TWI632177B - Liquid crystal alignment film, liquid crystal display element and manufacturing method of the same - Google Patents

Abstract

The invention provides a liquid crystal alignment film, a liquid crystal display element and a manufacturing method thereof. The liquid crystal alignment film includes a bridge structure represented by formula (1): Formula (1) In Formula (1), T represents an aliphatic, alicyclic or aromatic structure; Q represents an organic group containing a photoreactive group; and k represents an integer of 1 or more.

Description

Liquid crystal alignment film, liquid crystal display element and manufacturing method thereof

The present invention relates to a liquid crystal alignment film, a liquid crystal display element, and a method for manufacturing the same, and more particularly, to a liquid crystal alignment film capable of forming a liquid crystal display element with little residual polymerizable compound and excellent long-term reliability, and a liquid crystal having the liquid crystal alignment film A display element and a method for manufacturing the liquid crystal display element.

With the development of liquid crystal displays toward large-sized display specifications, in order to overcome the problem of viewing angles in large-sized displays, the wide-viewing angle technology of liquid crystal display panels must also continue to improve and breakthrough. Multi-domain Vertical Alignment (MVA) liquid crystal display panel is a common wide viewing angle technology. The multi-domain vertical alignment type liquid crystal display panel is formed with protrusions in the liquid crystal panel, and the protrusions can limit the direction in which the liquid crystal molecules are tilted, thereby achieving a wide viewing angle display effect. However, the multi-domain vertical alignment type liquid crystal display panel cannot avoid problems caused by insufficient transmittance and contrast of the protrusions and slow response speed of the liquid crystal molecules.

In recent years, in order to solve the above problems, a polymer stabilized alignment (Polymer Sustained Alignment, PSA) technology has been developed. This technology uses a gap between a pair of substrates composed of a substrate with a patterned conductive film and a substrate without a patterned conductive film, or a pair of substrates composed of two substrates with a patterned conductive film. In the gap, a liquid crystal composition containing a polymerizable compound is held, and the liquid crystal composition is irradiated with ultraviolet light to polymerize the polymerizable compound while a voltage is applied between the conductive films, thereby exhibiting a pretilt angle characteristic and controlling the liquid crystal alignment direction. This technology enables the conductive film to form a specific structure, thereby achieving the effects of widening the viewing angle and speeding up the response of liquid crystal molecules, thereby solving the problems of unavoidable light transmittance and contrast of the multi-domain vertical alignment type liquid crystal display panel.

However, in order to polymerize the aforementioned polymerizable compound, a large amount of ultraviolet rays such as 100,000 J / m ² must be irradiated. Therefore, in addition to the problem of decomposition of the liquid crystal molecules, unreacted compounds that cannot be polymerized even when irradiated with ultraviolet rays remain in the liquid crystal layer. problem. The remaining unreacted compounds are bonded to each other in the liquid crystal layer, which results in poor long-term reliability of the panel, and thus cannot reach a practical level.

Therefore, how to improve the above problems is actually one of the goals actively studied by those skilled in the art.

In view of this, the present invention provides a liquid crystal alignment film capable of forming a liquid crystal display element with little residual polymerizable compound and excellent long-term reliability, a liquid crystal display element including the liquid crystal alignment film, and a method for manufacturing the liquid crystal display element.

The present invention provides a liquid crystal alignment film, including a bridge structure represented by formula (1): Formula (1) In Formula (1), T represents an aliphatic, alicyclic or aromatic structure; Q represents an organic group containing a photoreactive group; and k represents an integer of 1 or more.

In an embodiment of the present invention, the photoreactive group includes a vinyl group, a (meth) acrylic group, an anthracenyl group, a cinnamoyl group, a chalconyl group, At least one of a coumarin group, a maleimide group, or a stilbenyl group.

In an embodiment of the present invention, the above-mentioned bridging structure is obtained from a compound (A) having a maleic acid group through a radical polymerization reaction, and the compound (A) having a maleic acid group is It has two or more polymerizable maleic acid amino groups in the molecule.

In an embodiment of the present invention, the above-mentioned free radical polymerization reaction occurs on a double bond formed after the compound (A) having a maleic acid amino group undergoes a dehydration ring-closing reaction.

In one embodiment of the present invention, the compound (A) having a maleic acid amino group is obtained by reacting a maleic anhydride derivative (a1) and a diamine component (a2).

In an embodiment of the present invention, the diamine component (a2) includes a diamine compound (a2-1) represented by the formula (2): Formula (2) In formula (2), R _a represents -CH _2- , -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO -, -OCO-, -CON (CH ₃ )-or -N (CH ₃ ) CO-. R _b represents a carbon number of from 1 to 20 non-substituted or fluorine-substituted linear alkylene group, and in the alkylene arbitrary -CH ₂ - may be -CF ₂ -, - CH = CH -Or the following substituents, which include: -O-, -COO-, -NHCO-, -NH-, carbocyclyl or heterocyclic group, wherein when two or more -CH _2- When substituted with the substituent, the substituents are not adjacent. R _c represents -CH _2- , -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH _{3) -, - N (CH} 3) CO-, carbocyclic group or heterocyclic group. R _d represents a vinyl phenyl group, -CR _e = CH ₂ , a carbocyclic group, a heterocyclic group, or a group represented by the following structural formula, and R _e represents a hydrogen atom or a methyl group which may be substituted by a fluorine atom: .

In an embodiment of the present invention, the diamine component (a2) further includes a diamine compound (a2-2) represented by the formula (3): Formula (3) In Formula (3), R ₃ represents -O-, , , , ,or ; R ₄ represents a steroid-containing group, an alkylene group having 2 to 30 carbon atoms, or an organic group represented by the formula (3-1): Formula (3-1) In formula (3-1), R ₅ represents a hydrogen atom, a fluorine atom or a methyl group; R ₆ , R ₇ or R ₈ each independently represents a single bond, -O-, , , , , Or an alkylene group having 1 to 3 carbon atoms; R ₉ represents or Wherein R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a fluorine atom or a methyl group; R ₁₀ represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, Alkoxy, -OCH ₂ F, -OCHF ₂ or -OCF _{3 having} a carbon number of 1 to 12; a represents 1 or 2; b, c, and d each independently represent an integer of 0 to 4; e, f, and g each Independently represents an integer from 0 to 3, and e + f + g ≧ 1; h and i each independently represent 1 or 2; when there are multiple R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R _In the case of ₁₁ or R ₁₂ , a plurality of R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ or R ₁₂ are each the same or different.

In an embodiment of the present invention, based on the diamine component (a2) being 100 moles, the amount of the diamine compound (a2-1) used is 5 moles to 70 moles.

In an embodiment of the present invention, based on the diamine component (a2) being 100 moles, the amount of the diamine compound (a2-2) used is 3 moles to 50 moles.

The present invention also provides a liquid crystal display element including the liquid crystal alignment film as described above.

The invention further provides a method for manufacturing a liquid crystal display element, which includes at least the following steps: forming a liquid crystal alignment film as described above on a pair of substrates including a conductive film, respectively. The substrate on which the liquid crystal alignment film is formed is arranged so that the liquid crystal alignment film faces each other. A liquid crystal composition is injected between the substrates to form a liquid crystal cell. And applying a voltage between the conductive films, and irradiating the liquid crystal cell with light in a state where the voltage is applied.

Based on the above, the liquid crystal alignment film of the present invention includes a specific bridging structure, so there is no problem that unreacted compounds remain in the liquid crystal layer. Furthermore, the liquid crystal alignment film of the present invention contains a bridging structure of an organic group containing a photoreactive group, so that no unreacted compounds remain in the liquid crystal layer, and the long-term reliability of the panel is excellent, so it is suitable for manufacturing liquid crystal alignment. Film and liquid crystal display element.

