TWI658097B - Liquid crystal display element, liquid crystal alignment film and liquid crystal alignment treatment agent - Google Patents

Abstract

The present invention relates to a liquid crystal display device that provides the adhesion between a liquid crystal layer and a vertical liquid crystal alignment film, or the liquid crystal has high vertical alignment, transparency when no voltage is applied, and scattering characteristics when a voltage is input. A vertical liquid crystal alignment film used for the liquid crystal display element and a liquid crystal alignment treatment agent used therefor.

A liquid crystal display element having a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing the following components (A) and (B).

Component (A): a polymer containing at least one structure selected from the group consisting of an aliphatic ring, an aromatic ring, and a linear alkyl group, and having a side chain capable of vertically aligning the liquid crystal

Component (B): at least one generator selected from the group consisting of a photoradical generator, a photoacid generator, and a photobase generator.

Description

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

The present invention relates to a transmission-scattering liquid crystal display element that exhibits a transparent state when no voltage is input, and a scattering state when a voltage is input, a liquid crystal alignment film used therefor, and a liquid crystal alignment treatment agent used to form the liquid crystal alignment film.

As a liquid crystal display element using a liquid crystal material, a TN (Twisted Nematic) mode has been put into practical use. This mode is for optical switching using the optical rotation characteristics of liquid crystals. When used as a liquid crystal display element, a polarizing plate must be used. However, the use of a polarizing plate reduces the light utilization efficiency.

As a liquid crystal display element that does not use a polarizing plate and has high light utilization efficiency, there are liquid crystal display elements that switch between a liquid crystal transmission state (also referred to as a transparent state) and a scattering state, and it is generally known to use a polymer dispersed liquid crystal ( Polymer Dispersed Liquid Crystal (PDLC) or Polymer Network Liquid Crystal (PNLC).

These liquid crystal display elements are used by having a liquid crystal layer between a pair of substrates having electrodes, and a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal composition is a liquid crystal display element manufactured by performing the step of curing the liquid crystal composition in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity, and forming a cured composite of a liquid crystal and a polymerizable compound. The liquid crystal display element controls the transmission state and the scattering state of the liquid crystal by a voltage input.

Liquid crystal display elements using conventional PDLC or PNLC have a white turbidity (scattering) state due to the random orientation of the liquid crystal molecular phase when no voltage is input, and the liquid crystals are aligned in the direction of the electric field when voltage is input. (Liquid crystal display elements controlled by scattering are also referred to as normal type elements). However, in order to obtain a transmission state, a constant voltage must be input to this normal-type element. Therefore, in most applications in which a transparent state is used, for example, power consumption when used in a window glass is large.

Compared with normal devices, PDLC has a transmission state when there is no voltage input, and PDLC has a scattering state when voltage is input (a liquid crystal display device that performs such transmission scattering control is also called an inverse device) (for example, refer to Patent Literature) 1 or 2).

Prior art [Patent Literature]

[Patent Document 1] Japanese Patent No. 2885116

[Patent Document 2] Japanese Patent No. 4132424

In the reverse type device, since the liquid crystal must be aligned in a vertical position, a liquid crystal alignment film (also referred to as a vertical liquid crystal alignment film) that aligns liquid crystals in a vertical position is used. At this time, since the vertical liquid crystal alignment film is a highly hydrophobic film, the adhesion between the liquid crystal layer and the liquid crystal alignment film is reduced. Therefore, it is necessary to introduce a large amount of a polymerizable compound (also referred to as a hardener) for improving the adhesion between the liquid crystal layer and the liquid crystal alignment film for the liquid crystal composition used in the reverse-type element. However, when a large amount of a polymerizable compound is introduced, the vertical alignment of the liquid crystal is hindered, and there is a problem that the transparency when no voltage is input and the scattering characteristics when the voltage is input are greatly reduced. Therefore, the liquid crystal alignment film used for the reverse type element must be the one with the higher vertical alignment of the liquid crystal.

The present invention aims to provide a liquid crystal display element having both of the above characteristics. That is, the present invention aims to provide a liquid crystal display device, which has high adhesion between the liquid crystal layer and the vertical liquid crystal alignment film, high vertical alignment of the liquid crystal, and good optical characteristics, that is, transparency when no voltage is input. The liquid crystal display element has good characteristics and scattering characteristics under voltage input. In addition, the purpose is to provide a liquid crystal alignment film and a liquid crystal alignment treatment agent used in the liquid crystal display element.

As a result of detailed research, the present inventors have found that 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 specific structure of a side chain and a specific structure generator has a great effect in achieving the above object. The present invention has been completed.

That is, this invention has the following summary.

(1) A liquid crystal display element having a liquid crystal layer between a pair of substrates having electrodes, and a liquid crystal containing a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The composition and at least one of the substrates further include a liquid crystal alignment film that aligns liquid crystals in a vertical direction. In a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity, the liquid crystal composition is cured to form a liquid crystal and a polymerizable compound. In the liquid crystal display element formed by the cured product composite, the liquid crystal alignment film is a liquid crystal display element obtained by using a liquid crystal alignment film containing the following (A) component and (B) component liquid crystal alignment treatment agent.

(A) Component: a polymer having at least one structure selected from the group consisting of the structures represented by the following formulas [1-1] and [1-2]

(B) component: at least one generator selected from the group consisting of a photoradical generator, a photoacid generator, and a photobase generator

(Y ¹ represents at least one selected from the group consisting of a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, -COO-, and -OCO-. Binding group. Y ² represents a single bond or-(CH ₂ ) _b- (b is an integer from 1 to 15). Y ³ represents a single bond selected from-(CH ₂ ) _c- (c is an integer from 1 to 15) , -O-, -CH ₂ O-, -COO-, and -OCO- are at least one type of bonding group. Y ⁴ represents at least one type selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring. A bivalent cyclic group or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton. Any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms And substituted by a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkoxy group or fluorine atom having 1 to 3 carbon atoms. Y ⁵ represents a divalent group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring. Cyclic groups. Any hydrogen atom on these cyclic groups can be 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, Substituted by a fluorine-containing alkoxy group or a fluorine atom. N represents an integer of 0 to 4. Y ⁶ represents an alkyl group selected from a carbon group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, Alkoxy group and fluorine-containing alkoxy group having 1 to 18 carbon atoms of at least 1 ).

[Chem 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-, and -OCO- are at least one type of bonding group. 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 polymer of the component (A) is selected from the group consisting of an acrylic polymer, a methacrylic polymer, a novolac resin, a polyhydroxystyrene, a polyimide precursor, a polyimide, a polyimide, and a polyimide The liquid crystal display device according to the above (1), in which at least one of the group consisting of an ester, cellulose and polysiloxane is used.

(3) The polymer is at least one selected from the group consisting of polyimide precursors and polyimide groups obtained as described below, and the liquid crystal display element described in (2) above. The polyfluorene imide precursor is obtained by using a diamine compound selected from a side chain having a structure of the aforementioned formula [1-1] and a diamine compound having a side chain of a structure of the formula [1-2]. Groups of at least one diamine compound obtained as part of the raw material.

(4) The said diamine compound is the liquid crystal display element as described in said (3) which is a diamine compound shown by following formula [1a].

(Y represents at least one selected from the group consisting of the structures represented by the aforementioned formulas [1-1] and [1-2]. N represents an integer of 1 to 4)

(5) The polymer of the component (A) is at least one selected from the group consisting of a polyimide precursor and a polyimide obtained by using a tetracarboxylic acid component represented by the following formula [3] as a part of a raw material. One kind of the liquid crystal display element as described in any one of (2) to (4) above.

(Z ¹ represents a structure selected from the following formulae (3a) to (3j))

(6) The liquid crystal display element according to any one of (3) to (5), wherein the polymer is polyimide.

(7) The polymer of the component (A) is a polysiloxane obtained by polycondensing an alkoxysilane represented by the following formula [A1], or a polymer selected from the following formula [A1] ] And the polysiloxane obtained by polycondensation of at least one type of alkoxysilane grouped by the alkoxysilane group represented by the formula [A3] and the liquid crystal display device according to (2) above.

(A ¹ ) _m Si (A ² ) _n (OA ³ ) _p [A1] (A ¹ represents a structure represented by the aforementioned formula [1-1] or formula [1-2]. Each of A ² represents hydrogen An atom or an alkyl group having 1 to 5 carbon atoms. A ³ each represents an alkyl group having 1 to 5 carbon atoms. M represents an integer of 1 or 2. n represents an integer of 0 to 2. p represents an integer of 0 to 3. But m + n + p is 4)

(B ¹ ) _m Si (B ² ) _n (OB ³ ) _p [A2] (B ¹ represents a group selected from the group consisting of vinyl, epoxy, amine, mercapto, isocyanate, methacryl group, At least one type of organic group having 2 to 12 carbon atoms in a group consisting of acryl, ureido, and cinnamyl groups. B ² each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. B ³ each represents a carbon number of 1 to 5 Alkyl group. M represents an integer of 1 or 2. n represents an integer of 0 to 2. p represents an integer of 0 to 3. However, m + n + p is 4)

[D7] (D ¹ ) _n Si (OD ² ) _4-n [A3] (D ¹ each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. D ² represents an alkyl group having 1 to 5 carbon atoms. N (Integer representing 0 ~ 3)

(8) The liquid crystal display element according to any one of (1) to (7) above, wherein the generator of the component (B) is a photo radical generator.

(9) The liquid crystal alignment treatment agent contains one selected from 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, and ethylene glycol mono Butyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, at least one solvent in the group represented by the following formula [D1], [D2], and [D3]: (1 ) To the liquid crystal display element according to any one of (8) to (8).

(D ¹ represents an alkyl group having 1 to 3 carbon atoms. D ² represents an alkyl group having 1 to 3 carbon atoms. D ³ represents an alkyl group having 1 to 4 carbon atoms)

(10) The liquid crystal alignment treatment agent described in (1) above, containing at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone. (9) The liquid crystal display element according to any one of the above.

(11) any one of the above (1) to (10), wherein the liquid crystal alignment treatment agent contains at least one compound selected from the group consisting of compounds having a structure represented by the following formulae [B1] to [B7]. The liquid crystal display element described.

(12) The liquid crystal display element according to any one of (1) to (11) above, wherein the substrate of the liquid crystal display element is a glass substrate or a plastic substrate.

(13) A liquid crystal alignment film used for the liquid crystal display element according to any one of (1) to (12) above.

(14) The liquid crystal liquid crystal alignment film described in (13) above, having a film thickness of 5 to 300 nm.

(15) A liquid crystal alignment treatment agent for forming a liquid crystal alignment film according to the above (13) or (14).

(16) A liquid crystal alignment treatment agent containing the components (A) and (B).

(17) A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to the above (16).

(18) A liquid crystal display element including the liquid crystal alignment film according to the above (17).

According to the present invention, a vertical liquid crystal alignment film obtained by using a liquid crystal alignment treatment agent containing a polymer having a specific structure of a side chain and a specific structure generator can be provided, and the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is high. The liquid crystal display element has a high vertical alignment of the liquid crystal and good optical characteristics, that is, the transparency when the voltage is not input and the scattering characteristics when the voltage is input. The reverse type element of the liquid crystal display element of the present invention can be used in a liquid crystal display for display purposes, and can control the transmission and blocking of light. Dimming window or shutter element, etc.

[Form of Implementing Invention] <Liquid crystal display element>

The liquid crystal display element of the present invention has a liquid crystal layer between a pair of substrates having electrodes, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat between the pair of substrates. At least one of the substrates further includes a liquid crystal alignment film that aligns liquid crystals in a vertical direction. When a part or the whole of the liquid crystal composition exhibits a liquid crystal state, the liquid crystal composition is cured to form a cured composite of liquid crystal and a polymerizable compound. In the obtained liquid crystal display device, the liquid crystal alignment film has a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing the following components (A) and (B).

(A) Component: a polymer (also referred to as a specific polymer) having at least one structure selected from the group consisting of the structures represented by the following formulas [1-1] and [1-2]

(B) Component: at least one generator (also referred to as a specific generator) selected from the group consisting of a photoradical generator, a photoacid generator, and a photobase generator.

(In the formula, Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , and n have the same meanings as above)

[化 10] -Y ⁷ -Y ⁸ [1-2] (wherein Y ⁷ and Y ^{8 have the} same meaning as above)

The vertical liquid crystal alignment film in the present invention can be obtained from a liquid crystal alignment treatment agent containing a specific generator that generates free radicals, acids or bases (also called catalysts) by active energy rays such as ultraviolet rays or heat. Therefore, when a liquid crystal display element is used to produce a hardened composite of a polymerizable compound when producing a liquid crystal display element, a catalyst or a liquid crystal layer is generated by a specific generator in a vertical liquid crystal alignment film by using ultraviolet rays or heating in the step of forming a liquid crystal layer. Stronger due to the adhesion with the vertical liquid crystal alignment film.

In addition, the specific side chain structure represented by the formula [1-1] contained in the specific polymer used in the liquid crystal display element of the present invention has a side chain site having the following organic group, and the organic group has a benzene ring and a ring Hexyl ring, heterocyclic ring, or divalent organic group with 17 to 51 carbon atoms in steroid skeleton. Since the ring and the side chain structure of the organic group show a rigid structure, a highly stable vertical alignment of the liquid crystal can be obtained.

From the above viewpoints, the liquid crystal display device of the present invention having a vertical liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a polymer having a specific side chain structure and a specific generator has high vertical alignment of liquid crystals and has good optical properties. Characteristics, that is, the transparency (transmission state) when voltage is not input and the scattering characteristics (scattering state) when voltage is input are good, and it can be used as a reverse type element with high adhesion between the liquid crystal layer and the vertical liquid crystal alignment film.

<Liquid crystal composition>

In the liquid crystal used in the liquid crystal composition for producing a liquid crystal display element of the present invention, a nematic liquid crystal or a smectic liquid crystal can be used. Among them, those with negative dielectric anisotropy are also preferred. From the viewpoint of low-voltage driving and scattering characteristics, it is preferable that the anisotropy of the dielectric constant is large and the anisotropy of the refractive index is large.

In addition, when a liquid crystal display element is driven as an active element such as a TFT (Thin Film Transistor), a high liquid crystal resistance and a high voltage holding ratio (also referred to as VHR) are required. Therefore, it is preferable to use fluorine-based or chlorine-based liquid crystals that have high resistance in liquid crystals and do not lower VHR by active energy rays such as ultraviolet rays. As the liquid crystal, it is preferable to use a larger complex refractive index (Δn).

The liquid crystal display element in the present invention is a host-guest element in which a dichroic dye can be dissolved in a liquid crystal composition. At this time, it is transparent when no voltage is input, and an element that becomes absorption (scattering) can be obtained when voltage is input.

In the liquid crystal display element of the present invention, the liquid crystal alignment direction is changed by 90 degrees by the presence or absence of voltage input. Therefore, in the liquid crystal display element of the present invention, due to the difference in the light absorption characteristics of the dichroic dye, a higher contrast can be obtained compared with the past host-guest type element that switched between random alignment and vertical alignment. In the host-guest device in which the dichroic dye is dissolved, the liquid crystal becomes colored when the liquid crystal is aligned in the horizontal direction, and becomes opaque only in the scattering state. Therefore, with the input voltage, when the self-voltage is not input, the colorless and transparent device can obtain colored opaque and colored and transparent components with alternate states.

The liquid crystal composition in the present invention contains a polymerizable compound that is polymerized by at least one of active energy rays such as ultraviolet rays and heat. The polymerization of the polymerizable compound is not related to the reaction form, and may form a liquid. A hardened composite of crystals and polymerizable compounds. Specific examples of the polymerization reaction include radical polymerization, cationic polymerization, negative ion polymerization, or addition polymerization. Here, the so-called cured product complex means a state where liquid crystal is present in a high molecular weight body (polymer) formed of a polymerizable compound.

The polymerizable compound may be any compound as long as it is soluble in the liquid crystal. However, when dissolving a polymerizable compound in a liquid crystal, it is necessary to show a temperature of a liquid crystal phase in a part or the whole of the liquid crystal composition. Even if a part of the liquid crystal composition displays a liquid crystal phase, the liquid crystal display element can be visually recognized, and the entire inside of the element may exhibit almost a single transparency and scattering characteristics.

