KR101831011B1 - Liquid crystal display element and liquid crystal aligning agent - Google Patents

Abstract

Provided is a liquid crystal display element of a vertical alignment system capable of accelerating a response speed without adding a photopolymerizable compound, a method of producing the liquid crystal display element, and a liquid crystal aligning agent suitable therefor. A liquid crystal aligning agent containing at least one member selected from the group consisting of a side chain (A) for vertically orienting a liquid crystal and a polyamic acid having a photoreactive side chain (B) and a polyimide obtained by imidating the side chain And a liquid crystal alignment layer is formed on the substrate. Two substrates are arranged so that the liquid crystal alignment layers face each other. A liquid crystal layer is interposed between the two substrates, and ultraviolet rays are irradiated while a voltage is applied to the liquid crystal layer A method of manufacturing a liquid crystal display element of a vertical alignment type.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal display (LCD)

The present invention relates to a liquid crystal display element of a vertical alignment type manufactured by irradiating ultraviolet rays while applying a voltage to liquid crystal molecules, and a liquid crystal aligning agent used for manufacturing the liquid crystal display element.

The liquid crystal display element of the method of responding liquid crystal molecules oriented perpendicularly to the substrate by an electric field (also referred to as a vertical alignment method) includes a step of irradiating ultraviolet rays while applying a voltage to the liquid crystal molecules in its manufacturing process There is. In such a liquid crystal display element, it is general to add a photopolymerizable compound to the liquid crystal composition in advance. Generally, the direction in which the liquid crystal molecules respond to an electric field is controlled by protrusions formed on the substrate or slits formed on the display electrodes, and the like. In this case, a photo-polymerizable compound is added to the liquid crystal composition, In the liquid crystal display element, since the polymer structure in which the direction in which the liquid crystal molecules are inclined is stored is formed on the liquid crystal alignment film, the response speed of the liquid crystal display element is increased as compared with a method in which the inclination direction of the liquid crystal molecules is controlled only by projections or slits (See, for example, Patent Document 1).

Recently, it has been reported that even when a photopolymerizable compound is added to a liquid crystal alignment film instead of adding it into a liquid crystal composition, the response speed of the liquid crystal display device is increased by going through the above-described steps (see, for example, See Document 1).

As a technique different from the above, there is a photo-alignment technique for controlling the direction in which liquid crystal molecules are tilted by ultraviolet irradiation (see, for example, Patent Document 2). However, in the case of the photo-alignment technique, anisotropy is previously given to the liquid crystal alignment film by using anisotropy of the polarized ultraviolet ray, and this technique is completely different from the technique of storing the direction of the liquid crystal molecules actually tilted as described above.

Japanese Patent Application Laid-Open No. 2003-307720 Japanese Patent Application Laid-Open No. 2003-114437

 SID 09 Digest 45.1

It is an object of the present invention to provide a liquid crystal display device of a vertical alignment type which is produced by irradiating ultraviolet rays while applying a voltage to liquid crystal molecules and capable of speeding up the response speed without adding a photopolymerizable compound to the liquid crystal composition or the liquid crystal alignment film A liquid crystal display element, a production method thereof, and a liquid crystal aligning agent suitable for the liquid crystal display element.

(R⁶ 은 -CH₂-, -O-, -COO-, -NHCO-, -NH-, -CH₂O-, -N(CH₃)-, -CON(CH₃)-, 또는 -N(CH₃)CO- 를 나타낸다. R⁷ 은 탄소 원자수 1 ∼ 20 의 직사슬상 알킬렌 (알킬렌은 비치환이어도 되고 불소 원자에 의해 치환되어 있어도 된다) 을 나타내고, 또한 알킬렌의 임의의 -CH₂- 는, -CF₂-, -CH=CH-, 또는 하기의 치환기 (이들 치환기는 서로 이웃하지 않는다) 로 치환되어 있어도 된다.
치환기：-O-, -COO-, -NHCO-, -NH-, 탄소 고리기, 또는 복소 고리기.
R⁸ 은 -CH₂-, -O-, -COO-, -OCO-, -NHCO-, -NH-, -N(CH₃)-, -CON(CH₃)-, -N(CH₃)CO-, 탄소 고리기, 또는 복소 고리기를 나타내고, R⁹ 가 비닐페닐기, -CR¹⁰=CH₂ 기, 탄소 고리기, 복소 고리기, 또는 이하의 식으로 나타내지는 기를 나타내고, R¹⁰ 은 수소 원자 또는 불소 원자로 치환되어 있어도 되는 메틸기를 나타낸다. 단, R⁸ 이 -OCO-, -NHCO- 또는 -N(CH₃)CO- 이고 R⁹ 가 -CH=CH₂ 또는 -C(CH₃)=CH₂ 인 것을 제외한다)
[화학식 2]

[2] 상기 액정 배향제가, 하기의 폴리아믹산 및 그것을 이미드화시켜 얻어지는 폴리이미드 중 적어도 1 종을 함유하는 액정 배향제인, 상기 [1] 에 기재된 액정 표시 소자의 제조 방법.
액정을 수직으로 배향시키는 측사슬 (A) 을 갖는 디아민 및 광 반응성의 측사슬 (B) 을 갖는 디아민을 함유하는 디아민 성분과 테트라카르복실산 2 무수물을 반응시켜 얻어지는 폴리아믹산.
[3] 상기 액정을 수직으로 배향시키는 측사슬 (A) 이, 하기 식 (a) 로 나타내지는, 상기 [1] 또는 [2] 에 기재된 액정 표시 소자의 제조 방법.
[화학식 1]

(식 (a) 중 l, m 및 n 은 각각 독립적으로, 0 또는 1 의 정수를 나타낸다. R¹ 은 탄소 원자수 2 ∼ 6 의 알킬렌기, -O-, -COO-, -OCO-, -NHCO-, -CONH-, 또는 탄소 원자수 1 ∼ 3 의 알킬렌-에테르기를 나타낸다. R², R³ 및 R⁴ 는, 각각 독립적으로, 페닐렌기 또는 시클로알킬렌기를 나타낸다. R⁵ 는 수소 원자, 탄소 원자수 5 ∼ 18 의 직사슬상 알킬기 혹은 불소 함유 알킬기, 또는 방향 고리기, 지방족 고리기, 복소 고리기 혹은 그것들로 이루어지는 대 (大) 고리형 (狀) 기를 나타낸다.)
[4] 상기 액정을 수직으로 배향시키는 측사슬 (A) 이, 상기 식 (a) 로 나타내지고, l, m 및 n 이 모두 1 이고, R² 가 페닐렌이고, R³ 이 페닐렌 또는 시클로헥실렌이고, R⁴ 가 시클로헥실렌이고, R⁵ 가 탄소 원자수 2 ∼ 24 의 알킬기이거나, 또는 l, m 및 n 이 모두 0 이고, R⁵ 가 탄소 원자수 12 ∼ 22 의 알킬기인, [1] 또는 [2] 에 기재된 액정 표시 소자의 제조 방법.
[5] 상기 광 반응성의 측사슬 (B) 이, 상기 식 (b) 로 나타내지고, R⁹ 가 비닐페닐기, -CH=CH₂, -C(CH₃)=CH₂, 또는 하기의 어느 것의 기인, [3] 에 기재된 액정 표시 소자의 제조 방법. (단, 식 (b) 의 R⁸ 이 -OCO-, -NHCO- 또는 -N(CH₃)CO- 이고 R⁹ 가 -CH=CH₂ 또는 -C(CH₃)=CH₂ 인 것을 제외한다.)
[화학식 4]

[6] 액정 배향제를 2 장의 기판 상에 도포하여 액정 배향층을 형성하고,
상기 액정 배향층이 대향하도록 2 장의 기판을 배치하고,
상기 2 장의 기판 사이에 액정층을 협지하여,
액정층에 전압을 인가하면서 자외선을 조사하는 것을 특징으로 하는 수직 배향 방식의 액정 표시 소자의 제조 방법에 사용되기 위한 액정 배향제로서,
상기 [1] 에 기재된 폴리아믹산 및 그 폴리아믹산을 이미드화시켜 얻어지는 폴리이미드로 이루어지는 군에서 선택되는 적어도 1 종을 함유하는 액정 배향제.
[7] 폴리아믹산이, 액정을 수직으로 배향시키는 측사슬 (A) 을 갖는 디아민 및 광 반응성의 측사슬 (B) 을 갖는 디아민을 포함하는 디아민 성분과 테트라카르복실산 2 무수물 성분을 반응시켜 얻어지는 폴리아믹산인, [6] 에 기재된 액정 배향제.
[8] 광 반응성의 측사슬 (B) 을 갖는 디아민이, 하기 식 (2) 로 나타내어지는 것을 특징으로 하는 [7] 에 기재된 액정 배향제.
[화학식 5]

(R⁶ 은 -CH₂-, -O-, -COO-, -NHCO-, -NH-, -CH₂O-, -N(CH₃)-, -CON(CH₃)-, 또는 -N(CH₃)CO- 를 나타낸다. R⁷ 은 탄소 원자수 1 ∼ 20 의 직사슬상 알킬렌 (알킬렌은 비치환이어도 되고 불소 원자에 의해 치환되어 있어도 된다) 을 나타내고, 또한 알킬렌의 임의의 -CH₂- 는, -CF₂-, -CH=CH-, 또는 하기의 치환기 (이들 치환기는 서로 이웃하지 않는다) 로 치환되어 있어도 된다.
치환기：-O-, -COO-, -NHCO-, -NH-, 탄소 고리기, 또는 복소 고리기.
R⁸ 은 -CH₂-, -O-, -COO-, -OCO-, -NHCO-, -NH-, -N(CH₃)-, -CON(CH₃)-, -N(CH₃)CO-, 탄소 고리기, 또는 복소 고리기를 나타내고, R¹¹ 은, 비닐페닐기, -CH=CH₂, -C(CH₃)=CH₂, 또는 하기의 어느 것의 기를 나타낸다. 단, 식 (2) 의 R⁸ 이 -OCO-, -NHCO- 또는 -N(CH₃)CO- 이고 R¹¹ 이 -CH=CH₂ 또는 -C(CH₃)=CH₂ 인 것을 제외한다.)
[화학식 6]

