TWI773684B - Liquid crystal alignment agent, production method of liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

A liquid crystal alignment agent which is capable of forming a liquid crystal alignment film with fast response speed and hard to form image stick, the production method for the liquid crystal alignment film formed from the liquid crystal alignment agent, and a liquid crystal display element having the same are provided. The liquid crystal alignment agent includes a polymer (A) a photo-sensitive polysiloxane (B) and a solvent (C). The polymer (A) is obtained by reacting a first mixture includes a tetracarboxylic dianhydride component (a1) and a diamine component (a2). The photo-sensitive polysiloxane (B) is obtained by reacting a polysiloxane (b1) including an epoxy group with a cinnamic acid derivative (b2) and a compound (b3) represented by formula (b3-1).

Description

Liquid crystal alignment agent, method for producing liquid crystal alignment film, and liquid crystal display element

The present invention relates to a liquid crystal alignment agent, a method for manufacturing a liquid crystal alignment film, and a liquid crystal display element, and in particular to a liquid crystal alignment agent that can form a liquid crystal alignment film with fast response speed and less image sticking, and is formed from the liquid crystal alignment agent. The manufacturing method of the liquid crystal alignment film and the liquid crystal display element having the above-mentioned liquid crystal alignment film.

Liquid crystal displays are widely used in televisions and various monitors. As LCD display elements, LCD display elements having the following liquid crystal cell (cell) types are known: Twisted Nematic (TN) type, Super Twisted Nematic (Super Twisted Nematic) type. Twisted Nematic (STN) type, In Plane Switching (IPS) type, changing the electrode structure of IPS type, etc., and fringe field switching (Fringe Field Switching) that improves the brightness by increasing the aperture ratio of the display element. Switching, FFS) type and so on.

There are three types of liquid crystal alignment methods of conventional liquid crystal cells: forming an organic film such as a liquid crystal alignment film on the surface of a substrate, and rubbing the surface of the organic film in a certain direction with a cloth such as rayon. ; Oblique vapor deposition of silicon oxide on the surface of the substrate; Use the LB method (Langmuir-Blodgett) to form a monomolecular film with long-chain alkyl groups, etc. Among them, from the viewpoints of substrate size, alignment uniformity of liquid crystal, processing time, and processing cost, rubbing treatment is the most common.

However, if the alignment of the liquid crystal is performed by rubbing treatment, the dust generated during the process is likely to adhere to the surface of the alignment film due to static electricity, resulting in poor display, especially with thin film transistors (Thin Film Transistor, TFT) The substrate of the element is easily generated by static electricity, which causes circuit damage of the TFT element and a decrease in productivity. Furthermore, in liquid crystal display elements that are increasingly required to be refined, as the pixel density increases, unevenness occurs on the surface of the substrate, and it tends to be difficult to uniformly perform rubbing treatment.

Then, in order to avoid the occurrence of the above-mentioned inconvenience, there is known a photo-alignment method for imparting alignment capability to a liquid crystal by irradiating a photosensitive film with polarized or non-polarized radiation (for example, Patent Document 1), which proposes a conjugated olefin A repeating unit of a ketone (conjugated enone) and a liquid crystal aligning agent having an imide structure. Thereby, static electricity and dust will not be generated, and uniform liquid crystal alignment can be achieved. In addition, compared with the rubbing process, this method can control the alignment direction of liquid crystal in any direction and precisely, and by using a mask or the like when irradiating radiation, a plurality of regions with different alignment directions of liquid crystal can be arbitrarily formed on one substrate. .

However, the photo-alignment liquid crystal display element prepared from the liquid crystal alignment film has the disadvantages of poor response speed and residual image characteristics, which cannot be accepted by the industry. Therefore, how to provide a liquid crystal alignment agent that can form a liquid crystal alignment film with fast response speed and less image sticking, so that the formed liquid crystal alignment film can have better display quality when applied to liquid crystal display elements Problems that those skilled in the art are eager to solve.

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2005-037654

In view of this, the present invention provides a liquid crystal alignment agent for liquid crystal display elements, and the liquid crystal alignment film prepared by using the liquid crystal alignment agent can improve the problems of response speed and image sticking.

The present invention provides a liquid crystal alignment agent comprising a polymer (A), a photosensitive polysiloxane (B) and a solvent (C). Polymer (A) is prepared by reacting a first mixture comprising a tetracarboxylic dianhydride component (a1) and a diamine component (a2). Photosensitive polysiloxane (B) is obtained by reacting epoxy-containing polysiloxane (b1), cinnamic acid derivative (b2) and compound (b3) represented by formula (b3-1);

In formula (b3-1), X ₁ represents a linear or branched alkylidene with 1 to 10 carbons, a linear or branched alkylene with 1 to 10 carbons, a carbon Linear or branched alkenylidene with a number of 2 to 10, linear or branched alkenylene with a carbon number of 2 to 10, divalent alicyclic group with a carbon number of 3 to 30, A divalent aryl group having 6 to 30 carbon atoms or a divalent heterocyclic group having 2 to 30 carbon atoms; X ₂ represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms.

In an embodiment of the present invention, the above-mentioned epoxy-containing polysiloxane (b1) includes a group represented by formula (b1-1), a group represented by formula (b1-2), and a group represented by formula (b1) -3) At least one of the bases represented by:

In formula (b1-1), B represents an oxygen atom or a single bond; m represents an integer from 1 to 3; n represents an integer from 0 to 6, wherein when n represents 0, B represents a single bond; * represents a bond,

In formula (b1-2), p represents an integer from 0 to 6; * represents a bond,

In formula (b1-3), 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; * represents a bond.

In an embodiment of the present invention, the above-mentioned epoxy-containing polysiloxane (b1) comprises a copolymer obtained by hydrolysis and partial condensation of the second mixture. The second mixture includes an epoxy group-containing silane compound (b1-I), and the epoxy group-containing silane compound (b1-I) has a structure represented by the formula (b1-I-1): Si(R _a ) _h (OR _b ) _4-h formula (b1-I-1)

In formula (b1-I-1), R _a represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an epoxy group containing and at least one R _a is an alkyl group containing an epoxy group or an alkoxy group containing an epoxy group; when R _a is plural, each of the h R _a is the same or different.

R _b represents a hydrogen atom, an alkyl group having a carbon number of 1 to 6, an aryl group having a carbon number of 1 to 6, or an aryl group having a carbon number of 6 to 15; when R _b is plural, (4-h) Rs _b are the same or different from each other.

h represents an integer of 1 to 3.

In an embodiment of the present invention, the above-mentioned cinnamic acid derivative (b2) is at least one selected from the group consisting of compounds represented by formula (b2-1) to formula (b2-2),

In formula (b2-1) and formula (b2-2), R represents a fluorine atom or a cyano group; a represents an integer of 0 to 4.

R ¹ and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 40 carbon atoms or a monovalent alicyclic organic group having 3 to 40 carbon atoms, and the alkyl group is unsubstituted or at least a part of the hydrogen atoms are Fluorine atom substitution.

R ² and R ⁴ each independently represent a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group, and R ² or R ⁴ is unsubstituted or at least A part of the hydrogen atoms are replaced by R ⁸ , and R ⁸ each independently represents a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having a carbon number of 1 to 5, the above-mentioned alkyl group or alkane group The oxy group is unsubstituted or at least part of the hydrogen atoms are substituted with halogen.

Y ¹ , Y ² , and Y ⁴ each independently represent a single bond, an oxygen atom, -COO- or -OCO-.

Y ⁵ represents a single bond, an alkylene group having 1 to 10 carbons, an alkenylene group having 2 to 10 carbons, or a divalent aromatic group.

When Y ⁵ represents a single bond, e represents 1, and R ⁵ represents a hydrogen atom; when Y ⁵ represents an alkylene group having a carbon number of 1 to 10, an alkenylene group having a carbon number of 2 to 10, or a divalent aromatic group In the case of a group, e represents 0 or 1, and R ⁵ represents a carboxylic acid group, a hydroxyl group, -SH, -NCO, -NHR', -CH=CH ₂ or -SO ₂ Cl, and R' represents a hydrogen atom or a carbon number of 1 to 6 alkyl groups.

Y ³ represents an oxygen atom or a divalent aromatic group.

R ⁶ represents a divalent aromatic group, a divalent heterocyclic group, or a divalent condensed ring group.

Y ⁶ represents an oxygen atom, -COO- or -OCO-.

R ⁷ represents a carboxylic acid group, a hydroxyl group, -SH, -NCO, -NHR", -CH=CH ₂ or -SO ₂ Cl, and R" represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Y ⁷ represents a single bond, -OCO-(CH ₂ ) _i -* or -O-(CH ₂ ) _j -*, wherein i and j each independently represent an integer from 1 to 10, and * each independently represents a bond with R ⁷ at the bond.

b, c, and f each independently represent an integer of 0 to 3.

In an embodiment of the present invention, the above-mentioned compound (b3) represented by formula (b3-1) is in the group consisting of compounds represented by formula (b3-2) and formula (b3-3). at least one,

In formula (b3-2), X ₃ represents a linear or branched alkylene group having 1 to 10 carbon atoms, a linear or branched alkylene group having 1 to 10 carbon atoms, and a linear or branched alkylene group having 1 to 10 carbon atoms. Linear or branched alkenylene, linear or branched alkenylene having 2 to 10 carbons; X ₂ represents a hydrogen atom or a linear or branched alkyl having 1 to 10 carbons.

In formula ( _b3-3 ), X4 and X5 represent a single bond or a linear or branched alkylene group with 1 to 10 carbon atoms or a linear or branched alkylene group with 1 to 10 carbon atoms; Cy represents Cyclopropylene, Cyclopropylidene, Cyclobutylene, Cyclobutylidene, Cyclopentylene, Cyclopentylidene ), Furanylene, Thiophenylene, Phenylene, Pyrrolidinylene, Pyrrolidinylidene, Cyclohexenylene, Sub Cyclohexenylidene, Piperidinylene, Piperidinylidene, Pyridinylene, pyridazinylene, pyrimidinylene, pyrimidine (pyrazinylene), 1H-indolylene (1H-indolylene) or naphthylene (naphthalenylene); X ₂ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.

In an embodiment of the present invention, based on the total amount of the monomers in the second mixture being 1 mol, the usage amount of the epoxy-containing silane compound (b1-I) is 0.5 mol to 1 mol .

In an embodiment of the present invention, based on the total amount of the monomers in the second mixture being 1 mol, the amount of the cinnamic acid derivative (b2) used is 0.3 mol to 0.9 mol.

In an embodiment of the present invention, based on the total amount of the monomers in the second mixture being 1 mol, the compound (b3) is used in an amount of 0.01 mol to 0.2 mol.

