TW201627485A - LCD element - Google Patents

Abstract

Provided is an LCD element having excellent liquid crystal vertical alignment properties, good transparency when voltage is applied and good scattering properties when voltage is not applied, and good adhesion with the liquid crystal layer. The LCD element comprises a liquid crystal layer formed by curing a liquid crystal composition by irradiation with UV light, the liquid crystal composition comprising liquid crystals and a polymerizable compound and being disposed between a pair of substrates having electrodes. At least one of the substrates has a liquid crystal alignment film that vertically aligns the liquid crystals, the liquid crystal composition contains a compound represented by formula [1], and the liquid crystal alignment film is obtained from a liquid crystal alignment agent comprising a polymer having a side chain structure represented by formula [2-1] or formula [2-2]. (X1: formula [1-a] - formula [1-g], etc.; X2, X3, X4 and X6: single bond, etc.; X5 and X7: benzene ring, etc.; X8: C1-18 alkyl group, etc.) (XA: H, etc.; XB: benzene ring, etc.; XC: C1-18 alkyl group) (Y1, Y2 and Y3: single bond, etc.; Y4 and Y5: benzene ring, etc.; Y6: C1-18 alkyl group, etc.) (Y7: single bond, etc.; Y8: C8-22 alkyl group, etc.).

Description

Liquid crystal display element

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

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

A liquid crystal display element which is not used with a polarizing plate and has high light utilization efficiency is a liquid crystal display element which is switched between a liquid crystal transmission state (also referred to as a transparent state) and a scattering state, and is generally known to have high use. Molecularly dispersed liquid crystal (also known as PDLC (Polymer Dispersed Liquid Crystal)) or polymer network liquid crystal (PNLC (Polymer Network Liquid Crystal)).

A liquid crystal display element using such a liquid crystal layer is provided between one of the electrodes, and a package is disposed between the pair of substrates. A liquid crystal composition containing a polymerizable compound polymerized by ultraviolet rays is cured by ultraviolet rays to form a liquid crystal layer, that is, a cured product of a liquid crystal and a polymerizable compound (for example, a polymer network) ) The liquid crystal display element. The liquid crystal display element regulates the transmission state and the scattering state of the liquid crystal by application of a voltage.

In the liquid crystal display device of the conventional PDLC or PNLC, when the liquid crystal molecules are applied in a random direction, the liquid crystal molecules are in a white turbid (scattering) state, and when the voltage is applied, the liquid crystals are arranged in the electrical direction, and the transmitted light is transmitted. Liquid crystal display elements (also known as standard type elements). However, in order to obtain a transmission state, in order to obtain a transmission state, it is necessary to apply a constant voltage, and it is often used in a transparent state, for example, in the case of use of a window glass, etc., resulting in a large consumption of electric power.

In addition, it is proposed to use a liquid crystal display element (also referred to as a reverse type element) which is a PDLC in a scattering state when a voltage is applied (see, for example, Patent Document 1 or Patent Document 2).

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 2885116

Patent Document 2: Japanese Patent No. 4132424

The polymerizable compound in the liquid crystal composition of the inversion type element is formed into a polymer network, and has a function of obtaining a desired optical property, and as a liquid crystal layer and a liquid crystal alignment film (also referred to as a vertical liquid crystal alignment film). The function of the adhesion hardener. In order to improve the adhesion to the liquid crystal alignment film, the polymer network must be made more tight, but when the polymer network becomes tight, the vertical alignment of the liquid crystal is hindered, and the optical characteristics of the inverted element are also Even if there is no problem when the voltage is applied, the transparency and the scattering characteristics at the time of voltage application are deteriorated. Therefore, the liquid crystal composition used for the inversion type element is required to have a high vertical alignment of the liquid crystal when the liquid crystal layer is formed.

Further, in the liquid crystal alignment film used for the inversion type element, in order to vertically align the liquid crystal, since it is a film having high hydrophobicity, there is a problem that the adhesion between the liquid crystal layer and the liquid crystal alignment film is lowered. Therefore, in the liquid crystal composition used for the inversion type element, a polymerizable compound having a hardener function must be introduced in a large amount. However, when a polymerizable compound is introduced in a large amount, the vertical alignment property of the liquid crystal is inhibited, so that there is a problem that the transparency at the time of voltage application and the scattering property at the time of voltage application are drastically reduced. Therefore, the liquid crystal alignment film used for the inversion type element is required to have a high vertical alignment property of the liquid crystal.

The present invention provides a liquid crystal having high vertical alignment property and good optical characteristics, that is, transparency when no voltage is applied and scattering characteristics when voltage is applied, and the adhesion between the liquid crystal layer and the liquid crystal alignment film is high. The liquid crystal display element serves the purpose.

The present inventors have attained the present invention in an effort to achieve the above object.

That is, the present invention is a liquid crystal display device comprising a liquid crystal layer in which a liquid crystal composition containing a liquid crystal and a polymerizable compound is disposed between one of the electrodes and the substrate is irradiated with ultraviolet rays, and at least one of the substrates is provided. A liquid crystal display device comprising a liquid crystal alignment film that vertically aligns liquid crystals, wherein the liquid crystal composition contains a compound represented by the following formula [1], and the liquid crystal alignment film is a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent. The liquid crystal alignment treatment agent contains a polymer having a side chain structure represented by the following formula [2-1] or formula [2-2],

(X ¹ represents at least one selected from the group consisting of the following formulas [1-a] to [1-g]. X ² represents a group selected from a single bond, -O-, -NH-, a group of -N(CH ₃ )-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO-, and -OCO- a binding group of at least one of the group. X ³ represents a single bond or -(CH ₂ ) _a - (a is an integer from 1 to 15). X ⁴ represents a group selected from a single bond, -O-, -OCH ₂ - , -COO- and -OCO- group consisting of at least one of the binding group .X ⁵ represents a benzene ring, a cyclohexane ring, or a steroid skeleton having a carbon number of 17 to 51 of the divalent organic group, said benzene Any hydrogen atom on the ring or cyclohexane ring group, which may 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, and a carbon number of 1 to 3 a fluorine-containing alkoxy group or a fluorine atom. The X ⁶ group represents at least one selected from the group consisting of a single bond, -O-, -OCH ₂ -, -CH ₂ O-, -COO-, and -OCO-. A bonding group. X ⁷ represents a benzene ring or a cyclohexane ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. Fluorinated alkyl group having 1 to 3 carbon atoms and fluorine having 1 to 3 carbon atoms Group or a fluorine atom substituted .p integer of 0 to 4 .X ⁸ are diagrams of selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, the carbon number of fluorine-containing alkyl group, having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 of the And at least one of the group consisting of fluoroalkoxy groups having 1 to 18 carbon atoms.

(X ^A represents a hydrogen atom or a benzene ring. X ^B represents a cyclic group selected from at least one selected from the group consisting of a benzene ring, a cyclohexane ring, and a hetero ring. X ^c represents a carbon number selected from carbon At least one of a group consisting of an alkyl group of ~18, 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.

(Y ¹ and Y ³ are each independently represented by a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, and -OCO- a binding group of at least one of the groups. Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15). Y ⁴ represents a ring selected from a benzene ring, a cyclohexane ring, and a hetero ring. a divalent cyclic group of at least one of the groups consisting of rings, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, and any hydrogen atom on the cyclic group may be 1 to 3 carbon atoms An alkyl group, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and Y ⁵ is selected from a benzene ring. a cyclic group of at least one of a group consisting of a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms and a carbon number of 1 to 3 An alkoxy group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, wherein n represents an integer of 0 to 4. Y ⁶ represents a group selected from carbon numbers 1 to 18. At least one of a group consisting of an alkyl group, 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.

[化4]-Y ⁷ -Y ⁸ [2-2]

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

According to the present invention, it is possible to provide an inverted element having excellent optical characteristics, that is, transparency when voltage is not applied and scattering characteristics at the time of voltage application, and high adhesion between the liquid crystal layer and the liquid crystal alignment film. According to the present invention, the mechanism for obtaining a liquid crystal display element having the above-described excellent characteristics, although not necessarily clear, is almost as estimated below.

The liquid crystal composition used in the present invention contains a liquid crystal, a polymerizable compound, and a compound represented by the above formula [1]. The specific compound represented by the formula [1] has a site of a rigid structure called a benzene ring or a cyclohexane ring, and a site where a polymerization reaction is carried out by ultraviolet rays represented by X ¹ in the formula [1]. Therefore, when the specific compound is contained in the liquid crystal composition, the vertical alignment of the liquid crystal is improved by the rigid structure of the specific compound, and the polymerization reaction is carried out at the site where the polymerization reaction is carried out, thereby improving the vertical alignment of the liquid crystal. Stability. Therefore, in order to improve the adhesion to the liquid crystal alignment film, even when the polymer network is tight, an inverted element which exhibits good optical characteristics without hindering the vertical alignment of the liquid crystal can be obtained.

In addition, the liquid crystal alignment film used in the present invention is obtained from a liquid crystal alignment treatment agent containing a polymer having a side chain structure represented by the above formula [2-1] or formula [2-2]. In particular, since the specific side chain structure represented by the formula [2-1] shows a rigid structure, the liquid crystal display element having the liquid crystal alignment film having the side chain structure can obtain a vertical alignment property of a high and stable liquid crystal. because Therefore, in particular, in the case of using the specific side chain structure represented by the formula [2-1], an inversion type element which exhibits good optical characteristics is obtained.

Further, the liquid crystal display element comprising the liquid crystal alignment film obtained from the liquid crystal composition of the present invention and the liquid crystal alignment treatment agent having a specific polymer having a specific side chain structure has good optical characteristics, that is, no voltage application. The transparency at the time and the scattering property at the time of voltage application are good, and further, the inversion type element having high adhesion between the liquid crystal layer and the liquid crystal alignment film is obtained.

<Liquid crystal display element>

The liquid crystal display device of the present invention is provided with a liquid crystal composition containing a liquid crystal and a polymerizable compound between a pair of electrodes, and a liquid crystal layer having a liquid crystal layer which is cured by irradiation with ultraviolet rays by an ultraviolet irradiation device. Further, at least one of the substrates is a liquid crystal display element having a liquid crystal alignment film in which liquid crystals are vertically aligned, and is suitable for use as a transmissive state when no voltage is applied, and as an inversion type element which is in a scattering state when voltage is applied.

The liquid crystal composition of the present invention contains a polymerizable compound which is polymerized by a liquid crystal and ultraviolet rays, and this polymerizable compound functions as a polymer network (curable resin). Further, the above-mentioned cured product of a liquid crystal layer-based liquid crystal and a polymerizable compound, and the above-mentioned cured product composite, as described above, means that, for example, liquid crystal exists in a polymer network formed by a polymerizable compound. status.

<specific compound ‧ liquid crystal composition>

The liquid crystal composition of the present invention contains a liquid crystal composition of a liquid crystal, a polymerizable compound, and a specific compound represented by the following formula [1].

The specific compound is a compound represented by the following formula [1].

In the formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and p are as defined above, but each of them is preferably the following.

From the viewpoint of the optical characteristics of the liquid crystal display element, X ^{I is} preferably the above formula [1-a], formula [1-b], formula [1-c] or formula [1-e]. More preferably, it is a formula [1-a], a formula [1-b] or a formula [1-c].

X ^{2 is} preferably a single bond, -O-, -CH ₂ O-, -CONH-, -COO- or -OCO- from the viewpoint of availability of a raw material or ease of synthesis. More preferably, it is a single bond, -O-, -COO- or -OCO-. X ^{3 is} preferably a single bond or -(CH ₂ ) _a - (a is an integer of 1 to 10). More preferably _{- (CH 2) a - (} a is an integer of 1 to 10). X ^{4 is} preferably a single bond, -O- or -COO- from the viewpoint of availability of a raw material or ease of synthesis. More preferably -O-.

X ^{5 is} preferably a benzene ring or a cyclohexane ring or a divalent organic group having a carbon number of 17 to 51 having a steroid skeleton, from the viewpoint of optical characteristics of the liquid crystal display element. More preferably, it is a benzene ring or a divalent organic group having a carbon number of 17 to 51 having a steroid skeleton. X ^{6 is} preferably a single bond, -O-, -COO- or -OCO- from the viewpoint of easiness of synthesis. More preferably a single bond, -COO- or -OCO-.

X ^{7 is} preferably a benzene ring or a cyclohexane ring from the viewpoint of optical characteristics of the liquid crystal display element. X ^{8 is} preferably an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms from the viewpoint of optical characteristics of the liquid crystal display element. More preferably, it is an alkyl group having 1 to 12 carbon atoms. p is preferably an integer of 0 to 2 from the viewpoint of availability of raw materials or ease of synthesis.

Preferred combinations of X ¹ to X ⁸ and p in the formula [1] are shown in Tables 1 to 9 below.

Among them, from the viewpoint of optical characteristics of the liquid crystal display element, it is preferably (1-1a) to (1-12a), (1-13a), (1-14a), (1-17a), (1- 18a), (1-21a), (1-22a), (1-25a)~(1-38a), (1-41a), (1-42a), (1-45a), (1-46a) , a combination of (1-49a)~(1-96a) or (1-121a)~(1-130a).