[9] 액정을 수직으로 배향시키는 측사슬 (A) 을 갖는 디아민이, 하기 식 (1) 로 나타내지는, 상기 [7] 에 기재된 액정 배향제.
[화학식 7]

(식 (a) 중 l, m 및 n 은 각각 독립적으로, 0 또는 1 의 정수를 나타낸다. R¹ 은 탄소 원자수 2 ∼ 6 의 알킬렌기, -O-, -COO-, -OCO-, -NHCO-, -CONH-, 또는 탄소 원자수 1 ∼ 3 의 알킬렌-에테르기를 나타낸다. R², R³ 및 R⁴ 는, 각각 독립적으로, 페닐렌기 또는 시클로알킬렌기를 나타낸다. R⁵ 는 수소 원자, 탄소 원자수 5 ∼ 18 의 직사슬상 알킬기 혹은 불소 함유 알킬기, 또는 방향 고리기, 지방족 고리기, 복소 고리기 혹은 그것들로 이루어지는 대 고리형기를 나타낸다.)
[10] 액정을 수직으로 배향시키는 측사슬 (A) 을 갖는 디아민이, 상기 식 (1) 로 나타내지고, l, m 및 n 이 모두 1 이고, R² 가 페닐렌이고, R³ 이 페닐렌 또는 시클로헥실렌이고, R⁴ 가 시클로헥실렌이고, R⁵ 가 탄소 원자수 2 ∼ 24 의 알킬기이거나, 또는 l, m 및 n 이 모두 0 이고, R⁵ 가 탄소 원자수 12 ∼ 22 의 알킬기인 디아민인, 상기 [9] 에 기재된 액정 배향제.
[11] 액정을 수직으로 배향시키는 측사슬 (A) 을 갖는 디아민이, 하기의 어느 것의 구조를 갖는 디아민인, 상기 [9] 에 기재된 액정 배향제.
[화학식 8]

The present invention is characterized by comprising the following constitution.
[1] Polyamic acid having a side chain (A) for vertically orienting a liquid crystal and a photoreactive side chain (B) represented by the following formula (b) and a polyimide obtained by imidizing the polyamic acid Is applied on two substrates to form a liquid crystal alignment layer,
Two substrates are arranged so that the liquid crystal alignment layers face each other,
A liquid crystal layer sandwiched between the two substrates,
Wherein the liquid crystal layer is irradiated with ultraviolet rays while applying a voltage to the liquid crystal layer.
[Chemical Formula 1]

(R ⁶ is _{-CH 2 -, -O-, -COO-,} -NHCO-, -NH-, -CH 2 O-, -N (CH 3) -, -CON (CH 3) -, or -N (CH ₃ ) CO-, R ⁷ represents a linear alkylene group having 1 to 20 carbon atoms (the alkylene may be unsubstituted or may be substituted by a fluorine atom), and arbitrary -CH ₂ - may be substituted with -CF ₂ -, -CH═CH-, or the following substituent (s) (these substituents are not adjacent to each other).
Substituent: -O-, -COO-, -NHCO-, -NH-, a carbon ring group, or a heterocyclic group.
R ⁸ is _{-CH 2 -, -O-, -COO-,} -OCO-, -NHCO-, -NH-, -N (CH 3) -, -CON (CH 3) -, -N (CH 3) CO-, carbocyclic group, or represents a heterocyclic ring, R ⁹ is a vinyl group, -CR ¹⁰ = CH ₂ group, a carbocyclic group, represents a group represented by the heterocyclic group, or a group represented by the formula below, R ¹⁰ is a hydrogen atom Or a methyl group which may be substituted with a fluorine atom. Except that R ⁸ is -OCO-, -NHCO- or -N (CH ₃ ) CO- and R ⁹ is -CH = CH ₂ or -C (CH ₃ ) = CH ₂ .
(2)

[2] The method for producing a liquid crystal display element according to [1], wherein the liquid crystal aligning agent is a liquid crystal aligning agent containing at least one of the following polyamic acid and polyimide obtained by imidizing the polyamic acid.
A polyamic acid obtained by reacting a diamine component containing a diamine having a side chain (A) vertically orienting a liquid crystal and a diamine having a photoreactive side chain (B) with a tetracarboxylic dianhydride.
[3] The method for producing a liquid crystal display element according to [1] or [2], wherein the side chain (A) for orienting the liquid crystal vertically is represented by the following formula (a).
[Chemical Formula 1]

(In the formula (a), l, m and n each independently represent an integer of 0 or 1. R ¹ represents an alkylene group having 2 to 6 carbon atoms, -O-, -COO-, -OCO-, NHCO-, -CONH-, or an alkylene-ether group having 1 to 3 carbon atoms, R ² , R ³ and R ⁴ each independently represent a phenylene group or a cycloalkylene group, R ⁵ represents a hydrogen atom , A linear alkyl group or a fluorine-containing alkyl group having 5 to 18 carbon atoms, or a cyclic group, aliphatic cyclic group, heterocyclic group or a large cyclic group composed thereof.
[4] The side chain (A) to orient the liquid crystal in the vertical, is represented by the formula (a), l, m and R n are both 1, R a ^divalent phenylene, R ³ is phenylene or cycloalkyl hexylene direction, and an R ⁴ is cyclohexylene, R ⁵ is either an alkyl group of carbon atoms 2 to 24, or l, m and n are are both 0, R ⁵ is an alkyl group having carbon atom number of 12 to 22, [ 1] or [2].
[5] The side chain (B) of the light-reactive substances, is represented by the formula (b), R ⁹ is a vinyl _{group, -CH = CH 2, -C (} CH 3) = CH 2, or one of the things to [3] The method for producing a liquid crystal display element according to [3]. Except that R ^{8 in} formula (b) is -OCO-, -NHCO- or -N (CH ₃ ) CO- and R ⁹ is -CH = CH ₂ or -C (CH ₃ ) = CH ₂ .)
[Chemical Formula 4]

[6] A liquid crystal aligning agent is applied onto two substrates to form a liquid crystal alignment layer,
Two substrates are arranged so that the liquid crystal alignment layers face each other,
A liquid crystal layer sandwiched between the two substrates,
A liquid crystal aligning agent for use in a method of manufacturing a liquid crystal display element of a vertical alignment system characterized by irradiating ultraviolet rays while applying a voltage to a liquid crystal layer,
A liquid crystal aligning agent containing at least one member selected from the group consisting of the polyamic acid according to [1] and the polyimide obtained by imidizing the polyamic acid.
[7] A process for producing a polyamic acid, which comprises reacting a diamine component containing a diamine having a side chain (A) vertically orienting a liquid crystal and a diamine having a photoreactive side chain (B) with a tetracarboxylic acid dianhydride component The liquid crystal aligning agent according to [6], which is a polyamic acid.
[8] The liquid crystal aligning agent according to [7], wherein the diamine having a photoreactive side chain (B) is represented by the following formula (2).
[Chemical Formula 5]

(R ⁶ is _{-CH 2 -, -O-, -COO-,} -NHCO-, -NH-, -CH 2 O-, -N (CH 3) -, -CON (CH 3) -, or -N (CH ₃ ) CO-, R ⁷ represents a linear alkylene group having 1 to 20 carbon atoms (the alkylene may be unsubstituted or may be substituted by a fluorine atom), and arbitrary -CH ₂ - may be substituted with -CF ₂ -, -CH═CH-, or the following substituent (s) (these substituents are not adjacent to each other).
Substituent: -O-, -COO-, -NHCO-, -NH-, a carbon ring group, or a heterocyclic group.
R ⁸ is _{-CH 2 -, -O-, -COO-,} -OCO-, -NHCO-, -NH-, -N (CH 3) -, -CON (CH 3) -, -N (CH 3) CO-, a carbon ring group or a heterocyclic group, and R ¹¹ represents a vinylphenyl group, -CH = CH ₂ , -C (CH ₃ ) = CH ₂ , or any of the following groups. Except that R ^{8 in} formula (2) is -OCO-, -NHCO- or -N (CH ₃ ) CO- and R ¹¹ is -CH = CH ₂ or -C (CH ₃ ) = CH ₂ . )
[Chemical Formula 6]

[9] The liquid crystal aligning agent according to the above-mentioned [7], wherein the diamine having a side chain (A) for orienting the liquid crystal vertically is represented by the following formula (1).
(7)

(In the formula (a), l, m and n each independently represent an integer of 0 or 1. R ¹ represents an alkylene group having 2 to 6 carbon atoms, -O-, -COO-, -OCO-, NHCO-, -CONH-, or an alkylene-ether group having 1 to 3 carbon atoms, R ² , R ³ and R ⁴ each independently represent a phenylene group or a cycloalkylene group, R ⁵ represents a hydrogen atom , A linear alkyl group or a fluorine-containing alkyl group having 5 to 18 carbon atoms, or a cyclic group, aliphatic cyclic group, heterocyclic group, or a cyclic group composed thereof.
Wherein the diamine having a side chain (A) orienting the liquid crystal vertically is represented by the formula (1), l, m and n are all 1, R ² is phenylene, R ³ is phenylene Or cyclohexylene, R ⁴ is cyclohexylene, R ⁵ is an alkyl group having 2 to 24 carbon atoms, or l, m and n are both 0 and R ⁵ is an alkyl group having 12 to 22 carbon atoms The liquid crystal aligning agent according to the above [9], which is a diamine.
[11] The liquid crystal aligning agent according to the above-mentioned [9], wherein the diamine having a side chain (A) for orienting the liquid crystal vertically is a diamine having any of the following structures.
[Chemical Formula 8]

[12] A liquid crystal alignment layer obtained by using the liquid crystal aligning agent according to any one of [6] to [11].