In an embodiment of the present invention, the molar ratio (b2)/(b3) of the above-mentioned cinnamic acid derivative (b2) and compound (b3) is 2 to 20.

In an embodiment of the present invention, based on 100 parts by weight of the above-mentioned polymer (A), the amount of photosensitive polysiloxane (B) used is 3 to 50 parts by weight; the solvent (C) The usage amount is 1000 to 3500 parts by weight.

The present invention further provides a method for manufacturing a liquid crystal alignment film, which includes the step of coating the above-mentioned liquid crystal alignment agent on a substrate.

The present invention further provides a liquid crystal display element, comprising: a liquid crystal alignment film prepared by the above-mentioned manufacturing method of the liquid crystal alignment film.

Based on the above, since the liquid crystal aligning agent of the present invention has a specific photosensitive polysiloxane (B), it is possible to form a liquid crystal display element with a fast response speed and less image sticking.

In order to make the above-mentioned features and advantages of the present invention more obvious and easy to understand, the following embodiments are given and described in detail with the accompanying drawings as follows.

100: Liquid crystal display element

110: Unit 1

112: The first substrate

114: The first conductive film

116: the first liquid crystal alignment film

120: Unit Two

122: Second substrate

124: second conductive film

126: The second liquid crystal alignment film

130: Liquid crystal unit

FIG. 1 is a side view of a liquid crystal display element according to an embodiment of the present invention.

<Liquid crystal alignment agent>

The present invention provides a liquid crystal alignment agent, comprising: a polymer (A), a photosensitive polysiloxane (B) and a solvent (C). In addition, the liquid crystal alignment agent may further include an additive (D) as necessary.

Each component of the liquid crystal aligning agent used in the present invention will be described in detail below.

Polymer (A)

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

In detail, the polymer (A) includes polyamic acid, polyimide, polyamic acid-polyimide block copolymer or a combination of these polymers. Wherein, the polyimide-based block copolymers include polyimide block copolymers, polyimide block copolymers, polyimide-polyimide block copolymers or the above-mentioned polymers combination of things. Polyimide polymers, polyimide polymers and polyimide-polyimide block copolymers can all be made from a mixture of tetracarboxylic dianhydride component (a1) and diamine component (a2) prepared by the reaction.

Tetracarboxylic dianhydride component (a1)

Tetracarboxylic dianhydride compounds (a1) include aliphatic tetracarboxylic dianhydride compounds, alicyclic tetracarboxylic dianhydride compounds, aromatic tetracarboxylic dianhydride compounds, from formula (a1-1) to formula (a1- 6) At least one of the tetracarboxylic dianhydride compounds represented, or a combination of the above compounds.

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

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

Specific examples of the alicyclic tetracarboxylic dianhydride compound may include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4- Cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclo butane tetra Carboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride , 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcycloheptyl -1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, or a combination of the above compounds.

Specific examples of the aromatic tetracarboxylic dianhydride compound may include, but are not limited to, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid Acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-diphenylethane tetracarboxylic dianhydride, 3,3',4,4'- Dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylene dianhydride, 4,4'- 4,4'-bis(3,4-dicarboxy phenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisosulfite Propyl diphthalic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(tris) Phenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid) dianhydride (Triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(anhydrotrimellitate), propylene glycol-bis(anhydrotrimellitate), 1,4 -Butanediol-bis(anhydrotrimellitate), 1,6-hexanediol-bis(anhydrotrimellitate), 1,8-octanediol-bis(anhydrotrimellitate) , 2,2-bis(4-hydroxyphenyl)propane-bis(anhydro trimellitate), 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5, 9b-Hexahydro-5-(tetrahydro-2,5-dioxy-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-dione), 1,3,3a,4,5,9b-hexahydro-5 -Methyl-5-(tetrahydro-2,5-dioxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a, 4,5,9b-Hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxy-3-furyl)-naphtho[1,2-c]-furan-1,3 -diketone, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxy-3-furyl)-naphtho[1, 2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxy-3 -furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro- 2,5-Di-oxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8 -Ethyl-5-(tetrahydro-2,5-dioxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a, 4,5,9b-Hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxy-3-furyl)-naphtho[1,2-c]-furan- Aromatic tetracarboxylic dianhydrides such as 1,3-dione and 5-(2,5-dioxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride A compound or a combination of the foregoing compounds.

The tetracarboxylic dianhydride compounds represented by formula (a1-1) to formula (a1-6) are shown below.

In formula (a1-5), 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 may each independently represent a hydrogen atom or an alkyl group.

Specific examples of the tetracarboxylic dianhydride compound represented by the formula (a1-5) include at least one of the compounds represented by the formula (a1-5-1) to the formula (a1-5-3).

In formula (a1-6), 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 (a1-6) is preferably a compound represented by the formula (a1-6-1).

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

Preferably, the tetracarboxylic dianhydride component (a1) includes but is not limited to 1,2,3,4-cyclobutane tetracarboxylic dianhydride (1,2,3,4-cyclobutane tetracarboxylic dianhydride), 1, 2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,4,5-cyclohexane Alkanetetracarboxylic acid Anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3',4,4'- Benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, a compound represented by formula (I-1), or a combination of the above compounds.

Based on the total molar number of the diamine component (a2) of 1.0 mol, the usage amount of the tetracarboxylic dianhydride component (a1) is preferably 0.2 mol to 2.0 mol, more preferably 0.3 mol to 0.3 mol to 1.2 moles.

Diamine component (a2)

The diamine compound (a2) includes an aliphatic diamine compound, an alicyclic diamine compound, an aromatic diamine compound, a diamine compound represented by formula (a2-1) to formula (a2-30), 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, 1,7-diamino-3-methylheptane 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 alicyclic diamine compounds 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 ]-undecane Carbendimethyldiamine, 4,4'-methylenebis(cyclohexylamine), or a combination of the foregoing.

Specific examples of the aromatic diamine compound include, but are not limited to, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl Di, 4,4'-diaminobenzylaniline, 4,4'-diaminostilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl Phenyl ether, 3,3'-diaminochalcone, 1,5-diaminonaphthalene, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethyl Hydrogen indene, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydroindene, hexahydro-4,7-methylhydroindenyl dimethylene Diamine, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4- (4-Aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl) ) Hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]zine, 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-diaminophenyl, 9,9-bis(4-aminophenyl)anthracene, 4,4' - Methylene-bis(2-chloroaniline), 4,4'-(p-phenylene isopropylidene) dianiline, 4,4'-(m-phenylene isopropylidene) dianiline , 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-bis[(4-amino-2-trifluoropropane Methyl)phenoxy]-octafluorobiphenyl, 5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenyl-methylene-1,3-diaminobenzene{5-[ 4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene}, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl) ) cyclohexane{1,1-bis[4- (4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane}, or a combination of the foregoing.

The diamine compounds represented by formula (a2-1) to formula (a2-30) are shown below.

、

、

、

，或

；B²表示具有甾(膽固醇(steroid))骨架的基、三氟甲基、氟原子、碳數為2至30的烷基、或衍生自吡啶、嘧啶、三嗪、哌啶或哌嗪等含氮原子環狀結構的一價基團。 In formula (a2-1), B ¹ represents -O-,

,

,

,

,or

; B ² represents a group having a steroid (steroid) skeleton, a trifluoromethyl group, a fluorine atom, an alkyl group with a carbon number of 2 to 30, or derived from pyridine, pyrimidine, triazine, piperidine or piperazine, etc. A monovalent group with a ring structure containing nitrogen atoms.

Specific examples of the compound represented by formula (a2-1) 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 (2,4-diaminophenyl propyl formate), 3,5-diaminophenyl propyl formate (3,5-diaminophenyl propyl formate) diaminophenyl propyl formate), 1-dodecoxy-2,4-diaminobenzene (1-dodecoxy-2,4-diaminobenzene), 1-hexadecoxy-2,4-diaminobenzene ( 1-hexadecoxy-2,4-diaminobenzene), 1-octadecoxy-2,4-diaminobenzene (1-octadecoxy-2,4-diaminobenzene), from formula (a2-1-1) to formula At least one of the compounds represented by (a2-1-6), or a combination of the above compounds.

Compounds represented by formula (a2-1-1) to formula (a2-1-6) are shown below.

In formula (a2-2), B ¹ is the same as B ¹ in formula (a2-1), and B ³ and B ⁴ each independently represent a divalent aliphatic ring, a divalent aromatic ring or a divalent heterocyclic group; B ⁵ represents an alkyl group having a carbon number of 3 to 18, an alkoxy group having a carbon number of 3 to 18, a fluoroalkyl group having a carbon number of 1 to 5, a fluoroalkoxy group having a carbon number of 1 to 5, a cyano group or halogen atom.

Specific examples of the compound represented by the formula (a2-2) include at least one of the compounds represented by the formula (a2-2-1) to (a2-2-13). Specifically, the compounds represented by the formula (a2-2-1) to the formula (a2-2-13) are shown below.

In formula (a2-2-10) to formula (a2-2-13), s represents an integer of 3 to 12.

In formula (a2-3), B ⁶ each independently represents a hydrogen atom, an acyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen atom, And B ⁶ in each repeating unit may be the same or different; u represents an integer of 1 to 3.

Specific examples of the compound represented by formula (a2-3) include when u is 1: p-diamine benzene, m-diamine benzene, o-diamine benzene or 2,5-diaminotoluene, etc.; when u When it is 2: 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diphenyl Aminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'- Dichloro-4,4'-diaminobiphenyl, 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4' -Diamino-5,5'-dimethoxybiphenyl or 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, etc.; or when u is 3: 1 , 4-bis(4'-aminophenyl)benzene, etc.

Specific examples of the compound represented by the formula (a2-3) preferably include p-diaminobenzene, 2,5-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-dimethylbenzene Oxy-4,4'-diaminobiphenyl, 1,4-bis(4'-aminophenyl)benzene, or a combination of the foregoing.

In formula (a2-4), v represents an integer of 2 to 12.

In formula (a2-5), w represents an integer of 1 to 5. The compound represented by the formula (a2-5) is preferably 4,4'-diamino-diphenyl sulfide.

In formula (a2-6), B ⁷ and B ⁹ each independently represent a divalent organic group, and B ⁷ and B ⁹ may be the same or different; B ⁸ represents derived from pyridine, pyrimidine, triazine, piperidine or piperidine A divalent group of a cyclic structure containing an ammonia atom such as an oxazine.

In formula (a2-7), B ¹⁰ , B ¹¹ , B ¹² and B ¹³ each independently represent a hydrocarbon group having 1 to 12 carbon atoms, and B ¹⁰ , B ¹¹ , B ¹² and B ¹³ 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 (a2-8), B ¹⁴ represents an oxygen atom or a cyclohexylene group; B ¹⁵ represents a methylene group (methylene, -CH ₂ -); B ¹⁶ represents a phenylene group or a cyclohexylene group; B ¹⁷ Represents a hydrogen atom or a heptyl group.

