TW201502252A - Liquid crystal display element, liquid crystal alignment film, and liquid crystal alignment treatment agent - Google Patents

Abstract

Provided is a liquid crystal display element having high vertical alignment in a liquid crystal, excellent transparency when no voltage is applied and scattering characteristics when a voltage is applied, and strong adhesion between a liquid crystal layer and a vertical liquid crystal alignment film. The liquid crystal display element is obtained by placing a liquid crystal layer between a pair of substrates provided with an electrode, disposing a liquid crystal composition containing a polymerizable compound polymerized by active energy rays and/or heat between the pair of substrates, providing at least one of the substrates with a liquid crystal alignment film such that the liquid crystal is aligned vertically, curing the liquid crystal composition while all or part of the liquid crystal composition exhibits liquid crystal properties, and forming a cured product composite of the liquid crystal and the polymerizable compound, wherein the liquid crystal display element is characterized in that the liquid crystal alignment film is obtained from a liquid crystal alignment treatment agent containing at least one type of polymer selected from the group consisting of polyimides and polyimide precursors represented by formula [1-1] or [1-2], and also containing a solvent having a boiling point of less than 180 DEG C, the solvent being contained in an amount constituting at least 50 mass% of the complete solvent. In formula [1-1], Y1, Y2, and Y3 are single bonds, etc.; Y4 and Y5 are benzene rings, etc.; Y6 is a C1-18 alkyl group, etc.; and n is an integer from 0 to 4. In formula [1-2], Y7 is a single bond, etc.; and Y8 is a C8-22 alkyl group.

Description

Liquid crystal display element, liquid crystal alignment film, and liquid crystal alignment treatment agent

The present invention relates to a transparent scattering type liquid crystal display element which is in a scattering state when no voltage is applied, a liquid crystal alignment film which the liquid crystal display element has, and a liquid crystal alignment treatment agent for forming the liquid crystal alignment film.

A liquid crystal display element using a liquid crystal material, for example, a TN (Twisted Nematic) mode has been put into practical use. In this mode, the light is switched by the optical rotation characteristics of the liquid crystal. When used as a liquid crystal display element, it is necessary to use a polarizing plate. However, since a polarizing plate is used, the utilization efficiency of light is lowered.

A liquid crystal display element having high light-utilizing efficiency without using a polarizing plate, for example, a liquid crystal display element that switches between a liquid crystal transmission state (also referred to as a transparent state) and a scattering state, and generally known to use a polymer dispersed liquid crystal (PDLC) (Polymer Dispersed Liquid Crystal) or polymer network liquid crystal (PNLC (Polymer Network Liquid Crystal)).

The liquid crystal display element using these is formed by a liquid crystal layer between a pair of substrates including electrodes, and the active energy lines are disposed between the pair of substrates. And a liquid crystal composition of a polymerizable compound which is polymerized by at least one of heat, and a part or the whole of the liquid crystal composition is cured in the liquid crystal state, and the liquid crystal composition is cured by a cured product of a liquid crystal and a polymerizable compound. The liquid crystal display element produced by the step of the body. The liquid crystal display element controls the transmission state and the scattering state of the liquid crystal by applying a voltage.

Conventionally, a liquid crystal display device using PDLC or PNLC has a white turbid (scattering) state when liquid crystal molecules are directed in a random direction when no voltage is applied, and liquid crystals are arranged in a direction of electric field when a voltage is applied, and light is transmitted through a transparent state (control) This transparent scattering liquid crystal display element is also referred to as a "Normal Mode" element. However, in order to obtain a transmission state, the normal type element must be constantly applied with a voltage. Therefore, when it is used in a transparent state, for example, when it is used in a window glass or the like, power consumption is large.

In contrast, there is a report of a PDLC element that is in a transmission state when no voltage is applied, and a PDLC element that is in a scattering state when a voltage is applied (a liquid crystal display element that controls such transmission and scattering is also referred to as a reverse type element) (see Patent Documents 1 and 2).

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent No. 2885116

[Patent Document 2] Japanese Patent No. 4132424

[Summary of the Invention]

The reverse type element must have the liquid crystals vertically aligned, and therefore a liquid crystal alignment film (also referred to as a vertical liquid crystal alignment film) that vertically aligns the liquid crystals is used.

At present, the liquid crystal alignment film which is mainly used in the industry is an organic film composed of a polyimide-based polymer which is excellent in durability and is suitable for the control of the pretilt angle of the liquid crystal. The polyamidene-based polymer is a polyaminic acid precursor of a polyimine precursor and/or a polyimide which is ruthenium imidized with poly-proline, and a liquid crystal alignment film is made of such a polymer. It is produced by a liquid crystal alignment agent.

The solvent of the liquid crystal alignment treatment agent using the polyimine-based polymer is such that the solvent solubility of the polyilylimine-based polymer is low, so N-methyl-2-pyrrolidone (also referred to as NMP) or the like is used. Highly polar solvent. These highly polar solvents have a high boiling point, for example, the boiling point of NMP is 200 ° C or higher. Therefore, in order to use the liquid crystal alignment treatment agent using NMP as a solvent, when the liquid crystal alignment film is produced, in order to eliminate the NMP remaining in the liquid crystal alignment film, it is necessary to fire at a high temperature of about 200 ° C near the boiling point of NMP. .

On the other hand, the substrate of the liquid crystal display element is thin and lightweight, but when a plastic substrate having low heat resistance is used, it is necessary to perform firing at the time of producing a liquid crystal alignment film at a lower temperature. Similarly, by lowering the firing temperature to a low temperature, the energy cost at the time of manufacturing the liquid crystal display element can be reduced.

Accordingly, an object of the present invention is to provide a liquid crystal display element which has a liquid crystal alignment film which can be fired at a low temperature even when a liquid crystal alignment agent of a polyimine polymer is used, and a vertical alignment of liquid crystal The optical property is high, and good optical characteristics are good in transparency when no voltage is applied and scattering characteristics when applied voltage, and liquid crystal display element having high adhesion between the liquid crystal layer and the vertical liquid crystal alignment film.

Further, an object of the present invention is to provide a vertical liquid crystal alignment film which the liquid crystal display element has and a liquid crystal alignment treatment agent which can form the vertical liquid crystal alignment film.

As a result of intensive studies, the present inventors have found that a liquid crystal display element using a vertical liquid crystal alignment film obtained by the following liquid crystal alignment treatment agent can effectively achieve the above object, and the liquid crystal alignment treatment agent contains a side having a specific structure. a polymer of at least one selected from the group consisting of a polyimine precursor of a chain and a polyimine which is ruthenium imidized with the polyimide precursor, and a solvent having a boiling point of less than 180 ° C contains a solvent as a whole. 50% by mass or more of the liquid crystal alignment treatment agent.

The present invention has the following key points.

(1) A liquid crystal display device comprising: a liquid crystal layer formed between one of the electrodes; and a polymerizable compound containing at least one of an active energy ray and heat disposed between the pair of substrates; In the liquid crystal composition, at least one of the substrates has a liquid crystal alignment film in which the liquid crystal is vertically aligned, and a part or the whole of the liquid crystal composition is cured in the liquid crystal state to form a liquid crystal and a hardening of the polymerizable compound. A liquid crystal display element formed of a complex of a polyimine precursor containing a group having a structure represented by the following formula [1-1] or [1-2] and a polycondensation film The yttrium imide precursor is a polymer selected from the group consisting of ruthenium imidized polyimine, and the solvent having a boiling point of less than 180° C. contains a liquid crystal alignment agent obtained by a liquid crystal alignment treatment agent having a total solvent content of 50% by mass or more. membrane, (Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Y ² represents a single bond or -( CH ₂ ) _b - (b is an integer from 1 to 15). Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO - or -OCO-. Y ^{4 is a} divalent cyclic group selected from a benzene ring, a cyclohexane ring and a hetero ring, or a divalent organic group having a steroid number of 17 to 51 carbon atoms, on the above cyclic group Any hydrogen atom may pass through an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or fluorine. Substituted by an atom. Y ⁵ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a hetero ring, and any hydrogen atom on the ring group may pass through an alkyl group having 1 to 3 carbon atoms and carbon. The number of alkoxy groups of 1 to 3, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and n is an integer of 0 to 4. Y ⁶ represents a carbon number. An alkyl group of 1 to 18, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms.

[Chemical 2]-Y ⁷ -Y ⁸ [1-2] (Y ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N (CH ₃ )CO-, -COO- or -OCO-. 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 the above (1), wherein the polymer is a diamine compound having a side chain having a structure represented by the above formula [1-1] or [1-2] for use as a part of a raw material A polymer obtained by grouping at least one of a polyimine precursor obtained and a polyimine imide obtained by subjecting the polyimine precursor to ruthenium.

(3) The liquid crystal display device according to (2) above, wherein the diamine compound is a diamine compound represented by the following formula [1a], (Y is a structure represented by the above formula [1-1] or [1-2], and n represents an integer of 1 to 4).

(4) The liquid crystal display element according to any one of the above (1), wherein the polymer is a part of a raw material obtained by using a second diamine compound represented by the following formula [2]. At least one selected from the group consisting of a polyimide precursor and a polyamidimide in which the polyimine precursor is ruthenium imidized.

(X represents a substituent selected from the structures of the following formula [2a], formula [2b], formula [2c] and formula [2d], and m represents an integer of 1 to 4)

(a represents an integer of 0 to 4, and in the formula [2b], b represents an integer of 0 to 4. X ¹ and X ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. X ³ represents an alkyl group having 1 to 5 carbon atoms. ).

(5) The liquid crystal display element according to any one of the above (1), wherein the polymer is a polymer obtained by using a tetracarboxylic acid component represented by the following formula [3] as a part of a raw material. At least one selected from the group consisting of a ruthenium imine precursor and a polyamidimide obtained by subjecting the polyimine precursor to ruthenium imidization, (Z ¹ represents a group selected from the structures of the following formulas [3a] to [3j]) (Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different. Z ⁶ and Z ^{7 each} represent a hydrogen atom or a methyl group, and each may be the same or different).

(6) The liquid crystal display element according to any one of the above (1), wherein the polymer is a polyimine.

(7) The liquid crystal display element according to any one of the above-mentioned (1), wherein the liquid crystal alignment treatment agent contains cyclopentanone or cyclohexanone as a solvent having a boiling point of less than 180 ° C, and the following At least one solvent selected from the group consisting of the solvents represented by the formula [A1] and the formula [A2], (A ¹ represents an alkyl group having 1 to 3 carbon atoms. A ² represents an alkyl group having 1 to 3 carbon atoms).

(8) The liquid crystal display element according to any one of the above (1), wherein the liquid crystal alignment treatment agent contains 1-hexanol and a ring. A solvent selected from the group consisting of hexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, and dipropylene glycol dimethyl ether.

(9) The liquid crystal display element according to any one of the above (1), wherein the liquid crystal alignment treatment agent contains N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ - at least one solvent selected from the group consisting of butyrolactone and a solvent represented by the following formula [A3], (A ³ represents an alkyl group having 1 to 4 carbon atoms).

(10) The liquid crystal display element according to any one of the above (1), wherein the content of the solvent in the liquid crystal alignment treatment agent is from 50 to 99.9% by mass.

The liquid crystal display element according to any one of the above-mentioned (1) to (10), wherein the liquid crystal alignment treatment agent contains a compound having a group having a structure represented by the following formulas [B1] to [B7]. At least one compound selected from the group, (W ¹ represents a hydrogen atom or a benzene ring. W ² represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring. W ³ represents an alkyl group having 1 to 18 carbon atoms, A fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms.

The liquid crystal display element according to any one of the above-mentioned (1), wherein the liquid crystal alignment treatment agent contains a compound represented by the following formula [6]. (X ¹ represents a structure selected from at least one of the groups represented by the following formulas [6a-1] to [6a-7]. X ² represents a group selected from a single bond, -CH ₂ -, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )-, and -N ( CH ₃ ) CO- is a bonding group of at least one of the groups. X ³ represents an alkyl group having 1 to 20 carbon atoms, -(CH ₂ -CH ₂ -O) _p - (p is an integer of 1 to 10) And at least one selected from the group consisting of -(CH ₂ -O-) _q - (q is an integer of 1 to 10) and an organic group having a benzene ring or a cyclohexane ring having 6 to 20 carbon atoms.

At this time, any -CH ₂ - group of the above alkylene group may be via -COO-, -OCO-, -CONH-, NHCO-, -CO-, -S-, -SO ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -OSi(CH ₃ ) ₂ - or -Si(CH ₃ ) ₂ O-substitution, hydrogen atoms bonded to any carbon atom A hydroxyl group (OH group), a carboxyl group (COOH group) or a halogen atom is substituted. X ⁴ represents a bonding group of at least one selected from the group consisting of a single bond, -CH ₂ -, -OCH ₂ -, and -O-CH ₂ -CH ₂ -. X ⁵ represents a structure in which at least one selected from the group consisting of the structures represented by the following formulas [6b-1] to [6b-8]. n represents an integer from 1 to 3. m represents an integer from 1 to 3)

(A ¹ represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. A ² , A ³ , A ⁵ , A ⁶ and A ⁹ each independently represent a hydrogen atom or an alkylene group having 1 to 3 carbon atoms. A ⁴ , A ⁷ and A ⁸ each independently represent an alkylene group having 1 to 3 carbon atoms)

(B ¹ represents a hydrogen atom or a benzene ring. B ² represents a cyclic group selected from at least one selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring. B ³ represents an alkyl group having 1 to 12 carbon atoms. And at least one selected from the group consisting of a fluorine-containing alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a fluorine-containing alkoxy group having 1 to 12 carbon atoms.

(13) The liquid crystal display device according to any one of (1) to (12) wherein the substrate of the liquid crystal display element is a glass substrate or a plastic substrate.

(14) A liquid crystal alignment film which is used for the liquid crystal display element according to any one of (1) to (13) above.

(15) The liquid crystal alignment film of (14) above, wherein the film thickness is 5 to 300 nm.

(16) A liquid crystal alignment treatment agent for forming the liquid crystal alignment film of the above (14) or (15).

The liquid crystal display device of the present invention has a liquid crystal alignment film which can be fired at a low temperature, and a plastic substrate can be used for the substrate. The liquid crystal has high vertical alignment property, good optical characteristics, that is, transparency when no applied voltage is applied, and scattering at an applied voltage. The characteristics are good, and the liquid crystal layer and the vertical liquid crystal alignment film have high adhesion, and can be used for a liquid crystal display for display purposes or a dimming window or an optical shutter element for controlling light transmission and blocking.

[Formation of the Invention]

The invention is described in detail below.

The present invention relates to a liquid crystal display device comprising a liquid crystal layer formed by one of the electrodes and a liquid crystal layer between the substrates, and a polymerizable compound which is polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates In the liquid crystal composition, at least one of the substrates has a liquid crystal alignment film that vertically aligns the liquid crystal, and a part or the whole of the liquid crystal composition is cured in the liquid crystal state to form a liquid crystal and polymerizability. The step of the hardened composite of the compound is produced.

The liquid crystal alignment film is a polyfluorene imine precursor containing a structure represented by the following formula [1-1] or [1-2] (also referred to as a group having a specific side chain structure) and the polyfluorene The imine precursor is a polymer of at least one selected from the group consisting of ruthenium imidized polyimine (also referred to as a specific polyamidene-based polymer), and a solvent having a boiling point of less than 180 ° C (also referred to as The specific solvent) is obtained by containing a liquid crystal alignment agent of 50% by mass or more of the entire solvent.

(Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Y ² represents a single bond or -( CH ₂ ) _b - (b is an integer from 1 to 15). Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO - or -OCO-. Y ^{4 is a} divalent cyclic group selected from a benzene ring, a cyclohexane ring and a hetero ring, or a divalent organic group having a steroid number of 17 to 51 carbon atoms, on the above cyclic group Any hydrogen atom may pass through an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or fluorine. Substituted by an atom. Y ⁵ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a hetero ring, and any hydrogen atom on the ring group may pass through an alkyl group having 1 to 3 carbon atoms and carbon. The number of alkoxy groups of 1 to 3, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and n is an integer of 0 to 4. Y ⁶ represents a carbon number. An alkyl group of 1 to 18, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms.

