TWI640574B - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The invention provides a good ultraviolet ray decay resistance and a high pretilt angle stability A liquid crystal alignment agent of a qualitative liquid crystal display element, a liquid crystal alignment film, and a liquid crystal display element having the above liquid crystal alignment film. The liquid crystal alignment agent includes a polymer (A), a polyoxyalkylene (B), and a solvent (C). The polymer (A) is obtained by a reaction of a mixture comprising a tetracarboxylic dianhydride component (a1) and a diamine component (a2) comprising the diamine compound (a2-1) represented by the formula (1). The polyoxyalkylene (B) contains a polymerizable unsaturated group, wherein the polymerizable unsaturated group includes a group represented by the formula (b1-1), a group represented by the formula (b1-2), or a combination of the two.

Description

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

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element, and more particularly to a liquid crystal alignment agent capable of forming a liquid crystal display element excellent in ultraviolet degradation resistance and high pretilt stability, and formed of the above liquid crystal alignment agent. A liquid crystal alignment film and a liquid crystal display element having the above liquid crystal alignment film.

With the development of liquid crystal displays toward large-size display specifications, in order to overcome the viewing angle problem under large-size display, the wide viewing angle technology of liquid crystal display panels must also continue to advance and break through. A 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 forms protrusions in the liquid crystal panel, and the protrusions can define a direction in which 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 the problem that the light transmittance and contrast due to the protrusions are insufficient and the response speed of the liquid crystal molecules is slow.

In recent years, in order to solve the above problems, a technology of Polymer Sustained Alignment (PSA) has been developed. This technique is a pair of substrates composed of a pair of substrates composed of a substrate having a patterned conductive film and a substrate having no patterned conductive film, or a substrate composed of two substrates having a patterned conductive film. In the gap, a liquid crystal composition containing a polymerizable compound is held, and a liquid crystal composition is irradiated with ultraviolet light to polymerize the polymerizable compound in a state where a voltage is applied between the conductive films, thereby exhibiting pretilt characteristics and controlling liquid crystal alignment. direction. This technology can form a specific structure of the conductive film, and achieve an effect of widening the viewing angle and speeding up the response of the liquid crystal molecules, thereby solving the problem that the transmittance and contrast of the multi-domain vertical alignment type liquid crystal display panel cannot be avoided.

However, in order to polymerize the polymerizable compound, it is necessary to irradiate a large amount of ultraviolet rays of, for example, 100,000 J/m ² , so that in addition to decomposition of the liquid crystal molecules, an unreacted compound which cannot be polymerized even if irradiated with ultraviolet rays remains in the liquid crystal layer. . The residual unreacted compounds are bonded to each other in the liquid crystal layer, resulting in poor pretilt stability of the panel, which makes it impossible to achieve practicality. Further, the kind of the liquid crystal molecules used in the liquid crystal layer must also be limited depending on the polymerizable compound to be added.

Therefore, how to improve the above problems and to provide a liquid crystal display element which is excellent in ultraviolet ray deterioration resistance and high pretilt angle stability is an object which is currently actively studied by those skilled in the art.

In view of the above, the present invention has developed a Surface Control Vertical Alignment (SCVA) technology, and provides a liquid crystal alignment agent capable of forming a liquid crystal display element excellent in ultraviolet degradation resistance and high pretilt stability, and the above liquid crystal. A liquid crystal alignment film formed of an alignment agent and a liquid crystal display element having the above liquid crystal alignment film.

The present invention provides a liquid crystal alignment agent comprising a polymer (A), a polyoxyalkylene (B), and a solvent (C). The polymer (A) is obtained by a reaction comprising a mixture of the tetracarboxylic dianhydride component (a1) and the diamine component (a2). The polyoxyalkylene (B) contains a polymerizable unsaturated group, wherein the polymerizable unsaturated group includes a group represented by the formula (b1-1), a group represented by the formula (b1-2), or a combination of the two.

Specifically, the diamine component (a2) includes the diamine compound (a2-1) represented by the formula (1):

In the formula (1), X ₁ and X ₃ each independently represent a methyl group, -O-, -COO-, -OCO-, -NHCO-, -CONH- or -NH-; X ₂ represents a single bond or carbon. The alkyl group is 1 to 20; X ₄ represents an oxygen atom or a sulfur atom.

In addition, the base represented by the formula (b1-1) and the formula (b1-2) is as follows:

In the formula (b1-1), A represents a hydrogen atom or a methyl group; a represents an integer of 1 to 3; Indicates the bond.

In the formula (b1-2), b represents an integer of 0 or 1, and * represents a bond.

In an embodiment of the present invention, the total amount of the diamine component (a2) used is 100 mol, and the diamine compound (a2-1) represented by the formula (1) is used in an amount of 5 to 50 mol. .

In an embodiment of the invention, the diamine component (a2) includes the diamine compound (a2-2) represented by the formula (2):

In the formula (2), X ₅ represents a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH- or -NH-; X ₆ represents a carbon number of 1 to 20 substituted by fluorine or not a substituted linear alkyl group in which any -CH ₂ - may be substituted by: -CH=CH-, -O-, -COO-, -NHCO-, -NH-, an extended carbon ring Or a heterocyclic group; X ₇ represents a hydrogen atom or a methyl group.

In one embodiment of the present invention, the total amount of the diamine component (a2) used is 100 moles, and the diamine compound (a2-2) represented by the formula (2) is used in an amount of 10 to 90 moles. .

In an embodiment of the invention, the decane monomer mixture forming the polyoxyalkylene (B) by the polycondensation reaction comprises a decane compound (b1) containing a polymerizable unsaturated group, and based on the total of the decane monomer mixture The amount used is 1.0 mole, containing polymerization The unsaturated alkyl decane compound (b1) is used in an amount of 0.1 to 0.9 mol.

In an embodiment of the invention, the polyoxyalkylene (B) contains an epoxy group-containing group, wherein the epoxy group-containing group includes a group represented by the formula (b2-1), and a formula ( At least one of a group represented by b2-2) and a group represented by formula (b2-3).

Specifically, the base represented by the formula (b2-1) to the formula (b2-3) is as follows:

In the formula (b2-1), B represents an oxygen atom or a single bond; c represents an integer of 1 to 3; d represents an integer of 0 to 6, wherein when d represents 0, B is a single bond, and * represents a bond.

In the formula (b2-2), e represents an integer of 0 to 6, and * represents a bond.

In the formula (b2-3), D represents an alkylene group having a carbon number of 2 to 6; E represents a hydrogen atom or an alkyl group having a carbon number of 1 to 6, and * represents a bond.

In an embodiment of the invention, the decane monomer mixture forming the polyoxyalkylene (B) by the polycondensation reaction comprises an epoxy group-containing decane compound (b2), and based on the total amount of the decane monomer mixture. The 1.0-mole, epoxy group-containing decane compound (b2) is used in an amount of 0.1 to 0.9 mol.

In an embodiment of the invention, the polymer (A) has a ruthenium iodide ratio of 30 to 90%.

In one embodiment of the present invention, the amount of the polymer (A) used is 100 parts by weight, the amount of the polyoxyalkylene (B) used is 1 to 25 parts by weight, and the amount of the solvent (C) used is 800~. 4000 parts by weight.

In an embodiment of the invention, the liquid crystal alignment agent further includes a photopolymerizable compound (D).

In one embodiment of the present invention, the photopolymerizable compound (D) is a photopolymerizable compound represented by the formula (3).

In the formula (3), R ₁ independently represents a polymerizable functional group represented by the formula (3-1) to the formula (3-5), a hydrogen atom, a halogen atom, -CN, -CF ₃ , -CF ₂ H, -CFH ₂ , -OCF ₃ , -OCF ₂ H, -N=C=O, -N=C=S or an alkyl group having 1 to 20 carbon atoms, wherein any of the above alkyl groups is -CH ₂ - Can be substituted by -O-, -S-, -SO ₂ -, -CO-, -COO-, -OCO-, -CH=CH-, -CF=CF- or -C≡C-, and contain a hydrogen atom In the functional group, the hydrogen atom may be optionally substituted by a halogen atom or -CN; and at least one of R _{1 is} a polymerizable functional group represented by the formula (3-1) to the formula (3-5). Y independently represents a saturated or unsaturated, independent ring, condensed ring or a divalent group of a spiro ring having a carbon number of 3 to 20, and any -CH ₂ - in the ring of the group Y may be substituted by -O-, optionally -CH= may be substituted by -N=, and any -H may be represented by a halogen atom, -CN, -NO ₂ , -NC, -N=C=O, -N=C=S, and 1 to 3 An alkyl group having 1 to 4 carbon atoms or a phenyl group substituted with a phenyl group, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 1 to 10 carbon atoms or a halogen having 1 to 10 carbon atoms In the above-mentioned linear alkyl group, branched alkyl group or haloalkyl group, any -CH ₂ - may be -O-, -CO-, -COO-, -OCO-, -OCOO-, - CH=CH- or -C≡C-substituted. Z independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, wherein any of -CH ₂ - in the above alkylene group may be -O-, -S-, -SO ₂ -, -CO- , -COO-, -OCO-, -OCOO-, -CH=CH-, -CF=CF-, -CH=N-, -N=CH-, -N=N-, -N(O)=N - or -C≡C-substituted, and any -H may be substituted by a halogen atom, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms. m represents an integer from 1 to 6, and when m is an integer from 2 to 6, the plurality of -YZ- may be the same or different.

In the formula (3-1) to the formula (3-5), R ₂ represents a hydrogen atom, a halogen atom, -CF ₃ or an alkyl group having a carbon number of 1 to 5, and * represents a bond.

In one embodiment of the photopolymerizable compound (D), at least one of R _{1 is} a polymerizable functional group represented by the formula (3-1) to the formula (3-3).

In one embodiment of the present invention, in the photopolymerizable compound (D), Y independently represents 1,4-cyclohexylene, 1,4-cyclohexenylene, and 1,4-phenylene. , naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, indole-2,7-diyl, bicyclo[2.2.2]octane-1,4-diyl, bicyclo[3.1. 0] a divalent group of a hexane-3,6-diyl or triptycene-1,4-diyl group. And any -CH ₂ - in the ring of the group Y may be substituted by -O-, any -CH= may be substituted by -N=, any -H may be halogen atom, -CN, -NO ₂ , -NC, -N=C=O, -N=C=S, having 1 to 3 alkyl groups having 1 to 4 carbon atoms or phenyl substituted decyl groups, linear alkyl groups having 1 to 10 carbon atoms Substituted by a branched or branched alkyl group or a haloalkyl group having 1 to 10 carbon atoms. And among the above linear alkyl group, branched alkyl group or haloalkyl group, any -CH ₂ - may be -O-, -CO-, -COO-, -OCO-, -OCOO-, -CH=CH - or -C≡C- is replaced.

In an embodiment of the invention, the group Y is at least one selected from the group consisting of functional groups represented by formula (3-6) to formula (3-29):

In the formula (3-6) to the formula (3-29), R ₃ represents a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen having 1 to 3 carbon atoms. Alkyl, * represents the bond.

In one embodiment of the present invention, the photopolymerizable compound (D) is at least one selected from the group consisting of compounds represented by formula (3-30) to formula (3-41):

In the formula (3-30) to the formula (3-41), R ₃ represents a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen having 1 to 3 carbon atoms. Alkyl; R ₄ independently represents a hydrogen atom or a methyl group; R ₅ independently represents a hydrogen atom, a halogen atom, a methyl group, -CF ₃ , -OCH ₃ , a phenyl group or two R ₅ groups on the same carbon atom to form a carbon The number is 6 to 15 saturated or unsaturated hydrocarbon rings; i, j independently represent an integer from 1 to 20.

