KR20130004486A - Liquid crystal display element and liquid crystal aligning agent - Google Patents

Abstract

The liquid crystal display element of the vertical alignment system which can speed up a response speed without adding a photopolymerizable compound, its manufacturing method, and the liquid crystal aligning agent suitable for it are provided. The liquid crystal aligning agent containing at least 1 sort (s) chosen from the group which consists of a polyamic acid which has a side chain (A) which orientates a liquid crystal perpendicularly, and a photoreactive side chain (B), and the imidized it 2 Apply | coated on a sheet | seat board | substrate, and form a liquid crystal aligning layer, arrange | position two board | substrates so that the said liquid crystal aligning layer may oppose, sandwich a liquid crystal layer between the said 2 board | substrates, and irradiate an ultraviolet-ray, applying a voltage to a liquid crystal layer The manufacturing method of the liquid crystal display element of a vertical alignment system.

Description

Liquid crystal display element and liquid crystal aligning agent {LIQUID CRYSTAL DISPLAY ELEMENT AND LIQUID CRYSTAL ALIGNING AGENT}

This invention relates to the liquid crystal display element of the vertical alignment system manufactured by irradiating an ultraviolet-ray in the state which applied the voltage to the liquid crystal molecule, and the liquid crystal aligning agent used for manufacture of this liquid crystal display element.

The liquid crystal display device of the system (also called a vertical orientation system) which makes a liquid crystal molecule orientate perpendicular to a board | substrate respond with an electric field includes the process of irradiating an ultraviolet-ray, applying a voltage to a liquid crystal molecule in the manufacturing process. There is. In such a liquid crystal display element, it is common to add a photopolymerizable compound to a liquid crystal composition previously. Usually, the direction in which the liquid crystal molecules in response to the electric field are inclined is controlled by projections formed on the substrate, slits formed in the display electrode, and the like. In the liquid crystal display device, since the polymer structure in which the direction in which the liquid crystal molecules are inclined is formed on the liquid crystal alignment film, the response speed of the liquid crystal display device is faster as compared with the method of controlling the inclination direction of the liquid crystal molecules only by protrusions or slits. It is called (for example, refer patent document 1).

Moreover, in recent years, even when a photopolymerizable compound is not added to a liquid crystal composition but also in a liquid crystal aligning film, it is reported that the response speed of a liquid crystal display element becomes fast by going through the said process (for example, nonpatent See Document 1).

As a technique different from the above, there exists a photo-alignment technique which controls the direction which a liquid crystal molecule tilts by ultraviolet irradiation (for example, refer patent document 2). However, in the case of the photo-alignment technique, it is a technique which gives anisotropy to a liquid crystal aligning film beforehand using the anisotropy of polarized ultraviolet-ray, and is completely different from the technique which memorize | stores the direction of the liquid crystal molecule which was inclined as mentioned above.

Japanese Laid-Open Patent Publication 2003-307720 Japanese Laid-Open Patent Publication 2003-114437

 SID 09 Digest 45.1

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal display device of a vertical alignment system manufactured by irradiating ultraviolet rays while applying a voltage to liquid crystal molecules, wherein the response speed can be increased without adding a photopolymerizable compound in the liquid crystal composition or the liquid crystal alignment film. It is providing the liquid crystal aligning agent suitable for a liquid crystal display element, its manufacturing method, and this liquid crystal display element.

This invention is characterized by the following structure as a summary.

[1] Liquid crystal aligning agent containing at least 1 sort (s) chosen from the group which consists of a polyamic acid which has a side chain (A) which orientates a liquid crystal perpendicularly | vertically, and a photoreactive side chain (B), and imidates it. Is applied onto two substrates to form a liquid crystal alignment layer,

Two board | substrates are arrange | positioned so that the said liquid crystal aligning layer may oppose,

The liquid crystal layer is sandwiched between the two substrates,

Ultraviolet rays are irradiated while applying a voltage to a liquid crystal layer, The manufacturing method of the liquid crystal display element of the vertical alignment system characterized by the above-mentioned.

[2] The method for producing a liquid crystal display device according to the above [1], wherein the liquid crystal aligning agent is a liquid crystal aligning agent containing at least one kind of the following polyamic acid and the polyimide obtained by imidizing it.

The polyamic acid obtained by making the diamine component and the tetracarboxylic dianhydride containing the diamine which has a side chain (A) which orientates a liquid crystal perpendicularly, and the diamine which has a photoreactive side chain (B) react.

[3] The method for producing a liquid crystal display device according to [1] or [2], in which the side chain (A) for orientating the liquid crystal vertically is represented by the following formula (a).

[Formula 1]

(1, m, and n in formula (a) 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, and R ⁵ represents a hydrogen atom; Or a linear alkyl group or a fluorine-containing alkyl group having 5 to 18 carbon atoms, or an aromatic ring group, an aliphatic ring group, a heterocyclic group or a large cyclic group consisting of them.)

[4] The method for producing a liquid crystal display device according to any one of the above [1] to [3], wherein the photoreactive side chain (B) is represented by the following Formula (b).

[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 having 1 to 20 carbon atoms (alkylene may be unsubstituted or substituted with a fluorine atom), and any of alkylene may be used. -CH ₂ -may be substituted with -CF _2- , -CH = CH-, or the following substituents (these substituents are not adjacent to each other).

A 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, R ⁹ represents a vinylphenyl group, -CR ¹⁰ = CH ₂ group, a carbon ring group, a heterocyclic group, or a group represented by the following formula, and R ¹⁰ is a hydrogen atom Or a methyl group which may be substituted with a fluorine atom.)

(3)

[5] The side chain (A) for vertically aligning the liquid crystal is represented by the formula (a), wherein l, m and n are all 1, R ² is phenylene, and R ³ is phenylene or cyclo When hexylene, R ⁴ is cyclohexylene, R ⁵ is an alkyl group having 2 to 24 carbon atoms, or when l, m and n are all 0, R ⁵ is an alkyl group having 12 to 22 carbon atoms, The manufacturing method of the liquid crystal display element in any one of [2]-[5].

[6] 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 any of the following: The manufacturing method of the liquid crystal display element in any one of said [3]-[5] which is a group of the thing.

[Formula 4]

[7] Liquid crystal alignment containing at least one member selected from the group consisting of a side chain (A) for vertically aligning the liquid crystal and a polyamic acid having a photoreactive side chain (B), and a polyimide obtained by imidizing it Two board | substrates which have a liquid crystal aligning layer formed from the agent,

A liquid crystal cell in which a liquid crystal layer is sandwiched between the two substrates arranged such that the liquid crystal alignment layers face each other;

The liquid crystal display element of the vertical alignment system which has a means which irradiates an ultraviolet-ray, applying a voltage to a liquid crystal layer.

[8] Liquid crystal aligning agent containing at least 1 sort (s) chosen from the group which consists of a polyamic acid which has a side chain (A) which orientates a liquid crystal perpendicularly | vertically, and a photoreactive side chain (B), and imidates it. .

[9] A polyamic acid obtained by reacting a diamine component containing a diamine having a side chain (A) for vertically aligning the liquid crystal and a diamine having a photoreactive side chain (B) with a tetracarboxylic dianhydride; It is a liquid crystal aligning agent containing at least 1 sort (s) chosen from the group which consists of polyimide obtained by hydration, and the diamine which has the said photoreactive side chain (B) is represented by following formula (2), The liquid crystal aligning characterized by the above-mentioned. My.

[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 having 1 to 20 carbon atoms (alkylene may be unsubstituted or substituted with a fluorine atom), and any of alkylene may be used. -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, or a heterocyclic group.

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

[Formula 6]

[10] The liquid crystal aligning agent according to any one of the above [7] to [9], in which a diamine having a side chain (A) for orientating the liquid crystal is represented by the following formula (1).

[Formula 7]

(1, m, and n in Formula (1) each independently represent the integer of 0 or 1. R <^1> is a C2-C6 alkylene group, -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, and R ⁵ represents a hydrogen atom; , A linear alkyl group having 5 to 18 carbon atoms or a fluorine-containing alkyl group, or an aromatic ring group, an aliphatic ring group, a heterocyclic group or a large cyclic group consisting of them.