[Y15]-Y ⁷ -Y ⁸ [1-2] (Y ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N (CH ₃ )CO-, -COO- or -OCO-. Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.

The liquid crystal display element of the invention is mainly applicable to no external power A reverse type element that becomes a transmission state when the voltage is applied and a scattering state when a voltage is applied.

Further, since the specific polyimine-based polymer used in the liquid crystal alignment treatment agent of the present invention has high solubility in a solvent, it can contain a plurality of low-polar solvents having a boiling point of less than 180 ° C as a solvent for a liquid crystal alignment treatment agent. .

Further, among the groups of the specific side chain structure contained in the specific polyamidimide polymer used in the liquid crystal alignment agent of the present invention, the formula [1-1] has a benzene ring or a cyclohexyl ring at the side chain portion. Or a heterocyclic ring or a divalent organic group having a carbon number of 17 to 51 having a steroid skeleton. The side chain structure of these rings and the organic group exhibits a rigid structure, and therefore, the use of a reverse type element having a vertical liquid crystal alignment film of the formula [1-1] can provide a vertical alignment of a high and stable liquid crystal.

A liquid crystal display element using a liquid crystal alignment film obtained by a liquid crystal alignment treatment agent containing a specific polyamidene-based polymer having a specific side chain structure of the present invention and a specific solvent, that is, a liquid crystal alignment treatment agent is a polyimine In the case of a polymer, the liquid crystal alignment film can be fired at a low temperature. Further, the liquid crystal has high vertical alignment property, and good optical characteristics, that is, transparency when no voltage is applied and scattering characteristics when a voltage is applied, and the liquid crystal layer and the liquid crystal alignment film have high adhesion.

<Liquid crystal display element>

The liquid crystal display device of the present invention comprises a liquid crystal layer between one of the electrodes and the substrate, and the active energy is disposed between the pair of substrates. A liquid crystal composition of a polymerizable compound in which at least one of a line and a heat is polymerized, and at least one of the substrates has a liquid crystal alignment film in which a liquid crystal is vertically aligned, and a part or the whole of the liquid crystal composition is in a liquid crystal state. The curing of the liquid crystal composition is carried out by a step of forming a cured composite of a liquid crystal and a polymerizable compound, and is applicable to a reversed element which is in a transparent state when no voltage is applied and a scattering state when a voltage is applied.

<LCD>

As the liquid crystal in the liquid crystal composition used in the liquid crystal display device of the present invention, nematic liquid crystal or smectic liquid crystal can be used. Among them, those having a negative dielectric anisotropy are preferred. Further, the point of low voltage driving and scattering characteristics of the element is preferably such that the anisotropy of the dielectric constant is large and the anisotropy of the refractive index is large. Further, in order to drive the liquid crystal display element as an active element such as a TFT (Thin Film Transistor), it is required that the liquid crystal has high resistance and a high voltage holding ratio (VHR). Therefore, the liquid crystal is preferably a fluorine-based or chlorine-based liquid crystal which has a high electric resistance and does not lower the VHR due to an active energy ray such as ultraviolet rays.

The liquid crystal display device of the present invention can also dissolve a dichroic dye as a host guest element in a liquid crystal composition. At this time, an element which is transparent when no voltage is applied and which absorbs (scatters) when a voltage is applied can be obtained.

Further, the alignment direction of the liquid crystal of the liquid crystal display element of the present invention is changed by 90 degrees due to the presence or absence of an applied voltage. Therefore, by using the difference in the light absorption characteristics of the dichroic dye, it is possible to obtain a liquid crystal display having a higher contrast than the conventional host-guest element that switches between the random alignment and the vertical alignment. element.

Further, the host-guest element in which the dichroic dye is dissolved becomes colored when the liquid crystal is aligned in the horizontal direction, and becomes opaque only in the scattering state. Therefore, it is also possible to obtain an element which is switched from a colorless transparent color without an applied voltage to a colored opaque, colored transparent state with an applied voltage.

<Polymerizable compound>

The liquid crystal composition of the liquid crystal display device of the present invention contains a polymerizable compound which is polymerized by at least one of an active energy ray such as ultraviolet rays and heat. In this case, the polymerization is carried out in any reaction form to form a cured product of a liquid crystal and a polymerizable compound. The reaction form of the specific polymerization may, for example, be a radical polymerization, a cationic polymerization, an anionic polymerization or a polyaddition reaction.

Here, the cured composite system refers to a state in which a liquid crystal exists in a high molecular weight body (polymer) formed by a polymerizable compound.

The polymerizable compound may be any compound as long as it is dissolved in the liquid crystal. However, when the polymerizable compound is dissolved in the liquid crystal, it is necessary to have a temperature at which a part or the whole of the liquid crystal composition exhibits a liquid crystal phase. When a liquid crystal phase is present in a part of the liquid crystal composition, it is sufficient to obtain the same transparency and scattering characteristics as the entire liquid crystal display element.

When the reaction form of the polymerizable compound is a radical polymerization, the following radical type polymerizable compound can be used.

For example, 2-ethylhexyl acrylate, butyl ethyl acrylate, butoxyethyl acrylate, 2-cyanoethyl acrylate, benzyl acrylate, Cyclohexyl acrylate, 2-hydroxypropyl acrylate, 2-ethoxyethyl acrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylaminoethyl acrylate , dicyclopentyl acrylate, dicyclopentenyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, isodecyl acrylate, lauryl acrylate, morpholine acrylate , phenoxyethyl acrylate, phenoxy diethylene glycol acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2 , 2,3,3-tetrafluoropropyl acrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate, 2-ethylhexyl methacrylate, butyl ethyl methacrylate Ester, butoxyethyl methacrylate, 2-cyanoethyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-hydroxypropyl methacrylate, 2-B Oxyethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, dicyclopentyl methacrylate, bicyclo Pentenyl methacryl Acid ester, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, isodecyl methacrylate, lauryl methacrylate, morpholine methacrylate, Phenoxyethyl methacrylate, phenoxy diethylene glycol methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl Acrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 4,4'-biphenyldiacrylate, diethylstilbestrol diacrylate, 1,4-bispropene oxime Oxybenzene, 4,4'-bispropenyloxy diphenyl ether, 4,4'-bispropenyloxy diphenylmethane, 3,9-[1,1-dimethyl-2-propene醯oxyethyl]-2,4,8,10-tetraspiro[5,5]undecane, α,α'-bis[4-propenyloxyphenyl]-1,4-diisopropyl Base benzene, 1,4-bis propylene oxime Tetrafluorobenzene, 4,4'-bispropenyloxy octafluorobiphenyl, diethylene glycol acrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, two Cyclopentyl diacrylate, glycerin diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol Tetraacrylate, pentaerythritol triacrylate, bis(trimethylol)propane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, 4,4'-dipropenyloxy oxime, 4,4 '-Dipropylene decyloxy dimethyl hydrazine, 4,4'-dipropylene decyloxydiethyl hydrazine, 4,4'-dipropylene decyloxydipropyl fluorene, 4,4'-dipropylene fluorene Oxydibutylphosphonium, 4,4'-dipropyleneoxydipentylphosphonium, 4,4'-dipropyleneoxydihexylfluorene, 4,4'-dipropyleneoxydifluoroantimony, 2,2,3,3,4,4-hexafluoropentanediol-1,5-diacrylate, 1,1,2,2,3,3-hexafluoropropyl-1,3-diacrylate , diethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol II Acrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol Tetramethacrylate, pentaerythritol trimethacrylate, bis(trimethylol)propane tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxypentamethacrylate, 2,2,3 a monomer such as 3,4,4-hexafluoropentanediol-1,5-dimethacrylate or the like.

In the present invention, for the purpose of improving the scattering characteristics at the time of applying a voltage, a polyfunctional radical type polymerizable compound having three or more functional groups is preferably used.

Specific examples thereof include trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, bis(trimethylol)propane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylic acid. Ester, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, bis(trimethylol)propane tetramethacrylate, dipentaerythritol hexamethacrylate, two Monomers such as pentaerythritol monohydroxypentamethacrylate and the like.

The radical type polymerizable compound can be used in one type or in a mixture of two or more types depending on the optical characteristics of the liquid crystal display element or the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film.

Further, when the reaction form of the polymerizable compound is a radical polymerization, a radical initiator which generates a radical due to ultraviolet rays can be introduced into the liquid crystal composition.

Specific examples thereof include tert-butylperoxy-iso-phthalate, 2,5-dimethyl-2,5-bis(benzylidenedioxy)hexane, and 1, 4-bis[α-(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert- Butyldioxy)hexene hydroperoxide, α-(iso-propylphenyl)-iso-propyl hydroperoxide, 2,5-dimethylhexane, tert-butyl hydroperoxide , 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-bis(tert-butyldioxy)valerate , cyclohexanone peroxide, 2,2',5,5'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra (tert-butyl Peroxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-pentylperoxycarbonyl)diphenyl Methyl ketone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3'-bis(tert-butylperoxycarbonyl)-4,4'- Organic peroxides such as dicarboxybenzophenone, tert-butylperoxybenzoate, di-tert-butyldiperoxyphthalate or 9,10-fluorene, 1 - guanidines such as chloranil, 2-chloroindole, octamethyl hydrazine, 1,2-benzopyrene, benzoin methyl, benzoin ethyl ether, α-methyl benzoine And benzoin derivatives such as α-phenylbenzene.

When the reaction form of the polymerizable compound is cationic polymerization or anionic polymerization, the following ionic polymerizable compound can be used.

Specifically, for example, 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. For example, a melamine derivative, a benzoguanamine derivative or a glycoluril in which a hydrogen atom of an amine group is substituted with a methylol group, an alkoxymethyl group or both can be used. The melamine derivative or the benzoguanamine derivative may be an oligomer. It is preferred that each of the triazine rings has an average of 3 or more and less than 6 hydroxymethyl groups or alkoxymethyl groups.

Examples of such a melamine derivative or a benzoguanamine derivative include, for example, one triazine ring per commercially available product, an average of 3.7 substituted MX-750, and one triazine ring one per methoxymethyl group. The oxymethyl group has an average of 5.8 substituted MW-30 (the above is manufactured by Sanwa Chemical Co., Ltd.) or Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. Methoxymethylated butoxymethylated melamine such as melamine, Cymel 235, 236, 238, 212, 253, 254, etc., butoxymethylated melamine such as Cymel 506, 508, etc. Carboxylated methoxymethylated isobutoxymethylated melamine of Cymel 1141, methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1123, methoxyl such as Cymel 1123-10 Methylated butoxymethylated benzoguanamine, a butoxymethylated benzoguanamine such as Cymel 1128, a carboxyl group-containing methoxymethylated ethoxymethyl group such as Cymel 1125-80 Benzoguanamine (above, Mitsui Cytec). Further, examples of the glycoluril include, for example, butoxymethylated glycoluril of Cymel 1170, and methylolated glycoluril of Cymel 1172.

A benzene or phenolic compound having a hydroxyl group or an alkoxy group, for example, 1,3,5-glycol (methoxymethoxy)benzene, 1,2,4-para(isopropoxymethoxy)benzene 1,4-bis(sec-butoxymethoxy)benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, and the like.

Further, as the ionic polymerizable compound, a compound containing a group such as an epoxy group or an isocyanate group and having a crosslinking group can be used. Specific examples thereof include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, and tetraglycidylamino diphenylene ( Diphenylene), tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyl etherethane, triphenylglycidyl Ethyl ether, bisphenol hexafluoroacetic acid diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2 -trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl metaxylenediamine ,2-(4-(2,3-epoxypropoxy)phenyl)-2-(4-(1,1-bis(4-(2,3-epoxyoxypropoxy)) Phenyl)ethyl)phenyl)propane, 1,3-bis(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-(4-(1) -(4-(2,3-Epoxypropoxyphenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol and the like.

The ionic polymerizable compound may be used in one type or in a mixture of two or more types depending on the optical characteristics of the liquid crystal display element or the adhesion properties of the liquid crystal layer and the vertical liquid crystal alignment film.

Further, when the reaction form of the polymerizable compound is cationic polymerization or anionic polymerization, an ion initiator which generates an acid or a base by ultraviolet rays may be introduced into the liquid crystal composition.

Specific examples thereof include a triazine compound, an acetophenone derivative compound, a dioxon compound, a diazomethane compound, a sulfonic acid derivative compound, a diarylsulfonium salt, a triarylsulfonium salt, and a triarylsulfonium compound. Salt, iron aromatic hydrocarbon complex, etc., but are not limited thereto. More specifically, for example, diphenylphosphonium chloride, diphenylsulfonium trifluoromethanesulfonate, diphenylsulfonate, diphenylsulfonate tosylate, diphenyl Bismuth bromide, diphenylphosphonium tetrafluoroborate, diphenylphosphonium hexafluoroantimonate, diphenylphosphonium hexafluoroarsenate, bis(p-tert-butylphenyl)phosphonium hexafluorophosphate , bis(p-tert-butylphenyl)indole mesylate, bis(p-tert-butylphenyl)phosphonium p-toluenesulfonate, bis(p-tert-butylphenyl)phosphonium trifluoride Methanesulfonate, bis(p-tert-butylphenyl)phosphonium tetrafluoroborate, bis(p-tert-butylphenyl)phosphonium chloride, bis(p-chlorophenyl)phosphonium chloride, Bis(p-chlorophenyl)phosphonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tris(p-methoxyphenyl)phosphonium tetrafluoroborate, tris(p- Methoxyphenyl) Hexafluorophosphate, tris(p-ethoxyphenyl)phosphonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tris(p-methoxyphenyl)phosphonium tetrafluoro Boric acid ester, tris(p-methoxyphenyl)phosphonium hexafluorophosphate, tris(p-ethoxyphenyl)phosphonium tetrafluoroborate or the like. Further, for example, bis[[(2-nitrobenzyl)oxy]carbonylhexane-1,6-diamine], nitrobenzylcyclohexylaminoformate, bis(methoxybenzyl) Hexamethylene dicarbamate, bis[[(2-nitrobenzyl)oxy]carbonylhexane-1,6-diamine], nitrobenzylcyclohexylaminoformate, Bis(methoxybenzyl)hexamethylenedicarbamate.

In the present invention, from the viewpoint of optical characteristics of the liquid crystal display element, among the polymerizable compounds, a radical type polymerizable compound is preferably used.

The amount of the polymerizable compound to be introduced into the liquid crystal composition is not particularly limited. However, when the amount of the polymerizable compound introduced is large, the polymerizable compound in the liquid crystal is not dissolved, or the liquid crystal composition does not exhibit a temperature of the liquid crystal phase, and the liquid crystal display element is transparent. The change in the state and the scattering state becomes small, and the optical characteristics are deteriorated.

In addition, when the amount of introduction of the polymerizable compound is small, the curability of the liquid crystal layer is lowered, and the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is lowered, and the alignment of the liquid crystal is liable to be disordered with respect to the mechanical external pressure. Therefore, the amount of the polymerizable compound to be introduced is preferably from 1 to 50 parts by mass, more preferably from 5 to 40 parts by mass, per 100 parts by mass of the liquid crystal. Particularly good is 11 to 30 parts by mass.

Further, the introduction amount of the radical initiator and the ion initiator which promote the reaction of the polymerizable compound is not particularly limited, and is preferably 100 mass with respect to the liquid crystal. The fraction is 0.01 to 10 parts by mass, and preferably 0.05 to 5 parts by mass. Particularly preferred is 0.05 to 3 parts by mass.

<specific side chain structure>

The liquid crystal display element of the present invention is an element having at least one of the substrates having a vertical liquid crystal alignment film that vertically aligns the liquid crystal. In this case, the vertical liquid crystal alignment film is formed by using a liquid crystal alignment treatment agent containing a specific polyamidimide polymer having a group represented by the following formula [1-1] or formula [1-2]. Liquid crystal alignment film.