In one embodiment of the present invention, the photopolymerizable compound (D) is used in an amount of 1 to 35 parts by weight based on 100 parts by weight of the polymer (A).

The present invention further provides a liquid crystal alignment film which is formed by the above liquid crystal alignment agent.

The present invention further provides a liquid crystal display element having the above liquid crystal alignment film.

Based on the above, the surface-controlled vertical alignment type liquid crystal alignment agent of the present invention, since the diamine component (a2) in the mixture forming the polymer (A) includes the diamine compound (a2-1) represented by the formula (1) Therefore, the pretilt stability of the liquid crystal display element can be increased. Further, the surface-controlled vertical alignment type liquid crystal alignment agent of the present invention contains a polyoxyalkylene (B) containing a polymerizable unsaturated group, and the liquid crystal display element is excellent in ultraviolet ray deterioration resistance, and thus is suitable for the production of liquid crystal. Alignment film and liquid crystal display element.

The above described features and advantages of the invention will be apparent from the following description.

<Liquid alignment agent>

The present invention provides a liquid crystal alignment agent comprising a polymer (A), a polyoxyalkylene (B), a solvent (C), and a photopolymerizable compound (D). Further, the liquid crystal alignment agent may further include the additive (E) if necessary.

Hereinafter, the respective components of the liquid crystal alignment agent used in the present invention will be described in detail.

Here, the following description means that acrylic acid and/or methacrylic acid is represented by (meth)acrylic acid, and acrylate and/or methacrylate is represented by (meth)acrylate; similarly, (meth) The acryl fluorenyl group means an acryl fluorenyl group and/or a methacryl fluorenyl group.

Polymer (A)

The polymer (A) is obtained by reacting a mixture comprising a tetracarboxylic dianhydride component (a1) and a diamine component (a2).

In detail, the polymer (A) includes polylysine, polyimine, polyfluorene Amino acid-polyimine block copolymers or combinations of these polymers. Wherein the polyamidene block copolymer comprises a polyphthalic acid block copolymer, a polyamidiene block copolymer, a poly-proline-polyimine block copolymer or the above polymerization a combination of things. The polyaminic acid polymer, the polyamidimide polymer and the poly-proline-polyimine block copolymer may be a mixture of the tetracarboxylic dianhydride component (a1) and the diamine component (a2). The reaction was prepared.

Tetracarboxylic dianhydride component (a1)

The tetracarboxylic dianhydride component (a1) includes an aliphatic tetracarboxylic dianhydride compound, an alicyclic tetracarboxylic dianhydride compound, an aromatic tetracarboxylic dianhydride compound, and the formula (a1-1) to the formula (a1) -6) at least one of the tetracarboxylic dianhydride compounds represented by the above, or a combination of the above compounds.

Specific examples of the aliphatic tetracarboxylic dianhydride compound, the alicyclic tetracarboxylic dianhydride compound, and the aromatic tetracarboxylic dianhydride compound are listed below, but the present invention is not limited to these specific examples.

Specific examples of the aliphatic tetracarboxylic dianhydride compound may include, but are not limited to, ethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride or a combination of the above compounds.

Specific examples of the alicyclic tetracarboxylic dianhydride compound may include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-ring Butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4- Cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3, 7-Dibutylcycloheptyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, bicyclo [2.2.2 ]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride or a combination of the above compounds.

Specific examples of the aromatic tetracarboxylic dianhydride compound may include, but are not limited to, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylfluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylate Acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'-4,4'-diphenylethane tetracarboxylic dianhydride, 3,3',4,4'- Dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl phthalic anhydride, 4,4'- Bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluorohetero Propyldiphthalic acid dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(three Phenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, double (triphenylphthalic acid)-4,4'- Phenyl methane dianhydride, ethylene glycol-bis (hydrogen trimellitate), propylene glycol-bis (hydrogen trimellitate), 1,4-butanediol-bis (hydrogen trimellitate), 1,6-hexanediol-bis(anhydrotrimellitic acid ester), 1,8-octanediol-bis(anhydrotrimellitic acid ester), 2,2-bis(4-hydroxyphenyl)propane- Bis(hydrogen trimellitate), 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5- Bis-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)naphtho[1,2-c]furan-1,3-dione)},1 ,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]- Furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)- Naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-di Oxyloxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5 -(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b -hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1 ,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]- Furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-di-oxy-3-furan -Naphtho[1,2-c]-furan-1,3-dione, 5-(2,5-di- oxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1, An aromatic tetracarboxylic dianhydride compound such as 2-dicarboxylic dianhydride or a combination of the above compounds.

The tetracarboxylic dianhydride compound represented by the formula (a1-1) to the formula (a1-6) is as follows.

In the formula (a1-5), A ¹ represents a divalent group containing an aromatic ring; r represents an integer of 1 to 2; and A ² and A ³ may be the same or different and each independently represents a hydrogen atom or an alkyl group. Specific examples of the tetracarboxylic dianhydride compound represented by the formula (a1-5) include at least one of the compounds represented by the formula (a1-5-1) to the formula (a1-5-3).

In the formula (a1-6), A ⁴ represents a divalent group containing an aromatic ring; and A ⁵ and A ⁶ may be the same or different and each independently represents a hydrogen atom or an alkyl group. The tetracarboxylic dianhydride compound represented by the formula (a1-6) is preferably a compound represented by the formula (a1-6-1).

The tetracarboxylic dianhydride component (a1) may be used singly or in combination of two or more.

The specific example of the tetracarboxylic dianhydride component (a1) preferably includes 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1, 2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, benzene tetracarboxylic dianhydride (pyromellitic dianhydride), 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 3,3',4,4'-biphenylfluorene tetracarboxylic dianhydride, or a combination of the above compounds.

The total mole number based on the diamine component (a2) is 100 moles, and the tetracarboxylic dianhydride component (a1) is used in an amount ranging from 20 to 200 moles; preferably from 40 to 180 moles; more preferably It is 50~150 moor.

Diamine component (a2)

The diamine component (a2) includes a diamine compound (a2-1) represented by the formula (1), a diamine compound (a2-2) represented by the formula (2), and other diamine compounds (a2-3). .

Diamine compound represented by formula (1) (a2-1)

The diamine component (a2) includes the diamine compound (a2-1) represented by the formula (1):

In the formula (1), X ₁ and X ₃ each independently represent a methyl group, -O-, -COO-, -OCO-, -NHCO-, -CONH- or -NH-; X ₂ represents a single bond or carbon. The alkyl group is 1 to 20; X ₄ represents an oxygen atom or a sulfur atom.

The bonding position of the two amine groups (-NH ₂ ) in the formula (1) is not particularly limited. Specifically, it is listed as the position of 2, 3, the position of 2, 4, the position of 2, 5, the position of 2, 6, the position of 3, 4 of the bonding group on the benzene ring with respect to the side chain or 3,5 position. Among them, from the viewpoint of reactivity in synthesizing polyamic acid, it is preferably a position of 2, 4, a position of 2, 5, or a position of 3, 5. In consideration of the easiness in synthesizing the diamine compound, it is more preferably a position of 2, 4 or a position of 3, 5.

Specifically, the diamine compound (a2-1) represented by the formula (1) is exemplified by the compounds represented by the following formulas (1-1) to (1-13), but is not limited thereto:

The diamine compound (a2-1) represented by the formula (1) may be used singly or in combination of two or more.

The total amount of the diamine component (a2) used is 100 moles, and the diamine compound (a2-1) represented by the formula (1) is used in an amount of 5 to 50 moles, preferably 8 to 45 moles. More preferably, it is 10~40 moor.

When the diamine component (a2) of the polymer (A) in the liquid crystal alignment agent does not contain the diamine compound (a2-1) represented by the formula (1), the pretilt stability of the liquid crystal display element is not Good question.

When the amount of the diamine compound (a2-1) represented by the formula (1) is in the above range, the liquid crystal display element can be further improved in the diamine component (a2) of the polymer (A) in the liquid crystal alignment agent. Pretilt stability.

Diamine compound (a2-2) represented by formula (2)

The diamine component (a2) may further include the diamine compound (a2-2) represented by the formula (2):

In the formula (2), X ₅ represents a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH- or -NH-; X ₆ represents a carbon number of 1 to 20 substituted by fluorine or not a substituted linear alkyl group in which any -CH ₂ - may be substituted by: -CH=CH-, -O-, -COO-, -NHCO-, -NH-, an extended carbon ring Or a heterocyclic group; X ₇ represents a hydrogen atom or a methyl group.

Bonding two-position amine (-NH _{2) (2)} is not particularly limited in the sum. Specifically, it is listed as the position of 2, 3 on the phenyl ring relative to the bonding group of the side chain, the position of 2, 4, the position of 2, 5, the position of 2, 6, or the position of 3, 4 or 3,5 position. Among them, from the viewpoint of reactivity in synthesizing polyamic acid, it is preferably a position of 2, 4, a position of 2, 5, or a position of 3, 5. In consideration of the easiness in synthesizing the diamine compound, it is more preferably a position of 2, 4 or a position of 3, 5.

Specifically, the diamine compound (a2-2) represented by the formula (2) is exemplified by the compounds represented by the following formulas (2-1) to (2-15), but is not limited thereto:

The diamine compound (a2-2) represented by the formula (2) may be used alone or in the group Use a variety of uses.

The total amount of the diamine component (a2) used is 100 moles, and the diamine compound (a2-2) represented by the formula (2) is used in an amount of 10 to 90 moles, preferably 15 to 80 moles. More preferably, it is 20~70 moor.

When the diamine component (a2-2) represented by the formula (2) is contained in the diamine component (a2) of the polymer (A) in the liquid crystal alignment agent, the ultraviolet ray decay resistance of the liquid crystal display element can be further improved.

Other diamine compounds (a2-3)

In the diamine component (a2), other diamine compound (a2-3) not belonging to the formula (1) or the formula (2) may be included as long as it does not affect the effect of the liquid crystal alignment agent of the present invention. The other diamine compound (a2-3) includes an aliphatic diamine compound, an alicyclic diamine compound, an aromatic diamine compound, a diamine compound having the formula (II-1) to the formula (II-30), or combination.

Specific examples of the aliphatic diamine compound include, but are not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane 1,6-Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane , 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-methyldecane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis(3-aminopropoxy)B Alkane, or a combination of the above compounds.

Specific examples of the alicyclic diamine compound include, but are not limited to, 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 ]- eleven Carboxydimethyldiamine, 4,4'-methylenebis(cyclohexylamine), or a combination of the above compounds.

Specific examples of the aromatic diamine compound include, but are not limited to, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl Bismuth, 4,4'-diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydroquinone, 6-amino-1-(4'-aminophenyl)-1,3, 3-trimethylhydroquinone, hexahydro-4,7-methyl bridge hydroquinone dimethylene diamine, 3,3'-diaminobenzophenone, 3,4'-diaminodi Benzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4- Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]碸, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 9,10-bis(4-aminophenyl)anthracene [9,10-bis(4-aminophenyl)anthracene], 2,7 -diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 4,4'-(p-phenylene) Propylene) 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-pentanyl) Cyclohexyl)cyclohexyl]phenyl-methylene-1,3-diaminobenzene {5-[4-(4-n-pentylcyclohexyl)cyclohexyl] Phenylmethylene-1,3-diaminobenzene}, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane {1,1-bis[ 4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane}, or a combination of the above compounds.