[11] The diamine having the side chain (A) for vertically aligning the liquid crystal is represented by the formula (1), wherein l, m and n are all 1, R ² is phenylene and R ³ is phenyl When ethylene or cyclohexylene, R ⁴ is cyclohexylene, R ⁵ is an alkyl group having 2 to 24 carbon atoms, or when l, m and n are all 0, R ⁵ is 12 to 22 carbon atoms; The liquid crystal aligning agent as described in said [10] which is a diamine which is an alkyl group.

[12] The liquid crystal aligning agent according to any one of [8] to [11], wherein the diamine having the side chain (A) for vertically aligning the liquid crystal is a diamine having any of the following structures.

[Formula 8]

[13] A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to any one of [8] to [12].

According to this invention, the liquid crystal display element which can speed up a response speed (shorten response time) is provided, without adding a photopolymerizable compound in a liquid crystal composition or a liquid crystal aligning film.

Moreover, the liquid crystal aligning agent of this invention is used for the liquid crystal display element of the vertical alignment system manufactured by irradiating an ultraviolet-ray, applying a voltage to a liquid crystal molecule, even if a photopolymerizable compound is not added in a liquid crystal composition or a liquid crystal aligning film, It is possible to obtain a liquid crystal display device having a faster response speed (shorter response time).

<Side chain which orients liquid crystal vertically>

The side chain (also called side chain A) which orientates a liquid crystal perpendicularly is a side chain which has the ability to orientate a liquid crystal molecule perpendicular | vertical to a board | substrate, and if it has this capability, the structure is not limited. As the side chain A, for example, a long chain alkyl group, a long chain fluoroalkyl group, a cyclic group having an alkyl group or a fluoroalkyl group at its terminal, a steroid group or the like is known, and is preferably used in the present invention. These groups may be directly bonded to the main chain of a polyamic acid or a polyimide as long as they have the said ability, and may be couple | bonded through the appropriate coupling group.

As said side chain A, what is represented by a following formula (a) can be illustrated.

[Chemical Formula 9]

R <^1> in said Formula (a) is C2-C6, Preferably it is an alkylene group of 2-4, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or a carbon atom The number 1-3 alkylene-ether group (-CCO-) is shown. Among these, from the viewpoint of ease of synthesis, -O-, -COO-, -CONH-, or an alkylene-ether group having 1 to 3 carbon atoms is preferable.

R ² , R ³ and R ⁴ each independently represent a phenylene group or a cycloalkylene group. The combination of l, m, n, R ² , R ³ and R ⁴ shown in the following table is preferable in view of the ease of synthesis and the ability to orient the liquid crystal vertically.

R <^5> represents a hydrogen atom, a C2-C24, preferably a 5-8 alkyl group or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or the large cyclic group which consists of them. When at least one of l, m, and n is 1, as a structure of R <^5> , Preferably they are a hydrogen atom, a C2-C14 alkyl group, or a C2-C14 fluorine-containing alkyl group, and Preferably it is a hydrogen atom, C2-C12, Preferably it is a 2-10 alkyl group, or a fluorine-containing alkyl group.

Moreover, when l, m, and n are all 0, as a structure of R <^5> , Preferably, they are a C12-C22, Preferably 12-20 alkyl group or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, and a complex It is a ring or the large cyclic group which consists of them, More preferably, it is a C12-20 alkyl group, Preferably it is a 12-18 alkyl group or a fluorine-containing alkyl group.

The ability to orientate the liquid crystal vertically varies depending on the structure of the side chain A. In general, the greater the amount of the side chain A contained in the polymer, the higher the ability to orient the liquid crystal vertically, and the lower the decrease. Moreover, compared with the side chain A of a long chain alkyl group, the side chain A containing a cyclic structure tends to orientate a liquid crystal perpendicularly even with a small content.

The amount of the side chain A present in the polyamic acid or the polyimide used in the present invention is not particularly limited as long as the liquid crystal aligning film is in a range in which the liquid crystal can be aligned vertically, but is 5 to 50 mol% based on the total amount of diamine to be used. Is preferable and 10-30 mol% is more preferable. Existence amount of side chain A, However, in the liquid crystal display element provided with the said liquid crystal aligning film, in order to make the response speed of a liquid crystal faster, presence of side chain A exists in the range which can maintain a vertical alignment. The amount is preferably as small as possible.

<Side chain of photoreactivity>

Said photoreactive side chain (also called side chain B) is a side chain which has a functional group which can generate a photoreaction by irradiation of an ultraviolet-ray, and can form a covalent bond, and if it has this capability, the structure is not limited Do not. As the side chain B, for example, a side chain having a vinyl group, an acryl group, a methacryl group, anthracenyl group, cinnamoyl group, a carbonyl group, a coumarin group, a maleimide group, a stilbene group, or the like as a photoreactive group Is known and is also preferably used in the present invention. These groups may be directly bonded to the main chain of a polyamic acid or a polyimide as long as they have the said ability, and may be couple | bonded through the appropriate coupling group.

As said side chain B, what is represented by a following formula (b) can be illustrated.

[Formula 10]

R ⁶ in the formula (b) is -CH _2- , -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-,- OCO-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-. R ⁶ can be formed by a conventional organic synthetic method, and from the viewpoint of ease of synthesis, -CH _2- , -O-, -COO-, -NHCO-, -NH-, or -CH ₂ O- Is preferred.

R <^7> in said Formula (b) represents linear alkylene of 1-20 carbon atoms (alkylene may be unsubstituted or may be substituted by the fluorine atom), and arbitrary -CH of alkylene 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.

Specifically as a carbon ring group and a heterocyclic group, the following structures are mentioned, It is not limited to this.

[Formula 11]

[Chemical Formula 12]

The alkylene of R ^{7 preferably} forms a flexible spacer (a group connecting R ⁶ and R ⁸⁾ between R ⁶ and R ⁸ to increase the response speed, and enhances the reaction efficiency of the photoreactive group. R ⁷ is preferably 1 to 20 carbon atoms, preferably 2 to 8 linear alkylenes.

The formula (b) in R ⁸ _{is, -CH 2 -, -O-, -NH-} , -N (CH 3) -, -CONH-, -NHCO-, -CH 2 O-, -COO-, - OCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO-, a carbon ring group, or a heterocyclic group. Among them, from the viewpoint of ease of synthesis, -CH _2- , -O-, -COO-, -OCO-, -NHCO-, -NH-, a carbon ring group or a heterocyclic group is preferable. 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- from the viewpoint of the response speed.

R ⁹ in the formula (b) is a vinyl group, -CR ¹⁰ = CH _2, carbocyclic group, represents a group represented by the heterocyclic group, or the formula, R ¹⁰ is a methyl group that may be substituted with a hydrogen atom or a fluorine atom Indicates.

[Chemical Formula 13]

[Formula 14]

[Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

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

[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 less.

(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 the response speed of the liquid crystal in the liquid crystal display element can be increased, but with respect to the total amount of diamine to be used, 10-95 mol% is preferable and 60-95 mol% is more preferable. In the case where the amount of the side chain B is required to make the response speed of the liquid crystal in the liquid crystal display element faster, the amount of the side chain B is preferably as much as possible within a range that does not affect other characteristics.

<Polyamic acid>

In the present invention, the polyamic acid having the side chain A and the side chain B is reacted with a diamine having a side chain A and a diamine having a side chain B and a tetracarboxylic dianhydride, or a diamine and By reaction of tetracarboxylic dianhydride having side chain A and / or tetracarboxylic dianhydride having side chain B, furthermore, diamine having side chain A and / or diamine having side chain B and side It can obtain by reaction of tetracarboxylic dianhydride which has a chain A, and / or tetracarboxylic dianhydride which has a side chain B.

Among these, it is preferable to obtain by reaction of the diamine which has side chain A, and the diamine which has side chain B, and tetracarboxylic dianhydride from the ease of raw material synthesis | combination, etc.

<Diamine compound which has a side chain A>

Examples of the diamine compound having a side chain A (hereinafter also referred to as diamine A) include diamines having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a large cyclic substituent consisting of them in the diamine side chain. Can be. Specifically, the diamine which has a side chain represented by said formula (a) is mentioned. More specifically, although diamine represented by following formula (1), (3), (4) or (5) is mentioned, It is not limited to this.

(26)

For l, m, n, and the definition of R ¹ ~ R ⁵ in the formula (1), the same as in the formula (a).

(27)

In Formulas (3) and (4), A ₁₀ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH _2- , -O-, -CO-, or -NH- And A ₁₁ represent a single bond or a phenylene group. a represents side chain A, and a 'represents an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or the large cyclic group which consists of these groups.