In order to make the above features and advantages of the present invention more comprehensible, embodiments are hereinafter given and described in detail as follows.

Here, it is explained that acrylic acid and / or methacrylic acid are represented by (meth) acrylic acid, and acrylate and / or methacrylic acid ester are represented by (meth) acrylate; similarly, (meth) Acrylofluorenyl refers to acrylfluorenyl and / or methacrylfluorenyl. ＜ Liquid crystal alignment film ＞

The invention provides a liquid crystal alignment film formed of a liquid crystal alignment agent. The liquid crystal alignment agent includes a compound (A) having a maleic acid group and a solvent (C). In addition, if necessary, the liquid crystal alignment agent may further include a polymer (B) and an additive (D).

The liquid crystal alignment film of the present invention includes a bridge structure represented by formula (1): Formula (1) In Formula (1), T represents an aliphatic, alicyclic or aromatic structure; Q represents an organic group containing a photoreactive group; and k represents an integer of 1 or more.

The above-mentioned photoreactive group-containing organic group is an organic group having a functional group capable of causing a photoreaction by irradiation of ultraviolet rays to form a covalent bond, and its structure is not limited as long as it has this ability. The photoreactive group includes a vinyl group, a (meth) acrylic group, an anthryl group, a cinnamic acid group, a chalcone group, a coumaryl group, a maleimide group, a distyryl group, or a combination thereof. . The photoreactive group may be directly bonded to the bridging structure, or may be bonded through an appropriate bonding group.

Examples of the photoreactive group include, but are not limited to, the group represented by the following formula. -R _a -R _b -R _c -R _d Formula (1-1)

In formula (1-1), R _a represents -CH _2- , -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-.

R _b represents an unsubstituted or fluorine-substituted linear alkylene group having a carbon number of 1 to 20, and any -CH ₂ -in the alkylene group may be -CF _2- , -CH = CH -, Or the following substituents, which include: -O-, -COO-, -NHCO-, -NH-, carbocyclyl or heterocyclic group, wherein when two or more -CH ₂ -When substituted with the substituent, the substituents are not adjacent.

R _c represents -CH _2- , -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH _{3) -, - N (CH} 3) CO-, carbocyclic group or heterocyclic group.

R _d represents a vinylphenyl group, -CR _e = CH ₂ , a carbocyclic group, a heterocyclic group, or a group represented by the following structural formula, and R _e represents a hydrogen atom or a methyl group which may be substituted with a fluorine atom.

When the bridging structure in the liquid crystal alignment film does not have an organic group containing a photoreactive group, after the liquid crystal display element prepared from the liquid crystal alignment film is irradiated with ultraviolet rays, the liquid crystal layer is still prone to the problem of polymerizable compounds remaining .

The bridging structure represented by the formula (1) is obtained from a compound (A) having a maleic acid group through a radical polymerization reaction, and the compound (A) having a maleic acid group has 2 in one molecule. Two or more polymerizable maleic acid amino groups are obtained by reacting a maleic anhydride derivative (a1) and a diamine component (a2).

Hereinafter, the compound (A) having a maleic acid group will be described in detail. Compounds with maleic acid ( A )

The compound (A) having a maleic acid group has two or more polymerizable maleic acid groups in one molecule, and is composed of a maleic anhydride derivative (a1) and a diamine component. (A2) obtained by reaction. Maleic anhydride derivative ( a1 )

Specific examples of the maleic anhydride derivative (a1) may include, but are not limited to, maleic anhydride, 2,3-dimethylmaleic anhydride, 2-methylmaleic anhydride, and 2,3-diethylmaleic anhydride , 2-ethylmaleic anhydride, or a combination of the above. Maleic anhydride, 2-methylmaleic anhydride or 2-ethylmaleic anhydride is preferred, and maleic anhydride or 2-methylmaleic anhydride is more preferred. The maleic anhydride derivative (a1) can be used alone or in combination. Diamine component ( a2 )

The diamine component (a2) includes a diamine compound (a2-1) represented by the formula (2) and a diamine compound (a2-2) represented by the formula (3). In addition, the diamine component (a2) may also include other diamine compounds (a2-3). Diamine compound ( a2-1 )

The diamine compound (a2-1) is a compound represented by formula (2). In Formula (2) Formula (2), R _a represents _{-CH 2 -, - O -,} - NH -, - N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - COO -, -OCO-, -CON (CH ₃ )-or -N (CH ₃ ) CO-. R _a can be formed by a general organic synthesis method, but from the viewpoint of ease of synthesis, -CH _2- , -O-, -NH-, -NHCO-, -CH ₂ O-, or -COO- is preferred. . R _b represents an unsubstituted or fluorine-substituted linear alkylene group having a carbon number of 1 to 20, and any -CH ₂ -in the alkylene group may be -CF _2- , -CH = CH -Or the following substituents, which include: -O-, -COO-, -NHCO-, -NH-, carbocyclyl or heterocyclic group, wherein when two or more -CH _2- When substituted with the substituent, the substituents are not adjacent. Preferably, R _b represents a linear alkylene group having 1 to 20 carbon atoms, and more preferably, R _b represents a linear alkylene group having 2 to 8 carbon atoms. Examples of the carbocyclic group include the following structures, but are not limited thereto. Examples of the heterocyclic group include the following structures, but are not limited thereto. R _c represents -CH _2- , -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH _{3) -, - N (CH} 3) CO-, carbocyclic group or heterocyclic group. Preferably, R _c represents -CH _2- , -O-, -NH-, -NHCO-, -COO-, -OCO-, carbocyclyl or heterocyclic group. Preferred examples are the same as those of R _b ; more preferably, R _c represents -CH _2- , -O-, -NH-, -NHCO-, -COO-, or -OCO-. R _d represents vinylphenyl, -CR _e = CH _2, a carbocyclic group, a heterocyclic group, or a group represented by the following structural formula, R _e represents a hydrogen atom or a methyl group may be substituted by fluorine atoms. Preferably, R _d represents a phenyl _{vinyl, -CH = CH 2, -C (} CH 3) = CH 2 or the following groups.

In formula (2), the bonding position of two amine groups (-NH ₂ ) is not particularly limited. Specifically, the benzene ring may be bonded to a 2,3 position, a 2,4 position, a 2,5 position, a 2,6 position, a 3,4 position, or a 3,5 position relative to a bonding group of a side chain. position. Among these, from the viewpoint of reactivity when synthesizing polyamic acid, the 2,4 position, the 2,5 position, or the 3,5 position is preferred. From the viewpoint of considering the ease when synthesizing a diamine compound, it is more preferably a 2,4 position or a 3,5 position.

Specific examples include the following compounds, but are not limited thereto. In the formula, X represents -C-, -O-, -NHCO-, -CONH-, -COO-, -OCO-, or -NH-, and l, m, and n each independently represent an integer of 0 to 20.

The diamine compound (a2-1) can be used alone or in combination. Based on the total usage of the diamine component (a2) is 100 mol, and the usage of the diamine compound (a2-1) may be 5 to 70 mol, preferably 10 mol to 60 mol, and more preferably 15 mol to 50 mol. When the usage amount of the diamine compound (a2-1) in the liquid crystal alignment film is within this range, the unreacted polymerizable compound remaining in the liquid crystal layer in the liquid crystal display element obtained from the liquid crystal alignment film less. Diamine compound ( a2-2 )

The diamine compound (a2-2) is a compound represented by the formula (3). Formula (3) In Formula (3), R ₃ represents -O-, , , , ,or ; R ₄ represents a steroid-containing group, an alkylene group having 2 to 30 carbon atoms, or an organic group represented by the formula (3-1): Formula (3-1) In formula (3-1), R ₅ represents a hydrogen atom, a fluorine atom or a methyl group; R ₆ , R ₇ or R ₈ each independently represents a single bond, -O-, , , , , Or an alkylene group having 1 to 3 carbon atoms; R ₉ represents or Wherein R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a fluorine atom or a methyl group; R ₁₀ represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, Alkoxy, -OCH ₂ F, -OCHF ₂ or -OCF _{3 having} a carbon number of 1 to 12; a represents 1 or 2; b, c, and d each independently represent an integer of 0 to 4; e, f, and g each Independently represents an integer from 0 to 3, and e + f + g ≧ 1; h and i each independently represent 1 or 2; when there are multiple R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R _In the case of ₁₁ or R ₁₂ , a plurality of R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ or R ₁₂ are each the same or different.