The diamine compound having the formula (a2-1) to the formula (a2-30) is shown below.

In the formula (II-1), G ¹ represents -O-, , , , ,or ; G ² represents a group having a steroid (steroid) skeleton, a trifluoromethyl group, a fluorine group, an alkyl group having 2 to 30 carbon atoms, or a derivative derived from pyridine, pyrimidine, triazine, piperidine or piperazine; a monovalent group containing a cyclic structure of a nitrogen atom.

Specific examples of the compound represented by the formula (II-1) include, but are not limited to, 2,4-diaminophenyl ethyl formate, 3,5-diaminophenylethylate B 3,5-diaminophenyl ethyl formate, 2,4-diaminophenyl propyl formate, 3,5-diaminophenyl propyl formate (3,5- Diaminophenyl propyl formate), 1-dodecoxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene 1-hexadecoxy-2,4-diaminobenzene), 1-octadecoxy-2,4-diaminobenzene, from formula (II-1-1) to formula At least one of the compounds represented by (II-1-6), or a combination of the above compounds.

The compound represented by the formula (II-1-1) to the formula (II-1-6) is shown below.

, G (II-1) and G ¹ in the same formula of formula (II-2) in ^1, G ³ and G ⁴ each independently represents a divalent aliphatic ring, a divalent aromatic ring or a divalent heterocyclic group; G ⁵ represents an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, a fluoroalkoxy group having 1 to 5 carbon atoms, or a cyano group or Halogen atom.

Specific examples of the compound represented by the formula (II-2) include at least one of the compounds represented by the formula (II-2-1) to the formula (II-2-13). Specifically, the compound represented by the formula (II-2-1) to the formula (II-2-13) is as follows.

In the formula (II-2-10) to the formula (II-2-13), s represents an integer of from 3 to 12.

In the formula (II-3), G ⁶ each independently represents a hydrogen atom, a fluorenyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen atom. And G ⁶ in each repeating unit may be the same or different; u represents an integer of 1 to 3.

Specific examples of the compound represented by the formula (II-3) include when p is 1: p-diamine benzene, m-diamine benzene, o-diamine benzene or 2,5-diaminotoluene, etc.; 2 hours: 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-di Aminobiphenyl, 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'-diaminobiphenyl, 2,2'-dichloro-4,4' -diamino-5,5'-dimethoxybiphenyl or 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl; or when u is 3: 1 , 4-bis(4'-aminophenyl)benzene, and the like.

Specific examples of the compound represented by the formula (II-3) preferably include p-diamine benzene, 2,5-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-dimethyl Oxy-4,4'-diamine A bisphenyl, 1,4-bis(4'-aminophenyl)benzene or a combination of the above compounds.

In the formula (II-4), v represents an integer of 2 to 12.

In the formula (II-5), w represents an integer of 1 to 5. The compound represented by the formula (II-5) is preferably 4,4'-diamino-diphenyl sulfide.

In the formula (II-6), G ⁷ and G ⁹ each independently represent a divalent organic group, and G ⁷ and G ⁹ may be the same or different; G ⁸ represents a derivative derived from pyridine, pyrimidine, triazine, piperidine or piperidine. a divalent group of a cyclic structure containing a nitrogen atom such as a azine.

In the formula (II-7), G ¹⁰ , G ¹¹ , G ¹² and G ¹³ each independently represent a hydrocarbon group having 1 to 12 carbon atoms, and G ¹⁰ , G ¹¹ , G ¹² and G ¹³ may be the same or different; X1 Each represents an integer from 1 to 3; X2 represents an integer from 1 to 20.

In the formula (II-8), G ¹⁴ represents an oxygen atom or a cyclohexane group; G ¹⁵ represents a methylene group (methylene, -CH ₂ -); G ¹⁶ represents a phenyl or cyclohexane group; G ¹⁷ Represents a hydrogen atom or a heptyl group.

Specific examples of the compound represented by the formula (II-8) include a compound represented by the formula (II-8-1), a compound represented by the formula (II-8-2) or a combination of the above compounds.

The compound represented by the formula (II-9) to the formula (II-30) is shown below.

In the formulae (II-17) to (II-25), G ¹⁸ preferably represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; and G ¹⁹ preferably represents a hydrogen atom. An alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

The other diamine compound (a2-3) may be used singly or in combination of two or more.

Specific examples of the other diamine compound (a2-3) include, but are not limited to, 1,2-diaminoethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamine group. Diphenylmethane, 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, ethyl 2,4-diaminophenylcarboxylate, 1-octadecyloxy-2,4-diaminobenzene, represented by formula (II-1-1) a compound, a compound represented by the formula (II-1-2), a compound represented by the formula (II-1-4), a compound represented by the formula (II-1-5), and a formula (II-2-1) a compound represented by the formula (II-2-11), p-diamine benzene, m-diamine benzene, o-diamine benzene, a compound represented by the formula (II-8-1), (II-26) to a compound represented by the formula (II-30), or a combination of the above compounds.

When the polymer (A) in the liquid crystal alignment agent contains at least one of the diamine compound (a2-3) represented by the formula (II-1) and the formula (II-2), the pretilt angle stability of the liquid crystal display element can be further improved. Sex.

When the diamine component (a2) of the polymer (A) in the liquid crystal alignment agent contains at least one of the diamine compound (a2) represented by the formula (II-26) to the formula (II-30) as the other two In the case of the amine compound (a2-3), the ultraviolet ray decay resistance of the liquid crystal display element can be further improved.

Method for preparing polymer (A)

The polymer (A) may include at least one of polyamic acid and polyimine. Further, the polymer (A) may further include a polyimide-based block copolymer. The preparation methods of the above various polymers are further explained below.

Method for preparing polylysine

The method for preparing the poly-proline is to first dissolve the mixture in a solvent, wherein the mixture comprises the tetracarboxylic dianhydride component (a1) and the diamine component (a2), and at 0 ° C to The polycondensation reaction was carried out at a temperature of 100 °C. After reacting for 1 hour to 24 hours, the reaction solution is subjected to distillation under reduced pressure with an evaporator to obtain a polyamic acid. Alternatively, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate. Next, the precipitate is dried by drying under reduced pressure to obtain polylysine.

The solvent used in the polycondensation reaction may be the same as or different from the solvent in the liquid crystal alignment agent described below, and the solvent used in the polycondensation reaction is not particularly limited as long as it is a soluble reactant and a product. The solvent preferably includes, but is not limited to, (1) an aprotic polar solvent such as N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide, An aprotic polar solvent such as N,N-dimethylformamide, dimethylhydrazine, γ-butyrolactone, tetramethylurea or hexamethylphosphoric acid triamide; or (2) a phenolic solvent, For example, a phenolic solvent such as m-cresol, xylenol, phenol or halogenated phenol. The solvent used in the polycondensation reaction is preferably used in an amount of from 200 parts by weight to 2000 parts by weight, and more preferably from 300 parts by weight to 1800 parts by weight, based on 100 parts by weight of the total amount of the mixture.

It is worth noting that in the polycondensation reaction, the solvent may be used in combination with an appropriate amount of a poor solvent, wherein the poor solvent does not cause precipitation of the polyamic acid. The poor solvent may be used singly or in combination of two or more, and includes, but is not limited to, (1) an alcohol such as methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, or 1,4-butane. An alcohol such as an alcohol or triethylene glycol; (2) a ketone such as a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; or (3) an ester such as: An ester of methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate or ethylene glycol ethyl ether acetate; (4) ethers such as diethyl ether, Ethylene glycol methyl ether, ethylene Ethers such as alcohol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether or diethylene glycol dimethyl ether; a halogenated hydrocarbon such as a halogenated hydrocarbon such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene or o-dichlorobenzene; or 6) Hydrocarbons, for example, hydrocarbons such as tetrahydrofuran, hexane, heptane, octane, benzene, toluene or xylene, or any combination of the above solvents. The amount of the poor solvent to be used is preferably from 0 part by weight to 60 parts by weight, and more preferably from 0 part by weight to 50 parts by weight, based on 100 parts by weight of the diamine component (a2).

Method for preparing polyimine

The method for preparing the polyimine is obtained by heating the polylysine prepared by the above method for preparing polyamic acid in the presence of a dehydrating agent and a catalyst. During heating, the proline functional group in the polylysine can be converted to a quinone imine functional group (ie, hydrazide) via a dehydration ring closure reaction.

The solvent used in the dehydration ring-closing reaction may be the same as the solvent (C) in the liquid crystal alignment agent, and therefore will not be further described herein. The amount of the solvent used in the dehydration ring-closure reaction is preferably from 200 parts by weight to 2000 parts by weight, and more preferably from 300 parts by weight to 1800 parts by weight, based on 100 parts by weight of the polylysine.

In order to obtain a preferred degree of ruthenium iodide, the operating temperature of the dehydration ring closure reaction is preferably from 40 ° C to 200 ° C, more preferably from 40 ° C to 150 ° C. If the operating temperature of the dehydration ring-closing reaction is lower than 40 ° C, the reaction of ruthenium imidization is incomplete, and the degree of ruthenium iodide of poly-proline is lowered. However, if the operating temperature of the dehydration ring-closure reaction is higher than 200 ° C, the weight average molecular weight of the obtained polyimine is low.

The dehydrating agent used in the dehydration ring-closure reaction may be selected from acid anhydride compounds, and specific examples thereof include acid anhydride compounds such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. The dehydrating agent is used in an amount of from 0.01 mol to 20 mol based on 1 mol of the polyglycolic acid. The catalyst used in the dehydration ring closure reaction may be selected from (1) a pyridine compound such as a pyridine compound such as pyridine, trimethylpyridine or lutidine; and (2) a tertiary amine compound, for example: A tertiary amine compound such as triethylamine. The amount of the dehydrating agent used is 1 mole, and the catalyst can be used in an amount of 0.5 mole to 10 moles.

The ruthenium iodide ratio of the polymer (A) may be from 30 to 90%, preferably from 35 to 85%, and more preferably from 40 to 80%. When the ruthenium imidation ratio of the polymer (A) in the liquid crystal alignment agent is within the above range, the ultraviolet ray decay resistance of the liquid crystal display element can be further improved.

Method for preparing polyamidene block copolymer

The polyamidene block copolymer is selected from the group consisting of polyphthalic acid block copolymers, polyamidiene block copolymers, polyamido acid-polyimine block copolymers or the above polymerizations. Any combination of objects.

The method for preparing the polyimine-based block copolymer is preferably first dissolving the starting material in a solvent and performing a polycondensation reaction, wherein the starting material comprises at least one poly-proline and/or at least one polyfluorene. The imine, and may further comprise a carboxylic anhydride component and a diamine component.

The carboxylic anhydride component and the diamine component in the starting material may be the same as the tetracarboxylic dianhydride component (a1) and the diamine component (a2) used in the method for preparing the polyamic acid, and used for The solvent in the polycondensation reaction may be the same as the solvent in the liquid crystal alignment agent described below. I will not repeat them here.

