KR102546376B1 - Liquid crystal display element - Google Patents

Abstract

A liquid crystal display element that has high liquid crystal vertical orientation, good optical properties, high adhesion between a liquid crystal layer and a liquid crystal alignment film, and can maintain properties for a long time even in a high temperature, high humidity or light irradiation environment. A liquid crystal alignment film having a liquid crystal layer cured by irradiating ultraviolet rays with respect to a liquid crystal composition containing a liquid crystal and a polymerizable compound disposed between a pair of substrates provided with electrodes, and at least one of the substrates orienting the liquid crystal vertically. As a liquid crystal display element provided with, the said liquid crystal aligning film is obtained from the liquid-crystal aligning agent containing the following (A) component and (B) component. (A) Component: At least 1 sort(s) of compound chosen from the group which consists of a compound of formula [1-1] and a compound of formula [1-2]. Component (B): A polymer having at least one structure selected from the group consisting of formula [2-1] and formula [2-2].

Description

Liquid crystal display element {LIQUID CRYSTAL DISPLAY ELEMENT}

[0001] The present invention relates to a transmission and scattering type liquid crystal display element which is in a transparent state when no voltage is applied and which is in a scattering state when a voltage is applied.

As a liquid crystal display element using a liquid crystal material, the TN mode is put into practical use. In this mode, switching of light is performed by utilizing the polarization characteristic of liquid crystal, and when used as a liquid crystal display element, it is necessary to use a polarizing plate. However, the use efficiency of light is lowered by using a polarizing plate.

As a liquid crystal display element with high light utilization efficiency without using a polarizing plate, there is a liquid crystal display element that switches between a transmission state (also referred to as a transparent state) and a scattering state of liquid crystal. In general, a polymer dispersed liquid crystal (PDLC) It is known that a polymer network type liquid crystal (also referred to as PNLC) or a polymer network type liquid crystal (also referred to as PNLC) is used.

In a liquid crystal display element using these, a liquid crystal composition containing a polymerizable compound polymerized by ultraviolet rays is placed between a pair of substrates provided with electrodes, and the liquid crystal composition is cured by irradiation with ultraviolet rays to form a liquid crystal layer. , that is, a cured product composite (for example, a polymer network) of a liquid crystal and a polymerizable compound is formed. In this liquid crystal display element, the transmission state and the scattering state of the liquid crystal are controlled by application of a voltage.

In a conventional liquid crystal display element using PDLC or PNLC, liquid crystal molecules are oriented in a random direction when no voltage is applied, resulting in a cloudy (scattering) state, and when voltage is applied, the liquid crystals are aligned in the direction of the electric field and transmit light. It is a liquid crystal display element (also referred to as a normal type element) that becomes a transmissive state. However, since a voltage must always be applied to a normal type element to obtain a transmissive state, power consumption increases when used in applications that are often used in a transparent state, such as window glass. .

On the other hand, a liquid crystal display element (also referred to as a reverse element) using a PDLC that enters a transmission state when no voltage is applied and becomes a scattering state when voltage is applied has been reported (see Patent Documents 1 and 2).

Japanese Patent No. 2885116 Japanese Patent No. 4132424

The polymerizable compound in the liquid crystal composition of the reverse type element forms a polymer network and has a role of obtaining desired optical properties and a role of a curing agent that enhances the adhesion between the liquid crystal layer and the liquid crystal alignment film. In order to improve the adhesion with the liquid crystal alignment film, it is necessary to make the polymer network more dense, but if the polymer network is made dense, the vertical alignment of the liquid crystal is inhibited, and the optical properties of the reverse type element, that is, transparency and voltage when no voltage is applied There is a problem of deteriorating the scattering characteristics upon application. Therefore, the liquid crystal composition used for the reverse type element needs to have high vertical orientation of the liquid crystal at the time of forming the liquid crystal layer.

Moreover, since the liquid crystal aligning film used for a reverse type element is a film|membrane with high hydrophobicity in order to orientate a liquid crystal vertically, the adhesiveness of a liquid crystal layer and a liquid crystal aligning film becomes low. Therefore, a large amount of a polymerizable compound that serves as a curing agent must be introduced into the liquid crystal composition used for the reverse type element. However, when a large amount of the polymerizable compound is introduced, the homeotropic alignment of the liquid crystal is inhibited, and there is a problem in that the transparency when no voltage is applied and the scattering characteristics when voltage is applied are greatly reduced.

Further, when a reverse type element is attached to a window glass of a vehicle or a building, the element may be used for a long time in a high-temperature, high-humidity environment or an environment exposed to light irradiation. Therefore, also in a severe environment, it is necessary that the vertical alignment property of a liquid crystal does not fall and that the adhesiveness of a liquid crystal layer and a liquid crystal aligning film is high.

The present invention has high vertical alignment of liquid crystal, good optical properties, that is, good transparency when no voltage is applied and scattering characteristics when voltage is applied, and also high adhesion between the liquid crystal layer and the liquid crystal alignment film, and furthermore, long time, high temperature, high humidity An object of the present invention is to provide a liquid crystal display element capable of maintaining these characteristics even under an environment exposed to light irradiation.

As a result of earnestly advancing research in order to achieve the above object, the present inventors have completed the present invention having the following gist.

1. A liquid crystal composition containing a liquid crystal and a polymerizable compound disposed between a pair of substrates equipped with electrodes, having a liquid crystal layer cured by irradiation with ultraviolet rays, and at least one of the substrates vertically aligning the liquid crystal As a liquid crystal display element provided with a liquid crystal aligning film, the said liquid crystal aligning film is obtained from the liquid-crystal aligning agent containing the following component, The liquid crystal display element characterized by the above-mentioned.

Component (A): At least one compound selected from the group consisting of a compound of the following formula [1-1] and a compound of the following formula [1-2].

Component (B): A polymer having at least one structure selected from the group consisting of the following formula [2-1] and formula [2-2].

[Formula 1]

(T ¹ represents at least one selected from the group consisting of an alkylene group having 1 to 20 carbon atoms and an organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring, and any of the above-mentioned alkylene groups having 1 to 20 carbon atoms -CH ₂ - is -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-, -CON(CH ₃ )-, -S- or -SO ₂ - T ² is a single bond, -O-, -NH-, -N(CH ₃ )-, -CH ₂ O-, -OCH ₂ -, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO-, and -OCO- ^. At least one selected from the group consisting of structures is shown.)

[Formula 2]

(T ^A represents a hydrogen atom or a benzene ring. T ^B represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. T ^C represents an alkyl group having 1 to 18 carbon atoms, a carbon number At least one selected from the group consisting of 1 to 18 fluorine-containing alkyl groups, 1 to 18 carbon atoms alkoxy groups, and 1 to 18 carbon atoms fluorine-containing alkoxy groups.)

[Formula 3]

(S ¹ represents at least one structure selected from the group consisting of structures of the following formula [1-a] to formula [1-l]. S ² represents a single bond or an alkylene group having 1 to 24 carbon atoms; Optional -CH ₂ - of the alkylene group is -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-, -CON(CH ₃ )-, -S - or -SO ₂ - S ³ is at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent divalent group having 17 to 51 carbon atoms having a steroid skeleton. Represents an organic group, and any hydrogen atom on the cyclic group is an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxy group of 1 to 3 carbon atoms, or a fluorine atom. S ⁴ represents at least one bonding group selected from the group consisting ^of a single bond, -O-, -OCH ₂ -, -CH ₂ O-, -COO- and -OCO-. represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, or a carbon atom of 1 It may be substituted with a fluorine-containing alkyl group of 3 to 3, a fluorine ^- containing alkoxy group of 1 to 3 carbon atoms, or a fluorine atom. at least one member selected from the group consisting of a yl group, a fluorine-containing alkyl group of 1 to 18 carbon atoms, an alkoxy group of 1 to 18 carbon atoms, and a fluorine-containing alkoxy group of 1 to 18 carbon atoms.)

[Formula 4]

(S ^A represents a hydrogen atom or a benzene ring. S ^B represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. ^SC is an alkyl group having 1 to 18 carbon atoms, a carbon number represents at least one selected from the group consisting of a fluorine-containing ^alkyl group of 1 to 18, an alkoxy group of 1 to 18 carbon atoms, and a ^fluorine -containing alkoxy group of 1 to 18 carbon atoms. indicate.)

[Formula 5]

(Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )- represents at least one bonding group selected from the group consisting of -N(CH ₃ )CO-, -COO- and -OCO- Y ² is a single bond or -(CH ₂ ) _b - (b is 1 to 15 Y ³ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- and -OCO- Y ⁴ is at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms and having a steroid skeleton. any hydrogen atom on the cyclic group is substituted with an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxy group of 1 to 3 carbon atoms, or a fluorine atom. Y ⁵ represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group of 1 to 3 carbon atoms, an alkyl group of 1 to 3 carbon atoms, It may be substituted with an alkoxy group of 3, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxy group of 1 to 3 carbon atoms, or a fluorine atom. n represents an integer of 0 to 4. Y ⁶ is an alkyl group of 1 to 18 carbon atoms , at least one selected from the group consisting of an alkenyl group of 2 to 18 carbon atoms, a fluorine-containing alkyl group of 1 to 18 carbon atoms, an alkoxy group of 1 to 18 carbon atoms, and a fluorine-containing alkoxy group of 1 to 18 carbon atoms.)

[Formula 6]

(Y ⁷ is a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- and -OCO- represents at least one bonding group selected from the group consisting of Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.)

2. The liquid crystal display element according to claim 1, wherein the compound of [1-1] of the component (A) is at least one selected from the group consisting of compounds of the following formula [1a-1] to formula [1a-6].

[Formula 7]

(Ta and Tb each represent an integer of 1 to 12. Tc to Tf each represent an integer of 1 to 10.)

3. The liquid crystal according to 1 above, wherein S ¹ in formula [1-2] is at least one structure selected from the group consisting of formula [1-a] to formula [1-d] and formula [1-f] display element.

4. The liquid crystal display element as described in said ¹ which is at least 1 sort(s) of structure chosen from the group which S1 in formula [1-2] consists of the structure of formula [1-h] - formula [1-l].

5. The polymer of component (B) is at least one selected from the group consisting of acrylic polymers, methacrylic polymers, novolac resins, polyhydroxystyrenes, polyimide precursors, polyimides, polyamides, polyesters, celluloses, and polysiloxanes The liquid crystal display element according to any one of 1 to 3 above.

6. (B) Polyimide precursor obtained by making the polymer of component react the diamine component containing the diamine compound which has the structure of said formula [2-1] or formula [2-2], and a tetracarboxylic acid component, or its The liquid crystal display element according to any one of 1 to 4 above, which is a polyimide obtained by imidizing a polyimide precursor.

7. Said liquid crystal display element as described in 6 in which the said diamine component contains diamine represented by following formula [2a].

[Formula 8]

(Y represents the formula [2-1] or formula [2-2]. n1 represents an integer of 1 to 4.)

8. The said liquid crystal display element as described in said 6 or 7 in which the said diamine component contains the diamine represented by following formula [3a].

[Formula 9]

(W represents the structure of formula [3] below. m1 represents the integer of 1-4.)

[Formula 10]

(W ¹ is a single bond, -O-, -NH-, -N(CH ₃ )-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ ) represents at least one bonding group selected from the group consisting of CO-, -COO-, and -OCO- W ² is a single bond, an alkylene group having 1 to 18 carbon atoms, or a benzene ring, a cyclohexane ring, or a heterocyclic ring; represents an organic group having 6 to 24 carbon atoms and having at least one type of cyclic group selected from the group consisting of, and any hydrogen atom on these cyclic groups is an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, or an organic group of 1 to 3 carbon atoms It may be substituted with a fluorine-containing alkyl group of 3 or a fluorine-containing alkoxy group of 1 to 3. W ³ is a single bond, -O-, -NH-, -N(CH ₃ )-, -CH ₂ O-, -CONH - ^, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- and -OCO-. a] to at least one structure selected from the group consisting of the structures of the formula [3-g].)

[Formula 11]

(W ^A represents a hydrogen atom or a benzene ring. W ^B represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. W ^C is an alkyl group having 1 to 18 carbon atoms, a carbon number At least one selected from the group consisting of 1 to 18 fluorine-containing alkyl groups, 1 to 18 carbon atoms alkoxy groups, and 1 to 18 carbon atoms fluorine-containing alkoxy groups.)

9. The liquid crystal display element as described in any one of said 6-8 in which the said tetracarboxylic-acid component contains tetracarboxylic dianhydride of following formula [4].

[Formula 12]

(Z represents at least one structure selected from the group consisting of structures of the following formula [4a] to formula [4k])

[Formula 13]

(Z ¹ to Z ⁴ each independently represent at least one selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom and a benzene ring. Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group.)

10. The polysiloxane obtained by the polymer of component (B) polycondensing an alkoxysilane of the following formula [A1], or polycondensation of an alkoxysilane of the formula [A1] and an alkoxysilane of the following formula [A2] or formula [A3] The liquid crystal display element as described in any one of said 1-4 containing the polysiloxane obtained by combining.

[Formula 14]

(A ¹ represents the structure of the formula [2-1] or formula [2-2]. A ² represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms. A ³ represents an alkyl group of 1 to 5 carbon atoms. m represents an integer of 1 or 2. n represents an integer of 0 to 2. p represents an integer of 0 to 3. However, m + n + p is 4.)

[Formula 15]

(B ¹ is an organic group having 2 to 12 carbon atoms and at least one selected from the group consisting of a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacryl group, an acryl group, a ureide group, and a cinnamoyl group. B ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms B ³ represents an alkyl group having 1 to 5 carbon atoms m represents an integer of 1 or 2 n represents an integer of 0 to 2 p represents an integer from 0 to 3. However, m + n + p is 4.)

[Formula 16]

(D ¹ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms. D ² represents an alkyl group of 1 to 5 carbon atoms. n represents an integer of 0 to 3.)

11. The liquid crystal display element as described in any one of Claims 1-10 in which the said liquid-crystal aligning agent contains at least 1 sort(s) of generator chosen from the group which consists of an optical radical generator, a photoacid generator, and a photobase generator.

12. The compound which has at least 1 sort(s) of substituent selected from the group which the said liquid-crystal aligning agent consists of an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a C1-C3 alkoxyalkyl group. The liquid crystal display element as described in any one of said 1-11 containing.

13. The liquid crystal aligning agent is 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclo The liquid crystal display element according to any one of 1 to 12 above, containing at least one solvent selected from the group consisting of hexanone, cyclopentanone, and solvents of the following formulas [D1] to formula [D3].

[Formula 17]

(D ^a , D ^b and D ^c each represent an alkyl group having 1 to 4 carbon atoms.)

14. The above 1 to which the liquid crystal aligning agent contains at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone. The liquid crystal display element as described in any one of 13.

15. The liquid crystal display device according to any one of 1 to 14, wherein the liquid crystal composition contains a compound of formula [1-1] or a compound of formula [1-2] according to 1 above.

16. The liquid crystal display element according to any one of 1 to 15, wherein the substrate of the liquid crystal display element is a glass substrate or a plastic substrate.

ADVANTAGE OF THE INVENTION According to this invention, favorable optical characteristics, that is, transparency when no voltage is applied and scattering characteristics when voltage is applied are good, and the adhesion between the liquid crystal layer and the liquid crystal alignment layer is high, and furthermore, an environment exposed to high temperature, high humidity or light irradiation for a long time. It is possible to provide a reverse type element capable of maintaining these characteristics even under the condition. The mechanism of why the liquid crystal display element having the above excellent characteristics is obtained by the present invention is not necessarily clear, but is estimated as follows.

The liquid crystal aligning film in the element of this invention is obtained from the liquid-crystal aligning agent containing the compound (it is also mentioned specific compound (1-1)) of said formula [1-1]. T ³ of the formula [1-1] is a site that undergoes a polymerization reaction by ultraviolet rays. Therefore, by irradiation of ultraviolet rays at the time of manufacturing a liquid crystal display element, the polymeric compound in a liquid crystal composition and specific compound (1) react, and the adhesiveness of a liquid crystal layer and a liquid crystal aligning film can be improved. Moreover, the isocyanate group of specific compound (1-1) thermally reacts with polar groups, such as an amino group and a hydroxyl group. Therefore, this isocyanate group reacts with the polar group which the polymer (it is also mentioned a specific polymer) of (B) component in a liquid-crystal aligning agent has by heating at the time of manufacture of a liquid crystal aligning film. Thereby, it is thought that the bond|bonding of a specific polymer and a liquid-crystal layer is formed through a specific compound (1-1), and the adhesiveness of a liquid-crystal layer and a liquid crystal aligning film becomes higher.

In addition, S ¹ of the compound of the formula [1-2] (also referred to as specific compound (1-2)) is a site having a polar group, and the structure of S ³ to S ⁶ has an effect of vertically orienting the liquid crystal It exhibits a high rigid structure. Therefore, when it is set as a liquid crystal aligning film, since specific compound (1-2) has a polar group of ^S1 , it is thought that the site|part of ^S3 - ^S6 transfers to the liquid crystal aligning film interface efficiently. It is thought that the homeotropic alignment of the liquid crystal becomes higher together with the rigid structure contained in the polymer by this.

Moreover, the liquid-crystal aligning agent containing the polymer (it is also mentioned a specific polymer) which the liquid crystal aligning film in this invention has the structure (it is also mentioned specific side chain structure) of said formula [2-1] or formula [2-2] is obtained from In particular, since Formula [2-1] shows a rigid structure, when this structure is used, the liquid crystal display element which shows high and stable vertical orientation of a liquid crystal can be obtained. Therefore, in the case of using Formula [2-1] in particular, a reverse type element exhibiting good optical characteristics is obtained.

Therefore, the liquid crystal display element of this invention expresses favorable optical characteristics, the adhesiveness of a liquid crystal layer and a liquid crystal aligning film is high, and becomes a liquid crystal display element which can maintain these characteristics for a long time.