Specific examples of the diamine compound (a2-2) include, but are not limited to, 2,4-diaminophenyl ethyl formate, 3,5-diaminophenyl ethyl formate ( 3,5-diaminophenyl ethyl formate), 2,4-diaminophenyl propyl formate, 3,5-diaminophenyl propyl formate), 1-dodecoxy-2,4-diaminobenzene, 1-dodecoxy-2,4-diaminobenzene, 1-dodecoxy-2,4-diaminobenzene hexadecoxy-2,4-diaminobenzene), 1-octadecoxy-2,4-diaminobenzene, from formula (3-1-1) to formula (3 -1-29), or a combination thereof. Equation (3-1-1) Equation (3-1-2) Equation (3-1-3) Equation (3-1-4) Formula (3-1-5) Formula (3-1-6) Formula (3-1-7) Formula (3-1-8) Formula (3-1-9) Formula (3-1-10) Formula (3-1-11) Formula (3-1-12) Formula (3-1-13) Formula (3-1-14) Formula (3-1-15) Formula (3-1-16) Formula (3-1-17) Formula (3-1-18) Formula (3-1-19) Formula (3-1-20) Formula (3-1-21) Formula (3-1-22) Formula (3-1-23) Formula (3-1-24) Formula (3-1-25) Formula (3-1-26) Formula (3-1-27) Formula (3-1-28) Formula (3-1-29) In Formulas (3-1-1) to (3-1-29), R ₁₃ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. R ₁₄ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. In the formulae (3-1-23) to (3-1-26), j represents an integer of 3 to 12.

Among the above diamine compounds (a2-2), 1-dodecyloxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, 1 -Octadecyloxy-2,4-diaminobenzene, formula (3-1-3), formula (3-1-8) to formula (3-1-15), formula (3-1-19 ) And formula (3-1-23).

The diamine compound (a2-2) can be used alone or in combination. Based on the total usage of the diamine component (a2) is 100 mol, and the usage of the diamine compound (a2-2) may be 3 to 50 mol, preferably 5 mol to 40 mol, and more preferably 10 mol to 30 mol. When the diamine compound (a2-2) is used for the liquid crystal alignment film, the liquid crystal display element prepared from the liquid crystal alignment film has better long-term reliability. Other diamine compounds ( a2-3 )

In addition to the diamine compound (a2-1) and the diamine compound (a2-2) described above, the diamine component (a2) of the present invention can also be used by selectively mixing other diamine compounds (a2-3). Other diamine compounds (a2-3) may include, but are not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diamine Pentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diamine Decane, 4,4'-diaminoheptane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1 , 7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylnonane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis (3-aminopropoxy ) Ethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, tricyclo [6‧2‧1‧0 ^2,7 ] -undecene Dimethyldiamine, 4,4'-methylenebis (cyclohexylamine), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4, 4'-diaminodiphenylphosphonium, 4,4'-diaminobenzidineaniline, 4,4'-diamine Diphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amino-1- (4'-aminophenyl) -1,3,3 -Trimethylhydroindene, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylhydroindene, hexahydro-4,7-methyl bridged indenyl di Methylene diamine, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-amine Phenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] fluorene, 1,4-bis (4-aminophenoxy) benzene, 1,3- Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 9,10 -Bis (4-aminophenyl) anthracene (9,10-bis (4-aminophenyl) anthracene), 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4 , 4'-methylene-bis (2-chloroaniline), 4,4 '-(p-phenylene isopropylidene) bisaniline, 4,4'-(m-phenylene isopropylidene) ) Bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [(4-amino-2 -Trifluoromethyl) phenoxy] -octafluorobiphenyl, 5- [4- (4-n-pentyl Cyclohexyl) cyclohexyl] phenyl-methylene-1,3-diaminobenzene (5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diaminobenzene) or 1,1- Bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane (1,1-bis [4- (4-aminophenoxy) phenyl] -4- ( 4-ethylphenyl) cyclohexane, a compound represented by the formula (4-1) to the formula (4-23), or a combination thereof.

Formula (4-1) In formula (4-1), R _{3 is} as described above, and R ₁₅ represents a trifluoromethyl group, a fluoro group, or is derived from pyridine, pyrimidine, triazine, piperidine, piperazine, etc. A monovalent group containing a nitrogen atom ring structure.

Formula (4-2) In formula (4-2), R _{3 is} as described above, and R ₁₆ and R ₁₇ represent an aliphatic ring, an aromatic ring, or a heterocyclic group, and R ₁₈ represents a carbon number It is an alkyl group of 3 to 18, an alkoxy group of 3 to 18 carbons, a fluoroalkyl group of 1 to 5 carbon atoms, a fluoroalkoxy group of 1 to 5 carbon atoms, a cyano group or a halogen atom.

The other diamine compound (a2-3) represented by the formula (4-2) is preferably selected from compounds represented by the following formulae (4-2-1) to (4-2-5): Formula (4-2-1) Formula (4-2-2) Formula (4-2-3) Formula (4-2-4) Formula (4-2-5)

Formula (4-3) In Formula (4-3), R ₁₉ represents a hydrogen atom, a fluorenyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. Or halogen, and R ₁₉ in each repeating unit may be the same or different, and p ₁ is an integer of 1 to 3. The other diamine compound (a2-3) represented by the formula (4-3) is preferably selected from (1) when p ₁ is 1: p-diaminebenzene, m-diaminebenzene, ortho-diamine Benzene or 2,5-diamine toluene, etc .; (2) when p ₁ is 2: 4,4'-diamine-based biphenyl, 2,2'-dimethyl-4,4'-diamine-based Benzene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro -4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-di Aminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl or 4,4'-diamino-2,2'-bis ( (3) When p ₁ is 3: 1,4-bis (4'-aminophenyl) benzene and the like. Of these, p-diaminebenzene, 2,5-diaminetoluene, 4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl are more preferred. And 1,4-bis (4'-aminophenyl) benzene.

Formula (4-4) In Formula (4-4), p ₂ is an integer of 2-12.

Formula (4-5) In Formula (4-5), p ₃ is an integer of 1 to 5. Formula (4-5) is preferably 4,4'-diamino-diphenylsulfide.

Formula (4-6) In formula (4-6), R ₂₀ and R ₂₂ are the same or different and each represents a divalent organic group; R ₂₁ represents a derivative derived from pyridine, pyrimidine, triazine, piperidine, or piperazine A divalent group having a cyclic structure such as a nitrogen atom.

Formula (4-7) In formula (4-7), R ₂₃ , R ₂₄ , R _25, and R ₂₆ are the same or different, and each represents a hydrocarbon group having 1 to 12 carbons; p ₄ represents an integer of 1 to 3 ; P ₅ represents an integer from 1 to 20.

Formula (4-8) In formula (4-8), R ₂₇ represents an oxygen atom or a cyclohexane group; R ₂₈ represents -CH _2- ; R ₂₉ represents a phenyl group or a cyclohexane group; and R ₃₀ represents Hydrogen atom or heptyl. The other diamine compound (a2-3) represented by the formula (4-8) is preferably selected from compounds represented by the following formula (4-8-1) and formula (4-8-2): Formula (4-8-1) Formula (4-8-2)

The other diamine compounds (a2-3) represented by the formula (4-9) to the formula (4-15) are as follows: Formula (4-9) Formula (4-10) Formula (4-11) Formula (4-12) (4-13) Formula (4-14) Formula (4-15) In formulas (4-9) to (4-15), R _{31 is} preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R ₃₂ is more than A hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is preferred.

