. After fixing the board|substrate of 2 sheets bonded together with a clip, it thermosetted at 150 degreeC for 1 hour, and the sample for adhesive evaluation was produced.

[Measurement of adhesion]

The sample substrate prepared above was used with a tabletop precision universal testing machine (manufactured by Shimadzu Corporation, AGS-X500N) to fix the ends of the upper and lower substrates, then pressurized from the upper part of the center of the substrate, and the strength at the time of peeling ( N) was measured. The value which standardized this peeling strength (N) by the adhesive area (mm<2>) was made into the seal adhesiveness (N/mm<2>) in each sample, and when larger than 5 N/mm<2>, it evaluated as "good|favorableness". When it was less than 5 N/mm<2>, it evaluated as "defect".

The evaluation result about each liquid crystal display element of the said Examples 1-4 and Comparative Example 1 is shown in Table 3 below.

Industrial Applicability

The liquid crystal aligning agent of this invention is useful for formation of the liquid crystal aligning film in a wide liquid crystal display element, such as an IPS drive system, an FFS drive system.

In addition, the specification of Japanese Patent Application No. 2018-227376 for which it applied on December 4, 2018, a claim, drawing, and all content of an abstract are referred here, and it takes in as an indication of the specification of this invention.

Claims (19)

The following (A) component and (B) component are contained, The liquid crystal aligning agent characterized by the above-mentioned.
(A) Component: The polymer (A) which has a repeating unit represented by following formula (1).
(B) Component: The polymer (B) which has a repeating unit represented by following formula (3).

(R ₁ to R ₄ 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, an alkynyl group having 2 to 6 carbon atoms, or a fluorine atom containing 1 to 6 carbon atoms. is a monovalent organic group or a phenyl group, and _{at least one of R 1} to R ₄ represents a group other than a hydrogen atom in the above definition, Y ₁ represents a divalent organic group having a partial structure represented by the following formula (H). )

(Q ³ is a structure represented by -(CH ₂ ) _n - (n is an integer of 2 to 20), and any -CH ₂ - may be substituted with -O-, provided that oxygen atoms are directly bonded to each other. There is no case. Any hydrogen atom on the two benzene rings may be substituted with a monovalent organic group. * indicates a bond.)

(X ₃ represents a tetravalent organic group derived from aromatic acid dianhydride. Y ₃ is a divalent organic group having a partial structure represented by the following formula (m), and * is a bond. R ₃₀ is a hydrogen atom, or represents an alkyl group having 1 to 4. Z ₃₁ and Z ₃₂ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkenyl group having 2 to 10 carbon atoms, or a substituent An alkynyl group having 2 to 10 carbon atoms, a tert-butoxycarbonyl group, or a 9-fluorenylmethoxycarbonyl group which may be present is shown.)

The method of claim 1,
(A) The liquid crystal aligning agent whose component is a polymer which further has a repeating unit represented by following formula (2).

(X ₂ represents a tetravalent organic group having an alicyclic structure or more five-membered ring. Y ₂ represents a divalent organic group having a partial structure represented by the formula (H).) 3. The method according to claim 1 or 2,
The formula (1), X ₂ of X _1, equation (2), and each independently represent the following formula (X2-1) ~ (X2-12) to which the tetravalent organic group orientation, the liquid crystal shown in claim.

4. The method according to any one of claims 1 to 3,
_{The liquid crystal aligning agent whose Y<1>} , Y<_2> of said Formula (1), (2) is a bivalent organic group which has the partial structure shown by any of following formula (H-1) - (H-6) each independently.

5. The method according to any one of claims 1 to 4,
_{The liquid crystal aligning agent whose Y<1>} , Y<_2> of said Formula (1), (2) is a divalent organic group represented by any of following formula (h-1) - (h-7) each independently.

6. The method according to any one of claims 1 to 5,
The liquid crystal aligning agent in which the said polymer (A) has at least 1 type of repeating unit further selected from the group which consists of a repeating unit represented by following formula (4), and a repeating unit represented by following formula (5).

(R ₄₁ to R _{44 have the same definitions as R 1} to R _{4 in} the formula (1), respectively, and Y ₄ and Y ₅ represent a divalent organic group represented by the following formula (I). X ₅ is the formula (2) of X ₂ and agree.)

(Q represents a single bond or an oxygen atom, and n represents 0 to 2. Any hydrogen atom on the benzene ring may be substituted with a monovalent organic group.) 7. The method of claim 6,
The formula (4) of Y ₄ and Y ₅ are of the formula (5), the formula (I-1) ~ (I -3) of the divalent organic group represented In any case, the liquid crystal alignment.