(28)

In Formula (5), A ₁₄ may be substituted by the fluorine atom, represents 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- * (wherein a bond to which "*" has been attached is bonded to A ₃ ), and A ₁₇ represents an oxygen atom or -COO- * (wherein The bond to which "*" has been attached represents (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 0 or an integer of 1.

The bonding position of two amino groups (-NH ₂ ) in Formula (1) is not limited. Specifically, the 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position, 3, 5 position on a benzene ring is mentioned with respect to the coupling group of a side chain. Especially, from a viewpoint of the reactivity at the time of synthesize | combining a polyamic acid, 2, 4 position, 2, 5 position, or 3, 5 position are preferable. If the ease in synthesizing a diamine compound is also taken into consideration, 2, 4 position or 3, 5 position is more preferable.

Although the diamine represented by a following formula [A-1]-a formula [A-24] can be illustrated as a specific structure of Formula (1), It is not limited to this.

[Formula 29]

A <_1> is a C2-C24 alkyl group or a fluorine-containing alkyl group in a formula [A-1]-a formula [A-5].

(30)

Formula [A-6] and the formula [A-7] of, A _{2 is, -O-, -OCH 2 -, -CH} 2 O-, -COOCH 2 -, or represents a -CH ₂ OCO-, A ₃ Is a C1-C22 alkyl group, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.

(31)

Formula [A-8] ~ formula [A-10] of, A ₄ are, -COO-, -OCO-, -CONH-, -NHCO- , -COOCH 2 -, -CH 2 OCO-, -CH 2 O -, -OCH _2- , or -CH ₂ -are represented. A <_5> represents a C1-C22 alkyl group, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.

(32)

Formula [A-11] and the equation [A-12] of, A is _6, -COO-, -OCO-, -CONH-, -NHCO- , -COOCH 2 -, -CH 2 OCO-, -CH 2 O -, -OCH _2- , -CH _2- , -O-, or -NH-, and A ₇ represents a fluorine group, cyano group, trifluoromethyl group, nitro group, azo group, formyl group, acetyl group, acetok A time period or a hydroxyl group is shown.

(33)

In formula [A-13] and formula [A-14], A <_8> represents a C3-C12 alkyl group and the cistran isomer of 1, 4- cyclohexylene is a trans isomer, respectively.

[Formula 34]

In formula [A-15] and formula [A-16], A <_9> represents a C3-C12 alkyl group and the cistran isomer of 1, 4- cyclohexylene is a trans isomer, respectively.

(35)

(36)

[Formula 37]

Although the diamine represented by a following formula [A-25]-a formula [A-30] is mentioned as a specific example of the diamine represented by Formula (3), It is not limited to this.

(38)

Wherein [A-25] ~ formula [A-30], A ₁₂ are, -COO-, -OCO-, -CONH-, -NHCO- , -CH 2 -, or, -O-, -CO- - NH <-> represents and A <_13> represents a C1-C22 alkyl group or a fluorine-containing alkyl group.

Although the diamine represented by a following formula [A-31]-a formula [A-32] is mentioned as a specific example of the diamine represented by Formula (4), It is not limited to this.

[Chemical Formula 39]

Among these, [A-1], [A-2], [A-3], [A-4], [A-5], [A] from the viewpoint of the ability to orient the liquid crystal vertically and the response speed of the liquid crystal. A-25], [A-26], [A-27], [A-28], [A-29], and [A-30] are preferable.

The said diamine compound can also be used 1 type or in mixture of 2 or more types according to the characteristics, such as liquid crystal aligning property, pretilt angle, voltage retention characteristic, and stored charge, when it is set as a liquid crystal aligning film.

In order to achieve the objective of this invention, it is preferable that 5-50 mol% of the diamine component used for the synthesis | combination of a polyamic acid is diamine A. Furthermore, it is preferable that 5-30 mol% of a diamine component is diamine A, Especially preferably, it is 5-15 mol%.

<Diamine compound which has a side chain B>

As a diamine compound (also called diamine B) which has a side chain B, a vinyl group, an acryl group, methacryl group, anthracenyl group, cinnamoyl group, a carbonyl group, a coumarin group, a maleimide group, a stilbene group in a diamine side chain Diamine which has photoreactive groups, such as these, is mentioned as an example. Specifically, the diamine which has a side chain represented by said formula (b) is mentioned. More specifically, although diamine represented by following General formula (2) is mentioned, it is not limited to this, for example.

[Formula 40]

Formula (2) of, 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 having 1 to 20 carbon atoms (alkylene may be unsubstituted or substituted with a fluorine atom), and optionally -CH ₂ -of alkylene is -CF _2- , -CH = CH-, or the following substituents (these substituents are not adjacent to each other) may be substituted.

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 any of the following groups.

(41)

The bonding position of two amino groups (-NH ₂ ) in Formula (2) is not specifically limited. Specifically, the 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position, 3, 5 position on a benzene ring is mentioned with respect to the coupling group of a side chain. Especially, from a viewpoint of the reactivity at the time of synthesize | combining a polyamic acid, 2, 4 position, 2, 5 position, or 3, 5 position are preferable. If the ease in synthesizing a diamine compound is also taken into consideration, 2, 4 position or 3, 5 position is more preferable.

Although the following compounds are specifically mentioned, It is not limited to this.

(42)

(43)

(44)

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

The said diamine compound mixes 1 type, or 2 or more types according to the response speed of the liquid crystal at the time of using it as a liquid crystal aligning film, the pretilt angle, voltage holding | maintenance characteristics, accumulated charge, etc., and making a liquid crystal display element when it used as a liquid crystal aligning film. It can also be used.

In order to achieve the objective of this invention, it is preferable that 10-95 mol% of the diamine component used for the synthesis | combination of a polyamic acid is diamine B. Furthermore, it is more preferable that 40-95 mol% of a diamine component is diamine B, Especially preferably, it is 70-95 mol%.

<Other diamine compound>

The polyamic acid used for this invention can use together other diamine compounds other than diamine A and diamine B as a diamine component, unless the effect of this invention is impaired. 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-m-phenyl Rendiamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl Alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3, 3'-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, 3,3'-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, 4,4 '-Sulfonyldianiline, 3,3'-sulfonyldianiline, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3- Aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'- Diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3, 3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3 ' -Diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2 ' Diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2, 7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl Propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl 4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1 , 3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 '-[1,4-phenyl Lenbis (methylene)] dianiline, 4,4 '-[1,3-phenylenebis (methylene)] dianiline, 3,4'-[1,4-phenylenebis (methylene)] dianiline, 3 , 4 '-[1,3-phenylenebis (methylene)] dianiline, 3,3'-[1,4-phenylenebis (methylene)] dianiline, 3,3 '-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-amino Phenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis ( 4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate ), Bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N '-(1, 4-phenylene) bis (4-aminobenzamide), N, N '-(1,3-phenylene) bis (4-aminobenzamide), N, N'-(1,4-phenylene) bis (3-aminobenzamide), N, N '-(1,3-phenylene) bis (3-aminobenzamide), N, N'-bis (4-aminophenyl) terephthalamide, N, N'- Bis (3-aminophenyl) terephthalamide, N, N'-bis (4-aminofe Nil) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4'-bis (4-aminophenoxy) diphenyl Sulfone, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'- Bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane, 2 , 2'-bis (4-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (3-amino-4-methylphenyl) propane, 3,5-diamino Benzoic acid, 2,5-diaminobenzoic acid, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) Butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis ( 4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1, 7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy ) Octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3 -Aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1 Alicyclic diamines such as aromatic diamines such as, 12- (3-aminophenoxy) dodecane, bis (4-aminocyclohexyl) methane and bis (4-amino-3-methylcyclohexyl) methane, 1,3- Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diami Aliphatic diamines such as nononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.

The said other diamine compound can also be used 1 type or in mixture of 2 or more types according to the characteristics, such as liquid crystal aligning property, pretilt angle, voltage retention characteristic, and stored charge, when it sets as a liquid crystal aligning film.

&Lt; Tetracarboxylic acid dianhydride &gt;

In the synthesis | combination of the polyamic acid used for this invention, the tetracarboxylic dianhydride made to react with the said diamine component is not specifically limited. The specific example of tetracarboxylic acid which is a raw material for obtaining tetracarboxylic dianhydride is given below.

Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3, 6,7-anthracenetetracarboxylic 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) sulfone, bis ( 3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3, 4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2 , 6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfontetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 1, 3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, oxydi Taltetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic 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, 1, 3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofuranttetracarboxylic acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentylacetic 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 , 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-butanete Lacarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydrinaphthalene-1,2-dicarboxylic acid, bicyclo [2, 2,2] octo-7-ene-2,3,5,6-tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexane-1,2- Dicarboxylic acid, tetracyclo [6,2,1,1,0,2,7] dodeca-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane- 2: 3,5: 6 dicarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid, etc. are mentioned.

Tetracarboxylic dianhydride can be used together with one type or two types or more according to the characteristics, such as liquid crystal alignability, voltage retention characteristic, and stored charge, when it is set as a liquid crystal aligning film.

<Synthesis of polyamic acid>

In obtaining a polyamic acid by reaction of a diamine component and tetracarboxylic dianhydride, a well-known synthetic method can be used. Generally, it is a method of making a diamine component and tetracarboxylic dianhydride react in an organic solvent. Reaction of a diamine component and tetracarboxylic dianhydride is advantageous at the point which advances comparatively easily in an organic solvent, and does not produce a by-product.

As an organic solvent used for the said reaction, if the produced polyamic acid melt | dissolves, it will not specifically limit. Moreover, even if it is an organic solvent which does not melt a polyamic acid, you may mix and use it with the said solvent in the range in which the produced polyamic acid does not precipitate. In addition, since water in an organic solvent inhibits a polymerization reaction and further causes hydrolysis of the produced polyamic acid, it is preferable to use what dried the organic solvent.

Below, the specific example of an organic solvent is given.

N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone , 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethyl Sulfone, hexamethylsulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl iso amyl ketone, methyl isopropyl ketone, methyl 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, propylene glycol 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, amyl acetate Butyl Butyrate, Butyl Ether, Di Sobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, Methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Propionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxypropionic acid butyl, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol. These organic solvents may be used alone or in combination.

When reacting a diamine component and a tetracarboxylic dianhydride component in an organic solvent, the solution which disperse | distributed or dissolved the diamine component in the organic solvent is stirred, and the tetracarboxylic dianhydride component is disperse | distributed or dissolved in an organic solvent as it is. And a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic dianhydride component and a diamine component, and the like. Any of these methods may be used. Moreover, when a diamine component or tetracarboxylic dianhydride component consists of multiple types of compounds, it may be made to react in the state mixed previously, may be made to react individually one by one, and the low molecular weight reacted separately may also be mixed and reacted. It is good also as a high molecular weight body.

The temperature at the time of making a diamine component and the tetracarboxylic dianhydride component react can select arbitrary temperature, For example, it is -20 degreeC-150 degreeC, Preferably it is the range of -5 degreeC-100 degreeC. Moreover, reaction can be performed in arbitrary concentration, for example, it is 1-50 mass%, Preferably it is 5-30 mass%.

The ratio of the total mole number of the tetracarboxylic dianhydride component to the total mole number of the diamine component in the polymerization reaction can be selected according to the molecular weight of the polyamic acid to be obtained. As in the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced. If it shows a preferable range, it is 0.8-1.2.

The method for synthesizing the polyamic acid used in the present invention is not limited to the above method, and similarly to the general method for synthesizing polyamic acid, instead of the tetracarboxylic dianhydride, tetracarboxylic acid or tetracarboxyl having a corresponding structure. The corresponding polyamic acid can also be obtained by making it react by a well-known method using tetracarboxylic-acid derivatives, such as a dihalide.

<Polyimide>

As a method of imidating said polyamic acid and making it a polyimide, the heat | fever imidation which heats the solution of a polyamic acid as it is, and the catalyst imidation which adds a catalyst to the solution of a polyamic acid are mentioned.

In the polyimide used for this invention, the imidation ratio with respect to a polyimide from a polyamic acid does not necessarily need to be 100%.

The temperature at the time of thermally imidating a polyamic acid in a solution is 100 degreeC-400 degreeC, Preferably it is 120 degreeC-250 degreeC, The method of performing while removing the water produced | generated by the imidation reaction out of system is preferable.

Catalyst imidation of a polyamic acid can be performed by adding a basic catalyst and an acid anhydride to the solution of a polyamic acid, and stirring at -20-250 degreeC, Preferably it is 0-180 degreeC. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times, of the amide acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times, of the amide acid group. Pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned as a basic catalyst, Especially, since pyridine has suitable basicity for advancing reaction, it is preferable. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like, and among them, acetic anhydride is preferred because the purification after completion of the reaction is facilitated. The imidation ratio by catalyst imidation can be controlled by adjusting catalyst amount, reaction temperature, and reaction time.

When recovering the produced polyamic acid or polyimide from the reaction solution of polyamic acid or polyimide, the reaction solution may be poured 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 being poured into the poor solvent can be dried by filtration or recovery, normal temperature or heating under normal pressure or reduced pressure. Moreover, the impurity in a polymer can be reduced when the polymer which precipitated and collect | recovered is re-dissolved in an organic solvent, and repeats the operation of reprecipitation recovery 2 to 10 times. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like, and the use of three or more types of poor solvents selected from these is preferable because the efficiency of purification is further increased.

<Liquid crystal aligning agent>

A liquid crystal aligning agent is a coating liquid for forming a liquid crystal aligning film, and is a solution which the resin component for forming a liquid crystal aligning film melt | dissolved in the organic solvent. Here, the said resin component is a resin component containing at least 1 sort (s) of polymer chosen from the group which consists of said polyamic acid and polyimide. In that case, 1 mass%-20 mass% are preferable, content of a resin component becomes like this. More preferably, it is 3 mass%-15 mass%, Especially preferably, it is 3-10 mass%.

In the liquid crystal aligning agent used for this invention, the polyamic acid which all have a side chain A and a side chain B, or the polyimide which imidated this may be sufficient, and the mixture of these polyamic acid and a polyimide may be sufficient as it. Furthermore, another polymer other than that may be mixed. In that case, 0.5 mass%-15 mass% are preferable, and, as for content of this other polymer in a resin component, More preferably, they are 1 mass%-10 mass%. Such other polymers include, for example, polyamic acid or polyimide having no side chain A and side chain B at the same time.

The molecular weight of the polymer of the said resin component is 5,000-1,000,000 in the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method, when the intensity | strength of the coating film obtained thereon, the workability at the time of coating film formation, and the uniformity of a coating film are considered. It is preferable to carry out, More preferably, it is 10,000-150,000.

The organic solvent used for the liquid crystal aligning agent used for this invention will not be specifically limited if it is an organic solvent in which the resin component mentioned above is dissolved. One type of solvent may be sufficient as this organic solvent, and two or more types of mixed solvent may be sufficient as it. If it dares to give an example of an organic solvent, the organic solvent illustrated by the said polyamic-acid synthesis | combination will be mentioned. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N- Dimethyl propanamide is preferable from the viewpoint of the solubility of the resin component.

Moreover, since the solvent as shown below improves the uniformity and smoothness of a coating film, it is preferable to mix and use it with the solvent with high solubility of a resin component. For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol , Ethyl carbitol, ethyl carbitol 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 Ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, di Hexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3 Methyl methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxy Lopionic acid, 3-methoxypropionate, 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy- 2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-e Oxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, 2-ethyl-1-hexanol, etc. are mentioned. These solvent may mix multiple types. When using these solvent, it is preferable that it is 5-80 mass% of the whole solvent contained in a liquid crystal aligning agent, More preferably, it is 20-60 mass%.

As a liquid crystal aligning agent, you may contain the component of that excepting the above. As the example, the compound which improves the film thickness uniformity and surface smoothness at the time of apply | coating a liquid crystal aligning agent, the compound which improves the adhesiveness of a liquid crystal aligning film, and a board | substrate, etc. are mentioned.

As a compound which improves the uniformity and surface smoothness of a film thickness, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products, Inc.), Megapack F171, F173, R-30 (manufactured by Dainippon Ink, Inc.), Fluoride FC430, FC431 (manufactured by Sumitomo 3M, Inc.). ), Asahigard AG710, Saffron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.), etc. are mentioned. When using these surfactant, the use ratio is 0.01-2 mass parts with respect to 100 mass parts of the resin component contained in a liquid crystal aligning agent, More preferably, it is 0.01-1 mass part.