In the formula [1-1], Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, from the viewpoint of availability of raw materials or ease of synthesis, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferred. . More preferably a single _{bond, - (CH 2) a -} (a is an integer of 1 to 10), - O -, - CH 2 O- or -COO-.

Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 15). Among them, a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10) is preferable.

Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, from the viewpoint of easiness of synthesis, a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferable. More preferably a single _{bond, - (CH 2) c -} (c is an integer of 1 to 10), - O -, - CH 2 O- or -COO-.

Y ⁴ is selected from a bivalent cyclic group derived from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may have an alkyl group having 1 to 3 carbon atoms and a carbon number of 1 to 3 The alkoxy group, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom is substituted. Further, Y ⁴ may be a divalent organic group selected from an organic group having a carbon number of 17 to 51 of a steroid skeleton. Among them, from the viewpoint of easiness of synthesis, a benzene ring, a cyclohexane ring or an organic group having a carbon number of 17 to 51 having a steroid skeleton is preferred.

Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may have an alkyl group having 1 to 3 carbon atoms and an alkyl group having 1 to 3 carbon atoms. The oxy group, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom are substituted. Among them, a benzene ring or a cyclohexane ring is preferred.

n represents an integer from 0 to 4. Among them, from the viewpoint of availability of raw materials or ease of synthesis, it is preferably 0 to 3. More preferably 0~2.

Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

A preferred combination of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [1-1], for example, 13 items of International Publication WO2011/132751 (2011.10.27 publication) The same combination of (2-1) to (2-629) disclosed in Tables 6 to 47 of Table 34. Further, in each table of the international publication, Y ¹ to Y ⁶ of the present invention are represented by Y1 to Y6, but Y1 to Y6 can be interpreted as Y ¹ to Y ⁶ . Further, in (2-605) to (2-629) disclosed in the respective tables of the International Publications, the organic group having a carbon number of 17 to 51 having a steroid skeleton of the present invention has a carbon number of 12 to 25 having a steroid skeleton. The organic group is represented, but an organic group having a carbon number of 12 to 25 having a steroid skeleton can be interpreted as an organic group having a carbon number of 17 to 51 having a steroid skeleton.

[化17]-Y ⁷ -Y ⁸ [1-2]

In the formula [1-2], Y ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, - COO- or -OCO-. Among them, a single bond, -O-, -CH ₂ O-, -CONH-, -CON(CH ₃ )- or -COO- is preferred. More preferably, it is a single bond, -O-, -CONH- or -COO-.

Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms. Among them, an alkyl group having 8 to 18 carbon atoms is preferred.

The group of the specific side chain structure in the present invention is preferably a structure represented by the formula [1-1] from the viewpoint of obtaining a vertical alignment property of a liquid crystal which is high and stable.

A method of introducing a specific side chain structure into a specific polyimine-based polymer, preferably a diamine compound having a group having a specific side chain structure is used for a part of a raw material. In particular, a diamine compound (also referred to as a specific side chain type diamine compound) represented by the following formula [1a] is preferably used.

In the formula [1a], Y represents a structure represented by the above formula [1-1] or formula [1-2].

n represents an integer from 1 to 4. Of these, it is preferably 1.

The specific side chain type diamine compound is preferably a diamine compound having a structure represented by the following formula [1-1a] from the viewpoint of obtaining a vertical alignment property of a liquid crystal which is high in stability.

In the formula [1-1a], Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, from the viewpoint of availability of raw materials or ease of synthesis, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO is preferred. -. More preferably a single _{bond, - (CH 2) a -} (a is an integer of 1 to 10), - O -, - CH 2 O- or -COO-.

Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 15). Among them, a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10) is preferable.

Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, from the viewpoint of easiness of synthesis, a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferable. More preferably a single _{bond, - (CH 2) c -} (c is an integer of 1 to 10), - O -, - CH 2 O- or -COO-.

Y ^{4 is a} divalent cyclic group selected from a benzene ring, a cyclohexane ring and a hetero ring, and any hydrogen atom on the cyclic group may have an alkyl group having 1 to 3 carbon atoms and a carbon number of 1 to 3. An alkoxy group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. Further, Y ⁴ may be a divalent organic group selected from an organic group having a carbon number of 17 to 51 of a steroid skeleton. Among them, from the viewpoint of easiness of synthesis, a benzene ring, a cyclohexane ring or an organic group having a carbon number of 17 to 51 having a steroid skeleton is preferred.

Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may have an alkyl group having 1 to 3 carbon atoms and an alkyl group having 1 to 3 carbon atoms. The oxy group, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom are substituted. Among them, a benzene ring or a cyclohexane ring is preferred.

n represents an integer from 0 to 4. Among them, from the viewpoint of availability of raw materials or ease of synthesis, it is preferably 0 to 3. More preferably 0~2.

Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

A preferred combination of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [1-1a], for example, 13 items of International Publication WO2011/132751 (2011.10.27 publication) The same combination of (2-1) to (2-629) disclosed in Tables 6 to 47 of Table 34. Further, in each table of the international publication, Y ¹ to Y ⁶ of the present invention are represented by Y1 to Y6, but Y1 to Y6 can be interpreted as Y ¹ to Y ⁶ . Further, in (2-605) to (2-629) disclosed in the respective tables of the International Publications, the organic group having a carbon number of 17 to 51 having a steroid skeleton of the present invention has a carbon number of 12 to 25 having a steroid skeleton. The organic group is represented, but an organic group having a carbon number of 12 to 25 having a steroid skeleton can be interpreted as an organic group having a carbon number of 17 to 51 having a steroid skeleton.

Among them, (2-25)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-268)~(2-315) ), a combination of (2-364)~(2-387), (2-436)~(2-483), (2-603)~(2-615), and the like. The most preferable combinations are (2-49)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-603)~(2- 606), (2-607)~(2-609), (2-611), (2-612), (2-624), and the like.

In the formula [1-1a], m is an integer of 1 to 4. It is preferably 1.

Specifically, for example, there are compounds having the structures represented by the following formulas [1a-1] to [1a-31].

(R ¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-. R ² is a linear or branched alkyl group having 1 to 22 carbon atoms, carbon a linear or branched alkoxy group of 1 to 22, a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkane having 1 to 22 carbon atoms. Oxy.)

(R ³ represents a -COO -, - OCO -, - CONH -, - NHCO -, - COOCH 2 -, - CH 2 OCO -, - CH 2 O -, - OCH 2 - or -CH ₂ -.R ⁴ is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxy group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms. Or a linear or branched fluoroalkoxy group having a carbon number of 1 to 22.

(R ⁵ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ - , -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ -, -O- Or -NH-. R ⁶ is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a decyl group, an ethyl group, an ethoxy group or a hydroxy group.

(R ⁷ is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer.)

(R ⁸ is a linear or branched alkyl group having 3 to 12 carbon atoms, and each of the cis-trans isomers of 1,4-cyclohexylene is a trans isomer.)

(A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom. A ₃ is a 1,4-cyclohexylene group or a 1,4-phenylene group. A ₂ is an oxygen atom. or -COO - * (but attaching "*" is bonded to a ₃ bonded with the bond) .A ₁ is an oxygen atom or -COO - * (but attaching "*" key and the bonding (CH ₂₎ a ₂₎ Bond). Further, a ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1. )

In the above formula [1a-1] to [1a-31], the diamine compound of a particularly preferred structure is of the formula [1a-1] to the formula [1a-6], and the formula [1a-9] to the formula [1a-13]. , formula [1a-22] ~ formula [1a-31].

The vertical alignment of the liquid crystal display element in the liquid crystal display element and the adhesion of the liquid crystal layer to the vertical liquid crystal alignment film of the specific side chain type diamine compound The viewpoint is preferably 10 mol% or more and 80 mol% or less of the entire diamine component. More preferably, it is 10 mol% or more and 70 mol% or less.

The specific side chain type diamine compound can be used in one type depending on the solubility of the specific polyimine-based polymer in the solvent, the vertical alignment of the liquid crystal when the vertical liquid crystal alignment film is used, and the optical characteristics of the liquid crystal display element. Or use 2 or more types.

In order to produce a diamine component for a specific polyimine-based polymer, a second diamine compound (also referred to as a second diamine compound) represented by the following formula [2] is preferably used.

In the formula [2], X represents a substituent selected from the group consisting of the following formula [2a], formula [2b], formula [2c] or formula [2d].

In the formula [2a], a represents an integer of 0 to 4. Among them, from the viewpoint of availability of raw materials or ease of synthesis, an integer of 0 or 1 is preferable. In the formula [2b], b represents an integer of 0 to 4. Among them, from the viewpoint of availability of raw materials or ease of synthesis, an integer of 0 or 1 is preferable.

In the formula [2c], X ¹ and X ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. In the formula [2d], X ³ represents an alkyl group having 1 to 5 carbon atoms. In the formula [2], m represents an integer of 1 to 4. Of these, it is preferably 1.

Specific examples of the diamine compound represented by the following formula [2] are not limited to these examples.

a diamine compound represented by the formula [2], except 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diamino group Phenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diamine Examples of the benzoic acid and the 3,5-diaminobenzoic acid include a diamine compound having the structure represented by the following formulas [2-1] to [2-6].

Among them, preferred are 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diamino group. Resorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, formula [2-1], formula [2-2] or formula [2-3] A diamine compound represented. Particularly preferred are 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 3,5-diaminobenzoic acid, formula [2-1] or formula [ The diamine compound represented by 2-2].

The diamine compound represented by the formula [2] may have characteristics such as solubility of a specific polyimine-based polymer in a solvent, vertical alignment of a liquid crystal when a vertical liquid crystal alignment film, and optical characteristics of a liquid crystal display element. Use 1 type or mix 2 types or more.

A diamine component for a specific polyimine-based polymer, for example, a diamine compound other than the diamine compound represented by the formula [1-1], the formula [1-2] or the formula [2] (also referred to as another diamine) The compound) can be used as a diamine compound. Specific examples of other diamine compounds are exemplified below, but are not limited thereto.

For example, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-di Methoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diamino Biphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diamine Biphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodi Phenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl-bis ( 4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-di Aminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3' -diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-A (3,4'-Diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl (2,3'-diaminodiphenyl) Amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diamine Naphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7- Diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4- Phenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl) Butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxyl) Benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1 , 3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)]diphenylamine, 4,4'-[1,3-phenylene Bis(methylene)]diphenylamine, 3,4'-[1,4-phenylenebis(methylene)]diphenylamine, 3,4'-[1,3-phenylene bis(arylene) Methyl)]diphenylamine, 3,3'-[1,4-phenylenebis(methylene)]diphenylamine, 3,3'-[1,3-phenylene bis (methylene Diphenylamine, 1,4-phenylphenylbis[(4-aminophenyl)methanone], 1,4-phenylphenylbis[(3-aminophenyl)methanone], 1, 3-phenylphenyl bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylene bis(4) -aminobenzoic acid ester), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3 - phenyl bis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis( 4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-amino group Benzoguanamine, N,N'-(1,3-phenylene)bis(4-aminobenzoguanamine), N,N'-(1,4-phenylene)bis(3- Aminobenzoquinone), N,N'-(1,3-phenylene)bis(3-aminobenzoguanamine), N,N'-bis(4-aminophenyl)-p-benzene Dimethylamine, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)m-xylyleneamine, N,N '-bis(3-aminophenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenyl Base, 2, 2'- Bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis ( 4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoro Propane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methyl Phenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy) Butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxyl) Pentane, 1,6-bis (4- Aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3- Aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis (4) -aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis ( 3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12 - bis(4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane, bis(4-amino group -3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1 , 7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and the like.

Further, the other diamine compound may, for example, be an alkyl group, a fluorine-containing alkyl group or a heterocyclic ring in the side chain of the diamine compound.

Specifically, for example, there are diamine compounds represented by the following formulas [DA1] to [DA13].

(p represents an integer from 1 to 10)

The diamine compound represented by the following formula [DA2] to [DA7] can be used as the other diamine compound insofar as the effect of the present invention is not impaired.

(In the formula [DA4], m represents an integer of 0 to 3. In the formula [DA7], n represents an integer of 1 to 5.)

The diamine compound represented by the following formula [DA8] to [DA11] can be used as the other diamine compound insofar as the effect of the present invention is not impaired.

(A ¹ represents a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N ( CH ₃ )CO-, m ¹ and m ² each represent an integer of 0 to 4, and m ¹ + m ² represents an integer of 1 to 4. m ³ and m ⁴ each represent an integer of 1 to 5. A ² represents a carbon number. a linear or branched alkyl group of 1 to 5, m ⁵ represents an integer of 1 to 5. A ³ represents a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-, may be the same or different. Further, m ⁶ represents an integer from 1 to 4.

Further, a diamine compound represented by the following formula [DA12] can be used within the range which does not impair the effects of the present invention.

(A ¹ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ ) CO-.A ² is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or a divalent organic group of an aromatic hydrocarbon group. A ³ is a single bond, -O-, -NH- , -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO- or -O(CH ₂ ) _m - (m is an integer from 1 to 5.) A ⁴ is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4.

Further, as the other diamine compound, a diamine compound represented by the following formula [DA13] or formula [DA14] can also be used.

Other diamine compounds, depending on the specific polyamidiene polymer to solvent The solubility, the vertical alignment of the liquid crystal when the liquid crystal alignment film is vertical, and the optical characteristics of the liquid crystal display element can be used in one type or in a mixture of two or more types.

In order to produce a tetracarboxylic acid component for a specific polyimine-based polymer, it is preferred to use a tetracarboxylic acid di-anhydride represented by the following formula [3], a tetracarboxylic acid or a tetracarboxylic acid as the tetracarboxylic acid derivative. An acid dihalide compound, a tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound (all collectively referred to as a specific tetracarboxylic acid component).

In the formula [3], Z ¹ is a group selected from the structures of the following formulas [3a] to [3j]. )

In the formula [3a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different.

In the formula [3g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group, and each may be the same or different.

In the compound having a structure represented by the formula [3] of the specific tetracarboxylic acid component, Z ¹ is preferably a formula [3a] or a formula [3c] from the viewpoints of easiness of synthesis or easiness of polymerization reactivity in producing a polymer. a group having a structure represented by the formula [3d], the formula [3e], the formula [3f] or the formula [3g]. More preferably, the group represented by the formula [3a], the formula [3e], the formula [3f] or the formula [3g] is particularly preferably represented by the formula [3e], the formula [3f] or the formula [3g]. The group of the structure.

The specific tetracarboxylic acid component is preferably at least 1 mol% of the total tetracarboxylic acid component. More preferably, it is 5 mol% or more, and more preferably 10 mol% or more. Very good for 15~100%.

When a specific tetracarboxylic acid component having a structure of the formula [3e], the formula [3f] or the formula [3g] is used, the desired effect can be obtained by using the amount of 20 mol% or more of the entire tetracarboxylic acid component. . It is preferably 30 mol% or more. Further, all of the tetracarboxylic acid component may be a tetracarboxylic acid component having a structure of the formula [3e], the formula [3f] or the formula [3g].

In the specific polyimine-based polymer, other tetracarboxylic acid components other than the specific tetracarboxylic acid component may be used within a range that does not impair the effects of the present invention.

The other tetracarboxylic acid component may, for example, be a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a dicarboxylic acid dihalide compound, a dicarboxylic acid dialkyl ester compound or a dialkyl ester dihalide compound shown below.

Specifically, for example, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-decanetetracarboxylic acid, 1,2,5,6-nonanedicarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4 '-Biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl) Bismuth, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2 - bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2,3, 4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9, 10-decanetetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

The specific tetracarboxylic acid component and the other tetracarboxylic acid component are characterized by the solubility of the specific polyimine-based polymer in a solvent, the vertical alignment of the liquid crystal when the liquid crystal alignment film is vertical, and the optical characteristics of the liquid crystal display element. It can be used in one type or in two or more types.

