TWI653494B - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The present invention provides a method capable of forming excellent UV-resistant decay and colorless unevenness. A liquid crystal alignment agent for a liquid crystal display element, a liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film. The liquid crystal alignment agent includes a polymer (A), a polysiloxane (B), a photopolymerizable compound (C), and a solvent (D). The polymer (A) is obtained by reacting a mixture including a tetracarboxylic dianhydride component (a1) and a diamine component (a2). The diamine component (a2) includes at least one of the diamine compounds (a2-1) represented by the formula (II).

The polysiloxane (B) contains an ethylenically unsaturated group, and is selected from the group consisting of , , -O- and At least one functional group in the formed group.

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 with excellent ultraviolet decay resistance and colorless phase unevenness, and a liquid crystal formed by the liquid crystal alignment agent. An alignment film and a liquid crystal display element having the liquid crystal alignment film.

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

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

However, in order to polymerize a polymerizable compound, a large amount of ultraviolet rays such as 100,000 J / m ² must be irradiated. Therefore, in addition to the possibility that liquid crystal molecules may be decomposed, unreacted compounds that are not polymerized by irradiating ultraviolet rays also remain in the liquid crystal layer and form impurities. Contamination causes a problem of mura in the liquid crystal display element, and particularly adversely affects electrical characteristics. In addition, the type of liquid crystal molecules used in the liquid crystal layer must also be limited depending on the polymerizable compound added.

Therefore, how to solve the problem of impurity contamination in the liquid crystal layer and provide a liquid crystal display element with excellent UV resistance and no color unevenness is a subject actively studied by those skilled in the art.

In view of this, the present invention has developed a surface controlled vertical alignment (Surface (Control Vertical Alignment, SCVA) technology, and provides a liquid crystal alignment agent capable of forming a liquid crystal display element with excellent ultraviolet decay resistance and no color unevenness, a liquid crystal alignment film formed from the liquid crystal alignment agent, and a liquid crystal having the liquid crystal alignment film. Display element.

The invention provides a liquid crystal alignment agent, which includes a polymer (A), a polysiloxane (B), a photopolymerizable compound (C), and a solvent (D). The polymer (A) is obtained by reacting a mixture including a tetracarboxylic dianhydride component (a1) and a diamine component (a2). The diamine component (a2) includes at least one of the diamine compounds (a2-1) represented by the formula (II).

Specifically, the diamine compound (a2-1) represented by Formula (II) is shown below.

In formula (II), R ¹⁴ represents -O-, , , , or . R ¹⁵ represents an organic group represented by the formula (II-1).

The organic group represented by formula (II-1) is shown below.

In the formula (II-1), R ¹⁶ represents a hydrogen atom, a fluorine atom, or a methyl group. R ¹⁷ , R ¹⁸ or R ¹⁹ each independently represents a single bond, -O-, , , , , Or an alkylene group having 1 to 3 carbon atoms. R ²⁰ means or Wherein R ²² and R ²³ each independently represent a hydrogen atom, a fluorine atom or a methyl group. R ²¹ represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, -OCH ₂ F, -OCHF ₂ or -OCF ₃ . k represents 1 or 2. l, m, and n each independently represent an integer of 0 to 4. o, p, and q each independently represent an integer from 0 to 3, and o + p + q ≧ 3. r and s each independently represent 1 or 2. When multiple R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²² or R ²³ are present, multiple R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²² or R ²³ Each is the same or different.

In addition, the polysiloxane (B) contains an ethylenically unsaturated group, and is selected from the group consisting of , , -O- and At least one functional group in the formed group.

In an embodiment of the present invention, the ethylenically unsaturated group includes , , At least one of the bases represented.

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

In formula (3), R ¹ each independently represents a polymerizable functional group represented by formula (3-1) to 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 may be passed through- Functional group substituted with O-, -S-, -SO _2- , -CO-, -COO-, -OCO-, -CH = CH-, -CF = CF-, or -C≡C-, and containing a hydrogen atom In the formula, any hydrogen atom may be 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 a carbon number of 3 Divalent group of saturated or unsaturated independent ring, condensed ring or spiro ring to 20, wherein any -CH ₂ -in the ring may be substituted by -O-, any -CH = may be substituted by -N =, any -H can pass through a halogen atom, -CN, -NO ₂ , -NC, -N = C = O, -N = C = S, through 1 to 3 alkyl or phenyl groups having 1 to 4 carbon atoms. Substituted silyl, linear alkyl having 1 to 10 carbons, branched alkyl having 1 to 10 carbons, or haloalkyl having 1 to 10 carbons, and in the alkyl group, any -CH ₂ -may be substituted by -O-, -CO-, -COO-, -OCO-, -OCOO-, -CH = CH- or -C≡C-; 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 alkylene group may pass through -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 with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms; f represents an integer of 1 to 6, and when f When it is an integer of 2 to 6, a plurality of -YZ- are the same or different.

The polymerizable functional groups represented by the formulas (3-1) to (3-5) are shown below.

In the formulae (3-1) to (3-5), R ² represents a hydrogen atom, a halogen atom, -CF ₃ or an alkyl group having 1 to 5 carbon atoms.

In one embodiment of the present invention, at least one of R ¹ of the photopolymerizable compound (C) is a polymerizable functional group represented by the formulae (3-1) to (3-3).

In an embodiment of the present invention, each of Y of the photopolymerizable compound (C) independently represents 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, or naphthalene -2,6-diyl, tetralin-2,6-diyl, fluorene-2,7-diyl, bicyclic [2.2.2] octane-1,4-diyl, bicyclic [3.1.0] Divalent group of hexane-3,6-diyl or triptycene-1,4-diyl; any -CH ₂ -in the ring may be substituted by -O-, any -CH = may be -N = substitution, any -H may pass through a halogen atom, -CN, -NO ₂ , -NC, -N = C = O, -N = C = S, have 1 to 4 carbon atoms through 1 to 3 Alkyl or phenyl substituted silyl (that is, a group formed by substitution of 1 to 3 hydrogen atoms of a silyl group with an alkyl or phenyl group having 1 to 4 carbon atoms), a carbon number of 1 A linear or branched alkyl group of 10 to 10, or a haloalkyl group having 1 to 10 carbon atoms; and in the alkyl group, any -CH ₂ -may be -O-, -CO-, -COO -, -OCO-, -OCOO-, -CH = CH- or -C≡C- substitution.

In one embodiment of the present invention, each of the aforementioned Ys independently represents at least one selected from the group consisting of functional groups represented by formula (3-6) to formula (3-30).

In the formulae (3-6) to (3-30), 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 group having 1 to 3 carbon atoms. alkyl.

In one embodiment of the present invention, the photopolymerizable compound (C) is at least one selected from the group consisting of compounds represented by formula (3-31) to formula (3-42).

In the formulae (3-31) to (3-42), each of R ⁴ independently represents a hydrogen atom or a methyl group; each of R ⁵ independently represents a hydrogen atom, a halogen atom, a methyl group, -CF ₃ , -OCH ₃ , or phenyl group. Or two R ⁵ on the same carbon atom form a saturated or unsaturated hydrocarbon ring having 6 to 15 carbon atoms; g and h each independently represent an integer of 1 to 20.

In one embodiment of the present invention, the fluorene imidization rate of the polymer (A) is 30% to 90%.

In an embodiment of the present invention, based on 100 parts by weight of the polymer (A), the used amount of the polysiloxane (B) is 3 to 25 parts by weight; the photopolymerizable compound (C) Is used in an amount of 1 to 35 parts by weight; the use of the solvent (D) The amount is 800 to 4000 parts by weight.

The present invention also provides a liquid crystal alignment film, which is formed by the above-mentioned liquid crystal alignment agent.

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

Based on the above, in the surface-controlled vertical alignment type liquid crystal alignment agent of the present invention, in addition to the polymer and the solvent, a photopolymerizable compound is added to the liquid crystal alignment agent. Therefore, the liquid crystal layer is not contaminated by impurities. Further, the surface-controlled vertical alignment type liquid crystal alignment agent of the present invention contains both a polysiloxane and a photopolymerizable compound having a specific structure, so that the liquid crystal display element has excellent resistance to ultraviolet decay and has no problem of color unevenness. Therefore, it is suitable for manufacturing liquid crystal alignment films and liquid crystal display elements.

In order to make the above features and advantages of the present invention more comprehensible, the following specific embodiments are described in detail below.

<Liquid crystal alignment agent>

The invention provides a liquid crystal alignment agent, which includes a polymer (A), a polysiloxane (B), a photopolymerizable compound (C), and a solvent (D). In addition, if needed, The liquid crystal alignment agent may further include an additive (E).

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

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

Polymer (A)

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

In detail, the polymer (A) includes polyamidic acid, polyamidoimide, polyamidopolyimide block copolymer, or a combination of these polymers. Among them, the polyfluorene-based block copolymer includes a polyfluoride-based block copolymer, a polyfluoride-based imide block copolymer, a polyfluoride-based polyimide-block copolymer, or the above-mentioned polymerization. Combination of things. Polyamic acid polymers, polyimide polymers, and polyamic acid-polyimide block copolymers may be composed of a mixture of a tetracarboxylic dianhydride component (a1) and a diamine component (a2). Prepared by the reaction.

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 a compound of formula (I-1) To at least one of the tetracarboxylic dianhydride compounds represented by formula (I-6), or a combination of the aforementioned 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 thereof.