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

Examples include 2-ethylhexyl acrylate, butylethyl acrylate, butoxyethyl acrylate, 2-cyanoethyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-hydroxy Propyl acrylate, 2-ethoxyethyl acrylate, N, N-diethylamino ethyl acrylate, N, N-dimethylamino ethyl 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-tetrafluoro Propyl acrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate, 2-ethylhexyl methacrylate, butyl ethyl methacrylate, butoxyethyl methyl Acrylate, 2-cyanoethyl methacrylic acid Ester, benzyl methacrylate, cyclohexyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethoxyethyl acrylate, N, N-diethylaminoethylmethyl Acrylate, N, N-dimethylaminoethyl methacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl Methacrylate, isobornyl methacrylate, isodecyl methacrylate, lauryl methacrylate, morpholine methacrylate, phenoxyethyl methacrylate, phenoxy diethylene glycol Alcohol methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,4,4,4- Hexafluorobutyl methacrylate, 4,4'-bisphenol diacrylate, diethylstilbestrol diacrylate, 1,4-bispropenyloxydiphenyl, 4,4'-bispropenyloxydiphenyl ether , 4,4'-bispropenyloxydiphenylmethane, 3,9- [1,1-dimethyl-2-propenyloxyethyl] -2,4,8,10-tetra Spiro [5,5] undecane, α, α'-bis [4-propenyloxyphenyl] -1,4- Diisopropylbenzene, 1,4-bispropenyloxytetrafluorobenzene, 4,4'-bispropenyloxyoctafluorobisphenol, diethylene glycol acrylate, 1,4-butanedi Alcohol diacrylate, 1,3-butylene glycol diacrylate, dicyclopentyl diacrylate, glycerol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate Ester, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypenta Acrylate, 4,4'-dipropenyloxydistyrene, 4,4'-dipropenyloxydimethylstilbene, 4,4'-dipropenyloxydiethyl Stilbene, 4,4'-dipropenyloxydipropyl stilbene, 4,4'-dipropylene Fluorenyloxy dibutyl stilbene, 4,4'-dipropylene fluorenyloxy dipentyl stilbene, 4,4'-dipropylene fluorenyloxy dihexyl stilbene, 4,4 ' -Dipropenyloxydifluorostilbene, 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-butylene glycol dimethyl Acrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, Pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxypentamethacrylate, 2,2,3, Monomers and oligomers such as 3,4,4-hexafluoropentanediol-1,5-dimethacrylate.

Among them, it is also preferable to use a polyfunctional radical polymerizable compound having three or more functional groups for the purpose of improving the scattering characteristics at the time of voltage input.

Specific examples include trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, and trimethylol Propane trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, bistrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxypentamethacrylic acid Monomers and oligomers such as esters.

The above-mentioned radical polymerizable compound is used in combination with optical characteristics of a liquid crystal display element or characteristics of adhesion between a liquid crystal layer and a vertical liquid crystal alignment film. Properties, you can use 1 type or a mixture of 2 or more types.

In addition, when the reaction form of the polymerizable compound is radical polymerization, a radical initiator that generates radicals by ultraviolet rays can be introduced into the liquid crystal composition.

Specific examples include tert-butylperoxy-iso-butyrate, 2,5-dimethyl-2,5-bis (benzylidenedioxy) hexane, 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 Oxide, 2,2 ', 5,5'-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) ) Benzophenone, 3,3 ', 4,4'-tetra (tert-pentylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (tert-hexyl (Oxycarbonyl) benzobenzophenone, 3,3'-bis (tert-butylperoxycarbonyl) -4,4'-dicarboxybenzophenone, tert-butylperoxybenzoic acid Esters, organic peroxides such as di-tert-butyl diperoxy isophthalate; 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone Quinones; methyl benzoin, benzoin ethyl ether, benzoin methyl alpha], alpha] -phenyl benzoin benzoin derivatives and the like.

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

Specifically, it is a compound which has at least 1 kind of crosslinking forming group chosen from the group which consists of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group.

For example, a melamine derivative, a benzomelamine derivative, or a glycoluril may be used in which the hydrogen atom of the amine group is substituted by methylol, alkoxymethyl, or both. The melamine derivative or the benzomelamine derivative may be an oligomer. Each of these is a triazine ring, preferably having a methyl group or an alkoxymethyl group of 3 or more and less than 6 on average.

Examples of such melamine derivatives or benzomelamine derivatives include MX-750, which is substituted with an average of 3.7 methoxymethyl groups per triazine ring, and an average of 3.7 methoxymethyl groups per triazine ring. 5.8 MW-30 substituted by methoxymethyl (the above is made by Sanwa Chemical Co., Ltd.), or methoxymethylation such as CYMEL300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. Melamine, CYMEL235, 236, 238, 212, 253, 254 and other methoxymethylated butoxymethylated melamine, CYMEL506, 508 and other butoxymethylated melamine, such as CYMEL1141 containing methoxymethyl Methylated isobutoxymethylated melamine, such as methoxymethylated ethoxymethylated benzomelamine such as CYMEL1123, methoxymethylated butoxymethylated benzomelamine such as CYMEL1123-10 2. Butoxymethylated benzomelamine such as CYMEL1128; methoxymethylated ethoxymethylated benzomelamine containing carboxyl group such as CYMEL1125-80 (the above is made by Mitsui Cytec) Examples of the glycoluril include butoxymethylated glycoluril such as CYMEL1170, and methylolated glycoluril such as CYMEL1172.

Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxy group include 1,3,5-ginsyl (methoxymethoxy) benzene, 1,2,4-ginseng (iso Propoxymethoxy) benzene, 1,4-bis (sec-butoxymethoxy) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, and the like.

In addition, as the ionic polymerizable compound, a compound having an epoxy group-containing and isocyanate group-containing crosslinkable forming group can be used. Specific examples include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylamino diphenylphenyl, and tetraglycidyl -M-xylylene diamine, tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexa Fluoracetamidine diglycidyl ether, 1,3-bis (1- (2,3-glycidoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4, 4-bis (2,3-glycidoxy) octafluorobisphenol, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine, 2- (4- (2,3- Glycidoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-glycidoxy) phenyl) ethyl) phenyl) propane, 1,3- Bis (4- (1- (4- (2,3-glycidoxy) phenyl) -1- (4- (1- (4- (2,3-glycidoxyphenyl))- 1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like.

The said ionic polymerizable compound has characteristics of combining optical characteristics or adhesiveness of a liquid crystal layer and a vertical liquid crystal alignment film, and can be used by 1 type or by mixing 2 or more types.

When the reaction form of the polymerizable compound is cationic polymerization or negative ion polymerization, an ionic initiator that generates an acid or a base by ultraviolet rays may be introduced into the liquid crystal composition.

Specifically, triazine compounds, acetophenone derivative compounds, difluorene compounds, diazomethane compounds, and sulfonic acid derivatives can be used. Compounds, diaryl iodonium salts, triarylsulfonium salts, triarylsulfonium salts, iron aromatic hydrocarbon complexes, and the like, but are not limited thereto.

More specific examples include diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium methanesulfonate, diphenyliodonium p-toluenesulfonic acid, and diphenyliodine. Onium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium six Fluorophosphate, bis (p-tert-butylphenyl) iodonium methanesulfonate, bis (p-tert-butylphenyl) iodonium p-toluenesulfonic acid, bis (p-tert-butylphenyl) ) Iodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium tetrafluoroborate, bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorobenzene Group) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, tris (p-methoxyphenyl) sulfonium Tetrafluoroborate, tris (p-methoxyphenyl) sulfonium hexafluorophosphonate, tris (p-ethoxyphenyl) sulfonium tetrafluoroborate, triphenylphosphonium chloride, triphenyl鏻 bromide, tri (p-methoxyphenyl) 鏻 tetrafluoroborate, tris (p-methoxyphenyl) 鏻 hexafluorophosphonate, or tris (p-ethoxyphenyl) 鏻 tetra fluorine Salt.

In addition, bis [[(2-nitrobenzyl) oxy] carbonylhexane-1,6-diamine], nitrobenzylcyclohexylaminoformate, and bis (methoxy Benzyl) hexamethylene diaminocarbamate, bis [[(2-nitrobenzyl) oxy] carbonylhexane-1,6-diamine], nitrobenzylcyclohexylamine Methylformate or bis (methoxybenzyl) hexamethylene diaminocarbamate.

In the liquid crystal display element of the present invention, it is preferable to use a radical polymerizable compound from the viewpoint of the optical characteristics of the element.

No content of polymerizable compounds in the liquid crystal composition It is particularly limited, but if the content of the polymerizable compound is too large, the polymerizable compound will not be dissolved in the liquid crystal, the temperature at which the liquid-crystal-free composition exhibits a liquid crystal phase, or the change in the transparent state and the scattering state of the device will be small, resulting in optical characteristics. Worse. In addition, when the content of the polymerizable compound is too small, the curability of the liquid crystal layer is reduced, and the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is reduced, and the liquid crystal alignment with mechanical external pressure is liable to be confused. Therefore, the content of the polymerizable compound is preferably 1 to 50 parts by mass for 100 parts by mass of the liquid crystal, and 5 to 40 parts by mass is also preferred. Particularly preferred is 11 to 30 parts by mass.

The content of the radical initiator and the ionic initiator that promotes the reaction of the polymerizable compound is not particularly limited, but it is preferably 0.01 to 10 parts by mass for 100 parts by mass of the liquid crystal, and 0.05 to 5 parts are also preferred. Part by mass is preferred, and particularly preferred is 0.05 to 3 parts by mass.

<Specific polymer>

The liquid crystal display element of the present invention is an element in which at least one of the substrates has a vertical liquid crystal alignment film in which liquid crystal alignment is vertical. The vertical liquid crystal alignment film at this time is made of a specific polymer containing at least one specific side chain structure grouped with a specific side chain structure selected from the following formulae [1-1] and [1-2]. A liquid crystal alignment film obtained by a liquid crystal alignment treatment agent.

Y ¹ represents at least one bond selected from the group consisting of a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, -COO-, and -OCO-. base. Among them, from the standpoint 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- are good. It is 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 from 1 to 15). Among them, a single bond or-(CH ₂ ) _b- (b is an integer from 1 to 10) is preferred.

Y ³ represents at least one selected from the group consisting of a single bond,-(CH ₂ ) _c- (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO-, and -OCO-. Combined base. Among them, from the standpoint of ease of synthesis, a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ O-, or -COO- are preferred. More preferably, it is a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 10), -O-, -CH ₂ O-, or -COO-.

Y ⁴ is at least one type of divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring. Any hydrogen atom on these cyclic groups may be an alkyl group having 1 to 3 carbon atoms and 1 carbon number. It is substituted by alkoxy group of ~ 3, fluorine-containing alkyl group having 1 to 3 carbon atoms, fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine atom. In addition, Y ⁴ may be a divalent organic group selected from organic groups having 17 to 51 carbon atoms having a steroid skeleton. Among them, from the standpoint of ease of synthesis, an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring, or a steroid skeleton is preferred.

Y ⁵ represents at least one type of divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring. Any hydrogen atom on these cyclic groups may be an alkyl group having 1 to 3 carbon atoms and 1 carbon number. It is substituted by an alkoxy group of ~ 3, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Among them, a benzene ring or a cyclohexane ring is also preferable.

n represents an integer from 0 to 4. Among these, from the viewpoint of availability of raw materials or ease of synthesis, 0 to 3 is preferred. It is preferably 0 to 2.

Y ⁶ represents a group selected from the group consisting of 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 and a fluorine-containing alkoxy group having 1 to 18 carbon atoms. At least one. 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 are also preferable. An alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms is preferred. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

Preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n include the tables on pages 13 to 34 of International Publication WO2011 / 132751 (published on 2011.10.27). The same combinations of (2-1) to (2-629) as disclosed in 6 to Table 47. In addition, Y1 to Y6 in each table of the International Publication are equivalent to Y ¹ to Y ^{6 in the} present invention. Moreover, in (2-605) to (2-629) disclosed in the tables of the International Publication, the organic groups having a carbon number of 12 to 25 having a steroid skeleton are equivalent to those having a carbon number of 17 to 51 having a steroid skeleton. base.

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

[Chem 12] -Y ⁷ -Y ⁸ [1-2] Y ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ )-,- At least one type of binding group grouped by N (CH ₃ ) CO-, -COO-, and -OCO-. Among them, a single bond, -O-, -CH ₂ O-, -CONH-, -CON (CH ₃ )-, or -COO- is also preferable. It is preferably 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 also preferable.

As the specific side chain structure, it is preferable to use a structure represented by the formula [1-1] from the viewpoint of obtaining liquid crystal vertical alignment with high stability.

The specific polymer having a specific side chain structure is not particularly limited, but is selected from acrylic polymers, methacrylic polymers, novolac resins, polyhydroxystyrene, polyimide precursors, and polyimide Preferably, at least one polymer in the group consisting of polyamine, polyester, cellulose, and polysiloxane is preferred. Among them, polyimide precursors, polyimide or polysiloxane are also preferred.

When a polyimide precursor or polyimide (collectively referred to as a polyimide-based polymer) is used for a specific polymer, these polyimide precursors are obtained by reacting a diamine component with a tetracarboxylic acid component. Or polyimide is preferred.

The polyfluorene imide precursor has a structure represented by the following formula [A].

(R ¹ represents a tetravalent organic group. R ² represents a divalent organic group. A ¹ and A ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, each of which may be the same or different. A ³ and A ⁴ represent a hydrogen atom 1, 1 to 5 carbon or alkyl groups, each 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. Examples of the tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic dihalide, A dialkyl tetracarboxylic acid compound or a dialkyl tetracarboxylic acid dihalide.

The polyfluorene-imide polymer can be obtained relatively easily by using a tetracarboxylic dianhydride represented by the following formula [B] and a diamine compound represented by the following formula [C] as raw materials. D] It is preferable that the polyamidoacid formed by the structural formula of the repeating unit shown above or the polyamidoimide which is polyimidated by the polyamidoacid is preferably used. Among them, as a specific polyimide-based polymer, it is preferable to use polyimide from the viewpoint of physical and chemical stability of the vertical liquid crystal alignment film.

(R ¹ and R ² are the same as defined in formula (A))

(R ¹ and R ² are the same as defined in formula (A))

In addition, according to a general synthetic method, an alkyl group having 1 to 8 carbon atoms of A ¹ and A ² represented by the formula [A] and an A represented by the formula [A] can be introduced into the polymer of the formula [D] obtained above. ³ and A ^{4 are} 1 to 5 carbon or alkyl groups.

As a method for introducing the specific side chain structure into the polyfluorene-imide-based polymer, it is preferable to use a diamine compound having a specific side chain structure as a part of the raw material. In particular, it is preferable to use a diamine compound (also referred to as a specific side chain type diamine compound) represented by the following formula [1a].

Y represents a structure represented by the aforementioned formula [1-1] and formula [1-2]. The preferred combination of Y ¹ to Y ⁶ and n in the formula [1-1] and the preferred combination of Y ⁷ and Y ⁸ in the formula [1-2] are as described above.

m represents an integer from 1 to 4. Among them, 1 is preferred.

As the specific side chain type diamine compound, a diamine compound having a structure represented by the aforementioned formula [1-1] is preferably used from the viewpoint that vertical alignment of a highly stable liquid crystal can be obtained.

Specific examples include structures represented by the following formulas [1a-1] to [1a-31].

(R ¹ each independently represents at least one type of binding group selected from the group consisting of -O-, -OCH _2- , -CH ₂ O-, -COOCH _2- , and -CH ₂ OCO-. R ² each independently represents a carbon number 1 to 22 linear or branched alkyl groups, 1 to 22 carbon linear or branched alkoxy groups, 1 to 22 carbon linear or branched fluoroalkyl groups, or 1 carbon number ~ 22 linear or branched fluorine-containing alkoxy)

(R ³ each independently represents selected from -COO-, -OCO-, -CONH-, -NHCO-, -COOCH _2- , -CH ₂ OCO-, -CH ₂ O-, -OCH _2- , and -CH _2- Groups of at least one binding group. Each of R ⁴ independently represents a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxy group having 1 to 22 carbon atoms, and 1 to 22 carbon atoms. 22 straight or branched fluorine-containing alkyl group, or straight or branched fluorine-containing alkoxy group having 1 to 22 carbon atoms)

(R ⁵ each independently represents selected from -COO-, -OCO-, -CONH-, -NHCO-, -COOCH _2- , -CH ₂ OCO-, -CH ₂ O-, -OCH _2- , -CH _2- At least one type of bonding group formed by -O- and -NH-. Each of R ⁶ independently represents a group selected from fluoro, cyano, trifluoromethyl, nitro, azo, methyl, and ethyl (At least one of the group consisting of acetoxy, ethoxyl, and hydroxyl)

(R ⁷ each independently represents a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomers of 1,4-cyclohexyl are each a trans isomer)

(R ⁸ each independently represents a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomers of 1,4-cyclohexyl are each 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 1,4-cyclohexyl or 1,4-phenylene, and A ₂ is an oxygen atom or- COO- * (but the bond with "*" is bound to A ₃ ), A ₁ is an oxygen atom or -COO- * (but the bond with "*" is bound to (CH ₂ ) a ₂ ) ). (A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1)

In the above formulas [1a-1] to [1a-31], the specific side chain type diamine compound having a particularly preferable structure is the formula [1a-1] to the formula [1a-6], the formula [1a-9] to the formula [1a-13] or formula [1a-22] to formula [1a-31].