More preferably (1-1a)~(1-4a), (1-9a), (1-12a), (1-25a)~(1-28a), (1-33a), (1-36a) , (1-49a)~(1-52a), (1-61a)~(1-64a), (1-85a)~(1-88a), (1-121a), (1-122a), ( A combination of 1-125a) or (1-126a).

Particularly preferred are (1-3a), (1-4a), (1-9a), (1-10a), (1-27a), (1-28a), (1-33a), (1-34a) , (1-49a)~(1-52a), (1-61a)~(1-64a), (1-85a)~(1-88a), (1-121a), (1-122a), ( A combination of 1-125a) or (1-126a).

Specific examples of the specific compound include a compound represented by the following formula [1a-1] to formula [1a-6], and it is preferred to use these.

In the formula [1a-1] to the formula [1a-6], X ^a ~ X ^k and p1 to p9 are as defined above, but each of them is preferably the following.

From the point of view of the optical characteristics of the liquid crystal display element, X ^a , X ^b , X ^d , X ^f , X ^h and X ^{k are} preferably independently an alkyl group having 1 to 12 carbon atoms or a carbon number of 1 to 12 Alkoxy group. More preferably, it is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. From the viewpoint of the availability of the raw material or the ease of synthesis, X ^c and X ^{i are} preferably independently -O- or -COO-, respectively. From the viewpoint of the availability of raw materials or the ease of synthesis, X ^e , X ^g and X ^{j are} preferably independently -COO- or -COO-, respectively. Preferably, p1, p3, p5, p7, p8 and p9 are each independently an integer from 1 to 10. More preferably, it is an integer of 1 to 8 from the viewpoint of optical characteristics of the liquid crystal display element. Preferably, p2, p4 and p6 are each independently an integer of 1 or 2.

The use ratio of the specific compound in the liquid crystal composition is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the total of the liquid crystal and the polymerizable compound from the viewpoint of the optical characteristics of the liquid crystal display device. More preferably, it is 0.5 to 15 parts by mass, and particularly preferably 1 to 10 parts by mass.

Moreover, these specific compounds may be used in combination of one type or two types or more depending on the optical characteristics of the liquid crystal display element or the adhesion between the liquid crystal layer and the liquid crystal alignment film.

In the liquid crystal in the liquid crystal composition, nematic liquid crystal, smectic liquid crystals or cholesteric liquid crystal can be used. Among them, those having a negative dielectric anisotropy are preferred. Further, 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. Further, in view of the respective physical property values of the phase transition temperature, the dielectric anisotropy, and the refractive index anisotropy, two or more types of liquid crystals can be used in combination.

In order to drive a liquid crystal display element as an active element such as a TFT (Thin Film Transistor), the liquid crystal resistance is high and electric The pressure retention rate (also known as VHR) is high. Therefore, in the liquid crystal, it is preferable to use a fluorine-based or chlorine-based liquid crystal which does not lower the VHR by using an active energy ray such as ultraviolet rays.

Further, in the liquid crystal display device, a dichroic dye may be dissolved in the liquid crystal composition to form a guest host element. In this case, it is transparent when no voltage is applied, and becomes an element that absorbs (scatters) when a voltage is applied. Further, in this liquid crystal display device, the direction of the director of the liquid crystal (direction of alignment) is changed by 90 degrees due to the presence or absence of voltage application. Therefore, this liquid crystal display element is highly contrasted with the conventional guest type element which is switched in the random alignment and the vertical alignment by utilizing the difference in the light absorption characteristics of the dichroic dye. Further, the guest-type element in which the dichroic dye is dissolved is colored when the liquid crystal alignment is horizontal, and becomes opaque only in the scattering state. Therefore, as voltage is applied, an element that switches from a colorless transparent when no voltage is applied to a colored opaque, colored transparent state can be obtained.

The polymerizable compound in the liquid crystal composition may be a cured product of a liquid crystal composition (for example, a polymer network) by a polymerization reaction by ultraviolet rays, that is, a liquid crystal layer may be formed. In this case, a monomer of the polymerizable compound may be introduced into the liquid crystal composition, or a polymer which can polymerize the monomer in advance may be introduced into the liquid crystal composition. However, even in the case of a polymer, it is necessary to have a site where polymerization is carried out by ultraviolet rays. More preferably, the liquid crystal composition is operated, that is, from the viewpoint of suppressing the high viscosity of the liquid crystal composition or the solubility to the liquid crystal, it is preferred to introduce a monomer into the liquid crystal composition and to produce the liquid crystal display element. Purple Irradiation of the external line, a method of causing polymerization to form a cured product.

The polymerizable compound is preferably a compound dissolved in a liquid crystal. However, when the polymerizable compound is dissolved in the liquid crystal, it is preferred that a part or the whole of the liquid crystal composition has a temperature at which the liquid crystal phase is displayed. Even if a part of the liquid crystal composition exhibits a liquid crystal phase, it is preferable to visually confirm that the liquid crystal element has almost the same transparency and scattering characteristics.

The polymerizable compound may be a compound which is subjected to a polymerization reaction by ultraviolet rays. In this case, it may be polymerized in a reaction form to form a cured product of a liquid crystal composition. Specific reaction forms include radical polymerization, cationic polymerization, anionic polymerization, or polyaddition reaction. Among them, radical polymerization is preferred. In this case, as the polymerizable compound, the following radical type polymerizable compound (monomer) and an oligomer thereof can be used. Further, as described above, a polymer which polymerizes these monomers can also be used.

Examples of the monofunctional polymerizable compound (also referred to as a monofunctional monomer) include 2-ethylhexyl acrylate, butyl ethyl acrylate, butoxyethyl acrylate, and 2-cyanoethyl acrylate. , benzyl acrylate, cyclohexyl acrylate, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, ethoxyethyl acrylate, N, N-diethylaminoethyl acrylate, N, N -Dimethylaminoethyl acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, isodecyl acrylate, isodecyl acrylate , lauryl acrylate, wortene acrylate, phenoxy hexyl acrylate, phenoxy diethylene glycol acrylate, 2,2,2-trifluoroethyl acrylate, 2, 2, 3, 3 ,3-pentafluoropropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate Ester, 2,2,3,4,4,4-hexafluorobutyl acrylate, 2-ethylhexyl methacrylate, butyl ethyl methacrylate, butoxyethyl methacrylate, Cyanoethyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethoxyethyl acrylate , N,N-diethylaminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate Ester, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, isodecyl methacrylate, isodecyl methacrylate, lauryl methacrylate, wortene methacrylate, phenoxy Alkyl methacrylate, phenoxy diethylene glycol methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate Ester or 2,2,3,4,4,4-hexafluorobutyl methacrylate, and oligomers thereof.

Examples of the difunctional polymerizable compound (also referred to as a difunctional monomer) include 4,4′-biphenyldiacrylate, diethylstilbestrol diacrylate, and 1,4-bispropene oxide. Benzobenzene, 4,4'-bispropenyloxydiphenyl ether, 4,4'-bispropenyloxydiphenylmethane, 3,9-[1,1-dimethyl-propenyloxy -2,4,8,10-tetraspiro[5,5]undecane, α,α'-bis[4-propenyloxyphenyl]-1,4-diisopropylbenzene, 1 , 4-bisacryloxytetrafluorobenzene, 4,4'-bisacryloxy octafluorobiphenyl, diethylene glycol acrylate, 1,4-butanediol diacrylate, 1,3- Butanediol diacrylate, dicyclopentyl diacrylate, glycerin diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tetraethylene glycol diacrylate, 1, 9-decanediol diacrylate, polyethylene glycol diacrylate, poly Propylene glycol diacrylate, 1,9-decanediol dimethacrylate, polyethylene glycol dimethacrylate or polypropylene glycol dimethacrylate, and oligomers thereof.

Examples of the polyfunctional polymerizable compound (also referred to as a polyfunctional monomer) include trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, and dipentaerythritol. Hexaacrylate, dipentaerythritol monohydroxypentaacrylate, 4,4'-dipropylene stilbene stilbene (Stilbene), 4,4'-dipropylene decyloxy dimethyl stilbene, 4,4' -dipropylene decyloxydiethylstilbene, 4,4'-dipropylene decyloxydipropyl stilbene, 4,4'-dipropylene decyloxydibutyl stilbene, 4,4 '-Dipropylene decyloxydipentyl stilbene, 4,4'-dipropylene decyloxydihexyl stilbene, 4,4'-dipropylene decyloxydifluorostilbene, 2,2, 3,3,4,4-hexafluoropentanediol-1,5-diacrylate, 1,1,2,2,3,3-hexafluoropropyl-1,3-diacrylate, diethyl Diol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, new Pentanediol dimethacrylate, tetraethylene glycol dimethacrylate Trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxy five Methacrylate or 2,2,3,3,4,4-hexafluoropentanediol-1,5-dimethacrylate, and oligomers thereof.

These radical-type polymerizable compounds correspond to the optical properties of the liquid crystal display element or the adhesion of the liquid crystal layer to the liquid crystal alignment film. It can also be used in combination of 1 type or 2 types or more. In order to promote the formation of a cured composite of a liquid crystal composition, in order to promote radical polymerization of a polymerizable compound in a liquid crystal composition, it is preferred to introduce a radical generating initiator which generates a radical by ultraviolet rays (also It is called a polymerization initiator.

For example, tert-butyl peroxyl-iso-phthalate, 2,5-dimethyl-2,5-bis(benzylidenedioxy)hexane, 1,4-double [ Α-(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butyl hydroperoxide, 2,5-dimethyl-2,5-bis(tert-butyl dioxygen) Hexene hydrogen peroxide, α-(iso-propylphenyl)-iso-propyl hydroperoxide, 2,5-dimethylhexane, tert-butyl hydroperoxide, 1,1-double (tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-bis(tert-butyldioxy)valerate, cyclohexanone peroxide, 2,2',5,5'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-butylhexyloxycarbonyl)benzol Ketone, 3,3',4,4'-tetra(tert-pentylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone , 3,3'-bis(tert-butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate, di-tert-butyl diper An organic peroxide such as oxyphthalic acid ester or 9,10-fluorene, 1-chloroindole, 2-chloroindole, octamethylguanidine or 1,2-benzopyrene Ape, A benzoin derivative such as benzoin methyl, benzoin ethyl ether, α-methylbenzoin, α-phenylbenzoin or the like.

These radical initiators may be used alone or in combination of two or more kinds depending on the optical properties of the liquid crystal display element or the adhesion between the liquid crystal layer and the liquid crystal alignment film.

As the polymerizable compound, the following ionic type polymerizability can also be used. Compound. Specifically, it is a compound having a crosslinking-forming group selected from at least one selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group.

More specifically, the crosslinkable compound having at least one selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group is specifically WO (International Publication, The following is the same as the cyanuric acid derivative or benzoguanamine derivative described on pages 39 to 40 of 2013/125595 (2013.8.29 publication), WO2011/132751 (2011.10.27 publication), 62-66 pages. The crosslinked compound represented by the formula [6-1] to the formula [6-48] is disclosed.

Further, as the ionic polymerizable compound, a compound having a crosslinking-forming group containing an epoxy group or an isocyanate group can also be used. Specifically, a crosslinkable compound having an epoxy group or an isocyanate group described in pages 37 to 38 of WO 2013/125595 (published in 2013.8.29) is mentioned.

When an ionic polymerizable compound is used, it is intended to promote the polymerization reaction, and an acid or a base ion initiator may be introduced by ultraviolet light.

Specifically, for example, a triazine-based compound, an acetophenone derivative compound, a dioxon-based compound, a diazomethane-based compound, a sulfonic acid derivative compound, a diaryliodonium salt, a triarylsulfonium salt, or a triaryl group can be used. Base salts, iron aromatic hydrocarbon complexes, and the like, but are not limited thereto. More specifically, for example, diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium methanesulfonate, diphenyliodonium tosylate, diphenyl Iodine iodide bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodine Hexafluorophosphate, bis(p-tert-butylphenyl)iodonium mesylate, bis(p-tert-butylphenyl)iodonium tosylate, bis(p-tert-butyl Phenyl)iodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium tetrafluoroborate, bis(p-tert-butylphenyl)iodonium chloride, double (p- Chlorophenyl)iodonium chloride, bis(p-chlorophenyl)iodonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tris(p-methoxyphenyl)phosphonium Fluoroborate, tris(p-methoxyphenyl)phosphonium hexafluorophosphate, tris(p-ethoxyphenyl)phosphonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, Tris(p-methoxyphenyl)phosphonium tetrafluoroborate, tris(p-methoxyphenyl)phosphonium hexafluorophosphate, tris(p-ethoxyphenyl)phosphonium tetrafluoroborate, double [ [2-Nitrobenzyl)oxy]carbonylhexane-1,6-diamine], nitrobenzylcyclohexylaminoformate, bis(methoxybenzyl)hexamethylenediamine Formate, bis[[2-nitrobenzyl And oxy]carbonylhexane-1,6-diamine], nitrobenzylcyclohexylaminoformate or bis(methoxybenzyl)hexamethylenedicarbamate.

<specific side chain structure>

The specific side chain structure of the present invention is represented by the following formula [2-1] or formula [2-2].

In the formula [2-1], Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n are as defined above, but each of them is preferably the following.