As a specific example of the compound which improves the adhesiveness of a liquid crystal aligning film and a board | substrate, a functional silane containing compound, an epoxy group containing compound, etc. are mentioned. 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- -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3- 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-xylenediamine, 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) a Minopropyl trimethoxysilane etc. are mentioned.

Moreover, in order to further improve rubbing tolerance of the liquid crystal aligning film obtained using the liquid crystal aligning agent of this invention, 2,2'-bis (4-hydroxy-3, 5- dihydroxy methylphenyl) propane, tetra (methoxymethyl) You may add phenol compounds, such as bisphenol. When using these compounds, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of the resin component contained in a liquid crystal aligning agent, More preferably, it is 1-20 mass parts.

As a liquid crystal aligning agent used for this invention, you may add the dielectric and electrically conductive material for the purpose of changing electrical characteristics, such as dielectric constant and electroconductivity of a liquid crystal aligning film, in addition to the above, as long as the effect of this invention is not impaired.

Moreover, also among the above-mentioned liquid crystal aligning agents, the polyamic acid # obtained by making the diamine component containing @diamine A and diamine B, and tetracarboxylic dianhydride react, and the polyimide # obtained by imidating it contains at least 1 sort (s). a liquid crystal aligning agent, a diamine, B is a diamine represented by the formula (2), in addition, the R ⁸ in the formula _{(2) -CH 2 -, -O-} , -COO-, -OCO-, -NHCO- or -NH-, R ¹¹ is -CR ¹⁰ = CH ₂ group, R ¹⁰ is a methyl group which may be substituted with a hydrogen atom or a fluorine atom, the liquid crystal aligning agent is a liquid crystal aligning agent newly provided by the present invention (this invention Also called liquid crystal aligning agent).

The liquid crystal aligning agent of this invention is not only useful as a liquid crystal aligning agent for manufacturing the liquid crystal display element of this invention, but can also be used suitably also for the use of the liquid crystal aligning film manufactured by a rubbing process or a photo-alignment process.

<Liquid crystal aligning film>

After apply | coating and baking on a board | substrate, the liquid crystal aligning agent of this invention can be used as an orientation process by a rubbing process, light irradiation, etc., or a vertical alignment use etc. can be used as a liquid crystal aligning film without an orientation process. Under the present circumstances, it will not specifically limit, if it is a board | substrate with high transparency as a board | substrate to be used, Plastic substrates, such as a glass substrate, an acryl substrate, and a polycarbonate board | substrate, etc. can be used. Moreover, it is preferable to use the board | substrate with which the ITO electrode etc. for liquid crystal drive were formed from a viewpoint of the simplification of a process. In the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as it is a substrate on one side, and in this case, a material that reflects light such as aluminum can be used.

Although the coating method of a liquid crystal aligning agent is not specifically limited, Industrially, the method of performing by screen printing, offset printing, flexographic printing, an inkjet, etc. is common. Other coating methods include dips, roll coaters, slit coaters, spinners, and the like, which may be used depending on the purpose.

Baking after apply | coating a liquid crystal aligning agent can be performed at arbitrary temperature of 100-350 degreeC, Preferably it is 120 degreeC-300 degreeC, More preferably, it is 150 degreeC-250 degreeC. This firing can be performed in a hot plate, a hot air circulation furnace, an infrared furnace, or the like.

Although the thickness of the film after baking is not specifically limited, Preferably it is 5-300 nm, More preferably, it is 10-100 nm.

When making a liquid crystal align horizontally or diagonally, the coating film after baking is processed by rubbing or polarized ultraviolet irradiation.

<Liquid crystal display element>

The liquid crystal display element of this invention is at least 1 sort (s) chosen from the group which consists of a side chain (A) which orientates a liquid crystal perpendicularly, and the polyamic acid which has photoreactive side chain (B), and the polyimide obtained by imidating it. Two board | substrates which have a liquid crystal aligning layer formed from the liquid crystal aligning agent containing, and

A liquid crystal cell in which a liquid crystal layer is sandwiched between the two substrates arranged such that the liquid crystal alignment layers face each other;

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

Although it will not specifically limit, if it is a board | substrate with high transparency as a board | substrate used for the liquid crystal display element of this invention, Usually, it is a board | substrate with a transparent electrode for driving a liquid crystal on a board | substrate. As a specific example, the thing similar to the board | substrate described by the said <liquid crystal aligning film> can be mentioned. In the liquid crystal display element of this invention, you may use the board | substrate with which the conventional electrode pattern and protrusion pattern were formed. However, the liquid crystal display of the present invention is operable even in a structure in which a line / slit electrode pattern of 1 to 10 µm is formed on one side substrate, and a slit pattern and protrusion pattern are not formed on the opposing substrate, and the liquid crystal of this structure By the display, the process at the time of manufacture can be simplified and high transmittance | permeability 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, but in a reflective liquid crystal display device, it is possible to use an opaque substrate such as a silicon wafer as long as only one substrate. At this time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.

The said liquid crystal aligning layer is a resin film for orienting a liquid crystal perpendicularly to a board | substrate, and is formed using the said liquid crystal aligning agent. The process of forming a liquid crystal aligning layer on a board | substrate can apply the coating method described by said <liquid crystal aligning film>, and the baking method after apply | coating.

As a method of clamping a liquid crystal layer between two board | substrates, the well-known method of manufacturing a liquid crystal cell is mentioned. As an example of liquid crystal cell manufacture, a pair of board | substrates with which the liquid crystal aligning layer was formed is prepared, a spacer is spread | dispersed on the liquid crystal aligning layer of a single side board | substrate, and the other one side board | substrate is bonded together so that a liquid crystal aligning layer surface may become inside ( And a method of injecting and sealing the liquid crystal under reduced pressure, or dropping the liquid crystal onto the surface of the liquid crystal alignment layer in which the spacer is dispersed, and then bonding the substrate to perform sealing. The thickness of the spacer at this time becomes like this. Preferably it is 1-30 micrometers, More preferably, it is 2-10 micrometers.

Although the liquid crystal used for the liquid crystal display element of this invention can speed up the response speed of a liquid crystal even if it is a liquid crystal which does not add a photopolymerizable compound, you may use the liquid crystal which added the photopolymerizable compound.

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 the ultraviolet ray is maintained while maintaining the voltage. The method of investigation can be mentioned. Here, a function generator can be used as a means for applying a voltage to a liquid crystal layer, and existing apparatuses, such as a high pressure mercury lamp, can be used as a means for irradiating an ultraviolet-ray. As a voltage added between electrodes, it is 5-30 Vp-p, Preferably, it is 5-20 Vp-p. The wavelength of ultraviolet rays becomes like this. Preferably it is 250-400 nm, More preferably, it is 300-400 nm. The irradiation amount of ultraviolet ray is 1-60 J / cm <2>, Preferably it is 40 J / cm <2> or less, The one with little ultraviolet irradiation amount can suppress the reliability fall which consists of destruction of the member which comprises a liquid crystal display, Moreover, since manufacturing efficiency becomes high by reducing ultraviolet irradiation time, it is preferable.

By the above process, the photoreactive group of the said side chain B reacts, and the direction which a liquid crystal molecule tilts is memorized, and the response speed of a liquid crystal display element becomes quick.

Example

Hereinafter, although an Example of this invention demonstrates more concretely, it is not limited to these.

[Synthesis of polyamic acid]

The symbol of compounds, such as tetracarboxylic dianhydride used below, was shown.

(Tetracarboxylic dianhydride)

C-1 ： 1,2,3,4-cyclobutanetetracarboxylic 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] benzene

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

[Chemical Formula 45]

(Organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cellosolve

In addition, DA-2 and DA-3 which were obtained like the reference synthesis examples described below were used among the said diamine compounds.

(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 ° C, 10 g of 2,4-dinitrofluorobenzene dissolved in 20 mL of toluene was added dropwise, and the mixture was stirred at 100 ° C for 6 hours. After completion of the reaction, 50 mL of pure water was added and stirred, followed by addition of ethyl acetate to extract the organic layer. Anhydrous magnesium sulfate was added to the organic layer, dehydrated to dryness, and after filtration, the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate / hexane = 7/3 (volume ratio, which is the same below), and 13.2 g of 2,4-dinitro-1- (4-vinyloxy) butoxybenzene Was obtained (yield 90%).