In addition, for the present invention, the vertical alignment of the liquid crystal and the vertical From the viewpoint of the adhesiveness of the straight liquid crystal alignment film, these specific side chain type diamine compounds are preferably 10 mol% or more and 80 mol% or less of the entire diamine component. It is preferably 10 mol% or more and 70 mol% or less.

The above-mentioned specific side chain type diamine compound can be used in combination with the solubility of a polyfluorene-imide polymer to a solvent, the vertical alignment of a liquid crystal when forming a vertical liquid crystal alignment film, and the optical characteristics of a liquid crystal display element. Use by mixing 2 or more types.

As a diamine component at the time of producing the said polyfluorene-imide-type polymer, it is preferable to use the 2nd diamine compound (it is also called a 2nd diamine compound) shown by following formula [2].

In the formula [2], X represents a substituent selected from the structure of the following formula [2a], formula [2b], formula [2c], and formula [2d].

a represents an integer from 0 to 4. Which is obtained from raw materials or synthetic From the standpoint of ease, an integer of 0 or 1 is preferred.

b represents an integer from 0 to 4. Among them, an integer of 0 or 1 is preferred from the viewpoint of availability of raw materials or ease of synthesis.

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.

m represents an integer from 1 to 4. Among them, 1 is preferred.

Although the specific structure of the diamine compound represented by said formula [2] is mentioned, it is not limited to these examples.

That is, examples of the diamine compound represented by the formula [2] include 2,4-dimethyl-m-phenylene diamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diamine In addition to amine benzoic acid, 2,5-diamino benzoic acid, and 3,5-diamino benzoic acid, diamines having a structure represented by the following formulae [2-1] to [2-6] can also be cited Compound.

Among them, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diamine Amino resorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, formula [2-1], formula [2-2] Or a diamine compound represented by the formula [2-3] is preferable. Particularly preferred are 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 3,5-diaminobenzoic acid, formula [2-1] or A diamine compound represented by the formula [2-2].

The diamine compound represented by the formula [2] is used in combination with the solubility of a polyfluorene-imide-based polymer in a solvent, the vertical alignment of a liquid crystal when it becomes a vertical liquid crystal alignment film, and the optical characteristics of a liquid crystal display element. Use two or more types.

As the diamine component in the production of the polyfluorene-imide-based polymer, a diamine compound (also referred to as another diamine compound) other than the diamine compound represented by the formula [1a] and the formula [2] can be used. Specific examples of other diamine compounds are given below, but are not limited thereto.

Examples include m-phenylene diamine, p-phenylene diamine, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl , 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4 , 4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'- Diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl Phenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diamine Diphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'- Diaminodiphenyl ether, 4,4'-sulfofluorenyldiphenylamine, 3,3'-sulfofluorenyldiphenylamine, bis (4-aminophenyl) silane, bis (3-aminophenyl) Silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-diphenylamine sulfide, 3,3'-diphenylamine sulfide, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenyl Amine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3,3'-diaminodiphenyl) ) Amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3 ' -Diaminodiphenyl) amine, 4,4'- Aminobenzophenone, 3,3'-diaminobenzobenzophenone, 3,4'-diaminobenzobenzophenone, 1,4-diaminonaphthalene, 2,2'- Diaminobenzophenone, 2,3'-diaminobenzobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis ( 4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-amine Phenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl-4-amine Phenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) ) Benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminophenylmethyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4'- [1,4-phenylenebis (methylene)] diphenylamine, 4,4 '-[1,3-phenylenebis (methylene)] diphenylamine, 3,4'-[1,4 -Phenylene bis (methylene)] diphenylamine, 3,4 '-[1,3-phenylene bis (methylene)] diphenylamine, 3,3'-[1,4-phenylene Bis (methylene)] diphenylamine, 3,3 '-[1,3-phenylenebis (methylene)] diphenylamine, 1,4-phenylenebis [(4-aminophenyl) Ketone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3- Phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzene Formate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminobenzene) Base) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) ) Isophthalate, N, N '-(1,4-phenylene) bis (4-aminobenzamide), N, N'-(1,3-phenylene) bis (4-aminobenzidine), N, N '-(1,4-phenylene) bis (3-aminobenzidine), N, N'-(1,3-phenylene ) Double (3 -Aminobenzidine), N, N'-bis (4-aminophenyl) p-xylylenediamine, N, N'-bis (3-aminophenyl) p-xylylenediamine , N, N'-bis (4-aminophenyl) m-xylylenediamine, N, N'-bis (3-aminophenyl) m-xylylenediamine, 9,10-bis (4 -Aminophenyl) anthracene, 4,4'-bis (4-aminophenoxy) diphenylphosphonium, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane , 2,2'-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-Aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2'-bis (4-aminophenyl) propane , 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (3-amino-4-methylphenyl) propane, 1,3-bis (4-aminophenoxy) Propyl) propane, 1,3-bis (3-aminophenoxy) propane, 1,4- Bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5 -Bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1, 7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1, 8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1 10, 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-3-methylcyclohexyl) methane, 1,3-diaminopropane, 1,4-diaminobutane , 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminon-heptane, 1,8-diaminooctane, 1,9-diaminononane Alkanes, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and the like.

Moreover, as another diamine compound, the side chain of a diamine compound has an alkyl group, a fluorine-containing alkyl group, or a heterocyclic ring.

Specific examples of the diamine compounds represented by the following formulae [DA1] to [DA12] can be used without impairing the effects of the present invention.

(p is an integer from 1 to 10)

(m represents an integer from 0 to 3. n represents an integer from 1 to 5)

(A ¹ represents a single bond, -CH _2- , -C ₃ 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 )-and- N (CH ₃ ) CO— at least one type of binding group. M ¹ and m ² each represent an integer of 0 to 4, and m ¹ + m ^{2 each} represents an integer of 1 to 4. m ³ and m ⁴ each represent An integer of 1 to 5. A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms. 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 )-and -N (CH ₃ ) CO-, at least one type of binding group. M ⁶ represents (1 to 4 integers)

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

As another diamine compound, a diamine compound represented by the following formula [DA13] or [DA14] can be used.

The other diamine compounds mentioned above are blended with the solubility of a polyfluorene-imide polymer to a solvent, the vertical alignment of a liquid crystal when it becomes a vertical liquid crystal alignment film, And the optical characteristics of the liquid crystal display element, etc., one type or a mixture of two or more types can be used.

As the tetracarboxylic acid component in the production of the polyfluorene-imide polymer, a tetracarboxylic dianhydride represented by the following formula [3] or a tetracarboxylic acid derivative thereof, a tetracarboxylic acid dihalide, a tetracarboxylic acid A dialkyl carboxylic acid compound or a dialkyl tetracarboxylic acid dihalide (both collectively referred to as a specific tetracarboxylic acid component) is preferred.

Z ¹ is a group selected from the group consisting 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 represent a hydrogen atom or a methyl group, and each may be the same or different.

In the structure represented by the formula [3] of the specific tetracarboxylic acid component, Z ^{1 is} represented by the formula [3a], the formula [3c], and the formula from the viewpoint of ease of synthesis or ease of polymerization reactivity at the time of polymer production. [3d], Formula [3e], Formula [3f], or Formula [3g] are preferable. The structure represented by formula [3a], formula [3e], formula [3f], or formula [3g] is preferred, and formula [3e], formula [3f], or formula [3g] is particularly preferred.

The specific tetracarboxylic acid component is preferably at least 1 mole% of the all-tetracarboxylic acid component. It is preferably 5 mol% or more, and particularly preferably 10 mol% or more. Among them, 10 to 90 mole% is more preferable.

When a specific tetracarboxylic acid component having a structure of formula [3e], formula [3f], or formula [3g] is used, the amount used is 20 mol% or more of the total tetracarboxylic acid component, so that the desired effect can be obtained. It is preferably at least 30 mol%. And all the tetracarboxylic acid components may be tetracarboxylic acid components having a structure of formula [3e], formula [3f] or formula [3g].

In the polyfluorene imide polymer, a tetracarboxylic acid component other than the specific tetracarboxylic acid component can be used without impairing the effect of the present invention.

Examples of other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, dicarboxylic acid dihalides, dicarboxylic acid dialkyl ester compounds, or dialkyl ester dihalides.

That is, other tetracarboxylic acid components include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8 -Naphthalene tetracarboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2, 3,3 ', 4'-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenone tetracarboxylic acid, bis (3,4-dicarboxyphenyl) pyrene, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4- Dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-di Carboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylfluorenetetracarboxylic acid, 3,4,9,10-fluorenetetracarboxylic acid or 1,3-diphenyl-1,2,3 , 4-cyclobutane tetracarboxylic acid.

Specific tetracarboxylic acid components and other tetracarboxylic acid components can be used in combination with the solubility of the polyfluorene-imide-based polymer in the solvent, the vertical alignment properties of the liquid crystal when it becomes a vertical liquid crystal alignment film, and the optical characteristics of the liquid crystal display element. Use 1 type or mixed 2 or more types.

The method for synthesizing the polyfluorene-based polymer is not particularly limited. It is generally obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, at least one type of tetracarboxylic acid component selected from the group consisting of tetracarboxylic acids and their derivatives is reacted with a diamine component made of one or more types of diamine compounds to obtain polyamic acid. Specifically, the method is to use a method of polycondensing a tetracarboxylic dianhydride and a first- or second-stage diamine compound to obtain polyamidonic acid, and a dehydrating polycondensation reaction of a tetracarboxylic acid and a first- or second-stage diamine compound. A method of obtaining polyamic acid afterwards, or a method of polycondensing a dicarboxylic acid dihalide with a first- or second-stage diamine compound to obtain a polyamino acid.

To obtain polyalkylamino acid alkyl esters, a method of polycondensing a tetracarboxylic acid having a carboxylic acid group into a dialkyl ester and a diamine compound of class 1 or 2 can be used, and the carboxylic acid group can be dialkylated. A method for polycondensation of an esterified dicarboxylic acid dihalide with a class 1 or 2 diamine compound, or a polyfluorene Method for converting carboxylic acid carboxyl group into ester.

In order to obtain polyimide, a method of closing the polyamidic acid or polyalkylamic acid alkyl ester into polyimide can be used.

The reaction between the diamine component and the tetracarboxylic acid component is generally performed in a solvent containing the diamine component and the tetracarboxylic acid component. The solvent to be used at this time is only required to dissolve the produced polyimide precursor, and is not particularly limited. Although specific examples of the solvent used for the reaction are given below, they are not limited thereto.

Examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, Dimethyl sulfene, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

These can be used alone or in combination. In addition, even if it is a solvent that does not dissolve the polyfluorene imide precursor, it can be used after being mixed with the above-mentioned solvent only in a range where the generated polyfluorene imide precursor is not precipitated. In addition, the water in the solvent will hinder the polymerization reaction and cause the polyimide precursor produced by further hydrolysis. Therefore, it is preferable to use a solvent that is dehydrated and dried.

A method for adding a diamine component and a tetracarboxylic acid component in a solvent by dispersing or stirring the diamine component in a solvent, and dissolving the solution, directly adding or dispersing or dissolving the tetracarboxylic acid component in a solvent, Conversely, a method of adding a diamine component to a solution after dispersing or dissolving a tetracarboxylic acid component in a solvent, a method of adding a diamine component and a tetracarboxylic acid component alternately, and the like may be used. In addition, when using a plurality of types of diamine components or tetracarboxylic acid components for the reaction, they may be mixed in advance. The reaction may be carried out, or the reactions may be carried out in sequence, and further, the low-molecular-weight bodies of the respective reactions may be mixed into a polymer. The polymerization temperature at this time may be selected from any temperature of -20 to 150 ° C, but is preferably in the range of -5 to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a polymer with a high molecular weight. If the concentration is too high, the viscosity of the reaction solution is too high, which makes it difficult to stir uniformly. Therefore, it is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction is performed at a high concentration in the initial stage, and a solvent may be added thereafter.

For the polymerization reaction of the polyfluorene imide precursor, the ratio of the total molar number of the diamine component to the total molar number of the tetracarboxylic acid component is preferably 0.8 to 1.2. As with the general polycondensation reaction, the closer the mole ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

The polyimide of the present invention is a polyimide obtained by subjecting the aforementioned polyimide precursor to ring closure. With respect to the polyimide, the ring closure ratio of the amido acid group (also referred to as the amidation ratio) It does not have to be at 100%, and can be arbitrarily adjusted according to the purpose or purpose.

Examples of the method for fluorinating a polyfluorene imide precursor include hot fluorimidation in which a polyfluorene imide precursor solution is directly heated, or adding a catalyst to a solution of a polyfluorene imine precursor. The catalyst is imidization.

The temperature at which the polyimide precursor is thermally imidized in a solution is 100 to 400 ° C, preferably 120 to 250 ° C, while the water generated by the imidization reaction is excluded from the system. Perform better.

The catalyst of the polyfluorene imine precursor is imidized by adding an alkaline catalyst and an acid anhydride to the solution of the polyfluorine imide precursor, at a temperature of -20 ~ 250 ° C, preferably 0 to 180 ° C, can be stirred. The amount of alkaline catalyst is 0.5 to 30 mole times of the amino acid group, preferably 2 to 20 mole times of the amino acid group, and the amount of acid anhydride is 1 to 50 mole times of the amino acid group, preferably 3 to 30. Mortimer. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has moderate alkalinity during the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, when acetic anhydride is used, purification after the reaction can be easily performed, so it is preferable. The rate of imidization through the catalyst imidization can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

When a polyfluorene imide precursor or a polyfluorene imide reaction solution is used to recover the generated polyfluorene imide precursor or polyfluorene imide, the reaction solution can be simply put into a solvent to precipitate it. Examples of the solvent used for the precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, n-heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. Wait. After the polymer which has been put into the solvent to precipitate the precipitate is recovered by filtration, it can be dried at normal temperature or heating under normal pressure or reduced pressure. In addition, the polymer recovered by precipitation is redissolved in a solvent, and the operation of reprecipitation and recovery is repeated 2 to 10 times to reduce impurities in the polymer. Examples of the solvent at this time include alcohols, ketones, and hydrocarbons. When three or more solvents selected from these solvents are used, purification efficiency can be further improved.

When considering the molecular weight of the polyfluorene imide polymer, the weight of the vertical liquid crystal alignment film obtained as a result, the workability during the formation of the vertical film, and the coating property are measured by the weight measured by GPC (Gel Permeation Chromatography) method The average molecular weight is preferably 5,000 to 1,000,000, more preferably 10,000 ~ 150,000.

When a polysiloxane is used for a specific polymer, the polysiloxane is obtained by polycondensing an alkoxysilane represented by the following formula [A1], or the formula [A1] is selected from a formula selected from A polysiloxane (also collectively referred to as a polysiloxane polymer) obtained by polycondensation of at least one alkoxysilane grouped by an alkoxysilane group represented by formula [A3] is preferred.

An alkoxysilane represented by the formula [A1] is represented by the following formula [A1].

[化 40] (A ¹ ) _m Si (A ² ) _n (OA ³ ) _p    [A1]

A ¹ represents a structure represented by the aforementioned formula [1-1] or formula [1-2]. The preferred combination of Y ¹ to Y ⁶ and n in formula [1-1] and the preferred combination of Y ⁷ and Y ⁸ in formula [1-2] are as described above.

Among them, from the viewpoint of obtaining the vertical alignment of a highly stable liquid crystal, it is preferable that A ¹ be the structure represented by the formula [1-1].

A ² each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred.