<Specific Polyimine Polymer>

The specific polyimine-based polymer of the present invention is preferably a polyimine precursor obtained by reacting a diamine component with a tetracarboxylic acid component, and a polyazide-forming precursor of the polyimine precursor. At least one selected from the group consisting of quinone imines.

The polyimine precursor refers to a structure represented by the following formula [A].

(R ¹ is a tetravalent organic group, and R ² is a divalent organic group. A ¹ and A ^{2 each} represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each may be the same or different. A ³ and A ⁴ represent a hydrogen atom. The alkyl group or the ethyl group having 1 to 5 carbon atoms may be the same or different. n represents a positive integer.

The diamine component is a diamine compound having two primary or secondary amine groups in the molecule, and the tetracarboxylic acid component is, for example, a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic acid dihalide compound, or a tetracarboxylic acid. A dialkyl ester compound or a dialkyl tetracarboxylate dihalide compound.

The specific polyimine-based polymer is preferably obtained by using a tetracarboxylic dianhydride represented by the following formula [B] and a diamine compound represented by the following formula [C] as a raw material, which can be easily obtained. A polyaminic acid consisting of a structural formula of a repeating unit represented by the following formula [D] or a polyimine which is ruthenium imidized with the polyamic acid. Among them, a specific polyimine-based polymer preferably has a polyimine from the viewpoint of physical and chemical stability of a vertical liquid crystal alignment film.

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

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

Further, in the polymer of the formula [D] obtained above, an alkyl group having 1 to 8 carbon atoms of A ¹ and A ² represented by the formula [A] and a formula [A] may be used in the usual synthesis method. A ³ and A ^{4 have} an alkyl group having 1 to 5 carbon atoms or an ethylene group.

<Method for Producing Specific Polyimine Polymers>

In the present invention, a method of synthesizing a specific polyimine-based polymer is not particularly limited. It is usually obtained by reacting a diamine component with a tetracarboxylic acid component. In general, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acid and a derivative thereof is reacted with a diamine component composed of one or a plurality of diamine compounds to obtain a polyfluorene. Amino acid. Specifically, the following method can be used, even if a tetracarboxylic dianhydride is subjected to polycondensation with a primary or secondary diamine compound to obtain a poly-proline, a tetracarboxylic acid and a primary or secondary diamine A method in which a compound undergoes a dehydration-polycondensation reaction to obtain a poly-proline acid or a method in which a dicarboxylic acid dihalide is polycondensed with a primary or secondary diamine compound to obtain a poly-proline.

In order to obtain a polyalkyl phthalate, the following method can be used, and even a method in which a dialkyl esterified tetracarboxylic acid of a carboxylic acid group is subjected to polycondensation with a primary or secondary diamine compound is used. A method in which an acid group is subjected to polycondensation of a dialkyl esterified dicarboxylic acid dihalide with a primary or secondary diamine compound or a method of converting a carboxyl group of polylysine to an ester.

In order to obtain a polyimine, a method of ring-closing the polyamic acid or polyalkyl amide to form a polyimine can be used.

The reaction of the diamine component with the tetracarboxylic acid component is usually carried out in a solvent. The solvent to be used at this time is not particularly limited as long as it is a specific solvent having a boiling point of less than 180 ° C or a polyimide precursor formed by dissolution. In particular, when a specific polyimine is produced, a solvent having a high boiling point can also be used.

The specific solvent having a boiling point of less than 180 ° C is, for example, a solvent represented by cyclopentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, the following formula [A1] and formula [A2]. At least one solvent selected from the group.

(In the formula [A1], A ¹ represents an alkyl group having 1 to 3 carbon atoms. In the formula [A2], A ² represents an alkyl group having 1 to 3 carbon atoms.)

Further, examples of the high boiling point solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, and 1,3-dimethyl-imidazolidinone.

These can be used alone or in combination. In addition, even if it is a solvent that does not dissolve the polyimide precursor, the resulting polyimide precursor does not precipitate. The range can also be used in combination with the above solvents.

Further, since the water in the solvent hinders the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, the solvent is preferably dried by dehydration.

When the diamine component and the tetracarboxylic acid component are reacted in a solvent, for example, a solution in which a diamine component is dispersed or dissolved in a solvent is stirred, and the tetracarboxylic acid component is directly or dispersed or dissolved in a solvent, and then added. In contrast, a method in which a diamine component is added to a solution in which a tetracarboxylic acid component is dispersed or dissolved in a solvent, a method in which a diamine component and a tetracarboxylic acid component are alternately added, and the like can be used.

Further, when a plurality of kinds of the diamine component or the tetracarboxylic acid component are used for the reaction, the reaction may be carried out in advance in a mixed state or in a separate sequential reaction, or a mixed reaction of a low molecular weight compound of an individual reaction may be used as a polymer. The polymerization temperature at this time may be any temperature from -20 ° C to 150 ° C, preferably from -5 ° C to 100 ° C.

Further, the reaction can be carried out at any concentration. However, when the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction liquid is too high and uniform stirring becomes difficult. Therefore, it is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then a solvent can be added.

In the polymerization reaction of the polyimine precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably from 0.8 to 1.2. As with the general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimine precursor becomes.

Polyimine is a polyimine obtained by ring-closing the polyimine precursor. In the polyimine, the ring closure ratio (also referred to as the ruthenium imidation ratio) of the proline group does not necessarily need to be 100. %, can be adjusted according to the purpose or purpose.

The method for imidating the polyimine precursor ruthenium may, for example, be a hydrazine imidization in which a solution of a polyimide precursor is directly heated or a catalyst in which a catalyst is added to a solution of a polyimide precursor.醯imination.

The temperature at which the polyimine precursor is thermally imidated in the solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, and the water generated by the hydrazine imidization reaction is discharged to the system. It is better to perform at the same time.

The catalyst oxime imidization of the polyimide precursor can be stirred at -20 to 250 ° C, preferably 0 to 180 ° C by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor. Come on. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the proline group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to the amidate group. 30 moles.

The basic catalyst is, for example, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine or the like, and pyridine is preferred because it has a moderate basicity required for carrying out the reaction.

The acid anhydride is, for example, acetic anhydride, trimellitic anhydride or pyromellitic anhydride. When acetic anhydride is used, purification after completion of the reaction becomes easy, which is preferable. The imidization ratio of the imidization of the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

When the produced polyimine precursor or polyimine is recovered from the reaction solution of the polyimine precursor or the polyimine, the reaction solution may be precipitated in a solvent.

The solvent used for the precipitation is, for example, methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water or the like. After the solvent is introduced and the precipitated polymer is filtered and recovered, it can be dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, the polymer recovered by the precipitation is redissolved in the solvent, and the operation of reprecipitation and recovery is repeated 2 to 10 times to reduce impurities in the polymer. In the solvent at this time, for example, an alcohol, a ketone, a hydrocarbon or the like is used. When three or more types of solvents selected from the above are used, the efficiency of purification can be further improved, which is preferable.

The molecular weight of the polyimine-based polymer is preferably a weight average molecular weight measured by a GPC (Gel Permeation Chromatography) method, in consideration of the strength of the liquid crystal alignment film obtained, the workability at the time of film formation, and the coating property. It is 5,000 to 1,000,000, more preferably 10,000 to 150,000.

<Liquid alignment treatment agent>

The liquid crystal alignment treatment agent of the present invention is a coating solution for forming a liquid crystal alignment film, and a specific polyimine containing a group having a specific side chain structure represented by the above formula [1-1] or formula [1-2]. A coating solution of a polymer and a specific solvent.

All of the polymer components in the liquid crystal alignment agent may be a specific polyimine-based polymer or may be a polymer other than a specific polyamidene-based polymer. In this case, the content of the polymer other than the specific polyimine-based polymer is 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the specific polyimine-based polymer.

a polymer other than a specific polyimine polymer, such as A polyimine-based polymer having a group having a specific side chain structure represented by the above formula [1-1] or formula [1-2]. Further, for example, polymers such as polyamide, polyester, acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, cellulose, polyoxyalkylene, and the like are available.

The content of all the polymers in the liquid crystal alignment agent can be appropriately selected from the viewpoint of the coating method of the liquid crystal alignment agent or the film thickness of the object. Among them, the content of all the polymers in the liquid crystal alignment agent is preferably from 0.1 to 50% by mass from the viewpoint of forming a uniform vertical liquid crystal alignment film by coating. Among them, it is preferably from 1 to 40% by mass, particularly preferably from 1 to 35% by mass.

The content of the solvent in the liquid crystal alignment agent can be appropriately selected from the viewpoint of the coating method of the liquid crystal alignment agent or the film thickness of the object. Among them, the content of the solvent in the liquid crystal alignment treatment agent is preferably from 40 to 99.9% by mass from the viewpoint of forming a uniform vertical liquid crystal alignment film by coating. Among them, it is preferably from 50 to 99% by mass, particularly preferably from 55 to 99% by mass.

In the liquid crystal alignment treatment agent of the present invention, a specific solvent having a boiling point of less than 180 ° C which is 50% by mass or more of the entire solvent is contained. The specific solvent is not particularly limited, and is preferably represented by the above solvent, namely cyclopentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, the following formula [A1] and formula [A2]. At least one solvent selected from the group consisting of solvents.

The solvent contained in the specific solvent-based liquid crystal alignment treatment agent is 50% by mass or more, preferably 55% by mass or more. From the viewpoint of firing at the time of producing a vertical liquid crystal alignment film at a low temperature, it is preferably 60% by mass or more. More preferably, it is 70 to 100% by mass.

In addition, when the solvent of the liquid crystal alignment treatment agent is less than 50% by mass of the entire solvent, a solvent having a high boiling point other than the specific solvent (also referred to as a specific high boiling point solvent) can be used. Specific examples thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, and 1,3-dimethyl-imidazolidinone, which are represented by the following formula [A3]. Solvents, etc.

In the formula [A3], A ³ represents an alkyl group having 1 to 4 carbon atoms. Among them, an alkyl group having 1 or 2 carbon atoms is preferred.

Among the specific high-boiling solvents, the solvent of the liquid crystal alignment treatment agent is preferably N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone or the solvent represented by the above formula [A3]. .

The specific high-boiling point solvent is preferably 1 to 49% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. Among them, it is preferably from 1 to 40% by mass, particularly preferably from 5 to 25% by mass.

In the liquid crystal alignment treatment agent of the present invention, an organic solvent (also referred to as a weak solvent) which improves the coating property or surface smoothness of the vertical liquid crystal alignment film when a liquid crystal alignment treatment agent is applied, for example, a solvent other than a specific solvent can be used. Specific examples of the weak solvent are given below, but are not limited to these examples.

For example, there are ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butene Alcohol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1- Heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methyl ring Hexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4 -butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl Ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, two Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone , 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate , ethylene glycol monoacetate, ethylene glycol diacetate, propyl carbonate, ethylene carbonate, 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol Monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, mercapto alcohol, diethylene glycol, propylene glycol Propylene glycol monobutyl ether, 1-(butoxyethoxy)propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl Ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, Ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl acetate, Diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid n- Butyl ester, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3- Methyl ethyl ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-methoxy Butyl propyl propionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether is preferably used.

Among these weak solvents, a weak solvent having a boiling point of 180 ° C or higher is preferably 1 to 49% by mass based on the total amount of the solvent contained in the liquid crystal alignment treatment agent. Among them, it is preferably from 1 to 40% by mass, particularly preferably from 1 to 25% by mass.

Further, the weak solvent having a boiling point of less than 180 ° C is preferably from 1 to 90% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. Among them, it is preferably from 1 to 80% by mass, particularly preferably from 5 to 60% by mass.

In order to improve the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film, the liquid crystal alignment agent of the present invention preferably introduces a compound having a group having a structure represented by the following formulas [B1] to [B7] ( Also referred to as a close compound, at least one compound selected from the group. In this case, the group represented by the structures [B1] to [B7] preferably has two or more groups in the compound.

In the formula [B4], W ¹ represents a hydrogen atom or a benzene ring.

In the formula [B7], W ² represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring, and W ³ represents an alkyl group having 1 to 18 carbon atoms and a carbon number of 1 to a fluorine-containing alkyl group of 18, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms.

Specifically, a compound represented by the following formula [6] is preferably used.

In the formula [6], X ¹ represents at least one selected from the group consisting of the structures represented by the following formulas [6a-1] to [6a-7]. Among them, from the viewpoint of easiness of production of the adhesion-sensitive compound of the present invention, it is preferably a formula [6a-1], a formula [6a-2], a formula [6a-3], a formula [6a-5] or a formula [ The structure indicated by 6a-6]. More preferably, it is a structure represented by the formula [6a-1], the formula [6a-3], the formula [6a-5] or the formula [6a-6].

In the formula [6a-2], A ¹ represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. Among them, from the viewpoint of easiness of production of the adhesion-producing compound, a hydrogen atom or an alkylene group having 1 to 2 carbon atoms is preferred. More preferably, it is a hydrogen atom or a methyl group.

In the formula [6a-3], A ² represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms. Among them, from the viewpoint of easiness of production of the adhesion-producing compound, a hydrogen atom or an alkylene group having 1 to 2 carbon atoms is preferred. More preferably, it is a hydrogen atom or a methyl group.

In the formula [6a-5], A ³ and A ⁵ each independently represent a hydrogen atom or an alkylene group having 1 to 3 carbon atoms. Among them, from the viewpoint of easiness of production of the adhesion-producing compound, a hydrogen atom or an alkylene group having 1 to 2 carbon atoms is preferred. More preferably, it is a hydrogen atom or a methyl group.

In the formula [6a-5], A ⁴ is an alkylene group having 1 to 3 carbon atoms. Among them, from the viewpoint of easiness of production of the adhesion-producing compound, an alkylene group having 1 to 2 carbon atoms is preferred.

In the formula [6a-6], A ⁶ and A ⁹ each independently represent a hydrogen atom or an alkylene group having 1 to 3 carbon atoms. Among them, from the viewpoint of easiness of production of the adhesion-producing compound, a hydrogen atom or an alkylene group having 1 to 2 carbon atoms is preferred. More preferably, it is a hydrogen atom or a C 1 alkyl group (methyl).

In the formula [6a-6], A ⁷ and A ⁸ each independently represent an alkylene group having 1 to 3 carbon atoms. Among them, from the viewpoint of easiness of production of the adhesion-producing compound, an alkylene group having 1 to 2 carbon atoms is preferred.

In the formula [6], X ² is a single bond, -CH ₂ -, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH At least one selected from the group consisting of _2- , -COO-, -OCO-, -CON(CH ₃ )-, and -N(CH ₃ )CO-. Among them, from the viewpoint of easiness of synthesis of the adhesion compound, a single bond, -CH ₂ -, -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH is preferred. ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. More preferably, it is a single bond, -CH ₂ -, -O-, -NH-, -CONH-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. Particularly preferred is a single bond, -O-, -CONH-, -OCH ₂ -, -COO- or -OCO-.

In the formula [6], X ³ represents an alkylene group having 1 to 20 carbon atoms, -(CH ₂ -CH ₂ -O) _p - (p represents an integer of 1 to 10), -(CH ₂ -O-) _q - (q is an integer of 1 to 10) and at least one selected from the group consisting of an organic group having a benzene ring or a cyclohexane ring having 6 to 20 carbon atoms. In this case, any -CH ₂ - group of the above alkyl group may be -COO-, -OCO-, -CONH-, NHCO-, -CO-, -S-, -SO ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -OSi(CH ₃ ) ₂ - or -Si(CH ₃ ) ₂ O- is substituted, and a hydrogen atom bonded to any carbon atom may be Substituted by a hydroxyl group (OH group), a carboxyl group (COOH group) or a halogen atom. Among them, from the viewpoint of easiness of production of the adhesion compound, an alkylene group having 1 to 20 carbon atoms, -(CH ₂ -CH ₂ -O) _p - (p is an integer of 1 to 10), -( CH ₂ -O-) _q - (q is an integer of 1 to 10) or a structure represented by the following formula [6c-1] to formula [6c-5] is preferred. More preferably, the alkyl group having 1 to 15 carbon atoms, -(CH ₂ -CH ₂ -O) _p - (p is an integer of 1 to 10), -(CH ₂ -O-) _q - (q is 1~) An integer of 10), a structure represented by the following formula [6c-1], formula [6c-3], formula [6c-4] or formula [6c-5]. Particularly preferred are an alkylene group having 1 to 15 carbon atoms, -(CH ₂ -CH ₂ -O) _p - (p is an integer of 1 to 10), a formula [6c-1], a formula [6c-4] or a formula [6c-5] shows the structure.