The other diamine compounds (a2-3) represented by the formula (4-16) to the formula (4-23) are as follows: (4-16) (4-17) (4-18) (4-19) Formula (4-20) Formula (4-21) (4-22) (4-23)

Among the other diamine compounds (a2-3), 1,2-diaminoethane, 4,4'-diaminodicyclohexylmethane, and 4,4'-diaminodiphenyl are preferred. Methane, 4,4'-diaminodiphenyl ether, 5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diaminobenzene, 1, 1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane, p-diaminebenzene, m-diaminebenzene, o-diaminebenzene A compound represented by the formula (4-8-1), or a combination thereof.

The other diamine compounds (a2-3) can be used alone or in combination. Based on the total usage of the diamine component (a2) is 100 mol, and the usage of other diamine compounds (a2-3) may be 0 to 70 mol, preferably 5 mol to 60 mol, more preferably It is 10 mol to 50 mol.

The method for producing the maleic acid-containing compound (A) of the present invention is not limited. Generally, it is obtained by reacting a maleic anhydride derivative (a1) and a diamine component (a2) in an organic solvent. Got. There is no particular limitation on the kind of the organic solvent as long as it can dissolve the reactants. Specific examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylmethylene, and N-methylhexanone. Lactam, γ-butyrolactone, acetone, methyl ethyl ketone, ethylene glycol n-butyl ether, dioxane, tetrahydrofuran, or a combination thereof. The solvent may be used singly or in combination. The reaction temperature of the maleic anhydride derivative (a1) and the diamine component (a2) is generally 0 to 100 ° C, preferably 0 to 80 ° C, and more preferably 0 to 70 ° C. The reaction time is generally 1 to 5 hours, preferably 2 to 4 hours.

The ratio of the maleic anhydride derivative (a1) to the diamine component (a2) is based on the molar ratio of the acid anhydride group of the maleic anhydride derivative (a1) to the amine group of the diamine component (a2). Is generally 0.5 to 2.5, preferably 0.8 to 2.0, and more preferably 1.0 to 1.8.

The compound (A) having a maleic acid group according to the present invention has a weight average molecular weight measured in terms of polystyrene measured in accordance with Gel Permeation Chromatography (GPC) of 2,500 to 150,000, preferably It is 3,500 to 100,000, and more preferably 4,500 to 80,000. Polymer ( B )

The polymer (B) of the present invention is selected from the group consisting of polyesters, polyesterimines, polyamidoimines, polyamidoimides, polyamidoimides, polyamidoamines, and A polymer of at least one of polyfluorene-based polymers. Among them, the polyfluorene-imide-based polymer includes a polyfluorene-acid (B-1) and / or a polyfluorene-imide (B-2) and / or a polyfluorine-based block copolymer (B-3).

The polyfluorene-based block copolymer (B-3) includes a polyfluorine-based block copolymer (B-3-1) and / or a polyfluorene-based block copolymer (B-3). -2) and / or polyamido-polyamido block copolymer (B-3-3).

The polyfluorene imide-based block copolymer (B-3) is, for example, a polyfluorene of a first polyfluorene acid block represented by formula (5-1) and a second polyfluorine acid block having a different structure. Amino acid block copolymer (B-3-1); Formula (5-1) In the formula, J ¹ and J ² represent the same or different divalent organic groups; K ¹ and K ² represent the same or different divalent organic groups; when J ¹ and J ² are the same, K ¹ and K ² are different and vice versa, or J ¹ , J ² and K ¹ and K ² are different at the same time; x ¹ and y ¹ each independently represent an integer from 1 to 2,000, and z represents 1 to 100 Integer.

Polyimide block copolymer (B-3-2) of the first polyfluorene imine block represented by the formula (5-2) and the second polyfluorene imine block having a different structure; Formula (5-2) In the formula, J ³ and J ⁴ represent the same or different divalent organic groups; K ³ and K ⁴ represent the same or different divalent organic groups; when J ³ and J ⁴ are the same, K ³ and K ⁴ are different and vice versa, or J ³ , J ⁴ and K ³ and K ⁴ are different at the same time; x ¹ and y ¹ each independently represent an integer from 1 to 2,000, and z represents 1 to 100 Integer.

And a polyamic acid-polyfluorene imine block copolymer (B-3-3) of a polyfluorene acid block and a polyfluorine imine block represented by formula (5-3). Formula Formula (5-3) in, J ^5, J ⁶ 4 represents the same or different monovalent organic group; K ^5, K ⁶ of the same or different divalent organic group; J ^5, J ⁶ is the same, K ⁵ and K ⁶ are different and vice versa, or J ⁵ , J ⁶ and K ⁵ and K ⁶ are different at the same time; x ¹ and y ¹ each independently represent an integer from 1 to 2,000, and z represents 1 to 100 Integer.

The polymer (B) of the present invention is preferably a polyfluorene-imide-based polymer. The tetracarboxylic dianhydride compound and the diamine compound used in the polyfluorene imide-based polymer are not particularly limited. Specific examples of tetracarboxylic dianhydride compounds include, but are not limited to, ethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2- Dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3- Dichloro-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1 , 2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,5,6-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, dicycloheptanetetracarboxylic dianhydride, 3,3'-dicyclohexyl-1,1', 2,2'-tetracarboxylic Acid dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride (3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, tetracyclo [6.2.1 ^{1 , 3} .0 ^2,7 ] dodecane-4,5,9,10-tetracarboxylic dianhydride, 3, 4-Dicarboxyl-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dimeric Oxy-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione (1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5 -dioxo-3-furanyl) -napht ho [1,2-c] -furan-1,3-dione), 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-dioxan Yl-3-furyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (tetra Hydrogen-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro -7-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a , 4,5,9b-hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3 -Dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furyl) -naphtho [1,2 -c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furan ) -Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro- 2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxanyltetrahydrofuranyl) -3 -Methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclic [3.3.0] -octane-2,4,6,8-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ' -(Tetrahydrofuran-2 ', 5' -Dione) (3-oxabicyclo [3.2.1] -octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione)), pyromellitic dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'- Biphenyltetracarboxylic dianhydride, 2,3,3 ', 4-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4, 4'-biphenylphosphonium tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7- Naphthalene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,5,6-anthracene tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether di Anhydride, bis (3,4-dicarboxyphenyl) fluorene dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride , 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane Dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 2,3,4,5-pyridinetetracarboxylic dianhydride, 2,6-bis (3,4-dicarboxyphenyl) ) Pyridine dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1, 2,3,4-furantetracarboxylic dianhydride, 4,4'- Bis (3,4-dicarboxybenzyl) diphenylmethane dianhydride, 4,4'-bis (3,4-dicarboxybenzyl) diphenylethane dianhydride, 4,4'-bis (3,4-dicarboxybenzyl) diphenylpropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylmethane dianhydride, 4,4'-bis (3 , 4-dicarboxyphenoxy) diphenylethane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 4,4'-bis (3, 4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylphosphonium dianhydride, 3,3 ', 4,4'- Perfluoropropylene diphthalic acid dianhydride, 3,3 ', 4,4'-perfluoroisopropylidene diphthalic acid dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride (bis (phthalic acid) phenylphosphine oxide dianhydride), bis (phthalic acid) phenylsulphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride triphenylphthalic acid) dianhydride), m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) Acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitic anhydride) (ethy lene glycol-bis (anhydrotrimellitate)), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydrous Trimellitic anhydride), 1,8-octanediol-bis (anhydrotrimellitic anhydride), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitic anhydride), formula (6-1) to a tetracarboxylic dianhydride compound represented by the formula (6-6), or a combination of the aforementioned compounds. These compounds can be used singly or in combination. Formula (6-1) In formula (6-2), R ₄₁ and R ₄₃ each independently represent a divalent organic group containing an aromatic ring, R ₄₂ and R ₄₄ each independently represent a hydrogen atom or an alkyl group, and R ₄₂ and R ₄₄ each exist in a plural number. Can be the same or different.