A ³ each represents an alkyl group having 1 to 5 carbon atoms. Among them, from the viewpoint of reactivity of polycondensation, an alkyl group having 1 to 3 carbon atoms is preferred.

m represents an integer of 1 or 2. Among them, 1 is preferred from the viewpoint of synthesis.

n represents an integer from 0 to 2.

p represents an integer from 0 to 3. Among them, from the viewpoint of reactivity of polycondensation, an integer of 1 to 3 is preferred. It is preferably 2 or 3.

m + n + p means 4.

Specific examples of the alkoxysilane represented by the formula [A1] include the alkoxysilane represented by the following formulas [A1-1] to [A1-32].

(R ¹ each independently represents an alkyl group having 1 to 3 carbon atoms. R ² each independently represents an alkyl group having 1 to 3 carbon atoms. M each independently represents 2 or 3. n each independently represents 0 or 1)

(R ¹ each independently represents an alkyl group having 1 to 3 carbon atoms. R ² each independently represents an alkyl group having 1 to 3 carbon atoms. M each independently represents 2 or 3. n each independently represents 0 or 1. R ³ each independently represents Selected from -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO-, -OCH _2- , -CH ₂ O-, -COOCH ₂ -and -CH ₂ OCO- at least one type of bonding group. R ⁴ each independently represents a group selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy fluorine-containing alkyl group, and a fluorine-containing alkoxy group. (At least one species in a group)

(R ¹ each independently represents an alkyl group having 1 to 3 carbon atoms. R ² each independently represents an alkyl group having 1 to 3 carbon atoms. M each independently represents 2 or 3. n each independently represents 0 or 1. R ³ each independently represents Selected from -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO-, -OCH _2- , -CH ₂ O-, -COOCH ₂ -and -CH ₂ OCO- are at least one group. R ⁴ each independently represents an alkyl group, alkoxy group, fluorine-containing alkyl group or fluorine-containing alkoxy group, fluorine (At least one group selected from the group consisting of methyl, cyano, trifluoromethyl, nitro, azo, methyl, methyl, ethyl, ethoxy and hydroxy)

(R ¹ each independently represents an alkyl group having 1 to 3 carbon atoms. R ² each independently represents an alkyl group having 1 to 3 carbon atoms. M each independently represents 2 or 3. n each independently represents 0 or 1. R ³ each independently represents Selected from -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO-, -OCH _2- , -CH ₂ O-, -COOCH ₂ -and -CH ₂ OCO- at least one type of bonding group. R ⁴ each independently represents a group selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy fluorine-containing alkyl group, and a fluorine-containing alkoxy group. (At least one species in a group)

(R ¹ each represents an alkyl group having 1 to 3 carbon atoms. R ² each represents an alkyl group having 1 to 3 carbon atoms. M represents 2 or 3. n represents 0 or 1. B ⁴ represents a carbon number which may be substituted by a fluorine atom Alkyl group of 3 to 20. B ³ represents 1,4-cyclohexyl or 1,4-phenylene. B ² represents an oxygen atom or -COO- * (however, a bond with "*" is bonded to B ³ ). B ¹ represents an oxygen atom or -COO- * (however, a bond with "*" attached to (CH ₂ ) a ² )). a ¹ represents an integer of 0 or 1. a ² represents an integer from 2 to 10. a ³ represents an integer of 0 or 1)

The alkoxysilane represented by the above formula [A1] is used in combination with the solubility of a polysiloxane polymer to a solvent, the vertical alignment of a liquid crystal when it becomes a vertical liquid crystal alignment film, and further the optical characteristics of a liquid crystal display element, etc. Use 1 type or mix 2 or more types.

The alkoxysilane represented by the formula [A2] is represented by the following formula [A2].

[化 55] (B ¹ ) _m Si (B ² ) _n (OB ³ ) _p    [A2]

B ¹ each represents a carbon number of 2 to 12 having at least one group selected from the group consisting of a vinyl group, an epoxy group, an amine group, a mercapto group, an isocyanate group, a methacryl group, an acryl group, a urea group, and a cinnamyl group. Organic base. Among them, a vinyl group, an epoxy group, an amine group, a methacryl group, an acryl group, or a urea group is also preferable from the viewpoint of easy availability. Preferred is methacrylfluorenyl, acrylfluorenyl or ureido.

B ² each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is also preferable.

B ³ each represents an alkyl group having 1 to 5 carbon atoms. Among them, from the viewpoint of reactivity of polycondensation, an alkyl group having 1 to 3 carbon atoms is preferred.

m represents an integer of 1 or 2. Among them, 1 is preferred from the viewpoint of synthesis.

n represents an integer from 0 to 2.

p represents an integer from 0 to 3. Among them, from the viewpoint of reactivity of polycondensation, an integer of 1 to 3 is preferred. It is preferably 2 or 3.

m + n + p means 4.

Specific examples of the alkoxysilane represented by the formula [A2] include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylethylene silane, and dimethoxymethyl Vinyl vinyl silane, triethoxy Vinyl ethylene silane, ethylene trimethoxy silane, ethylene ginseng (2-methoxyethoxy) silane, m-styreneethyltriethoxysilane, p-styreneethyltriethoxysilane, m- Styrylmethyltriethoxysilane, p-styrenemethyltriethoxysilane, 3- (N-styrenemethyl-2-aminoethylamino) propyltrimethoxysilane, diethyl (3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, 3- (2-aminoethyl) Amine) propyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyl Triethoxysilane, 3-aminopropyltrimethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, 3-mercaptopropyl (dimethoxy) methylsilane, ( 3-mercaptopropyl) triethoxysilane, (3-mercaptopropyl) trimethoxysilane, 3- (triethoxysilyl) propylisocyanate Esters, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl Acrylate, 3- (trimethoxysilyl) propyl acrylate, 3- (triethoxysilyl) ethyl methacrylate, 3- (trimethoxysilyl) ethyl methyl Acrylate, 3- (triethoxysilyl) ethyl acrylate, 3- (trimethoxysilyl) ethyl acrylate, 3- (triethoxysilyl) methylmethyl Acrylate, 3- (trimethoxysilyl) methacrylate, 3- (triethoxysilyl) methacrylate, 3- (trimethoxysilyl) methacrylate , Γ-ureapropyltriethoxysilane, γ-ureapropyltrimethoxysilane, γ-ureapropyltripropoxysilane, (R) -N-1-phenylethyl-N'-triethoxysilylpropylurea, (R) -N-1-phenylethyl-N'-trimethoxysilylpropyl Diurea, bis [3- (trimethoxysilyl) propyl] urea, bis [3- (tripropoxysilyl) propyl] urea, 1- [3- (trimethoxysilyl) ) Propyl] urea and the like.

The alkoxysilane represented by the above formula [A2] is used in combination with the solubility of the polysiloxane polymer to the solvent, the vertical alignment of the liquid crystal when it becomes a vertical liquid crystal alignment film, and further the optical characteristics of the liquid crystal display element, etc. Use 1 type or mix 2 or more types.

An alkoxysilane represented by the formula [A3] is represented by the following formula [A3].

[化 56] (D ¹ ) _n Si (OD ² ) _4-n    [A3]

D ¹ each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, but these may be substituted with a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, or the like. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred.

D ² each represents an alkyl group having 1 to 5 carbon atoms. Among them, from the viewpoint of reactivity of polycondensation, an alkyl group having 1 to 3 carbon atoms is preferred.

n represents an integer from 0 to 3.

Specific examples of the alkoxysilane represented by the formula [A3] include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, Methyltriethoxysilane, ethyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, propyltriethoxysilane, methyltriethoxysilane, dimethyl Dimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dibutoxydimethylsilane, (chloromethyl) triethoxysilane, 3-chloropropyldisilane Methoxymethylsilane, 3-chloropropyltriethoxysilane, 2-cyanoethyltriethoxysilane, trimethoxy (3,3,3-trifluoropropyl) silane, hexyltrimethoxy Silyl, 3-trimethoxysilylpropyl chloride and the like.

In the formula [A3], examples of the alkoxysilane whose n is 0 include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

The alkoxysilane represented by the above formula [A3] is used in combination with the solubility of a polysiloxane polymer to a solvent, the vertical alignment of a liquid crystal when it becomes a vertical liquid crystal alignment film, and further the optical characteristics of a liquid crystal display element, etc. Use 1 type or mix 2 or more types.

The polysiloxane polymer is a polysiloxane obtained by polycondensing an alkoxysilane represented by the formula [A1], or a compound selected from the formula [A1] and the formula [A2] and the formula [A3] This is a polysiloxane obtained by polycondensation of at least one type of alkoxysilane grouped by alkoxysilane. That is, only polysiloxane obtained by polycondensation with an alkoxysilane represented by formula [A1], and polysilicon obtained by polycondensation of two types of alkoxysilane represented by formula [A1] and formula [A2] Oxane, a polysiloxane obtained by polycondensing two types of alkoxysilanes represented by formula [A1] and formula [A3], or formulas [A1], [A2], and [A3] Any of polysiloxanes obtained by polycondensing three types of alkoxysilanes.

Among them, from the viewpoint of polycondensation reactivity or the solubility of a polysiloxane polymer to a solvent, a plurality of types of alkoxysilanes are polycondensed. The combined polysiloxane is preferred. That is, a polysiloxane obtained by polycondensing two types of alkoxysilanes represented by formula [A1] and formula [A2], and two types of alkoxysilanes represented by formula [A1] and formula [A3] The polysiloxane obtained by performing polycondensation or the polysiloxane obtained by polycondensing three types of alkoxysilanes represented by formula [A1], [A2], and [A3] is preferable.

For the production of the above-mentioned polysiloxane polymer, when a plurality of types of alkoxysilanes are used, the alkoxysilane represented by the formula [A1] is preferably 1 to 40 mol% of all alkoxysilanes, and it is more preferable It is 1 to 30 mole%. The alkoxysilane represented by the formula [A2] is preferably 1 to 70 mol% of all alkoxysilanes, and more preferably 1 to 60 mol%. The alkoxysilane represented by formula [A3] is preferably 1 to 99 mol% of all alkoxysilanes, and more preferably 1 to 80 mol%.

The method for producing the polysiloxane polymer is not particularly limited. The method for producing the polysiloxane polymer in the present invention includes a method of polycondensing an alkoxysilane represented by the aforementioned formula [A1] in a solvent, and combining the formula [A1] with the aforementioned formula [A2]. ] A method of polycondensing an alkoxysilane represented by a solvent in a solvent, a method of polycondensing an alkoxysilane represented by the formula [A1] and the aforementioned formula [A3] in a solvent, and a method of formula [A1] A method of polycondensing an alkoxysilane represented by the formula [A2] and the formula [A3] in a solvent. The polysiloxane polymer of the present invention is a solution obtained by polycondensing these alkoxysilanes and then dissolving them uniformly in a solvent.

The method of polycondensing a polysiloxane polymer is not specifically limited. Examples include alkoxysilanes in alcohol-based solvents or glycol-based solvents. In a solvent, hydrolysis is performed. Method of polycondensation reaction. At this time, hydrolysis. The polycondensation reaction can be partially hydrolyzed or completely hydrolyzed. When the hydrolysis is completely carried out, it is theoretically sufficient to add only 0.5 times the molar amount of water of all the alkoxy groups in the alkoxysilane, but it is better to add an excess amount of water more than 0.5 times the molar amount. To obtain a polysiloxane polymer, use the above hydrolysis. The amount of water for the polycondensation reaction can be appropriately selected according to the purpose, but it is preferably 0.5 to 2.5 times the molar amount of all the alkoxy groups in the alkoxysilane.

Also, to promote hydrolysis. For the purpose of the polycondensation reaction, acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, and fumaric acid, bases such as ammonia, methylamine, ethylamine, ethanolamine, and triethylamine can be used. A chemical compound, or a metal salt such as hydrochloric acid, nitric acid, or oxalic acid is used as a catalyst. In addition, the solution dissolved in alkoxysilane can be heated to promote hydrolysis. Polycondensation reaction. The heating temperature and heating time at this time can be appropriately selected depending on the purpose. For example, conditions such as heating and stirring at 50 ° C for 24 hours, and then stirring for 1 hour under reflux conditions can be mentioned.

In addition, as another method of polycondensation, a method of heating a mixture of an alkoxysilane, a solvent, and oxalic acid, and then performing a polycondensation reaction may be mentioned. Specifically, a method of adding oxalic acid to a solvent in advance as a solution of oxalic acid, and then mixing the alkoxysilane with the solution being heated. The amount of oxalic acid used in the above reaction at this time is preferably 0.2 to 2.0 mol for 1 mol of all alkoxy groups in the alkoxysilane. In addition, the reaction can be performed at a solution temperature of 50 to 180 ° C. However, if it does not cause evaporation or volatilization of the solvent, it may be performed under reflux for tens of minutes to tens of hours.

For the polycondensation reaction of making a polysiloxane polymer, use plural When the alkoxysilanes represented by the aforementioned formulas [A1], [A2], and [A3] are used, a mixture of a plurality of alkoxysilanes may be mixed in advance to perform the reaction, or a plurality of alkoxy groups may be sequentially added. The reaction was carried out under silane.

The solvent used for the polycondensation reaction of the alkoxysilane is not particularly limited as long as it can dissolve the alkoxysilane. Moreover, even if it is a solvent which does not dissolve an alkoxysilane, it can be dissolved only when the polycondensation reaction of an alkoxysilane is performed. As a solvent used in the polycondensation reaction, alcohol is generally generated by the polycondensation reaction of an alkoxysilane. Therefore, a solvent having a good compatibility with an alcohol solvent, a glycol solvent, a glycol ether solvent, or an alcohol is used. Solvent. Specific examples of the solvent used in such a polycondensation reaction include alcohol-based solvents such as methanol, ethanol, propanol, butanol, and diacetone alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and adipic acid. Alcohol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2- Pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol or Ethanol solvents such as 1,6-hexanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl Ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropylene Ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol mono Methyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene Alcohol, propylene glycol dipropyl ether, or dibutyl ether, glycol ether-based solvents, N- methyl-2- Pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylmethane, tetramethylurea, Hexamethylphosphine triamine, m-cresol and other solvents with good compatibility with alcohol.

In the present invention, when a polycondensation reaction is performed, these solvents may be used singly or in combination of two or more kinds.

The solution of the polysiloxane polymer obtained by the above-mentioned method is such that the concentration of silicon atoms in the peralkoxysilane loaded as a raw material converted into SiO ₂ (also referred to as SiO ₂ converted concentration) is 20 masses. % Or less is preferred. Among them, 5 to 15% by mass is also preferable. By selecting any concentration in this concentration range, gel generation in the solution can be suppressed, and a solution of a uniform polysiloxane polymer can be obtained.

In the present invention, the solution of the polysiloxane polymer obtained by the above method can be directly used as a specific polymer, and if necessary, the solution of the polysiloxane polymer obtained by the above method can be concentrated or diluted by adding a solvent. Or it can be used as a specific polymer after being substituted by other solvents.

The solvent (also referred to as an added solvent) used when the above-mentioned solvent is added to be diluted may be a solvent used in the polycondensation reaction or other solvents. This addition solvent is only required to uniformly dissolve the polysiloxane polymer, and it is not particularly limited, and one type may be used or two or more types may be arbitrarily selected and used. Examples of the added solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, methyl acetate, ethyl acetate, and ethyl lactate, in addition to the solvents used in the aforementioned polycondensation reaction. Ester-based solvents.

When a polymer other than the polysiloxane polymer is used for the specific polymer, the other polymer is mixed with the polysiloxane polymer. Before, it is preferable that the alcohol generated during the polycondensation reaction of the polysiloxane polymer is distilled off under normal pressure or reduced pressure.

<Specific generator>

The vertical liquid crystal alignment film in the present invention is obtained from a liquid crystal alignment treatment agent containing at least one specific generator grouped by a photoradical generator, a photoacid generator, and a photobase generator selected from the component (B).

The photoradical generator is not particularly limited as long as it can generate radicals by ultraviolet rays, and examples thereof include tert-butylperoxy-iso-butyrate and 2,5-dimethyl -2,5-bis (benzylidenedioxy) hexane, 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-propylhydroperoxide Oxide, 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) benzene Acetophenone, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (tert-pentylperoxy Carbonyl) benzophenone, 3,3 ', 4,4'-tetra (tert-hexylperoxycarbonyl) benzophenone, 3,3'-bis (tert-butylperoxycarbonyl) ) -4,4'-Dicarboxybenzophenone, tert-butylperoxybenzoate, di-tert-butyldiperoxyisophthalate Other organic peroxides may include quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, benzoin methyl, Benzoin derivatives such as benzoin ethyl ether, α-methyl benzoin, and α-phenyl benzoin.