Y ^{1 is} preferably a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or from the viewpoint of availability of a raw material or ease of synthesis. -COO-. More preferably a single _{bond, - (CH 2) a -} (a is an integer of 1 to 10), - O -, - CH 2 O- or -COO-. Y ^{2 is} preferably a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10). Y ^{3 is} preferably a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- from the viewpoint of easiness of synthesis. More preferably a single _{bond, - (CH 2) a -} (a is an integer of 1 to 10), - O -, - CH 2 O- or -COO-. From the viewpoint of easiness of synthesis, Y ^{4 is} preferably a benzene ring, a cyclohexane ring or an organic group having a carbon number of 17 to 51 having a steroid skeleton.

Y ^{5 is} preferably a benzene ring or a cyclohexane ring. Y ^{6 is} preferably 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. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred are alkyl groups having 1 to 9 carbon atoms or alkoxy groups having 1 to 9 carbon atoms. n is preferably 0 to 3, more preferably 0 to 2, from the viewpoint of availability of raw materials or ease of synthesis.

A preferred combination of Y ¹ to Y ⁶ and n can be exemplified by (2-1) to (2-629) as disclosed in Tables 6 to 47 of pages 13 to 34 of WO2011/132751 (2011.10.27). ) the same combination. Further, in the tables of the International Publications, Y ¹ to Y ^{6 of the} present invention are represented as Y1 to Y6, but Y1 to Y6 are interpreted as Y ¹ to Y ⁶ . Further, in (2-605) to (2-629), which are disclosed in the respective tables of the International Publications, the organic group having a carbon number of 17 to 51 having a steroid skeleton of the present invention represents a carbon number of 12 having a steroid skeleton. The organic group of ~25 organic group, but having a carbon number of 12 to 25 of the steroid skeleton, is interpreted as an organic base having a carbon number of 17 to 51 of a steroid skeleton.

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

[化9]-Y ⁷ -Y ⁸ [2-2]

In the formula [2-2], Y ⁷ and Y ⁸ are as defined above, but each of them is preferably the following.

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

As described above, the specific side chain structure of the present invention is preferably a specific side chain structure represented by the formula [2-1] from the viewpoint of obtaining a vertical alignment property of a highly stable liquid crystal.

<specific polymer>

The specific polymer having a specific side chain structure is not particularly limited, but is preferably selected from an acrylic polymer, a methacrylic polymer, A polymer of at least one of the group consisting of a novolac resin, a polyhydroxystyrene, a polyimine precursor, a polyimine, a polyamine, a polyester, a cellulose, and a polyoxyalkylene. More preferably, it is a polyimine precursor, a polyimine or a polyoxyalkylene.

When a polyimine precursor or a polyamidene (collectively referred to as a polyimine-based polymer) is used as the specific polymer, it is preferred that the diamine component and the tetracarboxylic acid component are reacted. Polyimine precursor or polyimine.

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

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

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

Polyimine polymer, which is represented by the following formula [B] The acid dianhydride and the diamine represented by the following formula [C] are used as a raw material, and it is preferable to use a structural formula of a repeating unit represented by the following formula [D] for the reason of being relatively simple. Proline or the polyamidimide of the polyamid.

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

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

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

As a method of introducing the specific side chain structure described above into a polyamidene-based polymer, it is preferred to use a diamine having a specific side chain structure in one of the raw materials. Minute. Particularly preferred is a diamine (also referred to as a specific side chain type diamine) represented by the following formula [2a].

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

Further, the details and preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2-1] are as described above, and Y ⁷ in the formula [2-2] The details and preferred combinations of Y ⁸ are as described above.

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

Specific examples of the specific side chain type diamine having a specific side chain structure represented by the formula [2-1] include the formulas described in pages 15 to 19 of WO 2013/125595 (published in 2013.8.29). 1]~ The diamine compound of the formula [2-6], the formula [2-9]~form [2-36]. Still, described in WO2013 / 125595 of the formula [2-1] to the formula [2-3], and R ₂ in the formula [2-4] to Formula [2-6] is selected from the group consisting of R ₄ represents a carbon number of lines 1 At least one of the group consisting of an alkyl group of ~18, 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. Further, the A ₄ in the formula [2-13] represents a linear or branched alkyl group having 3 to 18 carbon atoms. Further, R ₃ in the formula [2-4] to the formula [2-6] represents at least one selected from the group consisting of -O-, -CH ₂ O-, -COO-, and -OCO-.

Among them, the preferred diamine is the formula [2-1]~form [2-6], the formula [2-9]~form [2-13] or the formula [2-22]~form described in WO2013/125595 [ 2-31] diamine compound.

Further, the diamine represented by the following formula [2a-32] to the formula [2a-36] is preferable from the viewpoint of the vertical alignment of the liquid crystal and the optical characteristics of the liquid crystal display element when the liquid crystal alignment film is used.

(R ¹ represents -CH ₂ O-; and R ² represents an alkyl group having 3 to 12 carbon atoms).

(R ³ represents an alkyl group having 3 to 12 carbon atoms, and a cis-trans isomer of a 14-cyclohexyl group is a trans isomer).

Specific examples of the specific side chain type diamine having the specific side chain structure represented by the above formula [2-2] include the formula [DA1] described in page 23 of WO 2013/125595 (2013.8.29 publication). [DA11] diamine compound. Further, in WO 2013/125595, A ₁ in the formula [DA1] to the formula [DA5] represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.

The ratio of use of the specific side chain type diamine is from the point of the vertical alignment of the liquid crystal when the liquid crystal alignment film is formed, and the adhesion between the liquid crystal layer of the liquid crystal display element and the liquid crystal alignment film, and the total amount of the diamine component. Preferably, it is 10 to 80 mol%, more preferably 20 to 70 mol%.

In addition, the specific side chain type diamine can be mixed by the solubility of the solvent of the polyimine-based polymer, the vertical alignment of the liquid crystal when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. Use of two or more species.

As the diamine component for producing the above polyimine-based polymer, a diamine (also referred to as a second diamine) represented by the following formula [2b] is preferably used.

The T system represents a substituent selected from at least one of the groups consisting of the structures represented by the following formulas [2-1b] to [2-4b]. The r system represents an integer from 1 to 4. Among them, an integer of 1 is preferred.

In the formula [2-1b], a represents an integer of 0 to 4. Among them, from the viewpoint of availability of raw materials or easiness of synthesis, an integer of 0 or 1 is preferred. In the formula [2-2b], b represents an integer of 0 to 4. Among them, from the viewpoint of availability of raw materials or easiness of synthesis, an integer of 0 or 1 is preferred. In the formula [2-3b], T ¹ and T ^{2 each} independently represent a hydrocarbon group having 1 to 12 carbon atoms. In the formula [2-4b], T ³ represents an alkyl group having 1 to 5 carbon atoms.

Although the specific structure of the second diamine is listed below, it is not limited to these examples. For example, in addition to 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diaminophenol, 3,5- Diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or Examples of the 3,5-diaminobenzoic acid include diamines having the structures represented by the following formulas [2b-1] to [2b-6].

Among them, preferred are 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-di Amino resorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, formula [2b-1], formula [2b-2] Or a diamine represented by the formula [2b-3]. From the viewpoint of the solubility of the solvent of the polyimine-based polymer or the optical characteristics of the liquid crystal display element, it is particularly preferably 2,4-diaminophenol, 3,5-diaminophenol, 3, 5-Diaminobenzyl alcohol, 3,5-diaminobenzoic acid, diamine represented by the formula [2b-1] or the formula [2b-2].

The ratio of use of the second diamine is preferably from 1 to 50 mol%, more preferably 1%, based on the total adhesion of the liquid crystal layer of the liquid crystal display device to the liquid crystal alignment film. ~40% by mole, especially preferably 5~40% by mole.

In addition, the second diamine may be mixed in one type or in combination with the solubility of the solvent of the polyimine-based polymer, the vertical alignment of the liquid crystal when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. Two or more types are used.

As a diamine component for producing a polyimine-based polymer, a specific side chain type diamine and a diamine other than the second diamine (also referred to as other diamines) can be used without impairing the effects of the present invention. ).

Specifically, other diamine compounds described on pages 19 to 23 of WO 2013/125595 (published at No. 2013.8.29), the formula [DA12] described in the same paragraph on page 24, and the formula [DA15]~[DA20] And the diamine compound of the formula [DA26]~[DA28] described on pages 25 to 26 of the same publication. In addition, other diamines may be used in combination of one type or two or more types depending on each characteristic.

The tetracarboxylic acid component represented by the following formula [3], or a tetracarboxylic acid derivative thereof, which is a tetracarboxylic acid component, is preferably a tetracarboxylic acid or a tetracarboxylic acid. A carboxylic acid dihalide, a dialkyl tetracarboxylate or a dialkyl tetracarboxylate dihalide (collectively referred to as a specific tetracarboxylic acid component).

The Z system indicates a structure in which at least one of the groups consisting of the following formulas [3a] to [3k] is selected.

Z in the above formula [3] is preferably the above formula [3a], formula [3c], formula [3d], formula [in view of easiness of synthesis or easiness of polymerization reactivity in polymer production). 3e], formula [3f], formula [3g] or formula [3k]. More preferably, the formula [3a], the formula [3e], the formula [3f], the formula [3g] or the formula [3k], from the point of view of the optical characteristics of the liquid crystal display element, is particularly preferably the formula [3a], Formula [3e], formula [3f] or formula [3g].

The use ratio of the specific tetracarboxylic acid component is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, based on the total tetracarboxylic acid component. Among them, from the viewpoint of the optical characteristics of the liquid crystal display element, it is particularly preferably from 10 to 90 mol%.

Further, when a specific tetracarboxylic acid component of the above formula [3e], formula [3f], formula [3g] or formula [3k] is used, the amount thereof used is 20 mol% or more of the entire tetracarboxylic acid component. And get the desired effect. More preferably 30% by mole or more. Further, all of the tetracarboxylic acid component may be a tetracarboxylic acid component of the formula [3e], the formula [3f], the formula [3g] or the formula [3k].

In the polyamidene-based polymer, the effect of the present invention is not impaired In the following, other tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used. Examples of the other tetracarboxylic acid component include a tetracarboxylic acid, a tetracarboxylic dianhydride, a dicarboxylic acid dihalide, a dicarboxylic acid dialkyl ester or a dialkyl ester dihalide.

Specifically, other tetracarboxylic acid components described on pages 27 to 28 of WO 2013/125595 (published in 2013.8.29) are mentioned. In addition, the specific tetracarboxylic acid component and the other tetracarboxylic acid component may be used alone or in combination of two or more kinds depending on the respective properties.

The method of synthesizing the polyimine-based polymer is not particularly limited. It is usually obtained by reacting a diamine component with a tetracarboxylic acid component. Specifically, the method described in pages 29 to 30 of WO 2013/125595 (published in 2013.8.29) is mentioned.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in a solvent containing a diamine component and a tetracarboxylic acid component. The solvent used in this case is not particularly limited as long as it dissolves the produced polyimide intermediate precursor.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and the like can be mentioned. Methyl hydrazine or 1,3-dimethyl-imidazolidinone or the like. Further, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula may be used. [D-1]~ Solvent represented by the formula [D-3].

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

These may be used alone or in combination. Further, even if it is a solvent which does not dissolve the polyimide precursor, it can be used in the above-mentioned solvent in the range in which the produced polyimide precursor is not precipitated. Further, since the water in the organic solvent hinders the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, the organic solvent is preferably used by dehydration.

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

When the polysiloxane is used for the specific polymer, the polyoxyalkylene obtained by polycondensing the alkoxysilane represented by the following formula [A1] or the alkoxy group represented by the formula [A1] is preferred. A polydecane which is obtained by polycondensation of decane, an alkoxy decane represented by the following formula [A2], and/or an alkoxy decane represented by the formula [A3] (collectively, also referred to as a polyoxyalkylene-based polymer).

Alkoxy decane represented by the formula [A1]: [Chem. 22] (A ¹ ) _m Si(A ² ) _n (OA ³ ) _p [A1]

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

In the present invention, from the viewpoint of the vertical alignment of the liquid crystal when the liquid crystal alignment film is formed and the optical characteristics of the liquid crystal display element, the preferred structure A ¹ is a specific side chain structure represented by the formula [2-1].

In the formula [A1], A ² , A ³ , m, n and p are as defined above. Among them, preferred are as follows. A ^{2 is} preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. A ^{3 is} preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of reactivity of polycondensation. m is preferably an integer of 1 from the point of synthesis. n represents an integer from 0 to 2. p is preferably an integer of 1 to 3, more preferably an integer of 2 or 3, from the viewpoint of reactivity of polycondensation. m+n+p is an integer of 4.

Specific examples of the alkoxydecane having a specific side chain structure represented by the formula [2-1] include the formula [A1-1] described in pages 41 to 44 of WO 2014/061779 (published on Apr. 4, 2014). The alkoxydecane of the formula [A1-22] and the formula [A1-25] to the formula [A1-32]. Further, in WO214/061779, the R ² system of the formula [A1-19]~form [A1-22] and the formula [A1-25]~form [A1-31] represents the selection from -O-, -CH At least one of the group consisting of ₂ O-, -COO-, and -OCO-.

Among them, a preferred alkoxy decane is a formula [A1-9]~[A1] described in WO2014/061779 from the viewpoint of the vertical alignment of the liquid crystal when the liquid crystal alignment film is formed and the optical characteristics of the liquid crystal display element. -21], formula [A1-25]~form [A1-28] or formula [A1-32].