These compounds can be used singly or in combination. Formula (6-3) Formula (6-4) Formula (6-5) Formula (6-6)

Among the above-mentioned tetracarboxylic dianhydride compounds, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and 2,3 are preferred. , 5-tricarboxycyclopentylacetic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3 ' , 4,4'-biphenylphosphonium tetracarboxylic dianhydride.

Specific examples of the diamine compound used in the polymer (B) of the present invention are the same as the diamine compounds listed in the compound (A) having a maleic acid group, and will not be repeated here.

In the polymer (B) of the invention, the polyamidic acid (B-1) is obtained by a polycondensation reaction of a tetracarboxylic dianhydride compound and a diamine compound. Among them, the amine group based on the diamine compound is 1 equivalent, and the acid anhydride group of the tetracarboxylic dianhydride compound is 0.2 to 2 equivalents, preferably 0.8 to 1.2 equivalents.

In the polycondensation reaction of polyamic acid (B-1), the reaction temperature of the tetracarboxylic dianhydride compound and the diamine compound in an organic solvent is generally -20 to 150 ° C, preferably 0 to 100 ° C. However, the organic solvent is not particularly limited as long as it can dissolve the reactant and the product. Specific examples of the organic solvent include, but are not limited to, N-methyl-2-pyrrolidone, N, N-dimethylacetamidamine, N, N-dimethylformamidine, dimethylsulfine, γ-butane Aprotic polar solvents such as lactone, tetramethyl urea and hexamethyl phosphate triamine; phenol solvents such as m-cresol, xylenol, phenol, and halogenated phenols. The organic solvents may be used singly or in combination.

Among the above organic solvents, an appropriate amount of a lean solvent such as alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc. may be used in a range where the polymer produced does not precipitate. Specific examples of the lean solvent include, but are not limited to, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, acetone, methyl ethyl ketone, and methyl alcohol. Isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl Ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether , Tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, Toluene, xylene, etc. The lean solvent may be used singly or in combination.

The obtained polyamic acid (B-1) reaction solution is poured into a large amount of a lean solvent, and the obtained precipitate is dried under reduced pressure or the reaction solution is distilled under reduced pressure using an evaporator to obtain polyfluorene. Amino acid (B-1). In addition, the polyamidic acid (B-1) can be dissolved in an organic solvent again, and then precipitated with a lean solvent, or it can be distilled under reduced pressure in an evaporator, and can be purified by repeating the above-mentioned process once or several times. Polyamic acid (B-1).

In the polymer (B) of the present invention, the polyfluorene imine (B-2) is obtained by further dehydrating and closing (polyimine) the polyfluorine acid (B-1).

Polyimide (B-1) is treated by amidine imidization. For example, polyamidate (B-1) is dissolved in an organic solvent, and dehydrated by heating in the presence of a dehydrating agent and amidimide catalyst. Closed loop reaction. The temperature of the imidization is generally 40 to 200 ° C, preferably 80 to 150 ° C. Specific examples of the dehydrating agent used include, but are not limited to, acid anhydride compounds such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. The amount of the dehydrating agent used is based on 1 mole of polyamic acid (B-1), preferably 0.01 to 20 mol is better. The specific imidization catalyst includes, but is not limited to, tertiary amines such as pyridine, trimethylpyridine, dimethylpyridine, and triethylamine. The usage amount of the imidization catalyst is based on 1 mole of the dehydrating agent. It is preferably 0.5 to 10 moles. Specific examples of the solvent used for the fluorination treatment include the solvents listed in the aforementioned polycondensation reaction of polyamic acid (B-1), and details are not described herein again.

In addition, the obtained polyimide (B-2) reaction solution can be further processed in the same manner as in the aforementioned polyamidic acid (B-1) purification method to obtain a purified polyimide (B-2).

Among the polymers (B) of the present invention, the polyfluorene-based block copolymer (B-3) can be exemplified by the polyfluorine-based block copolymer (B-3-1) depending on the type of monomer. ), Polyfluorene imine block copolymer (B-3-2), polyfluorene acid-polyfluorene imine block copolymer (B-3-3). The polyfluorene-based block copolymer (B-3) is selected from polyfluorine (B-1), polyfluorine (B-2), a tetracarboxylic dianhydride compound, or a diamine compound. The compound is obtained by further polycondensation reaction in an organic solvent. Selection of compounds, for example: 2 types of polyimide (B-1) with different terminal groups and different structures; 2 types of polyimide (B-2) with different terminal groups and different structures; terminal group phase Polyammonium acid (B-1) and polyimide (B-2) which are different and different in structure; polyamine acid (B-1) and tetracarboxylic dianhydride compound and diamine compound, of which tetracarboxylic acid At least one of the acid dianhydride compound and the diamine compound is different in the structure of the tetracarboxylic dianhydride compound and the diamine compound used in the condensation reaction of the polyfluorinated acid (B-1); the polyfluorinated imine (B-2) And a tetracarboxylic dianhydride compound and a diamine compound, in which at least one of the tetracarboxylic dianhydride compound and the diamine compound is used in a condensation reaction with polyfluoreneimine (B-2) The structures of amine compounds are different; polyamine (B-1) and polyimide (B-2) and tetracarboxylic dianhydride compounds and diamine compounds, of which at least tetracarboxylic dianhydride compounds and diamine compounds A tetracarboxylic dianhydride compound and a diamine compound used in the condensation reaction with polyamidic acid (B-1) and polyimide (B-2) have different structures; 2 Polyammonium acid (B-1) and tetracarboxylic dianhydride compounds and diamine compounds with different structures; 2 polyimide (B-2) and tetracarboxylic dianhydride compounds and diamines with different structures Compounds; 2 types of polyamines (B-1) and diamine compounds whose terminal groups are acid anhydride groups and different structures; 2 types of polyamines (B-1) whose terminal groups are amine groups and different structures and Tetracarboxylic dianhydride compounds; 2 polyimide (B-2) and diamine compounds whose terminal groups are acid anhydride groups and have different structures; 2 polyimide compounds whose terminal groups are amine groups and have different structures ( B-2) and tetracarboxylic dianhydride compounds.

In the polycondensation reaction of the polyfluorene imide-based block copolymer (B-3), the reaction temperature is generally 0 to 200 ° C, and preferably 0 to 100 ° C. Specific examples of the solvent to be used are the same as those listed in the aforementioned polycondensation reaction of polyamic acid (B-1), and are not repeated here.

In addition, the obtained polyimide-based block copolymer (B-3) reaction solution can be processed in the same manner as the aforementioned polyamidic acid (B-1) purification method, and further processed to obtain a purified polyimide-based block copolymer. Block copolymer (B-3).

The polymer (B) of the present invention has a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography method of 2,000 to 200,000, preferably 3,000 to 100,000, and more preferably 4,000 to 50,000.