Specific examples of the compound represented by the formula (a2-8) include the compound represented by the formula (a2-8-1), the compound represented by the formula (a2-8-2), or a combination of the above compounds.

The compounds represented by the formula (a2-9) to the formula (a2-30) are shown below.

In formula (a2-17) to formula (a2-25), B ¹⁸ preferably represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; B ¹⁹ preferably represents a hydrogen atom , an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

The diamine compound (a2) may be used alone or in combination of two or more.

Specific examples of the diamine compound (a2) preferably include, but are not limited to, 1,2-diaminoethane, 3,3'-diaminochalcone, and 4,4'-diaminostilbene , 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 5-[4-(4-n-pentane Alkylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethyl) phenyl)cyclohexane, ethyl 2,4-diaminophenylcarboxylate, 1-octadecyloxy-2,4-diaminobenzene, compound represented by formula (a2-1-1) , the compound represented by the formula (a2-1-2), the compound represented by the formula (a2-1-4), the compound represented by the formula (a2-1-5), the compound represented by the formula (a2-2-1) The compound represented by the formula (a2-2-11), p-diamine benzene, m-diamine benzene, o-diamine benzene, The compound represented by the formula (a2-8-1), the compound represented by the formula ( a2-26) to a compound represented by formula (a2-30), or a combination of the above compounds.

Process for preparing polymer (A)

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

Method for preparing polyamide

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

The solvent used in the polycondensation reaction may be the same as or different from the solvent used in the liquid crystal aligning 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) aprotic polar solvents, such as: N-methyl-2-pyrrolidinone (N-methyl-2-pyrrolidinone; NMP), N,N-dimethylacetamide, Aprotic polar solvents such as N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea or hexamethylphosphoric triamine; or (2) phenolic solvents, For example, phenolic solvents such as m-cresol, xylenol, phenol, and halogenated phenols. 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 100 parts by weight of the total used amount of the first mixture.

It is worth noting that in the polycondensation reaction, the solvent can be used in combination with an appropriate amount of poor solvent, wherein the poor solvent will not cause the precipitation of polyamide acid. The poor solvent can be used alone 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-butanediol Alcohols such as alcohol or triethylene glycol; (2) ketones, such as: ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; (3) esters, such as: Methyl acetate, ethyl acetate, acetic acid Esters of butyl ester, diethyl oxalate, diethyl malonate or ethylene glycol ethyl ether acetate; (4) ethers, such as: diethyl ether, ethylene glycol methyl ether, ethylene glycol Ethers such as alcohol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether or diethylene glycol dimethyl ether; (5 ) halogenated hydrocarbons such as: dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene or o-dichlorobenzene, etc.; or ( 6) Hydrocarbons, such as: tetrahydrofuran, hexane, heptane, octane, benzene, toluene or xylene and other hydrocarbons or any combination of the above solvents. The amount of the lean solvent used is preferably 0 to 60 parts by weight, and more preferably 0 to 50 parts by weight, based on 100 parts by weight of the diamine component (a-2).

Method for preparing polyimide

The method for preparing polyimide is obtained by heating the polyamic acid prepared by the above-mentioned method for preparing polyamic acid in the presence of a dehydrating agent and a catalyst. During the heating process, the aramidic acid functional group in the polyamic acid can be converted into an imidimine functional group via a dehydration ring-closure reaction (ie, imidization).

The solvent used in the dehydration ring-closing reaction can be the same as the solvent (C) in the liquid crystal alignment agent, so it is not repeated here. The amount of the solvent used in the dehydration ring-closure 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.

In order to obtain a better degree of imidization of the polyamic acid, the operating temperature of the dehydration ring-closure reaction is preferably 40°C to 200°C, more preferably 40°C to 150°C. If the operating temperature of the dehydration ring-closure reaction is lower than 40 °C, the imidization reaction is not complete, and the Degree of imidization of oligomeric amides. However, if the operating temperature of the dehydration ring-closure reaction is higher than 200°C, the weight-average molecular weight of the obtained polyimide is relatively low.

The dehydrating agent used in the dehydration ring-closure reaction can be selected from acid anhydride compounds, such as acid anhydride compounds such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. The dehydrating agent is used in an amount of 0.01 mol to 20 mol based on 1 mol of the polyamide. The catalyst used in the dehydration ring-closure reaction can be selected from (1) pyridine compounds, such as: pyridine compounds such as pyridine, collidine or lutidine; (2) tertiary amine compounds, such as: Tertiary amine compounds such as triethylamine. The catalyst may be used in an amount of 0.5 mol to 10 mol based on 1 mol of the dehydrating agent.

The imidization rate of the polymer (A) may be 0% to 50%, preferably 0% to 45%, and more preferably 0% to 40%.

Method for preparing polyimide-based block copolymer

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

The method for preparing the polyimide-based block copolymer is preferably to first dissolve the starting material in a solvent and carry out a polycondensation reaction, wherein the starting material includes at least one polyamide acid and/or at least one polyamide imine, and may further include a carboxylic acid 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 polyamic acid, and The solvent used in the polycondensation reaction can be the same as the solvent (C) in the following liquid crystal alignment agent, and details are not described herein.

The solvent used in the polycondensation reaction is preferably used in an amount of 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight, based on 100 parts by weight 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 materials preferably include but are not limited to (1) two kinds of polyamides with different end groups and different structures; (2) two kinds of polyimides with different end groups and different structures; (3) ) Polyamides and polyimides with different terminal groups and different structures; (4) Polyamides, carboxylic anhydride components and diamine components, wherein the difference between the carboxylic acid anhydride component and the diamine component At least one of the structures is different from the carboxylic acid anhydride component and the diamine component used to form the polyamide acid; (5) the polyimide, the carboxylic acid anhydride component and the diamine component, wherein, the carboxylic acid anhydride component At least one of the components and the diamine component is different in structure from the carboxylic acid anhydride component and the diamine component used to form the polyimide; (6) polyamide acid, polyimide, and carboxylic acid anhydride components and the diamine component, wherein at least one of the carboxylic acid anhydride component and the diamine component has a different structure from the carboxylic acid anhydride component and the diamine component used to form the polyamide acid or polyimide; ( 7) Two kinds of structurally different polyamide acids, carboxylic anhydride components and diamine components; (8) Two kinds of structurally different polyimide, carboxylic acid anhydride components and diamine components; (9) Two kinds of end groups are acid anhydride groups and structurally different polyamic acid and diamine components; (10) Two kinds of end groups are amine groups and structurally different polyamic acid and carboxylic anhydride components; (11) Two kinds of end groups are polyimide and diamine components with different structures and acid anhydride groups; or (12) two kinds of polyimide and carboxylic acid anhydride components with amine groups and different structures.

In the range that does not affect the efficacy of the present invention, polyimide, polyimide and polyimide-based block copolymers are preferably terminal-modified polymers whose molecular weights are adjusted first. By using the terminal-modified polymer, the coating performance of the liquid crystal alignment agent can be improved. The method of preparing the terminal-modified polymer can be prepared by adding a monofunctional compound at the same time as the polyamide acid undergoes a polycondensation reaction.

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

The polymer (A) of the present invention has a weight average molecular weight of 10,000 to 100,000 in terms of polystyrene as measured by gel permeation chromatography, preferably 20,000 to 80,000, more preferably 30,000 to 70,000.

Photosensitive polysiloxane (B)

Photosensitive polysiloxane (B) is obtained by reacting epoxy-containing polysiloxane (b1), cinnamic acid derivative (b2) and compound (b3) represented by formula (b3-1);

In formula (b3-1), X ₁ represents a linear or branched alkylidene with 1 to 10 carbons, a linear or branched alkylene with 1 to 10 carbons, a carbon Linear or branched alkenylidene with a number of 2 to 10, linear or branched alkenylene with a carbon number of 2 to 10, divalent alicyclic group with a carbon number of 3 to 30, A divalent aryl group having 6 to 30 carbon atoms or a divalent heterocyclic group having 2 to 30 carbon atoms; X ₂ represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms.

Specific examples and synthesis methods of the epoxy group-containing polysiloxane (b1), the cinnamic acid derivative (b2), and the ethylenically unsaturated compound (b3) will be described below.

Epoxy-containing polysiloxane (b1)

The epoxy group contained in the epoxy-containing polysiloxane (b1) is, for example, a glycidyl group, a glycidyloxy group, an epoxycyclohexyl group, or a propylene oxide group. base (oxetanyl group).

Specifically, the epoxy-containing polysiloxane (b1) includes at least one selected from the groups represented by formula (b1-1) to formula (b1-3):

In formula (b1-1), B represents an oxygen atom or a single bond; m represents an integer from 1 to 3; n represents an integer from 0 to 6, wherein when n represents 0, B represents a single bond; * represents a bond.

In formula (b1-2), p represents an integer of 0 to 6; * represents a bond.

In formula (b1-3), 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; * represents a bond.

The epoxy group-containing group preferably includes a group represented by formula (b1-1-1), a group represented by formula (b1-2-1), and a group represented by formula (b1-3-1) at least one of.

Epoxy-containing silane compound (b1-I)

The epoxy-containing polysiloxane (b1) preferably comprises a copolymer obtained by hydrolysis and partial condensation of the second mixture, the second mixture comprising the epoxy-containing silane compound (b1-I), The epoxy group-containing silane compound (b1-I) has a structure represented by the following formula (b1-I-1): Si(R _a ) _h (OR _b ) _4-h formula (b1-I-1)

Formula (b1-I-1), R _a represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an epoxy group-containing group an alkyl group or an alkoxy group containing an epoxy group, and at least one R _a is an alkyl group containing an epoxy group or an alkoxy group containing an epoxy group; when R _a is plural, each of the h R _a is the same or different .

R _b represents a hydrogen atom, an alkyl group having a carbon number of 1 to 6, an aryl group having a carbon number of 1 to 6, or an aryl group having a carbon number of 6 to 15; when R _b is plural, (4-h) Rs _b are the same or different from each other.

h represents an integer of 1 to 3.

In more detail, when R _a in formula (b1-I-1) represents an alkyl group having 1 to 10 carbon atoms, specifically, R _a is, for example, methyl, ethyl, n-propyl, isopropyl , n-butyl, tert-butyl, n-hexyl or n-decyl. In addition, R _a may be an alkyl group having another substituent on the alkyl group, and specifically, R _a is, for example, trifluoromethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3- mercaptopropyl or 3-isocyanatopropyl.

When R _a in the formula (b1-I-1) represents an alkenyl group having a carbon number of 2 to 10, specifically, R _a is, for example, a vinyl group. In addition, R _a may be an alkenyl group having another substituent on the alkenyl group, and specifically, R _a is, for example, 3-acryloyloxypropyl or 3-methacryloyloxypropyl.