The alkoxy decane represented by the formula [A1] is suitable for the solubility of the solvent of the polyoxyalkylene polymer, the vertical alignment of the liquid crystal when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. It can be used in combination of one type or two or more types.

Alkoxydecane represented by the formula [A2]: [Chem. 23] (B ¹ ) _m Si(B ² ) _n (OB ³ ) _p [A2]

In the formula [A2], B ¹ , B ² , B ³ , m, n and p are as defined above. Among them, preferred are as follows. B ^{1 is} preferably an organic group having a vinyl group, an epoxy group, an amine group, a methacryl fluorenyl group, an acryl fluorenyl group or a ureido group from the viewpoint of ease of availability. More preferably, it is an organic group having a methacryl fluorenyl group, an acryl fluorenyl group or a ureido group. B ^{2 is} preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

B ^{3 is} preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of reactivity of polycondensation. m is preferably an integer of 1 from the point of synthesis. The n system represents an integer from 0 to 2.

p is preferably an integer of 1 to 3, more preferably an integer of 2 or 3, from the viewpoint of reactivity of polycondensation. m+n+p is 4.

Specific examples of the alkoxydecane represented by the formula [A2] include alkoxydecane represented by the formula [A2] described in pages 45 to 46 of WO 2014/061779 (published on Apr. 4, 2014).

Among them, allyl triethoxy decane, allyl trimethoxy decane, diethoxymethyl vinyl decane, dimethoxymethyl vinyl decane, triethoxy vinyl decane, Vinyl trimethoxy fluorene Alkane, vinyl ginseng (2-methoxyethoxy) decane, 3-(triethoxydecyl) propyl methacrylate, 3-(trimethoxydecyl) propyl acrylate, 3- (trimethoxydecyl)propyl methacrylate, 3-glycidoxypropyl (dimethoxy)methyl decane, 3-glycidoxypropyl (diethoxy) methyl decane, 3-glycidoxypropyltrimethoxydecane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane.

From the viewpoint of the adhesion between the liquid crystal layer of the liquid crystal display element and the liquid crystal alignment film, 3-(triethoxydecyl)propyl methacrylate and 3-(trimethoxydecylalkyl) are particularly preferable. Propyl acrylate, 3-(trimethoxydecyl)propyl methacrylate, 3-glycidoxypropyl (dimethoxy)methyl decane, 3-glycidoxypropyl (diethyl) Oxy)methylnonane, 3-glycidoxypropyltrimethoxydecane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane. The alkoxydecane represented by the formula [A2] may be used alone or in combination of two or more.

Alkoxydecane represented by the formula [A3]: [Chem. 24] (D ¹ ) _n Si(OD ² ) _4-n [A3]

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

Specific examples of the alkoxydecane represented by the formula [A3] include the formula described on page 47 of WO 2014/061779 (published on Apr. 4, 2014). Alkoxydecane represented by [A3].

In the formula [A3], examples of the alkoxydecane in which n is 0 include tetramethoxynonane, tetraethoxydecane, tetrapropoxydecane or tetrabutoxydecane. As the alkoxydecane of the formula [A3], it is preferred to use such alkoxydecane. The alkoxydecane represented by the formula [A3] may be used alone or in combination of two or more.

The polyoxyalkylene-based polymer is a polyoxyalkylene obtained by polycondensing an alkoxysilane represented by the above formula [A1] or an alkoxydecane represented by the formula [A1], and the above formula [A2] is represented. A polyoxyalkylene obtained by polycondensation of an alkoxy decane and/or an alkoxy decane represented by the formula [A3]. In other words, the polyoxyalkylene-based polymer is obtained by polycondensation of only a polyoxyalkylene obtained by polycondensation of an alkoxysilane represented by the formula [A1], and alkoxysilane of the formula [A1] and the formula [A2]. The obtained polyoxyalkylene, a polyoxyalkylene obtained by polycondensing the two kinds of alkoxysilanes represented by the formula [A1] and the formula [A3], and the formula [A1], the formula [A2] and the formula [A3] Any one of the polyoxoxanes obtained by polycondensation of the three alkoxydecanes.

Among them, from the viewpoint of the reactivity of the polycondensation or the solubility of the solvent of the polyoxyalkylene-based polymer, a polyoxyalkylene obtained by polycondensing a plurality of alkoxysilanes is preferable. In other words, it is preferred to use a polyoxyalkylene obtained by polycondensing two alkoxysilanes represented by the formula [A1] and the formula [A2], and two alkoxydecanes represented by the formula [A1] and the formula [A3]. The polyoxyalkylene obtained by the polycondensation and any of the polyoxyalkylenes obtained by polycondensing the three kinds of alkoxysilanes represented by the formula [A1], the formula [A2] and the formula [A3].

When a polyoxyalkylene-based polymer is produced, when a plurality of alkoxydecanes are used, the use of the alkoxydecane represented by the formula [A1] is used in all The alkoxydecane is preferably from 1 to 40 mol%, more preferably from 1 to 30 mol%. Further, the use of the alkoxydecane represented by the formula [A2] is preferably from 1 to 70 mol%, more preferably from 1 to 60 mol%, based on the total alkoxydecane. Further, the use of the alkoxydecane represented by the formula [A3] is preferably from 1 to 99 mol%, more preferably from 1 to 80 mol%, based on the total alkoxydecane.

The method for producing the polycondensation reaction of the polyoxyalkylene-based polymer is not particularly limited. Specifically, the method described in pages 49 to 52 of WO 2014/061779 (published on Apr. 4, 2014) is mentioned.

In the polycondensation reaction for producing a polyoxyalkylene-based polymer, when a plurality of alkoxydecanes represented by the formula [A1], the formula [A2] or the formula [A3] are used, even if a mixture of a plurality of alkoxydecanes is previously mixed The reaction is carried out, and a plurality of alkoxydecane may be added in order, and the reaction is carried out.

In the present invention, a solution of the polyoxyalkylene-based polymer obtained by the above method can be directly used as a specific polymer, and if necessary, a solution of the polyoxyalkylene-based polymer obtained by the above method can be concentrated, It can be used as a specific polymer by adding a solvent or diluting it or substituting it into another solvent.

The solvent (also referred to as an additive solvent) used in the dilution may be a solvent or other solvent used in the polycondensation reaction. The solvent to be added is not particularly limited as long as it is uniformly dissolved in the polyoxyalkylene polymer, and one type or two or more types can be used. Examples of the solvent to be used in the polycondensation reaction include a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone, and an ester of methyl acetate, ethyl acetate or ethyl lactate. A solvent or the like. Further, a polyoxyalkylene-based polymer is used in addition to a specific polymer. In the case of the polymer, it is preferred to distill off the alcohol produced during the polycondensation reaction of the polyoxyalkylene polymer at normal pressure or under reduced pressure before mixing the polymer other than the polyoxyalkylene polymer.

<Liquid alignment treatment agent>

The liquid crystal alignment treatment agent is a solution for forming a liquid crystal alignment film, and contains a specific polymer and a solvent having a specific side chain structure of the above formula [2-1] or formula [2-2].

The specific polymer is not particularly limited as described above, but is preferably selected from the group consisting of an acrylic polymer, a methacrylic polymer, a novolak resin, a polyhydroxystyrene, a polyimine precursor, and a polyimine. a polymer of at least one of the group consisting of polyamine, polyester, cellulose, and polyoxyalkylene. More preferably, it is a polyimine precursor, a polyimine or a polyoxyalkylene. Further, one or two or more of these polymers may be used for the specific polymer.

All of the polymer components of the liquid crystal alignment agent may be specific polymers, or may be mixed with other polymers. In this case, the content of the polymer other than the polymer is 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the specific polymer. The polymer other than the above may be a polymer having no specific side chain structure represented by the above formula [2-1] or formula [2-2].

The content of the solvent in the liquid crystal alignment agent can be appropriately selected from the viewpoint of the coating method for obtaining the liquid crystal alignment agent or the film thickness of the object. Among them, from the point of view of forming a uniform liquid crystal alignment film by coating, The content of the solvent in the liquid crystal alignment agent is preferably from 50 to 99.9% by mass, more preferably from 60 to 99% by mass. Particularly good is 65 to 99% by mass.

The solvent used for the liquid crystal alignment treatment agent is not particularly limited as long as it can dissolve a specific polymer. Wherein, the specific polymer is a polyimine precursor, a polyimide, a polyamide or a polyester, or an acrylic polymer, a methacrylic polymer, a novolac resin, a polyhydroxystyrene, a fiber When the solubility of the solvent of the gas or polysiloxane is low, it is preferred to use a solvent (also referred to as a solvent A) as shown below.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-pyrrolidone, dimethyl azine, γ-butane Ester, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-pentanone. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferably used. Moreover, these may be used singly or in combination.

When the specific polymer is an acrylic polymer, a methacrylic polymer, a novolac resin, a polyhydroxystyrene, a cellulose or a polyoxyalkylene, the specific polymer is a polyimine precursor, a polyimine, a poly When the solubility of the solvent of the specific polymer of the guanamine or the polyester is high, a solvent (also referred to as a solvent B) as shown below can be used.

Specific examples of the solvent B include the poor solvents described in pages 35 to 37 of WO 2013/125595 (published in 2013. 8.29).

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, Cyclohexanone, cyclopentanone or the above formula [D1]~[D3] Agent.

Further, when such a solvent B is used, the coating property of the liquid crystal alignment agent is improved, and it is preferred to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ of the solvent A in combination. - Butyrolactone is used. More preferably, γ-butyrolactone is used in combination.

In the solvent B type, since the coating property or surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be improved, a polyimine precursor, a polyimine, a polyamine can be used for a specific polymer. Or polyester, it is preferably used together with the aforementioned solvent A. In this case, the solvent B is preferably from 1 to 99% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. Among them, it is preferably from 10 to 99% by mass. More preferably, it is 20 to 95% by mass.

In the liquid crystal alignment treatment agent of the present invention, it is preferred to introduce a production agent (also referred to as a specific production agent) selected from at least one of the group consisting of a photo-radical generator, a photo-acid generator, and a photobase generator. ). Among them, in the specific production agent, a photoradical generator is preferably used from the viewpoint of adhesion between the liquid crystal layer and the liquid crystal alignment film.

The photo-radical generating agent is not particularly limited as long as it can generate a radical by ultraviolet rays, and examples thereof include tert-butyl peroxyl-iso-phthalate and 2,5-dimethyl group. -2,5-bis(benzylidenedioxy)hexane, 1,4-bis[α-(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butyl Hydrogen peroxide, 2,5-dimethyl-2,5-bis(tert-butyldioxy)hexene hydroperoxide, α-(-iso-propylphenyl)-iso-propyl peroxidation Hydrogen, 2,5-dimethylhexane, tert-butyl hydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl -4,4-bis(tert-butyldioxy)pentanoic acid Ester, cyclohexanone peroxide, 2,2',5,5'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra (tert-butyl Oxidative carbonyl)benzophenone, 3,3',4,4'-tetra(tert-pentylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxidation) Carbonyl)benzophenone, 3,3'-bis(tert-butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butyl peroxybenzoate or di-tert- An organic peroxide such as butyl diperoxyisophthalate or 9,10-fluorene, 1-chloroindole, 2-chloroindole, octamethylguanidine or 1,2-benzophenone A benzoin derivative such as anthraquinone, benzoin methyl, benzoin ethyl ether, α-methylbenzoin or α-phenylbenzoin.

In addition, the photoacid generator and the photobase generator are not particularly limited as long as they can generate an acid or a base by ultraviolet rays, and examples thereof include a triazine compound, an acetophenone derivative compound, and a diterpenoid compound. A diazomethane-based compound, a sulfonic acid derivative compound, a diaryliodonium salt, a triarylsulfonium salt, a triarylsulfonium salt or an iron arene complex. More specifically, for example, diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium methanesulfonate, diphenyliodonium tosylate, diphenyl Iodine iodide bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodine Hexafluorophosphate, bis(p-tert-butylphenyl)iodonium mesylate, bis(p-tert-butylphenyl)iodonium mesylate, bis(p-tert-butyl Phenyl)iodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium tetrafluoroborate, bis(p-tert-butylphenyl)iodonium chloride, double (p- Chlorophenyl)iodonium chloride, bis(p-chlorophenyl)iodonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tris(p-methoxyphenyl)phosphonium Fluoroborate, three (p- Methoxyphenyl)phosphonium hexafluorophosphate, tris(p-ethoxyphenyl)phosphonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tris(p-methoxybenzene) Tetrafluoroborate, tris(p-methoxyphenyl)phosphonium hexafluorophosphate, tris(p-ethoxyphenyl)phosphonium tetrafluoroborate, bis[[(2-nitrobenzyl) )oxy]carbonylhexane-1,6-diamine], nitrobenzylcyclohexylcarbamate, bis(methoxybenzyl)hexamethylenedicarbamate, bis[[ (2-nitrobenzyl)oxy]carbonylhexane-1,6-diamine], nitrobenzylcyclohexylcarbamate or bis(methoxybenzyl)hexamethylenediamine Formate and so on.