Based on the use amount of the compound (A) having a maleic acid group as 100 parts by weight, the use amount of the polymer (B) may be 3 to 100 parts by weight, preferably 10 to 80 parts by weight, and more preferably 15 To 60 parts by weight. When the polymer (B) is contained in the liquid crystal alignment film, the liquid crystal display element prepared from the liquid crystal alignment film has better long-term reliability. Solvent ( C )

The solvent (C) of the liquid crystal alignment agent of the present invention may be selected from the solvents used in the manufacturing process of the compound (A) and the polymer (B) having the maleic acid amino group described above, and will not be repeated here. The use amount of the compound (A) having a maleic acid group is 100 parts by weight, and the use amount of the solvent (C) is 500 to 5,000 parts by weight, preferably 800 to 4,000 parts by weight, and more preferably 1,000 to 3,000. Parts by weight. Additive ( D )

In the liquid crystal alignment agent of the present invention, a functional silane-containing compound or an epoxy compound may be added within a range that does not impair the required physical properties. Specific examples of functional silane-containing compounds include, but are not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-amine Propyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyl Dimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxy Silane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine Amine, 10-trimethoxysilyl-1,4,7-triazine, 10-triethoxysilyl-1,4,7-triazine, 9-trimethoxysilyl-3 , 6-Diazinyl acetate, 9-triethoxysilyl-3,6-diazinyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzene Methyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Bis (ethylene oxide) -3-aminopropyltrimethoxysilane, N-bis (ethylene oxide) -3-aminopropyltriethoxysilane, or a combination thereof.

Specific examples of the epoxy compound include, but are not limited to, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly Propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoxin Pentylene glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m- Xylene diamine, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'- Diaminodiphenylmethane, 3- (N-allyl-N-epoxypropyl) aminopropyltrimethoxysilane, 3- (N, N-diepoxypropyl) aminopropyl Trimethoxysilane, or a combination of the above.

Based on the amount of the compound (A) having a maleic acid group being 100 parts by weight, the amount of the additive (D) may be 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight, and more preferably 3 to 30 parts by weight. Manufacturing method of liquid crystal alignment agent

The liquid crystal alignment agent of the present invention includes a compound (A) having a maleic acid group and a solvent (C), and a polymer (B) or an additive (D) may be further added. The liquid crystal alignment agent is manufactured by dissolving a compound (A), a polymer (B), and an additive (D) having a maleic acid group in a solvent (C) and mixing them uniformly. It is generally 0 to 200 ° C, and preferably 0 to 100 ° C. Formation of liquid crystal alignment film

A method for manufacturing a liquid crystal alignment film is obtained by applying the liquid crystal alignment agent to a substrate, and then performing dehydration ring closure and radical polymerization reaction.

First, on one side of a substrate provided with a transparent conductive film, the liquid crystal alignment agent of the present invention is coated on the substrate by a method such as a roll coating method, a spin coating method, a printing method, or an ink-jet method. . Among these, the printing method is preferred. Next, the coating surface is subjected to a heat treatment to form a liquid crystal alignment agent into a coating film.

Specific examples of the substrate include, but are not limited to, glass such as alkali-free glass, soda lime glass, hard glass (Pales glass), quartz glass, etc .; polyethylene terephthalate, polybutene terephthalate Plastic transparent substrates such as polyether, polycarbonate, polycarbonate, etc.

The heat treatment for forming the liquid crystal alignment film includes a pre-bake treatment after the application of the liquid crystal alignment agent. The pre-bake treatment can volatilize the organic solvent to form a coating film. The heat treatment temperature is generally 30 to 150 ° C, preferably 50. To 120 ° C, more preferably 60 to 100 ° C. The pre-baking treatment may be performed at any time from 0.1 minutes to 30 minutes, preferably from 0.5 minutes to 15 minutes, and more preferably from 1 minute to 5 minutes.

After the coating film is formed, a post-bake process is further performed to simultaneously perform dehydration ring closure (fluorene imidization) and radical polymerization reaction to form a fluorinated alignment film coating film. The post-baking treatment temperature is generally 100 to 350 ° C, preferably 120 to 280 ° C, and more preferably 150 to 250 ° C. The post-baking treatment may be performed at any time from 5 minutes to 240 minutes, preferably 10 minutes to 100 minutes, and more preferably 20 minutes to 90 minutes. The heating can be performed by a generally known method, for example, a heating plate, a hot-air circulation furnace, or an infrared furnace can be used for heating.

In the process of forming a liquid crystal alignment film according to the present invention, ultraviolet irradiation may be performed first, and then post-heating treatment may be performed. A liquid polymerization initiator or a thermal polymerization initiator may be added to the liquid crystal alignment agent as required.

Among them, the dehydration ring-closing (fluorene imidization) reaction is a process in which maleimide amino acid group is imidized to form a maleimide group. A specific example of the reaction is shown in reaction formula (1): Reaction Formula (1)

In the free radical polymerization, a compound containing a C = C double bond, such as a maleimide-containing imino group, is polymerized to form a bridge structure. In addition, the radical polymerization reaction occurs on the double bond generated after the dehydration ring-closing reaction of the compound (A) having a maleic acid group. A specific example of this reaction is shown in Reaction Formula (2): Reaction formula (2)

Specific examples of the fluorene imidized alignment film obtained through dehydration ring closure (fluorene imidization) and radical polymerization reaction are alignment films with a bridge structure represented by the following formula. Manufacturing method of liquid crystal display element

The liquid crystal display element of the present invention can be manufactured by the following method.

First, the above-mentioned liquid crystal alignment film is formed on a pair of substrates including a conductive film, and the substrate on which the liquid crystal alignment film is formed is arranged in such a manner that the liquid crystal alignment film faces each other, and is placed on the substrate. A liquid crystal composition is injected therebetween to form a liquid crystal cell, and then a voltage is applied between the conductive films, and the liquid crystal cell is irradiated with light under a voltage application state. Finally, a polarizing plate is bonded to the outer surface of the liquid crystal cell to obtain a liquid crystal display element of the present invention. The substrate used is the same as the substrate used in the formation of the liquid crystal alignment film, and is not repeated here.

As the conductive film, a transparent conductive film such as a NESA film made of SnO ₂ or an ITO film made of In ₂ O ₃ -SnO _{2 is} preferably used. The conductive film is preferably a patterned conductive film which is divided into a plurality of regions. When such a conductive film structure is formed, when a voltage is applied between the conductive films, by applying different voltages to each region, the pretilt direction of the liquid crystal molecules in each region can be changed, thereby further improving the viewing angle property.

The liquid crystal cell can be produced by, for example, the following two methods.

The first method is currently known. First, the two substrates are arranged to face each other with a gap (cell gap) therebetween, and the respective liquid crystal alignment films are opposed to each other. Using a sealant, the peripheral parts of the two substrates are bonded together, and divided by the substrate surface and the sealant. After filling and filling the liquid crystal in the intercellular space, the injection hole is sealed, and a liquid crystal cell can be manufactured.

The second method is a method called an ODF (One Drop Fill) method. Apply a UV-curable sealing material to a predetermined position on one of the two substrates forming the liquid crystal alignment film, and then drop the liquid crystal on the liquid crystal alignment film surface. Then, attach the other substrate so that the liquid crystal alignment film faces the liquid crystal alignment film. Next, the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant to produce a liquid crystal cell.

Among them, examples of the sealant include epoxy resin containing a hardener and alumina balls as a spacer.

The liquid crystal composition may be a nematic liquid crystal having negative dielectric anisotropy, such as a dicyanobenzene-based liquid crystal, a pyridazine-based liquid crystal, a Schiff base-based liquid crystal, an azo-based liquid crystal, and biphenyl. Polymerizable compounds are added to liquid crystals such as liquid crystals such as phenylcyclohexane, and liquid crystals such as phenylcyclohexane-based liquid crystals. Generally known compounds can be used as the polymerizable compound, and there is no particular limitation on the type, for example, a compound having an acrylyl group and a liquid crystal skeleton. In addition, a polymerizable compound and a polymerization initiator may be added to the liquid crystal in combination. The addition amount of the polymerizable compound is generally 0.1 wt% to 1 wt%.

The voltage to be applied may be, for example, a direct current or an alternating current of 5 V to 50 V.