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-cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclo Butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl Cycloheptyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, bicyclo [2.2.2] -oct-7 -Ene-2,3,5,6-tetracarboxylic dianhydride or a combination thereof.

Specific examples of the aromatic tetracarboxylic dianhydride compound may include, but are not limited to, 3,4-dicarboxyl-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylpyrenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'-4,4'-diphenylethanetetracarboxylic dianhydride, 3,3 ', 4,4'- Dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4, 4'-bis (3,4-dicarboxyphenoxy) Diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylhydrazone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane Dianhydride (4,4'-bis (3,4-dicarboxy phenoxy) diphenylpropane dianhydride), 3,3 ', 4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3', 4 , 4'-Diphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene- Bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-di Phenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydromellitate), 1,4-butanediol-bis (anhydromellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane- Bis (anhydrotrimellitic acid ester), 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5- Dioxo-3-furyl) -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-di one)}, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro- 2,5-dioxo-3-furyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7 -Ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3 -Dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetrahydro-2,5-dioxo-3-furyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furyl) -naphtho [1,2 -c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride A group tetracarboxylic dianhydride compound or a combination of the aforementioned compounds.

The tetracarboxylic dianhydride compounds represented by formula (I-1) to formula (I-6) are shown below.

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

In Formula (I-6), A ⁴ represents a divalent group containing an aromatic ring; 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 (I-6) is preferably a compound represented by the formula (I-6-1).

The tetracarboxylic dianhydride component (a1) can be used alone or in combination.

Specific examples of the tetracarboxylic dianhydride component (a1) preferably include 1,2,3,4-cyclobutane tetracarboxylic dianhydride (1,2,3,4-cyclobutane tetracarboxylic acid dianhydride), 1, 2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,4,5-cyclo Hexanetetracarboxylic dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3 ' , 4,4'-benzophenonetetracarboxylic dianhydride and 3,3 ', 4,4'-biphenylfluorenetetracarboxylic dianhydride, or a combination of the above compounds.

Based on the total mole number of the diamine component (a2) is 100 moles, the amount of the tetracarboxylic dianhydride component (a1) is preferably in the range of 20 moles to 200 moles; the tetracarboxylic dianhydride component The amount of (a1) is more preferably in the range of 30 to 120 mol.

Diamine component (a2)

The diamine component (a2) includes a diamine compound (a2-1) represented by the formula (II). Specifically, the diamine compound (a2-1) represented by Formula (II) is shown below.

In formula (II), R ¹⁴ represents -O-, , , , or R ¹⁵ represents an organic group represented by formula (II-1).

In formula (II-1), R ¹⁶ represents a hydrogen atom, a fluorine atom, or a methyl group; R ¹⁷ , R ^18, or R ¹⁹ each independently represents a single bond, -O-, , , , , Or an alkylene group having 1 to 3 carbon atoms; R ²⁰ represents or Wherein R ²² and R ²³ each independently represent a hydrogen atom, a fluorine atom or a methyl group; R ²¹ represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, Alkoxy, -OCH ₂ F, -OCHF ₂ or -OCF _{3 having a} carbon number of 1 to 12; k represents 1 or 2; l, m, and n each independently represent an integer of 0 to 4; o, p, and q each Independently represents an integer from 0 to 3, and o + p + q ≧ 3; r and s each independently represent 1 or 2; when there are multiple R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²² or R ^In the case of ²³ , a plurality of R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ^22, or R ²³ are each the same or different.

Specific examples of the diamine compound (a2-1) include at least one of the diamine compounds represented by the formula (II-2) to the formula (II-9), or a combination thereof.

In the formulae (II-2) to (II-9), B ¹¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

The diamine compound represented by the formula (II-2) to the formula (II-9) is preferably at least one of the diamine compounds represented by the formula (II-10) to the formula (II-14), or combination.

The above-mentioned diamine compound (a2-1) can be used alone or in combination.

Based on the total amount of the diamine component (a2) being 100 mol, the amount of the diamine compound (a2-1) may be 5 mol to 50 mol, preferably 10 mol to 40 mol, more It is preferably 15 mol to 30 mol.

If the diamine component (a2) of the liquid crystal alignment agent does not use the diamine compound (a2-1), the liquid crystal display element has poor UV resistance.

Diamine compound (a2-2)

The diamine compound (a2-2) includes an aliphatic diamine compound, an alicyclic diamine compound, an aromatic diamine compound, a diamine compound having a formula (III-1) to a formula (III-25), or a combination thereof .

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-diaminononane, 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-methylnonane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis (3-aminopropoxy) ethyl Alkane, or a combination of the above.

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, isophorone diamine, tetrahydrodicyclopentadiene diamine, tricyclo [6.2.1.0 ^2,7 ] -unda Carbenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine), or a combination thereof.

Specific examples of the aromatic diamine compound include, but are not limited to, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl Hydrazone, 4,4'-diaminobenzylanilide, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylhydroindene, 6-amino-1- (4'-aminophenyl) -1,3, 3-trimethylindane, hexahydro-4,7-methyl bridgedindene Dimethylenediamine, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4 -Aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] fluorene, 1,4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 9 , 10-bis (4-aminophenyl) anthracene [9,10-bis (4-aminophenyl) anthracene], 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene , 4,4'-methylene-bis (2-chloroaniline), 4,4 '-(p-phenylene isopropylidene) bisaniline, 4,4'-(m-phenylene isopropylidene) Propyl) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [(4-amino -2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenyl-methylene-1,3-diamine Benzene {5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diaminobenzene}, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4 -Ethylbenzene ) {1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane}, cyclohexane or a combination of the above compounds.

The diamine compounds having the formula (III-1) to the formula (III-25) are shown below.

In formula (III-1), B ¹² represents -O-, , , , ,or ; B ¹³ represents a group having a steroid (cholesterol) skeleton, a trifluoromethyl group, a fluoro group, an alkyl group having 2 to 30 carbon atoms, or derived from pyridine, pyrimidine, triazine, piperidine, or piperazine, etc. A monovalent group containing a nitrogen atom ring structure.

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

The compounds represented by the formula (III-1-1) to the formula (III-1-6) are shown below.

(III-2), the same formula (III-1) of the formula B ¹² and B ^12, B ¹⁴ and B ¹⁵ each independently represents a divalent aliphatic ring, a divalent aromatic ring or a divalent heterocyclic group; B ¹⁶ represents an alkyl group having 3 to 18 carbons, an alkoxy group having 3 to 18 carbons, a fluoroalkyl group having 1 to 5 carbons, a fluoroalkoxy group having 1 to 5 carbons, cyano or Halogen atom.

Specific examples of the compound represented by the formula (III-2) include at least one of compounds represented by the formula (III-2-1) to the formula (III-2-13). Specifically, the compounds represented by formula (III-2-1) to formula (III-2-13) are shown below.

In the formulae (III-2-10) to (III-2-13), s represents an integer of 3 to 12.

In formula (III-3), B ¹⁷ 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 or a halogen atom having 1 to 5 carbon atoms, And B ¹⁷ 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 (III-3) include when u is 1: p-diaminebenzene, m-diaminebenzene, o-diaminebenzene, 2,5-diaminotoluene, and the like; when u When 2: 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'-diamine Biphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl or 4,4'-diamino-2,2'-bis (tri Fluoromethyl) biphenyl and the like; or when u is 3: 1,4-bis (4'-aminophenyl) benzene and the like.

Specific examples of the compound represented by the formula (III-3) preferably include p-diaminobenzene, 2,5-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-dimethyl Oxy-4,4'-diaminobiphenyl, 1,4-bis (4'-aminophenyl) benzene or a combination of the foregoing.

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

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

In formula (III-6), B ¹⁸ and B ²⁰ each independently represent a divalent organic group, and B ¹⁸ and B ²⁰ may be the same or different; B ¹⁹ represents a derivative derived from pyridine, pyrimidine, triazine, piperidine, or piperidine Divalent group of a cyclic structure containing a nitrogen atom such as a azine.

In formula (III-7), B ²¹ , B ²² , B ²³ and B ²⁴ each independently represent a hydrocarbon group having a carbon number of 1 to 12, and B ²¹ , B ²² , B ²³ and B ²⁴ may be the same or different; X1 Each independently represents an integer of 1 to 3; X2 represents an integer of 1 to 20.

In formula (III-8), B ²⁵ represents an oxygen atom or a cyclohexyl group; B ²⁶ represents a methylene group (methylene, -CH _2- ); B ²⁷ represents a phenylene group or a cyclohexane group; B ²⁸ Represents a hydrogen atom or a heptyl group.

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

The compounds represented by the formula (III-9) to the formula (III-30) are shown below.

In formulae (III-17) to (III-25), B ^{29 is} preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; B ^{30 is} preferably a hydrogen atom An alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

The aforementioned diamine compound (a2) may be used alone or in combination.

Specific examples of the diamine compound (a2) preferably include, but are not limited to, 1,2-diaminoethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl ether, 5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diaminobenzene, 1, 1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane, ethyl 2,4-diaminophenylformate, -1-1), a compound represented by formula (III-1-2), a compound represented by formula (III-1-5), a compound represented by formula (III-2-1), The compound represented by (III-2-11), p-diaminebenzene, m-diaminebenzene, o-diaminebenzene, a compound represented by formula (III-8-1), or a combination of the above-mentioned compounds.

Based on the total amount of the diamine component (a2) being 100 mol, the amount of the diamine compound (a2-2) may be 50 mol to 95 mol, preferably 60 mol to 90 mol , More preferably 70 mol to 85 mol.