In the liquid crystal alignment treatment agent of the present invention, for the purpose of improving the adhesion between the liquid crystal layer and the liquid crystal alignment film, it is preferable to contain a composition selected from the following formulas [b-1] to [b-8]. A compound of at least one of the classes (also referred to as a specific adhesive compound).

In the formula [b-4], B ^a represents a hydrogen atom or a benzene ring. Among them, a hydrogen atom is preferred. In the formula [b-8], B ^b represents a cyclic group selected from at least one selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring. B ^c is at least one selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group, an alkoxy group, and a fluorine-containing alkoxy group. Among them, an alkyl group having 1 to 12 carbon atoms or an alkoxy group is preferred.

More specifically, the specific adhesive compound is preferably a compound represented by the following formula [7A].

In the formula [7A], M ¹ represents at least one selected from the group consisting of the following formulas [a-1] to [a-7]. Among them, from the viewpoint of easiness of production, the formula [a-1], the formula [a-2], the formula [a-3], the formula [a-5] or the formula [a-6] is preferable. More preferably, it is a formula [a-1], a formula [a-3], a formula [a-5] or a formula [a-6].

A ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, from the viewpoint of easiness of production, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable. More preferably, it is a hydrogen atom or a methyl group.

A ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Among them, from the viewpoint of easiness of production, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable. More preferably, it is a hydrogen atom or a methyl group.

A ³ , A ⁵ , A ⁶ and A ^{9 each} independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Among them, from the viewpoint of easiness of production, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable. More preferably, it is a hydrogen atom or a methyl group.

A ⁴ , A ⁷ and A ⁸ independently represent an alkylene group having 1 to 3 carbon atoms. Among them, from the viewpoint of easiness of production, an alkylene group having 1 to 2 carbon atoms is preferred.

In the formula [7A], M ² represents a group selected from a single bond, -CH ₂ -, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, _{-OCH 2 -, - COO -,} - OCO-, CON (CH 3) - and the group consisting of -N (CH ₃₎ CO- in at least one of the binding group. Among them, from the viewpoint of easiness of production, a single bond, -CH ₂ -, -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO is preferred. -, -OCO-, CON(CH ₃ )- or -N(CH ₃ )CO-. More preferably, it is a single bond, -CH ₂ -, -O-, -NH-, -CONH-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. Particularly preferred is a single bond, -O-, -CONH-, -OCH ₂ -, -COO- or -OCO-.

Formula [. 7A] in, M ³ represents a system selected from the group consisting of carbon atoms having the alkyl group having 1 to 20 _{extension, - (CH 2 -CH 2 -O} ) p - (p represents an integer of 1 to 10), - (CH ₂ - O-) _q - (q represents an integer of 1 to 10), and at least one of the group consisting of a benzene ring having 6 to 20 carbon atoms or an organic group of a cyclohexane ring. At this time, any -CH ₂ - group of the above alkylene group may be -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -S-, -SO ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, OSi(CH ₃ ) ₂ - or -Si(CH ₃ ) ₂ O-substituted, a hydrogen atom bonded to any carbon atom may be hydroxyl group ( OH group), carboxyl group (COOH group) or halogen atom substitution. Among them, from the viewpoint of easiness of production, an alkylene group having 1 to 20 carbon atoms, -(CH ₂ -CH ₂ -O) _p -, -(CH ₂ -O-) _q - or the following Formula [c-1]~Form [c-5]. More preferably, it is an alkyl group having 1 to 15 carbon atoms, -(CH ₂ -CH ₂ -O) _p -, -(CH ₂ -O-) _q -, the following formula [c-1], formula [c -3], formula [c-4] or formula [c-5]. Particularly preferred are an alkylene group having 1 to 15 carbon atoms, -(CH ₂ -CH ₂ -O) _p -, formula [c-1], formula [c-4] or formula [c-5].

In the formula [7A], M ⁴ represents a bonding group selected from at least one selected from the group consisting of a single bond, -CH ₂ -, -OCH ₂ -, and O-CH ₂ -CH ₂ -. Among them, from the viewpoint of easiness of production, a structure represented by a single bond, -CH ₂ - or -OCH ₂ - is preferred. M ⁵ represents a structure selected from at least one of the groups consisting of the above formulas [b-1] to [b-8]. Among them, from the viewpoint of easiness of production, the formula [b-1], the formula [b-2] or the formula [b-6] is preferred. More preferably, it is of the formula [b-1] or the formula [b-2]. The n system represents an integer from 1 to 3. Among them, from the viewpoint of easiness of production, it is preferably an integer of 1 or 2, especially an integer of 1. The m system represents an integer of 1 to 3, and particularly preferably an integer of 1 or 2 from the viewpoint of ease of manufacture.

The specific adhesive compound is preferably a compound selected from at least one of the group consisting of the following formula [7a-1] and the formula [7a-5].

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

Further, as the specific adhesive compound, the following may be used.

For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) propylene methoxy ethoxy trihydroxyl a compound having three polymerizable unsaturated groups in a molecule such as a propane or a glycerol polyglycidyl ether poly(meth)acrylate, and further an ethylene glycol di(meth)acrylate or a diethylene glycol di Methyl) acrylate, tetraethylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, propylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, butyl Diol (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di(meth) acrylate, propylene oxide bisphenol type di(meth) acrylate, 1 ,6-hexanediol II (Meth) acrylate, glycerol di(meth) acrylate, pentaerythritol di(meth) acrylate, ethylene glycol diglycidyl ether di(meth) acrylate, diethylene glycol diglycidyl ether II ( Methyl) acrylate, diglycidyl phthalate di(meth) acrylate or hydroxytrimethylacetic acid (Pivalic acid) neopentyl glycol di(meth) acrylate having two polymerizations in the molecule a compound of an unsaturated group, furthermore 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2- Hydroxypropyl (meth) acrylate, 2-(methyl) propylene oxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol A compound having one polymerizable unsaturated group in the molecule, such as (meth) acrylate, 2-(meth) propylene methoxy hexyl phosphate or N- hydroxymethyl (meth) acrylamide.

The content of the specific adhesive compound in the liquid crystal alignment agent is preferably 0.1 to 150 parts by mass based on 100 parts by mass of the total polymer component. The effect of the crosslinking reaction is preferably from 0.1 to 100 parts by mass, particularly preferably from 1 to 50 parts by mass, per 100 parts by mass of the total polymer component. The specific adhesive compound may be used alone or in combination of two or more.

The liquid crystal alignment treatment agent of the present invention preferably contains a compound having an epoxy group, an isocyanate group, an oxetanyl group or a cyclic carbonate group, or has a group selected from a hydroxyl group, a hydroxyalkyl group and a lower alkoxy group. A compound of at least one of the group consisting of alkyl groups (collectively also referred to as a specific crosslinkable compound). In this case, it is preferred that these groups have two or more compounds.

Specific examples of the crosslinkable compound having an epoxy group or an isocyanate group include crosslinking of an epoxy group or an isocyanate group described on pages 37 to 38 of WO 2013/125595 (published at No. 2013.8.29). Sex compounds.

Specific examples of the crosslinkable compound having an oxetanyl group include the crosslinkable compounds represented by the formula [4a] to the formula [4k] disclosed in pages 58 to 59 of WO2011/132751.

Specific examples of the crosslinkable compound having a cyclic carbonate group include the crosslinkable compounds represented by the formulas [5-1] to [5-42] disclosed in pages 76 to 82 of WO2012/014898.

Specific examples of the crosslinkable compound having at least one selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group include 39 of WO 2013/125595 (2013.8.29 publication). The cyanuric acid derivative or benzoguanamine derivative described in pages ~40, and the formula [6-1]~ described in pages 62-66 of WO2011/132751 (2011.10.27) [6-48] shows a crosslinkable compound.

The content of the specific crosslinkable compound in the liquid crystal alignment agent is preferably 0.1 to 100 parts by mass based on 100 parts by mass of the total polymer component. The effect of the crosslinking reaction is preferably from 0.1 to 50 parts by mass, particularly preferably from 1 to 30 parts by mass, per 100 parts by mass of the total polymer component.

In the liquid crystal alignment treatment agent, in order to promote the charge movement in the liquid crystal alignment film and to promote the elimination of electric charge of the element, the inclusion of the content disclosed in pages 69 to 73 of WO2011/132751 (2011.10.27) may be added. [M1]~ A heterocyclic amine compound of the formula [M156]. Although the amine compound may be directly added to the liquid crystal alignment treatment agent, it is preferably added in a solvent having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass, in a suitable solvent. The solvent is not particularly limited as long as it is an organic solvent capable of dissolving a specific polymer.

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

Examples of the compound which improves the uniformity of the film thickness of the liquid crystal alignment film or the surface smoothness include a fluorine-based surfactant, a rhodium-based surfactant, and a nonionic surfactant. Specifically, a surfactant described in pages 42 to 43 of WO 2013/125595 (published in 2013.8.29) is mentioned.

The amount of the surfactant to be used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent.

Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include a functional decane-containing compound or an epoxy group-containing compound. Specifically, a compound described in pages 43 to 44 of WO 2013/125595 (published in 2013.8.29) is mentioned.

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

In the liquid crystal alignment agent, a dielectric material or a conductive material for changing the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film may be added as a compound other than the above.

<Method for Producing Liquid Crystal Alignment Film and Liquid Crystal Display Element>

The substrate used for the liquid crystal display device of the present invention is not particularly limited as long as it has a high transparency, and an acrylic substrate, a polycarbonate substrate, or PET (polyethylene terephthalate) can be used in addition to the glass substrate. A plastic substrate such as an ester substrate can be used as the film. When the liquid crystal display element is used as a reversing element, it is preferably a plastic substrate or a film when used in a dimming window or the like. Further, from the viewpoint of simplification of the process, it is preferable to form an ITO (Indium Tin Oxide) electrode, an IZO (Indium Zinc Oxide) electrode, an IGZO (Indium Gallium Zinc Oxide) electrode, an organic conductive film, or the like for driving liquid crystal. The substrate. Further, in the case of a reflective inversion type element, a substrate in which a metal such as a tantalum wafer or aluminum or a multilayer film of a dielectric material is formed may be used as the substrate on only one side.

At least one of the liquid crystal display element substrates of the present invention is a liquid crystal alignment film having, for example, vertically aligned liquid crystal molecules. This liquid crystal alignment film is obtained by coating and baking a liquid crystal alignment treatment agent on a substrate, and then performing an alignment treatment by rubbing treatment or light irradiation. However, in the case of the liquid crystal alignment film of the present invention, it can be used as a liquid crystal alignment film even without such alignment treatment. use.

The coating method of the liquid crystal alignment treatment agent is not particularly limited, but industrially, there are screen printing, lithography, offset printing, inkjet method, dipping method, roll coating method, slit coating method, and spin coating. The method and the spray method can be appropriately selected depending on the type of the substrate or the film thickness of the liquid crystal alignment film.

After applying the liquid crystal alignment treatment agent to the substrate, the heating means such as a hot plate or a heat cycle type oven (infrared) type oven can be used in the range of 30 to 300 depending on the type of the substrate or the solvent used for the liquid crystal alignment treatment agent. The temperature of ° C, preferably 30 to 250 ° C, allows the solvent to evaporate and becomes a liquid crystal alignment film. In particular, in the case where a plastic substrate is used for the substrate, it is preferably treated at a temperature of 30 to 150 °C.

When the thickness of the liquid crystal alignment film after firing is too thick, the surface of the display element that consumes electric power becomes unfavorable, and when it is too thin, the reliability of the element is lowered, preferably 5 to 500 nm, more preferably 10 ~300nm, especially preferably 10~250nm.

The liquid crystal composition used in the present invention is a liquid crystal composition as described above, and a space for regulating the electrode gap (also referred to as a gap) of the liquid crystal display element can also be introduced.

The method of 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 for the substrate, one of the liquid crystal alignment films is formed, and a part of the four sides of the substrate is removed, and a sealant is applied, and then the surface of the liquid crystal alignment film is formed inside. An empty cell that is bonded to the other side substrate is fabricated. And can be enumerated At the place where the sealant is applied, a liquid crystal composition is injected under reduced pressure to obtain a method of injecting a liquid crystal composition into a unit cell.

Further, when a plastic substrate or a film is used as the substrate, one of the liquid crystal alignment films is prepared to be formed on the substrate, and the liquid crystal composition is dropped by an ODP (One Drop Filling) method or an inkjet method on the substrate on one side, and then The substrate on the other side is bonded to obtain a method of injecting a liquid crystal composition into the unit cell. In the present invention, since the adhesion between the liquid crystal layer and the liquid crystal alignment film is high, the sealant may not be applied to the four sides of the substrate.

The gap of the liquid crystal display element can be controlled by the aforementioned space or the like. As described above, the method is a method in which a liquid crystal composition is introduced into a space of a desired size, or a method using a substrate having a column space of a desired size. Further, when a plastic or a film substrate is used for the substrate, and the substrate is bonded and laminated, no space is introduced, and the gap can be adjusted.

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

The liquid crystal display element of the present invention is obtained by curing a liquid crystal composition by irradiation of ultraviolet rays, and forming a liquid crystal layer of a cured product of a liquid crystal and a polymerizable compound. The hardening of the liquid crystal composition is carried out by injecting ultraviolet rays into the liquid crystal composition injected into the unit cell. In this case, examples of the light source of the ultraviolet irradiation device to be used include a metal halide lamp or a high pressure mercury lamp. Further, the wavelength of the ultraviolet light is preferably from 250 to 400 nm, particularly preferably from 310 to 370 nm. Further, heat treatment may be performed after the ultraviolet rays are irradiated. The temperature at this time is preferably 40 to 120 ° C, and particularly preferably 40 to 80 ° C.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but not limited thereto. The abbreviations are as follows.