<Specific compound (1-1)>

It is a compound represented by said formula [1-1]. In formula [1-1], T ¹ , T ² , T ³ and T ⁴ are as defined above, but especially, T ¹ is an alkyl having 1 to 12 carbon atoms from the viewpoint of the adhesion between the liquid crystal layer and the liquid crystal aligning film. Rengi is preferred. Moreover, the C6-C18 organic group which has a benzene ring or a cyclohexane ring is also preferable.

T ² is preferably a single bond, -O-, -CH ₂ O-, -OCH ₂ -, -CONH-, -NHCO-, -COO- or -OCO-.

T ³ is the adhesive point between the liquid crystal layer and the liquid crystal aligning film, and the formula [1-a], formula [1-b], formula [1-c], formula [1-d] or formula [1-f] is preferable More preferable ones are formula [1-a], formula [1-b], formula [1-d] or formula [1-f].

Preferable combinations of T ¹ to T ³ in formula [1] are shown in Table 1 and Table 2 below.

Especially, (1-1a) - (1-8a), (1-10a), (1-15a) - (1-17a), (1-22a) or (1-23a) is preferable. More preferable are (1-1a) to (1-4a) in view of the above.

As a more specific specific compound (1-1), the compound of said formula [1a-1] - formula [1a-6] is mentioned.

In the formula [1a-1] to the formula [1a-6], Ta to Tf are as defined above, but among these, Ta and Tb preferably have an integer of 1 to 10, respectively. More preferable is an integer of 1 to 8. Each of Tc to Tf is preferably an integer of 1 to 8. A more preferable thing is an integer of 1-6.

As specific compound (1-1) in this invention, the compound of formula [1a-1], formula [1a-2], formula [1a-5], or formula [1a-6] is preferable.

As for the usage-amount of the specific compound (1-1) in a liquid-crystal aligning agent, 0.1-80 mass parts is preferable with respect to 100 mass parts of specific polymers from the point of the optical characteristic of a liquid crystal display element. More preferred is 0.1 to 60 parts by mass, and particularly preferred is 1 to 50 parts by mass. Moreover, these specific compounds can also be used individually or in mixture of two or more types according to each characteristic.

<Specific compound (1-2)>

It is a compound represented by said formula [1-2]. In Formula [1-2], S ¹ , S ² , S ³ , S ⁴ , S ⁵ , S ⁶ and sA are as defined above. Especially, S ¹ is a formula [1-a] to a formula [1-d], a formula [1-f], or a formula [1-h] to a formula [1 in terms of optical properties in a liquid crystal display element. -l] is preferred. A more preferable thing is the structure of formula [1-a], formula [1-b], formula [1-d], formula [1-f], or formula [1-h] - formula [1-j]. Especially preferred are formula [1-a], formula [1-b], formula [1-d], formula [1-h] or formula [1-i].

S ² is preferably a single bond or an alkylene group having 1 to 18 carbon atoms. Especially, a single bond or a C1-C12 alkylene group is preferable. S ³ is preferably a divalent organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring, or a steroid skeleton from the viewpoint of the optical characteristics of the liquid crystal display element. S ⁴ is preferably a single bond, -O-, -COO- or -OCO- from the viewpoint of ease of synthesis. More preferable is a single bond, -COO- or -OCO-. S ⁵ is preferably a benzene ring or a cyclohexane ring in view of the optical properties of the liquid crystal display element. S ⁶ is preferably an alkyl group of 1 to 18 carbon atoms, an alkoxy group of 1 to 18 carbon atoms, or an alkenyl group of 2 to 18 carbon atoms from the viewpoint of the optical characteristics of the liquid crystal display element. A more preferable thing is a C1-C12 alkyl group, a C1-C12 alkoxy group, or a C2-C12 alkenyl group. sA is preferably an integer of 0 to 2 from the viewpoint of availability of raw materials and ease of synthesis. More preferable is an integer of 1 or 2.

Preferred combinations of S ¹ to S ⁶ and sA in formula [1-2] are shown in Tables 3 to 43 below.

As a more specific specific compound (1-2), Preferably, the compound of the following formula [1a-1] - formula [1a-24] is mentioned.

[Formula 18]

In the above formula, s ¹ represents an integer of 1 to 12, respectively. Especially, the integer of 1-8 is preferable from the point of the optical characteristic of a liquid crystal display element. s ² represents an integer of 0 to 4, respectively. Especially, the integer of 1 or 2 is preferable from the point of the optical characteristic of a liquid crystal display element. S ^a represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO- indicate Especially, -O- or -COO- is preferable from the point of availability of a raw material or synthesis|combination easiness.

S ^b represents an alkyl group of 1 to 18 carbon atoms, a fluorine-containing alkyl group of 1 to 18 carbon atoms, an alkoxy group of 1 to 18 carbon atoms, or a fluorine-containing alkoxy group of 1 to 18 carbon atoms. Especially, a C1-C12 alkyl group or a C1-C12 alkoxy group is preferable. A more preferable thing is a C1-C8 alkyl group or a C1-C8 alkoxy group.

[Formula 19]

In the above formula, s ³ represents an integer of 1 to 12, respectively. Especially, the integer of 1-8 is preferable from the point of the optical characteristic of a liquid crystal display element. Each of S ^c represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Especially, -COO- or -OCO- is preferable from the point of availability of a raw material or synthesis|combination easiness. S ^d represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO- indicate Especially, -O- or -COO- is preferable from the point of availability of a raw material or synthesis|combination easiness.

^Se each represents an alkyl group of 1 to 18 carbon atoms, a fluorine-containing alkyl group of 1 to 18 carbon atoms, an alkoxy group of 1 to 18 carbon atoms, or a fluorine-containing alkoxy group of 1 to 18 carbon atoms. Especially, a C1-C12 alkyl group or a C1-C12 alkoxy group is preferable. A more preferable thing is a C1-C8 alkyl group or a C1-C8 alkoxy group.

[Formula 20]

[Formula 21]

In the above formula, s ⁴ represents an integer of 0 to 4, respectively. Especially, the integer of 1 or 2 is preferable from the point of the optical characteristic of a liquid crystal display element.

S ^f represents an alkyl group of 1 to 18 carbon atoms, a fluorine-containing alkyl group of 1 to 18 carbon atoms, an alkoxy group of 1 to 18 carbon atoms, or a fluorine-containing alkoxy group of 1 to 18 carbon atoms. Especially, a C1-C12 alkyl group or a C1-C12 alkoxy group is preferable. A more preferable thing is a C1-C8 alkyl group or a C1-C8 alkoxy group.

[Formula 22]

[Formula 23]

In the above formula, s ⁵ represents an integer of 1 to 12, respectively. Especially, the integer of 1-8 is preferable from the point of the optical characteristic of a liquid crystal display element. s ⁶ represents an integer of 0 to 4, respectively. Especially, the integer of 1 or 2 is preferable from the point of the optical characteristic of a liquid crystal display element.

S ^g respectively represents a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxy group, or a C1-C18 fluorine-containing alkoxy group. Especially, a C1-C12 alkyl group or a C1-C12 alkoxy group is preferable. A more preferable thing is a C1-C8 alkyl group or a C1-C8 alkoxy group.

[Formula 24]

In the above formula, each of ^Sh represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Especially, -COO- or -OCO- is preferable from the point of availability of a raw material or synthesis|combination easiness.

^Si each represents a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxy group, or a C1-C18 fluorine-containing alkoxy group. Especially, a C1-C12 alkyl group or a C1-C12 alkoxy group is preferable. A more preferable thing is a C1-C8 alkyl group or a C1-C8 alkoxy group.

[Formula 25]

In the above formula, s ⁷ represents an integer of 1 to 12, respectively. Especially, the integer of 1-8 is preferable from the point of the optical characteristic of a liquid crystal display element.

Each of S ^j represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Especially, -COO- or -OCO- is preferable from the point of availability of a raw material or synthesis|combination easiness.

S ^k respectively represents a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxy group, or a C1-C18 fluorine-containing alkoxy group. Especially, a C1-C12 alkyl group or a C1-C12 alkoxy group is preferable. A more preferable thing is a C1-C8 alkyl group or a C1-C8 alkoxy group.

As for the usage ratio of the specific compound (1-2) in a liquid-crystal aligning agent, 0.1-30 mass parts is preferable with respect to 100 mass parts of specific polymers from the point of the optical characteristic of a liquid crystal display element. More preferred is 0.5 to 20 parts by mass, and particularly preferred is 1 to 10 parts by mass. Moreover, these specific compounds can be used 1 type or in mixture of 2 or more types according to each characteristic.

<Specific side chain structure>

A specific side chain structure is selected from the group which consists of said Formula [2-1] and Formula [2-2].

In formula [2-1], Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n are as defined above, but among them, the following ones are preferred.

Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- from the viewpoint of the availability of raw materials and ease of synthesis. desirable. More preferable ones are single bonds, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-. Y ² is preferably a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10).

Y ³ is preferably a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- from the viewpoint of synthetic ease. More preferable ones are a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-. Y ⁴ is preferably an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring, or a steroid skeleton from the viewpoint of ease of synthesis. Y ⁵ is preferably a benzene ring or a cyclohexane ring.

Y ⁶ is preferably an alkyl group of 1 to 18 carbon atoms, an alkenyl group of 2 to 18 carbon atoms, a fluorine-containing alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 18 carbon atoms, or a fluorine-containing alkoxy group of 1 to 10 carbon atoms. A more preferable thing is a C1-C12 alkyl group, a C2-C18 alkenyl group, or a C1-C12 alkoxy group. Particularly preferred is an alkyl group of 1 to 9 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, or an alkoxy group of 1 to 9 carbon atoms. n is preferably from 0 to 3, and more preferably from 0 to 2, from the viewpoint of availability of raw materials and ease of synthesis.

Preferred combinations of Y ¹ to Y ⁶ and n are (2-1) to (2-629) listed in Tables 6 to 47 on pages 13 to 34 of International Publication WO2011/132751 (published on October 27, 2011) and The same combination can be mentioned. In addition, in each table|surface of international publication gazette, ^Y1 - ^Y6 in this invention is shown as Y1-Y6, but Y1-Y6 shall be read as ^Y1 - ^Y6 . In addition, in (2-605) to (2-629) published in each table of International Publication, the organic group having 17 to 51 carbon atoms having a steroid skeleton in the present invention is an organic group having 12 to 25 carbon atoms having a steroid skeleton Although shown as an organic group, an organic group having 12 to 25 carbon atoms having a steroid skeleton is read as an organic group having 17 to 51 carbon atoms having a steroid skeleton.

Among them, (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) to (2-315) , (2-364) to (2-387), (2-436) to (2-483) or a combination of (2-603) to (2-615) is preferable. Especially preferred are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-603) to (2-606). ), a combination of (2-607) to (2-609), (2-611), (2-612) or (2-624).

Y ⁷ and Y ⁸ in the formula [2-2] are as defined above, but among them, the following ones are preferred.

Y ⁷ is preferably a single bond, -O-, -CH ₂ O-, -CONH-, -CON(CH ₃ )- or -COO-. More preferably, it is a single bond, -O-, -CONH-, or -COO-. Y ⁸ is preferably an alkyl group having 8 to 18 carbon atoms.

It is preferable that the specific side chain structure in this invention uses Formula [2-1] especially from the point from which the vertical alignment property of a highly stable liquid crystal can be obtained.

<Specific Polymer>

The specific polymer having a specific side chain structure is at least selected from the group consisting of acrylic polymers, methacrylic polymers, novolak resins, polyhydroxystyrenes, polyimide precursors, polyimides, polyamides, polyesters, celluloses and polysiloxanes. One polymer is preferred. A more preferable thing is a polyimide precursor, polyimide, or polysiloxane.

As a specific polymer, when using a polyimide precursor or a polyimide (it is also collectively called a polyimide-type polymer), the polyimide precursor or polyimide obtained by making a diamine component and a tetracarboxylic-acid component react for these is preferable.

A polyimide precursor has a structure of following formula [A].

[Formula 26]

(R ¹ represents a tetravalent organic group. R ² represents a divalent organic group. A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. A ³ and A ⁴ each independently represent hydrogen represents an atom, an alkyl group or an acetyl group having 1 to 5 carbon atoms, and n represents a positive integer.)

The diamine component is a diamine compound having two primary or secondary amino groups in the molecule, and the tetracarboxylic acid component is a tetracarboxylic acid compound, tetracarboxylic dianhydride, tetracarboxylic acid dihalide compound, Tetracarboxylic acid dialkyl ester compound or tetracarboxylic acid dialkyl ester dihalide compound is mentioned.

The polyimide-based polymer has a repeating unit of the following formula [D] for the reason that it can be obtained relatively simply by using tetracarboxylic dianhydride of the following formula [B] and a diamine compound of the following formula [C] as raw materials A polyamic acid or a polyimide obtained by imidizing the polyamic acid is preferred.

[Formula 27]

(R ¹ and R ² have the same meaning as defined in Formula [A].)

[Formula 28]

(R ¹ and R ² have the same meaning as defined in formula [A].)

Further, by a conventional synthetic method, to the polymer of formula [D] obtained above, an alkyl group having 1 to 8 carbon atoms of A ¹ and A ² in formula [A], and carbon atoms of A ³ and A ⁴ in formula [A] 1 to 5 alkyl groups or acetyl groups may be introduced.

As a method for introducing a specific side chain structure into the polyimide polymer, it is preferable to use a diamine compound having a specific side chain structure for a part of the raw material. It is preferable to use the diamine compound (it is also mentioned specific diamine compound (1)) of the said formula [2a] especially.

In the formula [2a], Y represents the formula [2-1] or the formula [2-2]. In addition, the details and preferable combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2-1] are as in the formula [2-1], and the formula [2 Details and preferable combinations of Y ⁷ and Y ⁸ in -2] are as in the above formula [2-2].

m represents the integer of 1-4. Especially, the integer of 1 is preferable.

As a specific diamine compound which has a specific side chain structure of formula [2-1], specifically, formula [2-1] described in international publication WO2013/125595 (published on August 29, 2013) - page 19 - The diamine compound of formula [2-6], formula [2-9] - formula [2-36] is mentioned. In addition, in description of international publication WO2013/125595, R _<2> in formula [2-1] - formula [2-3], and R _<4> in formula [2-4] - formula [2-6] is carbon number 1 At least one selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, a fluorine-containing alkyl group of 1 to 18 carbon atoms, an alkoxy group of 1 to 18 carbon atoms and a fluorine-containing alkoxy group of 1 to 18 carbon atoms. Moreover, A _<4> in formula [2-13] represents a C3-C18 linear or branched alkyl group. Moreover, R _<3> in formula [2-4] - formula [2-6] represents at least 1 sort(s) chosen from the group which consists of -O-, _-CH2O- , -COO-, and -OCO-.

Especially, a preferable diamine compound is formula [2-1] described in international publication WO2013/125595 - formula [2-6], formula [2-9] - formula [2-13], or formula [2-22 ] - It is the diamine compound of formula [2-31].

More preferably, it is a diamine compound represented by the following formula [2a-32] - the formula [2a-41] from the point of the optical characteristic of a liquid crystal display element.

[Formula 29]

[Formula 30]

(R ¹ and R ² each represent an alkyl group having 3 to 12 carbon atoms.)

[Formula 31]

[Formula 32]

(R ³ and R ⁴ each represent an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of 1,4-cyclohexylene is the trans isomer.)

The most preferable thing is the diamine compound represented by said formula [2a-35] - formula [2a-37], formula [2a-40], or formula [2a-41] from the point of the optical characteristic of a liquid crystal display element.

Specifically, as the specific diamine compound (1) having the specific side chain structure of the formula [2-2], the formula [2a-37 described in pages 23 to 24 of International Publication WO2015/012368 (published on January 29, 2015) ] - the diamine compound of formula [2a-46] is mentioned.

The use ratio of a specific diamine compound (1) is 10-80 mol% with respect to the whole diamine component from the point of the adhesiveness of the liquid crystal layer and liquid crystal aligning film in the vertical alignment property of liquid crystal at the time of setting it as a liquid crystal aligning film, and a liquid crystal display element is preferable, and 20 to 70 mol% is more preferable. Moreover, a specific diamine compound (1) can be used 1 type or in mixture of 2 or more types according to each characteristic.

It is preferable to use the diamine compound (it is also mentioned specific diamine compound (2)) of said formula [3a] as a 2nd diamine compound for the diamine component for manufacturing a polyimide type polymer.

In the formula [3a], W ¹ , W ² , W ³ and W ⁴ are as defined above, but among them, the following ones are preferred.

W ¹ is preferably a single bond, -O-, -CH ₂ O-, -CONH-, -CON(CH ₃ )- or -COO- from the viewpoint of the availability of raw materials or synthetic easiness. More preferable is -O-, -CH ₂ O- or -COO-. W ² is preferably a single bond, an alkylene group of 1 to 18 carbon atoms, or an organic group of 6 to 12 carbon atoms having a benzene ring or cyclohexane ring. A more preferable one is an alkylene group having 2 to 10 carbon atoms from the viewpoint of the optical properties of the liquid crystal display element.

W ³ is preferably a single bond, -O-, -CH ₂ O-, -CO-, or -OCO-, from the viewpoint of availability of raw materials and ease of synthesis. W ⁴ has a preferable structure of the formula [3-a], formula [3-b], formula [3-c] or formula [3-e] from the viewpoint of the optical characteristics of the liquid crystal display element. m represents the integer of 1-4. Especially, the integer of 1 is preferable.

As a specific diamine compound (2), the diamine compound of the following formula [3a-1] - a formula [3a-27] can be specifically, mentioned, It is preferable to use these.

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

(In the formula [3a-1] to the formula [3a-27], d1 represents an integer of 2 to 10.)

10-70 mol% is preferable with respect to the whole diamine component, and, as for the usage ratio of a specific diamine compound (2), 20-60 mol% is more preferable with respect to the adhesive point of the liquid crystal layer and liquid crystal aligning film in a liquid crystal display element, do. Moreover, a specific diamine compound (2) can be used 1 type or in mixture of 2 or more types according to each characteristic.