When the polymer (A) in the liquid crystal alignment agent contains at least one of the diamine compounds represented by the formula (III-1) and the formula (III-2), the liquid crystal display element can be further improved. The problem of uneven hue.

The polymer (A) may include at least one of polyamic acid and polyimide. The polymer (A) may further include a polyfluorene-based block copolymer. The methods for preparing the various polymers described above are further described below.

Method for preparing polymer (A)

The polymer (A) may include at least one of polyamic acid and polyimide. The polymer (A) may further include a polyfluorene-based block copolymer. The methods for preparing the various polymers described above are further described below.

Method for preparing polyamic acid

The method for preparing polyamic acid is to first dissolve the mixture in a solvent, where the mixture includes a tetracarboxylic dianhydride component (a1) and a diamine component (a2), and polymerize at a temperature of 0 ° C to 100 ° C. Condensation reaction. After reacting for 1 hour to 24 hours, the reaction solution is distilled under reduced pressure using an evaporator to obtain polyamic acid. Alternatively, the reaction solution is poured into a large amount of a lean solvent to obtain a precipitate. Then, the precipitate is dried under reduced pressure to obtain polyamic acid.

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 can dissolve the reactant and the 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, N, N-dimethylformamide, Aprotic polar solvents such as dimethyl sulfene, γ-butyrolactone, tetramethyl urea or hexamethyl phosphate triamine; or (2) phenolic solvents such as m-cresol, xylenol, Phenol-based solvents such as phenols and halogenated phenols. The use amount of the solvent used in the polycondensation reaction is preferably 200 parts by weight to 2000 parts by weight, and more preferably 300 parts by weight to 1800 parts by weight based on the total use amount of the mixture.

It is worth noting that in the polycondensation reaction, an appropriate amount of a lean solvent can be used in combination with the solvent, wherein the lean solvent does not cause the polyamic acid to precipitate. The lean solvent can be used singly or in combination, and it includes but is not limited to (1) alcohols, such as: methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butane Alcohols or alcohols such as triethylene glycol; (2) ketones, such as: ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; (3) esters, such as: Esters such as 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 glycol 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 Ethers such as alkyl ethers; (5) halogenated hydrocarbons, such as: dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, or o-dichloro Halogenated hydrocarbons such as benzene; or (6) hydrocarbons, for example: hydrocarbons such as tetrahydrofuran, hexane, heptane, octane, benzene, toluene or xylene, or any combination of the above solvents. Based on the use amount of the diamine component (a2) being 100 parts by weight, the use amount of the lean solvent is preferably 0 to 60 parts by weight, and more preferably 0 to 50 parts by weight.

Method for preparing polyfluorene

The method for preparing polyimide is obtained by heating the polyamidic acid prepared by the method for preparing polyamidic acid in the presence of a dehydrating agent and a catalyst. During the heating process, the arsenic acid functional group in the polyarsenic acid can be converted into the arsonimine functional group (ie, arsonimation) via a dehydration ring-closure reaction.

The solvent used in the dehydration ring-closing reaction can be the same as the solvent (D) in the liquid crystal alignment agent, so it will not be repeated here. The amount of the solvent used in the dehydration ring-closing reaction is preferably 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight, based on 100 parts by weight of the polyamic acid used.

In order to obtain a better degree of polyimidation of the polyimide, the operating temperature of the dehydration ring-closing reaction is preferably 40 ° C to 200 ° C, and more preferably 40 ° C to 150 ° C. If the operating temperature of the dehydration ring-closing reaction is lower than 40 ° C, the imidization reaction is not complete, and the degree of imidization of the polyacid is reduced. However, if the operating temperature of the dehydration ring-closing reaction is higher than 200 ° C, the weight average molecular weight of the obtained polyfluorene imine is low.

The dehydrating agent used in the dehydration ring-closing reaction may be selected from acid anhydride compounds', and specific examples thereof include acid anhydride compounds such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. Based on 1 mole of polyamic acid, the amount of dehydrating agent used is 0.01 to 20 moles. The catalyst used in the dehydration ring-closing reaction may be selected from (1) pyridine compounds, such as pyridine, trimethylpyridine, or dimethylpyridine; and (2) tertiary amine compounds, such as: Tertiary amines such as triethylamine. Based on the amount of dehydrating agent used is 1 mole, the amount of catalyst used can be 0.5 to 10 moles.

The amidation ratio of the polymer (A) may be 30% to 90%, preferably 35% To 88%, and more preferably 30% to 85%. When the fluorinated imidization ratio of the polymer (A) in the liquid crystal alignment agent is within the above range, the ultraviolet decay resistance of the liquid crystal display element can be further improved.

Method for preparing polyfluorene imide block copolymer

The polyimide-based block copolymer is selected from the group consisting of a polyimide block copolymer, a polyimide block copolymer, a polyimide-polyimide block copolymer, or the above-mentioned polymerization. Any combination of things.

The method for preparing a polyfluorene-based block copolymer is preferably firstly dissolving a starting material in a solvent and performing a polycondensation reaction, wherein the starting material includes at least one polyamidic acid and / or at least one polyfluorene Imine, and may further include a carboxylic anhydride component and a diamine component.

The carboxylic acid 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 a polyamic acid, and are used for The solvent in the polycondensation reaction may be the same as the solvent in the liquid crystal alignment agent described below, and details are not described herein again.

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

The starting material preferably includes, but is not limited to, (1) two polyamido acids with different terminal groups and different structures; (2) two polyimines with different terminal groups and different structures; (3 ) Polyamines and polyimines having different terminal groups and different structures; (4) Polyamines, carboxylic anhydride components, and diamine components, among which the carboxylic anhydride component and the diamine component At least one of them is different from the structure of the carboxylic acid anhydride component and the diamine component used to form the polyamidic acid; (5) the polyfluorene imine, the carboxylic acid anhydride component, and the diamine component, wherein the carboxylic acid anhydride component And at least one of the diamine component is different from the structure of the carboxylic acid anhydride component and the diamine component used to form the polyfluorene imine; (6) the polyfluorine acid, the polyfluorene imine, the carboxylic acid anhydride component and A diamine component, wherein at least one of the carboxylic acid anhydride component and the diamine component is different from the structure of the carboxylic acid anhydride component and the diamine component used to form the polyamidic acid or the polyimide; (7 ) Two kinds of polyfluorinated acid, carboxylic anhydride and diamine components with different structures; (8) two kinds of polyfluorinated imine, carboxylic anhydride and diamine components with different structures; (9) two Polyamino acids and diamine components with different terminal groups being acid anhydride groups and different structures; (10) polyamino acids and carboxylic acid anhydride components with different terminal groups having amine groups and structural differences; (11) two Anhydride And structurally distinct polyimide and a diamine component; or (12) two terminal amino groups of the polyimide and structurally distinct parts and a carboxylic anhydride group.

As long as the efficacy of the present invention is not affected, the polyamidic acid, polyamidoimide, and polyamidoimide block copolymer are preferably terminally modified polymers after molecular weight adjustment. By using a terminal-modified polymer, the coating performance of the liquid crystal alignment agent can be improved. The method for preparing the terminal-modified polymer can be prepared by adding a polyfunctional compound while the polyamic acid is undergoing a polycondensation reaction.

Specific examples of monofunctional compounds include, but are not limited to (1) monobasic anhydrides, such as: maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecyl Alkyl succinic anhydride or n-hexadecyl succinic acid Monobasic acid anhydrides such as anhydrides; (2) Monoamine compounds, such as: aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecyl Alkylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecanylamine, n-octadecylamine, or n-eicosylamine And other monoamine compounds; or (3) monoisocyanate compounds, such as monoisocyanate compounds such as phenyl isocyanate or naphthyl isocyanate.

The polymer (A) of the present invention has a polystyrene-equivalent weight average molecular weight as measured by Gel Permeation Chromatography (GPC) of 2,000 to 200,000, preferably 3,000 to 100,000, and more preferably It is 4,000 to 50,000.

Polysiloxane (B)

The polysiloxane (B) contains an ethylenically unsaturated group, and is selected from the group consisting of , , -O- and At least one functional group in the formed group.

The step of preparing the polysiloxane (B) includes: step (i) self-condensing the polysiloxane compound containing the epoxy group-containing silane compound (b1); or the epoxy group-containing silane compound (b1) and Copolycondensation of other silane compounds (b2) to polysiloxane compounds; and step (ii) reacting the above polysiloxane compounds with ethylenically unsaturated compounds (b3) to obtain polysiloxanes (B) .

The epoxy group-containing silane compound (b1) contains an epoxy group-containing group including a group represented by formula (1-1), a group represented by formula (1-2), and a group represented by formula (1-3) At least one of the bases represented.

Specifically, the group represented by Formula (1-1), the group represented by Formula (1-2), and the group represented by Formula (1-3) are shown below.

In the formula (1-1), 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.

The base represented by the formula (1-2) is shown below.

In Formula (1-2), e represents an integer of 0 to 6.

The base represented by the formula (1-3) is shown below.

In the formula (1-3), D represents an alkylene group having 2 to 6 carbon atoms; E represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Hereinafter, a method for producing the epoxy group-containing silane compound (b1), other silane compound (b2), ethylenically unsaturated compound (b3), and polysiloxane (B) will be described in detail.