To a 500 mL three-necked flask was added 2.12 g of the dinitro compound, 20 mL of toluene, and 80 mL of a 10% by mass aqueous ammonium chloride solution. The inside of the system was heated to 70 ° C, 4.2 g of iron (electrolytic iron) was added and stirred at 70 ° C for 2.5 hours. 30 mL of 5 mass% sodium hydrogencarbonate aqueous solution was added after completion | finish of reaction, and the precipitate was filtered and wash | cleaned with toluene. The filtrate was extracted with ethyl acetate, anhydrous magnesium sulfate was added to the organic layer, dehydrated to dryness, and after filtration, the solvent was distilled off 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 target substance (yield 38%). The result measured by <^1> H-NMR of the target object is shown below. From this result, the obtained solid confirmed that it was a target diamino compound, ie, 4- (4- (vinyloxy) butoxy) benzene-1,3-diamine.

Reference Synthesis Example 2 Synthesis of DA-3

To a 300 mL three neck flask, 5.11 g of 10-undecen-1-ol, 2.37 g of pyridine, and 100 mL of tetrahydrofuran were added. System inside was made into 0 degreeC by ice cooling, 8.3g of 3, 5- dinitro benzoyl chlorides were added, and it stirred at room temperature for 2 hours. After completion of the reaction, 20 mL of pure water was added and stirred, followed by addition of ethyl acetate to extract the organic layer. Anhydrous magnesium sulfate was added to the organic layer, dehydrated to dryness, and after filtration, the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate / hexane = 7/3 to give 6.9 g of undec-10-enyl-3,5-dinitrobenzoate (yield 63%).

To the 300 mL three-neck flask, 6.55 g of the dinitro compound, 50 mL of tetrahydrofuran, and 50 mL of pure water were added, the system was stirred, 17.06 g of tin chloride was added, and the mixture was stirred at 60 ° C for 2 hours. 400 ml of 5 mass% sodium hydrogencarbonate was added after completion | finish of reaction, and pH was set to 7-8. Thereafter, 160 ml of ethyl acetate was added to remove the white precipitate by filtration, and the organic layer was extracted with ethyl acetate. The organic layer was dehydrated by adding anhydrous magnesium sulfate, filtered and then solvent distilled off 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 target substance (yield 82%). The result measured by <^1> H-NMR of the target object is shown below. From this result, the obtained solid confirmed that it was a target diamino compound, ie, undece-10-enyl-3,5-diaminobenzoate.

<Measurement of Molecular Weight of Polyamic Acid and Polyimide>

The molecular weight of the polyamic acid in the following synthesis examples uses a room temperature gel permeation chromatography (GPC) device (GPC-101) manufactured by Showa Denko Co., Ltd. and a column (KD-803, KD-805) manufactured by Shodex Corporation. Was measured as follows.

Column temperature: 50 ° C

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

Flow rate: 1.0 ml / min

Standard sample for calibration curve preparation: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) by Tosoh Corporation, and polyethylene glycol (molecular weight about 12,000, 4,000, 1,000) by Polymer Lab.

&Lt; Synthesis Example 1 &

As tetracarboxylic dianhydride, NMP 7.69 using 0.78 g (3.96 mmol) of C-1, 0.85 g (3.20 mmol) of DA1 and 0.30 g (0.80 mmol) of DA-7 as a diamine component It reacted at room temperature for 16 hours in g, and obtained the solution whose concentration of polyamic acid (PAA-1) is 20 mass%. 8.0 g of this polyamic acid solution (PAA-1) was diluted using 12.0 g of NMP and 5.3 g of BCS, and 6 mass% of polyamic acid (PAA-1), 74 mass% of NMP, and 20 mass% of BCS. A liquid crystal aligning agent (A1) was obtained. Moreover, the number average molecular weight of PAA-1 was 20,500, and the weight average molecular weight was 63,000.

&Lt; Synthesis Example 2 &

As tetracarboxylic dianhydride, NMP 7.51 using 0.78 g (3.96 mmol) of C-1, 0.95 g (3.60 mmol) of DA1 and 0.15 g (0.40 mmol) of DA-7 as a diamine component It reacted at room temperature for 16 hours in g, and obtained the solution whose concentration of polyamic acid (PAA-2) is 20 mass%. 8.0 g of this polyamic acid solution (PAA-2) was diluted using 12.2 g of NMP and 5.3 g of BCS, and 6 mass% of polyamic acid (PAA-2), 74 mass% of NMP, and 20 mass% of BCS. A liquid crystal aligning agent (A2) was obtained. In addition, the number average molecular weight of PAA-2 was 25,200, and the weight average molecular weight was 86,400.

&Lt; Synthesis Example 3 &

As tetracarboxylic dianhydride, 0.49 g (2.48 mmol) of C-1, 0.59 g (2.25 mmol) of DA1 and 0.095 g (0.25 mmol) of DA-8 were used as a diamine component, and NMP 4.70 It reacted at room temperature for 16 hours in g, and obtained the solution whose concentration of polyamic acid (PAA-3) is 20 mass%. 4.7 g of this polyamic acid solution (PAA-3) was diluted using 7.8 g of NMP and 3.1 g of BCS, so that 6% by mass of polyamic acid (PAA-3), 74% by mass of NMP, and 20% by mass of BCS. Phosphorus liquid crystal aligning agent (A3) was obtained. Moreover, the number average molecular weight of PAA-3 was 20,400, and the weight average molecular weight was 57,800.

&Lt; Synthesis Example 4 &

As tetracarboxylic dianhydride, 0.49 g (2.48 mmol) of C-1, 0.59 g (2.25 mmol) of DA1, and 0.11 g (0.25 mmol) of DA-9 were used, and NMP 4.75 It reacted at room temperature for 16 hours in g, and obtained the solution whose concentration of polyamic acid (PAA-4) is 20 mass%. 4.7 g of this polyamic acid solution (PAA-4) was diluted using 7.9 g of NMP and 3.2 g of BCS, so that 6% by mass of polyamic acid (PAA-4), 74% by mass of NMP, and 20% by mass of BCS. A liquid crystal aligning agent (A4) was obtained. Moreover, the number average molecular weight of PAA-4 was 19,100, and the weight average molecular weight was 55,000.

&Lt; Synthesis Example 5 &

As tetracarboxylic dianhydride, 0.47 g (2.40 mmol) of C-1, 0.39 g (1.75 mmol) of DA2 and 0.28 g (0.75 mmol) of DA-7 were used as the diamine component, and NMP 4.57 It reacted at room temperature in g for 16 hours, and obtained the solution whose concentration of polyamic acid (PAA-5) is 20 mass%. 4.5 g of this polyamic acid solution (PAA-5) was diluted using 7.6 g of NMP and 3.0 g of BCS, and 6 mass% of polyamic acid (PAA-5), 74 mass% of NMP, and 20 mass% of BCS. A liquid crystal aligning agent (A5) was obtained. Moreover, the number average molecular weight of PAA-5 was 16,700, and the weight average molecular weight was 52,900.

&Lt; Synthesis Example 6 &

As tetracarboxylic dianhydride, 0.47 g (2.40 mmol) of C-1, 0.44 g (2.00 mmol) of DA2, and 0.19 g (0.50 mmol) of DA-7 were used as a diamine component, and NMP 4.41 It reacted at room temperature in g for 16 hours, and obtained the solution whose concentration of polyamic acid (PAA-6) is 20 mass%. 4.4 g of this polyamic acid solution (PAA-6) was diluted using 7.3 g of NMP and 2.9 g of BCS, and 6 mass% of polyamic acid (PAA-6), 74 mass% of NMP, and 20 mass% of BCS. Phosphorus liquid crystal aligning agent (A6) was obtained. Moreover, the number average molecular weight of PAA-6 was 24,400, and the weight average molecular weight was 93,500.

&Lt; Synthesis Example 7 &

As tetracarboxylic dianhydride, 0.49 g (2.48 mmol) of C-1, 0.53 g (1.75 mmol) of DA3 and 0.28 g (0.75 mmol) of DA-7 were used, and NMP 5.20 It reacted at room temperature in g for 16 hours, and obtained the solution whose concentration of polyamic acid (PAA-7) is 20 mass%. 5.4 g of this polyamic acid solution (PAA-7) were diluted using 9.0 g of NMP and 3.6 g of BCS, and 6 mass% of polyamic acid (PAA-7), 74 mass% of NMP, and 20 mass% of BCS. Phosphorus liquid crystal aligning agent (A7) was obtained. In addition, the number average molecular weight of PAA-7 was 20,900, and the weight average molecular weight was 78,900.