When R _a in formula (b1-I-1) represents an aryl group having a carbon number of 6 to 15, specifically, R _a is, for example, phenyl, tolyl, or naphthyl. In addition, R _a may be an aryl group having another substituent on the aryl group, and specifically, R _a is, for example, p-hydroxyphenyl (o-hydroxyphenyl), 1-(p-hydroxyphenyl)ethyl (1-(p-hydroxyphenyl) ethyl) -(o-hydroxyphenyl)ethyl), 2-(p-hydroxyphenyl)ethyl (2-(o-hydroxyphenyl)ethyl), or 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl ( 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl).

Furthermore, when R _a in formula (b1-I-1) represents an epoxy group-containing alkyl group or an epoxy group-containing alkoxy group, a specific example of R _a is the aforementioned epoxy group-containing polysiloxane. The epoxy group contained in the alkane (b1) will not be repeated here.

In addition, when R _b of formula (b1-I-1) represents an alkyl group having 1 to 6 carbon atoms, specifically, R _b is, for example, methyl, ethyl, n-propyl, isopropyl, or n-butyl base. When R _b in the formula (b1-I-1) represents an acyl group having 1 to 6 carbon atoms, specifically, R _b is, for example, an acetyl group. When R _b in the formula (b1-I-1) represents an aryl group having a carbon number of 6 to 15, specifically, R _b is, for example, a phenyl group.

Specific examples of the epoxy group-containing silane compound (b1-I) include 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, 3-(N-allyl-N-glycidyl group) aminopropyl trimethoxysilane, 3-glycidyl ether propyl trimethoxy silane, 3-glycidyl ether propyl triethoxy silane, 3-glycidyl ether propyl methyl dimethyl dimethyl Oxysilane, 3-glycidyl propyl methyl diethoxy silane, 3-glycidyl propyl dimethyl methoxy silane, 3-glycidyl propyl dimethyl ethoxy Silane, 2-glycidylethyltrimethoxysilane, 2-glycidylethyltriethoxysilane, 2-glycidylethylmethyldimethoxysilane, 2-glycidylether Ethyl ethyl methyl diethoxy silane, 2-glycidyl ether ethyl dimethyl methoxy silane, 2-glycidyl ether ethyl dimethyl ethoxy silane, 4-glycidyl ether butyl base three Methoxysilane, 4-Glycidyl Butyltriethoxysilane, 4-Glycidylbutylmethyldimethoxysilane, 4-Glycidylbutylmethyldiethoxysilane, 4-Glycidyl Glyceryl ether-based butyldimethylmethoxysilane, 4-glycidyl ether-based butyldimethylethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2- (3,4-Epoxycyclohexyl)ethyltriethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyl triethoxysilane, ((3-ethyl-3-epoxypropanyl)methoxy)propyltrimethoxysilane, ((3-ethyl-3-epoxypropanyl)methoxy) Propyltriethoxysilane, ((3-ethyl-3-epoxypropanyl)methoxy)propylmethyldimethoxysilane or ((3-ethyl-3-epoxypropanyl) Methoxy)propane dimethylmethoxysilane, commercially available products such as DMS-E01, DMS-E12, DMS-E21, EMS-32 (manufactured by JNC), or a combination of the above compounds.

Specific examples of the epoxy group-containing silane compound (b1-I) preferably include 3-glycidyl propyl trimethoxy silane, 2-glycidyl ethyl trimethoxy silane, 4-glycidyl ether butyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, ((3 -Ethyl-3-epoxypropanyl)methoxy)propyltrimethoxysilane, ((3-ethyl-3-epoxypropanyl)methoxy)propyltriethoxysilane, DMS- E01, DMS-E12 or a combination of the above compounds.

The epoxy group-containing silane compound (b1-I) is used in an amount of 0.5 to 1.0 mol, preferably 0.6 to 1.0 mol, more preferably 0.7 mol, based on 1 mol of the total amount of monomers in the second mixture to 1.0 moles.

When the epoxy group-containing silane compound (b1-I) is not contained in the second mixture, the epoxy group-containing polysiloxane (b1) does not contain the above-mentioned epoxy group, and further, the obtained liquid crystal alignment The liquid crystal alignment film formed by the agent has a poor response speed and is prone to image sticking.

Other silane compounds (b1-II)

Preferably, the second mixture used to react to generate the epoxy-containing polysiloxane (b1) further comprises other silane compounds (b1-II), and the other silane compounds (b1-II) have the following formula: Structure shown in (b1-II-1): Si(R _c ) _k (OR _d ) _4-k formula (b1-II-1)

In formula (b1-II-1), R _c represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an acid anhydride group-containing group. Alkyl; when _Rc is plural, each of the k _Rcs is the same or different.

R _d represents a hydrogen atom, an alkyl group having 1 to 6 carbons, an aryl group having 1 to 6 carbons, or an aryl group having 6 to 15 carbons; when R _d is plural, (4-k) R _d Each is the same or different.

k represents an integer of 0 to 3.

When R _c in formula (b1-II-1) represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, the specific examples thereof are the same as those in the comparative example. The best example is as shown in the aforementioned R _a , which is not repeated here.

When R _c in the formula (b1-II-1) represents an acid anhydride group-containing alkyl group, the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. Specifically, the alkyl group containing an acid anhydride group is, for example, but not limited to, ethyl succinic anhydride represented by formula (b1-II-1-1), propyl group represented by formula (b1-II-1-2) Succinic anhydride or propylglutaric anhydride represented by formula (b1-II-1-3). It is worth mentioning that the acid anhydride group is a group formed by intramolecular dehydration of dicarboxylic acid, wherein the dicarboxylic acid is, for example, succinic acid or glutaric acid.

When R _d in formula (b1-II-1) represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, the specific examples thereof are the same as those in the comparative example. The preferred example is as shown in the aforementioned R _b , which is not repeated here.

The other silane compound (b1-II) may be used alone or in combination, and the other silane compound (b1-II) includes a compound having 1 silicon atom. Compounds having one silicon atom include silane compounds having four hydrolyzable groups, silane compounds having three hydrolyzable groups, silane compounds having two hydrolyzable groups, and silanes having one hydrolyzable group compound, or a combination thereof.

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

Specific examples of silane compounds having three hydrolyzable groups include methyltrimethoxysilane (MTMS), methyltriethoxysilane, methyl triisopropoxysilane, Methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyl ethyltri-n-butoxysilane (ethyltri-n-butoxysilane), n-propyltrimethoxysilane (n-propyltrimethoxysilane), n-propyltriethoxysilane (n-propyltriethoxysilane), n-butyltrimethoxysilane ( n-butyltrimethoxysilane), n-butyltriethoxysilane (n-butyltrimethoxysilane) triethoxysilane), n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyl trimethoxysilane, ethylene Vinyltriethoxysilane (vinyltriethoxysilane), 3-acryoyloxypropyltrimethoxysilane (3-acryoyloxypropyltrimethoxysilane), 3-methylacryloyloxypropyltrimethoxysilane (MPTMS) ), 3-methylacryloyloxypropyltriethoxysilane (3-methylacryloyloxypropyltriethoxysilane), phenyltrimethoxysilane (PTMS), phenyltriethoxysilane (PTES), p- p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyl 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane ), trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane (3,3,3-trifluoropropyltrimethoxysilane) , 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-( Triphenoxysilyl)propylsuccinic anhydride (3-tripheno xysilyl propyl succinic anhydride), manufactured by Shin-Etsu Chemical Commercially available product: 3-(trimethoxysilyl propyl succinic anhydride) (trade name X-12-967), commercially available product manufactured by WACKER: 3- (3-(triethoxysilyl)propyl succinic anhydride) (trade name GF-20), 3-(trimethoxysilyl)propyl glutaric anhydride (3-(trimethoxysilyl)propyl succinic anhydride) )propyl glutaric anhydride, TMSG), 3-(triethoxysilyl)propyl glutaric anhydride, 3-(triethoxysilyl)propyl glutaric anhydride ( 3-(triphenoxysilyl)propyl glutarie anhydride) or a combination of the above compounds.

Specific examples of the silane compound having two hydrolyzable groups include methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl [2-(Perfluoro-n-octyl)ethyl]dimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiacetoxysilane , di-n-butyldimethoxysilane, or a combination of the above compounds.

Specific examples of the silane compound having one hydrolyzable group include methoxydimethylsilane, methoxytrimethylsilane, methoxymethyldiphenylsilane, tri-n-butylethoxysilane, or Combinations of the above compounds.

Other silane compounds (b1-II) are preferably tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane Silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane, Dimethyldiethoxysilane, or a combination of the above.

The amount of the other silane compound (b1-II) used is 0 to 0.5 mol, preferably 0 to 0.4 mol, more preferably 0 to 0.3 mol, based on the total amount of monomers in the second mixture is 1 mol.

The second mixture may further contain a commercially available silane monomer, and specific examples thereof include KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, and X-21-5843 , X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X -22-170D, X-22-170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40 -2655A, X-40-2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250 , X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A , KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (Shin-Etsu Chemical); Glass Resin (GLASS RESIN, Showa Denko); SH804, SH805, SH806A, SH840, SR24 , 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, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (made by JNC) ; MS51, MS56 (manufactured by Mitsubishi Chemical); and partial condensates of GR100, GR650, GR908, GR950 (manufactured by Showa Denko).

Production method of epoxy group-containing polysiloxane (b1)

The epoxy group-containing polysiloxane (b1) used for the photosensitive polysiloxane (B) of the present invention includes at least one epoxy group-containing polysiloxane (b1) obtained as follows. Specific examples of this method include, but are not limited to, continuous stirring when a catalyst is added during the polycondensation reaction, and batch addition of a silane compound during the polycondensation reaction.

The polycondensation reaction to form the epoxy group-containing polysiloxane (b1) can be carried out using a general method, for example, adding an organic solvent, water or optionally a catalyst to the above-mentioned silane compound or a mixture thereof, followed by using oil The bath or the like is heated at 50°C to 150°C, and the preferred heating time is 0.5 hours to 120 hours. During heating, the mixed solution can be stirred or placed under reflux conditions.

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

Specific examples of the organic solvent include hydrocarbon compounds such as toluene and xylene; methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone, 2-butanone , 2-hexanone and other ketone solvents; ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and other esters Solvents; ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc.; 1-hexanol, 4-methyl 2-pentanol, ethylene glycol mono Methyl ether, ethylene glycol monoethyl 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, etc. Alcohol solvents; N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide Amide-based solvents such as amines, triamide hexamethylphosphate, 1,3-dimethyl-2-imidazolidinone, etc., or a combination of the above organic solvents.