Epoxy-containing silane compound (b1)

The epoxy group-containing silane compound (b1) contains an epoxy group-containing group such as 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 (1-1), a group represented by the above formula (1-2), and a group represented by the above formula (1-3) At least one.

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

Specific examples of the epoxy-containing silane compound (b1) include 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 3- (N-allyl-N-glycidyl) Aminopropyltrimethoxysilane, 3-glycidyletherpropyltrimethoxysilane, 3-glycidyletherpropyltriethoxysilane, 3-glycidyletherpropylmethyldimethoxy Silane, 3-glycidyl ether propyl methyl diethoxy silane, 3-glycidyl ether propyl dimethyl methoxy silane, 3-glycidyl ether propyl dimethyl ethoxy silane, 2-glycidyl ether ethyltrimethoxysilane, 2-glycidyl ether ethyltriethoxysilane, 2-glycidyl ether ethylmethyldimethoxysilane, 2-glycidyl ether ethyl Methyl methyl diethoxysilane, 2-glycidyl ether ethyl dimethyl methoxysilane, 2-glycidyl ether ethyl dimethyl ethoxysilane, 4-glycidyl ether butyl trimethyl Oxysilane, 4-glycidyl ether butyl triethoxy silane, 4-glycidyl ether butyl methyl dimethoxy silane, 4-glycidyl ether butyl methyl diethoxy silane, 4-glycidyl Oleyl butyl dimethyl methoxysilane, 4-glycidyl butyl dimethyl ethoxy silane, 2- (3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propane Trimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, ((3-ethyl-3-epoxypropylalkyl) methoxy) propyltrimethoxysilane ((3-ethyl-3-glycidyl) methoxy) propyltriethoxysilane, ((3-ethyl-3-glycidyl) methoxy) propylmethyldi Methoxysilane or ((3-ethyl-3-glycidyl) methoxy) propanedimethylmethoxysilane, or a combination thereof.

Specific examples of the epoxy group-containing silane compound (b1) include 3-glycidyletherpropyltrimethoxysilane, 2-glycidyletherethyltrimethoxysilane, and 4-glycidyletherbutyl. Trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, ((3-ethyl Propyl-3-glycidyl) methoxy) propyltrimethoxysilane, ((3-ethyl-3-glycidyl) methoxy) propyltriethoxysilane or a combination of the above compounds .

The total amount of the epoxy group-containing silane compound (b1) and other silane compounds (b2) is 1.00 mol, and the amount of the epoxy group-containing silane compound (b1) is 0.30 to 1.00 mol, preferably 0.35 to 0.95 moles, more preferably 0.40 to 0.90 moles.

Other silane compounds (b2)

The other silane compound (b2) is, for example, a compound having one silicon atom. The compound having one silicon atom includes a silane compound having four hydrolyzable groups, a silane compound having three hydrolyzable groups, a silane compound having two hydrolyzable groups, and a silane having one hydrolyzable group. Compound, or a combination thereof.

Specific examples of the silane compound having four hydrolyzable groups include tetrachlorosilane Alkane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-second butoxysilane, or a combination thereof.

Specific examples of the silane compound having three hydrolyzable groups include trichlorosilane, trimethoxysilane, triethoxysilane, fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, and methyltrisiloxane. Chlorosilane, methyltrimethoxysilane, methyltriethoxysilane, 2- (trifluoromethyl) ethyltrichlorosilane, 2- (trifluoromethyl) ethyltrimethoxysilane, 2- ( (Trifluoromethyl) ethyltriethoxysilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, mercaptomethyltrichlorosilane, 3-mercaptopropyltrichlorosilane Silane, thiomethyltrimethoxysilane, thiomethyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane Silane, phenyltriethoxysilane, or a combination thereof.

Specific examples of the silane compound having two hydrolyzable groups include methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, dimethyldichlorosilane, and dimethyldimethoxy Silane, dimethyldiethoxysilane, methyl [2- (perfluoron-octyl) ethyl] dichlorosilane, methyl [2- (perfluoron-octyl) ethyl] dimethoxysilane , 3-mercaptopropylmethyldichlorosilane, 3-mercaptopropylmethyldimethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, or a combination thereof.

Specific examples of the silane compound having one hydrolyzable group include chlorodimethylsilane, methoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, and methoxytrimethylsilane. Methylsilane, chloromethyldiphenylsilane, methoxy Methyldiphenylsilane, or a combination of the above.

Specific examples of commercially available products of other silane compounds (b2) include KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, and 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 (made by Shin-Etsu Chemical); glass resin (GLASS RESIN, manufactured by Showa Denko); SH804, SH805, SH806A, SH840, SR2400, SR2402 SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (made by Toray Dow Corning); FZ3711, FZ3722 (made 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, D MS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (manufactured by JNC); MS51, MS56 (manufactured by Mitsubishi Chemical); and partial condensation of GR100, GR650, GR908, GR950 (manufactured by Showa Denko), etc. Thing.

Other silane compounds (b2) are preferably tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane Alkane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, thiomethyltrimethoxysilane, thiomethyltriethoxysilane, dimethyl Dimethoxysilane, dimethyldiethoxysilane, or a combination thereof.

The total amount of the epoxy-based silane compound (b1) and other silane compounds (b2) is 1.00 mol, and the amount of other silane compounds (b2) is 0.00 to 0.70 mol, preferably 0.05 to 0.65 mol. Ear, more preferably 0.10 to 0.60 mole.

Ethylene unsaturated compound (b3)

The ethylenically unsaturated compound (b3) includes an ethylenically unsaturated compound having a carboxylic acid group, an ethylenically unsaturated compound having an amine group, an ethylenically unsaturated compound having a hydroxyl group, or a combination thereof.

Specific examples of the ethylenically unsaturated compound having a carboxylic acid group include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2- (meth) acrylic acid ethyl phthalate, and 2- (meth) acrylic acid ethyl phthalate, maleic acid, monomethyl maleate, monoethyl maleate, fumaric acid, monomethyl fumarate, fumaric acid Monoethyl ester, itaconic acid, cinnamic acid, crotonic acid, perillic acid, 4-vinylacetoxystyrene, p-vinylbenzoic acid, 2-propenyloxyethyl-2-hydroxyethyl-o-benzene Dicarboxylic acid, 4- (2-methyl-acrylic acid) benzoic acid, (meth) acrylic acid ethyl succinic acid, phthalic acid monohydroxyethyl acrylate, or a combination of the foregoing compounds. Examples of products of the compound include Light-ester HO-MS, Light-ester HO-HH, HOA-MPL, HOA-MS, HOA-HH (manufactured by Kyoeisha), and M-5400 (manufactured by Toa Synthetic Corporation). )Wait.

Specific examples of the ethylenically unsaturated compound having an amine group include vinylbenzylamine, aminoethyl (meth) acrylate, or a combination thereof.

Specific examples of the ethylenically unsaturated compound having a hydroxyl group include compounds represented by the formulae (b3-1) to (b3-10).

In the formulae (b3-1) to (b3-10), R ⁶ represents a hydrogen atom or a methyl group, and t1, t2, and t3 represent an integer of 1 or more.

Specific examples of the ethylenically unsaturated compound (b3) include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2- (meth) acrylic acid ethyl phthalate, Hexahydrophthalate 2- (meth) acrylic acid ethyl ester, p-vinylbenzoic acid, p-vinylbenzylamine, aminoethyl methacrylate, hydroxyethyl 2-methacrylate, Hydroxypropyl 2-methacrylate, p-vinylphenol, o- (2-methylallyloxy) phenol, or a combination thereof.

The molar equivalent ratio (b3) / (b1) of the ethylenically unsaturated compound (b3) to the epoxy-containing silane compound (b1) is 0.20 to 0.80, preferably 0.25 to 0.70, and more preferably 0.30 to 0.60.

When the polysiloxane (B) in the liquid crystal alignment agent uses an ethylenically unsaturated compound (b3), the problem of uneven hue of the liquid crystal display element can be improved. Especially when the ethylenically unsaturated compound (b3) contains , , With at least one of the groups shown, the problem of uneven hue of the liquid crystal display element can be further improved.

The polysiloxane (B) of the present invention has a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography method of 500 to 100,000, preferably 800 to 50,000, and more preferably 1,000 to 20,000.

Preparation method of polysiloxane (B) Step (i)

The polycondensation reaction of the polysiloxane compound can be carried out by a general method. For example, an organic solvent, water, or a further selective catalyst is added to the silane compound or a mixture thereof, followed by an oil bath or the like at 50 ° C to 150 ° C. The heating time is preferably 0.5 to 120 hours. During heating, the mixed solution may be stirred or placed under reflux conditions.

The organic solvent is not particularly limited, and may be the same as or different from the solvent (D) 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-pentyl ketone, diethyl ketone, and cyclohexanone. ; Ester compounds such as ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc .; ethylene glycol dimethyl ether, Ether compounds such as ethylene glycol diethyl ether, tetrahydrofuran, and dioxane; 1-hexanol, 4-methyl 2-pentanol, ethylene glycol monomethyl ether, and ethylene glycol monoethyl Alcohol compounds such as ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, or a combination of the above organic solvents .

These organic solvents may be used alone or in combination.

The use amount of the organic solvent is preferably 10 to 1200 parts by weight, and more preferably 30 to 1,000 parts by weight, based on 100 parts by weight of all the silane compounds.

Based on the hydrolyzable group of all silane compounds being 1 mol, the amount of water used is preferably 0.5 mol to 100 mol, more preferably 1 mol to 30 mol.