As the diamine component for producing the polyimide polymer, diamine compounds other than the specific diamine compound (1) and the specific diamine compound (2) (also referred to as other diamine compounds) can be used as long as the effects of the present invention are not impaired. may be

Specifically, the second diamine compound of the formula [2b] described on pages 25 to 26 of International Publication WO2015/012368 (published on January 29, 2015), other diamine compounds described on pages 27 to 30 of the same publication, and The diamine compound of the formula [DA1] - the formula [DA14] described in pages 30-32 of this publication is mentioned. Moreover, other diamine compounds can be used 1 type or in mixture of 2 or more types according to each characteristic.

As the tetracarboxylic acid component for producing the polyimide polymer, tetracarboxylic dianhydride of the above formula [4] or tetracarboxylic acid derivative thereof, tetracarboxylic acid dihalide, tetracarboxylic acid Acid dialkyl esters or tetracarboxylic acid dialkyl ester dihalides (all collectively referred to as specific tetracarboxylic acid components) are preferred.

In the above formula [4], Z is as defined above, but among others, from the ease of synthesis and the ease of polymerization reactivity at the time of producing a polyimide polymer, the above formula [4a], formula [4c], formula [ A structure of formula [4d], formula [4e], formula [4f], formula [4g] or formula [4k] is preferred. More preferable ones are formula [4a], formula [4e], formula [4f], formula [4g] or formula [4k] in view of the optical properties of the liquid crystal display element.

As for the usage ratio of a specific tetracarboxylic acid component, 1 mol% or more is preferable with respect to all the tetracarboxylic acid components. More preferably, it is 5 mol% or more, and even more preferably, it is 10 mol% or more. Especially, 10-90 mol% is especially preferable from the point of the optical characteristic of a liquid crystal display element.

Moreover, when using the specific tetracarboxylic acid component of the said formula [4e], formula [4f], formula [4g], or formula [4k], the usage-amount is 20 mol% or more of the whole tetracarboxylic acid component By doing so, the desired effect is obtained. More preferably, it is 30 mol% or more. Moreover, the tetracarboxylic-acid component of formula [4e], formula [4f], formula [4g], or formula [4k] may be sufficient as all the tetracarboxylic-acid components.

Other tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used for the polyimide polymer, as long as the effects of the present invention are not impaired. Examples of other tetracarboxylic acid components include tetracarboxylic acid, tetracarboxylic dianhydride, dicarboxylic acid dihalide, dicarboxylic acid dialkyl ester or dialkyl ester dihalide shown below.

Specifically, other tetracarboxylic acid components described in pages 34 to 35 of International Publication WO2015/012368 (published on January 29, 2015) are exemplified. Moreover, a specific tetracarboxylic-acid component and other tetracarboxylic-acid components can be used 1 type or in mixture of 2 or more types according to each characteristic.

A method for synthesizing the polyimide polymer is not particularly limited. It is usually obtained by reacting a diamine component and a tetracarboxylic acid component. Specifically, the method described in pages 35-36 of international publication WO2015/012368 (published on January 29, 2015) is mentioned.

Reaction of a diamine component and a tetracarboxylic acid component is normally performed in the solvent containing a diamine component and a tetracarboxylic acid component. The solvent is not particularly limited as long as the produced polyimide precursor dissolves therein.

Specifically, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolidinone; etc. are mentioned. Moreover, when the solvent solubility of a polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the said formula [D1] - formula [D3] solvents may be used. Moreover, these may be used independently or may be used, mixing. In addition, even if it is a solvent that does not dissolve the polyimide precursor, you may mix it with said solvent and use it within the range in which the produced|generated polyimide precursor does not precipitate. In addition, moisture in the organic solvent inhibits the polymerization reaction and causes the resulting polyimide precursor to hydrolyze. Therefore, it is preferable to use a dehydrated organic solvent.

Polyimide is a polyimide obtained by ring closure of a polyimide precursor, and in this polyimide, the ring closure rate of the amic acid group (also referred to as the imidation rate) is not necessarily 100%, and can be prepared arbitrarily depending on the use or purpose. there is. Especially, 30 to 80% is preferable from the point of the solubility to the solvent of a polyimide-type polymer. More preferable is 40 to 70%.

The molecular weight of the polyimide-based polymer is preferably 5,000 to 1,000,000 as Mw (weight average molecular weight) measured by the GPC method in consideration of the strength of the liquid crystal aligning film obtained therefrom, workability at the time of forming the liquid crystal aligning film, and coating properties and more preferably 10,000 to 150,000.

<Polysiloxane polymer>

When polysiloxane is used for a specific polymer, the polysiloxane obtained by polycondensing the alkoxysilane of the formula [A1] or the alkoxysilane of the formula [A1] and the alkoxysilane of the formula [A2] or the formula [A3] Polysiloxanes obtained by polycondensation (the above polysiloxanes are collectively referred to as polysiloxane polymers) are preferred.

Alkoxysilane of formula [A1]:

In the formula [A1], A ¹ represents the structure of the formula [2-1] or formula [2-2]. In addition, the details and preferable combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2-1] are as described above, and in the formula [2-2] Details and preferred combinations of Y ⁷ and Y ⁸ are as described above.

In this invention, the point of the optical characteristic in the vertical alignment property of the liquid crystal at the time of setting it as a liquid crystal aligning film and a liquid crystal display element to the specific side chain structure of Formula [2-1] is preferable.

In the formula [A1], A ² , A ³ , m, n and p are as defined above, but among these, the following are preferable. A ² is preferably a hydrogen atom or an alkyl group of 1 to 3 carbon atoms. In view of the reactivity of polycondensation, A ³ is preferably an alkyl group of 1 to 3 carbon atoms. m is preferably an integer of 1 from the viewpoint of synthesis. n represents the integer of 0-2. In view of the reactivity of polycondensation, p is preferably an integer of 1 to 3, more preferably an integer of 2 or 3. m + n + p is an integer of 4.

Specifically, as an alkoxysilane having a specific side chain structure of formula [2-1], formula [2a-1] described in pages 17 to 21 of International Publication No. 2015/008846 (published on January 22, 2015) to formula [2a -32]. Especially, from the point where the vertical alignment property of high and stable liquid crystal can be obtained, Formula [2a-9] - Formula [2a-21], Formula [2a-25] - Formula [2a-28], or Formula [2a-32] Alkoxysilanes of are preferred. The alkoxysilane of formula [A1] can mix and use 2 or more types according to each characteristic.

Alkoxysilane of formula [A2]:

In the formula [A2], B ¹ , B ² , B ³ , m, n and p are as defined above, but among these, the following are preferable.

B ¹ is preferably an organic group having a vinyl group, an epoxy group, an amino group, a methacryl group, an acryl group, or a ureide group in terms of availability. More preferable is an organic group having a methacryl group, an acryl group or a ureide group. B ² is preferably a hydrogen atom or an alkyl group of 1 to 3 carbon atoms. In view of the reactivity of polycondensation, B ³ is preferably an alkyl group of 1 to 3 carbon atoms. m is preferably an integer of 1 from the viewpoint of synthesis. n represents the integer of 0-2. In view of the reactivity of polycondensation, p is preferably an integer of 1 to 3, and more preferably an integer of 2 or 3. m + n + p is 4.

Specifically as an alkoxysilane of formula [A2], the alkoxysilane of formula [2b] described on pages 22-23 of International Publication No. 2015/008846 (published on January 22, 2015) is mentioned.

Especially, 3-(triethoxysilyl) propyl methacrylate, 3-(trimethoxysilyl) propyl acrylate, 3-(trimethoxysilyl) propyl methacrylate from the point of adhesiveness of a liquid crystal layer and a liquid crystal aligning film. rate, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyl (diethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane or 2-(3,4-epoxy) Cyclohexyl)ethyltrimethoxysilane is preferred.

The alkoxysilane of formula [A2] can be used 1 type or in mixture of 2 or more types according to each characteristic.

Alkoxysilane of formula [A3]:

In the formula [A3], D ¹ , D ² and n are as defined above, but among them, the following are preferable. D ¹ is preferably a hydrogen atom or an alkyl group of 1 to 3 carbon atoms. D ² is preferably an alkyl group of 1 to 3 carbon atoms from the viewpoint of the reactivity of polycondensation. n represents the integer of 0-3.

Specifically as an alkoxysilane of formula [A3], the alkoxysilane of formula [2c] described on page 24 of international publication 2015/008846 (published on January 22, 2015) is mentioned.

In formula [A3], examples of alkoxysilanes in which n is 0 include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, and examples of alkoxysilanes of formula [A3] include these Preference is given to using alkoxysilanes. Moreover, according to each characteristic, the alkoxysilane of Formula [A3] can be used 1 type or in mixture of 2 or more types.

The polysiloxane-based polymer is a polysiloxane obtained by polycondensing an alkoxysilane of the formula [A1], or a polysiloxane obtained by polycondensing an alkoxysilane of the formula [A1] and an alkoxysilane of the formula [A2] or [A3]. am. That is, the polysiloxane polymer is a polysiloxane obtained by polycondensing only the alkoxysilane of the formula [A1], a polysiloxane obtained by polycondensing two types of alkoxysilanes of the formula [A1] and the formula [A2], the formula [A1] and the formula [ It is any one of the polysiloxane obtained by polycondensing two types of alkoxysilanes of [A3], and the polysiloxane obtained by polycondensing three types of alkoxysilanes of formula [A1], formula [A2] and formula [A3].

Especially, the polysiloxane obtained by polycondensing multiple types of alkoxysilanes is preferable from the viewpoint of the reactivity of polycondensation and the solubility of the polysiloxane-based polymer in a solvent. That is, polysiloxane obtained by polycondensing two types of alkoxysilanes of formula [A1] and formula [A2], polysiloxane obtained by polycondensing two types of alkoxysilanes of formula [A1] and formula [A3], and formula [A1]. ], it is preferable to use any one of polysiloxanes obtained by polycondensing three types of alkoxysilanes of formulas [A2] and formulas [A3].

When using multiple types of alkoxysilanes when manufacturing a polysiloxane type polymer, 1-40 mol% is preferable among all alkoxysilanes, and, as for the use of the alkoxysilane of Formula [A1], 1-30 mol% is more preferable do. Moreover, 1-70 mol% is preferable among all the alkoxysilanes, and, as for the use of the alkoxysilane of Formula [A2], 1-60 mol% is more preferable. Moreover, 1-99 mol% is preferable among all the alkoxysilanes, and, as for the use of the alkoxysilane of Formula [A3], 1-80 mol% is more preferable.

A method for polycondensing the polysiloxane-based polymer is not particularly limited. Specifically, the method described in pages 26-29 of International Publication No. 2015/008846 (published on January 22, 2015) is exemplified.

In the present invention, the solution of the polysiloxane-based polymer obtained by the above method may be used as a specific polymer as it is, and the solution of the polysiloxane-based polymer obtained by the above method may be concentrated, diluted by adding a solvent, or other It may be substituted with a solvent and used as a specific polymer.

The solvent used for dilution (also referred to as an additive solvent) may be a solvent used for polycondensation reaction or other solvents. This additive solvent is not particularly limited as long as the polysiloxane-based polymer is uniformly dissolved, and one or two or more types can be arbitrarily selected and used. As such an additive solvent, in addition to the solvent used for the polycondensation reaction, for example, ketone solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate or ethyl lactate A solvent etc. are mentioned. In addition, when a polysiloxane-based polymer and other polymers are used for a specific polymer, alcohol generated during the polycondensation reaction of the polysiloxane-based polymer is distilled off under normal pressure or reduced pressure before mixing the other polymer with the polysiloxane-based polymer. It is desirable to put

<liquid crystal aligning agent>

A liquid-crystal aligning agent is a solution for forming a liquid crystal aligning film, and is a solution containing the specific polymer and solvent which have a specific compound and specific side chain structure.

As for content of the specific compound (1-1) in a liquid-crystal aligning agent, 0.1-80 mass parts is preferable with respect to 100 mass parts of specific polymers. Especially, 0.1-60 mass parts are preferable from the adhesive point of a liquid crystal layer and a liquid crystal aligning film. Most preferably, it is 1-50 mass parts. Moreover, a specific compound can be used 1 type or in mixture of 2 or more types.

As for content of the specific compound (1-2) in a liquid-crystal aligning agent, 0.1-30 mass parts is preferable with respect to 100 mass parts of specific polymers from the point of the optical characteristic of a liquid crystal display element. More preferred is 0.5 to 20 parts by mass, and particularly preferred is 1 to 10 parts by mass.

Although you may add specific compounds (1-1) and (1-2) directly to the solution of a specific polymer, it is preferable to add, after using a suitable solvent as a solution of 0.1-10 mass % of concentration. The solvent in this case is not particularly limited as long as it is a solvent that dissolves the specific polymer described above. Moreover, it is preferable to stir and make it react after mixing a specific compound and a specific polymer from the point which promotes reaction of the isocyanate group in a specific compound and the polar group in a specific polymer, and can improve the adhesiveness of a liquid crystal layer and a liquid crystal aligning film. The temperature at that time is preferably 0 to 100°C, more preferably 10 to 60°C. Moreover, as for time, 1 to 24 hours are preferable.

As the specific polymer, at least one polymer selected from the group consisting of acrylic polymers, methacrylic polymers, novolak resins, polyhydroxystyrenes, polyimide precursors, polyimides, polyamides, polyesters, celluloses, and polysiloxanes is preferable. do. A polyimide precursor, polyimide or polysiloxane is more preferred, and a polyimide precursor or polyimide is most preferred. Moreover, 2 or more types can be used for a specific polymer.

As for the polymer component in a liquid-crystal aligning agent, all may be a specific polymer, and polymers other than that may be mixed. 0.5-15 mass parts is preferable with respect to 100 mass parts of specific polymers, and, as for content of a polymer other than that, 1-10 mass parts are more preferable. As a polymer other than that, the said polymer which does not have a specific side chain structure is mentioned.

Content of the solvent in a liquid-crystal aligning agent can be suitably selected from the point of obtaining the coating method of a liquid-crystal aligning agent, and the target film thickness. Especially, from the point which forms a uniform liquid crystal aligning film by application|coating, 50-99.9 mass % is preferable in a liquid-crystal aligning agent, as for content of a solvent, 60-99 mass % is more preferable, and 65-99 mass % is particularly preferred.

The solvent used for a liquid-crystal aligning agent will not be specifically limited if it is a solvent which dissolves a specific polymer. Among them, when the specific polymer is a polyimide precursor, polyimide, polyamide or polyester, or when the solubility of an acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, cellulose or polysiloxane in a solvent is low, , It is preferable to use the solvent A class described on page 58 of International Publication No. 2014/171493 (published on October 23, 2014). Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone. Moreover, these may be individual and may be mixed and used.

When the specific polymer is an acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, cellulose or polysiloxane, the specific polymer is a polyimide precursor, polyimide, polyamide or polyester, and the solvent of these specific polymers In the case of high solubility to , solvent B described in pages 58 to 60 of International Publication No. 2014/171493 (published on October 23, 2014) can be used. Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopenta It is preferable to use paddy or the solvent of the said formula [D1] - formula [D3].

In addition, when using these solvents B, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-buty of the solvent A, for the purpose of improving the coating properties of the liquid crystal aligning agent It is preferable to use together with rolactone. More preferably, γ-butyrolactone is used in combination.

Since these solvent B can improve the coating film property and surface smoothness of the liquid crystal aligning film at the time of apply|coating a liquid-crystal aligning agent, when a polyimide precursor, polyimide, polyamide, or polyester is used for a specific polymer, the said solvent A It is preferable to use in combination with Ryu. As for solvent B, 1-99 mass % of the whole solvent contained in a liquid-crystal aligning agent is preferable. Especially, 10-99 mass % is preferable. More preferably, it is 20-95 mass %.

It is preferable to introduce|transduce at least 1 sort(s) of generator (it is also mentioned a specific generator) chosen from the group which consists of an optical radical generator, a photoacid generator, and a photobase generator into a liquid-crystal aligning agent. Specifically as a specific generator, the specific generator described in pages 54-56 of International Publication No. 2014/171493 (published on October 23, 2014) is mentioned. Especially, it is preferable to use an optical radical generating agent for a specific generator from the point of adhesiveness of a liquid crystal layer and a liquid crystal aligning film.

The compound (it is also mentioned an adhesive compound) of following formula [7a-1] - formula [7a-5] can be used for the liquid-crystal aligning agent for the purpose of improving the adhesiveness of a liquid-crystal layer and a liquid-crystal aligning film.

[Formula 41]

(n2 represents an integer from 1 to 10. m2 represents an integer from 1 to 10.)

Moreover, as an adhesive compound, the compound described in pages 61-63 of International Publication No. 2014/171493 (published on October 23, 2014) can also be used.

As for content of the adhesive compound in a liquid-crystal aligning agent, 0.1-150 mass parts is preferable with respect to 100 mass parts of all polymer components. In order for the crosslinking reaction to proceed and the desired effect to be expressed, 0.1 to 100 parts by mass is more preferable, and particularly 1 to 50 parts by mass is most preferable with respect to 100 parts by mass of all the polymer components. Moreover, adhesive compounds can be used 1 type or in mixture of 2 or more types according to each characteristic.

In the liquid crystal aligning agent, a compound having an epoxy group, an isocyanate group, an oxetane group, a compound having a cyclocarbonate group, a compound having at least one group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group (generically, a specific crosslinking property Also referred to as a compound) is preferably contained. It is necessary to have two or more of these groups in a compound.

Specifically as a crosslinkable compound which has an epoxy group or an isocyanate group, the compound described in 63 pages - 64 pages of international publication 2014/171493 (published on October 23, 2014) is mentioned.

Specifically as a crosslinkable compound which has an oxetane group, the compound of formula [4a] - formula [4k] published on pages 58-59 of International Publication WO2011/132751 (published on October 27, 2011) is mentioned.

Specific examples of the crosslinkable compound having a cyclocarbonate group include compounds of the formulas [5-1] to [5-42] published on pages 76 to 82 of International Publication WO2012/014898 (published on February 2, 2012). there is.

Specifically as a crosslinking compound having a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group, a melamine derivative or a benzoguanamine derivative described on pages 65 to 66 of International Publication No. 2014/171493 (published on October 23, 2014), and The compound of the formula [6-1] - the formula [6-48] published on pages 62-66 of international publication WO2011/132751 (published on October 27, 2011) is mentioned.