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According to the present invention, there is provided a liquid crystal display element capable of quickly responding (shortening the response time) without adding a photopolymerizable compound in the liquid crystal composition or in the liquid crystal alignment film.

The liquid crystal aligning agent of the present invention can be used in a liquid crystal display device of a vertical alignment type which is produced by irradiating ultraviolet rays while applying a voltage to liquid crystal molecules, (Response time is short) can be obtained.

<Side Chain for Vertically Orienting Liquid Crystal>

A side chain (also referred to as a side chain A) for vertically orienting a liquid crystal is a side chain having an ability to align liquid crystal molecules perpendicularly to a substrate, and the structure is not limited as long as the liquid crystal molecule has this ability. As the side chain A, for example, an alkyl group having a long chain, a fluoroalkyl group having a long chain, a cyclic group having an alkyl group or a fluoroalkyl group at a terminal, and a steroid group are known and are preferably used in the present invention. These groups may be bonded directly to the main chain of the polyamic acid or polyimide as long as they have the above capability, or they may be bonded via a suitable bonding group.

The side chain A may be exemplified by the following formula (a).

[Chemical Formula 9]

R ¹ in the formula (a) represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, -O-, -COO-, -OCO-, -NHCO-, -CONH- or a carbon atom Represents an alkylene-ether group (-CCO-) having a number of 1 to 3. Among them, -O-, -COO-, -CONH-, or an alkylene-ether group having 1 to 3 carbon atoms is preferable in terms of ease of synthesis.

R ² , R ³ and R ⁴ each independently represent a phenylene group or a cycloalkylene group. M, n, R ² , R ³ and R ⁴ shown in the following table is preferable in terms of easiness of synthesis and capability of vertically orienting the liquid crystal.

R ⁵ represents a hydrogen atom, an alkyl group having 2 to 24 carbon atoms, preferably 5 to 8 carbon atoms, or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a large cyclic group formed therefrom. When at least one of l, m and n is 1, the structure of R ⁵ is preferably a hydrogen atom, an alkyl group having 2 to 14 carbon atoms, or a fluorine-containing alkyl group having 2 to 14 carbon atoms, Preferably a hydrogen atom, an alkyl group having 2 to 12 carbon atoms, preferably 2 to 10 carbon atoms, or a fluorine-containing alkyl group.

When l, m and n are all 0, the structure of R ⁵ is preferably an alkyl group or a fluorine-containing alkyl group having 12 to 22 carbon atoms, preferably 12 to 20 carbon atoms, an aromatic ring, an aliphatic ring, A cyclic group, or a cyclic group composed thereof, and more preferably an alkyl group or a fluorine-containing alkyl group having 12 to 20 carbon atoms, preferably 12 to 18 carbon atoms.

The ability to align the liquid crystal vertically differs depending on the structure of the side chain A. In general, the larger the amount of the side chain A contained in the polymer, the higher the ability to vertically align the liquid crystal, and the lower it becomes. In addition, the side chain A containing the cyclic structure tends to align the liquid crystal vertically even with a small content, as compared with the side chain A of the long chain alkyl group.

The amount of the side chain A present in the polyamic acid or polyimide used in the present invention is not particularly limited as long as the liquid crystal alignment film can orient the liquid crystal vertically, but it is preferably 5 to 50 mol% , More preferably from 10 to 30 mol%. When the response speed of the liquid crystal is intended to be faster in the liquid crystal display element having the above liquid crystal alignment film, it is preferable that the presence of the side chain A is within the range capable of maintaining the vertical alignment, It is preferable that the amount is as small as possible.

&Lt; Side chain of photoreactive &

The light-reactive side chain (also referred to as side chain B) is a side chain having a functional group capable of forming a covalent bond by causing a photoreaction upon irradiation with ultraviolet rays. Do not. Examples of the side chain B include a side chain having a vinyl group, an acryl group, a methacryl group, an anthracenyl group, a cinnamoyl group, a carnonyl group, a coumarin group, a maleimide group, a stilbene group, etc. as a photoreactive group And is preferably used in the present invention. These groups may be bonded directly to the main chain of the polyamic acid or polyimide as long as they have the above capability, or they may be bonded via a suitable bonding group.

The side chain B may be exemplified by the following formula (b).

[Chemical formula 10]

R ⁶ in the above formula (b) represents -CH ₂ -, -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -COO-, _{OCO-, -CON (CH 3) -} , or -N (CH ₃₎ represents a CO-. R ⁶ may be formed by a common organic synthetic method, and from the viewpoint of easiness of synthesis, -CH ₂ -, -O-, -COO-, -NHCO-, -NH-, or -CH ₂ O- .

R ⁷ in the formula (b) represents a linear alkylene group having 1 to 20 carbon atoms (alkylene may be unsubstituted or may be substituted by a fluorine atom), and arbitrary -CH ₂ - may be substituted with -CF ₂ -, -CH = CH-, or the following substituents (these substituents are not adjacent to each other).

Substituent: -O-, -COO-, -NHCO-, -NH-, a carbon ring group, a heterocyclic group.

Specific examples of the carbon ring group and heterocyclic group include the following structures, but the present invention is not limited thereto.

(11)

[Chemical Formula 12]

In order to increase the response speed of the R ⁷ alkylene, it is preferable to form a flexible spacer (a group connecting R ⁶ and R ⁸⁾ between R ⁶ and R ⁸ to increase the reaction efficiency of the photo reactive group And R &lt; ⁷ &gt; is a linear alkylene group having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms.

R ⁸ in the formula (b) represents -CH ₂ -, -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -COO-, _{OCO-, -CON (CH 3) -} , -N (CH 3) represents a CO-, carbocyclic group, or a heterocyclic ring. Among them, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -NH-, a carbon ring group or a heterocyclic group is preferable in terms of ease of synthesis. Specific examples of the carbon ring group and the heterocyclic group are as described above. R ⁸ is more preferably -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, or -NH- in view of the response speed.

R ¹⁰ in the formula (b) represents a vinylphenyl group, -CR ¹⁰ ═CH ₂ , a carbon ring group, a heterocyclic group, or a group represented by the following formula, and R ¹⁰ represents a hydrogen atom or a methyl group .

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

Among them, R ⁹ is more preferably a vinylphenyl group, -CH═CH ₂ , -C (CH ₃ ) ═CH ₂ or the following groups from the viewpoint of photoreactivity.

[Chemical Formula 22]

(23)

&Lt; EMI ID =

From the viewpoint of the response speed, it is particularly preferable that R ⁹ is a vinyl group, -C (CH ₃ ) = CH ₂ or the following groups.

(25)

The amount of the side chain B present in the polyamic acid or polyimide used in the present invention is not particularly limited as long as it can accelerate the response speed of the liquid crystal in the liquid crystal display element, Is preferably 10 to 95 mol%, and more preferably 60 to 95 mol%. When the response speed of the liquid crystal in the liquid crystal display element is intended to be faster, the abundance of the side chain B is preferably as large as possible without affecting other characteristics.

<Polyamic acid>

In the present invention, the polyamic acid having the side chain A and the side chain B can be obtained by reacting a diamine having a side chain A and / or a side chain B with a tetracarboxylic acid dianhydride, , A tetracarboxylic acid dianhydride having a side chain A and / or a tetracarboxylic dianhydride having a side chain B, and further by reacting a diamine having a side chain A and a diamine having a side chain B with a side chain A tetracarboxylic acid dianhydride having a chain A and / or a tetracarboxylic dianhydride having a side chain B can be obtained.

Of these, it is preferable to obtain by reacting a diamine having a side chain A and / or a diamine having a side chain B with a tetracarboxylic acid dianhydride in the ease of raw material synthesis and the like.

&Lt; Diamine compound having side chain A &gt;

Examples of the diamine compound having a side chain A (hereinafter also referred to as a diamine A) include diamines having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring or a cyclic substituent formed therefrom on the diamine side chain . Specifically, a diamine having a side chain represented by the above formula (a) can be mentioned. More specifically, for example, diamines represented by the following formulas (1), (3), (4), or (5) are exemplified, but the present invention is not limited thereto.

(26)

The definitions of l, m, n and R ¹ to R ⁵ in the formula (1) are the same as those in the formula (a).

(27)

In the formulas (3) and (4), A ₁₀ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH- , A ₁₁ represents a single bond or a phenylene group. a represents a side chain A, and a 'represents an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a large cyclic group composed of these groups.

(28)

In the formula (5), A ₁₄ may be substituted with a fluorine atom or an alkyl group having 3 to 20 carbon atoms, and A ₁₅ represents a 1,4-cyclohexylene group or a 1,4-phenylene group. A ₁₆ represents an oxygen atom, or -COO- * (provided that a bonding hand to which "*" is bonded is bonded to A ₃ ), A ₁₇ represents an oxygen atom or -COO- * Quot; * &quot; is combined with (CH ₂ ) a ₂ ). A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1.

The bonding position of two amino groups (-NH ₂ ) in the formula (1) is not limited. Specifically, examples of the bonding group of the side chain include positions 2, 3, 2, 4, 2, 5, 2, 6, 3, 4, 3, 5 on the benzene ring. Among them, 2, 4 position, 2, 5 position, or 3, 5 position is preferable from the viewpoint of reactivity when synthesizing polyamic acid. When the ease of synthesis of the diamine compound is also considered, positions 2 and 4, or positions 3 and 5 are more preferable.

Specific examples of the formula (1) include diamines represented by the following formulas [A-1] to [A-24], but the present invention is not limited thereto.

[Chemical Formula 29]

In the formulas [A-1] to [A-5], A ₁ is an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group.

(30)

In formula [A-6] and formula [A-7], A ₂ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO- and A ₃ Is an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.