(* indicates a bond.) 8. The method according to any one of claims 1 to 7,
The liquid crystal aligning agent in which the said polymer (A) has at least 1 type of repeating unit chosen from the group which consists of a repeating unit further represented by following formula (6), and a repeating unit represented by following formula (7).

(R ₆₁ to R _{64 have the same definitions as R 1} to R _{4 in} the formula (1), respectively, and Y ₆ and Y ₇ are each independently a divalent organic group having a partial structure represented by the following formula (J-1); or a divalent organic group represented by the following formula (J-2). X ₇ is synonymous with _{X 2} in the formula (2).)

(Q ₅ is a single bond, -(CH ₂ ) _n - (n is an integer from 1 to 20), or any -CH _{2 - of -(CH 2} ) _n - -O under the condition that they are not adjacent to each other -, -COO-, -OCO-, -NQ ₉ -, -NQ ₉ CO-, -CONQ ₉ -, -NQ ₉ CONQ ₁₀ -, -NQ ₉ COO-, -OCOO- is a group substituted with, Q ₉ and Q ₁₀ each independently represents a hydrogen atom or a monovalent organic group;
Q ₆ and Q ₇ each independently represent a group having -H, -NHD, -N(D) ₂ , -NHD , or a group having -N(D) ₂ . Q ₈ represents a group having -NHD, -N(D) ₂ , -NHD or a group having -N(D) ₂ . D represents a carbamate-based protecting group. However, _{at least one of Q 5} , Q ₆ and Q ₇ has a carbamate protecting group in the group. *1 indicates a bond.) 9. The method of claim 8,
The liquid crystal aligning agent whose partial structure represented by the said Formula (J-1) is a partial structure represented by any one of following formula (J-1-a) - (J-1-d).

10. The method according to any one of claims 1 to 9,
_{The liquid crystal aligning agent with which X<3>} of said Formula (3) is chosen from following formula (X3-1) - (X3-2).

(x and y are each independently a single bond, ether, carbonyl, ester, alkanediyl group having 1 to 5 carbon atoms, 1,4-phenylene, sulfonyl or amide group. j and k are each independently , which is 0 or 1. * indicates a bond.) 11. The method according to any one of claims 1 to 10,
_{The liquid crystal aligning agent whose Y<3>} of said Formula (3) is a divalent organic group represented by (Y3-1) or (Y3-2).

12. The method according to any one of claims 1 to 11,
The liquid crystal aligning agent in which the said polymer (B) has at least 1 sort(s) of repeating unit chosen from the group which consists of the repeating unit represented by following formula (8), and the repeating unit represented by following formula (9).

(X ₈ is a tetravalent organic group having an alicyclic structure of five or more rings, and X ₉ is a tetravalent organic group having an alicyclic structure of five or more rings or a tetravalent organic group derived from an aromatic acid dianhydride. Y ₈ is It is synonymous with _{Y 3} of said Formula (3) _{. Y 9} is a divalent organic group which has a partial structure represented by the following formula (n-1) or (n-2): Z ₈₁ , Z ₈₂ , Z ₉₁ , Z ₉₂ has the same definitions as Z ₃₁ and Z _{32 in} Formula (3) above, R ₈ and R ₉ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Q ₁ , Q ₂ is a hydrogen atom or a methyl group indicate.)

13. The method according to any one of claims 1 to 12,
The liquid crystal aligning agent whose content rate of the said polymer (A) and the said polymer (B) is 5/95-95/5 by weight ratio of polymer (A)/polymer (B). The liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of Claims 1-13. A liquid crystal display element provided with the liquid crystal aligning film of Claim 14. The manufacturing method of the liquid crystal aligning film which has following process (A)-(C).
Process (A): The process of apply|coating the liquid crystal aligning agent in any one of Claims 1-13 on a board|substrate.
Process (B): The process of heating the coating film of the liquid crystal aligning agent obtained at the process (A), and obtaining a film|membrane.
Process (C): The process of irradiating the ultraviolet-ray which polarized to the film|membrane obtained by the process (B). 17. The method of claim 16,
The manufacturing method of the liquid crystal aligning film further including the following process (D).
Step (D): A step of calcining the film obtained in the step (C) at 100°C or higher and at a higher temperature than the step (B). 18. The method according to any one of claims 16 to 17,
The manufacturing method of the liquid crystal aligning film which heats a coating film in the temperature range of 40-180 degreeC in the said process (B). A liquid crystal display element provided with the liquid crystal aligning film obtained by the manufacturing method of the liquid crystal aligning film in any one of Claims 16-18.