&Lt; Synthesis Example 8 &

As tetracarboxylic dianhydride, 0.49 g (2.48 mmol) of C-1, 0.61 g (2.00 mmol) of DA3, and 0.19 g (0.50 mmol) of DA-7 were used, and NMP 5.13 It reacted at room temperature in g for 16 hours, and obtained the solution whose concentration of polyamic acid (PAA-8) is 20 mass%. 5.3 g of this polyamic acid solution (PAA-8) was diluted using 8.8 g of NMP and 3.5 g of BCS, and 6 mass% of polyamic acid (PAA-8), 74 mass% of NMP, and 20 mass% of BCS. Phosphorus liquid crystal aligning agent (A8) was obtained. In addition, the number average molecular weight of PAA-8 was 18,800, and the weight average molecular weight was 67,300.

<Synthesis example 9>

As tetracarboxylic dianhydride, 0.49 g (2.48 mmol) of C-1, 0.46 g (2.00 mmol) of DA4, and 0.19 g (0.50 mmol) of DA-7 were used, and NMP 4.55 It reacted at room temperature for 16 hours in g, and obtained the solution whose concentration of polyamic acid (PAA-9) is 20 mass%. 4.5 g of this polyamic acid solution (PAA-9) was diluted using 6.5 g of NMP and 3.0 g of BCS, and 6 mass% of polyamic acid (PAA-9), 74 mass% of NMP, and 20 mass% of BCS. A liquid crystal aligning agent (A9) was obtained. Moreover, the number average molecular weight of PAA-9 was 17,600, and the weight average molecular weight was 47,100.

&Lt; Synthesis Example 10 &

As tetracarboxylic dianhydride, 0.49 g (2.48 mmol) of C-1, 0.52 g (2.25 mmol) of DA4 and 0.09 g (0.25 mmol) of DA-7 were used as the diamine component, and NMP 4.41 It reacted at room temperature for 16 hours in g, and obtained the solution whose concentration of polyamic acid (PAA-10) is 20 mass%. 4.3 g of this polyamic acid solution (PAA-10) was diluted using 6.1 g of NMP and 2.8 g of BCS, so that 6% by mass of polyamic acid (PAA-10), 74% by mass of NMP, and 20% by mass of BCS. A liquid crystal aligning agent (A10) was obtained. Moreover, the number average molecular weight of PAA-10 was 19,500, and the weight average molecular weight was 55,500.

&Lt; Synthesis Example 11 &

As tetracarboxylic dianhydride, 0.49 g (2.48 mmol) of C-1, 0.82 g (2.00 mmol) of DA5 and 0.19 g (0.50 mmol) of DA-7 were used as the diamine component. It reacted at room temperature for 16 hours in g, and obtained the solution whose concentration of polyamic acid (PAA-11) is 20 mass%. 5.0 g of this polyamic acid solution (PAA-11) were diluted using 6.3 g of NMP and 3.3 g of BCS, and 6 mass% of polyamic acid (PAA-11), 74 mass% of NMP, and 20 mass% of BCS. A liquid crystal aligning agent (A11) was obtained. Moreover, the number average molecular weight of PAA-11 was 17,000, and the weight average molecular weight was 56,000.

&Lt; Synthesis Example 12 &

As tetracarboxylic dianhydride, 0.49 g (2.48 mmol) of C-1, 0.93 g (2.25 mmol) of DA5, and 0.19 g (0.25 mmol) of DA-7 were used, and NMP 6.03 It reacted at room temperature in g for 16 hours, and obtained the solution whose concentration of polyamic acid (PAA-12) is 20 mass%. 5.0 g of this polyamic acid solution (PAA-12) was diluted using 6.3 g of NMP and 3.3 g of BCS, so that 6% by mass of polyamic acid (PAA-12), 74% by mass of NMP, and 20% by mass of BCS. A liquid crystal aligning agent (A12) was obtained. Moreover, the number average molecular weight of PAA-12 was 19,500, and the weight average molecular weight was 59,000.

&Lt; Synthesis Example 13 &

As tetracarboxylic dianhydride, 0.49 g (2.48 mmol) of C-1, 0.64 g (2.00 mmol) of DA-10 and 0.19 g (0.50 mmol) of DA-7 were used as a diamine component, It reacted for 16 hours at room temperature in NMP 5.26g, and obtained the solution whose concentration of polyamic acid (PAA-14) is 20 mass%. 5.0 g of this polyamic acid solution (PAA-14) were diluted using 6.3 g of NMP and 3.3 g of BCS, and 6 mass% of polyamic acid (PAA-14), 74 mass% of NMP, and 20 mass% of BCS. Phosphorus liquid crystal aligning agent (A13) was obtained. Moreover, the number average molecular weight of PAA-14 was 17,500, and the weight average molecular weight was 57,000.

&Lt; Synthesis Example 14 &

As tetracarboxylic dianhydride, 0.49 g (2.48 mmol) of C-1, 0.72 g (2.25 mmol) of DA-10 and 0.09 g (0.25 mmol) of DA-7 were used as a diamine component, It reacted at room temperature for 16 hours in NMP5.20g, and obtained the solution whose concentration of polyamic acid (PAA-15) is 20 mass%. 5.0 g of this polyamic acid solution (PAA-15) was diluted using 6.3 g of NMP and 3.3 g of BCS, and 6 mass% of polyamic acid (PAA-15), 74 mass% of NMP, and 20 mass% of BCS. A liquid crystal aligning agent (A14) was obtained. Moreover, the number average molecular weight of PAA-15 was 18,500, and the weight average molecular weight was 59,000.

<Comparative Synthesis Example 1>

As tetracarboxylic dianhydride, 1.30 g (6.65 mmol) of C-1, 0.68 g (6.30 mmol) of DA-6 and 0.26 g (0.7 mmol) of DA-7 were used as the diamine component. It reacted at room temperature for 16 hours in 12.74 g of NMP, and obtained the solution whose concentration of polyamic acid (PAA-13) is 20 mass%. 10.0 g of this polyamic acid solution (PAA-13) was diluted using 16.7 g of NMP and 6.7 g of BCS, and 6 mass% of polyamic acid (PAA-13), 74 mass% of NMP, and 20 mass% of BCS. A liquid crystal aligning agent (A15) was obtained. Moreover, the number average molecular weight of PAA-13 was 18,700, and the weight average molecular weight was 58,000.

&Lt; Example 1 &gt;

The liquid crystal aligning agent [A1] obtained by the synthesis example 1 was spin-coated to the ITO surface of the ITO electrode substrate in which the ITO electrode pattern whose pixel size is 100 x 300 microns and whose line / space is 5 microns, respectively is formed. After drying for 90 second on the 80 degreeC hotplate, baking was performed for 60 minutes in the 160 degreeC hot air circulation type oven, and the liquid crystal aligning film of 100-nm-thick film was formed.

Moreover, after spin-coating the liquid crystal aligning agent [A1] obtained by the synthesis example 1 to the ITO surface in which the electrode pattern is not formed, and drying for 90 second on an 80 degreeC hotplate, it is 60 in the hot air circulation type oven of 160 degreeC. Firing was performed for a minute to form a liquid crystal alignment film having a film thickness of 100 nm. These two board | substrates were prepared, after spread | dispersing a 6 micrometers bead spacer on the liquid crystal aligning film surface of one board | substrate, the sealing compound was printed from on. After attaching the other board | substrate with the liquid crystal aligning film surface inside, the sealing compound was hardened and the empty cell was produced. Liquid crystal MLC-6608 (Merck & Co., Ltd. brand name) was injected into this empty cell by the pressure reduction injection method, and the liquid crystal cell was produced.

The response speed characteristic of these liquid crystal cells was measured by the method mentioned later. Then, UV (ultraviolet ray) was irradiated 20J from the outer side of this liquid crystal cell in the state which applied the voltage of 20 Vp-p to this liquid crystal cell. Then, the response speed characteristic was measured again and the response speed in UV irradiation back and front was compared. The results are shown in Table 2.