(31)

In the formulas [A-8] to [A-10], A ₄ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ -, or -CH ₂ -. A ₅ represents an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.

(32)

In the formulas [A-11] and [A-12], A ₆ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ -, -CH ₂ -, -O- or -NH-, A ₇ represents a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a formyl group, A period, or a hydroxyl group.

(33)

In the formulas [A-13] and [A-14], A ₈ represents an alkyl group having 3 to 12 carbon atoms and the cis trans isomer of 1,4-cyclohexylene is a trans isomer.

(34)

In the formulas [A-15] and [A-16], A ₉ represents an alkyl group having 3 to 12 carbon atoms and the cis trans isomer of 1,4-cyclohexylene is a trans isomer.

(35)

(36)

(37)

Specific examples of the diamine represented by the formula (3) include diamines represented by the following formulas [A-25] to [A-30], but the present invention is not limited thereto.

(38)

In formula [A-25] to formula [A-30], A ₁₂ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, NH-, and A ₁₃ represents an alkyl group or a fluorine-containing alkyl group having 1 to 22 carbon atoms.

Specific examples of the diamine represented by the formula (4) include diamines represented by the following formulas [A-31] to [A-32], but the present invention is not limited thereto.

[Chemical Formula 39]

Among these, [A-1], [A-2], [A-3], [A-4], [A- 5], and [A-2] are preferable from the viewpoints of the ability to vertically align liquid crystals, A-25], [A-26], [A-27], [A-28], [A-29] and [A-30].

The diamine compound may be used alone or in combination of two or more thereof depending on the properties such as liquid crystal alignability, pretilt angle, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.

In order to achieve the object of the present invention, it is preferable that 5 to 50 mol% of the diamine component used in the synthesis of polyamic acid is diamine A. Further, it is preferable that 5 to 30 mol% of the diamine component is diamine A, particularly preferably 5 to 15 mol%.

&Lt; Diamine compound having side chain B &gt;

Examples of the diamine compound having a side chain B (also referred to as diamine B) include a vinyl group, an acryl group, a methacryl group, an anthracenyl group, a cinnamoyl group, a carnonyl group, a coumarin group, a maleimide group, , And the like. Specifically, diamines having a side chain represented by the above formula (b) can be mentioned. More specifically, examples thereof include diamines represented by the following general formula (2), but the present invention is not limited thereto.

(40)

In formula (2), R ⁶ represents -CH ₂ -, -O-, -COO-, -NHCO-, -NH-, -CH ₂ O-, -N (CH ₃ ) -, -CON (CH ₃ ) -, or -N (CH ₃₎ represents a CO-. R ⁷ represents a straight-chain alkylene having 1 to 20 carbon atoms (alkylene may be unsubstituted or may be substituted by fluorine atom), and arbitrary -CH ₂ - of alkylene may be replaced by -CF ₂ -, -CH = CH-, or the following substituents (these substituents are not adjacent to each other).

Substituent: -O-, -COO-, -NHCO-, -NH-, a carbon ring group, or a heterocyclic group.

R ⁸ is _{-CH 2 -, -O-, -COO-,} -OCO-, -NHCO-, -NH-, -N (CH 3) -, -CON (CH 3) -, or -N (CH ₃ ) CO-, and R ¹¹ represents a vinylphenyl group, -CH = CH ₂ , -C (CH ₃ ) = CH ₂ , or a group of any of the following.

(41)

The bonding position of two amino groups (-NH ₂ ) in the formula (2) is not particularly limited. Specifically, examples of the bonding group of the side chain include positions 2, 3, 2, 4, 2, 5, 2, 6, 3, 4, 3, 5 on the benzene ring. Among them, 2, 4 position, 2, 5 position, or 3, 5 position is preferable from the viewpoint of reactivity when synthesizing polyamic acid. When the ease of synthesis of the diamine compound is also considered, positions 2 and 4, or positions 3 and 5 are more preferable.

Specifically, the following compounds are exemplified, but the present invention is not limited thereto.

(42)

(43)

(44)

X represents independently a bonding group selected from the group consisting of -C-, -O-, -NHCO-, -CONH-, -COO-, -OCO-, and -NH-, and l, m, And n each independently represents an integer of 0 to 20;

The above-mentioned diamine compound may be mixed with one kind or two or more kinds depending on the properties such as the liquid crystal alignment property, the pretilt angle, the voltage holding property, the charge accumulation, and the response speed of the liquid crystal when the liquid crystal display device is used as the liquid crystal alignment film. .

In order to achieve the object of the present invention, it is preferable that 10 to 95 mol% of the diamine component used in the synthesis of polyamic acid is diamine B. Further, it is more preferable that 40 to 95 mol% of the diamine component is diamine B, and particularly preferably 70 to 95 mol%.

&Lt; Other diamine compounds &gt;

As long as the effect of the present invention is not impaired, the polyamic acid used in the present invention can be used in combination with other diamine compounds other than diamine A and diamine B as a diamine component. Specific examples thereof are given below.

p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- Diaminodiphenol, 3,5-diaminophenol, 3,5-diaminobenzyl, 2,4-diaminophenol, 3,5-diaminophenol, Alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, Dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diamino Biphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'- diaminobiphenyl, Diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl Methane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diamino Phenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, Bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl- bis (3-aminophenyl) silane, Aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'- Diaminodiphenylamine, 2,3-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3, (2,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl Diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2 ' - diaminobenzophenone, 2,3'-diaminobenzophenone, Diaminonaphthalene, 1,6-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,6-diaminonaphthalene, Bis (4-aminophenyl) ethane, 1, 3-bis (4-aminophenyl) ) Propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4- Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1, (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, Phenylene bis (methylene)] dianiline, 4,4 '- [1,3-phenylenebis (methylene)] dianiline, 3,4' - [ , 4'- [1,3-phenylenebis (methylene)] dianiline, 3,3 '- [1,4-phenylenebis (methylene)] dianiline, Phenylenebis [(3-amino)] phenanthrene [(4-aminophenyl) methanone] Phenylenemethanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [ Aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate) Bis (3-aminophenyl) isophthalate, bis (4-aminophenyl) isophthalate, N, N ' Bis (4-aminobenzamide), N, N '- (1,4-phenylene) bis (3-aminobenzamide), N, N '- (1,3-phenylene) bis (3-aminobenzamide), N, N'- Bis (3-aminophenyl) terephthalamide, N, N'-bis (4- (4-aminophenoxy) anthracene, 4,4'-bis (4-aminophenoxy) diphenyl Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis [ Bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'- Bis (3-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, Bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis Butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, Heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) heptane, ) Octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) (Aminophenoxy) undecane, 1,12- (4-aminophenoxy) undecane, 1,11- (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane and the like, alicyclic diamines such as 1,3- Diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diamine Aliphatic diamines such as nonanoyl, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.

The other diamine compounds may be used alone or in combination of two or more, depending on the properties such as liquid crystal alignability, pretilt angle, voltage holding characteristics, and accumulated charge when used as a liquid crystal alignment film.

&Lt; Tetracarboxylic acid dianhydride &gt;

In the synthesis of the polyamic acid to be used in the present invention, the tetracarboxylic acid dianhydride to be reacted with the diamine component is not particularly limited. Specific examples of the tetracarboxylic acid which is a raw material for obtaining the tetracarboxylic acid dianhydride are shown below.

Naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, Anthracene tetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4- Biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, bis (3,4- Dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2- Dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridine tetracarboxylic acid, 2 , 6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid, oxydi Tetracarboxylic acid, 1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid , 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, Dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cycloheptane tetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid, Cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid, bicyclo [4,3,0] nonane-2,4,7,9-tetracarboxylic acid, bicyclo [ , 4,0] decane-2,4,7,9-tetracarboxylic acid, bicyclo [4,4,0] decane-2,4,8,10-tetracarboxylic acid, tricyclo [6.3.0.0 <2,6>] undecane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butane Dicarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydrinaphthalene-1,2-dicarboxylic acid, bicyclo [ 2,2] octo-7-ene-2,3,5,6-tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexane- Dicarboxylic acid, tetracyclo [6,2,1,1,0,2,7] dodeca-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxy norbornane- 2: 3,5: 6 dicarboxylic acid, and 1,2,4,5-cyclohexanetetracarboxylic acid.

The tetracarboxylic acid dianhydride can be used alone or in combination of two or more, depending on the properties such as liquid crystal aligning property, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.

<Synthesis of polyamic acid>

The polyamic acid can be obtained by the reaction of the diamine component and the tetracarboxylic acid dianhydride by a known synthetic method. Generally, this is a method of reacting a diamine component and a tetracarboxylic acid dianhydride in an organic solvent. The reaction between the diamine component and the tetracarboxylic acid dianhydride is advantageous in that it proceeds relatively easily in an organic solvent and does not generate by-products.

The organic solvent used in the reaction is not particularly limited as long as it dissolves the produced polyamic acid. In addition, an organic solvent which does not dissolve polyamic acid may be used in combination with the solvent insofar as the produced polyamic acid does not precipitate. Further, water in the organic solvent inhibits the polymerization reaction, and further causes hydrolysis of the produced polyamic acid. Therefore, it is preferable to use an organic solvent which is dehydrated and dried.

Specific examples of the organic solvent are given below.

N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N- , 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, But are not limited to, sulfone, hexamethyl sulfoxide,? -Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, But are not limited to, cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, Ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, Propylene glycol monomethyl ether, propyleneglycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether , Diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, , Butyl butylate, butyl ether, di N-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, But are not limited to, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, Propionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol. These organic solvents may be used alone or in combination.

When the diamine component and the tetracarboxylic acid dianhydride component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred and the tetracarboxylic acid dianhydride component is dispersed or dissolved in the organic solvent as it is A method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride component is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic acid dianhydride component and a diamine component, and the like And any of these methods may be used. When the diamine component or the tetracarboxylic acid dianhydride component is composed of a plurality of compounds, they may be reacted in a preliminarily mixed state, or they may be sequentially reacted individually, and further the individually reacted low molecular weight compounds are mixed and reacted Or may be a high molecular weight material.