The catalyst is not particularly limited. 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, piperidine, pyrrolidine, and pyrrole; triethylamine, triethylamine Tertiary organic amines such as n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, and other tertiary organic amines such as tetramethylammonium hydroxide Amines, etc., or a combination of the above.

The amount of catalyst used varies depending on the reaction conditions such as type, temperature, etc., and can be appropriately set. For example, based on 1 mol of all silane compounds, the addition amount of the catalyst is 0.01 mol to 5 mol, preferably 0.03 to 3 mol, more preferably 0.05 to 1 mol.

From the viewpoint of stability, after the completion of the polycondensation reaction, the organic solvent layer fractionated from the reaction liquid is preferably washed with water. When performing this washing | cleaning, it is preferable to wash | clean with water containing a small amount of salt, for example, about 0.2 weight% of ammonium nitrate aqueous solution etc. The cleaning can be performed until the water layer after the cleaning becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate, molecular sieves, etc. as needed, and then the organic solvent is removed to obtain a polysiloxane compound. .

Step (ii)

The polysiloxane compound and the ethylenically unsaturated compound (b3) are reacted to obtain the polysiloxane (B) of the present invention. The reaction between the polysiloxane compound and the ethylenically unsaturated compound (b3) can be performed in the presence of a catalyst and an organic solvent. The reaction between the polysiloxane compound and the ethylenically unsaturated compound (b3) may be performed in the presence of a hardening accelerator.

The specific example of the catalyst in step (ii) is the same as the specific example of the catalyst in step (i), and is not repeated here.

Based on 100 parts by weight of the ethylenically unsaturated compound (b3), the catalyst may be used in an amount of 0 to 100 parts by weight, preferably 0.01 to 50 parts by weight, and more preferably 0.1 to 20 parts by weight .

The organic solvent in the step (ii) is not particularly limited, and may be the same as or different from the organic solvent in the step (i) and the solvent (D) contained in the liquid crystal alignment agent of the present invention. Specific examples of the organic solvent are preferably 2-butanone, 2-hexanone, methyl isobutyl ketone, n-butyl acetate, or a combination thereof.

Specific examples of the hardening accelerator include benzyldimethylamine, 2,4,6-tris Tertiary amines such as (dimethylaminomethyl) phenol, cyclohexyldimethylamine, triethanolamine; 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2- Phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl 4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyano Ethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis (hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-phenyl-4,5-bis [(2'-cyanoethoxy) methyl Group) imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-n-undecanyl imidazolium trimellitate, 1- ( 2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2, 4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazole ) Ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4 ' -Methylimidazolyl- (1 ')] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4 -Imidazole compounds such as diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine isocyanurate adducts; diphenylphosphine, triphenyl Organophosphorus compounds such as phenylphosphine and triphenyl phosphite; benzyl triphenyl phosphonium chloride, tetra-n-butyl phosphonium bromide), methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium-O, O-diethyl Tetra-n-butyl phosphonium-O, O-diethyl phosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium benzotriazolate Tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butyl phosphonium tetraphenylborate, tetraphenyl phosphonium tetraphenylborate, etc. ; Diazabicyclic olefins such as 1,8-diazabicyclo [5.4.0] undecene-7 or its organic acid salts; zinc octoate, tin octoate, aluminum acetylacetone complex And other organometallic compounds; quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride; boron trifluoride (boron boron compounds such as trifluoride) and triphenyl borate; metal halogen compounds such as zinc chloride and tin tetrachloride; amine addition accelerators such as dicyandiamide or adducts of amines and epoxy resins High melting point dispersion type latent hardening accelerator; the above-mentioned imidazole compound Organophosphorus compounds or quaternary phosphonium salts and other hardening accelerators with polymer-encapsulated microcapsule-type latent hardening accelerators; amine salt-type latent hardening accelerators; Lewis acid salts, buturonic acid salts (Bronsted acid salt) and other high-temperature dissociation-type thermal cationic polymerization-type latent hardening accelerators.

Specific examples of the hardening accelerator are preferably quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.

The reaction temperature of the above reaction may be 0 ° C to 200 ° C, and preferably 50 to 150 ° C. The reaction time of the above reaction may be from 0.1 hours to 50 hours, preferably 0.5 hours. Time to 20 hours.

Based on the use amount of the polymer (A) being 100 parts by weight, the use amount of the polysiloxane (B) is 3 to 25 parts by weight, preferably 4 to 20 parts by weight, and more preferably 5 to 15 parts by weight.

If the polysiloxane (B) is not used for the liquid crystal alignment agent, the liquid crystal display element has a problem of poor UV resistance.

Photopolymerizable compound (C)

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

In formula (3), R ¹ each independently represents a polymerizable functional group represented by formula (3-1) to 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 may be passed through- Functional group substituted with O-, -S-, -SO _2- , -CO-, -COO-, -OCO-, -CH = CH-, -CF = CF-, or -C≡C-, and containing a hydrogen atom In the formula, an arbitrary hydrogen atom may be 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 a carbon number of 3 Divalent group of saturated or unsaturated independent ring, condensed ring or spiro ring to 20, wherein any -CH ₂ -in the ring may be substituted by -O-, any -CH = may be substituted by -N =, any -H can pass through a halogen atom, -CN, -NO ₂ , -NC, -N = C = O, -N = C = S, through 1 to 3 alkyl or phenyl groups having 1 to 4 carbon atoms. Substituted silyl, linear alkyl having 1 to 10 carbons, branched alkyl having 1 to 10 carbons, or haloalkyl having 1 to 10 carbons, and in the alkyl group, any -CH ₂ - may be -O -, - CO -, - COO -, - OCO -, - OCOO -, - CH = CH- or -C≡C- Z each independently represents a single bond or an alkylene group having a carbon number of 1 to 20, wherein the extension of any alkyl -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- substitution, and any -H may be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms; f represents an integer of 1 to 6, and when f When it is an integer of 2 to 6, a plurality of -YZ- are the same or different.

The polymerizable functional groups represented by the formulas (3-1) to (3-5) are shown below.

In the formulae (3-1) to (3-5), R ² represents a hydrogen atom, a halogen atom, -CF ₃ or an alkyl group having 1 to 5 carbon atoms.

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 formula (3), specifically, Y each independently represents 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetra Naphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] octane-1,4-diyl, bicyclo [3.1.0] hexane-3,6-diyl Or a divalent group of triptycene-1,4-diyl; any -CH ₂ -in the ring may be substituted with -O-, any -CH = may be substituted with -N =, any -H Silicon substituted by halogen atom, -CN, -NO ₂ , -NC, -N = C = O, -N = C = S, substituted by 1 to 3 alkyl or phenyl groups having 1 to 4 carbon atoms Group, linear or branched alkyl group having 1 to 10 carbon atoms, or haloalkyl group having 1 to 10 carbon atoms; and in the alkyl group, any -CH ₂ -can be replaced by -O-, -CO-, -COO-, -OCO-, -OCOO-, -CH = CH- or -C≡C-.

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

In the formulae (3-6) to (3-30), 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 group having 1 to 3 carbon atoms. alkyl.

The photopolymerizable compound (C) is preferably at least one selected from the group consisting of compounds represented by the formulas (3-31) to (3-42).

In the formulae (3-31) to (3-42), each of R ⁴ independently represents a hydrogen atom or a methyl group; each of R ⁵ independently represents a hydrogen atom, a halogen atom, a methyl group, -CF ₃ , -OCH ₃ , or phenyl group. Or two R ⁵ on the same carbon atom form a saturated or unsaturated hydrocarbon ring having 6 to 15 carbon atoms; g and h each independently represent an integer of 1 to 20.

Specific examples of the photopolymerizable compound (C) include at least one of the compounds represented by the formula (3-43) to the formula (3-97).

The photopolymerizable compound (C) is particularly preferably at least one of compounds represented by the formula (3-44) to the formula (3-50) or the formula (3-69) to the formula (3-97). When the photopolymerizable compound (C) is a compound represented by formula (3-44) to formula (3-50) or formula (3-69) to formula (3-97), the resistance of the produced liquid crystal display element Ultraviolet decay is particularly good.

The photopolymerizable compound (C) may be used alone or in combination.

The use amount of the photopolymerizable compound (C) is 1 to 35 parts by weight, preferably 3 to 30 parts by weight, and more preferably 5 to 25 parts by weight based on the use amount of the polymer (A).

If the photopolymerizable compound (C) is not used for the liquid crystal alignment agent, the liquid crystal display element has a problem of uneven hue.

Solvent (D)

The solvent used in the liquid crystal alignment agent of the present invention is not particularly limited, as long as it dissolves the polymer (A), the polysiloxane (B) and other arbitrary components and does not react therewith, it is preferably The same solvents as those used in the synthesis of the polyamic acid may be used together with the lean solvents used in the synthesis of the polyamino acid.

Specific examples of the solvent (D) 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 n-butyl ether), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, 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- N, N-dimethyl acetamide and so on. The solvent (D) can be used alone or in combination.

Based on 100 parts by weight of the polymer (A), 800 to 4000 parts by weight of the solvent (D), preferably 900 to 3500 parts by weight, and more preferably 1000 to 3000 parts by weight.

Additive (E)

To the extent that the efficacy of the present invention is not affected, the liquid crystal alignment agent may optionally add an additive (E), wherein the additive (E) includes a compound having at least two epoxy groups, a silane compound having a functional group, Or a combination.