As the light to be irradiated, for example, ultraviolet rays including visible light with a wavelength of 150 to 800 nm and visible light may be used, and ultraviolet rays including light with a wavelength of 300 to 400 nm can be preferably used. As a light source for irradiating light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a heavy hydrogen lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. The ultraviolet rays in the aforementioned preferable wavelength region can be obtained by a method in which the aforementioned light source is used in combination with, for example, a color filter and a diffraction grating.

As the light irradiation amount, preferably 1,000 J / m ² or more and less than 100,000 J / m ^2, more preferably 1,000 to 50,000 J / m ^2. When manufacturing a conventionally known PSA mode liquid crystal display element, a light irradiation amount of about 100,000 J / m ² is required. However, in the method of the present invention, even when the light irradiation amount is 50,000 J / m ² or less, and further 10,000 J / m ² or less, a good liquid crystal display element can be obtained, thereby contributing to reducing the manufacturing of the liquid crystal display element. cost.

Examples of the polarizing plate attached to the outer surface of the liquid crystal include a polarizing plate formed of a polarizing film called "H film" obtained by sandwiching polyvinyl alcohol with a protective film of cellulose acetate and stretching and aligning while absorbing iodine. The film itself forms a polarizing plate.

The present invention will be further described with reference to the following examples, but it should be understood that these examples are merely illustrative and should not be construed as limitations of the implementation of the present invention. Synthesis example of the compound ( A ) having a maleic acid group

The following describes Synthesis Example A-1 to Synthesis Example A-12 of Compound (A) having a maleamic acid group: Synthesis Example A-1

A 500 ml four-necked flask was provided with a nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer, and nitrogen was introduced. Then, in a four-necked flask, 3.95 g (0.015 mol) of the diamine compound Da1 (abbreviated as a2-1-1) and 2.82 g (0.0075 mol) of 1-octadecyloxy-2,4 were added. -Diaminobenzene (abbreviated as a2-2-1) and 50 g of tetrahydrofuran (hereinafter abbreviated as THF), and stirred at room temperature until dissolved. Next, 2.81 g (0.025 mole) of 2-methylmaleic anhydride (abbreviated as a1-1) was added, and the reaction was performed at room temperature for 3 hours. After the reaction was completed, the reaction solution was filtered, and the filtered solid was repeated After being washed and filtered three times with THF, put into a vacuum oven and dried at a temperature of 60 ° C., a compound (A-1) having a maleic acid group can be obtained. Synthesis Example A-2 to Synthesis Example A-12 and Comparative Synthesis Example A-13 to Comparative Synthesis Example A-15

Synthesis Example A-2 to Synthesis Example A-12 and Comparative Synthesis Example A-13 to Comparative Synthesis Example A-15 were prepared in the same procedure as Synthesis Example A-1, respectively, to prepare a compound having a maleic acid group (A -2) to the compound (A-15) having a maleic acid amino group, and the difference lies in that the type of the monomer and its usage amount are changed (as shown in Table 1).

The compounds corresponding to the abbreviations in Table 1 are shown below.

[Table 1] Polymer (B) Synthesis Example

Synthesis Example B-1 to Synthesis Example B-3 of Polymer (B) will be described below: Synthesis Example B-1

A 500 ml four-necked flask was provided with a nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer, and nitrogen was introduced. Then, in a four-necked flask, 20.0 g (0.1 mol) of 4,4'-diaminodiphenyl ether and 180 g of N-methylpyrrolidone (hereinafter referred to as NMP) were added at room temperature. Stir until dissolved. Add 10.9 g (0.05 mol) of pyromellitic dianhydride, 9.8 g (0.05 mol) of cyclobutane tetracarboxylic dianhydride, and 50 g of NMP, and react at room temperature for 6 hours. The reaction is complete. Then, the reaction solution was poured into 1500 ml of water to precipitate the polymer. The polymer obtained by filtration was repeatedly washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60 ° C to obtain a polymer (B- 1). Synthesis Example B-2

A 500 ml four-necked flask was provided with a nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer, and nitrogen was introduced. Then, in a four-necked flask, 10.8 g (0.1 mol) of p-diaminebenzene and 100 g of NMP were added and stirred at room temperature until dissolved. Add 33.0 g (0.11 mole) of 3,4-dicarboxyl-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride and 60 g of NMP, and react at room temperature for 6 hours. After the end, 97 g of NMP, 2.55 g of acetic anhydride, and 19.75 g of pyridine were added, the temperature was raised to 60 ° C., and stirring was continued for 2 hours to perform the amidine imidization reaction. After the reaction is complete, the reaction solution is poured into 1500 ml of water to precipitate the polymer. The polymer obtained by filtration is repeatedly washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60 ° C. B-2). Synthesis Example B-3

A 500 ml four-necked flask was provided with a nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer, and nitrogen was introduced. Then, in a four-necked flask, 3 g of the polymer (B-1) obtained in Synthesis Example B-1 and 17 g of NMP were added and stirred at room temperature until dissolved. Then, 3 g of the polymer (B-2) obtained in Synthesis Example B-2 and 17 g of NMP were added and reacted at 60 ° C for 6 hours. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate the polymer. The polymer obtained by filtration was repeatedly washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60 ° C to obtain a polymer (B-3). The liquid crystal alignment agent, the liquid crystal with embodiment examples and comparative examples to a display element and a liquid crystal film

Hereinafter, Examples 1 to 15 and Comparative Examples 1 to 5 of the liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display element will be described. Example 1 a. Liquid crystal alignment agent

100 parts by weight of the compound having a maleic acid group (A-1) obtained in Synthesis Example 1 was dissolved in 2000 parts by weight of N-methyl-2-pyrrolidone (C-1) and 1,000 parts by weight of ethylenediamine. In the alcohol n-butyl ether (C-2), the liquid crystal alignment agent of Example 1 can be formed by continuously stirring until completely dissolved with a stirring device at room temperature. b. Liquid crystal alignment film and liquid crystal display element

Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the procedure shown below. First, the liquid crystal alignment agent was spin-coated on two glass substrates each having an ITO electrode, where the ITO electrodes were slits with a line / space of 5 μm each. )pattern. Thereafter, pre-baking is performed on a hot plate at a temperature of 80 ° C. for 2 minutes, and in a circulating oven, post-baking is performed at a temperature of 230 ° C. for 15 minutes to form a liquid crystal alignment film of Example 1.

For the two glass substrates formed with the liquid crystal alignment film prepared in the above steps, one of the glass substrates was coated with hot-press adhesive, and the other glass substrate was coated with a 4 μm spacer, and then, the two glass substrates were coated with a spacer. The bonding was performed, and then a pressure of 10 kg was applied with a hot press, and the hot-press bonding was performed at a temperature of 150 ° C. Then, a liquid crystal injection machine (manufactured by Shimadzu Corporation, model: ALIS-100X-CH) was used to inject negative dielectric anisotropic liquid crystal (Merck, model: MLC 6883), in which 0.1% by weight of 4,4 was added to the liquid crystal. '4'-biphenylene methacrylate (4,4'-biphenylene methacrylate) is used as a polymerizable compound, and then the liquid crystal injection port is sealed with an ultraviolet curing adhesive, and then cured by ultraviolet light. Next, after applying an alternating current of 20 V between the two ITO electrodes and irradiating 30 J of ultraviolet rays while the liquid crystal is in a driving state, the liquid crystal display element of Example 1 can be obtained. The liquid crystal display element of Example 1 was evaluated by each measurement evaluation method described below, and the results are shown in Table 2. Examples 2 to 15 and Comparative Examples 1 to 3

The liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element of Examples 2 to 15 and Comparative Examples 1 to 3 were prepared by the same steps as in Example 1, and the difference was that the type and The amount used is shown in Table 3. The liquid crystal display elements prepared in Examples 2 to 15 and Comparative Examples 1 to 3 were evaluated by the evaluation method described later. The results are shown in Table 2.