The temperature at which the diamine component is reacted with the tetracarboxylic acid dianhydride component can be selected from any temperature and is, for example, in the range of -20 ° C to 150 ° C, preferably -5 ° C to 100 ° C. The reaction can be carried out at any concentration, for example, 1 to 50 mass%, preferably 5 to 30 mass%.

The ratio of the total molar number of the tetracarboxylic acid dianhydride component to the total molar number of the diamine component in the above polymerization reaction can be selected in accordance with the molecular weight of the polyamic acid to be obtained. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polyamic acid. It is 0.8 to 1.2 if it shows a preferable range.

The method of synthesizing the polyamic acid to be used in the present invention is not limited to the above method. Instead of the above tetracarboxylic acid dianhydride, a tetracarboxylic acid or tetracarboxylic acid The corresponding polyamic acid can also be obtained by reacting it with a known method using a tetracarboxylic acid derivative such as an acid dihalide.

<Polyimide>

Examples of the method of imidizing the polyamic acid to form polyimide include heat imidization in which a solution of polyamic acid is heated as it is, and catalyst imidation in which a catalyst is added to a solution of polyamic acid.

In the polyimide used in the present invention, the imidization rate from the polyamic acid to the polyimide does not necessarily have to be 100%.

The temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, and the method is preferably carried out while removing water generated by the imidization reaction from the system.

The catalyst imidation of polyamic acid can be carried out by adding a basic catalyst and acid anhydride to a solution of polyamic acid and stirring at -20 to 250 캜, preferably 0 to 180 캜. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, pyridine is preferred because it has a basicity suitable for proceeding the reaction. As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be given. Of these, use of acetic anhydride is preferable since the purification after completion of the reaction becomes easy. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

In the case of recovering the polyamic acid or polyimide produced from the reaction solution of polyamic acid or polyimide, the reaction solution may be put into a poor solvent and precipitated. Examples of poor solvents to be used in the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer precipitated by charging into a poor solvent can be recovered by filtration and then dried at normal temperature or under reduced pressure or by heating. In addition, when the polymer precipitated and recovered is redissolved in an organic solvent and reprecipitation and recovery are repeated 2 to 10 times, impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be mentioned. When three or more poor solvents selected from these are used, the purification efficiency is more preferable.

<Liquid Crystal Aligner>

The liquid crystal aligning agent is a coating liquid for forming a liquid crystal alignment film and is a solution in which a resin component for forming a liquid crystal alignment film is dissolved in an organic solvent. Here, the resin component is a resin component comprising at least one polymer selected from the group consisting of the above-mentioned polyamic acid and polyimide. At this time, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

In the liquid crystal aligning agent used in the present invention, the resin component may be either a polyamic acid having all of the side chain A and the side chain B, a polyimide obtained by imidizing the side chain A and the side chain B, a mixture of the polyamic acid and the polyimide , And further, other polymers may be mixed. At this time, the content of such another polymer in the resin component is preferably 0.5% by mass to 15% by mass, and more preferably 1% by mass to 10% by mass. Such another polymer may, for example, be a polyamic acid or polyimide which does not have the side chain A and the side chain B at the same time.

The molecular weight of the polymer of the resin component is preferably from 5,000 to 1,000,000 in terms of weight average molecular weight measured by GPC (Gel Permeation Chromatography) in consideration of the strength of the coating film obtained therefrom, the workability in forming a coating film, , And more preferably from 10,000 to 150,000.

The organic solvent used in the liquid crystal aligning agent used in the present invention is not particularly limited as long as it is an organic solvent capable of dissolving the above-mentioned resin component. The organic solvent may be one kind of solvent or two or more kinds of mixed solvents. Examples of the organic solvent include organic solvents exemplified by the above-mentioned polyamic acid synthesis. Among them, N-methyl-2-pyrrolidone,? -Butyrolactone, N-ethyl-2-pyrrolidone, Dimethyl propanamide and the like are preferable from the viewpoint of the solubility of the resin component.

In addition, the following solvents improve the uniformity and smoothness of the coating film, and therefore it is preferable to mix them in a solvent having a high solubility of the resin component. Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol , Ethylcarbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether , Propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene Glycol monomethyl ether, propylene glycol monome Ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl But are not limited to, ether, 3-methyl-3-methoxybutanol, diisopropylether, ethylisobutylether, diisobutylene, amyl acetate, butylbutylate, butylether, diisobutylketone, methylcyclohexene, Butyl acetate, propyleneglycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3-ethylhexyl acetate, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, Methyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxy Methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy- Propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- Propoxypropanol), lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, lactic acid isoamyl ester, 2-ethyl-1-hexanol and the like. These solvents may be mixed with a plurality of kinds. When these solvents are used, it is preferably 5 to 80 mass%, more preferably 20 to 60 mass%, of the total solvent contained in the liquid crystal aligning agent.

The liquid crystal aligning agent may contain components other than those described above. Examples thereof include a compound which improves film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, a compound which improves the adhesion between the liquid crystal alignment film and the substrate, and the like.

Examples of the compound that improves film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent. More specifically, for example, EF301, EF303, EF352 (manufactured by TOKEM PRODUCTS CO., LTD.), Megafac F171, F173, R-30 (manufactured by Dainippon Ink and Chemicals Inc.), Fluorad FC430 and FC431 (manufactured by Sumitomo 3M ), Asahi Guard AG710, Sapron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass). When these surfactants are used, the use ratio thereof is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass based on 100 parts by mass of the resin component contained in the liquid crystal aligning agent.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment layer and the substrate include a functional silane-containing compound and an epoxy group-containing compound. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 Tetraglycidyl-2,4-hexanediol, N, N, N ', N', -tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N', -tetraglycidyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxy Silane, 3- (N, N-diglycidyl) Aminopropyltrimethoxysilane, and the like.

(4-hydroxy-3,5-dihydroxymethylphenyl) propane, tetra (methoxymethyl) propane and the like are used in order to further enhance the rubbing resistance of the liquid crystal alignment film obtained using the liquid crystal aligning agent of the present invention. A phenol compound such as bisphenol may be added. When these compounds are used, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass based on 100 parts by mass of the resin component contained in the liquid crystal aligning agent.

As the liquid crystal aligning agent to be used in the present invention, a dielectric substance or a conductive substance may be added for the purpose of changing electric characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effect of the present invention is not impaired.

Among the liquid crystal aligning agents described above, among liquid crystal aligning agents described above, {a polyamic acid obtained by reacting a diamine component containing diamine A and diamine B with a tetracarboxylic acid dianhydride} and {a polyimide obtained by imidizing it} As the liquid crystal aligning agent, it is preferable that the diamine B is a diamine represented by the formula (2) and R ^{8 in the} formula (2) is -CH ₂ -, -O-, -COO-, -OCO-, -NHCO- or -NH-, R ¹¹ is a -CR ¹⁰ ═CH ₂ group, and R ¹⁰ is a methyl group which may be substituted with a hydrogen atom or a fluorine atom is a liquid crystal aligning agent newly provided by the present invention Of liquid crystal aligning agent).

The liquid crystal aligning agent of the present invention is useful not only as a liquid crystal aligning agent for producing the liquid crystal display element of the present invention but also as a liquid crystal alignment film produced by rubbing treatment or photo alignment treatment.

&Lt; Liquid crystal alignment film &

The liquid crystal aligning agent of the present invention can be used as a liquid crystal alignment film without rubbing treatment, light irradiation or the like, or with a liquid crystal alignment film without vertical alignment treatment, after coating and baking on a substrate. At this time, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. It is preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed from the viewpoint of simplifying the process. In the reflection type liquid crystal display device, an opaque material such as a silicon wafer can be used as long as it is a substrate on only one side. In this case, a material that reflects light such as aluminum can also be used as the electrode in this case.

The method of applying the liquid crystal aligning agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and inkjet are generally used. Other coating methods include dip, roll coater, slit coater, and spinner, and these may be used depending on the purpose.

The baking after application of the liquid crystal aligning agent can be carried out at any temperature of 100 to 350 ° C, preferably 120 to 300 ° C, and more preferably 150 to 250 ° C. This firing can be performed in a hot plate, a hot air circulation furnace, an infrared furnace, or the like.

The thickness of the film after firing is not particularly limited, but is preferably 5 to 300 nm, and more preferably 10 to 100 nm.

When the liquid crystal is horizontally oriented or tilted, the coated film after firing is treated by rubbing, polarized ultraviolet irradiation, or the like.

<Liquid crystal display element>

The liquid crystal display element of the present invention comprises at least one member selected from the group consisting of a side chain (A) for vertically orienting a liquid crystal and a polyamic acid having a photoreactive side chain (B) and a polyimide obtained by imidizing the side chain And a liquid crystal alignment layer formed from a liquid crystal aligning agent containing the liquid crystal alignment layer,

A liquid crystal cell in which a liquid crystal layer is sandwiched between the two substrates arranged so that the liquid crystal alignment layer faces each other,

And means for irradiating ultraviolet rays while applying a voltage to the liquid crystal layer.

The substrate used in the liquid crystal display element of the present invention is not particularly limited as long as it is a substrate having high transparency. Usually, it is a substrate on which a transparent electrode for driving liquid crystal is formed. Specific examples include the same substrates as those described in the &lt; liquid crystal alignment layer &gt;. In the liquid crystal display element of the present invention, a substrate on which a conventional electrode pattern or projection pattern is formed may be used. However, the liquid crystal display of the present invention is operable in a structure in which a line / slit electrode pattern of 1 to 10 mu m is formed on a unilateral substrate and a slit pattern or a projection pattern is not formed on the counter substrate, By the display, the manufacturing process can be simplified, and a high transmittance can be obtained.