The photoacid generator and photobase generator are not particularly limited as long as they can generate acids or bases only by ultraviolet rays. Examples include triazine compounds, acetophenone derivative compounds, and Perylene compounds, diazomethane compounds, sulfonic acid derivative compounds, diaryl iodonium salts, triarylsulfonium salts, triarylsulfonium salts, iron aromatic hydrocarbon complexes, and the like. More specific examples include diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium methanesulfonate, diphenyliodonium p-toluenesulfonate, and diphenyl Iodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium Hexafluorophosphate, bis (p-tert-butylphenyl) iodonium methanesulfonate, bis (p-tert-butylphenyl) iodonium p-toluenesulfonic acid, bis (p-tert-butylbenzene Group) iodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium tetrafluoroborate, bis (p-tert-butylphenyl) iodonium chloride, bis (p-chloro Phenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, tris (p-methoxyphenyl) sulfur Onium tetrafluoroborate, tris (p-methoxyphenyl) sulfonium hexafluorophosphonate, tris (p-ethoxyphenyl) sulfonium tetrafluoroborate, triphenylphosphonium chloride, triphenyl Sulfonium bromide, tris (p-methoxyphenyl) sulfonium tetrafluoroborate, tris (p-methoxyphenyl) sulfonium hexafluorophosphonate, tris (p-ethoxyphenyl) sulfonium fluorine Acid salt, bis [[(2-nitrobenzyl) oxy] carbonylhexane-1,6-diamine], nitrobenzylcyclohexylaminocarbamate, bis (methoxybenzyl Hexamethylidene diaminocarbamate, bis [[(2-nitrobenzyl) oxy] carbonylhexane-1,6-diamine], nitrobenzylcyclohexylaminomethyl Acid esters, bis (methoxybenzyl) hexamethylene diaminocarbamates, and the like.

As the specific generator in the present invention, it is preferable to use a photo radical generator from the effect of improving the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film.

<Liquid crystal alignment treatment agent>

The liquid crystal alignment treatment agent of the present invention is a coating solution used for forming a vertical liquid crystal alignment film, and the coating solution contains the component (A) and has at least one selected from the group consisting of the formulas [1-1] and [1-2]. The specific polymer having a specific side chain structure and the coating solution of the (B) component are at least one specific generator selected from the group consisting of a photoradical generator, a photoacid generator, and a photobase generator, and a solvent.

The specific polymer having a specific side chain structure is not particularly limited, and examples thereof include acrylic polymers, methacrylic polymers, novolac resins, polyhydroxystyrene, polyimide precursors, and polyfluorenes. Preferably, at least one of the group consisting of imine, polyamide, polyester, cellulose, and polysiloxane is used. Among them, polyimide precursor, polyimide or polysiloxane is preferred, and polyimide or polysiloxane is particularly preferred. In addition, one or two or more of these polymers can be used as the specific polymer.

All polymer components in the liquid crystal alignment treatment agent may be specific polymers, or other polymers other than these may be mixed. At this time, the content of other polymers other than this is 0.5 to 15 parts by mass, and preferably 1 to 10 parts by mass for 100 parts by mass of the specific polymer. Examples of other polymers include the aforementioned polymers that do not contain the specific side chain structure represented by the formula [1-1] or the formula [1-2].

The specific generator in the liquid crystal alignment treatment agent is at least one specific generator selected from the group consisting of a photo radical generator, a photoacid generator, and a photobase generator. Among these, from the viewpoint of improving the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film, it is preferable to use a photo radical generator. The content of the specific generator in the liquid crystal alignment treatment agent is preferably 0.01 to 50 parts by mass for 100 parts by mass of all polymer components. Among them, 0.01 to 30 parts by mass is more preferable, and particularly preferable is 0.1 to 20 parts by mass.

The content of the solvent in the liquid crystal alignment treatment agent may be appropriately selected according to a coating method of the liquid crystal alignment treatment agent or obtaining a target film thickness. Among them, from the viewpoint of forming a uniform vertical liquid crystal alignment film by coating, the content of the solvent in the liquid crystal alignment treatment agent is preferably 50 to 99.9% by mass. Among them, 60 to 99% by mass is preferable, and 65 to 99% by mass is particularly preferable.

The solvent used for the liquid crystal alignment treatment agent is only a solvent dissolved in a specific polymer, and is not particularly limited.

Where a specific polymer is a polyimide precursor, polyimide, polyimide or polyester, or acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, cellulose, When the solubility of polysiloxane to a solvent is low, it is better to use a solvent (also referred to as a solvent A) as described below.

Examples include N, N-dimethylformamidine, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylmethylene, γ-butyrolactone, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, 4-hydroxy-4-methyl-2-pentanone, and the like.

N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone Or γ-butyrolactone is preferred. These can be used alone or in combination.

When the specific polymer is an acrylic polymer, a methacrylic polymer, a novolac resin, polyhydroxystyrene, cellulose or polysiloxane, or a polyimide precursor, polyimide, polyimide, polyimide When an ester or the like has high solubility in a solvent, the solvents shown below (also referred to as solvents B) can be used.

Examples include ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, and 2-methyl alcohol. 1-butanol, iso-pentyl alcohol, tert-pentyl alcohol, 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-methylcyclohexanol, 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 di Methyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl ether Glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl ethyl Ester, 1-methylpentyl ethyl Ester, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, butyl carbonate, 2 -(Methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl 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 mono Ethyl 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-ethoxyethyl (Oxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate Ester, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate , Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate , Ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, Cyclohexanone, cyclopentanone and the like. Further, a solvent represented by the following formula [D1], [D2], or [D3] can be used.

(D ¹ represents an alkyl group having 1 to 3 carbon atoms. D ² represents an alkyl group having 1 to 3 carbon atoms. D ³ represents an alkyl group having 1 to 4 carbon atoms)

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, and dipropylene glycol dimethyl ether are also used. , Cyclohexanone, cyclopentanone, and the solvent represented by the above formula [D1], [D2], or [D3] are preferred.

These solvents type B can improve the coating property or surface smoothness of the vertical liquid crystal alignment film when applying the liquid crystal alignment treatment agent, and use polyimide precursor, polyimide, polyimide, or polyester for specific polymers. In this case, it may be used after being mixed with the aforementioned solvent A. In this case, the solvent B is preferably 1 to 70% by mass of the entire solvent contained in the liquid crystal alignment treatment agent. Among them, 10 to 60% by mass is more preferable. It is preferably 20 to 60% by mass. Moreover, when the solubility of a polyimide precursor, polyimide, polyimide, polyester, etc. in a solvent is high, only the solvent type B may be used.

The liquid crystal alignment treatment agent contains a compound having a structure selected from the following formulae [B1] to [B7] for the purpose of improving the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film (also referred to as adhesion). Sex compound) is preferably a group of at least one compound. At this time, it is preferable that the structures represented by these formulas [B1] to [B7] have two or more compounds.

W ¹ represents a hydrogen atom or a benzene ring.

W ² represents at least one type of divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring.

W ³ represents a group selected from the group consisting of 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 and a fluorine-containing alkoxy group having 1 to 18 carbon atoms. At least one.

More specifically, the following may be mentioned.

Examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) propenyloxyethoxytrioxide. Compounds having three polymerizable unsaturated groups in the molecule, such as methylolpropane or glycerol polyglycidyl ether poly (meth) acrylate; further examples include ethylene glycol di (meth) acrylate and diethylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate , Butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type two (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether bis ( (Meth) acrylates, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate Compounds with two polymerizable unsaturated groups in the molecule, such as hydroxypivalic acid neopentyl glycol di (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (methyl ) Acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) propenyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (Meth) acrylate, glycerol mono (meth) acrylate, 2- (meth) acrylfluorenyloxyethyl phosphate, or N-hydroxymethyl (meth) acrylamide with 1 in the molecule Compounds of polymerizable unsaturated groups, etc.

Alternatively, a compound represented by the following formula [7] may be used.

(E ₁ represents a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, and a phenanthrene ring. E ₂ represents a group selected from A group of the following formula [7a] or [7b]. N represents an integer of 1 to 4)

When a photo-radical generator is used as a specific generator, since the effect of improving the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is large, the compound having the structure represented by the formulae [B1] to [B6] is used for the adhesive compound. The compound or the compound represented by the formula [7] is preferable. Among them, a compound having a structure represented by Formula [B1] to Formula [B5] or a compound represented by Formula [7] is preferably used.

The above-mentioned adhesive compound is an example of the compound, but it is not Limited to these. Moreover, the adhesive compound may be 1 type or a combination of 2 or more types.

The content of the adhesive compound is preferably 0.1 to 150 parts by mass for 100 parts by mass of all polymer components. When the cross-linking reaction is to be performed, the effect is preferably 0.1 to 100 parts by mass, and particularly preferably 1 to 50 parts by mass, for 100 parts by mass of all polymer components.

On the premise that the effects of the present invention are not impaired, a compound having an epoxy group, an isocyanate group, an oxetanyl group, or a cyclic carbonate group may be introduced into the liquid crystal alignment treatment agent, or a compound selected from a hydroxyl group, a hydroxyalkyl group, and A compound (also collectively referred to as a crosslinkable compound) having at least one substituent group formed by a lower alkoxyalkyl group. In this case, the crosslinkable compound must have two or more of these substituents.

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, Tetraglycidylaminodiphenyl, Tetraglycidyl-m-xylylenediamine, Tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, Tetraphenylglycidyl ether E Alkane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetamidine diglycidyl ether, 1,3-bis (1- (2,3-glycidoxy) -1-trifluoromethyl-2 , 2,2-trifluoromethyl) benzene, 4,4-bis (2,3-glycidoxy) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl bis Toluenediamine, 2- (4- (2,3-glycidoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-glycidoxy)) benzene ) Ethyl) phenyl) propane, 1,3-bis (4- (1- (4- (2,3-glycidoxy) phenyl) -1- (4- (1- (4- (2,3-glycidoxy) phenyl) -1-methylethyl) phenyl) ethyl Group) phenoxy) -2-propanol and the like.

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

Specific examples include crosslinkable compounds represented by formulas [4a] to [4k] disclosed on pages 58 to 59 of International Publication WO2011 / 132751 (published on 2011.10.27).

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].

Specific examples include crosslinkable compounds represented by formulas [5-1] to [5-42] disclosed on pages 76 to 82 of International Publication WO2012 / 014898 (published on February 2, 2012).

Examples of the crosslinkable compound having at least one kind of substituent selected from the group consisting of a hydroxyl group and an alkoxy group include an amine-based resin having a hydroxyl group or an alkoxy group, and examples thereof include a melamine resin, a urea resin, and guanidine. Resin, glycoluril-formaldehyde resin, succinylamine-formaldehyde resin, ethylenic urine -Formaldehyde resin and so on. Specifically, a melamine derivative, a benzomelamine derivative, or a glycoluril can be used in which the hydrogen atom of the amine group is substituted by a methylol group or an alkoxymethyl group or both. The melamine derivative or the benzomelamine derivative may exist in a dimer or trimer form. These are preferably those having an average of 3 to 6 hydroxymethyl or alkoxymethyl groups per triazine ring.

As an example of such a melamine derivative or a benzomelamine derivative, an average of 3.7 methoxymethyl groups substituted for MX-750 per triazine ring and 5.8 formazan per one triazine ring are sold. Methoxymethyl substituted MW-30 (the above is made by Sanwa Chemical Co., Ltd.) or CYMEL300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and other methoxymethylated melamine, CYMEL235, 236, 238, 212, 253, 254 and other methoxymethylated butoxymethylated melamine, CYMEL506, 508 and other butoxymethylated melamine, such as CYMEL1141, methoxymethylated isobutyl group containing carboxyl group Oxymethylated melamine, such as methoxymethylated ethoxymethylated benzomelamine such as CYMEL1123, methoxymethylated butoxymethylated benzomelamine such as CYMEL1123-10, such as CYMEL1128 Butoxymethylated benzomelamine, such as methoxymethylated ethoxymethylated benzomelamine containing a carboxyl group, such as CYMEL1125-80 (the above is made by Mitsui cyanamide company). Examples of glycolurides include butoxymethylated glycolurils such as CYMEL1170, hydroxymethylated glycolurils such as CYMEL1172, and methoxymethylolated glycols such as Powder link 1174. Urea and so on.

As benzene with hydroxy or alkoxy group, or phenolic compound Examples of the substance include 1,3,5-gins (methoxymethyl) benzene, 1,2,4-gins (isopropoxymethyl) benzene, 1,4-bis (sec-butoxy) (Methyl) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, and the like.

More specific examples include crosslinkable compounds represented by formulas [6-1] to [6-48] disclosed on pages 62 to 66 of International Publication WO2011 / 132751 (published on 2011.10.27).

The content of the crosslinkable compound is preferably from 0.1 to 100 parts by mass for 100 parts by mass of all polymer components. When the cross-linking reaction is to be performed to express the intended effect, for 100 parts by mass of all polymer components, 0.1 to 50 parts by mass is preferred, and 1 to 30 parts by mass is particularly preferred.

In the liquid crystal display device of the present invention, as a compound that promotes the charge movement in the liquid crystal alignment film and promotes the decharge of the device, it can be disclosed in pages 69 to 73 of International Publication WO2011 / 132751 (published on 2011.10.27). The nitrogen represented by the formulae [M1] to [M156] contains a heterocyclic amine compound. The amine compound can be directly added to the liquid crystal alignment treatment agent, but it is better to add a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass in an appropriate solvent. The solvent may be any organic solvent that dissolves the specific polymer, and is not particularly limited.

As long as the effect of the present invention is not impaired, the liquid crystal alignment treatment agent may be a compound that improves the uniformity of the film thickness or the surface smoothness of the vertical liquid crystal alignment film when the liquid crystal alignment treatment agent is applied. Further, a compound or the like that improves the adhesion between the vertical liquid crystal alignment film and the substrate can be used.

Examples of the compound that improves the uniformity of the thickness of the vertical liquid crystal alignment film or the surface smoothness include a fluorine-based surfactant and a polysiloxane-based interface. Agents, non-ionic surfactants, etc.

More specific examples include EFTOP EF301, EF303, EF352 (above manufactured by Tochem Products), Megafac F171, F173, R-30 (above manufactured by Dainippon Ink Co., Ltd.), FLUORAD FC430, FC431 (above Sumitomo 3M) Manufacturing), Asahi GuardAG710, SURFLONS-382, SC101, SC102, SC103, SC104, SC105, SC106 (the above are manufactured by Asahi Glass Co., Ltd.). The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass for 100 parts by mass of all polymer components contained in the liquid crystal alignment treatment agent.

Specific examples of the compound that improves the adhesion between the vertical liquid crystal alignment film and the substrate include a compound containing a functional silane or a compound containing an epoxy group as shown below.

Examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-urea Propyltrimethoxysilane, 3-Ureapropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrisilane Ethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1 , 4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazepine Ethyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-amino Propyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-amino Propyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane , Ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 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-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N , N, N ', N'-tetraglycidyl-4, 4'-diaminodiphenylmethane and the like.

When using these compounds which make the substrate adhere, it is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, for 100 parts by mass of all polymer components contained in the liquid crystal alignment treatment agent. If it is less than 0.1 parts by mass, the effect of improving adhesion cannot be expected. If it is more than 30 parts by mass, the storage stability of the liquid crystal alignment treatment agent may be deteriorated.

To the liquid crystal alignment treatment agent, in addition to the above-mentioned compounds, a dielectric body or a conductive substance may be added for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the vertical liquid crystal alignment film, so long as the effects of the present invention are not impaired. .

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

As a substrate for liquid crystal display devices, it is only a substrate with high transparency The plate is not particularly limited, and other than glass substrates, acrylic substrates, polycarbonate substrates, PET (polyethylene terephthalate) substrates, and plastic substrates such as these films can be used. When a liquid crystal display element is used as a reverse type element and is used in a dimming window or the like, a plastic substrate is preferred. From the viewpoint of simplicity of the process, it is preferable to use a substrate formed of an ITO (Indium Tin Oxide) electrode or the like for driving the liquid crystal. In the case of a reflective reverse type device, not only a single-sided substrate, but also a silicon wafer, a metal such as aluminum, or a substrate formed with a dielectric multilayer film can be used.