Compounds having at least two epoxy groups include, but are not limited to, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-di Bromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl- M-xylylenediamine, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4 '-Diaminodiphenylmethane, 3- (N, N-diepoxypropyl) aminopropyltrimethoxysilane, or a combination of the above compounds.

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

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

Specific examples of the silane compound having a functional group include, but are not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2 -Aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl Methyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyl Trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriamine Ethylenetriamine, 10-trimethoxysilyl-1,4,7-triazine, 10-triethoxysilyl-1,4,7-triazine, 9-trimethoxysilane -3,6-diazinyl acetate, 9-triethoxysilyl-3,6-diazinyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane , A combination -3- N- bis (oxyethylene) -3-aminopropyl trimethoxy Silane, N- bis (oxyethylene) aminopropyl triethoxysilane Silane, or the above compounds.

The additive (E) may be used alone or in combination.

Based on 100 parts by weight of the polymer (A), it has a functional group The amount of the silane compound used may be 0 to 10 parts by weight, and preferably 0.5 to 10 parts by weight.

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

<Preparation method of liquid crystal alignment agent>

The method for preparing the liquid crystal alignment agent of the present invention is not particularly limited, and it can be prepared by a general mixing method. For example, the polymer (A), polysiloxane (B), and photopolymerizable compound (C) prepared in the above manner are first mixed uniformly to form a mixture. Next, the solvent (D) is added under the condition of a temperature of 0 ° C. to 200 ° C., and the additive (E) is optionally added. Finally, the stirring is continued with a stirring device until dissolved. In addition, it is preferable to add the solvent (D) at a temperature of 20 ° C to 60 ° C.

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

<Method for Forming Liquid Crystal Alignment Film>

After the liquid crystal alignment agent of the present invention is applied to a substrate, if necessary, a coating film obtained through a pre-bake, post-bake, or other heat treatment is used as a liquid crystal alignment film. The coating film may be subjected to rubbing, irradiation with polarized light or light of a specific wavelength, or an ion beam, or ultraviolet rays may be irradiated while a voltage is applied to the liquid crystal display element after the liquid crystal is filled. As a surface Controls vertical alignment film.

In this case, the substrate 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, polyarylate, polyurethane, polyfluorene, polyether, polyetherketone, trimethylpentene, polyolefin, Polyethylene terephthalate, (meth) acrylonitrile, cellulose triacetate, cellulose diacetate, or cellulose acetate butyrate and the like. From the viewpoint of simplification of the process, the substrate is preferably a substrate on which an indium tin oxide (ITO) electrode for liquid crystal driving is formed. When the reflective liquid crystal display element is a single-sided substrate, an opaque material such as a silicon wafer may be used. In addition, an electrode at this time may be made of a material that reflects light.

The application 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, inkjet method, spraying method, and roller coating. Cloth, dipping, slit coating, spin coating, etc. From the viewpoint of productivity, the transfer printing method widely used in industry is also applicable to the present invention.

After the liquid crystal alignment agent is applied by the method described above, a coating film can be formed through pre-baking and post-baking treatments. Although the pre-baking step after applying the liquid crystal alignment agent is not necessary, it is preferable to further perform the pre-baking step when the substrates are not fixed after coating or when the substrates are not baked immediately after coating. . In this pre-baking step, the organic solvent may be volatilized to such an extent that the shape of the coating film is not deformed due to the transportation of the substrate or the like. The conditions for the pre-baking treatment are not particularly limited, and for example, it is performed at any temperature of 40 ° C to 150 ° C, preferably 50 ° C to 120 ° C, and more preferably 60 ° C to 100 ° C. Pre-baking process can be at 0.1 It is performed at any time from minutes to 30 minutes, preferably from 0.5 minutes to 15 minutes, and more preferably from 1 minute to 5 minutes.

The conditions of the post-baking treatment are not particularly limited, and for example, it is performed at any temperature of 100 ° C to 350 ° C, preferably 120 ° C to 300 ° C, and more preferably 150 ° C to 250 ° C. The post-baking treatment may be performed at any time from 5 minutes to 240 minutes, preferably 10 minutes to 100 minutes, and more preferably 20 minutes to 90 minutes. The heating can be performed by a generally known method, for example, a heating plate, a hot-air circulation furnace, or an infrared furnace can be used for heating.

The thickness of the liquid crystal alignment film obtained after the 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 manufacturing method thereof>

The liquid crystal display element of the present invention includes a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention. The liquid crystal display element of this invention can be manufactured as follows.

In detail, 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 fabricating 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. The liquid crystal cell includes: two substrates arranged opposite to each other, a liquid crystal layer provided between the substrates, and a substrate and the liquid crystal layer. The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention is used.

Specifically, a vertical alignment type liquid crystal display element including a liquid crystal cell, wherein the liquid crystal cell is produced by applying the liquid crystal alignment agent of the present invention A liquid crystal alignment film is formed on the two substrates by pre-baking and post-baking processes. Then, the two substrates are arranged in an opposite manner to the liquid crystal alignment film, and a liquid crystal is held between the two substrates. The formed liquid crystal layer is a liquid crystal layer that is disposed in contact with the liquid crystal alignment film. Finally, a voltage is applied to the liquid crystal alignment film and the liquid crystal layer, and ultraviolet rays are irradiated at the same time.

As described above, the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention is used to polymerize a polymerizable compound while irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, and at the same time, the ethylene contained in the polysiloxane is polymerized. The organic unsaturated groups react with each other, or the ethylenically unsaturated group reacts with the polymerizable compound, so that the alignment of the liquid crystal can be more efficiently fixed, and a liquid crystal having excellent ultraviolet decay resistance and colorless phase unevenness can be formed. Display element.

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

(method one)

A pair of substrates having a liquid crystal alignment film formed is prepared, and spacers such as beads are spread on the liquid crystal alignment film of one of the substrates, and the two liquid crystal alignment films are bonded to each other in an opposite manner. One substrate was then injected with liquid crystal under reduced pressure and sealed.

(Method Two)

A pair of substrates with a liquid crystal alignment film is prepared. After spacers such as beads are spread on the liquid crystal alignment film of one of the substrates, the liquid crystal is dropped, and then the two liquid crystal alignment films are bonded to each other in an opposite manner. The substrate is sealed.

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

A step of applying a voltage to the liquid crystal alignment film and the liquid crystal layer while irradiating ultraviolet rays to produce a liquid crystal cell. For example, a voltage is applied between electrodes provided on a 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 UV light. The voltage applied between the electrodes is, for example, 5Vp-p to 30Vp-p, and preferably 5Vp-p to 20Vp-p. The amount of ultraviolet irradiation is, for example, 1J to 60J, preferably 40J or less, and more preferably 10J or less. The smaller the amount of ultraviolet irradiation, the lower the reliability caused by the destruction of the liquid crystal or the material constituting the liquid crystal display element can be suppressed, 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 radiation, and therefore, even at a low radiation amount of about 5 J, a liquid crystal display element having a sufficiently fast response speed can be formed.

In this way, when a voltage is applied to the liquid crystal alignment film and the liquid crystal layer and ultraviolet rays are simultaneously irradiated, the polymerizable compound can be reacted to form a polymer. In addition, the ethylenically unsaturated group of the polysiloxane can also be irradiated with ultraviolet rays When reacting with each other 'or with a polymerizable compound. By the above reaction, the liquid crystal alignment film can obtain a better cured structure, so that the obtained liquid crystal display element has the properties of good resistance to ultraviolet decay and uneven coloring.

In addition, the above-mentioned liquid crystal alignment agent can be used not only as a liquid crystal alignment agent for manufacturing liquid crystal display elements of a vertical alignment method such as a surface-controlled vertical alignment type (SCVA) liquid crystal display, but also can be applied to those produced by rubbing treatment or light alignment treatment. Use of liquid crystal alignment film.

The liquid crystal includes a nematic liquid crystal or a dish-shaped liquid crystal. LCD specific Examples include, but are not limited to, liquid crystals with positive dielectric anisotropy. Biphenyl-based liquid crystals, phenyl cyclohexane-based liquid crystals, and ester liquid crystals can be used, for example. , Terphenyl liquid crystal, biphenyl cyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals ), Bicyclooctane-based liquid crystals, cubic-based liquid crystals, or a combination of the above liquid crystals. In addition, a cholesteric liquid crystal such as cholesteryl chloride, cholesteryl nonanoate, and cholesteryl carbonate may be further added to the liquid crystal; Chiral agents sold under the trade names "C-15" and "CB-15" (Merck); p-decyloxymethylene-p-amino-2-methylbutyl cinnamate (p -decyloxybenzylidene-p-amino-2-methyl butyl cinnamate) and other ferroelectric liquid crystals are used.

In addition, specific examples of the liquid crystal may include a liquid crystal having a negative dielectric anisotropy. For example, dicyanobenzene-based liquid crystal, pyridazine-based liquid crystal, Greek 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 present invention will be further described with reference to the following examples, but it should be understood that these examples are merely illustrative and should not be construed as limitations of the implementation of the present invention.