In a high-performance device such as a TFT-type device, a device such as a transistor is formed between an electrode for liquid crystal driving and a substrate.

In the case of a transmissive liquid crystal device, it is common to use a substrate as described above. In a reflective liquid crystal display device, an opaque substrate such as a silicon wafer can be used as long as it is only on one substrate. At this time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.

The liquid crystal alignment layer is a resin film for aligning the liquid crystal perpendicularly to the substrate, and is formed using the liquid crystal aligning agent. As the step of forming the liquid crystal alignment layer on the substrate, the coating method described in the &lt; liquid crystal alignment film &gt; and the firing method after application can be applied.

As a method for holding the liquid crystal layer between the two substrates, a known method of manufacturing a liquid crystal cell can be mentioned. For example, a pair of substrates on which a liquid crystal alignment layer is formed is prepared. Spacers are dispersed on the liquid crystal alignment layer of the substrate of the single chamber, and the substrates of the other single chamber are bonded A method in which liquid crystal is injected under reduced pressure, or a method in which a liquid crystal is dropped on a liquid crystal alignment layer surface on which a spacer is dispersed, and then a substrate is bonded and sealed. The thickness of the spacer at this time is preferably 1 to 30 占 퐉, more preferably 2 to 10 占 퐉.

The liquid crystal used in the liquid crystal display element of the present invention may be a liquid crystal to which a photopolymerizable compound is not added, but also a liquid crystal to which a photopolymerizable compound is added may be used.

In the step of applying a voltage to the liquid crystal layer and irradiating ultraviolet rays while forming an electric field, for example, a voltage is applied to the liquid crystal layer by applying a voltage between electrodes provided on the substrate, and ultraviolet rays And the like. Here, as a means for applying a voltage to the liquid crystal layer, a function generator can be used, and as a means for irradiating ultraviolet rays, a conventional device such as a high-pressure mercury lamp or the like can be used. The voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The wavelength of ultraviolet rays is preferably 250 to 400 nm, and more preferably 300 to 400 nm. The irradiation dose of ultraviolet rays is, for example, 1 to 60 J / cm 2, preferably 40 J / cm 2 or less. When the amount of ultraviolet radiation is small, reliability deterioration due to breakage of members constituting the liquid crystal display can be suppressed, Further, since the ultraviolet ray irradiation time can be reduced, the production efficiency is increased, which is preferable.

By the above process, the photoreactive group of the side chain B reacts and the direction in which the liquid crystal molecules incline is memorized, whereby the response speed of the liquid crystal display element is increased.

Example

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not construed as being limited thereto.

[Synthesis of polyamic acid]

The abbreviations of the compounds such as the tetracarboxylic acid dianhydride used below are shown.

(Tetracarboxylic acid dianhydride)

C-1: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

(Diamine compound)

DA-6: p-phenylenediamine

DA-7: 1,3-Diamino-4-octadecyloxybenzene

DA-8: 1,3-Diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy]

DA-9: 1,3-Diamino-4- {trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy}

[Chemical Formula 45]

(Organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

Of the above diamine compounds, DA-2 and DA-3 were obtained in the same manner as in Reference Synthesis Example described below.

(Reference Synthesis Example 1) Synthesis of DA-2

To a 500 mL (milliliter) three-necked flask, 5.94 g of tetramethylene glycol monovinyl ether, 5.70 g of triethylamine, and 30 mL of toluene were added. The inside of the system was heated to 100 占 폚, and 10 g of 2,4-dinitrofluorobenzene dissolved in 20 ml of toluene was added dropwise, followed by stirring at 100 占 폚 for 6 hours. After completion of the reaction, 50 mL of pure water was added and stirred, and then ethyl acetate was added to extract the organic layer. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration and drying, followed by filtration, followed by solvent distillation using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate / hexane = 7/3 (volume ratio, the same applies hereinafter) to obtain 13.2 g of 2,4-dinitro- 1- (4-vinyloxy) butoxybenzene (Yield: 90%).

To a 500 mL three-necked flask, 2.12 g of the dinitro compound, 20 mL of toluene, and 80 mL of a 10% by mass aqueous ammonium chloride solution were added. The inside of the system was heated to 70 占 폚, and 4.2 g of iron (electrolytic iron) was added, followed by stirring at 70 占 폚 for 2.5 hours. After completion of the reaction, 30 mL of a 5 mass% aqueous solution of sodium hydrogencarbonate was added, and the precipitate was filtered and washed with toluene. The filtrate was extracted with ethyl acetate, and anhydrous magnesium sulfate was added to the organic layer, followed by dehydration and drying. After filtration, solvent distillation was carried out using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate / hexane = 7/3 to obtain 0.59 g of the desired product (yield: 38%). The results of ¹ H-NMR measurement of the target product are shown below. From this result, it was confirmed that the obtained solid was the desired diamino compound, namely, 4- (4- (vinyloxy) butoxy) benzene-1,3-diamine.

(Reference Synthesis Example 2) Synthesis of DA-3

A 300 mL three-necked flask was charged with 5.11 g of 10-undecen-1-ol, 2.37 g of pyridine, and 100 mL of tetrahydrofuran. The inside of the system was cooled to 0 ° C by ice-cooling, and 8.3 g of 3,5-dinitrobenzoyl chloride was added, followed by stirring at room temperature for 2 hours. After completion of the reaction, 20 mL of pure water was added and stirred, and ethyl acetate was added to extract the organic layer. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration and drying, followed by filtration, followed by solvent distillation using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate / hexane = 7/3 to obtain 6.9 g of undec-10-enyl-3,5-dinitrobenzoate (yield: 63%).

6.55 g of the dinitro compound, 50 mL of tetrahydrofuran, and 50 mL of pure water were added to a 300 mL three-necked flask, and the inside of the system was stirred. 17.06 g of tin chloride was added and stirred at 60 ° C for 2 hours. After completion of the reaction, 400 ml of 5 mass% sodium hydrogencarbonate was added to adjust the pH to 7 to 8. Thereafter, 160 ml of ethyl acetate was added, and the white precipitate was removed by filtration, and the organic layer was extracted with ethyl acetate. The organic layer was dehydrated and dried by adding anhydrous magnesium sulfate, filtered, and then subjected to solvent distillation using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate / hexane = 7/3 to obtain 4.5 g of the desired product (yield: 82%). The results of ¹ H-NMR measurement of the target product are shown below. From these results, it was confirmed that the obtained solid was the intended diamino compound, i.e., undec-10-enyl-3,5-diaminobenzoate.

<Molecular weight measurement of polyamic acid and polyimide>

The molecular weight of the polyamic acid in the following Synthesis Examples was measured using a room temperature gel permeation chromatography (GPC-101) manufactured by Showa Denko K.K. and a column (KD-803, KD-805) And measured as follows.

Column temperature: 50 ° C

Eluent: 30 mmol / L of lithium bromide-hydrate (LiBr.H ₂ O), 30 mmol / L of phosphoric acid-anhydrous crystal (o-phosphoric acid) as an additive, N, N'-dimethylformamide Furan (THF) of 10 ml / L)

Flow rate: 1.0 ml / min

Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight about 900,000, 150,000, 100,000, 30,000) manufactured by Toso Corporation and polyethylene glycol (molecular weight about 12,000, 4,000, 1,000) manufactured by Polymer Research Laboratory.

&Lt; Synthesis Example 1 &

NMP 7.69 (3.96 mmol) was obtained by using 0.78 g (3.96 mmol) of C-1 as a tetracarboxylic acid dianhydride and 0.85 g (3.20 mmol) of DA1 and 0.30 g g for 16 hours at room temperature to obtain a solution having a concentration of polyamic acid (PAA-1) of 20 mass%. 8.0 g of the polyamic acid solution (PAA-1) was diluted with 12.0 g of NMP and 5.3 g of BCS to prepare a solution containing 6 mass% of polyamic acid (PAA-1), 74 mass% of NMP and 20 mass% To obtain a liquid crystal aligning agent (A1). The number average molecular weight of PAA-1 was 20,500, and the weight average molecular weight was 63,000.

&Lt; Synthesis Example 2 &

NMP 7.51 (3.96 mmol) was added to a tetrahydrofuran solution containing 0.78 g (3.96 mmol) of C-1 as a tetracarboxylic acid dianhydride, 0.95 g (3.60 mmol) of DA1 as a diamine component and 0.15 g g for 16 hours at room temperature to obtain a solution having a concentration of polyamic acid (PAA-2) of 20 mass%. 8.0 g of the polyamic acid solution (PAA-2) was diluted with 12.2 g of NMP and 5.3 g of BCS to obtain a solution containing 6 mass% of polyamic acid (PAA-2), 74 mass% of NMP and 20 mass% To obtain a liquid crystal aligning agent (A2). The number average molecular weight of PAA-2 was 25,200, and the weight average molecular weight was 86,400.

&Lt; Synthesis Example 3 &

NMP 4.70 (2.48 mmol) was obtained by using 0.49 g (2.48 mmol) of C-1 as a diamine component, 0.59 g (2.25 mmol) of DA1 and 0.095 g g for 16 hours at room temperature to obtain a solution having a concentration of polyamic acid (PAA-3) of 20 mass%. 4.7 g of the polyamic acid solution (PAA-3) was diluted with 7.8 g of NMP and 3.1 g of BCS to obtain 6 mass% of polyamic acid (PAA-3), 74 mass% of NMP and 20 mass% To obtain a liquid crystal aligning agent (A3). The number average molecular weight of PAA-3 was 20,400, and the weight average molecular weight thereof was 57,800.