The solvent used in the polycondensation reaction is preferably used in an amount of from 200 parts by weight to 2000 parts by weight, and more preferably from 300 parts by weight to 1800 parts by weight, based on 100 parts by weight of the starting material. The operation temperature of the polycondensation reaction is preferably from 0 ° C to 200 ° C, and more preferably from 0 ° C to 100 ° C.

Preferably, the starting material comprises, but is not limited to, (1) two polyamido acids having different terminal groups and different structures; (2) two kinds of polyamidiamines having different terminal groups and different structures; a poly-proline and a polyamidiamine having different terminal groups and different structures; (4) a poly-proline, a carboxylic anhydride component and a diamine component, wherein the carboxylic anhydride component and the diamine component At least one of the structure is different from the structure of the carboxylic anhydride component and the diamine component used to form the polyamic acid; (5) a polyimine, a carboxylic anhydride component and a diamine component, wherein the carboxylic anhydride group At least one of the diamine component and the carboxylic anhydride component used in forming the polyimine are different from the structure of the diamine component; (6) poly-proline, polyimine, and carboxylic anhydride components And a diamine component, wherein at least one of the carboxylic anhydride component and the diamine component is different from the structure of the carboxylic anhydride component and the diamine component used to form the polyamic acid or the polyimine; 7) two structurally different polylysine, carboxylic anhydride component and diamine component; (8) two structurally different polyimine, carboxylic anhydride component and diamine component; (9) Two terminal groups are anhydride groups and structures a different polyamic acid and a diamine component; (10) two polyamines having a terminal group which is an amine group and having a different structure, and a carboxylic anhydride component; (11) the two terminal groups are an acid anhydride group and a structural phase a different polyimine and a diamine component; or (12) a polyimine and a carboxylic anhydride component in which the terminal groups are amine groups and have different structures.

Polylysine, polyimine, in the range that does not affect the efficacy of the present invention Further, the polyimide-based block copolymer is preferably a terminal-modified polymer obtained by first adjusting the molecular weight. The coating property of the liquid crystal alignment agent can be improved by using a terminal-modified polymer. The manner of preparing the terminal-modified polymer can be obtained by adding a monofunctional compound while carrying out a polycondensation reaction of poly-proline.

Specific examples of the monofunctional compound include, but are not limited to, (1) a monobasic acid anhydride such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, ortho-fourth a monobasic anhydride such as an alkyl succinic anhydride or n-hexadecyl succinic anhydride; (2) a monoamine compound such as aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, N-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, A monoamine compound such as n-octadecylamine or n-icosylamine; or (3) a monoisocyanate compound such as a monoisocyanate compound such as phenyl isocyanate or naphthyl isocyanate.

The polymer (A) of the present invention has a polystyrene-equivalent weight average molecular weight of 2,000 to 200,000, preferably 5,000 to 150,000, more preferably measured by Gel Permeation Chromatography (GPC). It is 10,000~100,000.

Polyoxane (B)

The polyoxyalkylene (B) contains a polymerizable unsaturated group, and the polymerizable unsaturated group includes a group represented by the formula (b1-1), a group represented by the formula (b1-2), or a combination of the two.

Specifically, the base represented by the formula (b1-1) is as follows:

In the formula (b1-1), A represents a hydrogen atom or a methyl group; and a represents an integer of 1 to 3.

In addition, the base represented by the formula (b1-2) is as follows:

In the formula (b1-2), b represents an integer of 0 or 1.

In detail, the polyoxyalkylene (B) may further contain an epoxy group-containing group, and the epoxy group-containing group includes a group represented by the formula (b2-1) and represented by the formula (b2-2). At least one of a group and a group represented by the formula (b2-3). When the polyoxyalkylene (B) further contains an epoxy group-containing group, the ultraviolet ray decay resistance of the liquid crystal display element can be further improved.

Specifically, the group represented by the formula (b2-1) is as follows.

In the formula (b2-1), B represents an oxygen atom or a single bond; c represents an integer of 1 to 3; d represents an integer of 0 to 6, wherein when d represents 0, B is a single bond, and * represents a bond.

Further, the group represented by the formula (b2-2) is as follows.

In the formula (b2-2), e represents an integer of 0 to 6, and * represents a bond.

The group represented by the formula (b2-3) is as follows.

In the formula (b2-3), D represents an alkylene group having a carbon number of 2 to 6; E represents a hydrogen atom or an alkyl group having a carbon number of 1 to 6, and * represents a bond.

The polyoxyalkylene (B) may be obtained by self-polymerization condensation of a decane compound (b1) containing a polymerizable unsaturated group; or a decane compound (b1) containing a polymerizable unsaturated group and a decane compound containing an epoxy group (b2) ) Copolymerization condensation. Besides, the monomer forming the polyoxyalkylene (B) may further include other decane compound (b3) within a range not affecting the efficacy of the present invention.

a decane compound containing a polymerizable unsaturated group (b1)

The polymerizable unsaturated group contained in the polymerizable unsaturated group-containing decane compound (b1) includes a group represented by the above formula (b1-1), a group represented by the above formula (b1-2), or a combination thereof.

Specific examples of the polymerizable unsaturated group-containing decane compound (b1) include 3-(meth)acryloxypropyltrichlorodecane, 3-(meth)acryloxypropyltrimethoxydecane, and 3 -(Meth)acryloxypropyltriethoxydecane, 2-(meth)acryloxyethyltrichlorodecane, 2-(meth)acryloxyethyltrimethoxydecane, 2-(Methyl)propenyloxyethyltriethoxydecane, 4-(methyl)propenyloxybutyltrichlorodecane, 4-(methyl)propenyloxybutyltrimethoxydecane 4-(Methyl)propenyloxybutyltriethoxydecane, vinyltrichlorodecane, vinyltrimethoxydecane, vinyltriethoxydecane,allyltrichloroanthracene Alkane, allyltrimethoxydecane, allyltriethoxydecane, methylvinyldichlorodecane,divinyldichlorodecane,divinyldimethoxydecane,chlorovinyldimethyloxane , methoxyvinyl dimethyl decane, or a combination of the above compounds.

Specific examples of the polymerizable unsaturated group-containing decane compound (b1) preferably include 3-(meth)acryloxypropyltrichlorodecane, 3-(meth)acryloxypropyltrimethoxy group. Decane, vinyltrichloromethane, vinyltrimethoxydecane, allyltrimethoxydecane, or a combination of the above.

The total amount of the decane compound (b1) containing the polymerizable unsaturated group, the epoxy group-containing decane compound (b2), and the other decane compound (b3) is 1.0 mol, and the polymerizable unsaturated group-containing decane compound ( The amount of b1) used is 0.1 to 0.9 m, preferably 0.2 to 0.8 m, more preferably 0.3 to 0.7 m.

When the decane compound (b1) containing a polymerizable unsaturated group is not used for the polymerization of the polyoxane (B), the liquid crystal display element obtained has a problem that the ultraviolet ray deterioration resistance is not good.

Epoxy group-containing decane compound (b2)

The epoxy group-containing group contained in the epoxy group-containing decane compound (b2) is, for example, a glycidyl group, a glycidyloxy group, an epoxycyclohexyl group or an epoxy group. Oxetanyl group.

Specifically, the epoxy group-containing group may include a group represented by the above formula (b2-1), a group represented by the above formula (b2-2), and a group represented by the above formula (b2-3). to One less.

The epoxy group-containing group preferably includes a group represented by the formula (b2-1-1), a group represented by the formula (b2-2-1), and a group represented by the formula (b2-3-1). At least one of them.

Specific examples of the epoxy group-containing decane compound (b2) include 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, 3-(N-allyl-N-glycidyl) Aminopropyltrimethoxydecane, 3-glycidyl ether propyl trimethoxy decane, 3-glycidyl ether propyl triethoxy decane, 3-glycidyl ether propyl methyl dimethoxy Decane, 3-glycidyl ether propyl methyl diethoxy decane, 3-glycidyl ether propyl dimethyl methoxy decane, 3-glycidyl ether propyl dimethyl ethoxy decane, 2-Glycidyl ether ethyl trimethoxy decane, 2-glycidyl ether ethyl triethoxy decane, 2-glycidyl ether ethyl methyl dimethoxy decane, 2-glycidyl ether B Methyldiethoxy decane, 2-glycidyl ether ethyl dimethyl methoxy decane, 2-glycidyl ether ethyl dimethyl ethoxy decane, 4-glycidyl ether butyl trimethyl Oxydecane, 4-glycidyl ether butyl triethoxy decane, 4-glycidyl ether butyl methyl dimethoxy decane, 4-glycidyl ether butyl methyl diethoxy decane, 4-glycolate Oleic ether butyl dimethyl methoxy decane, 4-glycidyl ether butyl Dimethylethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-( 3,4-epoxycyclohexyl)propyltrimethoxydecane, 3-(3,4-epoxycyclohexyl)propyltriethoxydecane, ((3-ethyl-3-epoxypropane) Methoxy)propyltrimethoxydecane, ((3-ethyl-3-epoxypropenyl)methoxy)propyltriethoxydecane, ((3-ethyl-3-epoxypropanyl) Methoxy)propylmethyldimethoxydecane or ((3-ethyl-3-epoxypropenyl)methoxy)propane dimethylmethoxydecane, or a combination of the above.

Specific examples of the epoxy group-containing decane compound (b2) preferably include 3-glycidyl ether propyl trimethoxy decane, 2-glycidyl ether ethyl trimethoxy decane, and 4-glycidyl ether butyl Trimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, (3-ethyl Benzyl-3-epoxypropenyl)methoxy)propyltrimethoxydecane, ((3-ethyl-3-epoxypropenyl)methoxy)propyltriethoxydecane or a combination of the above compounds .

The total amount of the decane compound (b1) containing the polymerizable unsaturated group, the epoxy group-containing decane compound (b2), and the other decane compound (b3) is 1.0 mol, and the epoxy group-containing decane compound (b2) The amount of use is from 0.1 to 0.9 mol, preferably from 0.2 to 0.8 mol, more preferably from 0.3 to 0.7 mol.

In the decane compound for polymerization of the polyoxyalkylene (B), when the epoxy group-containing decane compound (b2) is used, the ultraviolet ray decay resistance of the liquid crystal display element can be further improved.

Other decane compounds (b3)

The other decane compound (b3) is, for example, a compound having one ruthenium atom. The compound having one ruthenium atom includes a decane compound having four hydrolyzable groups, a decane compound having three hydrolyzable groups, a decane compound having two hydrolyzable groups, and a decane having one hydrolyzable group. a compound, or a combination thereof.

Specific examples of the decane compound having 4 hydrolyzable groups include tetrachlorodecane, tetramethoxydecane, tetraethoxydecane, tetra-n-propoxydecane, tetraisopropoxydecane, tetra-n-butoxydecane. , four second butoxydecane, or a combination of the above compounds.

Specific examples of the decane compound having three hydrolyzable groups include trichlorodecane, trimethoxy decane, triethoxy decane, fluorotrichloro decane, fluorotrimethoxy decane, fluorotriethoxy decane, and methyl three. Chlorodecane, methyltrimethoxydecane, methyltriethoxydecane, 2-(trifluoromethyl)ethyltrichlorodecane, 2-(trifluoromethyl)ethyltrimethoxydecane, 2-( Trifluoromethyl)ethyltriethoxydecane, hydroxymethyltrichlorodecane, hydroxymethyltrimethoxydecane, hydroxyethyltrimethoxydecane, decylmethyltrichlorodecane, 3-mercaptopropyltrichloride Decane, decylmethyltrimethoxydecane, decylmethyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane,phenyltrichlorodecane,phenyltrimethoxy A decyl alkane, a phenyl triethoxy decane, or a combination of the above compounds.