Synthesis example of polymer (A)

The following describes Synthesis Example A-1-1 to Synthesis Example A-1-6 of the polymer (A):

Synthesis Example A-1-1

A 500 ml four-necked flask was provided with a nitrogen inlet, a stirrer, a condenser, and a thermometer, and nitrogen was introduced. Then, in a four-necked flask, 1.16 g (0.0025 mol) of a diamine compound (abbreviated as a2-1-1) represented by the formula (II-10) and 4.86 g (0.045 mol) of p-di Aminobenzene (abbreviated as a2-2-1), 0.49 g (0.0025 mole) of 4,4'-diaminodicyclohexylmethane (abbreviated as a2-2-4), and 80 g of N-methyl- 2-Pyrrolidone (abbreviated as NMP), and 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 is completed, the reaction solution is poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, repeatedly washed with methanol and filtered three times, put into a vacuum oven, and dried at a temperature of 60 ° C. to obtain a polymer (A-1-1).

Synthesis Example A-1-2 to Synthesis Example A-1-6

Synthesis Examples A-1-2 to A-1-6 are the same as Synthesis Example A-1-1 The steps are to separately prepare the polymer (A-1-2) to the polymer (A-1-6), and the difference is that the type of the monomer and the amount of use thereof are changed (as shown in Table 1).

The following describes Synthesis Example A-2-1 to Synthesis Example A-2-11 of Polymer (A):

Synthesis Example A-2-1

A 500 ml four-necked flask was provided with a nitrogen inlet, a stirrer, a condenser, and a thermometer, and nitrogen was introduced. Then, in a four-necked flask, 1.16 g (0.0025 mol) of a diamine compound (abbreviated as a2-1-1) represented by the formula (II-10) and 4.86 g (0.045 mol) of p-di Aminobenzene (abbreviated as a2-2-1), 0.49 g (0.0025 mole) of 4,4'-diaminodicyclohexylmethane (abbreviated as a2-2-4), and 80 g of N-methyl- 2-Pyrrolidone (abbreviated as NMP), and 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. 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 imidization reaction. After the reaction is completed, the reaction solution is poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, and repeatedly washed with methanol and filtered three times, put into a vacuum oven, and dried at a temperature of 60 ° C. to obtain a polymer (A-2-1).

Synthesis Example A-2-2 to Synthesis Example A-2-11

Synthesis Examples A-2-2 to A-2-11 are the same as Synthesis Example A-2-1 Steps to prepare the polymer (A-2-2) to the polymer (A-2-11), and the difference is that the type of monomer and its amount of use are changed (as shown in Table 1).

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

Synthesis example of polysiloxane (B)

The following describes Synthesis Example B-1 to Synthesis Example B-7 of the polysiloxane (B):

Synthesis Example B-1

A 500 ml three-necked flask was equipped with a stirrer, a condenser, and a thermometer. Then, in a three-necked flask, 0.3 mol of 4-glycidyl ether butyltrimethoxysilane (hereinafter referred to as GBTMS), 0.7 mol of methyltrimethoxysilane (hereinafter referred to as MTMS) and 6 Grams of propylene glycol monomethyl ether (hereinafter referred to as PGME), and triethylamine (hereinafter referred to as TEA) aqueous solution (20 grams of TEA / 200 grams of H ₂ O) was added within 30 minutes while stirring at room temperature. . 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. within 30 minutes. When the internal temperature of the solution reached 75 ° C., the mixture was continuously heated and stirred for 6 hours . After the reaction is completed, the organic layer is taken out and washed with a 0.2% by weight ammonium nitrate aqueous solution to obtain a solution containing a polysiloxane compound.

Next, 0.1 mol of monoethyl fumarate (hereinafter abbreviated as MEF) and 0.2 g of a hardening accelerator UCAT 18X (manufactured by SAN-APRO) were added to the solution containing a polysiloxane compound. Then, the three-necked flask was immersed in an oil bath at 30 ° C. and stirred for 10 minutes, and then the oil bath was heated to 115 ° C. within 30 minutes. When the internal temperature of the solution reached 100 ° C., heating and stirring were continued for 24 hours. After the reaction is completed, the organic layer is taken out, washed with water, dried with magnesium sulfate, and the solvent is removed to obtain polysiloxane (B-1).

Synthesis Example B-2 to Synthesis Example B-7

The polysiloxane (B-2) to polysiloxane (B-7) of Synthesis Example B-2 to Synthesis Example B-7 were prepared in the same procedure as Synthesis Example B-1, and were different in that : Change the kind of reactant of polysiloxane (B) and its use amount, the kind of catalyst and solvent and its use amount, reaction temperature and polycondensation time (as shown in Table 2).

Synthesis example B'-1 to Synthesis example B'-3

The polysiloxanes (B'-1) to (B'-3) of Synthesis Example B'-1 to Synthesis Example B'-3 were prepared in the same steps as those of Synthesis Example B-1, and The difference lies in that: the type of the reactant of the polysiloxane (B) and its use amount, the type of the catalyst and the solvent and their use amount, the reaction temperature and the polycondensation time (shown in Table 2).

The compounds corresponding to the abbreviations in Table 2 are shown below.

Examples and comparative examples of liquid crystal alignment agents, liquid crystal alignment films, and liquid crystal display elements

Examples 1 to 15 and Comparative Examples 1 to 12 of the liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display element will be described below:

Example 1 a. Liquid crystal alignment agent

100 parts by weight of the polymer (A-1-1), 5 parts by weight of the polysiloxane (B-1), and 8 parts by weight of the photopolymerizable compound (C- 1), 1200 parts by weight of N-methyl-2-pyrrolidone (abbreviated as D-1) and 1200 parts by weight of ethylene glycol n-butyl ether (abbreviated as D-2), and at room temperature, using a stirring device By continuing to stir until dissolved, the liquid crystal alignment agent of Example 1 can be formed.

b. Liquid crystal alignment film and liquid crystal display element

Using the obtained liquid crystal alignment agent, a liquid crystal cell was produced in the procedure shown below. The liquid crystal alignment agent was spin-coated on two glass substrates each having an ITO electrode, wherein the ITO electrode was a slit pattern with a line / space of 5 μm each. . Next, pre-bake at 80 ° C. for 2 minutes on a hot plate, and post-bake at 220 ° C. for 20 minutes in a circulating oven to form the liquid crystal alignment film of Example 1.

For the two glass substrates on which the liquid crystal alignment film was formed, one of the glass substrates was coated with a hot-pressing adhesive, and the other was dispersed with a 4 μm spacer. Next, the two glass substrates were bonded together, and then a pressure of 10 kg was applied by a hot press, and the bonding was performed by hot pressing at a temperature of 150 ° C. Then, a liquid crystal injection machine (made by Shimadzu Corporation, model: ALIS-100X-CH) was used to inject the liquid crystal, and then the liquid crystal injection port was sealed with an ultraviolet curing adhesive, and then cured by irradiation with an ultraviolet light. Next, an alternating current of 20 Vp-p was applied between the two ITO electrodes, and 30 J of ultraviolet rays were irradiated while the liquid crystal was in a driving state to obtain a liquid crystal display element of Example 1. The liquid crystal display element of Example 1 was evaluated by each evaluation method described later, and the results are shown in Table 3.

Examples 2 to 15

The liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element of Example 2 to Example 15 were separately prepared in the same steps as in Example 1, and the difference was that the type of the component and the amount of use were changed, as shown in Table 3. Show. The liquid crystal display elements obtained in Examples 2 to 15 were evaluated in an evaluation method described later, and the results are shown in Table 3.

Comparative Example 1 to Comparative Example 12

The liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element of Comparative Example 1 to Comparative Example 12 were separately prepared in the same steps as in Example 1. The difference was that the type of the component and the amount of use were changed, as shown in Table 4. . The liquid crystal display elements obtained in Comparative Examples 1 to 12 were evaluated in the evaluation method described later, and the results are shown in Table 4.

The compounds corresponding to the abbreviations in Tables 3 and 4 are shown below.

<Evaluation method> a. Rate of imidization

The fluorene imidization ratio refers to the total number of fluorene imine functional groups and the number of fluorene imine rings in the polymer, and the ratio of the number of fluorene imine rings is calculated as a percentage.

The detection method is to separately dry the polymer of the synthesis example under reduced pressure, and then dissolve it in an appropriate deuteration solvent (for example, deuterated dimethylsulfinium), using tetramethylsilane as a reference material, and 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 (%).

△ 1: Peak area generated by chemical shift of NH matrix protons around 10ppm; △ 2: Peak areas of other protons; α: NH in polymer precursor (polyamic acid) Proportion of the number of one proton of the base relative to the number of other protons.

b. UV decay resistance

The ultraviolet decay resistance of a liquid crystal display element was evaluated by the voltage holding ratio of the liquid crystal display element. Furthermore, the measurement method of the voltage holding ratio of a liquid crystal display element is as follows.

The voltage holding ratios of the liquid crystal display elements of the examples and comparative examples were measured using an electrical measuring machine (manufactured by Toyo Co., Ltd. Model 6254). The test condition is to apply a voltage of 4 volts, and release the voltage after 2 milliseconds, and measure the voltage retention rate (counted as V1) after 1667 milliseconds since the release. Next, after the liquid crystal display element was irradiated with 30 mJ / cm ² of ultraviolet light (ultraviolet irradiation machine model: KN-SH48K1; manufactured by Kogyo Kogyo), the voltage retention rate after ultraviolet light irradiation was measured under the same test conditions (calculated as V2). Finally, the percentage change of the voltage holding rate (calculated as V ^UV-decay (%)) can be obtained by calculating with mathematical formula (2). The lower the percentage change in the voltage holding ratio, the better the UV-resistant decay resistance of the liquid crystal display element.