&Lt; Synthesis Example 4 &

NMP 4.75 (2.48 mmol) was obtained by using 0.49 g (2.48 mmol) of C-1 as a tetracarboxylic acid dianhydride and 0.59 g (2.25 mmol) of DA1 as a diamine component and 0.11 g g for 16 hours at room temperature to obtain a solution having a concentration of polyamic acid (PAA-4) of 20 mass%. 4.7 g of the polyamic acid solution (PAA-4) was diluted with 7.9 g of NMP and 3.2 g of BCS to obtain a solution containing 6 mass% of polyamic acid (PAA-4), 74 mass% of NMP and 20 mass% (A4) as a liquid crystal aligning agent. The number average molecular weight of PAA-4 was 19,100, and the weight average molecular weight thereof was 55,000.

&Lt; Synthesis Example 5 &

NMP 4.57 (2.40 mmol) was obtained by using 0.47 g (2.40 mmol) of C-1 as a tetracarboxylic acid dianhydride and 0.39 g (1.75 mmol) of DA2 as a diamine component and 0.28 g g for 16 hours at room temperature to obtain a solution having a concentration of polyamic acid (PAA-5) of 20 mass%. 4.5 g of the polyamic acid solution (PAA-5) was diluted with 7.6 g of NMP and 3.0 g of BCS to prepare a solution containing 6 mass% of polyamic acid (PAA-5), 74 mass% of NMP and 20 mass% To obtain a liquid crystal aligning agent (A5). The number average molecular weight of PAA-5 was 16,700, and the weight average molecular weight was 52,900.

&Lt; Synthesis Example 6 &

NMP 4.41 (2.40 mmol) was obtained by using 0.47 g (2.40 mmol) of C-1 as a tetracarboxylic acid dianhydride and 0.44 g (2.00 mmol) of DA2 as a diamine component and 0.19 g g for 16 hours at room temperature to obtain a solution having a concentration of polyamic acid (PAA-6) of 20 mass%. 4.4 g of the polyamic acid solution (PAA-6) was diluted with 7.3 g of NMP and 2.9 g of BCS to obtain a solution containing 6 mass% of polyamic acid (PAA-6), 74 mass% of NMP and 20 mass% To obtain a liquid crystal aligning agent (A6). The number average molecular weight of PAA-6 was 24,400, and the weight average molecular weight thereof was 93,500.

&Lt; Synthesis Example 7 &

NMP 5.20 (2.48 mmol) was used as tetracarboxylic acid dianhydride using 0.49 g (2.48 mmol) of C-1, 0.53 g (1.75 mmol) of DA3 and 0.28 g g for 16 hours at room temperature to obtain a solution having a concentration of polyamic acid (PAA-7) of 20 mass%. 5.4 g of the polyamic acid solution (PAA-7) was diluted with 9.0 g of NMP and 3.6 g of BCS to obtain a solution containing 6 mass% of polyamic acid (PAA-7), 74 mass% of NMP and 20 mass% To obtain a liquid crystal aligning agent (A7). The number average molecular weight of PAA-7 was 20,900, and the weight average molecular weight was 78,900.

&Lt; Synthesis Example 8 &

NMP 5.13 (2.48 mmol) was obtained by using 0.49 g (2.48 mmol) of C-1 as a tetracarboxylic acid dianhydride and 0.61 g (2.00 mmol) of DA3 as a diamine component and 0.19 g g for 16 hours at room temperature to obtain a solution having a concentration of polyamic acid (PAA-8) of 20 mass%. 5.3 g of the polyamic acid solution (PAA-8) was diluted with 8.8 g of NMP and 3.5 g of BCS to obtain 6 mass% of polyamic acid (PAA-8), 74 mass% of NMP and 20 mass% To obtain a liquid crystal aligning agent (A8). The number average molecular weight of PAA-8 was 18,800, and the weight average molecular weight was 67,300.

&Lt; Synthesis Example 9 &

NMP 4.55 (2.48 mmol) was obtained by using 0.49 g (2.48 mmol) of C-1 as a tetracarboxylic acid dianhydride and 0.46 g (2.00 mmol) of DA4 as a diamine component and 0.19 g g for 16 hours at room temperature to obtain a solution having a concentration of polyamic acid (PAA-9) of 20 mass%. 4.5 g of the polyamic acid solution (PAA-9) was diluted with 6.5 g of NMP and 3.0 g of BCS to prepare a solution containing 6 mass% of polyamic acid (PAA-9), 74 mass% of NMP and 20 mass% To obtain a liquid crystal aligning agent (A9). The number average molecular weight of PAA-9 was 17,600, and the weight average molecular weight was 47,100.

&Lt; Synthesis Example 10 &

NMP 4.41 (2.48 mmol) was obtained by using 0.49 g (2.48 mmol) of C-1 as a tetracarboxylic acid dianhydride and 0.02 g (2.25 mmol) of DA- g for 16 hours at room temperature to obtain a solution having a concentration of polyamic acid (PAA-10) of 20 mass%. 4.3 g of the polyamic acid solution (PAA-10) was diluted with 6.1 g of NMP and 2.8 g of BCS to obtain a solution containing 6 mass% of polyamic acid (PAA-10), 74 mass% of NMP and 20 mass% To obtain a liquid crystal aligning agent (A10). The number average molecular weight of PAA-10 was 19,500, and the weight average molecular weight was 55,500.

&Lt; Synthesis Example 11 &

(2.00 mmol) of DA5 and 0.19 g (0.50 mmol) of DA-7 were used as tetracarboxylic acid dianhydride, 0.49 g (2.48 mmol) of C-1, g for 16 hours at room temperature to obtain a solution having a concentration of polyamic acid (PAA-11) of 20 mass%. 5.0 g of the polyamic acid solution (PAA-11) was diluted with 6.3 g of NMP and 3.3 g of BCS to prepare a solution containing 6 mass% of polyamic acid (PAA-11), 74 mass% of NMP and 20 mass% To obtain a liquid crystal aligning agent (A11). The number average molecular weight of PAA-11 was 17,000, and the weight average molecular weight was 56,000.

&Lt; Synthesis Example 12 &

NMP 6.03 (2.48 mmol) was obtained by using 0.49 g (2.48 mmol) of C-1 as a tetracarboxylic acid dianhydride and 0.93 g (2.25 mmol) of DA5 as a diamine component and 0.19 g g for 16 hours at room temperature to obtain a solution having a concentration of polyamic acid (PAA-12) of 20 mass%. 5.0 g of the polyamic acid solution (PAA-12) was diluted with 6.3 g of NMP and 3.3 g of BCS to prepare a solution containing 6 mass% of polyamic acid (PAA-12), 74 mass% of NMP and 20 mass% To obtain a liquid crystal aligning agent (A12). The number average molecular weight of PAA-12 was 19,500, and the weight average molecular weight was 59,000.

&Lt; Synthesis Example 13 &

0.49 g (2.48 mmol) of C-1 as a tetracarboxylic acid dianhydride, 0.64 g (2.00 mmol) of DA-10 as a diamine component and 0.19 g (0.50 mmol) of DA- And reacted in 5.26 g of NMP at room temperature for 16 hours to obtain a solution having a concentration of polyamic acid (PAA-14) of 20 mass%. 5.0 g of this polyamic acid solution (PAA-14) was diluted with 6.3 g of NMP and 3.3 g of BCS to obtain a solution containing 6 mass% of polyamic acid (PAA-14), 74 mass% of NMP and 20 mass% To obtain a liquid crystal aligning agent (A13). The number average molecular weight of PAA-14 was 17,500, and the weight average molecular weight thereof was 57,000.

&Lt; Synthesis Example 14 &

0.49 g (2.48 mmol) of C-1 as a tetracarboxylic acid dianhydride, 0.72 g (2.25 mmol) of DA-10 as a diamine component and 0.09 g (0.25 mmol) of DA- And reacted in 5.20 g of NMP at room temperature for 16 hours to obtain a solution having a concentration of polyamic acid (PAA-15) of 20 mass%. 5.0 g of the polyamic acid solution (PAA-15) was diluted with 6.3 g of NMP and 3.3 g of BCS to prepare a solution containing 6 mass% of polyamic acid (PAA-15), 74 mass% of NMP and 20 mass% To obtain a liquid crystal aligning agent (A14). The number average molecular weight of PAA-15 was 18,500, and the weight average molecular weight thereof was 59,000.

<Comparative Synthesis Example 1>

1.30 g (6.65 mmol) of C-1 as a tetracarboxylic acid dianhydride, 0.68 g (6.30 mmol) of DA-6 as a diamine component and 0.26 g (0.7 mmol) of DA- And reacted in 12.74 g of NMP at room temperature for 16 hours to obtain a solution having a concentration of polyamic acid (PAA-13) of 20 mass%. 10.0 g of the polyamic acid solution (PAA-13) was diluted with 16.7 g of NMP and 6.7 g of BCS to obtain a solution containing 6 mass% of polyamic acid (PAA-13), 74 mass% of NMP and 20 mass% Of the liquid crystal aligning agent (A15). The number average molecular weight of PAA-13 was 18,700, and the weight average molecular weight thereof was 58,000.

&Lt; Reference Example 1 &

The liquid crystal aligning agent [A1] obtained in Synthesis Example 1 was spin-coated on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 x 300 microns and a line / space of 5 microns was formed. After drying for 90 seconds on a hot plate at 80 占 폚, firing was performed for 60 minutes in a hot air circulating oven at 160 占 폚 to form a liquid crystal alignment film having a thickness of 100 nm.

The liquid crystal aligning agent [A1] obtained in Synthesis Example 1 was spin-coated on the ITO surface on which the electrode pattern was not formed, and dried on a hot plate at 80 DEG C for 90 seconds. Thereafter, a 60 DEG C hot air circulating oven Minute firing was performed to form a liquid crystal alignment film having a thickness of 100 nm. These two substrates were prepared, a bead spacer of 6 mu m was dispersed on the liquid crystal alignment film surface of one substrate, and a sealant was printed thereon. The other substrate was adhered with the liquid crystal alignment film face inward, and then the sealant was cured to prepare an empty cell. A liquid crystal cell was prepared by injecting liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) into this empty cell by a low pressure injection method.