Specific examples of the decane compound having two hydrolyzable groups include methyl dichlorodecane, methyl dimethoxy decane, methyl diethoxy decane, dimethyl dichloro decane, and dimethyl dimethoxy group. Decane, dimethyldiethoxydecane, methyl[2-(perfluoro-n-octyl)ethyl]dichlorodecane, methyl[2-(perfluoro-n-octyl)ethyl]dimethoxy Decane, 3-mercaptopropylmethyldichlorodecane, 3-mercaptopropylmethyldimethoxydecane, diphenyldichlorodecane, diphenyldimethoxydecane, or a combination of the above compounds.

Specific examples of the decane compound having one hydrolyzable group include chlorodimethyl decane, methoxy dimethyl decane, chlorotrimethyl decane, bromotrimethyl decane, iodine trimethyl decane, and methoxy three. Methyl decane, chloromethyl diphenyl decane, methoxymethyl diphenyl decane, or a combination of the above compounds.

Specific examples of commercially available products of other decane compounds (b3) include KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21. -5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D , X-22-170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X -40-2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40 -9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220 L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (manufactured by Shin-Etsu Chemical Co., Ltd.); glass resin (GLASS RESIN, manufactured by Showa Denko); SH804, SH805, SH806A, SH840, SR2400, SR2402 SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (manufactured by Toray Dow Corning); FZ3711, FZ3722 (manufactured by NUC); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (manufactured by JNC); MS51, MS56 (manufactured by Mitsubishi Chemical Corporation); and GR100, GR650, GR908, GR950 (made by Showa Denko) Partial condensate.

The other decane compound (b3) is preferably tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane. , 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, decylmethyltrimethoxydecane, decylmethyltriethoxydecane, dimethyldimethoxydecane, dimethyl A bis ethoxy decane, or a combination of the above compounds.

The total amount of the decane compound (b1), the epoxy group-containing decane compound (b2), and the other decane compound (b3) based on the polymerizable unsaturated group is 1.0 mol, and the other decane compound (b3) is used in an amount of 1.0 mol. 0 to 0.8 moles, preferably 0.1 to 0.7 moles, more preferably 0.2 to 0.6 moles.

The polycondensation reaction for forming the polyoxyalkylene (B) can be carried out by a general method, for example, by adding an organic solvent, water or optionally further adding a catalyst to the above decane compound or a mixture thereof, followed by 50 ° C using an oil bath or the like. The heating to 150 ° C preferably takes place from 0.5 hours to 120 hours. While heating, the mixture may be stirred or placed under reflux.

The above organic solvent is not particularly limited and may be the same as or different from the solvent (C) contained in the liquid crystal alignment agent of the present invention.

Specific examples of the organic solvent include hydrocarbon compounds such as toluene and xylene; ketone compounds such as methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone. ; ethyl acetate, n-butyl acetate, isoamyl acetate, C An ester compound of diol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc.; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane ( Dioxane) and other ether compounds; 1-hexanol, 4-methyl 2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol An alcohol compound such as mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether or propylene glycol mono-n-propyl ether, or a combination of the above organic solvents.

The above organic solvents may be used singly or in combination of two or more.

The organic solvent is preferably used in an amount of 10 parts by weight to 1200 parts by weight, more preferably 30 parts by weight to 1,000 parts by weight based on 100 parts by weight of all of the decane compound.

The water is preferably used in an amount of from 0.5 mol to 100 mol, more preferably from 1 mol to 30 mol, based on 1 mol of the hydrolyzable group of all the decane compounds.

The catalyst is not particularly limited, and preferably, the catalyst is selected from the group consisting of an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, or a combination thereof.

Specific examples of the acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid, polybasic acid anhydride, or a combination thereof.

Specific examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, or a combination thereof.

Specific examples of the organic base include primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperididine, pyrrolidine, pyrrole, etc.; triethylamine, three N-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene A tertiary organic amine such as (diazabicycloundecene); a quaternary organic amine such as tetramethylammonium hydroxide; or a combination of the above compounds.

The amount of the catalyst to be used varies depending on the reaction conditions such as the type and temperature, and can be appropriately set, for example, 1 mol based on all the decane compound, and the amount of the catalyst added is 0.01 mol to 5 m, preferably 0.03 moles to 3 moles, more preferably 0.05 moles to 1 mole.

From the viewpoint of stability, after completion of the polycondensation reaction, it is preferred to wash the organic solvent layer fractionated from the reaction liquid with water. In the case of performing the cleaning, it is preferred to use a water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2% by weight or the like. The cleaning can be carried out until the water layer after the cleaning is neutral, and then the organic solvent layer is dried with an anhydrous agent such as anhydrous calcium sulfate or molecular sieves, and then the organic solvent is removed to obtain a polyoxyalkylene. B).

The polysiloxane (B) of the present invention has a polystyrene-equivalent weight average molecular weight of from 500 to 100,000, preferably from 1,000 to 80,000, more preferably from 5,000 to 50,000, as measured by gel permeation chromatography.

The polysiloxane (B) is used in an amount of 1 to 25 parts by weight, preferably 2 to 20 parts by weight, and more preferably 3 to 15 parts by weight, based on 100 parts by weight of the polymer (A).

When the liquid crystal alignment agent does not use polyoxyalkylene (B), the liquid crystal display element has a problem that the ultraviolet ray deterioration resistance is poor.

Solvent (C)

The solvent used in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is a polymer (A), a polyoxane (B) and other optional components, and does not react with it, preferably The solvent used in the synthesis of the polyamic acid may be used in combination with the poor solvent used in the synthesis of the polyamic acid.

Specific examples of the solvent (C) include, but are not limited to, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, γ-butyrolactam, 4-hydroxy-4- Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, 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 Ester, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate or N,N-dimethylformamide or N,N-dimethylacetamide or the like. The solvent (C) may be used singly or in combination of two or more.

The solvent (C) is used in an amount of 800 to 4000 parts by weight, preferably 900 to 3500 parts by weight, more preferably 1,000 to 3,000 parts by weight, based on 100 parts by weight of the polymer (A).

Photopolymerizable compound (D)

The liquid crystal alignment agent of the present invention further contains a photopolymerizable compound (D). When the photopolymerizable compound (D) is contained in the liquid crystal alignment agent, the pretilt stability of the liquid crystal display element can be further improved.

The photopolymerizable compound (D) is a compound represented by the formula (3).

In the formula (3), R ₁ each independently represents a polymerizable functional group represented by the formula (3-1) to the formula (3-5), a hydrogen atom, a halogen atom, -CN, -CF ₃ , -CF ₂ H, -CFH ₂ , -OCF ₃ , -OCF ₂ H, -N=C=O, -N=C=S or an alkyl group having 1 to 20 carbon atoms, wherein any of the above alkyl groups is -CH ₂ - Can be substituted by -O-, -S-, -SO ₂ -, -CO-, -COO-, -OCO-, -CH=CH-, -CF=CF- or -C≡C-, and contain a hydrogen atom In the functional group, any hydrogen atom may be substituted with a halogen atom or -CN; at least one of R ₁ is a polymerizable functional group represented by the formula (3-1) to the formula (3-5). Y independently represents a saturated or unsaturated, heterocyclic, condensed or spiro bivalent group having a carbon number of 3 to 20, and any -CH ₂ - in the ring of the group Y may be substituted by -O-, arbitrary -CH= may be substituted by -N=, any -H may be via a halogen atom, -CN, -NO ₂ , -NC, -N=C=O, -N=C=S, with 1 to 3 carbons The alkyl group or the phenyl group-substituted fluorenyl group having 1 to 4, the linear alkyl group having 1 to 10 carbon atoms, the branched alkyl group having 1 to 10 carbon atoms or the haloalkyl group having 1 to 10 carbon atoms And in the above linear alkyl group, branched alkyl group or haloalkyl group, any -CH ₂ - may be via -O-, -CO-, -COO-, -OCO-, -OCOO-, -CH =CH- or -C≡C-substituted. Z each independently represents a single bond or an alkylene group having a carbon number of 1 to 20, wherein any -CH ₂ - in the above alkyl group may be -O-, -S-, -SO ₂ -, -CO- , -COO-, -OCO-, -OCOO-, -CH=CH-, -CF=CF-, -CH=N-, -N=CH-, -N=N-, -N(O)=N - or -C≡C-substituted, and any -H may be substituted by a halogen atom, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms. m represents an integer of 1 to 6, and when m is an integer of 2 to 6, a plurality of -YZ- are the same or different.

The polymerizable functional group represented by the formula (3-1) to the formula (3-5) is as follows.

In the formula (3-1) to the formula (3-5), R ₂ represents a hydrogen atom, a halogen atom, -CF ₃ or an alkyl group having a carbon number of 1 to 5, and * represents a bond.

In the formula (3), at least one of R ₁ is preferably a polymerizable functional group represented by the formula (3-1) to the formula (3-3).

In the formula (3), specifically, Y each independently represents 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetra Hydrogenonaphthalene-2,6-diyl, indole-2,7-diyl, bicyclo[2.2.2]octane-1,4-diyl, bicyclo[3.1.0]hexane-3,6-diyl Or a divalent group of triptycyl-1,4-diyl. And any -CH ₂ - in the ring of the group Y may be substituted by -O-, any -CH= may be substituted by -N=, and any -H may be via a halogen atom, -CN, -NO ₂ , - NC, -N=C=O, -N=C=S, having 1 to 3 alkyl groups having 1 to 4 carbon atoms or phenyl substituted decyl groups, linear alkyl groups having 1 to 10 carbon atoms or A branched alkyl group or a haloalkyl group having a carbon number of 1 to 10 is substituted. And among the above linear alkyl group, branched alkyl group or haloalkyl group, any -CH ₂ - may be -O-, -CO-, -COO-, -OCO-, -OCOO-, -CH=CH -or-C≡C- is substituted.

Y preferably each independently represents at least one selected from the group consisting of functional groups represented by formula (3-6) to formula (3-30):

In the formula (3-6) to the formula (3-29), R ₃ represents a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen having 1 to 3 carbon atoms. Alkyl, * represents the bond.

The photopolymerizable compound (D) is preferably at least one selected from the group consisting of compounds represented by formula (3-30) to formula (3-41):

In the formula (3-30) to the formula (3-41), R ₃ represents a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen having 1 to 3 carbon atoms. Alkyl; R ₄ each independently represents a hydrogen atom or a methyl group; R ₅ each independently represents a hydrogen atom, a halogen atom, a methyl group, -CF ₃ , -OCH ₃ , a phenyl group or two R ₅ groups on the same carbon atom to form a carbon The number is 6 to 15 saturated or unsaturated hydrocarbon rings; g and h each independently represent an integer of 1 to 20.

When the liquid crystal alignment agent of the present invention contains a compound selected from the formula (3-30) to the formula (3-41) When at least one of the group consisting of the compounds represented by the compound is used as the photopolymerizable compound (D), the liquid crystal display element exhibits better pretilt stability.

More specifically, the photopolymerizable compound (D) includes at least one of the compounds represented by the formula (3-42) to the formula (3-96).