In the formula [6], X ⁴ represents at least one of a bonding group selected from the group consisting of a single bond, -CH ₂ -, -OCH ₂ -, and O-CH ₂ -CH ₂ -. Among them, a structure represented by a single bond, -CH ₂ - or -OCH ₂ - is preferred from the viewpoint of easiness of synthesis of the adhesion compound.

In the formula [6], X ⁵ represents at least one selected from the group consisting of the structures represented by the following formulas [6b-1] to [6b-8]. Among them, the structure represented by the formula [6b-1], the formula [6b-2] or the formula [6b-6] is preferred from the viewpoint of easiness of synthesis of the adhesion compound. More preferably, it is a structure represented by the formula [6b-1] or the formula [6b-2].

In the formula [6b-4], B ¹ represents a hydrogen atom or a benzene ring.

In the formula [6b-8], B ² represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring.

In the formula [6b-8], B ³ represents an alkylene group having 1 to 12 carbon atoms, a fluorine-containing alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a carbon number of 1 to 12; At least one selected from the group consisting of fluorine-containing alkoxy groups.

In the formula [6], n represents an integer of 1 to 3. Among them, 1 or 2 is preferred from the viewpoint of easiness of synthesis of the adhesion compound. More preferably 1.

In the formula [6], m represents an integer of 1 to 3. Among them, 1 or 2 is preferred from the viewpoint of easiness of synthesis of the adhesion compound.

More specific structures of the adhesion compound include, for example, the following formulas [6-1a] to [6-3a], formulas [6-1b] to [6-3b], and formula [6-1c] to [6- 3c] and a compound represented by the formula [6-1d] to [6-3d].

X ^a in the formula [6-1a], X ^{d in the} formula [6-2a] and X ^g in the formula [6-3a] each independently represent a single bond, -O-, -CONH-, -OCH ₂ - And at least one selected from the group consisting of -COO- and -OCO-. Among them, a single bond, -O-, -OCH ₂ - or -OCO- is preferred from the viewpoint of easiness of production of the adhesion compound. More preferably, it is a single bond, -O- or -OCH ₂ -.

X ^b in the formula [6-1a], X ^{e in the} formula [6-2a] and X ^h in the formula [6-3a] each independently represent an alkylene group having 1 to 15 carbon atoms, -(CH ₂ - At least one selected from the group consisting of CH ₂ -O) _p - (p is an integer of 1 to 10), the formula [6c-1], the formula [6c-4], and the formula [6c-5] . In this case, any -CH ₂ - group of the aforementioned alkylene group may be -COO-, -OCO-, -CONH-, NHCO-, -CO-, -S-, -SO ₂ -, -CF ₂ - , -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -OSi(CH ₃ ) ₂ - or -Si(CH ₃ ) ₂ O-, substituted with a hydrogen atom bonded to any carbon atom It may be substituted by a hydroxyl group (OH group), a carboxyl group (COOH group) or a halogen atom.

X ^c in the formula [6-1a], X ^{f in the} formula [6-2a] and X ⁱ in the formula [6-3a] each independently represent a single bond, -CH ₂ - and -OCH ₂ - At least one of the bonding groups selected in the group.

N1 in the formula [6-1a], n2 in the formula [6-2a], and n3 in the formula [6-3a] each independently represent an integer of 1 or 2. Among them, 1 is preferred.

M1 in the formula [6-1a], m2 in the formula [6-2a], and m3 in the formula [6-3a] each independently represent an integer of 1 or 2. Among them, 1 is preferred.

X ^a in the formula [6-1b], X ^{d in the} formula [6-2b] and X ^g in the formula [6-3b] are each independently represented by a single bond, -O-, -CONH-, -OCH ₂ At least one of the bonding groups selected from the group consisting of -, -COO-, and -OCO-. Among them, a single bond, -O-, -OCH ₂ - or -OCO- is preferred from the viewpoint of easiness of production of the adhesion compound. More preferably, it is a single bond, -O- or -OCH ₂ -.

X ^b in the formula [6-1b], X ^{e in the} formula [6-2b] and X ^h in the formula [6-3b] each independently represent an alkylene group having a carbon number of 1 to 15, -(CH ₂ -CH ₂ -O) _p - (p is an integer of 1 to 10), at least 1 selected from the group consisting of the structures represented by the formula [6c-1], the formula [6c-4], and the formula [6c-5] Kind. In this case, any -CH ₂ - group of the aforementioned alkylene group may be -COO-, -OCO-, -CONH-, NHCO-, -CO-, -S-, -SO ₂ -, -CF ₂ - , -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -OSi(CH ₃ ) ₂ - or -Si(CH ₃ ) ₂ O-, substituted with a hydrogen atom bonded to any carbon atom It may be substituted by a hydroxyl group (OH group), a carboxyl group (COOH group) or a halogen atom.

X ^c in the formula [6-1b], X ^{f in the} formula [6-2b] and X ⁱ in the formula [6-3b] each independently represent a single bond, -CH ₂ - and -OCH ₂ - At least one type of bonding group.

A ¹ in the formula [6-1b], A ^{2 in the} formula [6-2b] and A ³ in the formula [6-3b] each independently represent a hydrogen atom or an alkylene group having 1 to 2 carbon atoms. Among them, a hydrogen atom or a methyl group is preferred.

N1 in the formula [6-1b], n2 in the formula [6-2b], and n3 in the formula [6-3b] each independently represent an integer of 1 or 2. Among them, 1 is preferred.

M1 in the formula [6-1b], m2 in the formula [6-2b], and m3 in the formula [6-3b] are each independently an integer of 1 or 2. Among them, 1 is preferred.

X ^a in the formula [6-1c], X ^d in the formula [6-2c] and X ^g in the formula [6-3c] are each independently represented by a single bond, -O-, -CONH-, -OCH ₂ At least one of the bonding groups selected from the group consisting of -, -COO-, and -OCO-. Among them, a single bond, -O-, -OCH ₂ - or -OCO- is preferred from the viewpoint of easiness of production of the adhesion compound. More preferably, it is a single bond, -O- or -OCH ₂ -.

X ^b in the formula [6-1c], X ^e in the formula [6-2c] and X ^h in the formula [6-3c] each independently represent an alkylene group having a carbon number of 1 to 15, -(CH ₂ -CH ₂ -O) _p - (p is an integer of 1 to 10), at least 1 selected from the group consisting of the structures represented by the formula [6c-1], the formula [6c-4], and the formula [6c-5] Kind. In this case, any -CH ₂ - group of the aforementioned alkylene group may be -COO-, -OCO-, -CONH-, NHCO-, -CO-, -S-, -SO ₂ -, -CF ₂ - , -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -OSi(CH ₃ ) ₂ - or -Si(CH ₃ ) ₂ O-, substituted with a hydrogen atom bonded to any carbon atom It may be substituted with a hydroxyl group (OH group), a carboxyl group (COOH group) or a halogen atom.

X ^c in the formula [6-1c], X ^f in the formula [6-2c] and X ⁱ in the formula [6-3c] each independently represent a single bond, -CH ₂ - and -OCH ₂ - At least one of the bonding groups selected in the group.

A ¹ in the formula [6-1c], A ⁴ in the formula [6-2c] and A ⁷ in the formula [6-3c] each independently represent a hydrogen atom or an alkylene group having 1 to 2 carbon atoms. Among them, a hydrogen atom or a methyl group is preferred.

A ² in the formula [6-1c], A ⁵ in the formula [6-2c], and A ⁸ in the formula [6-3c] each independently represent an alkylene group having 1 to 2 carbon atoms.

A ³ in the formula [6-1c], A ⁶ in the formula [6-2c] and A ⁹ in the formula [6-3c] each independently represent a hydrogen atom or an alkylene group having 1 to 2 carbon atoms. Among them, a hydrogen atom or a methyl group is preferred.

N1 in the formula [6-1c], n2 in the formula [6-2c], and n3 in the formula [6-3c] each independently represent an integer of 1 or 2. Among them, 1 is preferred.

M1 in the formula [6-1c], m2 in the formula [6-2c], and m3 in the formula [6-3c] each independently represent an integer of 1 or 2. Among them, 1 is preferred.

X ^a in the formula [6-1d], X ^{d in the} formula [6-2d] and X ^g in the formula [6-3d] are each independently represented by a single bond, -O-, -CONH-, -OCH ₂ At least one of the bonding groups selected from the group consisting of -, -COO-, and -OCO-. Among them, a single bond, -O-, -OCH ₂ - or -OCO- is preferred from the viewpoint of easiness of production of the adhesion compound. More preferably, it is a single bond, -O- or -OCH ₂ -.

X ^b in the formula [6-1d], X ^{e in the} formula [6-2d] and X ^h in the formula [6-3d] each independently represent an alkylene group having a carbon number of 1 to 15, -(CH ₂ -CH ₂ -O) _p - (p is an integer of 1 to 10), at least 1 selected from the group consisting of the structures represented by the formula [6c-1], the formula [6c-4], and the formula [6c-5] Kind. In this case, any -CH ₂ - group of the aforementioned alkylene group may be -COO-, -OCO-, -CONH-, NHCO-, -CO-, -S-, -SO ₂ -, -CF ₂ - , -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -OSi(CH ₃ ) ₂ - or -Si(CH ₃ ) ₂ O-, substituted with a hydrogen atom bonded to any carbon atom It may be substituted with a hydroxyl group (OH group), a carboxyl group (COOH group) or a halogen atom.

X ^c in the formula [6-1d], X ^{f in the} formula [6-2d] and X ⁱ in the formula [6-3d] each independently represent a single bond, -CH ₂ - and -OCH ₂ - At least one type of bonding group.

A ¹ in the formula [6-1d], A ^{5 in the} formula [6-2d] and A ⁸ in the formula [6-3d] each independently represent a hydrogen atom or an alkylene group having 1 to 2 carbon atoms. Among them, a hydrogen atom or a methyl group is preferred.

A ² in the formula [6-1d], A ^{6 in the} formula [6-2d] and A ⁹ in the formula [6-3d] each independently represent an alkylene group having 1 to 2 carbon atoms.

A ³ in the formula [6-1d], A ^{7 in the} formula [6-2d] and A ¹⁰ in the formula [6-3d] each independently represent an alkylene group having 1 to 2 carbon atoms.

A ⁴ in the formula [6-1d], A ^{8 in the} formula [6-2d] and A ¹¹ in the formula [6-3d] each independently represent a hydrogen atom or an alkylene group having 1 to 2 carbon atoms. Among them, a hydrogen atom or a methyl group is preferred.

N1 in the formula [6-1d], n2 in the formula [6-2d], and n3 in the formula [6-3d] each independently represent an integer of 1 or 2. Among them, 1 is preferred.

M1 in the formula [6-1d], m2 in the formula [6-2d], and m3 in the formula [6-3d] each independently represent an integer of 1 or 2. Among them, 1 is preferred.

The adhesive compound is preferably a compound selected from the group consisting of the compounds represented by the following formulas [6-1] and [6-5].

(In the formula [6-4], n represents an integer of 1 to 10, and in the formula [6-5], m represents an integer of 1 to 10).

More specifically, for example, there are compounds shown below.

For example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, tris(meth)acryloyloxyethoxy trishydroxyl a compound having three polymerizable unsaturated groups in a molecule such as methyl propane or glycerol polyglycidyl ether poly(meth)acrylate; ethylene glycol di(meth)acrylate, diethylene glycol di(a) Acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, dibutyl Alcohol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide bisphenol A di(meth)acrylate, propylene oxide bisphenol type di(meth)acrylic acid Ester, 1,6-hexanediol di(meth)acrylate, glycerol (Meth) acrylate, pentaerythritol di(meth) acrylate, ethylene glycol diglycidyl ether di(meth) acrylate, diethylene glycol diglycidyl ether di(meth) acrylate, benzene a compound having two polymerizable unsaturated groups in a molecule such as diglycidyl dicarboxylate di(meth)acrylate or hydroxydimethylpropionic acid neopentyl glycol di(meth)acrylate; Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate Ester, 2-(methyl)propenyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono(meth) acrylate, 2 A compound having one polymerizable unsaturated group in the molecule such as (meth)acryloxyethyl phosphate or N-methylol (meth) acrylamide.

The above-mentioned adhesive compound is an example, but is not limited thereto. Moreover, the adhesive compound used for the liquid crystal alignment treatment agent may be one type or a combination of two or more types.

The content of the adhesion-sensitive compound in the liquid crystal alignment agent is preferably 0.1 to 150 parts by mass based on 100 parts by mass of the total polymer component. In order to carry out the crosslinking reaction, the effect of exhibiting the object is preferably 0.1 to 100 parts by mass, particularly preferably 1 to 50 parts by mass, per 100 parts by mass of the total polymer component.

In the liquid crystal alignment treatment agent of the present invention, a compound having an epoxy group, an isocyanate group, an oxetane group or a cyclic carbonate group may be introduced or may have a range which does not impair the effects of the present invention. At least selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group A compound of one substituent (also collectively referred to as a crosslinkable compound). In this case, these substituents must have two or more of the crosslinkable compounds.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, and the like. Glycidylamino diphenylene, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenyl glycidyl ether ethane , triphenyl glycidyl ether ethane, bisphenol hexafluoroacetam diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl -2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl Inter-xylylenediamine, 2-(4-(2,3-epoxypropoxy)phenyl)-2-(4-(1,1-bis(4-(2,3-epoxy)) Propoxy)phenyl)ethyl)phenyl)propane, 1,3-bis(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-(4-) (1-(4-(2,3-Ethoxypropyloxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol and the like.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetanyl groups represented by the following formula [4].

Specifically, for example, the formula [4a]~ disclosed in items 58 to 59 of International Publication WO2011/132751 (2011.10.27 publication) is mentioned. A crosslinkable compound represented by [4k].

The crosslinkable compound having a cyclic carbonate group is a crosslinkable compound having at least two cyclic carbonate groups represented by the following formula [5].

Specifically, for example, the crosslinkable compound represented by the formula [5-1] to the formula [5-42] disclosed in 76-82 of the International Publication WO2012/014898 (published 2012.2.2) is mentioned.

The crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group may, for example, be an amine-based resin having a hydroxyl group or an alkoxy group, such as a melamine resin, a urea resin, or a guanamine resin. , glycoluril-formaldehyde resin, amber-decylamine-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, a melamine derivative, a benzoguanamine derivative, or a glycoluril in which a hydrogen atom of an amine group is substituted with a methylol group or an alkoxymethyl group or both may be used. The melamine derivative or the benzoguanamine derivative may also be present in the form of a dimer or a trimer. It is preferred that each of the triazine rings has an average of 3 or more and 6 or less hydroxymethyl groups or alkoxymethyl groups.