As for content of the specific crosslinkable compound in a liquid-crystal aligning agent, 0.1-100 mass parts is preferable with respect to 100 mass parts of all polymer components. In order for the crosslinking reaction to proceed and the desired effect to be expressed, 0.1 to 50 parts by mass is more preferred, and particularly 1 to 30 parts by mass is most preferred, based on 100 parts by mass of all the polymer components.

Formula [M1] published on pages 69-73 of International Publication WO2011/132751 (published on October 27, 2011) - formula [M1] - formula [ M156] nitrogen-containing heterocyclic amine compound may be added.

The compound which improves the uniformity of the film thickness and surface smoothness of the liquid crystal aligning film at the time of apply|coating a liquid-crystal aligning agent can be used for a liquid-crystal aligning agent, unless the effect of this invention is impaired. Moreover, the compound etc. which improve the adhesiveness of a liquid crystal aligning film and a board|substrate can be used.

As a compound which improves the uniformity and surface smoothness of the film thickness of a liquid crystal aligning film, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned. Specifically, the surfactant described on page 67 of International Publication No. 2014/171493 (published on October 23, 2014) is exemplified. Moreover, as for the use ratio, 0.01-2 mass parts are preferable with respect to 100 mass parts of all the polymer components contained in a liquid-crystal aligning agent, and a more preferable one is 0.01-1 mass part.

Specifically as a compound which improves the adhesiveness of a liquid crystal aligning film and a board|substrate, the compound described in 67-69 pages of international publication 2014/171493 (published on October 23, 2014) is mentioned. Moreover, 0.1-30 mass parts is preferable with respect to 100 mass parts of all the polymer components contained in a liquid-crystal aligning agent, and, as for the use ratio, it is 1-20 mass parts more preferable.

You may add a dielectric material and a conductive material to a liquid-crystal aligning agent for the purpose of changing electric characteristics, such as the dielectric constant and conductivity of a liquid crystal aligning film, other than the compound other than the above.

<liquid crystal composition>

The liquid crystal composition contains a polymerizable compound that polymerizes between the liquid crystal and ultraviolet light, and the polymerizable compound serves to form a polymer network (curable resin). In addition, the liquid crystal layer described above is a cured product composite of a liquid crystal and a polymerizable compound, and the cured product composite herein is, as described above, for example, liquid crystal present in a polymer network formed of a polymerizable compound. means state.

As the liquid crystal, a nematic liquid crystal, a smectic liquid crystal or a cholesteric liquid crystal can be used. Especially, what has negative dielectric anisotropy is preferable. Further, from the viewpoint of low-voltage driving and scattering characteristics, it is preferable that the dielectric constant anisotropy is large and the refractive index anisotropy is large. In addition, two or more types of liquid crystals may be mixed and used according to the physical property values of the phase transition temperature, dielectric constant anisotropy, and refractive index anisotropy.

In order to drive a liquid crystal display element as an active element such as a TFT, it is required that the liquid crystal has a high electrical resistance and a high voltage holding ratio (VHR). Therefore, it is preferable to use a fluorine-type or chlorine-type liquid crystal which has high electrical resistance and does not lower VHR by active energy rays such as ultraviolet rays for the liquid crystal.

In the liquid crystal display element, a dichroic dye may be dissolved in the liquid crystal composition to form a guest host type element. In this case, an element that is transparent when no voltage is applied and absorbs (scatters) when a voltage is applied is obtained. In addition, in this liquid crystal display element, the direction of the director of the liquid crystal (direction of orientation) changes 90 degrees depending on the presence or absence of voltage application. Therefore, this liquid crystal display element can obtain higher contrast than conventional guest host type elements that switch between random alignment and vertical alignment by utilizing the difference in light absorption characteristics of dichroic dyes. Moreover, in the guest host type element in which the dichroic dye was dissolved, when the liquid crystal is oriented in the horizontal direction, it becomes colored and becomes opaque only in a scattering state. Therefore, as a voltage is applied, it is also possible to obtain an element that switches from colorless and transparent to colored opaque and colored transparent states when no voltage is applied.

As the polymerizable compound, any compound capable of forming a cured product (for example, a polymer network) of the liquid crystal composition through a polymerization reaction with ultraviolet light may be used. A monomer of a polymerizable compound may be introduced into the liquid crystal composition, or a polymer obtained by polymerizing the monomer in advance may be introduced into the liquid crystal composition. However, even when it is made of a polymer, it is necessary to have a site that undergoes a polymerization reaction with ultraviolet rays. More preferably, from the viewpoint of handling of the liquid crystal composition, that is, suppression of increase in viscosity of the liquid crystal composition and solubility in the liquid crystal, a monomer is introduced into the liquid crystal composition, and a polymerization reaction is performed by irradiation with ultraviolet rays during production of the liquid crystal display device. A method of forming a cured product is preferred.

The polymerizable compound may be any compound as long as it dissolves in the liquid crystal. However, when the polymerizable compound is dissolved in the liquid crystal, it is necessary to have a temperature at which part or all of the liquid crystal composition exhibits a liquid crystal phase. Even when a part of the liquid crystal composition exhibits a liquid crystal phase, it is only necessary to visually check the liquid crystal display element and obtain substantially uniform transparency and scattering characteristics throughout the element.

The polymerizable compound may be a compound that undergoes a polymerization reaction with ultraviolet light, and at that time, polymerization may proceed in any reaction format to form a cured product of the liquid crystal composition. Radical polymerization, cationic polymerization, anionic polymerization, or polyaddition reaction is mentioned as a specific reaction format. Especially, as for the reaction form of a polymeric compound, radical polymerization is preferable. As the polymerizable compound, it is preferable to use a radical polymerizable compound (monomer) and an oligomer thereof. Moreover, as mentioned above, the polymer which polymerized these monomers can also be used.

Specifically, the monofunctional polymerizable compound, the bifunctional polymerizable compound, and the polyfunctional polymerizable compound described in pages 58-60 of International Publication No. 2015/012368 (published on January 29, 2015) are exemplified. Moreover, you may use 1 type or a mixture of 2 or more types according to each characteristic of a radical type polymerizable compound.

Further, in order to promote the formation of a cured product of the liquid crystal composition, it is preferable to introduce a radical initiator (also referred to as a polymerization initiator) that generates radicals by ultraviolet rays for the purpose of accelerating radical polymerization of polymerizable compounds in the liquid crystal composition. Specifically, the radical initiator described in pages 13-14 of International Publication No. 2014/171493 (published on October 23, 2014) is exemplified. In addition, the radical initiator may be used singly or in combination of two or more types according to each characteristic.

As the polymerizable compound, an ionic polymerizable compound can also be used. Specifically, it is a compound having at least one cross-linking group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group.

Specifically, melamine derivatives and benzoguanamine derivatives, 1,3,5-tris (methoxymethoxy) benzene, and 1,2 described on pages 14 to 15 of International Publication No. 2014/171493 (published on October 23, 2014) ,4-tris(isopropoxymethoxy)benzene, 1,4-bis(sec-butoxymethoxy)benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, and International Publication 2014/ Epoxy described on pages 15 to 16 of No. 171493 (published on October 23, 2014) and compounds containing an isocyanate group are exemplified.

In the case of using an ionic polymerizable compound, an ionic initiator that generates an acid or a base by ultraviolet light may be introduced for the purpose of accelerating the polymerization reaction. Specifically, the ion initiator described in pages 16-17 of International Publication No. 2014/171493 (published on October 23, 2014) is exemplified.

It is preferable to contain the compound of said formula [1-2] in the liquid crystal composition of this invention. In formula [1-2], S ¹ , S ² , S ³ , S ⁴ , S ⁵ , S ⁶ and sA are as defined above, but among them, the following ones are preferred. S ¹ is preferably the above formula [1-a] to formula [1-f] and formula [1-h] to formula [1-j] in view of optical characteristics of the liquid crystal display element. More preferable ones are formula [1-a], formula [1-b], formula [1-d], formula [1-i] or formula [1-j]. S ² is preferably a single bond or an alkylene group having 1 to 18 carbon atoms. Especially, a single bond or a C1-C12 alkylene group is preferable. Optional -CH ₂ - of the alkylene group is -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-, -CON(CH ₃ )-, -S - or -SO ₂ - may be substituted.

S ³ is preferably a divalent organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring, or a steroid skeleton from the viewpoint of the optical characteristics of the liquid crystal display element. S ⁴ is preferably a single bond, -O-, -COO- or -OCO- from the viewpoint of ease of synthesis. More preferable is a single bond, -COO- or -OCO-. S ⁵ is preferably a benzene ring or a cyclohexane ring in view of the optical properties of the liquid crystal display element. S ⁶ is preferably an alkyl group having 1 to 18 carbon atoms, an alkoxy group or an alkenyl group from the viewpoint of the optical properties of the liquid crystal display element. More preferably, it is an alkyl group, an alkoxy group, or an alkenyl group having 1 to 12 carbon atoms. sA is preferably an integer of 0 to 2, more preferably 1 or 2, from the viewpoint of availability of raw materials and ease of synthesis.

The compound of the formula [1-2] added to the liquid crystal composition of the present invention (hereinafter also referred to as a liquid crystal added compound) is the same as the compound of the formula [1-2] to be contained in the above-described liquid crystal aligning agent, including those preferred. do. That is, the compound of the said formula [1a-1] - formula [1a-24] is mentioned.

The amount of the liquid crystal additive compound used in the liquid crystal composition is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 30 parts by mass, based on 100 parts by mass of the liquid crystal composition excluding the liquid crystal additive compound, from the viewpoint of the optical properties of the element. part, particularly preferably 1 to 20 parts by mass. A liquid crystal addition compound can mix and use 2 or more types.

<The manufacturing method of a liquid crystal alignment film and a liquid crystal display element>

The substrate used for the liquid crystal display element is not particularly limited as long as it is a substrate having high transparency, and in addition to glass substrates, plastic substrates such as acrylic substrates, polycarbonate substrates, and PET (polyethylene terephthalate) substrates, and even films thereof can be used. there is. When using a liquid crystal display element as a reverse type element for a light control window or the like, a plastic substrate or film is preferable. Further, from the viewpoint of simplifying the process, it is preferable to use a substrate on which an ITO (indium tin oxide) electrode, an IZO (indium zinc oxide) electrode, an IGZO (indium gallium zinc oxide) electrode, an organic conductive film, or the like for driving a liquid crystal is formed. do. Further, in the case of a reflective reverse type element, a substrate formed with a silicon wafer or a metal such as aluminum or a dielectric multilayer film can be used as long as it is a substrate on one side.

A liquid crystal display element has a liquid crystal alignment film in which at least one side of a board|substrate vertically orientates liquid crystal molecules. After apply|coating and baking a liquid-crystal aligning agent on a board|substrate, this liquid crystal aligning film carries out orientation processing by a rubbing process, light irradiation, etc., and can be obtained. However, in the case of the liquid crystal aligning film in this invention, it can use as a liquid crystal aligning film even without these orientation processing.

The coating method of the liquid crystal aligning agent is not particularly limited, but industrially, there are screen printing, offset printing, flexographic printing, inkjet method, dip method, roll coater method, slit coater method, spinner method, spray method, etc. It can select suitably according to the film thickness of the liquid crystal aligning film made into the kind of board|substrate or the objective.

After applying the liquid crystal aligning agent on the substrate, by heating means such as a hot plate, a heat circulation type oven, an IR (infrared ray) type oven, depending on the type of substrate or the solvent used for the liquid crystal aligning agent, 30 to 300 °C, preferably at a temperature of 30 to 250 °C, the solvent can be evaporated to obtain a liquid crystal alignment film. In particular, when a plastic substrate is used for the substrate, it is preferable to process at a temperature of 30 to 150°C.

When the thickness of the liquid crystal alignment film after baking is too thick, the power consumption of the liquid crystal display element is disadvantageous, and when it is too thin, the reliability of the element may decrease. Therefore, it is preferably 5 to 500 nm, more preferably 10 to 300 nm. , particularly preferably 10 to 250 nm.

In the liquid crystal composition used for the liquid crystal display element, a spacer for controlling an electrode gap (also referred to as a gap) of the liquid crystal display element may be introduced.

The injection method of the liquid crystal composition includes, for example, the following method. That is, when a glass substrate is used for a board|substrate, a pair of board|substrates with a liquid crystal aligning film are prepared, 4 pieces of one side board|substrates apply|coat the sealing compound except a part, and then the surface of a liquid crystal aligning film is inside Thus, an empty cell to which the substrate on the other side is bonded is manufactured. Then, a method of obtaining a liquid crystal composition injection cell by injecting the liquid crystal composition under reduced pressure from a place where no sealant is applied is exemplified. In addition, when using a plastic substrate or film for a substrate, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and a liquid crystal is deposited on one substrate by an ODF (One Drop Filling) method or an inkjet method. A method of obtaining a liquid crystal composition injection cell by dropping the composition and bonding the substrate on the other side thereafter is exemplified. In this invention, since the adhesiveness of a liquid crystal layer and a liquid crystal aligning film is high, it is not necessary to apply sealing compound to four pieces of a board|substrate.

The gap of the liquid crystal display element can be controlled with a spacer or the like. The method includes a method of introducing a spacer of a desired size into the liquid crystal composition, a method of using a substrate having a column spacer of a desired size, and the like. Further, when a plastic or film substrate is used for the substrate and bonding of the substrate is performed by lamination, the gap can be controlled without introducing a spacer.

The size of the gap is preferably 1 to 100 μm, more preferably 2 to 50 μm, and particularly preferably 5 to 20 μm. When the gap is too small, the contrast of the liquid crystal display element is lowered, and when the gap is too large, the driving voltage is increased.

In a liquid crystal display device, a liquid crystal composition is cured by irradiation of ultraviolet rays to form a liquid crystal layer of a cured product composite of a liquid crystal and a polymerizable compound. Curing of the liquid crystal composition is performed by irradiating ultraviolet rays to the liquid crystal composition injection cell. The light source of the ultraviolet irradiation device may be, for example, a metal halide lamp or a high-pressure mercury lamp. Moreover, 250-400 nm is preferable and, as for the wavelength of an ultraviolet-ray, 310-370 nm is preferable. Heat treatment may be performed after irradiation with ultraviolet rays, and the temperature at that time is preferably 40 to 120°C, more preferably 40 to 80°C.

Example

Although the present invention will be described in more detail by way of examples below, the present invention is not construed as being limited to these examples.

<Example A series>

The meanings of symbols such as compounds used below are as follows.

<liquid crystal composition>

[Formula 42]

(liquid crystal) L1: MLC-6608 (manufactured by Merck)

(polymerizable compound)

[Formula 43]

(photoinitiator)

[Formula 44]

A1: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxy]benzene

A2: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxymethyl]benzene

A3: 1,3-diamino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene

A4: Diamine compound of the following formula [A4]

A5: 1,3-diamino-4-octadecyloxybenzene

[Formula 45]

[Formula 46]

C1: m-phenylenediamine

C2: 3,5-diaminobenzoic acid

D1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

D2: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

[Formula 47]

<Specific compound>

[Formula 48]

<Specific accelerator>

[Formula 49]

<Adhesive compound>

[Formula 50]

<Crosslinkable compound>

[Formula 51]

<Solvent>

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

BCS: ethylene glycol monobutyl ether

PB: propylene glycol monobutyl ether

PGME: Propylene glycol monomethyl ether

"Measurement of Molecular Weight of Polyimide Polymers"

It was measured as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko) and columns (KD-803, KD-805) (manufactured by Shodex).

Column temperature: 50 ℃

Eluent: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr H ₂ O) is 30 mmol/L (liter), phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/L , tetrahydrofuran (THF) at 10 mL/L)

Flow rate: 1.0 ml/min

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

"Measurement of imidation rate of polyimide polymer"

20 mg of polyimide powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific Co., Ltd.)) and mixed with deuterated dimethyl sulfoxide (DMSO-d6, 0.05% by mass TMS (tetramethylsilane)) product) (0.53 ml) was added and ultrasonic was applied to dissolve completely. A 500 MHz proton NMR was measured for this solution with an NMR measuring device (JNW-ECA500) (manufactured by JEOL Datum Co., Ltd.). For the imidation rate, a proton derived from a structure that does not change before and after imidation is determined as a standard proton, and the peak integration value of this proton and the proton peak integration derived from the NH group of amic acid appearing around 9.5 ppm to 10.0 ppm The values were used and determined by the following formula.

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

(x is the peak integration value of protons derived from the NH group of amic acid, y is the peak integration value of standard protons, α is polyamic acid (imidation rate is 0%), one NH group proton of amic acid in the case of is the ratio of the number of reference protons to

<Synthesis Example 1>

D2 (6.89 g, 27.5 mmol), A1 (8.49 g, 22.3 mmol) and C2 (2.26 g, 14.9 mmol) were mixed in NMP (38.9 g) and reacted at 50 ° C. for 5 hours, then D1 ( 1.80 g, 9.18 mmol) and NMP (19.5 g) are added, reacted at 40 ° C. for 6 hours, and the resin solid content concentration is 25% by mass (hereinafter referred to as _CR 25%) Polyamide acid solution (1) got The number average molecular weight (Mn) of this polyamic acid was 21,300, and the weight average molecular weight (Mw) was 67,700.

<Synthesis Example 2>

After adding NMP to the polyamic acid solution (1) (30.0 g) obtained in Synthesis Example 1 and diluting to 6% by mass, acetic anhydride (2.50 g) and pyridine (2.40 g) were added as an imidation catalyst, It was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (2). The imidation rate of this polyimide was 55%, Mn was 19,000, and Mw was 50,200.

<Synthesis Example 3>

D2 (6.12 g, 24.5 mmol), A1 (7.55 g, 19.8 mmol), B1 (2.62 g, 9.91 mmol) and C2 (0.50 g, 3.29 mmol) were mixed in NMP (36.8 g) and 50 After making it react at degreeC for 5 hours, D1 (1.60g, 8.16 mmol) and NMP (18.4g) were added, it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (3) of 25% _{of CR} was obtained. Mn of this polyamic acid was 20,200 and Mw was 63,500.