Equation (3-90)

The photopolymerizable compound (D) is particularly preferably at least one of a compound represented by the formula (3-43) to the formula (3-49) or the formula (3-68) to the formula (3-96). When the photopolymerizable compound (D) is a compound represented by the formula (3-43) to the formula (3-49) or the formula (3-68) to the formula (3-96), the precursor of the produced liquid crystal display element The stability of the dip is particularly good.

The photopolymerizable compound (D) can be used singly or in combination of two or more.

The photopolymerizable compound (D) is used in an amount of 1 to 35 parts by weight, preferably 3 to 30 parts by weight, more preferably 5 to 25 parts by weight, based on 100 parts by weight of the polymer (A).

Additive (E)

The liquid crystal aligning agent may also optionally add the additive (E), wherein the additive (E) includes a compound having at least two epoxy groups, a decane compound having a functional group, within a range not impairing the efficacy of the present invention, Or a combination thereof.

Compounds having at least two epoxy groups include, but are not limited to, ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, tripropylene glycol diepoxypropyl ether , polypropylene glycol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, glycerol diepoxypropyl ether, 2,2-di Bromo neopentyl glycol diepoxypropyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N',N'-tetraepoxypropyl- M-xylylenediamine, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane, N,N,N',N'-tetraepoxypropyl-4,4 '-Diaminodiphenylmethane, N,N-epoxypropyl-p-glycidoxyaniline, 3-(N,N-diepoxypropyl)aminopropyltrimethoxydecane, Or a combination of the above compounds.

The above compounds having at least two epoxy groups may be used singly or in combination of two or more.

The compound having at least two epoxy groups may be used in an amount of from 0 to 40 parts by weight, and preferably from 0.1 to 30 parts by weight, based on 100 parts by weight of the polymer (A).

Specific examples of the decane compound having a functional group include, but are not limited to, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2 -Aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyl Methyldimethoxydecane, 3-ureidopropyltrimethoxy silane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyl Trimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriamine, N-trimethoxydecylpropyltri Ethylenetriamine, 10-trimethoxydecyl-1,4,7-trioxane, 10-triethoxydecyl-1,4,7-trioxane, 9-trimethoxydecane Base-3,6-dimercaptoacetate, 9-triethoxydecyl-3,6-dimercaptoacetate, N-benzyl-3-aminopropyltrimethoxydecane, N-Benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxysulfonium , A combination -3- N- bis (oxyethylene) -3-aminopropyl trimethoxy Silane, N- bis (oxyethylene) aminopropyl triethoxysilane Silane, or the above compounds.

The decane compound having a functional group may be used in an amount of from 0 to 10 parts by weight, and preferably from 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer (A).

The additive (E) may be used singly or in combination of two or more.

The amount of the additive (E) to be used is preferably from 0.5 to 50 parts by weight, and more preferably from 1 to 45 parts by weight, based on 100 parts by weight of the total amount of the polymer (A).

<Preparation method of liquid crystal alignment agent>

The preparation method of the liquid crystal alignment agent of the present invention is not particularly limited, and it can be produced by a general mixing method. For example, the polymer (A) and the polyoxyalkylene (B) prepared in the above manner are first mixed to form a mixture. Next, the solvent (C) is added under the conditions of a temperature of 0 ° C to 200 ° C, and the photopolymerizable compound (D) and the additive (E) are selectively added, and finally stirred with a stirring device until dissolved. Further, it is preferred to add the solvent (C) at a temperature of from 20 ° C to 60 ° C.

The liquid crystal alignment agent of the present invention has a viscosity of usually 15 cps to 35 cps, preferably 17 cps to 33 cps, and more preferably 20 cps to 30 cps at 25 °C.

<Method of Forming Liquid Crystal Alignment Film>

After applying the liquid crystal alignment agent of the present invention to a substrate, the coating film obtained by heat treatment such as pre-bake or post-bake is used as a liquid crystal alignment film as needed. Further, the coating film may be rubbed, irradiated with polarized light or light of a specific wavelength, or treated with an ion beam, or irradiated with ultraviolet rays in a state where a voltage is applied to the liquid crystal display element after the liquid crystal is filled. As a surface control vertical alignment film.

In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency. The substrate is, for example, a glass plate, polycarbonate, poly(meth)acrylate, polyether oxime, polyarylate, polyurethane, polyfluorene, polyether, polyether ketone, trimethylpentene, polyolefin, Polyethylene terephthalate, (meth)acrylonitrile, cellulose triacetate, cellulose diacetate or cellulose acetate Butyrate) and so on. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an indium tin oxide (ITO) electrode for liquid crystal driving or the like is formed. Further, when the reflective liquid crystal display device is a single-sided substrate, an opaque material such as a germanium wafer or the like may be used, and a material that reflects light such as aluminum may be used as the electrode at this time.

The coating method of the liquid crystal alignment agent is not particularly limited, and examples thereof include a printing method such as screen printing, offset printing, flexo printing, an inkjet method, a spray coating method, and a roll coating method. Fabrication, dipping, slit coating, spin coating, and the like. From the viewpoint of productivity, a transfer printing method widely used in the industry can also be applied to the present invention.

After the liquid crystal alignment agent is applied by the above method, a coating film can be formed by pre-baking and post-baking treatment. The pre-baking step after the application of the liquid crystal alignment agent is not necessary, but the pre-bake step is preferably carried out when the substrate is not fixed, or when the substrate is not fixed immediately after coating or after baking. . In the pre-baking step, the organic solvent may be volatilized as long as the shape of the coating film is not deformed by the substrate or the like. The conditions of the pre-baking treatment are not particularly limited, and are, for example, carried out at any temperature of 40 ° C to 150 ° C, preferably 50 ° C to 120 ° C, more preferably 60 ° C to 100 ° C. The pre-baking treatment can be carried out at any time from 0.1 minutes to 30 minutes, preferably from 0.5 minutes to 15 minutes, more preferably from 1 minute to 5 minutes.

The conditions of the post-baking treatment are not particularly limited, and are, for example, carried out at any temperature of from 100 ° C to 350 ° C, preferably from 120 ° C to 300 ° C, more preferably from 150 ° C to 250 ° C. The post-baking treatment can be carried out at any time from 5 minutes to 240 minutes, preferably from 10 minutes to 100 minutes, more preferably from 20 minutes to 90 minutes. Above plus The heat can be heated by a generally known method such as a heating plate, a hot air circulating furnace or an infrared furnace.

The thickness of the liquid crystal alignment film obtained after post-baking is not particularly limited and may be, for example, 1 to 1000 nm, preferably 5 to 500 nm, and more preferably 10 to 300 nm.

<Liquid crystal display element and method of manufacturing the same>

The liquid crystal display element of the present invention comprises a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention. The liquid crystal display element of the present invention can be produced by the following method.

More specifically, the liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above method and then forming a liquid crystal cell by a known method. Specific examples of the liquid crystal display element include, for example, a vertical alignment type liquid crystal display element including a liquid crystal cell, wherein the liquid crystal cell has two substrates disposed oppositely, a liquid crystal layer disposed between the substrates, and a liquid crystal layer disposed on the substrate and the liquid crystal layer The above liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention.

Specifically, a vertical alignment type liquid crystal display element having a liquid crystal cell in which a liquid crystal cell is produced by applying the liquid crystal alignment agent of the present invention to two substrates and pre-baking and post-baking Forming a liquid crystal alignment film, and then arranging the two substrates in a direction opposite to each other, and holding a liquid crystal layer composed of liquid crystal between the two substrates, that is, contacting the liquid crystal alignment film to provide a liquid crystal layer Finally, a voltage is applied to the liquid crystal alignment film and the liquid crystal layer while irradiating ultraviolet rays.

When the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention is used as described above, ultraviolet rays are applied while applying a voltage to the liquid crystal alignment film and the liquid crystal layer. When the polymerizable unsaturated groups are allowed to react with each other, the alignment of the liquid crystal can be more efficiently immobilized, and a liquid crystal display element having excellent ultraviolet light decay resistance and good pretilt angle stability can be formed.

The method of holding the liquid crystal layer between two substrates is, for example, the following two known methods:

(method one)

Preparing a pair of substrates on which a liquid crystal alignment film is formed, and spacers such as beads are scattered on the liquid crystal alignment film of one of the substrates, and the two liquid crystal alignment films are further laminated in an opposing manner. One substrate was then injected into the liquid crystal under reduced pressure and sealed.

(Method Two)

Preparing a pair of substrates on which a liquid crystal alignment film is formed, and spreading a spacer such as beads on a liquid crystal alignment film of one of the substrates, dropping the liquid crystal, and then bonding the two liquid crystal alignment films to each other in an opposing manner. The substrate is sealed.

In the above two methods, the thickness of the spacer is preferably from 1 to 30 μm , more preferably from 2 to 10 μm .

A step of applying a voltage to the liquid crystal alignment film and the liquid crystal layer and simultaneously irradiating the ultraviolet ray to produce a liquid crystal cell, for example, applying a voltage between the electrodes provided on the substrate to apply an electric field to the liquid crystal alignment film and the liquid crystal layer to maintain the state of the electric field Under, ultraviolet rays are irradiated. Among them, the voltage applied between the electrodes is, for example, 5 Vp-p to 30 Vp-p, preferably 5 Vp-p to 20 Vp-p. The irradiation amount of the ultraviolet rays is, for example, 1 J to 60 J, preferably 40 J or less, more preferably 10 J or less. The less the amount of ultraviolet radiation, the more it can suppress the cause. The reliability of the destruction of the liquid crystal or the material constituting the liquid crystal display element is lowered, and the manufacturing efficiency can be improved by reducing the ultraviolet irradiation time. According to the present invention, the response speed can be increased even with a small amount of ultraviolet irradiation. Therefore, even when the irradiation amount is low, for example, about 5 J, a liquid crystal display element having a sufficiently fast response speed can be formed.

When a voltage is applied to the liquid crystal alignment film and the liquid crystal layer and ultraviolet rays are irradiated, the polymerizable unsaturated groups can be reacted with each other. By the above reaction, the liquid crystal alignment film can be obtained with a preferable cured structure, so that the obtained liquid crystal display element has a property of excellent ultraviolet ray decay resistance and good pretilt angle stability.

Further, the liquid crystal alignment agent can be used not only as a liquid crystal alignment agent for a liquid crystal display element of a vertical alignment type such as a surface-aligned vertical alignment type (SCVA) liquid crystal display, but also for a rubbing treatment or a photo alignment treatment. The use of liquid crystal alignment film.

The above liquid crystal includes nematic liquid crystal or dish-shaped liquid crystal or the like. Specific examples of the liquid crystal include, but are not limited to, liquid crystal having positive dielectric anisotropy, and for example, biphenyl-based liquid crystals, phenyl cyclohexane-based liquid crystal, Ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals (dioxane- Based on liquid crystals), bicyclooctane-based liquid crystals, cubane-based liquid crystals, or a combination of the above liquid crystals. Further, for example, cholesteryl chloride may be further added to the aforementioned liquid crystal. Chloride, cholesteryl carbonate, cholesteric liquid crystal, etc.; under the trade names "C-15", "CB-15" (Merck) Manufacturing) a chiral agent for sale; a strong dielectric such as p-decyloxybenzylidene-p-amino-2-methyl butyl cinnamate A liquid crystal (ferroelectric liquid crystal) or the like is used.