The response speed characteristics of these liquid crystal cells were measured by a method described later. Thereafter, 20 Vp-p voltage was applied to the liquid crystal cell, and UV (ultraviolet) was irradiated from the outside of the liquid crystal cell for 20 seconds. Thereafter, the response speed characteristics were measured again, and the response speeds before and after the UV irradiation were compared. The results are shown in Table 2.

<Reference Examples 2 to 4, Examples 5 to 12 and Reference Examples 13 and 14> and <Comparative Example 1>

The liquid crystal aligning agent [A1] was changed to the liquid crystal aligning agents [A2] to [A14] obtained in Synthesis Examples 2 to 14 and the liquid crystal aligning agent [A15] obtained in Comparative Synthesis Example 1, respectively, , A liquid crystal cell was prepared in the same manner as in Reference Example 1, and the response speed was measured. The results are shown in Table 2.

[Response speed characteristics]

A time change of the luminance of the liquid crystal panel when a square wave of voltage ± 4 V and a frequency of 1 kHz was applied to a liquid crystal cell to which no voltage was applied was introduced by an oscilloscope. A voltage of 0% and a voltage of +4 V is applied to the luminance when the voltage is not applied and the saturated luminance is set to 100%, and the time for which the luminance varies from 10% to 90% Respectively.

As can be seen from Table 2, in the liquid crystal cell of the examples, the response speed after UV irradiation was improved. On the other hand, in the comparative example, no change in response speed was observed before and after UV irradiation. In Examples 1 and 2, Examples 5 and 6, Examples 7 and 8, Examples 9 and 10, and Examples 11 and 12, the introduction amount of tilted side chains was small, and the degree of improvement in response speed after UV irradiation was large . Further, in Reference Examples 2, 3, and 4, the degree of improvement in the response speed after UV irradiation was large in the case of using a side chain having a low vertically aligning ability even if the amounts of introduced tilting side chains were the same.

Also in Reference Examples 13 and 14 as described above, the introduction rate of the tilt expression side chains was small, and the degree of improvement in response speed after UV irradiation was large. In Reference Examples 1 and 13 and Reference Examples 2 and 14, in the case of using DA-10 having a long alkyl spacer even when the amounts of introduced tilted side chains were the same and the photoreactive groups were the same, , And the degree of improvement in response speed after UV irradiation was high.

Industrial availability

The liquid crystal display element of the present invention can be used as a screen of a liquid crystal television or a screen of various information display devices.

The liquid crystal aligning agent of the present invention can be used for producing a liquid crystal display element of a vertical alignment system produced by irradiating ultraviolet rays while applying a voltage to liquid crystal molecules, And can be used for a liquid crystal display device.

The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2010-043372 filed on February 26, 2010 are hereby incorporated herein by reference as the disclosure of the specification of the present invention.

Claims (12)

A diamine component containing 5 to 50 mol% of a diamine having a side chain (A) for vertically orienting liquid crystal and 10 to 95 mol% of a diamine having a photoreactive side chain (B) represented by the following formula (b) A liquid crystal aligning agent containing at least one of a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride component and a polyimide obtained by imidizing the polyamic acid is applied on two substrates to form a liquid crystal alignment layer,
Two substrates are arranged so that the liquid crystal alignment layers face each other,
A liquid crystal layer sandwiched between the two substrates,
Wherein the liquid crystal layer is irradiated with ultraviolet rays while applying a voltage to the liquid crystal layer.

(R ⁶ is _{-CH 2 -, -O-, -COO-,} -NHCO-, -NH-, -CH 2 O-, -N (CH 3) -, -CON (CH 3) -, or -N (CH ₃ ) CO-, R ⁷ represents a linear alkylene group having 1 to 20 carbon atoms (the alkylene may be unsubstituted or may be substituted by a fluorine atom), and arbitrary -CH ₂ - may be substituted with -CF ₂ -, -CH═CH-, or the following substituent (s) (these substituents are not adjacent to each other).
Substituent: -O-, -COO-, -NHCO-, -NH-, a carbon ring group, or a heterocyclic group.
R ⁸ is _{-CH 2 -, -O-, -COO-,} -OCO-, -NHCO-, -NH-, -N (CH 3) -, -CON (CH 3) -, -N (CH 3) CO-, represents a carbon-ring group, or a heterocyclic ring, R ⁹ is a vinyl group, -CR ¹⁰ = CH ₂ group, a carbocyclic group, a heterocyclic group, or represents a group to represent one of [formula 2], R ¹⁰ Represents a hydrogen atom or a methyl group which may be substituted with a fluorine atom. Except that R ⁸ is -OCO-, -NHCO- or -N (CH ₃ ) CO- and R ⁹ is -CH = CH ₂ or -C (CH ₃ ) = CH ₂ .
(2)

delete The method according to claim 1,
Wherein the side chain (A) for vertically orienting the liquid crystal is represented by the following formula (a).

(In the formula (a), l, m and n each independently represent an integer of 0 or 1. R ¹ represents an alkylene group having 2 to 6 carbon atoms, -O-, -COO-, -OCO-, NHCO-, -CONH-, or an alkylene-ether group having 1 to 3 carbon atoms, R ² , R ³ and R ⁴ each independently represent a phenylene group or a cycloalkylene group, R ⁵ represents a hydrogen atom , A linear alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group, or a cyclic group, aliphatic cyclic group, heterocyclic group or a large cyclic group composed thereof. The method of claim 3,
Wherein the side chain (A) for vertically orienting the liquid crystal is represented by the formula (a), l, m and n are all 1, R ² is phenylene, R ³ is phenylene or cyclohexylene , R ⁴ is cyclohexylene, R ⁵ is an alkyl group having 2 to 24 carbon atoms, or 1, m and n are both 0 and R ⁵ is an alkyl group having 12 to 22 carbon atoms. Gt; The method of claim 3,
Wherein the photoreactive side chain (B) is represented by the formula (b) and R ⁹ is a vinylphenyl group, -CH═CH ₂ , -C (CH ₃ ) ═CH ₂ or one of the following formulas And a method for manufacturing a liquid crystal display element. Except that R ^{8 in} formula (b) is -OCO-, -NHCO- or -N (CH ₃ ) CO- and R ⁹ is -CH = CH ₂ or -C (CH ₃ ) = CH ₂ .)
[Chemical Formula 4]

A liquid crystal aligning agent is applied on two substrates to form a liquid crystal alignment layer,
Two substrates are arranged so that the liquid crystal alignment layers face each other,
A liquid crystal layer sandwiched between the two substrates,
A liquid crystal aligning agent for use in a method of manufacturing a liquid crystal display element of a vertical alignment system characterized by irradiating ultraviolet rays while applying a voltage to a liquid crystal layer,
A thermoplastic resin composition comprising the diamine component containing 5 to 50 mol% of a diamine having a side chain (A) vertically orienting a liquid crystal and 10 to 95 mol% of a diamine having a photoreactive side chain (B) A liquid crystal aligning agent containing at least one of polyamic acid obtained by reacting a carboxylic acid dianhydride component and polyimide obtained by imidizing the polyamic acid. delete The method according to claim 6,
Wherein the diamine having the light-reactive side chain (B) is represented by the following formula (2).

(R ⁶ is _{-CH 2 -, -O-, -COO-,} -NHCO-, -NH-, -CH 2 O-, -N (CH 3) -, -CON (CH 3) -, or -N (CH ₃ ) CO-, R ⁷ represents a linear alkylene group having 1 to 20 carbon atoms (the alkylene may be unsubstituted or may be substituted by a fluorine atom), and arbitrary -CH ₂ - may be substituted with -CF ₂ -, -CH═CH-, or the following substituent (s) (these substituents are not adjacent to each other).
Substituent: -O-, -COO-, -NHCO-, -NH-, a carbon ring group, or a heterocyclic group.
R ⁸ is _{-CH 2 -, -O-, -COO-,} -OCO-, -NHCO-, -NH-, -N (CH 3) -, -CON (CH 3) -, -N (CH 3) CO-, a carbon ring group or a heterocyclic group, and R ¹¹ represents a vinylphenyl group, -CH = CH ₂ , -C (CH ₃ ) = CH ₂ , or one of the following groups. Except that R ^{8 in} formula (2) is -OCO-, -NHCO- or -N (CH ₃ ) CO- and R ¹¹ is -CH = CH ₂ or -C (CH ₃ ) = CH ₂ . )
[Chemical Formula 6]

The method according to claim 6,
A liquid crystal aligning agent represented by the following formula (1), wherein the diamine having a side chain (A) for vertically orienting the liquid crystal is represented by the following formula (1).

(1), l, m and n each independently represent an integer of 0 or 1. R ¹ represents an alkylene group having 2 to 6 carbon atoms, -O-, -COO-, -OCO-, - NHCO-, -CONH-, or an alkylene-ether group having 1 to 3 carbon atoms, R ² , R ³ and R ⁴ each independently represent a phenylene group or a cycloalkylene group, R ⁵ represents a hydrogen atom , A linear alkyl group or a fluorine-containing alkyl group having 2 to 24 carbon atoms, or a cyclic group, aliphatic cyclic group, heterocyclic group, or a cyclic group composed thereof. 10. The method of claim 9,
Wherein diamine having a side chain (A) for vertically orienting the liquid crystal is represented by the formula (1), l, m and n are all 1, R ² is phenylene, R ³ is phenylene or cyclo Hexylene, R ⁴ is cyclohexylene, R ⁵ is an alkyl group having 2 to 24 carbon atoms, or l, m and n are both 0 and R ⁵ is an alkyl group having 12 to 22 carbon atoms , Liquid crystal aligning agent. 10. The method of claim 9,
Wherein the diamine having a side chain (A) for orienting the liquid crystal vertically is a diamine having a structure of one of the following formulas (8).
[Chemical Formula 8]

A liquid crystal alignment layer obtained by using the liquid crystal aligning agent according to any one of claims 6 and 8 to 11.