<Synthesis Example 4>

After adding NMP to the polyamic acid solution (3) (30.0 g) obtained in Synthesis Example 3 and diluting to 6% by mass, acetic anhydride (2.51 g) and pyridine (2.42 g) were added as an imidation catalyst, It was made to react at 50 degreeC for 4 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (4). The imidation rate of this polyimide was 54%, Mn was 17,500, and Mw was 48,800.

<Synthesis Example 5>

After mixing D2 (0.80 g, 3.20 mmol), A2 (2.55 g, 6.46 mmol) and B1 (2.56 g, 9.69 mmol) in PGME (16.8 g) and reacting at 50 ° C. for 12 hours, D1 ( 2.50 g, 12.7 mmol) and PGME (8.40 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (5) of 25% of _CR was obtained. Mn of this polyamic acid was 17,100 and Mw was 40,800.

<Synthesis Example 6>

D1 (3.30 g, 16.8 mmol), A2 (3.36 g, 8.52 mmol), B1 (1.80 g, 6.81 mmol) and C1 (0.18 g, 1.66 mmol) were mixed in PGME (26.0 g) and 50 It was made to react at degreeC for 12 hours, and the polyamic acid solution (6) of 25% of _CR was obtained. Mn of this polyamic acid was 15,900 and Mw was 39,200.

<Synthesis Example 7>

After mixing D2 (6.89 g, 27.5 mmol), A5 (8.40 g, 22.3 mmol) and C2 (2.26 g, 14.9 mmol) in NMP (38.7 g) and reacting at 50 ° C. for 5 hours, D1 ( 1.80 g, 9.18 mmol) and NMP (19.4 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (7) of 25% of _CR was obtained. Mn of this polyamic acid was 20,500 and Mw was 65,300.

<Synthesis Example 8>

D3 (3.50 g, 15.6 mmol), A2 (2.50 g, 6.34 mmol) and B1 (2.51 g, 9.50 mmol) were mixed in PGME (25.5 g), reacted at 50°C for 15 hours, and _CR 25 A % polyamic acid solution (8) was obtained. Mn of this polyamic acid was 14,800 and Mw was 37,900.

<Synthesis Example 9>

D3 (3.50 g, 15.6 mmol), A4 (1.56 g, 3.17 mmol), B1 (2.51 g, 9.50 mmol) and C2 (0.48 g, 3.15 mmol) were mixed in NEP (24.1 g) and 50 It was made to react at degreeC for 12 hours, and the polyamic acid solution of 25% of _CR was obtained.

After adding NEP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass %, acetic anhydride (2.50 g) and pyridine (2.38 g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 2 hours. . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (9). The imidation rate of this polyimide was 48%, Mn was 16,500, and Mw was 44,200.

<Synthesis Example 10>

D4 (3.37 g, 11.2 mmol), A3 (2.46 g, 5.69 mmol), B1 (1.50 g, 5.68 mmol) and C2 (0.43 g, 2.83 mmol) were mixed in NMP (16.6 g) and 50 After making it react at degreeC for 5 hours, D1 (0.55g, 2.80 mmol) and NMP (8.31g) were added, it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution of 25% _{of CR} was obtained.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass %, acetic anhydride (2.50 g) and pyridine (2.38 g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (10). The imidation ratio of this polyimide was 57%, Mn was 17,300, and Mw was 45,800.

<Synthesis Example 11>

After mixing D5 (1.30 g, 6.13 mmol), A2 (3.67 g, 9.30 mmol) and B1 (1.64 g, 6.21 mmol) in PGME (16.8 g) and reacting at 50 ° C. for 12 hours, D1 ( 1.80 g, 9.18 mmol) and PGME (8.42 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (11) of 25% of _CR was obtained. Mn of this polyamic acid was 15,500 and Mw was 35,100.

<Synthesis Example 12>

After mixing D5 (1.70 g, 8.01 mmol), A4 (1.60 g, 3.25 mmol) and B1 (3.43 g, 13.0 mmol) in PGME (16.6 g) and reacting at 50 ° C. for 12 hours, D1 ( 1.57 g, 8.01 mmol) and PGME (8.30 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (12) of 25% of _CR was obtained. Mn of this polyamic acid was 13,800 and Mw was 32,500.

Table 44 shows the polyimide-based polymer obtained in each synthesis example.

"Manufacture of Liquid Crystal Composition"

(Preparation of Liquid Crystal Composition (1))

Liquid crystal composition (1) was obtained by mixing L1 (2.40 g), R1 (1.20 g), R2 (1.20 g) and P1 (0.012 g).

(Preparation of Liquid Crystal Composition (2))

Liquid crystal composition (2) was obtained by mixing L1 (2.40 g), R1 (1.20 g), R2 (1.20 g), P1 (0.012 g) and S1 (0.024 g).

(Preparation of Liquid Crystal Composition (3))

Liquid crystal composition (3) was obtained by mixing L1 (2.40 g), R1 (1.20 g), R2 (1.20 g), P1 (0.012 g) and S1 (0.12 g).

(Preparation of Liquid Crystal Composition (4))

Liquid crystal composition (4) was obtained by mixing L1 (2.40 g), R1 (1.20 g), R2 (1.20 g), P1 (0.012 g) and S2 (0.048 g).

"Manufacture of liquid crystal aligning agent"

In Examples 1-15 and Comparative Examples 1-3 described later, the manufacture example of the liquid-crystal aligning agent was described. These liquid-crystal aligning agents were used also for manufacture of a liquid crystal display element and its evaluation. Moreover, in Table 45 - Table 47, the liquid-crystal aligning agent obtained by these Examples and a comparative example is shown.

"Manufacture of liquid crystal display element and evaluation of liquid crystal orientation (glass substrate)"

A liquid crystal display element was manufactured using the liquid-crystal aligning agent obtained in Examples 1-4 and 10 and the comparative examples 1 and 2. Specifically, these liquid-crystal aligning agents were filtered under pressure with a membrane filter having a pore diameter of 1 μm, and a 100 × 100 mm glass substrate with an ITO electrode washed with pure water and IPA (isopropyl alcohol) (length: 100 mm) , width: 100 mm, thickness: 0.7 mm) on an ITO surface, and heat treatment was performed on a hot plate at 100 ° C. for 5 minutes and at 210 ° C. for 30 minutes in a heat circulation type clean oven to obtain a film thickness of 100 nm An ITO substrate with a phosphorus liquid crystal aligning film was obtained. Two obtained ITO substrates with a liquid crystal aligning film were prepared, and a 6 µm spacer was applied to the liquid crystal aligning film surface of one of the substrates. Then, the said liquid crystal composition was dripped on the liquid crystal aligning film surface which apply|coated the spacer of the board|substrate by ODF method, Then, it bonded so that the liquid crystal aligning film interface of the other board|substrate may face, and obtained the liquid crystal display element before a process. .

The liquid crystal display element before this process was irradiated with ultraviolet rays for 90 seconds of irradiation time by cutting a wavelength of 350 nm or less using a metal halide lamp having an illuminance of 20 mW. The temperature in the irradiation apparatus at the time of irradiating an ultraviolet-ray to a liquid crystal cell was controlled to 25 degreeC. In this way, a liquid crystal display element (reverse type element) was obtained.

The liquid-crystal orientation was evaluated using this liquid crystal display element. The liquid-crystal orientation observed this element with a polarization microscope (ECLIPSE E600WPOL, manufactured by Nikon Corporation), and confirmed whether or not the liquid crystal was orientating vertically. As a result, in all the liquid crystal display elements of Examples and Comparative Examples, the liquid crystals were vertically aligned.

"Manufacture of liquid crystal display element and evaluation of liquid crystal orientation (plastic substrate)"

A liquid crystal display element was manufactured using the liquid-crystal aligning agent obtained in Examples 5-9, 11-15 and the comparative example 3. Specifically, a 150 × 150 mm PET (polyethylene terephthalate) substrate with an ITO electrode (length: 150 mm, width: 150 mm, thickness: 0.2 mm) was coated with a bar coater on an ITO surface, and heat treatment was performed on a hot plate at 100° C. for 5 minutes and at 120° C. for 2 minutes in a heat circulation type clean oven to obtain a film thickness of 100 nm. An ITO substrate with a phosphorus liquid crystal aligning film was obtained. Two obtained ITO substrates with a liquid crystal aligning film were prepared, and a 6 µm spacer was applied to the liquid crystal aligning film surface of one of the substrates. Then, the liquid crystal composition was dripped on the liquid crystal aligning film surface of the board|substrate to which the spacer was apply|coated by ODF method, and then, it bonded so that the liquid crystal aligning film interface of the other board|substrate might face each other, and obtained the liquid crystal display element before a process.

In the liquid crystal display element before this process, the liquid crystal display element (reverse type element) was obtained by the method similar to said "production of a liquid crystal display element and evaluation of liquid-crystal orientation (glass substrate)".

Using this liquid crystal display element, the liquid-crystal orientation was evaluated by the method similar to said "production of a liquid crystal display element and evaluation of liquid-crystal orientation (glass substrate)". As a result, in all the liquid crystal display elements of Examples and Comparative Examples, the liquid crystals were vertically aligned.

"Evaluation of optical properties (transparency and scattering properties)"

Optical characteristics (transparency and scattering characteristics) were evaluated using the liquid crystal display element (glass substrate/plastic substrate) obtained by the above method.

Evaluation of transparency at the time of no voltage application was performed by measuring the transmittance|permeability of the liquid crystal display element in the state of no voltage application. Specifically, the transmittance was measured in a measuring device under conditions of UV-3600 (manufactured by Shimadzu Corporation), a temperature of 25 degrees, and a scanning wavelength of 300 to 800 nm. In the case of a liquid crystal display element (glass substrate), the glass substrate with an ITO electrode was used as a reference, and in the case of a liquid crystal display element (plastic substrate), a PET substrate with an ITO electrode was used. Evaluation was made based on the transmittance|permeability of a wavelength of 450 nm, and transparency was made excellent, so that the transmittance|permeability was high.

Moreover, evaluation of the transmittance|permeability after storing the liquid crystal display element manufactured by the said method in the temperature of 60 degreeC and the constant temperature and humidity chamber of 70% for 12 hours was also performed. This evaluation was made into the excellent thing, so that the thing with the lower ratio of the transmittance|permeability after storage in a constant temperature and humidity chamber specifically, with respect to the transmittance|permeability (initial value) immediately after said liquid crystal display element manufacture was low.

In addition, evaluation of transmittance after irradiation of 2 J/cm 2 ultraviolet rays in terms of 365 nm using a tabletop UV curing device (HCT3B28HEX-1) (manufactured by Senlight Co., Ltd.) was performed on the liquid crystal display element manufactured by the above method did Specifically, the lower the rate of decrease in the transmittance after ultraviolet irradiation with respect to the transmittance (initial value) immediately after the above liquid crystal display element production, the more excellent this evaluation was.

Further, in Examples 1 to 8 and 10, in addition to the above standard tests, evaluation of the transmittance after storage in a constant temperature and humidity chamber at a temperature of 60°C and a humidity of 70% for 24 hours was performed as an intensive test. In addition, the evaluation method is the same conditions as the above.

Tables 48 to 50 show values of transmittance (%) immediately after liquid crystal display element production (initial stage), after storage in a constant temperature and humidity chamber (constant temperature and humidity), and after ultraviolet irradiation (ultraviolet rays).

Evaluation of the scattering characteristic at the time of voltage application was performed by visually observing the alignment state of the liquid crystal by applying 30 V to the liquid crystal display element (glass substrate) by alternating current drive. Specifically, those in which the liquid crystal display element was clouded, that is, those in which scattering characteristics were obtained were regarded as excellent in this evaluation (good marks in the table).

Moreover, confirmation of the orientation state of the liquid crystal after storing the liquid crystal display element manufactured by the said method in the temperature of 60 degreeC and the constant temperature and humidity chamber of 70% of humidity for 12 hours was also performed. Specifically, those in which the liquid crystal display element was clouded, that is, those in which scattering characteristics were obtained were regarded as excellent in this evaluation (good marks in the table).

In addition, the alignment state of the liquid crystal after irradiating the liquid crystal display element manufactured by the above method with an ultraviolet ray of 2 J/cm 2 in terms of 365 nm using a tabletop UV curing device (HCT3B28HEX-1) (manufactured by Senlight Co., Ltd.) Verification was also performed. Specifically, those in which the liquid crystal display element was clouded, that is, those in which scattering characteristics were obtained were regarded as excellent in this evaluation (good marks in the table).

Tables 48 to 50 show the results of scattering characteristics immediately after liquid crystal display element production (initial stage), after storage in a constant temperature and humidity chamber (constant temperature and humidity), and after ultraviolet irradiation (ultraviolet rays).

"Evaluation of the adhesiveness of a liquid crystal layer and a liquid crystal aligning film"

The adhesiveness of a liquid crystal layer and a liquid crystal aligning film was evaluated using the liquid crystal display element (glass substrate and plastic substrate) obtained by the said method.

The liquid crystal display element was stored in a constant temperature and humidity chamber at a temperature of 60°C and a humidity of 70% for 30 hours, and the presence or absence of bubbles in the liquid crystal display element and peeling of the element were confirmed. Specifically, this evaluation made it excellent in this evaluation that the bubble was not seen in the element and peeling (the state in which the liquid crystal layer and the liquid crystal aligning film were peeling off) of the element did not occur (good display in a table|surface).

In addition, the presence or absence of air bubbles in the liquid crystal display element and the element Peeling was also confirmed. Specifically, in the same manner as above, a case in which bubbles were not observed in the element and peeling of the element did not occur was regarded as excellent in this evaluation (good mark in the table).

Moreover, in Examples 1-4, 7, 8, and 10, in addition to the said standard test, as an intensive test, the adhesiveness after storage in a constant temperature and humidity chamber of 60 degreeC and 70% of humidity for 72 hours was also evaluated. In addition, the evaluation method is the same conditions as the above.

Table 51 - Table 53 show the adhesive result (adhesiveness) of the liquid crystal layer and liquid crystal aligning film after storage in a constant temperature and humidity chamber (constant temperature and humidity) and after ultraviolet irradiation (ultraviolet rays).

<Example 1>

NMP (14.6 g) and Z2 (0.163 g) were added to the polyamic acid solution (1) (6.50 g) obtained in Synthesis Example 1, and the mixture was stirred at 25°C for 24 hours. Then, BCS (19.5g) was added, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (1).

<Example 2>

After adding NEP (21.6 g) to the polyimide powder (2) (1.50 g) obtained in Synthesis Example 2 and stirring at 60°C for 24 hours, Z1 (0.300 g) was added and stirring was performed at 25°C for 24 hours. did Then, PB (14.4g) was added, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (2).

<Example 3>

NMP (14.6 g) and Z2 (0.163 g) were added to the polyamic acid solution (3) (6.50 g) obtained in Synthesis Example 3, and the mixture was stirred at 25°C for 24 hours. Then, BCS (19.5g) was added, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (3).

<Example 4>

To the polyimide powder (4) (1.50 g) obtained in Synthesis Example 4, NEP (21.6 g) was added and stirred at 60°C for 24 hours, then Z1 (0.300 g) was added and stirred at 25°C for 24 hours. did Then, PB (14.4g) was added, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (4).

<Example 5>

γ-BL (6.06 g), PGME (30.6 g) and Z2 (0.188 g) were added to the polyamic acid solution (5) (5.00 g) obtained in Synthesis Example 5, and stirred at 25°C for 24 hours to form a liquid crystal. An orientation treatment agent (5) was obtained.

<Example 8>

γ-BL (6.06 g), PGME (30.6 g) and Z2 (0.188 g) were added to the polyamic acid solution (5) (5.00 g) obtained in Synthesis Example 5, and the mixture was stirred at 25°C for 24 hours. Then, N1 (0.063g), M1 (0.063g), and K1 (0.088g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (6).

<Example 9>

γ-BL (8.08 g), PGME (28.6 g) and Z1 (0.125 g) were added to the polyamic acid solution (6) (5.00 g) obtained in Synthesis Example 6, and the mixture was stirred at 40°C for 12 hours. Then, N1 (0.038g) and K1 (0.125g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (7).

<Example 10>

NMP (14.6 g) and Z2 (0.163 g) were added to the polyamic acid solution (7) (6.50 g) obtained in Synthesis Example 7, and the mixture was stirred at 25°C for 24 hours. Then, BCS (19.5g) was added, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (8).

<Example 11>

To the polyamic acid solution (8) (5.00 g) obtained in Synthesis Example 8, γ-BL (4.04 g), PB (4.04 g), PGME (28.6 g) and Z2 (0.375 g) were added and stirred at 25°C. Stir for 24 hours. Then, N1 (0.088g) and K1 (0.063g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (9).

<Example 12>

γ-BL (8.41 g) and PGME (33.6 g) were added to the polyimide powder (9) (1.30 g) obtained in Synthesis Example 9, and after stirring at 60°C for 24 hours, Z1 (0.260 g) was added. and stirred at 40°C for 12 hours. Then, N1 (0.065g) and K1 (0.039g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (10).

<Example 13>

γ-BL (6.31 g) and PGME (35.7 g) were added to the polyimide powder (10) (1.30 g) obtained in Synthesis Example 10, and after stirring at 60°C for 24 hours, Z2 (0.455 g) was added. and stirred at 25°C for 24 hours. Then, N1 (0.065g) and K1 (0.130g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (11).

<Example 14>

γ-BL (6.06 g), PGME (30.6 g) and Z2 (0.125 g) were added to the polyamic acid solution (11) (5.00 g) obtained in Synthesis Example 11, and the mixture was stirred at 25°C for 24 hours. Then, N1 (0.063g) and K1 (0.088g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (12).

<Example 15>

To the polyamic acid solution (12) (5.00 g) obtained in Synthesis Example 12, γ-BL (4.04 g), PGME (32.6 g) and Z2 (0.063 g) were added, and the mixture was stirred at 25°C for 24 hours. Then, N1 (0.063g) and K1 (0.088g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (13).

<Comparative Example 1>

NMP (14.6g) and BCS (19.5g) were added to the polyamic acid solution (1) (6.50g) obtained in the synthesis example 1, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (14).