Examples of such a melamine derivative or a benzoguanamine derivative include, for example, a triazine ring of a commercially available product, an average of 3.7 substituted MX-750, and a triazine ring per methoxymethyl group. The methoxymethyl group has an average of 5.8 substituted MW-30 (manufactured by the above, Sanwa Chemical Co., Ltd.) or Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. Melamine melamine, Cymel 235, 236, 238, Methoxymethylated butoxymethylated melamine of 212, 253, 254, etc., butoxymethylated melamine of Cymel 506, 508, etc., such as carboxylated methoxymethylated isobutoxy of Cymel 1141 Methylated melamine, methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1123, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, For example, a butoxymethylated benzoguanamine of Cymel 1128, a carboxyl group-containing methoxymethylated ethoxymethyl benzoguanamine such as Cymel 1125-80 (above, manufactured by Mitsui Cyanamid Co., Ltd.). Further, examples of the glycoluril include, for example, butoxymethylated glycoluril of Cymel 1170, methylolated glycoluril such as Cymel 1172, methoxymethylolated glycoluril such as Powderlink 1174, and the like.

The crosslinkable compound of a benzene or a phenolic compound having a hydroxyl group or an alkoxy group, for example, 1,3,5-glycol (methoxymethyl)benzene, 1,2,4-para (isopropoxy) Methyl)benzene, 1,4-bis(sec-butoxymethyl)benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, and the like.

More specifically, a crosslinkable compound represented by the formula [6-1] to the formula [6-48] disclosed in pages 62 to 66 of International Publication WO2011/132751 (2011.10.27) is mentioned. .

The content of the crosslinkable compound in the liquid crystal alignment agent is preferably 0.1 to 100 parts by mass based on 100 parts by mass of the total polymer component. In order to carry out the crosslinking reaction and exhibit the intended effect, it is preferably 0.1 to 50 parts by mass, particularly preferably 1 to 30 parts by mass, based on 100 parts by mass of the total polymer component.

In the liquid crystal alignment treatment agent of the present invention, vertical liquid crystal matching can be added A compound which shifts the charge in the film and promotes the charge extraction of the element, as disclosed in pages 69 to 73 of International Publication WO2011/132751 (2011.10.27), and is represented by the formula [M1] to [M156]. Azaheterocyclic amine compound. These amine compounds may be directly added to the liquid crystal alignment treatment agent, but it is preferably added after a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7 mass%, using a suitable solvent. The solvent is not particularly limited as long as it is an organic solvent in which the specific polyimine-based polymer is dissolved.

In the liquid crystal alignment treatment agent of the present invention, a compound which improves the uniformity of the film thickness of the vertical liquid crystal alignment film or the surface smoothness when the liquid crystal alignment treatment agent is applied can be used without departing from the effects of the present invention. Further, a compound which enhances the adhesion between the vertical liquid crystal alignment film and the substrate can be used.

Examples of the compound which improves the uniformity of the film thickness of the vertical liquid crystal alignment film or the surface smoothness include a fluorine-based surfactant, a rhodium-based surfactant, and a nonionic surfactant.

Specifically, for example, EFTOP EF301, EF303, EF352 (above, Thochem Products), MEGAFAC F171, F173, R-30 (above, manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (above, Sumitomo 3M) Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.). The ratio of use of the surfactant is 100 parts by mass, preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent.

Specific examples of the compound which enhances the adhesion between the vertical liquid crystal alignment film and the substrate include, for example, a functional decane-containing compound or an epoxy group-containing compound.

For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-( 2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyl Trimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethyl Oxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl-1,4,7 - triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9 -triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethyl Oxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(ethylene oxide)-3-aminopropyl Trimethoxy decane, N-bis(ethylene oxide)-3-amine Propyl triethoxy decane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether , neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1 , 3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-double (N, N-diglycidyl Aminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.

When the compound is adhered to the substrate, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent. When the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the storage stability of the liquid crystal alignment agent may be deteriorated.

In addition to the above-described compounds, the liquid crystal alignment treatment agent of the present invention may be added for the purpose of changing the electrical properties such as the dielectric constant or the electrical conductivity of the vertical liquid crystal alignment film, without impairing the effects of the present invention. Electrical or conductive material.

<Vertical liquid crystal alignment film. Manufacturing method of liquid crystal display element>

The substrate used for the liquid crystal display device of the present invention is not particularly limited as long as it is a substrate having high transparency, and an acrylic substrate, a polycarbonate substrate, a PET (polyethylene terephthalate) substrate or the like can be used in addition to the glass substrate. Plastic substrates, etc.

When a liquid crystal display element is used as a reverse type element for a dimming window or the like, a plastic substrate is preferred. Further, from the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode or the like for liquid crystal driving is formed. Further, in the case of a reflective reverse type element, a metal such as a tantalum wafer or aluminum or a substrate on which a dielectric multilayer film is formed may be used as the substrate on one side.

At least one of the substrates of the liquid crystal display device of the present invention has a liquid crystal A vertical liquid crystal alignment film with vertically aligned molecules. This vertical liquid crystal alignment film is obtained by applying a liquid crystal alignment treatment agent onto a substrate, baking it, and performing an alignment treatment by rubbing treatment or light irradiation. Further, in the case of the vertical liquid crystal alignment film of the present invention, such non-alignment treatment can also be used as a vertical liquid crystal alignment film.

The coating method of the liquid crystal alignment treatment agent is not particularly limited, and industrially, there are screen printing, offset printing, letterpress printing, ink jet method, dipping method, roll coating method, slit coating method, and spinner method. In the spray method or the like, the film thickness of the liquid crystal alignment film may be appropriately selected depending on the type of substrate or the purpose.

After the liquid crystal alignment treatment agent is applied onto the substrate, it can be heated at 30 to 300 ° C in accordance with the solvent used in the liquid crystal alignment treatment agent by a heating means such as a hot plate, a heat cycle type oven, or an IR (infrared) type oven. Preferably, the solvent is evaporated at a temperature of 30 to 250 ° C, and a vertical liquid crystal alignment film can be obtained by firing.

When the thickness of the vertical liquid crystal alignment film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if the thickness is too thin, the reliability of the element is lowered, so it is preferably 5 to 300 nm, more preferably It is 10~200nm.

The liquid crystal composition used for the liquid crystal display device has at least a liquid crystal composition of a liquid crystal and a polymerizable compound. Other than the liquid crystal and the polymerizable compound, for example, a spacer for controlling the electrode gap (also referred to as gap) of the above-mentioned initiator or liquid crystal display element can be mentioned.

The method of injecting the liquid crystal composition is not particularly limited, and examples thereof include the following methods. That is, when the substrate is a glass substrate, vertical liquid crystal is prepared. One of the substrates of the pair of alignment films was subjected to removal of a part of the substrate on one side, and then a sealant was applied. Then, the surface of the vertical liquid crystal alignment film was placed inside, and the substrate on the other side was bonded to form an empty cell. Then, for example, a method in which a liquid crystal composition is injected into a unit cell is obtained by injecting a liquid crystal composition under reduced pressure from a place where a sealant is not applied.

Further, when a plastic substrate is used as the substrate, for example, a substrate on which one pair of vertical liquid crystal alignment films are formed is prepared, and a liquid crystal composition is dropped on a single-sided substrate by an ODF (One Drop Filling) method or an inkjet method. Then, the substrate on the other side is bonded to obtain a method in which the liquid crystal composition is injected into the unit cell. At this time, in the liquid crystal display element of the present invention, since the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is high, it is not necessary to apply a sealant to the four sheets of the substrate.

The gap of the liquid crystal display element can be controlled by a spacer or the like. This method may, for example, be a method of introducing a spacer of a desired size into the liquid crystal composition or a method of using a substrate having a columnar spacer of a desired size. Further, the size of the gap is preferably 1 to 100 μm, more preferably 2 to 50 μm. Very good is 3~30μm. When the gap is too small, the contrast of the liquid crystal display element is lowered, and if the gap is too large, the driving voltage of the element becomes high.

The liquid crystal display device of the present invention is obtained by curing a liquid crystal composition in a part or the whole of a liquid crystal composition in a liquid crystal state to form a cured product of a liquid crystal and a polymerizable compound.

The curing of the liquid crystal composition is performed by injecting the liquid crystal composition obtained as described above into at least one of irradiation and heating of the active energy ray. Here, the active energy ray is preferably ultraviolet ray. Ultraviolet The line has a wavelength of, for example, 250 nm to 400 nm, preferably 310 nm to 370 nm. Further, in the heat treatment, the temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, the ultraviolet treatment and the heat treatment may be performed simultaneously or after the ultraviolet treatment. In the present invention, the curing of the liquid crystal composition is preferably performed by ultraviolet rays alone.

As described above, in the present invention, a liquid crystal display element using a vertical liquid crystal alignment film obtained by a liquid crystal alignment treatment agent containing a specific polymer has high vertical alignment property, good optical characteristics, that is, transparency without an applied voltage. The scattering characteristics are good with an applied voltage, and the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is high. Therefore, the liquid crystal display element of the present invention is used for a liquid crystal display element of a transportation machine and a transportation machine of an automobile, a railway, an airplane, etc., specifically, a dimming window or an indoor mirror light for controlling transmission and interruption of light. Shutter element, etc.

In particular, as described above, since the transparency at the time of no applied voltage and the scattering characteristic at the time of applying a voltage are good, when the element is used for a glass window of a vehicle, compared with the case of using a conventional reverse type element, at night time The light extraction efficiency is high, and the glare effect from the external light is also prevented from becoming high. Therefore, the safety in driving the vehicle or the comfort in riding is further improved. Moreover, when a liquid crystal display element is produced from a film substrate and is bonded to a glass window of a vehicle, the reliability of the element is higher than that of the conventional reverse type element. That is, it is less likely to cause defects or deterioration due to low adhesion of the liquid crystal layer and the vertical alignment film.

In addition, the liquid crystal display device of the present invention can also be used for an LCD (Liquid Crystal Display) or an OLED (Organic Light-emitting Diode). A light guide plate of a display device such as a display or a back plate of a transparent display using the display. Specifically, when used for a backplane of a transparent display, a transparent display and a liquid crystal display element can be matched, and when a screen is displayed on a transparent display, the liquid crystal display element can suppress entry of light from the back surface. Thereby, when the liquid crystal display element is displayed on the screen on the transparent display, the applied voltage becomes a scattering state, and the screen display can be made clear, and after the screen is displayed, it becomes a transparent state without an applied voltage.

[Examples]

The invention will be described in more detail below by way of examples, without being limited thereto.

"Abbreviations for Compounds Used in Synthesis Examples, Examples and Comparative Examples" (liquid crystal)

L1: MLC-6608 (manufactured by Merck)

(polymerizable compound)

R1: a compound represented by the following formula [R1]

(photoinitiator)

P1: a compound represented by the following formula [P1]

(specific side chain type diamine compound)

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

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

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

A4: a diamine compound represented by the following formula [A4] (corresponding to the formula [1-1])

A5: 1,3-diamino-4-octadecylbenzene (equivalent to formula [1-2])

(2nd bisamine compound)

B1: 3,5-diaminobenzoic acid

B2: a diamine represented by the formula [B2]

(other diamine compounds)

C1: p-phenylenediamine

C2: m-phenylenediamine

(tetracarboxylic acid component)

D1:1,2,3,4-cyclobutane tetracarboxylic dianhydride

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

D3: a tetracarboxylic dianhydride represented by the following formula [D3]

D4: a tetracarboxylic dianhydride represented by the following formula [D4]

<Adhesive compound>

M1: a compound represented by the following formula [M1]

M2: a compound represented by the following formula [M2]

M3: a compound represented by the following formula [M3]

<Crosslinking compound>

K1: a compound represented by the following formula [K1]

<solvent> (solvent having a boiling point of less than 180 ° C)

PGME: propylene glycol monomethyl ether

MCS: ethylene glycol monomethyl ether

ECS: ethylene glycol monoethyl ether

PCS: ethylene glycol monopropyl ether

BCS: ethylene glycol monobutyl ether

PB: propylene glycol monobutyl ether

(solvent having a boiling point of 180 ° C or higher)

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

"Measurement of molecular weight of polyamidene-based polymers"

The molecular weight of the polyimine precursor and the polyimine is a normal temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko Co., Ltd.) and a column (KD-803, KD-805, Shodex). Company system), as measured below.

Column temperature: 50 ° C

Dissolution: N,N'-dimethylformamide (additive is 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) is 10ml/L)

Flow rate: 1.0ml/min

Standard sample for the production of calibration lines: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (made by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000 and 1,000) (Polymer) Laboratories company).

"Determination of the imidization rate of polyamidiamine"

20 mg of polyimine powder was placed in an NMR sampling tube stand (NMR sampling tube stand, 5 (manufactured by Kusano Scientific Co., Ltd.), a solution of dimethyl hydrazine (DMSO-d6, 0.05% by mass of TMS (tetramethyl decane)) (0.53 ml) was added thereto, and ultrasonic waves were applied to completely dissolve. This solution was measured for proton NMR at 500 MHz using an NMR measuring machine (JNW-ECA500) (manufactured by JEOL Co., Ltd.). The ruthenium imidization rate is determined by using a proton from a structure which has no change before and after imidization as a reference proton, and the peak value of the proton is used and the NH group derived from proline which occurs near 9.5 ppm to 10.0 ppm. The proton peak cumulative value was obtained by the following equation.

醯 imidization rate (%) = (1-α.x/y) × 100

In the above formula, x is the proton peak cumulative value derived from the NH group of valine acid, y is the peak cumulative value of the reference proton, and α is the relative proline acid when the polyproline (the imidization ratio is 0%) The ratio of the number of reference protons of one NH matrix.

"Synthesis of specific polyamidene polymers" <Synthesis Example 1>

D1 (2.96 g, 15.1 mmol), A1 (2.91 g, 7.65 mmol), B1 (0.93 g, 6.11 mmol) and C2 (0.17 g, 1.57 mmol) were mixed in MCS (20.9 g), and reacted at 40 ° C Hour, got To a polyamic acid solution (1) having a resin solid concentration of 25% by mass. The polyamic acid had a number average molecular weight of 24,600 and a weight average molecular weight of 73,900.

<Synthesis Example 2>

D2 (3.83 g, 15.3 mmol), A2 (6.04 g, 15.3 mmol) and B1 (2.33 g, 15.3 mmol) were mixed in MCS (26.4 g), and reacted at 50 ° C for 2 hours, then D1 (2.94 g) was added. 15.0 mmol) and MCS (23.8 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25% by mass. The polyamine has a number average molecular weight of 16,800 and a weight average molecular weight of 55,900.

<Synthesis Example 3>

D2 (3.83 g, 15.3 mmol), A2 (6.04 g, 15.3 mmol) and B1 (2.33 g, 15.3 mmol) were mixed in NMP (26.4 g), and reacted at 50 ° C for 2 hours, then D1 (2.94 g) was added. 15.0 mmol) and NMP (23.8 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

After adding NMP to 6% by mass, the obtained polyaminic acid solution (30.0 g) was added, and acetic anhydride (3.90 g) and pyridine (2.40 g) as a ruthenium catalyst were added thereto at 70 ° C. Reaction for 2 hours. This ruthenium solution was poured into methanol (460 ml), and the obtained precipitate was obtained by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a quinone powder. End (3). The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 21,500, and a weight average molecular weight of 59,400.

<Synthesis Example 4>

D2 (2.64 g, 10.6 mmol), A3 (4.56 g, 10.5 mmol), B1 (1.60 g, 10.5 mmol) and B2 (1.07 g, 5.26 mmol) were mixed in NMP (21.9 g), and reacted at 80 ° C. After the hour, D1 (3.02 g, 15.8 mmol) and NMP (17.2 g) were added, and the mixture was reacted at 40 ° C for 8 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

After the NMP was added and diluted to 6 mass%, the obtained polyamic acid solution (30.0 g) was added, and acetic anhydride (3.88 g) and pyridine (2.40 g) as a ruthenium-imiding catalyst were added thereto at 50 ° C. Reaction for 2 hours. This ruthenium solution was poured into methanol (460 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (4). The polyimine had a hydrazine imidation ratio of 56%, a number average molecular weight of 19,100, and a weight average molecular weight of 53,100.