The above-mentioned organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent used is preferably 10 g to 1200 g, more preferably 30 g to 1,000 g, based on a total amount of 1 mol of the silane compound in the second mixture.

Water is preferably used in an amount of 50 g to 500 g, based on a total amount of 1 mole of the silane compound in the second mixture.

The catalyst is not particularly limited. Preferably, the catalyst is selected from acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds, 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; Tertiary organic amines such as n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, etc.; quaternary organic amines such as tetramethylammonium hydroxide Amines, etc., or a combination of the above compounds.

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

From the viewpoint of stability, after the completion of the polycondensation reaction, the organic solvent layer fractionated from the reaction solution is preferably washed with water. When this cleaning is performed, it is preferable to perform the cleaning using water containing a small amount of salt, for example, an ammonium nitrate aqueous solution of about 0.2 wt %. Cleaning can be performed until the water layer after 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 the organic solvent is removed to obtain the epoxy group-containing. Polysiloxane (b1).

When the epoxy group-containing polysiloxane (b1) used in the photosensitive polysiloxane (B) does not include an epoxy group-containing polysiloxane (b1) obtained in the above-mentioned manner, the The liquid crystal alignment film formed by the prepared liquid crystal alignment agent has a poor response speed and is prone to image sticking.

cinnamic acid derivative (b2)

The cinnamic acid derivative (b2) is at least one selected from the group consisting of compounds represented by formula (b2-1) and formula (b2-2):

In formula (b2-1) and formula (b2-2), R represents a fluorine atom or a cyano group; a represents an integer of 0 to 4.

R ¹ and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 40 carbon atoms or a monovalent alicyclic organic group having 3 to 40 carbon atoms, and some or all of the hydrogen atoms of the alkyl group may be replaced by fluorine atoms replace.

R ² and R ⁴ each independently represent a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group, and R ² or R ⁴ is unsubstituted or at least A part of the hydrogen atoms are replaced by R ⁸ , and R ⁸ each independently represents a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having a carbon number of 1 to 5, the above-mentioned alkyl group or alkane group The oxy group is unsubstituted or at least part of the hydrogen atoms are substituted with halogen.

Y ¹ , Y ² , and Y ⁴ each independently represent a single bond, an oxygen atom, -COO- or -OCO-.

Y ⁵ represents a single bond, an alkylene group having 1 to 10 carbons, an alkenylene group having 2 to 10 carbons, or a divalent aromatic group.

When Y ⁵ represents a single bond, e represents 1, and R ⁵ represents a hydrogen atom; when Y ⁵ represents an alkylene group having a carbon number of 1 to 10, an alkenylene group having a carbon number of 2 to 10, or a divalent aromatic group In the case of a group, e represents 0 or 1, and R ⁵ represents a carboxylic acid group, a hydroxyl group, -SH, -NCO, -NHR', -CH=CH ₂ or -SO ₂ Cl, and R' represents a hydrogen atom or a carbon number of 1 to 6 alkyl groups.

Y ³ represents an oxygen atom or a divalent aromatic group.

R ⁶ represents a divalent aromatic group, a divalent heterocyclic group, or a divalent condensed ring group.

Y ⁶ represents an oxygen atom, -COO- or -OCO-.

R ⁷ represents a carboxylic acid group, a hydroxyl group, -SH, -NCO, -NHR", -CH=CH ₂ or -SO ₂ Cl, and R" represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Y ⁷ represents a single bond, -OCO-(CH ₂ ) _i -* or -O-(CH ₂ ) _j -*, wherein i and j each independently represent an integer from 1 to 10, and * each independently represents a bond with R ⁷ at the bond.

b, c, and f each independently represent an integer of 0 to 3.

Preferably, in the compound represented by formula (b2-1), Y ⁵ is a single bond and R ⁵ is a carboxyl group, or Y ⁵ is a methylene group, an alkylene group or a divalent aromatic group and R ⁵ is carboxyl.

Preferably, in the compound represented by formula (b2-2), R ⁷ is a carboxyl group.

Preferably, specific examples of the compound represented by formula (b2-1) are shown in the following formulas (b2-1-1) to (b2-1-24):

The above R ¹ is the same as the above-mentioned definition, and will not be repeated here; d is an integer from 0 to 10.

Specific examples of the compound represented by the formula (b2-2) are represented by the following formulae (b2-2-1) to (b2-2-3):

The above-mentioned R ³ is the same as the above-mentioned definition, and will not be repeated here.

In a specific example of the present invention, based on the total amount of monomers in the mixture being 1 mol, the amount of the cinnamic acid derivative (b2) used is 0.3 to 0.9 mol, preferably 0.3 to 0.85 mol, more Preferably, it is 0.3 to 0.8 moles.

When the reactant of the photosensitive polysiloxane (B) does not contain the cinnamic acid derivative (b2), the response speed of the liquid crystal alignment film formed by the prepared liquid crystal alignment agent is poor and image sticking is likely to occur.

Moreover, a part of the said cinnamic acid derivative (b2) can be replaced with the compound represented by following formula (b2-3) in the range which does not impair the effect of this invention.

W ¹⁵ -W ¹⁶ -W ¹⁷ type (b2-3)

In formula (b2-3), W ¹⁵ represents an alkyl group or an alkoxy group with a carbon number of 4 to 20 or a monovalent organic group with a carbon number of 3 to 40 containing an alicyclic group, wherein the above alkyl group or A part or all of the hydrogen atoms of the alkoxy group can be substituted by fluorine atoms; W ¹⁶ represents a single bond or a phenylene group, wherein, when W ¹⁵ is an alkoxy group, W ¹⁶ is a phenylene group; W ¹⁷ represents a carboxylic acid group, Hydroxyl, -SH, -NCO or -NHW, wherein W represents at least one of a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, -CH=CH ₂ and -SO ₂ Cl.

Compound (b3) represented by formula (b3-1)

Compound (b3) has a structure represented by formula (b3-1);

In formula (b3-1), X ₁ represents a linear or branched alkylidene with 1 to 10 carbons, a linear or branched alkylene with 1 to 10 carbons, a carbon Linear or branched alkenylidene with a number of 2 to 10, linear or branched alkenylene with a carbon number of 2 to 10, divalent alicyclic group with a carbon number of 3 to 30, A divalent aryl group having 6 to 30 carbon atoms or a divalent heterocyclic group having 2 to 30 carbon atoms; X ₂ represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms.

Preferably, compound (b3) represented by formula (b3-1) is at least one of the group consisting of compounds represented by formula (b3-2) and formula (b3-3):

In formula (b3-2), X ₃ represents a linear or branched alkylene group having 1 to 10 carbon atoms, a linear or branched alkylene group having 1 to 10 carbon atoms, and a linear or branched alkylene group having 1 to 10 carbon atoms. Linear or branched alkenylene, linear or branched alkenylene having 2 to 10 carbons; X ₂ represents a hydrogen atom or a linear or branched alkyl having 1 to 10 carbons.

In formula (b3-3), X ₄ and X ₅ represent a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms or a linear or branched alkylene group having 1 to 10 carbon atoms; Cy Indicates Cyclopropylene, Cyclopropylidene, Cyclobutylene, Cyclobutylidene, Cyclopentylene, Cyclopentylene ( Cyclopentylidene, Furanylene, Thiophenylene, phenylene, Pyrrolidinylene, Pyrrolidinylidene, Cyclohexenylene, Cyclohexenylidene, Piperidinylene, Piperidinylidene, Pyridinylene, pyridazinylene, pyrimidinylene, pyrimidine pyrazinylene, 1H-indolylene or naphthalenylene; X ₂ represents a hydrogen atom or a straight or branched chain alkyl group having 1 to 10 carbon atoms.

Specific examples of the compound (b3) represented by the formula (b3-2) may include compounds represented by the following formulae (b3-2-1) to (b3-2-38).

Specific examples of the compound (b3) represented by the formula (b3-3) may include compounds represented by the following formulae (b3-3-1) to (b3-3-106).

The compound (b3) represented by the formula (b3-1) is used in an amount of 0.01 to 0.2 mol, preferably 0.01 to 0.18 mol, more preferably 0.01 to 0.18 mol, based on the total mol of the second mixture of 1.0 mol. 0.03 to 0.18 moles.

When the reactant of the photosensitive polysiloxane (B) does not contain the compound (b3) represented by the formula (b3-1), the response speed of the liquid crystal alignment film formed by the prepared liquid crystal alignment agent is slow and Afterimages are prone to occur.

The molar ratio (b2)/(b3) of the cinnamic acid derivative (b2) to the compound (b3) represented by the formula (b3-1) is 2 to 20, preferably 2.2 to 20, more preferably 2.2 to 20. 18.

When the molar ratio between the cinnamic acid derivative (b2) and the compound (b3) represented by the formula (b3-1) falls within the above range, the performance of the liquid crystal alignment film formed by the prepared liquid crystal alignment agent can be further improved. Response speed and afterimage problems.

Method for producing photosensitive polysiloxane (B)

The photosensitive polysiloxane (B) used in the present invention can be obtained by mixing the epoxy group-containing polysiloxane (b1), the cinnamic acid derivative (b2), and the compound represented by the formula (b3-1) ( b3) Reaction synthesis in the presence of a catalyst.

As the catalyst, a known compound such as an organic salt or a curing accelerator that can promote the reaction between an epoxy compound and an acid anhydride can be used.

The above-mentioned organic salts include primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, etc. Tertiary organic amines such as amine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, and quaternary organic amines such as tetramethylammonium hydroxide, etc. Among these organic amines, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine, or tetramethylammonium hydroxide such as tetramethylammonium hydroxide are preferred. grade organic amines.

Specific examples of the above-mentioned hardening accelerators include tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine, and triethanolamine; 2-methylamine; Imidazole, 2-n-heptylimidazole, 2-n-alkylimidazole, 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-cyano Ethyl)-2-5-n-undecylimidazole, 1-(2-cyanoethyl)-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]imidazole, 1-(2-cyanoethyl-2-n-undecylimidazolium 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-undecylimidazolium)ethyl-S-triazine, 2,4-diamino-6-[ 2'-Ethyl-4'-methylimidazolyl-(1')]ethyl-S-triazine, trimeric isocyanate adduct of 2-methylimidazole, trimerization of 2-phenylimidazole Isocyanate adducts, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-S-triazine trimeric isocyanate adducts and other imidazole compounds ;Organophosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite; benzyl triphenyl phosphonium chloride, tetra-n-butyl phosphonium bromide, methyl triphenyl Phosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-normal Butylphosphonium-O,O-diethylphosphonium dithiosulfate (tetra-n-butylphosphonium-O,O-diethylphosphoro dithionate), tetra-n-butylphosphonium benzotriazole salt (tetra-n-butylphosphonium benzotriazolate), tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, etc.; 1,8-diazabicyclo[5.4 .0] Diazabicycloalkenes such as undecene-7 or its organic acid salts; organometallic compounds such as zinc octoate, tin octoate, aluminum acetylacetone complex, etc.; tetraethyl bromide Quaternary ammonium salts of ammonium, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride, etc.; boron compounds such as boron trifluoride, triphenyl borate, etc. ; metal halogen compounds such as zinc chloride and tin tetrachloride; high melting point dispersion type latent hardening accelerators such as amine addition accelerators such as dicyandiamide or adducts of amines and epoxy resins; Microcapsules in which the surfaces of the above-mentioned imidazole compounds, organophosphorus compounds or quaternary phosphonium salts are coated with polymers (microcapsule) type latent hardening accelerator; amine salt type latent hardening accelerator; high temperature dissociation type thermal cationic polymerization latent hardening accelerator such as Lewis acid salt, Bronsted acid salt, etc. Hardening accelerator, etc.