<Comparative Example 2>

NEP (21.6g) and PB (14.4g) were added to the polyimide powder (2) (1.50g) obtained in the synthesis example 2, and it stirred at 60 degreeC for 24 hours, and obtained the liquid-crystal aligning agent (15).

<Comparative Example 3>

γ-BL (6.06g) and PGME (30.6g) were added to the polyamic acid solution (5) (5.00g) obtained in Synthesis Example 5, and stirred at 25°C for 4 hours to obtain a liquid crystal aligning agent (16) got it

As for the liquid-crystal aligning agent obtained by said Examples 1-15 and Comparative Examples 1-3, abnormality, such as turbidity and precipitation, was not seen in any, and it was confirmed that it is a uniform solution.

Using these liquid-crystal aligning agents (1)-(16) and the liquid-crystal composition (1)-(4) mentioned above in the combination shown in Table 48-Table 51, manufacture and evaluation of a liquid crystal display element according to the said procedure conducted. Those results are shown in Tables 48 to 51. In addition, Example 6 is a liquid crystal display element using the liquid-crystal aligning agent (5) and the liquid-crystal composition (2), and Example 7 is a liquid crystal display element using the liquid-crystal aligning agent (5) and the liquid-crystal composition (3) am.

*1: Disorder of liquid-crystal orientation was observed at various points in the element.

As can be seen from the foregoing, compared to Comparative Examples, the examples became elements having good transparency, particularly after storage in a constant temperature and humidity chamber and after ultraviolet irradiation, when no voltage was applied. Moreover, it became an element with high adhesiveness of a liquid crystal layer and a liquid crystal aligning film. Moreover, even if a plastic substrate was used for the substrate of the element, these characteristics were good.

Specifically, compared with the comparative example which does not contain the element of the Example containing a specific compound in a liquid-crystal aligning agent, transparency after irradiating an ultraviolet-ray especially at high temperature and high humidity became a result high. More specifically, in the comparison under the same conditions, it is a comparison between Example 1 and Comparative Example 1, a comparison between Example 2 and Comparative Example 2, and a comparison between Example 5 and Comparative Example 3.

In the specific side chain structure, when formula [2-1] is used, compared to the case where formula [2-2] is used, transparency at the time of no voltage application of the element increases, and furthermore, it is carried out in the stress test for a long time in a constant temperature and humidity chamber. Even after storage, the result was that the transparency at the time of no voltage application became higher. Moreover, evaluation of the adhesiveness of a liquid crystal layer and a liquid crystal aligning film WHEREIN: When the specific side chain structure of formula [2-1] was used, after carrying out by the stress test for a long time and storing in the constant temperature and humidity chamber, the result with higher adhesiveness was obtained. . Specifically, it is a comparison of Examples 1 and 10 under the same conditions in standard tests and stress tests.

In addition, when a specific compound was introduced into the liquid crystal composition, the transparency of the element when no voltage was applied increased, and furthermore, the transparency when no voltage was applied became higher even after being stored in a constant temperature and humidity chamber for a long time in the stress test. . The larger the introduction amount of the specific compound, the greater the effect. Specifically, it is a comparison between Example 5 and 6 or 7 under the same conditions in the standard test and the stress test.

Moreover, when a specific generating agent, an adhesive compound, and a specific crosslinkable compound were introduce|transduced in the liquid-crystal aligning agent, the adhesiveness of the liquid-crystal layer and liquid-crystal aligning film in an element was improved more. Specifically, it is a comparison of Examples 7 and 8 under the same conditions in the stress test.

Moreover, when a polyimide-type polymer was used for a specific polymer, when a specific diamine compound (2) was used for a diamine component, the adhesiveness of the liquid crystal layer and liquid crystal aligning film in an element was improved more. Specifically, it is a comparison between Examples 1 and 3 and a comparison between Examples 2 and 4 under the same conditions in the stress test.

<Example B series>

The meanings of the symbols used below are as follows. In addition, the abbreviation used in Example A series is the same respectively.

<Monomer>

E2: octadecyltriethoxysilane,

E3: 3-methacryloxypropyltrimethoxysilane,

E4: 3-ureidopropyltriethoxysilane, E5: tetraethoxysilane

[Formula 52]

[Formula 53]

<Solvent>

ECS: Ethylene glycol monoethyl ether

EC: Diethylene glycol monoethyl ether

"Synthesis of Polyimide Polymers"

<Synthesis Example 1>

D2 (6.89 g, 27.5 mmol), A1 (8.49 g, 22.3 mmol) and C2 (2.26 g, 14.9 mmol) were mixed in NMP (38.9 g) and reacted at 50 ° C. for 5 hours, then D1 ( 1.80 g, 9.18 mmol) and NMP (19.5 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (1) of 25% of _CR was obtained. Mn of this polyamic acid was 21,300 and Mw was 67,700.

<Synthesis Example 2>

After adding NMP to the polyamic acid solution (1) (30.0 g) obtained in Synthesis Example 1 and diluting to 6% by mass, acetic anhydride (2.50 g) and pyridine (2.40 g) were added as an imidation catalyst, It was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (2). The imidation rate of this polyimide was 55%, Mn was 19,000, and Mw was 50,200.

<Synthesis Example 3>

D2 (6.12 g, 24.5 mmol), A1 (7.55 g, 19.8 mmol), B1 (2.62 g, 9.91 mmol) and C2 (0.50 g, 3.29 mmol) were mixed in NMP (36.8 g) and 50 After making it react at degreeC for 5 hours, D1 (1.60g, 8.16 mmol) and NMP (18.4g) were added, it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (3) of 25% _{of CR} was obtained. Mn of this polyamic acid was 20,200 and Mw was 63,500.

<Synthesis Example 4>

After adding NMP to the polyamic acid solution (3) (30.0 g) obtained in Synthesis Example 3 and diluting to 6% by mass, acetic anhydride (2.51 g) and pyridine (2.42 g) were added as an imidation catalyst, It was made to react at 50 degreeC for 4 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (4). The imidation rate of this polyimide was 54%, Mn was 17,500, and Mw was 48,800.

<Synthesis Example 5>

After mixing D2 (0.80 g, 3.20 mmol), A2 (2.55 g, 6.46 mmol) and B1 (2.56 g, 9.69 mmol) in PGME (16.8 g) and reacting at 50 ° C. for 12 hours, D1 ( 2.50 g, 12.7 mmol) and PGME (8.40 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (5) of 25% of _CR was obtained. Mn of this polyamic acid was 17,100 and Mw was 40,800.

<Synthesis Example 6>

D1 (3.30 g, 16.8 mmol), A2 (3.36 g, 8.52 mmol), B1 (1.80 g, 6.81 mmol) and C1 (0.18 g, 1.66 mmol) were mixed in PGME (26.0 g) and 50 It was made to react at degreeC for 12 hours, and the polyamic acid solution (6) of 25% of _CR was obtained. Mn of this polyamic acid was 15,900 and Mw was 39,200.

<Synthesis Example 7>

After mixing D2 (6.89 g, 27.5 mmol), A5 (8.40 g, 22.3 mmol) and C2 (2.26 g, 14.9 mmol) in NMP (38.7 g) and reacting at 50 ° C. for 5 hours, D1 ( 1.80 g, 9.18 mmol) and NMP (19.4 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (7) of 25% of _CR was obtained. Mn of this polyamic acid was 20,500 and Mw was 65,300.

<Synthesis Example 8>

D3 (3.50 g, 15.6 mmol), A2 (2.50 g, 6.34 mmol) and B1 (2.51 g, 9.50 mmol) were mixed in PGME (25.5 g), reacted at 50°C for 15 hours, and _CR 25 A % polyamic acid solution (8) was obtained. Mn of this polyamic acid was 14,800 and Mw was 37,900.

<Synthesis Example 9>

D3 (3.50 g, 15.6 mmol), A4 (1.56 g, 3.17 mmol), B1 (2.51 g, 9.50 mmol) and C2 (0.48 g, 3.15 mmol) were mixed in NEP (24.1 g) and 50 It was made to react at degreeC for 12 hours, and the polyamic acid solution of 25% of _CR was obtained.

After adding NEP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass %, acetic anhydride (2.50 g) and pyridine (2.38 g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 2 hours. . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (9). The imidation ratio of this polyimide was 48%, Mn was 16,500, and Mw was 44,200.

<Synthesis Example 10>

D4 (3.37 g, 11.2 mmol), A3 (2.46 g, 5.69 mmol), B1 (1.50 g, 5.68 mmol) and C2 (0.43 g, 2.83 mmol) were mixed in NMP (16.6 g) and 50 After making it react at degreeC for 5 hours, D1 (0.55g, 2.80 mmol) and NMP (8.31g) were added, it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution of 25% _{of CR} was obtained.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass %, acetic anhydride (2.50 g) and pyridine (2.38 g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (10). The imidation ratio of this polyimide was 57%, Mn was 17,300, and Mw was 45,800.

<Synthesis Example 11>

After mixing D5 (1.30 g, 6.13 mmol), A2 (3.67 g, 9.30 mmol) and B1 (1.64 g, 6.21 mmol) in PGME (16.8 g) and reacting at 50 ° C. for 12 hours, D1 ( 1.80 g, 9.18 mmol) and PGME (8.42 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (11) of 25% of _CR was obtained. Mn of this polyamic acid was 15,500 and Mw was 35,100.

<Synthesis Example 12>

After mixing D5 (1.70 g, 8.01 mmol), A4 (1.60 g, 3.25 mmol) and B1 (3.43 g, 13.0 mmol) in PGME (16.6 g) and reacting at 50 ° C. for 12 hours, D1 ( 1.57 g, 8.01 mmol) and PGME (8.30 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (12) of 25% of _CR was obtained. Mn of this polyamic acid was 13,800 and Mw was 32,500.

Table 42 shows the polyimide polymer obtained in each synthesis example.

<Synthesis Example 13>

ECS (28.3 g), E1 (4.10 g), E3 (7.45 g) and E5 (32.5 g) were mixed in a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube to prepare a solution of an alkoxysilane monomer. did To this solution, a solution previously prepared by mixing ECS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst was added dropwise at 25°C over 30 minutes, and further at 25°C for 30 minutes. Stir. Then, after heating using an oil bath and making it reflux for 30 minutes, the mixed solution of the methanol solution (1.20g) whose content of E4 adjusted previously is 92 mass %, and ECS (0.90g) was added. Furthermore, after making it reflux for 30 minutes, it stood to cool and obtained the polysiloxane solution (1) whose _SiO2 conversion density|concentration is 12 mass %.

<Synthesis Example 14>

In a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, EC (25.4 g), E1 (8.20 g), E3 (19.9 g) and E5 (20.0 g) were mixed to prepare an alkoxysilane monomer solution. did To this solution, a solution previously prepared by mixing EC (12.7 g), water (10.8 g), and oxalic acid (1.10 g) as a catalyst was added dropwise at 25°C over 30 minutes, and further at 25°C for 30 minutes. Stir. Then, after heating using an oil bath and making it recirculate|reflux for 30 minutes, the mixed solution of the methanol solution (1.20g) and EC (0.90g) of 92 mass % of E4 content previously adjusted was added. Furthermore, after refluxing for 30 minutes, it stood to cool and obtained the polysiloxane solution (2) whose _SiO2 conversion density|concentration is 12 mass %.

<Synthesis Example 15>

In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, EC (29.2 g), E1 (4.10 g) and E5 (38.8 g) were mixed to prepare an alkoxysilane monomer solution. To this solution, a solution previously prepared by mixing EC (14.6 g), water (10.8 g), and oxalic acid (0.50 g) as a catalyst was added dropwise at 25°C over 30 minutes, and further at 25°C for 30 minutes. Stir. Then, after heating using an oil bath and making it recirculate|reflux for 30 minutes, the mixed solution of the methanol solution (1.20g) and EC (0.90g) of 92 mass % of E4 content previously adjusted was added. Furthermore, after making it reflux for 30 minutes, it stood to cool and obtained the polysiloxane solution (3) whose _SiO2 conversion density|concentration is 12 mass %.

<Synthesis Example 16>

ECS (28.3 g), E2 (4.07 g), E3 (7.45 g) and E5 (32.5 g) were mixed in a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube to prepare a solution of an alkoxysilane monomer. did To this solution, a solution previously prepared by mixing ECS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst was added dropwise at 25°C over 30 minutes, and further at 25°C for 30 minutes. Stir. Then, after heating using an oil bath and making it reflux for 30 minutes, the mixed solution of the methanol solution (1.20g) whose content of E4 adjusted previously is 92 mass %, and ECS (0.90g) was added. Furthermore, after making it reflux for 30 minutes, it stood to cool and obtained the polysiloxane solution (4) whose _SiO2 conversion density|concentration is 12 mass %.

Table 43 shows the polysiloxane polymer obtained in each synthesis example.

"Manufacture of Liquid Crystal Composition"

Liquid crystal compositions (1) to (4) were prepared in the same manner as in the Examples of the A series.

"Manufacture of liquid crystal aligning agent"

In Examples 1-20 and Comparative Examples 1-5 described later, the manufacture example of the liquid-crystal aligning agent was described. These liquid-crystal aligning agents were used also for manufacture of a liquid crystal display element and its evaluation. In Table 54 - Table 56, the liquid-crystal aligning agent obtained by these Examples and a comparative example is shown.

"Manufacture of liquid crystal display element and evaluation of liquid crystal orientation (glass substrate)"

Using the liquid-crystal aligning agent obtained in Examples 1-4, 10, 16, 17, 20 and Comparative Examples 1, 2, 4, a liquid crystal display element was manufactured according to the same procedure as the Example of the A series described above. . In addition, in all the liquid crystal display elements of these Examples and Comparative Examples, the liquid crystals were vertically aligned.

"Manufacture of liquid crystal display element and evaluation of liquid crystal orientation (plastic substrate)"

Using the liquid-crystal aligning agent obtained in Examples 5-9, 11-15, 18, 19 and Comparative Examples 3 and 5, the liquid crystal display element was manufactured according to the procedure similar to the Example of above-mentioned A-series.

"Evaluation of optical properties (transparency and scattering properties)"

Optical characteristics (transparency and scattering characteristics) were evaluated for the obtained liquid crystal display device (glass substrate/plastic substrate).

In addition, in Examples 1 to 8, 10, 16, 17, and 20, in addition to the above standard test, as an intensive test, evaluation of transmittance after storage in a constant temperature and humidity chamber at a temperature of 60 ° C. and a humidity of 70% for 24 hours conducted. In addition, the evaluation method is the same conditions as the examples of the A series.

Tables 57 to 59 show the values of the transmittance (%) of the liquid crystal display element and immediately after production (initial stage), after storage in a constant temperature and humidity chamber (constant temperature and humidity), and after ultraviolet irradiation (ultraviolet rays).

"Evaluation of the adhesiveness of a liquid crystal layer and a liquid crystal aligning film"

About the obtained liquid crystal display element (glass substrate/plastic substrate), the adhesiveness of a liquid crystal layer and a liquid crystal aligning film was evaluated.

In addition, in Examples 1 to 4, 7, 8, 10, 16, and 20, in addition to the above standard test, as an emphasis test, evaluation of adhesion after storage in a constant temperature and humidity chamber at a temperature of 60 ° C. and a humidity of 70% for 72 hours was also conducted. In addition, the evaluation method is the same conditions as the Example of A series. Tables 57 to 59 show the results of adhesion between the liquid crystal layer and the liquid crystal aligning film after (constant temperature and humidity) storage (constant temperature and humidity) and ultraviolet irradiation (ultraviolet rays).

<Example 1>

T3 (0.069g), NMP (12.4g) and BCS (16.5g) were added to the polyamic acid solution (1) (5.50g) obtained in the synthesis example 1, and it stirred at 25 degreeC for 4 hours, liquid-crystal aligning agent (1) was obtained.

<Example 2>

NEP (16.8 g) and PB (16.8 g) were added to the polyimide powder (2) (1.40 g) obtained in Synthesis Example 2, and the mixture was stirred at 60°C for 24 hours. Then, T3 (0.070g) was added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (2).

<Example 3>

T3 (0.069g), NMP (12.4g) and BCS (16.5g) were added to the polyamic acid solution (3) (5.50g) obtained in the synthesis example 3, and it stirred at 25 degreeC for 4 hours, liquid-crystal aligning agent (3) was obtained. Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution. Manufacture and evaluation of the liquid crystal display element were performed using the obtained liquid-crystal aligning agent (3) and liquid-crystal composition (1).

<Example 4>

NEP (16.8 g) and PB (16.8 g) were added to the polyimide powder (4) (1.40 g) obtained in Synthesis Example 4, and the mixture was stirred at 60°C for 24 hours. Then, T3 (0.070g) was added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (4).

<Example 5>

To the polyamic acid solution (5) (4.00 g) obtained in Synthesis Example 5, T3 (0.030 g), γ-BL (4.85 g) and PGME (24.5 g) were added, stirred at 25°C for 4 hours, and liquid crystal An orientation treatment agent (5) was obtained.

<Example 8>

To the polyamic acid solution (5) (4.00 g) obtained in Synthesis Example 5, T3 (0.030 g), N1 (0.050 g), M1 (0.050 g), K1 (0.070 g), γ-BL (4.85 g) and PGME (24.5g) was added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (6).

<Example 9>

To the polyamic acid solution (6) (4.00 g) obtained in Synthesis Example 6, T1 (0.070 g), N1 (0.030 g), K1 (0.100 g), γ-BL (6.47 g) and PGME (22.9 g) were added. It added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (7).

<Example 10>

T3 (0.050g), NMP (9.00g) and BCS (12.0g) were added to the polyamic acid solution (7) (4.00g) obtained in Synthesis Example 7, and it stirred at 25°C for 4 hours, liquid-crystal aligning agent (8) was obtained.

<Example 11>

To the polyamic acid solution (8) (4.00 g) obtained in Synthesis Example 8, T3 (0.010 g), N1 (0.070 g), K1 (0.050 g), γ-BL (6.47 g), PB (1.62 g) and PGME (21.3g) was added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (9).