Further, specific examples of the liquid crystal may include a liquid crystal having a negative dielectric anisotropy, and for example, a dicyanobenzene-based liquid crystal, a pyridazine-based liquid crystal, or a pyridazine-based liquid crystal may be used. Schiff base-based liquid crystal, azoxy-based liquid crystal, biphenyl-based liquid crystal, phenyl cyclohexane-based Liquid crystal), or a combination of the above liquid crystals.

The invention is further described in the following examples, but it should be understood that these examples are merely illustrative and are not to be construed as limiting.

Synthesis example of polymer (A)

The synthesis examples A-1-1 to A-1-3 of the polymer (A), the synthesis examples A-2-1 to A-2-10, and the comparative synthesis examples A'-1-1, A'-1 are explained below. -2, A'-2-1, A'-2-2:

Synthesis Example A-1-1

A nitrogen inlet, a stirrer, a condenser, and a thermometer were placed in a 500-mL four-necked flask, and nitrogen gas was introduced. Then, in a four-necked flask, 0.58 g (0.0025 mol) of a diamine compound represented by the formula (1-1) (abbreviated as a2-1-1) and 5.14 g (0.0475 mol) of p-two were added. Amine benzene (abbreviated as a2-3-1) and 80 g of N-methyl-2-pyrrolidone (abbreviated as NMP) were stirred at room temperature until dissolved. Next, 9.80 g (0.05 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (abbreviated as a1-1) and 20 g of NMP were added, and reacted at room temperature for 2 hours. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, washed repeatedly with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60 ° C to obtain a polymer (A-1-1).

Synthesis Examples A-1-2, A-1-3, and Comparative Synthesis Examples A'-1-1, A'-1-2

Synthesis Examples A-1-2, A-1-3, and Comparative Synthesis Examples A'-1-1, A'-1-2 were prepared in the same manner as in Synthesis Example A-1-1, respectively. -1-2), (A-1-3), (A'-1-1), and (A'-1-2), and the difference lies in: changing the type of monomer and its usage (such as 1)).

Synthesis Example A-2-1

A nitrogen inlet, a stirrer, a condenser, and a thermometer were placed in a 500-mL four-necked flask, and nitrogen gas was introduced. Then, in a four-necked flask, 3.71 g (0.015 mol) of a diamine compound represented by the formula (1-7) (abbreviated as a2-1-4) and 2.64 g (0.01 mol) were added ( 2-3) represented by a diamine compound (abbreviated as A2-2-2), 1.62 g (0.015 mol) of p-diamine benzene (abbreviated as a2-3-1), 4.31 g (0.01 mol) of the diamine compound represented by formula (II-29) (abbreviated as a2-3-2) and 80 g of N-methyl-2-pyrrolidone (abbreviated as NMP) and stirred until dissolved at room temperature. Next, 9.80 g (0.05 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (abbreviated as a1-1) and 20 g of NMP were added. After reacting at room temperature for 6 hours, 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 carry out the oxime imidization reaction. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, washed repeatedly with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60 ° C to obtain a polymer (A-2-1).

Synthesis Examples A-2-2 to A-2-10 and Comparative Synthesis Examples A'-2-1, A'-2-2

Synthesis Examples A-2-2 to A-2-10 and Comparative Synthesis Examples A'-2-1, A'-2-2 were prepared in the same manner as in Synthesis Example A-2-1, respectively. -2-2) to (A-2-10) and (A'-2-1), (A'-2-2), and the difference lies in: changing the type of monomer and its usage (such as 1)).

The compounds corresponding to the abbreviations in Table 1 are as follows:

Synthesis example of polyoxyalkylene (B)

The synthesis examples B-1 to B-6 of the polyoxyalkylene (B) and the comparative synthesis examples B'-1, B'-2 are described below:

Synthesis Example B-1

A stirrer, a condenser, and a thermometer were placed on a three-necked flask having a volume of 500 ml. Then, in a three-necked flask, 0.1 mol of 3-propenyloxypropyltrimethoxydecane (hereinafter abbreviated as GAPTS) and 0.5 mol of 2-glycidyl ether ethyltrimethoxydecane were added (hereinafter Abbreviated as GETMS), 0.4 mol of 4-glycidyl ether butyl trimethoxy decane (hereinafter referred to as GBTMS) and 600 g of propylene glycol monomethyl ether (hereinafter referred to as PGME), and stirred at room temperature. An aqueous solution of Triethylamine (hereinafter abbreviated as TEA) (20 g of TEA/200 g of water) was added over 30 minutes. Next, the three-necked flask was immersed in an oil bath at 30 ° C and stirred for 30 minutes, and then the oil bath was heated to 90 ° C in 30 minutes. When the internal temperature of the solution reached 75 ° C, heating and stirring were continued for polycondensation for 6 hours. . After completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight aqueous solution of ammonium nitrate to obtain a polyoxyalkylene (B-1).

Synthesis Example B-2 to Synthesis Example B-6

The polysiloxanes (B-2) to (B-6) of Synthesis Examples B-2 to B-6 were prepared in the same manner as in Synthesis Example B-1, and were distinguished by changing the polyoxyalkylene oxide. (B) The type of the reactants and the amount of the reactants, the type of the catalyst and the solvent, and the amount thereof used, Temperature and polycondensation time (as shown in Table 2).

Synthesis Example B'-1, Synthesis Example B'-2

The polysiloxanes (B'-1) and (B'-2) of Synthesis Examples B'-1 and B'-2 were prepared in the same manner as in Synthesis Example B-1, and the difference was that: The type of the reactant of the polyoxyalkylene (B) and the amount thereof, the kind of the catalyst and the solvent, the amount thereof, the reaction temperature, and the polycondensation time (as shown in Table 2).

The compounds corresponding to the abbreviations in Table 2 are as follows.

Embodiments and Comparative Examples of Liquid Crystal Aligning Agent, Liquid Crystal Alignment Film, and Liquid Crystal Display Element

Hereinafter, Examples 1 to 16 and Comparative Examples 1 to 9 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 polymer (A-1-1), 1 part by weight of polyoxyalkylene (B-1), and 800 parts by weight of N-methyl-2-pyrrolidone (abbreviated as C-1) were weighed. Further, the liquid crystal alignment agent of Example 1 was formed by continuously stirring to dissolve at room temperature with a stirring device.

b. Liquid crystal alignment film and liquid crystal display element

Using the liquid crystal alignment agent obtained above, a liquid crystal cell was produced in the order shown below. The liquid crystal alignment agent was applied to two glass substrates each having an ITO electrode by spin coating, wherein the ITO electrode was a slit pattern each having a line/space of 5 μm. . Subsequently, the film was prebaked at 80 ° C for 2 minutes on a hot plate, and then post-baked at 220 ° C for 20 minutes in a circulating oven to form the liquid crystal alignment film of Example 1.

For the above two glass substrates on which the liquid crystal alignment film was formed, one of the sheets was coated with a thermocompression adhesive, and the other was spread with a spacer of 4 μm . Next, the two glass substrates were bonded together, and a pressure of 10 kg was applied thereto by a hot press, and hot press bonding was carried out at a temperature of 150 °C. Then, after injecting liquid crystal with a liquid crystal injection machine (manufactured by Shimadzu Corporation, model: ALIS-100X-CH), the liquid crystal injection port was sealed with ultraviolet light hardening, and hardened by irradiation with an ultraviolet lamp. Next, a liquid crystal display element of Example 1 was obtained by applying 20 Vp-p alternating current between two ITO electrodes and irradiating ultraviolet rays of 30 J while the liquid crystal was driven. The liquid crystal display elements of Example 1 were evaluated for each evaluation method described later, and the results are shown in Table 3.

Embodiment 2 to Embodiment 16

The liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display element of Example 2 to Example 16 were separately prepared in the same manner as in Example 1, and the difference was that the type of the component and the amount thereof were changed, as shown in Table 3. Table 4 shows. The liquid crystal display elements obtained in Examples 2 to 16 were evaluated in the evaluation methods described later, and the results are shown in Table 3.

Comparative Example 1 to Comparative Example 9

The liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display element of Comparative Example 1 to Comparative Example 9 were separately prepared in the same manner as in Example 1, except that the type of the component and the amount thereof were changed, as shown in Table 4. . The liquid crystal display elements obtained in Comparative Examples 1 to 9 were evaluated in the evaluation methods described later, and the results are shown in Table 4.

The compounds corresponding to the abbreviations in Tables 3 and 4 are as follows.

<Evaluation method>

a. 醯 imidization rate

The ruthenium amination rate means the ratio of the number of ruthenium rings calculated as a percentage based on the total number of guanamine functional groups and the number of quinone rings in the polymer, expressed as a percentage.

The detection method is that the polymer of the synthesis example is dried under reduced pressure, and then dissolved in a suitable deuteration solvent, for example, deuterated dimethyl hydrazine, using tetramethyl decane as a reference material, ¹ H-NMR measurement results ^{(1 H-Nuclear magnetic resonance,} 1 H-NMR) at room temperature (e.g. 25 ℃), then from equation (1) can be obtained (PEI) ratio (%).

Δ1: the peak area produced by the chemical shift of the NH proton near 10 ppm; Δ2: peak area of other protons; α: ratio of the number of protons of the NH group in the precursor of the polymer (polyproline) to the number of other protons.

b. Pretilt stability

The method described by TJ Scheffer et al., Journal of Applied Physics, J. Appl. Phys., No. 19, 2013 (1980), using He-Ne. The pretilt angle of the center point of the manufactured liquid crystal display element was measured by a crystal rotation method of laser light; and then the pretilt angle of the center point after the application of the manufactured liquid crystal display element for 24 hours at 7 V was measured, and applied according to voltage The pretilt angle stability was evaluated by the change of the pretilt angle before and after.

The value obtained by subtracting the pretilt angle after the voltage application from the pretilt angle before the voltage application is used as an evaluation value of the pretilt stability. The lower the evaluation value of the pretilt stability, the better the pretilt stability of the liquid crystal display element.

The evaluation criteria of the pretilt stability are as follows.

◎: Evaluation value <0.4°

○: 0.4° ≦ evaluation value <1°

△: 1 ° ≦ evaluation value < 2 °

×: 2° ≦ evaluation value

c. UV resistance

The ultraviolet ray decay resistance of the liquid crystal display element is evaluated by the voltage holding ratio of the liquid crystal display element. Further, the amount of voltage holding ratio of the liquid crystal display element The measurement method is as follows.

The voltage holding ratio of the liquid crystal display elements of the examples and the comparative examples was measured by an electric measuring machine (manufactured by Toyo Corporation, Model No. 6254). The test condition was that a voltage of 4 volts was applied, the voltage was released after 2 milliseconds, and the voltage holding ratio after 1667 milliseconds was released (calculated as V1). Next, after the liquid crystal display element was irradiated with ultraviolet light of 30 mJ/cm ² (UV type irradiation machine model: KN-SH48K1; manufactured by Pico Energy Co., Ltd.), the voltage holding ratio after ultraviolet light irradiation was measured under the same test conditions (calculated as V2). Finally, the percentage change in voltage holding ratio (calculated as V ^UV-decay (%)) can be obtained by mathematical formula (2). The lower the percentage change in the voltage holding ratio, the better the ultraviolet ray decay resistance of the liquid crystal display element.

The evaluation criteria for the percentage change in voltage holding ratio are as follows.