The evaluation criteria for the percentage change in voltage holding ratio are shown below.

◎: V ^UV-decay <3%

○: 3% ≦ V ^UV-decay <5%

△: 5% ≦ V ^UV-decay <10%

╳: 10% ≦ V ^UV-decay

c. uneven hue

The liquid crystal display elements of the examples and comparative examples were irradiated with a backlight of a standard C light source, and the liquid crystal display elements were observed through a polarizing plate to see if the liquid crystal display elements had uneven hue. The evaluation criteria of hue unevenness are shown below.

：: No unevenness in hue occurred.

○: Slight unevenness in hue occurs, but it is not obvious.

△: Significant uneven hue appears.

╳: Severe hue unevenness occurs.

<Evaluation Results>

From Tables 3 and 4, it is known that the liquid crystal display elements (Examples 1 to Implementation) prepared with a liquid crystal alignment agent using the polymer (A), polysiloxane (B), and photopolymerizable compound (C) together Example 15) In contrast, the liquid crystal display elements of Comparative Example 1, Comparative Example 2, Comparative Example 9, Comparative Example 10, Comparative Example 12 without using the diamine compound (a2-1), and without using polysiloxane (B) The liquid crystal display elements of Comparative Examples 3 to 6 and Comparative Examples 9 to 11 do not have ultraviolet decay resistance. In addition, compared with a liquid crystal display element (Examples 1 to 15) obtained by using a liquid crystal alignment agent of a polymer (A), a polysiloxane (B) and a photopolymerizable compound (C), The liquid crystal display elements of Comparative Example 7, Comparative Example 8, Comparative Example 11, and Comparative Example 12 using the photopolymerizable compound (C) had a problem of severe hue unevenness.

In addition, when using a polymer (A) having an imidization ratio of 30% to 90% (ie, a polymer (A-2-4) to a polymer (A-2-9)) (Examples 9 to Examples) In the case of Example 14), the liquid crystal display element has better UV degradation resistance.

When polysiloxane (B) (i.e., polysiloxane (B-2) to polysiloxane (B-6)) containing a specific ethylenically unsaturated group is used (Example 2 to Example 5) (Example 8 to Example 11, Example 13 and Example 14), the problem of uneven hue of the liquid crystal display element can be further improved.

In addition, when at least one of the compounds represented by the formulae (3-31) to (3-42) is used as the photopolymerizable compound (C) (Examples 3 to 5, Example 7, and Example 10) (Example 11, Example 14, and Example 15), the liquid crystal display element has better resistance to ultraviolet decay.

When the polymer (A) contains a diamine compound represented by formula (III-1) or formula (III-2) (Example 3, Example 4, Example 8, Example 9, Example 12), The problem of uneven hue of the liquid crystal display element can be further improved.

In summary, in the surface-controlled vertical alignment type liquid crystal alignment agent of the present invention, in addition to the polymer and the solvent, a photopolymerizable compound is added to the liquid crystal alignment agent instead of the polymer stable alignment type. The photopolymerizable compound is added to the liquid crystal layer, thereby solving the problem that the conventional liquid crystal layer is contaminated with impurities.

On the other hand, the liquid crystal alignment agent of the present invention contains a polyethylsiloxane having a specific ethylenically unsaturated group, so that the liquid crystal display element has excellent ultraviolet decay resistance, and contains a photopolymerizable compound to make the liquid crystal display element colorless. The problem of unevenness is therefore suitable for manufacturing a liquid crystal alignment film and a liquid crystal display element.

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

Claims (10)

A liquid crystal alignment agent comprising: a polymer (A); a polysiloxane (B); a photopolymerizable compound (C); and a solvent (D), wherein the polymer (A) is obtained by reacting a mixture The mixture includes a tetracarboxylic dianhydride component (a1) and a diamine component (a2), and the diamine component (a2) includes the diamine compound (a2-1) represented by formula (II) At least one of In formula (II), R ¹⁴ represents -O-, , , , or R ¹⁵ represents an organic group represented by formula (II-1), In formula (II-1), R ¹⁶ represents a hydrogen atom, a fluorine atom, or a methyl group; R ¹⁷ , R ^18, or R ¹⁹ each independently represents a single bond, -O-, , , , , Or an alkylene group having 1 to 3 carbon atoms; R ²⁰ represents or Wherein R ²² and R ²³ each independently represent a hydrogen atom, a fluorine atom or a methyl group; R ²¹ represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, Alkoxy, -OCH ₂ F, -OCHF ₂ or -OCF _{3 having a} carbon number of 1 to 12; k represents 1 or 2; l, m, and n each independently represent an integer of 0 to 4; o, p, and q each Independently represent integers from 0 to 3, and o + p + q ≧ 3; r and s each independently represent 1 or 2; when there are multiple R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²² or R ^In the case of ²³ , a plurality of R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ^22, or R ²³ are each the same or different, and the polysiloxane (B) contains an ethylenically unsaturated group, and Selected from , , -O- and At least one functional group in the group consisting, wherein the ethylenically unsaturated group includes , , At least one of the bases represented, where * represents a bonding position. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the photopolymerizable compound (C) is a compound represented by formula (3), In formula (3), R ¹ each independently represents a polymerizable functional group represented by formula (3-1) to 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 alkyl groups -CH ₂ -may Substituted by -O-, -S-, -SO _2- , -CO-, -COO-, -OCO-, -CH = CH-, -CF = CF-, or -C≡C-, and containing a hydrogen atom In the functional group, any of the hydrogen atoms may be substituted with 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 is independently represented A divalent group of a saturated or unsaturated independent ring, condensed ring, or spiro ring having 3 to 20 carbon atoms, wherein any -CH ₂ -in the ring may be substituted with -O-, and any -CH = may be substituted -N = substitution, any -H may pass through a halogen atom, -CN, -NO ₂ , -NC, -N = C = O, -N = C = S, have 1 to 4 carbon atoms through 1 to 3 Alkyl or phenyl substituted silyl, linear alkyl having 1 to 10 carbons, branched alkyl having 1 to 10 carbons or haloalkyl having 1 to 10 carbons, and said In the alkyl group, any -CH ₂ -may pass through -O-, -CO-, -COO-, -OCO-, -OCOO-, -CH = CH- or -C≡C- substitution; Z each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, wherein any -CH ₂ -in the alkylene group may be passed through -O-,- S-, -SO _2- , -CO-, -COO-, -OCO-, -OCOO-, -CH = CH-, -CF = CF-, -CH = N-, -N = CH-, -N = N-, -N (O) = N- or -C≡C-, 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. Substitution; f represents an integer from 1 to 6, and when f is an integer from 2 to 6, multiple -YZ- are the same or different; In the formulae (3-1) to (3-5), R ² represents a hydrogen atom, a halogen atom, -CF ₃ or an alkyl group having 1 to 5 carbon atoms. The liquid crystal alignment agent according to item 2 of the scope of patent application, wherein at least one of R ¹ of the photopolymerizable compound (C) is polymerizable represented by the formulae (3-1) to (3-3) Functional group. The liquid crystal alignment agent according to item 2 of the scope of patent application, wherein each of Y of the photopolymerizable compound (C) independently represents 1,4-cyclohexyl, 1,4-cyclohexenyl, 1, 4-phenylene, naphthalene-2,6-diyl, tetralin-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] octane-1,4-diyl , A bicyclic [3.1.0] hexane-3,6-diyl or triptycene-1,4-diyl divalent group; any -CH ₂ -in the ring may pass -O- Substitution, any -CH = can be replaced by -N =, any -H can be replaced by a halogen atom, -CN, -NO ₂ , -NC, -N = C = O, -N = C = S, by 1 to 3 alkyl or phenyl substituted silyl groups having 1 to 4 carbon atoms, linear or branched alkyl groups having 1 to 10 carbon atoms, or haloalkyl groups having 1 to 10 carbon atoms; In the alkyl group, any -CH ₂ -may be substituted with -O-, -CO-, -COO-, -OCO-, -OCOO-, -CH = CH-, or -C≡C-. The liquid crystal alignment agent according to item 4 of the scope of patent application, wherein Y each independently represents at least one selected from the group consisting of functional groups represented by formula (3-6) to formula (3-30), Formula (3-6) Formula (3-7) Formula (3-8) Formula (3-9) In the formulae (3-6) to (3-30), 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 group having 1 to 3 carbon atoms. alkyl. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the photopolymerizable compound (C) is at least one selected from the group consisting of compounds represented by formulas (3-31) to (3-42) One, In the formulae (3-31) to (3-42), each of R ⁴ independently represents a hydrogen atom or a methyl group; each of R ⁵ independently represents a hydrogen atom, a halogen atom, a methyl group, -CF ₃ , -OCH ₃ , or phenyl group. Or two R ⁵ on the same carbon atom form a saturated or unsaturated hydrocarbon ring having 6 to 15 carbon atoms; g and h each independently represent an integer of 1 to 20. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the polymer (A) has an imidization ratio of 30% to 90%. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the use amount of the polysiloxane (B) is 3 to 25 parts by weight based on 100 parts by weight of the polymer (A); The use amount of the photopolymerizable compound (C) is 1 to 35 parts by weight; the use amount of the solvent (D) is 800 to 4000 parts by weight. A liquid crystal alignment film is formed from the liquid crystal alignment agent according to any one of the first to eighth patent application scopes. A liquid crystal display element includes the liquid crystal alignment film according to item 9 of the scope of patent application.