<Example 12>

γ-BL (6.47 g) and PGME (25.9 g) were added to the polyimide powder (9) (1.00 g) obtained in Synthesis Example 9, and the mixture was stirred at 60°C for 24 hours. Then, T2 (0.050g), N1 (0.050g), and K1 (0.030g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (10).

<Example 13>

γ-BL (6.47 g) and PGME (25.9 g) were added to the polyimide powder (10) (1.00 g) obtained in Synthesis Example 10, and the mixture was stirred at 60°C for 24 hours. Then, T3 (0.030g), N1 (0.050g), and K1 (0.100g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (11).

<Example 14>

To the polyamic acid solution (11) (4.00 g) obtained in Synthesis Example 11, T3 (0.030 g), N1 (0.050 g), K1 (0.070 g), γ-BL (4.85 g) and PGME (24.5 g) were added. It added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (12).

<Example 15>

T2 (0.070 g), N1 (0.050 g), K1 (0.070 g), γ-BL (3.23 g) and PGME (26.1 g) were added to the polyamic acid solution (12) (4.00 g) obtained in Synthesis Example 12. It added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (13).

<Example 16>

To the polysiloxane solution (1) (11.0 g) obtained in Synthesis Example 13, T3 (0.066 g), BCS (9.50 g), PB (3.17 g) and ECS (9.33 g) were added, followed by stirring at 25°C for 4 hours. , The liquid-crystal aligning agent (14) was obtained.

<Example 18>

To the polysiloxane solution (2) (8.50 g) obtained in Synthesis Example 14, T2 (0.071 g), PB (9.89 g), PGME (9.89 g) and EC (5.71 g) were added, followed by stirring at 25°C for 4 hours. , The liquid-crystal aligning agent (15) was obtained.

<Example 19>

To the polysiloxane solution (3) (8.50 g) obtained in Synthesis Example 15, T1 (0.071 g), N1 (0.051 g), M1 (0.204 g), PB (9.89 g), PGME (9.89 g) and EC (5.71 g) ) was added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (16).

<Example 20>

To the polysiloxane solution (4) (11.0 g) obtained in Synthesis Example 16, T3 (0.066 g), BCS (9.50 g), PB (3.17 g) and ECS (9.33 g) were added, followed by stirring at 25°C for 4 hours. , The liquid-crystal aligning agent (17) was obtained.

<Comparative Example 1>

NMP (12.4g) and BCS (16.5g) were added to the polyamic acid solution (1) (5.50g) obtained in the synthesis example 1, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (18).

<Comparative Example 2>

NEP (16.8g) and PB (16.8g) were added to the polyimide powder (2) (1.40g) obtained by the synthesis example 2, and it stirred at 60 degreeC for 24 hours, and obtained the liquid-crystal aligning agent (19).

<Comparative Example 3>

γ-BL (4.85g) and PGME (24.5g) were added to the polyamic acid solution (5) (4.00g) obtained in Synthesis Example 5, and it stirred at 25 degreeC for 4 hours, and liquid-crystal aligning agent (20) got it

<Comparative Example 4>

BCS (9.50 g), PB (3.17 g) and ECS (9.33 g) were added to the polysiloxane solution (1) (11.0 g) obtained in Synthesis Example 13, stirred at 25°C for 4 hours, and liquid crystal aligning agent (21 ) was obtained.

<Comparative Example 5>

To the polysiloxane solution (2) (8.50 g) obtained in Synthesis Example 14, PB (9.89 g), PGME (9.89 g) and EC (5.71 g) were added, stirred at 25°C for 4 hours, and liquid crystal aligning agent (22 ) was obtained.

As for the liquid-crystal aligning agent obtained in Examples 1-20 and Comparative Examples 1-5, abnormality, such as muddiness and precipitation, was not seen in any, and it was confirmed that it is a uniform solution.

These liquid-crystal aligning agents (1)-(20) and said liquid-crystal composition (1)-(4) were used in the combination shown in Table 47 - Table 52, manufacture and evaluation of a liquid crystal display element according to the said procedure conducted. Those results are shown in Tables 47 to 52.

In addition, Example 6 is a liquid crystal display element using the liquid crystal aligning agent (5) and the liquid crystal composition (2), and Example 7 is a liquid crystal display element using the liquid crystal aligning agent (5) and the liquid crystal composition (3), Example 17 is a liquid crystal display element using the liquid crystal aligning agent (14) and the liquid crystal composition (3).

Compared to Comparative Examples, the Examples provided devices with good optical properties, that is, good transparency at the initial stage, after storage in a constant temperature and humidity chamber, and after ultraviolet irradiation without voltage application. Furthermore, it became an element with high adhesiveness of a liquid crystal layer and a liquid crystal aligning film. In particular, even when a plastic substrate was used for the substrate of the device, these characteristics were good.

Specifically, the element of Example containing a specific compound in the liquid-crystal aligning agent has higher transparency at the time of no voltage application immediately after element manufacture compared with the comparative example which does not contain it, and furthermore, it irradiated an ultraviolet-ray at high temperature and high humidity. Even after that, it became a result with high transparency. More specifically, in the comparison under the same conditions, Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 5 and Comparative Example 3, Example 16 and Comparative Example 4 of, and a comparison of Example 18 and Comparative Example 5.

In the specific side chain structure, when formula [2-1] is used, compared to the case where formula [2-2] is used, transparency at the time of no voltage application of the element increases, and furthermore, it is carried out in the stress test for a long time in a constant temperature and humidity chamber. Even after storage, the result was that the transparency at the time of no voltage application became higher. Moreover, evaluation of the adhesiveness of a liquid crystal layer and a liquid crystal aligning film WHEREIN: When Formula [2-1] was used, even after storing in the constant temperature and humidity chamber for a long time implemented by the stress test, the result with higher adhesiveness was obtained. Specifically, in the comparison under the same conditions in the standard test and the stress test, it is a comparison between Examples 1 and 10 and a comparison between Examples 16 and 20.

In addition, when a specific compound is introduced into the liquid crystal composition, the transparency of the element when no voltage is applied increases, and furthermore, the transparency when no voltage is applied is higher even after being stored in a constant temperature and humidity chamber for a long time in the stress test. It became. The larger the introduction amount of the specific compound, the greater the effect. Specifically, in the comparison under the same conditions in the standard test and the stress test, it is a comparison between Example 5 and 6 or 7, and a comparison between Examples 16 and 17.

Moreover, when a specific generating agent, an adhesive compound, and a specific crosslinkable compound were introduce|transduced in the liquid-crystal aligning agent, the adhesiveness of the liquid-crystal layer and liquid-crystal aligning film in an element was improved more. Specifically, in the comparison on the same conditions in the stress test, it is a comparison between Examples 7 and 8.

Moreover, when a polyimide-type polymer was used for a specific polymer, when a specific 2nd diamine compound was used for a diamine component, the adhesiveness of the liquid crystal layer and liquid crystal aligning film in an element was improved more. Specifically, in the comparison on the same conditions in the stress test, it is a comparison between Examples 1 and 3 and a comparison between Examples 2 and 4.

<Example C series>

The meaning of the abbreviation used below is the same as the meaning of the abbreviation defined in the above embodiment A series and embodiment B series.

<Synthesis Example 1>

D2 (6.89 g, 27.5 mmol), A1 (8.49 g, 22.3 mmol) and C2 (2.26 g, 14.9 mmol) were mixed in NMP (38.9 g) and reacted at 50 ° C. for 5 hours, then D1 ( 1.80 g, 9.18 mmol) and NMP (19.5 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (1) of 25% of _CR was obtained. The number average molecular weight (also referred to as Mn) of this polyamic acid was 21,300, and the weight average molecular weight (also referred to as Mw) was 67,700.

<Synthesis Example 2>

After adding NMP to the polyamic acid solution (1) (30.0 g) obtained in Synthesis Example 1 and diluting to 6% by mass, acetic anhydride (2.50 g) and pyridine (2.40 g) were added as an imidation catalyst, It was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (2). The imidation rate of this polyimide was 55%, Mn was 19,000, and Mw was 50,200.

<Synthesis Example 3>

D2 (6.12 g, 24.5 mmol), A1 (7.55 g, 19.8 mmol), B1 (2.62 g, 9.91 mmol) and C2 (0.50 g, 3.29 mmol) were mixed in NMP (36.8 g) and 50 After making it react at degreeC for 5 hours, D1 (1.60g, 8.16 mmol) and NMP (18.4g) were added, it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (3) of 25% _{of CR} was obtained. Mn of this polyamic acid was 20,200 and Mw was 63,500.

<Synthesis Example 4>

After adding NMP to the polyamic acid solution (3) (30.0 g) obtained in Synthesis Example 3 and diluting to 6% by mass, acetic anhydride (2.51 g) and pyridine (2.42 g) were added as an imidation catalyst, It was made to react at 50 degreeC for 4 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (4). The imidation rate of this polyimide was 54%, Mn was 17,500, and Mw was 48,800.

<Synthesis Example 5>

After mixing D2 (0.80 g, 3.20 mmol), A2 (2.55 g, 6.46 mmol) and B1 (2.56 g, 9.69 mmol) in PGME (16.8 g) and reacting at 50 ° C. for 12 hours, D1 ( 2.50 g, 12.7 mmol) and PGME (8.40 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (5) of 25% of _CR was obtained. Mn of this polyamic acid was 17,100 and Mw was 40,800.

<Synthesis Example 6>

D1 (3.30 g, 16.8 mmol), A2 (3.36 g, 8.52 mmol), B1 (1.80 g, 6.81 mmol) and C1 (0.18 g, 1.66 mmol) were mixed in PGME (26.0 g) and 50 It was made to react at degreeC for 12 hours, and the polyamic acid solution (6) of 25% of _CR was obtained. Mn of this polyamic acid was 15,900 and Mw was 39,200.

<Synthesis Example 7>

After mixing D2 (6.89 g, 27.5 mmol), A5 (8.40 g, 22.3 mmol) and C2 (2.26 g, 14.9 mmol) in NMP (38.7 g) and reacting at 50 ° C. for 5 hours, D1 ( 1.80 g, 9.18 mmol) and NMP (19.4 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (7) of 25% of _CR was obtained. Mn of this polyamic acid was 20,500 and Mw was 65,300.

<Synthesis Example 8>

D3 (3.50 g, 15.6 mmol), A2 (2.50 g, 6.34 mmol) and B1 (2.51 g, 9.50 mmol) were mixed in PGME (25.5 g), reacted at 50°C for 15 hours, and _CR 25 A % polyamic acid solution (8) was obtained. Mn of this polyamic acid was 14,800 and Mw was 37,900.

<Synthesis Example 9>

D3 (3.50 g, 15.6 mmol), A4 (1.56 g, 3.17 mmol), B1 (2.51 g, 9.50 mmol) and C2 (0.48 g, 3.15 mmol) were mixed in NEP (24.1 g) and 50 It was made to react at degreeC for 12 hours, and the polyamic acid solution of 25% of _CR was obtained.

After adding NMP to the obtained polyamic acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (2.50g) and pyridine (2.38g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 2 hours. . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (9). The imidation rate of this polyimide was 48%, Mn was 16,500, and Mw was 44,200.

<Synthesis Example 10>

D4 (3.37 g, 11.2 mmol), A3 (2.46 g, 5.69 mmol), B1 (1.50 g, 5.68 mmol) and C2 (0.43 g, 2.83 mmol) were mixed in NMP (16.6 g) and 50 After making it react at degreeC for 5 hours, D1 (0.55g, 2.80 mmol) and NMP (8.31g) were added, it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution of 25% _{of CR} was obtained.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass %, acetic anhydride (2.50 g) and pyridine (2.38 g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (10). The imidation ratio of this polyimide was 57%, Mn was 17,300, and Mw was 45,800.

<Synthesis Example 11>

After mixing D5 (1.30 g, 6.13 mmol), A2 (3.67 g, 9.30 mmol) and B1 (1.64 g, 6.21 mmol) in PGME (16.8 g) and reacting at 50 ° C. for 12 hours, D1 ( 1.80 g, 9.18 mmol) and PGME (8.42 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (11) of 25% of _CR was obtained. Mn of this polyamic acid was 15,500 and Mw was 35,100.

<Synthesis Example 12>

After mixing D5 (1.70 g, 8.01 mmol), A4 (1.60 g, 3.25 mmol) and B1 (3.43 g, 13.0 mmol) in PGME (16.6 g) and reacting at 50 ° C. for 12 hours, D1 ( 1.57 g, 8.01 mmol) and PGME (8.30 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (12) of 25% of _CR was obtained. Mn of this polyamic acid was 13,800 and Mw was 32,500.

Table 63 shows the polyimide-based polymers obtained in each synthesis example.

"Manufacture of Liquid Crystal Composition"

Liquid crystal compositions (1) to (4) were prepared in the same manner as in the Examples of the A series.

"Manufacture of liquid crystal aligning agent"

In Examples 1-15 and Comparative Examples 1-9 described later, the manufacture example of the liquid-crystal aligning agent was described. These liquid-crystal aligning agents were used also for manufacture of a liquid crystal display element and its evaluation. In Table 64 - Table 66, the liquid-crystal aligning agent obtained by these Examples and a comparative example is shown.

"Manufacture of liquid crystal display element and evaluation of liquid crystal orientation (glass substrate)"

Using the liquid-crystal aligning agent obtained in Examples 1-4 and 10 and Comparative Examples 1-6, the liquid crystal display element was manufactured according to the procedure similar to the Example of A series mentioned above. In addition, in all the liquid crystal display elements of these Examples and Comparative Examples, the liquid crystals were vertically aligned.

"Manufacture of liquid crystal display element and evaluation of liquid crystal orientation (plastic substrate)"

Using the liquid-crystal aligning agent obtained in Examples 5-9, 11-15 and Comparative Examples 6-9, the liquid crystal display element was manufactured according to the procedure similar to the Example of A series mentioned above.

"Evaluation of optical properties (transparency and scattering properties)"

Optical characteristics (transparency and scattering characteristics) were evaluated using the obtained liquid crystal display element (glass substrate/plastic substrate).

Further, in Examples 1 to 8 and 10, in addition to the above standard tests, evaluation of transmittance after storage in a constant temperature and humidity chamber at a temperature of 80°C and a humidity of 90% for 24 hours was performed as an intensive test. . The evaluation method is the same conditions as in the examples of the A series.

Tables 67 to 69 show transmittances (%) immediately after liquid crystal display element production (initial stage), after storage in a constant temperature and humidity chamber (constant temperature and humidity), and after ultraviolet irradiation (ultraviolet rays).

"Evaluation of the adhesiveness of a liquid crystal layer and a liquid crystal aligning film"

The adhesiveness of a liquid crystal layer and a liquid crystal aligning film was evaluated using the obtained liquid crystal display element (glass substrate/plastic substrate).

Further, in Examples 1 to 4, 7, 8 and 10, in addition to the above standard tests, as an intensive test, adhesion after storage in a constant temperature and humidity chamber at a temperature of 80°C and a humidity of 90% for 60 hours was also evaluated. . The evaluation method is the same conditions as in the examples of the A series.

Tables 70 to 72 show the results of adhesion between the liquid crystal layer and the liquid crystal aligning film after storage in a constant temperature and humidity chamber (constant temperature and humidity) and after ultraviolet irradiation (ultraviolet rays).

<Example 1>

NMP (14.6 g) and Z2 (0.163 g) were added to the polyamic acid solution (1) (6.50 g) obtained in Synthesis Example 1, and the mixture was stirred at 25°C for 24 hours. Then, T3 (0.082g) and BCS (19.5g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (1).

<Example 2>

After adding NEP (21.6 g) to the polyimide powder (2) (1.50 g) obtained in Synthesis Example 2 and stirring at 60°C for 24 hours, Z1 (0.300 g) was added and stirring was performed at 25°C for 24 hours. did Then, T3 (0.075g) and PB (14.4g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (2).

<Example 3>

NMP (14.6 g) and Z2 (0.163 g) were added to the polyamic acid solution (3) (6.50 g) obtained in Synthesis Example 3, and the mixture was stirred at 25°C for 24 hours. Then, T3 (0.082g) and BCS (19.5g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (3).

<Example 4>

To the polyimide powder (4) (1.50 g) obtained in Synthesis Example 4, NEP (21.6 g) was added and stirred at 60°C for 24 hours, then Z1 (0.300 g) was added and stirred at 25°C for 24 hours. did Then, T3 (0.075g) and PB (14.4g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (4).

<Example 5>

γ-BL (6.06 g), PGME (30.6 g) and Z2 (0.188 g) were added to the polyamic acid solution (5) (5.00 g) obtained in Synthesis Example 5, and the mixture was stirred at 25°C for 24 hours. Then, T3 (0.038g) was added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (5).

<Example 8>

γ-BL (6.06 g), PGME (30.6 g) and Z2 (0.188 g) were added to the polyamic acid solution (5) (5.00 g) obtained in Synthesis Example 5, and the mixture was stirred at 25°C for 24 hours. Then, T3 (0.038g), N1 (0.063g), M1 (0.063g) and K1 (0.088g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (6).

<Example 9>

γ-BL (8.08 g), PGME (28.6 g) and Z1 (0.125 g) were added to the polyamic acid solution (6) (5.00 g) obtained in Synthesis Example 6, and the mixture was stirred at 40°C for 12 hours. Then, T1 (0.088g), N1 (0.038g), and K1 (0.125g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (7).

<Example 10>

NMP (14.6 g) and Z2 (0.163 g) were added to the polyamic acid solution (7) (6.50 g) obtained in Synthesis Example 7, and the mixture was stirred at 25°C for 24 hours. Then, T3 (0.082g) and BCS (19.5g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (8).

<Example 11>

To the polyamic acid solution (8) (5.00 g) obtained in Synthesis Example 8, γ-BL (4.04 g), PB (4.04 g), PGME (28.6 g) and Z2 (0.375 g) were added and stirred at 25°C. Stir for 24 hours. Then, T3 (0.013g), N1 (0.088g), and K1 (0.063g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (9).