The compounds corresponding to the abbreviations in Table 2 are shown below. < Evaluation method > a. Residual of polymerizable compound

A 10-volt AC voltage having a frequency of 60 Hz was applied between the electrodes of the liquid crystal display elements of the examples and comparative examples, and the liquid crystal was driven, and 100,000 J / m ² of ultraviolet light was irradiated. ; Solar Energy Industrial Manufacturing). Next, the liquid crystal layer was taken out, and the residual amount (γ) of the polymerizable compound was measured by High Performance Liquid Chromatography (HPLC).

The evaluation criteria of the polymerizable compound residue are shown below. ◎: γ <500ppm ○: 500ppm ≦ γ <800ppm △: 800ppm ≦ γ <1000ppm ╳: γ ≧ 1000ppm b. Long-term reliability

Applying an alternating voltage 10 volts 60 hertz frequency component between the electrodes, the liquid crystal in a state belonging to the drive, the irradiated ultraviolet 30,000 J / m ² (the UV irradiation machine Model KN-SH48K1 embodiment of the liquid crystal display of the examples and comparative examples ; Solar Energy Industrial Manufacturing). Next, using the method described in "TJScheffer, et.al., J. Appl. Phys., Vol. 19, 2013 (1980)", a liquid crystal evaluation device (central precision mechanism, model OMS-CM4RD) was passed through He- Ne laser light crystal rotation method, measuring the center point of the liquid crystal display element, can measure the first pretilt angle (P1). Then, after the liquid crystal display element was placed in an oven at 60 ° C. for 200 hours, the same position as described above was measured to obtain a second pretilt angle (P2). Finally, the long-term reliability R is calculated by the following formula: R (°) = │P1－P2│ Mathematical formula (1)

The evaluation criteria for long-term reliability are shown below. ◎: R <1.0 ○: 1.0 ≦ R <1.5 △: 1.5 ≦ R <2.0 ╳: R ≧ 2.0

[Table 2] ＜ Evaluation results ＞

As can be seen from Table 2, compared with a liquid crystal display element (Example 1 to Example 15) made of a liquid crystal alignment film having a bridge structure represented by Formula (1), it does not have a bridge represented by Formula (1) A liquid crystal display element having a structure (Comparative Examples 1 to 5) has a problem that a polymerizable compound remains.

In addition, when the total amount of use based on the diamine component (a2) is 100 mol, and the amount of use of the diamine compound (a2-1) is 5 to 70 mol (Examples 1 to 7, and Example 9) Up to Example 11 and Examples 13 to 15), a liquid crystal display device having less unreacted polymerizable compounds remaining in the liquid crystal layer can be obtained.

When the diamine component (a2) contains the diamine compound (a2-2) represented by the formula (3) (Example 1, Example 2, Example 4, Example 6 to Example 9, Example 12 and Example 13), the long-term reliability of the liquid crystal display element is better.

In addition, when the polymer (B) is contained in the liquid crystal alignment film (Example 5, Example 9, Example 11 and Example 14), the long-term reliability of the liquid crystal display element is better.

In summary, the liquid crystal alignment film of the present invention includes a specific bridge structure, so there is no problem that unreacted compounds remain in the liquid crystal layer. Furthermore, since the liquid crystal alignment film of the present invention contains a bridging structure of an organic group containing a photoreactive group, there is no unreacted compound remaining in the liquid crystal layer, and there is no problem of poor long-term reliability, so it is suitable for manufacturing liquid crystals. Alignment film and liquid crystal display element.

Although the present invention has been disclosed as above with the examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouching without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the attached patent application.

no.

no.

Claims (8)

A liquid crystal alignment film includes a bridge structure represented by formula (1): In formula (1), T represents an aliphatic or aromatic structure; Q represents an organic group containing a photoreactive group; and k represents an integer of 1 or more, wherein the bridging structure consists of a maleic acid group The compound (A) is obtained by a radical polymerization reaction, and the compound (A) having a maleic acid amino group has 2 or more polymerizable maleic acid amino groups in one molecule. The compound (A) having a maleic acid amino group is obtained by reacting a maleic anhydride derivative (a1) and a diamine component (a2), wherein the photoreactive group includes vinyl, (meth) acrylic acid At least one of an alkyl group, an anthryl group, a cinnamic acid group, a chalcone group, a coumarin group, a maleimide group, or a stilbyl group. The liquid crystal alignment film according to item 1 of the scope of the patent application, wherein the radical polymerization reaction occurs on a double bond generated after the compound (A) having a maleic acid amino group undergoes a dehydration ring-closing reaction. The liquid crystal alignment film according to item 1 of the scope of patent application, wherein the diamine component (a2) comprises a diamine compound (a2-1) represented by the formula (2): In formula (2), R _a represents -CH _2- , -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO -, -CON (CH ₃ )-or -N (CH ₃ ) CO-; R _b represents an unsubstituted or fluorine-substituted linear alkylene group having a carbon number of 1 to 20, and the alkylene group Any -CH ₂ -in the group may be substituted by -CF _2- , -CH = CH-, or the following substituents, which include: -O-, -COO-, -NHCO-, -NH-, Carbocyclyl or heterocyclyl, wherein when two or more -CH ₂ -are substituted with the substituent, the substituents are not adjacent; R _c represents -CH _2- , -O-, -NH -, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO-, carbon A cyclic group or a heterocyclic group; _Rd represents a vinyl phenyl group, -CR _e = CH ₂ , a carbocyclyl group, a heterocyclic group, or a group represented by the following structural formula, and R _e represents a hydrogen atom or a fluorine atom Substituted methyl: . The liquid crystal alignment film according to item 1 of the scope of patent application, wherein the diamine component (a2) further comprises a diamine compound (a2-2) represented by the formula (3): In formula (3), R ₃ represents -O-, , , , ,or ; R ₄ represents a steroid-containing group, an alkylene group having 2 to 30 carbon atoms, or an organic group represented by the formula (3-1): In the formula (3-1), R ₅ represents a hydrogen atom, a fluorine atom or a methyl group; R ₆ , R ₇ or R ₈ each independently represents a single bond, -O-, , , , , Or an alkylene group having 1 to 3 carbon atoms; R ₉ represents or Wherein R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a fluorine atom or a methyl group; R ₁₀ represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, Alkoxy, -OCH ₂ F, -OCHF ₂ or -OCF _{3 having} a carbon number of 1 to 12; a represents 1 or 2; b, c, and d each independently represent an integer of 0 to 4; e, f, and g each Independently represents an integer from 0 to 3, and e + f + g ≧ 1; h and i each independently represent 1 or 2; when there are multiple R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R _In the case of ₁₁ or R ₁₂ , a plurality of R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ or R ₁₂ are each the same or different. The liquid crystal alignment film according to item 3 of the scope of patent application, wherein based on the diamine component (a2) being 100 moles, the amount of the diamine compound (a2-1) used is 5 moles to 70 Mor. The liquid crystal alignment film according to item 4 of the scope of patent application, wherein based on the diamine component (a2) being 100 moles, the amount of the diamine compound (a2-2) used is 3 moles to 50 Mor. A liquid crystal display element includes the liquid crystal alignment film according to any one of claims 1 to 6 of a patent application scope. A method for manufacturing a liquid crystal display element includes: forming a liquid crystal alignment film according to any one of claims 1 to 6 on a pair of substrates including a conductive film; and forming the liquid crystal alignment. The substrate of the film is arranged in such a manner that the liquid crystal alignment film is opposite to each other; a liquid crystal composition is injected between the substrates to form a liquid crystal cell; and a voltage is applied between the conductive films, and the light is used in the state of the applied voltage. The liquid crystal cell is irradiated.