<Synthesis Example 5>

D2 (2.50 g, 10.0 mmol), A4 (2.96 g, 6.00 mmol), B1 (1.52 g, 10.0 mmol), B2 (0.41 g, 2.00 mmol) and C1 (0.22 g, 2.00 mmol) in NMP (19.0 g) The mixture was mixed and reacted at 80 ° C for 5 hours. Then, D1 (1.92 g, 9.80 mmol) and NMP (9.50 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a resin. A polyamic acid solution having a solid concentration of 25% by mass.

After the NMP was added to the obtained polyamidamine solution (30.0 g) to be diluted to 6 mass%, acetic anhydride (4.01 g) and pyridine (2.50 g) as a ruthenium catalyst were added thereto at 50 ° C. Reaction for 2 hours. This ruthenium solution was poured into methanol (460 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (5). The polyimine had a hydrazine imidization ratio of 49%, a number average molecular weight of 14,900, and a weight average molecular weight of 46,200.

<Synthesis Example 6>

D3 (5.45 g, 24.3 mmol), A2 (5.81 g, 14.7 mmol), B1 (1.12 g, 7.36 mmol) and B2 (0.50 g, 2.46 mmol) were mixed in NMP (38.6 g) and reacted at 40 ° C A polyamic acid solution having a resin solid content concentration of 25% by mass was obtained in 10 hours.

After adding NMP to 6% by mass in the obtained polyamidic acid solution (30.0 g), acetic anhydride (4.00 g) and pyridine (2.48 g) as a ruthenium amide catalyst were added thereto at 70 ° C. Reaction for 2 hours. This ruthenium solution was poured into methanol (460 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (6). The polyimine had a hydrazine imidation ratio of 63%, a number average molecular weight of 16,900, and a weight average molecular weight of 47,900.

<Synthesis Example 7>

D3 (5.45g, 24.3mmol), A4 (3.63g, 7.37) Methyl) and B1 (2.61 g, 17.2 mmol) were mixed in NMP (35.1 g), and reacted at 40 ° C for 5 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

After the NMP was added and diluted to 6 mass% in the obtained polyamidic acid solution (30.0 g), acetic anhydride (8.00 g) and pyridine (2.48 g) as a ruthenium catalyst were added thereto at 50 ° C. Reaction for 3 hours. This ruthenium solution was poured into methanol (460 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (7). The polyimine had a hydrazine imidation ratio of 54%, a number average molecular weight of 18,100, and a weight average molecular weight of 48,800.

<Synthesis Example 8>

D4 (4.59 g, 15.3 mmol), A3 (6.62 g, 15.3 mmol), B1 (1.86 g, 12.2 mmol) and B2 (0.62 g, 3.05 mmol) were mixed in NMP (27.6 g) and reacted at 40 ° C After 8 hours, D1 (2.94 g, 15.0 mmol) and NMP (22.3 g) were added, and the mixture was reacted at 25 ° C for 10 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

After the NMP was added and diluted to 6 mass% in the obtained polyamidic acid solution (30.0 g), acetic anhydride (7.24 g) and pyridine (2.24 g) as a ruthenium catalyst were added thereto at 40 ° C. Reaction for 1.5 hours. This ruthenium solution was poured into methanol (460 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (8). The polyimide imidization ratio of this polyimine is 71%, number average The molecular weight was 16,400 and the weight average molecular weight was 36,900.

<Synthesis Example 9>

D2 (3.83 g, 15.3 mmol), A5 (5.76 g, 15.3 mmol) and B1 (2.33 g, 15.3 mmol) were mixed in NMP (26.4 g), and reacted at 50 ° C for 2 hours, then D1 (2.94 g) was added. 15.0 mmol) and NMP (23.8 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid concentration of 25% by mass.

After adding NMP to 6% by mass in the obtained polyamidic acid solution (30.0 g), acetic anhydride (3.88 g) and pyridine (2.42 g) as a ruthenium catalyst were added thereto at 70 ° C. Reaction for 2 hours. This ruthenium solution was poured into methanol (460 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (9). The polyimine had a hydrazine imidation ratio of 61%, a number average molecular weight of 19,200, and a weight average molecular weight of 56,200.

<Synthesis Example 10>

D2 (3.83 g, 15.3 mmol) and B1 (4.66 g, 30.6 mmol) were mixed in NMP (37.7 g), and reacted at 50 ° C for 2 hours, then D1 (2.94 g, 15.0 mmol) and NMP (12.6 g) were added. The reaction was carried out at 40 ° C for 6 hours to obtain a polyamic acid solution (10) having a resin solid content concentration of 25% by mass. The polyamine has a number average molecular weight of 24,500 and a weight average molecular weight of 77,500.

<Synthesis Example 11>

In the polyamic acid solution (10) (30.0 g) obtained by the synthetic method of Synthesis Example 10, NMP was added and diluted to 6 mass%, and acetic anhydride (3.85 g) and pyridine as a ruthenium catalyst were added. 2.40 g), allowing to react at 70 ° C for 2 hours. This ruthenium solution was poured into methanol (460 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (11). This polyimine had a hydrazine imidation ratio of 59%, a number average molecular weight of 22,200, and a weight average molecular weight of 61,500.

<Synthesis Example 12>

D2 (3.83 g, 15.3 mmol), A2 (6.04 g, 15.3 mmol) and B1 (2.33 g, 15.3 mmol) were mixed in NMP (26.4 g), and reacted at 50 ° C for 2 hours, then D1 (2.94 g) was added. 15.0 mmol) and NMP (23.8 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (12) having a resin solid concentration of 25% by mass. The polyamine has a number average molecular weight of 18,700 and a weight average molecular weight of 62,100.

Table 1 shows the ruthenium imidization ratio of the specific polyimine-based polymer obtained in Synthesis Examples 1 to 12, and the tetracarboxylic acid component and the diamine component used for the synthesis of the polymer.

"Manufacture of liquid crystal alignment agent"

In the examples 1 to 21 and the comparative examples 1 to 6, the production examples of the liquid crystal alignment treatment agent are described. The obtained liquid crystal alignment treatment agent is also used for production and evaluation of liquid crystal display elements.

The liquid crystal alignment treatment agent obtained in Examples 1, 2, 4, 6 to 21 and Comparative Examples 1 to 3 and 5 and the specific polyamidene-based polymer, solvent, adhesive compound, cross-linking compound and The usage amount is shown in Table 2~4.

Using the liquid crystal alignment treatment agent obtained in the examples and the comparative examples, "production of liquid crystal display element (glass substrate and plastic substrate)", "evaluation of liquid crystal alignment (glass substrate and plastic substrate)", and "optical characteristics (transmittance) Evaluation of scattering characteristics) (glass substrate and plastic substrate) and "evaluation of adhesion between liquid crystal layer and vertical liquid crystal alignment film (glass substrate and plastic substrate)".

"Production of liquid crystal composition" (Production of liquid crystal composition (1))

L1 (11.5 g), R1 (1.73 g), and P1 (0.12 g) were mixed, and when heated, the mixture was cooled to 25 ° C to obtain a liquid crystal composition (1) which showed uniform liquid crystallinity.

(Production of liquid crystal composition (2))

The mixture of L1 (12.0 g), R1 (2.40 g), and P1 (0.12 g) was heated, and after cooling to 25 ° C, a liquid crystal composition (2) having a uniform liquid crystal property was obtained.

"Production of Liquid Crystal Display Element (Glass Substrate)"

The liquid crystal alignment treatment agent obtained in the examples and the comparative examples has a pore diameter The 1 μm membrane filter was filtered under pressure, and the solution was spin-coated on a 100×100 mm ITO electrode glass substrate washed with pure water and IPA (isopropyl alcohol) (length: 100 mm, width: 100 mm, thickness: The ITO surface of 0.7 mm) was heat-treated at 100 ° C for 2 minutes on a hot plate to obtain an ITO substrate with a vertical liquid crystal alignment film having a film thickness of 100 nm.

Two sheets of the obtained ITO substrate with a vertical liquid crystal alignment film were prepared, and a spacer of 6 μm was applied to the vertical liquid crystal alignment film surface of one of the substrates. Then, the liquid crystal composition is dropped by the ODF method on the vertical liquid crystal alignment film surface of the substrate, and then bonded to the vertical liquid crystal alignment film interface of the other substrate to obtain a pre-treatment element.

Then, a metal halide lamp having an illuminance of 60 mW was used to remove a wavelength of 350 nm or less, and ultraviolet rays of 7 J/cm ² in terms of 365 nm were irradiated to obtain a liquid crystal display element (glass substrate). The temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was controlled to 25 °C.

"Production of Liquid Crystal Display Devices (Plastic Substrate)"

The liquid crystal alignment treatment agent obtained in the example was filtered under pressure with a membrane filter having a pore diameter of 1 μm, and this solution was spin-coated on a 150×150 mm ITO electrode-attached PET (polyethylene terephthalate) washed with pure water. The ITO surface of the diester) substrate (length: 150 mm, width: 150 mm, thickness: 0.2 mm) was heat-treated at 100 ° C for 2 minutes on a hot plate to obtain an ITO substrate with a vertical liquid crystal alignment film having a thickness of 100 nm. . The obtained ITO substrate with a vertical liquid crystal alignment film is prepared in two pieces, one of which is based on The vertical liquid crystal alignment film of the panel was coated with a 6 μm spacer. Then, the liquid crystal composition is dropped by the ODF method on the vertical liquid crystal alignment film surface of the substrate, and then bonded to the vertical liquid crystal alignment film interface of the other substrate to obtain a pre-treatment element.

Then, a metal halide lamp having an illuminance of 60 mW was used, and a wavelength of 350 nm or less was removed by using a metal halide lamp having an illuminance of 60 mW, and ultraviolet rays of 7 J/cm ² in terms of 365 nm were irradiated to obtain a liquid crystal display element (plastic substrate). The temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was controlled to 25 °C.

In the liquid crystal display device (glass substrate and plastic substrate), the liquid crystal alignment treatment agent and the liquid crystal composition are described in Tables 5 to 7.

"Evaluation of Liquid Crystal Alignment (Glass Substrate and Plastic Substrate)"

Liquid crystal display elements (glass substrates and plastic substrates) produced under the same conditions as described above were evaluated for liquid crystal alignment. Specifically, this device was observed with a polarizing microscope (ECLIPSE E600WPOL, manufactured by NIKON Co., Ltd.), and it was confirmed whether or not the liquid crystal was vertically aligned, and the liquid crystal was evaluated as a vertical alignment (in Tables 5 to 7, "good").

Then, the liquid crystal display element (glass substrate and plastic substrate) in which the liquid crystal alignment property was evaluated was stored in a high temperature bath at a temperature of 100 ° C for 144 hours. After storage, the liquid crystal alignment property was evaluated under the same conditions as described above. Specifically, the liquid crystal alignment property was not observed to be scattered, and the liquid crystal uniform alignment was excellent in the evaluation (in Tables 5 to 7, "good").

Liquid crystal display elements (glass substrate and plastic substrate) are described in Tables 5 to 7. The evaluation result of the liquid crystal alignment.

"Evaluation of optical properties (transparency and scattering properties) (glass substrate and plastic substrate)"

The liquid crystal display elements (glass substrate and plastic substrate) produced under the same conditions as above were evaluated for optical characteristics (transparency and scattering characteristics).

The transparency at the time of no applied voltage was measured by measuring the transmittance of the liquid crystal display element (glass substrate and plastic substrate) in the state where no applied voltage was applied. Specifically, the measurement device was measured using UV-3600 (manufactured by Shimadzu Corporation), temperature 25 ° C, and control group (reference example) using the above-mentioned ITO electrode glass substrate (or PET substrate) at a scanning wavelength of 300 to 800 nm. . The transmittance was evaluated at a wavelength of 450 nm, and the higher the transmittance, the better the evaluation (Tables 8 to 10 indicate the values of the transmittance).

The scattering characteristics at the time of applying a voltage were performed by externally driving a liquid crystal display element (a glass substrate and a plastic substrate) with an AC drive of 40 V to visually observe the alignment state of the liquid crystal. Specifically, the device is white turbid, that is, the scatter characteristic is evaluated as excellent (in Tables 8 to 10, "good").

Tables 8 to 10 show the evaluation results of optical characteristics (transparency and scattering characteristics) of liquid crystal display elements (glass substrates and plastic substrates).

"Evaluation of adhesion between liquid crystal layer and vertical liquid crystal alignment film (glass substrate and plastic substrate)"

The liquid crystal display element (glass substrate and plastic substrate) produced under the same conditions as described above was evaluated for adhesion between the liquid crystal layer and the vertical liquid crystal alignment film. Specifically, the liquid crystal display element (glass substrate and plastic substrate) was stored in a high-temperature and high-humidity bath at a temperature of 80 ° C and a humidity of 90% RH for 24 hours, and the presence or absence of bubbles in the element and the peeling of the element were confirmed. At this time, in the case where no bubbles were observed in the element and no peeling of the element (the state in which the liquid crystal layer and the vertical liquid crystal alignment film were peeled off) were excellent in this evaluation (in Tables 8 to 10, "good" is indicated).

Tables 8 to 10 show the results of evaluation of the adhesion between the liquid crystal layer of the liquid crystal display device (glass substrate and plastic substrate) and the vertical liquid crystal alignment film.

<Example 1>

MCS (16.0 g), NMP (3.90 g), BCS (11.8 g), M2 (0.25 g) were added to the polyamic acid solution (1) (10.0 g) having a solid content concentration of 25% by mass of the resin obtained in Synthesis Example 1. And K1 (0.13g) was stirred at 25 ° C for 5 hours to obtain a liquid crystal alignment treatment agent (1). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (1) and liquid crystal composition (1), a liquid crystal display element (glass substrate) was produced, and the above evaluation was performed.

<Example 2>

The resin having a solid content concentration of 25% by mass was obtained in Synthesis Example 2. MCS (18.9 g) and PB (14.4 g) were added to the amine acid solution (2) (10.5 g), and the mixture was stirred at 25 ° C for 5 hours to obtain a liquid crystal alignment treatment agent (2). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (2) and liquid crystal composition (1), a liquid crystal display element (glass substrate and plastic substrate) was produced and subjected to the above evaluation.

<Example 3>

Using the liquid crystal alignment treatment agent (2) obtained in Example 2 and the liquid crystal composition (2), a liquid crystal display element (glass substrate) was produced and subjected to the above evaluation.

<Example 4>

PGME (21.2 g) and γ-BL (2.40 g) were added to the polyimine powder (3) (1.50 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to obtain a liquid crystal alignment treatment agent (3). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (3) and the liquid crystal composition (1), and the above evaluation was performed.

<Example 5>

The liquid crystal display element (glass substrate) prepared by using the liquid crystal alignment treatment agent (3) obtained in Example 4 and the liquid crystal composition (2) was subjected to the above evaluation. price.

<Example 6>

In the polyimine powder (3) (1.50 g) obtained in Synthesis Example 3, PGME (21.2 g) and γ-BL (2.40 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. M2 (0.45 g) and K1 (0.15 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (4). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (4) and liquid crystal composition (1), a liquid crystal display element (glass substrate and plastic substrate) was produced and subjected to the above evaluation.

<Example 7>

In the polyimine powder (3) (1.60 g) obtained in Synthesis Example 3, PGME (12.5 g), ECS (10.0 g) and γ-BL (2.50 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. M1 (0.56 g) was added to this solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (5). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (5) and the liquid crystal composition (2), and the above evaluation was performed.

<Example 8>

ECS (8.50 g), PCS (14.6 g) and NEP (1.20 g) were added to the polyimine powder (4) (1.55 g) obtained in Synthesis Example 4, and stirred at 70 ° C for 24 hours to obtain a liquid crystal alignment treatment agent. (6). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (6) and the liquid crystal composition (2), and the above evaluation was performed.

<Example 9>

In the polyimine powder (4) (1.60 g) obtained in Synthesis Example 4, PGME (20.1 g), PB (2.50 g) and γ-BL (2.50 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. M2 (0.56 g) and K1 (0.16 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (7). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (7) and the liquid crystal composition (1), and the above evaluation was performed.