L1: MLC-6608 (made by Mok)

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 represented by the following formula [A4]

A5: 1,3-diamino-4-octadecyloxybenzene

B1: 3,5-diaminobenzoic acid

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

C1: m-phenylene diamine

(tetracarboxylic dianhydride)

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

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

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

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

D5: tetracarboxylic dianhydride represented by the following formula [D5]

E1: alkoxydecane monomer represented by the following formula [E1]

E2: octadecyltriethoxydecane

E3: 3-methacryloxypropyltrimethoxydecane

E4: 3-ureidopropyltriethoxydecane

E5: tetraethoxy decane

N1: a photoradical generator represented by the following formula [N1]

<Specific Adhesive Compound>

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

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

BCS: ethylene glycol monobutyl ether

PB: propylene glycol monobutyl ether

PGME: propylene glycol monomethyl ether

ECS: ethylene glycol monoethyl ether

EC: diethylene glycol monoethyl ether

"Measurement of molecular weight of polyamidene-based polymers"

Using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko Co., Ltd.) and a column (KD-803, KD-805) (manufactured by Shodex Co., Ltd.), the measurement was carried out as follows.

Column temperature: 50 ° C

Solvent: N,N-dimethylformamide (as an additive, lithium bromide monohydrate (LiBr‧H ₂ O) is 30 mmol/L (liter), and phosphoric acid-anhydrous crystal (o-phosphoric acid) is 30 mmol/L, Tetrahydrofuran (THF) is 10ml/L)

Flow rate: 1.0ml/min

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

"Determination of the imidization ratio of polyamidene-based polymers"

20 mg of polyimine powder was placed in a NMR (Nuclear Magnetic Resonance) sample tube sampling tube standard (Sampling tube Standard), ψ 5 (manufactured by Kusano Scientific Co., Ltd.), and dimethyl hydrazine (DMSO-d6, 0.05 mass) was added. %TMS (tetramethyl decane) mixture (0.53 ml), applied with ultrasonic waves to completely dissolve. This solution was measured for proton NMR at 500 MHz in an NMR measuring machine (JEW-ECA500) (manufactured by JEOL Ltd., Japan). The ruthenium imidization ratio is determined by using a proton derived from a structure which is not changed before and after imidization as a reference proton, and the peak value of the proton is used, and the proline which is derived from the vicinity of 9.5 to 10.0 ppm is used. The peak value of the proton peak of the NH group is obtained by the following formula.

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

(x is the proton peak value of the NH group derived from proline, y is the peak value of the reference proton, and α is relative to the proline in the case of poly-proline (0% imidization) One of the NH protons, the ratio of the number of reference protons).

"Synthesis of Polyimine Polymers" <Synthesis Example 1>

D1 (3.00 g, 15.3 mmol), A1 (2.95 g, 7.75 mmol), B1 (0.94 g, 6.18 mmol) and C1 (0.17 g, 1.57 mmol) were mixed in PGME (21.2 g) at 40 ° C The reaction was carried out for 24 hours to obtain a polyamic acid solution (1) having a resin solid content concentration of 25% by mass.

The polyamino acid had a number average molecular weight (Mn) of 10,100 and a weight average molecular weight (Mw) of 43,600.

<Synthesis Example 2>

D2 (3.83 g, 15.3 mmol), A2 (6.11 g, mmol) and B1 (2.36 g, 15.5 mmol) were mixed in NMP (30.6 g), and reacted at 80 ° C for 5 hours, and then D1 (3.00) was added. g, 15.3 mmol) and NMP (15.3 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 Mn of the polyamic acid was 22,500. Mw is 67,100.

<Synthesis Example 3>

The polyamic acid solution (2) (30.0 g) obtained in Synthesis Example 2 was added to NMP and diluted to 6% by mass, and then acetic anhydride (3.90 g) and pyridine (2.40 g) were added as a ruthenium-imiding catalyst. It was allowed to react at 60 ° C for 2 hours. The reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain polyfluorene. Imine powder (3). The polyimide imineization rate of this polyimine was 60%, Mn was 20,100, and Mw was 57,100.

<Synthesis Example 4>

D2 (2.55g, 10.2mmol), A3 (4.47g, 10.3mmol), B1 (1.57g, 10.3mmol) and B2 (1.05g, 5.17mmol) were mixed in NMP (25.3g), and it was made at 80 degreeC. After reacting for 5 hours, D1 (3.00 g, 15.3 mmol) and NMP (12.6 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After the obtained polyaminic acid solution (30.0 g) was added to NMP and diluted to 6% by mass, acetic anhydride (3.85 g) and pyridine (2.42 g) were further added as a ruthenium catalyzed catalyst at 50 ° C. Reaction for 3 hours. The reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (4). The polyamidimide had a ruthenium iodide ratio of 56%, an Mn of 18,500, and a Mw of 54,000.

<Synthesis Example 5>

D2 (2.55 g, 10.2 mmol), A4 (3.05 g, 6.19 mmol), B1 (1.57 g, 10.3 mmol), B2 (0.42 g, 2.07 mmol) and C1 (0.22 g, 2.03 mmol) in NMP (19.6 g) After mixing and reacting at 80 ° C for 5 hours, D1 (2.00 g, 10.2 mmol) and NMP (9.82 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a resin solid content concentration of 25% by mass. Polylysine solution.

After the obtained polyaminic acid solution (30.0 g) was added to NMP and diluted to 6% by mass, acetic anhydride (3.85 g) and pyridine (2.50 g) were further added as a ruthenium catalyzed catalyst at 50 ° C. Reaction for 2 hours. The reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (5). The polyimide imineization rate of this polyimine was 49%, Mn was 16,100, and Mw was 49,800.

<Synthesis Example 6>

D3 (5.50 g, 24.5 mmol), A2 (5.889, 14.9 mmol), B1 (1.13 g, 7.43 mmol) and B2 (0.51 g, 2.51 mmol) were mixed in NMP (39.1 g), and reacted at 40 ° C After 12 hours, a polyamic acid solution having a resin solid content concentration of 25% by mass was obtained.

After the obtained polyaminic acid solution (30.0 g) was added to NMP and diluted to 6% by mass, acetic anhydride (3.85 g) and pyridine (2.48 g) were further added as a ruthenium catalyzed catalyst at 60 ° C. Reaction for 2.5 hours. The reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (6). The polyimide imineization rate of this polyimine was 63%, Mn was 17,200, and Mw was 49,100.

<Synthesis Example 7>

D3 (5.50 g, 24.5 mmol), A4 (3.67 g, 7.45 mmol) and B1 (2.65 g, 17.4 mmol) were mixed in NMP (35.5 g) at 40 ° C The reaction was carried out for 12 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After the obtained polyaminic acid solution (30.0 g) was added to NMP and diluted to 6% by mass, acetic anhydride (3.85 g) and pyridine (2.50 g) were further added as a ruthenium catalyzed catalyst at 50 ° C. Reaction for 3 hours. The reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (7). The polyamidimide had a ruthenium iodide ratio of 54%, an Mn of 17,400, and a Mw of 47,800.

<Synthesis Example 8>

D4 (4.59 g, 15.3 mmol), A3 (6.70 g, 15.5 mmol), B1 (1.89 g, 12.4 mmol) and B2 (0.63 g, 3.10 mmol) were mixed in NMP (33.6 g) at 50 ° C After the reaction for 8 hours, 1 (3.00 g, 15.3 mmol) and NMP (16.8 g) were further added to D, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content of 25% by mass.

After the obtained polyaminic acid solution (30.0 g) was added to NMP and diluted to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.30 g) were further added as a ruthenium catalyzed catalyst at 70 ° C. Reaction for 3 hours. The reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (8). The polyamidimide had an imidization ratio of 71%, an Mn of 17,100, and a Mw of 38,800.

<Synthesis Example 9>

D5 (1.68 g, 7.92 mmol), A2 (2.53 g, 6.41 mmol), B1 (0.49 g, 3.22 mmol), and B2 (1.30 g, 6.40 mmol) were mixed in PGME (15.1 g) at 50 ° C After reacting for 24 hours, D1 (1.55 g, 7.90 mmol) and PGME (7.54 g) were further added, and the mixture was reacted at 50 ° C for 12 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass (9). . This polyamic acid had an Mn of 10,500 and a Mw of 48,500.

<Synthesis Example 10>

D2 (3.83 g, 15.3 mmol), A5 (5.84 g, 15.5 mmol) and B1 (2.36 g, 15.5 mmol) were mixed in NMP (30.0 g), and reacted at 80 ° C for 5 hours, and then D1 ( 3.00 g, 15.3 mmol) and NMP (15.0 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After the obtained polyaminic acid solution (30.0 g) was added to NMP and diluted to 6% by mass, acetic anhydride (3.90 g) and pyridine (2.40 g) were further added as a ruthenium catalyzed catalyst at 60 ° C. Reaction for 2 hours. The reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (10). The polyamidimide had a ruthenium imidation ratio of 61%, an Mn of 19,000 and a Mw of 58,100.

<Synthesis Example 11>

D2 (3.83g, 15.3mmol) and B1 (4.72g, 31.0mmol) The mixture was mixed with NMP (23.1 g), and reacted at 80 ° C for 5 hours, and then D1 (3.00 g, 15.3 mmol) and NMP (11.5 g) were further added and reacted at 40 ° C for 6 hours to obtain a resin solid content concentration. It is a 25% by mass polyamine solution (11). This polyamic acid had an Mn of 25,900 and a Mw of 79,100.

<Synthesis Example 12>

After the polyacrylic acid solution (11) (30.0 g) obtained in Synthesis Example 11 was added to NMP and diluted to 6% by mass, acetic anhydride (3.85 g) and pyridine (2.40 g) were further added as a ruthenium amide catalyst. It was allowed to react at 60 ° C for 2 hours. The reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (12). The polyimide imineization rate of this polyimine was 59%, Mn was 21,200, and Mw was 60,100.

The polyimide-based polymers obtained in Synthesis Examples 1 to 12 are shown in Table 10.

"Synthesis of polyoxyalkylene polymers" <Synthesis Example 13>

A solution of alkoxydecane monomer was prepared by mixing ECS (28.3 g), E1 (4.10 g), E3 (7.45 g), and E5 (32.5 g) in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube. In the solution, a solution prepared by mixing ECS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst was added dropwise at 25 ° C for 30 minutes, and further stirred at 25 ° C for 30 minutes. Then, the mixture was heated under an oil bath for 30 minutes, and then a mixed solution of a methanol solution (1.20 g) and ECS (0.90 g) having a content of E4 of 92% by mass was added. Further, the mixture was refluxed for 30 minutes, and then cooled to obtain a polyoxysilane solution (1) having a SiO ₂ conversion concentration of 12% by mass.

<Synthesis Example 14>

A solution of alkoxydecane monomer was prepared by mixing EC (25.4 g), E1 (8.20 g), E3 (19.9 g) and E5 (20.0 g) in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube. 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 was added, and the mixture was dropped at 25 ° C for 30 minutes, and further stirred at 25 ° C for 30 minutes. Then, the mixture was refluxed for 30 minutes using an oil bath, and then a mixed solution of a methanol solution (1.20 g) and EC (0.90 g) having a content of E4 of 92% by mass was added. Further, after refluxing for 30 minutes, the mixture was cooled to obtain a polyoxyalkylene solution (2) having a SiO ₂ conversion concentration of 12% by mass.

<Synthesis Example 15>

A solution of alkoxydecane monomer was prepared by mixing EC (29.2 g), E1 (4.10 g) and E5 (38.8 g) in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube. In this solution, a solution prepared by mixing EC (14.6 g), water (10.8 g), and oxalic acid (0.50 g) as a catalyst was added, and the mixture was dropped at 25 ° C for 30 minutes, and further stirred at 25 ° C for 30 minutes. Then, the mixture was refluxed for 30 minutes using an oil bath, and then a premixed solution of a methanol solution (1.20 g) and EC (0.90 g) having a content of E4 of 92% by mass was added. Further, the mixture was refluxed for 30 minutes, and then cooled to obtain a polyoxoxane solution (3) having a SiO ₂ conversion concentration of 12% by mass.

<Synthesis Example 16>

A solution of alkoxydecane monomer was prepared by mixing ECS (28.3 g), E2 (4.07 g), E3 (7.45 g) and E5 (32.5 g) in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube. In the solution, a solution prepared by mixing ECS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst was added dropwise at 25 ° C for 30 minutes, and further stirred at 25 ° C for 30 minutes. Then, the mixture was refluxed for 30 minutes using an oil bath, and then a premixed solution of a methanol solution (1.20 g) having an E4 content of 92% by mass and ECS (0.90 g) was added. After further refluxing for 30 minutes, the mixture was allowed to cool to obtain a polyoxoxane solution (4) having a SiO ₂ conversion concentration of 12% by mass.

The polyoxyalkylene-based polymers obtained in Synthesis Examples 13 to 16 are shown in Table 11.