<Example 12>

γ-BL (8.41 g) and PGME (33.6 g) were added to the polyimide powder (9) (1.30 g) obtained in Synthesis Example 9, and after stirring at 60°C for 24 hours, Z1 (0.260 g) was added. and stirred at 40°C for 12 hours. Then, T2 (0.065g), N1 (0.065g), and K1 (0.039g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (10).

<Example 13>

γ-BL (6.31 g) and PGME (35.7 g) were added to the polyimide powder (10) (1.30 g) obtained in Synthesis Example 10, and after stirring at 60°C for 24 hours, Z2 (0.455 g) was added. and stirred at 25°C for 24 hours. Then, T3 (0.039g), N1 (0.065g), and K1 (0.130g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (11).

<Example 14>

γ-BL (6.06 g), PGME (30.6 g) and Z2 (0.125 g) were added to the polyamic acid solution (11) (5.00 g) obtained in Synthesis Example 11, and the mixture was stirred at 25°C for 24 hours. Then, T3 (0.038g), N1 (0.063g), and K1 (0.088g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (12).

<Example 15>

To the polyamic acid solution (12) (5.00 g) obtained in Synthesis Example 12, γ-BL (4.04 g), PGME (32.6 g) and Z2 (0.063 g) were added, and the mixture was stirred at 25°C for 24 hours. Then, T2 (0.088g), N1 (0.063g), and K1 (0.088g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (13).

<Comparative Example 1>

NMP (14.6g) and BCS (19.5g) were added to the polyamic acid solution (1) (6.50g) obtained in the synthesis example 1, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (14).

<Comparative Example 2>

NMP (14.6 g) and Z2 (0.163 g) were added to the polyamic acid solution (1) (6.50 g) obtained in Synthesis Example 1, and the mixture was stirred at 25°C for 24 hours. Then, BCS (19.5g) was added, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (15).

<Comparative Example 3>

T3 (0.082g), NMP (14.6g) and BCS (19.5g) were added to the polyamic acid solution (1) (6.50g) obtained in Synthesis Example 1, and it stirred at 25 degreeC for 8 hours, liquid-crystal aligning agent (16) was obtained.

<Comparative Example 4>

NEP (21.6g) and PB (14.4g) were added to the polyimide powder (2) (1.50g) obtained by the synthesis example 2, and it stirred at 60 degreeC for 24 hours, and obtained the liquid-crystal aligning agent (17).

<Comparative Example 5>

After adding NEP (21.6 g) to the polyimide powder (2) (1.50 g) obtained in Synthesis Example 2 and stirring at 60°C for 24 hours, Z1 (0.300 g) was added and stirring was performed at 25°C for 24 hours. did Then, PB (14.4g) was added, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (18).

<Comparative Example 6>

T3 (0.075 g), NEP (21.6 g) and PB (14.4 g) were added to the polyimide powder (2) (1.50 g) obtained in Synthesis Example 2, and stirred at 60 ° C. for 24 hours, liquid-crystal aligning agent ( 19) was obtained.

<Comparative Example 7>

γ-BL (6.06g) and PGME (30.6g) were added to the polyamic acid solution (5) (5.00g) obtained in Synthesis Example 5, and it stirred at 25°C for 4 hours to obtain the liquid-crystal aligning agent (20) got it

<Comparative Example 8>

γ-BL (6.06 g), PGME (30.6 g) and Z2 (0.188 g) were added to the polyamic acid solution (5) (5.00 g) obtained in Synthesis Example 5, and stirred at 25°C for 24 hours to form a liquid crystal. An orientation treatment agent (21) was obtained.

<Comparative Example 9>

To the polyamic acid solution (5) (5.00 g) obtained in Synthesis Example 5, T3 (0.038 g), γ-BL (6.06 g) and PGME (30.6 g) were added, stirred at 25°C for 8 hours, and liquid crystal An orientation treatment agent (22) was obtained.

As for the liquid-crystal aligning agent obtained in Examples 1-15 and Comparative Examples 1-9, abnormality, such as muddiness and precipitation, was not seen in any, and it was confirmed that it is a uniform solution.

These liquid-crystal aligning agents (1)-(22) and said liquid-crystal composition (1)-(4) were used in the combination shown in Table 67 - Table 72, manufacture and evaluation of a liquid crystal display element according to the said procedure conducted. In addition, Example 6 is a liquid crystal display element using the liquid-crystal aligning agent (5) and the liquid-crystal composition (2), and Example 7 is a liquid crystal display element using the liquid-crystal aligning agent (5) and the liquid-crystal composition (3) am.

Compared with Comparative Examples, the examples provided liquid crystal display elements with good optical properties, that is, particularly good transparency after storage in a high-temperature, high-humidity chamber and after ultraviolet irradiation, when no voltage was applied. Furthermore, it became an element with high adhesiveness of a liquid crystal layer and a liquid crystal aligning film. Moreover, even if a plastic substrate was used for the substrate of the element, these characteristics were good.

Specifically, the example element containing specific compound (1) and specific compound (2) in a liquid-crystal aligning agent did not contain it, or compared with the comparative example containing any one, especially high temperature, high humidity, but ultraviolet rays were irradiated Transparency in the back became high, and it became the result that the adhesiveness of a liquid crystal layer and a liquid crystal aligning film also became high. More specifically, it is a comparison between Example 1 and Comparative Examples 1 to 3, a comparison between Example 2 and Comparative Examples 4 to 6, and a comparison between Example 5 and Comparative Examples 7 to 9 under the same conditions.

In the specific side chain structure, when formula [3-1] is used, compared to the case where formula [3-2] is used, the transparency at the time of no voltage application of the liquid crystal display element increases, and furthermore, the long time constant temperature carried out by the stress test Even after storing in a humidity chamber, the result was that the transparency at the time of no voltage application became higher. Moreover, in evaluation of the adhesiveness of a liquid crystal layer and a liquid crystal aligning film, when using the specific side chain structure of formula [3-1], even after storing in a constant temperature and humidity chamber for a long time performed by the stress test, these adhesiveness is higher result has become Specifically, it is a comparison between Example 1 and Example 10 under the same conditions in the standard test and the stress test.

In addition, when a specific liquid crystal additive compound is introduced into the liquid crystal composition, the transparency of the liquid crystal display element when no voltage is applied increases, and the transparency when no voltage is applied is higher even after storage in a constant temperature and humidity chamber for a long time in the stress test. resulted in an increase. The larger the introduction amount of the specific liquid crystal additive compound, the greater the effect. Specifically, it is a comparison between Example 5 and 6 or 7 under the same conditions in the standard test and the stress test. Moreover, when a specific generator, an adhesive compound, and a specific crosslinkable compound were introduced in the liquid crystal aligning agent, the adhesiveness between the liquid crystal layer and the liquid crystal aligning film in the liquid crystal display element was further improved. Specifically, it is a comparison of Examples 7 and 8 under the same conditions in the stress test.

Moreover, when a polyimide-type polymer was used for a specific polymer, when a specific diamine compound (2) was used for a diamine component, the adhesiveness of the liquid crystal layer and liquid crystal aligning film in an element was improved more. Specifically, it is a comparison between Examples 1 and 3 and a comparison between Examples 2 and 4 under the same conditions in the stress test.

The liquid crystal display element of the present invention can be suitably used for a liquid crystal display for display purposes, a light control window or an optical shutter element for controlling transmission and blocking of light, and the like.

Further, the liquid crystal display element of the present invention is a liquid crystal display element used in transport equipment and transportation machines such as automobiles, railways, and aircraft, specifically, an optical shutter element used in a light control window and a room mirror that control transmission and blocking of light. etc. can be used suitably. In particular, when this element is used as a reverse-type element, transparency when no voltage is applied and scattering characteristics when voltage is applied are good, so when used for a vehicle window, the light introduction efficiency at night is higher than before, In addition, the effect of preventing glare from external light is also high. Therefore, the safety when driving the vehicle and the comfort when riding can be further improved. In addition, when the present element is made of a film and used by attaching it to a vehicle window, the reliability of the element is higher than before.

In addition, this element can be used also for the light guide plate of display devices, such as LCD and OLED, and the backing plate of the transparent display using these displays. Specifically, in the case of using the second plate of a transparent display, for example, when displaying a screen on a transparent display by combining a transparent display and the present element, the present element suppresses light entering from the rear surface. can This element enters a scattering state in which a voltage is applied when displaying on a screen on a transparent display, enabling clear screen display, and after the screen display is finished, it enters a transparent state in which no voltage is applied.

In addition, the entire contents of the specifications, claims, and abstracts of Japanese Patent Applications Nos. 2015-040263, 2015-040264 and 2015-040265 filed on March 2, 2015 are hereby incorporated herein by reference. It is taken as an indication of the specification of the invention.

Claims (16)

A liquid crystal alignment film having a liquid crystal layer cured by irradiating ultraviolet rays with respect to a liquid crystal composition containing a liquid crystal and a polymerizable compound disposed between a pair of substrates provided with electrodes, and at least one of the substrates orienting the liquid crystal vertically. As a liquid crystal display element provided with, the said liquid crystal aligning film is obtained from the liquid-crystal aligning agent containing the following component, The liquid crystal display element characterized by the above-mentioned.
Component (A): At least one compound selected from the group consisting of a compound of the following formula [1-1] and a compound of the following formula [1-2].
Component (B): A polymer having at least one structure selected from the group consisting of the following formula [2-1] and formula [2-2].

(T ¹ represents at least one selected from the group consisting of an alkylene group having 1 to 20 carbon atoms or an organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring, and any of the above-mentioned alkylene groups having 1 to 20 carbon atoms -CH ₂ - is -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-, -CON(CH ₃ )-, -S- or -SO ₂ - T ² is a single bond, -O-, -NH-, -N(CH ₃ )-, -CH ₂ O-, -OCH ₂ -, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO-, and -OCO-. T ³ is represented by the following formula [1-a] to formula [1-g] represents at least one structure selected from the group consisting of

(T ^A represents a hydrogen atom or a benzene ring. T ^B represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. T ^C represents an alkyl group having 1 to 18 carbon atoms, a carbon number At least one selected from the group consisting of 1 to 18 fluorine-containing alkyl groups, 1 to 18 carbon atoms alkoxy groups, and 1 to 18 carbon atoms fluorine-containing alkoxy groups.)

(S ¹ represents at least one structure selected from the group consisting of structures of the following formula [1-a] to formula [1-l]. S ² represents a single bond or an alkylene group having 1 to 24 carbon atoms; Optional -CH ₂ - of the alkylene group is -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-, -CON(CH ₃ )-, -S - or -SO ₂ - S ³ is at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent divalent group having 17 to 51 carbon atoms having a steroid skeleton. Represents an organic group, and any hydrogen atom on the cyclic group is an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxy group of 1 to 3 carbon atoms, or a fluorine atom. S ⁴ represents at least one bonding group selected from the group consisting ^of a single bond, -O-, -OCH ₂ -, -CH ₂ O-, -COO- and -OCO-. represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, or a carbon atom of 1 It may be substituted with a fluorine-containing alkyl group of 3 to 3, a fluorine ^- containing alkoxy group of 1 to 3 carbon atoms, or a fluorine atom. at least one member selected from the group consisting of a yl group, a fluorine-containing alkyl group of 1 to 18 carbon atoms, an alkoxy group of 1 to 18 carbon atoms, and a fluorine-containing alkoxy group of 1 to 18 carbon atoms.)

(S ^A represents a hydrogen atom or a benzene ring. S ^B represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. ^SC is an alkyl group having 1 to 18 carbon atoms, a carbon number represents at least one selected from the group consisting of a fluorine-containing ^alkyl group of 1 to 18, an alkoxy group of 1 to 18 carbon atoms, and a ^fluorine -containing alkoxy group of 1 to 18 carbon atoms. indicate.)

(Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )- represents at least one bonding group selected from the group consisting of -N(CH ₃ )CO-, -COO- and -OCO- Y ² is a single bond or -(CH ₂ ) _b - (b is 1 to 15 Y ³ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- and -OCO- Y ⁴ is at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms and having a steroid skeleton. any hydrogen atom on the cyclic group is substituted with an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxy group of 1 to 3 carbon atoms, or a fluorine atom. Y ⁵ represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group of 1 to 3 carbon atoms, an alkyl group of 1 to 3 carbon atoms, It may be substituted with an alkoxy group of 3, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxy group of 1 to 3 carbon atoms, or a fluorine atom. n represents an integer of 0 to 4. Y ⁶ is an alkyl group of 1 to 18 carbon atoms , an alkenyl group of 2 to 18 carbon atoms, a fluorine-containing alkyl group of 1 to 18 carbon atoms, an alkoxy group of 1 to 18 carbon atoms, and a fluorine-containing alkoxy group of 1 to 18 carbon atoms.)

(Y ⁷ is a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- and -OCO- represents at least one bonding group selected from the group consisting of Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.) According to claim 1,
(A) The liquid crystal display element which is at least 1 sort(s) chosen from the group which the compound of [1-1] of component consists of a compound of following formula [1a-1] - formula [1a-6].

(Ta and Tb each represent an integer of 1 to 12. Tc and Td each represent an integer of 1 to 10, and Te and Tf each represent an integer of 1 to 6.) According to claim 1,
(A) A liquid crystal display in which S ¹ in formula [1-2] of component is at least one structure selected from the group consisting of formula [1-a] to formula [1-d] and formula [1-f] device. According to claim 1,
(A) The liquid crystal display element which is at least 1 sort(s) of structure chosen from the group which S ^<1> in formula [1-2] of a component consists of formula [1-h] - formula [1-l]. According to claim 1,
A liquid crystal in which the polymer of component (B) is at least one selected from the group consisting of acrylic polymers, methacrylic polymers, novolac resins, polyhydroxystyrenes, polyimide precursors, polyimides, polyamides, polyesters, celluloses, and polysiloxanes. display element. According to claim 1,
(B) The polyimide precursor obtained by making the polymer of component react the diamine component and tetracarboxylic acid component containing the diamine compound which has the structure of formula [2-1] or formula [2-2], or its polyimide precursor A liquid crystal display element that is a polyimide imidized. According to claim 6,
The liquid crystal display element in which the said diamine compound is represented by following formula [2a].

(Y represents the formula [2-1] or formula [2-2]. n1 represents an integer of 1 to 4.) According to claim 6,
The liquid crystal display element in which the said diamine component contains the diamine compound of following formula [3a].

(W represents the structure of formula [3] below. m1 represents the integer of 1-4.)

(W ¹ is a single bond, -O-, -NH-, -N(CH ₃ )-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ ) represents at least one bonding group selected from the group consisting of CO-, -COO-, and -OCO- W ² is a single bond, an alkylene group having 1 to 18 carbon atoms, or a benzene ring, a cyclohexane ring, or a heterocyclic ring; represents an organic group having 6 to 24 carbon atoms and having at least one type of cyclic group selected from the group consisting of, and any hydrogen atom on these cyclic groups is an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, or an organic group of 1 to 3 carbon atoms It may be substituted with a fluorine-containing alkyl group of 3 or a fluorine-containing alkoxy group of 1 to 3. W ³ is a single bond, -O-, -NH-, -N(CH ₃ )-, -CH ₂ O-, -CONH - ^, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- and -OCO-. a] to at least one structure selected from the group consisting of formula [3-g].)

(W ^A represents a hydrogen atom or a benzene ring. W ^B represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. W ^C is an alkyl group having 1 to 18 carbon atoms, a carbon number At least one selected from the group consisting of 1 to 18 fluorine-containing alkyl groups, 1 to 18 carbon atoms alkoxy groups, and 1 to 18 carbon atoms fluorine-containing alkoxy groups.) According to claim 6,
The liquid crystal display element in which the tetracarboxylic acid component contains tetracarboxylic dianhydride of the following formula [4].

(Z represents at least one structure selected from the group consisting of structures of the following formula [4a] to formula [4k].)

(Z ¹ to Z ⁴ each independently represent at least one selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom and a benzene ring. Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group.) According to claim 1,
(B) polysiloxane obtained by polycondensing an alkoxysilane of the following formula [A1], or polycondensation of an alkoxysilane of the formula [A1] and an alkoxysilane of the following formula [A2] or formula [A3] A liquid crystal display element containing polysiloxane obtained by

(A ¹ represents the structure of the formula [2-1] or formula [2-2]. A ² represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms. A ³ represents an alkyl group of 1 to 5 carbon atoms. m represents an integer of 1 or 2. n represents an integer of 0 to 2. p represents an integer of 0 to 3. However, m + n + p is 4.)

(B ¹ is an organic group having 2 to 12 carbon atoms and at least one selected from the group consisting of a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacryl group, an acryl group, a ureide group, and a cinnamoyl group. B ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms B ³ represents an alkyl group having 1 to 5 carbon atoms m represents an integer of 1 or 2 n represents an integer of 0 to 2 p represents an integer from 0 to 3. However, m + n + p is 4.)

(D ¹ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms. D ² represents an alkyl group of 1 to 5 carbon atoms. n represents an integer of 0 to 3.) According to any one of claims 1 to 10,
The liquid crystal display element in which the said liquid-crystal aligning agent contains at least 1 sort(s) of generator chosen from the group which consists of an optical radical generator, a photoacid generator, and a photobase generator. According to any one of claims 1 to 10,
The liquid crystal aligning agent contains a compound having at least one substituent selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and an alkoxyalkyl group having 1 to 3 carbon atoms. A liquid crystal display element to do. According to any one of claims 1 to 10,
The liquid crystal aligning agent is 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone , cyclopentanone and a liquid crystal display element containing at least one solvent selected from the group consisting of solvents of the following formula [D1] to formula [D3].

(D ^a , D ^b and D ^c each represent an alkyl group having 1 to 4 carbon atoms.) According to any one of claims 1 to 10,
The liquid crystal display element in which the said liquid crystal aligning agent contains at least 1 sort(s) of solvent chosen from the group which consists of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and (gamma)-butyrolactone. According to any one of claims 1 to 10,
The liquid crystal display device in which the liquid crystal composition contains the compound of the formula [1-1] or the compound of the formula [1-2]. According to any one of claims 1 to 10,
The liquid crystal display element in which the substrate of the liquid crystal display element is a glass substrate or a plastic substrate.