In the liquid crystal display element of the present invention, at least one of the substrates has a vertical liquid crystal alignment film that aligns liquid crystal molecules in a vertical alignment. The vertical liquid crystal alignment film is obtained by applying a liquid crystal alignment treatment agent on a substrate, roasting it, and then performing alignment treatment by rubbing treatment or light irradiation. In addition, the vertical liquid crystal alignment film in the present invention can be used as a vertical liquid crystal alignment film even without performing these alignment treatments.

The application method of the liquid crystal alignment treatment agent is not particularly limited. Industrially, there are screen printing, offset printing, flexographic printing, inkjet method, dipping method, roll coating method, slit coating method, rotation method, spray method, etc. The thickness of the vertical liquid crystal alignment film according to the type or purpose of the substrate can be appropriately selected.

After the liquid crystal alignment treatment agent is coated on the substrate, the solvent used for the liquid crystal alignment treatment agent is mixed with a heating plate, a thermal cycle type oven, an IR (infrared) type oven, and the like at a temperature of 30 to 300 ° C, preferably A vertical liquid crystal alignment film can be obtained after the solvent is evaporated at a temperature of 30 to 250 ° C. If the thickness of the vertical liquid crystal alignment film after firing is too thick, it will be disadvantageous on the power consumption level of the liquid crystal display element. If it is too thin, it will be reduced. The reliability of this device is preferably 5 to 300 nm, and more preferably 10 to 200 nm.

The liquid crystal composition used for the liquid crystal display element is a liquid crystal composition having at least a liquid crystal and a polymerizable compound. Examples other than the liquid crystal and the polymerizable compound include a spacer for controlling an electrode gap (also referred to as a pitch) of the initiator or the liquid crystal display element.

The method for injecting the liquid crystal composition is not particularly limited, and examples thereof include the following methods. In other words, when a glass substrate is used as the substrate, one pair of substrates of a vertical liquid crystal alignment film is prepared. Four sealants on one side of the substrate are coated with a sealant, and then the surface of the vertical liquid crystal alignment film is placed inward and downward to produce a sticker. Closing air cells on one side of the substrate. A method of injecting the liquid crystal composition under a reduced pressure from the place where the sealant is not applied to obtain a liquid crystal composition injected into the cell can be mentioned.

When a plastic substrate is used as the substrate, a pair of substrates of a vertical liquid crystal alignment film is prepared. A liquid crystal composition is dropped on a single-sided substrate by an ODF (One Drop Filling) method or an inkjet method, and then bonded to another For a single-sided substrate, a method for obtaining a liquid crystal composition to be injected into a cell can be cited.

In the liquid crystal display element of the present invention, in order to improve the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film, a sealant may not be applied to the four substrates.

The distance between the liquid crystal display elements can be controlled by a spacer or the like. This method is a method of introducing a spacer having a desired size into the liquid crystal composition, or a method using a substrate having a columnar spacer having a desired size. The size of the pitch is preferably 1 to 100 μm, and more preferably 2 to 50 μm. Particularly preferred is 3 to 30 μm. If the pitch is too small, the LCD display The contrast of the display element will be reduced. If it is too large, the drive voltage of this element will become high.

The liquid crystal display element of the present invention is obtained by curing a liquid crystal composition in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity to form a cured composite of liquid crystal and a polymerizable compound. The hardening of the liquid crystal composition is performed by injecting the liquid crystal composition obtained above into a unit cell by at least one of a treatment method of irradiation and heating with active energy rays. Among them, ultraviolet rays are preferred as the active energy rays. The ultraviolet light has a wavelength of 250 to 400 nm, and preferably 310 to 370 nm. In the heat treatment, the temperature is 40 to 120 ° C, and preferably 60 to 80 ° C. Further, both the ultraviolet treatment and the heat treatment may be performed simultaneously, or the heat treatment may be performed after the ultraviolet treatment. The curing of the liquid crystal composition is preferably performed only by ultraviolet treatment.

As described above, a liquid crystal display element using a vertical liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a specific polymer, as a reverse-type element, has a high adhesion between the liquid crystal layer and the vertical liquid crystal alignment film, and the liquid crystal has high vertical alignment. It has good optical characteristics, that is, the transparency when no voltage is input and the scattering characteristics when voltage is input. It can be used in liquid crystal displays or light control windows or shutter elements that control the transmission and blocking of light.

In addition, it can be applied to liquid crystal display elements used in transportation equipment and transportation machinery such as automobiles, railways, and aircrafts. Specifically, it can be used as a light control window or a shutter for controlling the transmission and blocking of light. Components, etc.

In particular, compared with the case where a reverse-type element is used in the past, it has good transparency when voltage is not input and scattering characteristics when voltage is input. When used in the glass windows of vehicles, the light extraction efficiency at night is high, and the effect of preventing glare from external light is also improved. Therefore, it is possible to further improve the safety when driving a vehicle or the comfort when riding a vehicle.

In addition, when a liquid crystal display element is made of a thin-film substrate, when compared with a conventional reverse-type element, the liquid crystal display element is less likely to be caused by the lower adhesion between the liquid crystal layer and the vertical alignment film when compared with a conventional reverse type element. Defective or degraded, further improving reliability.

In addition, the light guide plate of a display device such as an LCD (Liquid Crystal Display) or an OLED (Organic Light-emitting Diode) display, or a back plate of a transparent display of these displays can be used. Specifically, when used in the back panel of a transparent display, the transparent display is combined with the liquid crystal display element of the present invention, and when the image is displayed on the transparent display, it can be used to suppress the light incident from the back side by the liquid crystal display element. Thereby, when the liquid crystal display element of the present invention performs image display on a transparent display, it becomes a scattering state via voltage input, which can make the image display clear, and after the image display ends, the voltage becomes a transparent state without input.

[Example]

Examples are given below to explain the present invention in more detail, but the present invention is not limited to these.

"Abbreviations for compounds used in Synthesis Examples, Examples, and Comparative Examples"

L1 (Liquid Crystal): MLC-6608 (Merck)

R1 (polymerizable compound): a compound represented by the following formula [R1]

P1 (photoinitiator): 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

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

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

A4: a diamine compound represented by the following formula [A4]

A5: 1,3-diamino-4-octadecyloxybenzene

(Second Diamine Compound)

B1: 3,5-diaminobenzoic acid

B2: a diamine compound represented by the following formula [B2]

(Other diamine compounds)

C1: p-phenylene diamine

C2: m-phenylene diamine

(Tetracarboxylic acid component)

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

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

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

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

(Alkoxysilane)

E1: an alkoxysilane represented by the following formula [E1]

E2: Octadecyltriethoxysilane

E3: 3-methacryloxypropyltrimethoxysilane

E4: 3-ureapropyltriethoxysilane

E5: Tetraethoxysilane

(Specific generator)

S1: Photo radical generator represented by the following formula [S1]

S2: Photo radical generator represented by the following formula [S2]

(Adhesive compound)

M1: 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]

(Crosslinkable compound)

K1: Compound represented by the following formula [K1]

(Solvent)

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

PGME: propylene glycol monomethyl ether

ECS: ethylene glycol monoethyl ether

BCS: ethylene glycol monobutyl ether

PB: propylene glycol monobutyl ether

EC: Diethylene glycol monoethyl ether

"Method for measuring molecular weight of polyimide-based polymer"

The molecular weights of the polyimide precursor and polyimide were determined using a normal temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko Corporation), and a column (KD-803, KD-805) (Shodex (Manufactured by the company) was measured as follows.

Column temperature: 50 ℃

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

Flow rate: 1.0ml / min

Use calibration curves to prepare standard samples: TSK standard polyethylene oxide (molecular weight; approximately 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; approximately 12,000, 4,000, and 1,000) (polymer Laboratory company).

"Determination method of polyimide's imidation ratio"

Put 20 mg of polyfluorene imine powder into a NMR (Nuclear Magnetic Resonance) sample tube (NMR standard sampling tube, 5 (manufactured by Kusano Science Co., Ltd.), deuterated dimethylsulfinium (DMSO-d6, 0.05% by mass TMS (tetramethylsilane) mixed product) (0.53 ml) was added, and ultrasonic waves were added to completely dissolve. This solution was used to measure a proton NMR at 500 MHz using an NMR measuring machine (JNW-ECA500) (manufactured by Japan Electronics Standard Corporation). The hydrazone imidization rate is determined by using protons from structures that have not changed before and after hydrazone imidization as the reference protons, using the peak value of protons and the NH groups from hydrazones that appear near 9.5 to 10.0 ppm. The proton peak integrated value is obtained by the following formula.

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

For the above formula, x is the integrated value of the proton peak derived from the NH group of amido acid, y is the integrated value of the peak of the reference proton, and α is the amidine in the case of polyamidic acid (the amidation ratio is 0%). Ratio of the number of reference protons of one NH matrix proton of an acid.

<Synthesis example 1>

D1 (2.96g, 15.1mmol), A1 (2.91g, 7.65mmol), B1 (0.93g, 6.11mmol) and C2 (0.17g, 1.57mmol) were mixed in NEP (21.0g), and the mixture was subjected to 8 at 40 ° C The reaction was carried out for an hour, and a polyamic acid solution (1) having a resin solid content concentration of 25% by mass was obtained. The number average molecular weight of this polyamic acid was 23,600, and the weight average molecular weight was 71,800.

<Synthesis example 2>

D2 (3.83g, 15.3mmol), A2 (6.04g, 15.3mmol) and B1 (2.33g, 15.3mmol) were mixed in NMP (26.4g), and after reacting at 50 ° C for 2 hours, D1 (2.94g) was added , 15.0 mmol) and NMP (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 number average molecular weight of this polyamic acid was 22,500, and the weight average molecular weight was 67,100.

<Synthesis example 3>

NMP was added to the polyphosphonic acid solution (2) (30.0 g) obtained in Synthesis Example 2 and diluted to 6% by mass, and then acetic anhydride (3.90 g) and pyridine (2.40 g) were added as the phosphonium imidization catalyst. ), And reacted at 70 ° C for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polymer. Amidine powder (3). The polyimide has an imidization ratio of 60%, a number average molecular weight of 20,100, and a weight average molecular weight of 57,100.

<Synthesis example 4>

D2 (2.64g, 10.6mmol), A3 (4.56g, 10.5mmol), B1 (1.60g, 10.5mmol) and B2 (1.07g, 5.26mmol) were mixed in NMP (21.9g), and carried out at 80 ° C. 5 hours reaction. Thereafter, D1 (3.02 g, 15.8 mmol) and NMP (17.2 g) were added, and a reaction was performed at 40 ° C. for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting it to 6% by mass, as a phosphonium imidization catalyst, acetic anhydride (3.85 g) and pyridine (2.42 g) were added, and the temperature was 50 ° C. The reaction was carried out for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (4). The polyimide has a fluorene imidation ratio of 56%, a number average molecular weight of 18,500, and a weight average molecular weight of 54,000.

<Synthesis example 5>

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

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting it to 6% by mass, as a phosphonium imidization catalyst, acetic anhydride (4.00 g) and pyridine (2.50 g) were added, and the temperature was 50 ° C. The reaction was carried out for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (5). The polyimide has a fluorene imidation ratio of 49%, a number average molecular weight of 16,100, and a weight average molecular weight of 49,800.

<Synthesis example 6>

D3 (5.45g, 24.3mmol), A2 (5.81g, 14.7mmol), B1 (1.12g, 7.36mmol) and B2 (0.50g, 2.46mmol) were mixed in NMP (38.6g), and the temperature was 10 ° C for 10 The reaction was carried out for an hour, and a polyamic acid solution having a resin solid content concentration of 25% by mass was obtained.

NMP was added to the obtained polyamic acid solution (30.0 g), diluted to 6% by mass, and then acetonitrile (4.00 g) and pyridine (2.48 g) were added as a phosphonium imidization catalyst, and the process was performed at 70 ° C. 2 hours reaction. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (6). The polyimide has a imidation ratio of 63%, a number average molecular weight of 17,200, and a weight average molecular weight of 49,100.

<Synthesis example 7>

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

NMP was added to the obtained polyamic acid solution (30.0 g), diluted to 6% by mass, and then used as a phosphonium imidization catalyst, acetic anhydride (8.00 g) and pyridine (2.50 g) were added. Hour response. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imide powder (7). The polyimide has a fluorinated imidization rate of 54%, a number average molecular weight of 17,400, and a weight average molecular weight of 47,800.

<Synthesis example 8>

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

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting it to 6 mass%, as a phosphonium imidization catalyst, acetic anhydride (7.25 g) and pyridine (2.22 g) were added, and the reaction was performed at 40 ° C 1.5 hours reaction. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imide powder (8). The polyimide has an imidization ratio of 71% and a number average molecular weight of 17,100 and a weight average molecular weight of 38,800.

<Synthesis example 9>

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

After adding NMP to the obtained polyamidic acid solution (30.0 g) and diluting it to 6 mass%, as a phosphonium imidization catalyst, acetic anhydride (3.90 g) and pyridine (2.40 g) were added, and the temperature was 70 ° C. The reaction was carried out for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imide powder (9). The polyimide has a fluorene imidization rate of 61%, a number average molecular weight of 19,000, and a weight average molecular weight of 58,100.

<Synthesis example 10>

D2 (3.83g, 15.3mmol) and B1 (4.66g, 30.6mmol) were mixed in NMP (37.5g), and after reacting at 50 ° C for 2 hours, D1 (2.94g, 15.0mmol) and NMP (12.8g) were added. ), And reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (10) having a resin solid content concentration of 25% by mass. The number average molecular weight of this polyamic acid was 25,900, and the weight average molecular weight was 79,100.

<Synthesis example 11>

To the polyamidic acid solution (10) (30.0 g) obtained in Synthesis Example 10, NMP was added and diluted to 6% by mass, and then, as a phosphonium imidization catalyst, acetic anhydride (3.85 g) and pyridine (2.40 g) were added. ), And reacted at 70 ° C for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imine powder (11). The polyimide has a fluorene imidation rate of 59%, a number average molecular weight of 21,200, and a weight average molecular weight of 60,100.

The polyfluorene-based polymer is shown in Table 1.

"Synthesis of Polysiloxane Polymers" <Synthesis example 12>

In a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, ECS (28.3 g), E1 (4.10 g), E3 (7.45 g), and E5 (32.5 g) were mixed to prepare a solution of an alkoxysilane monomer. In this solution, a solution prepared by mixing ECS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst in advance was dropped at 25 ° C over 30 minutes, and further performed at 25 ° C for 30 minutes. Stir for minutes. After that, the mixture was heated for 30 minutes under reflux using an oil bath, and then a mixed solution of a 92% by mass methanol solution (1.20 g) of E4 and ECS (0.90 g) prepared in advance was added. After further refluxing for 30 minutes, the solution was left to cool to obtain a polysiloxane solution (1) having a SiO ₂ conversion concentration of 12% by mass.

<Synthesis Example 13>

In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, EC (25.4 g), E1 (8.20 g), E3 (19.9 g), and E5 (20.0 g) were mixed to prepare a solution of an alkoxysilane monomer. In this solution, a solution prepared by mixing EC (12.7 g), water (10.8 g), and oxalic acid (1.10 g) as a catalyst in advance was added dropwise at 25 ° C over 30 minutes, and further performed at 25 ° C for 30 minutes. Stir for minutes. After that, the mixture was heated under reflux using an oil bath for 30 minutes, and a mixed solution of a 92% by mass methanol solution (1.20 g) of E4 and EC (0.90 g) prepared in advance was added. After further refluxing for 30 minutes, after leaving to cool, a polysiloxane solution (2) having a SiO ₂ conversion concentration of 12% by mass was obtained.

<Synthesis Example 14>

In a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, ECS (29.2 g), E1 (4.10 g), and E5 (38.8 g) were mixed to prepare a solution of an alkoxysilane monomer. In this solution, a solution prepared by mixing ECS (14.6 g), water (10.8 g), and oxalic acid (0.50 g) as a catalyst in advance was dropped at 25 ° C over 30 minutes, and further performed at 25 ° C for 30 minutes. Stir for minutes. After that, the mixture was heated for 30 minutes under reflux using an oil bath, and a mixed solution of a 92% by mass methanol solution (1.20 g) of E4 and ECS (0.90 g) prepared in advance was added. After further refluxing for 30 minutes, after leaving to cool, a polysiloxane solution (3) having a SiO ₂ conversion concentration of 12% by mass was obtained.