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

Based on 100 parts by weight of the photosensitive polysiloxane (B), the usage amount of the catalyst is 100 parts by weight or less, preferably 0.01 to 100 parts by weight, and more preferably 0.1 to 20 parts by weight.

The reaction temperature is preferably 0°C to 200°C, and more preferably 50°C to 150°C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

The synthesis reaction of the photosensitive polysiloxane (B) can be carried out in the presence of an organic solvent as necessary. The organic solvent is not particularly limited, and can be the same as or different from the organic solvent used in the preparation of the epoxy group-containing polysiloxane (b1) and the solvent (C) contained in the liquid crystal alignment agent of the present invention. same. Specific examples of the above organic solvent are preferably 2-butanone, 2-hexanone, methyl isobutyl ketone, n-butyl acetate, or a combination thereof.

The photosensitive polysiloxane (B) of the present invention has a polystyrene-converted weight average molecular weight of 2,000 to 20,000, preferably 3,000 to 18,000, as measured by Gel Permeation Chromatography (GPC). , more preferably 5,000 to 15,000.

Based on the total usage amount of the polymer (A) being 100 parts by weight, the usage amount of the photosensitive polysiloxane (B) is 3 parts by weight to 50 parts by weight, preferably 5 parts by weight to 50 parts by weight, and more preferably 5 to 45 parts by weight.

Solvent (C)

The solvent used in the liquid crystal aligning agent of the present invention is not particularly limited, as long as it can dissolve the polymer (A), the photosensitive polysiloxane (B) and other arbitrary components and does not react with them. Preferably, it is the same solvent used in the synthesis of the polyamic acid described above, and at the same time, the poor solvent used in the synthesis of the polyamic acid can also be used in combination.

Specific examples of the solvent (C) include, but are not limited to, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol Monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, Ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Or N,N-dimethylformamide or N,N-dimethylacetamide (N,N-dimethyl acetamide). The solvent (C) may be used alone or in combination of two or more.

Based on 100 parts by weight of polymer (A), the amount of solvent (C) used is 1000 to 3500 parts by weight, preferably 1000 to 3000 parts by weight, and more preferably 1200 to 3000 parts by weight parts by weight.

Additives (D)

Within the scope of not affecting the efficacy of the present invention, the liquid crystal alignment agent can also optionally add additives (D), wherein the additives (D) include compounds with at least two epoxy groups, silane compounds with functional groups, or a combination thereof.

Compounds with 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-Diglycidyl Ether Bromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl- m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4 '-diaminodiphenylmethane, 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, or a combination of the foregoing.

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

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

Specific examples of silane compounds having functional groups include, but are not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane, -aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyl Dimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethyl Oxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethyl Oxysilyl-1,4,7-triazdecane, 10-triethoxysilyl-1,4,7-triazdecane, 9-trimethoxysilyl-3,6-diazdecane Nonyl acetate, 9-triethoxysilyl-3,6-diaznonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-amino Propyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(ethylene oxide)-3 -aminopropyltrimethoxysilane, N-bis(ethylene oxide)-3-aminopropyltriethoxysilane, or a combination of the foregoing.

The silane compound having a functional group can be used alone or in combination.

Based on 100 parts by weight of the polymer (A), the amount of the functional group-containing silane compound may be 0 to 10 parts by weight, and preferably 0.5 to 10 parts by weight.

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

<Preparation method of liquid crystal alignment agent>

The preparation method of the liquid crystal alignment agent of the present invention is not particularly limited, and can be prepared by a general mixing method. For example, the polymer (A) prepared in the above-mentioned manner and the photosensitive polysiloxane (B) are uniformly mixed to form a mixture. Next, the solvent (C) is added at a temperature of 0°C to 200°C, and the additive (D) is optionally added, and finally the stirring device is continuously stirred until dissolved. In addition, it is preferable to add the solvent (C) 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 15cps to 35cps, preferably 17cps to 33cps, and more preferably 20cps to 30cps.

<Preparation method of liquid crystal alignment film>

The liquid crystal alignment agent of the present invention can be suitably used to form a liquid crystal alignment film by a photo-alignment method.

The method of forming a liquid crystal alignment film includes, for example, applying a liquid crystal alignment agent to a substrate to form a coating film, and irradiating the coating film with polarized or non-polarized radiation from a direction inclined relative to the surface of the coating film; or A method of imparting liquid crystal alignment energy to the coating film by irradiating the coating film with polarized radiation in a direction perpendicular to the film surface.

First, the liquid crystal aligning agent of the present invention is coated on the substrate provided with the patterned transparent conductive film by an appropriate coating method such as a roll coating method, a spin coating method, a printing method, and an ink-jet method. Transparent conductive film side. After coating, the coating surface is subjected to pre-bake treatment and then post-bake treatment to form a coating film. The purpose of the above-mentioned pre-baking treatment is to volatilize the organic solvent in the pre-coating layer. The conditions of the prebaking treatment are, for example, at 40 to 120° C. for 0.1 ~5 minutes. The conditions of the post-baking treatment are preferably at 120-300°C, more preferably at 150-250°C, preferably for 5-200 minutes, more preferably for 10-100 minutes. The thickness of the coating film after post-baking is preferably 0.001 to 1 μm, and more preferably 0.005 to 0.5 μm.

The substrate can be made of glass such as float glass, soda lime glass, etc.; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether, or polycarbonate. formed transparent substrates, etc.

As the transparent conductive film, a NESA film formed of SnO ₂ , an ITO film formed of In ₂ O ₃ -SnO ₂ , or the like can be used. In order to form these transparent conductive film patterns, a photo-etching technique, a method of using a mask when forming the transparent conductive film, or the like can be used.

When coating the liquid crystal aligning agent, in order to improve the adhesion between the substrate or the transparent conductive film and the coating film, functional silane compounds, titanate compounds, etc. may be pre-coated on the substrate and the transparent conductive film.

Next, a liquid crystal alignment film is formed from the coating film by irradiating the coating film with polarized or non-polarized radiation to impart alignment energy to the liquid crystal. Here, as the radiation, for example, ultraviolet rays including light with a wavelength of 150 to 800 nm and visible light can be used, and preferably, ultraviolet rays including light with a wavelength of 300 to 400 nm are used. When the radiation used is polarized light (linearly polarized light or partially polarized light), it may be irradiated from a direction perpendicular to the coating film surface, or may be irradiated from an oblique direction in order to impart a pretilt angle. On the other hand, when irradiating non-polarized radiation, it is necessary to irradiate from a direction inclined with respect to the coating film surface.

As a light source for irradiating radiation, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, or an excimer laser can be used. The ultraviolet rays in the above-mentioned preferable wavelength region can be obtained by a method of using the above-mentioned light source in combination with, for example, a filter, a diffraction grating, or the like.

The irradiation dose of radiation is preferably 1 J/m ² or more and less than 10000 J/m ² , more preferably 10 to 3000 J/m ² . In addition, in order to impart liquid crystal alignment energy to a coating film formed of a conventionally known liquid crystal alignment agent by a photo-alignment method, a radiation exposure amount of 10000 J/m ² or more is required. However, when the liquid crystal aligning agent of the present invention is used, even if the radiation exposure amount in the photo-alignment method is 3000 J/m ² or less, further 1000 J/m ² or less, and further 300 J/m ² or less, a good Alignment of liquid crystals, thereby helping to reduce the manufacturing cost of liquid crystal display elements.

<Liquid crystal display element and its production method>

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.

Two substrates on which the liquid crystal alignment films were formed as described above were prepared, and liquid crystal was arranged between the two substrates to manufacture a liquid crystal cell. In order to manufacture a liquid crystal cell (cell), the following two methods are mentioned, for example.

The first method: first, arrange the two substrates with a gap (cell gap) facing each other, so that the respective liquid crystal alignment films face each other; use a sealant to attach the peripheral parts of the two substrates together; The liquid crystal is injected into the interstitial space divided by the sealant; and the injection hole is closed, so that the liquid crystal cell can be manufactured.

The second method: a method called the One Drop Fill (ODF) method. First, on one of the two substrates for forming the liquid crystal alignment film For example, apply an ultraviolet curable sealing material to the specified part of the substrate; drop liquid crystal on the surface of the liquid crystal alignment film; then, attach another substrate to make the liquid crystal alignment film face each other; Thereby, a liquid crystal cell can be produced.

In the case of using any of the above methods, it is desirable to subsequently heat the liquid crystal cell to a temperature at which the liquid crystal to be used exhibits an isotropic phase, and then slowly cool to room temperature, thereby removing the flow alignment when filling the liquid crystal.

Then, the liquid crystal display element of this invention can be obtained by bonding a polarizing plate to the outer surface of a liquid crystal cell. Here, when the liquid crystal alignment film is horizontally aligned, by adjusting the angle formed by the polarization directions of the linearly polarized radiation irradiated on the two substrates on which the liquid crystal alignment film is formed, and the angle between each substrate and the polarizer, a TN type can be obtained. Or liquid crystal display elements of STN type liquid crystal cells. On the other hand, when the liquid crystal alignment film is vertically aligned, by forming a liquid crystal cell, the directions of the easy-to-align axes of the two substrates on which the liquid crystal alignment film is formed are made parallel, and the polarizing plate is aligned with the The liquid crystal cells are attached together so that the polarization direction and the easy alignment axis are at an angle of 45°, and a liquid crystal display element having a vertical alignment type liquid crystal cell can be formed.

As the sealant, for example, epoxy resin containing a curing agent and alumina balls as spacers can be used.

Specific examples of liquid crystals include nematic liquid crystals, discotic liquid crystals, and the like.