<Examples 2-14> and <Comparative Example 1>

As shown in Table 2, a liquid crystal aligning agent [A1] is changed into the liquid crystal aligning agent [A2] obtained from the synthesis examples 2-14, and the liquid crystal aligning agent [A15] obtained by the comparative synthesis example 1, respectively. Except what was done, the liquid crystal cell was produced like Example 1, and the response speed was measured. The results are shown in Table 2.

Response speed characteristic

The oscilloscope introduced the time change of the brightness | luminance of a liquid crystal panel when the square wave of voltage +/- 4V and the frequency of 1 Hz was applied to the liquid crystal cell to which no voltage was applied. When the voltage is not applied, a luminance of 0% and a voltage of ± 4 V are applied, and the value of saturated luminance is set to 100%, and the time at which the luminance changes from 10% to 90% is used as the response speed of the rise. It was.

As can be seen from Table 2, in the liquid crystal cell of the example, the response speed after UV irradiation was improved. On the other hand, in the comparative example, the change of the response speed was not seen before and after UV irradiation. In Example 1, 2, Example 5, 6, Example 7, 8, Example 9, 10, and Examples 11, 12, the less the amount of introduction of the tilt expression side chain was, the greater the improvement in response speed after UV irradiation. . Moreover, in Example 2, 3, 4, even if the introduction amount of the tilt expression side chain was the same, when the side chain with low vertical alignment capability was used, the improvement degree of the response speed after UV irradiation was large.

Moreover, also in Examples 13 and 14 similarly to the above, the thing with little introduction amount of the tilt expression side chain had the big improvement of the response speed after UV irradiation. In Examples 1 and 13 and Examples 2 and 14, the amount of introduction of the tilt expression side chain was the same, and when DA-10 with long alkyl spacers was used even when the photoreactive group was the same, compared with the case where DA-1 was used. , The improvement degree of the response speed after UV irradiation was large.

Industrial availability

The liquid crystal display element of this invention can be used as a screen of a liquid crystal television or a screen of various information display apparatuses.

Moreover, the liquid crystal aligning agent of this invention can be used for manufacturing the liquid crystal display element of the vertical alignment system manufactured by irradiating an ultraviolet-ray, applying a voltage to a liquid crystal molecule, and is manufactured without including such a process. It can also be used for a liquid crystal display element.

In addition, the JP Patent application 2010-043372, the claim, and all the content of the abstract for which it applied on February 26, 2010 are referred here, and it takes in as an indication of the specification of this invention.

Claims (13)

Two liquid crystal aligning agents containing at least 1 sort (s) chosen from the group which consists of a polyamic acid which has a side chain (A) which orientates a liquid crystal perpendicularly, and a photoreactive side chain (B), and the polyimide obtained by imidating it Apply on the substrate to form a liquid crystal alignment layer,
Two board | substrates are arrange | positioned so that the said liquid crystal aligning layer may oppose,
The liquid crystal layer is sandwiched between the two substrates,
Ultraviolet rays are irradiated while applying a voltage to a liquid crystal layer, The manufacturing method of the liquid crystal display element of the vertical alignment system characterized by the above-mentioned. The method of claim 1,
The manufacturing method of the liquid crystal display element of the vertical alignment system whose said liquid crystal aligning agent is a liquid crystal aligning agent containing at least 1 sort (s) of the following polyamic acid and the polyimide obtained by imidating it.
The polyamic acid obtained by making the diamine component and the tetracarboxylic dianhydride containing the diamine which has a side chain (A) which orientates a liquid crystal perpendicularly, and the diamine which has a photoreactive side chain (B) react. 3. The method according to claim 1 or 2,
The side chain (A) which orientates the said liquid crystal vertically is a manufacturing method of the liquid crystal display element of a vertical alignment system represented by a following formula (a).
[Formula 1]

(1, m, and n in formula (a) 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, and R ⁵ represents a hydrogen atom; Or a linear alkyl group or a fluorine-containing alkyl group having 5 to 18 carbon atoms, or an aromatic ring group, an aliphatic ring group, a heterocyclic group or a large cyclic group consisting of them.) The method according to any one of claims 1 to 3,
The manufacturing method of the liquid crystal display element of the vertical alignment system in which the said photoreactive side chain (B) is represented by following formula (b).
(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 having 1 to 20 carbon atoms (alkylene may be unsubstituted or substituted with a fluorine atom), and any of alkylene may be used. -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, 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, R ⁹ represents a vinylphenyl group, -CR ¹⁰ = CH ₂ group, a carbon ring group, a heterocyclic group, or a group represented by the following formula, and R ¹⁰ is a hydrogen atom Or a methyl group which may be substituted with a fluorine atom.)
(3)

6. The method according to any one of claims 2 to 5,
Side chain (A) which orientates the liquid crystal vertically is represented by the above formula (a), wherein l, m and n are all 1, R ² is phenylene and R ³ is phenylene or cyclohexylene , R ⁴ is cyclohexylene, R ⁵ is an alkyl group having 2 to 24 carbon atoms, or when l, m and n are all 0, R ⁵ is an alkyl group having 12 to 22 carbon atoms; The manufacturing method of the liquid crystal display element of this. 6. The method according to any one of claims 3 to 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 to any group of one of, The manufacturing method of the liquid crystal display element of a vertical alignment system.
[Chemical Formula 4]

It is formed from the liquid crystal aligning agent containing the side chain (A) which orientates a liquid crystal perpendicularly | vertically, and the polyamic acid which has photoreactive side chain (B), and at least 1 sort (s) chosen from the group which consists of a polyimide obtained by imidating it. Two board | substrates which have a liquid crystal aligning layer,
A liquid crystal cell in which a liquid crystal layer is sandwiched between the two substrates arranged such that the liquid crystal alignment layers face each other;
The liquid crystal display element of the vertical alignment system which has a means which irradiates an ultraviolet-ray, applying a voltage to a liquid crystal layer. The liquid crystal aligning agent containing at least 1 sort (s) chosen from the group which consists of a polyamic acid which has a side chain (A) which orientates a liquid crystal perpendicularly, and a photoreactive side chain (B), and the polyimide obtained by imidating it. Polyamic acid obtained by reacting the diamine component containing the diamine which has a side chain (A) which orientates a liquid crystal perpendicularly, and the diamine which has a photoreactive side chain (B), and tetracarboxylic dianhydride and imidated it It is a liquid crystal aligning agent containing at least 1 sort (s) chosen from the group which consists of polyimide, The diamine which has the said photoreactive side chain (B) is represented by following formula (2), The liquid crystal aligning agent characterized by the above-mentioned.
[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 having 1 to 20 carbon atoms (alkylene may be unsubstituted or substituted with a fluorine atom), and any of alkylene may be used. -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, or a heterocyclic group.
R ⁸ is —CH ₂ —, —O—, —COO—, —OCO—, —NHCO—, —NH—, —N (CH ₃ ) —, —CON (CH ₃ ) —, or —N (CH ₃₎ Represents CO-, and R ¹¹ represents a vinylphenyl group, -CH = CH ₂ , -C (CH ₃ ) = CH ₂ , or any of the following groups.)
[Chemical Formula 6]

10. The method according to any one of claims 7 to 9,
The liquid crystal aligning agent in which the diamine which has a side chain (A) which orientates the said liquid crystal is represented by following formula (1).
(7)

(1, m, and n in formula (a) 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, and R ⁵ represents a hydrogen atom; , A linear alkyl group having 5 to 18 carbon atoms or a fluorine-containing alkyl group, or an aromatic ring group, an aliphatic ring group, a heterocyclic group or a large cyclic group consisting of them. 11. The method of claim 10,
The diamine which has a side chain (A) which orientates the said liquid crystal perpendicularly is represented by said Formula (1), l, m, and n are all 1, R <^2> is phenylene and R <^3> is phenylene or cyclo Diamine wherein R ⁵ is an alkyl group having 12 to 22 carbon atoms when hexylene, R ⁴ is cyclohexylene, R ⁵ is an alkyl group having 2 to 24 carbon atoms, or when l, m and n are all 0; Phosphorus liquid crystal aligning agent. The method according to any one of claims 8 to 11,
The liquid crystal aligning agent whose diamine which has a side chain (A) which orientates the said liquid crystal vertically is diamine which has a structure of any of the following.
[Chemical Formula 8]

The liquid crystal aligning film obtained using the liquid crystal aligning agent in any one of Claims 8-12.