◎: V ^UV-decay <3%

○: 3% ≦V ^UV-decay <5%

△: 5% ≦V ^UV-decay <10%

×: 10% ≦V ^UV-decay

Comparative Example 10

The liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display element of Comparative Example 10 were prepared in the same manner as in Comparative Example 1, in which the kinds of the components and the amounts thereof were substantially the same, except that they were in the liquid crystal layer used. Further, 2.4% by weight of the photopolymerizable compound (D-1) was added. When the obtained liquid crystal display element was also evaluated by the above evaluation method, the pretilt stability and the ultraviolet ray deterioration resistance were all expressed as ×.

<evaluation result>

From Table 3 and Table 4, it is known that a polymer (A) containing a diamine compound (a2-1) represented by the formula (1) and a fluorene compound (b1) containing a polymerizable unsaturated group are simultaneously used. Compared with the liquid crystal display elements (Examples 1 to 16) obtained by the liquid crystal alignment agent of oxyalkylene (B), the liquid crystal display elements of Comparative Examples 1 to 9 are not resistant to ultraviolet ray deterioration and have poor pretilt stability. .

Further, when a polymer (A) having a ruthenium iodide ratio of 30% to 90% (i.e., polymers (A-2-2) to (A-2-9)) is used (Examples 5 to 12), The liquid crystal display element is more resistant to ultraviolet light deterioration.

Further, when a polyoxyalkylene (B) having an epoxy group-containing group (i.e., polyoxyalkylene (B-1) to (B-4)) is used (Examples 1 to 4, 7, 8, 11) 12), the liquid crystal display element has better UV degradation resistance.

Further, when at least one of the compounds represented by the formula (3-43) to the formula (3-49) and the formula (3-68) to the formula (3-96) is used as the photopolymerizable compound (D) (implementation Example 4, At 5, 7, 9, and 13), the pretilt angle stability of the liquid crystal display element is particularly good.

In addition, when the polymer (A) contains at least one of the diamine compound (a2-2) represented by the formula (2) (Examples 3 to 8, 15, 16), the resistance of the liquid crystal display element can be further improved. UV decay.

Further, according to the evaluation results of Comparative Example 10, when the photopolymerizable compound (D) was further added to the liquid crystal layer to be used, the liquid crystal display element was not resistant to ultraviolet ray decay and pretilt stability.

As described above, in the surface-controlled vertical alignment type liquid crystal alignment agent of the present invention, the diamine component (a2) in the mixture forming the polymer (A) includes the diamine compound represented by the formula (1) (a2- 1) Therefore, the pretilt stability of the liquid crystal display element can be improved.

On the other hand, the liquid crystal alignment agent of the present invention contains a polyoxyalkylene having a specific polymerizable unsaturated group (for example, an acryloxy group, a methacryloxy group, and a carbon-carbon double bond), and the liquid crystal display element is resistant to ultraviolet rays. It is suitable for the manufacture of liquid crystal alignment films and liquid crystal display elements because of its low degradation.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

Claims (17)

A liquid crystal alignment agent comprising: a polymer (A) obtained by reacting a mixture comprising a tetracarboxylic dianhydride component (a1) and a diamine component (a2); a polyoxyalkylene (B); and a solvent (C); wherein the diamine component (a2) comprises a diamine compound (a2-1) represented by the formula (1) and a diamine compound (a2-2) represented by the formula (2); In the formula (1), X ₁ and X ₃ each independently represent a methyl group, -O-, -COO-, -OCO-, -NHCO-, -CONH- or -NH-; X ₂ represents a single bond or carbon. The alkyl group is 1 to 20; X ₄ represents an oxygen atom or a sulfur atom; in the formula (2), X ₅ represents a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH- Or -NH-; X ₆ represents a linear alkyl group having 1 to 20 carbon atoms substituted or unsubstituted, wherein any -CH ₂ - may be substituted by the following group: -CH=CH-, -O-, -COO-, -NHCO-, -NH-, an extended carbocyclic group or a heterocyclic group; X ₇ represents a hydrogen atom or a methyl group; and the polyoxyalkylene (B) contains a polymerizable unsaturated group The polymerizable unsaturated group includes a group represented by the formula (b1-1), a group represented by the formula (b1-2), or a combination of the two, In the formula (b1-1), A represents a hydrogen atom or a methyl group; a represents an integer of 1 to 3; * represents a bond, In the formula (b1-2), b represents an integer of 0 or 1, and * represents a bond. The liquid crystal alignment agent according to claim 1, wherein the total amount of the diamine component (a2) is 100 mol, and the diamine compound represented by the formula (1) (a2-1) The usage amount is 5~50 moor. The liquid crystal alignment agent according to claim 1, wherein the total amount of the diamine component (a2) used is 100 mol, and the diamine compound represented by the formula (2) (a2-2) The usage amount is 10~90 m. The liquid crystal alignment agent according to claim 1, wherein the decane monomer mixture forming the polyoxyalkylene (B) by a polycondensation reaction comprises a decane compound (b1) containing a polymerizable unsaturated group, And the total amount of the decane monomer mixture used is 1.0 mol, and the polymerizable unsaturated group-containing decane compound (b1) is used in an amount of 0.1 to 0.9 mol. The liquid crystal alignment agent according to claim 1, wherein the polyoxyalkylene (B) contains an epoxy group-containing group, and the epoxy group-containing group includes the formula (b2-1) a base represented by, a group represented by the formula (b2-2), and at least one of the groups represented by the formula (b2-3), In the formula (b2-1), B represents an oxygen atom or a single bond; c represents an integer of 1 to 3; d represents an integer of 0 to 6, wherein when d represents 0, B is a single bond, and * represents a bond, In the formula (b2-2), e represents an integer of 0 to 6, and * represents a bond, In the formula (b2-3), D represents an alkylene group having a carbon number of 2 to 6; E represents a hydrogen atom or an alkyl group having a carbon number of 1 to 6, and * represents a bond. The liquid crystal alignment agent according to claim 5, wherein the decane monomer mixture forming the polyoxyalkylene (B) by a polycondensation reaction comprises an epoxy group-containing decane compound (b2), and is based on The total amount of the decane monomer mixture used is 1.0 mol, and the epoxy group-containing decane compound (b2) is used in an amount of 0.1 to 0.9 mol. The liquid crystal alignment agent according to claim 1, wherein the polymer (A) has a ruthenium iodide ratio of 30 to 90%. The liquid crystal alignment agent according to claim 1, wherein the polysiloxane (B) is used in an amount of 1 to 25 parts by weight based on 100 parts by weight of the polymer (A). The solvent (C) is used in an amount of 800 to 4000 parts by weight. The liquid crystal alignment agent according to claim 1, which further comprises a photopolymerizable compound (D). The liquid crystal alignment agent according to claim 9, wherein the photopolymerizable compound (D) is a photopolymerizable compound represented by the formula (3). In the formula (3), R ₁ independently represents a polymerizable functional group represented by the formula (3-1) to the formula (3-5), a hydrogen atom, a halogen atom, -CN, -CF ₃ , -CF ₂ H, -CFH ₂ , -OCF ₃ , -OCF ₂ H, -N=C=O, -N=C=S or an alkyl group having 1 to 20 carbon atoms, wherein any -CH ₂ - in the alkyl group Can be substituted by -O-, -S-, -SO ₂ -, -CO-, -COO-, -OCO-, -CH=CH-, -CF=CF- or -C≡C-, and contain a hydrogen atom In the functional group, the hydrogen atom may be optionally substituted by a halogen atom or -CN; at least one of R _{1 is} a polymerizable functional group represented by formula (3-1) to formula (3-5); Y independently represents carbon a number of 3 to 20 saturated or unsaturated, independent ring, condensed ring or a divalent group of a spiro ring, and any -CH ₂ - in the ring of the group Y may be substituted by -O-, and any -CH= may be Substituted by -N=, any -H may be halogen atom, -CN, -NO ₂ , -NC, -N=C=O, -N=C=S, having 1 to 3 carbon numbers of 1 to 4 An alkyl or phenyl substituted indenyl group, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms, and said straight chain alkyl, branched alkyl or haloalkyl, any of -CH ₂ - may be -O -, - CO -, - COO- -OCO-, -OCOO-, -CH=CH- or -C≡C-substituted; Z independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, wherein any of the alkylene groups is - CH ₂ - may be -O-, -S-, -SO ₂ -, -CO-, -COO-, -OCO-, -OCOO-, -CH=CH-, -CF=CF-, -CH=N -, -N=CH-, -N=N-, -N(O)=N- or -C≡C-substituted, and any -H may be a halogen atom, an alkyl group having a carbon number of 1 to 10 or a haloalkyl group having a carbon number of 1 to 10; m represents an integer of 1 to 6, and when m is an integer of 2 to 6, a plurality of -YZ- may be the same or different; In the formula (3-1) to the formula (3-5), R ₂ represents a hydrogen atom, a halogen atom, -CF ₃ or an alkyl group having a carbon number of 1 to 5, and * represents a bond. The liquid crystal alignment agent according to claim 10, wherein at least one of R ₁ in the photopolymerizable compound (D) is a polymerizable property represented by the formula (3-1) to the formula (3-3) Functional group. The liquid crystal alignment agent according to claim 10, wherein, in the photopolymerizable compound (D), Y independently represents 1,4-cyclohexylene, 1,4-cyclohexenylene, and 1 , 4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, indole-2,7-diyl, bicyclo[2.2.2]octane-1,4-di a divalent group of a bis-cyclo[3.1.0]hexane-3,6-diyl or triptycene-1,4-diyl group; and any -CH ₂ - in the ring of the group Y may be -O-substituted, any -CH= may be substituted by -N=, any -H may be halogen atom, -CN, -NO ₂ , -NC, -N=C=O, -N=C= S, having 1 to 3 alkyl groups having 1 to 4 carbon atoms or phenyl substituted decyl groups, a linear alkyl group or a branched alkyl group having 1 to 10 carbon atoms, or a halogen having 1 to 10 carbon atoms substituted alkyl, and said linear alkyl, branched alkyl or haloalkyl, any of -CH ₂ - may be -O -, - CO -, - COO -, - OCO -, - OCOO- , -CH=CH- or -C≡C- is substituted. The liquid crystal alignment agent according to claim 12, wherein the group Y is at least one selected from the group consisting of functional groups represented by formula (3-6) to formula (3-29). : In the formula (3-6) to the formula (3-29), R ₃ represents a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen having 1 to 3 carbon atoms. Alkyl, * represents the bond. The liquid crystal alignment agent according to claim 9, wherein the photopolymerizable compound (D) is selected from the group consisting of compounds represented by formula (3-30) to formula (3-41). At least one of: In the formula (3-30) to the formula (3-41), R ₃ represents a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen having 1 to 3 carbon atoms. Alkyl; R ₄ independently represents a hydrogen atom or a methyl group; R ₅ independently represents a hydrogen atom, a halogen atom, a methyl group, -CF ₃ , -OCH ₃ , a phenyl group or two R ₅ groups on the same carbon atom to form a carbon The number is 6 to 15 saturated or unsaturated hydrocarbon rings; i, j independently represent an integer from 1 to 20. The liquid crystal alignment agent according to the ninth aspect of the invention, wherein the photopolymerizable compound (D) is used in an amount of from 1 to 35 parts by weight based on 100 parts by weight of the polymer (A). A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of claims 1 to 15. A liquid crystal display element having the liquid crystal alignment film according to item 16 of the patent application.