<Synthesis Example 15>

In a 200-ml four-necked reaction flask equipped with a thermometer and a reflux tube, EC (28.3 g), E2 (4.07 g), E3 (7.45 g), and E5 (32.5 g) were mixed to prepare a solution of an alkoxysilane monomer. In this solution, a solution prepared by mixing EC (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst in advance was dropped at 25 ° C over 30 minutes, and further performed at 25 ° C for 30 minutes. Stir for minutes. After that, the mixture was heated for 30 minutes under reflux using an oil bath, and a mixed solution of 92% by mass of a methanol solution (1.20 g) of E4 and EC (0.90 g) prepared in advance was added. After further refluxing for 30 minutes, after leaving to cool, a polysiloxane solution (4) having a SiO ₂ conversion concentration of 12% by mass was obtained.

The polysiloxane polymer (polysiloxane solution) is shown in Table 2.

"Making a Liquid Crystal Composition" (Manufacture of liquid crystal composition (1))

L1 (11.5 g), R1 (1.73 g), and P1 (0.12 g) were mixed, and after heating (100 ° C) and cooling to 25 ° C, a uniform liquid crystal composition (1) showing liquid crystal properties was obtained.

(Manufacture of liquid crystal composition (2))

L1 (12.0g), R1 (2.40g) and P1 (0.12g) were mixed, and after heating this, it cooled to 25 degreeC, and obtained the uniform liquid crystal composition (2) which shows liquid crystallinity.

`` Creating a liquid crystal display element (glass substrate) ''

The liquid crystal alignment treatment agent of the examples or comparative examples described later was subjected to pressure filtration with a membrane filter having a pore diameter of 1 μm to produce a liquid crystal display element. Specifically, the solution is washed with pure water and IPA (isopropyl alcohol). 100 × 100mm glass substrate with ITO electrode (vertical: 100mm, horizontal: 100mm, thickness: 0.7mm) was spin-coated on the ITO surface, on a hot plate at 100 ° C for 2 minutes, and in a thermal cycle type aseptic oven Heat treatment was performed at 210 ° C. for 10 minutes to obtain an ITO substrate with a vertical liquid crystal alignment film with a film thickness of 100 nm. Two pieces of the obtained ITO substrate with a vertical liquid crystal alignment film were prepared, and a spacer of 6 μm was coated on the vertical liquid crystal alignment film surface of the one substrate. Thereafter, the vertical liquid crystal alignment film surface on which the spacer is coated is dropped with the aforementioned liquid crystal composition by an ODF (One Drop Filling) method, and then the vertical liquid crystal alignment film interface of the other substrate is bonded to form an opposite direction to obtain a treatment. Former liquid crystal display element.

Before the obtained liquid crystal display element was processed, a metal halide lamp with an illuminance of 60 mW was used to block a wavelength below 350 nm, and ultraviolet radiation at 7 J / cm ² converted at 365 nm was obtained to obtain a liquid crystal display element. The temperature in the irradiation device when the unit cell was irradiated with ultraviolet rays was controlled at 25 ° C.

`` Creating a liquid crystal display element (plastic substrate) ''

The liquid crystal alignment treatment agent of the examples or comparative examples described later was subjected to pressure filtration with a membrane filter having a pore diameter of 1 μm to produce a liquid crystal display element. Specifically, this solution is an ITO surface of a 150 × 150 mm PET (polyethylene terephthalate) substrate (length: 150 mm, width: 150 mm, thickness: 0.2 mm) with an ITO electrode washed with pure water. The coating was carried out with a bar coater, and heated on a hot plate at 100 ° C for 2 minutes, and in a thermal cycle type aseptic oven at 150 ° C for 1 minute to obtain ITO with a vertical liquid crystal alignment film with a film thickness of 100 nm. Substrate. Prepare 2 pieces An ITO substrate with a vertical liquid crystal alignment film is attached to the surface of the vertical liquid crystal alignment film of the one substrate, and a spacer of 6 μm is applied. Thereafter, the vertical liquid crystal alignment film surface on which the spacer is coated is dripped with the aforementioned liquid crystal composition by the ODF method, and then the vertical liquid crystal alignment film interface of the other substrate is bonded to form an opposite direction to obtain a liquid crystal display element before processing. .

Before the obtained liquid crystal display element was processed, a metal halide lamp with an illuminance of 60 mW was used to block a wavelength below 350 nm, and ultraviolet radiation at 7 J / cm ² converted at 365 nm was obtained to obtain a liquid crystal display element. The temperature in the irradiation device when the unit cell was irradiated with ultraviolet rays was controlled at 25 ° C.

`` Evaluation of liquid crystal alignment (glass substrate) ''

The liquid crystal display element (glass substrate) obtained by the above-mentioned method was used to evaluate liquid crystal alignment. The liquid crystal alignment was observed by a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) to confirm whether the liquid crystal alignment was vertical. Specifically, the liquid crystal alignment is vertical as the excellent one in this evaluation (the good ones are shown in Tables 8 to 12).

The liquid crystal display element (glass substrate) having completed the evaluation of the liquid crystal alignment property was stored in a high-temperature tank at a temperature of 100 ° C for 240 hours. Thereafter, under the same conditions as above, the alignment of the liquid crystal was evaluated. Specifically, those who did not see the liquid crystal alignment disorder and uniformly aligned the liquid crystals were regarded as the excellent ones in this evaluation (the ones shown as good in Tables 8 to 12).

`` Evaluation of liquid crystal alignment (plastic substrate)

Using the liquid crystal display element (plastic substrate) obtained by the above method, Evaluation of liquid crystal alignment. The alignment of the liquid crystal was observed by a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon), and it was confirmed whether the alignment of the liquid crystal was vertical. Specifically, the liquid crystal alignment is vertical as the excellent one in this evaluation (the good ones are shown in Tables 8 to 11).

Next, the liquid crystal display element (plastic substrate) whose evaluation of the liquid crystal alignment was completed was stored in a high-temperature tank at a temperature of 100 ° C for 240 hours. Thereafter, under the same conditions as above, the alignment of the liquid crystal was evaluated. Specifically, those who did not see the liquid crystal alignment disorder and uniformly aligned the liquid crystals were regarded as the excellent ones in this evaluation (the ones shown as good in Tables 8 to 11).

`` Evaluation of optical characteristics (transparency and scattering characteristics) (glass substrate) ''

The liquid crystal display element (glass substrate) obtained by the above method was used to evaluate optical characteristics (transparency and scattering characteristics).

The evaluation of the transparency when no voltage is input is performed by measuring the transmittance of a liquid crystal display element (glass substrate) in a state where no voltage is input. A specific measuring device was UV-3600 (manufactured by Shimadzu Corporation), and the transmittance was measured at a temperature of 25 ° C. as a reference on the glass substrate with an ITO electrode and a scanning wavelength of 300 to 800 nm. The evaluation was performed with a transmittance of a wavelength of 450 nm, and the one with the higher transmittance was regarded as the better of this evaluation (the transmittance values are shown in Tables 13 to 17).

The scattering characteristics at the time of voltage input are that in a liquid crystal display element (glass substrate), 40V is input under AC drive, and the alignment state of the liquid crystal is visually observed. Specifically, those who present this element as white turbidity, those who will soon obtain the scattering characteristics, are regarded as excellent in this evaluation (the ones shown in Tables 13 to 17 are good).

"Evaluation of Optical Properties (Transparency and Scattering Properties) (Plastic Substrate)"

The liquid crystal display element (plastic substrate) obtained by the above method was used to evaluate optical characteristics (transparency and scattering characteristics).

The transparency when no voltage is input is measured by measuring the transmittance of a liquid crystal display element (plastic substrate) in a state where no voltage is input. Specifically, UV-3600 (manufactured by Shimadzu Corporation) was used in the measurement device, and the transmittance was measured at a temperature of 25 ° C. as a reference on a PET substrate with the above-mentioned ITO electrode and a scanning wavelength of 300 to 800 nm. The evaluation was performed at a transmittance of 450 nm, and the one with the higher transmittance was regarded as the better of this evaluation (the transmittance values are shown in Tables 13 to 16).

The scattering characteristics at the time of voltage input are as follows: a liquid crystal display element (plastic substrate) is driven with an AC voltage of 40 V, and the alignment state of the liquid crystal is visually observed. Specifically, those who present this element with white turbidity, that is, those who have obtained the scattering characteristics, are regarded as those who are excellent in this evaluation (the ones shown in Tables 13 to 16 are good).

`` Evaluation of adhesion (adhesion of liquid crystal layer and vertical liquid crystal alignment film) (glass substrate) ''

Using the liquid crystal display element (glass substrate) subjected to the evaluation of the above-mentioned optical characteristics, the adhesion of the liquid crystal layer and the vertical liquid crystal alignment film was evaluated. Specifically, the liquid crystal display element (glass substrate) is kept in a high-temperature and high-humidity tank at a temperature of 80 ° C. and a humidity of 90% RH for 48 hours, and the presence or absence of air bubbles in the element and the peeling of the element are confirmed. At this time, no bubbles were seen in the element, and Those who did not cause peeling of the device (the peeling state of the liquid crystal layer and the vertical liquid crystal alignment film) were regarded as being excellent in this evaluation (goods shown in Tables 13 to 17).

`` Evaluation of adhesion (adhesion of liquid crystal layer and vertical liquid crystal alignment film) (plastic substrate) ''

Using the liquid crystal display element (plastic substrate) subjected to the evaluation of the above-mentioned optical characteristics, the adhesion evaluation of the liquid crystal layer and the vertical liquid crystal alignment film was performed. Specifically, the liquid crystal display element (plastic substrate) is stored in a high-temperature and high-humidity tank at a temperature of 80 ° C. and a humidity of 90% RH for 48 hours, and the presence of air bubbles in the element and the peeling of the element are confirmed. At this time, if no bubbles were seen in the device, and no peeling of the device was caused (the peeling state of the liquid crystal layer and the vertical liquid crystal alignment film), it was regarded as the excellent one in this evaluation (the good ones are shown in Tables 13 to 16).

<Example 1>

To the polyamic acid solution (1) (10.5 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 1, NEP (16.8 g), BCS (16.5 g), S1 (0.263 g), and M2 (0.263 g) were added. ) And K1 (0.132 g), and stirred at 25 ° C. for 5 hours to obtain a liquid crystal alignment treatment agent (1). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (1) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 2>

To the polyamic acid solution (2) (10.0 g) of the resin solid content concentration of 25% by mass obtained in Synthesis Example 2, NMP (16.0 g), BCS (15.7 g), and S2 (0.125 g) were added, and the temperature was 25 ° C. It stirred for 5 hours, and obtained the liquid-crystal aligning agent (2). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using the liquid crystal alignment treatment agent (2) and the liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 3>

Using the liquid crystal alignment treatment agent (2) and the liquid crystal composition (2) obtained in Example 2, production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), and evaluation of optical characteristics (glass substrate) And evaluation of adhesion (glass substrate).

<Example 4>

NMP (16.0 g) and BCS (10.7 g) were added to the polyfluorene imine powder (3) (1.70 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. To this solution, S2 (0.085 g) was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (3). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that it was a uniform solution. recognize.

Using a liquid crystal alignment treatment agent (3) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 5>

Using the liquid crystal alignment treatment agent (3) and the liquid crystal composition (2) obtained in Example 4, production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), and evaluation of optical characteristics (glass substrate) And evaluation of adhesion (glass substrate).

<Example 6>

To the polyfluorene imide powder (3) (1.70 g) obtained in Synthesis Example 3, NEP (16.2 g) and PB (10.8 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. To this solution, S2 (0.085 g), M2 (0.51 g), and K1 (0.17 g) were added, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (4). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (4) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 7>

To the polyfluorene imine powder (3) (1.80 g) obtained in Synthesis Example 3, γ- BL (4.20 g) and PGME (24.0 g) were added, and the mixture was stirred and dissolved at 70 ° C for 24 hours. To this solution, S2 (0.09 g), M2 (0.36 g), and K1 (0.18 g) were added, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (5). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (5) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate, plastic substrate), evaluation of liquid crystal alignment (glass substrate, plastic substrate), and evaluation of optical characteristics ( Glass substrate, plastic substrate), and evaluation of adhesion (glass substrate, plastic substrate).

<Example 8>

NEP (15.1 g), BCS (2.70 g), and PB (9.60 g) were added to the polyfluorene imine powder (4) (1.75 g) obtained in Synthesis Example 4, and stirred at 70 ° C for 24 hours to dissolve it. S1 (0.088 g), M2 (0.35 g), and K1 (0.088 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 (6). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (6) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 9>

Using the liquid crystal alignment treatment agent (6) and the liquid crystal composition (2) obtained in Example 8, the production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), and evaluation of optical characteristics (glass substrate) were performed. And evaluation of adhesion (glass substrate).

<Example 10>

Γ- BL (4.20 g), PGME (21.2 g), and ECS (2.80 g) were added to the polyfluorene imide powder (4) (1.80 g) obtained in Synthesis Example 4, and stirred at 70 ° C for 24 hours to dissolve it. . To this solution, S2 (0.126 g), M2 (0.27 g), and K1 (0.18 g) were added, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (7). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (7) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate, plastic substrate), evaluation of liquid crystal alignment (glass substrate, plastic substrate), and evaluation of optical characteristics ( Glass substrate, plastic substrate), and evaluation of adhesion (glass substrate, plastic substrate).

<Example 11>

Γ- BL (1.30 g), PGME (22.0 g), and EC (2.60 g) were added to the polyfluorene imide powder (4) (1.65 g) obtained in Synthesis Example 4, and stirred at 70 ° C for 24 hours to dissolve it. . To this solution, S2 (0.083 g) and M2 (0.33 g) were added, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (8). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (8) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 12>

Γ- BL (2.80 g), PGME (24.0 g), and EC (2.60 g) were added to the polyfluorene imide powder (5) (1.80 g) obtained in Synthesis Example 5, and stirred at 70 ° C for 24 hours to dissolve it. . To this solution, S2 (0.27 g) and K1 (0.27 g) were added, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (9). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Production of liquid crystal display elements (glass substrates, plastic substrates), evaluation of liquid crystal alignment (glass substrates, plastic substrates), and evaluation of optical characteristics using a liquid crystal alignment treatment agent (9) and a liquid crystal composition (2) ( Glass substrate, plastic substrate), and evaluation of adhesion (glass substrate, plastic substrate).

<Example 13>

NMP (16.9 g), BCS (5.60 g), and PB (5.60 g) were added to the polyimide powder (5) (1.80 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. To this solution, S2 (0.018 g) and M3 (0.09 g) were added, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (10). No turbidity or precipitation was observed in the liquid crystal alignment treatment agent. Often, the results were confirmed as a homogeneous solution.

Using a liquid crystal alignment treatment agent (10) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 14>

To the polyfluorene imide powder (5) (1.80 g) obtained in Synthesis Example 5, γ- BL (2.80 g) and PGME (25.4 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. S1 (0.09 g), M2 (0.54 g), and K1 (0.09 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). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (11) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 15>

NMP (16.5 g) and PB (11.0 g) were added to the polyfluorene imide powder (5) (1.75 g) obtained in Synthesis Example 5, and the mixture was stirred and dissolved at 70 ° C for 24 hours. To this solution, S1 (0.263 g) and M1 (0.70 g) were added, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (12). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution. The result of the liquid was confirmed.

Using a liquid crystal alignment treatment agent (12) and a liquid crystal composition (2), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 16>

Γ- BL (5.60 g), PGME (19.7 g), and ECS (2.80 g) were added to the polyimide powder (6) (1.80 g) obtained in Synthesis Example 6, and stirred at 70 ° C for 24 hours to dissolve it. . S1 (0.126 g), M2 (0.54 g), and K1 (0.09 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). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (13) and a liquid crystal composition (2), production of a liquid crystal display element (glass substrate, plastic substrate), evaluation of liquid crystal alignment (glass substrate, plastic substrate), and evaluation of optical characteristics ( Glass substrate, plastic substrate), and evaluation of adhesion (glass substrate, plastic substrate).