<Example 10>

ECS (16.5 g), BCS (2.40 g) and NEP (4.70 g) were added to the polyimine powder (4) (1.50 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. M3 (0.23 g) was added to this solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (8). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (8) and the liquid crystal composition (1), and the above evaluation was performed.

<Example 11>

ECS (20.0 g) and γ-BL (3.50 g) were added to the polyimine powder (5) (1.50 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. K1 (0.23 g) was added to this solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (9). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate and plastic substrate) was produced using the obtained liquid crystal alignment treatment agent (9) and liquid crystal composition (2), and the above evaluation was performed.

<Example 12>

PGME (13.1 g), PB (9.50 g), and γ-BL (1.20 g) were added to the polyimine powder (5) (1.52 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. M3 (0.08 g) was added to this solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (10). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (10) and the liquid crystal composition (1), and the above evaluation was performed.

<Example 13>

PGME (20.0 g), PB (1.20 g), and γ-BL (2.40 g) were added to the polyimine powder (5) (1.50 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. M2 (0.95 g) and K1 (0.08 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (11). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate and plastic substrate) was produced using the obtained liquid crystal alignment treatment agent (11) and the liquid crystal composition (1), and the above evaluation was performed.

<Example 14>

ECS (11.8 g) and PCS (11.8 g) were added to the polyimine powder (5) (1.50 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. M1 (0.60 g) was added to this solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (12). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (12) and the liquid crystal composition (2), and the above evaluation was performed.

<Example 15>

PGME (23.8 g) and γ-BL (1.30 g) were added to the polyimine powder (6) (1.60 g) obtained in Synthesis Example 6, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. M2 (0.48 g) and K1 (0.08 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (13). confirm This liquid crystal alignment treatment agent was found to be a uniform solution without any abnormality such as turbidity or precipitation.

The liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (13) and the liquid crystal composition (1), and the above evaluation was performed.

<Example 16>

To the polyimine powder (6) (1.50 g) obtained in Synthesis Example 6, PGME (23.5 g) was added, and the mixture was stirred at 70 ° C for 24 hours to dissolve. K1 (0.16 g) was added to this solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (14). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (14) and the liquid crystal composition (2), and the above evaluation was performed.

<Example 17>

PGME (24.3 g) was added to the polyimine powder (7) (1.55 g) obtained in Synthesis Example 7, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. M2 (0.39 g) and K1 (0.16 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (15). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate and plastic substrate) was produced using the obtained liquid crystal alignment treatment agent (15) and the liquid crystal composition (1), and the above evaluation was performed.

<Example 18>

PGME (20.0 g) and γ-BL (3.50 g) were added to the polyimine powder (7) (1.50 g) obtained in Synthesis Example 7, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. M3 (0.15 g) and K1 (0.08 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (16). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (16) and the liquid crystal composition (1), and the above evaluation was performed.

<Example 19>

MCS (9.40 g), BCS (11.8 g), and NMP (2.40 g) were added to the polyimine powder (8) (1.50 g) obtained in Synthesis Example 8, and stirred at 70 ° C for 24 hours to obtain a liquid crystal alignment treatment agent ( 17). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (17) and the liquid crystal composition (2), and the above evaluation was performed.

<Example 20>

PGME (19.4 g), PB (2.40 g), and γ-BL (2.40 g) were added to the polyimine powder (8) (1.55 g) obtained in Synthesis Example 8, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. M2 (0.47g) and K1 (0.16g) were added to this solution, and stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent. (18). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (18) and the liquid crystal composition (1), and the above evaluation was performed.

<Example 21>

PGME (16.5 g), PB (2.40 g), and γ-BL (4.70 g) were added to the polyimine powder (9) (1.50 g) obtained in Synthesis Example 9, and stirred at 70 ° C for 24 hours to obtain a liquid crystal alignment treatment. Agent (19). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (19) and the liquid crystal composition (1), and the above evaluation was performed.

<Comparative Example 1>

NMP (25.0 g) and BCS (8.20 g) were added to a polyamic acid solution (10) (10.5 g) having a solid content concentration of 25% by mass of the resin obtained in Synthesis Example 10, and stirred at 25 ° C for 5 hours to obtain a liquid crystal alignment. Treatment agent (20). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (20) and the liquid crystal composition (1), and the above evaluation was performed.

<Comparative Example 2>

NMP (18.8 g) was added to the polyimine powder (11) (1.50 g) obtained in Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (4.70 g) was added to this solution, and the mixture was stirred at 25 ° C for 5 hours to obtain a liquid crystal alignment treatment agent (21). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (21) and the liquid crystal composition (1), and the above evaluation was performed.

<Comparative Example 3>

NMP (23.8 g) and BCS (7.80 g) were added to a polyamic acid solution (12) (10.0 g) having a solid content concentration of 25% by mass of the resin obtained in Synthesis Example 12, and stirred at 25 ° C for 5 hours to obtain a liquid crystal alignment. Treatment agent (22). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (22) and the liquid crystal composition (1), and the above evaluation was performed.

<Comparative Example 4>

The liquid crystal display element (glass substrate) produced by using the liquid crystal alignment treatment agent (22) obtained in Comparative Example 3 and the liquid crystal composition (2) was subjected to the above evaluation.

<Comparative Example 5>

The polyimine powder (3) (1.60 g) obtained in Synthesis Example 3 was added. NMP (20.1 g) was stirred at 70 ° C for 24 hours to dissolve. BCS (5.00 g) was added to this solution, and the mixture was stirred at 25 ° C for 5 hours to obtain a liquid crystal alignment treatment agent (23). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

The liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (23) and the liquid crystal composition (1), and the above evaluation was performed.

<Comparative Example 6>

The liquid crystal display element (glass substrate) produced by using the liquid crystal alignment treatment agent (23) obtained in Comparative Example 5 and the liquid crystal composition (2) was subjected to the above evaluation.

From the above results, in the examples, even when a liquid crystal alignment treatment agent of a polyimine-based polymer was used, a liquid crystal display element which can be fired at a low temperature to produce a liquid crystal alignment film can be obtained.

Further, the liquid crystal display element using the vertical liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example, the liquid crystal display element compared with the liquid crystal display element using the vertical liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the comparative example, High, good optical characteristics, that is, transparency when there is no applied voltage and scattering characteristics when applied voltage, and liquid crystal layer and vertical liquid crystal The adhesion of the alignment film is high.

In particular, the liquid crystal alignment treatment agent of the comparative example uses a high-boiling solvent in a large amount in the same manner as the material of the prior art. Therefore, when the liquid crystal alignment film is fired at a low temperature, the liquid crystal display element is stored in a high-temperature bath, and the liquid crystal alignment is found. Chaos. Further, after the device was stored in a high-temperature and high-humidity bath, bubbles were formed in the device, and peeling occurred between the liquid crystal layer and the vertical liquid crystal alignment film. On the other hand, when the liquid crystal alignment treatment agent of the example was used, no such problem occurred.

In other words, the polymer is the same, and the solvent of the liquid crystal alignment treatment agent is a liquid crystal alignment treatment agent containing a specific solvent of 50% by mass or more of the solvent, and a comparative example containing a plurality of high-boiling solvents, specifically, examples. 2, in comparison with Comparative Example 3, Example 3 and Comparative Example 4, Example 4 and Comparative Example 5, and Example 5 and Comparative Example 6, the liquid crystal display element of the comparative example was stored in a high temperature bath and found. Liquid crystal alignment is scattered. Further, after the device is stored in a high-temperature and high-humidity bath, the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is lowered.

In particular, when a liquid crystal composition (2) having a large content of a polymerizable compound in a liquid crystal composition is used, peeling occurs between the liquid crystal layer of the element and the vertical liquid crystal alignment film.

[Industrial Applicability]

A liquid crystal display element using a vertical liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a polymer having a group having a specific side chain structure of the present invention, even if a liquid crystal alignment treatment using a polyimide pigment polymer The liquid crystal alignment film can be fired at a low temperature, and the liquid crystal has high vertical alignment property and good optical characteristics, that is, transparency when no voltage is applied and scattering characteristics when applied voltage, and the liquid crystal layer and The vertical liquid crystal alignment film has high adhesion.

Therefore, the liquid crystal display device of the present invention can be used for a liquid crystal display for display purposes, a dimming window for controlling transmission and blocking of light, an optical shutter element, and the like, particularly for a substrate of a liquid crystal display element. Plastic liquid crystal display, dimming window and optical shutter element.

The entire contents of the specification, the scope of the application, and the abstract of the Japanese Patent Application No. 2013-063629, filed on March 26, 2013, are hereby incorporated by reference.

Claims (16)

A liquid crystal display device comprising: a liquid crystal layer having a liquid crystal layer formed between one of the electrodes; and a liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat between the pair of substrates; Further, at least one of the substrates has a liquid crystal alignment film in which the liquid crystal is vertically aligned, and a part or the whole of the liquid crystal composition is cured in the liquid crystal state to form a cured product of the liquid crystal and the polymerizable compound. In the liquid crystal display device, the liquid crystal alignment film contains a polyimine precursor having a group having a structure represented by the following formula [1-1] or [1-2] and the polyimine precursor a polymer obtained by at least one selected from the group consisting of ruthenium imidized polyimine, and a solvent having a boiling point of less than 180 ° C contains a liquid crystal alignment film obtained by disposing a liquid crystal alignment agent of 50% by mass or more of the entire solvent. (Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, and Y ² represents a single bond or -( CH ₂ ) _b - (b is an integer from 1 to 15), Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO - or -OCO-, Y ^{4 is a} divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a steroidal skeleton having 17 to 51 carbon atoms, on the above cyclic group Any hydrogen atom may pass through an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or fluorine. Substituted by an atom, Y ⁵ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on the cyclic group may pass through an alkyl group having 1 to 3 carbon atoms and carbon. Alkoxy groups of 1 to 3, fluorine-containing alkyl groups having 1 to 3 carbon atoms, fluorine-containing alkoxy groups having 1 to 3 carbon atoms or fluorine atoms, n is an integer of 0 to 4, and Y ⁶ is a carbon number. An alkyl group of 1 to 18, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms) [Chemical 2]-Y ⁷ -Y ⁸ [1-2] (Y ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- Or -O CO-, Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms. The liquid crystal display element of claim 1, wherein the polymer is a part of a raw material from a diamine compound having a side chain having a structure represented by the above formula [1-1] or [1-2] A polymer obtained by arranging at least one selected from the group consisting of a polyimine precursor and a polyimine imide of the polyimine precursor. The liquid crystal display device of claim 2, wherein the diamine compound is a diamine compound represented by the following formula [1a], (Y is a structure represented by the above formula [1-1] or [1-2], and n represents an integer of 1 to 4). The liquid crystal display element according to any one of claims 1 to 3, wherein the polymer is a polyfluorene obtained by using a second diamine compound represented by the following formula [2] as a part of a raw material. At least one selected from the group consisting of an imine precursor and a polyamidimide in which the polyimine precursor is subjected to ruthenium imidization (X represents a substituent selected from the structures of the following formula [2a], formula [2b], formula [2c] and formula [2d], and m represents an integer of 1 to 4) (In the formula [2a], a represents an integer of 0 to 4, and in the formula [2b], b represents an integer of 0 to 4, and in the formula [2c], X ¹ and X ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. In the formula [2d], X ³ represents an alkyl group having 1 to 5 carbon atoms). The liquid crystal display element according to any one of claims 1 to 4, wherein the polymer is a polyimine obtained by using a tetracarboxylic acid component represented by the following formula [3] as a part of a raw material. At least one selected from the group consisting of a precursor and a polyamidimide in which the polyimine precursor is subjected to hydrazine imidization, (Z ¹ represents a group selected from the structures of the following formulas [3a] to [3j]) (In the formula [3a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each of them may be the same or different. In the formula [3g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group. Each can be the same or different). The liquid crystal display element according to any one of claims 1 to 5, wherein the polymer is polyimine. The liquid crystal display device of any one of the above-mentioned liquid crystal alignment treatment agents, wherein the liquid crystal alignment treatment agent contains cyclopentanone or cyclohexanone as a solvent having a boiling point of less than 180 ° C, and the following formula [A1] And at least one solvent selected from the group consisting of the solvents represented by the formula [A2], (In the formula [A1], A ¹ represents an alkyl group having 1 to 3 carbon atoms, and in the formula [A2], A ² represents an alkyl group having 1 to 3 carbon atoms). The liquid crystal display element according to any one of claims 1 to 7, wherein the liquid crystal alignment treatment agent contains 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, A solvent selected from the group consisting of propylene glycol monobutyl ether, ethylene glycol monobutyl ether, and dipropylene glycol dimethyl ether. The liquid crystal display element according to any one of claims 1 to 8, wherein the liquid crystal alignment treatment agent comprises N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ -butyrolactone. And at least one solvent selected from the group consisting of solvents represented by the following formula [A3], (In the formula [A3], A ³ represents an alkyl group having 1 to 4 carbon atoms). The liquid crystal display element of any one of the above-mentioned liquid crystal alignment treatment agents, wherein the content of the solvent in the liquid crystal alignment treatment agent is 50 to 99.9% by mass. The liquid crystal display device of any one of the above-mentioned liquid crystal alignment treatment agents, wherein the liquid crystal alignment treatment agent contains a compound having a group represented by the following formulas [B1] to [B7]. Select at least one compound, (In the formula [B4], W ¹ represents a hydrogen atom or a benzene ring, and in the formula [B7], W ² represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring. W ³ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. The liquid crystal display element according to any one of the above aspects of the present invention, wherein the liquid crystal alignment treatment agent contains a compound represented by the following formula [6]. (X ¹ represents a structure of at least one selected from the group consisting of the structures represented by the following formulas [6a-1] to [6a-7], and X ² represents a single bond, -CH ₂ -, -O-, - NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )-, and -N(CH ₃ ) at least one selected from the group consisting of CO-, X ³ represents an alkyl group having 1 to 20 carbon atoms, -(CH ₂ -CH ₂ -O) _p - (p is 1 to 10) At least one selected from the group consisting of an integer), -(CH ₂ -O-) _q - (q is an integer of 1 to 10), and an organic group having a benzene ring or a cyclohexane ring having 6 to 20 carbon atoms. When any of the -CH ₂ - groups of the above alkylene group may be via -COO-, -OCO-, -CONH-, NHCO-, -CO-, -S-, -SO ₂ -, -CF ₂ -, - C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -OSi(CH ₃ ) ₂ - or -Si(CH ₃ ) ₂ O-substituted, a hydrogen atom bonded to any carbon atom may pass through a hydroxyl group (OH group), a carboxyl group (COOH group) or a halogen atom, and X ⁴ represents at least one selected from the group consisting of a single bond, -CH ₂ -, -OCH ₂ -, and -O-CH ₂ -CH ₂ - A bond group, and X ⁵ represents a structure selected from at least one of the groups represented by the following formulas [6b-1] to [6b-8], and n represents 1 An integer of ~3, m represents an integer from 1 to 3) (A ¹ represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms, and A ² , A ³ , A ⁵ , A ⁶ and A ⁹ each independently represent a hydrogen atom or an alkylene group having 1 to 3 carbon atoms, A ⁴ , A ⁷ and A ⁸ each independently represent an alkylene group having 1 to 3 carbon atoms) (B ¹ represents a hydrogen atom or a benzene ring, B ² represents a cyclic group selected from at least one selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring, and B ³ represents an alkyl group having 1 to 12 carbon atoms; And at least one selected from the group consisting of a fluorine-containing alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a fluorine-containing alkoxy group having 1 to 12 carbon atoms. The liquid crystal display device according to any one of claims 1 to 12, wherein the substrate of the liquid crystal display device is a glass substrate or a plastic substrate. A liquid crystal alignment film for use in a liquid crystal display element according to any one of claims 1 to 13. For example, the liquid crystal alignment film of claim 14 has a film thickness of 5 to 300 nm. A liquid crystal alignment treatment agent for forming a liquid crystal alignment film of claim 14 or 15.