In the case of TN-type or STN-type liquid crystal cells, nematic liquid crystals with positive dielectric anisotropy are preferred, such as biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals ( phenylcyclohexane-based liquid crystal), ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane Liquid crystals (dioxane-based liquid crystals), bicyclooctane-based liquid crystals, cubane-based liquid crystals, etc. In addition, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate and the like may be further added to the aforementioned liquid crystals; Chiral agents sold under the trade names "C-15" and "CB-15" (manufactured by Merck &Co.); p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate (p -decyloxybenzylidene-p-amino-2-methyl butyl cinnamate) and other ferroelectric liquid crystals are used.

On the other hand, in the case of a vertically aligned liquid crystal cell, a nematic liquid crystal having negative dielectric anisotropy is preferred, and for example, dicyanobenzene-based liquid crystal, pyridazine liquid crystal can be used. (pyridazine-based liquid crystal), Schiff base-based liquid crystal, azoxy-based liquid crystal, biphenyl-based liquid crystal, phenyl ring Hexane-based liquid crystal (phenyl cyclohexane-based liquid crystal), etc.

As the polarizing plate used outside the liquid crystal cell, polyvinyl alcohol is sandwiched between a cellulose acetate protective film and made of polyvinyl alcohol. A polarizing plate formed by a polarizing film called "H film" obtained by absorbing iodine while stretching alignment, or a polarizing plate formed by the H film itself.

The thus-produced liquid crystal display element of the present invention is excellent in display performance and does not deteriorate in display performance even when used for a long time.

FIG. 1 is a side view of a liquid crystal display element according to an embodiment of the present invention. The liquid crystal display element 100 includes a first cell 110 , a second cell 120 and a liquid crystal cell 130 , wherein the second cell 120 is disposed separately from the first cell 110 , and the liquid crystal cell 130 is disposed between the first cell 110 and the second cell 120 .

The first unit 110 includes a first substrate 112, a first conductive film 114 and a first liquid crystal alignment film 116, wherein the first conductive film 114 is located between the first substrate 112 and the first liquid crystal alignment film 116, and the first liquid crystal alignment film 116 is located on one side of the liquid crystal cell 130 .

The second unit 120 includes a second substrate 122, a second conductive film 124 and a second liquid crystal alignment film 126, wherein the second conductive film 124 is located between the second substrate 122 and the second liquid crystal alignment film 126, and the second liquid crystal alignment film 126 is located on the other side of the liquid crystal cell 130 . In other words, the liquid crystal cell 130 is located between the first liquid crystal alignment film 116 and the second liquid crystal alignment film 126 .

The first substrate 112 and the second substrate 122 are selected from transparent materials, etc., wherein the transparent materials include but are not limited to alkali-free glass, soda lime glass, hard glass (Pyles glass), quartz glass for liquid crystal display devices , polyethylene terephthalate, polybutylene terephthalate, polyether terephthalate or polycarbonate, etc. The materials of the first conductive film 114 and the second conductive film 124 are selected from tin oxide (SnO ₂ ), indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), and the like.

The first liquid crystal alignment film 116 and the second liquid crystal alignment film 126 are respectively the above-mentioned liquid crystal alignment films, and their functions are to form a pretilt angle of the liquid crystal cell 130 . In addition, when a voltage is applied to the first conductive film 114 and the second conductive film 124, an electric field may be generated between the first conductive film 114 and the second conductive film 124. The electric field can drive the liquid crystal cell 130 , thereby changing the arrangement of liquid crystal molecules in the liquid crystal cell 130 .

The present invention will be further described with reference to the following embodiments, but it should be understood that these embodiments are only illustrative, and should not be construed as limiting the implementation of the present invention.

Synthesis example of polymer (A)

Synthesis Example A-1-1 to Synthesis Example A-1-10 of the polymer (A), and Synthesis Example A-2-1 to Synthesis Example A-2-4 are described below:

Synthesis Example A-1-1

A nitrogen inlet, a stirrer, a condenser and a thermometer were set on a four-necked conical flask with a volume of 500 ml, and nitrogen was introduced. Then, in a four-necked conical flask, add 5.41 grams (0.05 moles) of p-diamine benzene (abbreviated as a2-1) and 80 grams of N-methyl-2-pyrrolidone (N-methyl-2- pyrrolidone, abbreviated as NMP), and stirred at room temperature until dissolved. Next, 10.91 g (0.05 mol) of pyromellitic dianhydride (abbreviated as a1-1) and 20 g of NMP were added and reacted at room temperature for 2 hours. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60° C. to obtain a polymer (A-1-1).

Synthesis Example A-1-2 to Synthesis Example A-1-10

Synthesis Example A-1-2 to Synthesis Example A-1-10 are the same steps as those of Synthesis Example A-1-1 to prepare polymer (A-1-2) to polymer (A-1-10), respectively , and the difference lies in: changing the type of monomer and its usage amount (as shown in Table 1).

Synthesis Example A-2-1

A nitrogen inlet, a stirrer, a condenser and a thermometer were set on a four-necked conical flask with a volume of 500 ml, and nitrogen was introduced. Then, in a four-necked conical flask, add 5.41 grams (0.05 moles) of p-diamine benzene (abbreviated as a2-1) and 80 grams of N-methyl-2-pyrrolidone (N-methyl-2- pyrrolidone, abbreviated as NMP), and stirred at room temperature until dissolved. Next, 10.91 grams (0.05 moles) of pyromellitic dianhydride (abbreviated as a1-1) and 20 grams 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 imidization reaction. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60° C. to obtain the polymer (A-2-1).

Synthesis Example A-2-2 to Synthesis Example A-2-4

Synthesis Example A-2-2 to Synthesis Example A-2-4 are the same steps as Synthesis Example A-2-1 to prepare polymer (A-2-2) to polymer (A-2-4), respectively , and the difference lies in: changing the type of monomer and its usage amount (as shown in Table 1).

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

Synthesis example of photosensitive polysiloxane (B)

Synthesis Examples B-1 to B-15 and Comparative Synthesis Example B'-1 to Comparative Synthesis Example B'-3 of the photosensitive polysiloxane (B) are described below:

Synthesis Example B-1

Step 1: Set up a stirrer, a condenser and a thermometer on a three-necked flask with a volume of 500 ml. Then, in a three-necked flask, add 1.00 moles of 2-glycidyl ether ethyl trimethoxysilane (hereinafter referred to as GETMS) and 600 grams of propylene glycol monomethyl ether (hereinafter referred to as PGME), and put them in a room A triethylamine (Triethylamine, hereinafter abbreviated as TEA) aqueous solution (20 g TEA/200 g H ₂ O) was added within 30 minutes while stirring at a warm temperature. Next, the three-necked flask was immersed in an oil bath at 30°C and stirred for 30 minutes, then the oil bath was heated to 90°C within 30 minutes, and when the internal temperature of the solution reached 75°C, the heating and stirring were continued for 6 hours for polycondensation. . After the reaction is completed, the organic layer is taken out and washed with a 0.2 wt % ammonium nitrate aqueous solution to obtain a solution containing a polysiloxane compound.

Step 2: Add 0.90 mol of cinnamic acid derivative 5HBPA and 0.01 mol of 5-aminovaleric acid (abbreviated as b3-1) to the solution containing the polysiloxane compound. Then, the three-necked flask was immersed in a 30°C oil bath and stirred for 10 minutes, then the oil bath was heated to 115°C within 30 minutes, and 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-15

The polysiloxanes (B-2) to polysiloxane (B-15) of Synthesis Example B-2 to Synthesis Example B-15 were prepared in the same steps as those of Synthesis Example B-1, and the difference was that : Change the epoxy group-containing polysiloxane (b1), cinnamic acid derivative (b2), compound (b3), the type and amount of solvent and catalyst used, the reaction temperature and the polycondensation time, as shown in Table 2, shown in Table 3.

Comparative Synthesis Example B'-1 to Comparative Synthesis Example B'-3

The polysiloxanes (B'-1) to polysiloxane (B'-3) of Synthesis Example B'-1 to Synthesis Example B'-3 were prepared in the same procedure as Synthesis Example B-1, and The difference lies in: changing the type of the reactant of the epoxy group-containing polysiloxane (b1) and its usage, the type of the cinnamic acid derivative (b2) and its usage, the type of the compound (b3) and its usage. Table 2 and Table 3 show the usage amount, catalyst and solvent type and usage amount, reaction temperature and polycondensation time.

The compounds corresponding to the abbreviations in Table 2 and Table 3 are as follows

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

Examples 1 to 16 and Comparative Examples 1 to 11 of the liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display element are described below:

a. Liquid crystal alignment agent

Weigh 100 parts by weight of polymer (A-1-1), 3 parts by weight of polysiloxane (B-1) and 1000 parts by weight of N-methyl-2-pyrrolidone (referred to as C-1), And at room temperature, the liquid crystal alignment agent of Example 1 can be formed by continuously stirring with a stirring device until it dissolves.

b. Liquid crystal alignment film and liquid crystal display element

The liquid crystal alignment agent was coated on a glass substrate with a conductive film composed of ITO by spin coating, and then pre-baked on a heating plate at a temperature of 70 ° C for 3 minutes, and in a circulating oven at a temperature of Post-bake at 220°C for 20 minutes to obtain a coating film.

Using a Hg-Xe lamp and a Glan-Taylor prism, the surface of the coating film was irradiated with polarized ultraviolet rays containing a bright line of 313 nm for 50 seconds from a direction inclined at 40° from the normal to the substrate, thereby imparting liquid crystal Alignment can be made into a liquid crystal alignment film. At this time, the illuminance of the irradiated surface at a wavelength of 313 nm was 2 mW/cm ² . The same operation was repeated to produce two (one pair) substrates having a liquid crystal alignment film.

Next, by screen printing, an epoxy resin bonding agent containing alumina balls having a diameter of 5.5 μm was applied to the outer periphery of the surface on which the liquid crystal alignment film of the pair of substrates was formed. After the adhesive was applied, the substrates were bonded so that the liquid crystal alignment film surfaces of the respective substrates faced each other and the irradiation direction of the polarized ultraviolet rays became anti-parallel, and then heated at 150° C. Press fit.

Then, the liquid crystal injection port was injected|thrown-in from the liquid crystal injection port, and the liquid crystal injection port was sealed with the epoxy resin type adhesive agent. In order to eliminate the flow alignment during liquid crystal injection, it was heated to 150° C. and then slowly cooled to room temperature. Finally, the polarizing plates are attached to both outer sides of the substrate so that the polarizing directions are perpendicular to each other and the polarizing direction of the ultraviolet rays of the liquid crystal alignment film is 45° to obtain the liquid crystal display element of Example 1. Table 4 shows the results of evaluating the liquid crystal display element of Example 1 by the following evaluation methods.