<Example 17>

Γ- BL (2.80 g), PGME (22.6 g), and EC (2.80 g) were added to the polyfluorene imide powder (6) (1.80 g) obtained in Synthesis Example 6, and stirred at 70 ° C for 24 hours to dissolve it. . To this solution, S2 (0.09 g), M2 (0.27 g), and K1 (0.09 g) were added, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (14). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (14) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate, plastic substrate), evaluation of liquid crystal alignment (glass substrate, plastic substrate), and evaluation of optical characteristics ( Glass substrate, plastic substrate), and evaluation of adhesion (glass substrate, plastic substrate).

<Example 18>

NEP (16.8 g) and PB (9.00 g) were added to the polyfluorene imide powder (6) (1.65 g) obtained in Synthesis Example 6, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. To this solution, S2 (0.017 g) and M3 (0.248 g) were added, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (15). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (15) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 19>

To the polyfluorene imine powder (7) (1.70 g) obtained in Synthesis Example 7, γ- BL (6.70 g) and PGME (20.0 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. S1 (0.34 g) and M2 (0.255 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). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (16) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 20>

Γ-BL (6.70 g) and PGME (20.0 g) were added to the polyfluorene imide powder (7) (1.70 g) obtained in Synthesis Example 7, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. To this solution, S2 (0.051 g), M1 (0.425 g), and K1 (0.085 g) were added, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (17). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (17) and a liquid crystal composition (2), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 21>

NEP (16.0 g) and PB (10.7 g) were added to the polyimide powder (8) (1.70 g) obtained in Synthesis Example 8, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. To this solution, S2 (0.085 g) was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (18). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that it was a uniform solution. recognize.

Using a liquid crystal alignment treatment agent (18) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 22>

Γ-BL (2.80 g), PGME (22.6 g), and ECS (2.80 g) were added to the polyfluorene imide powder (8) (1.80 g) obtained in Synthesis Example 8, and stirred at 70 ° C for 24 hours to dissolve it. . To this solution, S2 (0.126 g), M2 (0.54 g), and K1 (0.18 g) were added, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (19). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Production of liquid crystal display elements (glass substrate, plastic substrate), evaluation of liquid crystal alignment (glass substrate, plastic substrate), and evaluation of optical characteristics using liquid crystal alignment treatment agent (19) and liquid crystal composition (1) ( Glass substrate, plastic substrate), and evaluation of adhesion (glass substrate, plastic substrate).

<Example 23>

NEP (16.5 g), BCS (5.50 g), and PB (5.50 g) were added to the polyimide powder (8) (1.75 g) obtained in Synthesis Example 8, and the mixture was stirred at 70 ° C. for 24 hours and dissolved. S1 (0.088g), M2 (0.35g), and K1 (0.088g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain liquid crystal alignment. Treatment agent (20). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (20) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 24>

NEP (14.6 g) and BCS (12.0 g) were added to the polyimide powder (9) (1.70 g) obtained in Synthesis Example 9, and the mixture was stirred at 70 ° C. for 24 hours to be dissolved. S2 (0.17 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (21). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (21) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 25>

Γ-BL (1.30 g), PGME (24.0 g), and EC (1.30 g) were added to the polyfluorene imine powder (9) (1.70 g) obtained in Synthesis Example 9, and stirred at 70 ° C for 24 hours to dissolve . S1 (0.085g), M2 (0.51g), and K1 (0.17g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment portion. Physiological agent (22). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (22) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 26>

ECS (10.8g), BCS (4.20g), and S2 (0.09g) were added to the polysiloxane solution (1) (15.0g) obtained in Synthesis Example 12, and stirred at 25 ° C for 5 hours to obtain a liquid crystal alignment treatment.剂 (23). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Production of liquid crystal display elements (glass substrate, plastic substrate), evaluation of liquid crystal alignment (glass substrate, plastic substrate), and evaluation of optical characteristics using a liquid crystal alignment treatment agent (23) and a liquid crystal composition (1) ( Glass substrate, plastic substrate), and evaluation of adhesion (glass substrate, plastic substrate).

<Example 27>

Using the liquid crystal alignment treatment agent (23) and the liquid crystal composition (2) obtained in Example 26, production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), and evaluation of optical characteristics (glass substrate) were performed. And evaluation of adhesion (glass substrate).

<Example 28>

EC (3.70g), PB (11.3g), and S2 (0.09g) were added to the polysiloxane solution (2) (15.0g) obtained in Synthesis Example 13, and stirred at 25 ° C for 5 hours to obtain a liquid crystal alignment treatment.剂 (24). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (24) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 29>

Using the liquid crystal alignment treatment agent (24) and the liquid crystal composition (2) obtained in Example 28, production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), and evaluation of optical characteristics (glass substrate) were performed. And evaluation of adhesion (glass substrate).

<Example 30>

To the polysiloxane solution (3) (16.0 g) obtained in Synthesis Example 14, ECS (13.0 g), PB (3.00 g), S2 (0.192 g), and M2 (0.384 g) were added, and the reaction was performed at 25 ° C for 5 minutes. After stirring for hours, a liquid crystal alignment treatment agent (25) was obtained. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Liquid crystal alignment treatment agent (25) and liquid crystal composition (2) Production of display elements (glass substrate, plastic substrate), evaluation of liquid crystal alignment (glass substrate, plastic substrate), evaluation of optical characteristics (glass substrate, plastic substrate), and evaluation of adhesion (glass substrate, Plastic substrate).

<Example 31>

To the polysiloxane solution (3) (15.0 g) obtained in Synthesis Example 14, ECS (6.50 g), PGME (2.80 g), BCS (5.60 g), S1 (0.09 g), and M2 (0.54 g) were added. After stirring at 25 ° C for 5 hours, a liquid crystal alignment treatment agent (26) was obtained. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (26) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Example 32>

To the polysiloxane solution (4) (15.0 g) obtained in Synthesis Example 15 were added EC (9.40 g), BCS (5.60 g), S1 (0.018 g), and M2 (0.18 g), and the reaction was performed at 25 ° C for 5 hours. By stirring, a liquid crystal alignment treatment agent (27) was obtained. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (27) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass-based board).

<Comparative example 1>

NMP (16.8g) and BCS (16.5g) were added to the polyamic acid solution (10) (10.5g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 10, and stirred at 25 ° C for 5 hours to obtain Liquid crystal alignment treatment agent (28). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (28) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Comparative example 2>

NMP (14.1 g) and BCS (9.40 g) were added to the polyfluorene imine powder (11) (1.50 g) obtained in Synthesis Example 11 and stirred at 70 ° C. for 24 hours to obtain a liquid crystal alignment treatment agent (29). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (29) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Comparative example 3>

NMP (16.0 g) and BCS (15.7 g) were added to the polyamic acid solution (2) (10.0 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2, and stirred at 25 ° C for 5 hours to obtain Liquid crystal alignment treatment agent (30). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (30) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Comparative Example 4>

Using the liquid crystal alignment treatment agent (30) and liquid crystal composition (2) obtained in Comparative Example 3, production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), and evaluation of optical characteristics (glass substrate) And evaluation of adhesion (glass substrate).

<Comparative example 5>

NMP (14.1 g) and BCS (9.40 g) were added to the polyfluorene imine 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 (31). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (31) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass-based board).

<Comparative Example 6>

Using the liquid crystal alignment treatment agent (31) and the liquid crystal composition (2) obtained in Comparative Example 5, production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), and evaluation of optical characteristics (glass substrate) And evaluation of adhesion (glass substrate).

<Comparative Example 7>

EC (9.40 g) and PB (11.3 g) were added to the polysiloxane solution (2) (15.0 g) obtained in Synthesis Example 13, and stirred at 25 ° C for 5 hours to obtain a liquid crystal alignment treatment agent (32). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the result was confirmed to be a uniform solution.

Using a liquid crystal alignment treatment agent (32) and a liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical characteristics (glass substrate), and adhesion Evaluation (glass substrate).

<Comparative Example 8>

Using the liquid crystal alignment treatment agent (32) and the liquid crystal composition (2) obtained in Comparative Example 7, production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), and evaluation of optical characteristics (glass substrate) And evaluation of adhesion (glass substrate).

* 1: The liquid crystal is not aligned vertically.

* 2: Seeing disordered LCD alignment.

* 3: Since the liquid crystal is not aligned vertically, it cannot be measured.

* 4: The liquid crystal layer of the device is peeled from the vertical liquid crystal alignment film.

* 5: Bubbles were seen inside the device.

From the above results, it is known that compared with the liquid crystal display element of the comparative example, the liquid crystal display element of the example has a higher adhesion between the liquid crystal layer and the vertical liquid crystal alignment film, and the liquid crystal has a higher vertical alignment property, which is good. Optical characteristics, that is, transparency when no voltage is input and scattering characteristics when the voltage is input are good.

On the other hand, the liquid crystal display element of the comparative example has poor adhesion between the liquid crystal layer and the vertical alignment film. After storage in a high-temperature tank, the alignment of the liquid crystal is disturbed, or after storage in a high-temperature and high-humidity tank, it is not visible in the element. To bubbles, or peeling between the liquid crystal layer and the vertical alignment film.

Specifically, examples using the same specific polymer and a radical generator containing the component (B) and comparative examples not containing the same, that is, Example 2 and Comparative Example 3, Example 3 and Comparative Example 4, and Example 4 In comparison with Comparative Example 5, Example 5 and Comparative Example 6, Example 28 and Comparative Example 7, and Example 29 and Comparative Example 8, no clear difference was confirmed.

[Industrial availability]

The liquid crystal display element of the present invention has high adhesion between the liquid crystal layer and the vertical liquid crystal alignment film, and the vertical alignment of the liquid crystal is also high. It has good optical characteristics, that is, transparency when voltage is not input and scattering when voltage is input. The characteristic is good, and it can be applied to the reverse type element.

It is particularly useful as a liquid crystal display for display purposes, a dimming window or a shutter element that controls the transmission and blocking of light. When the element is made of a plastic substrate such as a thin film substrate, it can be placed on the glass or window of a support. Glass.

Moreover, the entire contents of the specification, the scope of the patent application, and the abstract of Japanese Patent Application No. 2013-085918 filed on April 16, 2013 are cited in the specification of this case.

Claims (15)

A liquid crystal display element having a liquid crystal layer between a pair of substrates having electrodes, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat between the pair of substrates, At least one of the substrates further includes a liquid crystal alignment film that vertically aligns the liquid crystal. The liquid crystal composition is cured in a state where part or all of the liquid crystal composition exhibits liquid crystallinity to form a cured composite of liquid crystal and a polymerizable compound. The obtained liquid crystal display element is characterized in that the liquid crystal alignment film is a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing the following (A) component and (B) component; (A) component: having a component selected from the following The polymer (B) component of at least one structure grouped by the structures represented by the formulas [1-1] and [1-2]: selected from the group consisting of a photoradical generator, a photoacid generator, and a photobase generator Clusters of at least 1 generator (Y ¹ represents at least one selected from the group consisting of a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, -COO-, and -OCO-. Binding group; 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-, and -OCO-; at least one type of binding group; Y ⁴ represents at least one type selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring; A bivalent cyclic group or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton. Any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms. 1, 1 to 3 carbon-containing fluoroalkyl groups, 1 to 3 carbon-containing fluoroalkoxy groups or fluorine atoms; Y ⁵ represents a divalent group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring Cyclic groups. Any hydrogen atom on these cyclic groups can be 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, Substituted by a fluorine-containing alkoxy group or a fluorine atom; n represents an integer from 0 to 4; Y ⁶ represents an alkyl group selected from a carbon group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, Alkoxy group and fluorine-containing alkoxy group having 1 to 18 carbon atoms of at least 1 ) [Chem ^{2] -Y 7 -Y 8 [1-2} ] (Y 7 represents a single bond _{selected, -O -, - CH 2 O} -, - CONH -, - NHCO -, - CON (CH 3) - , -N (CH ₃ ) CO-, -COO-, and -OCO-, at least one type of bonding group; 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 according to claim 1, wherein the polymer of the component (A) is selected from the group consisting of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, and polyimide At least one of amines, polyamines, polyesters, celluloses, and polysiloxanes. The liquid crystal display element of claim 2, wherein the polymer is at least one selected from the group consisting of the following polyimide precursors and polyimide, and the polyimide precursor is selected from the group consisting of [1-1] Polyamines having a side chain diamine compound having a structure of [1-1] and at least one type of diamine compound having a side chain diamine compound having a structure of formula [1-2] Imine precursor. The liquid crystal display element according to claim 3, wherein the diamine compound is a diamine compound represented by the following formula [1a]; (Y represents at least one selected from the group consisting of the structures represented by the formulas [1-1] and [1-2]; n represents an integer of 1 to 4). The liquid crystal display device according to any one of claims 2 to 4, wherein the polymer of the component (A) is selected from polyimide obtained by using a tetracarboxylic acid component represented by the following formula [3] as a part of a raw material. At least one of the groups of precursors and polyimide; (Z ¹ represents a structure selected from the following formulae [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 represent a hydrogen atom or a methyl group, and each may be the same or different). The liquid crystal display device according to claim 3 or 4, wherein the polymer is polyimide. The liquid crystal display element of claim 2, wherein the polymer of the component (A) is a polysiloxane obtained by polycondensing an alkoxysilane represented by the following formula [A1], or a polycondensation formula [A1] and A polysiloxane obtained from at least one type of alkoxysilane grouped by alkoxysilanes represented by the following formulae [A2] and [A3]; [Chem. 6] (A ¹ ) _m Si (A ² ) _n (OA ³ ) _p [A1] (A ¹ represents at least ^one selected from the group consisting of the structures represented by the aforementioned formulas [1-1] and [1-2]; each of A ² represents a hydrogen atom or a carbon number 1 to 5 alkyl groups; A ³ each represents an alkyl group having 1 to 5 carbon atoms; m represents an integer of 1 or 2; n represents an integer of 0 to 2; p represents an integer of 0 to 3; but m + n + p 4) [Chem. 7] (B ¹ ) _m Si (B ² ) _n (OB ³ ) _p [A2] (B ¹ each has a group selected from the group consisting of vinyl, epoxy, amine, mercapto, isocyanate, methyl At least one organic group of 2 to 12 carbons in which at least one of the groups allyl propylene fluorenyl, propylene fluorenyl, ureido, and cinnamyl; B ² each represents a hydrogen atom or an alkyl group having 1 to 5 carbons; B ³ each Represents an alkyl group having 1 to 5 carbon atoms; m represents an integer of 1 or 2; n represents an integer of 0 to 2; p represents an integer of 0 to 3; but m + n + p is 4) [Chem. 8] (D ¹ ) _n Si (OD ² ) _4-n [A3] (D ¹ each represents a hydrogen atom or an alkyl group having 1 to 5 carbons; D ² represents an alkyl group having 1 to 5 carbons; n represents an integer of 0 to 3). The liquid crystal display element according to any one of claims 1 to 4, wherein the generator of the component (B) is a photo radical generator. The liquid crystal display element according to any one of claims 1 to 4, wherein the liquid crystal alignment treatment agent contains one selected from 1-hexanol, cyclohexanol, 1,2-ethanediol, and 1,2-propanedi Alcohol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, solvents represented by the following formula [D1], [D2], and [D3] Grouped at least 1 solvent; (D ¹ represents an alkyl group having 1 to 3 carbon atoms; D ² represents an alkyl group having 1 to 3 carbon atoms; D ³ represents an alkyl group having 1 to 4 carbon atoms). The liquid crystal display device according to any one of claims 1 to 4, wherein the liquid crystal alignment treatment agent contains a material selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone. Clusters of at least 1 solvent. The liquid crystal display element according to any one of claims 1 to 4, wherein the liquid crystal alignment treatment agent contains at least one selected from the group consisting of a compound having a structure represented by the following formulae [B1] to [B7]. Compound (W ¹ represents a hydrogen atom or a benzene ring; W ² represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring; w ³ represents an alkyl group having 1 to 18 carbon atoms, and 1 to ³ carbon atoms. At least one group consisting of a fluorine-containing alkyl group of 18, an alkoxy group having 1 to 18 carbon atoms, and a fluorine-containing alkoxy group having 1 to 18 carbon atoms). The liquid crystal display element according to any one of claims 1 to 4, wherein the substrate of the liquid crystal display element is a glass substrate or a plastic substrate. A liquid crystal alignment film characterized by being used in a liquid crystal display element according to any one of claims 1 to 12. For example, the liquid crystal liquid crystal alignment film of claim 13, wherein the film thickness is 5 to 300 nm. A liquid crystal alignment treatment agent characterized by using a liquid crystal alignment film as claimed in claim 13 or 14.