"Modulation of liquid crystal composition" (Liquid crystal composition (1))

L1 (2.40 g), R1 (1.20 g), R2 (1.20 g), S1 (0.024 g), and P1 (0.012 g) were mixed to obtain a liquid crystal composition (1).

(Liquid crystal composition (2))

L1 (2.40 g), R1 (1.20 g), R2 (1.20 g), S1 (0.24 g), and P1 (0.012 g) were mixed to obtain a liquid crystal composition (2).

(Liquid crystal composition (3))

L1 (2.40 g), R1 (1.20 g), R2 (1.20 g), S2 (0.048 g), and P1 (0.012 g) were mixed to obtain a liquid crystal composition (3).

(Liquid crystal composition (4))

L1 (2.40 g), R1 (1.20 g), R2 (1.20 g), and P1 (0.012 g) were mixed to obtain a liquid crystal composition (4).

"Production of Liquid Crystal Display Element and Evaluation of Liquid Crystal Alignment (Glass Substrate)"

The liquid crystal alignment treatment agents obtained in Examples 4, 11, 12, 16, 17, and 20, and Comparative Examples 1, 3, and 5 were subjected to pressure filtration using a membrane filter having a pore size of 1 μm. The obtained solution was washed with pure water and IPA (isopropyl alcohol) to a 100×100 mm glass substrate with an ITO electrode (vertical: The ITO surface of 100 mm, horizontal: 100 mm, thickness: 0.7 mm) was spin-coated, heated on a hot plate at 100 ° C for 5 minutes, and heat-treated in a heat cycle type clean oven at 210 ° C for 30 minutes to obtain a film thickness. It is a 100 nm ITO substrate with a liquid crystal alignment film. Two pieces of the obtained ITO substrate with a liquid crystal alignment film were prepared, and a liquid crystal alignment film surface of one of the substrates was applied to a space of 6 μm. Then, the liquid crystal alignment film surface of the space in which the substrate is applied is applied, and the liquid crystal composition is dropped by an ODF (One Drop Filling) method, and then the liquid crystal alignment film interface is faced to the other substrate. Liquid crystal display element before processing.

The liquid crystal display element before the treatment was irradiated with ultraviolet light at a wavelength of 350 nm or less using a metal halide lamp having an illuminance of 20 mW, and irradiated for 30 seconds. At this time, the temperature in the irradiation device when the liquid crystal cell was irradiated with ultraviolet rays was controlled at 25 °C. Thereby, a liquid crystal display element (reverse type element) was obtained.

The liquid crystal alignment element was evaluated using this liquid crystal display element. In the liquid crystal alignment system, the device was observed with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) to confirm whether or not the liquid crystal was aligned vertically. Specifically, the liquid crystal is aligned vertically, and this evaluation is excellent (good in Tables 15 to 17).

The liquid crystal display element which completed the liquid crystal alignment evaluation mentioned above was stored in the thermostat of temperature 90 for 96 hours. Then, the liquid crystal alignment property was evaluated under the same conditions as above. Specifically, in the case where no interference was observed in the liquid crystal alignment property and the liquid crystal was uniformly aligned, this evaluation was excellent (good in Tables 15 to 17).

"Production of Liquid Crystal Display Devices and Evaluation of Liquid Crystal Alignment (Plastic Substrate)"

The liquid crystal alignment treatment agents obtained in Examples 1 to 3, 5 to 10, 13 to 15, 18, 19, and Comparative Examples 2 and 4 were subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm. The obtained solution was washed with pure water and IPA (isopropyl alcohol) to a 150 × 150 mm PET (polyethylene terephthalate) substrate with an ITO electrode (vertical: 150 mm, horizontal: 150 mm, thickness: The 0.2 mm) ITO surface was coated on a bar coater, and dried on a hot plate at 100 ° C for 5 minutes, and heat-treated in a heat cycle type clean oven at 120 ° C for 2 minutes to obtain a film thickness of 100 nm. ITO substrate of liquid crystal alignment film. Two pieces of the obtained ITO substrate with a liquid crystal alignment film were prepared, and a liquid crystal alignment film surface of one of the substrates was applied to a space of 6 μm. Then, the liquid crystal alignment film surface of the space in which the substrate is applied is applied, the liquid crystal composition is dropped by the ODF method, and then the liquid crystal alignment film interface facing the other substrate is bonded to obtain a liquid crystal display before the treatment. element.

The liquid crystal display element before the treatment was irradiated with ultraviolet light at a wavelength of 350 nm or less using a metal halide lamp having an illuminance of 20 mW, and irradiated for 30 seconds. At this time, the temperature in the irradiation device when the liquid crystal cell was irradiated with ultraviolet rays was controlled at 25 °C. Thereby, a liquid crystal display element (reverse type element) was obtained.

The liquid crystal alignment element was evaluated using this liquid crystal display element. In the liquid crystal alignment system, the device was observed with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) to confirm whether or not the liquid crystal was aligned vertically. Specifically, the liquid crystal is aligned vertically, which is excellent in this evaluation (Tables 15 to 17). Good indication).

The liquid crystal display element which completed the liquid crystal alignment evaluation mentioned above was stored in the thermostat of temperature 90 for 96 hours. Then, the liquid crystal alignment property was evaluated under the same conditions as above. Specifically, in the case where no interference was observed in the liquid crystal alignment property and the liquid crystal was uniformly aligned, this evaluation was excellent (good in Tables 15 to 17).

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

The optical characteristics (transparency and scattering characteristics) of the liquid crystal display element (glass substrate and plastic substrate) obtained by the above method were evaluated.

The evaluation of the transparency at the time of no voltage application was performed by measuring the transmittance of the liquid crystal display element (glass substrate and plastic substrate) in a voltage-free application state. Specifically, the transmittance was measured in a measuring apparatus using UV-3600 (manufactured by Shimadzu Corporation) at a temperature of 25 ° C and a scanning wavelength of 300 to 800 nm. In the case of a liquid crystal display element (glass substrate), the glass substrate with the ITO electrode described above and the liquid crystal display element (plastic substrate) are used as a reference (reference example), and the PET substrate with the ITO electrode described above is used. The evaluation is based on the transmittance at a wavelength of 450 nm, and the higher the transmittance, the more excellent the transparency.

Further, in Examples 1 to 3, 5 to 7, 13 to 17, and 20, in addition to the above-described standard test, the transmittance of the liquid crystal display element after storage for 144 hours in a thermostat having a temperature of 90 was carried out as an emphasis test. evaluation of. Still, the evaluation method is the same as the above. The values of the transmittance (%) are shown in Tables 15 to 17.

The evaluation of the scattering characteristics at the time of voltage application was performed on a liquid crystal display element (glass substrate and plastic substrate), and 30 V was applied by an alternating current drive, and the alignment state of the liquid crystal was visually observed. Specifically, those whose components are white turbid, that is, the scattering characteristics are obtained, are excellent in this evaluation (good in Tables 15 to 17).

"Evaluation of the adhesion of the liquid crystal layer to the liquid crystal alignment film"

The liquid crystal display element (glass substrate and plastic substrate) obtained by the above method was used to evaluate the adhesion of the liquid crystal layer and the liquid crystal alignment film.

The liquid crystal display element (glass substrate and plastic substrate) was kept in a constant temperature and humidity chamber at a temperature of 80 ° C and a humidity of 90% RH for 24 hours, and the presence or absence of bubbles in the liquid crystal display element and the peeling of the element were confirmed. Specifically, in the case where no air bubbles were observed in the element and peeling of the element (a state in which the liquid crystal layer and the liquid crystal alignment film were peeled off), the evaluation was excellent (good in the table).

Further, in Examples 1 to 3, 5 to 7, 13 to 17, and 20, in addition to the above-described standard test, the evaluation was carried out in a constant temperature and humidity chamber at a temperature of 80 ° C and a humidity of 90% RH. Evaluation after hours. Still, the evaluation method is the same as the above. The results (adhesiveness) of the adhesion between the liquid crystal layer and the liquid crystal alignment film are shown in Tables 15 to 17.

<Modulation of Liquid Crystal Alignment Treatment Agent> <Liquid alignment treatment agent (1)>

The polyamic acid solution (1) (5.50 g) obtained by synthesizing the resin having a solid content of 25% by mass was added to PGME (20.7 g) and γ-BL. (4.38 g), the mixture was stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (1). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (2)>

The polyamic acid solution (1) (10.0 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 1 was added with N1 (0.125 g), M1 (0.375 g), K1 (0.175 g), and PGME (37.6 g). And γ-BL (7.96 g), and stirred at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (2). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (3)>

The polyamic acid solution (2) (5.50 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2 was added with NMP (10.5 g) and BCS (14.6 g), and stirred at 25 ° C for 4 hours to obtain a liquid crystal. Orientation treatment agent (3). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (4)>

The polyimine powder (3) (1.45 g) obtained in Synthesis Example 3 was added with γ-BL (3.08 g) and PGME (27.7 g), and stirred at 60 ° C for 24 hours to obtain a liquid crystal alignment treatment agent (4). . In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (5)>

The polyimine powder (4) (1.40 g) obtained in Synthesis Example 4 was added with γ-BL (2.97 g) and PGME (26.7 g), and stirred at 60 ° C for 24 hours to obtain a liquid crystal alignment treatment agent (5). . In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (6)>

To the polyimine powder (4) (1.40 g) obtained in Synthesis Example 4, γ-BL (2.97 g) and PGME (26.7 g) were added, and the mixture was stirred at 60 ° C for 24 hours, and then N1 (0.098 g) was added. M1 (0.42 g) and K1 (0.07 g) were stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (6). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (7)>

To the polyimine powder (4) (1.45 g) obtained in Synthesis Example 4, γ-BL (6.15 g) and PGME (24.6 g) were added, and the mixture was stirred at 60 ° C for 24 hours, and then N1 (0.073 g) was added thereto. K1 (0.145 g) was stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (7). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (8)>

To the polyimine powder (5) (1.45 g) obtained in Synthesis Example 5, γ-BL (6.15 g) and PGME (24.6 g) were added, and the mixture was stirred at 60 ° C for 24 hours, and then N1 (0.044 g) was added. M1 (0.145g) and K1 (0.073g), stirred at 25 ° C After 4 hours, a liquid crystal alignment treatment agent (8) was obtained. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (9)>

The polyimine powder (6) (1.40 g) obtained in Synthesis Example 6 was added with γ-BL (2.97 g) and PGME (26.7 g), and stirred at 60 ° C for 24 hours, and then N1 (0.007 g) was added thereto. K1 (0.098 g) was stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (9). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (10)>

The polyimine powder (7) (1.45 g) obtained in Synthesis Example 7 was added with γ-BL (13.9 g), BCS (7.69 g) and PB (9.23 g), and stirred at 60 ° C for 24 hours, and then added. N1 (0.102 g), M2 (0.073 g), and K1 (0.073 g) were stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (10). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (11)>

To the polyimine powder (8) (1.45 g) obtained in Synthesis Example 8, NEP (12.3 g), BCS (9.23 g) and PB (9.23 g) were added, and the mixture was stirred at 60 ° C for 24 hours. Then, N1 (0.073 g) and K1 (0.044 g) were added, and the mixture was stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (11). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (12)>

The polyamic acid solution (9) (5.50 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 9 was added to PGME (20.7 g) and γ-BL (4.38 g), and stirred at 25 ° C for 4 hours. A liquid crystal alignment treatment agent (12) was obtained. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (13)>

The polyamic acid solution (9) (5.50 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 9 was added to PGME (20.7 g) and γ-BL (4.38 g), and stirred at 25 ° C for 4 hours. Then, N1 (0.069 g), M2 (0.138 g) and K1 (0.097 g) were added, and the mixture was stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (13). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (14)>

The polyimine powder (10) (1.45 g) obtained in Synthesis Example 10 was added with γ-BL (3.08 g) and γ-BL (27.7 g), and stirred at 60 ° C for 24 hours to obtain a liquid crystal alignment treatment agent ( 14). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (15)>

The polyaluminoxane solution (1) (12.5 g) obtained in Synthesis Example 13 was added. ECS (1.73 g), BCS (9.55 g), and PB (9.55 g) were stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (15). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (16)>

To the polyoxane solution (2) (12.0 g) obtained in Synthesis Example 14, N1 (0.072 g), M1 (0.288 g), EC (0.14 g), PB (10.7 g) and PGME (9.17 g) were added. The mixture was stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (16). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (17)>

In the polyoxane solution (3) (12.0 g) obtained in Synthesis Example 15, EC (0.14 g), PB (10.7 g) and PGME (9.17 g) were added, and stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment. Agent (17). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (18)>

In the polyoxane solution (4) (12.0 g) obtained in Synthesis Example 16, ECS (1.66 g), BCS (9.17 g) and PB (9.17 g) were added, and stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment. Agent (18). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid Crystal Alignment Treatment Agent (19) (Comparative Example)>

The polyamic acid solution (11) (5.50 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 11 was added with NMP (10.5 g) and BCS (14.6 g), and stirred at 25 ° C for 4 hours to obtain a liquid crystal. Orientation treatment agent (19). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Liquid alignment treatment agent (20) (comparative example)>

The polyimine powder (12) (1.45 g) obtained in Synthesis Example 12 was added with γ-BL (3.08 g) and PGME (27.7 g), and stirred at 60 ° C for 24 hours to obtain a liquid crystal alignment treatment agent (20). . In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

<Examples 1 to 20, and Comparative Examples 1 to 5>

Any one of the liquid crystal compositions (1) to (4) and any one of the liquid crystal alignment treatment agents (1) to (20) are used in combination of the following Tables 12 to 17 to prepare an evaluation. The liquid crystal display element performs evaluation of the liquid crystal display element. The results of these are shown in Tables 12-14.