Example 2 to Example 16

The liquid crystal alignment agents, liquid crystal alignment films and liquid crystal display elements of Examples 2 to 16 were prepared in the same steps as those of Example 1, and the difference was that the types of components and their usage amounts were changed, as shown in Table 4, shown in Table 5. The liquid crystal display elements produced in Examples 2 to 16 were evaluated in the following evaluation method, and the results are shown in Tables 4 and 5.

Comparative Example 1 to Comparative Example 11

The liquid crystal alignment agents, liquid crystal alignment films and liquid crystal display elements of Comparative Example 1 to Comparative Example 11 were prepared in the same steps as in Example 1, except that the types of components and their usage amounts were changed, as shown in Table 5. . For Comparative Example 1 to Comparative Example 11 The obtained liquid crystal display element was evaluated by the evaluation method described later, and Table 5 shows the results.

The compounds corresponding to the abbreviations in Tables 4 and 5 are shown below.

Evaluation method 1. Response speed:

First, the liquid crystal display elements of each example and the comparative example were irradiated with a visible light lamp without applying a voltage, and the brightness of the light passing through the liquid crystal display element at this time was measured by a photomultiplier tube, and the light passing through the liquid crystal display element at this time was measured. The luminance of the light of the element was set to 0% relative light transmittance. Next, the same test was performed on the liquid crystal display element under the condition that an alternating voltage of 10 V was applied for 5 seconds, and the luminance of the light passing through the liquid crystal display element at this time was set to 100% relative light transmittance. After that, the same test was performed on the liquid crystal display element under the condition of applying 3.5V AC voltage, and the elapsed time for the relative light transmittance from 10% to 90% was measured, and the elapsed time was defined as the response speed of the liquid crystal display element, Its evaluation criteria are as follows:

◎: Response speed≦10msec

○: 10msec<response speed≦20msec

╳: Response speed>20msec

2. Afterimage test:

The liquid crystal alignment agents of Examples and Comparative Examples were fabricated into liquid crystal alignment films, and liquid crystal display elements having the liquid crystal alignment films were fabricated. The above-mentioned liquid crystal display element was applied with a voltage of DC 17V at an ambient temperature of 100°C for 20 hours, and flicker was eliminated by The residual voltage (residual DC voltage (mV)) in the liquid crystal cell immediately after cutting off the DC voltage was obtained by using the flicker elimination method, and evaluated according to the following criteria:

◎: Residual DC voltage≦50mV

○: 100mV≦Residual DC voltage<50mV

△: 300mV≦Residual DC voltage<100mV

╳: Residual DC voltage>300mV

<Evaluation result>

From Tables 3 to 4, it is known that the liquid crystal alignment formed by the liquid crystal alignment agent (Example 1 to Example 16) of a specific photosensitive polysiloxane having both the cinnamic acid derivative (b2) and the compound (b3) The response speed of the film is fast, and it is not easy to produce afterimages.

On the other hand, since the liquid crystal aligning agents of Comparative Examples 1 to 11 do not have a specific photosensitive polysiloxane having both the cinnamic acid derivative (b2) and the compound (b3), the liquid crystal aligning agents of Comparative Examples 1 to 11 The 11's response speed and afterimage evaluation were poor.

In addition, when the amount of the cinnamic acid derivative (b2) and the compound (b3) of the photosensitive polysiloxane (B) in the liquid crystal alignment agent falls within a specific range (Example 1- 16), the response speed and afterimage performance of the liquid crystal alignment film formed by the prepared liquid crystal alignment agent can be further improved.

In addition, when the molar ratio (b2)/(b3) of the cinnamic acid derivative (b2) to the compound (b3) in the photosensitive polysiloxane (B) in the liquid crystal alignment agent falls within the range of 2 to 20 (Examples 2-4, 6-8, 10-16), the response speed is more prominent.

In conclusion, the liquid crystal aligning agent of the present invention has a specific photosensitive polysiloxane (B) having both the cinnamic acid derivative (b2) and the compound (b3), so that the response speed of the liquid crystal display element can be improved, And it is not easy to produce afterimages, and is suitable for liquid crystal display elements.

Although the present invention has been disclosed above by the embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field can make some changes and modifications without departing from the spirit and scope of the present invention. Therefore, The protection scope of the present invention shall be determined by the scope of the appended patent application.

100: Liquid crystal display element

110: Unit 1

112: The first substrate

114: The first conductive film

116: The first liquid crystal alignment film

120: Unit Two

122: Second substrate

124: second conductive film

126: The second liquid crystal alignment film

130: Liquid crystal unit

Claims (11)

A liquid crystal alignment agent, comprising: a polymer (A), a photosensitive polysiloxane (B), and a solvent (C), wherein the polymer (A) is obtained by reacting a first mixture, and the first A mixture includes a tetracarboxylic dianhydride component (a1) and a diamine component (a2); the photosensitive polysiloxane (B) is composed of epoxy-containing polysiloxane (b1), cinnamic acid The derivative (b2) is obtained by reacting with the compound (b3) represented by the formula (b3-3);

In formula (b3-3), X ₄ and X ₅ represent a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, or a linear or branched alkylene group having 1 to 10 carbon atoms; Cy Represents cyclopropane, cyclopropane, cyclobutane, cyclobutane, cyclopentylene, cyclopentylene, furan, thiophenyl, phenyl, pyrrole Peridyl, pyrrolidylene, cyclohexenylene, cyclohexenylene, piperidinyl, piperidinylene, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1H- Indolylene or naphthylene; X ₂ represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms. The liquid crystal aligning agent according to claim 1, wherein the epoxy group-containing polysiloxane (b1) includes a group represented by the formula (b1-1) and is represented by the formula (b1-2) at least one of the base of and the base represented by formula (b1-3),

In formula (b1-1), B represents an oxygen atom or a single bond; m represents an integer from 1 to 3; n represents an integer from 0 to 6, wherein when n represents 0, B represents a single bond; * represents a bond,

In formula (b1-2), p represents an integer from 0 to 6; * represents a bond,

In formula (b1-3), 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; * represents a bond. The liquid crystal aligning agent according to claim 1, wherein the epoxy group-containing polysiloxane (b1) comprises a copolymer obtained by hydrolysis and partial condensation of the second mixture, the The second mixture includes an epoxy group-containing silane compound (b1-I) having a structure represented by the following formula (b1-I-1): Si( R _a ) _h (OR _b ) _4-h Formula (b1-I-1) In formula (b1-I-1), R _a represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 2 to 10 carbon atoms. 10 alkenyl, aryl having 6 to 15 carbons, epoxy-containing alkyl or epoxy-containing alkoxy, and at least one R _a is epoxy-containing alkyl or epoxy-containing When R _a is plural, each of h R _a is the same or different; R _b represents a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an acyl group with a carbon number of 1 to 6 or a carbon number of The aryl group of 6 to 15; when R _b is plural, each of (4-h) R _b is the same or different; and h represents an integer of 1 to 3. The liquid crystal aligning agent according to claim 3, wherein the epoxy group-containing silane compound (b1-I) is used in an amount of 1 mol based on the total amount of monomers in the second mixture 0.5 mol to 1 mol. The liquid crystal aligning agent according to claim 1, wherein the cinnamic acid derivative (b2) is in the group consisting of compounds represented by formula (b2-1) to formula (b2-2). at least one,

In formula (b2-1) and formula (b2-2), R represents a fluorine atom or a cyano group; a represents an integer of 0 to 4; R ¹ and R ³ each independently represent a hydrogen atom and an alkane having 1 to 40 carbon atoms group or a monovalent alicyclic organic group with a carbon number of 3 to 40, the alkyl group is unsubstituted or at least a part of the hydrogen atoms are substituted by fluorine atoms; R ² and R ⁴ each independently represent a divalent aromatic group group, divalent alicyclic group, divalent heterocyclic group or divalent condensed ring group, and the R ² or the R ⁴ is unsubstituted or at least a part of the hydrogen atoms are substituted by R ⁸ , The R ⁸ each independently represents a halogen atom, a nitro group, a cyano group, an alkyl group having a carbon number of 1 to 5, or an alkoxy group having a carbon number of 1 to 5, and the alkyl group or the alkoxy group is a non-carbon group. Substituted or at least a part of the hydrogen atoms are substituted by halogen; Y ¹ , Y ² , Y ⁴ each independently represent a single bond, an oxygen atom, -COO- or -OCO-; Y ⁵ represents a single bond, an extension having 1 to 10 carbon atoms. An alkyl group, an alkenylene group or a divalent aromatic group having a carbon number of 2 to 10; when Y ⁵ represents a single bond, e represents 1, and R ⁵ represents a hydrogen atom; when Y ⁵ represents a carbon number of 1 to 10 In the case of an alkylene group, an alkenylene group with a carbon number of 2 to 10, or a divalent aromatic group, e represents 0 or 1, and R ⁵ represents a carboxylic acid group, a hydroxyl group, -SH, -NCO, -NHR, - CH=CH ₂ or -SO ₂ Cl, R represents a hydrogen atom or an alkyl group with a carbon number of 1 to 6; Y ³ represents an oxygen atom or a divalent aromatic group; R ⁶ represents a divalent aromatic group, a divalent aromatic group Heterocyclic group or divalent condensed ring group; Y ⁶ represents oxygen atom, -COO- or -OCO-; R ⁷ represents carboxylic acid group, hydroxyl, -SH, -NCO, -NHR", -CH=CH ₂ or -SO ₂ Cl, R" represents a hydrogen atom or an alkyl group with a carbon number of 1 to 6; Y ⁷ represents a single bond, -OCO-(CH ₂ ) _i -* or -O-(CH ₂ ) _j -* , wherein i and j each independently represent an integer from 1 to 10, and * each independently represents a bond with R ⁷ ; b, c, and f each independently represent an integer from 0 to 3. The liquid crystal alignment agent according to claim 3, wherein, based on the total amount of the monomers in the second mixture being 1 mol, the usage amount of the cinnamic acid derivative (b2) is 0.3 mol to 0.9 moles. The liquid crystal aligning agent as described in item 3 of the claimed scope, wherein based on the The total amount of the monomers in the second mixture is 1 mol, and the compound (b3) is used in an amount of 0.01 mol to 0.2 mol. The liquid crystal aligning agent according to claim 1, wherein the molar ratio (b2)/(b3) of the cinnamic acid derivative (b2) to the compound (b3) is 2 to 20. The liquid crystal alignment agent according to claim 1, wherein the photosensitive polysiloxane (B) is used in an amount of 3 to 50 parts by weight based on 100 parts by weight of the polymer (A); The solvent (C) is used in an amount of 1000 to 3500 parts by weight. A method for manufacturing a liquid crystal alignment film, comprising: applying the liquid crystal alignment agent according to any one of the first to ninth claims in the application scope on a substrate. A liquid crystal display element, comprising: a liquid crystal alignment film produced by the method for producing a liquid crystal alignment film as described in claim 10.

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