However, in Tables 12 to 14, *1 to *3 mean the following.

*1: The content ratio (parts by mass) of a specific specific agent for 100 parts by mass of all the polymers. *2: The content ratio (parts by mass) of the specific adhesive compound to 100 parts by mass of the total polymer. *3: The content ratio (parts by mass) of a specific crosslinkable compound in 100 parts by mass of the total polymer.

Further, in Tables 15 to 17, *1 to *5 mean the following.

*1: The liquid crystal is not vertically aligned. *2: No interference of liquid crystal alignment was observed at several locations within the component. *3: A very small amount of air bubbles were found in the component. *4: A small amount of bubbles were found in the component (more than *3). *5: Since the liquid crystal is not vertically aligned, it cannot be evaluated.

It can be clearly seen from Tables 12 to 17 above that the liquid crystal display element of the embodiment is liquid crystal after storage in a constant temperature and humidity chamber as compared with the comparative example. The transparency at the time of the alignment and the voltage-free application is good, and the adhesion between the liquid crystal layer and the liquid crystal alignment film is also high. Especially in the substrate of the liquid crystal display element, these characteristics are good even if a plastic substrate is used.

In particular, in the liquid crystal composition, in the embodiment including the specific compound, even if the liquid crystal display element is stored in the constant temperature bath, no interference is observed in the liquid crystal alignment, and the liquid crystal display element is further improved. Transparency when no voltage is applied. Specifically, the comparison of the same conditions, that is, the comparison between Example 4 and Comparative Example 3, Example 5 and Comparative Example 4, and Example 16 and Comparative Example 5.

Further, when the amount of the specific compound in the liquid crystal composition is large, the transparency of the liquid crystal display element at the time of voltage-free application is high as compared with the case of less. Specifically, comparison is made between the same conditions, that is, the comparison between the embodiment 2 and the embodiment 3, and the embodiment 16 and the embodiment 17.

Further, in the specific side chain structure, when the specific side chain structure of the formula [2-1] is used, the transparency at the time of voltage-free application of the liquid crystal display element is improved as compared with the case of using the formula [2-2]. It is emphasized that the test is carried out, and even after being stored in a constant temperature bath for a long period of time (for 144 hours in a thermostat having a temperature of 90 ° C), the transparency at the time of voltage application is increased. In the evaluation of the adhesion between the liquid crystal layer and the liquid crystal alignment film, when the specific side chain structure of the formula [2-1] is used, it is carried out as an emphasis test, and is stored in a constant temperature bath for a long time (at the above temperature of 80 ° C, humidity). After the 90% RH thermostat was stored for 48 hours, the adhesion was high. Specifically, it is a comparison of the same conditions emphasizing the test, that is, comparison between Example 5 and Example 15, and Example 16 and Example 20.

In addition, when a specific generation agent, a specific adhesive compound, and a specific crosslinkable compound are introduced into the liquid crystal alignment treatment agent, the liquid crystal layer of the liquid crystal display element and the liquid crystal alignment film are denser than those in the case where the liquid crystal display element is not introduced. The result of more improved sex. Specifically, it is a comparison of the same conditions emphasizing the test, that is, comparison between Example 1 and Example 2, Example 6 and Example 7, and Example 13 and Example 14.

[Industrial availability]

The liquid crystal display element of the present invention is a liquid crystal display which is intended to be used for display, and is used in a transporting machine or a transporting machine such as an automobile, a railway, an aircraft, etc., to regulate a light transmission window or an optical shutter element, particularly Anti-transformation components, etc.

In particular, when the element is used in a glass window of a vehicle, the light-harvesting efficiency is high at night and the effect of preventing glare from external light is also improved as compared with the conventional reverse-type element. Therefore, the safety in the operation of the vehicle or the comfort in riding can be further improved. Moreover, when the element is made of a film and is attached to a glass window of a vehicle, the adhesion between the liquid crystal layer and the liquid crystal alignment film is low compared with the conventional inversion type element, and it is difficult to cause the cause. Better or worse, so improve the reliability of components.

Further, the present device is used for a light guide plate of a display device such as an LCD or an OLED, or a back plate of a transparent display. Specifically, in the case where the back sheet of the transparent display is used, and when the transparent display and the element are displayed on the transparent display, the light from the back surface can be suppressed from penetrating.

The entire contents of the specification, the scope of the patent application, and the Abstract of the Japanese Patent Application No. 2014-195601, filed on Sep. 25, 2014, are hereby incorporated by reference.

Claims (13)

A liquid crystal display device having a liquid crystal layer that is cured by irradiating ultraviolet rays between a liquid crystal and a liquid crystal composition containing a polymerizable compound disposed between one of the electrodes, and at least one of the substrates is provided to vertically align the liquid crystal In the liquid crystal display device of the liquid crystal alignment film, the liquid crystal composition has a compound represented by the following formula [1], and the liquid crystal alignment film is obtained from a liquid crystal alignment treatment agent, and the liquid crystal alignment treatment agent contains a polymer of a side chain structure represented by the formula [2-1] or the formula [2-2], (X ¹ represents at least one selected from the group consisting of the following formulas [1-a] to [1-g]; and X ² represents a group selected from a single bond, -O-, -NH-, a group of -N(CH ₃ )-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO-, and -OCO- a binding group of at least one of the groups; X ³ represents a single bond or -(CH ₂ ) _a - (a is an integer from 1 to 15); and X ⁴ represents a group selected from a single bond, -O-, -OCH ₂ - a bonding group of at least one of -COO- and -OCO-; X ⁵ represents a divalent organic group having a benzene ring, a cyclohexane ring, or a steroid skeleton having 17 to 51 carbon atoms, Any hydrogen atom on the benzene ring or cyclohexane ring group may 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, and a carbon number of 1 to 3. a fluorine-containing alkoxy group or a fluorine atom; X ⁶ means at least one selected from the group consisting of a single bond, -O-, -OCH ₂ -, -CH ₂ O-, -COO-, and -OCO- a bonding group; X ⁷ represents a benzene ring or a cyclohexane ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or carbon. a fluorine-containing alkyl group having 1 to 3 and a fluorine-containing alkane having 1 to 3 carbon atoms Group or a fluorine atom; p represents an integer of 0 to 4; X ⁸ represents a system selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, the carbon number of fluorine-containing alkyl group of 1 to 18 carbon atoms, alkoxy of 1 to 18 and At least one of the group consisting of fluoroalkoxy groups having 1 to 18 carbon atoms; (X ^A represents a hydrogen atom or a benzene ring; X ^B represents a cyclic group selected from at least one selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring; and X ^c represents a carbon number selected from carbon At least one of a group consisting of an alkyl group of ~18, 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; (Y ¹ and Y ³ are each independently represented by a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, and -OCO- a binding group of at least one of the groups; Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15); and Y ⁴ represents a selected from a benzene ring, a cyclohexane ring, and a hetero a divalent cyclic group of at least one of the groups consisting of rings, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, and any hydrogen atom on the cyclic group may be 1 to 3 carbon atoms An alkyl group, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom; and Y ⁵ means a ring selected from a benzene ring and a ring a cyclic group of at least one of a group consisting of a hexane ring and a heterocyclic ring, and 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. a group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom; n represents an integer of 0 to 4; and Y ⁶ represents an alkyl group selected from carbon numbers 1 to 18. At least one of a group consisting of 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; [Chemical 4] -Y ⁷ -Y ⁸ [2-2] (Y ⁷ represents a group selected from a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N ( CH ₃₎ CO -, - COO- -OCO- groups and consisting of at least one of the binding group; the Y ⁸ are diagrams of carbon atoms from 8 to 22 carbon atoms or a fluorinated alkyl group of 6 to 18) . The liquid crystal display element of claim 1, wherein the compound represented by the above formula [1] is at least one selected from the group consisting of compounds represented by the following formulas [1a-1] to [1a-6]. , (X ^a , X ^b , X ^d , X ^f , X ^h and X ^k each independently represent an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms; X ^c and X ⁱ each independently represent -O -, -COO- or -OCO-; X ^e , X ^g and X ^j respectively represent -CH ₂ -, -O-, -COO- or -OCO-; p1, p3, p5, p7, p8 and p9 respectively Independently represents an integer from 1 to 12; p2, p4, and p6 each independently represent an integer of 1 or 2.) The liquid crystal display element of claim 1 or 2, wherein the liquid crystal alignment treatment agent comprises an acrylic polymer, a methacrylic polymer, a novolac resin, a polyhydroxystyrene, a polyimine precursor, and a polyfluorene. A liquid crystal alignment treatment agent for a polymer of at least one of the group consisting of imine, polyamine, polyester, cellulose, and polyoxyalkylene. The liquid crystal display element of claim 1 or 2, wherein the liquid crystal alignment treatment agent comprises a diamine component and a polyimine component, and the diamine component contains the above formula [2-1] or formula [2-2] A diamine represented by a side chain structure which is a polyimine precursor obtained by a reaction with a tetracarboxylic acid component or a polyimine which is imidized with the polyimine precursor. The liquid crystal display element of claim 4, wherein the diamine is a diamine represented by the following formula [2a], (Y represents a structure represented by the above formula [2-1] or formula [2-2]; m represents an integer of 1 to 4). The liquid crystal display element according to any one of claims 4 to 5, wherein the tetracarboxylic acid component comprises a tetracarboxylic dianhydride represented by the following formula [3]. (Z is a structure selected from at least one of the groups consisting of the structures represented by the following formulas [3a] to [3k]); (Z ¹ to Z ⁴ each independently represent at least one selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom, and a benzene ring; and Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group). The liquid crystal display device of claim 1 or 2, wherein the liquid crystal alignment treatment agent comprises a polyoxyalkylene obtained by polycondensing an alkoxysilane represented by the following formula [A1], or the formula [A1] a polyoxyalkylene obtained by polycondensation of an alkoxydecane represented by the following alkoxydecane represented by the following formula [A2] and/or an alkoxysilane represented by the formula [A3], [Chem. 10] (A ¹ _m Si(A ² ) _n (OA ³ ) _p [A1] (A ¹ represents a side chain structure represented by the above formula [2-1] or formula [2-2]; and A ² represents a hydrogen atom or a carbon number 1 to 5 alkyl; A ³ represents an alkyl group having 1 to 5 carbon atoms; m represents an integer of 1 or 2; n represents an integer of 0 to 2; and p represents an integer of 0 to 3; +n+p is 4); [11] (B ¹ ) _m Si(B ² ) _n (OB ³ ) _p [A2] (B ¹ means having a group selected from a vinyl group, an epoxy group, an amine group, a fluorenyl group An organic group having 2 to 12 carbon atoms of at least one of the group consisting of isocyanate groups, methacryl groups, acryl groups, ureido groups and cinnamyl groups; and B ² groups representing hydrogen atoms or carbon numbers 1~ the 5 alkyl; B represents a carbon-based ³ alkyl group of 1 to 5; m represents an integer of 1 or 2 lines of; ~ n-2 line represents an integer of 0; p represents an integer of 0 to 3, Department of However, m + n + p is 4); [Formula _{^{12] (D 1) n Si}} (OD 2) 4-n [A3] (D 1 represents a hydrogen atom or a carbon-based alkyl group of 1 to 5; D ² It is an alkyl group having 1 to 5 carbon atoms; n is an integer of 0 to 3). The liquid crystal display device according to any one of claims 1 to 7, wherein the liquid crystal alignment treatment agent contains at least one selected from the group consisting of a photo radical generator, a photoacid generator, and a photobase generator. Producer. The liquid crystal display device according to any one of claims 1 to 8, wherein the liquid crystal alignment treatment agent contains a group having a structure selected from the group consisting of the following formulas [b-1] to [b-8] a compound of at least one of the group, (B ^a represents a hydrogen atom or a benzene ring; B ^b represents a cyclic group selected from at least one selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring; and B ^c represents a carbon number selected from carbon At least one of a group consisting of an alkyl group of ~18, 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. The liquid crystal display element according to any one of claims 1 to 9, wherein the liquid crystal alignment treatment agent contains a group selected from the group consisting of an epoxy group, an isocyanate group, an oxetanyl group, a cyclic carbonate group, a hydroxyl group, and a hydroxy alkane. A compound of a substituent of at least one of the group consisting of a lower alkoxyalkyl group. The liquid crystal display element according to any one of claims 1 to 10, wherein the liquid crystal alignment treatment agent contains a solvent selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethanediol, and 1,2-propane Alcohol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, and a group of compounds represented by the following formula [D1]~[D3] At least one 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; and D ³ represents an alkyl group having 1 to 4 carbon atoms). The liquid crystal display element according to any one of claims 1 to 11, wherein the liquid crystal alignment treatment agent is selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone. A solvent of at least one of the group consisting of. The liquid crystal display device according to any one of claims 1 to 12, wherein the substrate of the liquid crystal display element is a glass substrate or a plastic substrate.